1

o

2

3

4

5

6

7

8

Date/

Time SRPS-1 (TUE) / Room 201 SRPS-2 (TUE) / Room 202 SRPS-3 (TUE) / Room 203 GISAS-1 (TUE) / Room 204

9:50

17:50

Almut Stribeck"Polyurethane Materials Under Load.

Hard-Domain Morphology

Transformations Linking Chemical

Structure and Properties"

Liangbin Li"Studying structural evolutions of

polymer under harsh conditions with in-

situ synchrotron radiation techniques"

12:00

11:20

13:30

14:10

Lunch

Pallavi Pandit"Comparative in-situ studies of Au sputter

growth on homo and di-block co-polymer"

14:50

(chair: Sono Sasaki)

Tiberio.A. Ezquerra"Nanostructure and Function of Fullerene

and Polymer/Fullerene Gratings as

Revealed by Grazing Incidence X-ray

Scattering and Atomic Force Microscopy"

Xuechen Jiao"In-situ investigation of crystallite

structure evolution and its associated

anisotropic thermal expansion behaviors

in semiconducting polymer thin films"

Guoming Liu"Stress Induced Crystal Transition in

Polymers Studied by In-situ Synchrotron

X-ray Scattering"

Michael F Toney"Morphology in Organic Photovoltaics as

Probed by Grazing Incidence X-ray

Scattering"

Scientific Programs (2018 SRPS & 2018 GISAS)

9:00

9:20

10:00

10:40

Sep. 4 (Tuesday)

Break(Chair:Christine M. Papadakis)

Stephan V. Roth"Interface formation during rapid coating

processes"

Tad Koga"Perpendicular orientations of lamellar

microdomains on non-neutral

homopolymer nanocoating layers"

(Chair: Liangbin Li)

Atsushi Takahara"Synchrotron X-ray Scattering of

Polymeric Solids under Various

Mechanical Deformation States"

Break

(Chair: Stephan V. Roth)

Ronald Pandolfi"Xi-cam: Flexible High Throughput Data

Processing for GISAXS"

(Chair: Ronald Pandolfi)

Christine M. Papadakis"Morphologies and Solvent Distribution

During Solvent Vapor Annealing of Block

Copolymer Thin Films: In situ, Real-time

GISAXS Investigations"

Tomoyasu Hirai"Preparation of novel polymethyl

methacrylate brush with well-controlled

stereoregularity and characterization of its

ordered nanostructure"

Yu-Cheng Chiu"Intrinsically Stretchable and Healable

Semiconducting Polymer for Skin-

Inspired Wearable Transistors"

Myung Chul Choi"Nanoscale Assembly Architectures of

Tubulin Tubules"

Zhang Jiang"Recent Advancement in Grazing-

incidence X-ray Scattering for Three-

dimensional Structures in Thin Films and

Buried Nanostructures"

Guillaume Fleury"Nanostructured thin films from block

copolymer self-assembly: exquisite

symmetries from macromolecular design"

(Chair: Atsushi Takahara)

Shinji Ando"Temperature- and Pressure-Induced

Changes in Crystalline Structures of

Polyimides Analyzed by Synchrotron

Wide-Angle X-ray Diffraction"

(Chair: Tiberio Ezquerra)

Ya-Sen Sun"Effects of Cross-linking density of UV

Irradiated Polystyrene Chains on Domain

Orientation and Spatial Order of Block

Copolymer Nanodomains."

Sono Sasaki"Preferred Lamellar Orientation in Thin Films of

Biobased Poly(3-hydroxybutyrate-co-3-

hydroxyhexanoate) Investigated by GIWAXD

Measurements Using Synchrotron Radiation"

18:00

-

20:00

Marc Gensch"Optoelectronic properties of metal

clusters on polymer thin films during

sputter deposition"

(Chair: Ya-Sen Sun )

Eva M. Herzig"Time-resolved GISAXS/GIWAXS for

control and characterization of structure

formation in printed thin films

Dae Sung Chung"Surfactant Engineering to Enhance

Crystalline Orientation of Water-Borne

Polymer Semiconductors"

Peng Zhang"Long-range ordered crystalline structure

in micromolded diblock copolymer

ultrathin film via correlated crystal growth

at surface and beneath layers"

Giuseppe Portale"SAXS/WAXS/RAMAN/DSC: four

techniques in one. Application to the

P(VDF-co-TrFE) crystallization"

(Chair: Max Wolff)

Sung-Min Choi"Hierarchically Self-Assembled Binary

Nanoparticle Superlattices"

Detlef Beckers"GISAXS on a Multipurpose Laboratory

X-ray Diffractometer"

Hyungju Ahn"Industrial Applications of Small angle X-

ray Scattering in PAL"

15:30

15:50

16:30

16:50

17:10

Gennady Pospelov"Experiment planning, simulation and

fitting of GISAS data using BornAgain

framework"

Poster-1 (TUE)

(SR.P1 & GI.P1)

Yongjin Kim"Morphological Structure Details and

Electrical Memory Characteristics of

Poly(3-hexylthiophene) in Thin Films"

Opening Ceremony (Room 201 & 202)

Break

Wonchalerm Rungswang"Exploring In-situ Synchrotron

Investigation for Industrial use"

Max Wolff"Grazing incidence small angle neutron

scattering: The solid-liquid boundary

condition in hydrodynamics"

J. M. Sungil Park"Status and Challenges of the Neutron

Scattering Facility at HANARO after the

Long Shutdown since July 2014"

(Chair: Giuseppe Portale)

Wim Bras"When radiation plays tricks with the

sample"

(Chair: Almut Stribeck)

Soo-Young Park"Control of the micellar structures of the

block copolymers using solvent

selectivity"

(8:20-9:20)

Registration (HICO)

9

Date/

Time SRPS-4 (WED) / Room 201 SRPS-5 (WED) / Room 202 SRPS-6 (WED) / Room 203 GISAS-2 (WED) / Room 204

14:50

15:10

17:50

15:50

16:30

17:10

9:00

9:40

10:20

10:40

11:20

11:40

Scientific Programs (2018 SRPS & 2018 GISAS)

(Chair: Mari-Cruz Garcia-Gutierrez)

Shinichi Sakurai"Orienting Cylindrical Microdomains in an

SEBS Triblock Copolymer / Diluent Sheet

by Application of Temperature Gradient"

Guey-Sheng Liou"Recent Advances in Triphenylamine-

Based High-Performance Polymers"

(Chair: Toshifumi Satoh)

Du Yeol Ryu" Directed Self-assembly of High-

Molecular-Weight Block Copolymers:

Lamellae and Gyroid Structures"

(Chair: Aurora Nogales)

Jin Wang"High-Resolution X-ray Coherent Surface

Scattering Imaging"

(Chair: Byoung-Ki Cho)

David Babonneau"Real-time investigations of photochromic

Ag/TiO2 nanocomposite thin films under

UV and visible laser irradiation"

Myungeun Seo"Length Scale Control in Polymerization-

induced Microphase Separation"

Hyunjung Kim"Structural Dynamics Probed with

Ultrafast Coherent X-Rays from X-Ray

Free Electron Laser"

Kyung Taek Kim"Synthesis of Single Cubic Newtorks

having Large Open-space Lattices

Templated by Polymer Cubosomes"

Sigrid Bernstorff"GISAXS analysis of three-dimensional

Ge nanowire networks"

12:00

Poster-2 (WED)

(SR.P2 & GI.P2)

18:00

-

20:00

13:30

14:10

15:30

(Chair: Kyoung Taek Kim)

Yecheol Rho"Temperature-dependent structural

behavior of polymers containing adenine

moieties by simultaneous XRD-DSC

measurement"

(Chair: Jin Wang)

Young Yong Kim"3D Reconstruction of Pt nanoparticle in

Operando Condition using Coherent X-

ray Diffraction Imaging"

Byoung-Ki Cho"Complex Columnar Assemblies and of

1,2,3-Triazole-based Liquid Crystals"

Break

Jinhwan Yoon"Large Thermal Hysterisis for Volume

Phase Transition of Hydrogels Achieved

by Hydrophobic Junction of methyl

Cellulose"

Visit Vao-soongnern"Development a combined method of

molecular dynamic simulation and

synchrotron X-ray absorption

spectroscopy (MD-EXAFS) to

investigate the atomistic nanostructure of

polymer/salt complexes"

Calvin J. Brett"GI-SAXS/WAXS self-assembly study of spray deposited

metal precursor inks on bio-based polymers"Toshifumi Satoh

"Phase-separated structure of

oligosaccharide-based block copolymer"

Aurora Nogales"X Ray Photon Correlation Spectroscopy

for the study of polymer dynamics"

Hyotcherl Ihee"Watching reacting molecules by time-

resolved X-ray diffraction at synchrotrons

and XFELs

Mari-Cruz Garcia-Gutierrez"Hierarchical morphology and confinement

in nanostructured polymer blends

investigated by Nanofocus X-ray beams

and Resonant Soft X-ray Scattering"

Break

Break

So Yeon Kim"Microstructure of GO colloids in

Polymer Solutions with Small Angle

Scatterings"

Cheng Wang"Multimodal Resonant X-ray Scattering

for Polymer Materials"

Matthias Schwartzkopf"Real-Time Monitoring of Morphology

and Optical Properties during Sputter

Deposition for Tailoring Metal-Polymer

Interfaces"

(Chair: Sigrid Bernstorff)

Guillaume Freychet"Critical-Dimension Grazing incidence

small angle x-ray scattering"

(Chair: Peter Mueller-Buschbaum)

Daniel Söderberg"Initial investigations of cellulose thin

films using GISANS"

Tomoya Higashihara"Synthesis and Morphological Study of

Intrinsically Stretchable-Conjugated

Block Copolymers"

Lunch

Sep. 5 (Wednesday)

(Chair: Shinichi Sakurai)

Jin Kon Kim"Unconventional Micrdomains of Block

Copolymers"

(Chair: Hyunjung Kim)

Moonhor Ree"Principle Investigation of Coherent X-

ray Scattering"

Heung-Sik Kang"XFEL Performance Achieved at PAL-

XFEL"

(Chair: Daniel Söderberg)

Peter Mueller-Buschbaum"Next generation solar cells studied with

GISANS"

Adrian R. Rennie"Grazing Incidence Small Angle Neutron

Scattering from Particles below an

Interface"

(Chair: Moonhor Ree)

Jaehyun Park"Serial Femtosecond Crystallography

Program at the PAL-XFEL Facility"

Sang Soo Kim"Single Particle Imaging at PAL-XFEL' "

(Chair: Xiaobing Zuo)

Clement Blanchet"Biological SAXS: advances and

perspectives"

(Chair: Alexander Hexemer)

Mitsuhiro Shibayama"2D-Pair Distribution Analysis of

Uniaxially Deformed Nanocomposite

Gels"

Kyeong Sik Jin"Small Angle X-ray Scattering Studies on

Structures of Biological Macromolecules

in Solution"

(Chair: Kyeong Sik Jin)

Xiaobing Zuo"Structure and Dynamics of Non-coding

RNAs by Solution Small Angle X-ray

Scattering"

(Chair: Mitsuhiro Shibayama)

Alexander Hexemer"Machine Learning for Scattering on

Polymers"

Fenggang Bian"Development of Small Angle X ray

Scattering at Shanghai Synchrotron

Radiation Facility"

Siriwat Soontaranon

"Synchrotron SAXS activities at SLRI to

promote industrial and ASEAN user

community"

Marcus Hildebrandt"Roughness-Correlation of PMMA-

Polymer Brushes - Conformal Brushes"

Jongchan Lee"Pneumolysin and Its Domains: Structural

Characteristics in Biomimic Solutions and

Adhesion Characteristics to Biomimic

Brush Polymer Films"

Li Xiang"Topology Effects on Single Macromolecular

Structures in Solution and Morphological

Structures in Thin Films of Star Polymers"

10

Date/

Time SRPS-7 (THU) / Room 201 SRPS-8 (THU) / Room 202 GISAS-3 (THU) / Room 203 GISAS-4 (THU) / Room 204

17:50

Scientific Programs (2018 SRPS & 2018 GISAS)

9:00

9:40

10:00

10:20

10:40

(Chair: Byeongdu Lee)

Hideaki Yokoyama"GISAXS Study of Nanoporous Block

Copolymer Thin Films"

Ogawa Hiroki"Visualizing the Spatial Distribution of

the Nanostructures in Thin Films Using

GISAXS-CT"

(Chair: Paul Dumas)

Yuka Ikemoto"Property and Utilization Research of

Infrared Synchrotron Radiation"

Sebastian Grott"Morphological Investigations on fullerene-

free bulk heterojunction blends for

photovoltaic applications"

Hoyeol Lee"Tacticity Effects on Thin Film Morphologies of

Crystalline-Crystalline Brush Diblock

Copolymers "

15:50

16:30

14:50

15:30

Jaseung Koo"Structural & Dynamic Studies of

Confined Polymer Melts near Graphene

Oxide Surface Using Neutron

Reflectivity"

Pham Thi Ngoc Diep"Effects of A Liquid-type Nucleation Agent on

Isothermal and Non-isothermal Crystallization Behaviors

of Poly(L-Lactic Acid) as Revealed by synchrotron SAXS

/ WAXS"

Rasha Ahmed Hanafy Bayomi"Grain Coarsening on the Free Surface and in the

Thickness Direction of a Sphere-Forming

Triblock Copolymer Film"

Kilwon Cho"Surface-Directed Molecular Assembly of

Organic Semiconductors in Organic

Electronics"

Break

Hoichang Yang"Structur-Performance Correlations in

Organic Semiconductor-Based Devices:

Insights from X-ray Scattering Analyses"

(Chair: Isamu Akiba)

Hyun Hoon Song"Microstructural Investigation of butt-

fusion joint in HDPE pipes using wide and

small-angle X-ray scattering"

Hyo Jung Kim"Molecular Engineering for Organic

Photovoltaics"

Volker Körstgens"Spray Deposition of Water-processed

Active Layers for Hybrid Solar Cells

Investigated with in situ GISAXS and

GIWAXS"

(chair: Hyo Jung Kim)

Peng Zhang"Drying of electrically conductive

Au@PEDOT:PSS hybrid rods studied with

in situ microbeam GISAXS"

14:10

Wiebke Ohm"Morphological properties of air-brush

spray deposited enzymatic cellulose thin

films: a GISAXS study"

12:00

Break

Banquet (Hilton Hotel) &

Night Tour (Donggung Palace and Wolji Pond, Cheomseongdae Observatory)

Youngkyoo Kim"Organic Phototransistors with

Nanostructured Semiconducting Polymer

Sensing Channel Layers "

17:10

18:00

-

21:30

Amit Kumar Pandey"DSC and Simultaneous SAXS/WAXS

studies on Crystallization of Poly(L-

Mitsuhiro Shibayama"SANS Study on Thermoreversible

Physical Gels Crosslinked with DNA"

Alessandro Coati"Supported nanoparticles for catalysis:

operando studies of their structural and

morphological evolution during reactions

by grazing incidence X-ray scattering"

(Chair: Georges Hadziioannou)

Yunlan Su"Interfacial Effect on Crystallization

Behavior of Polymer Nanocomposites"

Ryohei Ishige"Structural Evolution in Polyimide

Precursor Films during Thermal Curing

Process Observed by Synchrotron X-ray

Diffraction Method"

(Chair: Mitsuhiro Shibayama)

Yuya Shinohara"Real-space molecular motion of water

observed with inelastic X-ray and neutron

scattering "

(Chair: Hoichang Yang)

Georges Hadziioannou"Structure - Property correlations for

thermoelectric polymers: Towards

efficient material design."

Zee Hwan Kim

"Nano-plasmonics: from single-molecule

chemistry to infrared nanoscopy"

Jehan KimInstrument development to perform In-

Situ GISAXS Experiments on 3C SAXS1

Beamline of PLS"

(Chair: Kakuya Yamamoto)

Kohji Tashiro"Development of Simultaneous Measurement System of FTIR,

WAXD and SAXS Data for the Study of Hierarchical Structure

Change of Polymers Subjected to the Various External Fields"

Rintaro Takahashi"Discontinuous Dodecamer−Icosamer

Transition of a Calix[4]arene-Derived

Surfactant Observed by Time-Resolved

Small-Angle X-ray Scattering"

(Chair: Hyun Hoon Song)

Takuya Yamamoto"Synthesis and Self-Assembly of Cyclic

Polymers and Structural Analysis of the

Molecular Aggregates"

Soo-Hyung Choi"Structure and Properties of Complex

Coacervate Core Micelles"

Brian J. Ree"Quantitative X-Ray Scattering Studies on Micellar

Morphologies of Topological Amphiphilic Block Copolymers"

(Chair: Yunlan Su)

Kazuhiko Omote (Rigaku)"Determination of Accurate Structure of

Periodic Nano-Devices by GISAXS "

Scott Barton (Xenocs)"Too, Advantages and Examples of GI-

SAXS in the Laboratory"

Sang-ho Lee"Solvent size dependent structure of

diblock copolymer micelles in n-alkanes

Shota Fujii"Self-assembly of Calix [4] arene-Based

Amphiphiles Bearing Polyethylene

Glycols: Another Example of “Platonic

Micelles"

Break

(Chair: Hideaki Yokoyama)

Byeongdu Lee"Model Tungsten Oxide Nanostructures

for Battery Applications: Structure

Characterization during Synthesis and In

Function"

Asmaa Qdemat"The spin structure of highly ordered

arrangements of magnetic nanoparticles"

Florian Jung"In situ GISAXS Investigations of pH and

Temperature Responsive Block Copolymer Thin

Films during Swelling in Water Vapor"

(Chair: Yuya Shinohara)

Changwoo Do"Structural analysis using scattering

contrast from SAXS and SANS"

Lunch

(Chair: Peng Zhang)

Giuseppe Portale"Mechanism of Block-copolymer self-

assembly during spin coating revealed by

ultrafast in-situ GISAXS"

(Chair: Kohji Tashiro)

Isamu Akiba"Effect of Hydration in Corona Layer on

Structural Change of Thermo-responsive

Polymer Micelles"

11:20

13:30

Sep. 6 (Thursday)

(Chair:Yuka Ikemoto)

Paul Dumas"Synchrotron Infrared spectroscopy:

Opportunities and challenges for polymer

science"

(Chair: Kazuhiko Omote)

Ralf Röhlsberger"Revealing complex magnetic order via

nuclear resonant GISAXS"

Jitraporn (Pimm) Vongsvivut"High-Resolution Macro ATR-FTIR

Microspectroscopic Technique at

Australian Synchrotron IR Beamline and

Its Applications for Polymer and

Composite Materials"

11

Date/

Time SRPS-9 (FRI)/ Room 201 GISAS-5 (FRI) / Room 202

10:20

12:00

Scientific Programs (2018 SRPS & 2018 GISAS)

Sep. 7 (Friday)

Brown Bag Lunch,

Facility Tour (Pohang Accelerator Laboratory) & Excursion (Yangdong Village)

12:20

-

17:00

Break

(Chair: Jinyou Lin)

Chin Hua Chia"Silver Nanoprisms Nanocellulose Film as Surfaced-enhanced Raman Scattering

Substrate"

(Chair: Katsuhiro Yamamoto)

Basab Chattopadhyay"Thin film crystallization: role of substrate and temperature gradient"

9:00

(Chair: Chin Hua Chia)

Jinyou Lin"In-situ characterization of SAXS/WAXS in polymer processing"

Myungwoong Kim"Design, Synthesis, and Characterization of Block Copolymers with a High

Interaction Parameter"

Keiji Tanaka"Swelling Behavior and Proton Conductivity of Polyelectrolytes in Thin Films"

9:40

(Chair: Basab Chattopadhyay)

Katsuhiro Yamamoto"Analysis of depth-dependent structures in polymer thin films by GISAXS utilizing

tender X-ray"

Kyuyoung Heo"Pore structure analysis and physical properties of nanoporous thin films"

Tae Joo Shin"In-situ GIXD Studies of the Conjugated Polymer-Phospholipid Composite Films:

Temperature & Gas Adsorption Effect"

10:40

11:20

Closing Remarks (Room 201 & 202)

12

Poster No Name Affiliation Title

SR.P1-1 Qianlei ZhangUniversity of Science and

Technology of China

Influence of process parameters on the formation of crystal-crosslinked network and crystal scaffold during film blowing of

polyethylene：an in-situ synchrotron radiation small- and wide-angle X-ray scattering study

SR.P1-2 Seung Won Song KAIST Directed self-assembly of sub-10 nm perpendicular lamellar pattern by fluorine copolymerized block copolymer

SR.P1-3 Sy Minh Tuan Hoang Duy Tan University Comparison between NDP and SIMS Analytical Methods to Determine the 10B and 6Li Depth Profiles

SR.P1-4 Changsub KIM POSTECH Thin Film Morphology Details of Crystalline-Amorphous Brush Diblock Copolymers Bearing Alkyl and Phosphonic Acid Moieties

SR.P1-5 Masashi Ohno Nissan Chemical Corporation Industrial Application of Neutron Reflectometry to the Interfacial Structures between Si-containing and Organic Thin Films

SR.P1-6 Kiyomasa Doi University of Kitakyushu Characterization of Biocompatible HPMA Copolymers Designed for DDS

SR.P1-7 Shotaro Miwa University of KitakyushupH-dependence of Core - Shell - Corona Micellar Characters from a hydrophobic - ionic hydrophilic - nonionic hydrophilic triblock

terpolymer

SR.P1-8 Jun Matsuno University of Kitakyushu Creation of highly stable micelles using hydrosilylation reaction

SR.P1-9 Taisei Miura University of Kitakyushu Dilute-solution properties of biocompatible PHPMA for drug delivery use

SR.P1-10 Kuan Hoon Ngoi POSTECH Structural Details and Properties of Iron Oxide Nanoparticles

SR.P1-11 Kazutaka Kamitani Kyushu Microphase-separated structure change of styrene-based triblock copolymer elastomer during mechanical deformation

SR.P1-12 Ji Ha Lee The university of Kitakyushu Morphological Transition of the Calix[4]arene Surfactant Mixture

SR.P1-13 Koichi Arai The university of Kitakyushu Creation of a polysaccharide-based DDS career reducing immunogenicity

SR.P1-14 Jong Dae JangKorea Atomic Energy

Research InstitutePhase behaviors of self-assembled structures of amphiphilic block copolymer in aqueous solution

SR.P1-15 Aljosa Hafner Institut Laue-Langevin Off-specular neutron reflectivity analysis for buried interfaces: arbitrary vertical interfacial profile approach

SR.P1-16 Ki Hyun Kim Korea University Miktoarm Architectural Effect on the Phase Behavior of PS-b-PLA Block Copolymer

SR.P1-17 Soh Jin Mun UNIST Tunable Liquid Crystallinity of Graphene Oxide in Semicrystalline Polymer Nanocomposites: A Small-Angle X-ray Scattering Study

SR.P1-18 Sol Mi Oh UNIST Initial solvent induced out-of-equilibrium behavior of polymer nanocomposites

SR.P1-19 Jonghyun Kim POSTECH Self-Assembly Behaviors of Amphiphilic Zwitterionic Brush Polymers at Air-Water Interfac

SR.P1-20 Seong Hoon Yu DGIST Facilitating Phase Transfer of Polymer Semiconductor in Mini-Emulsion Synthesis via Molecular Affinity Engineering

GI.P1-1 Chunming Yang Chinese Academy of Sciences GISAXS study on Micro-Structure of Layer-by-Layer Self-Assembly multilayer

GI.P1-2 Hoyeol Lee POSTECHCharacterization of thin-film structure and memory property of conducting poly(p-phenylene)-block-polythiophene and poly(dihexyl

dipropargyl malonate)

GI.P1-3 Wongi Park KAIST Supramolecular assemblies with p-n junction containing organic semiconductors via cylindrical nanoconfinement

GI.P1-4 Wooseop Lee Yonsei University Microdomain orientation of block copolymer controlled by surface modification extent using random copolymer brushes

GI.P1-5 Kuan Hoon Ngoi POSTECH Structural Details of Silicate Nanoparticles

GI.P1-6 Brian Ree Hokkaido University Thin Film Morphologies and Properties of Rotaxane-Containing Polymers and Block Copolymers 

GI.P1-7 Kiyeon Sim Inha University

GI.P1-8 Sooyong LeeKyungpook National

UniversityInvestigation of Bulk Heterojunction Nanostructure in Organic Solar Cells

GI.P1-9 Jin-Seong Kim KAIST Effect of Moving Branching Point of Side Chain in NDI-based Polymers on Their Electrical Properties and All-PSCs Performance

Poster No. Name Affiliation Title

SR.P2-1 Changsub Kim POSTECH Effects of Side Chain Length and Inter-Chain Interaction on the Thin Film Morphologies of Poly(n-alkyl isocyanate)s

SR.P2-2 Li Xiang POSTECH Structure and Biocompatibility Characteristics of Ionic Polymer Nanoparticles

SR.P2-3 Saki Izawa University of Kitakyushu Reverse micelle formation of lactone type sophorolipids in organic solvent

SR.P2-4 Kosuke Morimoto University of Kitakyushu Inclusion of water-soluble polymer into nanotube with hydrophilic interior consisting of amphiphilic cyclic peptide

SR.P2-5 Jongchan Lee POSTECH Synchrotron X-ray Scattering Studies of Protein A, Immunoglobulin G, and Their Mixtures in Buffered Solutions

SR.P2-6 Jia Chyi Wong POSTECH Structure and Biocompatibility Characteristics of Functional Polymeric Nanoparticles

SR.P2-7Supanont

Jamornsuriya

Suranaree University of

Technology

Detailed atomistic structures and x-ray scattering structure factors of amorphous vinyl polymers: A multiscale molecular modeling

approach

SR.P2-8 Masataka Araki Kitakyushu Relationship between alkyl chain length and aggregation number of calix[4]arene-based micelles bearing primary amines

SR.P2-9 Rena Tanaka Kitakyushu Structural stable nano-balls bearing polyethylene oxide for the application as DDS carriers

SR.P2-10 Nam young Ahn KAIST Self-assembly Behavior of Heteroarm Core Cross-Linked Star Polymers

SR.P2-11 Isaac Shin KAIST Microphase Separation Behavior of a Diblock Copolymer upon Selective Metal Ion Binding

SR.P2-12 Aljosa Hafner Institut Laue-Langevin Specular and off-specular neutron reflectivity to probe the effect of irreversible polymer adsorption

SR.P2-13 Min Su Jang DGISTSynthesis and characterization of highly soluble phenanthrol carbazole-based copolymer: Effects of thermal treatment on crystalline

order and charge carrier mobility

SR.P2-14 Sang-Woo Jeon Chonbuk National University Self-assembled structures of boron nitride nanotubes by hydrophobic interaction: A small angle X-ray scattering study

SR.P2-15 Min Guk Seo Pusan National UniversitySmall angle x-ray scattering study of comonomer composition on the segregation behaviour of poly(butyl acrylate)-b-poly(methyl

methacrylate-r-styrene)

SR.P2-16 Hoyeol Lee POSTECHNanoscale Thin Film Morphology and Electrical Memory Characteristics of Copolymers Bearing Phenyl, Thiophenyl, and Dipropargyl

Malonate Units

SR.P2-17 Dowan Kim Pusan National University Programmable volume phase transition of hydrogels for adaptive solar control windows

SR.P2-18 Hyun Suk Wang Korea University Vertical Block Copolymer Microdomains via Organic Nanoparticle Additives

SR.P2-19 Jin-Seong Kim KAIST Domain Structures of P3DDT-based Block Copolymers Depend on Regioregularity

GI.P2-1 Minyong Yang KAIST The study on dark-conglomerate phases of bent-shaped liquid crystal molecules in nano-confined geometry

GI.P2-2 Mingyuan Pei Inha University Ordering and Charge-Carrier Transport of Diketopyrrolopyrrole-based Polymers with Alkyl Side Chains Including Ester Linkers

GI.P2-3 Jonghyun Kim POSTECH Self-Assembling Characteristics and Properties of Brush Polymer/Lipid Hybrid Systems in Thin Films

GI.P2-4 Takuya Isono Hokkaido University 10 nm Scale Microphase Separation of Biomass-Based Block Copolymers Consisting of Maltoheptaose and Poly(δ-decanolactone)

GI.P2-5 Yeongsik Kim Yonsei University Interfacial Interaction Effect on Phase Transition Behavior of Block Copolymer Thin Films

GI.P2-6 Eun Byeol Han Inha University Hierarchical Nanostructures of Zinc Oxide and Polymer Hybrids for High-Performance Strain Sensors

GI.P2-7 Brian Ree Hokkaido University Morphological Structures and Properties of Novel Polymers Bearing Monomeric and Dimeric Adamantane Units

GI.P2-8 Chulyeon LeeKyungpook National

UniversityEffect of Organic Nanostructures on the Characteristics of Organic Memory Transistors

GI.P2-9 Dabin Lee Chung-Ang University Photothermal and antimicrobial smart fabrics based on polyacrylonitrile fibers composited with conjugated polymer nanoparticles

Poster Presentation (2018 SRPS & 2018 GISAS)

Sep. 4 (Tuesday)

Sep. 5 (Wednesday)

Poster Presentation (2018 SRPS & 2018 GISAS)

13

[Sep. 4 (Tuesday), GISAS-1]

Interface formation during rapid coating processes

Stephan V. Roth*1

1KTH & DESY, Germany, *stephan.roth@desy.de

The fabrication of functional coatings relies on advanced process technology. Physical vapor deposition (PVD)

and spray coating are two prominent examples. PVD allows for rapidly installing nanoparticles on surfaces

and inside thin films without additional ligands; spray coating is a rapid, scalable and roll-to-roll compatible

coating method. In order to tailor the nanostructure and the opto-electronic properties of functional layers

based on these methods, a detailed understanding of the dynamics of the coating processes is crucial [1,2]. In

my talk I will focus on time-resolved investigation of using both process technologies to fabricate designed

nanostructured layers. PVD is investigated in terms of industrial sputter rates and the influence on the

electronic properties [3]. Secondly, oblique angle PVD allows for creating hierarchical materials exploiting

selective deposition and nanostructured templates [4]. Spray coating is investigated in terms of colloidal layer

formation as a model system for porous templates [5]. Finally, I will give an outlook to future perspectives of

using nanobeams as an advanced tool for investigating locally curved interfaces [6]

References

[1] M. Schwartzkopf and S. V. Roth, Nanomaterials 6, 239 (2016)

[2] S. V. Roth, J. Phys.: Condens. Matter 28, 403003 (2016)

[3] M. Schwartzkopf, A. Hinz, O. Polonskyi, T. Strunskus, F. C. Löhrer, V. Körstgens, P. Müller-Buschbaum,

Franz Faupel, and S. V. Roth, ACS Appl. Mater. Interfaces 9, 5629-5637 (2017)

[4] S. V. Roth, G. Santoro, J. F. H. Risch, S. Yu, M. Schwartzkopf, T. Boese, R. Dohrmann, P. Zhang, B.

Besner, P. Bremer, D. Rukser, M. A. Rubhausen, N. J. Terrill, P. A. Staniec, Y. Yao, E. Metwalli, and P.

Müller-Buschbaum, ACS Appl. Mater. Interfaces 7, 12470-12477 (2015)

[5] G. Herzog, G. Benecke, A. Buffet, B. Heidmann, J. Perlich, J. F. H. Risch, G. Santoro, M. Schwartzkopf,

S. Yu, W. Wurth, and S. V. Roth, Langmuir 29, 11260-11266 (2013)

[6] S. V. Roth, R. Döhrmann, R. Gehrke, R. Röhlsberger, K. Schlage, E. Metwalli, V. Körstgens, M.

Burghammer, C. Riekel, C. David, and P. Müller-Buschbaum, J. Appl. Cryst. 48, 1827-1833 (2015)

14

Perpendicular orientations of lamellar microdomains on non-neutral

homopolymer nanocoating layers

Tadanori Koga1, Yuma Morimitsu1,2, Daniel Salatto1, Maya K. Endoh1, Keiji Tanaka2

1Department of Materials Science and Chemical Engineering, Stony Brook University, New York 11794-

2275, 2Department of Applied Chemistry, Kyushu University, Fukuoka 819-0395, Japan *tadanori.koga@stonybrook.edu

Over the last decades, block copolymer (BCP) thin films offer a simple and effective route to fabricate highly ordered periodic microdomain structures, which are potentially useful in nanofabrication applications. For most applications, control over the orientations of microdomain structures is of great importance. Recent advances have shown success in switching the orientations (i.e., parallel or perpendicular to a substrate surface) by tuning interactions at the top and bottom surfaces, film thickness, external forces such as electric field, shear force, chemically patterned substrates, thermal annealing above the glass transition temperatures of both blocks, and solvent vapor annealing. In this presentation, we show an alternative robust and simple route to control BCP orientations on polymer nanocoating layers composed of A or B homopolymer as “neutral substrates” for A-B diblock copolymers. A lamellar-forming polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) (Mn,PS=18.5k, Mn,PMMA=18k, microdomain spacing (L0)=20 nm) was used as a model. PS with a molecular weight (Mn), ranging from 4k to 2,000 k, and PMMA with Mn =94 k were used to prepare the polymer nanocoating layers via the established protocol [1]. The thicknesses of the nanocoating layers were estimated to be about 2 nm regardless of a choice of the polymers and molecular weights [1]. PS-b-PMMA thin films with a thickness of 60 nm (=3L0) were spin-coated on the polymer nanocoating layers composed of PS or PMMA. The surface morphology of the BCP films was characterized with atomic force microscopy. The in-situ microdomain structure of the BCP thin films on top of the nanocoating layers was investigated by grazing-incidence small-angle X-ray scattering at the Complex Materials Scattering beamline at NSLS-II (Brookhaven National laboratory, Upton, NY). The details will be discussed in the presentation.

Reference

[1] N. Jiang, J. Shang, X. Di, M. K. Endoh, T. Koga, Macromolecules, 47, 2014, 2682-2689

15

Comparative in-situ studies of Au sputter growth on homo and di-block

co-polymer

Pallavi Pandit*1, Matthias Schwartzkopf 1, Andre Rothkirch1, Alexander Hinz2, Oleksandr Polonskyi2,

Thomas Strunskus2, Simon Schaper3, Franziska C. Löhrer3, Volker Körstgens3, Franz Faupel2, Peter Müller-

Buschbaum3, and Stephan V. Roth1,4

1DESY, Notkestr. 85, D-22607 Hamburg, 2CAU zu Kiel, LS Materialverbunde, 24143 Kiel, 3Physik-

Department, LS Funktionelle Materialien, 85748 Garching, 4KTH, Teknikringen 56-58, SE-100 44

Stockholm, *pallavi.pandit@desy.de

Nanostructured gold (Au) attracts great technological interest and it is a promising candidate for functional,

optical and electronic applications. A tailored metal nanoparticle-polymer interface improves the functionality

of the system; attributed to the polymer-metal interactions, which are dominated by their interfacial interactions.

Sputter deposition technique has been used for depositing metallic layer of few nanometer thicknesses in a

controlled fashion on polymer surfaces [1]. To this end, we have investigated the morphological changes

occurring at the metal-polymer interface during deposition using GISAXS and GIWAXS [2]. Optical

properties of the system have also been studied in-situ and are correlated with the morphological properties of

the gold nanocluster on polystyrene, polymethelmethacrlate and the corresponding di-block co-polymer.

References

[1] Schwartzkopf et al., ACS Appl. Mater. Interfaces 9, 5629 (2017).

[2] Schwartzkopf et al., ACS Appl. Mater. Interfaces 7, 13547 (2015).

16

Morphologies and Solvent Distribution During Solvent Vapor Annealing of

Block Copolymer Thin Films: In situ, Real-time GISAXS Investigations

Anatoly V. Berezkin1, Florian Jung1, Dorthe Posselt2, Detlef-M. Smilgies3, Christine M. Papadakis*1,

1Soft Matter Physics Group, Physics Department, Technical University of Munich, 85748 Garching,

Germany, 2IMFUFA, Department of Science and Environment, Roskilde University, 4000 Roskilde,

Denmark, 3Cornell High Energy Synchrotron Source (CHESS), Wilson Laboratory, Cornell University,

Ithaca, New York 14853, U.S.A., *papadakis@tum.de

Block copolymer (BCP) thin films have been proposed for a number of nanotechnology applications. Solvent

vapor annealing (SVA) has emerged as a powerful technique for manipulating and controlling the structure of

BCP thin films. Due to high time resolution and compatibility with SVA environments, grazing-incidence

small-angle X-ray scattering (GISAXS) is an indispensable technique for studying the SVA process, providing

information of the BCP thin film structure both laterally and along the film normal. Especially, combined

GISAXS/SVA setups at synchrotron sources have enabled in-situ and real-time studies of the SVA process,

giving important insight into the pathways and mechanisms of SVA induced restructuring [1].

A new method is solvothermal vapor annealing (STVA) at elevated temperature with two independently

prepared vapors of different selectivities for the two blocks [2]. An example is shown where STVA with n-

heptane and toluene is applied to a thin film from a cylinder-forming polystyrene-b-poly(dimethyl siloxane)

(PS-b-PDMS) diblock copolymer. The film is first swollen in the vapor of n-heptane. This vapor is stepwise

replaced by the vapor of toluene. The initial cylindrical morphology is transformed into, among others, the

lamellar one. The morphologies determined from the 2D GISAXS maps are corroborated by the ones

calculated from thin films generated by computer simulations. This novel type of experiments allows probing

a trajectory in the phase diagram within few hours (Figure 1). To relate the morphologies to the distribution of

the two solvents in the two types of nanodomains, we use the intensities of the Bragg reflections in the 2D

GISAXS maps along with the measured swelling ratio of the film. This way, the overall polymer volume

fraction as well as the cylinder volume fraction can be determined throughout the STVA experiment. The

concept of determining the distribution of solvents in nanostructured BCP thin films can in the future be applied

to other functional polymer-solvent systems to improve the understanding of SVA and to optimize the

treatment conditions.

Figure 1. Navigating through phase

space of a BCP thin films is possible

using STVA with vapors of two

solvents having different selectivities.

A number of morphologies are

encountered on the way. These are

determined using in situ, real-time

GISAXS. The sketches are results

from computer simulations giving

GISAXS maps similar to the

measured ones [2].

References

[1] D. Posselt, J. Zhang, D.-M. Smilgies, A. V. Berezkin, I. I. Potemkin, C.M. Papadakis, Progr. Polym. Sci.

66, 80-115 (2017).

[2] A. V. Berezkin, F. Jung, D. Posselt, D.-M. Smilgies, C. M. Papadakis, Adv. Funct. Mater. 1706226 (2018).

17

Preparation of novel polymethyl methacrylate brush with well-controlled

stereoregularity and characterization of its ordered nanostructure

Tomoyasu Hirai*1, Atsushi Takahara1,

1Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka,

Japan, *t-hirai@cstf.kyushu-u.ac.jp

Polymer brushes are of great interest material as next generation

surface modifier to introduce low friction, good adhesion, and

antifouling properties in good solvent. These specific properties are

generated from the surface region of polymer brush. On the other hand,

the properties of the inside region of the polymer brush are not well

utilized. To overcome this problem, we focused on preparation of

polymer with well-controlled stereoregularity. The syndiotactic

polymethyl methacrylate (st-PMMA) shows helical structure with 1

nm diameter and accommodates functional molecules and polymers,

resulting in formation of inclusion complex and stereocomplex. If

this notion can be simply converted to a high-density polymer, it is

anticipated that inside of the polymer brush can be utilized. In this

presentation, we will report preparation of novel high-density st-

PMMA brush and characterization of its accommodation behavior

using grazing-incidence wide-X-ray diffraction (GIWAXD) measurements.

The high-density st-PMMA brush was synthesized on the basis of surface-initiated living anionic polymerization in the

presence of triethyl aluminum as a Lewis acid. On the basis of surface initiated living anionic polymerization, the st-

PMMAs with molecular weight in ranging from 6,000 to 83,000 were obtained. To evaluate the accommodation behavior

of st-PMMA brush, the high-density st-PMMA brush so obtained were soared in fullerene (C60 or C70) toluene solution

and the molecular aggregation structure was evaluated using GIWAXD measurements. The scattering vector is defined

as q = (4/)sin, where is Bragg angle. Figure 1shows the a) GIWAXD patterns of st-PMMA brush/C60 and st-PMMA

brush/C70 inclusion complex and b) schematic illustration of the st-PMMA brush/C60 inclusion complex. St-PMMA/C60

brush showed diffraction peaks at q = 3.35 nm-1 along the equatorial axis and q = 7.79 nm-1 along the meridional axis.

The former peak can be assigned to long-period structure of st-PMMA/C60 inclusion complex, while later is associated

with helical pitch of st-PMMA. This indicates that st-PMMA brush formed helical structure and encapsulated C60 in the

nanocavity, leading to a formation of inclusion complex. Moreover, the st-PMMA brush/C60 inclusion complex is oriented

perpendicular to the substrate. St-PMMA brush/C70 also showed diffraction peak at q = 3.23 nm-1 along the equatorial

axis, which indicated that they formed inclusion complex and is oriented perpendicular to the substrate. The diffraction

peak at q = 7.79 nm-1, which is assigned to the helical pitch of st-PMMA, could not be observed from the st-PMMA/C70

brush. This is because an asymmetric nature of C70 leads disordering alignment of C70 in st-PMMA helix, resulting in

formation of lack of ordering inclusion complex comparing with st-PMMA/C60.

It is also well-known that mixture of st-PMMA and isotactic PMMA (it-PMMA) forms stereocomplex. If this notion

simply converted to high-density polymer brush, free polymer can penetrate to the polymer brush, leading to the formation

of stereocomplex. To obtain clear contrast in GIWAXD measurements, 2,2,2-trifluoroethyl methacrylate (FEMA), which

consists of fluoro alkyl group with high electron density, was introduced to the st-PMMA brush (st-PMMA-r-PFEMA

brush). We immersed st-PMMA-r-PFEMA brush to it-PMMA solution, and subsequently GIWAXD measurements were

performed to evaluate the molecular aggregation structure. We could see specific diffraction peaks, which could be

assigned to domain spacing of cylindrical structure forming the stereocomplex, the pitch of the outermost helical structure

forming st-PMMA-r-PFEMA brush, the pitch of the inside of the double helical structure formed by it-PMMA, and the

distance between st-PMMA-r-PFEMA brush and the it-PMMA chains, respectively. We revealed that polymer brush

formed stereocomplex and the brush was oriented perpendicular to the substrate.

References

[1] Hirai, T., Takahara, A. et al., ACS Macro Lett. 7, 148-152 (2018).

[2] Hirai, T., Takahara, A. et al., Langmuir, in press.

Figure 1. GIWAXD patterns of st-PMMA brush/C60 and b) st-PMMA brush/C70 inclusion complex, and c) schematic illustration of st-PMMA/C60 inclusion complex.

18

Intrinsically Stretchable and Healable Semiconducting Polymer for Skin-

Inspired Wearable Transistors

Yu-Cheng Chiu12, Simon Rondequ-Gagne2, Jin Young Oh2, and Zhenan Bao2

11Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106,

Taiwan, 2 Department of Chemical Engineering, Stanford University, Stanford, California 94305-5025, USA

Developing a molecular design paradigm for conjugated polymers applicable to intrinsically stretchable

semiconductors is crucial toward the next generation of wearable electronics. Current molecular design rules

for high charge carrier mobility semiconducting polymers are unable to render the fabricated devices

simultaneously stretchable and mechanically robust. In this talk, we would like to present a new design concept

to address the above challenge, while maintaining excellent electronic performance. This concept involves

introducing chemical moieties to promote dynamic non-covalent crosslinking of the conjugated polymers.

These non-covalent covalent crosslinking moieties are able to undergo an energy dissipation mechanism

through breakage of bonds when strain is applied, while retaining its high charge transport ability. As a result,

our polymer is able to recover its high mobility performance (> 1cm2/Vs) even after 100 cycles at 100%

applied strain. Furthermore, we observed that the polymer can be efficiently repaired and/or healed with a

simple heat and solvent treatment. These improved mechanical properties of our fabricated stretchable

semiconductor enabled us to fabricate highly stretchable and high performance wearable organic transistors.

This material design concept should illuminate and advance the pathways for future development of fully

stretchable and healable skin-inspired wearable electronics.

19

Xi-cam: Flexible High Throughput Data Processing for GISAXS

Ronald J. Pandolfi 1, Daniel B. Allan 5, Elke Arenholz 1, Luis Barroso-Luque 1, Stuart I. Campbell 5, Thomas A. Caswell 5, Austin Blair 1, Francesco De Carlo 3, Sean Fackler 1, Amanda P. Fournier 2, Guillaume Freychet 1, Masafumi Fukuto

5, Doga Gursoy 3 ,8, Zhang Jiang 3, Harinarayan Krishnan 1, Dinesh Kumar 1, R. Joseph Kline 7, Ruipeng Li 5,

Christopher Liman, Stefano Marchesini 1, Apurva Mehta 2, Alpha T 1. N'Diaye, Dilworth (Dula) Y. Parkinson 1, Holden

Parks 1, Lenson A. Pellouchoud 2, Talita Perciano 1, Fang Ren 2, Shreya Sahoo 1, Joseph Strzalka 3, Daniel Sunday 7,

Christopher J. Tassone 2, Daniela Ushizima 1, Singanallur Venkatakrishnan 4, Kevin G. Yager 5,6, Peter Zwart 1, James

A. Sethian 1 and Alexander Hexemer *1

1Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA, USA, 2 Stanford Synchrotron Radiation

Lightsource, SLAC National Accelerator Laboratory 2575 Sand Hill Road, Menlo Park CA, USA, 3 Advanced Photon

Source, Argonne National Laboratory, 9700 South Cass Avenue, Lemont IL, USA, 4Oak Ridge National Laboratory,

P.O. Box 2008, Oak Ridge TN, USA, 5National Synchrotron Light Source II, Brookhaven National Laboratory, Upton

NY, USA, 6Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton NY, USA, 7National Institue

of Standards and Technology, 100 Bureau Dr, Gaithersburg MD, USA, 8Department of Electrical Engineering and

Computer Science, Northwestern University, 2145 Sheridan Rd, Evanston IL, USA, *ahexemer@lbl.gov

Xi-cam is the CAMERA platform for data management, analysis, and visualization. With increasing

capabilities and data demand for GISAXS beamlines, supporting software is under development to handle

larger data rates, volumes, and processing needs. We aim to provide a flexible and extensible approach to

GISAXS data treatment as a solution to these rising needs. The core of Xi-cam is an extensible plugin-based

GUI platform which provides users an interactive interface to processing algorithms. Plugins are available for

SAXS/GISAXS data and data series visualization, as well as forward modeling and simulation through

HipGISAXS[1]. With Xi-cam’s ‘advanced’ mode, data processing steps are designed as a graph-based

workflow, which can be executed locally or remotely. Remote execution utilizes HPC or de-localized resources,

allowing for effective reduction of high-throughput data. Xi-cam coordinates complex experimental plans,

interfacing with beamline controls systems (BlueSky) and data management (Databroker). Xi-cam is open-

source and cross-platform. The processing algorithms in Xi-cam include parallel cpu and gpu processing

optimizations, also taking advantage of external processing packages such as pyFAI[2]. Xi-cam is available

for download online[3].

References

[1] S. Chourou, A. Sarje, X.S. Li, E. Chan, A. Hexemer, "HipGISAXS: A High Performance Computing Code

for Simulating Grazing Incidence X-Ray Scattering Data," Journal of Applied Crystallography, vol. 46, no. 6,

1781-1795 (2013).

[2] PyFAI, a versatile library for azimuthal regrouping, J. Kieffer & D. Karkoulis; Journal of Physics:

Conference Series (2013) 425 (20), pp202012

[3] https://pypi.python.org/pypi/xicam/

20

Recent Advancement in Grazing-incidence X-ray Scattering for Three-

dimensional Structures in Thin Films and Buried Nanostructures

Zhang Jiang*1

1X-ray Science Division, Argonne National Laboratory, Lemont, IL 60439, U.S.A. *zjiang@aps.anl.gov

Grazing-incidence X-ray Scattering (GIXS) can provide invaluable data to reveal structure of surfaces,

interfaces and within thin films. Here, a deeper understanding of GIXS will be discussed beyond how GIXS

is typically analyzed nowadays. The general perception has been that GIXS data yields mostly the in-plane

structure and its correlation in planar and thin film samples, for example, defects and disordering in 2D

superlattices. To obtain the structure information of nanometer or even sub-nanometer resolution along the 3rd

dimension (normal to surface), one may take advantage of the interference of the scattering from parallel

surfaces of a thin film to enhance or reduce the scatterings from certain depths of the film (so called X-ray

standing wave or waveguide effect). That requires both a high-resolution grazing-incidence instrument and an

appropriate surface scattering theory for the data analysis. Multilayer DWBA theory has been developed

recently to take into account the depth-dependent electric field intensity profile, thus affording a nanometer or

even sub-nanometer spatial resolution on the depth information of the buried nanostructures, along with the

in-plane correlation of the structures. It is also found that with an incidence beam above the resonance energy,

the waveguide effect can also modulate the angular distribution of the exiting fluorescence, giving an element

sensitivity of the structures. Several examples will be provided on self-assembled block-copolymer thin films,

and nanoparticle membranes etc.

21

Experiment planning, simulation and fitting of GISAS data using

BornAgain framework

J. Fisher 1, M. Ganeva 1, G. Pospelov *1, W. Van Herck 1, J. Wuttke1, D. Yurov 1

1Forschungszentrum Jülich GmbH, Jülich Centre for Neutron Science at MLZ, Lichtenbergstr. 1, 85748

Garching, Germany, *g.pospelov@fz-juelich.de

A common software for the simulation and data analysis in the field of surface neutron and X-ray scattering is

of key importance for scientists running their experiments at various neutron and synchrotron facilities.

BornAgain (http://www.bornagainproject.org) is a free and open-source project that provides scientists with

the means to simulate and fit their specular, off-specular and GISAS data within a single framework. The name

of the software, BornAgain, indicates the central role of the distorted-wave Born approximation in the physical

description of the scattering process. The software is capable of modeling multilayer samples with smooth or

rough interfaces, various types of embedded nanoparticles and various models to treat finite size effects and

the coupling between the type and position of a particle. It also supports both nuclear and magnetic neutron

scattering, offering the user a way to analyze polarized GISANS. Carefully designed for a broad community

of users, BornAgain offers a modern graphical user interface with the possibility to perform real-time

simulations and to fit experimental data. An advanced Python API lets experienced users create complex

models. BornAgain is a multi-platform software released under the GPL3 license. It is adherent to object-

oriented design, fosters a professional approach to software development and lays a solid foundation for future

extensions in response to specific user needs.

References

[1] http://bornagainproject.org

22

[Sep. 5 (Wednesday), GISAS-2]

Next generation solar cells studied with GISANS

Peter Mueller-Buschbaum*1,

1TU Munich, Germany. *muellerb@ph.tum.de

Next generation solar cells such as for example organic solar cells are an interesting alternative to conventional

silicon based solar cells as they feature new possibilities introduced by using a different class of materials

namely polymers. Instead of expensive ultra-high vacuum technologies, fabrication can be done at room

temperature, using wet chemical processing, and thereby enabling usage of methods such as roll-to-roll

printing. As a consequence, the production of organic solar cells has the potential to become very cheap and

easy. Moreover, the use of polymers allows for flexible solar cells and light weight devices, which will be

usable in a very different fashion as compared to the immobile silicon solar panels. In addition, the energy

payback times of organic solar cells are significantly shorter as compared to the today’s silicon solar cells.

However, despite all these significant advantages of organic solar cells, still fundamental knowledge is very

limited. In particular, it is challenging to detect the complex morphologies, which are necessary to have high

efficiency organic solar cells. The combination of grazing incidence small and wide angle x-ray and neutron

scattering (GISAXS, GISANS and GIWAXS) allows for overcoming these challenges. Selected examples will

be shown to illustrate the possibilities arising from using the advanced scattering techniques in particular

highlighting the use of GISANS.

23

Grazing Incidence Small Angle Neutron Scattering from Particles below

an Interface

Shirin Nouhi1, Maja S. Hellsing1, Vassilios Kapaklis1, Adrian R. Rennie1*

1Centre for Neutron Scattering, Uppsala University, Box 516, 75120 Uppsala, Sweden *Adrian.Rennie@physics.uu.se

Changes of scattering have been observed as the grazing angle of incidence increases and probes different

depths in samples. A model [1] has been developed to describe the observed intensity in grazing incidence

small angle neutron scattering (GiSANS) experiments. This includes the significant effects of instrument

resolution, the sample transmission, which depends on absorption and scattering, as well as the sample

structure. The calculations are tested with self-organised structures of two colloidal samples with different size

particles. The model would allow calculations for various instruments with defined resolution and can be used

to design future improved experiments. The possibilities and limits of GiSANS for different studies are

discussed using the model calculations.

References

[1] S. Nouhi, M. S. Hellsing, V. Kapaklis, A. R. Rennie J. Appl. Cryst. 50, (2017), 1066-1074.

24

Initial investigations of cellulose thin films using GISANS

L. Daniel Söderberg1,2*, Calvin J. Brett1,2,3, Lucas Kreuzer4, Marc Gensch3,4, Martin Månsson5, Peter Müller-

Buschbaum4, Henrich Frielinghaus6, Stephan V. Roth3,7

1KTH Royal Institute of Technology, Department of Mechanics, Osquars backe 18, SE-100 44 Stockholm,

Sweden, 2Wallenberg Wood Science Center, KTH Royal Institute of Technology, SE-100 44 Stockholm,

Sweden, 3Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany, 4Lehrstuhl

für Funktionelle Materialien, Physik-Department, Technische Universität München, James-Franck-Str. 1, D-

85748 Garching, Germany, 5KTH Royal Institute of Technology, Department of Material- and Nanophysics,

Roslagstullbacken 21, SE-10691 Stockholm, Sweden, 6Jülich Centre for Neutron Science (JCNS) at Heinz

Maier-Leibnitz Zentrum (MLZ), Forschungszentrum Jülich GmbH, Lichtenbergstraße 1, 85748 Garching,

Germany, 7KTH Royal Institute of Technology, Department of Fibre and Polymer Technology, Teknikringen

56-58, SE-100 44 Stockholm, Sweden, *dansod@kth.se

In the quest for replacing the use of fossil resources by renewable materials cellulose, the most abundant bio-

based polymer on earth will have a vital role. Due to its nanoscale architecture, cellulose nanofibrils (CNF)

can be used as building-blocks for high-strength materials [1]. Within thin film technology cellulose films

from CNF can be used as barrier coatings; including the potential to fabricate conductive and transparent

coatings for organic electronic applications [2,3]. Furthermore, cellulose films as substrates with controlled

porosity offer unique opportunities for embedding functional layers. At the same time the investigation of the

scalable processes for fabricating CNF films is in the current focus. Spray coating as one method of choice is

a rapid and scalable technology, compatible with roll-to-toll procedures allowing for layer-by-layer deposition

[4]. However, spray coating of CNF has rarely been investigated [5]. One crucial question is the relation

between packing of the CNF, porosity and nanostructure in the range from some nm (fibril diameter) to several

hundred nm (fibril length) inside thin spray coated films. The CNF might be of globular morphology or more

elongated, depending on the film thickness and surface charge. The knowledge of the nature of porosity of the

thin film is crucial for subsequently functionalizing the pores by filling with functional polymers.

In order to approach a determination of the CNF nanostructure inside the thin film and investigate its barrier

properties, we performed grazing incidence small angle neutron scattering (GISANS) at KWS-1 (JCNS,

Garching). A thin film was fabricated by airbrush spray coating [5] using TEMPO CNF with a surface charge

of 1000 µmol/g as the building block. The CNF was dispersed in deuterated water and subsequently sprayed

on a cleaned, hydrophilic silicon substrate. Using an environmental cell, we investigated the uptake of

deuterated water in the 200 nm CNF thin film. We present here initial GISANS results on hydration and drying

of the thin CNF films.

References

[1] Håkansson et al., Nat. Commun. 5, 4018 (2014)

[2] Cervin et al., Appl. Mater. Interfaces 8, 11682 (2016)

[3] Hu et al., Energy Environ. Sci. 6, 513 (2013)

[4] Roth, J. Phys.: Condens. Matter 28, 403003 (2016)

[5] Bell et al., ACS Nano 11, 84 (2017)

25

Synthesis and Morphological Study of Intrinsically Stretchable

-Conjugated Block Copolymers

Miyane Satoshi1 and Tomoya Higashihara1*

1Department of Organic Material Science, Graduate School of Organic Material Science, Yamagata

University, 4-3-16, Jonan, Yonezawa 992–8510, Japan, *thigashihara@yz.yamagata-u.ac.jp

Semiconducting polymer has attracted great attention during the past decade due to their promising

applications in organic electronics, including light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs)

and organic thin film transistors (OTFTs). Due to their lightweight and flexible features, they are applicable

for wearable electronics, such as physiological monitoring and electronic skins. For advanced wearable

electronic applications, the stretchable feature of devices is even required. However, semiconducting polymers

themselves generally show less stretchability due to high crystallinity caused by their rigid backbones and

strong - interaction; therefore, it is important to develop intrinsically stretchable semiconducting polymers.

For example, Peng et al. reported that rod-coil-rod type triblock copolymers containing poly(3-hexylthiophene)

and poly(methyl acrylate) segments (P3HT-b-PMA-b-P3HT) displayed relatively high elongation at break of

140% and low Young’s modulus of 6 MPa.1 Wang et al. fabricated rod-coil type diblock copolymers composed

of P3HT and low-Tg poly(butyl acrylate) segments, i.e., (P3HT-b-PBA).2 The diblock copolymer showed high

hole mobility of 2.5 × 10-2 cm2V-1s-1 even under 100% strain. However, these polymers possessed insulating,

non-semiconducting polyacrylate segments. Here, we develop a soft-polythiophene derivative, P3SiHT, with

a trisiloxane unit in the side chains via a hexylene spacer unit. In addition, diblock (P3HT-b-P3SiHT) and

triblock (P3HT-b-P3SiHT-b-P3HT) copolymers could be synthesized based on Kumada catalyst-transfer

polycondensation. The results of atomic force microscopy and grazing incident small-angle X-ray scattering

indicate that the block copolymer thin films form a phase-separated structure between the P3HT and P3SiHT

domains. Organic thin film transistor devices were prepared to assess the electrical properties of the block

polymers. As a result, the block polymers showed comparable or even higher hole mobility than that of P3HT

homopolymer, probably due to the enhanced phase-separation and thus charge transportation. The mechanical

test of the bulk films indicates that P3HT-b-P3SiHT-b-P3HT shows lower tensile modulus and longer

elongation at break compared to the P3HT homopolymer.

References

[1] R. Peng, B. Pang, D. Hu, M. Chen, G. Zhang, X. Wang, H. Lu, K. Cho, L. Qiu, J. Mater. Chem. C 3, 3599-

3606 (2015).

[2] J. -T. Wang, S. Takashima, H. -C. Wu, C. –C. Shih, T. Isono, T. Kakuchi, T. Satoh, W. -C. Chen,

Macromolecules 50, 1442-1452 (2017).

SubstrateGate

Dielectric layerPolymer semiconductor

S D

P3HT-b-P3SiHT P3HT-b-P3SiHT-b-P3HT

mhavg =1.06 × 10-2 (cm2V-1s-1)

P3HT-b-P3SiHT-b-P3HT

P3HT

26

Critical-Dimension Grazing incidence small angle x-ray scattering

Guillaume Freychet1*, Dinesh Kumar1, Ronald Pandolfi1, Isvar Cordova1, Patrick Naulleau2 and Alexander

Hexemer1

1Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720 USA, 2Center for X-

ray Optics, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720 USA, *gfreychet@lbl.gov

As the lithographically manufactured nanostructures are shrinking in size, conventional techniques, such

as Scanning Electron Microscopes and Atomic Force Microscopes reach their resolution limits [1]. The Critical

Small-Angle X-ray Scattering (CD-SAXS) has emerged as one such promising modality to extract the profile

of line gratings [2].

To overcome the limitation inherent to the transmission geometry of CD-SAXS, i.e. the x-ray absorption

by the silicon wafer and the high acquisition time, we developed a high performance GISAXS approach to

reconstruct the depth profile of line gratings. To do so, the sample is placed on a stage spinning azimuthally,

i.e. perpendicular to the substrate as illustrated on figure 1a. The continuously and smoothly rotating sample

causes the lines to go in and out of the Bragg condition, resulting in sharp vertical lines, aka the Bragg rods.

We use the Distorted Wave Born Approximation (DWBA) to simulate the line profile along the Bragg rods.

Similar to the CD-SAXS approach, we are able reconstruct the shape of etched pattern illustrated on figure 1b,

by minimizing the difference between linecuts along the Bragg rods, and the DWBA simulation.

With the advent of high brightness sources and fast detectors, CD-GISAXS combine the fast X-ray

acquisition with high-speed data treatment and is promising to reach the timescale for an effective in-line

characterization method.

Figure 1:a) CD-GISAXS configuration with the beam along x and the sample rotation along z and b) the

corresponding line profile reconstructed.

Acknowledgements

This work was supported by the Center for Advanced Mathematics for Energy Research Applications

(CAMERA), by the Office of Science, Office of Basic Energy Sciences and US DoE.

References

[1] ITRS (2013). International Technology Roadmap for Semiconductors, http://www.itrs.net/.

[2] D.F. Sunday et al, J. MicroNanolithography MEMS MOEMS. 12 (2013) 031103 1–7.

[3] R. Pandolfi et al, J. Sync. Rad. (under preparation).

[4] G. Freychet et al, Proc. SPIE. 10585 (2018) 1058512.

27

Complex Columnar Assemblies and of 1,2,3-Triazole-based Liquid Crystals

Manh Linh Nguyen1 and Byoung-Ki Cho*1.

1Department of Chemistry, Dankook University, Korea, *chobk@dankook.ac.kr

One dimensional (1D) organization of pi-conjugated aromatic building blocks is an interesting research topic

because the electric and photophysical properties of such building blocks can be tuned by the columnar domain

orientation and packing order. To date, we have studied columnar-forming liquid crystals based on 1,2,3-

triazolyl unit which is capable of hydrogen-bonding interaction and orientation under electric-field. Among

the prepared LC molecules, hexacatenar series consisting of luminogenic naphthalenyl core showed peripheral

chain length-dependent complex columnar assemblies such as helically twisted column, 3D-correlated

undulated column. Depending on the stacking mode between the aromatic cores, photoluminescence (PL)

property changed dramatically. Moreover, the PL intensity was closely associated with the degree of hydrogen-

bonding of 1,2,3-triazolyl linkers. The details regarding these issues will be addressed in the presentation.

28

GI-SAXS/WAXS self-assembly study of spray deposited metal precursor inks on

bio-based polymers

C. J. Brett*1, 2, 3, N. Mittal1, 2, W. Ohm3, L. D. Söderberg1, 2, and S. V. Roth3,4

1Department of Mechanics, Royal Institute of Technology (KTH), Stockholm, Sweden, 2Wallenberg Wood

Science Center, Stockholm, Sweden, 3Photon Science, Deutsches Elektronen-Synchroton (DESY), Hamburg,

Germany, 4Department of Fibre and Polymer Technology, Royal Institute of Technology (KTH), Stockholm,

Sweden, *calvinbr@kth.se

The efficiency of miniaturization crucially relies on the ability to tailor complex systems on the nanoscale.

Especially the integration of electronics on flexible templates such as plastic foils, paper and textiles plays an

essential role. Hence, we applied Airbrush spray deposition - a scalable and rapid film fabrication process - to

fabricate nanostructured multilayer thin films containing metal precursor inks on cellulose nanofibril (CNF)

thin films1 with the aim of translating our basic finding to metal-organic decomposition inks. CNF as produced

from wood presents a renewable and sustainable bio-polymer which draws increasing attention as template

material for flexible, yet disposable electronics. In addition, metal-organic decomposition inks show the ability

of functionalization on these templates. By combining airbrush spray deposition with functionalized bio-based

hybrid materials as ink/CNFs we thus aim for scalable, industrially applicable, flexible electronics. In order to

fully understand the fabrication kinetics during film growth, we took the advantage of surface sensitive X-ray

scattering techniques with high temporal resolution in combination with in situ surface differential reflectance

spectroscopy2, see Fig. 1. We manipulated the ambient influences by increasing surface temperature which

inhibits the aggregation and facilitates the evaporation of carrier solvents and thus changed the

nanostructuring3 and the morphological growth4. Our study reveals very homogeneous CNF thin films with an

unprecedented roughness below 2 nm in combination with a tunable wettability. The functionalization with

silver nanoparticles from the precursor inks resulted in fully conductive and optical transparent thin films

followed in situ employing grazing incidence small- and wide-angle X-ray scattering.

Figure 1 In situ grazing incidence X-ray scattering airbrush spray setup. Additionally, in situ UV-Vis measurements are conducted in SDRS geometry.

References

[1] Roth, S. V. J. Phys. Condens. Matter 2016, 28 (403003), 37.

[2] Schwartzkopf, M.; Santoro, G.; Brett, C. J.; Rothkirch, A.; Polonskyi, O.; Hinz, A.; Metwalli, E.; Yao, Y.;

Strunskus, T.; Faupel, F.; Müller-Buschbaum, P.; Roth, S. V. ACS Appl. Mater. Interfaces 2015, 7 (24),

13547–13556.

[3] Zhang, P.; Santoro, G.; Yu, S.; Vayalil, S. K.; Bommel, S.; Roth, S. V. Langmuir 2016, 32 (17), 4251–

4258.

[4] Ohm, W.; Rothkirch, A.; Pandit, P.; Körstgens, V.; Müller-Buschbaum, P.; Rojas, R.; Yu, S.; Brett, C. J.;

Söderberg, L. D.; Roth, S. V.; submitted (2018)

29

Roughness Correlation of PMMA-Polymer Brushes – Conformal Brushes

Marcus Hildebrandt*1, Suan Yang2, Wael Ali2, Sedakat Altinpinar1, Jochen S. Gutmann1,2

1Department of Physical Chemistry, University of Duisburg-Essen, D-45141 Essen Germany, 2Deutsches

Textilforschungszentrum Nord-West, D-47798 Krefeld, Germany, *marcus.hildebrandt@uni-due.de

Polymer brushes are thin films consisting of polymer chains, which are tethered with one end to a solid surface.

At high grafting densities, repulsive forces between neighbouring chains lead to chain stretching and a brush

conformation is obtained. These thin films arouse interest from a theoretical, fundamental and applied science

point of view, such as roughness correlation. Polymer films with an overall thickness down to a few nanometres

can show a large relative deviation in local film thickness due to interfacial roughness between polymer layer

and substrate. In polymer electronics, like organic emitting diodes however, a constant quality across the entire

diode is required. Polymer brushes could transfer the roughness profile from one interface to an adjacent one

and ensure a locally defined film thickness across a large area, that is conformal brushes. By varying molecular

weight (brush length) and grafting density of the brushes, the coherence between these parameters and

correlated roughness can be studied.

In this work, roughness correlation of poly(methyl methacrylate) (PMMA) brush films, synthesized via

‘grafting-from’ method, was investigated by realizing grafting density and molecular weight gradients on a

silicon substrate. To do so, both parameters were varied in orthogonal directions and hence, a two-dimensional

system is obtained (Fig. 1).

Figure 1: (a) Scheme of two-dimensional system of polymer brushes with molecular weight and grafting

density gradient, (b) Scattering pattern of GISAXS-measurements with line cuts in qz-direction

Roughness correlation of polymer brushes was investigated with Grazing Incidence Small Angle X-ray

Scattering (GISAXS), which is a powerful tool to analyse interfaces of polymer thin films. The results show

oscillations in intensity of the scattered X-rays, proving a conformal brush layer on a silicon substrate and a

correlated roughness (Fig. 1).

References

[1] Jannis W. Ochsmann et. al., Macromolecules 45, 3129-3136 (2012).

[2] Peter Müller-Buschbaum et. al., Macromolecules 31, 3686-3692 (1998).

30

Real-time investigations of photochromic Ag/TiO2 nanocomposite thin films

under UV and visible laser irradiation

Daouda K. Diop1,2, Lionel Simonot1,2, Frédéric Pailloux1, Nils Blanc3, Nathalie Boudet3,

Nathalie Destouches2, David Babonneau*1

1Institut Pprime, Département Physique et Mécanique des Matériaux, UPR 3346 CNRS, Université de

Poitiers, Futuroscope Chasseneuil, France, 2Laboratoire Hubert Curien, UMR 5516 CNRS, Université de

Lyon, UJM-Saint-Etienne, Institut d’Optique Graduate School, Saint-Etienne, France, 3Université Grenoble

Alpes, CNRS, Grenoble INP, Institut Néel, CRG D2AM Beamline, ESRF, Grenoble, France, *david.babonneau@univ-poitiers.fr

Photochromism is defined as a reversible change of colour brought about by exposure of a material to

electromagnetic radiation, usually in the ultraviolet (UV) or visible spectral range. In 2003, multicolor

photochromism of nanoporous TiO2 films loaded with Ag nanoparticles has been reported for the first time

[1]. In the ensuing years, it has been shown that photochromism occurs only in the presence of O2 by photo-

activated redox reactions coupled with morphological changes of the Ag nanoparticles, which possibly sustain

a localized surface plasmon resonance (LSPR). Shrinkage and growth reactions activated by visible-light or

UV-light illumination strongly modify the nanoparticle size distribution, which in turn influences their

plasmonic properties. The resulting modifications manifest themselves as reversible changes in the absorbance

of the films, which are responsible for their colouration or discolouration.

In this presentation, laser-induced structural and optical changes in Ag/TiO2 thin films grown on glass and

flexible PET substrates by sol-gel method and magnetron sputtering deposition will be studied by

implementing real-time grazing incidence small-angle X-ray scattering (GISAXS) and optical transmission

measurements during UV-light and visible-light exposure. We will demonstrate the ability of this combined

approach to determine the evolution of the nanoparticle size distribution and plasmonic response during

exposure cycles [2]. We will show that there is a perfect correlation between the kinetics of morphological

evolution derived from GISAXS and the optical variations observed by transmittance measurements.

Furthermore, the photochromic reaction dynamics is strongly influenced by the nanostructure of the as-grown

samples and by the nature of the substrate.

References

[1] Y. Ohko, T. Tatsuma, T. Fujii, K. Naoi, C. Niwa, Y. Kubota, A Fujishima, Nat. Mater. 2, 29–31 (2003).

[2] D. Babonneau, D. K. Diop, L. Simonot, B. Lamongie, N. Blanc, N. Boudet, F. Vocanson, N. Destouches,

Nano Futures 2, 015002 (2018).

31

GISAXS analysis of three-dimensional Ge nanowire networks

Maja Buljan1*, Lovro Basioli1, Nikolina Nekić1, Sigrid Bernstorff 2**

1Ruđer Bošković Institute, 10000 Zagreb, Croatia, 2Elettra-Sincrotrone Trieste, I-34149 Basovizza, Italy, *mbuljan@irb.hr, http://www.irb.hr/eng/People/Maja-Buljan, **sigrid.bernstorff@elettra.eu

Semiconductor nano-structures attract a lot of attention and play an important role in various nanotechnology

applications due to the highly-designable electronic and optical properties. Ge and Si- based structures are

especially interesting due to their CMOS-compatibility and strong confinement effects. Here we present the

formation of Ge nanowire (NW) networks in an amorphous alumina matrix by magnetron sputtering deposition.

The NWs make a three-dimensional network with the nodes arranged in a regular body centered tetragonal

lattice.

The structural properties of the networks are analyzed by grazing incidence small angle y-ray scattering

(GISAXS). We show the formation of a wide range of structures differing by degree of ordering and by the

parameters of the NW network. Their structural properties are easily designable by the choice of the deposition

parameters. The produced materials are shown to have very interesting optical and electrical properties.

GISAXS map (left) and TEM image (right) of the Ge nanowire networks formed in alumina matrix

32

Real-Time Monitoring of Morphology and Optical Properties during Sputter

Deposition for Tailoring Metal-Polymer Interfaces

Matthias Schwartzkopf *1, Calvin J. Brett1,2, Marc Gensch1,3, Oleksandr Polonskyi4, Alexander Hinz4,

Thomas Strunskus4, Franziska C. Löhrer3, Volker Körstgens3, Franz Faupel4, Peter Müller-Buschbaum3 and

Stephan V. Roth1,2,

1DESY, 22607 Hamburg, Germany, 2KTH Royal Institute of Technology, 10044 Stockholm, Sweden; 3TUM,

85748 Garching, Germany, 4CAU, 24143 Kiel, Germany, *matthias.schwartzkopf@desy.de

Metal nanoparticles on polymer thin films promise various potential applications as functional coatings in solar

cells, biosensors, as reflective or antireflective coatings, and in heterogeneous catalysis. Fabricating such

nanocluster films with tailored morphology, their characterization and manipulation at the nanoscale are the

essential prerequisites and tools for implementing devices in all of these fields. Here, sputter deposition plays

a very important role in industrial and nanostructural processing. In order to tune the size-dependent

optoelectronic properties, it is mandatory to monitor how the growth kinetic affects the metal film morphology

and how it correlates to the optical properties during sputter deposition.

To obtain full control over the nanostructural evolution at the metal-polymer interface and its impact on

optoelectronic properties, we employed a combination of in situ time-resolved surface-sensitive X-ray

scattering (GISAXS) with in situ UV/Vis Specular Reflectance Spectroscopy (SRS) during sputter deposition

of gold (Au) on thin polystyrene films (PS) [1]. We monitored the evolution of the metallic layer morphology

according to changes in the key scattering features by geometrical modeling [2] and correlate the nanostructural

development to optical properties. The morphological characterization is complemented by X-ray reflectivity

and electron microscopy. This enables us to identify the different growth regimes including their specific

thresholds and permits better understanding of the growth kinetics of gold clusters and their self-organization

into complex nanostructures on polymer thin films.

During sputter deposition, a change in optical reflectivity of the pristine grey-blue PS film occurred ranging

from dark blue color due to the presence of isolated Au nanoclusters at the interface to bright red color from

larger Au aggregates [3]. Furthermore, a surface diffusion coefficient for Au on PS at room temperature

according to the interrupted coalescence model was calculated based on a real-time experiment.

Furthermore, the role of sputter deposition rate in tailoring metal layer morphologies on polymer thin films

has been investigated [4]. The deposition rate affects primarily the nucleation process and the adsorption-

mediated growth, whereas rather small effects on diffusion-mediated growth processes are observed. Only at

higher rates, initial particle densities are higher due to an increasing influence of random nucleation and an

earlier onset of thin film percolation occurs. Thus, our findings are of great interest for applications in organic

photovoltaics and organic electronics, which benefit from tailored metal-polymer interfaces.

References

[1] M. Schwartzkopf and S.V. Roth, Nanomaterials 6, 239 (2016).

[2] M. Schwartzkopf, A. Buffet , V. Körstgens, K. Schlage, J. Perlich, A. Rothkirch, G. Benecke, E. Metwalli ,

B. Heidmann, M. Rawolle, G. Herzog, P. Müller-Buschbaum, R. Röhlsberger, R. Gehrke, N. Stribeck and S.V.

Roth, Nanoscale, 5 5053-5062 (2013).

[3] M. Schwartzkopf, G. Santoro, C.J. Brett, A. Rothkirch, O. Polonskyi, A. Hinz, E. Metwalli, Y. Yao, T.

Strunskus, F. Faupel, P. Müller-Buschbaum and S.V. Roth, ACS Appl. Mater. Interfaces 7, 13547–13556

(2015).

[4] M. Schwartzkopf, A. Hinz, O. Polonskyi, T. Strunskus, F.C. Löhrer, V. Körstgens, P. Müller-Buschbaum,

F. Faupel and S.V. Roth, ACS Appl. Mater. Interfaces 9, 5629–5637 (2017).

33

[Sep. 6 (Thursday), GISAS-3]

Revealing complex magnetic order via nuclear resonant GISAXS

Ralf Röhlsberger*1

1Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany, *ralf.roehlsberger@desy.de

Knowledge about the magnetic properties of nanostructured materials is a key issue for designing functional

devices in the fields of information storage, sensor technology, or medical diagnostics. Recent developments

of novel routes for preparation of magnetic nanopatterns [1,2] raised the need for advanced tools to quantify

lateral heterogeneous magnetisation states. Addressing this demand, we have introduced new x-ray scattering

techniques, namely nuclear grazing incidence small angle scattering and nuclear surface diffraction. Both

techniques employ resonant off-specular scattering channels to allow for a unique insight into complex lateral

magnetisation states of nanopatterned systems, also under in-situ conditions. In this contribution, two of these

novel experimental approaches are presented and first results are discussed.

First, we present an x-ray scattering technique which allows disentangling magnetic properties of

heterogeneous systems with nanopatterned surfaces [3]. This technique combines the nanometer-range spatial

resolution of surface morphology features provided by grazing incidence small angle x-ray scattering and the

high sensitivity of nuclear resonant scattering to magnetic order. A single experiment thus allows attributing

magnetic properties to structural features of the sample; chemical and structural properties may be correlated

analogously. This technique enables one to reveal the correlation between structural growth and evolution of

magnetic properties for the study of magnetization reversal in a structurally and magnetically nanopatterned

sample system.

Second, nuclear resonant x-ray diffraction in grazing incidence geometry is used to determine the lateral

magnetic configuration in a one-dimensional lattice of ferromagnetic nanostripes [4]. During magnetic

reversal, strong nuclear superstructure diffraction peaks appear in addition to the electronic ones due to an

antiferromagnetic order in the nanostripe lattice. We show that the analysis of the angular distribution

together with the time dependence of the resonantly diffracted x rays reveals surface spin structures with

very high sensitivity. This scattering technique provides unique access to laterally correlated spin

configurations in magnetically ordered nanostructures and, in perspective, also to their dynamics.

References

[1] K. Schlage, S. Couet, S. V. Roth, U. Vainio, R. Rüffer, M. M. Abul Kashem, P. Müller-Buschbaum, R.

Röhlsberger, New J. Phys. 14, 043007 (2012)

[2] D. Erb, K. Schlage, R. Röhlsberger, Science Advances 1, e1500751 (2015)

[3] D. Erb, K. Schlage, L. Bocklage, R. Hübner, D. G. Merkel, R. Rüffer, H.-C. Wille, R. Röhlsberger, Phys.

Rev. Materials 1, 023001(R) (2017)

[4] K. Schlage, L. Dzemiantsova, L. Bocklage, H.-C. Wille, M. Pues, G. Meier, R. Röhlsberger, Phys. Rev.

Lett. 118, 237204 (2017).

34

Supported nanoparticles for catalysis: operando studies of their structural and

morphological evolution during reactions by grazing incidence X-ray scattering

Alessandro Coati*1, A. Vlad1, V. Dhanasekaran1, A. Resta1, and Y. Garreau1

1Synchrotron SOLEIL, France, *coati@synchrotron-soleil.fr

Grazing incidence X-ray scattering techniques are well adapted for the studies of supported nanoparticles under

gas environments. In particular the coupling of Diffraction (GIXD) and Small Angle Scattering (GISAXS)

allows to follow in real time the evolution of the atomic arrangement and of the morphology of nanoobjects

during a reaction. These techniques are available at SixS beamline at Synchrotron SOLEIL, which presents

two end stations: the first one dedicated to UHV studies (allowing gases exposures ranging from 10-10 to 10-

5 mbar) and the second one is equipped with a flow reactor (XCAT) where a gaz pressure of 2 bars can be

reached. Two examples concerning the evolution of bimetallic nanoparticles (NPs) in the presence of reactive

gases will be presented. In both the examples the reaction considered is the CO oxidation, which is a key

reaction for catalysis process [1]. The first results exploiting the coupling of GISAXS and GIXD in operando

conditions will be shown and the experimental setup described. The first experiment concerns the study of the

evolution of Au-Cu NPs supported on TiO2(110) during the reaction [2]. GIXD measurements show that, in

spite of being alloyed, NPs present a Cu segregation to their surface upon oxygen exposure at room temperature.

This process is reversible upon annealing at 300°C. Reorientation and/or recrystallization of the smallest NPs

is also observed. The second example concerns Au-Pd NPs synthesized by micelle nanolithography, a

technique allowing to yield a very sharp size distribution and a well-controlled composition of the NPs. Spin-

coating metal-loaded micelles on SiOx/Si(001) are exposed to oxygen or hydrogen plasma in order to remove

the polymer and form the nanoparticles. The influence of oxygen and hydrogen plasma treatment on the

reactivity and on the morphology of the nanoparticles is clearly evidenced.

References

[1] Jing Xu et al, Biphasic Pd-Au Alloy Catalyst for Low-Temperature CO Oxidation, J. Am. Chem. Soc. 2010,

132, 10398–10406.

[2] A. Wilson, et al., Phys. Rev. B 90 (2014) 075416.

35

Determination of Accurate Structure of Periodic Nano-Devices by GISAXS

Kazuhiko Omote1*, Yoshiyasu Ito1

1X-Ray Research Laboratory, Rigaku Corporation, Akishima 196-8666, Japan, *omote@rigaku.co.jp

The typical size of most recent semiconductor devises is shrinking around ten-nanometers and difficult to

inspect the precise structure by the current optical metrology. X-ray scattering is suited for inspecting them

due to its high-spatial resolution (short wavelength) and penetrating power. In addition, grazing incidence

geometry allows us to enhance sensitivity for the surface tiny structures, like semiconductor devices. The other

feature of semiconductor devises is its periodicity. For example, memory device has a huge number of the

periodic structure, which corresponds to a memory unit. Such a periodic structure creates specific X-ray

scattering pattern depending on the periodicity, only when the diffraction condition is fulfilled (q = ghk). Where

q is the scattering vector of scattered X-ray and ghk is the reciprocal vector of reflection indexes hk for the

surface two-dimensional periodic structure. In order to collect complete data set for the structural determination,

we have to rotate the sample appropriately to fulfill the diffraction condition of the periodicity of the sample.

We have built a thin beam optic to reduce the footprint on the sample surface at the grazing incidence geometry.

The beam is focused at the detector position in the parallel to the surface direction to improve the angular

resolution in this direction.

Distorted wave born approximation (DWBA) for multilayer structure is applied to take into account reflection

and refraction of X-ray in the structured layer [1]. In addition, we have formulated calculation of X-ray

scattering pattern by a periodic structured layer considering fluctuation from the average structure [2]. We

applied the present GISAXS method to evaluate nanoimprint template patterns. After the collecting X-ray data,

the samples were cut and measured by cross-sectional TEM to compare cross-sectional profile very precisely.

The obtained profiles were agreed very well for several samples having from 15 nm to 30 nm in space size [3].

In addition, we checked reproducibility of repeated measurements and confirmed 3 value of the

reproducibility was less than 0.2 nm for both space size and depth of those samples. The present method is

also applicable for evaluating two-dimensional hole and/or pillar structures and it will be presented at the

conference.

References

[1] Y. Ito and K. Omote, Meas. Sci. Techol., 22, 024008 (2011).

[2] K. Omote, Y. Ito, and Y. Okazaki, Proc. of SPIE, 7638, 763811 (2010).

[3] E. Yamanaka, R. Taniguch, M. Itoh, K. Omote, Y. Ito, K. Ogata, and Y. Hayashi, Proc. of SPIE, 9984,

99840V (2016).

36

Tools, Advantages and Examples of GI-SAXS in the Laboratory

Scott Barton

Xenocs/SAXSLAB, Amherst Massachusetts USA, scott.barton@saxslab.com

While researchers reflexively consider Grazing Incidence Small Angle X-ray Scattering (GI-SAXS) as an

application requiring Synchrotron Radiation (SR), new developments in laboratory x-ray sources, detectors

and collimation make Laboratory GI-SAXS practical and even provides advantages over SR. We’ll discuss

some of these new tools and how they can be considered as part of a generalized SAXS setup that includes

Transmission Scattering, Reflectivity and GI-SAXS. We’ll highlight advantages in the laboratory related to

data collection in beamstop-free mode and exposure to the entire plane of incidence, which is commonly

blocked in SR. Finally, we’ll look at some examples in semiconductors and polymers, including

complementary transmission SAXS from surface films on ultra-thin SiN substrates.

37

Interfacial Effect on Crystallization Behavior of Polymer Nanocomposites

Weiwei Zhao1, Yunlan Su*1, Xiangning Wen1, Dujin Wang1

1 Beijing National Laboratory for Molecular Sciences, Key Laboratory of Engineering Plastics, Institute of

Chemistry, the Chinese Academy of Sciences, Beijing 100190, China, *ylsu@iccas.ac.cn

Recently, polymer nanocomposites (PNCs) have gained considerable interest both in manufacture and

scientific domain. Introduction of high specific surface area nanoparticles (NP) into polymer matrix may result

in improvement of physicochemical properties such as mechanical strength, dielectric breakdown, and electric

conductivity. The characterization of the interaction between the polymer and the nanoparticles is of high

importance since it determines the physical and in some cases also the chemical properties of the composite

system [1]. Moreover, they were found to differ from bulk properties, primarily due to the modified structure

at the interfaces and the interactions across them.

Considerable interest has been drawn in polymers under confinement since they often exhibit different

condensed structures compared to their bulk courterparts. The interfacial and spatial confinement effects

introduced by nanoparticles strongly influence the crystallization of polymers and thus determine the ultimate

properties of PNCs [2]. Understanding the confined crystallization behavior in PNCs will not only enrich the

knowledge of polymer crystallization but also aid in the design and application of PNCs. In this work, the

crystallization behavior of poly(ethylene oxide) (PEO) confined by monodispersed Stöber silica (SiO2) was

systematically investigated by varying the size, concentration and surface chemistry of SiO2 as well as the

molecular weight (Mn) of polymers [3-4]. The current observation may provide an insight into the effect of

interfacial interaction as well as the interfacial structure on the crystallization of polymer matrix.

References

[1] J. Khan, S. E. Harton, P. Akcora, B. C. Benicewicz, S. K. Kumar, Macromolecules 42, 5741–5744 (2009).

[2] W.W. Zhao, Y. L. Su, D. J. Wang, Mod. Phys. Lett. B 31, 1730003 (2017).

[3] W.W. Zhao, Y. L. Su, X. Gao, J. J. Xu, D. J. Wang, J. Polym. Sci., Part B: Polym. Phys. 54, 414–423

(2016).

[4] W.W. Zhao, Y. L. Su, A. J. Muller, X. Gao, D. J. Wang, J. Polym. Sci., Part B: Polym. Phys. 55, 1608–

1616 (2017).

38

Structural Evolution in Polyimide Precursor Films during Thermal Curing

Process Observed by Synchrotron X-ray Diffraction Method

Ryohei Ishige*1, Kazuyuki Tanaka1, Shinji Ando1,

1Department of Chemical Science and Engineering, Tokyo Institute of Technology, E4-5-2-12-1, Ookayama,

Meguro-ku, Tokyo 152-8552, Japan, *rishige@polymer.titech.ac.jp

Abstract: Aromatic polyimides (PIs) film are widely used in industrial field, such as; insulating layers in

electronic circuits, thermal protection coatings on artificial satellites, alignment layer in liquid-crystalline (LC)

displays, owing to their high thermal and chemical stability and mechanical toughness. Although molecular

orientation of PI chain are not intentionally controlled in usual film-formation processes, highly oriented PI

films are attractive for optical retardation plate, rubbing-free alignment layer for LC display, and so on.

Recently, we focused lyotropic LC phase to control the chain orientation of PIs, inspired by previous work of

Neuber et al1, and successfully developed lyotropic LC PI-precursor solution at ambient temperature from

linear poly(amic ester)s (PAEs) with long alkylene side chains. In this study, we analyzed structural evolution

in the PAE films by in-situ measurements based on synchrotron radiation wide-angle X-ray diffraction (SR-

WAXD), conventional Fourier-transform polarized infrared absorption spectroscopy (pFT-IR), and new

method, p-polarized multi-angle incidence resolution spectroscopy (pMAIRS)2 in the mid-IR region, which

was developed to analyze in-plane/out-of-plane anisotropy in thin films. Thick films (~5 μm) prepared by

shearing of concentrated PAE solution in the LC phase and thin films (~300 nm) prepared by spin-coating of

the diluted PAE isotropic solution, were compared and the effect of the LC orientation field was discussed.

Experimental: The monomers and the PAEs were synthesized according to

previous papers (Fig. 1)1, 3. In-situ SR-WAXD measurements were conducted at

BL-10C or BL-6A in Photon Factory (PF) of High Energy Accelerator Energy

Source, Tsukuba, Japan (Proposal No. 2015G587, 2016G544, and 2017G693).

The wavelength of X-ray was 0.89 and 1.5 Å at BL-10C and BL-6A respectively.

FT-IR measurements were conducted with FT/IR-6100FF (JASCO), which was

equipped with AM-4000 rotation stage and home-made heating system4.

Results and discussion: In SR-WAXD patterns, a thick PAE solution

film sheared in the LC phase showed typical uniaxially oriented smectic

structure, in which the main chains and the layer normal were aligned in

the shear direction and the uniaxial orientation order parameter, S,

reached 0.8. The SR-WAXD and pFT-IR methods gave same S values,

indicating the LC phase was homogeneous. During the thermal

imidization process, the S value of PI segments was enhanced to reach

0.9, whereas that of PAE was once decreased and then recovered in the

early and late stages of imidization, respectively, as presented in Fig. 2.

This phenomenon can be explained by a model that PI segments with

much longer persistence length than PAE were spontaneously aligned

along the initial orientation direction of the PAE matrix. On the other

hand, a thin spin-coated film of the PAE and corresponding PI showed

relatively low planar orientation; S was about −0.1 and −0.2 for PAE and

PI films respectively. Furthermore, the S value estimated by SR-WAXD

was larger than that by pMAIRS for the PAE thin film but same as that

by pMAIRS for the PI thin film. This results implies that a heterogeneous

structure containing non-oriented region was generated in the initial PAE

film, because the PAE chains have shorter persistence lengths in diluted solution, and then quenched during

fast evaporation process of spin-coating. The heterogeneous structure was then converted into a homogeneous

structure, following an increase in the persistence length during thermal imidization.

References [1] C. Neuber, R. Giesa, H-W. Schmidt, Macromol. Chem. Phys. 203, 598–604 (2002) [2] T.

Hasegawa, J. Phys. Chem. B, 106, 4112–4115 (2002) [3] B. W. Harkness, J. Watanabe, Macromolecules, 24,

6759–6763 (1991) [4] R. Ishige, K. Tanaka, S. Ando, Macromol. Chem. Phys. 219, 1700370 (2017)

Fig. 2 Temperature dependence of S for

PAE (blue) and PI (red) by (a) SR-

WAXD, (b) FT-IR method and degree of

imidization, χ (green in panel b).

Fig. 1 Chemical structure of

PAE (R is alkylene chain).

39

Structure-Performance Correlations in Organic Semiconductor-Based Devices:

Insights from X-ray Scattering Analyses

Hoichang Yang1*

1 Department of Applied Organic Materials Engineering, Inha University, Incheon 22212, South Korea, *hcyang@inha.ac.kr

Organic semiconducting materials are essential for the fabrication of organic field-effect transistors,

photovoltaic cells, sensors, thermoelectric generator and complementary logic circuits. Recently, various

organic semiconductors have been synthesized to achieve high electrical properties in solid states, excellent

thermal and oxidative stability. These properties are originated from the intra- and inter-molecular π-

conjugated structures of the organic semiconductors. Our recent results for various organic semiconductor-

based electronics are summarized and analyzed. We performed a multiscale structural analysis by combining

different X-ray scattering methods (grazing Incidence X-ray diffraction/scattering, GIXD/GIXS, and X-Ray

Reflectivity, XRR), to achieve a deep knowledge of the molecular organization in the bulk, in the film, and in

the interface region, crucial for any technological development. In addition, in-situ X-ray scattering

measurements have proved to be extremely powerful for describing at nano-scale the structure of films during

the first stages of formation, as well as on the evolution of the molecular arrangement and of the surface

morphology during the film growth. Moreover, in-situ measurements give significant information on the

structural stability, the segregation and reversibility of solid state transformations, strongly related to the

optoelectrical properties of these materials.

40

Structure - Property correlations for thermoelectric polymers: Towards efficient

material design.

Geoffrey Prunet1, Ioannis Petsagkourakis1, Eleni Pavlopoulou1, Giuseppe Portale2, Xianjie Liu3,

Mats Fahlman3, Eric Cloutet, Guillaume Fleury1, and Georges Hadziioannou1

1 Laboratoire de Chimie des Polymères Organiques, CNRS - Bordeaux INP - Université de Bordeaux - UMR

5629, F-33607 Pessac, France, 2 Macromolecular Chemistry & New Polymeric Materials, Zernike Institute

for Advanced Materials, Nijenborgh 4, 9747 AG Groningen, The Netherlands, 3Linköping University,

Department of Physics, Chemistry and Biology, S-581 83 Linköping, Sweden

Conducting polymers (CPs) have recently gained the attention of the scientific community due to their

prospective use in thermoelectric applications [1,2]. Particularly, it has been proven that an important

parameter for tuning the thermoelectric properties and the charge transport behavior of the CP is the shape of

the DOS in the band edge, where a steeper band edge would be translated in a semi-metallic behavior for the

system, with higher thermoelectric efficiencies. However this shape can also be affected by the oxidation levels

of the systems [3,4]. In the present study we managed to elucidate the correlation between material structure,

electronic structure and electronic/ thermoelectric properties, through proper material design and keeping

constant the carrier concentration of the CPs. Additionally, for these systems a metal-to-insulator transition

was observed in low temperatures near 30K, which was diminished with increasing thin film crystallinity. Our

results underline that CPs with higher crystallinity will result in a 2-D charge transport behavior and a steeper

band edge, which are translated into higher carrier mobility (4.2 cm2/Vs) and higher Seebeck coefficient (44

μV/K). Finally, an experimental relationship between carrier mobility and Seebeck coefficient was extracted

highlighting the importance of CPs with high carrier mobility for thermoelectric applications.

ACKNOWLEDGEMENTS

The authors acknowledge financial support from Arkema and the Région Aquitaine as well as from the

Industrial Chair (Arkema/ANR) within the grant agreement no. AC-2013-365. I.P. is grateful to the Région

Aquitaine for financial support (Ph.D. grant #20111101004). The ESRF and NWO are acknowledged for

allocating beam time at the Dutch-Belgian beam line (DUBBLE) for the GIWAXS experiments. This work

was performed within the framework of the Labex AMADEUS ANR-10-LABEX-0042-AMADEUS with the

help of the French state Initiative d’Excellence IdEx ANR-10-IDEX-003-02.

References

[1] Bubnova, O. et al. Optimization of the thermoelectric figure of merit in the conducting polymer poly(3,4-

ethylenedioxythiophene). Nat. Mater. 10, 429–433 (2011).

[2] Kim, G.-H., Shao, L., Zhang, K. & Pipe, K. P. Engineered doping of organic semiconductors for enhanced

thermoelectric efficiency. Nat. Mater. 12, 719–723 (2013).

[3] Bubnova, O. et al. Semi-metallic polymers. Nat. Mater. 13, 190–194 (2013).

[4] Bubnova, O. & Crispin, X. Towards polymer-based organic thermoelectric generators. Energy Environ.

Sci. 5, 9345 (2012).

41

Surface-Directed Molecular Assembly of Organic Semiconductors

in Organic Electronics

Kilwon Cho

Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH)

Pohang 37673, Republic of Korea, kwcho@postech.ac.kr

The field of organic electronics such as organic light-emitting diodes (OLEDs), organic photovoltaics (OPVs),

and organic field effect transistors (OTFTs) has been developed vastly in the last three decades because they

are mechanically flexible, light weight, versatile in chemical design and synthesis, and can be easily processed

as well. In such organic electronic devices, microstructures of organic semiconductor thin films and interfacial

properties of the devices are key factors to the performance and lifetime of the devices. Controlling the surface

characteristics of underlying substrates can govern the mesoscale and/or nanoscale ordering of the organic

molecules assembled on them, and thus significantly affects the organic electronic devices on the whole. Here,

I will discuss the essence of the surface-directed molecular assembly approaches for controlling the growth of

organic semiconductor molecules on gate dielectrics and electrodes to achieve high performance OFETs and

OPVs.

References

1. H. S. Lee et al., J. Am. Chem. Soc. 130, 10556 (2008)

2. W. H. Lee et al., J. Am. Chem. Soc. 133, 4447 (2011)

3. W. H. Lee et al., Adv. Mater. 23, 1752 (2011)

4. B. Kang et al., Nat. Commun. 5, 4752 (2014)

5. B. Kang et al., Chem. Mater. 27, 4669 (2015)

6. S. B. Jo et al., ACS Nano 9, 8206 (2015)

7. N. N. Nguyen et al., Nano Lett. 15, 2474 (2015)

8. B. Kang et.al., Adv.Mater. 30, 1706480 (2018)

42

Organic Phototransistors with Nanostructured Semiconducting Polymer

Sensing Channel Layers

Youngkyoo Kim*1, Chulyeon Lee1, Hyemi Han1,2, Sungho Nam1,3, Hwajeong Kim1,4, Donal D. C. Bradley5

1Organic Nanoelectronics Laboratory and KNU Institute for Nanophotonics Applications (KINPA),

Department of Chemical Engineering, School of Applied Chemical Engineering, Kyungpook National

University, Daegu 41566, Korea, 2Center for Opto-Electronic Materials and Devices, Post-Silicon

Semiconducting Institute, Korea Institute of Science and Technology (KIST), Seoul 02792, Korea, 3Organic

Material Lab., Samsung Advanced Institute of Technology (SAIT), Samsung Electronics Co., Ltd., Suwon

16678, Korea, 4Priority Research Center, Research Institute of Environmental Science & Technology,

Kyungpook National University, Daegu 41566, Korea, 5Department of Physics, Clarendon Laboratory,

University of Oxford, Oxford OX1 3PU, United Kingdom, *ykimm@knu.ac.kr

A paradigm shift toward soft and flexible electronics has been initiated by wide spreading of smart mobile

phones with easy internet access functions and organic light-emitting device (OLED) displays, even though

basic researches on organic electronics with flexible organic thin films have been carried out for the last three

decades. In particular, very recent progress in the fourth industrial innovation, which mostly includes advanced

drones, humanoid robots, autonomous (flying) cars, wearable health monitoring systems, and the like, does

explicitly stress the necessity of soft/flexible electronics. Of various major technologies in soft electronics,

optical detectors have attracted keen attention because of their role like an eye in the front line of such mobile

systems. Although tremendous efforts have been and still being given on conventional inorganic

photodetectors in order to make them flexible, it is recognized that there are fundamental limitations for

achieving real softness because of their intrinsic rigid characteristics. On this account, organic photodetectors

based on semiconducting polymers have been spotlighted because polymers can deliver softness and/or

flexibility depending on their chemical structures. Our group has focused on organic phototransistors with

polymeric bulk heterojunction (BHJ) sensing channel layers which can maximize the optical sensitivity by

forming numerous nanoscale p-n junctions. This presentation will introduce our efforts on organic

phototransistors with flexibility and discuss the nanostructures in the polymeric BHJ sensing channel layers

which have been investigated by employing various techniques including synchrotron radiation grazing

incidence X-ray scattering.

References [1] Y. Kim, C.-S. Ha, Advances in Organic Light-Emitting Device, Trans Tech Publications: Stäfa-Züerich, Switzerland,

2008.

[2] H. Sirringhaus, P. J. Brown, R. H. Friend, M. M. Nielsen, K. Bechgaard, B. M. W. Langeveld-Voss, A. J. H. Spiering,

R. A. Janssen, E. W. Meijer, P. Herwig, D. M. de Leevw, Nature, 401, 685 (1999).

[3] Y. Kim, S. Cook, S. M. Tuladhar, S. A. Choulis, J. Nelson, J. R. Durrant, D. D. C. Bradley, M. Giles, I. McCulloch,

C.-S. Ha, M. Ree, Nat. Mater., 5, 197 (2006).

[4] S. Nam, J. Seo, S. Woo, W. H. Kim, H. Kim, D. D. C. Bradley, Y. Kim, Nat. Commun., 6, 8929 (2015).

[5] H. Hwang, H. Kim, S. Nam, D. D. C. Bradley, C.-S. Ha, Y. Kim, Nanoscale, 3, 2275 (2011).

[6] H. Han, S. Nam, J. Seo, C. Lee, H. Kim, D. D. C. Bradley, C.-S. Ha, Y. Kim, Sci. Rep., 5, 16457 (2015).

[7] S. Nam, H. Han, J. Seo, M. Song, H. Kim, T. D. Anthopoulos, I. McCulloch, D. D. C. Bradley, Y. Kim, Adv. Electron.

Mater., 2, 1600264 (2016).

[8] S. Nam, J. Seo, H. Han, H. Kim, D. D. C. Bradley, Y. Kim, ACS Appl. Mater. Interfaces, 9, 14983 (2017).

[9] S. Nam, S. G. Hahm, D. Khim, H. Kim, T. Sajoto, M. Ree, S. R. Marder, T. D. Anthopoulos, D. D. C. Bradley, Y.

Kim, ACS Appl. Mater. Interfaces, 10, 12921 (2018).

[10] H. Han, C. Lee, H. Kim, Y. Kim, Adv. Funct. Mater., 28, 1800704 (2018).

43

[Sep. 6 (Thursday), GISAS-4]

GISAXS Study of Nanoporous Block Copolymer Thin Films

Hideaki Yokoyama*1, Mizuki Shiojima1 and Kohzo Ito1

1The University of Tokyo, Japan, *yokoyama@molle.k.u-tokyo.ac.jp

Block copolymer consists of different polymers which ends are connected together. Generally, different

polymers are difficult to be mixed with each other and often show phase separation. In case of block copolymer,

phase separation cannot occur in large scale due to boundary of each block. Instead, it forms phase separation

structure in 10 – 100 nm scale, which is called microphase separation. Depending on volume fraction of each

block, various structures such as cylinders or lamellae can be formed [1]. If this structure is used as a template,

nanoporous materials can be obtained. So far, various methods to fabricate nanoporous materials were

developed [2]. Conventional method uses etching to remove a minor block. With this method, well-ordered

pores can be fabricated and their arrangement depends on initial microphase separation structure. Recently, a

new method was developed. In this method, a mixed organic solvent is used to swell block copolymer. The

solvent consists of a common solvent and a selective solvent which swells a minor block only. The common

solvent works as a plasticizer for a major block so that minor domain can be swollen. Next, the common

solvent is removed from the system to freeze the structure of major domain. Finally, the selective solvent is

evaporated, the minor domain shrinks and pores are fabricated. Using the conventional etching method,

nanoporous structure totally depends on block fraction. In contrast, porosity and connectivity of pores can be

tuned by varying composition of the mixed solvent with this new method. Purpose of this research is to

investigate how the nanoporous structure changes for precise structure control. Poly(styrne-b-2-vinylpyridine)

with different block fraction were used and processed with mixtures of methanol and THF. Nanoporous

structure was analyzed with scanning electron microscopy (SEM) and grazing incident x-ray scattering

(GISAXS). The porosity changes when THF, which is a common solvent, concentration in the mixed solvent

increased. At low THF concentration, porosity increased with THF concentration. When THF concentration

was low, isolated pores were packed hexagonally. After that, pores were gradually connected together and

formed random bicontinuous pores. When THF concentration increased more, structure transition occurred

and rod-like structures were formed. From GISAXS results, it was confirmed that these structures were not

locally but entirely formed. These changes in porosity and structure can be explained by swelling ratio of P2VP

domain.

References

[1] M. W. Matsen and F. S. Bates, Macromolecules, 1996, 29 (4), 1091-1098

[2] D. A. Olson, L. Chen, and M. A. Hillmyer, Chem. Mater., 2008, 20, 869-890

44

Visualizing the Spatial Distribution of the Nanostructures in Thin Films Using

GISAXS-CT.

H. Ogawa*1,2,7, Y. Nishikawa3 , M.Takenaka1,7, A. Fujiwara4, T. Kanaya1,5 and M. Takata6,7

1Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan, 2 JST PRESTO, 3Kyoto Institute of

Technology, 4 Kwansei Gakuin University, 5High Energy Accelerator Research Organization, 6Tohoku

University, 7RIKEN SPring-8 Center,*ogawa@scl.kyoto-u.ac.jp

Grazing-incidence small angle X-ray scattering (GISAXS) coupled with computed tomography (CT),

GISAXS-CT enables us to obtain the spatial distribution of the nanostructures in thin films with the high

resolution1). We focused on that visualized images are reconstructed from the intensities relating to each q

component. Since the scattering intensities depend on the q component, information such as size, shape,

surface and interface roughness of nanostructures is contained in the scattering intensities at each q component.

We fabricated thin films with the shape of four characters “F”, “S”, “B”, and “L” on a Silicon (Si)

substrate for the GISAXS-CT measurements, as shown in Figure 1. “F”,

“S”, “B”, and “L” shaped thin films were deposited by an ion beam sputter

coating method using Au, Au/Pt, Pt and Pt/Au materials, respectively.

GISAXS measurements were performed at the first experimental hutch of

the beamline BL03XU at SPring-8, Advanced Softmaterial beamline

(FSBL)2). The X-ray wavelength 𝜆 and sample-detector distance was set to

be 0.1 nm and 2275 mm, respectively. For the reconstruction of images in

the lateral directions using the CT method, the scan range of the sample is

14 mm within the 140 m step size in the direction perpendicular to the

incident beam (y - direction); the step size was comparable to the incident

beam width (the beam size in the horizontal direction). In the rotation scan

, we acquired the images with the step size of 3.0 o for 0.0 o ≤ <

180.0 o. The direction of the incident beam at = 0 o is indicated by an

arrow in Figure 1. Figures 2 (a) ~ 2 (c) show the reconstructing images

derived from the scattered intensities at different q positions (Figure 2(d)),

e.g. different structural information relating to the particle size, interparticle

correlation, the particle shape etc. When we reconstructed the image “F”

part from the scattered intensities at the peak of (qy, qz) = (0.45 nm-1, 0.48

nm-1) which was attributed to the correlation lengths of Au nanoparticles

(Figure 2(a)). To reconstruct the image corresponding to the correlation

length Au/Pt nanoparticles, we succeed in reconstructing the “S” part

dominant image in Figure 2(b). When we reconstructed image from the

intensities at (qy, qz) = (0.95 nm-1, 0.48 nm-1), the “B” part is clearly visible

(Figure 2(c)). Scattering intensities in the higher qy region were highly

attributed to that from Pt nanoparticles due to slow decay with qy-2 dependence. Consequently, these results

suggest that the individual images can be reconstructed from the scattering intensities relating to the particle

size, interparticle correlation, the particle shape3).

References:

[1] M. Kuhlmann, J. M. Feldkamp, J. Patommel, S. V. Roth, A. Timmann, R. Gehrke, P. Müller-Buschbaum, and G.

Schroer Langmuir, 25, 7241-7243 (2009).

[2] H. Ogawa. et al.. Polym. J. 45, 109-116 (2013).

[3] H. Ogawa, Y. Nishikawa, A. Fujiwara, M. Takenaka, Y-C, Wang, T. Kanaya, M. Takata, M. J. Appl. Cryst. 48, 1645-

1650 (2016).

Fig. 1. Optical microscope image of the sputter deposition sample on silicon wafer.

Fig. 2. Two dimensional images in the x - y plane obtained from projections at various q positions in 2D GISAXS images, and (d) 2D GISAXS image from Au and Au/Pt nanoparticles.

45

Model Tungsten Oxide Nanostructures for Battery Applications: Structure

Characterization during Synthesis and In Function

Jae Jin Kim1, Hyo Seon Suh2, Chun Zhou2, Anil U. Mane3, Byeongdu Lee4*, Soojeong Kim1, Jonathan D.

Emery5, Jeffrey W. Elam3, Paul F. Nealey2, Paul Fenter1, Timothy T. Fister1

1Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue,

Argonne, USA, 2Institute for Molecular Engineering, University of Chicago, 5747 South Ellis Avenue,

Chicago, USA, 3Energy Systems Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne,

USA, 4X-ray Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, USA, 5Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive,

Evanston, USA, *blee@anl.gov

Tungsten oxide (WO3−x) nanostructures with hexagonal in-plane arrangements were fabricated by sequential

infiltration synthesis (SIS), using the selective interaction of gas phase precursors with functional groups in

one domain of a block copolymer (BCP) self-assembled template. Such structures are highly desirable for

various practical applications and as model systems for fundamental studies. The nanostructures were

characterized by cross-sectional scanning electron microscopy, grazing-incidence small/wide-angle X-ray

scattering (GISAXS/GIWAXS), and X-ray absorption near edge structure (XANES) measurements at each

stage during the SIS process and subsequent thermal treatments, to provide a comprehensive picture of their

evolution in morphology, crystallography and electronic structure.[1]

In this talk, we first discuss the mechanism of the structure evolution, in particular the critical role of SIS Al2O3

seeds toward modifying the chemical affinity and free volume in a polymer for subsequent infiltration of gas

phase precursors. The insights into SIS growth obtained from this study are valuable to the design and

fabrication of a wide range of targeted nanostructures. We then present variation of the structure upon battery

cyclings, i.e lithiation and delithiation processes. Technical details including sample environment design and

data acquisition tactics to avoid beam damage will be discussed along with scientific insights including

structural stability and response upon the cycling.

References

[1] J. J. Kim et al., Nanoscale 10, 3469–3479 (2018).

46

The spin structure of highly ordered arrangements of magnetic nanoparticles

Asmaa Qdemat*1, Emmanuel Kentzinger1, Jin Xu2, Giuseppe Portale2, Marina Ganeva3, Stefan Mattauch3,

Johan Buitenhuis4, Xiao Sun1, Oleg Petracic1, Ulrich Rücker1, Thomas Brückel1

1 Jülich Centre for Neutron Science (JCNS) and Peter Grünberg Institute (PGI), JARA-FIT,

Forschungszentrum Jülich GmbH, 52425 Jülich, Germany, 2Zernike Institute for Advanced Materials,

Nijenborgh 4, 9747 AG Groningen, The Netherlands, 3Jülich Centre for Neutron Science,

Forschungszentrum Jülich, at Heinz Maier Leibnitz Zentrum MLZ, 85748 Garching, Germany, 4Institute of

Complex Systems (ICS-3), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany,

*a.qdemat@fz-juelich.de

Novel magnetic materials consisting of building blocks on the nanometer length scale along one, two or three

dimensions and in the presence of surfaces and interfaces promise new or enhanced magnetic properties and

functionalities.

Magnetic nanoparticles and their assembly in highly ordered structures are fundamentally interesting regarding

the understanding of magnetic interactions and for a rational design towards potential applications in

information technology as e.g. magnetic data storage media or as material for spintronics. With regard to these

applications, the main aspects of fundamental interest include magnetic anisotropy, Van-der-Waals forces and

interparticle interactions leading to aggregation or even ordered assemblies of nanoparticles.

Long-range ordering between magnetic nanoparticles in two and three-dimensions is obtained by assisted self-

assembly using pre-patterned substrates with a feature-size of the same order of magnitude as the diameter of

the nanoparticles.

This work focuses on the chemical and magnetic characterization of monolayers of CoFe2O4 nanoparticles on

silicon substrates. The system was characterized laterally by Scanning Electron Microscopy (SEM) and

Grazing Incidence Small Angle X-ray Scattering (GISAXS) at the laboratory high brilliance GALAXI

instrument [1] with simulation using the BornAgain software [2]. We deduce both the height profile of the

individual nanoparticles, and a hexagonal ordering between the nanoparticles. Macroscopic magnetization

measurements and polarized neutron reflectometry on a MARIA reflectometer [3] were used to find that the

nanoparticles are weakly magnetized with respect to bulk CoFe2O4 and that a random in plane relative

orientation of the nanoparticle magnetizations is obtained at zero applied field.

Figure 1: A 2-dimensional GISAXS pattern of a monolayer of CoFe2O4 nanoparticles on top of a silicon

substrate (left) and corresponding simulation using the BornAgain software (right).

Also, we report on the characterization of silica nanoparticles that are self-assembled from toluene-based

dispersions on pre-patterned substrates and in flat substrates laterally by Scanning Electron Microscopy (SEM)

and vertically by Grazing Incidence Small Angle X-ray Scattering (GISAXS). Simulation and data analysis is

performed using the Born Again software [2].

47

Figure 2: (a) SEM image of silica nanoparticles inside a pre-structured substrate. And 2-dimensional GISAXS

pattern of silica nanoparticles inside a pre-patterned substrate with the incoming beam oriented (b)

perpendicular and (c) parallel to the stripes, respectively.

References

[1] Jülich Centre for Neutron Science. (2016). GALAXI: Gallium anode low-angle x-ray instrument. Journal

of large-scale research facilities, 2, A61. http://dx.doi.org/10.17815/jlsrf-2-109.

[2] J. Burle, C. Durniak, J. M. Fisher, M. Ganeva, G. Pospelov, W. Van Herck and J. Wuttke, BornAgain –

Software for simulating and fitting X-ray and neutron small-angle scattering at grazing incidence, Version

1.11.0 (2013-2018), http://www.bornagainproject.org (2018).

[3] Jülich Centre for Neutron Science. (2015). MARIA: Magnetic reflectometer with high incident angle.

Journal of large-scale research facilities, 1, A8. http://dx.doi.org/10.17815/jlsrf-1-29.

48

In situ GISAXS Investigations of pH and Temperature Responsive

Block Copolymer Thin Films during Swelling in Water Vapor

Florian Jung*1, Panayiota A. Panteli2, Detlef-M. Smilgies3, Dorthe Posselt4, Constantinos Tsitsilianis5,

Costas S. Patrickios2, Christine M. Papadakis1

1Physics Department, Technical University of Munich, Garching 85748, Germany, 2Department of Chemistry, University of Cyprus, Nicosia 1678, Cyprus,

3Wilson Laboratory, Cornell University, Ithaca 14853, USA, 4Department of Science and Environment, Roskilde University, Roskilde 4000, Denmark,

5Department of Chemical Engineering, University of Patras, Patras 26504, Greece, *florian.jung@ph.tum.de

Responsive block copolymer thin films are of interest for many applications, e.g. as fast sensors or switchable

membranes [1]. Many such systems are based on physical hydrogels, where a stimuli-responsive midblock is

end-capped by hydrophobic end groups. In aqueous solution, the end blocks associate and act as crosslinks

which are bridged by the midblocks. The dynamics of the gel can be tuned by employing temperature

responsive polymers as end blocks. It has been shown that a weak gel is formed below the LCST of the end

blocks, while a frozen network is formed above the LCST [2]. In thin films, a responsive midblock, e.g. a

polyelectrolyte which is pH-responsive, may be used to tune the self-assembly process, while a temperature

change may be used to immobilize the end blocks and to freeze the so created nanostructure. The latter feature

is especially interesting for solvent vapor annealing (SVA), which is a versatile technique to improve long-

range order in polymer thin films and alter its morphology, but with the drawback that non-equilibrium

morphologies are often difficult to preserve during solvent removal [3,4].

In the present work, thin films from the telechelic pentablock terpolymer P(n-BuMA8-co-TEGMA8)-b-

PDMAEMA50-b-PEG46-b-PDMAEMA50-b-P(n-BuMA8-co-TEGMA8) were investigated in-situ during SVA

with water using grazing-incidence small-angle X-ray scattering (GISAXS). The endblocks are statistical

copolymers of the thermoresponsive TEGMA (triethylene glycol methyl ether methacrylate) and the

hydrophobic n-BuMA (n-butyl methacrylate). Increasing the temperature increases its hydrophobicity and thus

leads to a reduced mobility. The intermediate DMAEMA (2-(dimethylamino)ethyl methacrylate) block is a

weak cationic polyelectrolyte, which becomes ionized at low pH values and assumes a stretched conformation.

Moreover, it has an LCST at high pH values, which is why the permanently hydrophilic poly(ethylene glycol)

(PEG) block was added to stabilize the structure under those conditions.

The films of thicknesses of 60-80 nm were prepared via spin coating from aqueous solutions of different pH

values. The films were then subjected to SVA using water vapor, with experiments being performed at various

temperatures. The structural evolutions of the films were followed in-situ with time-resolved GISAXS. The

pH value during film preparation is found to play a major role: Films prepared at high pH values do not show

structural features in the 2D GISAXS maps, even after SVA with water. In contrast, films prepared at low pH

values feature a well-defined spherical morphology, which is enhanced after SVA.

References

[1] I. Tokarev, S. Minko, Soft Matter 5, 511–524 (2009).

[2] C. Tsitsilianis, F. Jung, C. M. Papadakis, C. S. Patrickios et al., Macromolecules 51, 2169–2179 (2018).

[3] D. Posselt, J. Zhang, D.-M. Smilgies, A. V. Berezkin, I. I. Potemkin, C.M. Papadakis, Progr. Polym. Sci.

66, 80-115 (2017).

[4] A. V. Berezkin, F. Jung, D. Posselt, D.-M. Smilgies, C. M. Papadakis, Adv. Funct. Mater., 17606226 (2018).

49

Mechanism of Block-copolymer self-assembly during spin coating revealed by

ultrafast in-situ GISAXS

Giuseppe Portale*1, Guillaume Fleury2, Daniel Hermida-Merino3,

1Zernike Institute for Advanced Materials, University of Groningen, the Netherlands, 2Laboratoire de Chimie

des Polymères Organiques (LCPO), Université de Bordeaux, France, 3DUBBLE CRG BM26@ESRF,

Netherlands Organization for Scientific Research (NWO), Grenoble, France *g.portale@rug.nl

Periodic structures of nanometer length scale obtained by block copolymer (BCP) self-assembly in thin films

constitute a versatile platform [1] for technological applications such as data storage, lithography,

nanostructured membranes, sensors or solar cells. Different methods including dip coating, spin coating, ink-

printing and slot-die coating can be employed to process BCP in thin films. Among them, spin coating is one

of the most versatile technique to process nanostructured block copolymer thin films finding numerous

applications in emerging technological fields such as nanolithography or organic electronics. Despite the

apparently simple use of the spin coating process, the mechanism of phase separation and structuring that

polymeric systems undergo during spin coating can be rather complex and follow a multistage process.

In this contribution we have used a recently developed combined laser/X-ray setup [2] to perform in-situ

synchrotron gracing incidence X-ray scattering (GISAXS) experiments during block copolymer structuring.

In particular, a poly(1,1-dimethyl silacyclobutane)-b-poly(methyl methacrylate) (PDMSB-b-PMMA) BCP has

been studied, showing fast self-assembly behavior. By tuning the processing parameters, this polymer is able

to form highly oriented out-of-equilibrium lamellar structure, characterized by an extremely low degree of

disorder. In order to elucidate the mechanism of formation of such a highly ordered structure, we have

performed simultaneous laser interferometry and GISAXS experiments with millisecond time resolution

during spin coating from THF solution. Our results show a multistage process (comprised of five different

stages) where the formation of transient micellar phases are clearly visible. These short-living micellar phases

undergo subsequent growth and coalescence and their assembly during spin coating is the key step to reach

highly ordered structures. Our observations are partially in line with what has been recently reported in

literature, [3] but present novel features previously never observed experimentally in ultrafast BCP phase

separation.

Figure 1. (left) structure of the PDMSB-b-PMMA block-copolymer. (right) Experimental setup used for in-

situ laser and GISAXS experiments.

References

[1] I. W. Hamley, Prog. Polym. Sci. 34, 1161 (2009).

[2] J. J. van Franeker, D. Hermida‐Merino, C. Gommes, K. Arapov, J.J. Michels, R. A. Janssen, G. Portale

Adv. Func. Mat. 27, 46 (2017)

[3] H. Ogawa, M. Takenaka, T. Miyazaki, A. Fujiwara, B. Lee, K. Shimokita, E. Nishibori, M. Takata,

Macromolecules 49, 3471 (2016).

Laser interferometry

X-rays

A

y

xz

50

Molecular Engineering for Organic Photovoltaics

Hyo Jung Kim*1, Sangmin Chae1, Ahra Yi1, Jiyeon Chli2, Hyun Hwi Lee3,

1Department of Organic Material Science and Engineering, Pusan National University, Busan 46241,

Korea, 2Korea Institute of Machinery and Materials (KIMM), Daejon 34103, Korea, 3Pohang Accelerator

Laboratory, POSTECH, Pohang 37673, Korea, *hyojkim@pusan.ac.kr

We present molecular engineering for Organic Photovoltaics (OPVs) in conjugated polymer systems with fs-

laser, molecular templating growth (MTG) with graphene, and solvent engineering. In case of poly(3-

hexylthiophene)(P3HT) films, face-on favorable nanostructure formed by fs-laser irradiation. The dipole

moment of P3HT could align along the electric field of irradiated laser, which induced face-on stacking of

P3HT polymers in the films. The vertical charge current increased in the fs-laser irradiated region due the

enhancement of face-on stacking. [1-4]

For the face-on favorable stacking of P3HT polymers, we adopted dry transferred graphene as a templating

layer. In contrast to conventional PMMA-assisted wet transferred wet transferred graphene, dry transferred

graphene is found in the current work to be quite suitable for use in the roll-to-roll process due to its lack of

PMMA residue, whose removal would require high-temperature annealing. When we produce a P3HT film

with a thickness of 30 nm, the face-on populations of P3HT were prominent on both the dry and wet transferred

graphene layers. As the film thickness is increased to 50 nm, the face-on population decreased on the wet

transferred graphene surface, but retained high levels on the dry transferred graphene.

Finally, we tried to control crystallinity of P3HT layer by solvent to form ideal BHJ (bulk heterojunction)

structure in Sequential (Sq) process for OPVs. In the Sq process, a bi-layered structure is formed by the

sequential deposition of the acceptor and donor layers, and the final BHJ nanostructure is formed at the

interface between the layers by carrying out an additional procedure involving thermal annealing and swelling.

We investigated the inter-diffusion of acceptor material at the interface in different crystalline structured layers

as a function of gradual thermal annealing. We found that the P3HT films made using a low-boiling-point

solvent had fewer crystalline regions and lots of amorphous regions, which enabled fullerene molecules to

readily penetrate into P3HT layer within a short period of time.

We took grazing-incidence wide-angle X-ray scattering and NEXAFS (Near Edge X-ray Absorption Fine

structure) for detail structural studies.

References

[1] S. Chae, K. H. Jo, S. W. Lee, H.-S. Geum, H. J. Kim, J. Choi, H. H. Lee, Macromol. Chem. Phys. 217,

537-543 (2016).

[2] S. Chae, A. Yi, C. M. Park, W. S. Chang, H. H. Lee, J. Choi, H. J. Kim, ACS Appl. Mater. Interfaces 9,

24422-24427 (2017).

[3] S. Chae, K. Jo, S. J. Won, A. Yi, J. Choi, H. H. Lee, J. H. Kim, H. J. Kim, Adv. Mater. Interfaces 4, 1701099

(2017).

[4] S. Chae, A. Yi, H. H. Lee, J. Choi, H. J. Kim, Journal of Materials Chemistry C (2018, in printing).

51

Spray Deposition of Water-processed Active Layers for Hybrid Solar Cells

Investigated with in situ GISAXS and GIWAXS

Volker Körstgens*1, Christoph Mayr1, Florian Buschek1, Hristo Iglev2, Reinhard Kienberger2,

Stephan V. Roth3,4 and Peter Müller-Buschbaum1

1Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München,

85748 Garching, Germany 2Lehrstuhl für Laser- und Röntgenphysik, Physik-Department,

Technische Universität München, 85748 Garching, Germany 3KTH Royal Institute of Technology,

10044 Stockholm, Sweden 4DESY, 22607 Hamburg, Germany *volker.koerstgens@ph.tum.de

Usually in the development of non-conventional solar cells one aims for highest power conversion efficiencies

and maximum lifetime of devices. Keeping this in the focus of research, often the sustainability of the

production process of the devices is overlooked. However in order to achieve an all-embracing green

technology, the materials applied and the required energy for device fabrication are of importance. Materials

in terms of functional components or as additives in the processing should be non-toxic and environmentally

friendly. In an optimum approach no organic solvents should be used for the coating of any of the layers of the

corresponding devices. High temperature processing steps should be reduced or avoided to improve the energy

payback times of the solar cells. Following this idea, we developed hybrid solar cells with an active layer based

on low temperature processed titanium dioxide and a water-soluble polymer [1]. In our approach TiO2

nanoparticles are produced with laser ablation in liquid in order to initiate a functionalization of TiO2 with the

polymer for the active layer. Combining these TiO2 nanoparticles and water-soluble poly[3-(potassium-6-

hexanoate)thiophene-2,5-diyl] (P3P6T) hybrid solar cells are realized. In order to improve conversion

efficiencies of these devices a vertical compositional gradient of the two components of the active layer was

introduced. For the fabrication of hybrid photovoltaic devices we applied spray-coating as the deposition

method for the active layer which could easily scale-up to industrial cost-effective fabrication. For the

deposition of the active layer with laser-ablated particles spray deposition provides a good control of the film

thickness. The morphology of the active layer is of major importance for the performance of hybrid solar cells.

As we are especially interested in how the morphology changes with ongoing deposition process, we use the

in situ GISAXS technique. This allows us to follow the development of the morphology of the active layer

with high spatial and temporal resolution [2, 3]. Whereas the mesoscale of the active layer for hybrid solar

cells was probed with in situ GISAXS, the crystallinity of the polymer and the inorganic component was

investigated with in situ GIWAXS. The changes of the morphology and the influence on photovoltaic

performance with the introduction of a compositional gradient are discussed. As the synchrotron-based

investigation allowed for a high temporal resolution of 0.1 s, insights into the very first stages of the deposition

process were obtained. From the overall situ study improvements for the spray deposition procedure are

derived that allow for a better control of the morphology of the devices.

References

[1] V. Körstgens, S. Pröller, T. Buchmann, D. Moseguí González, L. Song. Y. Yao, W. Wang, J. Werhahn,

G. Santoro, S.V. Roth, H. Iglev, R. Kienberger and P. Müller-Buschbaum, Nanoscale 7, 2900–2904 (2015).

[2] L. Song, W. Wang, V. Körstgens, D. Moseguí González, Y. Yao, N.K. Minar, J.M. Feckl, K. Peters,

T. Bein, D. Fattakhova-Rohlfing, G. Santoro, S.V. Roth, and P. Müller-Buschbaum, Adv. Funct. Mater. 26,

1498-1506 (2016).

[3] B. Su, H.A. Caller-Guzman, V. Körstgens, Y. Rui, Y. Yao, N. Saxena, G. Santoro, S.V. Roth and

P. Müller-Buschbaum, ACS Apl. Mater. Interfaces 9, 43724-43732 (2017).

52

Drying of electrically conductive Au@PEDOT:PSS hybrid rods studied

with in situ microbeam GISAXS

Peng Zhang*1, Roth Stephan2, Tobias Kraus1,3

1INM–Leibniz Institute for New Materials, Campus D2 2, 66123 Saarbrücken, Germany, 2 Deutsches Elektronen-Synchrotron (DESY), Notkestrasse 85, 22607 Hamburg, Germany, 3 Colloid and Interface Chemistry, Saarland

University, Campus D2 2, 66123 Saarbrücken, Germany, *peng.zhang@leibniz-inm.de

Nanoparticle-based “electronic inks” are suitable to print electrodes for touchscreen panels[1], biosensors[2],

and organic solar cells[3]. “Wet” printing and coating are possible even on soft substrates with complex

geometries, the processes are scalable on existing equipment, and provide short time-to-market. They all have

in common a drying step in which the solvent evaporates and leaves a solid fraction on the substrate. While

the process engineering of drying is well-established, little is known about the microscopic structure formation

in drying nanoparticle films and its effect on the properties (conductivity, mechanical flexibility, etc.) of the

final coating.

We will present a study on gold nanorods (AuNR) that carry a shell of the water-soluble conductive polymer

combination poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), a p-type material

commonly used in organic electronics.[4] Hybrid particles with AuNR cores and PEDOT:PSS shells become

conductive (with a conductivity of 1.01 × 104 S/cm[5]) immediately after drying and are suitable to print

conductive circuitry without sintering. We used an airbrush to spray a dispersion of AuNR@PEDOT:PSS

hybrid rods onto a horizontal substrate and obtained sparse layers of the hybrid rods upon drying. In situ

GISAXS with 2D correlation spectroscopy analysis was used to reconstruct the structure formation in the film.

Upon drying, the hybrid rods first formed assemblies with long-range order and then arranged on the silicon

substrate. The polymer shell with its PEDOT and PSS components phase-separated; a conductive PEDOT

layer and then a non-conductive PSS layer formed around the gold core as the swollen polymer layers dried.

We believe that this sequence contributes to the formation of a conductive network in the particle film that

leads to high conductivity immediately after drying.

References

[1] J. Schneider, P. Rohner, D. Thureja, M. Schmid, P. Galliker, and D. Poulikakos, Advanced Functional

Materials 26, 833 (2016). [2] K. Kubiak, Z. Adamczyk, J. Maciejewska, and M. Oćwieja, J. Phys. Chem. C 120, 11807 (2016). [3] M. Notarianni, K. Vernon, A. Chou, M. Aljada, J. Liu, and N. Motta, Sol. Energy 106, 23 (2014). [4] J. Kim, J. Lee, J. You, M.-S. Park, M. S. A. Hossain, Y. Yamauchi, and J. H. Kim, Materials Horizons 3, 517 (2016). [5] B. Reiser, L. Gonzalez-Garcia, I. Kanelidis, J. H. M. Maurer, and T. Kraus, Chem Sci 7, 4190 (2016).

53

Morphological Investigations on fullerene-free bulk heterojunction blends for

photovoltaic applications

Sebastian Grott*1, Lorenz Biessmann1, Nitin Saxena1, Wei Cao1, Sigrid Bernstroff2, Peter Müller-Buschbaum1

1 Technische Universität München, Physik-Department, Lehrstuhl für Funktionelle Materialien, James-

Franck-Str. 1, 85748 Garching, Germany, 2Elettra Sincrotrone Trieste, 34149 Basovizza, Italy, *sebastian.grott@ph.tum.de

In the last decades organic electronics (OE) have been in the focus of research due to their advantageous

properties. The ease in processablility, applicability of industrial up-scalable and low-cost production methods

and the flexibility of OE offer a wide range of possible application fields. Especially organic photovoltaics

(OPV) have drawn much attention, which originates from much lower energy payback times compared to their

conventional inorganic counterparts and power conversion efficiencies (PCE) surpassing 10 % , making them

a promising candidate to tackle the increasing energy demand. The most widely studied bulk heterojunction

system used for photovoltaic applications is P3HT:PCBM, which is already well understood, offers PCEs of

about 4 to 5 %. In the last decades optimized low-bandgap polymers, like PTB7, PTB7-Th and PBDB-T,

emerged with optimized properties for usage as donor materials. Also their counterparts, the acceptors were

investigated to replace the fullerene derivate by non-fullerene acceptor molecules, like ITIC, optimizing the

photoactive properties of the active layers in photovoltaic devices. Another important step is the morphology

present in the photoactive layer. Since it is known that the exciton diffusion length within the active layer of

bulk-heterojunction devices is about 10 nm the inner morphology and extraction pathways are key to an

efficient photovoltaic device. Within this study we investigate the morphological changes upon variation of

the active layer composition of photoactive thin films based on the bulk heterojunction system of PBDB-

T:ITIC and the evolution of morphological changes during the functional stacking of a photovoltaic device

caused by the building process. This is done by utilizing grazing incidence small angle X-ray scattering

(GISAXS) [1]. This technique gives insight into the applied layers of the built OPV. Making use of the

synchrotron light source ELETTRA in Italy, we are able to study the morphological changes during fabrication

of the individual layers of organic solar cell devices. The acquired data sets are evaluated using the software

DPDAK [2].

References

[1] A. Hexemer, P. Müller-Buschbaum, IUCrJ 2, 106-125 (2015).

[2] G. Benecke, et al., J. Appl. Crystallogr. 47, 1797-1803 (2014).

54

Tacticity Effects on Thin Film Morphologies of Crystalline-Crystalline

Brush Diblock Copolymers

Hoyeol Lee1, Takuya isono2, Kana Miyachi2, Yusuke Satoh2, Toyoji Kakuchi2,

Toshifumi Satoh2,*, and Moonhor Ree1,*,

1Faculty of Engineering and Graduate School of Chemical Sciences and Engineering and Frontier

Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan, 2Research

Center for Polymer Science, School of Materials and Engineering, Changchun University of Science and

Technology (CUST), Weixing Road 7989, Changchun, Jilin 130022, China, 3Department of Chemistry,

Division of Advanced Materials Science, and Polymer Research Institute, Pohang University of Science and

Technology, Pohang 37673, Republic of Korea, *satoh@eng.hokudai.ac.jp; ree@postech.ac.kr

A series of brush block copolymers consisting of poly(decyl glycidyl ether) and poly(10-hydroxyldecyl

glycidyl ether) (PHDGE) blocks, having four different types of chain tacticity, were investigated in the aspect

of tacticity-morphology correlationships. Their morphologies were investigated in detail by using synchrotron

grazing incidence X-ray scattering (GIXS) technique. The GIXS measurements were conducted in an in-situ

base during cooling run from the melt state and subsequent reheating run. In addition, the polymers were

examined differential scanning calorimetry during cooling run from the melt state and reheating run. In

particular, the measured in-situ GIXS (small- and wide-angle scattering) data were attempted to be analyzed

in detail. The GIXS and DSC analysis results are discussed in the views of crystallization-induced phase-

separation and overall crystallization considering the impact of tacticities.

55

Morphological properties of air-brush spray deposited enzymatic cellulose thin

films: a GISAXS study

Wiebke Ohm1*, André Rothkirch1, Pallavi Pandit1, Volker Körstgens2, Peter Müller-Buschbaum2, Ramiro

Rojas3,5, Shun Yu3,5, Calvin J. Brett1,4,5, Daniel L. Söderberg4,5, Stephan V. Roth1,3

1Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany, 2Lehrstuhl für

Funktionelle Materialien, Physik-Department, Technische Universität München, James-Franck-Str. 1, 85748

Garching, Germany, 3KTH Royal Institute of Technology, Department of Fibre and Polymer Technology,

Teknikringen 56-58, SE-100 44 Stockholm, Sweden, 4KTH Royal Institute of Technology, Department of

Mechanics, Osquars backe 18, SE-100 44 Stockholm, Sweden, 5Wallenberg Wood Science Center, KTH

Royal Institute of Technology, SE-100 44 Stockholm, Sweden,

*wiebke.ohm@desy.de

Flexible biopolymer substrates based on cellulose nanofibrils (CNFs) are gaining wide interest for

nanotechnology such as organic electronics, solar cells or diagnostics since they present a renewable and

sustainable replacement for synthetic polymers. For effective industrial fabrication, both the controlled

arrangement of the CNFs during the deposition process as well as the use of an industrial compatible deposition

process are crucial. Air-brush spray deposition is a versatile deposition technique that fulfils industrial demands

[1-2] and was thus chosen for preparation of CNF thin films.

We investigated all spray-deposited cellulose layers from aqueous CNF solution. Grazing incidence small and

wide angle x-ray scattering (GISAXS and GIWAXS) measurements in combination with atomic force

microscopy (AFM) was chosen to reveal the layer structure and morphology of the enzymatic CNF films, as

they present appropriate methods [3]. A thickness range between 86 nm and 2.1 µm was realized by applying

different spray coating procedures. For each spray coating step, layer build-up, surface topography,

crystallinity as well as the nanoscale structure are analyzed.

The main results are as follows: Without intermittent drying, the film thickness saturates; with intermittent

drying a linear increase of layer thickness with the number of spray pulses is realized, which is preferable for

layer-by-layer coating. A percolated CNF network was always observed. The crystallinity remains unchanged

while showing a strong texturing of the film. Analyzing the nanoscale structures, we could identify three

distinct structure sizes. Our results indicate that the smallest building blocks increasingly contribute to the

morphology inside the CNF network for thicker films, showing the importance of tailoring the CNF [4].

References

[1] Roth, S. V., J. Phys. Condens. Matter 28, 403003 (2016).

[2] Blell, R. et al., ACS Nano acsnano.6b04191 (2016).

[3] Ehmann, H. M. A. et al., ACS Macro Lett. 713–716 (2015).

[4] Zhu, H. et al., Curr. Org. Chem. 16, 1871–1875 (2012).

56

[Sep. 7 (Friday), GISAS-7]

Thin film crystallization: role of substrate and temperature gradient

Basab Chattopadhyay*1

1Norwegian University of Science and Technology (NTNU), India, *basab.chattopadhyay@ntnu.no

An increase or modification of structural order in the vicinity of a solid substrate is known for a wide range of

materials.For molecular materials, crystallizing on a solid surface it has been observed that new polymorphic

forms may exist near the interface with the substrate that have structures different to those observed in the bulk.

The control of such polymorphic forms is challenging and it is dependent on the post-deposition processing,

film thickness and nature of the surface. Rational design strategies has enabled synthesis of promising new

functional materials.However, the physical properties of such materials are highly dependent on molecular and

crystalline structures besides other factors like structural disorder, density of defects, purity, and temperature.

Thus, the reproducibility, reliability, and stability of the devices fabricated using such materials is strongly

correlated to their final crystal structure. In this context, crystallization promoted by the substrate and

processing in a temperature gradient enable one to access new forms or have an enhanced control of the

predefined structure. On one hand, the resulting forms have been found to have high phase purity and exhibit

remarkable stability over time whereas in certain cases they are transient in nature.1, 2 The current state of

understanding concerning the role of the substrate and temperature gradient in stabilizing certain polymorphic

phases will be presented, giving examples of systems, discussing their origins, and open scientific questions.

References

[1] A. O. F. Jones, B. Chattopadhyay, Y. H. Geerts, R. Resel, Adv. Funct. Mater. 26, 2233–2255 (2017).

[2] B. Chattopadhyay, L. Jacobs, P. Panini, I. Salzmann, R. Resel, Y. H. Geerts, Cryst. Growth Des. 18, 1272-

1277 (2018)

57

Swelling Behavior and Proton Conductivity of Polyelectrolytes in Thin Films

Keiji Tanaka *1

1 Department of Applied Chemistry and International Institute for Carbon-Neutral Energy Research (WPI-

I2CNER), Kyushu University, Fukuoka 819-0395, Japan, * k-tanaka@cstf.kyushu-u.ac.jp

In recent years, a polymer electrolyte Nafion® composed of hydrophobic Teflon skeleton and perfluoro side

chains having sulfonic acid groups attracts a great deal of attention in relation to environmental energy

problems. In this presentation, we will discuss the swelling behavior and proton conductivity for Nafion® and

Aquivion® thin films with our goal of miniaturizing solid polymer fuel cells. Polyelectrolyte films with a

thickness of approximately 50 nm was prepared on a solid substrate covered with SiOx by a spin-coating

method. After the film formation, the film was sufficiently dried in vacuum. Then, they were immersed into

water. The swelling ratio (σ), which is defined as the thickness ratio in dried and swollen state, increased with

increasing time, meaning that water molecules were diffused into the films and sorbed there. The time at

which the film reaches into an equilibrium swelling state was shorter for Nafion® than Aquivion® , which

possesses shorter side chains. In addition, the equilibrium σ value was larger for Nafion® than Aquivion® .

Thus, it is clear that the swelling kinetics is slower for Aquivion® than Nafion® . Finally, the in-plane proton

conductivity (σ) in the thin films, being in an equilibrium swollen state, was examined by alternating current

impedance measurement as a function of thickness. The σ value increased with decreasing thickness due to

the manifestation of the interfacial effect for both cases. Interestingly, the σ value was larger for Aquivion®

than Nafion® at a given thickness.

58

Analysis of depth-dependent structures in polymer thin films by GISAXS

utilizing tender X-ray

K.Yamamoto*1, Aikawa1. I.Saito1, and E. Miura1

1Graduate School of Engineering, Department of Life Science and Applied Chemistry, Gokiso-cho, Showa-

ku, Nagoya, 466-8555 JAPAN, *yamamoto.katsuhiro@nitech.ac.jp

Grazing incidence small-angle X-ray scattering method has been widely used to reveal nano-structures,

crystalline orientation, microphase-separation, of polymeric thin films polymeric material. Commonly, SAXS

and GISAXS measurements have been conducted using X-ray energies of 8–13 keV (hard X-ray). However,

under these conditions, the X-ray penetration depth rapidly reaches the thickness scale of the polymeric

materials in the vicinity of the critical angle of total reflectionacat the surface, making depth-resolved GISAXS

measurements with hard X-rays totally impractical. Okuda et al.1 demonstrated a depth-sensitive GISAXS

technique using soft X-rays with an energy of 1.77 keV. These investigations of structural relaxation near the

surface and the dynamic heterogeneity of polymer chains in a thin film. At even lower X-ray photon energies

(near the adsorption K edges of the soft material e.g., the oxygen, nitrogen, and carbon K edges), the fine

structure of the adsorption edge can be utilized in GISAXS. The grazing incidence resonant soft X-ray

scattering (GI-RSoXS)2 has been applied for

polymer blend thin films with low contrast in

the real part of the refractive index for the

hard X-rays but with significant differences

in the soft X-ray regime. Furthermore, the X-

ray penetration depth is drastically affected

by the changes in the X-ray photon energy

across the K-edge. The surface- and volume

sensitive structure of polymer blend filmshad

been analyzed using this technique.

The X-ray penetration depthLis defined as

the depth at which the X-ray intensity is

attenuated by 1/e. The value of Λ depends on

X-ray energy (in other words, wavelength λ),

the critical angle, αc, of total reflection, and the angle of incidence αi. Under experimental conditions with the

ideally flat surface, Λ is given by where β is the imaginary part of the complex refractive index.

The critical angle δ that specifies the deviation from the real part of the refractive index αc = √2𝛿.

We performed GISAXS measurement with low energy (tender) X-ray (around 2.40 keV) to precisely

investigate the depth profile of a microphase separated structure (hexagonally packed cylinders3, parallel

lamellar4, and depth-dependent liquid crystalline orientation5) of some block copolymers and/or liquid

crystalline polymers thin films on a silicon wafer. Here we present recent works of analysis on depth

dependency of the nano-structure in polymeric thin films, block copolymers and orientation of liquid

crystalline polymers.

References

[1] H. Okuda, S. Sakurai, et al.J. Appl. Cryst.2011, 44, 380.

[2] M. A. Ruderer, C. Wang, A. Hexemer, P. M-Buschbaum, P. et al.Macromolecules2013, 46, 4491.

[3] I. Saito, K. Yamamoto, et al.Macromolecules2015, 48, 8190.

[4] I. Saito, K. Yamamoto, et al.Polymer J.2016, 48, 399.

[5] D. Tanaka, K. Yamamoto, S. Nagano, T. Seki, et al.Langmuir2016, 32, 3737.

Figure 1. Penetration depth as a function of incident angle (left) and X-ray energy for typical poly(methacrylate)s.

59

In-situ GIXD Studies of the Conjugated Polymer-Phospholipid Composite

Films: Temperature and Gas Adsorption Effect

Juran Noh1, Dabin Lee1, Seong-hun Lee2, Chohee Hyun2, Bomi Lee1, Juhyun Park1* and Tae Joo Shin2*

1School of Chemical Engineering and Materials Science, Institute of Energy Converting Soft

Materials, Chung-Ang University, Seoul 06974, Republic of Korea, 2UNIST Central Research

Facilities & School of Natural Science, Ulsan National Institute of Science and Technology

(UNIST), Ulsan 44919, Republic of Korea, *tjshin@unist.ac.kr

Conjugated polymers, which have a band gap between their valence and conduction bands, can absorb energy

upon light irradiation with electron excitation from the valence to conduction band. The absorbed energy can

be emitted as light or heat, or charge carriers (electrons and holes) can be transferred to surroundings to

participate in photocatalytic reactions [1]. When they are in forms of nanomaterials, significantly enhanced

luminescence intensity and photostability were expected, in which the conjugated polymer chains can be

separated from surrounding continuous, free-flow media as a discontinuous phase, thereby considerably

reducing the radiationless decay and photodegradation. The fluorescence quantum yield of conjugated polymer

nanoparticles could be 39% in an aqueous medium, which was comparable to that of conjugated polymers

dissolved in non-polar solvents (40~50%) but much higher than that of conjugated polymer electrolytes (<5%)

[2]. Therefore, the conjugated polymers of nanomaterials forms have attracted significant attention in aqueous-

based applications (fluorescence imaging, photoaccoustic imaging, photothermal therapy, and etc.) and

photocatalytic reactions (water splitting for hydrogen generation and organic pollutant degradation) [3-7]. In

this study, the conjugated polymer nanoparticles made of the conjugated polymer and phospholipids were used

to prolong the photostabiliby of the conjugated backbones. The structural studies by the in-situ grazing-

incidence X-ray diffraction (GIXD) techniques under various temperature and gas conditions will be discussed

in detail.

References

[1] Y.-H. Ha, J. E. Lee, M.-C. Hwang, Y. J. Kim, J. -H. Lee, C. E. Park, Y. -H. Kim, Macromol. Res. 24, 457-

462 (2016); J. Park, J. Ind. Eng. Chem. 51, 27-43 (2017)

[2] J. Yoon, J. Kwag, T. J. Shin, J. Park, Y. M. Lee, Y. Lee, J. Park, J. Heo, C. Joo, T. J. Park, S. Kim, J. Park,

Adv. Mater. 26, 4559-4564 (2014).

[3] C. Wu, D. T. Chiu, Angew. Chem. Int. Ed. 52, 3086-3109 (2013; M. Elsabahy, G. S. Heo, S. M. Lim, G.

R. Sun, K. L. Wooley, Chem. Rev. 115, 10967-11011 (2015).

[4] K. Pu, A. J. Shuhendler, J. V. Jokerst, J. Mei, S. S. Gambhir, Z. Bao, J. Rao, Nat. Nanotechnol. 9, 233-239

(2014).

[5] S. Ghosh, N. A. Kouamé, L. Ramos, S. Remita, A. Dazzi, A. Deniset-Besseau, P. Beaunier, F. Goubard, P.

-H. Aubert, H. Remita, Nat. Mater., 14, 505-511 (2015).

[6] Y. –W. Su, W. -H. Lin, Y. -J. Hsu, K. -H. Wei, Small, 10, 4427-4442 (2014).

[7] J. Zhang, Y. Chen, X. Wang, Energy Environ. Sci. 8, 3092-3108 (2015).

Poster

60

Poster [Sep. 4 (Tuesday)]

GISAXS study on Micro-Structure of Layer-by-Layer Self-Assembly multilayer

Chunming Yang*1, Nie Zhao1, Jin Xin1, Guifei Li2, Kunxi Zhang*2, Ping Zhou1, Yuzhu Wang1, Xiuhong

Li1, Jie Wang1, Jingbo Li2 and Fenggang Bian*1

1 Shanghai Institute of Applied Physics, Chinese Academy of Sciences, China, * yangchunming@sinap.ac.cn

Grazing incidence small angle X-ray scattering (GISAXS) is a powerful tool for the study of surface and

internal structures of the films. In SAXS beamline (BL16B1) at SSRF, GISAXS opens to users since 2012,

which has been successfully applied to nano-structured condensed matter samples in the thin-film geometry

[1]. We have also developed new software for the GISAXS data pretreatment, called as “Pre-GISAXS” (Fig.

1). It is based on the GISAXS technique, we have characterized the surface structure of layer-by-layer self-

assembly Chitosan/Poly(ʟ-glutamic acid) (and Chitosan/Poly(styrene)-block-poly(acrylic acid)) multilayer.

An ordering long period structure within in-plane direction was firstly observed in polyelectrolyte multilayer,

which could be attributed to the specific domain on surface region of films. In the domain, nano-droplets

formed by polyeletrolyte molecules were arranged orderly along the free surface of films [2]. This ordering

structure was gradually disappeared with increasing bilayer number due to the complex coacervation of the

droplets into larger domain. Furthermore, resonant diffuse scattering in GISAXS pattern was observed to

become evident as the bilayer number of polyelectrolyte multilayer was increased, which could be a partially

roughness propagation effect between interface and surface and was always related to growth behavior during

self-assembly process., In addition, it is interested that the lateral cutoff length of resonant diffuse scattering

for these polyelectrolyte films was observed to be comparable to the long period value of the ordering

nanodroplets in polyelectrolyte multilayer, which could be one reason for why the long-period order can be

propagated from interface over several bilayers. Fig. 1: program interface of “Pre-GISAXS”. Fig. 2: Figure

6Figure 5 2D GISAXS patterns of PEM film as a function of deposition bilayers

References

[1] Nie, Zhao, Chunming Yang*, Qian Zhang, Xueming Lu, Yuzhu Wang*, Jie Wang*, Journal of Applied

Physics, 2014, 115(20), 204311.

[2] Nie Zhao, Chunming Yang*, Yuzhu Wang, Binyu Zhao, Fenggang Bian, Xiuhong Li, Jie Wang*, Materials

Science & Engineering C, 2016, 58, 352-358.

61

Characterization of thin-film structure and memory property of conducting

poly(p-phenylene)-block-polythiophene and poly(dihexyl dipropargyl malonate)

Hoyeol Lee1, Changsub Kim1, Xiang Li1, Moonhor Ree*1,

1Department of Chemistry, Division of Advanced Materials Science, Pohang University of Science and

Technology, Pohang 790-784, Republic of Korea. *ree@postech.ac.kr

It is well known that fully conjugated conducting polymers can form well-defined nanostructure via self-

assemblies. There are strong correlation between electrical property of the conducting polymers and their

nanostructure [1-2]. In this study, we report memory characteristics and thin-film morphology of a diblock

copolymer, poly(p-phenylene)-block-polythiophene (PPP-b-BT), and a homopolymer, poly(dihexyl

dipropargyl malonate) (PDHDPM). Write-Once-Read-Many (WORM) and Dynamic Random Access

Memory (DRAM) type memory behavior was found in PPP-b-BT; It showed WORM when the thickness of

the thin-film was thinner (~10 nm). DRAM was found at the thin-film thickness reached ~20 nm. However, in

case of PDHDPM, DRAM type memory behavior was not detected. Detailed structural investigations of thin-

film were performed by utilizing grazing-incidence X-ray scattering (GIXS) and X-ray Reflectivity (XRR), in

Pohang Accelerator Laboratory (PAL). In small angle region, it was found that PPP-b-BT have lamellar

morphology; this is due to phase separation between two blocks. In wide angle region, mixed edge-on/face-on

structure was found. In case of PDHDPM, featureless pattern was found in small angle region, and isotropic

ring type pattern was found in wide angle region.

References

[1] S. Fukuta, J. Seo, H. Lee, H. Kim, Y. Kim, M. Ree, T. Higashihara, Macromolecules 50, 3, 891-899 (2017)

[2] D. Wi, J. Kim, H. Lee, N. –G. Kang, J. Lee, M. –J. Kim, J. –S. Lee, M. Ree, J. Mater. Chem. C 4, 2017-

2027 (2016)

62

Supramolecular assemblies with p-n junction containing organic semiconductors

via cylindrical nanoconfinement

Wongi Park1, Minyong Yang1, Hyungju Ahn2, Tae Joo Shin3, Beatriz Feringán4, Teresa Sierra4, Raquel

Gimenez4 and Dong Ki Yoon1,5*

1Graduate School of Nanoscience and Technology, KAIST, Daejeon 34141, Republic of Korea 2Pohang Accelerator Laboratory, POSTECH, Pohang 37673, Republic of Korea

3UNIST Central Research Facilities & School of Natural Science, UNIST, Ulsan 44919, Republic of Korea 4Departamento de Química Orgánica, Instituto de Ciencia de Materiales de Aragon (ICMA), Facultad de

Ciencias, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain 5Department of Chemistry and KINC, KAIST, Daejeon 34141, Republic of Korea,

*nandk@kaist.ac.kr

Organic semiconductors have attracting great attention as next-generation semiconductor materials, for

example, in flexible electronics and organic photovoltaics. Organic semiconductors can be processed at low

cost by solution process, and the possibility of material modification by chemical synthesis varies. However,

if the orientation of the organic semiconductor crystal cannot be controlled successfully, it cannot exhibit the

highest performance. In order to solve this problem, people attached a flexible alkyl tail to the terminal of

organic semiconductor molecules to give a liquid crystal characteristic and studied the orientation of the

organic semiconductor. A representative example is the discotic molecule. However, these discotic molecules

are known to have selective electrical properties; electrons or holes. Most discotic molecules are p-type

molecules and ambipolar charge transport phenomena are extremely rare.

Recently, ambipolar discotic molecules have been reported through a p-n junction at the molecular level. They

showed high electrical properties for both electron and hole. However, due to the lack of a long range order,

they failed to be uniformly oriented, and their structure could not be precisely investigated.

In this experiment, we succeeded in uniformly orienting ambipolar discotic molecules using porous anodic

aluminum oxide (AAO) nanochannel. In particular, supramolecular structure was controlled by controlling the

size and surface chemistry of AAO nanochannel, and grazing incidence X-ray diffraction (GIXD) analysis was

successfully performed at the molecular level.

References

[1] Feringan et al, J. Am. Chem. Soc., 138(38), 12511 (2016) [2]

[2] Zhang et al, ACS nano, 9(2), 1759 (2015)

63

Microdomain orientation of block copolymer controlled by surface modification

extent using random copolymer brushes

Wooseop Lee*1, Seongjin Park, Du Yeol Ryu,

1Yonsei University, Korea, *leewooseop@yonsei.ac.kr

Perpendicular orientation of lamella-forming block copolymer (BCP) microdomains is necessary for the next-

generation nanoimprinting and lithography. Many researchers have suggested various techniques to establish

perpendicular nanostructures by controlling the interfacial interactions between BCP film and substrate. A

surface modification method using random copolymer brush is attractive due to its simplicity and effectiveness.

Hydroxyl-functionalized random copolymer brush chains were attached to the substrate by covalent bond.

Previous studies have thoroughly observed the influence of mole fractions or molecular weights of random

copolymer brush on the perpendicular orientation of BCP film. In this study, the interaction between substrate

and the block copolymer were controlled by covering the Si wafer surface with random copolymer. On these

modified substrates, PS-b-PMMA thin film was spun-cast with fine-tuned thickness and subsequently

thermally-annealed to form its equilibrium structure (lamella). We observed the thickness window of vertical

orientation and assessed the appropriate parametric extent of surface energy modification. The result provides

the idea of the proper extent of surface modification in order to achieve perpendicular orientation of BCP for

nanopattern fabrication.

64

Structural Details of Silicate Nanoparticles

Kuan Hoon Ngoi*1, Li Xiang1, Chin Hua Chia1, Moonhor Ree1

1POSTECH, Malaysia, *ngoikh@postech.ac.kr

A series of silicate nanoparticles were synthesized with varying compositions in solutions by polymerizations.

The chemical compositions and characteristics of synthesized particles were characterized by using various

analytical intrumentations: nuclear magnetic resonance and infrared spectrometers, thermogravimeter, and

differential scanning calorimeter. Post-thermal treatments were performed. Their structural details were

investigated by synchrotron solution X-ray scattering and grazing incidence X-ray scattering in order to get

structural shape, structural parameter details, and size distribution. All results will be discussed in the views of

polymerization condition, chemical composition, shape, size and size distribution, and morphology.

65

Thin Film Morphologies and Properties of

Rotaxane-Containing Polymers and Block Copolymers

Brian J. Ree1, Daisuke Aoki2, Toshifumi Satoh*1, Toshikazu Takata*2, Moonhor Ree*3

1Laboratory of Polymer Chemistry, Faculty of Engineering, Division of Applied Chemistry, Graduate School

of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Japan 2Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552, Japan

3Department of Chemistry, Division of Advanced Materials Science, Pohang University of Science and

Technology, Pohang 790-784, Republic of Korea. *satoh@eng.hokudai.ac.jp, takata.t.ab@m.titech.ac.jp,

ree@postech.ac.kr

Supramolecules, in particular polymer-based supramolecules have gained great attention because of (i)

challenges in polymer synthetic chemistry, (ii) expectations on unusual, unique structure and properties, and

(iii) possibility on new potential applications. In this study, rotaxane-containing polymers and their block

copolymers were prepared: one series of polymers are poly(-caprolactone)s with [2]rotaxane moiety in a fixed

mode and a mobile mode through the polymer backbone axle; another series of polymers are poly(-

valerolactone)s blocked with [2]rotaxane-linked polystyrene in a fixed mode and a mobile mode. These

interesting polymeric suparmolecules were subjected to the investigation of film morphologies and thermal

properties. The nanoscale thin film morphologies were examined by synchrotron grazing incidence small and

wide angle scatterings and X-ray reflectivity. The thermally-induced phase-transitions were analyzed using

differential scanning calorimetry. In addition, micelle formation behaviors were studied. The obtained thin

film morphologies, phase-transition and micelle formations will be discussed from the view of molecular

topology effects as well as of rotaxane presence and mobility effects.

66

Controlled Structures of π-Conjugated Semiconducting Polymers and Their

Deformability in Stretchable Field-Effect Transistors

Kiyeon Sim 1, Mingyuan Pei, Hoichang Yang 1,

1 Department of Applied Organic Materials Engineering, Inha University, Incheon 22212, South Korea, * rlduso3ozz@gmail.com

Ordering structures of molecular weight (MW)- and regioregularity-controlled poly(3-hexyl thiophene)s

(P3HTs), as solution-processable semiconducting polymers, are studied using grazing-incidence X-ray

diffraction (GIXD) and morphological analyses. P3HTs are synthesized and sequentially fractionated to have

well-controlled MWs (4 80 kDa), narrow molecular weight distribution (weight-average MW/number-

average MW < 1.5) and high regioregularity (>95%). Self-assembly of the conjugated chains from dilute P3HT

and P3HT-based blend solutions is significantly affected by the intrinsic -conjugated backbone structures,

causing different intra-, inter-molecular, and inter-domain charge-carrier transport along the ordered chains in

cast films. Solution-cast P3HT and blend films including highly-ordered and -interconnected structures

between -conjugated domains are used as channel layers in an organic field-effect transistor (OFET)

platform, specifically, with stretchable electrodes; solution-processable silver nanowire-based patterns can

yield high and stable conductivity below 50% strain. Optimized P3HT-based OFETs show high charge-carrier

mobility values up to 0.1 cm2/Vs, which can be maintained under stretching. In particular, the structural

deformability of these semiconducting films is systematically investigated using in-situ GIXD analysis.

67

Investigation of Bulk Heterojunction Nanostructure in Organic Solar Cells

Sooyong Lee1, Chulyeon Lee1, Hwajeong Kim2, Youngkyoo Kim*1

1Organic Nanoelectronics Laboratory and KNU Institute for Nanophotonics Applications (KINPA),

Department of Chemical Engineering, School of Applied Chemical Engineering, Kyungpook National

University, Daegu 41566, Republic of Korea, 2Research Institute of Environmental Science & Technology,

Kyungpook National University, Daegu 41566, Republic of Korea, *ykimm@knu.ac.kr

Organic solar cells based on polymeric bulk heterojunction-type light absorption layers have been

extensively studied because of their feasibility for low-temperature manufacturing of flexible solar

modules by employing easy wet-processes such as spin-coating, gravure printing, ink-jet printing,

spray coating, slot-die coating, etc. In particular, such polymer solar cells based on plastic film

substrates benefit high design freedom for solar module shapes. The power conversion efficiency of

polymer solar cells has recently passed 13% and now tackled ca. 14-15% by introducing

polymer:nonfullerene bulk heterojunction light absorption layers. However, the stability of all

organic solar cells, irrespective of the type of light absorption layers, is still under investigation for

improvement. Our group has also focused on the improved stability by introducing various

approaches. One of our particular approaches includes physical pressing processes for polymer solar

cells and making micro-patterns during the physical pressing process. In this presentation, the

nanostructure changes in polymer solar cells, which were investigated by employing various

techniques including synchrotron radiation grazing incidence X-ray scattering (diffraction) methods,

will be discussed together with the device performances of recent high efficiency polymer solar cells.

References

[1] S. L. Lee, J. Y. Seo, J. H. Jeong, C. Y. Lee, M. H. Song, H. J. Kim, Y. K. Kim, Curr. Photovoltaic Res. 5,

69-74 (2017).

[2] S. L. Lee, S. H. Nam, J. Y. Seo, J. H. Jeong, H. J. Kim, S. H. Woo, Y. K. Kim, Energy Technol. 2, 713-

720 (2014).

[3] H. J. Kim, S. H. Nam, J. H. Jeong, S. Y. Lee, J. Y. Seo, H. M. Han, Y. K. Kim, Korean J. Chem. Eng. 31,

1095-1104 (2014).

[4] S. H. Nam, M. J. Shin, H. J. Kim, Y. K. Kim, Nanoscale 2, 2384-2389 (2010).

[5] S. Y. Lee, S. H. Nam, H. J. Kim, Y. K. Kim, ACS Sustainable Chem. Eng. 1, 1280-1285 (2013).

68

Effect of Moving Branching Point of Side Chain in NDI-based Polymers on

Their Electrical Properties and All-PSCs Performance

Hoseon You1, Jinseong Kim1, Donguk Kim1, Felix Sunjoo Kim*2, and Bumjoon J. Kim*1

1Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and

Technology (KAIST), Daejeon 34141, Republic of Korea, 2School of Chemical Engineering and Materials

Science, Chung-Ang University (CAU), Seoul 06974, Republic of Korea, *bumjoonkim@kaist.ac.kr,

fskim@cau.ac.kr

Branching point of side chain in naphthalene diimide (NDI)-based conjugated polymers was systematically

controlled by incorporating different side chains, i.e. 2-hexyloctyl (P(NDI1-T)), 3-hexylnonyl (P(NDI2-T)),

4-hexyldecyl (P(NDI3-T)), and 5-hexylundecyl (P(NDI4-T)). The effect of branching point engineering on

their properties was investigated in terms of optical, electrochemical, structural and charge transport ability.

Interestingly, NDI-based polymers showed enhanced intermolecular interaction in solution as the branching

point was moved away from conjugated backbones. As-cast film of P(NDI3-T) and P(NDI4-T) exhibited

ordered lamellar diffraction up to third order. After thermal-annealing film, molecular ordering was gradually

developed in both face-on and edge-on directions. Consequently, P(NDI4-T) exhibited the highest electron

mobility of 0.22 cm2 V−1 s−1 along with reduced activation energy in organic field-effect transistor. When the

series of polymers was applied in all-polymer solar cell, the highest JSC was achieved in P(NDI3-T) blend film

with PBDTTTPD as a donor due to broader light absorption ability and enhanced electrical property of

P(NDI3-T), resulting in power conversion efficiency of 7.1 %.

69

Poster [Sep. 5 (Wednesday)]

The study on dark-conglomerate phases of bent-shaped liquid crystal molecules

in nano-confined geometry

Minyong Yang1, Wongi Park1, Mohamed Alaasar3,4, Carsten Tschierske3, and Dong Ki Yoon1,2*

1Graduate School of Nanoscience and Technology and Department of Chemistry, KAIST, Daejeon, 34141,

Korea. 2Department of Chemistry, KAIST, Daejeon, 34141, Korea. 3Institute of Chemistry, Martin Luther

University Halle-Wittenberg, Kurt Mothes Str. 2, 06120, Germany. 4Department of Chemistry, Faculty of

Science, Cairo University, Giza, Egypt

Dark conglomerate phase, especially observed within bent-shapes liquid crystal materials, is an intriguing

optical material for its layer-induced optical chirality, despite its achiral building block [1]. By the assembling

mechanism of bent-shaped liquid crystal molecules, dark conglomerate phase can be subdivided into three

major sub group; Helical Nano-filament (HNF) phase, sponge-like phase, and Helical Nano-crystallite (HNC)

phase. Among them, HNC phase can be specially generated with typical molecular design in which a bulky

substituent is positioned in central part of molecule and peripheral mesogenic wings are hardly linked with pi-

conjugated planar bond [2]. In this work, to study on the nature of self-assembly of bent-shaped liquid crystal

molecules in dark conglomerate phase, we used confined anodic aluminum oxide (AAO) nano-channel as a

confined geometry to reveal the assembling nature of HNC phase and to distinguish the dark conglomerate

phases in terms of molecular packing structure.

Fig. 1. Hierarchical structure of three typical Dark Conglomerate phases made of bent-shaped liquid

crystal molecule with intrinsic polarity.

References

[1] L. E. Hough et al, Science, 325, 452 (2009).

[2] M. Alaasar et al, Chem. Eur. J. 22, 6583 (2016)

Sponge phase

HNF phase

HNC phase

Smectic

layers

p

70

Ordering and Charge-Carrier Transport of Diketopyrrolopyrrole-based

Polymers with Alkyl Side Chains Including Ester Linkers

Mingyuan Pei*1, Hoichang Yang1, Min Ju Chon2, and Dong Hoon Choi2

1Inha University, Korea, 2Korea University, Korea, *mingyuan.pei@gmail.com

A series of Diketopyrrolopyrrole (DPP)-based copolymers, including DPP and bithiophene (BT) as electron-

acceptor (A) and electron-donor (D) backbone units, is synthesized to contain branched alkyl side chains,

which can be either directly coupled to the N positions of DPP or separated by an alkyl ester group. It is found

that the existence of ester moieties induces cohesive interactions between these side chains, in comparison to

the alkyl only side-chains with a weak van der Waals force. Optoelectrical and structural results of the DPPBT-

based copolymers show that the introduction of a proper alkyl ester spacer to branched alkyl chains can shorten

- overlapping distance between the DPPBT backbones up to 3.61 Å , as well as the development of the

two-dimensionally-extended domains. As semiconducting materials for organic field-effect transistors, the

DPPBT-based copolymers, including different side chains, are spun-cast on polymer-treated SiO2 dielectrics

from dilute chloroform solutions. An DPPBT-based copolymer with the properly-engineered side chain, propyl

ester-linked 2-dodecyl dodecyl chain, shows the highest hole mobility value of 2.30 cm2 V-1 s-1 and on and

off current ratio of above 106.

71

Self-Assembling Characteristics and Properties of Brush Polymer/Lipid Hybrid

Systems in Thin Films

Jonghyun Kim*1, Kyungho Kwon, Jehan Kim, Heesoo Kim, Moonhor Ree1

1POSTECH, Korea, *kjhyun@postech.ac.kr

Self-assembly characteristics of lipid-mimic brush polymer/lipid hybrid systems in nanoscale thin films were

investigated by using synchrotron grazing incidence X-ray scattering and X-ray reflectivity analysis. We made

two different hybrid systems: (i) poly(oxy(11-phosphorylcholineundecylthiomethyl)ethylene) (PECH-C11-

PC)/1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC); (ii) poly(oxy(n-dodecyl-thiomethyl)ethylene)

(PECH-C12)/DMPC. Both hybrid systems favorably assembled, forming multibilayer structures; but such

assembly structure formation and layer thickness were dependent on the hybrid compositions. Althogh such

multibilayer structure formations were achieved, the degree of mixing in the hybrid components was highly

dependent upon the bristle characteristics. Namely, PECH-C11-PC/DMPC hybrid revealed excellent mixing

behavior, whereas PECH-C12)/DMPC hydrid exhibited severe demixing behavior. The biocompatibilities of

these hybrid systems were additionally examined. All results will be discussed from the views of composition,

physicochemical nature, self-assembled structure and surface characteristics.

72

10 nm Scale Microphase Separation of Biomass-Based Block Copolymers

Consisting of Maltoheptaose and Poly(δ-decanolactone)

Takuya Isono*1, Brian J. Ree1, Hiroaki Mamiya2, Kenji Tajima1, Redouane Borsali3, Toshifumi Satoh1

1Faculty of Engineering and Graduate School of Chemical Sciences and Engineering, Hokkaido University,

Sapporo 060-8628, Japan. 2National Institute for Materials Science, Ibaraki 305-0047, Japan. 3Univ.

Grenoble Alpes, CNRS, CERMAV, 38000 Grenoble, France. *isono.t@eng.hokudai.ac.jp

Block copolymers (BCPs) have

attracted much attention for their potential

applications in the nanotechnology fields, such

as next-generation lithography, due to their

ability to self-assemble into microphase-

separated nanostructures. For such

applications, BCP materials that realize 10-nm

scale feature size are highly desirable. The

periodicity (domain-spacing, d) of the

microphase-separated structures can be

described as d ~ N2/3χ1/6, where N is the degree

of polymerization and χ is the Flory-Huggins

interaction parameter, indicating that the BCP

must possess both a low N value and a high χ value to be microphase separated into a small feature size. We

recently focused on the use of BCPs consisting of synthetic polymer and oligosaccharide to achieve high χ

value. Indeed, the oligosaccharide-based BCPs, such as polystyrene-b-maltoheptaose, produced well-ordered

microphase-separated nanostructures with 10 nm-scale periodicity[1]. In this presentation, we report a novel

oligosaccharide-containing BCP system consisting of maltohepotaose (MH) and poly(δ-decanolactone) (PDL)

blocks (MH-b-PDL-b-MH) as a sustainable alternative for nanostructure-forming BCPs, in which both

constitutional blocks can be derived from renewable biomass resources[2].

Well-defined MH-b-PDL-b-MHs with varying PDL lengths

were synthesized in three steps involving the controlled/living ring-

opening polymerization of δ-decanolactone (DL), end group

modification, and click reaction (Scheme 1). In the bulk state, MH-b-

PDL-b-MHs successfully microphase separated into hexagonally close-

packed cylindrical morphologies with small domain-spacing values of

12−14 nm. More importantly, these BCPs also self-assembled into

highly-ordered hexagonal cylindrical structures in the thin film state, as

revealed by atomic force microscopy (AFM) and grazing incidence

small angle X-ray scattering (GISAXS) analyses. The as-cast thin films

of MH-b-PDL-b-MHs (with PDL lengths of 9k and 13k) form horizontal

cylinders, although thermal annealing (180 °C, 30 min) resulted in a

drastic change in the domain orientation from horizontal to vertical

(Figure 1). Such switching of the cylindrical domain orientation

following thermal annealing is particularly appealing, as both the

horizontal and vertical cylinders are potentially useful for

nanolithographic applications on the sub-10 nm scale.

References

[1] I. Otsuka, Y. Zhang, T. Isono, C. Rochas, T. Kakuchi, T. Satoh, R. Borsali Macromolecules 48, 1509-1517

(2015).

[2] T. Isono, B. J. Ree, K. Tajima, R. Borsali, T. Satoh Macromolecules 51, 428-437 (2018).

1 0.5 0 0.5 1

1.5

1

0.5

0

1 0.5 0 0.5 1

1.5

1

0.5

0

180 °C,

30 min

AFM GISAXS

Scheme 1. Synthesis of MH-b-PDL-b-MH

Figure 1. AFM phase images

and GISAXS data of the MH-b-

PDL13k-b-MH thin films before

(upper) and after thermal

annealing (lower).

73

Interfacial Interaction Effect on Phase Transition Behavior of Block Copolymer

Thin Films

Yeongsik Kim*1, Seongjun Jo, Du Yeol Ryu,

1Yonsei University, Korea, *kim.yeongsik@yonsei.ac.kr

Understanding of phase transition behavior is important to design demanded structures such as long-range-

ordered lamellae, cylinder and other complicated morphologies. In this study, we investigated the phase

transition behavior of a symmetric and an asymmetric block copolymer (BCP) films on preferential wetting

condition depending on film thickness, then this transition behavior of thin film was compared with bulk

system. The phase transition behavior of film was investigated by ex-situ Grazing Incidence Small-Angle X-

ray Scattering (GISAXS) and Transmission Electron Microscopy (TEM).

74

Hierarchical Nanostructures of Zinc Oxide and Polymer Hybrids for

High-Performance Strain Sensors

Eunbyeol Han*1, Seulyi Lee, Hoichang Yang1,

1Inha University, Korea, *dmsquf5070@naver.com

Stretchable and deformable electronics are becoming one of the most interesting research fields due to the

modern society’s demand for portable and wearable devices. Via replacing rigid substrates by stretchable and

flexible ones, optoelectric and electromechanical devices, which have the potential to open promising

opportunities in a variety of fields, e.g., wearable sensors. Conventional rigid materials (e.g., ultrathin silicon)

have been used to fabricate strain sensors, however, they exhibit a small tolerable strain. Strain sensors with

high flexibility and stretchability can realize personal health monitoring, highly sensitive surgical gloves, etc.

Here, we demonstrate a novel type of stretchable strain sensor including piezoelectric ZnO nanocrystals grown

on flexible curved filaments or flat film surfaces to monitor human motions with wide ranges of strains (up to

50%). Crystal growth and development of ZnO can be controlled with (1) areal density of ZnO nano-seeds

pre-mounted on substrates, (2) hydrothermal process conditions such as precursor concentration, time, and

temperature, (3) physicochemical characteristics of the seeding surfaces. Crystalline structures of ZnO nano-

arrays grown on supporting surfaces are systematically investigated by grazing-incidence X-ray

scattering/diffraction and morphological analyses. It is found that ZnO crystals grown on polymer or metal

surfaces can be controlled with preferred shapes, sizes, and orientations. An optimized strain sensor including

ZnO nanowires on polymer surfaces can be operated at high strain (up to 50%), with high durability, fast

response, and high gauge factors.

75

Morphological Structures and Properties of Novel Polymers

Bearing Monomeric and Dimeric Adamantane Units

Brian J. Ree1, Kyuyoung Heo3, Taek Joon Lee3, Toshifumi Satoh*1,

Takashi Ishizone*2, Moonhor Ree*3

1Laboratory of Polymer Chemistry, Faculty of Engineering, Division of Applied Chemistry, Graduate School

of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Japan 2Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo

Institute of Technology, Tokyo 152-8552, Japan 3Department of Chemistry, Division of Advanced Materials Science, Pohang University of Science and

Technology, Pohang 790-784, Republic of Korea *satoh@eng.hokudai.ac.jp,

tishizon@polymer.titech.ac.jp, ree@postech.ac.kr

In this study a series of novel polymers containing monomeric and dimeric adamantine units in the backbone

or in the side group were investigated. Nanoscale thin films (300 nm thick) of these polymers were prepared

by solution casting and subsequent drying. Some of the thin films were further annealed thermally at various

conditions. Thin films were subjected to synchrotron grazing incidence X-ray scattering, spectroscopic

ellipsometry, and synchrotron X-ray reflectivity analyses. The polymers reveal very interesting optical

properties, in particular low refractive indices (i.e., low dielectric constants) and low or no optical anisotropies

depending upon the geometrical locations of adamantine units in the chemical structure. These novel polymers

are suitable for applications in advanced microelectronics as low dielectric materials. The optical and electrical

properties are discussed in conjunction with the thin film morphology, chain orientation, and electron density

(namely, mass density).

76