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Design and Synthesis of High Mobility

Materials and Their Application in


Organic Field-Effect Transistors

Yunqi Liu ( 刘云圻 )


liuyq@iccas.ac.cn

Institute of Chemistry, Chinese Academy


of Sciences, Beijing 100080, China
September 22, 2008
Organic Field-effect Transistors (OFETs)
Organic field-effect transistors (OFET)
are active devices, whose characteristics
are modulated by the electrical field
♣ Simple processability
♣ Low cost
♣ Flexibility

 Mobility
 On/off
 Threshold voltage
Organic FET Applications
pixel drivers for
active-matrix
displays and
detectors
Philips Research Penn State Univ.

Univ. Tokyo

Radio-frequency
Identification tags

Wireless power
transmission Electronic paper
Organic Semiconductors
Polymers Small-molecule materials
p-type
p-type
N N
N

N Cu N

S N N N
n

S
S S S S
S S S
n

F F

F F

n-type n-type F N F
N N
F F
O O F F F F F N Cu N
F F F F
N N N
N N F F

F F
N N F F
F F F F F
n
F F
Requirements for FET materials

• Largeπ-Conjugation
• Planar
• Strongly π- π interaction
• Crystal
Organic semiconductors
Carbon
Linear Planar Cyclic Nanotubes
R R

S S N N
N
N HN

S S S
N Cu N NH
. H2SO4
HN

N N N NH HN
S
NH N
R R
R R
S S
R S S S S R

N
S S S S
R R
N
O

 - conjugation
S S
Dibenzotetrathiafulvalene Bisimides:
S S
TTF New Building Blocks for Organic Electronic Materials

 A diverse library of derivatives with


various functionalities at the imide rings
 An electrically active TTF core, which LUMO
might endow them with novel electronic
properties

HOMO
Advanced Materials. 2007, 19, 3037.
(a)

(
b) (c)

dinterplanar = 3.42 Å dS−O = 3.16 Å, dS-S = 3.80 Å


Figure 3. Molecular structure (a) and stacking structures (b and c) of 1

The face-to-face columnar π -stacking and the side-by-side


intercolumnar S···O and S···S contacts increase the effective
dimensionality of the electronic structure and benefit charge
transport
Compound 2

More than 20 devices Three weeks


compound HOMO band gap mobility on/off ratio
(eV) (eV) (cm2/Vs)
1 −5.46 2.05 0.011−0.094 106−108
2 −5.42 2.06 0.12−0.40 106−108
DBTTF −4.97 2.79 0.001−0.003 102−103

Because of the strong electron-donating property of most TTF derivatives


(i.e. their high HOMO levels), their thin film are labile to oxygen, the
resulting dopants increase the conductivity of the film in the off or ungated
state and lead to the poor FET performance. Thus more electron deficient
TTF derivatives, having the relative low-lying HOMO levels, are promising
High-Performance Transistor Based on Individual Single-
Crystalline Micrometer Wire of PET

Backgroud:
• Fundamental aspects of
carrier transport, especially
the role of solid-state
packing, still remain unclear
• Studies on micro- and
nanomaterials, including
fibers, ribbons, and wires are
few perylo[1,12-b,c,d]thiophene (PET )
and its crystal packing

The extraordinary solid-state packing arrangement with the


likelihood of double-channel fashion induced by marked S···S
interactions

J. Am. Chem. Soc. 2007, 129, 1882.


FETs made of thin films
-3
-12 6.0x10
-80 V VD = -80 V
-5
-10 1x10 -3
5.0x10

Drain current 1/2 (A 1/2 )


Drain current (A)
Drain current ( µA)

-6
-8 10 4.0x10
-3

-60 V
-6 10
-7
3.0x10
-3

-4 -3
10
-8
2.0x10
-40 V
-2 -3
-9 1.0x10
10
-20 V
0 0V
-10
0.0
10
0 -20 -40 -60 -80 0 -20 -40 -60 -80 -100
Drain voltage (V) Gate voltage (V)

Characteristics mobility : 0.05 cm2/Vs,


of thin-film an on/off ratio: 1.2×105,
transistor based
threshold voltage : -6.3 V,
on PET at room
temperature subthreshold swing: 4 V per decade
Fabrication of FETs with single crystals wire

Transistors based
on an individual
single-crystalline
micrometer wire
of PET have been
fabricated with a
gold wire as
mask.

W: 1.8 µ m
L: 55 µ m
mobility : 0.8 cm2/Vs, an on/off ratio: 1.7×103, threshold voltage : -6 V,

Six transistors, Shelf-life test for one transistor under


mobility : 0.3-0.8 cm2/Vs, ambients for one week, mobility only
from 0.35 to 0.34 cm2/Vs and on/off
Good stability in air ratio unchanged
Single-Crystal Microribbons of an Indolo[3,2-
b]carbazole Derivative by Solution-Phase
Self-Assembly with Novel Mechanical,
Electrical and Optical Properties

Accepted
2TFMPOIND
F 3C
C8H17
N

N
C8 H17

CF3

 Carbazole as a building block


 Extended π -conjugation
 Alkyl chains improve solubility
 π −π stacking
 Alkyl−alkyl close contacts
 F⋅ ⋅ ⋅ H hydrogen bonds
 Self-assembling into 1D nano/micro single crystals
Crystal structure and intermolecular interactions

Quasi-planar structure with a small dihedral angle of 2.56o


3.378 Å cofacial π −π stacking
Alkyl-alkyl close contacts (2.301−2.331 Å, H-to-H)
F⋅ ⋅ ⋅ H hydrogen bonds (2.565−2.2.600 Å)
These intermolecular interactions facilitate charge transport
Field-effect transistors

L = 68 µ m, W = 1.2 µ m
µ = 0.084 cm2/Vs, on/off = 104
VT = −8.7 V
Stored at ambient for 32 days retained almost identical mobility
高迁移率材料与场效应晶体管
S S

S S S

J. Am. Chem. Soc., 2005, 127, 13281 Adv. Funct. Mater., 2006, 16, 426

N
N
O

J. Am. Chem. Soc., 2006, 128, 15940 J. Am. Chem. Soc., 2006, 128, 13058
电极修饰

J. Am. Chem. Soc., 2006, 128, 16418 Adv. Mater. ,


2008, 20, 1286

Adv. Mater. , 2008, 2008, 20, 3289


High mobility materials and OFETs
CNx

JACS 2005, 127, 2804


JACS 2005, JACS 2005, 127, 8614
127, 15700
1.6x10 (b) VD S = −100 V
-2

Al2O3/CNT
-2
1.2x10

lI DS 0.5 l(A 0.5 )


-3
8.0x10
-3
4.0x10
0 .0
-10 0 -50 0 50 100
VG S (V )
Adv. Mater., Adv. Mater.
2006, 18, 181 TiOPc 2007, 19, 2613 Adv. Mater.
2008, 20, 611
OFETs based on micro/nano single crystals

CuPc
1 1µ m
µ m
CuTCNQ
Adv. Mater.,
Adv. Mater., Adv. Mater., 2006, 18, 3010
2006, 18, 6568
2005, 17, 2953 5µ m
100-400 nm

500 nm

5µ m

111

011
Adv. Mater., Adv. Mater.,
J. Am. Chem. Soc.,
2007, 19, 2624 2008, 20, 1511
2006, 128, 12922
Research Roadmap of OFETs

Materials Circuits &


Device
Functionality
s
SemiconductorsHigh perform. Processing Tech.
RFID
p-type & n-typeParam. printing E-paper
Electrodes modula. ink-jet Displayer
Dielectrics Interface lithography
Integration
Chem. & Electro
Condensed Structure nic Application
Propert
Acknowledgements

Funding:
NSFC, MOST, CAS
Daoben Zhu, Wenping Hu, Jingui Qin, Deqing Zhang,
Zhaohui Wang, Zhigang Shuai, Wei Xu, Gui Yu, Buxing Han,
Kai Xiao, Yanming Sun, Ying Wang, Lei Fu, Chongan Di,
Hengjun Zhang, Xike Gao, Xianglong Li

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