2013.3.11

1

イオンビームを用いた物性改質および分析
Ion Beam Material Modifications & Analysis

松波紀明 (N. Matsunami)International Conference, Symposium(国際会議):•Ion Beam Modifications of Materials (IBMM),• Ion Beam Analysis (IBA),• Radiation Effects in Insulators (REI) ,• Atomic Collisions in Solids (ACS),• Swift Heavy Ions in Matter (SHIM),• Plasma Surface Interactions (PSI), • PFMC,• Plasma Based Ion Implantation & Deposition (PBIID),• Surface Modifications of Materials by Ion Beam
(SMMIB),2

Acknowledgements
Many staffs Nagoya University,

AIST(産総研), JAEA(原研),
NIFS (核融合研)
Many students

Outline
1. Interaction of ions with solids
2. Fundamentals of Ion Beam Analysis
3. Channeling
4. Ultra high-resolution proton energy loss
spectroscopy
5. Ion beam material modification(a)TiO2, catalysis, (b) doped-ZnO(c) Reaction of N ions with nitride film
6. Plasma Surface Dynamics with IBA
in-situ D detection under plasma exposure
7. Electronic sputtering
8. Ion impact effects on graphene, Mn-doped ZnO
9. Concluding remarks

34Collision of Energetic Ions with Atoms in Solids
1.Resulting in energy deposition
Elastic Collision（弾性衝突）;[atom knock-on（はじき出し）]collisions without electronic excitation
dpa (displacement per atom) isa measure of elastic collisions
Inelastic Collision（非弾性衝突）
electronic excitation & ionization,
usually no effects, however, in some cases
leading to atomic displacement

5*イオンビームによる物性改質
1. Energy Deposition (エネルギー付与）
2. Reaction of Ions with Atoms (イオンと物質との化学反応)

3. Reaction between Ions (イオン間化学反応)•電子・原子構造改質: Electronic & Atomic
Structure Modification•電気特性、光学特性、化学特性、磁気特性の改質
Characteristic Effects by Ion Impact?
*熱力学的非平衡：Non-thermal processing*[損傷（damage)というイメージからの脱却]

6*Ion Beam Analysis (non-destructive)
イオンビーム分析 (非破壊）組成、不純物、薄膜の厚さ (composition,
impurities, film thickness)
不純物（特に、H, C, N, O等軽元素, light
impurities)
2009 brings with it the 100th anniversary of thefirst Rutherford Backscattering Spectroscopy
experiment performed by H. Geiger and E.
Marsden (a student) under the supervision ofErnest Rutherford at the University of Manchester.

Ion Beam Analysis (イオンビーム分析)

7

k (kinematic factor) ---> m2 (質量)ΔE=(kEo – E1) =[dE/dx]*x ---> depth x (深さ）[dE/dx]: stopping power factor (阻止能因子)
ΔE=k∫dx(dE/dx)in/cosθ1 +∫dx(dE/dx)in/cosθ2
For small x (surface approximation, 表面近似),[dE/dx] ={k(dE/dx)Eo/cosθ1 +(dE/dx) kEo /cosθ2}

RBS: Rutherford Backscattering Spectroscopy（ラザフォード後方散乱法）
NRA: Nuclear Reaction Analysis（核反応分析法）ERD: Elastic Recoil Detection （弾性反跳法）

Samples (mainly Polycrystalline Thin Films）
Oxides；ZnO, ZnO(Al, In, Mn), Cu2O, CuO, TiO2, SiO2,
WO3, Fe2O3, SrCeO3, High Tc superconductors etc.
Nitrides；Si3N4, AlN, (TiN), Cu3N, WN etc
Others；Ｃ(graphite, graphene), Si, Sapphire, MgO, W, SiC
Equipments
In campus; Accelerators ２ MV AN VG,
KNVG (shut down March 2013)
２００ｋV ion accelerator
XRD、RF-sputter film deposition
Off campus; optical、AFM（AIST）
Plasma・Material Interaction（NIFS、JAEA）
High-energy ion、 RF-sputter depo.（JAEA）

8

9

Energy; ~ 200 MeV
Ion; H – Au
10 eV/u - 2 MeV/u

Low energy < 10 keV,
mainly elastic energy deposition
High energy >1 MeV
mainly inelastic energy deposition

10

Ph. D. Thesis: Uses of Channeling Technique for
Determination of Defect Concentration and
Structures in Crystals (1976)

Chu, Mayer, Nicolet,
Backscattering Spectrometry,
Academic Press, 1978

Tesmer et al. ed. Handbook of modern ion
beam material analysis , MRS, 1995

11

Location of Pb impurities in PbCl interstitials in KCl
For Al-0.1%Mn,
location of Mn
solute in Mn Alinterstitial (mixed
dumbbell, <100>split configuration).
Pb is located near facecenter within 0.04 nm.
Matsuanmi, Yokoyama, Itoh, Phys.
Stat. Sol. b75(1976)483.

Matsuanmi, Swanson, Howe,
Can. J. Phys. 56(1978)1057.

12

1976~1978,
Solid State Science Branch, Chalk River
Nuclear Laboratories, Atomic Energy ofCanada Limited (AECL), Chalk River, Ontario,
CanadaMont-Tremblant Prov. Park17

Ｓｕｒｆａｃｅ relaxation of Pt(111)Outward relaxation by 0.003 nm
Davies, Jackson, Matsunami, Norton, Andersen, Surf. Sci. 78(1978)274.

18

Unpublished data,
Explanation is difficult to the observations.

Proton Energy Loss Spectroscopy

19

100 keV Proton
Energy resolution ~20 eV,
adequate to resolve
surface monolayer.

Matsunami, Scanning
Microscopy 1(1987)1593.

20

100 keV P on W(111)
surfaceMonolayer resolution*Layer spacing
Lattice vibration of
surface layer
Matsunami, Kitoh, Knasaki, Itoh,
NIM B45(1990)412.

Au on Si(111),
Pd on Si(111), Pdsilicide formation
Kanasaki, Itoh, Matsunami,Appl. Phys. Lett. 51(1987)1072.

21

Energy loss in Carbon films with PELS；100 keV Proton

Zero energy loss;
No collisions with electrons(no pin hole)

Matsunami, NIM B115(19996)14.
松波、科研費Ｃ(H4-5)

Inelastic mean free path (IMFP)No collisions
with electrons

Matsunami, NIM
B115(1996)14.

22

23

Energy loss of 100
keV Protons in C film

?Peak around 200
eV

Matsunami, Kitoh, NIM
B85(1985)1994)556

Ag Nano cluster formation in SiO2-glass
150 keV Ag ion into SiO2-glass

Interactions
betweenimplanted Ag’s

Matsunami, Hosono,Appl. Phys. Lett. 63(1993)2050.

24

25

ＲＥＳＩＳＴＩＶＩＴＹ ＭＯＤＩＦＩＣＡＴＩＯＮ of High Tc Cu
oxide superconductors by ion impact

unpublished26

Low energy ion irradiation effects on HTc
spuerconductor (YBaCuO-1237, BiSrCaCuO-222310)
Irrad.

Unirrad.

unpublished

5 keV Ne, ~16 cm-2,
Projected range ~7 nm << film thickness ~100 nm
How ion irradiation effects beyond the projected
range?

Low energy ions (<10 eV) in solids ?

略歴1967(S42)
1971(S46)
1971(S46)
1976(S51)

1976(S51)
1976~1978
1986(S61)
1992(H4)
2003(H15)
2005(H17)~

松波紀明 2013.3.6
名古屋大学工学部原子核工学科入学
同上卒業
名古屋大学大学院工学研究科原子核専攻入学
同上終了、工学博士
学位論文：Uses of channeling technique fordetermination of defect concentration and structures in crystals
名古屋大学工学助手
Solid State Branch, Chalk River Nuclear Laboratory, Atomic Energy
Canada Limited (AECL)
名古屋大学工学講師
名古屋大学工学助教授
名古屋大学理工総研助教授
名古屋大学エコトピア科学研究所准教授

共同研究(学外)等
産総研 (2002 ~)核融合科学研究所（1980頃~）
原研東海 (1999 ~)＊産学連携重点研究（2007~ ）(代表:2007~2012）「高速重イオンによる電子励起効果と物性改質」＊プラズマ壁相互作用に関する調査:
炭素材の化学スパッタリング（2007~2010）

27

Ion irradiation effects on
catalytic activity of TiO2

28

TiO2 Film Characterization

Rutherford backscattering
spectroscopy (RBS)

X-ray diffraction20

Ti(101)a(101)
Ti(002)r(110)a(200)

10

0

20

30

0.6

1.8MeV He → TiO2 /Ti
Ti (Interface)

4

30

0.8

YIELD (10 counts)

INTENSITY (a.u.)40

40

2 (degree)

Structure
a：Anatase，r：Rutile was not observed.

50

0.4

Ti (S)

O

0.2

0
0.4

0.6

0.8

1

1.2

1.4

ENERGY (MeV)

Thickness
120 nmComposition O/Ti=2.0±0.1

Enhancement of photocatalytic activity ofanatase-TiO2 by N ion irradiation

100 keV N ion
irradiation＝＞enhancement by 2

2

2

2
-4

H EVOLUTION (10 cc/cm h)

3
2.5

29

1.5

Factors of enhancement

1

Valency modification（Ti+4 -> Ti+3 ）
●

0.5
0

0

0.2

0.4
+

0.6

1.2

1

0.8
16

2

100keV N IRRADIATION (10 /cm )H2 evolution vs N ion fluence●

Problems
Area modification？
Carbon contamination

Matsunami, Uebayashi, Hirooka, Shimura,
Tazawa, NIM B267 (2009)1654.

30

Similar enhancement (a factor of 1.5)
was observed for Ni-loaded RutileTiO2Optimization of Ni concentration by N
ion irradiation

31

Dopant replacement by ion impact: In-doped ZnO
3replacement?
Matsunami, Fukushima, Sataka,
Okayasu, Kakiuchida, NIM
B268(2010)3071.

-1

2

10

IZC3a

unir.

1

10

IZX5a

IZX5b

0

10

-1

-3

cm )

10

100

PRIZX5aXea6a

100 MeV Xe IZX5a210
MOBILITY
1

MOBILITY (cm /Vs)

・ Direct evidence of dopant

100 MeV Xe

unir.

Non-thermal effect

PRIZX5aXea7a

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・Conductivity：increase by
4 order of magnitude
・Main factor is the carrier(electron) conc. increase
due to dopant replacement.
In into Zn sites

CARRIER DENSITY(106% In doped ZnO
Unirrad.：5~0.03 Ohmcm

CONDUCTIVITY (Scm )

10

0.1
0.01
0.01

CARRIER DENSITY

0.1
1
10
100
1000
12
-2
100 MeV Xe FLUENCE(10 cm )

32

Similarly dopant-replacement
induced by ion impact, i.e.,
conductivity increase wasobserved for Al-doped ZnO, Mndoped ZnO.
*Direct evidence of dopantdisplacement by ion impact
XEAFS

33

Reaction of N ions withnitride films near film tosubstrate interface (Interface
reaction)

Interface reaction: non-thermal (AlN/Al2O3)
0.4

ENENRGY (MeV)
0.6
0.8

1

1.2

34

TRIM Simulation

8
1.8 MeV He -> AlN/R-Al O

3

YIELD (x10 COUNTS)

2

6

N(int.)
irrad.

N(surf.) irrad.

4

2

PPRBAN98aN2b 2k6.9.3

3

N(int.)
unirrad.

100 keV N
17-2
1.5x10 cm

Al(surf.)

unirrad.
0
100

200

300
400
CHANNEL NUMBER

Interface reaction
was also observedfor Si3N4 (amorphous,~0.2 µm) /SiO2.

500

600

•Increase of film
thickness by 100 keV
N ion irradiation• Optical reflectivity
also shows film
thickness increase•N-Al(Al2O3) reaction,
growth of AlN layer

Optical reflectivity

Refractive index

35

Oscillations: Interference of photon beams
between directly reflected and reflected from
AlN-Al2O3 well-defined interface
The shift of the wavelength lm at which the lm =4dn/j; reflectivity
minima with even integer j,reflectivity takes their maxima & minima maxima with odd integer j,
for n(AlN) > n(Al2O3)~1.8
towards longer wavelength, with thed : film thickness
measured refractive index => increase ofn : refractive index
film thickness

36

X-ray diffraction

FWHM of XRD rocking curve
decreases by N ion
irradiation => alignment ofgrain-orientation

Under ion irradiation,• Degradation of XRD
intensity,
does not become
amorphous
but disordered state• Decrease of a-axis
parameter• No diffraction peak otherthan AlN & Al2O3
Matsunami et al, NIM
B257(2007)433.

2012年12月26日 核融合科学研究所

Plasma Surface Dynamics with
Ion Beam Analysis for study ofdynamic retention of H isotopes
under plasma exposure
PS-DIBAを用いたプラズマ照射下における水素同位体吸蔵のその場計測
Yamagiwa, Nakamura, Matsunami, Ohno, Kajita, Takagi, Tokitani,
Masuzaki, Sagara, Nishimura, Phys. Scr. T145(2011)014042.

37

38

Plasma Surface Dynamics with Ion Beam Analysis (PS-DIBA)i) 高密度プラズマ照射下でのイオンビーム計測が可能
ii) 差動排気によってイオンビーム検出器とVan de Graaff加速器を保護
iii) プラズマ照射下でビーム照射量をモニタリングiv) 試料台の空冷によって試料温度制御

等方性黒鉛を用いた重水素吸蔵量その場計測

39

フラックスΓD一定で重水素プラズマ照射
及びNRA計測開始（斜線部）

試料温度を制御しながら、試料への重水素イオン照射を停止

試料温度を550Kから空冷により50K毎に温度を下げて吸蔵量計測

プラズマ照射中
吸蔵量 5.7×1016 Dcm-2
・・・合計の吸蔵量Nｔ
プラズマ照射停止後
吸蔵量 1.8×1016 Dcm-2

・・・静的吸蔵量Ns
劇的な減少
3.9×1016 Dcm-2
・・・動的吸蔵量Nd = Nt - Ns

ELECTRONIC SPUTTERING(in collaboration with JAEA)

High energy ions
136Xe
58Ni

40Ar

200, 100 MeV
90MeV
60 MeV(0.73 ~ 1.5 MeV/u)
Analysis of sputtered atoms: 1.8 MeV He RBS
Calibration of C-film Collection Efficiency

40

Samples: 15 Oxides & 3 Nitrides
a-SiO2, c-SiO2, ZnO, SCO, Y2O3, Al2O3, MgAl2O3,
MgO, SrTiO3, TiO2, CeO2, Cu2O, CuO, WO3, ZrO2,
Cu3N, AlN, Si3N4• Nearly stiochiometric• From the linear relationship between sputteredatoms in Carbon-foil and ion fluence with thecollector efficiency, the sputtering yields areevaluated.
• Sputtering yields Y are non linear with theelectronic stopping power; Y Sen with n>1.

41

Electronic Sputtering Yield Y(Electronic excitation effects)

Electronic excitation
into atomic
displacement*Eg ~ Maximum
available energy*Number of electron
hole pairs  1/Eg
*Efficiency factor ?

104

SPUTTERING YIELDCuO, WO3 & Cu3N,
The erosion yields aremuch larger than
the suggested
bandgap dependence.

42

PYSPEGe8gc 2k12.10.20

WO 3

103

Eg4

a-SiO2c-SiO2

Cu3N

102

CuO
Y2O3
Cu2O

101

TiO2

SCO
Si3N4
AlN

STO
CeO2

Al 2O3
MgAl 2O4

ZnO

100

ZrO2(YSZ)

10-1

MgO

Se=15 keV/nm
1

3

5

10

BAND GAP Eg (eV)

WO3, NIM B268(2010)3167. Cu3N, NIMB267(2009) 2653. Cu2O, NIM B266(2008)2986.

43

Mechanism of electronic sputtering?
Energy transfer from electronicsystem into atoms?

Ion impact effects on graphene
Rho(mOhmcm)
Rho(mOhmcm)
RHO'

PRGra#5c

0

10

RHO"
RHO"'
RhoCor.(Ohmcm)

ion irrad.
ceasedGraphen #5
7.54 nm2012.9.30
Sp.(0.407/ion)cor.

in Air

-1

10

1 day

unir.

RESISTIVITY (cm)

30 keV N

44

-2

10

0.001

0.01

0.1
1
10
100
+
15
-2
30 keV N FLUENCE (10 cm )1000

Matsunami, Tsuchiya, Mizuno,
Bandoh, 2013

magnetic property of 6%Mn-doped ZnO

45

MZ52e on a-Al2O3 substrate
Hext=0.1T

Temperature dependence

Teem
Below150K : Curie’s law -> Para-magnetic

Susceptibility (emu/cm3)

0.004
0.003

0.004

Mn-doped ZnO (as depo)

0.003
0.002

0.002

y=Σan xn

0.001

0.001

0

0
-0.0010

a0=-1.08486792e-04
a1=1.15631577e-02
6.30145782e-05|r|=9.77116997e-01-0.0010100
Temperature (K)200

0.1 1/T

0.2

0.3

y=Σan xna0=3.92928826e-05
a1=9.28827931e-03
3.70429287e-04|r|=5.04287536e-01

46

Ion impact effect on magnetic property
of 6%Mn-doped ZnO, 100 MeV Xe
g2 J(J+1)

Susceptibility
follows Curie
law (paramagnetic)

100MeV-Xe on MnZnOJ
5/2 Mn+2

30
20

unirrad.

4/2 Mn+3
3/2 Mn+4

10
0 9
10

2/2
1/2
1010 1011 1012 1013 1014 1015
Φ, ions/cm2

Matsunami, Okayasu, Sataka, et al. 2013

N ion energy deposition & implantation effects:
Mn(6%)-doped ZnO

30 keV N
Rp=47nm < film
thickness 140 nm
N ion implantation
effect107

RRESISTIVITY(Ohm*cm)

100 keV N
Rp=160nm >> film
thickness 55 nm
energy deposition
effect

47

106
5

10

30 keV N
unirrad

104
1000
100
10

N+ Ion(139nm) 注入+● N Ion (55nm) 照射
▼

1
0.1

100 keV N
0.01

0.1

1

10

ION FLUENCE (×1015cm-2)

Itoh, Matsunami, 2013

100

1000

48

Concluding remarks, future problems
・Challenge
・Valency modification by ions & its effects
・Ion implantation (inclusion) effects
・Displacement threshold energy for dpa
・Mechanism of electronic excitation into
atomic displacement

Thank you for your attention!