TGSW2018
Session 4-1
Ensemble of Light with Molecules, Materials, and Life for
Sustainable Society(持続可能な社会の実現に向けた光と分子・物質・生命科学のアンサンブル)

Program and Abstract

September 22, 2018
Venue: Room 202B, Tsukuba International Congress Center

Symposium: Organized by University of Tsukuba

ProgramMorning Session: Molecular Assembly (9:30-11:50)
9:30-9:35

Opening Remark (Yohei Yamamoto)

9:35-10:15

Prof. Amar Flood (Indiana Univ. USA)
Anions in Molecular Recognition, Switching, and Hierarchical Assembly

10:15-10:45

Dr. Katsuhiko Ariga (NIMS & Univ. of Tokyo, Japan)
Control of Molecular Machine, 2D Material, and Life at LangmuirInterface(15 min. break)

11:00-11:30

Prof. Hyo Jae Yoon (Korea Univ. Korea), Gyu Don Kong, Junji Jin,
Hyunsun Song,Mixing for Good: Charge Tunneling across Large-area MolecularElectronic Devices based on Mixed Self-Assembled Monolayers

11:30-11:50

Prof. Tatsuya Nabeshima (Univ. Tsukuba, Japan)
Design, Synthesis and Novel Functions of BODIPY Derivatives
Lunch Break (11:50-13:00)

Afternoon Session : Soft Optics, Lasers, Terahertz, etc. (13:00-17:25)
13:00-13:40

Dr. Jer-Shing Huang (Leibniz Inst. Germany), Jhih-Yuan Chen,
Zhan-Hong Lin, Soh Kushida, Yohei Yamamoto
Goos-Hänchen Shift and Plasmon Coupling of Whispering-gallery Modes
in a Self-assembled Fluorescent π-conjugated Polymer Sphere on Ultra
Flat Gold Surface

13:40-14:10

Dr. Yasuhiro Ishida (RIKEN, Japan)
Photonic Crystals Composed of 99% Water and 1% Inorganic Nanosheet

14:10-14:30

Dr. Takashi Nakanishi (NIMS, Japan)
Novel Soft Matter/Materials; Optoelectronically-active Alkyl-π Molecular
Liquids

(15 min. break)
14:45-15:25

Prof. Maurizio Ferrari (CNRS, Italy)
Glass and Glass-Ceramic Photonic Systems: advances and perspectives

15:25-15:45

Dr. Tadaaki Nagao (NIMS, Japan), Thang D. Dao, Kai Chen, Satoshi
Ishii, Robert P. H. Chang
Nanomaterials and Their Surface Functionalization for Infrared
Plasmonics Applications

15:45-16:05

Prof. Yohei Yamamoto (Univ. Tsukuba, Japan)
Self-Assembled Organic/Polymeric Microlasers and Photoswitchable
Arrays(15 min. break)

16:20-16:40

Dr. Fumio Sasaki (AIST, Japan)
Developments of organic semiconductor microcavities: from wafer
processes to solution processes

16:40-17:00

Prof. Tatsuya Mori (Univ. Tsukuba, Japan), Yasuhiro Fujii, Yue Jiang,
Leona Motoji, Suguru Kitani, Akitoshi Koreeda, Kentaro Shiraki, Yohei
Yamamoto, Seiji Kojima
Terahertz Time-Domain Spectroscopy of Lyophilized Protein Lysozyme–Universal Dynamics of Disordered System in the Terahertz Region–

17:00-17:20

Mr. Mario Ziegler (Leibniz Inst. Germany)
Metastable Atomic Layer Deposition

17:20-17:25

Closing Remarks (Prof. Tatsuya Nabeshima)

18:00-

Reception

Anions in Molecular Recognition, Switching, and Hierarchical AssemblyAmar Flood
Department of Chemistry, Indiana University
Anions are intimately related to the sustainable development of our society. The use of synthetic
receptors to manage anions provides the means to support the safe production of food, energy andwater. These include the overfertilization of crops with phosphate (H2PO4–) for high-yield foodproduction that contaminates waterways, hexafluorophosphate (PF6−) as the workhorse electrolyte
in Li-ion batteries, and perchlorate anions (ClO4−), a rocket-fuel propellant, that infiltrates drinking
water and damages human health. This talk will cover recent works tackling these anions withshape-persistent, and size-selective macrocycles, such as triazolophane [1], cyanostar [2], andtricarb [3], and with shape-dynamic and photoswitable foldamers [4]. Hierarchical assembly
involving anions will also be outlined, including those derived from the unexpected propensity for
anti-electrostatic polymerization of phosphate [5].

Cyanostar

Foldamer

Vis

UV

4.5 Å

Cl–

F– OH– Cl– CN– Br–

3.0

3.2

3.4

3.6

3.8

NO3–

4.0

I– H2PO4– ClO4– PF6– SbF6–

4.2

4.4

4.6

4.8

5.0

5.2

Diameter / ÅReferences: [1] Liu et al. Chem 2017, 3, 411427; [2] Lee et al. Nat. Chem. 2013, 5, 704; [3] Lee et
al. Chem. Eur. J. 2016, 22, 560; [4] Hua et al. JACS 2010, 132, 12838; [5] Fatila et al. Chem. Sci.
2018, 9, 2863

Control of molecular machine, 2D material, and life
at Langmuir interface
Katsuhiko Ariga1,2
1. WPI-MANA, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
2. Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha,
Kashiwa, Chiba 277-8561, Japan
E-mail address: ARIGA.Katsuhiko@nims.go.jp

Abstract: Here we propose a novel methodology “hand-operating nanotechnology” wheremolecular orientation, organization and even functions in nanometer-scale can be operated byour macroscopic (hand) operation. This concept can be realized at dynamic two-dimensional
medium such as thin films at the air-water interface, i.e., Langmuir monolayer because thismedium possess both features of bulk and molecular dimension. For example, we successfully
manipulated molecular machines at the air-water interface upon bulk (10-100 cm size) motionof the entire monolayer and realized “capture and release” of aqueous guest molecules using
molecular machine, steroid cyclophane (Figure 1). In addition, mechanically controlled chiralrecognition of amino acid and discrimination of nucleosides by the supramolecular monolayer
was successfully demonstrated. The
concept has been also applied toindicator-displacement
assay
for
sensor usage.
These examples demonstrateournewconcept,manualnanotechnology so-called, handoperating nanotechnology, with whichwecanmanually
controlnano/molecular
phenomenaandfunctions by macroscopic mechanicalforce such as hand motions. Using
hands for functional operation would
be most environmentally friendly andleast energy consuming technology.
In
addition,recentaccomplishmentsoncelldifferentiation control and 2D
nanocarbon fabrication at Langmuir
media will be presented.
Figure 1. Manipulation of molecular machine by macroscopic
mechanical motions.

Title: Mixing for Good: Charge Tunneling across Large-area MolecularElectronic Devices based on Mixed Self-Assembled Monolayers
Gyu Don Kong, Junji Jin, Hyunsun Song, Hyo Jae Yoon*
Department of Chemistry, Korea University, Seoul 02841, South Korea
Abstract
Molecular electronics promises miniaturization of electrical components into themolecular scale. An important goal in molecular electronics is to relate the rates
of charge transport by quantum tunneling across device to chemical andelectronic structure of molecule inside it. This goal is, however, difficult toachieve since the simplest molecular electronic device such as an electrodemolecule-electrode junction is even a complicated physical-organic system
where the complexities arising from ill-defined molecule-electrode interfaces andfrom complicated molecular structure on surface often exist. In large-area
molecular electronic devices, molecules are packed and disordered to someextent, and understanding how intermolecular interactions between molecules
affect the performance of devices is a significant challenge. This presentation
focuses on our recent effort to resolve this problem by harnessing mixed selfassembled monolayers to achieve molecular-level control of supramolecular
structure on surface, and a junction platform based on liquid metal top-electrodeto guarantee high-yield of working devices. We will show the synthesis andcharacterization of various pure and mixed monolayers composed of nalkanethiolates of different lengths, or organic molecular diode (4,4’-bipyridineterminated n-alkanethiolate) and non-rectifying n-alkanethiolates. The tunnelingbehaviors of these mixed monolayers as a function of the length difference
between the molecules inside monolayers and their molar ratio will be discussed
to evidence the supramolecular structural effect on the performance of tunnelingdevices.

Design, Synthesis and Novel Functions of BODIPY
Derivatives
Tatsuya Nabeshima1,2
1. Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
2. Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
E-mail address: nabesima@chem.tsukuba.ac.jp

Abstract: Dipyrrin-boron complex, BODIPY and its derivatives have been used as asensor, a bioimaging tool, etc., because they exhibit excellent photophysical properties
and photostability. However, applications of the BODIPY derivatives and analogs tofunctional host molecules that utilize a B-F unit as a binding site are interesting andimportant but still limited. Thus, we synthesized macrocyclic [1,2] and linear [3]
BODIPY oligomers as a host molecule, in which the BODIPY units work as an emissive
unit and a binding site for a guest through a new type of B-F•••cation interactions. Uv-vis
and fluorescence spectra of the cyclic and linear BODIPY derivatives were changed in thepresence of a cationic guest. A macrocyclic BODIPY trimer bearing m-phenylene
spacers exhibits high recognition ability to secondary ammonium salts, especially to
protonated adrenaline through noncovalent interactions including CH-pi interactions andhydrogen bonds between B-F and the ammonium protons.
Other functionalized BODIPYs, chiral derivatives showing CPL, and BODIPY analogs[4-9] will be also discussed.

Linear BODIPY Oligomers

Macrocyclic BODIPY Trimer
with p-phenylene spacers

Reference:[1] N. Sakamoto, C. Ikeda, T. Nabeshima, Chem. Commun., 46, 6732 (2010).
[2] T. Nakamura, G. Yamaguchi. T. Nabeshima, Angew. Chem. Int. Ed., 55, 9606 (2016).
[3] N. Sakamoto, C. Ikeda, M. Yamamura, and T. Nabeshima, Chem. Commun., 2012, 48, 4818 (2012).
[4] M. Saikawa, M. Daicho, T. Nakamura, J. Uchida, M. Yamamura, and T. Nabeshima, Chem. Commun., 52, 4014 (2016).
[5] N. Sakamoto, C. Ikeda, M. Yamamura, and T. Nabeshima, J. Am. Chem. Soc., 133, 4726 (2011).
[6] M. Yamamura, M. Albrecht, M. Albrecht, Y. Nishimura, T. Arai, and T. Nabeshima, Inorg. Chem., 53, 1355 (2014).
[7] M. Yamamura, H. Takizawa, Y. Gobo, and T. Nabeshima, Dalton Trans., 2016, 45, 6834(2016).
[8] M. Saikawa, T. Nakamura, J. Uchida, M. Yamamura, and T. Nabeshima, Chem. Commun., 52, 10727 (2016).
[9] Y. Gobo, M. Yamamura, T. Nakamura, and T. Nabeshima, Org. Lett., 18, 2719 (2016).

Goos-Hänchen Shift and Plasmon Coupling ofWhispering-gallery Modes in a Self-assembled Fluorescentπ-conjugated Polymer Sphere on Ultra Flat Gold Surface
Jhih-Yuan Chen1, Zhan-Hong Lin2, Soh Kushida3, Yohei Yamamoto3 and Jer-Shing Huang1,2,4,5*
1. Department of Chemistry, National Tsinghua University, Hsinchu 30013, Taiwan
2. Nanooptics Research Group, Leibniz Institute of Photonic Technology, Albert-Einstein Str. 9, D-07745 Jena, Germany
3. Division of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8573, Japan
4. Research Center for Applied Sciences, Academia Sinica, 128 Sec. 2, Academia Road, Nankang District, Taipei 11529, Taiwan
5. Department of Electrophysics, National Chiao Tung University, Hsinchu 30010, Taiwan
E-mail address: jer-shing.huang@leibniz-ipht.de

Abstract: Fluorescent π-conjugated polymer is semiconducting and can be electrically
pumped to generate light. A method to create self-assembled almost perfect microspheres
made of such polymer that support whispering-gallery modes (WGMs) has been developed by
Yamamoto and coworkers [1]. Toward electrical pumping of the WGMs, contact with noble
metals, such as gold could be necessary. To this aim, the influence of the substrate on the
optical properties of the microsphere cavity needs to be well understood. Here, wetheoretically and experimentally study the influence of atomically flat gold substrate [2] on the
WGMs of the fluorescent π-conjugated polymer microspheres (Fig. 1a). We selectively excite
different WGMs by controlling the position of the laser focal spot. Spectral shift and intensitychange due to the gold substrate have been observed and explained. For the spectral shift, wefound blue and red shift for the meridian TE and TM modes, respectively (Fig. 1b). We
attribute the different spectral shift is due to the opposite sign of Goos-Hächen shift of the
WGMs. As for the intensity, we found that gold substrate enhances the spectral intensity.
However, the intensity ratio of TE/TM is reduced because the TM modes couple into surface
plasmons on gold surface via Otto-coupling configuration (Fig. 1c) [3]. Our work gains
insight into the influence of gold substrate on the WGMs and provides important information
for the realization of electrically pumped WGM lasers, which may provide a practical lightsource of plasmonic integrated optical nanocircuits [4-6].

cExperiment

TE

TM
Simulation

TE

TM

Wavelength (nm)Emission IntensitybDistance to Gold (µm)

a

on Au

TM

on ITO

Wavelength (nm)Fig. 1. (a) Illustration of the concept of this work. The left inset shows the SEM image of the sphere and the right one
shows the simulated field distribution of the spheres in air. (b) Spectral shift or TE and TM obtained from experimentand FDTD simulations. The red shift of TM is due to the negative Goos-Hänchen shift. (c) Emission spectra of sphereon gold (upper, red) and ITO substrate (bottom, black).

Reference:[1] T. Adachi, L. Tong, J. Kuwabara, T. Kanbara, A. Saeki, S. Seki, Y. Yamamoto, J. Am. Chem. Soc. 135, 870-876 (2013).
[2] J.-S. Huang et al., Nat Commun. 1, 150 (2010).
[3] P. Biagioni, J.-S. Huang, B. Hecht, Rep. Prog. Phys. 75, 024402 (2012).
[4] J.-S. Huang, T. Feichtner, P. Biagioni, B. Hecht, Nano Lett. 9, 1897-1902 (2009).
[5] Y.-T. Hung, C.-B. Huang, J.-S. Huang, Opt. Exp. 20, 20342-20355 (2012).
[6] W.-H. Dai, F.-C. Lin, C.-B. Huang, J.-S. Huang, Nano Lett. 14, 3881-3886 (2014).

Photonic Crystals Composed of
99% Water and 1% Inorganic Nanosheet
Yasuhiro Ishida
RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
E-mail address: y-ishida@riken.jp

Abstract: Photonic crystals are ordered nanostructures with a periodicity of visible-lightwavelength, which can control the properties of lights, such as exhibiting structural colors. If a
fluid forms such a nanostructure, its structural color could be dynamically modulated byexternal stimuli. Indeed, some fish can dynamically change their colors by modulating theperiodic distance of crystalline guanine sheets cofacially oriented in their fluid cytoplasm. In
this presentation, we report that a dilute aqueous colloidal dispersion of negatively charged
titanate nanosheets, which we have extensively studied in these years [1–6], exhibits structural
colors [4,6].
In this particular colloidal dispersion, the nanosheets spontaneously adopt a cofacial geometry
with an ultralong periodic distance of up to 675 nm due to a strong electrostatic repulsion.
Because the periodic distance can be tuned over a wide range by the nanosheet concentration,
the reflection wavelength can be modulated from UV to visible and even to near-infrared region
up to 1,750 nm. The structural color becomes more vivid in a magnetic flux that inducesmonodomain structural ordering of the colloidal dispersion. The reflective color of the photonic
water can be modulated over the entire visible region in response to appropriate physical orchemical stimuli.

Fig. Pictures of the aqueous dispersion of titanate nanosheets (0.45 vol%) dropping from a thin capillary (upper) andits color modulation mechanism by tuning the periodic distance or the direction of the nanosheets in response to external
stimuli.

Reference:[1] M. Liu et al. Nature Commun. 4, 2029 (2013).
[2] M. Liu et al. Nature 517, 68 (2015).
[3] Y. S. Kim et al. Nature Mater. 14, 1002 (2015).
[4] K. Sano et al. Nature Commun. 7, 12559 (2016).
[5] K. Sano et al. Angew. Chem. Int. Ed. 57, 2532 (2018).
[6] K. Sano et al. Angew. Chem. Int. Ed. 57, in press (2018). DOI: 10.1002/anie.201807240

Novel Soft Matter/Materials; Optoelectronically-active
Alkyl-π Molecular Liquids
Takashi Nakanishi
Frontier Molecules Group, International Center for Materials Nanoarchitectonics (WPI-MANA),
National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044, Japan
E-mail address: nakanishi.takashi@nims.go.jp

Abstract: Our recent research interest is to develop novel ultimate-soft organic materials, i.e.,
room-temperature functional molecular liquids (FMLs) composed of a π-conjugated molecular
unit bearing bulky, flexible branched alkyl chains (Figure 1). There are no charged units on
the molecule, thus FMLs show a clear contrast with ionic liquids (ILs) in terms of functions intheir liquid form. The studies of multi-color tunable luminescent liquids based on blue-color
emitting, electron-donor type liquids1,2) and uncommon phase phenomena with thephotoconducting property of liquid fullerenes3,4) are designed simply by controlling a balanceof intermolecular interactions in the alkyl-π compounds, i.e., van der Waals and π-πinteractions among adjacent molecules, or “alkyl-π engineering”5). Here, the molecular designprinciple of FMLs based on analkylated-π molecular systems,
and their luminescent andoptoelectronic properties aswell as liquid phase control6)
are presented. The π-unit
molecular component described
in
this
paper
will
be
naphthalene7),
anthracene2,6),
pyrene8), phthalocyanine9). The
latest our attempt such as
supercooling phenomena ofblue
emitting
liquidanthracenes6) and developmentof liquids possessing spin-active
naturesynchronizedwithelectrochromism9)
willbemainly discussed in the Fig. 1. A schematic drawing of alkyl-π functional molecular liquids
and a photograph of typical blue emitting liquid.
presentation.
Reference:
1) Angew. Chem. Int. Ed., 2012, 51, 3391-3395. (Highlighted in Nature, 2012, 484, 9.)2) Nature Commun., 2013, 4, 1969.
3) Nature Chem., 2014, 6, 690-696.
4) J. Am. Chem. Soc., 2006, 128, 10384-10385.
5) Chem. Commun., 2017, 53, 10344-10357. (Feature Article)
6) Chem. Sci., 2018, 9, 6774-6778. (Hot Article, Backside Back Cover Page, Highlighted in ChemSci Pick of the Week)7) Phys. Chem. Chem. Phys., 2018, 20, 2970-2975. (Hot Article, Inside Front Cover Page)
8) Sci. Rep., 2017, 7, 3416.
9) Chem. Asian J., 2018, 13, 770-774.

Tsukuba Global Science Week (TGSW) symposium, session “Ensemble of Light with Molecules,
Materials, and Life for Sustainable Society”.
Glass and Glass-Ceramic Photonic Systems: advances and perspectives
Lidia Zur1,2, Thi Ngoc Lam Tran2,3,4, Alessandro Chiasera2, Yann G. Boucher5,6, Alessandro
Vaccari7, Francesco Prudenzano8, Damiano Massella9,2, Cesare Meroni9,2, Francesco Enrichi1,10,
Stefano Varas2, Cristina Armellini2, Andrea Chiappini2, Alessandro Carpentiero2, Maurizio
Mazzola2, Alexander Quandt11, Dominik Dorosz12, Anna Lukowiak13, Brigitte Boulard14, Daniele
Zonta3,2,15, Roberta Ramponi16, Giancarlo C. Righini1,17, *Maurizio Ferrari2,1
1

Centro di Studi e Ricerche “Enrico Fermi”, Piazza del Viminale 1, 00184 Roma, Italy
IFN-CNR CSMFO Lab. and FBK Photonics Unit via alla Cascata 56/C Povo, 38123 Trento, Italy
3
Dep. of Civil, Environmental and Mechanical Eng., Trento University Via Mesiano, 77, 38123 Trento, Italy
4
Ho Chi Minh City University of Technical Education, 1 Vo Van Ngan Street, Ho Chi Minh City, Viet Nam
5
CNRS FOTON (UMR 6082), CS 80518, 22305 Lannion, France
6
École Nationale d’Ingénieurs de Brest, CS 73862, 29238 Brest Cedex 3, France
7
FBK CMM-ARES Unit, Via Sommarive 18, 38123 Povo-Trento, Italy
8
Department of Electrical and Information Engineering, Polytechnic of Bari, Bari, Italy.
9
Department of Physics, Università di Trento, Via Sommarive 14, 38123 Povo-Trento, Italy
10
Division of Materials Science, Luleå University of Technology, 971 87 Luleå, Sweden
11
School of Physics, University of the Witwatersrand, Private Bag 3, 2050 Johannesburg, South Africa
12
AGH University of Science and Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland
13
Institute of Low Temperature and Structure Research PAS, Okolna St. 2, 50-422 Wroclaw, Poland
14
IMMM, UMR 6283, Université du Maine, Av. Olivier Messiaen, 72085 Le Mans cedex 09, France
15
Dep. of Civil and Environmental Eng. University of Strathclyde, 75 Montrose Street, Glasgow, G11XJ, UK
16
IFN-CNR and Department of Physics, Politecnico di Milano, p.zza Leonardo da Vinci 32, 20133 Milano, Italy
17
IFAC CNR, Metropolitan City of Florence, 50019, Italy2* maurizio.ferrari@ifn.cnr.it

Glass photonics is pervasive in a huge number of human activities and drive the research in the fieldof enabling technologies. Glass materials and photonic structures are the cornerstones of scientificand technological building in integrated optics. Photonic glasses, optical glass waveguides, planar
light integrated circuits, waveguide gratings and arrays, functionalized waveguides, photonic crystal
heterostructures, and hybrid microresonators are some examples of glass-based integrated opticaldevices that play a significant role in optical communication, sensing, biophotonics, processing, andcomputing. We present some recent results obtained by our consortium in rare earth doped photonic
glasses and confined structures, in order to give some highlights regarding the state of art in glass
photonics. To evidence the unique properties of transparent glass ceramics we will compare
spectroscopic and structural properties between the parent glass and the glass ceramics. Starting fromplanar waveguides we will move to spherical microresonators, a very interesting class of photonic
confined structures. Then we will present 1D-potonic crystals and opals allowing management of
optical and spectroscopic properties. We will conclude the short review with some remarks about themore significant applications such as laser action and structural sensing and the appealing perspective
for glass-based photonic structures.
The research activity is performed in the framework of COST Action MP1401 Advanced fibre laser and coherent source
as tools for society, manufacturing and lifescience (2014-2018, ERANET-LAC FP7 Project RECOLA - Recovery ofLanthanides and other Metals from WEEE (2017-2019) and Centro Fermi MiFo (2017-2020) project. L.T.N. Tranacknowledges Vietnamese Ministry of Education and Training for her PhD scholarship.

Tsukuba Global Science Week (TGSW) symposium, session “Ensemble of Light with Molecules,
Materials, and Life for Sustainable Society”.

Nanomaterials and Their Surface Functionalization for Infrared Plasmonics
Applications

Tadaaki Nagao1,2,3, Thang D. Dao1,3, Kai Chen1,3, Satoshi Ishii1,3, and Robert P.H. Chang4
1

International Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki,
Tsukuba City, Ibaraki 305-0044, Japan2
Department of Condensed Matter Physics, Graduate School of Science, Hokkaido University, Sapporo, Japan
3
CREST, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012, Japan
4
Department of Materials Science and Engineering, Northwestern University, 2220 Campus Dr., Evanston, Illinois
60208-3108, USA*

E-mail: NAGAO.Tadaaki@nims.go.jp

Abstract
Surface-Enhanced Infrared Absorption (SEIRA) is a phenomenon that vibrational signals from trace amount of analyteor sub-monolayer molecules adsorbed on solid surfaces are dramatically enhanced in their intensities. By utilizing the
localized surface plasmon resonances of infrared optical antennas and metamaterials, strong signal enhancement ofmolecules becomes operative in an effective manner to realize high sensitivity vibrational sensing. Recent developments
in nanostructure fabrication techniques as well as their surface functionalization techniques have enabled us to propose
and fabricate various types of advanced SEIRA nanodevices in nanophotonics and nano-biosensing field as well as inanalytical chemistry. Moreover, recent advances in searching appropriate infrared plasmonic materials beyond noble
metals have dramatically widened the possibilities to utilize low-cost base metal and conductive metal oxides for SEIRA
applications. In this talk, I introduce the detection of dilute molecules and pathogenic enzymes in solution by in situ ATRIR method using surface-functionalized Au nanogap broadband absorbers, as well as protein SEIRA sensing by surfacefunctionalized Al optical antennas and metamaterials. We also introduce our new approach utilizing infrared surface
plasmons of single crystal ITO nanorod array covered with phosphonic acid to detect proteins with high specificity andsensitivity.

Reference[1] T.D. Dao, S. Ishii, T. Yokoyama, T. Sawada, S. Ramu Pasupathi, K. Chen, Y. Wada, T. Nabatame, andT. Nagao, ACS Photonics 3, 1271-1278 (2016).
[2] Kai Chen, Thang Duy Dao, Tadaaki Nagao, Scientific Reports 7, 440691(2017).
[3] Kai Chen, Peijun Guo, Thang Duy Dao, Shi-Qiang Li, Satoshi Ishiii, Tadaaki Nagao, Robert P. H. Chang, Advanced
Optical Materials 5 [17], 1700091-1 (2017).

Self-Assembled Organic/Polymeric Microlasers andPhotoswitchable Arrays
Yohei Yamamoto1,2
1. Department of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8573, Japan
2. Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, Tsukuba, Ibaraki 305-8573, Japan
E-mail address: yamamoto@ims.tsukuba.ac.jp

Abstract: Optical microcavities play an important role for the next-generation lighttechnology. Recently, we succeeded in fabricating spherical microcavities from πconjugated polymers (CPs) by simple self-assembly process (Fig. 1a).[1] We found thatthe microcavities exhibit whispering gallery mode (WGM) resonant photoluminescence(PL) upon focused laser excitation, where PL generated inside the sphere is confined via
total internal reflection at the polymer/air interface.[2–12] The resonance occurs when the
wavelength of the light is an integer multiple of the circumference of the microsphere.
The CP-based microcavities have benefits to the conventional microcavities in thefollowing points:(1) Simple and low-energy fabrication process to obtain well-defined microspheres(2) The microcavities act as both cavity and emitter(3) The microcavities possess high refractive index and photoabsorptivity(4) Potent use for electrically-driven WGM and laser oscillation.
In this presentation, recent results on the fundamentals of the self-assembly of the CPs,
resonant PL from the CP microspheres, intra- and intersphere light energy conversion,
optically-pumped lasing (Fig. 1b), and the future prospects to realize light- andelectrically-driven WGM and lasing will be presented.

Fig. 1. Schematic representation of the self-assembled conjugated polymer microspheres,
optical and SEM micrographs (a), and lasing spectra (b).
Reference:[1] T. Adachi, et al., J. Am. Chem. Soc. 2013, 135, 870−876.
[2] K. Tabata, et al., Sci. Rep. 2014, 4, 5902/1−5.
[3] S. Kushida, et al., Macromolecules 2015, 48, 3928−3933.
[4] S. Kushida, et al., ACS Nano 2016, 10, 5543–5549.
[5] D. Okada, et al., ACS Nano 2016, 10, 7058–7063.
[6] D. Braam, et al., Sci. Rep. 2016, 6, 19635/1–6.
[7] Y. Yamamoto, Polym. J. 2016, 48, 1045–1050.
[8] S. Kushida, et al., Adv. Opt. Mater. 2017, 5, 1700123.
[9] S. Kushida, et al., J. Phys. Chem. Lett. 2017, 8, 4580–4586.
[10] O. Oki et al., Mater. Chem. Front. 2018, 2, 270–274.
[11] S. Nakajima et al., Chem. Commun. 2018, 54, 2534–2537.
[12] D. Okada et al., Nano Lett. 2018, 18, 4396–4402.

Tsukuba Global Science Week (TGSW) symposium, session “Ensemble of Light with
Molecules, Materials, and Life for Sustainable Society”.
Developments of organic semiconductor maicrocavities: from wafer processes to solution
processes
Fumio Sasaki
Electronics and Photonics Research Institute, National Institute of Advanced Industrial
Science and Technology (AIST).
1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan
Phone: +81-29-861-5475 E-mail: f-sasaki@aist.go.jp
Practical application of organic electronic luminescence (EL) is progressing steadily, and not
only a small display but also large screen display product development is proceeding.
Meanwhile, even in the field of lighting where higher brightness is required, a high brightness
light source over 200 lm/W which far exceeds the fluorescent light has already been realized
at the research level. The high brightness LEDs with high energy efficiency light sources aremainly made from a group III-V inorganic semiconductors. Furthermore, lighting applicationsof laser diode (LD) are also expected from the viewpoint of energy saving, becaule LD withthe stimulated emission has higher energy efficiency than that of LED with the spontaneousemission. Recently, LD puts into practical use in the field of high performance headlights andlaser projectors. However, LD with current injected lasing is realized only in inorganic
semiconductor material systems. Many reserchers have tried actively to realize current
injected organic semiconductor lasers, but almost all of the trial have failed. More recently,
reports on current injected optical amplification in light emitting transistors (LETs) usingorganic single crystals have been reported at the Japan Applied Physics Society. They usedorganic single crystal of thiophene/phenylene co-oligomers (TPCOs), examples of molecular
structures are shown below. We have developed formation of microcavities by wafer process
and realized reduction of optically pumped lasing in TPCOs. We will outline the formation of
microcavities by wafer processes in TPCO organic semiconductor materials, and related
topics of microcavity formations by solution processes including an organic/inorganic
complex perovskite semiconductor material.
This work was partly supported by JSPS KAKENHI Grant Number 25390060 and 17H02771.

S

S

S

S

Tsukuba Global Science Week (TGSW) symposium, session “Ensemble of Light with Molecules,
Materials, and Life for Sustainable Society”.
Terahertz time-domain spectroscopy of lyophilized protein lysozyme-universal dynamics of disordered system in the terahertz region*Tatsuya Mori1, Yue Jiang1, Yasuhiro Fujii2, Suguru Kitani3, Akitoshi Koreeda2, Leona Motoji1,
Wakana Terao1, Kentaro Shiraki1, Yohei Yamamoto1, and Seiji Kojima1
1

Division of Materials Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan
Department of Physical Sciences, Ritsumeikan University, 1-1-1 Noji-higashi, Kusatsu, Shiga 525-8577, Japan
3
Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 2268503, Japan2* mori@ims.tsukuba.ac.jp

Disordered materials show universal dynamics in the terahertz region, i.e., the so-called boson
peak (BP), and it is recognized as one of the unsolved problems in glass physics [1]. The BP
universally appears at the THz region in the spectrum of the density of states divided by the squared
frequency. The spectrum deviates from the Debye model for a crystalline system, and has been
experimentally and theoretically investigated for several decades [1,2]. Recently, we pointed outthat the BP in the infrared spectrum appears in the representation of α(ν)/ν2 [2-4], where α(ν) is theabsorption coefficient, although this fact is well known to past researchers.
On the other hand, in the self-similar disordered structure, such as a polymer glass and proteins, it
is expected to exhibit the fractal dynamics called a fracton. The fracton will appear above the boson
peak frequency [6,7], because the dynamics relates the inter-molecular vibrations of the monomer
structure of the self-similarity materials. However, there are few studies of the fracton by farinfrared spectroscopy, because the theoretical understanding of how the terahertz light and fractonmodes couple has not progressed. In this study, we propose how to detect fractal dynamics byterahertz spectroscopy using the protein lysozyme as an example.
References[1]. T. Nakayama, Rep. Prog. Phys. 65, 1195 (2002).
[2]. H. Mizuno, H. Shiba, A. Ikeda, Proc. Natl. Acad. Sci. USA 114, E9767 (2017).
[3]. T. Shibata, T. Mori, S. Kojima, Spectrochim. Acta A 150, 207 (2015).
[4]. M. Kabeya, T. Mori, Y. Fujii, A. Koreeda, B.W. Lee, J.H. Ko, S. Kojima, Phys. Rev. B 94, 224204 (2016).
[5]. W. Terao, T. Mori, Y. Fujii, A. Koreeda, M. Kabeya, S. Kojima, Spectrochim. Acta A 192, 446 (2018).
[6]. S. Alexander, R. Orbach, J. Phys. (Paris) 43, L625 (1982).
[7]. S. Saikan, T. Kishida, Y. Kanematsu, H. Aota, A. Harada, M. Kamachi, Chem. Phys. Lett. 166, 358 (1990).

Metastable atomic layer deposition
Mario Zieglerab, Sezin Yükselc, Sebastian Goerkea, Dana Cialla-Maya, Uwe Hübnera, Dong Wangb,
Heidemarie Schmidta, and Peter SchaafbaLeibniz Institute of Photonic Technology Jena (IPHT), Albert-Einstein-Straße 9, 07745 Jena,
Germanyb
Chair Materials for Electrical Engineering, Institute of Materials Science and Engineering andInstitute of Micro and Nanotechnologies MacroNano®, TU Ilmenau, Gustav-Kirchhoff-Str. 5, 98693
Ilmenau, GermanycFriedrich Schiller University Jena, Jena University Hospital, Institute of Physiology II,
Kollegiengasse 9, 07743 Jena, Germany

An important feature of atomic layer deposition (ALD) is the fact that the coating that has
been deposited is conformal to the substrate surface. Therefore, pre-patterned substrates areusually used for the fabrication of 3D nanostructures using ALD. Here, we present a new
method to generate 3D silver-silica nanostructures using plasma enhanced atomic layer
deposition (PEALD) of silica with tri-dimethyl-amino-silane (TDMAS) and oxygen plasma as
precursors. Unlike the conventional ALD, the coating of MS-ALD is not conformal to thesubstrate surface. Rather, the 3D nanostructures are self-assembled because of side-reactions.
The geometry of the formed nanostructures can be easily adjusted by tuning the deposition
parameters, such as dose time of both precursors and cycle numbers. By doing so, we
observed nanoporous and microporous sponge-like structures as well as nanowire likestructures with feature sizes of up to 10 µm (Fig. 1). This talk gives an overview over diverse
generated structures. In addition a suggestion for the growth theory is given.

Figure 1: SEM images of diverse structures generated using MSALD and an enzymatically generated nanoparticle astemplate (center)

TGSW2018
Session 4-1

Published on September 22, 2018
TREMS, University of Tsukuba
Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8571, Japan