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OPEN Surface Engineering of ZnO Thin

Film for High Efficiency Planar
Perovskite Solar Cells
received: 19 March 2015
accepted: 22 July 2015 Zong-Liang Tseng1,*, Chien-Hung Chiang1,* & Chun-Guey Wu1,2
Published: 28 September 2015
Sputtering made ZnO thin film was used as an electron-transport layer in a regular planar perovskite
solar cell based on high quality CH3NH3PbI3 absorber prepared with a two-step spin-coating. An
efficiency up to 15.9% under AM 1.5G irradiation is achieved for the cell based on ZnO film fabricated
under Ar working gas. The atmosphere of the sputtering chamber can tune the surface electronic
properties (band structure) of the resulting ZnO thin film and therefore the photovoltaic performance
of the corresponding perovskite solar cell. Precise surface engineering of ZnO thin film was found to
be one of the key steps to fabricate ZnO based regular planar perovskite solar cell with high power
conversion efficiency. Sputtering method is proved to be one of the excellent techniques to prepare
ZnO thin film with controllable properties.

Methylammonium lead halide (CH3NH3PbX3, X =  I, Cl or Br) has attracted extensive attention because
of its promising light-harvesting capability. Solid-state dye-sensitized solar cell based on perovskite sen-
sitizer and mesoporous metal oxide scaffold (conventional perovskite solar cell) achieves the conversion
efficiency over 17%1–4. Now solid state perovskite solar cells has reached the certified power conversion
efficiency over 20%5,6. In a conventional DSSC, mesoporous semi-conducting metal oxides are used to
adsorb a large number of dye molecules for absorbing the light and injecting electron to the anode to
produce the electricity. However, insulated mesoporous Al2O3 scaffold layer without electron accepting
ability was also developed in perovskite sensitized solar cells and demonstrated a PCE of up to 10.9%7.
Moreover, it was shown that perovskite materials which have low exciton binding energy and long car-
rier lifetime thus can be also applied in the planar heterojunction solar cells8,9 in which the mesoscopic
oxide scaffold layer is no longer required to achieve high efficiency. The merit of the planar (without
meso-superstructure) architecture is that it can be adopted by the low temperature solution process and
therefore the flexibility device10–14.
In a planar perovskite-based solar cell, a metal oxide dense film, such as TiO28,9 or ZnO15–17 is usually
used as an electron-transport layer to beneficially transfer the electrons and block the holes. The thin
metal oxide layer can be regarded as a modification agent to lower the work function of the modified ITO
anode18–20. It is well known that the intrinsic point defects, such as oxygen vacancy and metal interstitial,
have important impacts on the electronic properties of the metal oxides. It has been also commonly
accepted that the presence of oxygen vacancies (non-stoichiometry or zinc interstitials) in ZnO can
increase the charge density of ZnO to form native n-type semiconductor21–23. However, up to date, few
reports discussed the effects of the non-stoichiometry and defects of the metal oxide electron transport
layer on the photovoltaic performance of the planar perovskite solar cell.
In this study, we report the photovoltaic performance of the planar CH3NH3PbI3 perovskite solar cell
based on ZnO electron-transport layer prepared by sputtering deposition method. The stoichiometry
and therefore the properties of ZnO thin film was controlled by adjusting the ratio of working gases (Ar
and O2) in the vacuum chamber during radio frequency (RF) magnetron sputtering process. The effects

1
Research Center for New Generation Photovoltaics, National Central University, Jhong-Li, 32001, Taiwan, ROC.
2
Department of Chemistry, National Central University, Jhong-Li, 32001, Taiwan, ROC. *These authors contributed
equally to this work. Correspondence and requests for materials should be addressed to C.-G.W. (email: t610002@
cc.ncu.edu.tw)

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Figure 1. X-ray diffraction patterns of ZnO films deposited on ITO substrates prepared by sputtering
under working gas of pure Ar (ZnO-Ar) and Ar/O2 mixture (ZnO-10% and ZnO-20%). (The inset shows
a photograph (taken by Z.-L. Tseng) of a commercial patterned ITO substrate and ZnO films deposited on
ITO substrates).

of ZnO (thin film prepared under different working gas environments) properties on the photovoltaic
performance of the corresponding perovskite based solar cell were investigated. The highest efficiency up
to 15.9% (under AM1.5G irradiation) was achieved for the cell based on ZnO electron transport layer
prepared under pure Ar working gas. The results provide the useful information regarding to the chem-
ical engineering of the electronic (band structure) and electric (conductivity) properties of the electron
transport layer to enhance the photovoltaic performance of the planner perovskite solar cell.

Results and Discussion

The deposition rates for preparing ZnO films under pure Ar (ZnO-Ar), O2/Ar +  O2 =  10% (ZnO-10%),
and O2/Ar +  O2 =  20% (ZnO-20%) were 1.9, 1.3, and 1.3 nm/min, respectively. The thickness of all films
was controlled to be ca. 40 nm by adjusting the deposition time. X-ray diffraction patterns of all ZnO
films on the glass substrates prepared by sputtering under various working gases without substrate heat-
ing were displayed in Fig. 1. The pictures of the as-deposited (with or without the presence of O2) ZnO
films are displayed in the insert of Fig. 1. All ZnO films are highly transparent and the optical band-gap
estimated from the Uv/Vis absorption spectra (displayed in Figure S1 of the Electronic Supporting
Information, ESI) is 3.2 eV for all films, consistent with the high band-gap semi-conductor character-
istics. The diffraction patterns of ZnO-Ar, ZnO-10%, and ZnO-20% films are also similar. Only (0 0 2)
diffraction peak appeared at 2θ of 34° was observed indicating that all ZnO films showed a preferential
orientation with the c-axis perpendicular to the substrates. Furthermore the diffraction peak for all films
has similar intensity and line width suggesting that the crystallinity and crystallite size of ZnO films
grown under different working gases are very close with each other.
SEM images of ITO and ZnO films deposited on ITO substrates were shown in Fig. 2. ITO film
(Fig. 2(a)) was consisted of very homogeneous grains with the particle size of ca. 20 nm. ZnO films were
formed by the aggregated nano-crystals having the particle size less than 10 nm, laying on the top of ITO
grains, as shown in Fig. 2(b–d). The morphologies of ZnO films prepared under different working gases
are also similar, may be due to both films are very thin (40 nm) and using the same batch of substrate
(ITO).
CH3NH3PbI3 film deposited on the top of ZnO film was prepared with a two-step method we devel-
oped recently using solution process at low temperature24. The absorption spectra of CH3NH3PbI3 films
displayed in Fig. 3(a) shows a strong absorption at the wavelength between 400 nm to 800 nm, which has
the ability to harvest the visible light. The absorption coefficients (absorption divided by film thickness)
of the CH3NH3PbI3 films deposited on ZnO-Ar, ZnO-10% and ZnO-20% were 3.8 ×  104, 3.9 ×  104 cm−1
and 3.9 ×  104 cm−1 at 550 nm, respectively. The result revealed that perovskite films deposited on all ZnO
films have similar absorption intensity and they all are the highly dense film25,26 (The pictures of PbI2
on ZnO-Ar, and perovskite films deposited on the top of ZnO-Ar, ZnO-10% and ZnO-20% film were
displayed in Figure S2 of ESI). Figure 3(b) is the GIXRD patterns of perovskite films deposited on three
different ZnO films and the XRD pattern for PbI2 was also listed for the comparison. Eleven diffraction
peaks corresponding to the (110), (200), (211), (202), (220), (213), (310), (312), (224), (314), and (404)
planes of the CH3NH3PbI3 were observed27 and no peak belongs to PbI2 was detected. The crystallinity

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Figure 2. SEM images of (a) a commercial ITO substrate, (b) ZnO-Ar film, (c) ZnO-10% film, and
(d) ZnO-20% film coated on the ITO substrate. The inset in each picture shows the same images at higher
magnification.

Figure 3. (a) Absorption spectra and (b) XRD patterns of PbI2 film and CH3NH3PbI3 films deposited on
top of ZnO films.

and crystalline domain size of CH3NH3PbI3 film deposited on ZnO films made from different working
gases are also very alike, due to all perovskite films were prepared with nearly the same conditions.
Figure 4 illustrates the surface and cross-section SEM images of perovskite film deposited on ZnO-Ar,
ZnO-10% and ZnO-20% films. The surface morphology of CH3NH3PbI3 films are also very alike, exhib-
iting a dense-packed grains with the sizes of about 100 ~ 500 nm. Their morphology is similar to those
fabricated with solvent-engineering technology28 and vapor-assisted solution process29 reported previ-
ously. Dense and continuous perovskite film is essential for achieving high power conversion efficiency
of the resulting cell. Two-step spin-coating method is a way to fabricate dense perovskite film to be
applied in the planner heterojunction device when the electron transport layer with relatively smooth
surface was used24. The thickness and packing of the grain of the active perovskite film which acts as
a light harvester is also an important parameter for determining the photovoltaic performance of the
corresponding device. Figure 4(b,d,f) display the cross-section SEM images of perovskite films coated

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Figure 4. The surface and cross-sectional SEM images of perovskite films deposited on ZnO-Ar film (a,b),
deposited on ZnO-10% film (c,d), deposited on ZnO-20% (e, f) and (g) is the cross section image at low
magnification of perovskite deposited on ZnO-Ar to reveal the long-range homogeneous of perovskite film.

on top of ZnO-Ar, ZnO-10%, and ZnO-20% films. The thickness of perovskite films is all about 350 nm
and very dense without observable pine hole. It was known6,7 that perovskite absorber has long charge
carrier lifetime and exciton diffusion length. Therefore, perovskite film with the thickness of 350 nm
was able to harvest light sufficiently and transport the carriers (or excitons) to the electrode efficiently.
Figure 4(g) is a low magnification of the cross-section image which reveals that the film is very flat and
dense in a long distance (>10 um).
The physicochemical data discussed above confirmed that the structure, light absorption ability, mor-
phologies and thicknesses of perovskite films (prepared via two-step method) deposited on all ZnO films
(fabricated with and without the presence of O2 in working gas) are similar. However, the photovoltaic
performances of the corresponding devices (the device architecture used in this study is ITO/ZnO/
CH3NH3PbI3/spiro-OMeTAD/Ag) are significantly different. Figure 5(a) displayed the I-V curves of the
three best devices (device with the highest efficiency) measured at a 75 ms scanning delay time using
the reverse modes (from the open-circuit voltage (Voc) to the short-circuit current (Jsc)) under the illu-
mination of 1.5 G simulated Sun light. The corresponding photovoltaic parameters are listed in Table 1.
The highest PCE of the device based on CH3NH3PbI3 film deposited on ZnO-Ar is 15.9%. On the other
hand, the device based on perovskite deposited on ZnO-10% and ZnO-20% has the PCE of only 12.8 and
12.4%, respectively. Furthermore all photovoltaic parameters of the device based on ZnO-Ar are better
than those for the device based on ZnO-10% and ZnO-20% films. The statistical analysis of the photo-
voltaic parameters for the devices based on ZnO-Ar and ZnO-20% were also performance and listed in
Table S1, ESI. Figure S4 of ESI displayed the histograms of all photovoltaic parameters for ZnO-Ar and
ZnO-20% based cells. The data clearly revealed that the photovoltaic performance of perovskite solar
cells based on ZnO-Ar film is better than those using ZnO-20% as an electron transporting medium.
IPCE spectra of the best cells shown in Fig. 5(b) have two troughs at around 400 nm and 600 nm,
which are caused by the strong reflection of the glass/ITO substrate at these wavelength regions30. The
integrated current density of the cells based on ZnO-Ar, ZnO-10% and ZnO-20% derived from the IPCE
spectra shown in Fig. 5(b) are 20.0, 18.7 and 18.2 mAcm−2 respectively, which is 5 ~ 8% smaller than the
Jsc obtained from the I-V curves. A difference between the current density integrated from IPCE curve
and Jsc from I-V curve is generally observed in perovskite cell due to the method for measuring I-V and
IPCE is not the same, see the experimental section. Device based on ZnO-Ar film has the highest IPCE
values at the wavelength between 300 ~ 800 nm for the three best cells based on ZnO films fabricated
at different working gas. The external quantum efficiency (EQE or IPCE value) depends on the photon

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Figure 5. (a) I-V curves, (b) IPCE spectra, (c) Dark current curves of perovskite solar cell using ZnO-Ar,
ZnO-10%, and ZnO-20% as the electron transport layer.

Working gas VOC (V) JSC (mAcm−2) FF (%) PCE (%) Rs (Ohm-cm2)
pure argon 1.00 21.8 72.6 15.9 3.2
O2/(Ar +  O2) =  10% 0.92 20.3 68.1 12.4 3.7
O2/(Ar +  O2) =  20% 0.90 20.3 67.6 12.4 3.7

Table 1. Photovoltaic characteristics of the planner perovskite solar cell based ZnO anode prepared
under different atmosphere.

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Figure 6. X-ray photoelectron spectroscopy (XPS) spectra of ZnO-Ar and ZnO-20% films. (top) Zn2p
and (bottom) O1s.

absorption and carrier extraction. All Perovskite films deposited on ZnO films have similar absorption
spectra implying that they have the same light harvesting capability. Therefore the difference between
IPCE values is due to the difference in the carrier extraction by ZnO film. Indeed, the intensity of
the photoluminescence (from the recombination of perovskite exciton) of perovskite film deposited on
ZnO-Ar is significantly weaker than those for perovskite films deposited on ZnO-10% and ZnO-20% as
shown in Figure S3 of ESI. The weaker PL intensity for perovskite on ZnO-Ar indicated that the electron
transfer from perovskite to ZnO-Ar is more efficient. This may due to that ZnO-Ar has higher conduc-
tivity, or perovskite/ZnO-Ar has better interface contact, or the energy level of their frontier orbitals has
a better match. In other words the photovoltaic performance of the devices depends on the properties
of ZnO film prepared in varied working gases. This proposal was further confirmed by the dark current
curves shown in Fig. 5(c). Device based on ZnO-Ar film has the smallest dark current compared to
those based on ZnO-10% and ZnO-20%, suggesting that ZnO-Ar has better hole blocking ability. Since
the physicochemical properties of ZnO-10% and ZnO-20% are so similar, the following studies we focus
only on the differences between ZnO-Ar and ZnO-20% films.
The surface components and chemical states of ZnO films were investigated with X-ray photoelectron
spectroscopy (XPS). In XPS spectra, the binding energies of all elements have been calibrated by taking
the carbon C1s peak (285.0 eV) as a reference. The Zn 2p core electron for ZnO-Ar and ZnO-20% films
is at the same level, having two binding energies at 1021.5 eV and 1044.5 eV (see Fig. 6(a)). Nevertheless
the O1s peaks (Fig. 6(b) at binding energy ca. 530.2 eV (belonged to O in Zn-O of the framework) for
both films have a shoulder occurred at higher binding energy. This shoulder peak is associated with the
oxygen-defect sites related to oxygen atom vacancies or chemisorbed oxygen in ZnO framework31–34.
The O1s shoulder peak of ZnO-Ar film (prepared under pure argon atmosphere) was stronger than that
of ZnO-20% films (prepared under Ar/O2 mixed gas) suggesting that ZnO-Ar film has more defect site

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Figure 7. The illustration of the frontier orbitals energy levels for ZnO-Ar, ZnO-20% and perovskite.

(most probability are oxygen vacancies since the film was prepared under no oxygen environment).
More oxygen vacancies of ZnO-Ar film may result in higher conductivity. The sheet resistances of ITO,
ZnO-Ar, ZnO-10% and ZnO-20% films measured with van der pauw method were 9.9, 10.6, 23.4 and
24.7 Ω , respectively. ZnO-Ar film prepared without the presence of O2 does have higher conductivity, due
to more oxygen vacancies, consistent with the literature reports34–37. The series resistance calculated form
the I-V curves of the devices base on ZnO-Ar and ZnO-10%, and ZnO-20% was also listed in Table 1. As
expected, ZnO-Ar film has the highest conductivity and the corresponding cell also has the lowest series
resistance. Lower series resistance of ZnO-Ar based cell is one of the reasons for having higher Voc.
The oxygen non-stoichiometry may down-shift the valence edge of ZnO-Ar films34. The band gap
determined by fitting the linear regions of the square of the absorption coefficient (α 2) versus the photon
energy (displayed in Figure S1 of ESI) of ZnO-Ar and ZnO-20% films is the same, therefore the conduc-
tion band of ZnO-Ar film is also down-shift to lower energy. In order to get more information regarding
to the relative energy level of the Fermi level, valence band and conduction band of ZnO films, the
photoelectron spectra of ITO, ZnO-Ar and ZnO-20% were taken and displayed in Figure S5, ESI. ITO
has the highest work function and the work function of ZnO-Ar is higher than that of ZnO-20%, com-
bining the fact that ZnO-Ar and ZnO-20% have the same band gap, suggesting that ZnO-Ar has lower
valence band and conduction band when perovskite film was deposited as illustrated in Fig. 7. ZnO-Ar
with lower conduction band has higher driven force for the electron injection from perovskite to ZnO
and lower valance edge can block the hole more efficiently. Both resulting in higher charge extraction
efficient, therefore the corresponding device has higher Jsc. The hole blocking ability of ZnO-Ar film was
also supported by the dark current of the corresponding device shown in Fig. 5(c). Cell based ZnO-Ar
electron transporting layer has smaller dark current indicated that ZnO-Ar has better hole blocking
ability when other components in both cells are supposed to be the same. Compared with ZnO-20%,
ZnO-Ar has higher charge extraction efficiency, lower sheet resistance and better hole blocking ability,
the resulting cell has high Jsc, Voc and FF.
It was known that the regular perovskite solar cells exhibit a current hysteresis even at the scan rate
slower than 1.0 V per second because of changing the direction of the permanent dipoles of CH3NH3+
under different voltage scan directions38. Actually even crystalline silicon solar cell has a current hyster-
esis when the voltage scan rate is higher than 15 V per second due to the capacitive charging and dis-
charging effects39. The I-V curves of the devices based on ZnO-Ar and ZnO-20% films scan at different
directions and delay times (speeds) are displayed in Fig. 8. Both devices show current hysteresis under
different scan directions at scan rates from 1.0 V to 0.33 V per second and the current hysteresis decreases
as the scan time decreases. Nevertheless, the device based on ZnO-Ar film shows smaller current hys-
teresis compared to the cell used ZnO-20% anode for all scan rates studied in this article. Snaith et al.40
has been proposed that the hysteresis is a property of the perovskite absorber or the interface between
the perovskite and the charge collection layers. They measured the current hysteresis phenomenon of
the conventional perovskite solar cells with several architectures and concluded that the imperfect per-
ovskite/charge collection layer interface is the major factor causing the current hysteresis at different
scan directions. We did not find any difference between the perovskite absorber deposited on ZnO-Ar
and that deposited on ZnO-20%. Therefore the small degree of current hysteresis of the device based on

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Figure 8. The I-V curves of the champion cell under forward and reverse scan with various delay times
under AM 1.5G illumination for the devices base on ZnO-Ar (left) and ZnO-20% (right) electron
transporting layers. (the delay time is defined as the time used between two data points, the data were
taken every 0.01 V).

ZnO-Ar film suggested that the charge extraction by ZnO-Ar is more efficient than that by ZnO-20%.
Or the interface contact between perovskite and ZnO-Ar is better than that between perovskite and
ZnO-20%. The interface contact may not mean the real physical contact but more related to the better
matching of the energy level of the frontier orbitals as discussed in the previous paragraph.

Conclusion
In conclusion, ZnO films with various oxygen deficiencies were prepared by sputtering method under
different working gases. Combining with two-step spin coated perovskite film and spiro-OMeTAD hole
transport layer, the resulting regular planar perovskite solar cell achieves the highest power conver-
sion efficiency of 15.9% under AM1.5G irradiation. The electric and electronic properties of ZnO film
depends on the oxygen vacancies which can be controlled by the working gases during the sputtering
process. When ZnO (ZnO-Ar) film was fabricated under pure Ar, more oxygen vacancy was form in the
network, which lower shifts the HOMO and LUMO energy levels, compared to that (ZnO-20%) prepared
under O2 and Ar mixture. ZnO-Ar film is a better electron extractor and hole blocker, therefore all pho-
tovoltaic parameters of the corresponding cell are higher. These results provide a useful knowledge for
preparing metal oxides to be used in the planar perovskite solar cells.

Methods
Materials and Physicochemical Studies. PbI2, CH3NH3OH and HI(aq) were purchased from
Aldrich Co. and used as received. Patterned ITO-covered glass substrates with a sheet resistance of
10-ohm were obtained from Ruilong Inc., Taiwan. CH3NH3I was synthesized with the same method pub-
lished in literature31. Uv/Vis absorption and PL spectra were recorded with a Hitachi U-4100 and F-7000
spectrometers, respectively. The thickness of the films was measured with a depth-profile meter (Veeco

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Dektak 150, USA). XRD data were collected through a Brucker powder diffractometer (D8 Discover)
using Cu Kα 1 radiation. Scanning Electron Micrograph (SEM) was performed with a Hitachi S-4800
microscopy at 15 KV. Samples (surface and cross-section of film on the substrates) for SEM imaging were
mounted on a metal stub with a piece of conducting tape then coated with a thin layer of gold film to
avoid charging.

Device Fabrication and Photovoltaic performance Measurement. A frequency (RF) magnetron

sputtering method was used to prepare ZnO thin films on the patterned ITO-covered glass substrates.
Sputtering was carried out in a pure argon gas and mixing argon and oxygen (O2/(Ar +  O2) =  10%, 20%)
atmospheres with 4-inch ZnO ceramic target. The work pressure, gas flow rate, and RF power were main-
tained at 4 mtorr, 100 sccm, and 80 W, respectively. For depositing perovskite layer, first, several drops of
PbI2 precursor solution (1.0 M in DMF) were spin-coated on the top of ZnO coated ITO at a spin rate of
3000 rpm. After PbI2 layer being dried, CH3NH3I solution (50 mg in 1.0 mL isopropanol) was spin-coated
on top of PbI2 film at spin rates of 3000 rpm, 15 sec to form perovskite structure. More detailed infor-
mation about the two-step spin-coating method can be found in literature24. After perovskite film was
formed, 2,2′ ,7,7′ -tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′ -spirobifluorene (spiro-OMeTAD) used
as the hole transport layer was then deposited by spin-coating at 4,000 rpm for 30 s. The spiro-OMeTAD
precursor solution was prepared by dissolving 80 mg spiro-OMeTAD, 28.5 μ L 4-tert-butylpyridine and
17.5 μ L lithium bis(trifluoromethyl- sulphonyl)imide solution (520 mg in 1.0 mL acetonitrile) in 1 mL
chlorobenzene. The fabrication procedures were carried out in the ambient atmosphere at low tem-
perature (<100 °C). Finally, the device was transferred to a vacuum chamber for coating Ag electrode
(100 nm). The effective area of the device was 0.1 cm ×  0.2 cm defined by a non-reflective metal mask.
J-V characteristics of the cells were taken using a Keithley 4200 source measuring unit under a simulated
AM1.5G light (Wacom solar simulator) at 100 mAcm−2. The intensity of the simulated AM1.5G light was
calibrated by KG-5 Si diode. External quantum efficiency (EQE) or incident photo-to-current conversion
efficiency (IPCE) was measured in air. A chopper and lock-in amplifier were used for the phase sensitive
detection with QE-R3011 measurement system (Enlitech Inc., Taiwan).

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Acknowledgements
Financial support from the Ministry of Science and Technology (MOST), Taiwan, ROC (grand number:
NSC101-2113-M-008-008-MY3) was great acknowledged. The devices fabrication and photovoltaic
performance measurements were carried out in Advanced Laboratory of Accommodation and Research
for Organic Photovoltaics, MOST, Taiwan, ROC.

Author Contributions
C.G. and Z.L. wrote the whole manuscript, Z.L. performed the experiments and C.H. help the experiments
and discussed the results. All authors reviewed the manuscript.

Additional Information
Supplementary information accompanies this paper at http://www.nature.com/srep
Competing financial interests: The authors declare no competing financial interests.
How to cite this article: Tseng, Z.-L. et al. Surface Engineering of ZnO Thin Film for High Efficiency
Planar Perovskite Solar Cells. Sci. Rep. 5, 13211; doi: 10.1038/srep13211 (2015).
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