PREFACE
This annual report reviews the research activities of the Laboratory of Advanced
Science and Technology for Industry (LASTI) in the academic year of 2016 which is from
April 2016 to March 2017) including research activities using NewSUBARU light sourceat the site of SPring-8 and other research activities of the micro and nanoscale arecarried out energetically in the building of Center for Advanced Science and Technology(CAST) II.
The annual report describes that topics of the NewSUBARU research activities of thisyear including 1) the research and development of gamma ray application at BL2
beamline, 2) the next generation lithography by extreme ultraviolet (EUV) lithography
at BL3, BL9B, BL9C, and BL10 beamlines, 3) Lithographie, Galvanoformung, andAbformung (LIGA) process technology at BL2 and BL11 beamlines, 4) the chemical
analysis using soft X-ray absorption fine structure at (BL5, BL9A, and BL7 beamlines
and soft X-ray emission spectroscopy at BL5 and BL9A beamlines at soft x-ray energy
region, and 5) the nanoimprint lithographic technology at CAST.
Most of our research activities are being conducted in collaboration research works
with industries, government research institutes, and other universities.
We will continue to respond to the community’s demand by offering new science andtechnology.

Takeo Watanabe

Director of Laboratory of
Advanced Science andTechnology for Industry,
University of Hyogoi

ii

Staff of LASTI（In front of Advanced Research Building）

iii

The Organization ofLaboratory of Advanced Science and Technology for Industry
University of Hyogo
The organization
Director

Steering
Committee

Department ofLight and Particle Science and Technology

Department ofLight Application for Advanced Technology

Advanced Photon System
Beam Physics
Nanostructure Science and Technology
Guest Chair

Nano-science and Technology utilizing
Synchrotron Radiation
Nano-Micro System
Bio-Medical Technology (to be established)
Guest Chair

Staff (FY 2015)
Research and faculty staff
WATANABE Takeo, Professor , Director
MIYAMOTO Shuji, Professor
KANDA Kazuhiro, Professor
UTSUMI Yuichi, Professor
NIIBE Masahito, Associate Professor
SHOJI Yoshihiko, Associate Professor
HARUYAMA Yuichi, Associate Professor
YAMAGUCHI Akinobu, Associate Professor
AMANO Sho, Research Associate
HASHIMOTO Satoshi, Research Associate
HARADA Tetsuo, Research Associate
OKADA Makoto, Research Associate

Administrative staff
HAMAGAMI Akiyuki, General Manager
KOBORI Kazuyuki, Manager
KURODA Takashi, Chief
KAMIYA Miki, CAST
KANATANI Naoko, NewSUBARU
YAMAMOTO Keiko, CASTYOKOYAMA Yuka, CASTYANO Ayumi, CAST
FUJIMAKI Hisae, CASTYAMADA Miki, CAST
KUSUMOTO Kumi, CASTMORIGUCHI Miyuki, Harima Forum of
Science and Technology for 21st Century

Specially appointed staff
MOCHIZUKI Takayasu, Professor
KINOSHITA Hiroo, Professor
MATSUI Shinji, Professor
KUDOU Hiroto, Professor
TERANISHI Nobukazu,Professor
NAGATA Yutaka, Assistant Professor

Coordinator
FUKADA Noboru, NewSUBARUISHIKAWA Kazuko, NewSUBARUFUKUOKA Takao,CAST
Guest staff
OHKUMA Haruo, Professor
ASANO Yoshihiro, Professor
FUKUSHIMA Sei, Professor
HORIBE Hideo,Professor
BAN Hiroshi,Professor

Contact address
Advanced Research Building
3-1-2 Kouto, Kamigori-cho, Ako-gun, Hyogo, 678-1205 JAPAN.
T:+81-791-58-0249 F:+81-791-58-0242
NewSUBARU Synchrotron Radiation Facility
1-1-2 Kouto, Kamigori-cho, Ako-gun, Hyogo, 678-1205 JAPAN.
T:+81-791-58-2503 F:+81-791-58-2504
Web URL http://www.lasti.u-hyogo.ac.jp/,
http://www.lasti.u-hyogo.ac.jp/NS/
e-Maillasti@lasti.u-hyogo.ac.jp
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Part 1. Current Status of NewSUBARU
and Other Light Source

Staff of NewSUBARU（In front of NewSUBARU Facility）

NewSUBARU Storage Ring
Shuji Miyamoto, Satoshi Hashimoto, Yoshihiko Shoji
LASTI, University of Hyogo

Storage Ring Parameters
The machine parameters of the NewSUBARU
storage ring are listed in Table I. The machinecondition remains the same with last year during
the beginning half of the fiscal year 2016. In thelate half of FY2016, the NewSUBARU operated
without the 1.5 GeV high energy mode, because ofa failure of auxiliary power supply for the inverse
bending magnet. The failed power supply wascompleted update by the end of FY2016,
NewSUBARU has returned back to the normal
operation from the beginning of the FY 2017.

machin tuning(9.9 %)
machine study(6.3 %)

Beam downtime (3.0%)

User time(73.7%)

Total operation
2472h(100 %)Fig.1 Operating time breakdown of
NewSUBARU storage ring in FY2016.

Table I Main parameters of the NewSUBARU
storage ring.

user time, Friday is for 1.0 GeV or 1.5 GeV user
time. Night period or weekend is used for machine
study and user time with the special mode, such asa single bunch operation and a changing theelectron energy, if necessary. As mentioned above,in the late half of FY2016, the NewSUBARU
operated without the 1.5 GeV mode.
The total machine time in FY2016 was 2472 hrs,
121% of that of FY2015, excluding the beam downtime. Figure 1 shows the breakdown. The beam
down time includes not only the down by a failure,but also off-beam periods by a beam abort or others
due to the beam instability. The down time due tothe machine trouble was 3.0 % of the total
operation time. Main cause of this is the failure of
auxiliary power supply for the inverse bending
magnet.

Circumference
118.73 m
Lattice
DBA+Inv. bending
Number of bending mag. 12
Radius of curvature
3.217m
RF frequency
499.955 MHz
Betatron tunes
H: 6.30, V:2.23
Bunch length (sigma)
33ps (normal operation)
Harmonic number
198
Radiation loss per turn33.4 keV (@1GeV)Electron energy
1.0GeV
1.5GeV
Mode
TopUp
Decay
Natural energy spread
0.047%
0.072%Natural emittance
50 nm
112 nmStorage current
300 mA
350mA

Machine Trouble
The machine troubles in FY2015 are listed inTable II. The rate of hardware troubles wereincreasing due to the aging.
Figure 2 shows overview of the NewSUBARU
electron storage ring. The ring is consisted with 6
DBA cells with an inverse bending magnet at eachcells. There are 6 straight sections between each

Operation Status
The ring has two user-time operation modes, 1.0
GeV top-up operation mode and 1.5 GeV current
decay operation mode. The basic operation time is
9:00 - 21:00 of weekdays. Monday is used formachine R&D, Tuesday is for 1.5 GeV user time,
Wednesday and Thursday are for 1.0 GeV top-up

Table II Machine troubles in FY2016.
Group

Failure / trouble

down time (hr)Safty interlock
ControlBeam line, L4BT monitor, Emergency earthquake
GUI, VME, Operator console

5.93
3.50

MagnetOtherPower supply failure, interlock
Vacuum, Instability, UPS

62.12
3.10
74.65

1

Bending magnet (BM)Bending magnet (BM)Long undulatory

RF cavity

Short undulatory

inverse bending magnet(IBM)

Injection

Laser Compton scattering !-ray

Fig.2. Layout of NewSUBARU electron storage ring. The ring consists of 12 bending magnet, 6
inverse bending magnet, multipole magnets and steering magnets.
Machine Study and Special User Time
Table III shows the list of machine studies in FY
2016. One of the new study issues is new filling testof electron storage ring. The usual filling pattern foruser time is full fill 198 bunch plus two highcurrent 70 bunch. The ratio between high current
and low current bunches are 3:1 with total storage

cells, and they are used for an injection septum, an
acceleration RF cavity, two undulators and a laser
Compton scattering gamma ray source. A new
beam line is possible to install at the last straightsection.

Table III List of machine studies and special user mode in FY2016.
(unit is an operation shift = 12 hrs)
R & D theme and special user mode
New filling test for TOF
Special filling & ion trapping
Tuning of 1.5 GeV acceleration

responsible person
S.Miyamoto
Y.Shoji
S.Hashimoto & M Niibe

SR monitor (SR-2) tuning
Deceleration sequence

Y.Shoji
S.Miyamoto

(mA)

10

1

(mA)

10

1

(a)
0

operation shifts
5
4
6
2
1

I=2mA

100

200

ns

I=20mA
300

400
2016/10/3 12:07(b)0

I=2.04011mA

100

200

ns

300

I=19.742mA

400

Fig.3. Filling pattern of the electron bunch in the storage ring. Horizontal axis shows a lap time ofelectron circulation. (a) Model of filling pattern model of quasi single bunch operation. (b) Example
of a measured filling pattern of quasi single bunch operation. Total storage current is 300mA.

2

current of 300mA. We call this filling as“70+70+full fill 3:1”. The users, who want toapplicate the time resolved study by synchrotron
light, used single bunch electron mode where only
one electron bunch of RMS pulse width of about
30ps is stored. Single bunch operation mode is notcompatible with other synchrotron light users who
uses “70+70+full fill 3:1” filling. Because of thecurrent limit of 30mA for single bunch operation.
Figure 3 shows new filling pattern of the electron
bunch in the storage ring. (a) is a filling model for
quasi single bunch operation and (b) is an example
of measured filling pattern. There are regions
without an electron bunch of about 30 ns eachbefore and after the high-current bunch. The user
can use this high current bunch like a single bunchand can operate the total current of 300 mA. This
operation mode is compatible with othersynchrotron radiation users. It is possible to use
single bunch beams during normal daytime withthis filling.

Original auxiliary power supply was consisted of
two 50A/50V dropper power supplies. One of thesepower supplies was failed. Updated auxiliary power
supply is a 50A/100V switching power supply as
shown in Fig.4. In the late half of FY2016, theoperation cycles #5, #6, #7, NewSUBARU
operated only low energy mode of the electronenergy lower than 1GeV. The failed power supply
was completed update by the end of FY2016.
Bending magnet(BM) 12 coils

Inverse Bending
magnet (IBM) 6 coils

Auxiliary
power supply
 50A/100V 

Auxiliary Power Supply Update
Figure 4 shows schematic circuit diagram of thebending and inverse bending magnets and power
supplies are shown. The auxiliary power supply add
a lack current at high field strength region. This
current lack is due to different saturation
performance of magnetic field of inverse bending
magnet compare to the large bending magnet. This
correction is only required for high magnetic field
operation such as acceleration up to 1.5GeV
electron energy.

Main Powersupply795A/513V



MADOCA Control System
Fig.4. Schematic circuit diagram of the bending
and inverse bending magnets and power
supplies are shown. Updated auxiliary power
supplies adding a lack current on the inverse
bending magnets.

3

Beamlines
Masahito Niibe
LASTI, University of Hyogo
The arrangement of the beamlines in the
NewSUBARU synchrotron radiation facility is shownin Fig.1. Total nine beamlines are operating in the
NewSUBARU synchrotron radiation facility. Fourbeamlines of BL01, 03, 06 and 11 were constructeduntil 1999. Three beamlines of BL07, 09 and 10 werestarted the operation from 2000.
BL02 beamline was constructed for the usage of
LIGA in 2003.
BL03B beamline branched from the BL03 beamline
propose for the usage of the EUVL (extreme ultraviolet

lithography) microscope for the EUVL finished mask
inspection.
BL05 beamline was constructed in response to ademand in the industrial world in 2008, which is theenhancement of the analysis ability in the soft X-ray
region with the development of nanotechnology.
BL09B beamline branched from BL09 beamline forthe usage of the usage of the EUV interference
lithography to evaluate. And BL09C beamline branchedfrom BL09B beamline for the usage of the thickness
measurement of the carbon contamination originated to
the resist outgassing during the EUV exposure.

BL05B

BL05A

Fig. 1 Beamline arrangement in NewSUBARU.

4

I. BL01*Gamma-ray beam divergence : 0.5 mrad

BL01 is a beamline for research and developing newlight sources. This beamline is one of two longstraight section on NewSUBARU. Optical klystron was
installed at this straight section. Upstream side of thisbeamline (BL01B) is intended to be used for visible
and infrared light generated from free electron laser(FEL) or synchrotron radiation (SR). Downstream sideof this beamline (BL01A) is used for laser Compton
scattering gamma-rays source. Gamma-ray beamline
hutch just outside of the storage ring tunnel wasconstructed in

2004 for gamma-ray irradiation experiments.
Specification of this gamma-ray sources are listed inTable 1. New gamma-ray irradiation hutch "GACKO"
was installed at BL01A, collaborating with Konan
University. Table 2 shows the specification of“GACKO”.
Table 2. Specification of “GACKO”
Maximum gamma-ray power
0.33 mW
Maximum gamma-ray energy
1.7 MeV - 73
MeV
CO2 laser, wavelength/power
10.59 µm / 10W
1-1.7MeV gamma-ray flux
2×10^7γ/sec@10W/300mA
Nd:YVO4 laser,
1.064 µm/ 30W,
wavelength/power
0.532 µm/20W
10-17 MeV gamma-ray flux
5×10^7γ/sec@30W/300mA

Table 1. Specification of BL01 gamma beamGamma energy : 1.7 - 4 MeV
CO2 laser
Gamma flux* : 9 x106 γ/s
10.52 m: 6 x105 γ/s (1.5-1.7 MeV)
5W
(with 3mmφ collimator)
Gamma energy : 17 - 40 MeV
Nd laser
Gamma flux* : 7.5 x106 γ/s
1.064 m: 3 x105 γ/s (15-17 MeV)
0.532 m(with 3mmφ collimator)
5W*Electron beam energy : 1-1.5 GeV*Electron beam current : 250 mA

II. BL02
The LIGA (abbreviated name of Lithogaphic,
Galvanoformung and Abformung) process which
consists from deep x-ray lithography, electroforming,and molding process is one of the promising candidates
for such 3D micofabrication. More than hundreds
aspect ratio for microstructure can be attained by theusage of the higher energy x-rays (4-15 keV) fromsynchrotron radiation (SR) with deeper penetration
depth to the photosensitive resist. In this system wehave succeeded to enlarge the exposure area up to A4
size and the fabrication dimension from submicron tomillimeter by varying the energy of the x-ray source inaccordance with the size of desired microparts.
Microstructure with high aspect ratio over several
hundred will be achieved using the x-rays over 10 keV
since high energy x-ray has deep penetration depth tothe photo-sensitive resist materials. Whereas, in thecase of lithography for low energy x-rays from 1 keV to
2 keV, submicron structures with high aspect ratio will
be achieved using the x-rays mask with precise
line-width and thinner absorber, since low energy
x-rays has low penetration depth. Based on thisprinciple, the beamilne for x-ray exposure haveconstructed with continuous selectivity of x-rays from100 eV to 15 keV by using the x-ray mirrors (plane andcylindrical mirror) and Be film filters. The horizontal
angle of the outgoing SR could be obtained up to 12.5
mrad, which corresponds to the horizontal size of 220
mm (A4 horizontal size) at the exposure position. The
second characteristic performance of the beamline is
the high efficiency differential pumping system. This
was necessary for maintain the vacuum difference
between the storage ring (<10-9 Pa) and the end-station(<10-9 Pa) at which gasses for substrate cooling will be
introduced in the exposure apparatus.
The flexibility for the shapes and functions of
microstructure will be enlarged by achieving 3D
microfabrication process using multi step exposure atvarious configuration between x-ray mask andsubstrates. The relative positions between x-ray mask
and substrates, tilt and rotation angle to the SR incident
direction can be moved simultaneously during SR
exposure using 5 axis stages. The movement of eachaxis is controlled by the PC in terms of the scanningspeeds, scanning length, and repetition number. In orderto decrease the heat load of sample substrate sufferedduring SR irradiation helium introduction and substratecooling mechanism were also equipped. Specificationof spectrometer is listed in Table 3.

5

Table 3. Specification of the LIGA exposure system
OpticsPlane and cylindrical mirror, Be filters
Exposure energy
100 - 2 keV, and 4 – 15 keV
Exposure method
Proximity and multi-step exposure
Wafer size
A4 or 8 inch
Exposure area
230 mm(H) ×300 mm(V)
Exposure environment< 1 atm (He-gas)

III. BL03
BL03 is a beamline for the developing the next
generation lithographic technology so called extreme
ultraviolet lithography (EUVL). The exposure tool isinstalled at the end station. Using this exposure tool, theresearch and development of the next generation
lithography such as the less than 70 nm node is goingon process. The exposure wavelength is 13.5 nm.
The semiconductor industry plays a very
important role in the information technology (IT). In
2006, 256 Gbit DRAM with a gate length of 70 nm will
be demanded in the IT industry. The extreme ultraviolet
lithography (EUVL) is a promise technology for
fabricating a fine pattern less than 70 nm. To meet thisschedule, this technology has to be developed in thepilot line until 2004. As for the practical use, it is very
important that both to achieve large exposure area andto fabricate fine patterns. Therefore, at Himeji Instituteof Technology, large exposure field EUV camera
consists of three aspherical mirrors was developed.
First in the world, we fabricated 60 nm line and spacepattern in the large exposure area of 10 mm×10 mm ona wafer. Furthermore, BL03B beamline branches fromthe BL03 beamline propose for the usage of the EUVL
microscope for the EUVL finished mask inspection.
Table 4 shows the specification of ETS-1.

Table 4. Specification of the exposure tool (ETS-1)
Imaging optics
Three aspherical mirrors
Exposure wavelength13.5 nm
Numerical aperture
0.1
Demagnification
1/5
Resolution
60 nm
Depth of focus
0.9 µmExposure area (static)
30 mm×1 mm
Exposure area (scanning)
30 mm×28 mm
Mask size
4 inch, 8 inch, and ULE 6025
Wafer size
8 inchExposure environment
In vacuum
IV. BL05
BL05 was constructed in response to a demand in
the industrial world, which is enhancement of theanalysis ability in the soft x-ray region with thedevelopment of nanotechnology. BL05 consists of two
branch lines for use in the wide range from 50 eV to4000 eV. BL05A and BL05B are designed to cover theenergy range of 1300-4000 eV and 50-1300 eV,
respectively. The incident beam from the bending
magnet is provided for two branch lines throughdifferent windows of a mask. Therefore, these two
branch lines can be employed simultaneously. At theend stations of each branch, the transfer vessel systems
were mounted for the measurements of sample without

exposure to air. In addition, globe box was placed forthe preparation of samples into transfer vessel.
1) The double crystal monochromator was installedat the BL05A. InSb, Ge, Si, SiO2, Beryl and KTP
crystals are prepared for a double-crystal
monochromator. Toroidal mirrors are used as a
pre-mirror and a focusing mirror of BL05A. XAFS
measurement in the total electron yield mode andfluorescence XAFS measurement using SSD (SII
Vortex) can be performed. The fluorescence XAFS
spectra can be measured for samples at the end station
filled with He gas. Table 5 shows the specification of
monochromater.

6

Monochromator
Monochromator crystals
Energy range
Resolution

Table 5. Monochromator specification
Double crystal monochromator
SiO2（1010）, InSb（111）, Ge（111）, Beryl（1010）, KTP（110）, Si（111）1300-4000 eV
E/⊿E=3000

2) The constant-deviation monochromator consistingof a demagnifying spherical mirror and avaried-line-spacing plane grating (VLSPG), which canprovide high resolution, simple wavelength scanningwith fixed slits, was mounted on BL05B. The opticalsystem consists of a first mirror (M0), a second mirror(M1), an entrance slit (S1), a pre-mirror (M2), and threekinds of plane grating (G), an exit slit (S2) and afocusing mirror (M3). The including angle of themonochromator is 175°. Two measurement chambers
Monochromator
Grating
Energy range
Resolution

are prepared at the end station of BL05B. The XAFS
spectra in the total electron yield mode andfluorescence XAFS spectra using SDD (Ourstex) canbe measured in a high vacuum chamber. In addition,
the photoelectron spectrum can be measured using
spherical electron analyzer (VG Sienta, R3000) in an
ultrahigh-vacuum chamber. The chambers can be
replaced by each other within 1 hour. Table 6 shows the
specification of the monochromator.

Table 6. Monochromator specification
Varied-line-spacing plane grating monochromator
100 l/mm, 300 l/mm, 800 mm/l
50-1300 eV
E/⊿E=3000

V. BL06
BL06 has been mainly developed for irradiation
experiments such as photochemical reaction, SR-CVD,
photo-etching, surface modification. The whiteradiation beam from bending magnet is introduced tothe sample stage using a pair of mirror, whose incident
angle was 3°. The SR at BL06 sample stage had acontinuous spectrum from IR to soft x-ray, which was
lower than 1 keV. A differential pumping system can beutilized for experiments in a gas atmosphere, which isdifficult in the soft x-ray region. A sample holder can
install four pieces of samples at a time. By using heater
set in the sample holder, the sample can be heated fromroom temperature to 220 C. The temperature of sample
is monitored using a Cr-Al thermocouple mounted on
the sample holder.

VI. BL07A and BL07B
This beamline was designed for the development of
new materials by SR technology. This beamline
consists of two branch lines, which are provided withan incident beam from a 3-m-long undulator byswitching the first mirror. One of them is a highphoton-flux beamline with a multilayered-mirror
monochromator for the study of SR-process (BL07A)
and another is a high-resolution beamline with a variedline spacing grating monochromator for the evaluationof nano-structure characteristics by SR-spectroscopy(BL07B). The useful range of emitted photons from 50
to 800 eV is covered at both beamlines. The lightsource of BL07 is a 3-m length planar undulator, which
consists of 29 sets of permanent magnets, a period
length of which is 76 mm. The incident beam from theundulator is provided for two branch lines bytranslational switching of first mirror.
1) BL07A

The multilayered-mirror (MLM) monochromator,
which has high reflectivity in the soft X-ray region, wasinstalled at the BL07A. It consists of a switching mirror
chamber, a slit chamber, a MLM monochromator, afilter chamber and a reaction chamber. To obtain a large
photon flux, we decided to use only first mirror(switching mirror), M0, for focusing. The MLM
monochromator is designed to cover an energy range ofup to about 800 eV by combination of three kinds ofmirror pairs with 4 kinds of filter. The flux deliver by
this design is estimated to be between a maximum of1017 photons/s at 95 eV and a minimum 2 1014
photons/s at 300 eV for a 500 mA ring current. Table 7
shows the summary of BL07A. In addition, X-ray
fluorescence (XRF) apparatus using spherical variedline spacing grating was mounted at the downstream ofirradiation chamber. The poly capillary was used toenhance beam-condensing efficiency. Measurement
energy range was from 30 eV to 450 eV. This XRF

7

apparatus was expected to utilize the chemical analysis
on the light metals, Li and Be, and light elements, B, C
Energy
range
(eV)
50-60
60-95
90-140140-194
190-400
400-560

and N.

Material

Table 7. Summary of BL07A.
Multilayer mirror
spacinThicknenumber
g
ss
of
Ratio
layers

Mo/Si

20 nm

0.8

20

E/E

6.2 %

FiltermateriThickn
al
ess
Al

100
nm

None
Mo/B4C

11 nm

0.5

25

3.3 %
Ag

Ni/C

5 nm

0.5

60

550-800

2.5 %

Cr
Ni

100
nm
500
nm
500
nm

monochromator is designed to cover the energy range
50-800 eV with three gratings, of which including
angle are 168 . The VLSPG has been well known toobtain high resolution in extreme ultraviolet region bydiminishing various kinds of aberration. The total
resolving power about 3000 can be realized in thewhole energy region. Table 8 shows the specification of
the monochromator.

2) BL07B
The
constant-deviation
monochromatorconsisting of a demagnifying spherical mirror andvaried line spacing plane grating (VLSPG), which canprovide to high resolution, simple wavelength scanningwith fixed slits, was mounted on BL07B. The opticalsystem consists of a first mirror (M0), an entrance slit(S1), a premirror (M1), and three kinds of plane grating(G), an exit slit (S2) and a focusing mirror (M2). The

Table 8. Monochromator specification
Mount type
Hettrick-Underwood type
Grating G1, G2, G3
Plane VLS (600 l/mm, 1200 l/mm, 2400
l/mm)
Energy range
50-150 eV, 150 – 300 eV, 300-800 eVResolving power (E/ΔE)～3000
VII. BL09
A purpose of this beamline is studies on a soft x-ray
interferometry or a holographic exposure experimentwith making use of highly brilliant and coherent photon
beams radiated from 11 m long undulator in
NewSUBARU.
BL09 consists of M0 mirror, M1 mirror, G gratingand M2 and M3 mirror. M0 and M3 mirrors are used
for horizontal deflection and beam convergence, M1 isused for vertical beam convergence at the exit slit, andM2 is used for vertical deflection and beam
convergence. A monochromator is constructed by M1
and a plane grating. The maximum acceptance of theundulator beam is 0.64 mrad in horizontal and 0.27
mrad in vertical. The acceptance can be restricted by
4-jaw slits equipped at upstream of the M0 mirror.

BL09A beamline is used for material analysis:
X-ray absorption spectroscopy (XAS) and X-ray
photoelectron spectroscopy (XPS). In 2013, X-ray
emission spectrometer (XES) was introduced at theendstation of the BL-09A. The energy range andresolving power of the XES system was designed to beabout 50-600 eV and 1500, respectively.
BL09B beamline branched from BL09 beamline forthe usage of the EUV interference lithography for theevaluation of the exposure characteristics of EUV resist.
Coherence length of 1 mm at the resist exposure
position was achieved using BL09B beamilne. And
BL09C beamline branched from BL09B beamline forthe usage of the thickness measurement of the carbon
contamination originated to the resist outgassing during

8the EUV exposure. Table 9 shows the specification of

the monochromator.

Table 9. Monochromator specification
Mount typeMonk-Gillieson type
Grating
Plane VLS (300, 900, 1200 l/mm)
Energy range
50 – 750 eVResolving power (E/ΔE)～3000
VIII. BL10
BL10 is for the global use in the Himeji Institute ofTechnology. M0 mirror is used for horizontal deflection
and beam convergence, M1 is used for vertical beam
convergence at the exit slit, and M2 is used for verticaldeflection and beam convergence. A monochromator isconstructed by M1 and a plane grating. At the beginning,the multiplayers reflectivity measurement was carriedout at this beamline. The characteristics of this beamline
and the result of the Mo/Si multiplayers measurement
are carried out for the development of the EUV- mask
technology.
BL10 utilizes a monochromator of the varied line
spacing plane grating monochromator (VLS-PGM). Theline density of the monochromator in central region of
the gratings were 600, 1800 and 2,400 lines/mm. The
reflectometer is a two axis vacuum goniometer using
two Huber goniometers. One axis carries the sample,
which may for examplee be a mirror at the center of thereflectometer vacuum tank ( -motion). The other( -motion) carries the detector on a rotating arm. In

addition there are through-vacuum linear motions totranslate the sample in two orthogonal directions (x,y).
All motors are controlled by computer. The sample itself
is mounted on a kinematic holder. The control stage
monochromator rotation, and data analysis were
program using LABVIEW software. The reflectivity
result obtained at BL10 has a good agreement with that
at LBNL. Table 10 shows the specification the
monochromator.
The micro-CSM tool was adapted at the mostdownstream of the BL10 beamline for the EUV mask
defect inspection. This too is very effective for theinspection of the actinic patterned mask.
A large reflectometer was installed in a branch line
for large EUV optical component including EUV
collector mirrors. The reflectometer has a sample stage
with y, z, , , and Tilt axis, which can hold large
optical elements with a maximum weight of 50 kg, a
diameter of up to 800 mm, and a thickness of 250 mm.
The entire sample surface is able to be measured.

Table 10. Monochromator specification
Mount type
Hettrick-Underwood type
Grating
Plane VLS (600, 1800, 2400 l/mm)
Energy range
50 – 1,000 eVResolving power (E/ΔE)～1000

IX. BL11
A beam line BL11 is constructed for exposure
Hard X-ray Lithography (DXL) in the LIGA (German
acronym for Lithographite Galvanoformung and
Abformung) process. LIGA process, that utilizes auseful industrial application of SR, is one of thepromising technologies for fabrication of extremely
tall three-dimensional (3D) microstructures with alarge aspect ratio. This process was invented at theInstitut Fur Mikrostrukturtechnik (IMT) of the
Karlstuhe Nuclear Center (KfK) in 1980.
Microstructures with height of over a few hundredsµm have been widely applied to various fields such as
micro-mechanics, micro-optics, sensor and actuator
technology, chemical, medical and biologicalengineering, and so on. This beam line was designedby the criteria ; photon energy range from 2 keV to 8

keV, and a density of total irradiated photons 1011
photons/cm2. The BL11 can provide the most suitable
photon energy for microfabrication in X-ray
lithography, while the BL2 is equipped for fabricating
finepatternsubmicron-scale
structureandmicrostructure with high aspect ratio by selectivity of
X-rays using movable mirror system. That is, LIGA
process in NewSUBARU can provide the best 3D
microfabrication because the BL11 and BL2 arecomplementary. The beamline BL11 is consisting of anabsorber chamber, a first-mirror chamber (M1), a
4-way slit chamber, a Be and polyimide windowchamber, and an exposure chamber. The horizontal
angle of the outgoing SR could be obtained up to 17.8
mrad, providing a beam spot size on the exposure
mm2. The micron-scale structure withstage 809various configuration between x-ray mask andsubstrates. The exposure area of 200 mm × 200 mm
is brought to fruition. In order to decrease the heat loadof sample substrate suffered during SR irradiation,
helium introduction and substrate cooling system werealso equipped. The specification of the LIGA exposuresystem is listed in Table 11.

high aspect ratio will be achieved using the toroidal
typed mirror M1 which can produce a parallel
collimated beam of X-rays. In addition, thehomogeneity of the beam is excellently controlled by anovel adding system.
Using the precision stage in the exposure chamber,the flexibility for the shaped and functions of
microstructure will be enlarged by achieving 3D
microfabrication process using multi step exposure atTable 11. Specification of the LIGA exposure system
Exposure method
Proximity exposure
Wafer size
8 inch200 mm(H)×200 mm(V)
Exposure area
Exposure environment< 1atm (He-gas)

August 2016. As an organization crossing inuniversity courses, this center is consulted andadministered by all members of the LASTI related toanalysis, and in collaboration with the SR
Nanotechnology Center of Hyogo Prefecture, a wide
range of energy from hard X-rays to soft X-rays. We
aim to respond to various analysis needs of the area
on a one-stop basis.

Establishment of Research Center for Advanced
Synchrotron Radiation Analysis
In order to respond to diverse analysis needs fromindustries, it is necessary to advance technologicaldevelopment for analyzing beamlines (BLs) of
NewSUBARU synchrotron radiation facility toadvance integrated and strategic development ofanalyzing technology. For this reason, the ResearchCenter for Advanced SR Analysis was launched in

Acknowledgement
We would like to thank all the staff who work at
NewSUBARU synchrotron radiation researchfacility for their help to describe the update detailsof the beamlines.

10Laser Compton scattering gamma ray generated using Yb
fiber laser and Er fiber laser in NewSUBARU BL01
Kento Sugita, Yuusuke Morimoto, Satoshi Hashimoto, Sho Amano, Shuji Miyamoto
LASTI, University of Hyogo

Abstract

Laser Compton scattering (LCS) MeV gamma ray beams are produced by head on collision
between circling electron in NewSUBARU storage ring and laser photon. Using Yb fiber laser(1064nm) and Er fiber laser (1550nm) LCS-gamma flux is 1.0×103 photon/mA/W/s and 2.0×102
photon/mA/W/s, at gamma ray energy of 17MeV and 11MeV, respectively. These gamma rays arecollimated two collimators diameter of 6mm. These new pulse laser system are possible tosynchronize with the electron beam in the NewSUBARU storage ring. This system will be used
for time-of-flight experimental in future.

Introduction
We developed the high energies gamma ray
source using Laser Compton scattering at
NewSUBARU BL01 [1-3]. Laser Compton
scattering gamma ray (LCS-gamma) is producedby collision between relativistic electron instorage ring and laser photon. LCS-gamma
energy Eγ is described as following

E

1

4 2EL
4 EL
2 2
m ec 2the electron energy. This paper presents
performances of LCS-gamma systems using
new lasers for future application experiments
using γ-ray.
Generation and measurement of LCS-gamma
Figure 1 shows the system of LCS-gamma
source at BL01. The laser is injected into thestorage ring tunnel by passing two mirrors. In
the accelerator tunnel, the laser passes through amirror, a lens and a vacuum window into thevacuum duct. The laser beam axis is aligned tothe electron beam axis by adjusting two mirrors
at the outside. The scattered laser photon isboosted up to the gamma ray energy. The
generated γ -ray passes through the firstcollimator in tunnel and the second collimator in
optical hatch-1, to reach the optical hatch-2(GACKO).
Gamma ray flux was measured using NaI
detector at GACKO. New Yb fiber laser(KEOPSYS, wavelength 1064nm, pulse width 1ns) and Er fiber laser (KEOPSYS, wavelength
1550nm, pulse width 6ns) was introduced at
LCS-gamma system. Energies of γ -raygenerated with 1-GeV electron beam using Yb
laser and Er laser are calculated using Eq. (1) as

(1)

where

Ee
mec 2
EL is the energy of laser photon, γ is therelativistic coefficient, Ee is the kinetic energy ofcircling electron in the storage ring, me is therest mass of electron, c is the velocity of lightand θis the angle between the direction of theincident electron and the generated γ-ray. Theenergy of LCS-gamma-ray can be adjustable bychanging the laser wavelength or by changing

Fig1. LCS-gamma system at NewSUBARU BL01.

11

(b)

(a)

Fig2. Measured signal of the gamma photon flux as a function of energy using (a) Er-fiber laserand (b) Yb-fiber laser. large NaI detector was used.
17-MeV and 11-MeV, respectively. Collimatorsof 6mm in diameter are used in tunnel andhutch-1. The normalized fluxes of γ-ray were
measured to be 1.0 10 3 and 2.0 10 2 photons
mA-1W-1sec-1 using Er laser and Yb laser,
respectively. Figures 2 shows measured
LCS-gamma photon signals using a NaI
detector ( 8inch 12inch). Signals were recordedby multi channel analyzer (MCA). Verticalaxes are the intensity of gamma photon andhorizontal axes are the channel number of the
MCA. Channel of horizontal axis is equivalent
to energy of gamma photon. Approximately
2000 channel correspond to 20-MeV. Figure 3
shows the image of gamma-ray beam taken athatch-2. In this case, two 6mmφ collimators
were used, in the tunnel and in the hutch-1. The
image was recorded by a single photon
counting multi-pixel device MiniPix. The sizeof imaging area of MiniPix detector is
14mm 14mm with 256 256 resolution.
Shooting time of Figure 3 is 100 seconds in
integration. Diameter of LCS-gamma image isabout 8mm. This result is reasonable consider
the position of collimator and distance fromscattering point to the imaging position. Thisimaging device is useful to align small
irradiation targets in the gamma-ray hatch.

storage ring.
(a)

(b)

Fig3. LCS-gamma image taken by MiniPix.
(a) LCS-gamma image (b) line profile of
LCS-gamma image.

Future use
We have introduced two new laser system
into the LCS-gamma source beamline BL01.
These systems are useful for the study ofneutron time of flight measurement for photo
neutron.
Next step, we are planning to synchronize theselaser pulse with the circulating quasi-single
bunch electron in the NewSUBARU electron

Reference[1] S. Miyamoto et al., Radiat. Meas. 41 (2007)
S179.
[2] S. Amano et al., Nucl. Instr. and Meth. A(2009), doi:10.1016/j.nima2009.01.010[3] K. Horikawa et al., Nucl. Instr. and Meth.
Physics Research. A 618(2010) 209-215.

12

Development of fast positron measurement apparatus fordefects study in bulk materials
F. Hori, Y. Ueno, Y. Sumikura, A. Iwase, Graduate School of Eng., Osaka Pref. Univ.
K. Sugita, Y. Takemoto, S. Miyamoto, M. Terasawa, LASTI, Univ. of Hyogo
Abstract

We have been developed a new positron beam apparatus in a synchrotron radiation facility
NewSUBARU at LASTI, University of Hyogo, Japan. Highly energetic positrons were created via
pair creation in a Pb plate by injection of mono energetic gamma photons generated via laser
Compton scattering (LCS) of a high power Nd laser and GeV ordered electron circulating in astorage ring. Generated high energetic positrons are directly injected into target sample placed in a
vacuum chamber. By measuring positron annihilation Doppler broadening energy spectra, internal
defects and electron density distribution can be detected. We have performed positron annihilation
Doppler broadening measurement for bulk amorphous and crystal samples without destruction.

Introduction
Positron annihilation techniques are useful
tool to detect various types of defects and to
estimate local electronic state in solids. Recently,
there are many positron beam apparatus havebeen constructed in many research facilities but
they are almost all slow positron beam theenergy of about 10 keV. Such slow positron
beam can be reached and annihilated at only
near surface in solid, the maximum range of 10
nm at most. A new positron beam apparatus,
which can be generated as mega eV ordered fast
positron, has developed at NewSUBARU
photon facility. So far, we have successfully
detected defects generated in bulk iron samples
after fatigue stress applied [1]. By using thisapparatus, it is possible to detect defects existingin bulk materials. In our research study, we have
tried to detect defects, which are induced bydifferent conditions such as fatigue stress,
radiation damage, corrosion induced defects andtheir annealing behavior in bulk materials
without sample destruction. In this report, wehave shown the improvement of fast positron

apparatus and one of the positron measurement
results as a demonstration.
Positron system setup
Figure 1 shows that the schematic illustration of
positron generation and measurement system. The
LCS gamma ray generation and positronannihilation apparatus at the beam-line (BL01A) ofthe electron storage ring at the NewSUBARU SR
facility at LASTI, University of Hyogo. LCS
gamma rays an energy of 16.7 MeV have been
generated from laser light with a wavelength of1064 nm from a Nd laser and 1 GeV electron beam
circulating in the storage ring. By using LCS
gamma rays, positron and electron pair creation has
done in Pb target mounted on simple positron
apparatus in GACKO space as shown in this figure.
The generated positron and electron pairs can bebent to opposite directions according to themagnetic field and are then separated, while thepenetrated gamma ray photons are not influenced
by the magnetic field. Sample is placed where on
the line 8.3 MeV positron passing through in a

Figure 1 Schematic illustration of positron generation and annihilation measurement system at NewSUBARU.

13

Table 1

Positron generation system conditions

SR electron

Laser (Nd)LCS gamma ray

Positron

1 GeV1064 nm16.7 MeV

8.3 MeVFigure 2 Fast positron generation
annihilation measurement system.

normalized counts (arb. u.)

200 mA

andvacuum chamber, for positron annihilation Doppler
broadening measurement. Figure 2 shows the photoof developed fast positron generation and Doppler
broadening measurement system at NewSUBARU.
Positron annihilation signal of 511 keV gamma
photons were emitted from the sample and detectedby a HP-Ge detector with cooling device
X-COOLER-III. This measurement can be
performed in air, vacuum and any gas atmosphere.
To reduce the background radiation, the detector
was covered by 50 mm thick Pb block and theannihilation gamma rays were restricted by a 30
mm diameter Pb aperture. By using pure iron withthe size of 20 x 40 x 5 mm, measured system
conditions are listed in Table 1. LCS gamma andgenerated positrons by pair creation were more than
105 MeV-1s-1 and 3600 s-1 respectively [2].
Maximum count rate of the positron annihilation
gamma measured by HP-Ge was about 500 cps.
This value depends on incident laser power.

0.02

4.5 W

5

10 /MeV/s

100 500 cps

amorphous solid
crystalized solid

0.015

0.01

0.005

0
506

507 508 509 510 511 512 513 514 515 516
Energy [keV]

Figure 3 Positron annihilation Doppler profiles
in the bulk amorphous and crystal samples.

Figure 4 Calculated positron implanted depth inmetal by Monte Carlo simulation.

Positron annihilation measurement
The amorphous and crystal states of Zr-based
alloy samples with same chemical composition
were measured by using this positron measurement
system. This alloy can be molded as amorphousstate by rapidly quenching method above melting
point [3]. The shape of both samples is a cylinder
with 30 mm diameters and 40 mm height. Figure 3
shows the result of positron annihilation Doppler
broadening measurement for these alloys [4]. Thisdifference of energy distribution originated fromthe different atomic density. Relative atomic density
difference in these samples is about 0.4%. Figure 4
shows the positron annihilation depth profile
calculated by PENELOPE code based on the Monte
Carlo simulation [5]. As seen in this figure, incident
peak appears around 2 mm in this sample. Then, we
have successfully measured their different atomic
density originated from larger space of open
volume quenched in amorphous comparing to interatomic space of crystal state of same alloy.

Acknowledgement
This work was performed using NewSUBARUGACKO (Gamma Collaboration Hutch of Konan
University). The authors would like to express ourthanks to staff at the NewSUBARU SR facility for
their kind help in beam setup. This work was grantsupported by the Japan Society for the Promotion of
Science (JSPS) Research (Grant-in-Aid for
Scientific Research, B, no.26289365) and Metal
Technology Co. Ltd.
References[1] F.Hori et al., Jpn. J. Appl. Phys. conf. proc.2 011301(2014).
[2] K.Horikawa, S.Miyamoto, S.Amano, and T.Mochizuki:
Nucl. Instrum. Methods A 618 (2010) 209.
[3] Y.Yokoyama, A.Inoue, K.Fukaura, Mater. Trans. 43(2002) 2316.
[4] F.Hori, et.al., J. Phys. conf. Ser. 674 (2016) 012025.
[5] PENELOPE: Monte Carlo code developed by
Nuclear Energy Agency.

14

Mechanical stability of the main axis of the double multilayer
monochromator in BL07A
Masato Okui1) 2), Naoki Yato1), Ren Konno1), Akinobu Watanabe1), Osamu Shiga1),
Norio Murayama1), Sei Fukushima2) 3) and Kazuhiro Kanda2) 3)
1) Kohzu Precision Co., Ltd., 2) LASTI, Univercty of Hyogo,
3) Kobe Material Testing Laboratory Co., Ltd.

Abstract

Mechanical stability of the main axis of a monochromator is basement on machine study to gethigher beam stability from monochromator even if the other factors are more influence on the
problem. In this study, the mechanical stability of the main axis of MKZ-7NS type double
multilayer monochromator installed on BL07A in New SUBARU. Since about 1 hour after thestart of measurement when the monochromator would regard to reach thermal equilibrium, themeasured relative displacement was shown starting to have been decreased slowly as like linear
regression unlike the earlier exponential. The total relative displacement of the main axis theta1 ofthis monochromator in this experiment is about -1.6 arcsec during 6hours. The displacement would
be also stopped at this angle after then.

Introduction
Recently, necessary beam size for asynchrotron beamline is trend to smaller
than it of the decade before since a
beamline using micro beam is being
increased than the before. Therefore,
optical stability of monochromator on abeamline would need to keep higher frompoint of view of many user experiments
using micro beam than before.
There are many factors would havesignificant influence over the stability ofbeam position from monochromator
during experiment using beamline.
For example, thermal expansion of
mechanical parts by Compton scatteringor heat transfer from driving motor orvibration by compressor of cooling system
so on are considered as the one oftroubling factors on beam stability having
influence on.
However, it might be rare case that
only mechanical stability of an axis ofmonochromator is examined in beamline
in machine study of a monochromator.
The authors have considered themechanical stability should be basement
on machine study to get higher beamstability from monochromator even if theother factors are more influence on the
problem.
In this study, we were examined mechanicalstability of our MKZ-7NS type double
multilayer monochromator installed on BL07A
in New SUBARU as test case.

Experimental
The experiment was in performed on BL07A
in New SUBARU where Fig.1 shows the
panoramic view of that beamline and the photoof MKZ-7NS type monochromator.

(a)(b)
Fig.1. (a) Photograph of panoramicview of BL07A and (b) photographofMKZ-7NS type monochromator.
The MKZ-7NS type monochromator iscontrolled by an integrated computing algorismon the control application installed at personal
computer [1].
The specification and thesuitable feature for industrial use of this typemultilayer monochromator are also showed by
Okui et al. [1]. Fig.2 shows the schematic
system drawing.
Photon energy was 130eV in BL07A line at
this experiment, and then the ID gap of theundulator is 48.3mm in the beamline. Ring
energy was 1.5 GeV and decay mode.
After beam injection from the linac, the15

alignment all axes of monochromator tuned andjust immediately started measuring themechanical stability of main axis θ1.

of this MKZ-7NS monochromator.
From the result shown as Fig.3, the relative
position of the main axis θ1 from the initial
position have decreased as exponential since thestart of experiment till about 1hour after. This
exponential decrease would be able to presume
to have been influenced by thermal change ofseveral reason as like as Compton scattering or
motor and mechanical heating since the curve
would be exponential as like as thermal
diffusion equation.
Since about 1hour after the start ofmeasurement when the monochromator would
regard to reach thermal equilibrium as like theabove inference, the measured relative
displacement be shown starting to have been
decreased slowly as like linear regression unlike
the earlier exponential. This decrease continues
6 hours after then.
It can be suggested that this linear decrease
would be shown the mechanical stability of themain axis of the monochromator, MKZ-7NS.
The total relative displacement of the main
axis theta1 of this monochromator in thisexperiment is about -1.6 arcsec.
The direction of displacement is the decreaseof Bragg angle and that the direction is thegravity direction. This direction would be able
to just suggest the displacement of the main axis
would be caused by gravity.
However, this experiment suggests thismovement would be also stopped at a certain
smaller angle, -1.6arcsec. Thickness of meshedsurface of the gear of θ1 would be about 1μｍ
estimated by considering of the diameter ofworm wheel. It can be suggested that thislinear decrease would show the mechanicalstability of main axis θ1 of the monochromator,
MKZ-7NS.

Fig. 2. The schematic system drawings of
MKZ-7NS type monochromator
The positional motor pulse of all axes was
kept to the initial pulse so that the tuned
positions have never moved. The stability of θ1
was measured by ring scale encoder(Heidenhain RON886). And motor pulse of
the main axis θ1 was monitored by the motor
controller to confirm to fixing motor pulse of
the axis at the initial pulse.
Result and Discussion
Result of experiment is shown as Fig.3. In
the figure, the vertical axis shows relative thepositional displacement from the initial positionof the main axis θ1 after the all axes tuned andthe horizontal axis shows the elapsed time since
starting this experiment.

Acknowledgement
The authors appreciate for Mr. Shotaro
Tanaka University of Hyogo for his support inour beam time.
Fig. 3. Mechanical stability of the main axis
theta1 of MK-7NS type monochromator set on
BL07A in New SUBARU.
During the experiment, the count numbers of
motor pulse of the main axis θ1 was as same
numbers as the start count numbers. This factshows the main axis was not moved by thecontrol system. For this reason, it is justsuggested that the displacement of position
measured by read the ring encoder shall indicate
mainly the mechanical stability of the main axis

References[1] Okui et al., AIP Conference Proceedings
1741, 030033, (2016).

16

Energy Calibration and Spike Noise Reduction for
Ultra-soft X-ray Fluorescence Spectrum on BL07A
Sei Fukushima1,2＊, Hiroki Takamatsu1, Shotaro Tanaka1, Kazuhiro Kanda1
1: LASTI, University of Hyogo, 3-1-2 Koto Kamigori-cho, Ako-gun, Hyogo 678-1205 Japan
2: National Institute for Materials Science, 1-2-1 Sengen, Tsukuba-shi, Ibaraki 305-0047 Japan

Abstract

On the development and investigation of ultra-soft X-ray fluorescence spectroscopy, theestablishment of both energy calibration process and efficient noise reduction process should be soimportant for realization of the practical use. The results of the investigation about these twoprocesses are presented in this report for the high-performance type spectrometer on BL07A,.

Introduction
For analyzing the chemical state or
the electronic structure of valence band,
one of the most popular and widely usedmethod is XAFS (X-ray absorption finestructure) measurement. Of course,
NewSUBARU has been already executedand obtained many remarkable results inthe field of ultra-light elements. However,
one of the disadvantage points of XAFS
measurement is the necessity of sweep
the energy of incident X-rays. As known
well, the efficiency of excitation for corelevel of such ultra-light element is so low,
thus highly condensed monochromated
X-ray beam with high photon flux shouldbe necessary for measurement.
In contrast, the energy sweep ofincident X-rays are not necessary for
obtaining any fluorescent (characteristic)
X-rays from the samples. Thus, theexamination about the possibility of
application of fluorescent X-rays ofultra-light elements is important as apractical meaning.
Instead of the X-rays for excitation,

Fig.1

electron beam is also available forobtaining characteristic X-rays, and thismanner is already widely used as the
EPMA (electron probe micro analyzer)
analysis. This manner is also efficient for
the ultra-light elements, and, some of themembers of this group have alreadyfabricated EPMA system for the chemical
state analysis of ultra-light elements [1].
As already shown in the Annual report in2015FY, the spectrometer for fluorescent
X-rays was already confirmed its
specification, and has been continue toadjustment at BL07A.
Till the last FY, the adjustment ofspectrometer had been finished, and thesolution of some problems in beamline
had been made. And during this process,calibration manner of spectrometer andremoving the spike noise from themeasurement data were revealed as theitems which should be solved.
In this report, the countermeasures
are presented.

The schematic geometry of the ultra-soft X-ray fluorescence spectrometer*) present belonging: Kobe Material Testing Laboratory Co., Ltd.

17

Fig.2The pixel numbers at three peak
positions caused by the scattering of incident SR
source X-rays.

Fig.3 Pixel number – energy calibration curve
obtained with Fig.2 and eq.(1).
…(1)
If three or more sets of data which are consist
with the wave length (or the energy value) andthe pixel line number x corresponding with thatenergy value are obtained, eq.(1) is decided by thefitting procedure with a little adjustment of thevalues of r’ (or r1) and ’.

Energy calibration of the spectrometer
As already mention in previous report [1],the detector of the spectrometer for themeasurement of fluorescent X-rays is CCD
camera. The light receiving surface of CCD
camera is just set at the dispersion plane of thegrating of spectrometer. The dispersion direction

Ideally, the set of values of (x, ) should beobtained from the any fluorescent X-ray lines.
However, in the status, no lines were observed.
Thus, the peak position originated in the
excitation X-ray which was decided by the
set-up condition of the undurator and beamline
monochromater was used.
In Fig.2, 3 peaks are shown with its energy
calculated with the gap value of the undulator
and the each value of x. And, the obtained
calibration curvature is shown in Fig.3.

of the grating is made exactly to agree with thedirection of pixel lines on the plane of projection.
Thus, it is possible to obtain the fluorescent X-ray
spectrum by means of taking the total of thesignal strength of the line of pixels perpendicular
to the dispersion direction. And, the conversion
from the pixel line number to energy value is thenecessary step of obtaining any spectrum.
In Fig.1, the geometry between the grating
and the light receiving plane of CCD camera(camera surface) is shown. The notation and thetypical values of necessary variables are also
shown in this figure. In this CCD camera, the sizeof 1 pixel is 0.020mm, and if x is the pixel line
number, a1-0.02x is the distance between the topof the camera surface (the top of a1 in Fig.1) andthe xth pixel line. Thus, the wavelengthof
X-ray monochromated by this system can be
described as follows.

Spike noise cut filter
Fig.4 shows that the CCD image and aspectrum fabricated from this image whichwere obtained without any X-rays. A lot of

(a)

Fig.4

(b)

An example of background spectrum (a) and the CCD image (b) corresponding with (a).

18spikes are observed on this spectrum, and theseare significantly higher signal intensity than
average signal intensity (background). The
origin of these spike noise is the deteriorationof the CCD camera.
One of the effective numerical dataprocessing method for removing these spikenoise is Median filter. In comparison with the
any smoothing filter such as Savitzky-Golay
filter[2], data distortion due to any spike noiseon the processed spectrum can be suppressed.
However, if a measured spectrum has so small
structure that is hard to confirm before noise
cut processing, there is not the conclusive
evidence that such small structure should be
stored in Median filter. Thus, new numerical
process for only removing spike noise was tried
to apply.
As known well, the algorism of theMedian filter is as;
1. Take a data point xi set for all spectrum
data {x0, … xn}.
2. Take a consecutive data set {xi-m, … xi+m}
for xi.
3. Calculate the value of the median M ofthis set, and replace xi by M.
4. Take i +1 instead of i, then repeat the step
2 and 3.
The result by this process, due to the replacemost of all measured data by the median values,
it cannot be said with sure that any small andweak structure on the measured spectrum
should be stored on the processed spectrum.

Thus, a partly remodeled median filter was
tried to apply as a spike noise cut filter. The
algorism of this spike noise cut filter is as;
1. Take a data point xi set for all spectrum
data {x0, … xn}.
2. Take a consecutive data set {xi-m, … xi+m}
for xi.
3. Calculate the value of the median M ofthis set.
4. If xi ≧M, replace xi with (xi-1+xi+1)/2.
And if xi ＜M, nothing is operated.
5. Take i +1 instead of i, then repeat the step2, 3 and 4.
In above process, xi ≧M is the criterion forthat xi is a spike noise or not. And, no operation
when xi ＜M is the guarantee that any small
and weak structure is stored.
One of the results of this spike noise cut
filter is shown in Fig.5 as an example. It can beseen that almost all spike noise peaks are
removed by the processing with this filter.
Acknowledgement
The authors thank gratefully Kazunori
Tsukamoto and Dr. Toyohiko Tazawa (JEOLltd.) for the adjustment of the equipment.
References[1] S. Fukushima et al. Microchim. Acta 161
399 (2007)[2] A.Savitzkey et al. Anl. Chem. 36 1627
(1964)

Fig.5
An example of the results of the spike noise cut process. Almost
all noise spikes are removed.

19

Development of a transfer vessel system for XAS analysisof anaerobic samples in BL10
Yasuji Muramatsu and Keigo Yoshida
Graduate School of Engineering, University of Hyogo
Abstract
A transfer vessel system was developed for X-ray absorption analysis of anaerobic samples in
BL10. The system was designed considering the following conditions; (1) The usual
large-size sample plate can be transferred from a glovebox to the preparation chamber in
BL10, (2) Size of the vessel should be smaller than 300 x 200 x 200 mm3. The system has
been successfully developed and been used in the period of 2017B.
preparation chamber at the counter position of
the transfer vessel. The transfer vessel rod canhold the transfer holder with a M4 screw, andpull out the holder with sample plate from thevessel. The sample bank in the preparationchamber was improved; A sample bed for thetransfer holder is added to the bottom of sample
bank. The sample-plate on a sample holder canbe put on the additional sample bed. From thesample bed, only the sample plate can be heldby M3 screw and be pull out by the main sample
transfer rod.

1. Introduction
The analysis station for X-ray absorption
spectroscopy (XAS) has been developed andinstalled upstream the X-ray reflectometer in
BL10 at the NewSUBARU [1-4]. The XAS
station enables the chemical/electronic-state
analysis, and the X-ray reflectometer enables
layer structure analysis from the X-ray
reflectivity (XRR) measurements. For the XAS
analysis, a transfer vessel system has beenstrongly required to measure the anaerobic
samples such as electrode compounds andorganic/inorganic compounds which are easily
degraded by oxygen in atmosphere. Hence, thetransfer vessel system has been developed andinstalled into the XAS station in BL10. In thepresent article, design concept and schematics ofthe system are briefly described.
2. Design of the transfer vessel system
The transfer vessel system was designed,
based on the following concept;(1) The usual large-size sample plate (75mmL x
25 mmW) can be transferred from a glovebox tothe preparation chamber of the XAS station.
(2) Size of the vessel should be smaller than 300
x 200 x 200 mm3 to be used in a popular
glovebox.
To satisfy the above conditions, thesystem was designed as shown in Figure 1. The
main body of the transfer vessel is a cylinder
pipe sealed with an ICF70φ flanges with
O-rings. One flange is a manual gate valve andanother has a compact pressure gauge and asmall leak valve for gas-inlet/outlet. Sample
plate is put on a transfer holder in the vessel.
The vessel is connected to the preparationchamber through the manual gate valve. Size ofthe vessel is smaller than 300 x 200 x 200 mm3.
A transfer vessel rod is connected to theFig. 1 Schematics of the transfer vessel system

20

Fig. 2 Photos of a transfer vessel (a) and thetransfer vessel system installed in the XAS station
in BL10.

connected to the preparation chamber.
3. Transfer vessel system
Figure 2 shows the transfer vessel and the
XAS station employed the transfer vessel
system. The main body of the transfer vessel is
made
from
acrylic
resin(polymethyl-2-methylpropenoate) cylinder pipe.
This enables to easily observe inside the vessel
and to be compact without additional viewports.
Transfer of the anaerobic sample can be
performed with the following steps;(1) The transfer vessel involving asample-plate/holder in inert gas atmosphere isconnected to the preparation chamber.
(2) The preparation chamber is pumped with aroughing pump and a turbo molecular pump(TMP). On the pumping by TMP, the manualgate valve of the vessel is opened and the vessel
is pumped.
(3) Sample-plate/holder is pulled out from thevessel by the transfer rod. Then, it is put on asample bed in the preparation chamber.
(4) Only sample-plate is pulled out from the bed
by a main sample transfer rod, and transferred to
XAS main chamber.
The transfer vessel system will be open tousers in the period of 2017B.

References[1] Y. Muramatsu, A. Tsueda, T. Harada, and H.
Kinoshita, Adv. X-ray Chem. Anal., Japan, 43,
407-414 (2012).
[2] Y. Muramatsu, A. Tsueda, T. Uemura, T.
Harada, and H. Kinoshita, Adv. X-ray Chem.
Anal., Japan, 44, 243-251 (2013).
[3] T. Uemura, Y. Muramatsu, K. Nambu, T. Harada,and H. Kinoshita, Adv. X-ray Chem. Anal.,
Japan, 45, 269-278 (2014).
[4] T. Uemura, Y. Muramatsu, K. Nambu, D.
Fukuyama, M. Kuki, T. Harada, T. Watanabe,and H. Kinoshita, Adv. X-ray Chem. Anal.,
Japan, 46, 317-325 (2015).

21

Large area patterning using
a new deep x-ray lithography system (BL11)
Masaya Takeuchi1, Akinobu Yamaguchi1, Yuichi Utsumi1(Univ.Hyogo1)

Abstract

We developed a new deep x-ray lithography system (BL11) that fabricates highthree-dimensional microstructure with high aspect ratio at “NewSUBARU” synchrotron radiation
facility. In this study, we considered the beam scanning method that expose sample with uniform
intensity distribution in large patterning area and evaluated the processing characteristics of resist(PMMA).As a result, uniform processing depth of the deviation of a few percent was obtained.

Introduction
There have been rapid developments in theapplication of microsystems in advanced
industries such as intelligent information
systems, energy and environment conservations,and medical and biochemical services.
Microsystems typically consist of different typesof minute part for various applications. The
realizationofthree-dimensional(3D)
microstructures integrating multiple functions,such as electrical, optical, mechanical, andchemical functions in a restricted space, willbring many advantages to the industrial
applicability of such microsystems. Additionally,
demand for microfabrication with high aspectratio and high accuracy has been increasing
recently. To realize this requisition, thelithographite, galvanoformung and abformung
process (LIGA process), which consists ofdeep-X-ray lithography (DXL), electroforming,and molding, is a promising candidate [1]. The
LIGA process starts from the fabrication ofhigh-aspect-ratio polymer microstructures withheights greater than a few hundred microns
using DXL of a photosensitive polymer (resist)[2]. In the next step, a metal replica structure isformed by electroforming using the fabricatedpolymer microstructures as a master. The
obtained metal replica structure can be used as acomponent in a microsystem or as a mold insert
for final molding processes, such as hot
embossing and injection molding. The aspectratio of microstructures are decided at the X-ray
lithography step.
In this paper, we developed a new DXL systemthat enables a large area processing andgenerates with high parallelism (0.1 mrad) andhigh photon flux (1.7 kW/cm2). Using thissystem, we investigated the processing
characteristics of resist, and poroposed the beamscan method that exposes a large patterning areawith uniform intensity distribution on sample’s
surface.

Constitution of this system
Fig.1 shows a schematic diagram of thelithography system. This system consists of SR
beamline with x-ray optics and an exposure
apparatus with six-axis motion stages. The
beamline leads a SR beam from an electron
storage ring to an end station for exposure. The
SR beam propagates with enlarging horizontal
intensity distribution of the cross section andinserts to a toroidal mirror (Pt coating on single
crystal Si substrate). The x-ray beam collimatedby the mirror goes through two Be filters(300 µm and 125 µm thickness) for cutting
photon energy below 2 keV and reaches the
exposure apparatus. Fig.2 shows calculated SR
spectrum at exposure stage when the storage
ring energy is 1.0 GeV and 1.5 GeV operation
respectively where the storage ring current is
300 mA. These operation mode is selected
depending on required line width, shape,
processing depth, accuracy and throughput. Also,
by using ray tracing program SHADOW, thex-ray beam shape at the exposure stage wascalculated as shown in Fig.3. As a result, we
confirmed that the intensity distribution was
non-uniform arc shape at the cross section. Thisshows that the SR dose distribution is
non-uniform when the x-ray beam simply scans
the sample in the horizontal and verticaldirection.
Large area patterning
To solve above problem, we propose thescanning method that combines 2-dimentional
shift of sample in the Y-axis and X-axis
direction (Fig.4). we have attempted large area
microfabrication by using this method withpitch = 1 mm for 1.5 GeV operation.
Ploymethyl methacrylate (PMMA) was used as
photosensitive material. Also, GG developer(60 vol% dieyhylene glycol, 20 vol% morpholin,
15 vol% pure water, 5 vol% ethanolamine) was
utilized as developer and the development

22

Vertical direction (cm)condition was dip for 24 hours. Fig.5 shows theexperimental result. The average processing
depth was 323 µm, and the deviations were
below 1 % respectively. In this way, we havesucceeded obtaining uniform processing depth
in large patterning area of 8.5 cm × 10 cm.
Conclusion
The needs of 3D microstructure shifts for the
fabrication of the line width of dozen of microns
with high precision and high aspect ratio in various
industrial fields. We have developed a deep x-ray
lithography system that generates x-ray beam withhigh intensity and high parallelism in the universal
energy range from 2 keV to 7 keV. Additionally, we
have considered the beam scanning method
realizing uniform large area processing. As a resultof patterning using stainless steel mask, we haveobtained the pattern with uniform processing depthof the maximum deviation of below 1 %. Byutilizing this system, large area 3D microstructure
can be obtained with high aspect ratio and uniform
processing depth. It is expected that this x-ray
lithography system will offer some advantages in
the industrial applicability of LIGA process in thenear future.

0
1

5

4

3 2 1 0 1 2 3 4
Horizontal direction (cm)Fig.3 Calculated intensity distribution
at exposure stageY

5

Exposure stage

Patterning area
5 cm

・・・

4444

X

-5 cm
-5 cm

5 cm

Fig.4 Scanning method

Be filter

340 µmx-ray mask

Toroidal mirror

1

Pitch

4 –way slit
Storage ring

2

Beam

Exposure stage

resist3

30 µm

Exposureapparatus

Beamline

Energy density (W/cm2/0.1bw)

Fig.1 Schematic diagram of this lithography system

10

2

10

3

10

4

10

5

10

6

1

1.5 GeV
1.0 GeV2

蓄積電流 300 mA

Fig.5 Fabricated pattern for 1.5 GeV operation

References[1] E. W. Becker, W. Ehrfeld, P. Hagamann, A.
Maner, and D. Munchmeyer, Microelectron. Eng. 4,
35 (1986).
[2]. F. J. Panterbung, S. Achenbach, and S. Mohr,
Microsystems Tech. 4, (1998).

4 6 8 10

Photon energy (keV)

20

Fig.2 Calculated SR spectrum

at exposure stage for BL11

23

Part 2. Research Activities

Invited talk of Prof. Chary Rangacharyulu
at Advanced Technology Seminar 2017

Upgrade plan toward the higher-brightness radiation
source, NewSUBARU-2.0
Satoshi HASHIMOTOLASTI, University of Hyogo

Abstract

We have started to study the upgrade plans for the NewSUBARU storage ring. The“NewSUBARU-2.0” ring will have the lower electron beam emittance and generate thehigher-brightness radiation than the current ring. In this paper, the current status of the design
study is reported.

Introduction
NewSUBARU synchrotron radiation facility[1,2] has been operated for nearly 20 years. At
NewSUBARU, soft X-ray, EUV light and
gamma-ray by Compton scattering have beenused for mainly industrial applications.
The general layout of the NewSUBARU
storage ring is shown in Fig. 1. The ring has
two long and two short straight sections for
insertion devices. In one of two long straightsections, 10.8 m long undulator (LU) has been
installed and the other is for the gamma-ray
generation by the Compton scattering. In oneof the short straight sections, the short undulator(SU) is equipped.
The ring is composed from six unit
arrangements of electromagnets called “cell”.
Fig. 2 shows one cell composed from two 34
degrees bending magnets (BMs) and one -8
degrees inverse bending magnet (BI).
Horizontal and vertical beta functions andhorizontal dispersion function are shown in Fig.
3. 1.0 GeV Electron beams are injected from
SPring-8 Linac to the NewSUBARU ring. The
stored energy can be changed from 0.5 to 1.5
GeV. The natural emittance is 37 nm-rad at 1.0
GeV.
One of the possible upgrade plans of thestorage ring is the lower-emittance ring, which
can generate the higher-brightness radiation. It
is important for our facility to keep research
activities high for next two decades.
In
considering upgrade designs we assumed thatthe present building and shield tunnel are reusedas much as possible. Thus the circumference ofthe new ring must be almost same as the current
value (118m). The interesting problem is how
low the emittance can be possible at the small
and relatively low-energy ring. In simulation
works, tools like MADX[3], Bmad[4],elegant[5] are used. In this paper, we wish toreport the current status of the design studies ofthe future upgrade plans for the NewSUBARU
ring. Here we call it “NewSUBARU-2.0”.

Fig.1 Layout of the current NewSUBARU
storage ring.

Fig.2 Geometrical plot of magnets in
NewSUBARU per cell, which is composed fromtwo 34 deg. bending magnets (BMs) and one
inverse bending magnet (BI).

Fig. 3 Lattice functions of one cell of the
NewSUBARU ring. Horizontal and verticalbeta functions (upper) and horizontal dispersion(lower).
Low emittance lattices
The natural emittance27

x0

of an electron

beam in a storage ring is described in thefollowing simplified form [6],[nm rad] 1470

x0

E GeV
Jx

2

3

F
12 15 ,

where Jx horizontal damping partition,
deflection angle per bend, F factor depending on
the lattice type.
In NewSUBARU-2.0, keeping the bending
angle per cell 60 degrees, that is the same as thecurrent ring, we searched optimum solutions in
TBA and QBA lattice types.
In the case of TBA (Triple Bend Achromat)
lattice, a cell is composed from three 20 degrees
BMs as shown in Fig. 4. These BMs are
combined-types,
i.e.,
have
horizontally
defocusing quadrupole fields, and slightly
increase Jx (~1.2).
Optimizing latticefunctions by adjusting four quadrupole families
Q1~Q4, the minimum emittance is 5.5 nm-rad at
1.0 GeV.
In the case of QBA (Quadruple Bend
Achromat), where four 15 degrees BMs are used
per cell, the minimum emittance is 2.2 nm-rad.
The MBA (Multi Bend Achromat) whose
number of BMs is more than four is difficult
because of limited path length.
As a result, the emittance of 2.2~5.5 nm-rad,that is about one order smaller than the current
value, may be possible.

Fig. 6 Geometrical plot of Quadruple Bend
Achromat cell.

Fig. 7 Lattice functions of QBA: horizontal
and vertical beta functions (upper) andhorizontal dispersion (lower)
Synchrotron radiation from bending magnets
and wigglers
The critical photon energies at 1.0 and 1.5
GeV of NewSUBARU are 0.69 and 2.3 keV,
respectively.
Some users using X-ray as
micro-fabrication tools prefer higher-energy
photons and the operation at 1.5 GeV. Thus
about 40% of the user-time is operated at 1.5
GeV, and the remaining is 1.0 GeV. The
situation would be the same in the case of
NewSUBRU-2.0.
However, the increased
beam energy makes emittance worse, because of
its energy dependence.

Fig. 4
Geometrical plot of Triple Bend
Achromat cell.

Fig. 5 Lattice functions of TBA: horizontal andvertical beta functions (upper) and horizontal
dispersion (lower).

Fig. 8 Brightness of synchrotron radiationfrom bends and wigglers. Dotted lines are
bending radiation of NewSUBARU at 1.0 and
1.5 GeV.
The stored beam energy of
NewSUBARU-2.0 is 1.0 GeV.

28

Multi-pole damping wiggler in a shortstraight section is one of solutions for thisproblem. If the parameters are well defined,
such device can decrease emittance and also
generate the higher-energy photons than BM.
Emittance is determined in the balance between
radiation damping and radiation excitation,
W
0

where

1 I 5W I 50
1 I 2W I 20 ,

2
W
2
0W

Table 1 Typical wiggler parameters

Magnet type
w [T]
w [mm]
Nw
L [m]
w/ 0
w/
0

1 I 3W I 30
1 I 2W I 20 ,I 2 , I 3 , I 5 are radiation integrals0

Wiggler
#2
PM
1.5
200
10
2.0
0.91
1.01

Wiggler
#3
SC
3.6
64
31
1.984
0.64
1.31

Brightness of Long Undulator
One of the big features of NewSUBARU is
the 10.8m long undulator (LU), which is very
long compared to the total circumference of
118m. Fig. 9 shows brightness of LU in both
NewSUBARU
andNewSUBARU-2.0.
Because of the low emittance electron beam, LU
brightness in NewSUBARU-2.0 is several-times
larger than the present ring, if the stored current
is the same value. In addition to the present
LU, the installation of the second long undulator(LU2) in another straight section is most
attractive in NewSUBARU-2.0 for users.

W[6] and the indicesandindicate thatthe integral be taken over bending magnets
and wiggler magnets separately. σ denotes
horizontal beam size.

Using typical wiggler parameters shown in
Table 1, brightness curves are plotted in Fig. 8.
As shown in this figure the radiation intensityfrom multi-pole wiggler at 1.0 GeV issufficiently replaced to BM light at 1.5 GeVwith damping effect.

Fig. 9Wiggler
#1
SC
4.0
350
2
0.7
1.19
1.21

Brightness of LU radiation in NewSUBARU (left) and NewSUBARU-2.0 (right).

29

Phase Enhanced Harmonic Generation of thehigh-power EUV light
The alternative use of the long straightsection is the Phase Enhanced Harmonic
Generation (PEHG), which was proposed togenerate a high-power coherent radiation bymaking micro-bunches in an electron beam [7].
The high-power (~KW) radiation source by
PEHG for EUV Lithography was proposed [8].
The possibility of PEHG in NewSSUBARU-2.0
for EUVL light source is reported in the otherpaper of this annual report [9].

that many changes according to user’s opinions
would be included in the future draft.

Fig. 10 Proposed layouts of NewSUBARU-2.0.
“LU2” and “MU” denote “2nd Long Undulator”
and “Middle long Undulator”, respectively.

Compton Scattering Gamma-ray generation
Gamma-ray generation by Compton
scattering and its application has been an
important research field in NewSUBARU andthe situation will be the same in
NewSUBARU-2.0.
For the effective collisions between laser
photons and electrons, the overlap factor should
be close to unity, i.e., the photon beam waist
size should be equal to the electron beam size at
the center of straight section. However, in
NewSUBARU, the distance from a laser source
and the collision point in long straight section is
too long to efficiently focus laser beam.
Moving the Compton beam-line from thecurrent position to one of the short straightsection may be advantageous in the
NewSUBARU-2.0 ring.

Table 2 Typical parameters of NewSUBARU
and NewSUBARU-2.0 rings
Circumference [m]Beam energy [GeV]
Beam current [mA]
Insertion devices

Emittance [nm]NS1180.5-1.5500 (max.)
350 (top-up)
LU
ComptonSU
37

NS-2.0~118
0.5-1.5
<500
<300
LU
LU2 or
PEHG+MUMPW/SU
Compton
5.5 (TBA)
2.2 (QBA)

Acknowledgements
Thanks are due to Prof. S.Miyamoto of
LASTI, University of Hyogo, and my manycolleagues of NewSUBARU accelerator group(JASRI/SES), Dr.Y.Minagawa, Mr. K.Kajimoto,
Mr. K.Morisato, and Mr. H.Takeuchi.

Summary
For the upgrade of the NewSUBARU ring,
we have just started design study of thelow-emittance and high-brightness radiation
source, NewSUBARU-2.0.
The estimatedemittance is under 10 nm-rad. And we also
evaluated the usage of straight sections for
insertion devices. We would like to proposethat two short straight sections are used for
current short undulator or wiggler, and forCompton gamma-ray. And also one of twolong straight sections is used for the current
Long Undulator.
The other long straightsection can be used for another Long Undulator(LU2) as shown in Fig. 10 (left).
The
alternative usage is for both a middle longundulator (MU) and PEHG for EUVL lightsource as shown in Fig. 10 (right). Table 2
shows main parameters of NewSUBARU and
NewSUBARU-2.0 rings.
This is only the first step towards the future
upgrade in the accelerator researcher’s point ofview.
Dynamic aperture, tune survey,
chromatic correction, Intra-Beam Scattering, etc.
are in under work. It should be also mentioned

References[1] A.Ando et al., J. Synchrotron Rad., 5, 342-344(1998)[2] http://www.lasti.u-hyogo.ac.jp/NS-en[3] http://mad.web.cern.ch/mad/[4]https://wiki.classe.cornell.edu/ACC/ACL/Off
siteDoc[5] M. Borland, "elegant: A Flexible
aSDDS-Compliant Code for Accelerator
Simulation", Advanced Photon Source
LS-287, September 2000.
[6] Handbook of Accelerator Physics andEngineering, Wu.Chao, M.Tigner[7] Chao Feng, “Theoretical and Experimental
Studies on Novel High-Gain Seeded
Free-Electron Laser Schemes”, Springer Theses[8] Chao Feng et al., “Storage ring based EHG FEL
for EUV lithography”, High-Brightness Sourcesand Light-Driven Interactions (EUV, HILAS,
MICS) © 2016 OSA[9] S.Hashimoto et al., “Possibility of High-power
EUV light by PEHG scheme at NewSUBARU-2.0”,
in this Annual Report30Possibility of High-power EUV light by PEHG scheme
at NewSUBARU-2.0
Satoshi HASHIMOTO and Shuji MIYAMOTOLASTI, Univ. of Hyogo

Abstract

For the generation of coherent high-power radiations, many schemes based on accelerator and Free
Electron Laser (FEL) technologies have been proposed [1]. Phase-Enhanced Harmonic
Generation (PEHG) is one of these schemes and a high-power EUV light source for lithographyusing the PEHG at a storage ring was theoretically proposed [2]. We evaluated the possibility of
our storage ring as a high-power EUVL source in the case of the future upgrade plan
“NewSUBARU-2.0”.

Introduction
The lower-emittance electron storage ring
generates the higher-brightness radiation, forwhich many users are eager. As a future
upgrade plan of the NewSUBARU storage ring
[3,4], we have been performing design studiesof the lower-emittance ring “NewSUBARU2.0”. As a result of early simulation studies [5],the natural emittance of the NewSUBARU-2.0
ring is under 10 nm-rad.
As for insertion devices, one of the two longstraight sections in NewSUBARU-2.0 should be
used for the current 10.8 m Long Undulator(LU) as it is now. In the other long straightsection, installing the second Long Undulator
seems to be very attractive for radiation users.
On the other hand, another candidate of how to
use this section is the R&D for the generation of
the high-power EUV radiation by the PEHG
scheme. A general layout of the proposed
NewSUBARU-2.0 ring is shown in Fig. 1 [5].

Fig. 1 General layout of insertion devices
for the NewSUBARU-2.0 ring,ordered horizontally according to its energy. A
seed laser in visible range and an undulator(modulator) give electrons an energy
modulation. Transverse Gradient Undulator(TGU), where K parameter varies according to
the horizontal coordinate, gives electrons“merge” in its longitudinal phase-space. At
chicane magnets, the energy modulation isconverted to the density modulation by thedependence of electron’s path length on its
energy. The bunching factor at the entrance ofan undulator (radiator) includes relatively higher
harmonics of the seed laser wavelength. In theradiator, electron beams coherently radiate at
harmonics of the laser wavelength.

Phase-Enhanced Harmonic Generation
A high-power coherent radiation can begenerated from an electron beam that is bunched
or density modulated in radiation wavelength.
How to make micro-bunch effectively is a key
issue and many methods have been proposedand studied [1].
The PEHG scheme is illustrated in Fig. 2.
After the trajectory of an electron beam ishorizontally shifted by dogleg-1, electrons are

Fig.2

Typical PEHG parameters at NewSUBARU2.0

Layout of the Phase-Enhanced Harmonic Generation (PEHG) scheme.

31

At first, we examined the PEHG scheme
using the current NewSUBARU ring parameter.
However, it found to be difficult to sufficiently
full-fill the PEHG conditions because of toolarge emittance and beam size in horizontal.
Thus we simulated the PEHG bunching process
in the longitudinal phase-space in the case of
NewSUBARU-2.0 with smaller emittance andbeam size than the present ring.
Typical parameters of each component of the
PEHG scheme are listed in Table. 1. A seedlaser of wavelength 270 nm is used. Its 20th
harmonics corresponds to 13.5 nm needed for
EUVL. Fig. 3 shows the bunching factor at theentrance of the radiator, where the bunching
factor of the 20th harmonics is about 0.09.

Fig.3 Harmonic bunching factor at the radiator.
Summary
We studied the possibility of the high-gain
seeded FEL scheme called PEHG for thehigh-power EUV source for lithography in thecase of the NewSUBARU-2.0, the future
upgrade plan. Relatively large bunching factor
at the higher harmonics can be achieved. The
high-power EUV source using the PEHG can bepromising and one of attractive options in the
future NewSUBARU-2.0. Design studies on
the PEHG in NewSUBARU-2.0 in more detail
are in progress.

Table. I Typical parameters of PEHG the in
NewSUBARU-2.0 ring---------- Seed laser -------------------------wavelength [nm]270.0
harmonic number
20
power [MW]100.0
Rayleigh length [m]0.760
waist size [mm]0.256radius [mm]0.286
1.28E-03
area [cm2]7.80E+10
power density [W/cm2]
E-field strength [V/m]7.65E+08
normalized vector potential
6.43E-05---------- Electrons --------------------------average energy in gamma
1957.0energy spread in gamma
0.780
initial Hor. rms beam size [mm]0.050---------- Dogleg1 ----------------------------dispersion [m]0.600
D, dimensionless dispersion
4.783
Hor. beam size with dispersion [mm]0.244---------- Modulator --------------------------K parameter
1.800
total length [m]2.700
normarilzed vector potential
1.273
maximal modulation depth (in gamma)
2.165
A, maximal modulation amplitude
2.776---------- TGU --------------------------------K0
1.80
gradient Alpha [1/m]
56.00
T parameter of TGU
0.074---------- Chicane ----------------------------R56, the strength of the chicane-4.00E-05
B parameter-0.371

References[1] Chao Feng, “Theoretical and Experimental
Studies on Novel High-Gain Seeded
Free-Electron Laser Schemes”, Springer Theses[2] Chao Feng et al., “Storage ring based EHG FEL
for EUV lithography”, High-Brightness Sourcesand Light-Driven Interactions (EUV, HILAS,
MICS) © 2016 OSA[3] A.Ando et al., J. Synchrotron Rad., 5, 342-344(1998)[4] http://www.lasti.u-hyogo.ac.jp/NS-en[5] S.Hashimoto, “Upgrade plan toward the higherbrightness radiation source, NewSUBARU-2.0”, inthis Annual Report32Test of a gamma-ray diamond detector
A. Martens1, T. Williams1, S. Amano3, K. Cassou1, K. Dupraz1, E. Griesmayer2, S. Hashimoto3,
P. Kavrigin2, S. Miyamoto3, C. Ndiaye, A. Takemoto3, M. Yamaguchi3, F. Zomer1
1

LAL, Univ Paris-Sud, CNRS/IN2P3, Université Paris-Saclay, Orsay, France
martens@lal.in2p3.fr
2
Vienna University of Technology, Austria,
3
Laboratory of Advanced Science and Technology for Industry, University of Hyogo, Kouto, Hyogo, Japan.

Abstract

A 4-quadrant sCVD diamond sensor was installed and tested at NewSUBARU BL01 in June 2016.
Preliminary results are described here. They give confidence that such a radiation hard, fast andhardly destructive sensor is extremely useful for gamma beam monitoring, in particular at ELI-NPGBS.

Introduction
The Extreme Light Infrastructure Nuclear
Physics Gamma Beam System (ELI-NP GBS)
[1] is a novel source of photons with
unprecedented
spectraldensity,under
construction in Magurele Romania. Photons in
the range 200keV to 20MeV will be produced
by Compton scattering off electrons. A new
optical system is implemented in order to reacha spectral density greater than 5000 photons/(seV). The sub-picosecond synchronization andalignment within a few micrometers of thisapparatus require a thorough optimization
procedure with dedicated optical tools describedin Ref. [2]. The individual time separation
between each of the 32 successive collisions isapproximately 16 ns. A fast monitoring toolcapable of distinguishing 16 ns spaced bunchesof gamma-rays produced by this system would
be beneficial to confirm the bunch to bunch
performance and the final optimization of the
setup. The ability to evaluate the transverse
shape of the beam would be an additional asset
for such a detector, indeed the photon beampolarization is expected to be given by the laserbeam polarization, provided that on-axis
photons are selected and that smearing due tothe finite size and emittance of the beams is
negligible [3].
Diamond sensors are known to be fast andradiation hard detectors which make them better
candidates to accomplish the above mentioned
task with respect to the more usual (in the
nuclear physics community) solution consistingof using scintillating detectors [4, 5, 6]. They arealso used in the X-ray community with, among
others, excellence performance as an alignment
tool [7]. A first experiment with bunchedgamma-beams was conducted in 2015 at the
HIGS facility, showing the ability of thedetector to measure bunches separated by 16 ns[8]. The roughly flat energy dependence of the
response in the few MeV range was also
checked but more precise measurement would
be beneficial.
In order to further test the performance of adiamond sensor in the context of the online
monitoring of gamma-beams, a new experiment
was conducted in June 13 to 22, 2016 at
NewSUBARU. Preliminary results of thisexperiment are reported
Experimental setup
A 4-quadrant, 500 μm thick, single-crystal
chemical vapour deposited (sCVD) diamond
sensor, provided by CIVIDEC Instrumentation
GmbH [9], is placed in BL01 experimental
hutch, at about 22 meters from the interaction
point between the laser and the electron beams.
Each quadrant of the sensor is a square with 1.5
mm sides and is read-out with C6 or C2
amplifiers from CIVIDEC Instrumentation
GmbH, depending on the configuration of theexperiment. Waveforms from each amplifier are
digitalized synchronously thanks to a 8-channel
wavecatcher board [10] and stored to a local
computer for offline analysis. A dedicatedsystem allowing to carefully mount tungsten
foils 2 mm in front of the diamond sensor wasused during the experiment to investigate thesignal amplification introduced by theconversion of a significant part of the photons
into electrons achieved by this high-Z material.
Results
Several types of experiments were conducted.
Linearity tests of the sensor were performed bymeans of varying the laser-beam power (seeFigure 1) and the laser-beam Q-switch
frequency. As expected, increasing the laserbeam power at a given Q-swtich frequency, or
decreasing the Q-switch frequency at a constant33

average power, gives a rise in the yield ofdetected photons.

parameters can be reached. If this exercise seem
meaningless in the NewSUBARU setup,
Figure 1: Number of detected gamma (arbitraryunit) versus laser-beam average power in Watts.

Figure 3: Similar as Figure 2 but with a linear
polarization (preliminary).

The use of a W-foil of about 0.5mm allowed
to increase by a factor about 10 the detection
efficiency of the setup. Detailed simulations are
required to compare predictions with theobtained results. This work is still in progress.
Transverse scans of the gamma beam
allowed to measure the transverse shape of the
gamma beam. Some preliminary results areshown in Figures 1 and 2. These results wereobtained with two different configurations ofpolarization. The fact that the gamma-beam is
not perfectly circular in the case of a circularly
polarized laser-beam is related to the fact thatelectron beam sizes and emittance cannot be
neglected in the case of NewSUBARU. These
images are relatively free of background thanks
to the fact that the sensor is not sensitive tophotons below about 200 keV.
Detailed calculations taking into account all
known parameters of the electron and laser
beams are being held in order to extract the

because the laser-beam polarisation can bedirectly measured, it will not be the case bunch
per bunch in ELI-NP-GBS due to thecomplexity of the optical system. Such anindirect measurement through the transverse
shape of the gamma-beam may be proved usefulto check the polarisation of the gamma beam.
Conclusion
A 4-quadrant sCVD diamond sensor was
successfully tested at NewSUBARU BL01 in
June 2016. The results show that the expected
performance is reached. They give confidence inthe use of such type of sensor for a radiation
hard, fast and hardly destructive monitoring of
the gamma beam for the upcoming radiation
sources, and in particular at ELI-NP-GBS.
References[1] O.Adriani, et al., arXiv:physics.accph/1407.3669.
[2] K. Dupraz, et al., Phys. Rev. ST Accel.
Beams 17, 033501 (2014).
[3] V. Litvinenko, et al., Phys. Rev. Lett. 78
4569 (1997).
[4] Kölbl et al., IEEE Trans. Nucl. Science 6(2004).
[5] W. Drozdowski, NSS MIC proceedings
2008.
[6] Behnke et al., Nucl. Inst. Methods A(2002)[7] Desjardins, J. Synchrotron Rad. 21, 1217–
1223 (2014).
[8] T. Williams et al., Nucl. Inst. Methods inPhysics Research A 830 (2016) 391–396.
[9] CIVIDEC Instrumentation GmbH,www.cividec.at.
[10] wavecatcher reference

laser-beam polarisation from the transverse
shape of the gamma-beam. First results showedthat a precision of about 0.05 on the Stokes
Figure 2: Signal yield in the diamond sensor as afunction of its transverse position in the case ofa circularly polarized laser-beam (preliminary).
Dark dots correspond to missing measurement
points due to some malfunction of theacquisition software.

34

Test of Gamma-ray detector (LaBr3)
F. Camera1,2, G. Gosta1,2, N. Blasi2, B. Million2, A. Giaz2, O. Wieland2, F. M. Rossi1, H. Utsunomiya3, T.
Ari-izumi3, D. Takenaka3,, D. Filipescu4, I. Gheorghe4,5

1 University of Milano, Department of Physics, Via Celoria 16, 20133 Milano, Italy
2 INFN Section of Milano, Via Celoria 16, 20133 Milano, Italy
3 Konan University, Department of Physics, Okamoto 8-9-1, Higashinada, Kobe 658-8501, Japan
4 Extreme Light Infrastructure Nuclear Physics, "Horia Hulubei" National Institute for Physics and Nuclear Engineering (IFIN-HH), 30
Reactorului, 077125 Bucharest-Magurele, Romania
5 Faculty of Physics, University of Bucharest, Bucharest, Romania

Abstract

Intense beams of gamma-rays with energies ranging from 5 MeV to 38 MeV were used toilluminate two large volume (3.5" x 8") LaBr3:Ce detectors. The gamma-rays beams were
produced in the NewSUBARU facility and the measurements were performed in the GACKO
experimental hutch. The response function and the absolute detection efficiency of these two
detectors have been measured making use, as a reference, of a very large volume NaI(Tl) (8" x12") scintillator detector.

Introduction
The response function and the absolutedetection efficiency of LaBr3:Ce detectors are
known in case of low-medium energy gamma-rays,
see for example ref [1]. The response function andthe efficiency values for gamma rays with energy
higher than 10 MeV is in general extrapolated fromthe low energy values. At the moment, there arevery few measurements [2,3] of the response
function for gamma-rays up to 22 MeV and no
direct measurement of the LaBr3:Ce response
function and absolute detection efficiency for
gamma rays with energies higher than 22 MeV.
In the case of large volume LaBr3:Ce (3.5" x 8")
these measurements are even more important as
only with high energy gamma-rays the full volumeof the crystal will be used. In fact, to stop 661 or
1322 keV gamma rays only the first 5-10 cm of thedetector are used, as gamma-rays do not penetrate
deeply in the detector. Any GEANT extrapolation
for high energy gamma rays, therefore, needs to be
confirmed by experimental data.

energies used in the measurements. The gamma-ray
energies correspond to the maximum values in theenergy distributions.
Table 1. The maximum gamma beam energies andthe NewSUBARU storage ring electron energies
are listed in column one and two.
E [MeV]
5.53
6.04
9.00
13.00
14.99
16.93
20.99
24.02
29.02
34.03
38.00

Ee- [MeV]
550
575
704
849
914
974
1087
1162
1273
1380
1460

Experiments and Results
The measurements were performed in the GACKO
experimental hutch [4] of the NewSUBARU
synchrotron radiation facility located in the SPring8
site. The facility provides gamma beams using theLaser Compton Scattering (LCS) mechanism. A
GEANT4 simulation shows that the resulting
gamma beam is well collimated. The incident
gamma-ray energy distributions were obtained by
performing GEANT4 simulations of the response
functions of the LaBr3:Ce detector to the LCS
gamma-ray beam, involving the kinematics of LCS
and collimation geometry. Fig. 1 shows theextracted incident beam energy spectra while Fig. 2
shows the LaBr3:Ce measured spectra. Table 1
summarizes the electron and the gamma-ray

Figure 1: The incident gamma-ray energy spectrafrom GEANT4 simulations. The nominal beamenergy, corresponding to the maximum energy ofthe gamma-rays, is indicated over the spectrum.

35

In the measurements, for each beam energy wehave used two 3.5" x 8" crystals, each coupled to
two PMTs in order to disentangle crystals andPMT’s performances. The measurement of thedetector response function and of its non-linearity
was done using the laser beam in CW mode andusing a 5cm Pb absorber to avoid multiple gamma
rays in a single shot. For the measurement of theabsolute detection efficiency we have used the laser
beam in pulsed mode measuring the multi-phonon(MP) and single phonon (SP) spectra first with the
NaI(Tl) and then with the two LaBr3:Ce detectors.

measurement of the PMTs non-linearity curves.
Figure 5 and 6 show the multiple photon (MP)spectra (with and without beam) for the NaI(Tl)and one LaBr3:Ce detector (for gamma-rays of
9 MeV).

Figure 4: The non-linearity measured for the two
used PMT (P55 in the figure caption indicate PMT
R10233 S/N ZE5555 while P59 indicate PMT with
S/N ZE5559). The filled points indicate themeasured values, the dashed lines show third orderpolynomial curves which fitted the experimental
points.

Figure 2: The LaBr3:Ce measured gamma-ray
energy spectra. The maximum energy of the
gamma-rays is indicated over each spectrum
The analysis of the response function of the two
detectors is completed (see figure 3). We havefound that i) the two crystals, having the same size,
showed an identical behavior (within the error bars),ii) the PMTs showed a different degree of
non-linearity which can be parameterized using athird order polynomial as shown in figure 4.

Figure 5. The NaI(Tl) measured MP (black withbeam on, read for beam off) for the 9 MeV
incident gamma energy.

Figure 6. The LaBr3;Ce measured MP (blackwith beam on, read for beam off) for the 9 MeV
incident gamma energy.

Figure 3: The measured response function of both
crystals (C1 and C2 in the figure caption) coupled
to PMT R10233 S/N ZE5559. The gamma-ray
beam maximum energy was 9 MeV.

References[1] A. Nicolini et al. NIM A582(2007)554.
[2] M.Ciemala et al. NIMA608(2009)76[3] A.Giaz et al. NIMA 729(2013)910[4] H. Utsunomiya et al., NPN 25(2015)25.
.

The analysis of the data for the determinationof the absolute detection efficiency is notcompleted yet, as the first step consists in the36Improvement of Performancefor XAFS Measurements in BL05A
T. Hasegawa1, 2, 3, S. Fukushima2, 3 and K. Kanda3
1 Synchrotron Analysis L.L.C., 3-2-24 Wadamiya-dori, Hyogo-ku, Kobe-shi, Hyogo 652-0863 Japan
2 Kobe Material Testing Laboratory Co., Ltd., 47-13 Niijima, Harima-cho, Kako-gun, Hyogo 675-0155 Japan
3 LASTI, University of Hyogo, 3-1-2 Koto Kamigori-cho, Ako-gun, Hyogo 678-1205 Japan

Abstract

A renewed double crystal monochromator (DCM) improved performance of BL05A for X-ray
absorption fine structure (XAFS) measurements in the soft X-ray region. We were successful inincreasing of photon intensity by replacing the beryllium filter (45 m thickness) with previous
one (25 m thickness). In addition, we succeeded to obtain the sodium K-edge X-ray absorption
near edge structure (XANES) spectra, which enabled practical analysis in the X-ray region about

1keV.

Introduction
In the soft X-ray region around 1keV, X-ray
absorption fine structure (XAFS) spectroscopy
is important to industry because there are K
absorption edges of elements: sodium, magnesium,

than silicon), we succeeded to make the filter ofthickness from 45 m down to 25 m. Fig.1
shows a comparison of transmission of theberyllium filters with thickness between 45

aluminum and so on, in this energy region. Due tothese elements are abundant in the Earth’s crustand extremely wide variety of uses, XAFS analysisof them in the industry has high demand. BL05 is

m and 25 m. It can be seen that thetransmission is improved in the X-ray
region around 1keV.

constructed on the basis of strong demand ofindustrial users for XAFS spectroscopy on 2008
[1, 2]. BL05A, a branch line of BL05, is a unique1
0.9

double crystal monochromator (DCM) for XAFS
measurements in the soft X-ray region up to
4000eV in NewSUBARU. In BL05A, a

0.8

Golovchenco-type DCM has been used from2008, the operation for public use of BL05 has
started. But there was a problem with stability ofthe exit X-ray beam intensity, caused bydeterioration of a driving mechanical translating
system of the crystals on the DCM. So we
replaced the DCM to new one, calculation andcombination-type, in 2014. In this paper, we
report improved performance of BL05A for
XAFS measurements in the X-ray region about
1keV.

25 m thickness
45 m thickness

Transmission

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.4

1. Improvement of beryllium filter
Certain beamlines, such as the soft X-ray
beamlines, a beryllium filter is often used toprotect the vacuum within the storage ring fromcontamination because of providing a vacuum
isolation and transmitting the X-ray beam. The
beryllium filter in BL05A is located in the front
end, which is bonded to mounting flange andused to separate the ultra-high vacuum in thestorage ring with the front-end from the highvacuum in the beamline. For the purpose of
improving the transmission factor of X-rays at
the lower-energy region (e.g., the K absorption
edges of elements with atomic numbers less

1

2

4

Photon energy（keV）

Fig.1 Transmission of beryllinm filter.
2. Development of the available energy
range of BL05A for XAFS measurements
The renewed DCM was equipped with 2
pairs of crystals, Beryl (1010) and KTP (011),
due to covering the lower-energy than InSb
(111) crystal. Beryl crystals are often used for
XAFS measurements of magnesium, the other
KTP crystals are used for aluminum. But there37

is a problem that these crystals are likely to beaffected by radiation damage on synchrotron
light. Furthermore, the thermal loading of thecrystals gives rise to a difference in latticespacing. For the reason, high sensitive XAFS
measurements using these crystals are difficult.
In order to minimize these effects, we
introduced a water-cooling system to the DCM,
which stage equipped with the first crystals ismaintained at a precisely-controlled temperature
with 22.0 +/- 0.1 degrees Celsius accuracy. In
addition, the improvement of photon intensity
by replacing the filter led to obtain thehigh-quality magnesium and aluminum K-edge
XANES spectra [3, 4]. Then we tried to measure
the sodium K-edge XANES spectrum using
beryl crystals. In Fig.2, the measured sodium
K-edge XANES spectra of several sodium
compounds are shown. These samples were
mounted to a molybdenum holder withdouble-sided conductive tape. The spectra of thesamples were measured in the total electron
yield mode, but it can be seen that highly
sensitive spectra were obtained despite theinsulating powder. We verified that there isenough photon intensity in these lower-energy
region and can be obtained high-precision
XANES spectra, which provide a detailed
information related to chemical bond.

Normalized intensity（a.u.）

Na2SO4

Na2S2O3

Na2SO3

NaCl

1070

1080

1090

1100

1110

Photon energy（eV）

Fig.2 Na K-edge XANES spectra of
sodium compounds.

References[1] T. Hasegawa et al., Advances in X-ray Chem.
Anal. Jpn., 41, pp.99-106 (2010) [in Japanese].
[2] K. Kanda et al., J. Phys.: Conf. Ser., 425,
132005/1-4 (2013).
[3] T. Hasegawa et al., LASTI Annual Report,
vol.16, pp.73-74 (2014).
[4] T. Hasegawa et al., LASTI Annual Report,
vol.17, pp.16-17 (2015).

38

1120

Erosion process of fluorinated diamond-like carbon films by
exposure to soft X-rays
Kazuhiro Kanda1*, Hiroki Takamatsu1, Eri Miura-Fujiwara2, Hiroki Akasaka3, Akihiro Saiga4, Koji Tamada4
1 Laboratory of Advanced Science and Technology for Industry, University of Hyogo, Kamigori, Hyogo, Japan
2 School of Engineering, University of Hyogo, Himeji, Hyogo, Japan
3 School of Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo, Japan
4 National Institute of Technology, Tokyo College, Hachioji-shi, Tokyo, Japan

Abstract

The effect of soft X-ray irradiation on fluorinated diamond-like carbon (F-DLC) films wasinvestigated using synchrotron radiation (SR). The Vickers hardness of the F-DLC films
substantially increased from an initial value of 290 HV to 800 HV at a dose of 50 mA h, theremained constant at 1100 HV at doses of more than 300 mA h. This dose dependence wasconsistent with those of the film thickness, elemental composition, and sp2/(sp2+sp3) ratio ofcarbon in the film. A depth profile of the elemental composition inside each F-DLC film obtainedby measurement of the X-ray photoelectron spectrum (XPS) during sputtering showed that thecomposition ratio of fluorine was approximately constant from the surface to the neighborhood of
the substrate. Namely, fluorine atoms were desorbed by the SR irradiation from not only thesurface but also the substrate neighborhood. Modification by the SR irradiation was found to occur
in the entire F-DLC film of thickness 200 nm.

Introduction
Diamond-like carbon (DLC) film is anamorphous material that consists of sp2 hybridized
carbon, sp3 hybridized carbon, and hydrogen. DLC
films have been the subject of considerable attention
because of their exceptional properties, namely,
high hardness, low friction, chemical inertness, andgood electrical insulation. DLC films have therefore
been utilized as a coating material on edged tools,
automobile engines, molds, optical devices, andheads of computer hard disks owing to their
excellent properties. A huge market for DLCs isthus expected, and various novel DLC films havebeen synthesized and utilized for numerous
industrial purposes. One effective way to impart a
new property is to incorporate a heteroelement inaddition to carbon and hydrogen into a DLC film.
Fluorinated DLC (F-DLC) films are known to
exhibit particularly high insulation, a low dielectric
constant, a smooth surface, low surface free energy,
and chemical inertness, and are used to improve
tribological properties and for the corrosion
protection of steel and alloys. In addition, F-DLC
films are expected to be utilized as a coating
material on medical devices, electronic devices, andastronautical parts because of their excellent stain
resistance due to their low surface free energy. In
the industrial fields employing these applications,tolerance to X-rays is required. In general, DLC
films have very strong tolerance to soft X-ray
irradiation [1]. However, we have observed that theirradiation of soft X-rays on some DLC films
induces the etching and/or modification of the films[2-4]. In our previous study, we found that thesurface properties of F-DLC films were affected by

the irradiation of soft X-rays [5]. Upon SR
irradiation, the sudden desorption of fluorocarbon
species from the F-DLC film surface, increases insurface wettability, film density, and the ratio of sp2
hybridized carbon atoms, and decreases in the film
thickness and fluorine content of films wereobserved. These reactions stopped when the fluorine
ratio in the F-DLC films decreased to 10% as aconsequence of SR irradiation. In the present study
we attempt to clarify the surface modification
process of F-DLC films by the irradiation of soft
X-rays. We studied the effect of soft X-rays on thebulk properties of F-DLC films with the aim of
ensuring the safe use of F-DLC films in the X-ray
environments.
Experimental
Fluorinated DLC film was deposited on Si
wafer
using
an
amplitude-modulated
radio-frequency plasma-enhanced chemical vapor
deposition method (Nippon ITF) [6], which wassame sample as used in our previous study [5]. The
film thickness was estimated to be 216 nm by theobservation of a section image of F-DLC film usinga scanning electron microscope (SEM; JEOL,
JSM-6700). The fluorine and hydrogen contents ofas-deposited F-DLC film were estimated to be about
50 at.% and less than 4 at.%, respectively, using a
combinationof
Rutherford
backscattering
spectrometry (RBS) measurement and elastic recoil
detection analysis (ERDA) measurement. Thishydrogen was likely to have originated fromadsorbed molecules. In other words, the film wasconsidered to include no hydrogen. Such film has

39

been industrially used for coating rubber and resin section images of the F-DLC films were performed
to improve their abrasion resistance and sliding at several doses.
properties.
Figure 1 shows the dependence of the Vickers
The soft X-ray irradiation of F-DLC films hardness of the F-DLC films on the SR dose.
was carried out at BL06 in the NewSUBARU Vickers hardness was measured using a
synchrotron facility of the University of Hyogo. nanoindenter (ELIONIX NT-110a). In this
Details of the experimental apparatus at BL06 have measurement, the maximum load was 0.1 mN, using
been described in previous reports [7]. In brief, the a quadrilateral diamond as the indenter. The Vickers
SR extracted from a bending magnet, which is the hardness of the F-DLC film before irradiation waslight source of BL06, was introduced to the sample 290 HV, which markedly increased to 800 HVstage as a straight beam via a pair of mirrors. The after 50 mA h SR exposure. It further increased to
SR was irradiated onto the film surface
1100 HV after 300 mA h SR exposure, thenperpendicularly. The SR at the BL06 sample stage
remained constant at 1100 HV at doses of more
had a continuous spectrum from the infrared to soft
X-ray region and an energy below 1 keV. This than 300 mA h.
The depth profile of the elemental
energy range includes 300 eV and 690 eV, which arecompositionof the inside of the F-DLC film was
the ionization energies of a carbon K shell and ainvestigatedbythe measurement of XPS, while Ar
fluorine K shell, respectively. During the experiment,
sputtering.
XPS
spectra were measured using a
the electron energy of the NewSUBARU ring wasconventional
XPS
apparatus (ULVAC-PHI, PHI
1.0 GeV and the ring current was 300 mA in theKα line (1253.6 eV) as the
X-tool)with
theMg
top-up mode. The SR dose [mA h] was derived as
X-raysource.
Figure2shows
the depth profile of (a)the product of the ring current [mA] and thetheelemental
composition
ofthe
F-DLC film before
exposure time [h]. During the exposure of theirradiation,
(b)
that
after
irradiation
with an SR dose
F-DLC films to soft X-rays, the pressure in the-5irradiation chamber was on the order of 10 Pa and of 100 mA h, and (c) that after irradiation with an
the temperature of the sample stage was confirmed SR dose of 1000 mA h. The X-axis indicates theto be room temperature using a thermocouple. After number of cycles of Ar sputtering. In all films, thethe SR exposure, the modified F-DLC films were composition ratio of silicon suddenly increased after
about ten cycles. This increase indicated that the Si
stored in a dry box.
wafer substrate had been exposed by Ar sputtering.
The etching depth per sputtering cycle wasResults
The F-DLC films were exposed to SR to estimated to be about 20 nm for the F-DLC film
investigate their modification process upon the before irradiation. The composition ratio of fluorine
irradiation of soft X-rays. The dependence of the on the film surface was before irradiation about 0.4,
Vickers hardness of the F-DLC film on the SR dose in agreement with our previous measurement [5].
was measured for SR doses from 0 to 1000 mA h. The composition ratio of fluorine in the F-DLC film
The measurement of the depth profile of the before irradiation was slightly higher in theelemental composition from the surface to the neighborhood of the surface but approximately
substrate and the observation of surface images and constant from bulk to the neighborhood of thesubstrate. The mean composition ratio of fluorine
from the film surface to the substrate was estimatedto be 0.31. Upon SR irradiation, the composition
ratio of fluorine in the F-DLC film decreased; thecomposition ratio after SR irradiation was slightly
lower near the surface but approximately constantfrom bulk to the neighborhood of the substrate,
similarly to the F-DLC film before irradiation. In
other words, the thickness of the F-DLC film thatcan be modified by SR irradiation was greater than
200 nm. The mean composition ratio of fluorine
from the film surface to the substrate decreased to0.22 after an SR dose of 100 mA h and to 0.15 after
an SR dose of 1000 mA h.
Surface images and section images of theFig.1 Dependence of Vickers hardness of
F-DLC films were observed using a SEM, section of
F-DLC films on SR dose.
each F-DLC film was created by dividing the
F-DLC film with the Si wafer substrate. The F-DLC

40

film surface was coated with Au to impartconductivity because the charging of the film
surface by the irradiation of an electron beam was
expected because of the high insulation of the
F-DLC film. SEM images of F-DLC film surfaces
enlarged by a factor of 70,000 are shown in Fig. 3

Fig. 3 SEM images of F-DLC film surface (a)before irradiation and (b) after irradiation with
SR dose of 1000 mA h.

Fig. 4 SEM section images of F-DLC film (a)before irradiation and (b) after irradiation with
SR dose of 2000 mA h.
(a) before irradiation and in Fig. 3 (b) after
irradiation with an SR dose of 1000 mA h.
Numerous cracks were observed on the F-DLC film
surface before irradiation as shown in Fig. 3 (a).
Upon SR irradiation, the number of cracks increased
and their width decreased. Figures 4 (a) and (b)show section images of the F-DLC film enlarged bya factor of 70,000 before irradiation and after
irradiation with an SR dose of 2000 mA h,respectively. Many cracks that reached the substrate
were observed in both images. Species that desorbed
upon the irradiation of SR were considered to havepassed through these cracks.
Discussion
We investigated the effects of soft X-ray
irradiation on F-DLC films by focusing on thedepth of modification. The modification process ofthe F-DLC film by the irradiation of SR isconsidered to be as follows. (i) Carbon and/or
fluorine atoms in the F-DLC film were excited by
the soft X-rays corresponding to the ionizationenergies of the C K shell and/or F K shell. (ii)
Carbon-carbon bonds, which were bonded tofluorine atom, were decoupled and F-containing
species were desorbed from the F-DLC film. The
composition ratio of fluorine in the film decreased
because the main desorbed species were CF and
CF3. (iii) The desorption of CFx species caused adecrease in the film thickness. (iv) Carbon atoms
with an unpaired electron that remained afterFig. 2 Dependence of depth profile of elemental
composition of inner F-DLC film on SR dose(a) before irradiation, (b) after irradiation with
SR dose of 100 mA h, and (c) after irradiation
with SR dose of 1000 mA h.

41

desorption of CFx species coupled neighboringcarbon atoms also having an unpaired electron. This
coupling caused an increase in the sp2/(sp2+sp3)
ratio of carbon atoms in the F-DLC film because
carbon-carbon double bonds were formed by thiscoupling. (v) The process stopped when the fluorine
ratio in the F-DLC film decreased to 10% upon
the irradiation of SR with a dose of 300 mA h [5].
As a result, the film thickness, the composition ratioof fluorine, and the sp2/(sp2+sp3) ratio of carbon
atoms had a similar dependence on the dose; they
substantially changed up to a dose of 50 mA h andremained constant at doses of more than 300 mA h.
An increase in the Vickers hardness of the
F-DLC films was observed after SR irradiation in
the present work. The creation of new bonds
between carbon atoms in step (iv) of the above
process is considered to have enhanced the film
hardness. The Vickers hardness substantially
increased up to a dose of 50 mA h and remained
constant at doses of more than 300 mA h. Thisdependence of the Vickers hardness on the SR doseis in agreement with those of the film thickness,elemental composition, and sp2/(sp2+sp3) ratio of
the carbon in the film on the SR dose. This
indicated that modification by SR irradiation
proceeded on the film surface at the same time as
inside of the F-DLC film because the film hardness
was determined by the structure of the whole film.
This was proved from the measurement of the depth
profile of the elemental composition by XPS during

Ar sputtering, which indicated that the Fcomposition ratio changed almost uniformly fromthe surface of the film to the neighborhood of thesubstrate. The transmission of the F-DLC film inthe present work was estimated using the X-ray
database of the Center for X-ray Optics at
Lawrence Berkeley National Laboratory [8].
Assuming the elemental composition, density, andthickness substituted from the result of our previous
work [5], F/C ratio = 1, 1.99 g/cm-3, and 216 nm,
respectively, the transmission of this film wasestimated to be 0.29 at 287.2 eV, whichcorresponded to the absorption edge of the C
K-edge. Therefore, it was possible to excite carbon
atoms in the neighborhood of the substrate by
X-rays in the present experiment. As observed
using the SEM, numerous cracks that connected thesubstrate to the surface existed in the films. We
consider that the desorbed species were emitted
through these cracks.
The behavior of the F-DLC film upon SR
irradiation, such as the decrease in film thickness,the increase in the sp2/(sp2+sp3) ratio of carbon
atoms, and the increase in Vickers hardness,
stopped above an the SR dose of over 300 mA h.
This was ascribed to the decrease in the fluorine
content in the film to 15% by desorption of theF-containing species induced by the SR irradiation.
As a result, the F-DLC film whose F content was
lower than 15 % exhibited durability against theirradiation of soft X-rays.

Referencesby soft X-ray irradiation, Sens. Mater. 29(2017) in press.
[5] H. Takamatsu, M. Niibe, X.L. Zhou, K.
Komatsu, H. Saitoh, H. Akasaka, A. Saiga, K.
Tamada, M. Tagawa, K. Yokota, Y.
Furuyama, K. Kanda, Soft X-ray irradiation
effect on the fluorinated DLC film, submitted
to Diamond Relat. Mater.
[6] T. Nakahigashi, Y. Tanaka, K. Miyake, H.
Oohara, Properties of flexible DLC film
deposited by amplitude-modulated RF
P-CVD, Tribol. Int. 37 (2004) 907-912.
[7] K. Kanda, T. Ideta, Y. Haruyama, H.
Ishigaki, S. Matsui, Surface modification offluorocarbon polymers by synchrotron
radiation, Jpn. J. Appl. Phys. 42 (2003)
3983-3985.
[8] http://www.cxro.lbl.gov/[1] H. Kyuragi and T. Urisu, Synchrotron
radiation-induced etching of a carbon film inan oxygen gas, Appl. Phys. Lett. 50 (1987)
1254-1256.
[2] K. Kanda, K. Yokota, M. Tagawa, M.
Tode, Y. Teraoka, S. Matsui, Effect of thesoft X-rays on highly hydrogenateddiamond-like carbon films, Jpn. J. Appl.
Phys. 50 (2011) 055801.
[3] R. Imai, A. Fujimoto, M. Okada, S.
Matsui, T. Yokogawa, E. Miura, T. Yamasaki,
T. Suzuki, K. Kanda, Soft X-ray irradiation
effect on the surface and material propertiesof highly hydrogenated diamond-like carbon
thin films, Diamond Relat. Mater. 44 (2014)
8-10.
[4] K. Kanda, R. Imai, M. Niibe, H.
Yoshioka, K. Komatsu, H. Saitoh,
Modification
processesforhighlyhydrogenated diamond-like carbon thin films

42Surface modifications in Silica-Based Films
by Undurator Radiation with a multilayer spectrometer
K. Moriwaki, T.Miyamoto, Graduate School of Eng., Kobe Univ.,
and K.Kanda, LASTI/Univ. Hyogo

Abstract

Undurator radiation (UR) by the NewSUBARU (BL7A) is used for silica-based films
modifications for future applications of optical devices like waveguides. UR with or without amultilayer spectrometer is used for the samples, and the observed effects are compared. Increases
in the refractive index (about 10-3) are obtained by shortening the peak wavelength. The peakwavelength dependence is found in the experiments, but is not clear at the present stage. A
correlation is found between the absorbance increases and the refractive-index changes, whichsuggest the origin of the refractive-index change. This is also supported by the refractive index
decreases after removing the high absorbance layer in the sample. The difference between thesamples irradiated with and without the spectrometer may be caused by the irradiation intensity
and a sample temperature effect.

Introduction
Synchrotron radiation (SR) and undurator
radiation (UR) are used for radiation-induced
refractive index changes or other modifications
in silica-based glass for optical devices like
optical waveguides1,2). Especially, the former
experiments revealed differences between
UR-irradiated samples with and without aspectrometer2). UR is a very useful tool for thematerials modifications, because it can select a
useful wavelength, having very high intensity.
UR with a multilayer spectrometer would be
more useful for the purpose because it has highintensity and the most suitable wavelength canbe selected without higher order ones. In thisreport, modification effects are compared withor without the spectrometer further than that in
the previous repots2).

spectrometer. The photon energy dependence on
the refractive index is shown in Fig.2. The
refractive indices in Fig.2 have a peak at around
180eV peak energy, but reproducibility is not
clear
at
the
present
experiments.
1.51

without the spectrometer

Refractive index

1.50
1.49
1.48
1.47
1.46
1.45

Reference

20

Experiments and Results
Thermally grown SiO2 films on Si substrates
and fused quartz substrates were used for the
UR irradiation. UR with the first-peak energy
ranging from 80 to 300eV is used with thespectrometer.
Irradiatedsampleswerecharacterized by XPS (X-ray Photoelectron
Spectroscopy), optical absorption spectroscopy,
and refractive index measurements.
Figure 1 shows refractive index changes after
irradiation by UR without the spectrometer2).
Very high refractive index changes are
introduced in the samples that are mainly by thesurface reduction layer having Si-Si bonds1,2).
By using monochromatic irradiation with amultilayer film spectrometer, refractive index
rises are observed (Fig.2), but Si-Si bonds are
not found by XPS measurements. That may becaused by decrease in the irradiation intensity
and the temperature by UR with the

30

40

50

60

70

80

Peak energy(eV)90

100 110

Fig.1 Refractive index changes after
irradiation by UR without the spectrometer.

1.51

with the spectrometer

Refractive index

1.50
1.49
1.48
1.47
1.46
1.45
50

Reference

100

150

200

250

300

Peak energy(eV)Fig.2 Refractive index changes after
irradiation by UR with the spectrometer.

43remained comparing to the reference of theinitial one.

0.3

0.25

without the spectrometer

Absorbance

0.2

Absorbancewith the spectrometer

0.1

0.20

0.15

Reference
0.0
200

250

300

Wavelength(nm)

350

DATA
FIT

0.10

400

1.445

Fig.3 Optical absorbance for samples
irradiated by UR with and without the
spectrometer.

1.450

1.455

1.460

1.465

1.470

Refractive index

1.475

1.480

Fig.5 Correlation between absorbanceand refractive-index changes after
irradiation by UR with the spectrometer.

0.3

80eV
180eV
300eV
Reference

Absorbance

0.2

500nm

180,300eV

Si substrate

80eV

0.1

Penetration depth: 96nm

Reference
0.0
200

220

Etching(80nm,300nm)

SiO2

240

260

280

300

320

340

Wavelength(nm)Fig.4 Optical absorbance for samples
irradiated by UR with the spectrometer.
The peak photon energies are changed as
80, 180 and 300eV.

(a)

1.50

Irradiation:180eV , 500mA*A

1.49

Refractive index

Before etching
300nm etched

1.48
1.47

80nm etched

1.46

Absorbance increases are observed for the
samples irradiated by UR with and without the
spectrometer (Fig.3), although the increases are
relatively low for ones with the spectrometer.
Absorbance are also measured by changing thepeak photon energies (Fig.4). In Fig.4, changes
by the peak energy are found. Defects in thesamples by the UR irradiation may be the originof the refractive index changes, therefore,
correlation between the absorbance and therefractive index changes is expected, and isconfirmed as shown in Fig.5.
It is concerned that the defects generation isthe cause of the refractive index changes. That is
supported by the results of refractive index
decrease after removing the high absorbancelayer. Figure 6 shows refractive index decreases
gradually after etching an UR-irradiated sample.
The sample after 80nm etching shows a large
decrease in the index but a little change isReference

1.45
1.44
400

(b)

500

600

700

800

WaveLength(nm)900

Fig.6 (a) Cross-sectional view for an
UR-irradiated sample. (b) Measured
refractive-index changes after UR
irradiation with the spectrometer,
before and after etching by 80 and
300
Conclusions
UR irradiation with the spectrometer madedefects in the sample, which may be the originof the refractive-index changes. Further
investigations are needed to determine boththe cause of the changes and also the mosteffective radiation conditions for futureapplications

44

References[1] K.Moriwaki et al., LASTI Annual Report
vol.16 (2014).
[2] K.Moriwaki et al., LASTI Annual Report
vol.17 (2015).

45

Molecular orientation of imprinted photoreactive liquid
crystalline polymer measured by near-edge X-ray absorption
fine structure
Y. Haruyama1, M. Okada1, E. Nishioka2, M. Kondo2, N. Kawatsuki2, and S. Matsui1
1
LASTI, University of Hyogo, Ako, 678-1205, Japan
2
Graduate School of Engineering, University of Hyogo, Himeji, 671-2280, Japan

Abstract

Near-edge X-ray absorption fine structure (NEXAFS) spectra of polymethacrylate, which has ahexamethylene spacer group terminated with a 4-oxycinnamic acid in its side chain (P6CAM),
were measured at the C K-edge region. From the dependence on the incident angle of the linear
polarized synchrotron radiation in the NEXAFS spectra of imprinted P6CAM thin films, it was

found that the unoccupied * orbitals originating from aromatic ring sites in P6CAM thinfilms orient to the surface normal direction irrespective of the line direction formed by theimprint process.
Introduction
The studies on the photoinduced orientationof the polymeric films have attracted significant
attention for a potentially wide range ofapplications such as birefringent optical devices,the photo alignment layer of liquid crystal
displays, and optical memories. Opticalanisotropy of the polymeric films has beencreated by irradiating the linearly polarized UVlight to the films [1]. From the UV-vis spectra,
Kawatsuki et al., indicated that the liquid
crystals in P6CAM orient is perpendicular to thepolarization direction of the UV light [1].
Nanoimprint lithography is a promising
method to fabricate various nanostructures bypressing the mold to the resist. Recently, Okada
et al., had successfully demonstrated that thephotoreactive liquid crystalline polymer was
reoriented along to the line direction formed by
the imprint process [2]. However, themechanism of the molecular reorientation ofphotoreactive liquid crystalline polymer is notclear at present. To investigate the molecularreorientation of the photoreactive liquid
crystalline polymer, near-edge X-ray absorption
fine structure (NEXAFS) spectra were measured
at the C K-edge region.

was used as a photoreactive liquid crystalline
polymer. The chemical structure was shown infigure 1.
P6CAM was synthesized as
described in a previous paper [1]. P6CAM thinfilms of 200 nm thickness were prepared byspin-coating a tetrahydrofuran (THF) solution of
the polymers onto ITO coated glasses. The 2 mline and space patterns were formed on thesurface by the imprint process as shown infigure 2.
NEXAFS spectra measurements were carriedout using the beamline 7B of the NewSUBARU
facility at the University of Hyogo. To
investigate the molecular orientation of P6CAM
films, NEXAFS spectra at the C K-edge region
were measured by the total electron yield (TEY)method. The sample could be rotated around a
vertical axis to change the incidence angle of the
SR to the sample surface. The direction of thelinear polarization in the SR was horizontal.
NEXAFS spectra of P6CAM thin films wererecorded in parallel and perpendicularconfigurations, where the direction of linearlypolarized light in SR was parallel andperpendicular to that of the line pattern formedby imprint process on the surface, respectively.

Experiments
A polymethacrylate,
which
has
a
hexamethylene spacer group terminated with a4-oxycinnamic acid in its side chain (P6CAM),

P6CAM
n

O
O

O
4

OH
Fig.2 SEM image of the 2 m line and spacepattern formed by imprint process on thesurface of P6CAM.

O

Fig.1 Chemical structure of P6CAM.

46

Results and discussion
Figures 3(a) and 3(b) show the C K-edge
NEXAFS spectra of imprinted P6CAM thinfilms, measured by the TEY method, as afunction of incidence angle of the SR in paralleland perpendicular configurations, respectively.
A sharp peak at 284.8 eV, which was assigned totransitions from the C 1s orbital to the* orbitals originating fromunoccupied
aromatic ring sites, was observed. With
increasing the incidence angle, the intensity ofthe peak at 284.8 eV decreased gradually in theparallel configuration. In addition, the similar
angular dependence was observed in theperpendicular configuration.
These results
indicates that the unoccupied * orbitals
originating from aromatic ring sites in P6CAM
thin films orient to the surface normal direction
although the molecular axis of the liquid crystals
in the side chains of P6CAM is random.
Figure 4 shows the angular dependences ofthe * resonance intensity in the parallel andperpendicular configurations for imprinted
P6CAM thin films. The angular dependece of
the * resonance intensity in the parallel
configuration is almost same with that in theperpendicular configuration. Therefore, in thecase of the imprinted P6CAM thin films, thisindicates that the unoccupied * orbitals
originating from aromatic ring sites in P6CAM
thin films orient to the surface normal direction
irrespective of the line direction formed by theimprint process. This is contrast to the previous
result [2]. The difference may be attributed toFig.4 Angular dependence of the resonanceintensity in the parallel and perpendicularconfigurations for imprinted P6CAM thinfilms.
the detected area in each experimental method.
The NEXAFS spectra observed by the electron
yield method in this study is detectable only
near the surface region. On the other hands,
the whole area of the thin films is detectable in
the previous study [2]. Therefore, there is apossibility that the molecular ordering of theliquid crystals in P6CAM thin films differs
between the surface and the bulk.
References[1] N. Kawatsuki, T. Kawanishi, and E. Uchida:
Macromolecules 39, pp. 9357 (2006).
[2] M. Okada, S. Manabe, M. Kurita, M. Kondo, Y.

(a)Haruyama, K. Kanda, A. Emoto, H. Ono, N.
Kawatsuki, and S. Matsui: Jpn. J. Appl. Phys., 49,

pp. 128004 (2010).
[3] M. Okada, S. Manabe, M. Kurita, M. Kondo, Y.

Haruyama, K. Kanda, N. Kawatsuki, and S.
Matsui: Microelectronic Engineering 88, 2079
(2011).

(b)

Fig.3 C K-edge NEXAFS spectra ofimprinted P6CAM thin films as a function of
the incidence angle , relative to substratesurface in (a) parallel and (b) perpendicularconfigurations, respectively.

47

Development of fine-grained 316L steel with 1.0-2.0 mass%
TiC for nuclear reactor materials
Mititaka Terasawaa, Hiroaki Kurishitab, Tatsuaki Sakamotoc, Masahito Niibea, Heishichiro Takahashid, Satoru
Nishikawae, Atsusi Yamamotof, Michiru Yamashitag, Tohru Mitamuraa, Tohru Yamasakif & Masayoshi Kawaih
aLaboratory of Advanced Science & Technology for Industry, University of Hyogo, Kamigori-cho, Japan;
International Research Center for Nuclear Materials Science, IMR, Tohoku University, Ibaraki, Japan;c
Department of Materials Science and Biotechnology, Ehime University, Matsuyama, Japan;dCenter for Advanced Research of Energy and Materials, Hokkaido University, Sapporo, Japan;eNondestructive Evaluation Center, Japan Power Engineering and Inspecion Corporation, Yokohama, Japan;fGraduate School of Engineering, University of Hyogo, Himeji, Japan;gHyogo Prefectural Institute of Technology, Kobe, Japan;hHigh Energy Accelerator Research Organization (KEK), Tsukuba, Japanb

Abstract

Development of fine grain 316L with small amount of TiC for high radiation tolerant performance
was tried considering the fabrication process of thermo-mechanical treatments. The materials
obtained are UFG316L+2.0 mass% TiC with the grain size of 90 to 270 nm, depending on the final
annealing temperature from 700°C to 900°C. The materials was examined by TEM observation,
XANES spectroscopy, HVEM electron irradiation and Stress Corrosion Cracking by crevice bent
beam method in high temperature water with 8 ppm dissolved oxygen. The test results showed thematerial is generally excellent quality. Especially void swelling induced by the electron irradiation
at 400°C is less than 1/10 compared to the commercial SUS316L.

Introduction
Austenitic stainless steels have been employedextensively for nuclear power reactors for many
years, because the materials show very toughmechanical strength and excellent performances inthe environment of water coolant exposure andneutron irradiation in high temperature. Althoughvoid swelling induced by neutron irradiation is the
typical severe problem in fast breeder reactors(FBR), it has not been considered so far in the lightwater reactors (LWR) because the irradiation
fluence is much more lower than in FBR. However,void formation (swelling) was recognized at lower
temperature (400°C) even in LWR by Garner [1]. It
is noticed that swelling–creep interaction in fuel pin
cladding may cause the fuel pins to deform intospiral rods. As grain boundaries (GBs) of thepoly-crystal materials are great sink for the defects
produced by neutron irradiation, fine grainmaterials
areexpected
to
show
high
radiation-tolerant performance [2,3].
We tried to develop ultra-fine grain austenitic
stainless steels (UFG316L) with addition of
TiC-nanoparticles. In the previous paper, we
reported the fabrication of UFG316L+1.0 mass%
TiC, which was examined by neutron irradiation in
JMTR (JAEA) and high voltage electron
microscope (HVEM) 1.0 MeV electron irradiation.
Less hardening and low void swelling in theirradiations by neutron and/or high-energy electron
were recognized [4]. We have tried the fabricationof UFG316L+2.0 mass% TiC as the next step of thematerial development.
Experiments and Results
Powders of SUS316L (an average particle size:
44–105 μm) and TiC (0.57 μm) were used as thestarting materials. These powders were mixed toprovide the target compositions of SUS316L and
2.0 mass% TiC. These mixed powders together
with hard steel balls were put into a vessel made of
SUS316L steel and then subjected to mechanicalalloying (MA) treatment by vibrational ball millingfor 125 h in a purified hydrogen atmosphere(purity: 99.99999%). All of these procedures wereconducted in a specially designed glove box thatprevents the powders from being contaminated withoxygen and nitrogen in air before and after the MA
treatment. Hot isostatic pressing (HIP) treatment
was conducted at 850 °C at 196 MPa for 3 h in an
argon atmosphere. The HIPed compacts were
subjected to thermomechanical treatments (TMTs)
to introduce ultrafine grained, thermally stablenanostructures by using reverse transformation of
deformed martensite to austenite.
The grain sizes are as small as 90, 140, 190, and
270 nm, after heat treatment at 700°C, 750°C,
800°C, and 900°C, respectively.
In the present experiment, in situ observation of
the defects evolution in UFG316L+2%TiC
materials was performed during the material
irradiation with 1.0 MeV electron beam in the
HVEM facility in Hokkaido University, Japan.
Figure 1 shows the swelling as a function of the48

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by Oxygen and Nitrogen Plasmas
Ryo Tanaka1, Masahito Niibe1, Retsuo Kawakami2, Yoshitaka Nakano3, Takashi Mukai4
1
University of Hyogo, 2Tokushima University, 3Chubu University, 4Nichia Corporation.
Abstract
In order to understand the details of the surface damage to the AlGaN film by plasma etching,we etched it with oxygen and nitrogen plasmas, and analyzed by using NewSUBARU beamline
BL-09A. The peak of near-edge X-ray absorption fine structure (NEXAFS) spectra in the N-K
absorption edge was broadened by oxygen plasma etching with increased processing time. In thecase of nitrogen plasma, it was more broadened than the sample etched by oxygen plasma. And
the peak of X-ray emission spectroscopy indicated that the etching damage does not reach thebulk of the sample. From the above results, the changes in the crystalline structure of AlGaN are
considered to be caused by the effect of UV light irradiation from plasma. We found that thechange in the surface composition, the disordering of the crystalline structure occurred on ashallow region from the surface, and those did not occur on a deeper region of the sample.

Research background
Aluminum gallium nitride (AlGaN) is attracting agreat deal of attention as a new material forelectronic devices. AlGaN has a large band gap, ischemically stable, and is physically strong. In
particular, the AlGaN / GaN high electron mobility
transistor (HEMT) can realize high-speed
operation and low power consumption operations.
In the heterostructure of AlGaN / GaN, the lattice
constants of AlGaN and GaN are different so thatthe crystal is distorted, and the two-dimensional
electron gas (2DEG) is induced in the AlGaN/GaN
interface. Since the 2DEG has high carrier density
and high electron mobility, very fast switching
operation becomes possible. There are several
issues for realizing AlGaN/GaN HEMT devices
into practical use, one of the biggest problems is tomake normally-off HEMT devices.
Regularly, HEMT devices have normally-on
characteristics. Normally-on operation is a state inwhich drain current (ID) flows when gate voltage(VG) is 0 V. Normally-off operation is a state inwhich ID does not flow when VG is 0 V.
HEMT devices are expected to be used forhigh-current power amplifiers. Therefore devicesof the normally-off operation is required especiallyfrom the viewpoint of fail-safe. In recent years,
Kotara et al. [1] reported that AlGaN/GaN HEMT
devices turned to normally-off characteristics byusing CF4 plasma etching. According to this report,
a 25 nm AlGaN film was grown on a GaN
substrate with a thickness of 1.1 μm and thesurface was CF4 plasma etched. As a result, VG
was shifted to the normally off side by + 2 V
compared to the HEMT which was not
plasma-etched. In addition, Miyawaki et al. [2]studied that AlGaN/GaN HEMT devices turned
normally-off HEMT devices by using O2 or N2
plasma etching.
It seems that the reason normally-off is related tosurface damage by plasma etching and ion species
to be taken in. However, the mechanism of
normally-off HEMT devices are not yet clarified.
To investigate this mechanism in detail, we used
plasma etching with O2 gas and N2 gas (gaspressure was changed 10 to 100 mTorr andprocessing time was changed 5 to 100 min) to the
AlGaN/GaN substrate.
Experimental Methods
AlGaN films used were 100 nm thick un-doped
Al0.24Ga0.76N thin films which were grown on 4
μm thick bufferlayer of GaN by metal organic
chemical vapor deposition (MOCVD) in thisstudy(Nichia Corp.).
AlGaN sample was plasma etched at Kawakami
laboratory in Tokushima University. The
capacitively-coupled radio frequency plasma

50

(CCP) reactor was used for etching. Figure 2
shows a schematic diagram of the CCP reactor.
The apparatus had an asymmetric electrodestructure. The cathode area SK = 80 cm2, the anodearea SA = 1217 cm2, and the distance between theelectrodes was 4 cm. The radio frequency (RF)power was supplied at 13.56 MHz and VRF = 200
V. The anode electrode was grounded. In thisresearch, plasma etching was carried out by using
two types of gases, oxygen and nitrogen. The
processing gas pressure was from 10 to 100 mTorr,
and the treatment time was from 5 to 100 min.

a whole, as the gas pressure is higher and as thetreatment time becomes longer, the overall spectral
shape tends to be smoothened. This is probably
because the crystal structure of the AlGaN surface
was distorted by etching.
Figure 3 (b) shows the N-K NEXAFS spectra of
the AlGaN treated with oxygen plasma at 100
mTorr measured with TFY method. From this it
can be seen that there is not much change in the
spectra even if the processing time is changed.
This is probably because the influence of etchingon the inside of the AlGaN sample is small.
From the results of TEY and TFY measurementsof AlGaN samples treated with oxygen plasma,etching damage by oxygen plasma does not reachto the bulk, which shows that it influences only the
AlGaN surface (about ~ 3 nm).

Figure 2 Schematic diagram of capacity coupledplasma reactor
Evaluation Devices and Methods
For the evaluation of the etched samples, theanalysis of the etching damage was carried out by
X-ray absorption spectroscopy (XAS) at theBL-09A at the NewSUBARU synchrotron
radiation facility. The absorption coefficient wasmeasured by two methods: total electron yield(TEY) and total fluorescence yield (TFY). TEY isa method that can know the surface crystal statefrom the sample surface to about 3 nm [3]. TFY isknown that it is possible to observe the bulk
crystalline state from 10 nm to several 100 nm
from the sample surface.
In this study, an angle of incidence is defined as
the angle measured from the surface normal.

(a) TEY method(b) TFYmethod
Figure 3 N-K NEXAFS spectra of oxygen plasma
treated AlGaN samples
Figure 4 (a) shows the N-K NEXAFS spectra of
the AlGaN samples treated with nitrogen plasmameasured by TEY method. As shown in Fig. 4
when comparing the as-grown sample and theplasma etched sample as a whole, as the gaspressure is higher and as the treatment time
becomes longer, the overall spectral shape tends tobe smoothened. This is probably because thecrystal structure of the AlGaN surface wasdistorted by etching.
Comparing the spectra in Figure 3 (a) with thatof in Figure 4 (a), the spectra of nitrogen plasma
treated samples are much smoother than that ofoxygen plasma treated one. Therefore, it can beseen that etching damage by nitrogen plasma
etching is larger than that by oxygen plasma
etching. Figure 4(b) shows the N-K NEXAFS
spectra of the AlGaN treated with nitrogen plasma
at 100 mTorr measured with TFY method. Spectra

Results
Figure 3 (a) shows the N-K NEXAFS spectra of
the AlGaN sample subjected to oxygen plasma
treatment measured with TEY method. The angle
of incidence was 0 ° (normal incidence). The
figures show spectra obtained from the sample
etched by oxygen plasma at 100 mTorr.
As shown in Fig. 3 (a), when comparing theas-grown sample and the plasma etched sample as51

of samples etched at 5 min and 60 min could not
be observed. From this it can be seen that there is
not much change in the spectra even if the

100 mTorr

200

300

400

500

600

700

800

900

Wavelength (nm)processing time is changed. This is probably
because the influence of etching on the inside of
the AlGaN sample is small.
(a) TEY method(b) TFYmethod
Figure 4 N-K NEXAFS spectra of nitrogen plasma
treated AlGaN samples

band gap are generated, the bond breaks due toplasma emission, thereby increasing the etchingdamage.

(a) Ultraviolet spectrum of oxygen plasma(b) UV spectrum of nitrogen plasma
Figure 5 UV spectrum of plasma emission

Discussion
From the results of NEXAFS spectrum plasma
etching greatly influenced the sample surface(about ~ 3 nm). And under the same conditions, thenitrogen plasma etching was larger in etchingdamage than that of the oxygen plasma etching.
Our research group reported that the surface
roughness increased with ultraviolet light-assisted
irradiation of n-GaN samples using black light in
the previous work [5]. We also reported thatsimilar effects are generated by Ar and UV assisted
CF4 plasma [6]. This is probably because
ultraviolet light with photon energy corresponding
to a band gap is irradiated on the AlGaN surface,and electron-hole pairs are generated. The
formation of holes h+ on the surface weakened thebonding between Al-N and between Ga-N, whichis considered to promote plasma etching. In
addition, AlGaN has large dislocation density (~108 cm-2), so holes concentrate at dislocation sites,
making it difficult to be etched easily [7]. It seems
that pit-like defects were formed on the AlGaN
surface.
Figure 5 shows the ultraviolet spectrum emitted
from plasmas. Since the band gap energy (Eg) of
AlGaN is 3.67 eV, wavelength λ of thecorresponding energy is 338 nm.
In the emission spectrum from the nitrogenplasma in Fig. 5 (b), since photons with thewavelength (338 nm) corresponding to the AlGaN

References[1] P. Kotara et al., Phys. Status Solidi C 8, 2207
(2011).
O : 777nm[2] Miyawaki et al., 2014
autumn meeting ofApplied Physics Japan (2014)[3] T. Kotaka et al, Adv. X-Ray. Chem. Anal.,
Japan, 43 ISSN 0911-7806 (2012).
[4] M. Katsikini et al., Journal of Physics:
Conference Series 190, 012065 (2009).

Intensity (arb. unit)(a) N2 plasma
N2 : second positive system band
2P(0,0)100mTorr

2P(1,0)2P(0,1)
2P(0,2)50mTorr
10mTorr

280

320

360

400

Wavelength (nm)[5] R. Kawakami et al., Thin Solid Films 570, 81(2014).
[6] S. Hirai et al., E-Journal of Surface Science andNanotechnology, 13, 481-487 (2015).
[7] D. M. Follstaedt et al., Journal of Crystal
Growth, 310, 766-776 (2008).

52

Development of the Transmittance Measurement
for EUV Resist by Direct-Resist Coating on a Photodiode
Daiki Mamezaki, Masanori Watanabe, Tetsuo Harada, and Takeo Watanabe
Center for EUV Lithography, LASTI, University of Hyogo,
1-1-2 Kouto, Kamigori, Ako-gun, Hyogo, Japand.mame@lasti.u-hyogo.ac.jp,
To increase the sensitivity of extreme-ultraviolet (EUV) resist, the method of adding high absorption
material in base resin of the resist such as hafnium or zirconium metal has been developed. Since the
EUV absorption of the base resin increases, the secondary electron emissions would increase to have ahigh-resist-exposure sensitivity. Thus to achieve the high sensitive EUV resist, it is important to evaluate
EUV absorption of the EUV resist precisely. We have developed a novel transmittance measurement
method to evaluate EUV resist absorption with high precision at BL10 beamline of NewSUBARU
synchrotron light facility. In this novel method, a sample resist was coated on an EUV photodiodedirectly. The EUV transmittance of the resist was measured with photodiode signals before and after thecoating. The resist thickness uniformity coating on a photodiode has much smaller value compared tothat coating on a freestanding membrane. By novel method, the measurement precisions of the resist
thickness and the EUV transmittance were significantly improved. As the result, the high measurement
precision of absorption coefficient of 1% was achieved. This novel method will help the development ofhigh sensitive EUV resist with the high-absorption material.
Keywords: EUV resist, transmittance measurement, high absorption resist, metal resist

1. Introduction
The extreme-ultraviolet (EUV) lithography [1]is the most promising candidate for the
manufacturing of semiconductor electronic
devices. One of the critical technical issues of
EUV lithography is the development of EUV
resist which has the high resolution, the highsensitivity, the low line-width roughness, and low
outgassing simultaneously [2]. Especially, thehigh sensitivity is strongly required to relax the
specification of EUV light power and maintainthe high-lithographic throughput. To achieve thehigh sensitive resist, some groups reported
several methods in the paper [3, 4]. The key toincrease the sensitivity is employing thehigh-EUV-absorption-metal material such as
hafnium or zirconium in the base resin of EUV
resist. Since the EUV absorption of the base resin
increased and the secondary electron emissions
could increase, the resist sensitivity increased. Inorder to evaluate the effect of the high absorption
material, it is important to evaluate the EUV
absorption of the EUV resist precisely. The
absorption coefficient is calculated using thefollowing equation (1).

= ln

(1)

Where µ, D, and T are the absorption
coefficient, resist thickness and transmittance ofthe resist. In order to evaluate the absorption
coefficient of resist material, the precise
measurement the resist thickness and EUV
transmittance are required.
We
previously
performed[5-7]
thetransmittance measurement of EUV resist using
the EUV reflectometer at BL-10 beamline in the
NewSUBARU synchrotron light facility [8]. The
absorption coefficient was calculated by using thetransmittance and the resist thickness. In this53

previous
experiment[8],
silicon-nitride
freestanding membranes were used for the resist
transmittance measurement. The resist was coatedon the silicon-nitride membrane by spin-coating.
The EUV transmittance of the resist wascomputed by the EUV transmittances of themembrane before and after the resist coating.
Figure 1 shows schematic view of the membrane.
The thickness, window size and substrate size ofthe silicon-nitride membrane was 200 nm, 2 × 2
mm2 and 10 × 10 mm2, respectively. Since themembrane thickness was very thin, the membrane
was deflected by the stress after the resist spin
coating. And the resist thickness uniformity on
the membrane affected by the adhesion of theresist. As the results, the resist thickness
uniformity on the membrane became very large
to be approximately 10%. On the other hand,
EUV beam size on the sample of thereflectometer was 0.8 mm (horizontal) × 0.1 mm(vertical) in full width in half maximum (FWHM).
Since the beam size was comparable to themembrane-window size, the precision of thetransmittance measurement affected by the
non-uniformity of resist thickness. And before thetransmission measurement, it is necessary to alignthe membrane position precisely to the beam
position.
Thus to increase the transmission-measurement
precision, we have developed a noveltransmission-measurement method for EUV resist.
In the new method, sample resist was directcoated on an EUV sensitive photodiode, which isusually used for a measurement of the EUV lightintensity in the EUV energy region. The EUVtransmittance of the photoresist was computedwith photodiode signals before and after thecoating.

200 nmFig. 1. Schematic view of the silicon-nitride
membrane substrate used for the EUV resist
transmission measurement previously.

2. Experimental
2.1 Photoresist coating
It was used in this experiment that ZEP520A(Zeon Corp.) which was non-chemical-amplified
positive-tone resist and commonly used forelectron-beam lithography.
Schematic view of the photodiode (SXUV-100
Opto Diode) used in this experiment is shown in
Fig. 2.

Fig. 2. Schematic view of SXUV-100 in noveltransmission method.

Light-sensing area size of the photodiode was
10 × 10 mm2, which was much larger than the
beam size. Thus the beam alignment in the novel
method is much easier than that in the previous
method. The resist was coated on the sensing
area (10 × 10 mm2) by spin coating directly.
Uniform resist thickness was expected at the spin
coating process, because the photodiode surface
was flat and solid. The resist thickness wasmeasured using NanoSpec6100 (Nanometrics),

54which is a film thickness measurement system
based on an interference-spectrum measurement.
A film thickness measurement spot size in
NanoSpec6100 was 25 m in diameter. The
prebake process of the resist film coated on alight-sensing surface of the photodiode wasprovided using a hot plate. The prebake
temperature was 180°C, which was much lower
than the heat-resistant temperature of thephotodiode of 260°C.
Top surface layer of the photodiode was apassivating metal silicide [9, 10]. And the backside electrode was contacted to the anode. The
surface electrode was contacted to the cathode by
the wire. The wire of the photodiode-cathodeshown in Fig. 2 is very narrow wire and easy to
be cut off. During the spin-coating for the resist
coating, the wire was cut off several time. And,during the resist-baking process, the wire wasalso cut off by a heat stress. Thus, we contacted ametal electrode by a kinematic contact to thesurface electrode on the photodiode to measure
photodiode current. Even if the wire was cut off,the signal could be measured by the metalelectrode using this contact method.

before the resist coating. Then, the signal
distribution I(y) was measured after the resist
coating. The transmittance distribution T(y) was
calculated with I0(y) and I(y) by the equation ofT(x) = I(x)/ I0(x).
3. Result and discussions
3.1 The measurement of resist thickness
Figure 5 shows a measurement results of theresist thickness on the photodiode. The thickness
distributions for the four angles were measured,
where result in 90° was corresponded to vertical x
direction at the EUV transmittance measurement.
The average, maximum and minimum resist
thickness were 120.1 nm, 120.4 nm and 119.8nm,
respectively. Thus, the resist was coated on thephotodiode with high uniformity. Non-uniformity
was less than 0.5%, which was 20 times smaller
than the previous method with the silicon-nitride
membrane.
The resist transmittance region using
photodiode is < 2.5 mm at the radial position r,which the measurement region of 5-mm indiameter in this method was larger than themembrane window width size of 2 mm in theprevious measurement method.

2.2 Transmittance measurement method
In this study, the EUV mask reflectometer [11]was used for the EUV transmittance measurement,
which was located at the BL-10 beamline of
NewSUBARU synchrotron light facility. Figure 3
shows the photograph of the EUV mask
reflectometer installed at the BL10. The bending
magnet is used as a light source of the BL-10
beamline and white light is generated from thissource.
The
monochromator
typeis
Monk-Gillieson type [12] with a planevaried-line-spacing grating (VLSG). An energy
resolution of ( E/E) in EUV region isapproximately 1300.
In this experiment, the exposure wavelength
was 13.5 nm, and the exposure beam size at theresist sample position in the EUV mask
reflectometer was approximately 0.8 mm(horizontal) × 0.1 mm (vertical) in FWHM. Since
the sensing area of photodiode was much larger
than the beam size, it was easy to align the beam
position.
Figure 4 shows schematic diagram of themeasurement method of a EUV resist
transmittance. First, the photodiode-signal
distribution I0(y) along the vertical y direction at
the horizontal center position was measured

Fig. 3. Photograph of the EUV mask reflectometer.

55

Resist transmittance

0.70

0.65

0.60

0.55

-2

-1

0
1
Position (mm)2

Fig. 6. Measurement result of the resist transmittance.

3.3 Computation of the absorption coefficient
Figure 7 shows absorption coefficient
distribution which were calculated by themeasurement results of the resist thickness in 90°
and EUV transmittance. As a result, the computed
average absorption coefficient was 3.96 m-1.
The variation of the absorption coefficient in theevaluation area (r<2.5 mm) was less than 1%.
This residual variation of the measurement
precision would be small for resist absorption
measurement.

Fig. 4. Schematic diagram of the measurement methodof the resist-transmittance measurement.

Thickness (nm)

124

0°
45°
90°
135°

122

120

118
-3

-2

-1
0
1
Radial position (mm)2Absorption coefficient (μm-1)

ZEP520A
Average thickness (5×5 mm2) 120.1 nm

3Fig. 5. Measurement results of the resist thickness.

3.2 Transmittance measurement
Figure 6 shows the measurement result ofresist transmittance. The average resist
transmittance was 62.2%, and the non-uniformlyof the resist transmittance was 0.7%. Since theresist thickness was uniform shown in Fig. 5, thehighprecision
measurementof
EUV
transmittance was achieved.

4.10
4.05
4.00
3.95
3.90
3.85

-2

-1

0
1
Position (mm)2

Fig. 7. Computed result of absorption-coefficient on
the photodiode.

4. Conclusion
We have developed the novel method of theresist-transmittance measurement using thedirect-resist coating method on the photodiode.
The thickness nonuniformity of resist by spin
coating was significantly improved to be 0.5%,
because the photodiode surface was flat and solid.
Thus, the variations of the resist transmittance56

and the absorption coefficient were also improved
to 0.7% and 1%, respectively. We performed
precise EUV absorption-coefficient evaluation
using this novel method. This new method will
help the development of high-absorption material
to achieve high-sensitive-EUV-resist material.
In the near future, we will develop the resist
removal method to reuse the photodiode. And, we
will evaluate a metal-resist absorption using thisnovel method.
5. References
1. H. Kinoshita, K. Kurihara, Y. Ishii and Y.
Torii: J. Vac. Sci. & Technol., B7 (1989)
1648.
2. Mark Neisser and Stefan Wurm: Advanced
Optical Technologies, 4, (2015) 535.
3. Jing Jiang, Souvik Chakrabarty, Mufei Yu
and Christopher K. Ober: Journal of Scienceand Technology 27(2014) 663.
4. Jason K. Stowers, Alan Telecky, Michael
Kocsis, Benjamin L. Clark, Douglas A.
Keszler and Andrew Grenville: Proc. SPIE
7969 (2011) 15.
5. Atsushi Sekiguchi, Yoko Matsumoto, Tetsuo
Harada, Takeo Watanabe, and Hiroo
Kinoshita: Proc. of SPIE Vol. 9422 (2015)
2L.
6. Yasuyuki Fukushima, Takeo Watanabe, Tetuo
Harada and Hiroo Kinoshita: Journal of
Photopolymer Science and Technology 22(2009) 85.
7. Ryuji Ohnishi, Takeo Watanabe, Yasuyuki
Fukushima, Masafumi Osugi, and Hiroo
Kinoshita: Jpn. J. Appl. Phys. 48 (2009)
06FA08.
8. Masaki Kuki, Tomoyuki Uemura, Masato
Yamaguchi, Tetsuo Harada, Takeo Watanabe,
Yasuji Muramatsu and Hiroo Kinoshita:
Journal of Photopolymer Science andTechnology Vol. 28 (2015) 531.
9. R. Stuik and F. Bijkerk: Nuclear Instruments
and Methods in Physics Reserch 489 (2002)
370.
10. B. Kjornrattanawanich, R. Korde, C. N.
Boyer, G. E. Holland and J. F. Seely: IEEE
Transactions on Electron Devises, Vol. 53(2006) 218.
11. M. Hosoya, N. Sakaya, O. Nozawa, Y. Shiota,
K. Hamamoto, O. Nagarekawa, S. Shimojima,
T. Shoki, T. Watanabe, and H. Kinoshita: Jpn.
J. Appl. Phy. 47 (2008) 4898.

12. M. C. Hettrick and J. H. Underwood, AIP
Conf. Proc. 147 (1986) 237.

57

EUVL Research Activity at Center for EUV Lithography
Takeo Watanabe and Tetsuo Harada
Center for EUV Lithography,
Laboratory of Advanced Science and Technology for Industry, University of Hyogo,
3-1-2 Koto, Kamigori, Ako-gun, Hyogo, 678-1205, JapanThe advanced feature size patterning process of semiconductor conductor devices
has been strongly charged in the information-technology oriented society. Extreme
ultraviolet lithography (EUVL) is expected as a leading candidate of the next
generation lithography for semiconductor electronic devices. The technology issues
in EUV lithographic are the development of 1) EUV light source with high power andhigh stability, 2) EUV resist with simultaneous achievement of high resolution, highsensitivity, low line width roughness (LWR), and low outgassing. Center for EUVLin University of Hyogo has played an important role in the research and developmentof EUV lithography in two decades. Research and development of EUV lithography
toward HVM was started its development just before twenty years ago to develop full
field exposure tool employing tree aspherical imaging optics. In University of Hyogo
developed 1) large reflectometer for the reflectivity measurement of the collector
mirror for the EUV light source, 2) the EUV resist evaluation system such as the
EUV interference lithography and outgassing system using in-situ ellipsometer forthe evaluation of EUV resist of 10 nm and below, and X-ray absorption fine structure
for EUV resist chemical reaction analysis to increase EUV exposure sensitivity, 4)
the defects inspection of the actinic blanks and patterned mask. As the results, thoseevaluation tool could contribute EUV lithographic technology to lead to the HVM ofelectronic devices.
Keywords:
EUV lithography, interference lithography, PAG boundedpolymer, outgassing, in-situ ellipsometer, chemical reaction analysis,
XAFS, actinic blank inspection, actinic patterned mask inspection,
coherent scatterometry microscope

1. Introduction
EUVL [1] will be used in the semiconductor
electronic device high volume manufacturing
for the patterning in the 16 nm feature sizearound 2017 [2]. The top three issues of the
EUVL are the development of 1) source, 2)
resist, and 3) mask. For the EUV light source
development, high power and high stability of
EUV light source should be achieved tomaintain the wafer throughput [3]. EUV
source power of 250 W with the occupancy
rate of 75% is required for the HVM EUV
light source. And for the EUV power for
1000W, EUV light source on the basis of thefree electron laser source is planned on thebasis of the accelerator technology. For the
EUV resist development, the simultaneousachievement of the high resolution, sensitivity,
low LER, and low out gassing. For the mask
development, the defect inspection of theactinic blank and patterned mask and thepellicle to protection the mask from theparticle originated from the mask loading andunloading in the exposure tool.
Currently, on Feb. 25, 2015, ASML press
releaseannounced
that
using
ASML
NXE-3300B
exposure
beta
tool,
the
EUV-light-source power increased to 90 W at58

the intermediate focus position, and TSMC
semiconductor chip manufacturer exposed1022
wafersin
24hours.
10-nm-feature-size-pattering technology isrequired in 2020 for the high volume
manufacturing listed in the international
technology roadmap for semiconductor (ITRS)[2]. Now the 200 W at 60 min was
continuously achieved using laser- produced
plasma (LPP) system by reducing the diameterof the droplet and increasing CO 2 laser power.
For the EUVL extendability to the X nm
resolution achievement, since increasing thenumerical aperture of the imaging optics isneeded, imaging optics is designed for thehigh NA optics.
Center for EUV lithography (CEL) is
established in Oct. 2010 in Laboratory of
Advanced Science and Technology for
Industry of University of Hyogo to accelerated
the EUV lithographic technology toward
HVM.
This paper focuses on the EUVL R&D
activity at Center for EUV Lithography ofLaboratory of Advanced Science andTechnology for Industry, University of Hyogo.
CEL has three beamline such as BL3, BL9,and BL10 of NewSUBARU synchrotron lightfacility [4] for the R&D of EUVL as shown in
Fig. 1 which is the schematics.

In this SPIE spring microlithography meeting,
ASML announces that the conversion
efficiency increases by reducing the droplet
size from 34 to 27 m. In order to increase thepower, the conversion efficiency but also thecollection efficiency of the collector mirror
should increase. Thus the large reflectometeris installed at the BL10 beamline of the
NewSUBARU synchrotron light facility as
shown in Fig. 2. The vacuum chamber size andbase pressure are 2.6 m in diameter and 2.9 m
in height, and 2.0×10 -6 Pa, respectively. The
collector mirror can be settled on the sample
stage as shown in Fig 3, and the maximum

2.6 m

2.9 m

Fig. 2. Large reflectometer is installed at theBL10 beamline of the NewSUBARU synchrotron
light facility.

Fig. 1. The schematics view of NewSUBARU
synchrotron light facility.

2. Large Reflectometer for the High Power
EUV LPP Light Source
The high power and stability EUV source isrequired for HVM. The requirement of thesource power is >250 W at intermediate focus
position, and the occupancy rate is > 75%.

Fig. 3. The schematic view of the sample stageof the large reflectometer.

59

mount size of the collector mirror and weightare 800 mm in diameter and the thickness of
250 mm, and 50 kg of body weight,
respectively.
Figures 4 and 5 show the mirror sample,
and its reflectivity measurement result of theround robin of the reflectivity measurement
between PTB and University of Hyogo,
respectively. The diameter of the mirror is 412

3. Resist Evaluation System
3.1 EUV interference lithography
The resolution specification of ASML
NXE3350B EUV exposure tool is 16 nm. Thus
it cannot reach to the resolution of 10-nm
order. In order to accelerate the EUV resist
development of 10-nm order, it is verysignificant to develop the EUV interference
lithographic (EUV-IL) [5] exposure tool forthe resolution achievement of 10-nm order [4].
The EUV interference lithography had beendeveloped and replicated 15 nm line and space(L/S) resist pattern by using two window-typetransmission diffraction grating (TDG) on
which has 30 nm L/S grating pattern. In
addition, 28-nm-diameter-hole resist pattern
had been replicated by four window-type TDG
which has 40 nm L/S grating pattern [6, 7].
The replicated 15 nm L/S and 28 nm hole
resist patterns on a silicon wafer are shown in

Fig. 4. Photograph of the large collector
mirror used for the round-robin reflectivity
measurement between PTB and University of
Hyogo.

mm. The reflectivity measurement was carriedout from the center position of the mirror
sample to the left and right direction along theradial direction of the mirror sample. As theresults, since the reflectivity measurement
results between University of Hyogo and PTB
is consistent, the large reflectometer which wedeveloped has a capability to measure thereflectivity of the large collector to increase
the collection efficiency for the achievementof the high-EUV-power-light source.

Fig. 6. 15-nm-L/S pattern of the
inorganic-resist using EUV-IL.

Fig.5. Reflectivity measurement results of theround robin using large reflectometer atUniversity of Hyogo and PTB in Germany.

60

61

substrates and particle in the multilayer
modulate reflection phase of EUV, which are
printed as defects. This kind of defect is calledphase defect. Actinic inspection is required toevaluate printability of the phase defect.
Therefore, we have developed the EUV
microscopes for actinic mask observation at
BL3 beamline of NewSUBARU. The firstsystem of the EUV microscope consists
Schwarzschild objective and an electron
zooming tube [19]. Phase defect printability
was firstly investigated. And, capability ofdefect hide by an absorber pattern wasdemonstrated.
The second EUV-microscope system wasdeveloped with Tohoku University and EIDEC.
The optical layout is shown in Fig. 12 [20].
The mask sample was illuminated by asynchrotron radiation at an incident angle of13°. Its objective was configured as a
two-stage imaging system that formed a highmagnification (1470×) image on its CCD
camera. At first, Schwarzschild objective
formed a mask pattern image on theintermediate position with low magnificationof 30×, which had numerical aperture (NA) of
0.25. At second, this intermediate image wasmagnified (49×) by a concave mirror of M6.
The expected spatial resolution is higher than
30 nm. And expected field of view is verylarge of 160 m diameter.

refinement of the monochromator at the BL10
beamline. The W/Si aperiodic multilayer coatedgrating is employed for the monochromator toextend the photon energy region from 500 to

Fig.10. TEY-XAFS measurement result of theresist at fluorine absorption edge.

1100 eV as shown in Fig. 9 [18]. As the results,
the absorption peak signal of the fluorine 1s
core level can be measured clearly as shown in
Fig. 10. As the results of the TEY-XAFS
analysis applied to the EUV CA resist, it isfound that to satisfy the specification of the
EUV resist which require for high volume
manufacturing, all the chemical reaction should
be taken in account, such as the ionization andthe direct excitation reactions, as shown in
Fig.11. Increasing the sensitivity, it might havemore space to achieve the low LWR resist [17].
(a)Ph3S+X-Ph2S + Ph + X-

Ph2S + PhH + H+X(b)X-(for PAG)h

H+ + X1- + H+ + X2- + N1
orh
X- H+ + X3- + N2 + N3

Fig. 11. (a) The decomposition reaction by thesecondary electron generated from the ionization
reaction and (b) the decomposition reaction of theanion of PAG by the direct excitation reaction
under EUV irradiation. Where N 1 , N 2 , and N 3 are
non-ionic species which were generated in thosechemical reactions.

4. Mask Defect Inspection System
4.1 EUV microscope
An EUV mask is a reflective type, which isfundamentally different from DUV lithography.
It consists absorber layer, reflective multilayer,
and glass substrate. Bump and pit on the glass

Fig. 12. Schematics of an EUV microscope, which
consists of illumination optics and an imaging
optics.

62

Figure 13 shows bright-field EUV images oftest patterns with (a) 40 nm and (b) 30 nm half
pitches. Image contrast of 0.3 was achieved at
30-nm
half-pitch
pattern,which
wascorresponded to 7.5-nm half-pitch pattern at
the wafer position. This result demonstrated
very high resolution of the EUV microscope.
(a)imaging method. The micro-CSM records
diffraction from the defect directly. The defectimage is reconstructed by iterative calculation.
Figure 15 shows the schematic layout of
micro-CSM system [22]. The coherent EUV
illumination was focused on the mask using aFresnel zoneplate (FZP). The effective NA of
the FZP was about 0.08. The angle ofincidence of the main focused EUV ray wasapproximately 6.8°, which was similar to theangle of the EUV scanner (6.0°). The
estimated focused size was about 140 nm, anda CCD camera was used to record thediffraction patterns from the defects. The NAof the micro-CSM system was approximately
0.27. The expected spatial resolution was 30
nm.

(b)

Fig. 13. Bright-field EUV images of the finegrating patterns: (a) 40, and (b) 30 nm half-pitch
patterns. The bar indicates a length of 200 nm.

Figure 14 shows EUV-microscope images of
88-nm L/S pattern with the phase defects [21],which position was varied in the line.
Variation of EUV reflectivity loss by the phase
defect was clearly observed in the intensity
profile. This result shows the high capabilityof the EUV microscope to pinpoint the actual
position and affected area by the phase defect.
Fig. 15. Schematic view of micro-CSM system.

We observed actual defects on an EUV
mask, which were already inspected with theactinic blank inspection tool [23]. Figure 16
shows the observation result of (a) AFM and(b)(c) micro-CSM, respectively. This defectwas a hole-type phase defect with an area of
67 × 57 nm 2 . We successfully reconstructed
the actual defect image with 30-nm spatial
resolution, and quantitative intensity andphase contrast. The defect shape wasreconstructed as a point shape, which was
expected from the AFM image. Thisaberration-free micro-CSM images with

Fig. 14. EUV microscope images and intensity
profiles of the 88-nm L/S with phase defect.

4.2 Micro coherent EUV scatterometry
microscope
An EUV mask has 3-dimensional (3D)
structure for EUV wavelength, which isreflective type and consists of glass substrate,
reflective Mo/Si multilayer, and absorberpattern. Since the 3D structure affects thereflective phase, a phase-imaging microscopeof the EUV mask is important for EUV mask
development.
At BL10 beamline, we have developed alensless EUV microscope of micro coherent
EUV scatterometry microscope (micro-CSM)
to observe defects with quantitative phase
contrast. Micro-CSM is simple lensless
microscope based on the coherent diffraction

63

Fig. 16. The observation results of an actual
defect. (a) AFM results, (b) (c) the images
reconstructed by micro-CSM in intensity andphase contrast, respectively. The three panels
have the same spatial scale.

has a difficulty. In this situation, the highsensitivity achievement has the highest priority,
because the most significant issue of the EUV
lithography is the achievement of the highpower EUV source to maintain the wafer
throughput for HVM. If the high sensitive EUV
resist will achieve, it might be relaxing therequirement of the power of the EUV lightsource. In order to achieve high sensitivity of
the EUV resist, the chemical reaction analysis
using real EUV light is significant. In general,the content of the photosensitizing agent suchas a photoacid generator (PAG) in the EUV
chemically amplified resist [12-14] material isapproximately from 10 to 15% of the base resin.
In order to analysis of the cation and anion of
PAG, the conventional analysis methods suchas XPS, FT-IR, and Raman spectroscopy havenot enough sensitivity for the analysis of thechemical reaction analysis of the EUV resist.
Thus we applied x-ray absorption fine structure(XAFS) method for the chemical reaction
analysis of the EUV resist material. In thismethod, the total electron yield method is used
for the analysis of the chemical reaction,
because this method is very sensitive even if
the content of PAG is small.
Since it is found that the decomposition
reaction of the fluorine which consist of theonium salts employed as a PAG is significant in
the previous study [15-17], we increase thedetection sensitivity in the TEY method byrefinement of the monochromator at the BL10
beamline. The W/Si aperiodic multilayer coatedgrating is employed for the monochromator toextend the photon energy region from 500 to1100 eV as shown in Fig. 9 [18]. As the results,

Fig. 7. 28-nm-hole pattern of the inorganic
resist using EUV-IL.

employed adapted to the EUV-IL exposure
chamber. The relative-vibration-amplitude
spectra between TDG and wafer using theconventional air-spring bench and novel higher
weight bench are shown in Fig. 8, and therelative-vibration amplitude suppressed to beless than 1 nm which is enough for the 10 nm
patterning.
As the results, it is now ready to evaluate theresolution of 10 nm using EUV-IL at
NewSUBARU [11].

Fig.8. Relative-vibration-amplitude spectra
between TDG and wafer using the conventional
air-spring bench and novel higher weight bench.

3.2 EUV resist chemical reaction analysis
using X-ray absorption fine structure (XAFS)The EUV resist technical issue is to achieve
the high resolution, high sensitivity, low lineedge-roughness (LWR), and low outgassing.
Since there is a trade-off relationship between
the resolution, sensitivity, and LWR, thesimultaneous achievement of the requirement

Fig.9. Reflectivity comparison of the wideband
W/Si-multilayer, the Ni single-layer, the Pt
single-layer samples.

64has a difficulty. In this situation, the highsensitivity achievement has the highest priority,
because the most significant issue of the EUV
lithography is the achievement of the highpower EUV source to maintain the wafer
throughput for HVM. If the high sensitive EUV
resist will achieve, it might be relaxing therequirement of the power of the EUV lightsource. In order to achieve high sensitivity of
the EUV resist, the chemical reaction analysis
using real EUV light is significant. In general,the content of the photosensitizing agent suchas a photoacid generator (PAG) in the EUV
chemically amplified resist [12-14] material isapproximately from 10 to 15% of the base resin.
In order to analysis of the cation and anion of
PAG, the conventional analysis methods suchas XPS, FT-IR, and Raman spectroscopy havenot enough sensitivity for the analysis of thechemical reaction analysis of the EUV resist.
Thus we applied x-ray absorption fine structure(XAFS) method for the chemical reaction
analysis of the EUV resist material. In thismethod, the total electron yield method is used
for the analysis of the chemical reaction,
because this method is very sensitive even if
the content of PAG is small.
Since it is found that the decomposition
reaction of the fluorine which consist of theonium salts employed as a PAG is significant in
the previous study [15-17], we increase thedetection sensitivity in the TEY method byrefinement of the monochromator at the BL10
beamline. The W/Si aperiodic multilayer coatedgrating is employed for the monochromator toextend the photon energy region from 500 to1100 eV as shown in Fig. 9 [18]. As the results,

Fig. 7. 28-nm-hole pattern of the inorganic
resist using EUV-IL.

employed adapted to the EUV-IL exposure
chamber. The relative-vibration-amplitude
spectra between TDG and wafer using theconventional air-spring bench and novel higher
weight bench are shown in Fig. 8, and therelative-vibration amplitude suppressed to beless than 1 nm which is enough for the 10 nm
patterning.
As the results, it is now ready to evaluate theresolution of 10 nm using EUV-IL at
NewSUBARU [11].

Fig.8. Relative-vibration-amplitude spectra
between TDG and wafer using the conventional
air-spring bench and novel higher weight bench.

3.2 EUV resist chemical reaction analysis
using X-ray absorption fine structure (XAFS)The EUV resist technical issue is to achieve
the high resolution, high sensitivity, low lineedge-roughness (LWR), and low outgassing.
Since there is a trade-off relationship between
the resolution, sensitivity, and LWR, thesimultaneous achievement of the requirement

Fig.9. Reflectivity comparison of the wideband
W/Si-multilayer, the Ni single-layer, the Pt
single-layer samples.

65

Oxidation of mechanically ground h-BN
Yoshida Keigo and Yasuji Muramatsu
Graduate School of Engineering, University of Hyogo
Abstract
Oxidation of mechanically ground hexagonal boron nitride (h-BN) was determined from XANES
measurements in BL10/NewSUBARU and theoretical XANES analysis by using the discrete variational(DV) -Xα method. By the mechanical grinding (MG), the π* peak at 192 eV in h-BN drasticallydecreased, and three peaks were appeared in the MG-h-BN. However, in the 240-h milling with 20 balls,
only the 194 eV peak which is corresponding to the π* peak of B2O3 remained. This shows the final
product of MG-h-BN is B2O3. Theoretical analysis indicates that the three peaks are assigned to thepartially oxidized boron BOx (x=1~3) states.
Introduction
Mechanical alloying (MA) method has
been used for alloying in non-equilibrium states.
Thus, unstable products may often be
synthesized by MA. For example, in MA ofh-BN and graphite, B-N bonds were broken andB-O bonds were formed under atmospheric air[1]. This suggested that MA of h-BN provides B
radicals under anaerobic atmosphere, and the B
radicals easily react with oxygen to form boronoxides.
In the present study, to clarify theoxidation reaction of B radicals formed by themechanical grinding (MG) of h-BN, XANES of
MG product of h-BN exposed to atmospheric air
were measured in BL10/NewSUBARU.
Oxidized structures of the MG-h-BN wereanalyzed by the theoretical method.

Results and Discussion
Figure 1 shows the XAS spectra in the180-620 eV region of the MG-h-BN andreference compounds of h-BN and B2O3.
MG-h-BN samples exhibit BK, NK, and OK
absorption peaks. Oxidation of h-BN by MG
can therefore be confirmed from the OK
absorption peaks. As the MG reaction proceeds,
NK absorption peaks become lower. Especially,
MG-h-BN milled for 240 h with 20 balls exhibit
little NK peak. Hence, h-BN can be completely
milled and nitrogen can be thoroughly
eliminated by the MG condition.

Experiments
The commercially available h-BN
powders were put in a stainless steel (SUS)
vessel (40 mmφ x 65 mmL) with SUS balls (10mmφ) under argon atmosphere. The number ofballs was varied as 10 or 20. The vessel
containing the h-BN powders with balls was set
in a MA machine (8000M, SPEC CertiPrep),and mechanically ground for up to 240 h. Afterthe MG reactions, the MG-h-BN powders were
slowly exposed to the atmosphere. The
MG-h-BN powders were pressed and hold on
indium substrates for XANES measurements.
XANES measurements were performed in
an X-ray absorption spectroscopy (XAS) station[2] in the BL10 at New SUBARU. XANES in
the BK, CK, NK, and OK regions of MG-h-BN
were obtained by a total-electron-yield (TEY)method.
For XANES analysis, density of state(DOS) of probable B/N/O cluster models wascalculate with the discrete variational (DV) -Xα
method [3].

Fig. 1 XAS spectra of MG-h-BN and referenceh-BN and B2O3.
Figure 2 shows the BK-XANES of the66and satellite peaks a ~ c as the function of MGtime.
To assign the satellite peaks, DOS ofoxidized BN cluster models, B48N48-xOxH24(x=0~3), were calculated with the DV-Xα
method. In the cluster models, O atoms
substituted for N atoms around the center B
atom. Figure 4 shows the cluster models (h-BNmodel and O-substitutional models) and theirunoccupied B2p- and 2s-DOS. The π* peak of
the center B atom in the B48N48H24 model
exhibits higher-energy shifts as the B-O bondformations. The calculated π* peak shifts arecorresponding to the measured satellite peaks a~ c. Therefore, the satellites can be assigned; thesatellite a can be assigned to the BO, satellite bto the BO2, and satellite c to be BO3 in thetrigonal B configuration. In conclusion, h-BN
can be gradually oxidized by MG reaction andthe final product is B2O3.

MG-h-BN and the references. In the early stageof the MG reaction, three satellite peaks wereobserved at 192.7 eV (denoted as a), 193.2 eV(b) and 194 eV (c) in the higher energy side ofπ* peak at 192 eV). It should be noticed that thepeak c corresponds to the π* peak of B2O3.

Fig. 2 BK-XANES of MG-h-BN and referenceh-BN and B2O3.
Figure 3 shows the peak heights of the π*
peak and satellite peaks as the function of MG
time. In the final stage of the MG reactions, theπ* peak of h-BN and satellite peaks a and b
were disappeared, while only satellite peak c
was enhanced. Hence, it can be confirmed thatthe final product of MG-h-BN is B2O3 and thesatellites a and b suggest the intermediates ofboron oxides.

Fig. 4 Upper panel shows the oxidized BN
cluster models (h-BN, O-substitutional models;
sub1~sub3) of B48N48-xOxH24 (x=0~3). Lower
shows the unoccupied B2p- and B2s-DOS of thecluster models.
References[1] Y. Muramatsu, S. Kashiwai, T. Kaneyoshi, H.

Kouzuki, M. Motoyama, M. M. Grush, T. A.
Callcott, J. H. Underwood, E. M. Gullikson,
and R. C. C. Perera, ALS Compendium of User
Abstracts and Technical Reports, 1993-1996,
47 (1997).
[2] Y. Muramatsu, A. Tsueda, T. Uemura, K.
Nambu, T. Ouchi, T. Harada, T. Watanabe, andH. Kinoshita, LASTI Annual Report, 17, 27-28(2015).

Fig. 3 Peak intensities of the π* peak of h-BN,67

[3] H. Adachi, M. Tsukada, and C. Satoko, J. Phys.
Soc. Jpn., 45, 875-883 (1978).

68

XANES of fullerenes (C60, C70) simulated by CASTEP
Yuma Hirai and Yasuji Muramatsu
Graduate School of Engineering, University of Hyogo
Abstract
To discuss the electronic structure of pentagonal rings in hexagonal carbon layers, C K XANES offullerenes (C60 and C70) were measured in BL10/NewSUBARU and the XANES profiles weretheoretically simulated and discussed by the first principle calculations. C K XANES of them weresuccessfully simulated by CASTEP, and the fine structures can be assigned from the density of state(DOS). It can be confirmed that the π* peak splits into several peaks reflecting the symmetry which
depends on the local structure around pentagonal rings.
1. Introduction
X-ray absorption near-edge structure(XANES) is a powerful tool for local structureand electronic structure analyses. However, toclarify them from XANES, theoretical analysis
should be required to assign the peak structure
in XANES. Recently, the first principle
calculation method of CASTEP [1] has been
applied for XANES simulations.
In the present study, to demonstrate thecapability of CASTEP for XANES simulationsof large carbon molecules, XANES of fullerenes
and
C70)
were
measuredin(C60
BL10/NewSUBARU and simulated by CASTEP.
Additionally, fine structures of their XANES
were discussed, referring to the density of state(DOS) calculated by the DV-Xα molecularorbital method [2].

3. Results and Discussion
Fig. 1 shows the measured C K XANES
compared to the calculated XANES and theunoccupied DOS of C60. The measured C K
XANES which exhibits eight peaks (denoted bya ~ h) agrees to the previously

2. XANES measurements and calculations
Commercially available powder samplesof C60 and C70 were pressed and held on an
indium substrate and used as XANES
measurement sample. C K-XANES of them wasmeasured in BL10 at NewSUBARU by using a
total-electron-yield (TEY) method.
In the simulation of XANES by CASTEP,
each molecular model was put in the center of asupercell. In order to suppress intermolecularinteraction, the distance between the supercell
boundaries and the molecular model was set tolonger than 5 Å. After the structure optimizationby Material Studio package, ground-statecalculations were performed. Then, excited-statecalculations were carried out by providing corehole in the 1s orbital of the target atom.
Transition energy was corrected by the
Mizoguchi method [3]. XANES of individualcarbon atoms was calculated, and calculated
XANES of a molecule was obtained bysumming up the XANES of individual atoms.
To assign the peak structure of XANES,
unoccupied DOS was also calculated by the
DV-Xα method.

Fig. 1 Cluster mode or C60 (a), the measured andcalculated C K-XANES of C60 (b), and the69unoccupied DOS of C60 (c).
measured spectrum [4]. The peak structure canbe well reproduced by the calculated XANES.
The unoccupied C2p- and C2s-DOS exhibits
broader structure than the calculated XANES.
However, the broad C2p-DOS peaks canapproximately correspond to the peak a ~ h.
Only peak a consists of 2p-state. Thus, peak a
can be assigned to a π* peak. It should be notedthat the lowest peak of a is at 284.8 eV, which islower than the 285.5 eV π* peak of graphite.
Each carbon atom in C60 is shared by two
hexagonal ring and one pentagonal ring.
Therefore, the pentagonal ring results in the low
energy shift of the π* peak. Peaks b ~ h consistof hybridizes states with 2p- and 2s-orbitals.
Contribution of 2s-orbital in peaks b and c may
reflect the non-planar structure formed bypentagonal rings in hexagonal rings.
Figure 2 shows the measured C K
XANES compared to the calculated XANES
and the unoccupied DOS of C70. The measured
C K XANES which exhibits nine peaks (denotedby a ~ i) agrees to the previously measured
spectrum [4]. C70 consists of five different
carbon atoms due to the symmetry, as labelledby 1 ~ 5 in the cluster model. The calculated
XANES of each five carbon atom was obtained,
and summing them provides XANES of C70
molecule. The measured XANES profile can bewell reproduced by the calculated XANES.
Atoms C1 and C5, which are shared byhexagonal rings, exhibit peak b at 285.5 eV.
Atoms C2 ~ C4, which are shared by two
hexagonal rings and one pentagonal ring, exhibit
peaks a and c. Such the peak assignments
approximately agree to the DOS distribution.
The peak profile of C2 ~ C4 indicates that the
carbon atom shared by pentagonal andhexagonal rings split the π* peak, which isconsistent to the peak profile of C60.
Such the spectral analysis of C60 and C70
indicates that the π* peak in C K XANES ofcarbon atoms partially shared with pentagonal issplit into two peaks. This means that the
pentagonal ring makes the π* peak splitting
around 285.5 eV.

[4] L. J. Terminello, D. K. Shuh, F. J. Himpsel,
D. A. Lapiano-Smith, J. Stöhr, D. S. Bethune,
and G. Meijier, Chem. Phys. Lett., 182,
491-496 8(1991).

Reference[1] S. J. Clark, M. D. Segall, C. J. Pickard, P. J
Probert, K. Refson, M. C. Z. Payne,
Krystalloger., 220, 567-570 (2005).
[2] H. Adachi, M. Tsukada, and C. Satoko, J.
Phys. Soc. Jpn. 45, 875-883 (1978).
[3] T. Mizoguchi, I. Tanaka, S.-P. Gao, C. J. J.
Pickard, Phys. Condens. Mat., 21, 104204(2009).

70

Fig. 2 Cluster mode or C60 (a), the measured
and calculated C K-XANES of C60 (b), and theunoccupied DOS of C60 (c).

71Soft X-ray analyses of detonation nanodiamonds
to investigate surface sp2 carbon
for the dispersibility improvement
Masahiro Nishikawa1, Ming Liu1, and Yasuji Muramatsu2
1
Daicel Corporation, 2 University of Hyogo
Abstract
Gas-phase (air) oxidation is the most promising avenue for the dispersibility improvement of
detonation nanodiamonds (DND) in water or polar solvents. To elucidate oxidation
mechanism, we conducted X-ray absorption near edge structure (XANES) measurements at
BL-10 in the NewSUBARU SR facility. We found that the increase of edge carbon on sp2cluster was the key to increase oxygen functional groups on the surface, not increase of sp2
carbon content.
the temperature was raised to 450oC, sp2 carbon
content increased. It can be presumed that partof sp3 carbon phase changed to sp2 carbon atthat temperature.

Introduction
Dispersibility is the key to utilize detonation
nanodiamonds (DND) for various applications.
We have reported that gas-phase (air) oxidationof detonation nanodiamonds (DND) is one ofthe powerful tools to improve dispersibility inwater or polar solvents. It can be thought that itis because oxygen functional groups on thesurface increase by oxidation [1]. To elucidate
the oxidation mechanism, we investigated theamount and state of sp2 carbon on the surface of
DND samples obtained by different oxidation
conditions using soft X-ray near-edge structure(XANES).

Total electron yield* PeakExperiments
XANES measurements were carried out at
BL-10 [2] in the NewSUBARU SR facility.
CK-edge and OK-edge XANES were recordedby the total electron yield (TEY) method.
DND raw material for gas-phase oxidation
was manufactured by Daicel Corporation, of
which average primary particle diameter wasdetermined 4.5 nm according to Sherrer’s
equation by HMFW of the 111 peak of powder
X-ray diffraction analysis. Gas-phase oxidation
were performed by atmosphere furnace with theflow of 4% oxygen-nitrogen gas at different
temperatures between 250 and 450oC. Alloxidized DNDs by above conditions were welldispersed in water by bead-milling process [1].

* Peak

450℃
350℃
Untreated

Peak height ratio

280

285

290

295

400℃
250℃

300

305

310

350℃

400℃

450℃

Photon energy / eV

315

0.14
0.12
0.1
0.08
0.06
0.04
0.02
0

Untreated

250℃

Fig. 1 CK-edge XANES spectra of gas-phaseoxidized DND at various temperatures (upper)and sp2 carbon content estimation from the peakheight ratio of */ * (lower)

Results and Discussioni) Content of sp2 carbon
CK-edge XANES spectra of oxidized DND
samples are shown in Fig.1. We estimated sp2
carbon content from the peak height ratio of
π*(285 eV)/σ*(293 eV) and found that theamount of sp2 carbon was almost the same asthat of the untreated DND up to 400oC. Whenii) Edge carbon proportion
It was found that * peak for each sample
had a shoulder at about 284.5 eV (Fig. 2), which
had been attributed to edge carbon of sp2
cluster [3]. To estimate the proportion of thatshoulder peak, differential spectrum between
DND sample and HOPG (Highly Oriented
Pyrolytic Graphite), normalized at * peak, was72

obtained. That differential spectrum is called“pre-peak”. We compared the peak height ofeach sample and found that pre-peak heightincreased as the temperature rose. We deduced
that the proportion of edge carbon increased
with sp2 clusters broken-up into small
fragments.
Peak at 287 eV, which had been assigned tosp2 carbon bound to oxygen functional group [3],also increased as the temperature was raised.
That supported the hypothesis that oxygen
functional groups increased by the oxidation.

oxygen functional groups increased by theoxidation. That agrees with the results for the
peak at 287 eV of CK-edge XANES.

Total electron yieldShoulderTotal electron yield
Normarized peak height

520

525

530

535

540

545

550

555

560

Photon energy / eV

Fig. 3 OK-edge XANES spectra of gas-phaseoxidized DND at various temperatures, normalized
at 293 eV ( *) of CK-edge XANES
450℃
350℃
Untreated

282

283

1.4
1.2

284
285
286
Photon energy / eV287iv) Oxidation mechanism
We concluded that the increase of oxygen
functional group for the dispersibility improvement
may occur as the following;- Oxidation process broke-up sp2 carbon clusters
into small fractions that increased edge carbon
proportion, not sp2 carbon content.
- The edge carbon was subsequently oxidized
with oxygen to increase oxygen functionalgroups.

288

DND

Pre-peak

1

400℃
250℃

0.8
0.6

HOPG

0.4
0.2

References[1] M. Liu, A. Kume, M. Nishikawa, H. Ito, 10th
International Conference on New Diamond and Nano
Carbons Xi’an, China, p6-14 (2016).
[2] T. Uemura, Y. Muramatsu, K. Nambu, D.
Fukuyama, M. Kuki, T. Harada, T. Watanabe, and H.
Kinoshita, Adv. X-ray Chem. Anal., Japan, 46,
317-325 (2015).
[3] K. Murayama, T, Okada, Y. Muramatsu, 10th
International Symposium on Atomic Level
Characterizations for New Materials and Devices ’15
Shimane, Japan, 27p-P-38 (2015).

Differential

0

-0.2

Pre-peak height

450℃
400℃
350℃
250℃

(DND-HOPG)

282

283

284
285
286
Photon energy / eV

287

288

0.8
0.75
0.7
0.65
0.6
0.55
0.5

Untreated

250℃

350℃

400℃

450℃

Fig. 2 CK-edge XANES spectra of * peakregion of oxidized DND (upper), the differential
spectrum (black line, middle) and pre-peakheight of each sample (lower)iii) OK-edge XANES
OK-edge XANES analyses were also
conducted (Fig. 3). Peak height normalized at* peak of CK-edge XANES increased with thetreatment temperature raise, indicating that73

Deterioration and Depth-Profile Analysesof Organic Thin Film
Shogo Suehiro1, Eiji Takahashi1, Yousuke Azuma1,
Yasuko Mitsushita1, Yasuji Muramatsu2, and Yoshiyuki Suzuri3
1

Sumika Chemical Analysis Service, Ltd.,
1-135, Kasugade-Naka 3-chome, Konohana-ku, Osaka 554-0022, Japan
2
Graduate School of Engineering, University of Hyogo,
2167, Shosha, Himeji, Hyogo 671-2280 Japan
3
Innovation Center for Organic Electronics, Yamagata University,
1-808-48 Arcadia, Yonezawa, Yamagata 992-0119 Japan

Abstract

The manufacturing process affects the performance of devices consisted of multilayer organic thinfilms such as organic electroluminescent (OEL) devices. We conducted the deterioration and thedepth-profile analyses of B3PyMPM film by using soft XAS and XRR at BL10/NewSUBARU.
The differences of molecular orientation and surface structure due to manufacturing process andheating treatment are discussed in this report. Because the Ar-GCIB method hardly damaged

films, this method is helpful in analyzing organic thin films with depth information .

Introduction
Organic multilayer is the common structure for
OEL devices. Though the thickness of each layer isthe same in several devices, the performances are
not always the same because the molecularorientation, surface roughness, density, andcomposition ratio of each layer are affected by the
manufacturing processes. In this report, we will
introduce some cases of the deterioration and thedepth-profile analyses by using the soft X-ray
absorption spectroscopy (soft XAS) at BL10/NewSUBARU
for
thin
film
of
4,6-bis(3,5-di-3-pyridylphenyl)-2-methylpyrimidine (B3PyMPM) which is commonly used for theelectron transport layer of OEL devices.

the center for X-ray optics (CXRO).
2. Depth-profile analysis by the XAS measurementwith the GCIB method
B3PyMPM thin films were vacuum depositedor spin coated to 100 nm thickness onto an
Indium-Tin-Oxide (ITO) substrate. These films
were etched by the Ar-GCIB (Gas Cluster Ion
Beam) method. The etched areas were 2 mm inwidth and length, and 10 nm, 30 nm, and 50 nm in
depth. To examine the molecular orientation, theincident angles (θ) of soft XAS were tuned to anormal (90°) and a magic angle (54.5°).
Results and Discussion
1. Deterioration analysis of B3PyMPM film
The molecular orientation could be elucidated
by change of the π* peak to σ* peak intensity ratio
in the N K region of the X-ray absorption nearedge structure (XANES) spectra. This result
indicates that the vacuum deposited film shows thehorizontal orientation of B3PyMPMs before heat
treatment, but the orientation decreased after heat
treatment. The spin coated film does not show
the molecular orientation regardless of the heat
treatment.
In the XRR spectra shown in Table I, the X-ray
interference patterns, come from reflects at theinterface between the film and the substrate, appear
for the untreated films. However, that patterns does
not appear for the heat treatment films.
In SEM images shown in Table I, the roughnessof the film surface is getting large withcrystallization progress by heating. This result
indicates that the film preparation method have an

Experiments
The total electron yield (TEY) - XAS
measurements were performed across carbon
k-edge and nitrogen k-edge (C K and N K), and the
X-ray incident angle was varied as θ = 90°, 70°,
54.5° and 30° in XAS measurements. For the
X-ray reflectometry (XRR) measurement, the
X-ray incident angle was varied 5° - 20°.
1. Deterioration analysis of B3PyMPM film
B3PyMPM films were vacuum deposited orspin coated to 100 nm thickness onto silicon
substrate. In order to examine the degradation
process by XAS and XRR, those untreated films
and a heat treatment films, heated for 1 hour at
120°C, were compared. The density of state(DOS) was calculated using the discrete variational(DV)-Xα molecular orbital calculation and theelectron state was analyzed. The XRR results
were analyzed with the simulation soft offered by74

influence on a crystallization a surface of films.
Table I. Heat treatment effects for vacuum
deposited films with XRR and SEM.

2. Depth-profile analysis by the XAS measurementwith the GCIB method
The vacuum deposited and spin coated films
show the same N K - XANES spectra on the GCIB
processed surface regardless of the processed depth
shown in Figure 1. This result indicates that the
Ar-GCIB method hardly damage films. In otherwords, the Ar-GCIB method is helpful in analyzing
the angle variable XAS exactly at the processedarea in BL10.

Figure 1. N – K XANES spectra for vacuum
deposited films (a) and spin coated films (b)with untreated (A), GCIB treatment 10 nm (B),
30 nm (C), and 50 nm (D). The red curves
mean the incident angle was 90°, and the black
curves mean that was 54.5°.

Reference[1] F. Zheng, B. N. Park, S. Seo, P. G. Evans, F. J.
Himpsel: J. Chem. Phys., 126, 154702 (2007).

75

Analysis of adsorbed monolayer molecules formed by oil
additives on frictional surfaces by NEXAFS
Naoko Takahashi1, Masaru Okuyama1, Noritake Isomura1, Mamoru Tohyama1
Yasuji Kimoto1, Toshihide Ohmori1,
Yasuji Muramatsu2, Keita Nanbu2, Takahito Ouchi2
1
Toyota Central R&D Labs., Inc. , 2 University of Hyogo
Abstract
To understand frictional mechanism of automatic transmission, it is important to detectadsorbed monolayer molecules on the frictional surfaces formed by ATF (automatictransmission fluid) additives. We measured C K-edge spectra of the frictional surfaces, whichwere slid with base oil and ATFs with two types of amine-based additives. The spectra withadditives were successfully obtained and showed a unique feature, which was different fromthe spectrum of the base oil.
there are only few examples which havereported NEXAFS analysis for the additives.3-5)
NEXAFS has enough structure dependent
sensitivity to detect the adsorbed molecules on
the frictional surface and enable us to analyze
the detailed information of molecular structures
and their electronic states.
Table 1 shows examples of additives for ATF
or engine oil. As our first trial in this experiment,
we analyzed amine-based additives on thefrictional surfaces.

Introduction
Since friction reduction of mechanistic parts in
automobiles is important from the viewpoints ofenergy conservation and CO2 exhaust reduction,
analysis of the low friction surfaces is the key
technology to understand and improve theperformances. Particularly in the case of
lubricated surfaces with ATF, adsorbates fromthe additives significantly influence on thefriction properties and there analysis isnecessary to elucidate the friction mechanism.
In general, there are adequate methods toobtain the chemical and physical information ofadsorbed species of the additive, infrared
spectroscopy (IR), Raman spectroscopy andelectron probe micro analyzer (EPMA).
However, their analysis depth is too deep andlacks sensitivity to detect the adsorbed
molecules on the frictional surface shown in Fig.
1. On the other hand, X-ray photoelectron
spectroscopy (XPS) and time of flight secondary
ion mass spectrometry (TOF-SIMS) are able todetect the adsorbed molecules with highsensitivity because their analysis depth is only
several nanometers and shallow enough todetect the surface layer information. However, it
is still challenging for these methods toelucidate the detailed chemical structure for any
kind of molecules. For example, XPS cannot
discriminate between C-H and C-C bonds
clearly,1-2) and TOF-SIMS will decompose suchmolecules by ion irradiation and show confusingmass numbers for assignments. Therefore, adevelopment of alternative analytical method issignificantly important for tribological studies.
In this experiment, we tried to detectmonolayer-adsorbed molecules on thefrictional surfaces to analyze the adsorption
state of the ATF additives by near-edge X-ray
absorption fine structure (NEXAFS), althoughFig. 1 An estimated model of adsorbed stearate
molecules on the frictional iron surface.6)
Table 1 Representative additives of ATF andengine oil.
Amine based
friction modifier

Molybdenum based
friction modifier
Anti-wear agent
and Antioxidant
Metal-based cleaner

Ashless dispersant76

had different molecular structure. Currently, theassignment of the spectra is under investigation
by ab-initio DFT calculation to understandphysical and chemical structure of the adsorbed
layer. Such information is important to develop
and improve the frictional performance ofadditives.

Experimental
Block specimens after friction tests were used
for the analysis. The friction tests were carriedout by a block-on-ring type apparatus with
SUS440C block and AISI4620 ring (fig. 2).
Two
types
of
ATFs
containing
amine-based additives, oleylamine orpolyoxyethylene oleylamine, were applied
for the friction tests. The original base oil
without any additive was also used as a control.
Test parameters were as follows; load=289 N,
sliding velocity=0.3 m/s, oil temperature=80°C
and sliding time=30 minutes.
C K-edge NEXAFS spectra were measured in
BL10
at
New
SUBARUbyatotal-electron-yield (TEY) method with sample
current mode. The angle between the surface
and the direction vector of incident X-ray was
90 degrees and the spectra were acquired bymonitoring the sample drain current.

2 A schematic illustration
block-on-ring type apparatus

Fig.

of

Fig. 3 C K-edge NEXAFS spectra of thesurface of block specimens slid in base oil
and ATFs with two types of amine-based
additives, oleylamine or polyoxyethylene
oleylamine.
References[1] D. Briggs and M. P. Seah, Practical Surface
Analysis by Auger and X-ray Photoelectron
Spectroscopy 2nd ed. John Wiley & Sons
Ltd., New York, 598-635 (1990)[2] J. F. Moulder, W. F. Stickle, P. E. Sobol, K.
D. Bomben, Hand Book of X-ray
Photoelectron Spectroscopy (1995)[3] T. Uemura, Y. Muramatsu, K. Nanbu,
T. Harada and H. Kinoshita, Advances in
X-Ray Chemical Analysis, Japan, 45 (2014)[4] T. K. Sham, Chemical Applications ofSynchrotron Radiation X-ray applications,
World Scientific (2002)[5] J. C. Riviere and S. Myhra, Handbook ofSurface and Interface Analysis Methods for
Problem-Solving 2nd ed. CRC Press (2009)[6]T. Sakurai, Physical chemistry of lubrication
126 (1983)aResultIn the case of amine-based ATF additives,actual friction on a surface is necessary to takeeffect because frictional interaction such as heator pressure creates the adsorbed layer. The layer
remains even after removal of the oil by
washing process. We tried to detect C K-edge
NEXAFS spectra to obtain the details of thelayer because C K-edge information was
important to understand the molecular structure,for example π and bondings, in general.
Figure 3 shows the C K-edge spectra of
specimens after friction test. It is interesting tonote that the specimen without additives
exhibits clear C K-edge spectrum and we predictthat there was an organic thin film formed by
the base oil even without any additive. The two
specimens with additive containing ATFs show
identical spectra, which are different from thespectrum of the base oil. The results indicatethat the adsorbed layers created by additives
have similar structure even the original additives

77

Miniature Micro-Powder Feeder
Driven by Surface Acoustic Wave
Tsunemasa Saikia, b, Akinobu Yamaguchib, Michitaka Suzukib, and Yuichi UtsumibaHyogo Prefectural Institute of Technology, b University of Hyogo

Abstract

In this study, we investigated the relationship between powder transport efficiency and shape of aninter-digital transducer (IDT) that generates a surface acoustic wave (SAW). On the basis of theinvestigation, we fabricated a high-efficiency miniature feeder that possesses a powder storage
hopper for practical use. As the result, it was shown that the feeder with an IDT with 2000-µm
pitch size has transportation capability of 15 mg/s at 1 W.

IDT [3]. The IDTs were made of a 1-µm Al
layer and fabricated on a piezoelectric substrate(a 128-degree y-rotated x-propagating LiNbO3
wafer) by using photolithography, etching, anddicing processes. Incidentally, central axis
directions of the IDTs were matched with anoriental flat direction of the wafer. Then, when
the boosted voltage was applied to the IDT, a
SAW was generated and propagated on thepiezoelectric substrate. The SAW arrived at thecopper powder (total weight: 30 mg and average
particle diameter: approximately 100 µm), andthe powder was transported downstream of theSAW. The powder transportation was recordedwith a high-definition video camera, and electric
power PA instead of the burst wave voltage wasmeasured using a power meter. From therecorded videos, we evaluated the powdertransport speed S. The relationship between
powder transport speed and electric power
applied to the IDT is shown in Fig. 2. The
powder transport speed increased almost
linearly with the applied electric power. On theother hand, under the same electric power, thetransport speed became faster as the pitch size p
increased. The IDT with 2000-µm pitch size had
the highest powder transport efficiency in our
prepared IDTs (pitch sizes of 200, 400, 800, and2000 µm).

Introduction
In the electronics and drug-discovery
industries, physical operations, such astransportation and separation of micro powder,
are required. However, it is difficult toefficiently handle such powder because it canbehave not only as a solid but also as a liquid orgas. It has been impossible to transport a tiny
amount, from several hundred µg to several mg,
of dry powder if a general-purpose conveyor or
blower that has been miniaturized is used. An
ultrasonic wave device can be used to transport
tiny amounts of powder [1]. However, sincesuch devices consist of piezoelectric
multi-layers, their manufacturing process iscomplicated. We therefore focused on a surface
acoustic wave (SAW) device with a simple
structure and have been studying the basic
properties of SAW actuators for transporting
powder [2]. In this study, we investigated therelationshipbetweenpowdertransport
efficiency and shape of an inter-digitaltransducer (IDT) that generates a SAW andfabricated a high-efficiency miniature feederthat possesses a powder storage hopper forpractical use. Incidentally, we presented thisstudy at an international conference [3].
IDT suitable for powder transport
From the results from our previous liquidflow experiment involving SAW actuators [4],the pitch size, an IDT shape parameter, greatly
affected liquid flow characteristics. We thus
investigated the relationship between pitch sizeand powder transport efficiency of SAW
actuators. The experimental setup forinvestigating the relationship is shown in Fig. 1.
A function generator created 1-kHz burst
waveforms consisting of 2000 cycles of fD-Hz
sine waves, and a radio-frequency (RF)amplifier boosted the burst waveform voltage.
The fD was an experimental frequency value
obtained from the return loss characteristic of an

Micro-powder feeder with high efficient IDT
Based on these results, we fabricated aminiature SAW feeder with an IDT with
2000-μm pitch size. The powder transportation
behavior on the fabricated SAW feeder is shownin Fig. 3. The IDT’s aperture size and number ofstripline pairs are 10 mm and 10, respectively.
For practical use, the SAW feeder has a powderstorage hopper of 0.4 cm3. The hopper has aninverted cone shape with an apex angle of 60
degrees and a height of 10 mm and has a holediameter of 1 mm in its bottom. In theexperiment, 500 mg of copper powder was put

78

Function generator

RF amplifier

35
Transport speed S [mm/s]

in the hopper. The SAW feeder was thenoperated by applying 930 mW of electric power
to the IDT with the same method shown in Fig.
1. The generated SAW transported the powder
under the hopper. When there was not enoughpowder under the hopper, the amount of thepowder to replenish was supplied from thehopper by gravity. On the other hand, thepowder transporting on a substrate was
gradually collected using two guide walls(height: 2 mm, length: 35 mm, and convergenceangle: 20 degrees) until the powder arrived at anoutlet (an interspace between the guide walls of2 mm) of the SAW feeder and grains of thepowder fell one after the other. The weight of
the fallen powder m was measured using anelectronic balance located under the outlet.
Incidentally, the hopper and guide walls weremade of hard transparent resin (Fullcure720)
and fabricated using a 3D printer (Stratasys Inc.
Connex500). A temporal change in the weight of
the fallen powder (i.e., supplied) from the SAW
feeder is shown in Fig. 4. The powder weightsupplied from the SAW feeder driven at about 1
W increased gradually with elapsed time t andreached about 90% of the initial storage weightin the hopper after about 30 s. From the slope ofthe straight line determined using the leastsquare method, the transportation capability of
the SAW feeder was estimated to be about 15
mg/s. This indicates that, by slowing thetransport speed, the fabricated SAW miniature
feeder can supply powder with high accuracy ofseveral mg or less.

Pitch size p (Drive frequency fD)
200 µm (34.8 MHz)
400 µm (15.7 MHz)
800 µm (8.7 MHz)
2000 µm (3.3 MHz)

30
25
20
15
10
5
0
0

500
1000
1500
2000
Applied electric power PA [mW]

2500

Fig. 2 Relationship between powder transport
speed and electric power in each ITD’s pitchsize
Absorber Hopper Piezoelectric substrate
Guide walls

SMA jack
PCB
IDT

Outlet(a) t = 2 s
75mm
17mm
35mm

(b) t = 10 s

High-definition
video camera

Fig. 3 Photographs of powder transportation
behavior on fabricated SAW feeder

Dual-direction
couplerMovingPowderIDT SAWPower meter
Piezoelectric
substrate

Fig. 1 Experimental setup for observing powdertransport behavior by using SAW

Supplied powder weight m [mg]

SAW actuator

500
400
300
200
100
0
0

5

10

15

20

25

30

35

Elapsed time t [s]Fig. 4 Temporal change in powder weightsupplied from SAW feeder

79References[1] M. Mracek, J. Wallaschek, A System for
Powder Transport Based on Piezoelectrically
Excited Ultrasonic Progressive Waves,
Mertericals Chemistry and Physics, 90,
378-380 (2005).
[2] T. Saiki, Y. Arisue, K. Kuramoto, H. Shizuka,
M. Takeo, K. Maenaka, Y. Utsumi, Direction
Control of Powder Transport on Solid
Substrate by Drive Frequency of Surface
Acoustic Wave Actuator, Proc. of 38th
International Conference on Micro and Nano
Engineering (MNE2012), P270-022 (2012).
[3] T. Saiki, A. Tsubosaka, A. Yamaguchi, M.
Takeo, M. Suzuki and Y. Utsumi,
Development of Miniature Micro-Powder
Feeder Driven by Surface Acoustic Wave for
Practical Use, Proc. of 42nd International
Conference on Micro and Nano Engineering(MNE2016), Wed-C2-159 (2016).
[4] T. Saiki, K. Okada, and Y. Utsumi, Highly
Efficient Liquid Flow Actuator Operated by
Surface Acoustic Waver, Electronics andCommunications in Japan, 94, 10, 10-16(2011).

80

C-, N-, O-XANES analyses of complex suites of organic
compounds produced by laboratory simulations of
extraterrestrial environments
Yoko Kebukawa1, Shusuke Misawa1, Hitomi Abe1, Shingo Enomoto1, Yasuji Muramatsu2, Takahito Ouchi2,
Sohta Hamanaka2, Hitoshi Fukuda3, Yoshiyuki Oguri3, Satoshi Yoshida4, Isao Yoda3,
and Kensei Kobayashi1
1
Yokohama National University, 2University of Hyogo, 3Tokyo Institute of Technology,4National Institute for Quantum and Radiological Sciences and Technology
Abstract
We conducted C, N, O K-edge X-ray absorption near edge structure (XANES) analyses forcomplex suites of organic compounds synthesized by simulating experiments for various
extraterrestrial environments at BL10, NewSUBARU. Variations in functional groupchemistry were observed depending on the starting materials and experimental conditions.
compounds. We have been investigated thesecomplex organic compounds with C, N, O
K-edge X-ray absorption near edge structure(XANES) spectroscopy. In order to understandthe nature and chemistry of the extraterrestrialorganic matter including amino acid precursors.

Introduction
Primitive
meteorites,suchascarbonaceous chondrites contain a few wt.%
organic matter. The most of organic carbon (>70
wt.%C) exists as in the form of solvent insolubleorganic
matter(IOM)
withcomplexmacromolecular structures. Rest of the organiccarbon is in the form of solvent extractableorganic compounds that include tens of
thousands of different molecular compositions,with possibly millions of diverse structures [1].
Some of them, such as amino acids andnucleobases could have been contributed to theemergence of life in the early earth. The origins
and formation processes of these diverse
extraterrestrial organic matter were not wellknown.
In the very low temperature (~10-50 K)
molecular cloud, chemical reactions would be
driven by cosmic rays and UV and occurred in
the ice mantles on the silicate dust grains.
Laboratory experiments showed that variousorganic molecules including amino acids were
produced by particle irradiations or UV to icesthat consist of simple molecules such as H2O,
CO and CH3OH [e.g. 2]. The Solar Systemformed from such molecular cloud bygravitational
collapse.
Smallbodies(“planetesimals”)
accretedfrom
dust.
Planetesimals formed far enough from the Sun
contains icy dust. Internal heating of theplanetesimals containing icy dust turned ice intoaqueous solution. Chemical reactions involving
liquid water could produce organic matter [e.g.
3].
Simulated experiments for various
extraterrestrial environments produces complex
suites of organic compounds. Amino acids areproduced by acid hydrolysis of these organic

Simulated interstellar media
Gas mixtures of CO, NH3 and H2O withand without CH4 were irradiated with 2 mC of
2.5 MeV protons from a Tandem accelerator atTokyo Institute of Technology. The products are
hereafter abbreviated to as CAW (without CH4)
and CMAW (with CH4). Gas mixtures of
CH3OH, NH3, H2O were irradiated with 290
MeV/u C+ ion at room temperature and 77 K
from Heavy Ion Medical Accelerator in Chiba(HIMAC) at National Institute of Radiological
Sciences (NIRS). The products are hereafter
abbreviated to as MeAW. The experimental
products were collected with pure water, if
necessary. A few drops of each product wasdried on a Al plate for C,N,O-XANES analyses
at BL10, NewSUBARU (NS).
C-XANES of CAW showed peaks at
284.0 eV (C1), 285.5 eV (C3), 288.6 eV (C5)and 290.0 eV (C6), while CMAW showedsimilar features but less 290.0 eV peak (Fig. 1)[4]. Possible assignments of these peaks arearomatic/olefinic C=C for 285.5 eV (C3),carbonyl/carboxyl O-C=O for 288.6 eV (C5),and carbamoyl N-C=O for 290.0 eV [5]. Less
carbamoyl in CMAW might indicate thatmajority of C=O in CMAW is adjacent tomethyl/ethyl carbon rather than amines.
C-XANES of MeAW irradiated at room
temperature (r.t.) and 77K showed peaks at
283.7 eV (C1), 288.6 eV (C4), 290.0 eV (C5)(Fig. 2) [4]. In addition, MeAW(r.t.) showed81285.2 eV and MeAW(77K) showed 287.2 eV(C3) which is assigned to aliphatic carbon.
These results indicated that lower temperaturesamples tend to have more aliphatic structuresand higher temperature samples tend to havemore aromatic structures.

nitrogen (95%) and methane (5%) was prepared
as a simulated Titan tropospheric atmosphere.
The pressure corresponds to that of Titan at analtitude of 10 km. The gas mixtures were
irradiated with 1 to 5 mC protons from a
Tandem accelerator at Tokyo Institute ofTechnology. After proton irradiation, theproducts inside Pyrex tube were collected withseveral kinds of solvents that have different
polar character, and were analyzed by
C,N,O-XANES using BL10/NS.
C,N-XANES analyses showed that thetholins contained amine groups, cyanide
functional groups and aliphatic moieties (Fig. 3)[7]. Molecular structures of tholins shows somevariations depend on the solvents used forextraction, indicating that tholins contains
various compounds with different polarity.

Total electron yield (A.U.)

Fig. 1 C-XANES spectra of CAW (CO, NH3,
H2O) and CMAW (CO, CH4, NH3, H2O)
irradiated by proton [4].

Fig. 2 C-XANES spectra of MeAW (CH3OH,
NH3, H2O) irradiated by C+ ion at room
temperature (r.t.) and 77K [4].
Simulated Titan atmosphere
Titan is the largest moon of Saturn, which
has a dense atmosphere mostly consisted ofnitrogen and methane. An active organic
chemistry is considered to take place in theatmosphere due to irradiation by solar UV light,
Saturnian magnetospheric electrons and cosmic
rays as energy sources. Complex organic
materials produced in laboratory simulations
have often been called “tholins”, which containhydrocarbon, nitrile and heterocyclic aromatic
moieties. Most laboratory works have simulated
reactions in the higher atmosphere of Titan
caused by solar UV and Saturnian
magnetospheric electrons. In the lower
atmosphere, cosmic rays could have larger
contribution, Taniuchi et al. [6] studied thattholins formed by proton irradiations produced awide variety of amino acid after acid hydrolysis.
A 700 Torr (93 kPa) of gas mixture of

Fig. 3 C-XANES and N-XANES spectra of
Titan tholins irradiated by 1 mC proton,
extracted by tetrahydrofuran (THF), acetonitrile,and methanol (MeOH) [7].
Simulatedaqueousalterationinplanetesimals
Carbonaceous chondrites that are samples
from aqueously altered parent bodies, containvarious organic matter, which mostly consists ofinsoluble organic matter (IOM), and also
contain some soluble organic compounds
including amino acids. Cody et al. [3] proposed
IOM formation via formose reaction starting82

with formaldehyde during aqueous activity inthe solar system small bodies. Additionalhydrothermal
experiments
showedthatammonia enhanced the yields of IOM likeorganic matter and simultaneously produced
amino acid precursors [8]. The most effective
heat source for melting water ice in small bodies
is considered to the decay of 26Al. However theeffects of radiation from 26Al, e.g. gamma-ray,
has not been reported yet. Thus the effects of
gamma-ray as an energy source for theformation of organic matter were evaluated.
The
starting
solutionscontained
formaldehyde, ammonia, water, with/without
Ca(OH)2 as a catalyst. Each solution was flame
sealed into glass tubes. Gamma-ray irradiation
experiments were conducted using 60Co sourceat Tokyo Institute of Technology. Heating
experiments were conducted at 150 °C for 24hours for comparison.
C-XANES spectra of the gamma-ray
irradiation samples and heated samples showedsome differences (Fig. 4). The gamma-ray
irradiation samples have dominated 285.0 eV(aromatic) and 290.0 eV (carbamoyl) peaks
compared to heated samples.
The results show that organic compounds
formed by the gamma-ray irradiation to theformaldehyde and ammonia water solutions
were different from those formed by heating,thus the reaction mechanisms would be different
between gamma-ray irradiation and heating.

References[1] P. Schmitt-Kopplin, Z. Gabelica, R. D.
Gougeon, A. Fekete, B. Kanawati, M. Harir, I.
Gebefuegi, G. Eckel, N. Hertkorn: PNAS, 107,2763 (2010).
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W. A. Schutte, P. A. Gerakines, M. Degroot:
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[3] G. D. Cody, E. Heying, C. M. O. Alexander, L.
R. Nittler, A. L. D. Kilcoyne, S. A. Sandford, R.
M. Stroud: PNAS, 108, 19171 (2011).
[4] S. Enomoto: Master thesis, Yokohama National
University (2017).
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Araki, A. Butterworth, H. Fleckenstein, G.
Flynn, M. K. Gilles, C. Jacobsen, A. L. D.
Kilcoyne, K. Messenger, S. A. Sandford, T.
Tyliszczak, A. J. Westphal, S. Wirick, H. Yabuta:
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Analytical Sciences, 29, 777-785 (2013).
[7] H. Abe: Master thesis, Yokohama National
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Kobayashi, M. E. Zolensky: Science Advances,3, e1602093 (2017)

Fig. 4 C-XANES of the products fromformaldehyde and ammonia water solutions by
gamma-ray irradiation and hydrothermal (HT)treatments.
Conclusions
We successfully obtained functional group
analysis of laboratory synthesized organic
matter simulating various extraterrestrial
environments using C,N,O-XANES at BL10/NS.
However, peak assignments of C,N,O-XANES
remain ambiguity. We further need analyses ofstandard compounds for solid peak assignments.

83Part 3. List of Publications

H. Hashimoto in a master's course of a graduate school won theBest Academic Poster Award in Photomask Japan 2016.

(1) Papers

List of publications

1.

"Positron annihilation Doppler broadening measurement for bulk amorphous alloy by using high energy
positron generated from LCS gamma-ray at NewSUBARU"
F. Hori, Y. Ueno, K. Ishii, T. Ishiyama, A. Iwase, S. Miyamoto, M. Terasawa
Journal of Physics: Conference Series 674 (2016) 012025.

2.

"Development of Compton X-ray spectrometer for high energy resolution single-shot high-flux hard
X-ray spectroscopy"
Sadaoki Kojima, Takahito Ikenouchi, Yasunobu Arikawa, Shohei Sakata, Zhe Zhang, Yuki Abe, Mitsuo Nakai,
Hiroaki Nishimura, Hirouyki Shiraga, Tetsuo Ozaki, Shuji Miyamoto, Masashi Yamaguchi, Akinori Takemoto,Shinsuke Fujioka, and Hiroshi Azechi
Review of Scientific Instruments, 87, 043502 (2016).

3.

"Spatial anisotropy of neutrons emitted from the 56Fe(γ, n)55Fe reaction with a linearly polarized γ-ray
beam"
T. Hayakawa, T. Shizuma, S. Miyamoto, S. Amano, A. Takemoto, M. Yamaguchi, K. Horikawa, H. Akimune, S.
Chiba, K. Ogata and M. Fujiwar
Physical Review C, 93, pp. 004313-1-4 (2016).

4.

"Proposal for selective isotope transmutation of long-lived fission products using quasi-monochromatic
γ-ray beams"
Takehito Hayakawa, Shuji Miyamoto, Ryoichi Hajima, Toshiyuki Shizuma, Sho Amano, Satoshi Hashimoto,
Tsuyoshi Misawa
Journal of Nuclear Science and Technology, 53, issue 12, pp.2064-2071 (2016).

5.

"Harmonics radiation of graphene surface plasmon polaritons in terahertz regime"
D. Li, Y. Wang, M. Nakajima, M. Hashida, Y. Wei, S. Miyamoto
Physics Letters A 380, pp.2181–2184 (2016).

6.

"Laser Compton Scattering Gamma-Ray Experiments for Supernova Neutrino Process"
Takehito Hayakawa, Shuji Miyamoto, Takayasu Mochizuki, Ken Horikawa, Sho Amano, Dazhi Li, Kazuo
Imasaki, Yasukazu Izawa, Kazuyuki Ogata and Satoshi Chiba
Plasma and Fusion Research, 11, 3406066 (2016).

7.

"Production of Medical 99mTc Isotope Via Photonuclear Reaction"
M. Fujiwaraa,, *, K. Nakai, N. Takahashi, T. Hayakawa, T. Shizuma, S. Miyamoto, G. T. Fan, A. Takemoto, M.
Yamaguchi, and M. Nishimura
Physics of Particles and Nuclei, 2017, Vol. 48, No. 1, pp. 124–133. © Pleiades Publishing, Ltd., (2017).
ISSN 1063-7796

8.

"Investigation of pitting corrosion of diamond-like carbon films using synchrotron-based spectromicro
scopy"
Sarayut Tunmee, Pat Photongkam, Chanan Euaruksakul, Hiroki Takamatsu, XiaoLong Zhou, Pornwasa
Wongpanya, Keiji Komatsu, Kazuhiro Kanda, Haruhiko Ito, and Hidetoshi Saitoh
Journal of Applied Physics 120, 195303 (2016).

9.

"Double crystal monochromator controlled by integrated computing on BL07A in NewSUBARU, Japan"
Masato Okui, Naoki Yato, Akinobu Watanabe, Baiming Lin, Norio Murayama, Sei Fukushima, Kazuhiro Kanda
AIP Conference Proceedings 1741, 030033(2016).

10. "Fabrication of hydrogenated amorphous silicon carbide films by decomposition of hexamethyldisilane
with microwave discharge flow of Ar"
1

87

Haruhiko Ito, Motoki Kumakura, Tsuneo Suzuki, Masahito Niibe, Kazuhiro Kanda, Hidetoshi Saitoh
Japanese Journal of Applied Physics 55, 06HC01 (2016).
11. "Structure and physical properties of stable isotopic amorphous carbon films"
Yutaro Suzuki, Yasuyoshi Kurokawa, Tsuneo Suzuki, Kazuhiro Kanda, Masahito Niibe, Masayuki Nakano,
Naoto Ohtake, Hiroki Akasaka
Diamond and Related Materials, 63, 115-119 (2016).
12. "Low-Temperature Activation in Boron Ion-Implanted Silicon by Soft X-Ray Irradiation"
Akira Heya, Naoto Matsuo, Kazuhiro Kanda
IEICE TRANS. ELECTRON., E99-C, (2016).
13. "結晶配向性と励起エネルギーを変化させたグラファイトにおける C-K 発光スペクトルの入／出射
角度依存性"
竹平徳崇，新部正人，荒木佑馬，徳島高
Ｘ線分析の進歩, 48, 129-136 (2017).
14. "Large take-off angle dependence of C-K emission spectra observed in highly oriented pyrolytic graphite"
Masahito Niibe, Takashi Tokushima, Noritaka Takehira, and Yuma Araki
J. Electron Spectrosc. Relat. Phonom., DOI: 10.1016/j.elspec.2017.02.001, (2017).
15. "AlGaN surfaces etched by CF4 plasma with and without the assistance of near-ultraviolet irradiation"
Retsuo Kawakami, Masahito Niibe, Yoshitaka Nakano, Takashi Mukai
Vacuum, 136, 28-35 (2017).
16. "Low energy soft X-ray emission spectrometer at BL-09A in NewSUBARU"
Masahito Niibe
SPring-8/SACLA Research Frontiers 2015, 149-150 (2016).
17. "Low Energy Soft X-ray Emission Spectrometer at BL-09A in NewSUBARU"
Masahito Niibe and Takashi Tokushima
Proc. SRI2015, AIP Conf. Proc., 1741, 030042 (2016).
18. "Developement of the Surface-sensitive Soft X-ray Absorption Fine Structure Measuremant Techniquefor Bulk Insulator"
Takumi Yonehara, Junji Iihara, Shigeki Uemura, Koji Yamaguchi, and Masahito Niibe
Proc. SRI2015, AIP Conf. Proc., 1741, 050025 (2016).
19. "Fabrication and characterization of fine-grained 316L steel with 2.0 mass% TiC"
M. Terasawa, H. Kurishita, T. Sakamoto, M. Niibe, H. Takahashi, S. Nishikawa, A. Yamamoto, M. Yamashita, T.
Mitamura, T. Yamasaki, M. Kawai
J. Nuclear Sci. Technol., 53, 1951-1959 (2016), DOI:10.1080/00223131.2016.1175390
20. "Damage Characteristics of n-GaN Crystal Etched with N2 Plasma by Soft X-ray Absorption
Spectroscopy"
Masahito Niibe, Takuya Kotaka, Retsuo Kawakami, Yoshitaka Nakano, Takashi Mukai
e-J. Surf. Sci. Nanotech, 14, 9-13 (2016).
21. "Surface Analysis of AlGaN Treated with CF4 and Ar Plasma Etching"
Shodai Hirai, Masahito Niibe, Retsuo Kawakami, Tatsuo Shirahama, Yoshitaka Nakano, Takashi Mukai
e-J. Surf. Sci. Nanotech, 13, 481-487 (2015).
22. "High-average-power water window soft X-rays from an Ar laser plasma"
S.Amano2

88Appl. Phys. Express, Vol.9, 076201 (2016)
23. "Micromachining using soft X-rays from laser-produced Xe plasma"
S.Amano, T.Inoue, and S.Miyamoto
Electro. Commum. in Japan, Vol.99, Issue 2, 3-9 (2016)24. "Depth analysis of molecular orientation induced by nanoimprint graphoepitaxy"
Makoto Okada, Ryosuke Fujii, Yuichi Haruyama, Hiroshi Ono, Nobuhiro Kawatsuki, and Shinji Matsui
Japanese Journal of Applied Physics, Vol. 56, 040302 1-4 (2017).
25. "Influence of film thickness on the reorientation structure of photoalignable liquid crystalline polymer
films"Y. Taniguchi, M. Kondo, Y. Haruyama, S. Matsui, and N. Kawatsuki
Polymer 90, pp. 290-294 (2016).
26. "Light stability tests of CH3NH3PbI3 perovskite solar cells using porous carbon counter electrodes"
Seigo Ito, Gai Mizuta, Shusaku Kanaya, Hiroyuki Kanda, Tomoya Nishina, Seiji Nakashima, Hironori Fujisawa,
Masaru Shimizu, Yuichi Haruyama and Hitoshi Nishino
Phys.Chem.Chem.Phys. 18, 27102-27108 (2016).
27. "ニュースバル放射光施設を活用したフォトマスク検査顕微鏡の開発"
原田哲男
姫路工業倶楽部部報工学レポート vol. 28, 2017/1/1.
28. "A Study on Enhancing EUV Resist Sensitivity"
A. Sekiguchi, T. Harada, and T. Watanabe
Proc. SPIE 10143 (2017) 1014322.
29. "EUV レジスト開発と歴史"
渡邊健夫
リソグラフィー技術その 40 年、S&T 出版、2016.12.9.
30. "Current Status and Prospect of EUVL Lithography for IoT"
Takeo Watanabe
Proceedings of the 20th SANKEN International Symposium (2016) 10.
31. "Development of EUV Lithographic Technology at University of Hyogo"
Takeo Watanabe, and Tetsuo Harada
Proceedings of the 14th International Conference on radiation Curing, RadTech Asia (2016) 43.
32. "Development of Actual EUV Mask Observation Method for Micro Coherent EUV Scatterometry
Microscope"
T. Harada, H. Hashimoto, and T. Watanabe
Proc. SPIE 9985 (2016) 99851T.
33. "Observation Results of Actual Phase Defects Using Micro Coherent EUV Scatterometry Microscope"
H. Hashimoto, T. Harada, and T. Watanabe
Proc. SPIE 9985 (2016) 99850K.
34. "Development of the Transmittance Measurement for EUV Resist by Direct-Resist Coating on a
Photodiode"
Daiki Mamezaki, Masanori Watanabe, Tetsuo Harada, and Takeo Watanabe,
J. Photopolym. Sci. Technol., 29 (2016) pp. 749 - 752.
35. "EUVL Research Activity at Center for EUV Lithography"
Takeo Watanabe, and Tetsuo Harada
J. Photopolym. Sci. Technol., 29 (2016) pp. 737 - 744.
389

36. "Extreme-ultraviolet collector mirror measurement using large reflectometer at NewSUBARU
synchrotron facility"
Haruki Iguchi, Hiraku Hashimoto, Masaki Kuki, Tetsuo Harada, Hiroo Kinoshita, Takeo Watanabe, Yuriy Y.
Platonov, Michael D. Kriese, and Jim R. Rodriguez
Jpn. J. Appl. Phys. 55, 06GC01 (2016)37. "EUV resist outgassing analysis for the new platform resists at EIDEC"
Eishi Shiobara, Yukiko Kikuchi, Shinji Mikami, Takeshi Sasami, Takashi Kamizono, Shinya Minegishi,
Takakazu Kimoto, Toru Fujimori, Takeo Watanabe, Tetsuo Harada, Hiroo Kinoshita, Satoshi Tanaka
Proc. SPIE 9776, 97762H (2016).
38. "Phase Imaging Results of Phase Defect Using Micro Coherent EUV Scatterometry Microscope"
Tetsuo Harada, Hiraku Hashimoto, Tsuyoshi Amano, Hiroo Kinoshita, and Takeo Watanabe
J. Micro-Nanolith. Mem. 15, 021007 (2016).
39. "Actual defect observation results of an extreme ultraviolet blank mask by coherent diffraction imaging"
Tetsuo Harada, Hiraku Hashimoto, Tsuyoshi Amano, Hiroo Kinoshita, and Takeo WatanabeAppl. Phys. Express 9, 035202 (2016).
40. "On-chip synthesis of ruthenium complex by microwave-induced reaction in a microchannel coupled with
post-wall waveguide"
Yuichi Utsumi, Akinobu Yamaguchi, Takeko Matsumura-Inoue, Mitsuyoshi Kishihara
Sensors and Actuators B: Chemical, 242, 384-388 (2017)41. "Highly sensitive detection and stochastic analysis of magnetization fluctuation induced in a nano-scale
magnetic wire"
A. Yamaguchi, K. Motoi and H. Miyajima,
Journal of Magnetism and Magnetic Materials, 401, 9-15 (2016)
42. "Real-space observation of magnetic vortex core gyration in a magnetic disc both with and without a pairtag"
Akinobu Yamaguchi, Hiroshi Hata, Minori Goto, Motoi Kodama, Yuichi Kasatani, Koji Sekiguchi, Yukio Nozaki,
Takuo Ohkochi, Masato Kotsugi, and Toyohiko Kinoshita
Japanese Journal of Applied Physics, 55, 023002 (2016)
43. "Anisotropic pyrochemical microetching of poly(tetrafluoroethylene) initiated by synchrotron
radiation-induced scission of molecule bonds"
Akinobu Yamaguchi, Hideki Kido, Yoshiaki Ukita, Mitsuyoshi Kishihara, and Yuichi Utsumi
Applied Physics Letters, 108, 051610 (2016)
44. "Dielectrophoresis-enabled surface enhanced Raman scattering on gold-decorated polystyrene
microparticle in micro-optofluidicdevices for high-sensitive detection"
Akinobu Yamaguchi, Takao Fukuoka, Ryo Takahashi, Ryohei Hara, Yuichi Utsumi
Sensors and Actuators B 230, 94-100 (2016)
45. "Synthesis of metallic nanoparticles through X-ray radiolysis using synchrotron radiation"
Akinobu Yamaguchi, Ikuo Okada, Takao Fukuoka, Ikuya Sakurai, and Yuichi Utsumi
Japanese Journal of Applied Physics 55, 055502-1-5 (2016)
46. "Direct digital manufacturing of a mini-centrifuge-driven centrifugal microfluidic device anddemonstration of a smartphone-based colorimetric enzyme-linked immunosorbent assay"
Yoshiaki Ukita, Yuichi Utsumi, Yuzuru Takamura
Analytical Methods, 8, 256-262 (2016)
47. "Trial Fabrication of PTFE-Filled Waveguide Bandpas Filter at Short Milimeter Wave Frequency by SR
Etching (放射光エッチングによる短ミリ波帯テフロン導波管バンドパスフィルタの試作)"
M. Kishihara, M. Murakami, A. Yamaguchi, Y. Utsumi and I. Ohta
電子情報通信学会和文論文誌 C, J99-C No.7, 361-364 (2016)
490

48. "Dielectrophoresis-enabled surface enhanced Raman scattering of glycine modified on
Au-nanoparticle-decorated polystyrene beads inmicro-optofluidic devices"
Akinobu Yamaguchi, Takao Fukuoka, Kazuhisa Kuroda, Ryohei Hara, Yuichi Utsumi
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 507, 118-123 (2016)49. "Rapid X-ray Fabrication of Microstructured Polytetrafluoroethylene Substrates by Anisotropic,
Pyrochemical Microetching"
Akinobu Yamaguchi, Hideki Kido, Yuichi Utsumi
Journal of Photopolymer Science and Technology, 29, 3, 403-407 (2016)
50. "One-Step Synthesis of Copper and Cupric Oxide Particles from the Liquid Phase by X-Ray Radiolysis
Using Synchrotron Radiation"
Akinobu Yamaguchi, Ikuo Okada, Takao Fukuoka, Mari Ishihara, Ikuya Sakurai, Yuichi Utsumi
Journal of Nanomaterials, 2016, Article ID 8584304 (2016)
51. "Interdigital transducer generated surface acoustic waves suitable for powder transport"
Tsunemasa Saiki, Akio Tsubosaka, Akinobu Yamaguchi, Michitaka Suzuki, Yuichi Utsumi
Advanced Powder Technology, 28, 491-498 (2017)52. "Synthesis of Cupric Particles Induced by X-ray Radiolysis"
Akinobu Yamaguchi, Ikuo Okada, Takao Fukuoka, Yuichi Utsumi
IEEJ Transactions on Electronics, Information and Systems, 137, 3, 400-405 (2016)
53. "Alternative Raman Spectroscopy of Glycine binding on Au-Nanoparticle-Decorated Polystyrene Beads
due to Aggregation induced by Dielectrophoresis in Micro-Optofluidic Devices"
A. Yamaguchi, T. Fukuoka and Y. Utsumi
Micro TAS 2016, M168h
54. "Anisotropic Pyrochemical Fabrication of Polytetrafluoroethylene and Metallic Nanoparticles Initiated by
Synchrotron Radiation for Microfluidic Devices"
A. Yamaguchi, H. Kido, Y. Ukita, M. Kishihara, T. Fukuoka and Y. Utsumi
Micro TAS 2016, W132g
55. "Fabrication of higher order three-dimensional layer stack nanostructure for molecular detection andelectrode"
A. Yamaguchi, T. Fukuoka, M. Ishihara and Y. Utsumi
Proc. SPIE 9929, 992906 (2016)56. "Synthesis of nanoparticles through X-ray radiolysis using synchrotron radiation"
A. Yamaguchi, I. Okada, T. Fukuoka, M. Ishihara, I. Sakurai and Y. Utsumi
Proc. SPIE 9929, 992919 (2016)
57. "X 線光化学反応による金属ナノ・マイクロ粒子生成 (Fabrication of Metallic Nano/Microscale particles by
Photochemical reaction initiated by X-ray Radiolysis in cupper (II) sulfate solution)"
山口明啓，岡田育夫，福岡隆夫，内海裕一
MES 2016, 2D2-4
58. "強誘電体／磁性体接合における磁気異方性の制御と磁区構造"
山口明啓，才木常正，内海裕一，大河内拓雄，保井晃，木下豊彦，山田啓介【A】基礎・材料・共通部門 マグネティクス研究会, 2016-9-20, MAG-16-134, 4 pages, IEEJ-MAG
59. "圧電体基板上に創製した微小磁性体の磁気特性"
山口明啓，才木常正，内海裕一，大河内拓雄，保井晃，木下豊彦，山田啓介【A】基礎・材料・共通部門 マグネティクス研究会, 2016-12-8, MAG-16-228, 4 pages, IEEJ-MAG
60. "Heat Transfer Performance of Sodium Encapsulating Engine Valves"
T. Kobayashi, I. Hashimoto, R. Hashimoto, H. Kanematsu, Y. Utsumi and M. Yamamoto
Advanced Experimental Mechanics, 1, 69-7 (2016)
59161. "Deformation Analysis of Soft Actuator having a Bellows Structure Operated by Inner Pressure"
T. Kobayashi, M. Fujiwara, Y. Utsumi, H. Kanematsu, M. Yamamoto and H. Taniguchi
Advanced Experimental Mechanics, 1, 185-189 (2016)62. "Measurement of Critical Cracking Strain of Organic Thin Films Prepared by Wet Coating Process"
T. Kobayashi, M. Munkhtsog, Y. Utsumi, H. Kanematsu, and T. Masuda
Proc. 14th European Vacuum Conference (EVC-14), Portorose, Slovenia, 2016
63. "Small immunoassay systems for medical diagnosis and environmental analysis"
T. Kobayashi, Y. Yoshimasa, Y. Utsumi
Proc. The Irago Conference 2016692

(2) International meetings
1.

"Therahertz Radiation From Graphene Surface Plasmon Polaritons"
Dazhi Li, Yuanyuan Wang, Makoto Nakajima, Masaki Hashida, Yanyu Wei, Shuji Miyamoto, Masahiko
Tani
41st International Conference on Infrared, Millimeter, and Terahertz waves (IRMMW-THz), 25-30 Sept.,
Copenhargen, Denmark (2016).

2.

"Laser Compton Scattering Gamma-Ray Beam Source for Nuclear Physics and Material
Research"
Shuji Miyamoto (Invited)
15th International Conference on X-Ray Lasers (ICXRL2016), Nara Kasugano International Forum, May
22 - 27 (2016).

3.

"Photon scattering measurement on Cr-52 with Linearly Polarized Photon Beam at
NewSUBARU"
T. Shizuma, T. Hayakawa, F. Minato, I. Daito, H. Ohgaki, S. Miyamoto
International Nuclear Physics Conference, Adelade, Australis, 11-16 Sept., (2016).

4.

"Measurement of neutron energy spectra for E =23.1 and 26.6 MeV mono-energetic photon
induced reaction on natC using laser electron photon beam at NewSUBARU"
Toshiro Itoga, Hiroshi Nakashima, Toshiya Sanami, Yoshihito Namito, Yoichi Kirihara, Shuji Miyamoto,
Akinori Takemoto, Masashi Yamaguchi and Yoshihiro Asano
13th International Conference on Radiation Shielding, Paris, France, Oct. 3-6 (2016).

5.

"Measurement of neutron spectra for photonuclear reaction with linearly polarized photons"
Yoichi Kirihara, Toshiro Itoga, Hiroshi Nakashima, Toshiya Sanami, Yoshihito Namito, Shuji Miyamoto,
Akinori Takemoto, Masashi Yamaguchi and Yoshihiro Asano
13th International Conference on Radiation Shielding, Paris, France, Oct. 3-6 (2016).

6.

"Electronics for HARPO: Design, Development and Validation of Electronics for a High
Performance Polarised-Gamma-Ray Detector"
Yannick Geerebaert, D. Bernard, P. Bruel, M. Frotin, B. Giebels, P. Gros, D. Horan, M. Louzir, P. Poilleux,
I. Semeniouk, S. Wang, D. Attié, D. Calvet, P. Colas, A. Delbart, P. Sizun, D. Götz AIM, S. Amano, S.
Hashimoto, T. Kotaka, Y. Minamiyama, S. Miyamoto, A. Takemoto, M. Yamaguchi, S. Daté, H. Ohkuma
20th Real Time Conference, Padova, Italy, 5-10 June (2016).

7.

"Laser Compton Scattering Gamma-ray Beam Generation and Applications"Shuji Miyamoto (Invited)
Carpathian Summer School of Physics 2016, “Exotic Nuclei & Nuclear / Particle Astrophysics (VI).
Physics with small accelerators”, Sinaia, Romania, June 26-July 9 (2016).

8.

"First measurement of polarization asymmetry of a gamma-ray beam between 1.74 to 74 MeV
with the HARPO TPC"
Philippe Gros, Sho Amano, David Attié, Denis Bernard, Philippe Bruel, Denis Calvet, Paul Colas, SchinDaté, Alain Delbart, Mickael Frotin, Yannick Geerebaert, Berrie Giebels, Diego Götz, S. Hashimoto,
Deirdr Horan, T. Kotaka, Marc Louzir, Y. Minamiyama, Shuji Miyamoto, H. Ohkuma, Patrick Poilleux,
Igor Semeniouk, Patrick Sizun, A. Takemoto, M. Yamaguchi, Shaobo Wang

1

93

SPIE Astronomical telescopes and instrumentation conference 2016 (2016).
Instrumentation and Methods for Astrophysics (astro-ph.IM); Instrumentation and Detectors(physics.ins-det)
9.

"NewSUBARU Gamma Beam Source - Status and Activities"
Shuji Miyamoto (Invited)
International Conference on Nuclear Photonics, Monterey, California, Oct. 16-21 (2016).

10. "PDCA Cycle Model of Drawing Process for Class Placement of Liberal Arts – The trial work of
the IR section at the University of Hyogo"
Y. Shoji and Y. Kokubo
5th International Conference on Data Science and Institutional Research, Kumamoto Japan, July 10-14(2016).
11. "Evaluation of amorphous carbon film by X-ray absorption spectroscopy"
Kazuhiro Kanda (Invited)
26th annual meeting of the Materials Research Society of Japan (MRS-J) Yokohama, Japan Dec. 19-22,(2016).
12. "Evaluation of amorphous carbon film by X-ray absorption spectroscopy"
Shotaro Tanaka, Makoto Okada, Takayuki Hasegawa, Masahito Niibe, and Kazuhiro Kanda
26th annual meeting of the Materials Research Society of Japan (MRS-J) Yokohama, Japan Dec. 19-22,(2016).
13. "Effect of the soft X-ray irradiation on the surface of fluorinated DLC films"
Hiroki Takamatsu, Makoto Okada, Masahito Niibe, and Kazuhiro Kanda
26th annual meeting of the Materials Research Society of Japan (MRS-J) Yokohama, Japan Dec. 19-22,(2016).
14. "Structural analysis of diamond-like carbon and related materials using NEXAFS andellipsometry"
Hidetoshi Saitoh, Satoru Arakawa, Sarayut Tunmee, Kazuhiro Kanda, Pat Photongkam, Nichada
Jeeranaikun, Ratchadaporn Supruangnet and Hideki Nakajima
1st Thailand Synchrotron Conference and Exhibition (TSCE2016) SLRI, Thailand, Feb. 26-28 (2016).
15. "Construction and Performance of the Compact Soft X-ray Emission Spectrometer at BL-09A in
NewBUBARU SR Facility” (invited)
Masahito Niibe, Noritaka Takehira, and Tahashi Tokushima
5th Annual Congress of AnalytiX-2017, 22-24 Mar. 2017, Fukuoka, Japan.
16. "Structural changes on neutron-irradiated highly oriented pyrolytic graphite under static highpressure and temperature"
T. Hisakuni, S. Suzuki, S. Honda, M. Niibe, M. Terasawa, Y. Higo, K. Niwase, H. Izumi, E. Taguchi, T.
Iwata
Symp. on Surf. Sci. & Nanotechnol. (SSSN-Kansai), 24-25 Jan. 2017, Kyoto, Japan.
17. "Irradiation effect in multi-walled carbon nanotubes by highly charged ions"
294

M. Kato,Y. Fujiwara, S. Honda, M. Terasawa, M. Niibe, M. Sakurai, N. Nishida, T. Tokui, K. Suzuki, K.
Betsumiya, K. Niwase, K.-Y. Lee
Symp. on Surf. Sci. & Nanotechnol. (SSSN-Kansai), 24-25 Jan. 2017, Kyoto, Japan.
18. "Electrical damage in n-GaN films treated by CF4 plasma"
Yoshitaka Nakano, Masahito Niibe and Retsuo Kawakami
Proceedings of International Symposium of Dry Process 2016, pp.73--74, Sapporo, Nov. 2016.
19. "A large take-off angle dependence of C-K emission spectra observed in highly oriented pyrolytic
graphite"
Masahito Niibe, Takashi Tokushima, Niritaka Takehira, Yuma Araki
39th inter’l Conf. on Vacuum Ultraviolet and X-ray Physics (VUVX2016), P_103, 3-8 July 2016, Zurich,
Switzerland.
20. "Soft X-ray Absorption Spectroscopy of Orientation, Oxygen Content, Chemical States of
Ion-irradiated Vertically Aligned Multiwalled Carbon Nanotubes"
S. Honda, F. Ideno, Y. Muramatsu, M, Niibe, M. Terasawa, E.M. Gullikson and K.-Y. Lee
39th inter’l Conf. on Vacuum Ultraviolet and X-ray Physics (VUVX2016), P_168, 3-8 July 2016, Zurich,
Switzerland.
21. "Effect of Ultraviolet Light-Assisted CF4 Plasma Irradiation on AlGaN Thin Film Surface"
Retsuo Kawakami, Masahito Niibe, Yoshitaka Nakano and Takashi Mukai
Proceedings of the 43rd International Symposium on Compound Semiconductors (ISCS2016),
pp.MoP-ISCS-096_1--MoP-ISCS-096_2, Toyama, Jun. 2016.
22. "Electrical Damage Investigation of n-GaN Films Treated by CF4 Plasma"
Yoshitaka Nakano, Masahito Niibe and Retsuo Kawakami
Proceedings of the 43rd International Symposium on Compound Semiconductors (ISCS2016),
pp.MoP-ISCS-LN-4_1--MoP-ISCS-LN-4_2, Toyama, Jun. 2016.
23. "Laser Plasma X-ray Source Based on Cryogenic Targets"
S. Amano
The 15th International Conference on X-Ray Lasers (ICXRL2016), Nara, May 22-27, 2016.
24. "Laser Plasma VUV~ X-ray Source Using Solid Rare Gas Targets"
S. Amano
The 39th International Conference on Vacuum Ultraviolet and X-ray Physics (VUVX2016), Zurich, Swiss,
July 3-8, 2016.
25. "Molecular orientation evaluation of negative-tone and positive-tone photo-cross-linkable liquid
crystalline polymer pattern fabricated by nanoimprint-graphoepitaxy"
Makoto Okada, Yusuke Taniguchi, Yuichi Haruyama, Hiroshi Ono, Nobuhiro Kawatsuki, and Shinji
Matsui
The 60th International Conference on Electron, Ion and Photon Beam Technology and Nanofabrication
2016, Pittsburgh, USA, 2016/6/1.
26. "Thin PDMS antisticking layer formed by using PDMS-disilanol for nanoimprinting"395

Makoto Okada and Shinji Matsui
The 60th International Conference on Electron, Ion and Photon Beam Technology and Nanofabrication
2016, Pittsburgh, USA, 2016/6/1.
27. "Evaluation of molecular orientation induced by simplified double nanoimprint-graphoepitaxy"
Makoto Okada, Ryosuke Fujii, Yuichi Haruyama, Hiroshi Ono, Nobuhiro Kawatsuki, and Shinji Matsui
The 42nd International Conference on Micro and Nano Engineering 2016, Vienna, Austria, 2016/9/21
28. "Depth analysis of molecular orientation induced by nanoimprint-graphoepitaxy"
Makoto Okada, Ryosuke Fujii, Yuichi Haruyama, Hiroshi Ono, Nobuhiro Kawatsuki, and Shinji Matsui
The 42nd International Conference on Micro and Nano Engineering 2016, Vienna, Austria, 2016/9/21.
29. "Simplified double nanoimprint-graphoepitaxy using L&S and flat pattern molds"
Makoto Okada, Ryosuke Fujii, Yuichi Haruyama, Hiroshi Ono, Nobuhiro Kawatsuki, and Shinji Matsui
The 15th International Conference on Nanoimprint and Nanoprint Technology 2016, Braga, Portugal,
2016/9/27, invited poster.
30. "Examination of depth profile of molecular orientation in L&S pattern fabricated bynanoimprint-graphoepitaxy"
Makoto Okada, Ryosuke Fujii, Yuichi Haruyama, Hiroshi Ono, Nobuhiro Kawatsuki, and Shinji Matsui
The 15th International Conference on Nanoimprint and Nanoprint Technology 2016, Braga, Portugal,
2016/9/27.
31. "High-aspect-ratio structure fabrication by room-temperature nanoimprinting"
Makoto Okada and Shinji Matsui
The 29th International Microprocesses and Nanotechnology Conference 2016, Kyoto, Japan, 2016/11/11.
32. "Evaluation of Thermal Nanoimprint Resin with PDMS Additive for Improving Release
Property"
Shogo Fukui, Makoto Okada, and Yuichi Haruyama
The 29th International Microprocesses and Nanotechnology Conference 2016, Kyoto, Japan, 2016/11/10.
33. "Molecular orientation in photoreactive liquid crystalline polymer films observed by NEXAFS"
Y. Haruyama, Y. Taniguchi, M. Kondo, N. Kawatsuki, M. Okada, and S. Matsui
The 39th International conference on Vacuum Ultraviolet and X-ray Physics, Zurich, Switzerland,
2016/7/5.
34. "Evaluation of damage in an organic thin film with cluster ion sputtering"
S. Fujita, Y. Nohara, M. Ohno, and Y. Haruyam
The 39th International conference on Vacuum Ultraviolet and X-ray Physics, Zurich, Switzerland,
2016/7/5.
35. "Observation Results of Actual Phase DefectsUsing Micro Coherent EUV Scatterometry
Microscope"
Hiraku Hashimoto, Tetsuo Harada, Takeo Watanabe
Photomask Japan 2016, Yokohama, Japan, 2016/4/7.
36. "Measurement Result of an EUV Collector MirrorUsing a Large Reflectometer at NewSUBARU"

496

Haruki Iguchi, Tetsuo Harada, Takeo Watanabe
Photomask Japan 2016, Yokohama, Japan, 2016/4/7.
37. "Defect Imaging Result with Quantitative Intensity and Phase Contrast Using Micro Coherent
EUV Scatterometry Microscope"
Tetsuo Harada, Hiraku Hashimoto, Takeo Watanabe, Hiroo Kinoshita
Photomask Japan 2016, Yokohama, Japan, 2016/4/8.
38. "EUVL Research Activity at Center for EUV Lithography"
Takeo Watanabe, Tetsuo Harada
ICPST33, Chiba, Japan, 2016/6/24.
39. "Development of the transmittance measurement for EUV resist by direct-resist coating on a
photodiode"
Daiki Mamezaki, Masanori Watanabe, Tetsuo Harada and Takeo Watanabe
ICPST33, Chiba, Japan, 2016/6/24.
40. "Observation results of actual phase defects using micro-coherent EUV scatterometry microscope"
Hiraku Hashimoto, Tetsuo Harada, Hiroo Kinoshita, Takeo Watanabe
Photomask Technology 2016, San Jose, USA, 2016/9/12.
41. "Development of actual EUV mask observation method for micro-coherent EUV scatterometry
microscope"
Tetsuo Harada, Hiraku Hashimoto, Hiroo Kinoshita, Takeo Watanabe
Photomask Technology 2016, San Jose, USA, 2016/9/12.
42. "EUV Resist Transmittance Measurement Using Photodiode Direct-Resist Coating Method"
Daiki Mamezaki, Masanori Watanabe, Tetsuo Harada, Takeo Watanabe
EUV Lithography Symposium 2016, Hiroshima, Japan, 2016/10/24.
43. "Development of Large EUV reflectometer in NewSUBARU Synchrotron Facility"
Tetsuo Harada, Haruki Iguchi, Takeo Watanabe
EUV Lithography Symposium 2016, Hiroshima, Japan, 2016/10/24.
44. "Actual Defect Imaging Result with Quantitative Intensity and Phase Contrast Using Micro
Coherent EUV Scatterometry Microscope"
Tetsuo Harada, Hiraku Hashimoto, Takeo Watanabe
EUV Lithography Symposium 2016, Hiroshima, Japan, 2016/10/24.
45. "Development of the negative-tone molecular resists for EB/EUVL having high EUV absorption
capacity"
Tomoaki Takigawa, Yuta Togashi, Takumi Toida, Takashi Sato, Masatoshi Echigo, Hiroto Kudo, Tetsuo
Harada, Takeo Watanabe
EUV Lithography Symposium 2016, Hiroshima, Japan, 2016/10/24.
46. "Defect and absorber phase imaging of EUV mask using synchrotron andhigh-harmonic-generation EUV source"
Tetsuo Harada, Takeo Watanabe
OSA International Workshop on Compact EUV & X-ray Light Sources, Hiroshima, Japan, 2016/10/28.
47. "Improvement of Mask-Defect-Detection Performance of Coherent EUV Scatterometry

597Microscope with High-Harmonic-Generation EUV Source"
Daiki Mamezaki, Tetsuo Harada, Yutaka Nagata, Takeo Watanabe
Micro Nano Conference, Kyoto, Japan, 2016/11/11.
48. "A study on enhancing EUV resist sensitivity"
Atsushi Sekiguchi, Tetsuo Harada, Takeo Watanabe
SPIE advanced Lithography 2017, San Jose USA, 2017/2/28.
49. "Rapid X-ray fabrication of microstructured polytetrafluoroethylene substrates by anisotropic,
pyrochemical microetching"
Akinobu Yamaguchi, Hideki Kido, Yuichi Utsumi
The 33rd International Conference of Photopolymer Science and Technology, June 22-24 (2016),
Makuhari, Chiba, Japan (招待講演)
50. "Fabrication of higher order three-dimensional layer stack nanostructure for molecular detectionand electrode"
Akinobu Yamaguchi, Takao Fukuoka, Mari Ishihara, Yuichi Utsumi
SPIE Optics + Photonics 2016, August 30 - September 1 (2016), San Diego, USA
51. "Synthesis of nanoparticles through X-ray radiolysis using synchrotron radiation"
Akinobu Yamaguchi, Ikuo Okada, Takao Fukuoka, Mari Ishihara, Ikuya Sakurai, Yuichi Utsumi
SPIE Optics + Photonics 2016, August 30 - September 1 (2016), San Diego, USA
52. "Development of Miniature Micro-Powder Feeder Driven by Surface Acoustic Wave for Practical
Use"
Tsunemasa Saiki, Akio Tsubosaka, Akinobu Yamaguchi, Masahiro Takeo, Michitaka Suzuki, Yuichi
Utsumi
The 42nd International Conference on Micro and Nano Engineering (MNE2016), September 19-23(2016), Vienna, Austria
53. "Alternative Raman Spectroscopy of Glycine Binding on Au-Nanoparticle-Decorated Polystyrene
Beads due to Aggregation induced by Dielectrophoresis in Micro-Optofluidic devices"
Akinobu Yamaguchi, Takao Fukuoka, Yuichi Utsumi
The 20th international conference on miniaturized systems for chemistry and life science (TAS2016),
October 10-15 (2016), Dublin, Ireland
54. "Anisotropic Pyrochemical Fabrication of Polytetrafluoroethylene and Metallic Nanoparticles
Initiated by Synchrotron Radiation For Microfluidic Devices"
Akinobu Yamaguchi, Hideki Kido, Yoshiaki Ukita, Mitsuyoshi Kishihara, Takao Fukuoka, Yuichi
Utsumi
The 20th international conference on miniaturized systems for chemistry and life science (TAS2016),
October 10-15 (2016), Dublin, Ireland
55. "Observation of magnetic domain structure initiated by competition among the magnetoelastic
anisotropy and shape anisotropy using XMCD-PEEM"
A. Yamaguchi, T. Ohkochi, A. Yasui, T. Kinoshita, and K. Yamada
61st Annual Conference on Magnetism and Magnetic Materials, October 31- November 4 (2016), New98Orleans, LA, USA
56. "Measurement of Critical Cracking Strain of Organic Thin Films Prepared by Wet Coating
Process"
T. Kobayashi, M. Munkhtsog, Y. Utsumi, H. Kanematsu, and T. Masuda
14th European Vacuum Conference (EVC-14), June 6-10 (2016), Portorose, Slovenia
57. "Small immunoassay systems for medical diagnosis and environmental analysis"
T. Kobayashi, Y. Yoshimasa, Y. Utsumi
The Irago Conference 2016, November 1-2 (2016), Tokyo, Japan799

(3) Academic degrees
1. Master of Engineering
Yuma Araki (University of Hyogo)
酸素プラズマ照射による TiO2 薄膜の光触媒活性の改善"Improvement of Photocatalytic Activity of TiO2 Thin Films by Oxygen Plasma Irradiation"
Noritaka Takehira (University of Hyogo)
ニュースバル軟Ｘ線発光分光器を用いたグラファイト材料の分析"Analysis of Graphite Materials using Soft X-ray Emission Spectrometer in NewSUBARU"
Hiroki Takamatsu (University of Hyogo)
フッ素化 DLC 薄膜の軟 X 線照射による改質過程の解明と膜特性変化"Modification Process and Variation of Film properties of Fluorinated DLC thin films by irradiation of soft
X-rays"
Shotaro Tanaka (University of Hyogo)
DLC 膜の特性の解明と宇宙利用の検討"Investigation on Properties of DLC Films and Application into Astronautics field"
Haruki Iguchi (University of Hyogo)
EUV 光源集光ミラー用大型反射率計の開発"Development of a large EUV reflectometer for an EUV collector mirror"
Hiraku Hashimoto (University of Hyogo)
集光型 EUV 回折顕微鏡による実欠陥観察法の開発"Actual defect observation using an EUV focused diffraction microscope"
Yuki Fukuda (University of Hyogo)
EUV 干渉露光用回折格子の開発および露光装置の高度化"Development of EUV interference lithography system and its diffraction grating"
Masaya Takeuchi (University of Hyogo)
汎用ディープ X 線リソグラフィービームライン(BL11)を用いた各種微細加工の検討"Investigation of microfabrications using deep X-ray lithography system beamline (BL11) for general-purpose"
2. Master of Science
Akinori Takemoto (University of Hyogo)
直線偏光ガンマ線による光核反応に関する研究"Studies of Photo Nuclear Reaction by Linearly Polarized Gamma-ray Beam"
Masashi Yamaguchi (University of Hyogo)
円偏光ガンマ線による磁気コンプトン散乱に関する研究"Studies of Magnetic Compton Scattering by Circular Polarized Gamma-ray Beam"

100

LASTI Annual Report Vol.18 (2016)________________________________________________________
September 2017, Published byLaboratory of Advanced Science and Technology for Industry
University of Hyogo
3-1-2 Kouto, Kamigori-Cho, Ako-gun, Hyogo 678-1205, JAPAN
Phone: +81-791-58-0249 / FAX: +81-791-58-0242
Editorial board
Kazuhiro KANDA (Editor in Chief)
NIIBE Masahito
SHOJI Yoshihiko
HARUYAMA Yuichi
YAMAGUCHI Akinobu
HARADA Tetsuo______________________________________________________________