www.advenergymat.

de
www.MaterialsViews.com

COMMUNICATION

Hot-Electron Injection in a Sandwiched TiOxAuTiOx

Structure for High-Performance Planar Perovskite
Solar Cells
Zhongcheng Yuan, Zhongwei Wu, Sai Bai, Zhouhui Xia, Weidong Xu, Tao Song,
Haihua Wu, Luhai Xu, Junjie Si, Yizheng Jin, and Baoquan Sun*
The organometallic halide perovskite materials, typically
CH3NH3PbX3 (X = Cl, I or Br), show wide and strong absorption over the incident solar spectrum, high mobility, extremely
long, and balanced electron-hole diffusion lengths, which
ensure it as new generation solar cell materials.[13] The power
conversion efficiencies (PCEs) of solar cells based on perovskite materials have boosted from 3.81% to 19.3% in recent
five years, surpassing almost all solution-processed solar cells
and amorphous silicon ones.[416] The structure of transparent
conducting oxide/TiOx/perovskite/hole transport layer (HTL)/
Au is the most commonly implemented device structure in
perovskite solar cells.[1719] Devices based on mesoporous TiOx
are generally fabricated on fluorine-doped tin oxide substrates
and a high annealing temperature (450500 C) is necessary
to form a well-connected structure path for electrons transport.[20] Apart from mesoporous structure, planar structure
shows much impressive improvement in devices performance
recently. Conings et al. fabricated perovskite devices with a
planar structure based on 500 C-annealed compact TiO2 layer
and poly(3-hexylthiophene) (P3HT) as HTL, which yielded a
PCE of 10.8%.[21] With a higher efficient HTL material of 2, 2,
7, 7-tetrakis-(N, N-di-p-methoxyphenylamine)-9, 9-spirobifluorene (Spiro-OMeTAD), a PCE of 14.83% was achieved.[22] The
high temperature annealing process for compact TiOx interlayer is an obstacle for its implementation on large-area and
flexible substrates. Accordingly, several ways have been proposed to decrease the annealing temperature of TiOx layer for
perovskite devices. Wang et al. have reported that enhanced conductivity and better electrical contact could be obtained upon a
low temperature (150 C) annealing treatment of the composite
film consisting of graphene nanoplates and TiO2 nanoparticles
(NPs).[23] Recently, Zhou et al. have incorporated yttrium into
TiOx film to increase the conductivity. Upon carefully controlled
Z. Yuan, Z. Wu, Z. Xia, W. Xu, Dr. T. Song, H. Wu,
L. Xu, Prof. B. Sun
Jiangsu Key Laboratory for Carbon-Based
Functional Materials and Devices
Institute of Functional Nano and Soft Materials (FUNSOM)
Soochow University
199 Renai Road, Suzhou, Jiangsu 215123, China
E-mail: bqsun@suda.edu.cn
Dr. S. Bai, J. Si, Prof. Y. Jin
State Key Laboratory of Silicon Materials
Department of Materials Science and Engineering
Zhejiang University
Hangzhou 310027, China

DOI: 10.1002/aenm.201500038

Adv. Energy Mater. 2015, 5, 1500038

perovskite film growth under certain humidity and electrode

modification, an extraordinary high PCE of 19.3% has been
achieved.[5] However, due to the poor crystallization of pristine
TiOx fabricated at low temperature process, the large amount
of trap states in TiOx result in inferior charge transport properties.[2426] Although other electron collection materials are available, the stability and complex fabrication processes of devices
are not satisfying as well.[27,28]
Herein, a structure of Au-NPs sandwiched between two layers
of low temperature- processed TiOx film are developed to act as
electron conductor to improve the charge extraction efficiency in
perovskite solar cells. The unique structure of Au-NPs embedded
in two layered TiOx films, which avoiding the direct contact
between Au-NPs and perovskite, is critical to achieve highperformance devices. Interestingly, hot carrier injection at the
metalsemiconductor Schottky barrier happens from Au-NPs to
TiOx under plasmonic light illumination (500600 nm), which is
longer than UV light wavelength (<400 nm) absorbed by pristine
TiOx. The plasmon-induced charge injection across the Schottky
barrier fills the trap state sites in TiOx matrix and results in
improved conductivity as well as increased surface potential of
the TiOx composites. Accordingly, the charge extraction properties are improved. The perovskite photovoltaic devices based
on TiOxAu-NPs composites achieve a PCE of 16.2% due to
improved charge extraction capability.
Device structure of indium tin oxide (ITO)/TiOx/perovskite/
HTL/Ag is shown in Figure 1a, where either P3HT or SpiroOMeTAD is used as HTL. The cross-sectional scanning electron microscopy (SEM) image of the planar perovskite device
is depicted in Figure 1b. The boundaries of different layers
are clearly visible. The thicknesses of TiOx film, perovskite
layer, P3HT film, and silver electrode are 100, 320, 45, and
150 nm according to the SEM image, respectively. Since all
the devices are fabricated on patterned ITO substrates, high
annealing temperature (over 300 C) would result in greatly
increased serial resistance of ITO. Therefore, a relative low temperature is preferred to fabricate the TiOx electron transport
layer. Unfortunately, the sol-gel processed TiOx films always
require a high temperature for crystallization to enhance its
charge transporting properties. X-ray diffraction (XRD) pattern
of TiOx thin film obtained at 150 and 500 C annealing process
are illustrated in Figure S1 (Supporting Information). Compared with the film annealed high temperature (500 C), the
low temperature-processed TiOx is amorphous, which contains
large amounts of trap states.[29,30] Therefore, devices based on
amorphous TiOx usually require high-energy UV exposure to
fill the trap states before becoming fully functionalized.

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

wileyonlinelibrary.com

(1 of 7) 1500038

www.advenergymat.de

COMMUNICATION

www.MaterialsViews.com

Figure 1. a) Scheme diagram of the device structure (ITO/TiOxAu-NPs/CH3NH3PbI3-xClx/HTM/Ag); Au-NPs are sandwiched between two TiOx layers.
HTL can be either P3HT or Sprio-OMeTAD. b) Cross-section SEM image of the device; here, P3HT acts as HTL.

Because low temperature processed amorphous TiOx displays

inferior transport properties, its film thickness plays a key role
on photovoltaic performance of perovskite solar cells. It has
to balance the charge transport properties and uniform film
coverage of the whole film. Here, P3HT is used as HTL. The
device based on a single layer TiOx (60 nm) only yields a PCE
of 7.76%, which is inferior to the one based on two layers TiOx
(100 nm; PCE: 9.38%). Further increasing TiOx thickness leads
to deteriorate perovskite device performance due to the poor
transporting properties of amorphous TiOx. Current density
versus voltage (JV) curves of these two kind devices are plotted
in Figure S2 (Supporting Information) and detailed parameters
are summarized in Table S1 (Supporting Information). The
device based on single layer TiOx degrades dramatically during
JV test, which may result from poor perovskite film morphology.[31] SEM images of perovskite films deposited on single
layer TiOx and double layers TiOx are depicted in Figure S3a,b
(Supporting Information). For perovskite film deposited on
single layer TiOx, more pin holes are observed on the surface
after annealing process. These pin holes can result direct contact between HTL and TiOx film, which leads to high possibility
of short circuit condition. Film quality of perovskite is improved
when fabricated on double layers TiOx (100 nm), which reveals
that a thicker layer of TiOx favors perovskite growth. This phenomenon complies well with former results that thicker TiOx
layer achieve better perovskite film quality under the same condition.[31] However, an overthick TiOx film leads to increased
serial resistance and impedes the charge carrier collection. Considering of this point, a thickness of 100 nm is optimized to
obtain an optimum device performance. However, the performance for the devices based on low temperature-annealed TiOx
is inferior to the one that processed under high temperature.[32]
Proper incorporation of Au-NPs can dramatically improve
the perovskite devices performance. There are several effective
routes to incorporate Au-NPs into organic solar cells. Mostly,
Au-NPs are used to increase light harvesting capability because
of the local field plasmonic enhancement, where light harvesting of polymer thin layer is enhanced with the incorporation of Au-NPs. It is worth noting that the spectrum range
of the enhanced light harvesting is in line with the individual
surface plasma resonance region of Au-NPs.[3335] Alternatively,
mixed TiOx/Au-NPs composites are used to enhance the charge
extraction efficiency under illumination condition by plasmonic

1500038 (2 of 7)

wileyonlinelibrary.com

excitation or charge carriers accumulation in organic solar cells.

The improved charge extraction in TiOx-NPs film upon plasmonic wavelength illumination is assumed to either enhance
charge injection from Au-NPs to TiOx or accumulate plasmonically excited electrons in metal NPs.[36,37] Although plasmonic
light trapping and charge extraction enhancements has been
widely reported in the organic solar cells, it seems that the similar plasmonic structure does not work in the perovskite solar
cells.[38] Here, Au-NPs are sandwiched between two TiOx layers
in order to avoid direct contact between Au-NPs and perovskite.
As shown in high resolution transmission electrons microscopy (TEM) images in Figure S4 (Supporting Information), the
synthesized Au-NPs exhibit narrow size distribution with diameter of 40 2 nm and are well dispersed in methanol for over
6 months. As shown in Figure S5 (Supporting Information),
the incorporated Au-NPs are well covered by the top TiOx layer,
which is verified by the atomic force microscopy (AFM) images
of TiOx film with/without Au-NPs embedded in. Two layers
pristine TiOx film is extremely uniform and root-mean-square
(RMS) roughness is just 0.80 nm. However, the incorporation of large sized Au-NPs leads to increased RMS to 2.07 nm.
And the roughness changes are distinguishable from the phase
images and three-dimensional images.
Avoidance of direct contact between Au-NPs and perovskite is a key to achieve an enhanced PCE of the corresponding
device, which is quite different from conjugated polymer/
fullerene derivative solar cell. JV curves and external quantum
efficiency (EQE) spectra of device fabricated with pristine TiOx,
with Au-NPs on top of two layers of TiOx and embedded into
two layers of TiOx are plotted in Figure 2. Device based on
Au-NPs without a capping TiOx layer exhibits a poor fill factor
(FF) and a low open-circuit voltage (Voc), yielding an inferior
PCE of 7.12%. This device performance is even poorer than
the one based on pristine TiOx (PCE: 9.38%). In addition, it is
also found that the mixture of Au-NPs and TiOx layer does not
work well in perovskite device, while this structure has been
verified to enhance the device performance in the organic solar
cells.[36,37] In previous report, Au-NPs had to be capped with
a thin layer of insulating SiO2 for perovskite solar cells fabrication to avoid direct contact between Au-NPs and perovskite
layer.[38] Here, we suspect that Au-NPs could form recombination centers for perovskite film, which deteriorates the device
performance. In the following discussions, the TiOx/Au-NPs

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2015, 5, 1500038

www.advenergymat.de
www.MaterialsViews.com

COMMUNICATION

Figure 2. a) JV curves and b) EQE spectra for the devices based on TiOx and TiOx/Au composites film. Here, P3HT acts as HTL.

composites are referred to sandwiched structure except further

explanation. According to the JV curves, the incorporation of
Au-NPs-embedded TiOx film results in the enhanced short-circuit current density (Jsc), the FF, and the Voc simultaneously.
Detailed electrical output characteristic statistics of devices
based on P3HT are summarized in Table 1. Devices based on
P3HT-HTL yield a champion PCE of 11.8%, showing 25%
enhancement in PCE compared with the reference device. The
calculated Jsc value by integrating the EQE curve with an AM
1.5G reference spectrum is 17.1 mAcm2, which is consistent
with the Jsc obtained from the JV curve (less than 2% error).
The devices based on Spiro-OMeTAD HTL show similar
enhanced photovoltaic performance with the TiOx/Au-NPs composites as electron conductor. JV curves and EQE spectra of the
devices fabricated with Spiro-OMeTAD are plotted in Figure 3a,b.
All electrical output parameters are enhanced for the device
based on TiOx/Au-NPs film, which achieves 20% improvement
of the PCE compared with the device based on pristine TiOx
film. The electrical output characteristics are also summarized in
Table 1. The EQE spectra are consistent with the Jsc values for the
devices with/without Au-NPs, respectively. A champion device
with a Voc of 1.08 V, a Jsc of 19.9 mA cm2, a FF of 75.6%, and
a PCE of 16.2% is achieved. The PCE histograms of devices are
summarized in Figure 3b. The devices fabricated with Au-NPs
yield an average PCE of 14.9%, showing a 3.23% error distribution. In addition, the JV curves listed in Figure S6 (Supporting
Information) demonstrate that different scanning orientation
and delays show minimal influence on devices efficiencies,
which reveals that there is no obvious hysteresis phenomenon
of our devices.[39] Photocurrent response toward switching light
on and off is plotted in Figure S6c (Supporting Information).
The device shows a fast rising photocurrent to maximum value

during immediate light illumination, corresponding to fast trap

filling process. These results demonstrate the presence of a small
density of charge traps in the films that supports our claim.
In order to figure out the reasons for performance enhancement of the perovskite solar cells based on TiOx/Au-NPs composites, morphological and electrical characterizations are carried out accordingly. It is well known that the morphology of
perovskite film plays a critical role on the corresponding device
performance.[31,32] Here, we found that there is no obvious difference between perovskite films deposited on double-layer
TiOx and TiOx/Au-NPs composite. The SEM images of perovskite film on TiOx film and TiOx film embedded with Au-NPs
are shown in Figure S7a,b (Supporting Information), respectively. The domain size and coverage ratio are similar in two
films with high uniformity, which ensure the good light harvesting capability. UVvis absorption spectra of perovskite films
that deposited on TiOx substrates with and without Au-NPs
embedded are plotted in Figure S8 (Supporting Information).
The absorption spectra indicate the similar absorption efficiencies for the two kinds of perovskite films. Therefore, the
morphology and absorption should not be major factors to
improve the device performance.
Moreover, electrical characterizations are carried out to
explore the origin of device enhancement. Serial resistances of
devices are extracted to evaluate the resistance loss in charge
extraction process. The serial resistances are obtained from the
JV curves tested under illumination condition. According to
the data in Table 1, the serial resistances of devices based on
P3HT decrease from 15.2 to 11.6 cm2, and the serial resistances of devices based on Spiro-OMeTAD drop from 10.8 to 5.20
cm2 as well. Accordingly, we suspect that Au-NPs incorporation enhances transport properties of TiOx film. The mobility

Table 1. Electrical output characteristics of the devices with P3HT and Spiro-OMeTAD as HTLs.
HTL

ETL

P3HT

Control Device

Spiro-OMeTAD

Voc [V]
0.95 (0.92
a)

0.03)b)

Jsc [mA cm2]

FF

PCE [%]

Rs[ cm2]

15.2 (15.4 0.3)

0.64 (0.63 0.02)

9.30 (9.03 0.25)

15.2

TiOx/Au-NPs (On top)

0.83 (0.85 0.02)

15.3 (15.0 0.6)

0.56 (0.53 0.04)

7.12 (7.05 0.37)

16.5

TiOx/Au-NPs (Embedded)

0.99 (0.95 0.02)

17.5 (17.1 0.5)

0.68 (0.68 0.01)

11.8 (11.3 0.4)

11.2

Control Device

1.00 (0.97 0.02)

18.3 (18.6 0.3)

0.72 (0.68 0.02)

13.2 (12.3 0.6)

10.8

TiOx/Au-NPs (Embedded)

1.08 (1.02 0.02)

19.9 (19.4 0.2)

0.76 (0.74 0.03)

16.2 (14.8 0.5)

5.25

a)

Numbers in bold are the maximum values of our devices; b)Data and statistics are based on at least 20 devices for each type.

Adv. Energy Mater. 2015, 5, 1500038

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

wileyonlinelibrary.com

(3 of 7) 1500038

www.advenergymat.de

COMMUNICATION

www.MaterialsViews.com

Figure 3. a) JV curves and b) EQE spectra for the devices based on TiOx and TiOx/Au-NPs composites film. Here, Spiro-OMeTAD acts as HTL;
c) Histograms of the PCEs of devices based on TiOx/Au-NPs composites film and Spiro-OMeTAD as HTL.

of low temperature-processed amorphous TiOx film is poorer

than that of the HTL material of P3HT (103101 cm2 V1 s1)
and doped Spiro-OMeTAD (103 cm2 V1 s1).[40,41] The charge
mobility of crystallized TiOx can reach 103 cm2 V1 s1
extracted from steady-state measurements of dye-sensitized
TiOx layer fabricated at 500 C annealing process. However, the
present amorphous TiOx should show much lower mobility due
to the large amount of trap states. The TiOx film mobility also
shows significant dependence on the charge carrier density.[42]
It is well known that trap states in TiOx need to be filled up by
electrons from carrier excitation (3.0 eV) if high quality film is
required.[43] Here, the hot carrier injection from Au-NPs can fill
up the trap states, leading to increased charge carrier density in
TiOx, which is expected to improve its mobility. The increased
mobility of TiOx can lead to balance extraction and transportation of electrons and holes, which dramatically decreases space
limited charges.[42] Here, we simplify the mobility measurement by testing the conductivity differences with and without
Au-NPs in TiOx. The conductivity test is conducted based on the
structure of ITO/TiOx/Ag (Device-a) and ITO/TiOx/Au-NPs/
TiOx/Ag (Device-b) under dark and illumination condition.
The device structures are depicted in Figure S9a (Supporting
Information), where both the thicknesses of TiOx films are
identical. The conductivity test results under dark condition are
illustrated in Figure S9b (Supporting Information), where pristine TiOx film and TiOx film incorporated with Au-NPs show
similar conductivity. However, upon xenon light illumination,
the conductivities of these two films are all enhanced and the
latter one shows much higher photoconductivity (Figure 4a),
which has a positive impact on devices performance in working
condition.[44,45] The increased conductivity is ascribed to the
hot electrons injection from Au-NPs to TiOx, which has been
investigated in previous reports.[4648] The mechanism diagram
of hot carrier injection process is depicted in Figure 4b. Upon
the light absorption in Au-NPs, the incident photons can excite
electrons into a higher energy state (hot electrons). The excited
hot electrons overcoming the Schottky junction barrier between
Au-NPs and TiOx could be injected into the semiconductor in
adjacent area and this also result in trap healing effect.[49]
An electron injection current test with a high resolution
voltage amplifier is utilized to verify hot electrons injection
from Au-NPs and TiOx. The schematic electrical diagram is
depicted in Figure S10 (Supporting Information). With the
voltage amplifier, the voltage between a fixed resistor with certain scope would be obtained under different wavelength light
illumination. Current is obtained by dividing the resistance

1500038 (4 of 7)

wileyonlinelibrary.com

with biased voltage. As shown in Figure S11 (Supporting Information), TiOx film shows strong absorbance in the short wavelength range of 300400 nm, while for Au-NPs, the absorbance
peak appears in the visible range of 500600 nm. The incident
light with ultraviolet wave band can excite TiOx and Au-NPs
simultaneously. According to Figure 4c, the obtained currents
at short wavelengths are almost the same. In the visible range,
the TiOx/Au-NPs composites display relative strong photocurrent response in the range of 500600 nm, and enhanced wavelength range matches absorption spectra of Au-NPs well. In
order to further confirm this phenomenon, a high energy laser
with a wavelength at 532 nm is utilized to excite the devices.
Regarding TiOx/Au-NPs composites film, only Au-NPs can harvest the light at 532 nm. The current dependent versus light
intensity for the device of device a and b under 0.5 V bias are
plotted in Figure 4d. With light intensity increasing, the current also increases linearly in the TiOx/Au composite film,
which reveals the current generation from Au-NPs light harvesting. On the contrary, the current level keeps consistent even
changing the light intensity in the pristine TiOx. The dramatically different light response supports that hot-carrier injection
phenomena takes place under illumination condition.
The injected electrons arising from Au-NPs plasmon decay
could fill the trap sites in the TiOx conduction band (CB),
which decrease the surface potential of TiOx.[36,50] Scanning
Kelvin probe microscopy (SKPM) test is conducted to verify the
changes of surface potential of TiOx film or TiOxAu-NPs composites film after light excitation, as shown in Figure 5. Both
samples are excited under xenon light for 5 min. before measurement. Before illumination, one with Au-NPs-embedded
show higher surface potential than pristine TiOx, which is
ascribed to that Au-NPs inject hot electrons into TiOx even at
natural light exposing. Upon light illumination, the injected
carriers from Au-NPs to TiOx lead to a higher carrier density in
TiOx, which in turn pull up the Fermi level position and lower
the work function of TiOx, whilst resulting in an enhanced builtin potential and a higher Voc of device.[36] This finding is in line
with the increased Voc of the perovskite devices when Au-NPs
are incorporated. Compared with the control device, the average
Voc of the devices based on TiOxAu-NPs composites and P3HT
increases from 0.92 to 0.95 V. The devices with Spiro-OMeTAD
showing the same trend, the average Voc increase from 0.97 to
1.02 V. The increased Voc is ascribed to enhance built-in potential and decreased energy barrier for carriers transport.[37,50]
To summarize, we have investigated that low temperatureprocessed amorphous TiOx can achieve high performance

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2015, 5, 1500038

www.advenergymat.de
www.MaterialsViews.com

COMMUNICATION
Figure 4. Electron injection current measurement: a) JV curves of conductivity test under illumination condition; b) Schematic electrical diagram of
hot carrier injection process from Au-NPs to TiOx; c) Photocurrent measurement for the device with and without Au-NPs sandwiched between TiOx
layers at different wavelengths light illumination (light intensity (8 mW cm2)); Inset shows the whole spectrum range of photocurrent measurement
as well as Au-NPs absorption spectrum; d) Photocurrent responses for the same devices in c) under 532 nm laser illumination with different light
intensity. A voltage of 0.5 V is biased.

perovskite devices by a uniqure sandwiched TiOxAu-NPs

TiOx composites structure. Compared with the pristine TiOx
perovskite device, the device incorporated with TiOxAu-NPs
composites shows 20%30% device performance enhancement.
The improved device performance is explained on the base of
enhanced conductivity and decreased surface potential of TiOx
film. The enhanced conductivity of TiOx layer can match hole
transporting capability, which decreases space limited charges.
And increasing surface potential of TiOx layer can result in
larger built-in potential in the device, which leads to improved
Voc. Both effects are ascribed to the plasmon-mediated hot carrier injection from Au-NPs to TiOx. In addition, the sandwiched
structure, where Au-NPs are embedded in TiOx matrix, also
avoids the direct contact between Au-NPs and perovskite. The
device displays poor performance if Au-NPs contact perovskite
directly, which is different from the organic solar cell. Based
on this low temperature-processed TiOxAu-NPs film, a champion PCE of 16.2% has been achieved. Our result promises
a simple and facile way to fabricate high quality TiOx film at
low temperature for high performance perovskite solar cells.

Adv. Energy Mater. 2015, 5, 1500038

Figure 5. Work function changes of TiOx film and TiOx/Au-NPs composites film embedded under xenon light illumination. The data are extracted
from SKPM measurement.

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

wileyonlinelibrary.com

(5 of 7) 1500038

www.advenergymat.de

COMMUNICATION

www.MaterialsViews.com

Experimental Section
Materials: Titanium (IV) isopropoxide (97%), sodium citrate
(C6H5Na3O72H2O, 99%), hydrogen tetrachloroaurate (III) hydrate
(HAuCl44H2O) and methylamine (CH3NH2) were purchased from
Sigma-Aldrich. 2-isopropanol (99.9%), lead chloride (PbCl2, 99.99%),
N, N-Dimethylformamide (DMF, 99.9%), HI (99%), and methyl alcohol
(99.8%. ultrapure) were obtained from Alfa Aesar Ltd. P3HT and SpiroOMeTAD were purchased from 1-Material Ltd. And all the materials
were used as received without further purification.
Solution Preparation: Au-NPs were synthesized according to previous
method.[51] The obtained Au-NPs were washed with distilled water for
four times to get rid of any residual long chain citrate. Then the Au-NPs
were dispersed in methanol. The TiOx precursor solution was prepared
by the reported method.[32] And the solution was prepared under
vigorous stirring overnight.
Methylammonium iodide (CH3NH3I) was synthesized by following
previously reported process.[7] And precursor solution of perovskite is
prepared by mixing PbCl2 with CH3NH3I powder with a molar ration of
3:1 in DMF. The mixture was kept stirred at 70 C overnight and filtered
through 0.45 m filter before usage.
Devices Fabrication Process: Patterned ITO substrates were thoroughly
cleaned with isopropanol, actone, ethanol, and water for sequence in
ultrasonic bath for 15 min, respectively. And then the substrates were
dried with high flow of nitrogen gas and treated with ozone for 20 min.
Titanium oxide precursor was spin-coated on the ITO substrates at
4000 rmp and then annealed at 150 C for 45 min. Au-NPs dispersion
in methanol (4.0 mg mL1) was casted onto the TiOx layer. A second
TiOx layer was used to cover the Au-NPs then annealed the substrates
at 150 C for 2 h. Then the substrates were transferred into in glovebox.
The precursor solution of perovskite was kept stirred at 70 C before
being coated on TiOx film. The precursor solution was deposited at
3500 rmp for 30 s and the substrates were annealed at 100 C. And it
generally takes 25 min for the film to change color from light yellow to
dark brown. Then either P3HT solution (15 mg mL1 in chlorobenzene)
or Spiro-OMeTAD one (80 mg mL1 in chlorobenzene) was spin-coated
on top of perovskite film with a rotation speed of 3000 rmp for 40 s.
Spiro-OMeTAD solution was prepared by mixing 17.5 L lithiumbis(trifluoromethanesulfonyl) imide (TFSI-Li) solution (520 mg Li-TFSI
in 1 mL acetonitrile) and 28.5 L 4-tertbutylpyridine with 80 mg SpiroOMeTAD in 1 mL chlorobenzene solution. Devices fabrication was
finished by depositing 120-nm-thick Ag film as electrode with a shadow
mask. The active area of each device is 7.25 mm2.
Measurements and Characterization: All the devices were tested
under simulated xenon light with an intensity of 100 mW cm2. And
light intensity was calibrated by a standard silicon solar cell 91150.
EQE spectrum was obtained with Newport monochromator 74125 and
the light intensity was calibrated by a Newport power meter 1918. The
statistics were all collected by a Keithley 2612. AFM images and SKPM
graph were acquired by a MultiMode V (Veeco). SEM and TEM images
were captured with FEI (Quanta 200FEG) and Tecnai transmission
electron microscopy (G2 F20). Regarding the electron injection current
test, current is obtained by dividing the resistance with voltage. The
voltage was amplified by the Stanford research systems model SR830
DSP Lock-in amplifier and a chopper controller (MODEL SR540).

Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.

Acknowledgements
This work was supported by the National Basic Research Program of
China (973 Program) (Grant No. 2012CB932402), the National Natural
Science Foundation of China (Grant Nos. 61176057, 91123005, and

1500038 (6 of 7)

wileyonlinelibrary.com

61211130358), the Priority Academic Program Development of Jiangsu

Higher Education Institutions, Natural Science Foundation of Jiangsu
Province of China (Grant No. BK20130310), Collaborative Innovation
Center of Suzhou Nano Science and Technology.
Received: January 7, 2015
Revised: February 9, 2015
Published online: March 12, 2015

[1] J. J. Choi, X. Yang, Z. M. Norman, S. J. Billinge, J. S. Owen, Nano

Lett. 2014, 14, 127.
[2] G. Xing, N. Mathews, S. Sun, S. S. Lim, Y. M. Lam, M. Gratzel,
S. Mhaisalkar, T. C. Sum, Science 2013, 342, 344.
[3] J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao,
M. K. Nazeeruddin, M. Grtzel, Nature 2013, 499, 316.
[4] A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, J. Am. Chem. Soc.
2009, 131, 6050.
[5] H. Zhou, Q. Chen, G. Li, S. Luo, T. B. Song, H. S. Duan, Z. Hong,
J. You, Y. Liu, Y. Yang, Science 2014, 345, 542.
[6] J. H. Im, C. R. Lee, J. W. Lee, S. W. Park, N. G. Park, Nanoscale 2011,
3, 4088.
[7] M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, H. J. Snaith,
Science 2012, 338, 643.
[8] D. Liu, T. L. Kelly, Nat. Photonics 2014, 8, 133.
[9] N. J. Jeon, H. G. Lee, Y. C. Kim, J. Seo, J. H. Noh, J. Lee, S. I. Seok,
J. Am. Chem. Soc. 2014, 136, 7837.
[10] N. J. Jeon, J. H. Noh, Y. C. Kim, W. S. Yang, S. Ryu, S. I. Seok, Nat.
Mater. 2014, 13, 897.
[11] Z. Wu, S. Bai, J. Xiang, Z. Yuan, Y. Yang, W. Cui, X. Gao, Z. Liu,
Y. Jin, B. Sun, Nanoscale 2014, 6, 10505.
[12] S. Bai, Z. Wu, X. Wu, Y. Jin, N. Zhao, Z. Chen, Q. Mei, X. Wang,
Z. Ye, T. Song, R. Liu, S.-t. Lee, B. Sun, Nano Res. 2014, 7, 1749.
[13] S. N. Habisreutinger, T. Leijtens, G. E. Eperon, S. D. Stranks,
R. J. Nicholas, H. J. Snaith, Nano Lett. 2014, 14, 5561.
[14] Q. Chen, H. Zhou, Z. Hong, S. Luo, H.-S. Duan, H.-H. Wang, Y. Liu,
G. Li, Y. Yang, J. Am. Chem. Soc. 2013, 136, 622.
[15] Q. Hu, J. Wu, C. Jiang, T. Liu, X. Que, R. Zhu, Q. Gong, ACS Nano
2014, 8, 10161.
[16] J. You, Z. Hong, Y. Yang, Q. Chen, M. Cai, T.-B. Song, C.-C. Chen,
S. Lu, Y. Liu, H. Zhou, ACS Nano 2014, 8, 1674.
[17] J. H. Heo, S. H. Im, J. H. Noh, T. N. Mandal, C.-S. Lim, J. A. Chang,
Y. H. Lee, H.-j. Kim, A. Sarkar, M. K. Nazeeruddin, Nat. Photonics
2013, 7, 486.
[18] O. Malinkiewicz, A. Yella, Y. H. Lee, G. M. Espallargas, M. Graetzel,
M. K. Nazeeruddin, H. J. Bolink, Nat. Photonics 2014, 8, 128.
[19] J. H. Noh, S. H. Im, J. H. Heo, T. N. Mandal, S. I. Seok, Nano Lett.
2013, 13, 1764.
[20] H. S. Kim, C. R. Lee, J. H. Im, K. B. Lee, T. Moehl, A. Marchioro,
S. J. Moon, R. Humphry-Baker, J. H. Yum, J. E. Moser, M. Gratzel,
N. G. Park, Sci. Rep. 2012, 2, 591.
[21] B. Conings, L. Baeten, C. De Dobbelaere, J. DHaen, J. Manca,
H. G. Boyen, Adv. Mater. 2014, 26, 2041.
[22] P. Docampo, F. Hanusch, S. D. Stranks, M. Dblinger, J. M. Feckl,
M. Ehrensperger, N. K. Minar, M. B. Johnston, H. J. Snaith, T. Bein,
Adv. Energy Mater. 2014, 4, 1400355.
[23] J. T. Wang, J. M. Ball, E. M. Barea, A. Abate, J. A. AlexanderWebber, J. Huang, M. Saliba, I. Mora-Sero, J. Bisquert, H. J. Snaith,
R. J. Nicholas, Nano Lett. 2014, 14, 724.
[24] X. Wang, Z. Feng, J. Shi, G. Jia, S. Shen, J. Zhou, C. Li, Phys. Chem.
Chem. Phys. 2010, 12, 7083.
[25] E. Hao, N. A. Anderson, J. B. Asbury, T. Lian, J. Phys. Chem. B 2002,
106, 10191.
[26] C. Richter, C. A. Schmuttenmaer, Nat. Nanotechnol. 2010, 5, 769.

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2015, 5, 1500038

www.advenergymat.de
www.MaterialsViews.com

Adv. Energy Mater. 2015, 5, 1500038

[40] Z. Bao, A. Dodabalapur, A. J. Lovinger, Appl. Phys. Lett. 1996, 69,

4108.
[41] W. H. Nguyen, C. D. Bailie, E. L. Unger, M. D. McGehee, J. Am.
Chem. Soc. 2014, 136, 10996.
[42] T. Leijtens, J. Lim, J. Teuscher, T. Park, H. J. Snaith, Adv. Mater. 2013,
25, 3227.
[43] C. S. Kim, S. S. Lee, E. D. Gomez, J. B. Kim, Y.-L. Loo, Appl. Phys.
Lett. 2009, 94, 113302.
[44] S. Chambon, E. Destouesse, B. Pavageau, L. Hirsch, G. Wantz,
J. Appl. Phys. 2012, 112, 094503.
[45] S. K. Pathak, A. Abate, P. Ruckdeschel, B. Roose, K. C. Gdel,
Y. Vaynzof, A. Santhala, S.-I. Watanabe, D. J. Hollman, N. Noel,
A. Sepe, U. Wiesner, R. Friend, H. J. Snaith, U. Steiner, Adv. Funct.
Mater. 2014, 24, 6046.
[46] S.-P. Ng, X. Lu, N. Ding, C.-M. L. Wu, C.-S. Lee, Solar Energy 2014,
99, 115.
[47] M. Haro, R. Abargues, I. Herraiz-Cardona, J. Martnez-Pastor,
S. Gimnez, Electrochim. Acta 2014, 144, 64.
[48] F. P. Garca de Arquer, A. Mihi, D. Kufer, G. Konstantatos, ACS
Nano 2013, 7, 3581.
[49] M. W. Knight, H. Sobhani, P. Nordlander, N. J. Halas, Science 2011,
332, 702.
[50] A. Guerrero, S. Chambon, L. Hirsch, G. Garcia-Belmonte, Adv.
Funct. Mater. 2014, 24, 6234.
[51] N. G. Basts, J. Comenge, V. C. Puntes, Langmuir 2011, 27, 11098.

2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

wileyonlinelibrary.com

(7 of 7) 1500038

COMMUNICATION

[27] F. Di Giacomo, S. Razza, F. Matteocci, A. DEpifanio, S. Licoccia,

T. M. Brown, A. Di Carlo, J. Power Sources 2014, 251, 152.
[28] D. Bi, S.-J. Moon, L. Hggman, G. Boschloo, L. Yang,
E. M. Johansson, M. K. Nazeeruddin, M. Grtzel, A. Hagfeldt, RSC
Adv. 2013, 3, 18762.
[29] M. Niederberger, M. H. Bartl, G. D. Stucky, Chem. Mater. 2002, 14,
4364.
[30] T. Peng, X. Xiao, F. Ren, J. Xu, X. Zhou, F. Mei, C. Jiang, J. Wuhan
Univ. Technol.-Mater. Sci. Ed. 2012, 27, 1014.
[31] G. E. Eperon, V. M. Burlakov, P. Docampo, A. Goriely, H. J. Snaith,
Adv. Funct. Mater. 2014, 24, 151.
[32] P. Docampo, J. M. Ball, M. Darwich, G. E. Eperon, H. J. Snaith,
Nat. Commun. 2013, 4, 2761.
[33] H. A. Atwater, A. Polman, Nat. Mater. 2010, 9, 205.
[34] L. Lu, Z. Luo, T. Xu, L. Yu, Nano Lett. 2013, 13, 59.
[35] J.-L. Wu, F.-C. Chen, Y.-S. Hsiao, F.-C. Chien, P. Chen, C.-H. Kuo,
M. H. Huang, C.-S. Hsu, ACS Nano 2011, 5, 959.
[36] D. Zhang, W. C. H. Choy, F. Xie, W. E. I. Sha, X. Li,
B. Ding, K. Zhang, F. Huang, Y. Cao, Adv. Funct. Mater. 2013, 23,
4255.
[37] F. Xie, W. C. H. Choy, W. E. I. Sha, D. Zhang, S. Zhang, X. Li,
C.-w. Leung, J. Hou, Energy Environ. Sci. 2013, 6, 3372.
[38] W. Zhang, M. Saliba, S. D. Stranks, Y. Sun, X. Shi, U. Wiesner,
H. J. Snaith, Nano Lett. 2013, 13, 4505.
[39] H.-S. Kim, N.-G. Park, J. Phys. Chem. Lett. 2014, 5, 2927.