materials

Article
Screen-Printed Fabrication of PEDOT:PSS/Silver
Nanowire Composite Films for Transparent Heaters
Xin He *, Ruihui He, Qiuming Lan, Weijie Wu, Feng Duan, Jundong Xiao, Mei Zhang,
Qingguang Zeng, Jianhao Wu and Junyan Liu
School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, Guangdong, China;
ruihuihe@yeah.net (R.H.); wyuqiuminglan@yeah.net (Q.L.); wjwu2016@126.com (W.W.);
duanfeng0922@163.com (F.D.); jundongxiao99@163.com (J.X.); zmjenny@163.com (M.Z.);
zengqg1979@126.com (Q.Z.); jhwuwyu@126.com (J.W.); liujunyanwyu@126.com (J.L.)
* Correspondence: hexinwyu@126.com or hexin@mail.wyu.edu.cn; Tel.: +86-750-329-6095

Academic Editors: Silvia Schintke and Giorgio Biasiol

Received: 24 October 2016; Accepted: 20 February 2017; Published: 23 February 2017

Abstract: A transparent and flexible film heater was fabricated; based on a hybrid structure
of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) and silver nanowires
(Ag NWs) using a screen printing; which is a scalable production technology. The resulting film
integrates the advantages of the two conductive materials; easy film-forming and strong adhesion
to the substrate of the polymer PEDOT:PSS; and high conductivity of the Ag NWs. The fabricated
composite films with different NW densities exhibited the transmittance within the range from 82.3%
to 74.1% at 550 nm. By applying 40 V potential on the films; a stable temperature from 49 ◦ C to 99 ◦ C
was generated within 30 s to 50 s. However; the surface temperature of the pristine PEDOT:PSS
film did not increase compared to the room temperature. The composite film with the transmittance
of 74.1% could be heated to the temperatures from 41 ◦ C to 99 ◦ C at the driven voltages from 15 V to
40 V; indicating that the film heater exhibited uniform heating and rapid thermal response. Therefore;
the PEDOT:PSS/Ag NW composite film is a promising candidate for the application of the transparent
and large-scale film heaters.

Keywords: screen printing; conductive film; transparent heater

1. Introduction
Transparent film heaters are widely used in defogging vehicle windows, heating outdoor displays,
or thermal therapies [1–6]. They are known for converting electric energy into heat energy, and
maintaining transparency. The temperature of the heater can be accurately controlled by changing
the input voltages. The most common transparent-heater is represented by indium tin oxide (ITO) [7].
However, the limited reserves and brittleness limit its further application in the next-generation devices.
Additionally, ITO exhibits a slow temperature response because of its intrinsic nature.
Several emerging nanomaterials are developed as transparent film heaters to substitute for ITO,
such as conductive polymers [8], carbon nanotubes [9,10], grapheme [1,11–13], metal meshes [14] and
nanowires [2,4,15–18]. However, there are several obstacles for these materials to overcome before
wide application in the film heater. For example, the conductive polymer PEDOT:PSS can be easily
fabricated as a uniform film, but its conductivity usually requires further improvement by chemical
modifications to achieve a high-performance heater [8,19,20]. Among these materials, the film heater
using the metal nanowires has shown excellent optoelectronic and heating performance. However,
the poor adhesion of metal network to the substrate limits its wide applications. Researchers have
used many strategies to address this issue. For instance, Ghosh et al. prepared a transparent film
by means of comprising Ag nanowires (NWs) in an ultrathin polyimide (PI) foil, exhibiting high

Materials 2017, 10, 220; doi:10.3390/ma10030220 www.mdpi.com/journal/materials

Materials 2017, 10, 220 2 of 10

transmittance (>90%), strong adhesion, and low surface roughness of 2.4 nm. The Ag NW-PI film with
a sheet resistance of 15 Ω/sq can generate a high temperature exceeding 100 ◦ Cat 17 V within 20 s [21].
To represent the advantages of various emerging-materials, two conductive structures are usually
hybridized to fabricate the film heater with high performance. For example, Choi et al. introduced
an Ag-grid/graphene hybrid structure using the hot-pressing transfer and electrohydrodynamic
jet printing, exhibiting the superior electrical properties and heating performance [22]. Sung and
Kim et al. reported a flexible Ag NW-polymer composite electrode with the transmittance of 84.3%
and sheet resistance of 10.76 Ω/sq via a continuous two-step spray-coating method. The conductivity
of PEDOT:PSS was improved by the use of dimethyl sulfoxide [20]. In general, the preparation of
the transparent film heaters in many publications requires spin-coating [21], vacuum filtration [23],
transfer process [5,17] or repeated coating [24]. Additionally, a chemical or heating treatment is
normally needed for improving the film performance [8,11,20]. Thus, the large-scale production of the
film heater is greatly restricted.
The screen printing is an environment-friendly and cost-effective method to fabricate uniform films.
It is one of the scalable production technologies [25–27]. In this study, a composite film has combined
PEDOT:PSS with Ag NWs using a screen-printed fabrication to gain a uniform film with good
conductivity. The whole process was carried out at the room temperature without any annealing or
chemical treatment. The effects of the mesh number and Ag NW concentration on the optoelectronic
properties of the printed films were demonstrated. The conductivity and adhesion of the films were
simultaneously improved as compared in the case of using one printing material. The PEDOT:PSS/Ag
NW composite film exhibited uniform heating and rapid thermal response. The film with the
transmittance of 74.1% at 550 nm could generate a steady temperature of 41 ◦ C at 15 V within
35 s. This reveals the promising application in the large-area, transparent and flexible film heater.

2. Experimental Section

2.1. Synthesis of Long Ag NWs

Long Ag NWs were synthesized according to a hydrothermal method [28]. Typically, 2 mmol
of glucose, 1.5 mmol of silver nitrate, and 0.3 mmol ferric sulfate were, respectively, dissolved
withdeionized (DI) water (the volume ratio of reactantsis 2:2:1) in a beaker at room temperature.
Then, the reactants were mixed together and magnetically stirred for several minutes to yield a
light-yellow solution. Following this, 4.5 g polyvinylpyrrolidone (PVP, K30) was introduced into it.
The mixture was consistently stirred until PVP totally dissolved, and then transferred into a Teflon
autoclave of 100 mL capacity, which was sealed and heated at 180 ◦ C for 6 h. After the hydrothermal
treatment, the gray-green precipitate was obtained. Then, the precipitate was washed with dilute nitric
acid solution for several times in order to get rid of the oxide layer on the NW surfaces. The excess nitric
acid was removed by centrifugations using ethanol. The long Ag NWs could be collected by repeated
suction filtration. Finally, the product was kept in ethanol to obtain a dispersion of long Ag NWs. The
diameter of the NWs is approximately 100 nm, and the length is up to hundreds of micrometers.

2.2. Fabrication of PEDOT:PSS/Ag NW Composite Films

PEDOT:PSS (Orgacon, EL-P3145, Agfa, Mortsel, Belgium)/Ag NW composite films were fabricated
by the screen-printed technology on the polyethylene terephthalate (PET) substrate. Before printing,
the substrates were washed by ethanol and deionized water respectively with assistance of ultrasonic
treatment for 15 min to remove the dust, grease and other impurities on the substrate surface. After
that, 4, 6, 8, and 12 mg of dried Ag NWs were respectively added into 1 mL PEDOT:PSS suspension,
and then the mixtures were stirred intensively to obtain homogeneous PEDOT:PSS/Ag NW inks.
Figure 1 shows a schematic illustration of fabrication procedure of the PEDOT:PSS/Ag NW
composite film. Firstly, the PET substrate was adsorbed on the nest by mechanical pump, and then the
cleaned printing mesh was adjusted to maintain an appropriate distance of 2 mm with the substrate.
Materials 2017, 10, 220 3 of 10

Figure 1 shows a schematic illustration of fabrication procedure of the PEDOT:PSS/Ag NW

Materials 2017, 10, 220 3 of 10
composite film. Firstly, the PET substrate was adsorbed on the nest by mechanical pump, and then
the cleaned printing mesh was adjusted to maintain an appropriate distance of 2 mm with the
FollowingFollowing
substrate. this, a PEDOT:PSS/Ag NW inkNW
this, a PEDOT:PSS/Ag wasink
dropped onto the
was dropped mask,
onto and the
the mask, andsqueegee quickly
the squeegee
quickly
pushedpushed
towardtoward
anotheranother side.
side. The The printed
printed filmsfinally
films were were finally at 60 ◦ at
heatedheated 60 °C
C for 15 for
min.15 min.

Figure
Figure1.1.Schematic
Schematicillustration
illustrationofofthe
thescreen-printed
screen-printedprocedure
procedureofofPEDOT:PSS/Ag
PEDOT:PSS/Ag NWNWcomposite
composite
films.
films.PEDOT:PSS:
PEDOT:PSS:poly(3,4-ethylenedioxythiophene)
poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate); NW:
poly(styrenesulfonate); nanowire.
NW: nanowire.

2.3. Characterization
2.3. Characterization
The surface morphologies of the printed films were observed using a field emission scanning
The surface morphologies of the printed films were observed using a field emission scanning
electron microscope (FESEM, Nova NanoSEM 430, FEI, Hillsboro, OR, USA). The nanostructures of
electron microscope (FESEM, Nova NanoSEM 430, FEI, Hillsboro, OR, USA). The nanostructures of the
the films were characterized using an X-ray diffractometer (XRD) (X’pert Pro MFD, Panalytical,
films were characterized using an X-ray diffractometer (XRD) (X’pert Pro MFD, Panalytical, Almelo,
Almelo, The Netherlands) with a Cu Kα radiation (λ = 0.154178 nm). The transmittances were
The Netherlands) with a Cu Kα radiation (λ = 0.154178 nm). The transmittances were collected by
collected by a UV-VIS spectrophotometer (UV2550, Shimadzu, Kyoto, Japan). The resistances of the
a UV-VIS spectrophotometer (UV2550, Shimadzu, Kyoto, Japan). The resistances of the films were
films were recorded by a multimeter (MS8229, MASTECH, Moon, PA, USA) and the sheet resistances
recorded by a multimeter (MS8229, MASTECH, Moon, PA, USA) and the sheet resistances of the
of the films were characterized by a four-probe system (SZ-82, Suzhou Telecommunication, Suzhou,
films were characterized by a four-probe system (SZ-82, Suzhou Telecommunication, Suzhou, China).
China). The heating performances of the films were measured using a two-terminal side contact
The heating performances of the films were measured using a two-terminal side contact configuration.
configuration. The applied DC voltage was supplied by a power supply (IT6720, ITECH, San Luis
The applied DC voltage was supplied by a power supply (IT6720, ITECH, San Luis Obispo, CA, USA)
Obispo, CA, USA) to the heater through two copper conductive tapes pasted at the film edges. The
to the heater through two copper conductive tapes pasted at the film edges. The temperatures and
temperatures and heat distributions of the transparent films were measured using an IR thermal
heat distributions of the transparent films were measured using an IR thermal imager (Ti32, Fluke,
imager (Ti32, Fluke, Washington, DC, USA).
Washington, DC, USA).
3. Results and Discussion
3. Results and Discussion
The mesh number was one of key factors to decide the film properties in the screen-printed
The mesh number was one of key factors to decide the film properties in the screen-printed
process. In the experiment, the uniform films could be fabricated as the mesh number was in the
process. In the experiment, the uniform films could be fabricated as the mesh number was in the
range of 200–350. The mesh size was, respectively 75, 60, 50, and 43 μm, corresponding to the mesh
range of 200–350. The mesh size was, respectively 75, 60, 50, and 43 µm, corresponding to the mesh
number 200, 250, 300, and 350. As shown, the mesh size was decreased with the increase of the mesh
number 200, 250, 300, and 350. As shown, the mesh size was decreased with the increase of the
number. When the mesh number was below 200, the tension force of conductive ink was not enough
mesh number. When the mesh number was below 200, the tension force of conductive ink was not
to form a stable ink column due to a large mesh size. The ink would cross the mesh because of the
enoughbefore
gravity to form a stablewhich
printing, ink column dueto
could lead tothe
a large mesh size.
fabrication The ink wouldfilm.
of a heterogeneous crossInthe mesh
case the because
mesh
number exceeded 350, the mesh size would be too small to make an ink that would fully coverInthe
of the gravity before printing, which could lead to the fabrication of a heterogeneous film. case
the mesh
PET number
substrate, and exceeded 350, the
the uniformity mesh
of the size would
composite film be too small
would to makeFigure
be damaged. an ink2A that would fully
presented a
cover the PET substrate, and the uniformity of the composite film would
typical SEM image of pristine PEDOT:PSS film printed using a 420 mesh, and many small bubbles be damaged. Figure 2A
presented
and holes awere
typical SEM image
observed of pristine
on the surface,PEDOT:PSS
generatingfilman printed using a 420
heterogeneous mesh,
film. For and many small
comparison,
bubbles
Figure 2Band holes were
displayed a SEM observed
image ofonthethe surface, generating
PEDOT:PSS/Ag an heterogeneous
NW composite film printedfilm.
withFora 350
comparison,
mesh.
Figure 2B displayed a SEM image of the PEDOT:PSS/Ag NW composite film
No obvious bubble or hole could be found on the film surface. The inset was a magnified SEM printed with a 350 mesh.
image
No obvious bubble or hole could be found on the film surface. The inset was
of the NW connections, suggesting that the NW surfaces had been covered by polymer PEDOT:PSS. a magnified SEM image
of the
The AgNW NWconnections,
network could suggesting that the
provide more NW surfaces
electron pathways, had been
and covered
greatly by polymer
enhanced PEDOT:PSS.
the conductivity
The Ag NW network could provide more electron pathways, and greatly
of the composite film. Meanwhile, the coverage of PEDOT:PSS on the Ag NWs could isolate the enhanced the conductivity
of thefrom
NWs composite
the air, film. Meanwhile,
preventing the coverage
the oxidation of PEDOT:PSS
of metallic Ag NWs andonenhancing
the Ag NWs could isolate
the adhesion to thethe
NWs
PET from the air, preventing the oxidation of metallic Ag NWs and enhancing the adhesion to the
substrate.
PET substrate.
Figure 2C–F showed the photographs and typical SEM images of the pristine PEDOT:PSS and
PEDOT:PSS/Ag NW film printed by a 350 mesh, respectively. The addition of Ag NWs in the inks
was 8 mg/mL. The transmittance of pristine PEDOT:PSS film was decreased from 85.1% to 76.2%
when 8 mg/mL Ag NWs were mixed with PEDOT:PSS ink. Nevertheless, the composite film
mentioned
Materials above
2017, 10, 220 showed distinct visibility and uniform distribution of the NWs on the substrate
4 of 10
(Figure 2B,F).

Figure 2.
Figure 2. SEM
SEM images
images of
of PEDOT:PSS
PEDOT:PSS film
film using
using aa 420
420 mesh
mesh(A)
(A)and
andPEDOT:PSS/Ag
PEDOT:PSS/AgNW NWfilm
filmusing
usinga
350 mesh (B); the insets were magnified images. Photographs (C,E) and SEM images (D,F)
a 350 mesh (B); the insets were magnified images. Photographs (C,E) and SEM images (D,F) of of pristine
PEDOT:PSS
pristine and PEDOT:PSS/Ag
PEDOT:PSS NW film
and PEDOT:PSS/Ag NWprinted usingusing
film printed a 350 mesh,
a 350 and
mesh, the
and theadded
addedAg Ag NWNW
concentration was 8 mg/mL.
concentration was 8 mg/mL.

To further analyze the relationship between the concentration of Ag NWs and the photoelectric
The 350 mesh was chosen to fabricate the films with high transparency and good uniformity.
properties of the composite film, the PEDOT:PSS/Ag NW composite films were fabricated with
Figure 2C–F showed the photographs and typical SEM images of the pristine PEDOT:PSS and
various additions of Ag NWs into the PEDOT:PSS inks. Figure 3A–D shows the SEM images of the
PEDOT:PSS/Ag NW film printed by a 350 mesh, respectively. The addition of Ag NWs in the
composite films printed using the 350 mesh with the Ag NW concentration of 4, 6, 8, and 12 mg/mL,
inks was 8 mg/mL. The transmittance of pristine PEDOT:PSS film was decreased from 85.1% to
respectively. As the length of the Ag NWs was larger than the mesh size, thus, several NWs got
76.2% when 8 mg/mL Ag NWs were mixed with PEDOT:PSS ink. Nevertheless, the composite film
curved and broken due to the extrusion in the printing process. When the Ag NW concentration
mentioned above showed distinct visibility and uniform distribution of the NWs on the substrate
increased, this made the crossed network in the film more intensive, which led to the increase in the
(Figure 2B,F).
conductivity while the transmittance declined for the composite films. Additionally, the NW
To further analyze the relationship between the concentration of Ag NWs and the photoelectric
concentration exceeded 12 mg/mL, and the NWs were hardly dispersed in the ink.
properties of the composite film, the PEDOT:PSS/Ag NW composite films were fabricated with various
Figure 3E demonstrates the XRD patterns of the pristine PEDOT:PSS and PEDOT:PSS/Ag NW
additions of Ag NWs into the PEDOT:PSS inks. Figure 3A–D shows the SEM images of the composite
films with Ag NW concentration ranging from 4 mg/mL to 12 mg/mL, and the standard card of
films printed using the 350 mesh with the Ag NW concentration of 4, 6, 8, and 12 mg/mL, respectively.
metallic silver was provided for reference. The two wide diffraction peaks in all films labeled by red
As the length of the Ag NWs was larger than the mesh size, thus, several NWs got curved and broken
diamonds were centered at 46.6° and 53.5°, which could be assigned to the presence of PEDOT:PSS.
due to the extrusion in the printing process. When the Ag NW concentration increased, this made
A weak diffraction peak at 38.1° was observed from the composite film with NW concentration of
the crossed network in the film more intensive, which led to the increase in the conductivity while
4 mg/mL. As the addition of Ag NWs increased, the intensity of the peak at 38.1° was gradually
the transmittance declined for the composite films. Additionally, the NW concentration exceeded
enhanced, and a new peak at 44.4° appeared. The two diffraction peaks marked with blue clubs
12 mg/mL, and the NWs were hardly dispersed in the ink.
matched well with the (111) and (200) reflection of the face centered cubic structure of metallic silver
Figure 3E demonstrates the XRD patterns of the pristine PEDOT:PSS and PEDOT:PSS/Ag NW
films with Ag NW concentration ranging from 4 mg/mL to 12 mg/mL, and the standard card of
metallic silver was provided for reference. The two wide diffraction peaks in all films labeled by red
diamonds were centered at 46.6◦ and 53.5◦ , which could be assigned to the presence of PEDOT:PSS.
A weak diffraction peak at 38.1◦ was observed from the composite film with NW concentration of
4 mg/mL. As the addition of Ag NWs increased, the intensity of the peak at 38.1◦ was gradually
Materials 2017, 10, 220 5 of 10

enhanced,
Materials 2017,and a new peak at 44.4◦ appeared. The two diffraction peaks marked with blue clubs
10, 220 5 of 10
matched well with the (111) and (200) reflection of the face centered cubic structure of metallic silver
(JCPDF
(JCPDF No. No. 01-087-0597), respectively.
respectively. Therefore,
Therefore, the
the content
content of
of the
the silver
silver in
in the
the composite
composite film
film was
was
increased
increased with
with the
the density
density of
of the
the Ag
Ag NWs
NWs in the ink. Furthermore, no other peaks could be observed,
indicating
indicating thethe absence
absence of
of other
other impurities
impurities in
inthe
thecomposite
compositefilms.
films.

Figure 3.
Figure 3. (A–D)
(A–D) SEM
SEMimages
imagesand
and(E)
(E)XRD
XRDpatterns
patternsofofPEDOT:PSS/Ag
PEDOT:PSS/Ag NW NW composite
composite films
films printed
printed
using the 350 mesh, and the Ag NW concentration was respectively 4, 6, 8 and 12
using the 350 mesh, and the Ag NW concentration was respectively 4, 6, 8 and 12 mg/mLmg/mL in the ink.

Figure 4A presents the optical transmittance spectra of PEDOT:PSS/Ag NW composite films

Figure 4A presents the optical transmittance spectra of PEDOT:PSS/Ag NW composite films
printed using the 350 mesh with Ag NW concentration ranging from 4 mg/mL to 12 mg/mL.
printed using the 350 mesh with Ag NW concentration ranging from 4 mg/mL to 12 mg/mL.
Compared to the pristine PEDOT:PSS film with transmittance of 85% and resistance of 50 kΩ, the
Compared to the pristine PEDOT:PSS film with transmittance of 85% and resistance of 50 kΩ, the
transmittance of the composite films was decreased from 82.3% to 74.1% at 550 nm, and the resistance
transmittance of the composite films was decreased from 82.3% to 74.1% at 550 nm, and the resistance
was reduced from 4 to 0.5 kΩ. The areas of the printed films were approximately 50 mm × 50 mm.
was reduced from 4 to 0.5 kΩ. The areas of the printed films were approximately 50 mm × 50 mm.
The changes in the transmittance and resistance of the composite films with the variation of Ag NW
The changes in the transmittance and resistance of the composite films with the variation of Ag NW
concentration are displayed in Figure 4B. It also shows that the transmittance of the film was slightly
concentration are displayed in Figure 4B. It also shows that the transmittance of the film was slightly
decreased and the conductivity of the film was greatly increased by the introduction of the
decreased and the conductivity of the film was greatly increased by the introduction of the conducting
conducting Ag NWs. The increasing conductivity of the composite films was caused by the
Ag NWs. The increasing conductivity of the composite films was caused by the percolation network of
percolation network of Ag NWs, which provides effective electron pathways. In the characterization
Ag NWs, which provides effective electron pathways. In the characterization process, it was found
process, it was found that the sheet resistance of the pristine PEDOT:PSS film was approximately
that the sheet resistance of the pristine PEDOT:PSS film was approximately 380 Ω/sq, exhibiting
380 Ω/sq, exhibiting uniform distribution on the film surface. However, the conductivity of the
uniform distribution on the film surface. However, the conductivity of the composite films with a
composite films with a high NW density was difficult to be evaluated using the sheet resistance,
high NW density was difficult to be evaluated using the sheet resistance, which varied from several to
which varied from several to hundreds of Ohms per square at the different locations on the film
hundreds of Ohms per square at the different locations on the film surface. We assume that the uneven
surface. We assume that the uneven distribution of the sheet resistance was brought by the Ag NWs
distribution of the sheet resistance was brought by the Ag NWs that might randomly be exposed to
that might randomly be exposed to air/embedded into polymer during the screen-printed process.
air/embedded into polymer during the screen-printed process. The surface where Ag NWs were
The surface where Ag NWs were naked had low sheet resistance, while the surface where Ag NWs
naked had low sheet resistance, while the surface where Ag NWs were embedded exhibited high
were embedded exhibited high sheet resistance.
sheet resistance.
The adhesions of the films to the PET substrate were tested using 3M Scotch tape. For
The adhesions of the films to the PET substrate were tested using 3M Scotch tape. For comparison,
comparison, a pristine Ag NW film was fabricated by rod coating. Figure 5A,B display optical
a pristine Ag NW film was fabricated by rod coating. Figure 5A,B display optical transmittance
transmittance spectra of the Ag NW film and PEDOT:PSS composite film before and after peeling of
spectra of the Ag NW film and PEDOT:PSS composite film before and after peeling of the tape.
the tape. The transmittance at 550 nm was increased from 75% to 81% for the Ag NW film. However,
The transmittance at 550 nm was increased from 75% to 81% for the Ag NW film. However, the
the transmittance of the composite film was maintained at 79%. The insets show photographs of the
transmittance of the composite film was maintained at 79%. The insets show photographs of the films
films before and after peeling, revealing that the Ag NW film on PET substrate was easy to peel off,
before and after peeling, revealing that the Ag NW film on PET substrate was easy to peel off, and the
and the composite film was hardly detached from the surface by the tape. The improved adhesion of
composite film was hardly detached from the surface by the tape. The improved adhesion of the Ag
the Ag NW network could be mainly attributed to the compact contact between Ag NWs and
PEDOT:PSS and good adhesion of the polymer to the substrate.
Materials 2017, 10, 220 6 of 10

NW network could be mainly attributed to the compact contact between Ag NWs and PEDOT:PSS
Materials 2017, 10, 220 6 of 10
and good
Materials adhesion
2017, of the polymer to the substrate.
10, 220 6 of 10

Figure 4. (A) Optical transmittance

transmittance spectra and (B) the variation of the transmittance at 550 nm and
Figure 4. (A)
Figure 4. (A) Optical
Optical transmittance spectra
spectra and
and (B)
(B) the
the variation
variation of
of the
the transmittance
transmittance at
at 550
550 nm
nm and
and
resistance
resistance of
of PEDOT:PSS/Ag
PEDOT:PSS/Ag NW
NW composite
composite films
films printed
printed using
using the
the 350
350 mesh
mesh with
with the
the concentration
concentration
resistance of PEDOT:PSS/Ag NW composite films printed using the 350 mesh with the concentration
of
of Ag NWs ranging from 4 to 12
12 mg/mL.
of Ag
Ag NWs
NWs ranging
ranging from
from 44 to
to 12 mg/mL.
mg/mL.

Figure 5. Optical transmittance spectra of the pristine Ag NW film (A) (A) and
and the
the PEDOT:PSS/Ag
PEDOT:PSS/Ag NW NW
Figure 5. Optical transmittance spectra of the pristine Ag NW film (A) and the PEDOT:PSS/Ag NW
composite film (B) before and after peeling of the tape, the insets show photographs of the films,
composite film (B) before and after peeling of the tape, the insets show photographs of the films, and
composite film (B) before and after peeling of the tape, the insets show photographs of the films, and
the
andblue dotted
the blue rectangles
dotted correspond
rectangles to the
correspond topeeling areas.
the peeling areas.
the blue dotted rectangles correspond to the peeling areas.

We
We investigated the the heating
heatingperformances
performancesof ofthe
thecomposite
compositefilms, films,which
whichwere weremeasured
measuredusing a
We investigated
investigated the heating performances of the composite films, which were measured using
using a
two-terminal
atwo-terminal
two-terminal side
sidecontact
contact configuration.
configuration. A schematic illustration of the film heater is presented in
side contact configuration. AA schematic
schematic illustration
illustration of of
thethe
filmfilm heater
heater is presented
is presented in
Figure
in Figure 6A.6A.Figure
Figure6B–D6B–Ddisplays the the
displays typical infrared
typical thermal
infrared images
thermal imagesof the
of pristine
the pristinePEDOT:PSS
PEDOT:PSS and
Figure 6A. Figure 6B–D displays the typical infrared thermal images of the pristine PEDOT:PSS and
PEDOT:PSS/Ag
and PEDOT:PSS/Ag NW films
NW with
films NW
with NWconcentration
concentration of 8
of and
8 and 12 12mg/mL
mg/mL at at4040V,V, respectively.
respectively.
PEDOT:PSS/Ag NW films with NW concentration of 8 and 12 mg/mL at 40 V, respectively.
To
To improve the the image contrast
contrast of the heating
heating films, the range of the temperature temperature bars were set as
To improve
improve the image image contrast of the the heating films, the range of the the temperature bars were set as
30–40
30–40 °C,°C,
◦ 30–70
C, 30–70 °C °C
◦ and
C and 30–100
and 30–100 °C.
◦
30–100 °C. The
C. The saturable
The saturable temperatures
saturable temperatures
temperatures of of the
of the films
filmswere
the films were measured
measured to be 32, 65,
were measured to be 32, 65,
and 99
and 99 °C, °C,
◦ respectively.
C, respectively.
respectively.
The surface
The surface temperatureofofthe thepristine
pristine PEDOT:PSS filmfilm
waswas not elevated comparedto theto the
surfacetemperature
temperature of the PEDOT:PSS
pristine PEDOT:PSS film not elevated
was not elevated compared
compared room
to the
room temperature
temperature even ateven
40 at
V. 40 V.
However, However,
once Ag once
NWs Ag
wereNWs addedwere intoadded
the into
ink, the
the ink,
printed the printed
composite
room temperature even at 40 V. However, once Ag NWs were added into the ink, the printed
composite
films couldfilmsgeneratecould generate
higher higher and
temperature temperature
more heat, and morewas
which heat, whichtowas
ascribed ascribed to the
the improvement of
composite films could generate higher temperature and more heat, which was ascribed to the
improvement
the of the film conductivity.
film conductivity.
improvement of the film conductivity.
Figure 6E shows the temperature evolution of the pristine and composite films with the Ag NW
Figure 6E shows the temperature evolution of the pristine and composite films with the Ag NW
addition of 4, 6, 8, and 12 mg/mL in the ink, respectively. All films were driven at 40 V for 150 s.
addition of 4, 6, 8, and 12 mg/mL in the ink, respectively. All films were driven at 40 V for 150 s.
By passing the current through the films, they could be heated from room temperature to a steady
By passing the current through the films, they could be heated from room temperature to a steady
temperature of 32, 49, 59, 65, and 99 °C within 30 s to 50 s, respectively. The temperature was
temperature of 32, 49, 59, 65, and 99 °C within 30 s to 50 s, respectively. The temperature was
elevated as the Ag NW density in the film increased, demonstrating that more electron pathways
elevated as the Ag NW density in the film increased, demonstrating that more electron pathways
was beneficial for the thermal generation. Figure 6F presents the temperature profiles of the
was beneficial for the thermal generation. Figure 6F presents the temperature profiles of the
 Materials 2017, 10, 220 7 of 10

PEDOT:PSS/Ag NW composite film with the NW concentration of 12 mg/mL, which was plotted
with the respect to the different voltages from 15 V to 40 V. When the potential was set as 15, 20, 25,
30, 35, and 40 V, the composite film reached the temperature of 41, 51, 66, 78, 91, and
Materials 2017, 10, 220 7 of 10
99 °C, respectively, indicating that the generated temperature of the film raised as the applied
voltage increased.

Figure
Figure 6. (A)
6. (A) Schematic
Schematic illustration
illustration of of a film
a film heater
heater based
based onon
thethe PEDOT:PSS/AgNW
PEDOT:PSS/Ag NWcomposite
compositefilm;
film; infrared thermal images of the pristine (B) and composite film with NW
infrared thermal images of the pristine (B) and composite film with NW concentration of 8 mg/mL concentration of (C);
8 mg/mL (C); 12 mg/mL (D); the applied voltage was 40 V; (E) evolution of the
12 mg/mL (D); the applied voltage was 40 V; (E) evolution of the generated temperature of the pristine generated
andtemperature
composite of the with
films pristine
the and composite
different Ag NW films with the different
concentrations Ag NW
ranging fromconcentrations
4 mg/mL to ranging
12 mg/mL,
the driving voltage was 40 V; and (F) evolution of the generated temperature ofofthe
from 4 mg/mL to 12 mg/mL, the driving voltage was 40 V; and (F) evolution thecomposite
generatedfilm
temperature of the composite film with the Ag NW concentration of 12 mg/mL at various voltages
with the Ag NW concentration of 12 mg/mL at various voltages changing from 15 V to 40 V.
changing from 15 V to 40 V.

Figure 6E7shows
Figure showsthe thetemperature
on/off response evolution of the
of the film pristine
heaters and
with thecomposite
Ag NW additionfilms with of 4,the
6, Ag
andNW
addition of 4, the
12 mg/mL; 6, 8,samples,
and 12 which
mg/mL in the
have beenink, respectively.
preserved for fourAll films were
months were characterized
driven at 40 under V for 150a s.
driving potential of 40 V. The heating and cooling time in each cycle was
By passing the current through the films, they could be heated from room temperature to a steady 80 and 70 s, respectively.
The heating
temperature oftemperature
32, 49, 59, 65, wasand the◦ C
in99 range of 47–49
within °C,
30 s to 5049–57 °C, and 76–79
s, respectively. The°C for the filmswas
temperature withelevated
the
Ag Ag
as the NWNW addition
density of in
4, the
6 and
film12increased,
mg/mL, respectively.
demonstrating Thethatcycling
morecurve showed
electron pathwaysrelatively
was stable
beneficial
for temperature recoverabilityFigure
the thermal generation. of the6Fheater
presentsbased on the PEDOT:PSS/Ag
the temperature profiles of NW composite films.NW
the PEDOT:PSS/Ag
Compared to the fresh-fabricated films with the saturable
composite film with the NW concentration of 12 mg/mL, which was plotted with temperature of 49, 59, and 99 °Ctheatrespect
40 V, to
the films with the Ag NW addition of 4 and 6 mg/mL exhibited a stable temperature, and the film
the different voltages from 15 V to 40 V. When the potential was set as 15, 20, 25, 30, 35, and 40 V,
with the Ag NW addition of 12 mg/mL showed a decrease in temperature after four months. We
the composite film reached the temperature of 41, 51, 66, 78, 91, and 99 ◦ C, respectively, indicating that
suppose that the film with a large Ag NW density was more easily oxidized during the process of
the generated temperature of the film raised as the applied voltage increased.
preservation, leading to the decrease of the heating temperature. The result agreed with the previous
Figure 7 shows
discussion. the on/off
In the case of the response
Ag NWs with of thea film
high heaters with the
concentration, theAg NW addition
composite of 4, 6, and
film exhibited
12 mg/mL;
inhomogeneous sheet resistance because the NWs were randomly exposed to air or embedded under
the samples, which have been preserved for four months were characterized into a
driving potential of 40 V. The heating and cooling time in each cycle was
polymer during the printing process. After a period of preservation, the exposed NWs were prone to 80 and 70 s, respectively.
Thebeheating temperature ◦ C, 49–57 ◦ C, and 76–79 ◦ C for the films with
oxidized, resulting in was in the range
the decrease of 47–49 temperature
of the saturable of the composite film.
the Ag NW The addition
discussion of above
4, 6 andsuggests
12 mg/mL, that respectively.
the pristine The cycling curve
PEDOT:PSS film showed
showed relatively
no obvious stable
temperature
temperature increase evenofatthe
recoverability 40 heater
V. Its poor
basedheating
on theperformance
PEDOT:PSS/Ag was attributed
NW composite to its high resistance
films. Compared
of the
to the commercial PEDOT:PSS
fresh-fabricated films with the in saturable
the study,temperature
which couldofbe49,improved
59, and 99 by◦ Cintroducing
at 40 V, theafilms smallwith
theamount
Ag NWofaddition
Ag NWs.ofThe 4 andcomposite
6 mg/mL films could rapidly
exhibited be temperature,
a stable heated within and 30 s the
to 50film
s. The
with composite
the Ag NW
addition of 12 mg/mL showed a decrease in temperature after four months. We suppose that the film
with a large Ag NW density was more easily oxidized during the process of preservation, leading
to the decrease of the heating temperature. The result agreed with the previous discussion. In the
case of the Ag NWs with a high concentration, the composite film exhibited inhomogeneous sheet
resistance because the NWs were randomly exposed to air or embedded into polymer during the
printing process. After a period of preservation, the exposed NWs were prone to be oxidized, resulting
in the decrease of the saturable temperature of the composite film.
PEDOT:PSS with easy film-forming and strong adhesion. By adding the Ag NWs with a low density
into the ink, the heating stability of the composite film could be maintained at least for four months
due to the protection of PEDOT:PSS from the air. Therefore, we propose that the film heater
with large area could be fabricated by scalable screen printing, revealing a bright application
prospect
Materials in 10,
2017, a 220
large-area heating production, such as defogging in vehicles, heating in outdoor
8 of 10
displays, or thermal therapies.

Figure 7.
Figure 7. On/off
On/offresponses
responsesof
of the
the film
film heaters
heaters with
with the
the Ag
Ag NW addition of
NW addition of 4,
4, 6,
6, and
and 12
12 mg/mL
mg/mL at
at 40 V
40 V
after four-month preservation.
after four-month preservation.

4. Conclusions
The discussion above suggests that the pristine PEDOT:PSS film showed no obvious temperature
In this
increase paper,
even at 40a V.
hybrid structure
Its poor heating of performance
PEDOT:PSS and was Ag NWs was
attributed to experimentally
its high resistancefabricated
of the
using a scalable screen-printed technology, resulting in a transparent
commercial PEDOT:PSS in the study, which could be improved by introducing a small amount and conductive film. The
uniformity
of Ag NWs.and Theoptoelectronic
composite films properties of the fabricated
could rapidly be heatedfilms
within were
30 sinfluenced
to 50 s. Theby composite
the mesh sizefilmsin
the fabrication
could process.
combine the A uniform
advantages of thefilm
Agcould
NWs withbe printed with a mesh and
good conductivity number ranging PEDOT:PSS
the polymer from 200 to
350. easy
with The film-forming
addition of theandAg NWs
strong into PEDOT:PSS
adhesion. By adding ink brought
the Ag a slight
NWs with a lowdecrease in the
density into the film
ink,
transmittance
the and significantly
heating stability increased
of the composite filmthe filmbe
could conductivity.
maintainedAscribed to four
at least for the improvement
months due to of the
optoelectronic
protection properties,from
of PEDOT:PSS thethe
composite films we
air. Therefore, exhibited
proposefast
thatresponse and uniform
the film heater with largetemperature
area could
distribution.
be fabricated This work is
by scalable expected
screen to berevealing
printing, helpful for the development
a bright of the transparent
application prospect conducting
in a large-area heating
films for thesuch
production, fabrication of large-scale,
as defogging uniform
in vehicles, filminheaters.
heating outdoor displays, or thermal therapies.

4. Conclusions
Acknowledgments: This work was supported by the Frontier and Key Technological Innovation Special
Foundation of Guangdong Province (Grant No. 2014B090915001); National Natural Science Foundation of
In this paper, a hybrid structure of PEDOT:PSS and Ag NWs was experimentally fabricated using
China (Grant No. 61307026); Natural Science Foundation of Guangdong Province (Grant No. 2014A030313621);
aCultivation
scalable screen-printed technology,
Fund of Outstanding Youngresulting
Teachers inin aHigher
transparent andofconductive
Education Guangdongfilm. The uniformity
Province (Grant No.
and optoelectronic
YQ2015161); properties
Innovative ofTeam
Research the fabricated filmsofwere
in University influenced
Guangdong by No.
(Grant the 2015KCXTD027);
mesh size in the Science
fabrication
and
process. A uniform
Technology Project offilm couldCity
Jiangmen be printed withJiangke
(Grant No. a mesh[2016]189).
number ranging from 200 to 350. The addition of
the Ag NWs into PEDOT:PSS ink brought a slight decrease in the film transmittance and significantly
Author Contributions: Xin He proposed the project; Xin He and Ruihui He wrote the paper; Ruihui He,
increased the Weijie
Qiuming Lan, film conductivity.
Wu and FengAscribed to the improvement
Duan peroformed of the optoelectronic
all the experiments; properties,
Jundong Xiao, Jianhao the
Wu and
composite films exhibited fast response and uniform temperature distribution. This work is expected
Junyan Liu analyzed the data; Mei Zhang and Qingguang Zeng revised the language of the paper. All authors
to be helpful
reviewed for the development of the transparent conducting films for the fabrication of large-scale,
the paper.
uniform film heaters.
Conflicts of Interest: The authors declare no conflict of interest.
Acknowledgments: This work was supported by the Frontier and Key Technological Innovation Special Foundation
References
of Guangdong Province (Grant No. 2014B090915001); National Natural Science Foundation of China (Grant
No. 61307026); Natural Science Foundation of Guangdong Province (Grant No. 2014A030313621); Cultivation
1.
Fund Bae, J.J.; Lim, S.C.;Young
of Outstanding Han, G.H.; Jo, Y.W.;
Teachers Doung,
in Higher D.L.; Kim,ofE.S.;
Education Chae, S.J.;Province
Guangdong Huy, T.Q.; van Luan,
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Author Contributions: Xin He proposed the project; Xin He and Ruihui He wrote the paper; Ruihui He,
Qiuming Lan, Weijie Wu and Feng Duan peroformed all the experiments; Jundong Xiao, Jianhao Wu and
Junyan Liu analyzed the data; Mei Zhang and Qingguang Zeng revised the language of the paper. All authors
reviewed the paper.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2017, 10, 220 9 of 10

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