HIsaoIshii

ＣｅｎｔｅｒｆｏｒＦｒｏｎｔ
Ｉｅｒ
Ｓｃｉｅｎｃｅ

Professor,CenterforFront1erScience●Molecular Physics II

1-33Yayoi-cho,inage-ku,
ハ．

１１■

へ０■

Ｉ

２６３-８５２２,JapanＧ⑤⑨
HIsaoIshii
Ｔｅｌ＋８１４３２９０３５２４
ishiil30@faculty.chiba-u,jp
Key word is “Interdisciplinary”

Nationa1UniversityCorporationChibaUnjversity

My carrier

Ph,DＣｅｎｔｅｒｆｏｒ
Ｆｒｏｎｔ
Ｉｅｒ
Ｓｃｉｅｎｃｅ

CHIBA
UNIVERSITY① Born in Okayama, grew up in Hyogo●

1-33Yayoi-cho,inage-ku,
ハ１．

１１■

へ０■

ＩＬｎＩＤａ­Ｓｎｌ，ＬｎｌＤａ② U.Tokyo (Faculty of liberal arts,
department of pure and applied scince)
Physics and Chemistry, Band Theory and Molecular Orbital②’ Graduate School of U. Tokyo (Prof. Y. Harada)“Organic molecule is opponent against ultra-high vacuum”
Electron spectroscopy of clean Si surface @ graduate school
Nickname of “The tallest chemist in Japan“ (L=195ｃｍ) was given.

２６３-８５２２,Japan
Ｔｅｌ＋８１４３２９０３５２４
ishiil30@faculty.chiba-u,jp

Physics and Chemistry 、＠乃叱側［h?ｍｉ$『inJq”､Organics and Inorganics
Spectroscopy and Device
Basic and Application
Scienceand Engineering③ Nagoya U (Assistant prof.: Facultyof Science,
4④ Tohoku U. (Associate prof.: Research Institute ofElectrical Communication, faculty of engineering
2002-2006 (prof. M. Niwano)l Organic electronic device, Infrared spectroscopy,
displacement current measurement.

Room #203, Building #2, Faculty of Science
Office hour is Tuesday Afternoon

Professor,CenterforFront1erScience

CHIBA
UNIVERSITY

Department of Chemistry) (Prof. K. Seki) 1991-2001③’ Institute of Molecular Science,③’’ Louisiana State U. (USA)l Electron spectroscopy of organic materials
l Electronic structures of organics by using synchrotron

石井 久夫 Hisao Ishiiishii130@faculty.chiba-u.jp

1１

ＬｎＩＤａ­Ｓｎｌ，ＬｎｌＤａ⑤ Chiba U. (Professor: Center for Frontier Science) 2006Fusion of spectroscopy and device studies.
Device Physics of Organic Electronics、＠乃叱側［h?ｍｉ$『inJq”､SendaiTokyo
Nagoya 2 5Himeji
3Chiba1’
1 1’ Osaka
Okazaki
3’Okayama

3’

Baton Rouge

2

Plan of this class
Objective: To be familiar with ….
@Basic properties of organic semiconductors and devices@How to handle organic semiconductor@Basics of electronic structure of organic semiconductors@How to measure their electronic structures especially photoelectron
spectroscopy● Criteria for judging grade score:Attendance + report341

Organic Materials in Daily Life

Merits and Demerits(?) of Organics
The number of molecules whichwere synthesized so far is very huge.
Wide range of variety of design.
Negative aspects? (endocrine
disturbing chemicals(環境ホルモン) ・multiple chemical sensitivity
syndrome(化学物質過敏症),Emission of dioxine upon the waste
incineration (産廃焼却時のダイオキシン放出）?
So far used as insulator

Let us imagine daily items….
Home electric appliances(cables, CD, DVD, printed board, LCD etc)
Pen, Ink, Paper….
Clothes, Synthetic fiber, Mask….
Plastic bottle, Food wrap
Foods
Human body, Living things, Medicine

5

Close to 100Million,
80 or 90% may be organics

6

Electric conductivity of organic and inorganic materials
History of Organic Semiconductors and Conductors
・1906 Pocchetino アントラセンの光伝導性(Discovery of photoconductivity ofanthracene)
・1941 Szent Gyorgyi 「生体系においては有機物質の電気伝導率が重要になるかもしれない」(Conductivity of organic materials may be a key in bio-related system)
・1948 Phthalocyanines (英国のEley、ロシアのVartanyan)、
多環芳香族炭化水素(polycyclic aromatic hydrocarbon) （日本の赤松、井口）・1954 最初の導電性の電荷移動錯体(First charge-transfer complex with highconductivity)（赤松、井口、松永）・1973,1975 (SN)X 金属性(Metallic)、超伝導性(Superconducting)・1977 導電性高分子、ポリアセチレンの発見 (The discovery of conducting polymer,polyacetylene （白川、MacDiarmid, Heeger)
・1987 有機EL素子の効率向上(Breakthrough to efficient organic
electronluminescent device) (C. Tang, Kodak)
・1991 K3C60 超伝導 (Superconductivity)
・1997 有機EL実用化開始(First OLLED in the market)
・2000-2002 幻の（？）有機FET超伝導 (Scientific misconduct by Shoen)
・2001 [Ni(tmdt)2] 最初の単成分有機金属 (First single-componet organic metal)
・2007 First TV using OLED・2017 First Large size OLED TV

Graphite

Polyacetylene

Soda glass
Pyrex glass
Sulfur (yellow)
Fused quartz

Alumina

7Anthracene
Teflon82

Photoconduction of Anthracene：1906

Hint to the concept of organic semiconductors 1
Graphite（黒鉛）is a semi-metal, and good conductor.

So, the fraction of graphite like
Polycyclic aromatichydrocarbon(縮合多環芳香族炭化水素) may be also conductor?

910Hint to the concept of organic semiconductors 2

Hint to the concept of organic semiconductors 3
銀塩写真(silver halide photography)の色素増感(Dye-sensitization)（→ コピー技術(Xerography)にも関連）植物が行う光合成は、一種の太陽電池。
(Photosynthesis is a kind of solar cell.)
ポルフィリン、フタロシアニンなどの生体を模したモデル分子
Porphyrin andphthalocyanine are biomimic molecules

AgBr微結晶
Agクラスタ

Eｇ

e－h+

AgBr
http://www.iis.u-tokyo.ac.jp/~tfujii/kougaku/watanabe.htmlより11Agクラスタ

e－Eｇ

h+

増感色素

AgBr

増感色素の電気特性が注目された

123

TTC

Examples of organic semiconductors(small molecules)
TPD

テト ラ チアナフタ セン

H2C
H2C

p-セクシフェニル (6P)

H2C
H2C

S S

H3C
N

H 2C

N

H 2C

S S

CH3

H2C
H2Cポルフィリン

Alq3

フタロシアニン

H 2C

C60

H2C
H2C
H2C

NNM
NNNNNNNM
NO

H 2C

AlNNN

O

H 2C

N

H2C

N

H2C

O

H 2C

TCNQ
CNCNC

H2C

CN

H2C

CN

H2C

C

H2C
H3C

Conducting Polymers

CH3
CH2
CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH213

Increase of conductivity by doping

14

A story of the discovery of“Shirakawa Polyacetylene”
ポリアセチレンを合成するための触媒(catalyst)は、チーグラー・ナッタ型触媒といいます。
通常の条件下で、この触媒を使ってポリアセチレンを合成すると、不溶・不融黒い粉末状になってしまいます。→膜にできない。
通常より１０００倍濃い触媒を使ってしまったという実験ミスから、触媒溶液の表面に、黒っぽい物質
偶然出来上がった物質は、見るからにいつものものとは違っていたので、普通だと「ごみができちゃった」と思って捨てかねないものです。
それを「何だろう？」と思って、詳しく調べたことが、大発見の第一番の要因でしょう。

Cis (1) and Trans(2)Polyacetylene

15164

Superconduction of K-doped C60

Carbon nanotube

CNT のタイプ
ジグザグ(zig-zag)
カイラル(キラル,chiral)
アームチェア(armchair)

http://www.jaist.ac.jp/ms/labs/fukugo/iwasa-lab/study/fullerene.html

17m,n の関係
(n,0)
m=0(n,m)n>m≧1(n,n)
n=m(≠0)導電性

金属、半導体金属、半導体

http://www.nanoelectronics.jp/

金属のみ

18

おまけ： Organic magnets

Graphene グラフェン
Monolayer graphite
Effective mass should be zero.
（Mobility： 15,000 cm2/Vs）

19205

History

Organic materials as electronic materials
Organic semiconductors, metals, superconductors, and alsomagnetic materials have been discovered.
Wide band gap （HOMO-LUMOギャップ）（more than 1.5 eV）
Extremely low concentration of thermal carriers → insulating
Wavefunction is localized within a molecule → Narrow band width

コピー機（ドラム)

太陽電池

Van der Waals intermolecular interaction → Molecular Solids
Application to electronic devices （Orgnic electroluminescent device,Organic solar cell, Organic transistor, Organic memory etc.）
Flexible device structure
Various function can be added by the modification of molecules.
Low cost, Low temperature process, Large area device, Printing
circuitLarge anisotropy

有機EL

CathodeETL
ehnh+ELHTL
Anodee有機トランジスタ
GateSourceDrain

分子デバイス

八瀬ら、電子材料2005年7月号より21226