有机光电半导体材料及其未来之应用
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S1
Fluorescence 25%
Intersystem crossing (ISC) Triplet exciton
T1
Phosphorescence 75%
S0
Ground state
Decay from singlet allowed by symmetry: fast and often efficient.
2021/2/2
26
First PLED Invented by Richard. H. Friend (Cambridge University, Cavendish Laboratory)1990
They used Al as the cathode material at that time.
CH CH CH CH CH CH
雙鍵
單鍵
H
H
H
H
H
H
H
C
C
C
C
C
C
C
Байду номын сангаас
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
2021/2/2
7
Bang Gap of Polyacetylene
………..
2021/2/2
……
Band Gap
8
Conjugated polymer
Alternating single-double bonds
28
Schematic Energy Level Diagram
2021/2/2
29
Processing for the fabrication of a typical PLED
Pre-cleaned ITO/glass substrate
Spin coating PEDOT layer & baking
• Since then, the field has dramatically expanded both commercially and scientifically, including OLED, PLED, transistors, potovoltaic, solar cells………
Lecture note of Prof. Chou, NTU Phys.
2021/2/2
25
What are PLEDs?
• Invented by Richard. H. Friend (University of Cambridge, Cavendish Laboratory) 1990年
• PLED 全名叫做高分子發光二極體 (Polymer Light-Emitting Diode) • Usually for single layer device configuration
hν1
hν2
non-radiation
Triplet excitons
phosphorescence
heat
ground state
2021/2/2
19
皮肌炎图片——皮肌炎的症状表现
• 皮肌炎是一种引起皮肤、肌肉、 心、肺、肾等多脏器严重损害的， 全身性疾病，而且不少患者同时 伴有恶性肿瘤。它的1症状表现如 下：
有機光電半導體材料及其 未來之應用
郭 宗 枋 助理教授
T.-F. Guo
Institute of Electro-Optical Science and Engineering, National Cheng Kung University, Tainan, Taiwan 701
成功大學 光電科學與工程研究所
• 1980’s – organic non-linear optical materials
• 1987 – Kodak first published the efficient organic light-emitting devices (OLED)
• 1990 – Cambridge groups publish the first polymer light-emitting diodes (PLED)
• 1、早期皮肌炎患者，还往往伴 有全身不适症状，如-全身肌肉酸 痛，软弱无力，上楼梯时感觉两 腿费力；举手梳理头发时，举高 手臂很吃力；抬头转头缓慢而费 力。
HTL
+ Anode
Operation of OLEDs
_ Cathode
ETL
_+_+_+_+_+_+_++_
ITO
Glass or PET substrate
2021/2/2
13
Scientific Interest in Organic Materials
• 1950’s – steady work on crystalline organics starts
• 1970’s – organic photoconductors (Xerography)
Before bias
2021/2/2
Biased device
31
Why they are so important?
Self-luminescent No viewing angle limitation Thin, Light weight Low operation voltage Flexible substrate application
Sigma bond
Delocalized electron cloud
2021/2/2
http://www.cdtltd.co.uk
9
Creating new materials from old materials
PPP
n
Eg = 3.0 eV
PA
n
Eg = 1.4 eV
PPV
Eg = 2.4 eV
12
Conjugated Polymers: Basic Materials and Chemistry
•Conduction polymers: Polyacetylene, Polyaniline, PEDOT/PSS… etc. •Semiconducting polymers: Polythiophenes, Oligothiophenes… etc. •Light-emitting/Photovoltaic Polymers: Poly-(para-phenylene-vinylene), Poly(paraphenylene), Polyfluorene… etc.
01/16/2007
NCKU Institite of Electro-Optical
1
Science & Engineering
Outlines
• Semiconductors • Organic semiconductors (energy and
delocalization of charge carriers) • OLEDs and PLEDs 基礎原理和應用 • Organnic photovoltaic and solar cells • Conclusions
2021/2/2
http://www.nobel.se/chemistry/laureates/2000/illpres/7.h tml
32
Recent progress of EL Panels
2021/2/2
18
Photophysics process
e-/h+
carrier separation carrier injection
dissociation
recombination
dissociation
Singlet excitons
fluorescence
Intersystem crossing T-T annihilation
(a) a conductor
2021/2/2
(b) a semiconductor
(c) an insulator
5
Beginning of orgnaic semiconductor (π bonding)
2021/2/2
Side-by-Side Bonding
6
Conjugated (共軛): alternatively double-single bonds
OO
OO
OO
S
S
S O
S +
O
O
S On
n
m
2021/2/2
SO3-
SO3H
PEDOT:PSS
Spin coating MEH-PPV layer & baking
Cathode deposition
O
*
O
MEH-PPV
n * Eg=2.1eV Orange-red or yellow
30
PLED Devices at NCKU
Localized! Charge cannot go anywhere!!!
2021/2/2
Delocalized! Charge carriers can move around!!!
11
Delocalization and Transport of Charge Carriers
2021/2/2
R1
n
R1 O
2021/2/2
n R2
Eg = 2.4 eV
O
R2
n
Eg = 2.1 eV
Through the structure engineering, polymers with different emitting colors were synthesized.
10
Delocalization of Charge Carriers in Polyacetylene
Display)
2021/2/2
15
OLED Basic Device Configuration
Double layers structure
• 電洞傳輸層-Hole Transport (injection) Layer (HTL)
• 電子傳輸層– Electron Transport Layer (ETL)
2021/2/2
14
What are the OLEDs?
• Invented by Dr. Ching W Tang （鄧青雲博士）(kodak) 1987年 • OLED 全名叫做有機發光二極體 (Organic Light-Emitting Diode) • 部分國外又稱 OEL為有機電激光顯示 (Organic Electroluminescence
Decay from triplet disallowed by symmetry: slow and usually inefficient.
2021/2/2
24
Device preparation
ITO/Glass substrate Vacuum<10-5 torr Organic materials
2021/2/2
21
Electroluminescence of O/PLED
Single layer device PLED
Double layer device
2021/2/2
Double layer device
OLED
22
Mechanism of Electroluminescence
hole (+) electron (-)
2021/2/2
2
Fundamental science of inorganic semiconductors
2021/2/2
3
Typical Semiconducting Materials
2021/2/2
4
Energy Band Diagram of a conductor, semiconductor, and insulator
• 發光層- Emitting Layer (EML)
2021/2/2
16
First OLED Invented by Dr. Ching W Tang (kodak) 1987
2021/2/2
17
Absorption, Fluorescence & Phosphorescence Process
2021/2/2
27
Synthetic Route to PPV
2021/2/2
J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, and A. B. Holmes, Nature, 347, 539 (1990).
+
2021/2/2
exciton (*)
+
or
3 symmetric states Triplets
1/ + 2
singlet triplet
1/
-
1 antisymmetric state
2 Singlet
23
Fluorescence and Phosphorescence
Singlet exciton
Fluorescence 25%
Intersystem crossing (ISC) Triplet exciton
T1
Phosphorescence 75%
S0
Ground state
Decay from singlet allowed by symmetry: fast and often efficient.
2021/2/2
26
First PLED Invented by Richard. H. Friend (Cambridge University, Cavendish Laboratory)1990
They used Al as the cathode material at that time.
CH CH CH CH CH CH
雙鍵
單鍵
H
H
H
H
H
H
H
C
C
C
C
C
C
C
Байду номын сангаас
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
2021/2/2
7
Bang Gap of Polyacetylene
………..
2021/2/2
……
Band Gap
8
Conjugated polymer
Alternating single-double bonds
28
Schematic Energy Level Diagram
2021/2/2
29
Processing for the fabrication of a typical PLED
Pre-cleaned ITO/glass substrate
Spin coating PEDOT layer & baking
• Since then, the field has dramatically expanded both commercially and scientifically, including OLED, PLED, transistors, potovoltaic, solar cells………
Lecture note of Prof. Chou, NTU Phys.
2021/2/2
25
What are PLEDs?
• Invented by Richard. H. Friend (University of Cambridge, Cavendish Laboratory) 1990年
• PLED 全名叫做高分子發光二極體 (Polymer Light-Emitting Diode) • Usually for single layer device configuration
hν1
hν2
non-radiation
Triplet excitons
phosphorescence
heat
ground state
2021/2/2
19
皮肌炎图片——皮肌炎的症状表现
• 皮肌炎是一种引起皮肤、肌肉、 心、肺、肾等多脏器严重损害的， 全身性疾病，而且不少患者同时 伴有恶性肿瘤。它的1症状表现如 下：
有機光電半導體材料及其 未來之應用
郭 宗 枋 助理教授
T.-F. Guo
Institute of Electro-Optical Science and Engineering, National Cheng Kung University, Tainan, Taiwan 701
成功大學 光電科學與工程研究所
• 1980’s – organic non-linear optical materials
• 1987 – Kodak first published the efficient organic light-emitting devices (OLED)
• 1990 – Cambridge groups publish the first polymer light-emitting diodes (PLED)
• 1、早期皮肌炎患者，还往往伴 有全身不适症状，如-全身肌肉酸 痛，软弱无力，上楼梯时感觉两 腿费力；举手梳理头发时，举高 手臂很吃力；抬头转头缓慢而费 力。
HTL
+ Anode
Operation of OLEDs
_ Cathode
ETL
_+_+_+_+_+_+_++_
ITO
Glass or PET substrate
2021/2/2
13
Scientific Interest in Organic Materials
• 1950’s – steady work on crystalline organics starts
• 1970’s – organic photoconductors (Xerography)
Before bias
2021/2/2
Biased device
31
Why they are so important?
Self-luminescent No viewing angle limitation Thin, Light weight Low operation voltage Flexible substrate application
Sigma bond
Delocalized electron cloud
2021/2/2
http://www.cdtltd.co.uk
9
Creating new materials from old materials
PPP
n
Eg = 3.0 eV
PA
n
Eg = 1.4 eV
PPV
Eg = 2.4 eV
12
Conjugated Polymers: Basic Materials and Chemistry
•Conduction polymers: Polyacetylene, Polyaniline, PEDOT/PSS… etc. •Semiconducting polymers: Polythiophenes, Oligothiophenes… etc. •Light-emitting/Photovoltaic Polymers: Poly-(para-phenylene-vinylene), Poly(paraphenylene), Polyfluorene… etc.
01/16/2007
NCKU Institite of Electro-Optical
1
Science & Engineering
Outlines
• Semiconductors • Organic semiconductors (energy and
delocalization of charge carriers) • OLEDs and PLEDs 基礎原理和應用 • Organnic photovoltaic and solar cells • Conclusions
2021/2/2
http://www.nobel.se/chemistry/laureates/2000/illpres/7.h tml
32
Recent progress of EL Panels
2021/2/2
18
Photophysics process
e-/h+
carrier separation carrier injection
dissociation
recombination
dissociation
Singlet excitons
fluorescence
Intersystem crossing T-T annihilation
(a) a conductor
2021/2/2
(b) a semiconductor
(c) an insulator
5
Beginning of orgnaic semiconductor (π bonding)
2021/2/2
Side-by-Side Bonding
6
Conjugated (共軛): alternatively double-single bonds
OO
OO
OO
S
S
S O
S +
O
O
S On
n
m
2021/2/2
SO3-
SO3H
PEDOT:PSS
Spin coating MEH-PPV layer & baking
Cathode deposition
O
*
O
MEH-PPV
n * Eg=2.1eV Orange-red or yellow
30
PLED Devices at NCKU
Localized! Charge cannot go anywhere!!!
2021/2/2
Delocalized! Charge carriers can move around!!!
11
Delocalization and Transport of Charge Carriers
2021/2/2
R1
n
R1 O
2021/2/2
n R2
Eg = 2.4 eV
O
R2
n
Eg = 2.1 eV
Through the structure engineering, polymers with different emitting colors were synthesized.
10
Delocalization of Charge Carriers in Polyacetylene
Display)
2021/2/2
15
OLED Basic Device Configuration
Double layers structure
• 電洞傳輸層-Hole Transport (injection) Layer (HTL)
• 電子傳輸層– Electron Transport Layer (ETL)
2021/2/2
14
What are the OLEDs?
• Invented by Dr. Ching W Tang （鄧青雲博士）(kodak) 1987年 • OLED 全名叫做有機發光二極體 (Organic Light-Emitting Diode) • 部分國外又稱 OEL為有機電激光顯示 (Organic Electroluminescence
Decay from triplet disallowed by symmetry: slow and usually inefficient.
2021/2/2
24
Device preparation
ITO/Glass substrate Vacuum<10-5 torr Organic materials
2021/2/2
21
Electroluminescence of O/PLED
Single layer device PLED
Double layer device
2021/2/2
Double layer device
OLED
22
Mechanism of Electroluminescence
hole (+) electron (-)
2021/2/2
2
Fundamental science of inorganic semiconductors
2021/2/2
3
Typical Semiconducting Materials
2021/2/2
4
Energy Band Diagram of a conductor, semiconductor, and insulator
• 發光層- Emitting Layer (EML)
2021/2/2
16
First OLED Invented by Dr. Ching W Tang (kodak) 1987
2021/2/2
17
Absorption, Fluorescence & Phosphorescence Process
2021/2/2
27
Synthetic Route to PPV
2021/2/2
J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, and A. B. Holmes, Nature, 347, 539 (1990).
+
2021/2/2
exciton (*)
+
or
3 symmetric states Triplets
1/ + 2
singlet triplet
1/
-
1 antisymmetric state
2 Singlet
23
Fluorescence and Phosphorescence
Singlet exciton