materials

Review
Inkjet-Printed Organic Transistors Based on Organic
Semiconductor/Insulating Polymer Blends
Yoon-Jung Kwon 1 , Yeong Don Park 2 and Wi Hyoung Lee 1, *
1 Department of Organic and Nano System Engineering, Konkuk University, Seoul 05029, Korea;
yjkwon@konkuk.ac.kr
2 Department of Energy and Chemical Engineering, Incheon National University, Incheon 22012, Korea;
ydpark@inu.ac.kr
* Correspondence: whlee78@konkuk.ac.kr; Tel.: +82-2-450-3468

Academic Editor: Volker Altstädt

Received: 18 March 2016; Accepted: 15 July 2016; Published: 2 August 2016

Abstract: Recent advances in inkjet-printed organic field-effect transistors (OFETs) based on organic
semiconductor/insulating polymer blends are reviewed in this article. Organic semiconductor/
insulating polymer blends are attractive ink candidates for enhancing the jetting properties, inducing
uniform film morphologies, and/or controlling crystallization behaviors of organic semiconductors.
Representative studies using soluble acene/insulating polymer blends as an inkjet-printed active
layer in OFETs are introduced with special attention paid to the phase separation characteristics
of such blended films. In addition, inkjet-printed semiconducting/insulating polymer blends for
fabricating high performance printed OFETs are reviewed.

Keywords: polymer blend; organic field-effect transistor; inkjet printing; organic semiconductor;
soluble acene; printed electronics

1. Introduction
Organic field-effect transistors (OFETs) have received much attention as key components for
enabling flexible electronics on plastic substrates [1,2]. Today, the performances of OFETs are
comparable to or exceed those of a-Si FETs. However, OFETs have several technological difficulties
including bias instability and time dependent degradation of performances [3,4]. Thus, OFETs may
not be able to replace traditional high-speed devices that are based on single crystal silicon. In this
regard, the merits of OFETs are mainly cost efficiency and plastic compatibility [5]. Considering that
cost-effective printing methods are technologically desirable for realizing large-area OFET arrays, all
layers (i.e., semiconductor, dielectric, electrode) consisting of OFETs could be fabricated via printing
methods [6–9]. For example, roll-to-roll printing such as gravure or offset printing provides patterned
electrodes, semiconductors, and dielectrics [10,11]. Consecutive roll-to-roll printing could therefore
reduce the production cost of OFETs. Notwithstanding these benefits of roll-to-roll printing, reducing
feature size and registration error are obstacles to the commercialization of roll-to-roll printed OFETs.
On the other hand, inkjet printing is technologically advantageous because the pattern can be directly
formed by dropping ink onto a desired region [12,13]. In addition, it is an economical method as no
waste is generated during the process. Moreover, feature size can be reduced by decreasing the size of
the nozzle [14]. Semiconducting layers of OFETs can also be successfully fabricated by inkjet printing
with organic semiconductor inks [15], exhibiting excellent device performances comparable to those of
OFETs based on spin-cast organic semiconducting layers.
The inkjet printing process is schematically shown in Figure 1. Inkjet printable materials
should have sufficient ink properties (i.e., surface tension, solvent evaporation rate, and solubility)
for successful ejection at the nozzle orifice. After ejection, the ink shoots out of the nozzle and

Materials 2016, 9, 650; doi:10.3390/ma9080650 www.mdpi.com/journal/materials

Materials 2016,
Materials 2016, 9,
9, 650
650 22 of
of 16
15

for successful ejection at the nozzle orifice. After ejection, the ink shoots out of the nozzle and
impacts the substrate while it spreads and dries during evaporation of the solvent [5]. Typically, Typically, the
outward convective flow in the pinned droplet results in a ring stain, as shown in the the inset
inset in
in Figure
Figure 1. 1.
This coffee
coffeering
ringeffect
effectis commonly
is commonly regarded
regardedas anasundesirable
an undesirableaspect aspect
of inkjet
ofprinting, since uniform
inkjet printing, since
morphology with reduced ring stain is necessary for inkjet-printed organic
uniform morphology with reduced ring stain is necessary for inkjet-printed organic semiconductor semiconductor films.
Besides morphology,
films. Besides morphology,the crystalline structure
the crystalline of theoforganic
structure the organicsemiconductor
semiconductor is also important
is also important for
improving
for improvingthe performances
the performances of OFETs basedbased
of OFETs on inkjet-printed organicorganic
on inkjet-printed semiconductor film. The
semiconductor type
film. of
The
solvent, concentration of ink, and/or substrate wettability can control the morphology
type of solvent, concentration of ink, and/or substrate wettability can control the morphology and and crystalline
structure
crystallineofstructure
inkjet-printed organic semiconductor
of inkjet-printed films. Many
organic semiconductor efforts
films. Many have beenhave
efforts made to enhance
been made to
field-effect mobilitiesmobilities
enhance field-effect of OFETs [15–17].
of OFETs Various
[15–17].review articles
Various have articles
review been presented
have been on inkjet-printed
presented on
OFETs [5,9]. ForOFETs
inkjet-printed example, it has
[5,9]. Forbeen demonstrated
example, it has that
beenblending an organic
demonstrated thatsemiconductor
blending an with organic an
insulating
semiconductorpolymer
with is advantageous
an insulating for enhancing
polymer jetting properties
is advantageous [18]. Since the
for enhancing solubility
jetting of organic
properties [18].
semiconductors is rather
Since the solubility limitedsemiconductors
of organic and crystallization can occur
is rather at theand
limited nozzle orifice, adding
crystallization canan insulating
occur at the
polymer can enhance
nozzle orifice, addingthe an jetting properties.
insulating polymer Incan
addition,
enhance suchthea jetting
blend approach
properties. is quite appealing
In addition, suchfora
reducing the cost is
blend approach of materials,
quite appealingenhancingfor mechanical
reducing the properties,
cost of reducing
materials,processing
enhancingsteps, and/or
mechanical
increasing
properties, device
reducingstabilities [19–40].
processing To obtain
steps, and/orcomparable
increasing or enhanced
device device[19–40].
stabilities performances,
To obtainthe
morphologies
comparable orand crystalline
enhanced structures
device of inkjet-printed
performances, organic semiconductor/insulating
the morphologies and crystalline structures polymer of
blend films need
inkjet-printed to be controlled.
organic Especially, charge
semiconductor/insulating transportblend
polymer alongfilms
the lateral
needdirection should be
to be controlled.
guaranteed when utilizing
Especially, charge transport organic
along semiconductor/insulating
the lateral direction should polymer blend film
be guaranteed whenin the active organic
utilizing layer in
OFETs [19].
semiconductor/insulating polymer blend film in the active layer in OFETs [19].

Figure 1. Schematic diagram showing the inkjet printing process. The right/top inset shows
Figure 1. Schematic diagram showing the inkjet printing process. The right/top inset shows
scanning electron microscopy (SEM) image of inkjet-printed poly(3,4-ethylenedioxythiophene)/
scanning electron microscopy (SEM) image of inkjet-printed poly(3,4-ethylenedioxythiophene)/
poly(styrenesulfonate) (PEDOT/PSS) electrode [5]. Copyright 2013 American Chemical Society.
poly(styrenesulfonate) (PEDOT/PSS) electrode [5]. Copyright 2013 American Chemical Society.

In this review article, inkjet-printed organic transistors based on organic semiconductor/insulating

In this
polymer review
blends article, inkjet-printed
are reviewed. The purposesorganic transistors
of the blend approachbased on organic
in inkjet printingsemiconductor/
are as follows:
insulating polymer blends are reviewed. The purposes of the blend approach
(1) enhancing jetting efficiency; (2) reducing materials cost; (3) increasing uniformity in inkjet printingin
are as follows: (1) enhancing jetting efficiency; (2) reducing materials cost; (3) increasing
inkjet-printed deposit; and (4) enhancing device performances. We will introduce topics from uniformity
in inkjet-printed deposit;
solution-processed small and (4) enhancing
molecular device performances.
semiconductor (namely, solubleWe will introduce topics
acene)/insulating from
polymer
solution-processed small molecular semiconductor
blends to semiconducting/insulating (namely,
polymer blends. Forsoluble acene)/insulating
each work reviewed, phasepolymer blends
separation
to semiconducting/insulating polymer blends. For each work reviewed, phase separation
control for guaranteeing charge transport along the lateral direction is also introduced and control for
guaranteeing
analyzed. charge transport along the lateral direction is also introduced and analyzed.

2. Soluble Acene/Insulating Polymer Blends

2. Soluble Acene/Insulating Polymer Blends
TIPS-pentacene (6,13-Bis(triisopropylsilylethynyl) pentacene) is a representative soluble
TIPS-pentacene (6,13-Bis(triisopropylsilylethynyl) pentacene) is a representative soluble acene
acene [41–43]. It has high solubility and co-facial stacking with reduced π–π stacking distance.
[41–43]. It has high solubility and co-facial stacking with reduced π–π stacking distance. Many
Many studies have utilized TIPS-pentacene as an active layer in OFETs [41]. When TIPS-pentacene/
studies have utilized TIPS-pentacene as an active layer in OFETs [41]. When
insulating polymer blends are used as an active layer of OFETs, the phase-separated structure typically
TIPS-pentacene/insulating polymer blends are used as an active layer of OFETs, the
contains TIPS-pentacene-top, insulating polymer-middle, and TIPS-pentacene- bottom tri-layers [34,44].
phase-separated structure typically contains TIPS-pentacene-top, insulating polymer-middle, and
TIPS-pentacene-bottom tri-layers [34,44]. Because the conducting channel in this phase-separated
Materials 2016, 9, 650 3 of 16
Materials 2016, 9, 650 3 of 15

Because
structuretheisconducting
guaranteed, channel
manyinresearchers
this phase-separated structureto
have attempted is guaranteed, many researchers have
utilize TIPS-pentacene/insulating
attempted to utilize TIPS-pentacene/insulating polymer blends as the
polymer blends as the active layer in OFETs. One of the merits for tri-layer phase-separation active layer in OFETs. Oneisofthat the
merits for tri-layer
insulating polymerphase-separation
in the middle can is that insulating
protect polymer in
the conducting the middle
channel can protect the conducting
(TIPS-pentacene-bottom layer)
channel
from atmospheric air. Thus, environmental stabilities of OFETs are greatly stabilities
(TIPS-pentacene-bottom layer) from atmospheric air. Thus, environmental enhanced. of OFETs
When
are greatly enhanced.
designing the inkjetWhen designing
printing the inkjet printing of TIPS-pentacene/insulating
of TIPS-pentacene/insulating polymer, the printabilitypolymer,and the
printability
microstructure andof microstructure of the ring-like
the ring-like deposits shoulddeposits should be considered.
be considered.
Madec
Madec et al. added amorphous polystyrene (PS) to TIPS-pentacene
et al. added amorphous polystyrene (PS) to TIPS-pentacene ink ink toto enhance
enhance thethe jetting
jetting
properties
properties of of the
the ink
ink [18]. Such aa blend
[18]. Such blend approach
approach is is beneficial
beneficial forfor the
the formation
formation of of uniform
uniform films.
films.
Droplet profiles of TIPS-pentacene (1 g/dL in anisole), TIPS-pentacene/PS
Droplet profiles of TIPS-pentacene (1 g/dL in anisole), TIPS-pentacene/PS blends (1:1 w/w, 1 g/dL in blends (1:1 w/w, 1 g/dL in
anisole), and PS (0.5 g/dL in anisole) are shown in Figure 2a–c. For TIPS-pentacene
anisole), and PS (0.5 g/dL in anisole) are shown in Figure 2a–c. For TIPS-pentacene ink, a distorted ink, a distorted
ligament
ligament with
withsatellites
satellitesisisdetected.
detected. This is typical
This in low-viscosity
is typical in low-viscosity Newtonian fluids.fluids.
Newtonian WhenWhenPS is added
PS is
to TIPS-pentacene ink, the stabilization of ligament and coalescing
added to TIPS-pentacene ink, the stabilization of ligament and coalescing of satellites can of satellites can lead to greater
lead to
control
greater of the droplet
control of the generation process (Figure
droplet generation process2b). This clearly
(Figure 2b). This indicates
clearly that the added
indicates insulating
that the added
polymer is beneficial for the inkjet drop ejection process. When TIPS-pentacene/PS
insulating polymer is beneficial for the inkjet drop ejection process. When TIPS-pentacene/PS blend blend solution in
anisole is inkjet-printed, the coffee staining effect induces the formation of artifacts
solution in anisole is inkjet-printed, the coffee staining effect induces the formation of artifacts at the at the edge of the
printed
edge of deposits
the printed(Figure 2d). However,
deposits (Figure 2d).in the case of anisole/acetophenone
However, (90/10), a uniform
in the case of anisole/acetophenone deposita
(90/10),
with high crystallinity is formed due to the reduced convective flow.
uniform deposit with high crystallinity is formed due to the reduced convective flow. BecauseBecause acetophenone has a high
boiling point while TIPS-pentacene has a limited solubility in this solvent,
acetophenone has a high boiling point while TIPS-pentacene has a limited solubility in this solvent, the coffee staining effect is
decreased but crystallinity
the coffee staining effect is is increasedbut
decreased significantly
crystallinity (Figure 2e). significantly (Figure 2e).
is increased

Figure 2. Droplet profiles of of (a)

(a) 6,13-Bis(triisopropylsilylethynyl)
6,13-Bis(triisopropylsilylethynyl) pentacene
pentacene (TIPS-pentacene,
(TIPS-pentacene, 11g/dL
g/dL
anisole); (b)
in anisole); (b) TIPS-pentacene/polystyrene
TIPS-pentacene/polystyrene (PS) (PS) blends
blends (1:1 w/w,
w/w, 11 g/dL
g/dL inin anisole);
anisole); and
and (c) PS
g/dL in
(0.5 g/dL inanisole.
anisole.Optical
Optical microscopy
microscopy images
images of inkjet-printed
of inkjet-printed TIPS-pentacene/PS
TIPS-pentacene/PS blendblend films
films using
using
(d) (d) anisole
anisole solution
solution or (e) anisole/acetophenone
or (e) anisole/acetophenone (90/10)(90/10)
mixedmixed solution
solution [18]. Copyright
[18]. Copyright 2010
2010 Royal
Royal Society
Society of Chemistry.
of Chemistry.

The TIPS-pentacene/insulating
The TIPS-pentacene/insulating polymerpolymer blend
blend was
was used
used for examining the
for examining the crystallization
crystallization
behavior of TIPS-pentacene in insulating polymer. Vertical phase-separation in
behavior of TIPS-pentacene in insulating polymer. Vertical phase-separation in spin-cast spin-cast blendblend
film
has been
film demonstrated
has been by several
demonstrated research
by several groups
research [19,34,44].
groups TheThe
[19,34,44]. morphologies
morphologies andand
structures
structuresof
inkjet-printed TIPS-pentacene/PS blend films with various blend ratios have been
of inkjet-printed TIPS-pentacene/PS blend films with various blend ratios have been examined examined by
Li et
by al.al.[45].
Li et [45]. Figure
Figure 3a,b
3a,b show
show polarized
polarized optical
optical microscopy
microscopy images
images of of the transition of
the transition of
TIPS-pentacene/PS blend
TIPS-pentacene/PS blend films
films with
with increasing
increasing wt
wt %
% of
of TIPS-pentacene
TIPS-pentacene atat substrate
substrate temperatures
temperatures of of
70 °C and 20 °C, respectively. When pure TIPS-pentacene in tetralin was used for inkjet-printing,
the depinning of the droplets resulted in TIPS-pentacene deposit with an irregular shape (Figure 3a,
100%). An increased content of PS and well-resolved TIPS-pentacene crystals with uniform
Materials 2016, 9, 650 4 of 16

70 ˝ C and 20 ˝ C, respectively. When pure TIPS-pentacene in tetralin was used for inkjet-printing, the
Materials 2016, 9, 650 4 of 15
depinning of the droplets resulted in TIPS-pentacene deposit with an irregular shape (Figure 3a, 100%).
An increased content
morphologies of PS and(80%,
were observed well-resolved TIPS-pentacene
67%). However, crystals with
further increasing theuniform
content morphologies
of PS to 50%
were observed (80%, 67%). However, further increasing the content of PS to 50% resulted
resulted in small crystals at the edge of the ring-like deposit. When the substrate temperature in small
was
crystals at the edge of the ring-like deposit. When the substrate temperature was decreased
decreased to 25 °C, the drying time was increased and the contact line depinning was magnified to 25 ˝ C,
the drying
(Figure 3b, time
100%). was increased
Because and the contact
tetralin—with a highline depinning
boiling was used
point—was magnified
as the(Figure
solvent,3b, 100%).
substrate
Because tetralin—with a high boiling point—was used as the solvent, substrate heating
heating was necessary to increase the solvent evaporation rate and decrease the contact line was necessary
to increase the solvent evaporation rate and decrease the contact line depinning.
depinning.

Figure 3.
Figure 3. Polarized
Polarized optical
optical microscopy
microscopyimages
imagesshowing
showingtransition
transitionof
ofTIPS-pentacene/PS
TIPS-pentacene/PS blend
blend films
films
withincreasing
with increasingwtwt % of%TIPS-pentacene:
of TIPS-pentacene: (a) Substrate
(a) Substrate temperature
temperature at Substrate
at 70 ˝ C; (b) 70 °C; (b) Substrate
temperature
temperature
at 20 ˝ C. Scaleatbar:
20 °C.
100Scale bar: Copyright
µm [45]. 100 μm [45]. Copyright
2011 Elsevier.2011 Elsevier.

OFETs with blend film (67% of TIPS-pentacene) exhibited superior electrical properties to
OFETs with blend film (67% of TIPS-pentacene) exhibited superior electrical properties to those of
those of FETs with pure TIPS-pentacene film (Figure 4a). Field-effect mobility showed a maximum
FETs with pure TIPS-pentacene film (Figure 4a). Field-effect mobility showed a maximum value at the
value at the TIPS-pentacene ratio of 67%–80% (Figure 4b). Interestingly, a low subthreshold slope
TIPS-pentacene ratio of 67%–80% (Figure 4b). Interestingly, a low subthreshold slope (sharp turn-on)
(sharp turn-on) in the blend OFETs is noticeable. This can be explained by the contact resistance
in the blend OFETs is noticeable. This can be explained by the contact resistance which might have
which might have originated from the phase-separated insulating polymer (here, PS). To
originated from the phase-separated insulating polymer (here, PS). To investigate the validity of this
investigate the validity of this assumption, scanning Kelvin probe microscopy (SKPM) was used to
assumption, scanning Kelvin probe microscopy (SKPM) was used to detect any potential drop at the
detect any potential drop at the contact region. Figure 4c,d show comparative topography and
contact region. Figure 4c,d show comparative topography and surface potential images. The bright
surface potential images. The bright regions in the topography images correspond to the Au
regions in the topography images correspond to the Au source/drain electrodes. The blend sample
source/drain electrodes. The blend sample exhibited a higher potential drop at the contact region
exhibited a higher potential drop at the contact region compared to that of the pure TIPS-pentacene
compared to that of the pure TIPS-pentacene sample. This implied the existence of hole trapping at
sample. This implied the existence of hole trapping at the contact region of the blend OFETs, thereby
the contact region of the blend OFETs, thereby contributing to a sharp turn-on as shown in Figure 4a.
contributing to a sharp turn-on as shown in Figure 4a.
The crystallization characteristics of the TIPS-pentacene/PS blend could also be affected by the
The crystallization characteristics of the TIPS-pentacene/PS blend could also be affected by
surface characteristics of the Au source/drain electrodes [46]. Polarized optical microscopy images
the surface characteristics of the Au source/drain electrodes [46]. Polarized optical microscopy
of the inkjet-printed deposits of the TIPS-pentacene and TIPS-pentacene/PS blend films on
images of the inkjet-printed deposits of the TIPS-pentacene and TIPS-pentacene/PS blend films
pentafluorobenzenethiol (PFBT) treated Au electrodes are shown in Figure 5a,c, respectively.
on pentafluorobenzenethiol (PFBT) treated Au electrodes are shown in Figure 5a,c, respectively.
Polarized optical microscopy images of the inkjet-printed deposits of the TIPS-pentacene and
Polarized optical microscopy images of the inkjet-printed deposits of the TIPS-pentacene and
TIPS-pentacene/PS blend films on trichlorophenylsilane (TCPS) treated SiO2/Si substrates are
TIPS-pentacene/PS blend films on trichlorophenylsilane (TCPS) treated SiO2 /Si substrates are shown
shown in Figure 5b,d, respectively. Highly crystalline TIPS-pentacene crystals were predominantly
in Figure 5b,d, respectively. Highly crystalline TIPS-pentacene crystals were predominantly observed
observed in the PFBT treated Au electrodes. The Raman intensity of the C–C ring stretch mode as a
in the PFBT treated Au electrodes. The Raman intensity of the C–C ring stretch mode as a function
function of the polarization angle as shown in Figure 5e–h taken from the red circled points in
of the polarization angle as shown in Figure 5e–h taken from the red circled points in Figure 5a–d
Figure 5a–d supports the presence of anisotropic TIPS-pentacene crystals on the PFBT treated Au
supports the presence of anisotropic TIPS-pentacene crystals on the PFBT treated Au and isotropic
and isotropic TIPS-pentacene crystals on the TCPS treated SiO2/Si. Importantly, the added PS did
not disturb the growth of the highly oriented TIPS-pentacene crystals. Instead, the
TIPS-pentacene/PS blend led to a uniform film with reduced variations in molecular orientation.
Thus, the field-effect mobility of OFETs based on the TIPS-pentacene/PS blend was increased to
more than 0.72 cm2/Vs, whereas the OFETs based on single TIPS-pentacene exhibited mobility of
Materials 2016, 9, 650 5 of 16

TIPS-pentacene crystals on the TCPS treated SiO2 /Si. Importantly, the added PS did not disturb the
growth of the highly oriented TIPS-pentacene crystals. Instead, the TIPS-pentacene/PS blend led to
a uniform
Materials 2016,film with reduced variations in molecular orientation. Thus, the field-effect mobility
9, 650 5 of of
15
OFETs based on the TIPS-pentacene/PS blend was increased to more than 0.72 cm2 /Vs, whereas the
OFETs
0.22 cmbased
2/Vs. on single TIPS-pentacene
Kjellander et al. enhanced exhibited mobility
the electrical of 0.22 cmof2 /Vs.
properties Kjellander et al.OFETs
TIPS-pentacene/PS enhanced by
the
usingelectrical
off-centeredproperties
inkjet of TIPS-pentacene/PS
printing [47]. Because theOFETs by using off-centered
crystallization inkjet printing
of TIPS-pentacene [47].
in the blend
Because
started atthe thecrystallization of TIPS-pentacene
edge of the ring-like droplet, theinTIPS-pentacene
the blend started at the met
crystals edgeatofthe
thecenter
ring-like droplet,
(Figure 5i).
Thus,
the the OFETs based
TIPS-pentacene on off-centered
crystals met at the printing led to higher
center (Figure 5i). Thus,field-effect mobility
the OFETs based(1.1
on cm /Vs) than
off-centered
2

that of the
printing ledOFETs
to higherbased on on-centered
field-effect (1.1 cm2(Figure
mobilityprinting 5j). that
/Vs) than Unipolar
of thecircuitry building
OFETs based blocks and
on on-centered
a radio-frequency
printing (Figure 5j).identification (RFID)
Unipolar circuitry transponder
building can aalso
blocks and be fabricatedidentification
radio-frequency using off-centered
(RFID)
inkjet-printedcan
transponder TIPS-pentacene/PS
also be fabricatedblends.
using off-centered inkjet-printed TIPS-pentacene/PS blends.

Figure 4.
Figure 4. (a)
(a) Transfer
Transfer characteristics
characteristics in
in saturation
saturation regime
regime(V (VDS == ´10
−10 V)
V) for field-effect transistors
for field-effect transistors
DS
(FETs) based on pure TIPS-pentacene (open circles in blue) and TIPS-pentacene/PS
(FETs) based on pure TIPS-pentacene (open circles in blue) and TIPS-pentacene/PS blend blend of 67 wt of
%
TIPS-pentacene (solid circles in red); (b) Average field-effect mobilities as a function of
67 wt % TIPS-pentacene (solid circles in red); (b) Average field-effect mobilities as a function of TIPS-pentacene
weight ratios in FETs
TIPS-pentacene with
weight TIPS-pentacene/PS
ratios blend film. 2D topography
in FETs with TIPS-pentacene/PS and corresponding
blend film. 2D topography surface
and
potential images were measured with scanning Kelvin probe microscopy (SKPM)
corresponding surface potential images were measured with scanning Kelvin probe microscopy (SKPM) of (c) pure
TIPS-pentacene
of film or (d) film
(c) pure TIPS-pentacene TIPS-pentacene/PS blend film (67
or (d) TIPS-pentacene/PS wt film
blend % TIPS-pentacene) [45]. Copyright
(67 wt % TIPS-pentacene) [45].
2011 Elsevier.
Copyright 2011 Elsevier.

Cho et al. used amorphous polycarbonate (APC) to blend with TIPS-pentacene to fabricate
Cho et al. used amorphous polycarbonate (APC) to blend with TIPS-pentacene to fabricate
FETs [48]. They calculated the Flory–Huggins parameters of several insulating polymers (PS, APC,
FETs [48]. They calculated the Flory–Huggins parameters of several insulating polymers (PS, APC,
and poly(α-methlystyrene) (PαMS)) and TIPS-pentacene, and found that APC has the highest value
and poly(α-methlystyrene) (PαMS)) and TIPS-pentacene, and found that APC has the highest value
for phase-separation. Thus, they used TIPS-pentacene/APC blends for fabricating FETs and
for phase-separation. Thus, they used TIPS-pentacene/APC blends for fabricating FETs and changed
changed the blending ratio while fixing the total concentration. The blend ratio of 1:4
the blending ratio while fixing the total concentration. The blend ratio of 1:4 (TIPS-pentacene/APC)
(TIPS-pentacene/APC) was found to be the optimum condition to exhibit high field-effect mobility
(Figure 6a). Interestingly, this condition exactly matched the maximum Gibbs free energy of mixing,
indicating that thermodynamically driven strong segregation is a reason for the observed results.
Materials 2016, 9, 650 6 of 16

was found to be the optimum condition to exhibit high field-effect mobility (Figure 6a).
Interestingly, this condition exactly matched the maximum Gibbs free energy of mixing, indicating
that thermodynamically
Materials 2016, 9, 650 driven strong segregation is a reason for the observed results. 6 of 15

Materials 2016, 9, 650 6 of 15

Figure
Figure 5.5. Polarized
Polarized optical
opticalmicroscopy
microscopyimagesimages of inkjet-printed
of inkjet-printed droplets
droplets containing
containing (a);TIPS-
(a); (b) (b)
TIPS-pentacene
pentacene and (c); (d) TIPS-pentacene/PS blend films deposited on (a); (c)
Figure 5. and (c); (d)optical
Polarized TIPS-pentacene/PS
microscopy blend images films
of deposited on (a);
inkjet-printed (c) pentafluorobenzenethiol
droplets containing (a); (b)
pentafluorobenzenethiol
(PFBT)-treated Auand and (b);(PFBT)-treated Au and (b); (d) trichlorophenylsilane (TCPS)-treated silicon
TIPS-pentacene (c); (d)(d)
trichlorophenylsilane
TIPS-pentacene/PS (TCPS)-treated
blend films silicon substrates;on
deposited (e–h) Raman
(a); (c)
substrates;
intensity of(e–h)
the Raman
C–C ringintensity
stretch of the C–C
mode as a ring stretch
function of mode as a function
polarization angle of polarization
taken from red angle
circle
pentafluorobenzenethiol (PFBT)-treated Au and (b); (d) trichlorophenylsilane (TCPS)-treated silicon
taken
pointsfrom red circle Copyright
in (a–d) points in (a–d) [46]. Copyright 2011 American Chemical Society; (i) Polarized
substrates; (e–h)[46].
Raman intensity2011 American
of the C–C ring Chemical Society;
stretch mode as (i) Polarized
a function of optical microscopy
polarization angle
optical
images microscopy
of ink-jet images
printed of ink-jet printed TIPS-pentacene/PS blends: on-centered (left) and
taken from red circle pointsTIPS-pentacene/PS
in (a–d) [46]. Copyrightblends:2011on-centered (left) andSociety;
American Chemical off-centered (right);
(i) Polarized
off-centered
(j) Average (right); (j)
field-effect Average
mobility field-effect
of FETsprintedmobility
based on of FETs based
on- and off-centered on on- and
ink-jet off-centered
printed deposits ink-jet
[47].
optical microscopy images of ink-jet TIPS-pentacene/PS blends: on-centered (left) and
printed
Copyrightdeposits
2013 [47]. Copyright 2013 Elsevier.
Elsevier.
off-centered (right); (j) Average field-effect mobility of FETs based on on- and off-centered ink-jet
printed deposits [47]. Copyright 2013 Elsevier.

Figure 6. (a) Average field-effect mobility (left) of FETs based on inkjet-printed

TIPS-pentacene/amorphous polycarbonate (APC) blends (left) and Gibbs free energy of mixing
Figure 6.6.a(a)
Figure as (a) Average
Average field-effect
field-effect mobility mobility (left) based
(left) ofmobility
FETs of FETs based onTIPS-pentacene/
on inkjet-printed inkjet-printed
(right) function of blending ratio; (b) Average and threshold voltage of FETs based on
TIPS-pentacene/amorphous
amorphous polycarbonate polycarbonate
(APC) blends (APC)
(left) blends
andrespect
Gibbs free(left) and Gibbs
energy mixture free
of mixing[48].energy
(right) as of mixing
a function
inkjet-printed TIPS-pentacene/APC blends with to solvent Copyright 2013
(right) as a function (b)
of blending of blending
Average ratio; (b) Average mobilityvoltage
and threshold
of FETsvoltage
based ofonFETs based on
Royal Societyratio;
of Chemistry. mobility and threshold inkjet-printed
inkjet-printed
TIPS-pentacene/APCTIPS-pentacene/APC blends to
blends with respect with respect
solvent to solvent
mixture [48]. mixture
Copyright [48]. Copyright
2013 2013
Royal Society
Royal Society
of Chemistry. of Chemistry.
Polarized optical microscopy images of the inkjet-printed lines of TIPS-pentacene and
TIPS-pentacene/APC blends are shown in Figure 7a–f, respectively. For this experiment, it was
Polarized optical microscopy images of the inkjet-printed lines of TIPS-pentacene and
ensured that the inkjet-printed lines were perpendicular to the source/drain electrodes by
TIPS-pentacene/APC blends are shown in Figure 7a–f, respectively. For this experiment, it was
considering the crystallization characteristics of TIPS-pentacene. Pure TIPS-pentacene in the
ensured that the inkjet-printed lines were perpendicular to the source/drain electrodes by
inkjet-printed lines yielded inclined crystals (Figure 7a). Importantly, well-oriented needle-shaped
considering the crystallization characteristics of TIPS-pentacene. Pure TIPS-pentacene in the
crystals in parallel directions occurred at the blend ratio of 1:4 (Figure 7d). The further increase of
inkjet-printed lines yielded inclined crystals (Figure 7a). Importantly, well-oriented needle-shaped
 Materials 2016, 9, 650 7 of 16

Polarized optical microscopy images of the inkjet-printed lines of TIPS-pentacene and

TIPS-pentacene/APC blends are shown in Figure 7a–f, respectively. For this experiment, it was
ensured that the inkjet-printed lines were perpendicular to the source/drain electrodes by considering
the crystallization characteristics of TIPS-pentacene. Pure TIPS-pentacene in the inkjet-printed lines
Materials 2016, inclined
yielded 9, 650 crystals (Figure 7a). Importantly, well-oriented needle-shaped crystals in parallel7 of 15
directions occurred at the blend ratio of 1:4 (Figure 7d). The further increase of APC content resulted
evolutions were related
in the formation to the
of plate-like calculation
wavy of the7e,f).
crystals (Figure Gibbs free
These energy of evolutions
morphological mixing thatwereshowed
related the
highest
to thevalue in the of
calculation blend ratio free
the Gibbs of 1:4 (Figure
energy 6a). Morphological
of mixing that showed theand theoretical
highest value in studies
the blendsupported
ratio
the ofobtained
1:4 (Figurehigh mobility at the
6a). Morphological blend ratio
and theoretical of supported
studies 1:4. The the mixed solvent
obtained approach
high mobility in the
at the
inkjet-printed TIPS-pentacene/APC blends is shown in Figure 8. The coffee staining effect appeared
blend ratio of 1:4. The mixed solvent approach in the inkjet-printed TIPS-pentacene/APC blends is
in allshown
solventin Figure 8. The coffee
compositions. staining effect
Especially, when appeared
a solventin all solvent
with compositions.
a low Especially,
boiling point when a
(e.g., chloroform)
solvent with a low boiling point (e.g., chloroform) was added to toluene, the
was added to toluene, the enhanced convective flow resulted in large edge walls. On the other enhanced convective flowhand,
resulted in large edge walls. On the other hand, when a solvent with a high boiling
when a solvent with a high boiling point (e.g., p-xylene) was added, the coffee staining effect point (e.g., p-xylene)
was added, the coffee staining effect decreased. Interestingly, when tetralin was added, the solvent
decreased. Interestingly, when tetralin was added, the solvent evaporation at the edge was very
evaporation at the edge was very slow, leading to an irregular edge profile confirmed by the surface
slow, leading to an irregular edge profile confirmed by the surface profile and polarized optical
profile and polarized optical microscopy image. Accordingly, the use of the toluene/p-xylene mixed
microscopy image. in
solvent resulted Accordingly, the use of
the highest field-effect the toluene/p-xylene
mobility in the applicationmixed solvent
of the active resulted
layer in OFETs in the
highest field-effect mobility in the application of the active layer in OFETs (Figure
(Figure 6b). This result indicated that a mixed solvent approach to control the inkjet-printed single 6b). This result
indicated that a mixed
TIPS-pentacene solvent
droplets wasapproach to control
also effective in the the
blend inkjet-printed singleofTIPS-pentacene
system consisting TIPS-pentacene droplets
and
was insulating
also effective in the blend system consisting of TIPS-pentacene and insulating polymer.
polymer.

Figure 7. Polarized
Figure optical
7. Polarized microscopy
optical microscopyimages images of (a) inkjet-printed
of (a) inkjet-printedTIPS-pentacene
TIPS-pentacene
andand
(b–f)(b–f)
TIPS-pentacene/APC
TIPS-pentacene/APC blends (1:1),
blends (1:1),(1:2),
(1:2),(1:4),
(1:4), (1:6), (1:8),respectively
(1:6), (1:8), respectively [48].
[48]. Copyright
Copyright 20132013 Royal
Royal
Society
Society of Chemistry.
of Chemistry.

Although the
Although theinkjet-printing
inkjet-printing of of TIPS-pentacene/insulating
TIPS-pentacene/insulating polymerpolymer
blend is ablend
rationalisapproach
a rational
to enhance
approach the electrical
to enhance properties
the electrical of OFETs, of
properties inkjet printing
OFETs, TIPS-pentacene
inkjet solution on insulating
printing TIPS-pentacene solution on
polymer can yield similar results [49]. Polarized optical microscopy images
insulating polymer can yield similar results [49]. Polarized optical microscopy images ofof TIPS-pentacene
TIPS-pentacene deposits on PαMS layers with various thicknesses are shown in Figure 9a. Two
types of PαMS with different molecular weights (59 and 858 kDa) were used. Because the solvent
tetralin for inkjet printing of TIPS-pentacene dissolved PαMS, the mixing of TIPS-pentacene and
PαMS occurred in the TIPS-pentacene droplet. A self-aligned bank was formed due to the coffee
staining effect (Figure 9a). The thickness and molecular weight of PαMS affected the final
 Materials 2016, 9, 650 8 of 16

deposits on PαMS layers with various thicknesses are shown in Figure 9a. Two types of PαMS
with different molecular weights (59 and 858 kDa) were used. Because the solvent tetralin for inkjet
printing of TIPS-pentacene dissolved PαMS, the mixing of TIPS-pentacene and PαMS occurred
in the TIPS-pentacene droplet. A self-aligned bank was formed due to the coffee staining effect
(Figure 9a). The thickness and molecular weight of PαMS affected the final morphologies of the dried
TIPS-pentacene/PαMS deposits. Especially, a highly crystalline characteristic of the TIPS-pentacene
crystals was observed when 30 nm-thick PαMS (59 kDa) and 7 nm-thick PαMS (858 kDa) were used.
This in turn resulted in the high field-effect mobility (0.7–0.8 cm2 /Vs) of the corresponding OFETs.
The method used in this approach could enhance the alignment of TIPS-pentacene and uniformity in
the performances
Materials 2016, 9, 650 of the OFETs, mainly due to the formation of the self-aligned bank. 8 of 15

Figure 8.Figure
Mixed solvent
8. Mixed approach
solvent approachininTIPS-pentacene/APC blends:
TIPS-pentacene/APC blends: (a) Profile
(a) Profile images;
images; (b) polarized
(b) polarized
optical microscopy
optical microscopy images;
images; (c) (c)
3D3D profile images;
profile images; and
and(d)(d)
schematic drawings
schematic of inkjet-printed
drawings of inkjet-printed
TIPS-pentacene/APC droplets [48]. Copyright 2013 Royal Society of Chemistry.
TIPS-pentacene/APC droplets [48]. Copyright 2013 Royal Society of Chemistry.

When 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TESADT) was used for

When 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TESADT) was used for
soluble acene [50], the blend of the diF-TESADT/insulating polymer typically led to a bilayer structure
soluble of
acene [50], the blend of the diF-TESADT/insulating polymer typically led to a bilayer
diF-TESADT-top/insulating polymer-bottom [24]. This is because diF-TESADT exhibits low surface
structureenergy
of diF-TESADT-top/insulating polymer-bottom
with a tendency to segregate at the air-film surface. Lee[24].
et al.This
usedis because diF-TESADT exhibits
a diF-TESADT/poly(methyl
low surface energy(PMMA)
methacrylate) with blend
a tendency to segregate
and a picoliter at the
fluidic dispenser air-film
similar surface.
to an inkjet printer Lee et al.a used a
to fabricate
diF-TESADT-top/PMMA-bottom bilayer structure [51]. Schematic drawings
diF-TESADT/poly(methyl methacrylate) (PMMA) blend and a picoliter fluidic dispenser similar to of the printing process
an inkjetand corresponding printed lines are shown in Figure 9b. Surface profiles of the diF-TESADT/PMMA
printer to fabricate a diF-TESADT-top/PMMA-bottom bilayer structure [51]. Schematic
blend before and after the selective removal of diF-TESADT are shown in Figure 9c, demonstrating
drawings of the printing process and corresponding printed lines are shown in Figure 9b. Surface
that a diF-TESADT-top/PMMA-bottom bilayer structure is spontaneously formed during printing.
profiles They
of theutilized
diF-TESADT/PMMA blend before
phase-separated diF-TESADT as a and after the selective
semiconductor removal of
and phase-separated diF-TESADT
PMMA as a are
shown in Figure
dielectric and9c, demonstrating
succeeded thatboth
in fabricating a the
diF-TESADT-top/PMMA-bottom
semiconductor and dielectric layers via bilayer structure is
a one-step
printing process [22].
spontaneously formed during printing. They utilized phase-separated diF-TESADT as a
semiconductor and phase-separated PMMA as a dielectric and succeeded in fabricating both the
semiconductor and dielectric layers via a one-step printing process [22].
drawings of the printing process and corresponding printed lines are shown in Figure 9b. Surface
profiles of the diF-TESADT/PMMA blend before and after the selective removal of diF-TESADT are
shown in Figure 9c, demonstrating that a diF-TESADT-top/PMMA-bottom bilayer structure is
spontaneously formed during printing. They utilized phase-separated diF-TESADT as a
semiconductor and phase-separated PMMA as a dielectric and succeeded in fabricating both9 of
Materials 2016, 9, 650 the16
semiconductor and dielectric layers via a one-step printing process [22].

Figure 9. (a) Polarized optical microscopy images of TIPS-pentacene deposits on poly(α-methlystyrene)

Figure 9. (a) Polarized optical microscopy images of TIPS-pentacene deposits on poly(α-methlystyrene)
(PαMS) layers of various thicknesses. Top: 59 kDa (1, 30, 60 nm), Bottom: 858 kDa (7, 40, 70 nm).
(PαMS) layers of various thicknesses. Top: 59 kDa (1, 30, 60 nm), Bottom: 858 kDa (7, 40, 70 nm).
Substrate temperaturewas
Substrate temperature waskept
kept at ˝70
at 70 °C [49].
C [49]. Copyright
Copyright 2010 Wiley;
2010 Wiley; (b) Schematic
(b) Schematic ofprocess
of printing printing
of
process of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene
2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TESADT)/poly(methyl
(diF-TESADT)/poly(methyl methacrylate)
methacrylate)
(PMMA) blend(PMMA) blendfluidic
using picoliter using dispensing
picoliter fluidic
system;dispensing
(c) Surface system; (c)diF-TESADT/PMMA
profiles of Surface profiles of
diF-TESADT/PMMA blend before and after selective removal of diF-TESADT [51].
blend before and after selective removal of diF-TESADT [51]. Copyright 2015 Nature Publishing Copyright 2015
Group.
Nature Publishing Group.
3. Semiconducting/Insulating Polymer Blends
The phase-separation characteristics of the films of semiconducting/insulating polymer blends
also show potential for use in the active layer of OFETs [25]. However, the phase-separations of
polymer/polymer blends are complicated phenomena [22,52] and can be affected by thermodynamic
and kinetic parameters. Thermodynamically, three component phase diagrams consisting of a
semiconducting polymer, an insulating polymer, and a solvent should be considered when examining
the phase-separation characteristics. Although it is beneficial for the application of polymer blends in
OFETs, vertical phase-separation can occur under well-controlled conditions with the kinetic control of
solvent evaporation as an indispensable step in obtaining a vertically phase-separated structure [19,32].
For example, the laterally/vertically phase-separated structures of polymer blends are affected by
the choice of solvent because of the effect of the evaporation speed of solvent [53]. In addition,
substrate wettability can influence the phase-separation morphology and the structure of polymer
blends [36]. Qiu et al. successfully fabricated a poly(3-hexylthiophene) (P3HT)-top/PMMA-bottom
bilayer structure by spin-casting a P3HT/PMMA blend solution onto a hydrophilic silicon substrate [4].
Thermodynamically, the reason for this behavior is that P3HT exhibits a lower surface energy than
PMMA. Although the same P3HT/PMMA blend was used, the PMMA-top/P3HT-bottom bilayer
structure is instead fabricated onto the hydrophobic substrate [7]. Several strategies have been
suggested to induce vertical phase separation in semiconducting/insulating polymer blends. Heriot et
al. proposed that lateral phase separation is much more common in polymer/polymer blends due to
their Marangoni-like instability [52].
In inkjet printing, the vertical phase-separation of polymer/polymer blends is difficult
to achieve due to the dynamic change of flow in the printed droplets. However, the use of
semiconducting/insulating polymer blends for fabricating an active layer in OFETs has unique merits.
Kwak et al. used poly(didodecylquaterthiophene-alt-didodecylbithiazole) (PQTBTz-C12)/PS blends
for the formation of an active layer by inkjet printing [54]. The chemical structure of PQTBTz-C12 is
shown in Figure 10a [55]. When a single PQTBTz-C12 solution is inkjet-printed, the ejected droplets
at the nozzle contain distorted ligaments and several satellites (Figure 10b, right). This is because
PQTBTz-C12 has low solubility in solvent (here, chlorobenzene). A change of color occurs in the
PQTBTz-C12 solution at various stages of aging (Figure 10b, left). As aging was increased, the
aggregation of PQTBTz-C12 occurred in 20–30 min. This reduced the solubility and crystallization
behavior of PQTBTz-C12, typically inducing nozzle clogging during inkjet printing. When PS
was added to the PQTBTz-C12 solution, no satellite was detected (Figure 10c, right). The aging
 Materials 2016, 9, 650 10 of 16

experiment with the PQTBTz-C12/PS blend demonstrated the long-term stability of the blend solution
(Figure 10c, left).
The inkjet-printed morphology of the PQTBTz-C12/PS blend is shown in Figure 11a. The regular
isolated holes in the image of the height of the blend indicate that the phase-separation characteristics
are complicated. By etching the PS-rich region with cyclohexane, it is possible to examine the
underlying PQTBTz-C12 layer (Figure 11b). A continuous PQTBTz-C12 layer with island-like domains
was detected. The schematic representation (inset of Figure 11a) shows the phase-separated structure
obtained in this study. Although a PS-top/PQTBTz-C12-bottom bilayer structure was formed, the
vertical phase-separation was not perfect. The cause of these vertical and lateral phase-separations
is illustrated in Figure 11c, which shows that when the PQTBTz-C12/PS blend was inkjet-printed,
PQTBTz-C12 with low solubility was solidified first and PS-top/PQTBTz-C12-bottom was formed
in the transient wetting layer. However, the Marangoni flow led to the extrusion of the PQTBTz-C12
bottom layer into the PS region, thereby leading to the formation of a dual phase-separated structure
with a laterally phase-separated PS layer at the top and a vertically phase-separated PQTBTz-C12 layer
at the bottom. When the electrical properties of the OFETs based on inkjet-printed PQTBTz-C12/PS
were measured, a field-effect mobility comparable to that of single PQTBTz-C12 was obtained. This was
Materials 2016, 9, 650 10 of 15
due to the continuous PQTBTz-C12 layer that was phase-separated first using the inkjet printing blend
solution. It is important to note that the environmental and electrical stabilities of the PQTBTz-C12/PS
were superior
OFETs wereto those of to
superior the single
those of thePQTBTz-C12 OFETs.
single PQTBTz-C12 The
OFETs. PSPSlayer
The phase-separated
layer phase-separated at
at the the top
might have protected
top might the PQTBTz-C12
have protected bottom
the PQTBTz-C12 layer.
bottom layer.

Figure Figure
10. (a)10. Chemical
(a) Chemical structure
structureofof poly(didodecylquaterthiophene-alt-didodecylbithiazole)
poly(didodecylquaterthiophene-alt-didodecylbithiazole)
(PQTBTz-C12);
(PQTBTz-C12). Photographic
Photographic images
images of solution
of solution (left),droplet
(left), droplet profile
profile (right)
(right)ofof
(b)(b)
PQTBTz-C12
PQTBTz-C12 and
and droplet profile of (c) PQTBTz-C12/PS blend. The photographic images on the left were collected at
droplet profile of (c) PQTBTz-C12/PS blend. The photographic images on the left were collected at
various stages of aging [54]. Copyright 2016 Wiley.
various stages of aging [54]. Copyright 2016 Wiley.
 Figure 10. (a) Chemical structure of poly(didodecylquaterthiophene-alt-didodecylbithiazole)
(PQTBTz-C12). Photographic images of solution (left), droplet profile (right) of (b) PQTBTz-C12 and
droplet
Materials profile
2016, 9, 650 of (c) PQTBTz-C12/PS blend. The photographic images on the left were collected at11 of 16
various stages of aging [54]. Copyright 2016 Wiley.

Figure 11.
Figure 11.Atomic
Atomic force
force microscopy
microscopy (AFM)(AFM)
height height (left)
(left) and phase and phase
(right) (right)
images of (a)images of (a)
inkjet-printed
inkjet-printed PQTBTz-C12/PS blend film and (b) remaining PQTBTz-C12
PQTBTz-C12/PS blend film and (b) remaining PQTBTz-C12 film after selective removal of PS. film after selective
removal
Insets of PS.
show Insets show
schematic schematic
drawings; drawings;
(c) Schematic (c) Schematicshowing
representations representations showing
formation formation of
of PQTBTz-C12/PS
PQTBTz-C12/PS blend film during drying of inkjet-printed droplets [54].
blend film during drying of inkjet-printed droplets [54]. Copyright 2016 Wiley. Copyright 2016 Wiley.

Other phase-separated structures for guaranteeing lateral charge transport are necessary in
semiconducting/insulating polymer blends due to the limited availability of vertical phase-separation
in polymer/polymer blends. Qiu et al. proposed that the change of solubility in the P3HT/PS
blend could produce a phase-separated structure with P3HT nanowires embedded in the insulating
polymer [28–30]. They achieved extremely low percolation behavior by utilizing the P3HT nanowires
and a phase-separated PS protected active channel. Furthermore, the environmental stability was
enhanced. Lim et al. adopted this technique to produce a phase-separated structure with P3HT
nanowires embedded in PS by inkjet printing P3HT/PS blends (Figure 12a) [56]. They found that the
addition of non-solvent (cyclohexanone, CHN) in the main solvent (chlorobenzene, CB) yielded the
formation of P3HT nanowires in a PS matrix and that the use of a P3HT/PS blend was beneficial for
increasing the environmental stability of OFETs (Figure 12b,c, respectively).
They examined the role of CHN in P3HT/PS (20:80) FETs. The field-effect mobility and Ion /Ioff of
P3HT/PS (20:80) FETs as a function of the CHN composition in CB/CHN mixed solvent are shown
in Figure 13a. Clear increases in electrical properties with the addition of 20% CHN were detected.
The reason for this behavior was revealed by examining the morphologies of the P3HT/PS blend films.
CB led to isolated P3HT aggregates while the CB/CHN mixed solvent resulted in P3HT nanowires
becoming embedded in the PS matrix (Figure 13b). The P3HT nanowires formed in PS were extremely
beneficial for lateral charge transport. A high on:off current ratio (Ion /Ioff ) in P3HT/PS FETs compared
to P3HT FETs is of interest for further study. The Ion /Ioff and field-effect mobility/conductivity as a
function of the P3HT content are shown in Figure 13c,d, respectively. Although the on-current was
increased slightly, the off-current was increased abruptly with increasing P3HT content. The reason for
the significant increase in the off-current was due to the increased bulk conductivity. Thus, the increase
 films. CB led to isolated P3HT aggregates while the CB/CHN mixed solvent resulted in P3HT
nanowires becoming embedded in the PS matrix (Figure 13b). The P3HT nanowires formed in PS
were extremely beneficial for lateral charge transport. A high on:off current ratio (Ion/Ioff) in
P3HT/PS FETs compared to P3HT FETs is of interest for further study. The Ion/Ioff and field-effect
mobility/conductivity as a function of the P3HT content are shown in Figure 13c,d, respectively.
Materials 2016, 9, 650 12 of 16
Although the on-current was increased slightly, the off-current was increased abruptly with
increasing P3HT content. The reason for the significant increase in the off-current was due to the
of Ionincreased
/Ioff observedbulk conductivity.
in the P3HT/PSThus, the increase
(20:80) of Ion
FETs was /Ioff observed
driven in the P3HT/PS
by a decrease (20:80) FETs was
in bulk conductivity. In their
driven by a decrease in bulk conductivity. In their study, Lim et al. successfully demonstrated that
study, Lim et al. successfully demonstrated that inkjet-printed semiconducting/insulating polymer
inkjet-printed semiconducting/insulating polymer blends are also beneficial for increasing Ion/Ioff of
blends are also beneficial for increasing Ion /Ioff of FETs [56].
FETs [56].

Figure 12. (a) Schematic showing inkjet printing of poly(3-hexylthiophene) (P3HT)/PS blend and
Figure 12. (a) Schematic showing inkjet printing of poly(3-hexylthiophene) (P3HT)/PS blend and
formation P3HT nanofibers embedded in PS. Environmental stabilities of FETs based on P3HT (b)
formation P3HT nanofibers embedded in PS; Environmental stabilities of FETs based on P3HT (b) and
and P3HT/PS (20:80) blend (c). Mixed solvent with chlorobenzene (CB) and cyclohexanone (CHN)
P3HT/PS(80:20)(20:80) blend
was used (c). Mixed
to prepare solvent
P3HT/PS with
blend chlorobenzene
solution (CB) 2010
[56]. Copyright and Wiley.
cyclohexanone (CHN) (80:20)
was used to prepare P3HT/PS blend solution [56]. Copyright 2010 Wiley.
Materials 2016, 9, 650 12 of 15

Figure 13.
13. (a)
(a) Field-effect
Field-effect mobility
mobility and
and IIon/I
/Ioff of P3HT/PS (20:80) FETs as a function of CHN
Figure on off of P3HT/PS (20:80) FETs as a function of CHN
composition in CB/CHN mixed solvent;
composition in CB/CHN mixed solvent; (b) AFM (b) AFM phase
phase images
images of
ofinkjet-printed
inkjet-printedP3HT/PS
P3HT/PS blend
blend
films from CB (left) and CB/CHN (80:20) mixed solvent (right); (c) I on/Ioff and (d) field-effect
films from CB (left) and CB/CHN (80:20) mixed solvent (right); (c) Ion /Ioff and (d) field-effect
mobility/conductivity as
mobility/conductivity as aa function
function of
of P3HT
P3HT content
content [56].
[56]. Copyright
Copyright 2010
2010 Wiley.
Wiley.

4. Conclusions
We reviewed recent advances in inkjet-printed organic transistors based on organic
semiconductor/insulating polymer blends. The inkjet printing process was described to provide
understanding of the drying behavior of inkjet-printed polymer blends. Soluble acene/insulating
polymer blends and semiconducting/insulating polymer blends are attractive inks for enhancing
Materials 2016, 9, 650 13 of 16

4. Conclusions
We reviewed recent advances in inkjet-printed organic transistors based on organic
semiconductor/insulating polymer blends. The inkjet printing process was described to provide
understanding of the drying behavior of inkjet-printed polymer blends. Soluble acene/insulating
polymer blends and semiconducting/insulating polymer blends are attractive inks for enhancing
jetting properties, film uniformity, and device performances of OFETs compared to single organic
semiconductor inks. The enhanced electrical properties can be understood by considering the
morphologies and structures of the blend films under the drying condition of inkjet-printed droplets.
The use of mixed solvent is a rational approach to control the phase-separation characteristics and/or
enhance the crystallinity of organic semiconductors. In OFETs based on inkjet-printed organic
semiconductor/insulating polymer blends, the appropriate blending of insulating polymer can
influence the crystallization characteristics of an organic semiconductor, while the insulating polymer
plays a role as a dielectric layer or protective layer from atmospheric water and oxygen. Here, the
control of phase separation to ensure lateral charge transport is a key to obtaining the suitable functions
of devices while increasing their electrical properties.

Acknowledgments: This paper was supported by Konkuk University in 2014.

Author Contributions: Wi Hyoung Lee suggested this review and organized all sections. Yoon-Jung Kwon,
Yeong Don Park, and Wi Hyoung Lee wrote the paper. Wi Hyoung Lee made careful proofreading for
the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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