N-Type 可溶性有機薄膜電晶體

材料三併環及四併環噻吩衍生物
之開發
CN NC CN
NC CN NC S S C15H31
S S Ar
Ar Ar
Ar
S C15H31 S S CN
C11H23 C11H23
NC
DTTR TTAR

1
Speaker : Chi-I Kao ( 高綺憶 )
Advisor : Prof. Ming-Chou Chen ( 陳銘洲 教
授)
 Outline
♫ Introduction
OTFT
Literature search
Molecular design
♫ Experiment
Synthesis of materials
♫ Results and Discussion
Physical properties : UV-vis. DPV. TGA.
Electronic characteristics
♫ Conclusions

2
Introduction

3
Thin Film Transistor
(TFT)

4
Thin Film Transistor (TFT)

N-type TFT P-type TFT

source drain
semiconductor
dielectric
substrate
gate dielectric

substrate

5
 Organic Thin Film Transistor
Organic semiconductor materials require:

1. High charge carrier mobility (μ)

2. High current on/off ratio (Ion / Ioff)
3. Stability
4. Process ability

conductive polymers
Organic semiconductor electrode

PS 、 PVP 、 PMMA semiconductor

polyester
gate
dielectric
substrate 6
 TFT Application

http://blog.naver.com/PostView.nhn?blogId=jkhan012&logNo=150077733041&parentCategoryNo=8&viewDate=&currentPage=1
&listtype=0
 Organic Thin Film Transistor
Organic semiconductor materials require:

1. High charge carrier mobility (μ)

2. High current on/off ratio (Ion / Ioff)
3. Stability
4. Processability

conductive polymers
Organic semiconductor electrode

PS 、 PVP 、 PMMA semiconductor

polyester
gate
dielectric
substrate 8
OTFT Applications

9
 Vapor Deposition Process
Vacuum Evaporation

Vacuum Chamber

10
Solution Deposition Process
Spin Coating Machine

Inkjet Printing

11
 Vapor v.s. Solution Deposition
Molecular
Area Procedure Cost μ
Arrangement
Vacuum More
Small Complicate More ordered High
Evaporation expensive
Solution
Large Easy Low Less ordered Low
Process

12
 Molecular Arrangement

Amorphous Polycrystal Crystal

μ High

13
 Charge Transfer Theory
Hopping
電 電
極 極

High mobility (μ) →

1. Excellent molecular arrangement
substrate
2. π- π interaction→ fused-rings

電 電
極
X 極

substrate

14
 Literature Research

 Pentacene

O
hv

O2
μ up to 5 cm2 / Vs O

a-Si:H ： ~ 1 cm2 / Vs
 Disadvantages ：
1. Low stability to light and oxygen resulting in photochemical
decomposition
2. Poor solubility 15
Kelley, T. W. Chem. Mater. 2004, 16, 4413-4422.
 N-type Semiconductor Materials
Withdrawing group
NC O
F F O C H O
O O O O 6 13
F
CN
F F F
N N C8H17 N N C8H17
N NC
N S S F
F F F
O O F S O S O CN
O O CN
BCNDI F F F NC
5FPE-NTCDI C6H13 NTI-8CN2
O
μ : 6 cm2/Vs μ : 0.31 cm2/Vs μ : 0.15 cm2/Vs
h-B(CN)-2T
Shukla, D. Chem.
Katz, H. E. Chem. Mater. 2009, 21, 94.
Mater. 2008, 20, μ : 0.11 cm2/Vs
7486. μ : 0.016 cm /Vs
2
Marks, T. J. Chem. Mater.
Aso, Y. J. Org. 2007,
Chem.19,
2011, 76, 6604.
2703.
CN-group Air Stable O
CN C6H13
NC CN CN F
NC S
S S NC S S F
NC CN NC CN F S S CN
Bu Bu F NC
TCNQ DCMT C6H13
O
h-B(CN)-2T
μ : 1.6 cm2/Vs μ : 0.2 cm2/Vs μ : 0.016 cm2/Vs
Frisbie, C. D. Adv. Mater. 2003, 15, Aso, Y. J. Org. Chem. 2011, 76,
Rogers, J. A. Adv. Mater. 1278. 16
6604.
2004, 16, 2097.
 Molecular Review
DFP series Withdrawing group N-type !
F F
F F F F
S S F F
S S F
F F
F
F F S S
F F S F F
F F
DFP-DTT  : 0.07 cm /Vs 2
DFP-TTA  : 0.30 cm2/Vs
Org. Electron. 2010, 11, 801. Adv. Funct. Mater. 2012, 22, 48.
F F
F F F F
S S F F
S S F
F F S S
S S F
CN S NCF F CN
F S S
F F F
NC CN NC S cm2C
S  : 0.32 15FH31F
S
DFPT-DTT S
: 0.08 cm2/Vs DFPT-TTA
Ar /Vs
Ar Ar
F
F F F F F Ar
SS C15H
S 31 S S S S15H31 F
C F CN
C H S
F 11 23
SC11H
S 23 F
F NC F
F F
DTTR
C11H23 S C11H23 F F F F C15H31 TTAR
S S S
F F
DFPT-DTTR  : 0.07 cm /Vs 2 DFPT-TTAR  : 0.15 cm /Vs 2

F F F F F F S S S C15H31
S S S S F F
S
F F F 17
S C11H23 S S C15H31 S S F
C11H23S S
F F F F F F
F F
DFPT-DTTR  : 0.10 cm2/Vs DFPT-TTAR  : 0.26 cm2/Vs
 Molecular Design
Air stable N-type Solubility Conjugation

CN NC
NC S S CN S S S C15H31 NC
S S NC
CN C H CN
C11H23 S C11H23 S S S
15 31

TCN-T-DTTR (1) TCN-TT-TTAR (4)

CN S S S S NC CN S S S C15H31S
CN
NC CN NC
S C11H23 S C11H23S S C15H31 S S S NC

TCN-TT-DTTR (2) TCN-TT-TTAR (5)

CN NC CN
S S S S S S S C15H31
NC CN NC
S S S S
S CN
C11H23 C11H23 C15H31 S S S
NC
TCN-bT-DTTR (3) TCN-bT-TTAR (6)
F F
S S S C15H31 F F
F S
S F 18
F F C15H31 S S S
F F
DFP-bT-TTAR (7)
 Experimental Section

19
 Synthesis of Molecule (14)

OH OH
Br S Br 1. n-BuLi
S Br2 S K2Cr2O7
C11H23 C11H23
Br Br 2. C11H23CHO
Br Br
8 9
75 % 47 %
O O
C11H23 S C11H23
S HSCH2COOEt NaOH
C11H23 C11H23
K2CO3 THF
EtOOC S S COOEt
Br Br
10 11
90 % 74 %

C11H23 S C11H23 C11H23 S C11H23 C11H23 S C11H23

Cu NBS
HOOC S S COOH S S Br S S Br
12 13 14
95 % 62 % 73 %

20
 Synthesis of Molecule (20)

O
Br S Br S SHCH2COOEt
Br 1. n-BuLi / THF
C15H31
2. C15H31COCl C15H31 K2CO3/ DMF
Br S S
Br Br
15 O 16
42 %

S S C15H31 S S C15H31
EtOOC NaOH HOOC Cu

S S COOEt THF S S COOH

C15H31 C15H31
17 18
70 % 98 %

S S C15H31 S S C15H31
Br
NBS
S S S S Br
C15H31 C15H31
19 20
80 % 96 %
21
 Synthesis of Ligands (28) and (32)

Br Br S
1. LDA HSCH2CO2Et COOEt
2. N-Formylpiperidine CHO K2CO3
S S S
24 25 26
82 % 97 %

NaOH S COOH Cu S

THF S S
27 28
99 % 72 %

S MgBr
S Br S
Ni(dppp)Cl2 S
32
97 %
22
Synthesis of Ligands (23) ,(31) and (35)
S DMF / POCl3 S HO OH S O
CHO
Cl Amberlyst15 O
Cl
21 / Toluene 22
60% 74%
n-BuLi S O
Bu3Sn
Bu3SnCl O
23
70%
S DMF / POCl3 S S O
CHO HO OH
Cl Amberlyst15 O
S Cl S S
28 29 / Toluene 30
63% 61%

S O
n-BuLi
O
Bu3SnCl Bu3Sn S
31
70%
DMF / POCl3 O
S S HO OH S
S S CHO S
Cl Amberlyst15 O
Cl
32 33 / Toluene 34
74% 89%

n-BuLi O 23
Bu3Sn S
S
Bu3SnCl O
35
 Synthesis of Molecules (39) ~ (44)
O H S S H
Bu3Sn S S S
O O O
C11H23 S C11H23
23 39 71 %
O O
S S S S S
Br Br Bu3Sn 1. Pd(PPh3)4 / Toluene H
H S S
+ O
S C11H23 S 2.HCl S S
C11H23 O
14 C11H23 S C11H23
31 40 68 %
O O
S S S S
S O
Bu3Sn H S S H
S
O C11H23 S C11H23
35 41 76 %

H S S C15H31
O O
Bu3Sn S S S
O O
C15H31 S S H
23 42 76 %
O
S
S S C15H31 Bu3Sn S H S S C15H31
Br 1. Pd(PPh3)4 / Toluene
+ O S S
S S Br S 2.HCl S
C15H31 O C15H31 S H
20 31 43 76 % S
O
O C15H31
O S S S 24
Bu3Sn S S H
S H S
O S S S
C15H31 O
35 44 60 %
 Synthesis of Molecules (1) ~ (6)
CN NC
H S S H
NC S S CN
S S S S
O O
C11H23 S C11H23 C11H23
C11H23 S
39 TCN-T-DTTR (1) 70%

O O S S
S S NC CN
H S S H S S
CN S S NC
S S
C11H23 S C11H23 C11H23 S C11H23
40 TCN-TT-DTTR (2) 88%

O O
S S S S S S S S
NC S S CN
H S S H
CN NC
C11H23 S C11H23 CN C11H23 S C11H23
41 TCN-bT-DTTR (3) 93%
CN
Pireridine / CH2Cl2 CN
H S S C15H31 S S C15H31
O NC
S S S S
O CN
C15H31 S S H C15H31 S S
NC
42 TCN-T-TTAR (4) 81%
O
S S
H C15H31 NC C15H31
S S S S
S CN S
S S NC
C15H31 S S H C15H31 S S
CN
S S
43 O TCN-TT-TTAR (5) 88%

O C15H31 S C15H31 NC 25
S S S S S
H S S H NC S S CN
C15H31 S S S CN C15H31 S S S
O
44 TCN-bT-TTAR (6) 60%
 Synthesis of Molecule (7)
F F

F Br
F F F F
1) n-BuLi / THF F F NBS
Bu3Sn F F Br
S 2) SnBu3Cl / THF S Pd(PPh3)4 / Toluene S THF S
F F F F
36 37 38
83 % 73 % 76 %

S SnBu3
S S C15H31 S S S C15H31
Br 36

S S Br Pd(PPh3)4 / Toluene S S S
C15H31 C15H31
14 DT-TTAR(45)
71 %

1) n-BuLi / THF F F
S S S C15H31 2) Bu SnCl
3 S S S C15H31 F F
F S
3) Pd(PPh3)4 / Toluene S F
C15H31 S S S
F F F F C15H31 S S S
45 S DFP-bT-TTAR (7) F F
Br F
67 %
38 F F

26
 Results and Discussion

27
 Synthesis of Molecule (1) ~ (6)
O
S CN S
H C15H31 NC C15H31
S S S S
S CN CN S
S S NC
C15H31 S S H Pireridine / CH2Cl2 C15H31 S S
CN
43 S TCN-TT-TTAR (5) 88%S
O

Base Catalyst Temperature Time Result

1 piperidine TiCl4 40 ℃ 4 hr 不純

2 NEt3 - r.t. 2 days 不完全反應

3 NEt3 - 40 ℃ 12 hr x

4 piperidine - 30℃ 3 hr ○
28
 Absorption Spectra (UV-Vis)
1.2
Conjugation↑ λonset ↑
F F
F F
F F
S S S S
S S
F
F C11H23 S C11H23 F
F

DFP-bT-DTTR (7')
1 CN NC
NC S S CN
S S
C11H23 S C11H23
0.8
TCN-T-DTTR (1)
CN
S S
NC CN
0.6 S S
S S NC
C11H23 S C11H23

0.4 TCN-TT-DTTR (2)

S S S S
NC S S CN
0.2 CN C11H23 S C11H23 NC

TCN-bT-DTTR (3) 29
0
300 350 400 450 500 550 600 650 700
 Absorption Spectra (UV-Vis)
F F
CE/ 通用格式
Conjugation↑ λonset ↑ F
S
S
S S C15H31
S
F F
F
F F C15H31 S S S
F F
DFP-bT-TTAR (7)
CE/ 通用格式
CN
NC S S C15H31
S S
C15H31 S S CN
CE/ 通用格式 NC
TCN-T-TTAR (4)
S
NC C15H31
S S
CE/ 通用格式 CN S S NC
C15H31 S S
CN
S
TCN-TT-TTAR (5)

CE/ 通用格式 S S S C15H31

NC
NC S S
CN S S CN
C15H31 S
TCN-bT-TTAR (6)
CE/ 通用格式

30
CE/ 通用格式
300 350 400 450 500 550 600 650 700
 Absorption Spectra (UV-Vis)
F F
F F
F F
Conjugation↑ λonset ↑ F
F
S
S
S S
S
S

F
F
C11H23 SC11H23
DFP-bT-DTTR (7')

CN NC
NC S S CN
S S
C11H23 S C11H23

TCN-T-DTTR (1)
CN
S S
NC CN
S S
S S NC
C11H23 S C11H23

TCN-TT-DTTR (2)

S S S S
NC S S CN
CN C11H23 S C11H23 NC

Compoun TCN-T- TCN-TT- TCN-bT- TCN-T- TCN-TT- TCN-bT-

TCN-bT-DTTR (3)
F F
d DFP-
DTTR(1) bT-
DTTR(2) TCN-bT-
DTTR(3)
CN DFP- TTAR(5)
TTAR(4) bT- TCN-bT-
TTAR(6)
Compound C H C H
F
S
S
S S
DTTR(7’) F
15 31 F
DTTR(3)S
NC S STTAR(7)
15 31
TTAR(6)
S F S
F F C15H31 S S S C15H31 S S CN
λonset (nm) DFP-bT-TTAR
616.5 (7) 628 F F 651.5 626.5
TCN-T-TTAR (4)
635.5
NC 656
NC λonset
S (nm)
C H
445 651.5 452
C15H31
656
S S 15 31 S S S NC 31
CN S NC S
S NC S
CN
E (eV)
UV C H
UV 15 31
S S
2.02 1.98CN
CN
1.91 C15H31 S
1.99 S
1.96
S 1.90
g
E (eV)
g 2.36
S 1.91 2.34 1.90
TCN-TT-TTAR (5) TCN-bT-TTAR (6)
 C u rre n r (A *1 0 -6 ) Energy Level (DPV)

C u rre n r (A *1 0 -6 )
Reduction Potencial (eV) Oxidation Potencial (eV)
CE/ CE/ CE/ 0 1 2
0
0 TCN-T-
TCN-T- DTTR (1)
DTTR (1) 1.324eV
1 -0.932eV -1 TCN-TT-
TCN-TT- DTTR (2)
2 DTTR (2) 1.220eV
-0.924eV -2
TCN-bT-
Fc+ / Fc DTTR (3)
TCN-bT- 1.092eV
3 DTTR (3) -3
-0.912eV DFP-bT-

4 HOMO = -(EOX + 4.2) -4

DTTR (7')
1.032 eV
C u rre n r (A *1 0 -6 )

LUMO = HOMO + Eg Potencial (eV)

Oxidation
0 1 2
0
CE/ Reduction
CE/ Potencial
CE/(eV)
TCN-T-
0 TTAR (4)
1.288 eV
TCN-T- Currenr (A*10-6)
TTAR (4) TCN-TT-
-0.928eV TTAR (5)
1 1.156eV
TCN-TT-
TTAR (5) TCN-bT-
-0.916eV TTAR (6)
-1
2 1.056eV
TCN-bT-
TTAR (6)
32
DFP-bT-
-0.900eV Fc / Fc
+
TTAR (7)
0.992 eV
3
 Energy Level (DPV)
Conjugation ↓ , HOMO ↑ LUMO ↓ , Eg ↓

CN NC
NC S S CN
S S
C11H23 S C11H23

TCN-T-DTTR (1)
CN
S S
NC CN
S S
S S NC
C11H23 S C11H23

TCN-TT-DTTR (2)

F F S S S S
F F CN
F F NC S S S S S S
S S S S NCCN S
C11H23 S S
C11H23 NCCN
S S F CN S NC
F C11H23 C11H23
F F 33
C11H23 S C11H23 TCN-bT-DTTR (3)
DFP-bT-DTTR (7') TCN-bT-DTTR (3)
 Energy Level (DPV)
Conjugation ↓ , HOMO ↑ LUMO ↓ , Eg ↓

CN
NC S S C15H31
S S
C15H31 S S CN
NC
TCN-T-TTAR (4)
F F S
NC S S SS CC15 H31
15H F F S S S C15
C H 31
15H31
F S 31 S S S NC
NC
CN S S S NCNC S S S
S NC F CN S CN
F F C15H31 S S SS S CN C15H31 SS S
S S CN
C15H31 CN C15H31 S
F F
DFP-bT-TTAR (7) S TCN-bT-TTAR (6)
TCN-TT-TTAR (5) TCN-bT-TTAR (6) 34
 Energy Level (DPV)
Conjugation ↓ , HOMO ↑ LUMO ↓ , Eg ↓

35
 TGA
Good thermal stability !

360 ℃

36
 Device Fabrications

Tobin. J. Marks Antonio Facchetti

Source (Au) Drain

semiconductor

Gate

37
 OTFT Performance
F F
F F S S S S F F C15H31S
F F S S S
F
F F
S C11H23 S C11H23S F
S C15H31 S S S F F
F F F F
F F
DFPTT-DTTR (11) DFPTT-TTAR (13)

Compound Carrier Sign Mobility μ (cm2V-1s-1)a

DFPTT-DTTR (11) N 0.10
DFPTT-TTAR (13) N 0.26
TCN-T-DTTR (1) N 0.1*
TCN-TT-DTTR (2) N 0.1*
TCN-bT-DTTR (3) N 0.1*
TCN-T-TTAR (4) N 0.1*
TCN-TT-TTAR (5) N 0.1*
TCN-bT-TTAR (6) N 0.1*
DFP-bT-TTAR (7) N 0.1*
38
a
the values obtain for at least 5 devices in vacuum
* 待測中
 Conclusion

39
 Conclusion
 成功合成出有機半導體材料併環噻吩衍生物 (1) ~ (7) ，均具有良好
F F
F F S S S C15H31S
的熱及環境穩定性。 F
F
S C15H31
F F S S S
 和 DFP F F
系列相比，由光學和電化學的結果得知，
DFPTT-TTAR (13) TCN 系列的 λ
cm2/Vs
onset 值有明顯的紅位移， LUMO 能階較低，有利於電子傳遞，由此
推測 TCN 系列為 n-type 有機半導體材料。
F F
F DFPTT-TTAR
S S 以溶液製程製成元件，其電性表現高達
S C15H31 F F S S S 0.26
C15H31 cm2/Vs
NC
S NC S
S S
S S F CN S S CN
F F C15H31 S C15H31 S
，為本實驗室目前開發的可溶性
F F n-type 半導體材料中電性表現最
DFP-bT-TTAR (7) TCN-bT-TTAR (6)

Compound (nm) TCN 系列的 LUMO 能階較

高的。由光學和電化學的結果得知，
λ onset LUMO(eV) Eg(eV)
Energy gap 較小，因此推測 TCN 系列會有更好的電性表
低， DFP-bT-TTAR
452 -2.9 2.34
現。 (7)
TCN-bT-TTAR(6) 656 -3.3 2.02 40
 所有化合物目前仍在待測中，期望所有可溶性 OTFT 半導體材料
化合物皆有好的電性表現。
 謝誌
‧ 陳銘洲老師

‧ 賴重光老師、吳春桂老師、王家麟老師

‧ 美國西北大學

‧ 國科會

‧ 實驗室的各位

鵬毅、侑珊、介元、偉豪學長姐
以農、俊傑、柏緯、啟銘同學
巧緯、忠奇、勝泓學弟妹

41
Thank you for your attention!!

42
 TCN-DTTRs

TCN-T-DTTR

current (A)
(1)
TCN-TT-DTTR
(2)

C C C C C C C C C C
voltage (A)

TCN-TTARs

TCN-T-TTAR
(4)
current (A)

TCN-TT-TTAR
(5)

47
Currenr (A*10-6)
Oxidation Potencial (eV)
CE/ CE/ CE/
CE/

TCN-T-DTTR (1)
1.324eV
CE/

TCN-TT-DTTR
(2) 1.220eV
CE/
TCN-bT-DTTR (3)
Fc/ Fc+ 1.092eV
CE/
DFP-bT-DTTR (7')
1.032 eV
CE/
Oxidation Potencial (eV)
CE/ CE/ CE/
CE/

TCN-T-TTAR (4)
1.288 eV
Currenr (A*10-6)

CE/
TCN-TT-TTAR
(5) 1.156eV

TCN-bT-TTAR
CE/ (6) 1.056eV
49
DFP-bT-TTAR
Fc/ Fc+ (7) 0.992 eV
CE/
Currenr (A*10-6) Energy Level (DPV)
Oxidation Potencial (eV)
0 1 2
0
TCN-T-DTTR (1)
1.324eV
-1
TCN-TT-DTTR (2)
1.220eV
-2
Fc+ / Fc TCN-bT-DTTR (3)
1.092eV
-3
DFP-bT-DTTR
(7') 1.032 eV
-4 Oxidation Potencial (eV) HOMO = -(EOX + 4.2)
0 1 2
0 LUMO = HOMO + Eg
TCN-T-TTAR (4)
1.288 eV
Currenr (A*10-6)

TCN-TT-TTAR
(5) 1.156eV

TCN-bT-TTAR
-1 (6) 1.056eV
53
Fc+ / Fc DFP-bT-TTAR
(7) 0.992 eV