Thin Solid Films 527 (2013) 291–298

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Thin Solid Films

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High-performance semiconductors based on oligocarbazole–thiophene derivatives

for solution-fabricated organic field-effect transistors
Gung-Pei Chang, Kuo-Huang Hsieh ⁎
Department of Chemical Engineering, National Taiwan University, 1, Sec. 4, Roosevelt Road, Taipei, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: A series of oligocarbazole–thiophenes based on a constant conjugate backbone (carbazole–bithiophene–carbazole)

Received 17 May 2012 with various n-alkyl chain lengths was prepared for application to organic field-effect transistors (OFETs). The
Received in revised form 11 December 2012 lengths of the n-alkyl substitutions attached on 9-position of carbazole moieties were methyl (CCzT2), hexyl
Accepted 11 December 2012
(C6CzT2), dodecyl (C12CzT2), and octadecyl (C18CzT2), called CxCzT2. Variations of n-alkyl chain lengths are
Available online 23 December 2012
proposed to figure out the optimization of OFET performance via solution fabrication of the active layer. Before
Keywords:
fabricating OFET devices, the thermal, optical, and electrochemical properties of CxCzT2 were fully characterized
Organic field-effect transistor (OFET) with thermogravimetric analysis, differential scanning calorimetry, ultraviolet–visible spectroscopy, and cyclic
Solution–fabrication voltammetry to realize the relationships of the structure to the properties. After fabricating CxCzT2 on Si/SiO2
Carbazole substrates via solution casting, the thin film morphologies were also studied with polarizing optical microscopy,
Thiophene atomic force microscopy, and X-ray diffraction to investigate the structural relationship to OFET performance. A
higher hole mobility was observed with C12CzT2 (3.6×10−2 cm2 V−1 s−1) due to its liquid crystal properties,
and the hole mobility could be further improved to 1.2×10−1 cm2 V−1 s−1 by the introduction of a phenyl-
self-assembled monolayer on the Si/SiO2 substrates. The excellent OFET performances of C12CzT2 by solution–
fabrication could be considered as a promising candidate for high-end OFET application.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Oligocarbazole semiconductors have been reported in organic
field-effect transistors (OFETs) with a view of high charge carrier
mobility due to high crystallinity [1,2]. Those tailor-made of energy
gap, energy levels, and facile synthesis of oligocarbazole semiconductors
are also considered to be competent for high-end application on organic
electronic devices [3–7]. For application of OFET, a key requirement to
obtain high charge carrier mobility is high quality thin film morphology
of the deposited organic active layer [8]. The charge carrier could facili-
tate transport continuously between adjacent molecules in defect-free
thin film. Thus, vacuum deposition of oligomeric semiconductors was
also applied to form high quality thin film morphology [9–11]. The
sublimation of oligomeric semiconductors under ultra-low pressure, ele-
vated temperature, slow deposition rate and proper substrate tempera-
ture could provide close packing and high crystal organic thin film to
yield high OFET performance. However, these manufacturing processes
are uneconomical for larger area fabrication. Therefore, solution pro-
cesses for depositing oligomeric semiconductors have attracted much
attention when trying to avoid the complexity of vacuum deposition.
To date, great efforts with solution-fabricated OFET based on oligo-
meric semiconductors have been widely reported. The main challenge
of solution-processable oligomeric semiconductors is to overcome the
⁎ Corresponding author. Tel.: +886 2 33663044; fax: +886 2 23623040.
E-mail address: khhsieh@ntu.edu.tw (K.-H. Hsieh).
poor solubility in common organic solvents caused by the strong π–π in-
teractions. Many strategies are considered to increase the solubility of
oligomeric semiconductors, with the most effective method being the in-
troduction of n-alkyl chain substitutions to the conjugate backbone. For
oligothiophenes and their corresponding derivatives, n-alkyl substituted
oligothiophenes at terminal positions (α,ω-dialkyloligothiophenes)
could be fabricated in high boiling point solvents (chlorobenzene,
o-dichlorobenzene, or 1,2,4-trichlorobenzene) at elevated temperatures
to yield slightly lower hole mobility than that fabricated with vacuum
deposition [12–15]. In general, α,ω-dialkyloligothiophenes still suffer
from poor solubility with common organic solvents and cannot operate
under mild conditions. When attempting to enhance the processability
of α,ω-dialkyloligothiophenes, the adjustment of n-alkyl substitutions
at β-positions (β,β′-dialkyloligothiophenes) provided great improve-
ment to the solubility in common organic solvents; however, the ultra-
low hole mobility was observed due to its disorder molecular packing
after solution fabrication [16]. Thus, the processability and the OFET per-
formance could not be balanced in this case. Therefore, another smart
way to enhance the solubility of α,ω-dialkyloligothiophenes without
sacrificing the charge carrier mobility was developed by introducing
polar moieties [17–23] or branched-alkyl chains [24–26] into the
α,ω-dialkyl substitutions. Compared with a linear conjugated backbone,
such as α,ω-dialkyloligothiophenes, other conjugated architectures such
as star-shaped oligothiophenes were also elaborated with enhanced sol-
ubility and desirable charge carrier mobility via solution fabrication
[27–30].

0040-6090/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2012.12.047
292 G.-P. Chang, K.-H. Hsieh / Thin Solid Films 527 (2013) 291–298
Scheme 1. Synthetic routes of oligocarbazole–thiophenes CxCzT2.
In this research, the compatibility of facile synthesis, solution
fabrication-capability, and high charge carrier mobility of oligomeric
semiconductors were aggregated in the development of oligocarbazole–
thiophene semiconductors. The conjugated backbones were built as line-
ar sandwich-like architectures with carbazole–bithiophene–carbazole
called CxCzT2 (x indicated the number of carbon atoms in the n-alkyl
chain substitutions), as shown in Scheme 1. The 9-position (nitrogen
atom) of 3-bromocarbazole was initially substituted with various
n-alkyl (methyl, hexyl, dodecyl and octadecyl) chain lengths, then
coupled with bithiophene at the terminal (α- and ω-) positions via the
Suzuki coupling reactions. The n-alkyl substitutions, tertial amine, and
slightly tilting molecular shape of CxCzT2 are supposed to provide good
solubility in common organic solvents for solution-processable OFET
fabrication. The energy levels of CxCzT2 such as the highest occupied mo-
lecular orbital (HOMO) and band gap (Eg) are considered for hole trans-
portation and well-matched with the work function of the gold source
and drain electrodes. The carbazole moieties of CxCzT2 are also regarded
for enhancing the crystallinity, molecular coplanarity, and π–π stacking to
form a favorite charge carrier channel. In the following sections, detailed
syntheses, characterizations, and application of CxCzT2 in OFETs are
presented and discussed in terms of n-alkyl chain lengths. This study
will help us to make a clear choice of n-alkyl chain lengths for the constant
conjugate backbone to obtain excellent solution fabrication-capable
OFETs.
2. Experiments
2.1. Materials
All starting materials such as 3-bromocarbazole, iodomethane,
1-bromohexane, 1-bromododecane, 1-bromooctadecane, sodium tert-
butoxide, tetrahydrofuran (THF), 2,2′-bithiophene-5,5′-diboronic
acid bis(pinacol) ester, potassium carbonate, aliquat 336 and
tetrakis(triphenylphosphine)palladium(0) [(PPh3)4Pd(0)] were
purchased from Aldrich (Missouri, USA) and used as received.
The precursors of CxCzT2 such as N-methyl-3-bromocarbazole,
N-hexyl-3-bromocarbazole, N-dodecyl-3-bromocarbazole and N-
octadecyl-3-bromocarbazole were prepared according to the liter-
atures [31–36].
2.2. Syntheses
2.2.1. Synthesis of 5,5′-Bis-(N-methyl-carbazole-3-yl)-2,2′-bithiophene
(CCzT2)
N-methyl-3-bromocarbazole (0.68 g, 2.6 mmol), 2,2′-bithiophene-
5,5′-diboronic acid bis(pinacol) ester (0.5 g, 1.2 mmol), phase transfer
agent aliquat 336, and tetrakis(triphenylphosphine)palladium(0)
(60 mg, 0.005 mmol) were added to a 100 mL Schlenk flask and
subjected to three vacuum/nitrogen refill cycles. THF (12 mL) and a nitro-
gen degassed aqueous solution of 2 M K2CO3 (5 mL) were added under
nitrogen and stirred for 10 min. The mixture was heated to 60 °C for
24 h and monitored via thin layer chromatography for reaction comple-
tion. After the reaction completion, the yellow precipitate was isolated
from the reaction mixture and further extracted with hot methanol and
hot acetone overnight. The yellow powder as product was collected and
yielded 0.33 g (53%). MS (ESI): m/z: 526.7 [M2−]; Elementary analysis.
Calcd. for C34H24N2S2 (524.7) C, 77.83; H, 4.61; N, 5.34; Found: C, 77.52;
H, 4.35; N, 4.96.
2.2.2. Synthesis of 5,5′-Bis-(N-hexyl-carbazole-3-yl)-2,2′-bithiophene
(C6CzT2)
N-hexyl-3-bromocarbazole (0.87 g, 2.6 mmol), 2,2′-bithiophene-
5,5′-diboronic acid bis(pinacol) ester (0.5 g, 1.2 mmol), phase trans-
fer agent aliquat 336, and tetrakis(triphenylphosphine)palladium(0)
(60 mg, 0.005 mmol) were added to a 100 mL Schlenk flask and
subjected to three vacuum/nitrogen refill cycles. THF (12 mL) and a
nitrogen degassed aqueous solution of 2 M K2CO3 (5 mL) were
added under nitrogen and stirred for 10 min. The mixture was heated
to 60 °C for 24 h and monitored via thin layer chromatography
for reaction completion. After the reaction completion, THF was
removed by rotary evaporation and the mixture was extracted with
dichloromethane/water. The combined extract was dried over anhy-
drous MgSO4 and concentrated. The crude product was subjected to
a silica gel column using a hexane/dichloromethane mixture (3:1
by volume) as eluent. The yellow powder as product was further col-
lected and yielded 0.49 g (yield 62%). MS (ESI): m/z: 663.27 [M +],
664.4 [M], 665.33 [M −], 666.47 [M 2−], 667.27 [M 3−]; Elementary
analysis. Calcd. for C44H44N2S2 (664.96) C, 79.47; H, 6.67; N, 4.21;
Found: C, 79.21; H, 6.34; N, 4.35.
2.2.3. Synthesis of 5,5′-Bis-(N- dodecyl-carbazole-3-yl)-2,2′-bithiophene
(C12CzT2)
N-dodecyl-3-bromocarbazole (1.09 g, 2.6 mmol), 2,2′-bithiophene-
5,5′-diboronic acid bis(pinacol) ester (0.5 g, 1.2 mmol), phase transfer
agent aliquat 336, and tetrakis(triphenylphosphine)palladium(0)
(60 mg, 0.005 mmol) were added to a 100 mL Schlenk flask and
subjected to three vacuum/nitrogen refill cycles. THF (12 mL) and a nitro-
gen degassed aqueous solution of 2 M K2CO3 (5 mL) were added under
nitrogen and stirred for 10 min. The mixture was heated to 60 °C for
24 h and monitored via thin layer chromatography for reaction comple-
tion. After the reaction completion, THF was removed by rotary evapora-
tion and the mixture was extracted with dichloromethane/water. The
combined extract was dried over anhydrous MgSO4 and concentrated.
Fig. 1. The 1H NMR spectrum of C6CzT2 (d-solvent: DMSO-d6).
 G.-P. Chang, K.-H. Hsieh / Thin Solid Films 527 (2013) 291–298 293

Fig. 3. UV–vis spectra of CxCzT2. (a) in 10−6 M chloroform solution. (b) toluene-casted
Fig. 2. Thermograms of CxCzT2. (a) TGA, (b) DSC. thin film at RT.

The resulting residue was recrystallized with acetone/methanol mixture

(1:1 by volume). The yellow powder as product was further collected 24 h and monitored via thin layer chromatography for reaction comple-
and yielded 0.67 g (67%). MS (ESI): m/z: 832.67 [M+], 833.47 [M], tion. After the reaction completion, THF was removed by rotary evapora-
834.53 [M−], 835.6 [M2−]; Elementary analysis. Calcd. for C56H68N2S2 tion and the mixture was extracted with dichloromethane/water. The
(833.28) C, 80.72; H, 8.23; N, 3.36; S, 7.70; Found: C, 80.79; H, 8.11; N, combined extract was dried over anhydrous MgSO4 and concentrated.
3.12. The resulting residue was recrystallized with acetone/methanol mixture
(1:1 by volume). The yellow powder as product was further collected
2.2.4. Synthesis of 5,5′-Bis-(N-octadecyl-carbazole-3-yl)-2,2′-bithiophene and yielded 0.69 g (yield 58%). (ESI): m/z: 1000.0 [M+], 1001.8 [M],
(C18CzT2) 1002.7 [M−], 1003.7 [M2−], 1004.6 [M3−], 1005.8 [M4−]; Elementary
N-octadecyl-3-bromocarbazole (1.31 g, 2.6 mmol), 2,2′-bithiophene- analysis. Calcd. for C68H92N2S2 (1001.6) C, 81.54; H, 9.26; N, 2.80 Found:
5,5′-diboronic acid bis(pinacol) ester (0.5 g, 1.2 mmol), phase transfer C, 81.38; H, 9.39; N, 2.62.
agent aliquat 336, and tetrakis(triphenylphosphine)palladium(0)
(60 mg, 0.005 mmol) were added to a 100 mL Schlenk flask and
subjected to three vacuum/nitrogen refill cycles. THF (12 mL) and a nitro- 2.3. Structure characterizations
gen degassed aqueous solution of 2 M K2CO3 (5 mL) were added under
nitrogen and stirred for 10 min. The mixture was heated to 60 °C for Proton nuclear magnetic resonance ( 1H NMR) spectra were
recorded by a Bruker AVIII 500 MHz FT-NMR. Mass spectra were
Table 1 recorded by a FINNIGAN LCQ Mass Spectrometer by electrospray
Phase transition temperatures, enthalpies and degradation temperatures of CxCzT2. ionization (ESI). Elementary analyses (EA) were recorded by a Foss
Phase transition temperatures 5 wt.% loss
Heraeus CHN-O-RAPID elementary analyzer.
(°C)/enthalpies (J/g) temperature Thermogravimetric analysis (TGA) and differential scanning
(°C)/char yield calorimetry (DSC) were performed under a nitrogen atmosphere at
Heating Cooling
(10 °C-min−1) (10 °C-min−1)
(wt.%)a a heating rate of 10 °C-min −1 using a Perkin Elmer Pyris-1-TGA and
TA instrument Q20-DSC, respectively. The absorption spectra were
CCzT2 308.4/51.5 258.6/42.2 427/50
C6CzT2 85.9/40.3b 182/63.7 ND 432/40 recorded with a Jasco Model UV/VIS/NIR V-570 Spectrometer. For
C12CzT2 85.2/25.7 131/9.5 141.3/54.6 81.7/41.2 75.4/17.3 406/24 the solution spectra, CxCzT2 were dissolved in chloroform (CHCl3,
C18CzT2 110.3/66.3 62.11/68.6 431/7 10 −6 M) and then put in quartz cells for measurements. For the
a
Char yield at 600°C. thin-film spectra, CxCzT2 were dissolved in toluene (4 mg-mL −1),
b
Crystalline temperature. filtered through 0.50 μm pore-sized polytetrafluoroethene membrane
294 G.-P. Chang, K.-H. Hsieh / Thin Solid Films 527 (2013) 291–298

syringe filters, and casted onto quartz substrates. Cyclic voltammetry

(CV) was performed with the use of a three-electrode cell in which in-
dium tin oxide (oligomer film area about 0.5–0.7 cm2) was used as a
working electrode. A platinum wire was used as an auxiliary electrode.
All cell potentials were taken with the use of a homemade Ag/AgCl, KCl
(sat.) reference electrode. The highest occupied molecular orbital
(HOMO) energy levels of CxCzT2 were determined from the onset oxi-
ox
dation (Eonset) based on the reference energy level of ferrocence (4.8 eV
below the vacuum level) according to the following relation:
ox
HOMO = −e(Eonset − Eferrocene 1/2 + 4.8) (eV). The lowest unoccupied
molecular orbital (LUMO) levels were estimated from HOMO values
and values from optical band gaps according to the equation:
LUMO = HOMO + Egopt. (eV).

2.4. Fabrication and characterization of the thin films and OFET devices
Fig. 4. Cyclic voltammograms of CxCzT2 on indium tin oxide glass at a scanning rate of
0.1 Vs−1 in dichloromethane.
Bottom-gate-top-contact OFETs were fabricated on a common
gate of highly p-doped silicon with a 300 nm thick thermally grown
SiO2 dielectric layer (Si/SiO2 capacitance, Ci = 11 nF cm −2). The
structural confirmations ( 1H NMR, EA and ESI MASS) of the rest olig-
self-assembled monolayers on Si/SiO2 substrates were carried out
omers were also examined to confirm the exact structures.
with phenyltrichlorosilane (PTS) and octyltrichlorosilane (OTS) in
The poorest solubility was observed with CCzT2 (methyl-
0.1 M toluene solution for 12 h, respectively. The organic thin films
substituted) due to strong π–π interactions induced by the conjugate
of semiconductors were cast from 0.5 wt.% CxCzT2/toluene solutions
backbone. The precipitation of CCzT2 was also observed during
at constant ambient conditions with a normal thickness around
the reaction of synthesis in the period. As longer n-alkyl chains
100 nm, and were confirmed using a surface profiler (Alpha Step
were substituted, the solubility of CxCzT2 increased drastically for
500, Tencor). The cast thin film morphologies of CxCzT2 were studied
common organic solvents (THF, chloroform, toluene, chlorobenzene,
with a ZEISS German Axioskop Polarizing Optical Microscope (POM)
1,2-dichlorobenzene) at room temperature. The improvement in solu-
and an atomic force microscopy (AFM) using NanoScope IIIA AFM
bility is attributed to the combinations of longer n-alkyl substitutions,
(Digital Instruments, Santa Barbara, CA) at room temperature. Com-
the polarity of tertial amine on carbazole moieties, and the slight tilting
mercial silicon cantilevers (Nanosensors, Germany) with typical
molecular shape. In contrast, some n-alkyl-substituted oligothiophene
spring constants of 21–78 Nm −1 were used to operate the AFM in a
derivatives, such as α,ω-DH6T, DH-BTZ-4T, and DHFTTF, still showed
tapping mode. X-ray diffraction (XRD) was performed by a X'Pert
a low solubility to common organic solvents due to their linear and
PRO X-ray diffractometer using Cu Kα1 radiation (λ = 1.5418 Å)
symmetrical molecular shapes.
with a typical scan range of 2–30°. Gold source and drain electrodes
were evaporated on top of the semiconductor layers (100 nm). For
3.2. Thermal properties of CxCzT2
all OFET measurements, channel length (L) of 100 μm and channel
width (W) of 1500 μm were used. The electrical characteristics of
In order to investigate the thermal stabilities and thermal phase
the FETs were measured under ambient conditions with Keithley
transition behaviors of CxCzT2, TGA and DSC were used under nitro-
4200 Semiconductor Parametric Analyzer. Field-effect mobilities
gen atmosphere, as shown in Fig. 2. TGA revealed that CxCzT2 are
were calculated in the saturation regime from the slope of the
thermally stable with the 5% weight loss temperature high above
source-drain current.
400 °C. In contrast, oligothiophenes based on α,ω-DH6T decomposes
at 320 °C under similar conditions [37,38]. According to the DSC anal-
3. Results and discussion yses of CxCzT2, the increase in the n-alkyl chain length of CxCzT2 re-
sults in a decrease in the major phase transition temperatures. The
3.1. Syntheses and characterizations of CxCzT2 thermal transition states and corresponding enthalpies of CxCzT2
are summarized in Table 1. CCzT2 and C18CzT2 show unique endother-
The preparations of CxCzT2 via the Suzuki coupling reactions are mic peaks during heating cycles at 308.4 and 110.3 °C, and correspond-
shown in Scheme 1. The yields of CCzT2, C6CzT2, C12CzT2 and ing crystallization temperatures upon cooling cycles at 258.6 and
C18CzT2 were 53%, 62%, 67% and 58%, respectively. The 1H NMR of 62.1 °C, respectively. C6CzT2 shows an exothermic peak at 85.9 °C
purified C6CzT2 shows the predicted proton assignments and exact and an endothermic peak at 182.0 °C indicative of a thermal crystal
integrated values of proton numbers, as shown in Fig. 1. Other transition and melting point during a heating scan, respectively. No

Table 2
The absorption wavelengths, energy levels, and energy gaps of CxCzT2.
abs,solutiona abs,filmb abs,film opt.c oxidation
λmax λmax λonset /Eg Eonset /HOMOd LUMOe

nm nm nm/eV V/eV eV

CCzT2 398 244 408 244 480/2.58 0.69/−5.03 −2.45

C6CzT2 400 245 411 243 481/2.58 0.69/−5.03 −2.45
C12CzT2 398 244 424 243 484/2.56 0.70/−5.04 −2.48
C18CzT2 398 244 422 242 483/2.57 0.69/−5.03 −2.46
a
The absorption maximum in 10−6 M chloroform solution.
b
The absorption maximum of toluene-casted thin film on quartz at RT.
c
Estimated from the absorption onset point of the thin film, Egopt. =1240/λonsetabs,film.
d oxidation
Calculated from cyclic voltammograms of CxCzT2 on indium tin oxide glass, HOMO=−e(Eonset −Eferrocene1/2)+4.8 (eV).
e
LUMO=HOMO+Egopt. (eV).
 G.-P. Chang, K.-H. Hsieh / Thin Solid Films 527 (2013) 291–298
Fig. 5. Polarizing optical micrograms of toluene-casted CxCzT2 thin film at RT. (a) CCzT2 on unmodified Si/SiO2 substrate. (b) C6CzT2 on unmodified Si/SiO2 substrate. (c) C12CzT2
on unmodified Si/SiO2 substrate. (d) C18CzT2 on unmodified Si/SiO2 substrate. (e) C12CzT2 on PTS-treated Si/SiO2 substrate. (f) C12CzT2 on OTS-treated Si/SiO2 substrate.
obvious crystallization is observed for C6CzT2 during the cooling
scan. C12CzT2 show multiple endothermic peaks at 85.2, 131.0, and
141.3 °C indicative of liquid crystalline behavior upon heating, and the
corresponding crystallization temperatures upon cooling at 75.4 and
81.7 °C. As shown in previous studies, liquid crystalline has been
shown to be a favorable property for predicting whether materials
have good charge transport mobilities [23,39]. Compared to similar
oligothiophene derivatives, high thermal phase transition temperatures
were observed with α,ω-DH6T (Tm: 304 °C) [38] and DHFTTF (Tm:
381 °C) [15]. In general, the lower thermal phase transition tempera-
ture region of CxCzT2 can ensure operation or fabrication in mild
condition.
3.3. Optical and electrochemical properties of CxCzT2
The optical properties of CxCzT2 in a chloroform solution and
toluene-casted thin film were studied with a UV–vis spectrometer, as
shown in Fig. 3. In a solution state, as shown in Fig. 3a, CxCzT2 show
two distinct peaks at 244 and 398 nm. The thin film absorption spectra
show two bands of peaks, as seen in Fig. 3b: one in the range of
350–500 nm and another in the range of 243–290 nm. Interestingly,
the toluene-casted CCzT2 and C6CzT2 show single broad peaks at 408
and 411 nm; C12CzT2 and C18CzT2 split two shoulders around 424
and 422 nm. These splits for the characteristic molecular orientations
are presumed to be caused by the longer n-alkyl chain [39]. By compar-
ing the absorption spectra in a chloroform solution and thin film, the
red-shifts are observed in the main peak around 400 nm as listed in
Table 2. The red-shifts indicate that J-aggregations (head-to-tail
295
molecular stacking) exist in a thin film state [40]. By comparing the ab-
sorption bands of CxCzT2, the longer wavelength absorption band
(350–500 nm) is indicative of the intramolecular charge transfer be-
tween carbazole and bithiophene and the shorter wavelength absorp-
tion band (243–290 nm) is assigned to the π–π⁎ transition. The
optical band gaps (Egopt.) of CxCzT2 are around 2.57 eV, calculated
according to the absorption edges of the thin films [15,41].
CV was used to investigate the HOMO energy levels of CxCzT2, as
shown in Fig. 4. The electrochemical characteristics of the onset oxi-
oxidation
dation (Eonset ) and HOMO are 0.69 V and − 5.03 eV, respectively.
In contrast, the HOMO energy levels of CxCzT2 are higher than
those of similar structures such as α,ω-DH6T (− 5.20 eV) [42] and
DHFTTF (− 5.36 eV) [15] due to the strong electron donating proper-
ties of carbazole moieties. The LUMO energy levels of CxCzT2 are
around − 2.46 eV calculated by the addition of HOMO and Eg opt. as
listed in Table 2 [41]. Similar optical–physical and electrochemical
properties of CxCzT2 are attributed to the constant conjugate back-
bone of carbazole–bithiophene–carbazole.
3.4. The thin-film morphologies of toluene-casted CxCzT2
The thin film morphologies of toluene-casted CxCzT2 on
unmodified Si/SiO2 substrates were characterized with POM and
AFM, as shown in Figs. 5 and 6. The thin films were all prepared at
room temperature under similar ambient conditions. A fragmental
and discontinuous morphology is observed with toluene-casted
CCzT2 thin film, as shown in Fig. 5a, due to its ultra-low solubility
in toluene, which indicates that CCzT2 could not be further fabricated
296 G.-P. Chang, K.-H. Hsieh / Thin Solid Films 527 (2013) 291–298

Fig. 6. Atomic force micrograms of toluene-casted CxCzT2 thin film at RT. (a) C6CzT2 on unmodified Si/SiO2 substrate. (b) C12CzT2 on unmodified Si/SiO2 substrate. (c) C18CzT2 on
unmodified Si/SiO2 substrate. (d) C12CzT2 on PTS-treated Si/SiO2 substrate. (e) C12CzT2 on OTS-treated Si/SiO2 substrate.

via toluene casting. As the longer n-alkyl chains (n-hexyl-, n-dodecyl-
and n-octadecyl-) were substituted, the oligomers could stack contin-
uously during the evaporation of toluene and cover the Si/SiO2
substrates in a larger area, as shown in Fig. 5b to d.
The AFM images also show the smooth and dense thin film mor-
phologies of these toluene-casted CxCzT2 with longer n-alkyl substi-
tutions, as shown in Fig. 6a to c. This easiness of high quality thin film
formation in large areas of CxCzT2s is the key requirement for the
preparation of economical solution-fabricated OFETs. In contrast, the
deposited-C12CzT2 show a unidirectional layer-by-layer morphology
compared to C6CzT2 and C18CzT2 due to its unique liquid crystalline
property as observed in DSC curves.
In reality, thin film morphologies are not only affected by
intermolecular interactions, but can also be affected by heterophase in-
teractions (oligomeric semiconductors to Si/SiO2 substrate) [43]. Thus,
the adjustments of the chemical compatibilities or surface polarities on
Si/SiO2 substrates are of interest in controlling the casted thin film
morphology of C12CzT2. The Si/SiO2 surfaces were pretreated with
phenyltrichlorosilane (PTS) and octyltrichlorosilane (OTS) to form a
phenyl- and octyl-self-assembled monolayer (SAM), respectively, be-
fore the casting of C12CzT2. The outer exposed phenyl groups and
octyl groups on Si/SiO2 substrates are expected to enhance the molecu-
lar orientation of C12CzT2 in two ways — π–π interactions and van der
Waals interactions, respectively. As shown in Fig. 6d, the C12CzT2 on
PTS-treated Si/SiO2 substrates aggregated to form a terrace morphology.
However, a mica-liked morphology was observed on OTS-treated
Si/SiO2 substrates, as shown in Fig. 6e.
3.5. XRD of toluene-casted CxCzT2 thin film
To investigate the effect of crystalline properties and molecular
packing of toluene-casted CxCzT2 on unmodified Si/SiO2 substrates,
experiments using XRD were performed, as shown in Fig. 7. The
toluene-casted C6CzT2, C12CzT2 and C18CzT2 on unmodified Si/SiO2
 G.-P. Chang, K.-H. Hsieh / Thin Solid Films 527 (2013) 291–298 297

Fig. 7. X-ray diffractograms of toluene-casted CxCzT2 thin films on unmodified Si/SiO2

substrates at RT. Inset: X-ray diffractograms of toluene-casted C12CzT2 on surface-
treated Si/SiO2 substrate.

substrates have similar diffraction peaks at 2.41° (dspacing: 36.7 Å) as

defined (100); this peak is presumed to be the reflection of a conjugate
backbone (carbazole–bithiophene–carbazole) [15,23]. The second order
diffraction peaks of C6CzT2, C12CzT2, and C18CzT2 are at 5.95° (14.8 Å,
010), 4.55° (19.3 Å, 010), and 3.51° (24.9 Å, 010), respectively. These sec-
ond order diffractions indicate the characteristic stack by n-alkyl chain
lengths of each oligomer. The interdigitated molecular orientations of
casted CxCzT2 thin film are presumed because of the π–π interactions
of conjugate backbones and the van der Waals interactions of n-alkyl
chain.
The casted C12CzT2 on PTS-treated and OTS-treated Si/SiO2 sub-
strates were also investigated using XRD, as shown in the inset of
Fig. 7. The qualitative diffraction peaks of C12CzT2 show no obvious
displacement. However, the higher intensity of second order 4.55° Fig. 8. OFET current–voltage curves of CxCzT2 on unmodified Si/SiO 2 substrates.
(a) Output characteristic (Ids–Vds) of C12CzT2. (b) Transfer characteristics (Ids–Vgs) of
diffraction of C12CzT2 is observed on OTS-treated Si/SiO2 substrate.
CxCzT2 (Vds =−100 V).

3.6. OFET device performances of CxCzT2

(SiO2, 300 nm, Ci =11 nF cm−2), respectively. As expected, the highest
The organic field-effect transistors were all fabricated in bottom- hole mobility is observed in C12CzT2 (μh =3.6×10−2 cm2 V−1 s−1),
gate-top-contact (drain and source gold electrodes were deposited due to the highest Ion/Ioff ratio. The hole mobility of C6CzT2 and
above the CxCzT2 thin films) device geometry. The OFET current– C18CzT2 is 1.4×10−3 and 1.3×10−4 cm2 V−1 s−1, respectively.
voltage curves were all measured under ambient conditions, as As an excellent hole mobility was observed in toluene-casted
shown in Fig. 8. The output characteristic (Ids–Vds) of C12CzT2 C12CzT2, the fine-tuned OFET device was carried out with the fabrica-
shows a standard linear and saturation region, as shown in Fig. 8a. tion of C12CzT2 on PTS- and OTS-treated Si/SiO2 substrates [43]. The
The Ids (drain-to-source current) curves of C12CzT2 are scaled up Ion/Ioff ratio of C12CzT2 on PTS- and OTS-treated Si/SiO2 substrate
progressively with the increased Vg (gate voltages); this field-effect was raised to 10 6 and 10 5.6, respectively. As shown in Fig. 9, lower
property is also observed in C6CzT2 and C18CzT2. “off currents (Ioff)” and higher “on currents (Ion)” were observed
The Ion/Ioff ratios, Vons (turn-on voltages), and Vts (threshold volt- for the trichlorosilane-treated Si/SiO2 substrates compared to the
ages) of CxCzT2 were read from the transfer characteristics (Ids–Vgs) unmodified Si/SiO2 substrate. The free hydroxyl groups on unmodified
data and summarized in Table 3. The Ion/Ioff ratios of C6CzT2, C12CzT2, Si/SiO2 substrate could act as p-type doping and charge carrier trapping
and C18CzT2 on unmodified Si/SiO2 substrates are 103.6, 105, and 102.5, sites to reduce the Ion/Ioff ratio of organic active layers during operation
respectively. The highest Ion/Ioff ratio of C12CzT2 is attributed to the liq- [44]. Thus, the elimination of free hydroxyl groups is expected to
uid crystal properties as discussed previously [23,39]. The lowest Ion/Ioff enhance the performance of trichlorosilane-treated OFET devices. By
ratio of C18CzT2 is presumed to result due to the hindrance of charge comparing the outer exposed groups of SAM, the π–π interactions
carrier travel caused by the octadecyl substitutions. According to this induced by the phenyl groups of SAM show a more significant
tendency, the length of n-alkyl substitutions had to be compromised by
the OFET performance such as the Ion/Ioff ratio in this development. Table 3
The hole mobility of these studied oligomers on unmodified OFET performances of CxCzT2.
Si/SiO2 substrates was also calculated in the saturation region as
Modifications of Film Ion/Ioff Hole mobility, μh Von (V) Vt (V)
described by Eq. (1): Si/SiO2 substrate thickness ratio (cm2 V−1 s−1)
    (nm)
1=2 μ h WC i 1=2 μ WC i 1=2
Ids ¼ V g− h V t: 1 C6CzT2 None 98 103.6 1.4 × 10−3 −12 −35.0
2L 2L C12CzT2 None 110 105 3.6 × 10−2 0 −23.9
C18CzT2 None 105 102.5 1.3 × 10−4 −2 −11.0
Here μh is the hole mobility, W is the channel width, L is the channel C12CzT2 PTS-treated 87 106 1.2 × 10−1 −8 −46.7
OTS-treated 98 105.6 5.1 × 10−2 −8 −47.0
length, and Ci is the capacitance of the gate insulator per unit area
298 G.-P. Chang, K.-H. Hsieh / Thin Solid Films 527 (2013) 291–298
Fig. 9. Transfer characteristics (Ids–Vgs) of C12CzT2 on unmodified, PTS-treated, and
OTS-treated Si/SiO2 substrate (Vds = −100 V).
enhancement to the Ion/Ioff ratio than octyl groups. The hole mobility of
C12CzT2 on PTS- and OTS-treated Si/SiO2 substrate is also raised to
1.2 × 10−1 and 5.1 × 10 −2 cm2 V−1 s−1, respectively. The remarkable
hole mobilities and easy of fabrication of C12CzT2 could make it a prom-
ising candidate for high-end OFET devices in economical manufacturing.
4. Conclusion
In this research, a series of oligocarbazole–thiophenes with a
constant conjugate backbone (carbazole–bithiophene–carbazole,
CxCzT2) via the Suzuki coupling reaction was presented. The thermal
stabilities of CxCzT2 were more than 400 °C. The variations in n-alkyl
chain lengths on carbazole moieties directly affected the thermal
phase behaviors of CxCzT2, and liquid crystal properties were ob-
served with dodecyl substitution (C12CzT2). As the conjugate back-
bones of CxCzT2 are constant, the optical and electrochemical
properties all lie within similar ranges. Synthesized CxCzT2 with lon-
ger n-alkyl chain substitutions are all solution fabrication-capable for
OFET devices with toluene to form high quality, continuous, and dense
thin film on Si/SiO2 substrates. Since liquid crystal properties are ob-
served for C12CzT2, the highest Ion/Ioff ratio (105) and hole mobility
(3.6 × 10 −2 cm2 V−1 s−1) are expected for other n-alkyl substituted
CxCzT2. The Ion/Ioff ratio and hole mobility of C12CzT2 are further
improved to 10 6 and 1.2 × 10 −1 cm2 V −1 s −1 on PTS-treated Si/SiO2
substrate. In this development of solution-fabricated OFET based on
CxCzT2, the excellent performance of C12CzT2 could be applied to
high-end OFET devices.
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