π 共役高分子球体からの共鳴
発光現象

筑波大学数理物質系物質工学域

山本洋平

第１回 CiRfSEシンポジウム（2015年3月13日 ＠筑波大学総合研究B棟）

Self-Assembly of π-Conjugated Polymersex) Regioregular Poly(3-hexyl thiophene): RR-P3HT

1D FiberSSn2D Sheet (Cast and Anneal)

Sirringhaus et al., Nature. 1999, 401, 685.

Liu et al., Macromolecules 2009, 42, 9390.

Toward Light-Emitting Photonic Crystals
No-Threshold Laser Oscillation by Charge Injection and Exciton Confinement

Vapor Diffusion Method          precipita(on3 days

Single-Component Polymers

PhotoelectricConversion Polymers
regioregular P3HT

Light-Emitting Polymers
F8C8H17

MDMOPPV
C8H17

OCH3nOnCH3
CHCl3 CH2Cl2 PhCl

CH3CH3THF toluene

MeOH

×

×

×

×

×

hexane

–

–

×

×

×

acetone

×

×

×

×



Toluene–Acetone

CHCl3 CH2Cl2 THF toluene
MeOH



×

×

CHCl3 PhCl
hexane××acetone×

×

Irregular Aggregates

Fused Spheres

5µm

n

CHCl3–Hexane

CHCl3–MeOH

Distorted Spheres

SS5µm

5µm

Alternating Copolymers
F8T2C8H17F8TMT2C8H17

C8H17

C8H17MeS

MeS

SSn
Me

Irregular Aggregates

MeWell-Shaped Spheres

2 µm

2 µm
CHCl3MeOH

J. Am. Chem. Soc. 2013, 135, 870.

nCH2Cl2PhCl

THF

×toluene×hexaneacetone×	×

5Well7Shaped5Spheres5	 Distorted5or5Fused5Spheres5×5 Irregular5Aggregate
No5PrecipitaCon

Alternating Copolymers
F8T2

F8TMT2

C8H17

C8H17

C8H17

C8H17SMeS

SnMe

F8EDOT
C8H17

C8H17O

F8BT
C8H17OSPCPDTBT
CH3 H3C

C8H17N

Well-Shaped Spheres

5µm
5µmnMeH3CnMeS

SNn

CH3S

SNMixtures

S NnMixtures

10µm

10µm

J. Am. Chem. Soc. 2013, 135, 870.

Why Spheres Formed ?
√ What kind of polymers form spheres ?
Low crystallinity is an important factor.
F8TMT2

F8T2
C8H17

C8H17

C8H17

C8H17

MeMeSSS

Sn

MeMen
2 µm

2 µm

44.5°

5.3° 18.7°

66.5°√ Why spheres ?
Hydrophobic alkyl chains tend to avoid contacting with polarsolvents, thus forming spherical assemblies (minimal surface area).
(No nonsolvent diffusion, no spheres were obtained)
J. Am. Chem. Soc. 2013, Polym. Chem. 2014.

Summary of the Spherical Formation
Alternating Copolymers

Single-Component Polymers
C8H17C8H17Spherical AssemblyO

MDMOPPVO

C8H17C8H17F8n

F8EDOTOS

C8H17 C9H19

C8H17nNS

F8TAZ2SNn

Me

C6H13

RR-P3HTSS
C6H13S
MeC6H13MeS

Ar-TMT2nArn

MeC 8H 17

rr-P3HTC 8H 17

Ar = F8Sn

C18H 37

Alternating Copolymers
C8H17nC9H19OCH3F8T2SSS
C8H17C8H17N

C8H17C8H17FC8H17C8H17F

N2,7-K

C8H17C18H 37n

N

N

3,6-K
F8BTn

C 8H 17F

F8TPn

C 8H 17F

FF

PTF

FFNS

F8TP2n

N
NN

SDOP

FFF

5 µm

PCPDTBTSNNn

AZOANISnO
C8H17ONDPP

N

Photoluminescence from a Single Sphere
PL of Thin Film of Spheres

PL of a Single Sphere

F8TMT2
C8H17Upon Photoirradiation

MeMeS
Med (µm)n

5 µm

PL Intensity (a. u.)SMe4.23 µm

d ~ 2.3 µm

PL Intensity (a. u.)

C8H173.32.92.62.3
500

600

500Wavelength
600 (nm)
700
Wavelength (nm)700

→ Whispering Gallery Mode(WGM) Photoemission

Whispering Gallery Mode (WGM) Photoemission

Arnold et al., Opt. Lett. 28, 272 (2003).

!" d = # n
Optical Path

V. D. Ta et al.,Laser &Photonics Rev. 7, 133 (2013).

! :Refractive Index! :Wavelength
n :Integer Number

WGM: Theoretical Simulations
C8H17

C8H17

Me

Mex

S

F8TMT2 =S
Me

PL#Intensity#(a.u.)

(d = 2.6 µm)

MeElectricFieldn

MagneticFieldzyTE mode

TM mode−11+(11111 " εµ % 2 λnE = 2π r(εµ ) 2 *(n + ) +1.85576(n + ) 3 − $' *22ε # εµ −1 &,)

1(11 −1+#Simulated# λnH = 2π r(εµ ) 2 *(n + 1 ) +1.85576(n + 1 ) 3 − 1 "$ εµ %' 2 *22µ # εµ −1 & spectra#,)Oraevsky, A. N.; Quant. Elect. 2002, 32, 377.

Wavelength#(nm)

Sci. Rep. 2014, 4, 5902.

WGM Photoemission from Various π-Conjugated
Polymer Spheres
Sci. Rep. 2014, 4, 5902.
C 8H 17

C18H 37MeC 8H 17 MeNSSMeNn

MeNSS

MeS

SSn

MeMeMeMen

MeN

MeNn

MeC 8H 17d (µm)

d (µm)d (µm)

4.2

5.5

2.6

6.8

3.3

4.3

2.4

5.4

2.6

3.7

2.2

3.3

2.3

3.1

1.9

2.4

1.6

2.6

1.5

PL Intensity (a. u.)d (µm)

500

600

Wavelength (nm)

700

500

600

Wavelength (nm)

700

500

600

Wavelength (nm)

700

1.8
700

800

Wavelength (nm)

Reports on WGM Photoemission
Microspheres or discs
by Lithography

K. J. Vahala,
Nature 2003, 424, 839.

Dye-Doped Dropletof Liquid or LCs

M. Humar et al.,Nat. Photon. 2009, 3, 595.

Dye-Doped Polymer
Colloids

V. D. Ta et al,
Sci. Rep. 2013, 3, 1362.

→ WGM Photoemission from a single π-conjugated polymer sphere is new !
(π-Conjugated polymer spheres act as cavity and light-emitter).

Sci. Rep. 2014, 4, 5902/1–5.

本マイクロ球体の特徴
１．自ら発光特性を有する（発光色素添加が不要）
２．高屈折媒体（共役系高分子）
３．共振器としての機能（マイクロ球体）
４．作製が容易（微細加工技術を必要としない）
５．電荷注入による電界発光・電流駆動レーザーが期待できるAcknowledgments
Univ. of Tsukuba
Polymer Synthesis

Prof. TakakiKanbara

Prof. Junpei
KuwabaraUniv. of Duisburg-Essenµ-PL

Prof. Axel Lorke

FP-TRMC, PL

Mr. Daniel Baam

Polymer Synthesis

Prof. Masashi
KijimaMr. Kosuke
Shibasaki

Dr. Sugiyasu

Osaka Univ.

Dr. PanProf. Shu Seki

NIMS

Prof. Akinori Saekiµ-PL

Dr. Nagao

Dr. Ishii

科研費若手Ａ(2012-2015), 物質•デバイス共同研究拠点
新学術領域(人工光合成, 2012-2013), 日独パートナーシッププログラム

Thank you for your attention !
AdachiTabataKanekoTong

Mizutaru

Okada

Kushida

Hosoe

Sakuraba
Aikyo

Yamamoto
Nakayama