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A New Transparent Conductor: Silver Nanowire Film
Buried at the Surface of a Transparent Polymer
By Xiao-Yan Zeng, Qi-Kai Zhang, Rong-Min Yu, and Can-Zhong Lu*
With the emergence of flexible plastic devices and the scarcity
of indium resources, great efforts have been made to develop
new flexible transparent conductors to replace indium tin oxide
(ITO),[1,2] examples including conductive polymers,[3,4] carbon
nanotubes (CNTs),[5–8] graphene,[9] metal grids,[10] and random
networks of metallic nanowires.[11,12] Among these contenders,
random silver nanowire (AgNW) networks show optoelectronic
performances very close to that of ITO[11,13] and are regarded
as the leading candidate material to replace ITO[14] (Table 1S
in Supporting Information). There are two critical issues that
currently prohibit AgNW films from large scale applications:
AgNW films deposited on bare substrates are highly coarse[12]
and can be easily removed by adhesion or friction.[11] In this
work, both of these critical issues were resolved by burying
the AgNW network just below the surface of a transparent
polymer matrix (such as polyvinyl alcohol, PVA) to form a trans-
parent surface conducting film. As a first demonstration of this
method, PVA was selected as the matrix because of its high
optical transparency. Compared with a AgNW film on a bare
substrate,[11,12] overall improvements were observed in terms of
electrical conduction, surface roughness, mechanical resistance,
chemical robustness, and thermal stability. The potential of
AgNW transparent electrodes for flexible devices was evaluated
by depositing simple organic light-emitting devices (OLEDs) on
the AgNW electrodes; these devices showed higher power effi-
ciency than with conventional ITO electrodes. We believe that
the method might boost large-scale applications of AgNW films
in flexible optoelectronic devices.
AgNWs with an average length of 5.4 μm and average
diameter of 49 nm (Figure 1S in the Supporting Information)
were fabricated using an air-assisted polyol method.[15,16] The
wet-chemical fabrication of AgNW–PVA films is illustrated in
Scheme 1S in the Supporting Information. Firstly, a uniform
AgNW network was deposited on a poly(ethylene terephtha-
late) (PET) substrate by vacuum filtration and transfer.[7,17–19]
Then, an aqueous solution of PVA (10 wt%) was cast or spin-
coated over the AgNW network, during which process the PVA
solution infiltrated through the pores and reached the surface
of PET to form a smooth PVA/PET interface. After drying at
80 °C for 1 h and and 100 °C for 1 h, the dried PVA matrix
together with all AgNWs was peeled off the PET surface
[∗] X.-Y. Zeng, Q.-K. Zhang, R.-M. Yu, Prof. C.-Z. Lu
The State Key Laboratory of Structural Chemistry
Fujian Institute of Research on the Structure of Matter
Chinese Academy of Sciences
Fuzhou, Fujian Province, 350002 (PR China)
E-mail: czlu@fjirsm.ac.cn
DOI: 10.1002/adma.201001811
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(Figure 1a). Unlike the highly coarse and porous AgNW film
on PET, a solid and smooth conductive surface was obtained
by burying the AgNW film at the surface of the PVA matrix. As
revealed by atomic force microscopy (AFM) (Figure 1b and c),
the surface of AgNW–PVA film was composed of conductive
AgNWs and insulating PVA, and the surface roughness (rms)
was significantly reduced from 30–100 nm (AgNWs on PET)
to 1–5 nm. Clearly, the unique structure of AgNW–PVA film
is distinct from the previously reported Ag–PVA nanocompos-
ites composited in bulk phase,[20] or transparent CNT films on
PET[18,21] in which nanotubes are deposited on a preformed
substrate.
Unlike the low transparency and poor electric conductivity
of PVA–AgNW bulk composites,[24] high transparency and
low sheet resistance (Rs) were retained in AgNW–PVA films.
As shown in Figure 1d, except for the broad surface plasmon
resonance bands[25] in UV region, near-neutral color and high
transparency are achieved across a wide range of the visual and
near-infrared spectrum. The latter merit is of special impor-
tance in flexible thin film tandem solar cells, in which NIR
photons need to be harvested effectively. It is notable that the
Rs of the AgNW–PVA film is about 10%–30% smaller than that
of AgNW film on bare PET prior to the coating of PVA solution
(Figure 1e). The reduced Rs values verify the reduced contact
resistance between the AgNWs, brought about by the tremen-
dous reduction in thickness when PVA is dried (about 92% for
10 wt% PVA solution). For the AgNW–PVA film produced with
a deposition density of 32 mg/m2, the optical transmission at
550 nm is 88.0% with Rs around 182 Ω, whereas at a depo-
sition density of 47.7 mg/m2 a transparent conducting film
with an optical transmission of 87.5% (at 550 nm) and Rs of
63 Ω was obtained, which is very close to the optoelectronic
requirements for touch screen panels.[26] In Figure 1f, we fur-
ther compare the optoelectronic performances of the AgNW–
PVA film with its competitors, including ITO on PET, CNTs,
and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)
(PEDOT:PSS). The AgNW–PVA film is more conductive than
the others, although the performances still lag behind those
of previously reported AgNW films on PET since the intrinsic
electric resistance of AgNWs (average diameter 49 nm) is at
least 3 times of that of the AgNWs used previously[11] (average
diameter 84 nm).
The more important advantage of burying the AgNW film
at the surface of the PVA matrix is the excellent mechanical
robustness against adhesion, friction, and bending. In spite
of the demonstrated robustness when an AgNW film depos-
ited on PET was bent to a curvature of 2.5 mm,[11] such
films cannot be adhered, wiped (seen in insert in Figure 2a)
or folded over. After being buried at the surface of PVA, the
intrinsically fragile network becomes mechanically robust,
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Figure 1. (a) Photograph of an AgNW–PVA film. Morphology images (tapping-AFM, 10 × 10 μm), section curves and roughness of AgNWs on bare PET
(b) and AgNW–PVA film (c) at deposition densities of 48 mg/m2 and 32 mg/m2, respectively. UV-Vis-NIR transmission spectra (d) and sheet resist-
ance (e) of AgNW–PVA film at different deposition densities. (f) Transmission (at 550 nm) and Rs values of AgNW–PVA films and typical transparent
conductors, including ITO on PET,[22] SWNT (Invisicon, Eikos),[21] PEDOT:PSS,[23] and AgNW film on PET reported by De and co-workers.[11]

since all the AgNWs are firmly anchored by the PVA matrix.
As shown in Figure 2a, at all deposition densities, no obvious
increase in Rs was observed after a standard tape test or after
being wiped over by finger, paper, or cloth. We further tested
the change in electrical resistance when AgNW–PVA elec-
trodes (Rs = 63 Ω, 3 mm × 30 mm) were totally folded to a
curvature of 100–200 μm (Figure 2b). An inorganic film of Al-
doped ZnO (AZO) was deposited on polyimide tape (3 mm ×
30 mm) as a comparison. It is unsurprising that the AZO
film cracked and resistance increased by a factor of 10 after
10 cycles of tensile folding or 2 cycles of compressive folding.
For the AgNW–PVA film (thickness 130 μm), the resistance
increase was only 2–3 times, even after 250 cycles of tensile
or compressive folding. The rise in resistance originates from
failed electrical contacts between AgNWs.[27] This result is
superior to that of ITO film coated on PET substrate,[26] and
comparable to that of PEDOT:PSS, CNT[28] and graphene[9,29]
films.
We further tested the thermal and chemical stability of
AgNW–PVA electrodes (Rs = 63 Ω, 3 mm × 30 mm). As shown
in Figure 2c, electric resistance increased linearly up to 240 °C
with a thermal coefficient of (7.9 ± 0.3) × 10−3 Ω/K, which prob-
ably originates from thermal expansion of polymer matrix.
From 240 °C to 290 °C, the gradual decrease in R indicates
the fusing together of the contacts between the AgNWs.[12] The
AgNW network is thermally stable at 330 °C, after which oxida-
tion leads to an exponential increase in R. As a comparison, it
was reported that an obvious rise in R occurred if AgNW films
on Si were annealed in air at 200 °C for 1 h.[12] The burying of
the AgNWs at the surface of PVA can also effectively protect
them from chemical attack by corrosive liquids, such as sulfu-
ration. As seen in Figure 2d, under the attack of aqueous Na2S

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Figure 2. (a) The variation of Rs values of AgNW–PVA films after tape test using 3M Scotch tape. The insert photos are AgNWs film on PET destroyed
by finger friction and tape adhesion. (b) The increase in resistance after cycles of folding up. 140 nm thick AZO film RF-sputtered on 48 μm thick poly-
imide film (Kapton) was also tested as a comparison. (c) The evolution of resistance as increasing temperature (5 °C/min) in air. (d) Electric resistance
vs. time relationship of AgNW–PVA electrode under the attack of aqueous Na2S solution.

solution (5 wt%) remarkable sulfuration occurred at 3–4 s for
an unprotected AgNW film, whereas this time was prolonged
up to 59 s for AgNW–PVA film.
As discussed above, AgNW–PVA film could be one of the
most promising substitutes for ITO in low-cost plastic devices.
Lee and co-workers have demonstrated the successful use of a
AgNW electrode in organic solar cells.[12] Here, we examined
the potential of AgNW–PVA films for applications by vacuum
depositing simple OLED devices (Figure 3a) on AgNW–PVA
electrodes: AgNW/PEDOT:PSS/NPB/Alq3/LiF/Al, in which
the PEDOT:PSS layer was used as the smooth layer and to
adjust the work function of the anode. An OLED device was
also deposited on commercially obtained ITO under the same
conditions and used as a reference. The results are shown in
Figure 3b–d and Figure 6S in Supporting Information.
As shown in Figure 3b, an OLED built on the AgNW elec-
trode with a thick PEDOT:PSS layer (D2, 67 nm) was more
luminous than one with a thin layer of PEDOT:PSS (D1, 53 nm).
But both AgNWs based OLED devices were less luminous
than that deposited on ITO (DR). The OLED turn-on voltage
(defined at 1 cd/m2) was 3.6 V, 6.9 V, and 6.6 V for DR, D1,
and D2 devices, respectively. At a forward bias >6 V, the current
density follows a DR > D1 > D2 order and thicker PEDOT:PSS
leads to smaller current due to the poor conductivity of the
PEDOT:PSS layer used here, whereas at smaller bias (3–5 V)
remarkable leakage current was observed in D1. Evidently,
thicker PEDOT:PSS layer can more effectively cover “bad” spots
and reduce leakage current. Removal of the PEDOT:PSS layer
leads to a short-circuit of AgNW-based device even at small
forward bias. When comparing the power efficiency of these
OLED devices, it was astonishing that D2, the AgNW-based
OLED device with PEDOT:PSS layer of 67 nm, shows a higher
power efficiency than that of the ITO-based OLED device at
current density <140 mA/cm2. It reaches 2.43 lm/W at current
density of 45.8 mA/cm2 (brightness of 1112 cd/m2). For the
ITO-based device, the highest power efficiency is 1.62 lm/W
at current density of 277.2 mA/cm2. As for the D1 device with
a PEDOT:PSS layer of 53 nm, the power efficiency is very low
due to large leakage current.
There are at least two reasons for the higher power efficiency
of the AgNW-based OLED device. Firstly, the AgNW film is
composed of conductive AgNWs and an insulating surface of
PVA, so the current density on the AgNWs is higher than that
upon PVA. Local current density around the AgNWs may be
high enough to drive the local light-emitting layer into a highly
efficient mode when the measured average current density is
still very low. Secondly, the light extraction efficiency may be
improved due to light scattering by AgNWs.[12] At higher cur-
rent densities (>128 mA/cm2) the OLED device degrades due to
the failure of local organic layers. Thus the AgNW-based OLED
devices are more suitable to being operated at low current den-
sities. Undoubtedly, the performances will be further improved
after the optimization of OLED structure and materials.
In conclusion, we have demonstrated that a flexible trans-
parent conducting film of AgNWs with superior mechanical,
thermal, and chemical robustness and ultralow surface rough-
ness can be fabricated by burying a AgNW film at the surface
of a transparent PVA matrix. It is feasible to bury the nanowire

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Figure 3. (a) OLED device structure based on ITO and AgNWs–PVA electrodes with the pixel size of 3 × 3 mm2. (b) Brightness and (c) current density
vs applied forward bias for OLED devices deposited on ITO (DR) and AgNW–PVA electrode (D1 and D2). The photo of turned-on D2 is shown as insert
in (b). (d) Power efficiency as the function of current density.
films at the surface of other transparent polymers, such as poly-
imide and PET. The work function of the nanowire film can be
tuned by covering it with a thin layer of graphene (work func-
tion of 4.6 eV[30]) to match that of ITO (4.7 eV). Consequently,
AgNW-based transparent electrodes could be used in a wide
range of flexible and cheap devices such as OLEDs and solar
cells as an alternative to ITO. We believe that this work is a
major step towards the large-scale application of AgNW films
in emerging flexible optoelectronic devices.
Experimental Section
Fabrication and characterization of AgNW–PVA film: AgNWs were
synthesized using an air-assisted polyol method,[15] and AgNWs films
were deposited on PET by a vacuum filtration and transfer method.[11]
Aqueous solutions (10 wt%) of PVA (PVA124, Kuraray) were cast or spin-
coated (1500 rpm for 15 s) on the nanowire films, then the AgNW–PVA
film was peeled off PET after it was dried at 80 °C for 1 h and 100 °C for
another hour. Microstructure analysis of AgNWs was performed using
SEM (Figure 1S in Supporting Information) and TEM (JEOL JEM-2010).
AFM analysis was carried out on a Nanoscope Multimode IIIa (Veeco
Instruments) operated in tapping mode. Optical transmission spectra
(300–800 nm) were recorded on a Lambda 900 (PerkinElmer) equipped
with a Φ150 mm integral labsphere. Sheet resistance was measured using
the 4-probe method. The mechanical, thermal, and chemical tests of the
AgNW–PVA film are described in detail in Supporting Information.
Fabrication and measurement of OLED devices: A AgNW film on PET
(47.8 mg/m2) was patterned into two parallel electrodes by tape adhesion.
Then PVA solution (10 wt%) was cast on glass and dried to form a patterned
AgNW–PVA sheet. Aqueous solution of PEDOT:PSS (Baytron P VP Al 4083
from H. C. Stark) was spin-coated on the patterned AgNW–PVA sheet.
The AgNW–PVA sheets (30 mm × 30 mm) and the patterned ITO glass
(thickness 180 nm, Rs = 67 Ω) were mounted into a vacuum deposition
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chamber. A 60 nm thick NPB and a 60 nm thick Alq3 layer were deposited
one after another. Finally, the cathode was fabricated by thermal evaporation
of a LiF layer (1 nm) and then an Al layer (100 nm). The I-V-B of the OLED
devices was measured at ambient conditions with a Keithley 2400 Source
meter and a Keithley 2000 multimeter equipped with a calibrated silicon
photodiode. Since the PVA substrate is very flexible, it was held together
with a 1 mm thick glass cover. No correction to brightness was made.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the 973 key program of MOST
(2006CB932904, 2007CB815304, 2010CB933501), the NSFC program
(20873150, 20821061, 20973173 and 50772113), the Chinese Academy of
Sciences (KJCX2-YW-M05, KJCX2-YW-319), the Youth Foundation of Fujian
Province (2008F3118), and China Postdoctoral Science Foundation.
Received: May 17, 2010
Revised: June 18, 2010
Published online: August 3, 2010
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