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1245

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Bulk heterojunction perovskite hybrid solar cells


with large ll factor
Kai Wang,a Chang Liu,a Pengcheng Du,a Jie Zhengb and Xiong Gong*a

Received 21st January 2015


Accepted 5th February 2015
DOI: 10.1039/c5ee00222b
www.rsc.org/ees

A major limitation to increasing the eciency of perovskite hybrid


solar cells (pero-HSCs) is the fact that the diusion length of the
electrons is shorter than that of the holes. To facilitate the electron
extraction eciency in pero-HSCs and to make this eciency
comparable with that of the holes, we fabricated bulk heterojunction
(BHJ) pero-HSCs by mixing perovskite materials with water-/alcoholsoluble fullerene derivatives. The observed enhanced short-circuit
current densities (JSC) and enlarged ll factors (FF) were a result of the
balance in the charge carrier extraction eciency and the enlarged
interfacial area between the perovskite materials and the fullerene
derivatives. Signicantly improved power conversion eciencies were
obtained for these BHJ pero-HSCs. A greater than 22% increase in
power conversion eciency was observed for the BHJ pero-HSCs
compared with planar heterojunction pero-HSCs. A remarkable 86.7%
FF, the highest reported value for pero-HSCs, was observed for the
BHJ pero-HSCs. Our strategy of using a BHJ structure in pero-HSCs
oers an ecient and simple way to further increase the performance
of these devices.

Introduction
Cost-eective and high-performance photovoltaic cells are
currently being investigated in both the academic and industrial sectors.17 Methylammonium lead halide (MAPbX3) perovskites have attracted much attention as novel photovoltaic
materials as a result of their excellent optical and electrical
properties.810 Power conversion eciencies (PCEs) of >17%
have been reported for perovskite hybrid solar cells (peroHSCs).11 However, as a result of the unbalanced electronhole
diusion lengths (the diusion length for the electrons is
shorter than that for the holes; Le, e/Le, h+ < 1),12 there is a
fundamental limitation to increasing the PCEs of pero-HSCs.13
a

Department of Polymer Engineering, The University of Akron, Akron, OH 44325, USA.


E-mail: xgong@uakron.edu; Fax: +1 330 972 3406

Department of Chemical & Biomolecular Engineering, The University of Akron, Akron,


OH 44325, USA

This journal is The Royal Society of Chemistry 2015

Broader context
Eciently and economically harnessing solar energy via photovoltaic (PV)
devices is one of the most promising solutions to the global energy crisis.
However, over 80% of the available PVs are silicon-based and/or inorganic
thin-lm solar cells, which are expensive and require critical processing
techniques. Organic PV cells have been developed to lower the costs, but
their eciency still lags behind their inorganic counterparts. Hybrid
organicinorganic halide perovskites have shown great potential as novel,
highly ecient and low-cost PV devices. However, the fundamental limitation of unbalanced charge carrier diusion lengths in perovskite
materials requires a mesoporous structure and/or a highly conductive
electron transfer layer to balance the charge extraction eciencies, which
complicates device processing. We report here a simple method of fabricating bulk heterojunction (BHJ) perovskite hybrid solar cells (pero-HSCs)
from a BHJ composite consisting of perovskite materials blended with
water-/alcohol-soluble fullerene derivatives to balance the charge extraction eciencies. A greater than 22% enhanced eciency was observed
from these BHJ pero-HSCs compared with planar heterojunction peroHSCs. This fabrication method for BHJ pero-HSCs oers an ecient and
simple way to increase the eciency of pero-HSCs.

To circumvent these problems, meso-superstructured peroHSCs (MS pero-HSCs) and planar heterojunction pero-HSCs
(PHJ pero-HSCs) have been developed. In MS pero-HSCs, mesostructured titanium dioxide (TiO2) is used as the electron
transport layer (ETL) and aluminum oxide (Al2O3) is used as the
insulating scaold to ensure ecient charge carrier separation
by enlarging the interfacial area.1417 However, the low electrical
conductivity of TiO2 contributes an additional charge transport
resistance within TiO2 itself,18 resulting in low PCEs for MS
pero-HSCs. In addition, TiO2 needs to be sintered at high
temperatures, which means that MS pero-HSCs are incompatible with large-scale, high-throughput manufacturing and
fabrication on exible plastic substrates. In PHJ pero-HSCs,
solution-processed n-type materials, such as fullerene derivatives with high electrical conductivity, are required for the
ETL.1922 However, the electron extraction eciencies of these ntype materials are still not high enough because the interface
between the perovskite materials and fullerene derivatives is

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insucient, which prevents any further increase in the PCE of


PHJ pero-HSCs. In addition, in both MS pero-HSCs and PHJ
pero-HSCs, the coarse surface of the solution-processed perovskite layer not only creates a poor contact between the fullerene
derivative and the perovskite lm, which decreases the electron
extraction eciency, but also introduces a large shunt resistance, resulting in a large leakage current and a low ll factor
(FF). As a result, low PCEs are observed for these pero-HSCs.2326
We report here bulk heterojunction (BHJ) pero-HSCs fabricated by blending perovskite materials with fullerene derivatives to improve the electron extraction eciency. An increased
short-circuit current density (JSC) and an increased FF with
correspondingly enhanced PCEs were observed for these BHJ
pero-HSCs. A remarkable FF of 86.7%, the highest reported for
pero-HSCs, was obtained for the BHJ pero-HSCs.

Experimental

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simultaneously mixing the MAI and A10C60 solutions together.


The concentration of MAI in both the pristine MAI ethanol
solution and the MAI:A10C60 ethanol solution was 35 mg mL1;
the concentration of A10C60 in the MAI:A10C60 ethanol solution
ranged from 2.5 to 20 mg mL1.
Preparation of perovskite lm
The CH3NH3PbI3 lms were prepared by a two-step solution
deposition method. PbI2 was rst spin-cast on the top of the
pre-heated (70  C) substrate from the warm (70  C) PbI2
supernatant, followed by thermal annealing at 70  C for 10 min
and then cooling to room temperature. Either a pure MAI layer
or a MAI:A10C60 BHJ composite layer was then spin-coated on
top of the PbI2 layer from the corresponding ethanol solutions,
followed by thermal annealing at 100  C for 2 h to covert PbI2
and MAI to CH3NH3PbI3.

Materials

Characterization of perovskite lm

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:


PSS) and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM)
were purchased from Clevious and 1-Material Inc., respectively,
and were used as received without further purication. Lead(II)
iodide (PbI2), anhydrous N,N-dimethylformamide, ethanol
(99.5%), hydroiodic acid (99.99%) and methylamine were
purchased from Sigma-Aldrich and were used as received
without further purication. Methylammonium iodide (MAI)
was synthesized following a previously reported method.27

Top-view and cross-sectional scanning electron microscopy


(SEM) images were obtained using a JEOL-7401 eld-emission
scanning electron microscope. Atomic force microscopy (AFM)
images were obtained using a Digital Instrument NanoScope
NS3A system to observe the surface morphologies and thicknesses of various thin lms. The X-ray diraction (XRD)
patterns of the thin lms coated on polyethylene terephthalate
substrates were obtained using a Bruker AXS Dimension D8
X-ray system. The photoluminescence (PL) spectra of the CH3NH3PbI3, CH3NH3PbI3:A10C60, CH3NH3PbI3/PC61BM and CH3NH3PbI3:A10C60/PC61BM thin lms were obtained on a Picoharp
300 instrument aer pre-amplication by PAM 102.

A10C60 fullerene derivative


A10C60 is a fullerene derivative, where A is a carboxylic acid
group regiospecically functionalized on the C60 head, which
imparts hydrophilicity on the surface of C60. A10C60 was
synthesized according to a previously reported method.28 An HP
8453 UV-visible spectrophotometer was used to measure the
absorption spectrum of a thin lm of A10C60 spin-cast onto a
quartz substrate from an ethanol solution. Cyclic voltammetry
(CV) measurements were carried out on a Gamry Reference 3000
instrument. We used a saturated silver chloride (AgCl) reference
electrode, a glassy carbon working electrode and a platinum
electrode counter. The CV curves were measured under a
nitrogen atmosphere in an ethanol solution containing 0.1 M
tetrabutylammoniumhexauorophosphate as the electrolyte.
The concentrations of the analytes were between 0.50 and
1.0 mmol L1. The potentials were calibrated with respect to the
potential of the Ag/AgCl electrode.
Preparation of the perovskite precursor
A PbI2 solution with a concentration of 400 mg mL1 was
prepared by dissolving PbI2 in N,N-dimethylformamide. The
PbI2 solution was stored overnight to give a clear PbI2 supernatant aer stirring at 70  C for 12 h. A pure MAI solution with a
concentration of 70 mg mL1 was prepared by dissolving MAI in
ethanol for further attenuation. A10C60 solutions with concentrations from 0 to 40 mg mL1 were prepared by dissolving
A10C60 in ethanol. A mixed MAI:A10C60 solution was prepared by

1246 | Energy Environ. Sci., 2015, 8, 12451255

Fabrication of pero-HSCs
Both PHJ and BHJ pero-HSCs were fabricated on pre-cleaned
indium tin oxide (ITO) coated glass. Aer the pre-cleaned ITO
substrates had been treated with UV-ozone for 20 min under an
ambient atmosphere, an approximately 40 nm thick lm of
PEDOT:PSS was spin-cast on top of the ITO substrates, followed
by thermal annealing at 150  C for 10 min under an ambient
atmosphere. Either a CH3NH3PbI3 or CH3NH3PbI3:A10C60 layer
was then spin-coated on top of the PEDOT:PSS layer from the
corresponding solution by the described two-step deposition
method. The thickness of the CH3NH3PbI3 and CH3NH3PbI3:A10C60 thin lms were measured to be about 300 nm. An
approximately 200 nm thick PC61BM ETL was then spin-cast
from a chlorobenzene solution on to the top of either the
CH3NH3PbI3 or CH3NH3PbI3:A10C60 layer. Finally, an approximately 100 nm thick layer of Al was deposited thermally on top
of the PC61BM ETL through a shadow mask under a vacuum
with a base pressure of 6  106 mbar. The area of the device
was measured to be 0.045 cm2.
Characterization of pero-HSCs
The current density versus voltage (JV) characteristics of the
pero-HSCs were obtained using a Keithley Model 2400 source
measuring unit. A Newport Air Mass 1.5 Global (AM1.5G) full-

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spectrum solar simulator was used as the light source. The light
intensity was 100 mW cm2 and was calibrated using a monosilicon detector with a KG-5 visible color lter from the National
Renewable Energy Laboratory to reduce the spectral mismatch.
The incident photon-to-electron conversion eciency (IPCE)
spectra were measured with the IPCE measurement set-up used
at European Solar Test Installation (ESTI) for cells and minimodules: a 300 W steady-state xenon lamp provides the source
light; up to 64 lters (820 nm width, range 3001200 nm) are
available on four lter wheels to produce the monochromatic
input, which is chopped at 75 Hz, superimposed on the bias light
and measured via the usual lock-in technique (the bias light is
necessary to examine the device close to the operating irradiance
conditions). Aer collecting the IPCE data, the soware integrated the data with the AM1.5G spectrum and gave the calculated JSC value, which was helpful for checking the accuracy of the
measurement. To extract the Nyquist plots, impedance spectra
were obtained using an HP 4194A impedance/gain-phase
analyzer, in the dark or under 1 sun illumination, with an
oscillating voltage of 10 mV and a frequency of 1 Hz to 1 MHz.
The pero-HSCs were held at their respective open-circuit potentials obtained from the (JV) measurements while the impedance
spectra were recorded.

Results and discussion


Fig. 1a shows the UV-visible absorption spectrum of the A10C60
thin lm. The inset shows the molecular structure of A10C60,
where the C60 head is regiospecically functionalized by
10 carboxylic acid groups. Similar to PC61BM,29 A10C60 has a
strong absorption at wavelengths < 500 nm, which implies that
A10C60 contributes the photocurrent in the pero-HSCs with a
device structure of ITO/PEDOT:PSS/CH3NH3PbI3:A10C60/
PC61BM/Al. Fig. 1b shows the CV curve of A10C60. The ELUMO and
EHOMO values of A10C60 are estimated to be 4.1 and 6.1 eV,
respectively, according to the empirical equations ELUMO e
onset
[Eonset
+ 4.4],30 where ELUMO is the
red + 4.4] and EHOMO e[Eox
lowest unoccupied molecular orbital energy level, Eonset
is the
red

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reduction potential, EHOMO is the highest occupied molecular


orbital energy level and Eonset
is the oxidization potential. Both
ox
the LUMO and HOMO energy levels of A10C60 are nearly the
same as those of PC61BM.29 These results indicate that the 10
carboxylic acid groups within C60 do not change the optical and
electrical properties of C60, but signicantly tune A10C60 to
possess hydrophobicity.
Fig. 2a shows the device structures of the BHJ pero-HSCs:
ITO/PEDOT:PSS/CH3NH3PbI3:A10C60/PC61BM/Al. For comparison, Fig. 2b shows the device structure of the PHJ pero-HSCs:
ITO/PEDOT:PSS/CH3NH3PbI3/PC61BM/Al. Fig. 2c shows the
LUMO and HOMO energy levels of CH3NH3PbI3, A10C60 and
PC61BM and the work functions of the ITO, PEDOT:PSS and Al
electrodes. In both devices, PC61BM acts as the ETL. Based on
the band alignment, there is no energy barrier to the electrons
transported from A10C60 to PC61BM ETL, thus there is a higher
electron extraction eciency and, consequently, a higher JSC is
expected from the BHJ pero-HSCs.
Fig. 3a shows the JV characteristics of the PHJ pero-HSCs
and the BHJ pero-HSCs. The PHJ pero-HSCs have a JSC of
17.31 mA cm2, an open-circuit voltage (VOC) of 0.86 V, a FF of
77.2% and a corresponding PCE of 11.45%. The device performance parameters of PHJ pero-HSCs are comparable with
previously reported values.31 However, the BHJ pero-HSCs have
a JSC of 19.41 mA cm2, a VOC of 0.88 V, a FF of 81.6% and a
corresponding PCE of 13.97%. The PCE of the BHJ pero-HSCs is
>22% higher than that of the PHJ pero-HSCs. The VOC values
from both the PHJ pero-HSCs and the BHJ pero-HSCs are the
same, which is in good agreement with the band alignment
shown in Fig. 2c. However, enhanced values of the JSC and FF
are seen for the BHJ pero-HSCs. The enhanced JSC value indicates that more electrons are extracted from the CH3NH3PbI3:A10C60 BHJ composite through the PC61BM ETL to the
corresponding Al electrode. The signicantly enlarged FF
(81.6%) promisingly indicates that more balanced charge
carriers are obtained from the BHJ pero-HSCs.32
The series resistance (RS) and shunt resistance (RSH) are
estimated from the slopes of the JV curves under open-circuit

(a) UV-visible absorption spectrum of A10C60 thin lm; inset, molecular structure of A10C60, a [5:1]-hexakisadducts of C60, in which the C60
head is regiospecically functionalized with 10 carboxylic acid groups. (b) Cyclic voltammetry curve of A10C60.
Fig. 1

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Fig. 2 Device structures of (a) PHJ and (b) BHJ pero-HSCs. (c) LUMO and HOMO energy levels of CH3NH3PbI3, A10C60 and PC61BM and the work
functions of the ITO, PEDOT:PSS and Al electrodes.

Fig. 3

(a) JV characteristics of the PHJ and BHJ pero-HSCs under AM 1.5 simulated illumination. (b) IPCE spectra of PHJ and BHJ pero-HSCs.

and short-circuit conditions, respectively. Table 1 summarizes


the RS and RSH values from both the PHJ and BHJ pero-HSCs.
Compared with the PHJ pero-HSCs, the smaller RS value from
the BHJ pero-HSCs originates from both the smaller contact
resistance and the bulk resistance of the CH3NH3PbI3:A10C60
BHJ composite, which indicates that high photocurrents are
anticipated to be generated from the BHJ pero-HSCs at low
applied voltages; the larger RSH for the BHJ pero-HSCs indicates
that short circuits or current leakages are minimized. As a
result, high JSC values, a large FF and consequently high PCE
Table 1

Photovoltaic performance of PHJ pero-HSCs and BHJ pero-

HSCs

Device

VOC
(V)

JSC
RS
RSH
PCE
(mA cm2) FF (%) (kU cm2) (kU cm2) (%)

PHJ pero-HSC 0.86 17.31


BHJ pero-HSC 0.88 19.41

77.2
81.6

0.92
0.75

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246.7
252.9

11.45
13.97

values are observed for the BHJ pero-HSCs. These results are
consistent with those observed from the JV characteristics of
the PHJ pero-HSCs and the BHJ pero-HSCs (Fig. 3a).
Fig. 3b presents the IPCE spectra of both the PHJ pero-HSCs
and the BHJ pero-HSCs. The IPCE spectra specify the ratio of the
extracted electrons to the incident photons at a given wavelength.
The PHJ pero-HSCs show a wide response from the visible to the
near-infrared region, with more than about 60% of the IPCE in
the range 500800 nm, which indicates that the charge-transfer
complexes are formed in the CH3NH3PbI3 thin lms.33 The BHJ
pero-HSCs exhibit a strong photo-response over the entire spectral region, with over 85% of the IPCE in the range 375800 nm.
In contrast with the PHJ pero-HSCs, an obvious enhanced IPCE
from the BHJ pero-HSCs is seen in the range 350500 nm, which
probably originates from the contribution of A10C60 in the CH3NH3PbI3:A10C60 BHJ active layer resulting from the strong
absorption of A10C60 between 350 and 500 nm (Fig. 1a). The
photocurrent densities estimated from the IPCE spectra are 16.21
and 18.83 mA cm2 for the PHJ pero-HSCs and BHJ pero-HSCs,

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respectively. These values are consistent with those obtained


from the JV characteristics (Fig. 3a).
Fig. 4 shows a histogram of the photovoltaic parameters for
the BHJ pero-HSCs. Over 200 BHJ pero-HSCs devices were
fabricated and characterized. Fig. 4 shows that the reproducibility of the JSC, FF, VOC and PCE were fairly high. The relative
standard deviation was 1.3%, which is extremely low compared
with previous reported data.34
A major issue in the pero-HSCs was the hysteresis of the
photocurrent.35 It has been reported36,37 that the origin of this

Energy & Environmental Science

photocurrent hysteresis can be ascribed to traps, the ferroelectric


properties of the perovskite materials and/or the electro-migration of ions in the pero-HSCs. To investigate the photocurrent
hysteresis in the BHJ pero-HSCs, we measured the JV characteristics using dierent scan directions [reverse scans (from a
positive to a negative bias) and forward scans (from a negative to
a positive bias)] and dierent scan rates (a high scan rate of 0.6 V
s1 and a low scan rate of 0.03 V s1).37 Fig. 5 shows the photocurrent hysteresis results for the BHJ pero-HSCs. Table 2
summarizes the device performance parameters of the BHJ pero-

Fig. 4 Histograms of photovoltaic parameters for BHJ pero-HSCs: (a) VOC; (b) JSC; (c) FF; and (d) PCE (n 200).

Fig. 5 JV characteristics of BHJ pero-PSCs with two dierent scan directions: forward scan (from negative bias to positive bias) and reverse
scan (from positive bias to negative bias) and at dierent scan rates: (a) 0.6; and (b) 0.03 V s1.

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Table 2 Device performance parameters of BHJ pero-HSCs


measured at dierent scan rates and in dierent scan directions

Scan rate
(V s1)

Scan
direction

VOC
(V)

JSC
(mA cm2)

FF (%)

PCE
(%)

0.6

Forward
Reverse
Forward
Reverse

0.88
0.88
0.86
0.88

19.40
19.54
19.58
19.72

80.80
83.10
75.10
78.30

13.85
14.34
12.65
13.59

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0.03

HSCs using dierent scan directions and rates. Larger PCEs were
seen for the BHJ pero-HSCs under the reverse scans compared
with those under the forward scans. At a high scan rate of 0.6 V
s1, the average PCE was 14.10%, higher than the 13.00%
obtained at a low scan rate of 0.03 V s1. These are similar to
previously reported values.37 However, the dierences in the PCEs
of the BHJ pero-HSCs using either dierent scan directions or
dierent scan rates were smaller than those reported from PHJ
pero-HSCs,37,38 indicating that the photocurrent hysteresis in the
BHJ pero-HSCs is weaker than that in the PHJ pero-HSCs.

Fig. 6 (a) JV characteristics and (b) IPCE spectra of BHJ pero-HSCs containing dierent percentages by weight of A10C60 to CH3NH3PbI3. (c)
JSC, VOC, FF and PCE values versus dierent percentages by weight of A10C60 to CH3NH3PbI3.

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Table 3

Photovoltaic performancea of BHJ pero-HSCs containing dierent ratios of A10C60 to CH3NH3PbI3

Device
BHJ pero-HSC

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Ratio of A10C60 to
CH3NH3PbI3 (% w/w)

VOC (V)

1.6
3.2
6.4
9.6
12.8

0.87
0.89
0.86
0.88
0.88

 0.02
 0.02
 0.03
 0.04
 0.03

JSCb (mA cm2)


17.28
17.52
18.08
19.41
20.17

 0.43
 0.29
 0.32
 0.35
 0.42

JSCc (mA cm2)


15.99
16.47
17.23
18.53
19.20

 1.05
 0.89
 0.95
 1.13
 1.53

FF (%)

PCE (%)

79.7  1.5
82.6  1.6
86.7  1.8
81.6  1.6
72.3  2.1

11.75  0.21
12.88  0.38
13.48  0.27
13.97  0.31
12.83  0.16

a
Average and standard deviation values were obtained based on over 30 cells from 6 dierent batches for each ratio.
characteristics. c JSC is estimated from the IPCE spectrum.

To investigate the contribution of A10C60 in the BHJ peroHSCs fabricated from the CH3NH3PbI3:A10C60 BHJ composite,
the change in device performance of the BHJ pero-HSCs with
the concentration (by weight) of A10C60 in the CH3NH3PbI3:A10C60 BHJ composite was studied. Fig. 6a and b show the JV
characteristics and the IPCE spectra of the BHJ pero-HSCs.
Fig. 6c shows the JSC, VOC, FF and PCE values plotted against the
ratios of A10C60 to CH3NH3PbI3. Table 3 summarizes the
photovoltaic performance parameters. As the ratio of A10C60 to
CH3NH3PbI3 was increased from 1.6 to 12.8%, the VOC had a
similar value of 0.88  0.04 V, but the JSC value increased from
17.28 to 20.17 mA cm2, an increment of about 17%, and the FF
initially increased from 79.7 to 86.7% and then decreased to
72.3%. Consequently, the PCE initially increased from 11.75 to
13.97% and then decreased to 12.83%. The FF of 86.7% is the
highest reported value for pero-HSCs.
The increased JSC values with increasing ratios of A10C60 to
CH3NH3PbI3 probably originate from the strong absorption of
A10C60, which contributes the photocurrent at wavelengths <
500 nm and more balanced electronhole transport by blending
more A10C60 with CH3NH3PbI3. In addition, the lm
morphology of CH3NH3PbI3A10C60 is modied by A10C60. A
larger amount of A10C60 probably forms a larger domain, which
is favorable for electron transport from the CH3NH3PbI3:A10C60
BHJ composite to the PC61BM ETL, resulting in an increased JSC
value from the BHJ pero-HSCs containing large amounts of
A10C60.
Based on the IPCE spectra, the JSC values of the pero-HSCs
containing dierent concentrations of A10C60 were estimated by
integrating the IPCE spectra from 375 to 800 nm. Table 3
summarizes the estimated JSC values. These estimated JSC values
are consistent with those observed from the JV characteristics
(Fig. 6a).
XRD was used to study the dierences between the pristine
CH3NH3PbI3 and CH3NH3PbI3:A10C60 BHJ composite thin lms
to help understand the dierent photovoltaic performances of
the PHJ pero-HSCs and the BHJ pero-HSCs. Fig. 7 shows the
XRD patterns of pristine CH3NH3PbI3 and the CH3NH3PbI3:A10C60 BHJ composite thin lms. The pristine A10C60 thin lm
was also investigated for comparison. Diraction peaks were
observed at 13.9, 28.5, 32.0, 40.6 and 43.6 for both the pristine
CH3NH3PbI3 and the CH3NH3PbI3:A10C60 BHJ composite thin
lms. These peaks correspond to the (110), (220), (310), (224)
and (314) planes,39,40 respectively, which indicates that

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JSC is observed from JV

Fig. 7 XRD patterns of thin lms of the CH3NH3PbI3:A10C60 BHJ


composite, pristine CH3NH3PbI3 and pristine A10C60.

Fig. 8 Tapping-mode AFM height images and corresponding AFM


phase images of (a and c) the pristine CH3NH3PbI3 layer and (b and d)
the CH3NH3PbI3:A10C60 BHJ composite layer.

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CH3NH3PbI3 was formed with an orthorhombic crystal structure in both pristine CH3NH3PbI3 and the CH3NH3PbI3:A10C60
BHJ composite thin lms. No representative peak for PbI2 was
detected in either the pristine CH3NH3PbI3 or the CH3NH3PbI3:A10C60 BHJ composite thin lms, indicating that PbI2 and
MAI react completely to generate CH3NH3PbI3 polycrystals.
However, there were small peaks at 17 and 25 in the spectra of
pristine A10C60 and the CH3NH3PbI3:A10C60 BHJ composite thin
lms, although the intensities were relatively weak in the
CH3NH3PbI3:A10C60 BHJ composite thin lms. These results
indicate that a small-scale A10C60 crystallinity is formed in the
CH3NH3PbI3:A10C60 BHJ composite thin lms. In addition, the
CH3NH3PbI3:A10C60 BHJ composite thin lm had a more
intense diraction peak at 32.0 than the pristine CH3NH3PbI3
thin lm, indicating that the high crystallinity of the CH3NH3PbI3 thin lm was formed by the introduction of A10C60 into the
CH3NH3PbI3:A10C60 BHJ composite. In summary, the A10C60 in
the CH3NH3PbI3:A10C60 BHJ composite did not change the
crystal structure of the CH3NH3PbI3, but inuenced the crystallinity of CH3NH3PbI3 on a small scale, indicating that these
two materials were not miscible.
Both AFM images and top-view SEM images were obtained to
study the morphological dierences between pristine CH3NH3PbI3 and the CH3NH3PbI3:A10C60 BHJ composite thin lms. Fig. 8
shows the AFM topographic images of pristine CH3NH3PbI3 and
the CH3NH3PbI3:A10C60 BHJ composite thin lms. Both thin

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lms show a relatively smooth surface morphology with a rootmean-square roughness (Rq) of about 10 nm. Such a at surface
suggests that either the CH3NH3PbI3 layer or the CH3NH3PbI3:A10C60 BHJ composite layer was completely covered by a PC61BM
layer with a thickness of about 200 nm, which resulted in indirect
contact between the active perovskite layer and the top cathode. A
small Rq value indicates a smoother surface with less sharp traps
or pinholes, which results in a high JSC value and a large FF.41
Fig. 8c and d show the phase images of CH3NH3PbI3 and the
CH3NH3PbI3:A10C60 BHJ composite thin lms. A binary phase
pattern was seen in the CH3NH3PbI3:A10C60 BHJ composite thin
lms (Fig. 8d), similar to that of the bi-continuous phase
morphology observed for the BHJ composite in polymer solar
cells.42 The BHJ interpenetrating network was essential for the
ecient extraction of electrons from the BHJ composite because
the enlarged interface areas between A10C60 and CH3NH3PbI3
facilitate more dissociation of the excitons. As a result, more free
electrons were extracted from CH3NH3PbI3 into the n-type A10C60
as a result of the decreased travel length.43 Thus the electron
extraction eciency was improved, resulting in a balanced
charge carrier extraction eciency and an enlarged FF was
observed for the BHJ pero-HSCs.
Fig. 9 compares the top-view and cross-sectional SEM
images of pristine CH3NH3PbI3 and the CH3NH3PbI3:A10C60
BHJ composite thin lms. Many large voids were seen in the
pristine CH3NH3PbI3 thin lms, whereas fewer large voids

Fig. 9 Top-view SEM images of (a) the pristine CH3NH3PbI3 layer and (b) the CH3NH3PbI3:A10C60 BHJ composite layer; insets (c and d) are higher
resolution images. Cross-sectional SEM images of (e) ITO/PEDOT:PSS/CH3NH3PbI3/PC61BM and (f) ITO/PEDOT:PSS/CH3NH3PbI3:A10C60/
PC61BM (some of the A10C60 domains inside CH3NH3PbI3:A10C60 can be observed in the region marked by broken lines).

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were seen in the CH3NH3PbI3:A10C60 BHJ composites thin


lms. This indicates that the thin lms formed by the CH3NH3PbI3:A10C60 BHJ composites were more homogeneous
than the pristine CH3NH3PbI3 thin lms. Thus it was speculated that these large voids were lled by A10C60 and a new
phase of A10C60, making the CH3NH3PbI3:A10C60 BHJ
composite thin lms more compact and denser. The insets in
Fig. 9c and d show high-resolution images of pristine CH3NH3PbI3 and the CH3NH3PbI3:A10C60 BHJ composite thin
lms at a magnication of 50 000. It is clear that the crystal
sizes in the pristine CH3NH3PbI3 thin lm (Fig. 9a) are almost
identical and homogeneous, whereas the crystal sizes in the
CH3NH3PbI3:A10C60 BHJ composite thin lms (Fig. 9b) are
inhomogeneous. The inhomogeneous crystal domains
observed in the CH3NH3PbI3:A10C60 BHJ composite thin lms
are of two dierent sizes: the domain size identical to that
shown in Fig. 9a is probably formed of CH3NH3PbI3 polycrystals, whereas the other type with dierent domain sizes is
probably formed from A10C60 crystals.
Fig. 9e and f show the cross-sectional SEM images of the ITO/
PEDOT:PSS/CH3NH3PbI3:A10C60/PC61BM and ITO/PEDOT:PSS/

Energy & Environmental Science

CH3NH3PbI3/PC61BM devices, respectively. The thickness of


each layer was consistent with that in the nal devices. Fig. 9e
shows the PHJ structure of CH3NH3PbI3/PC61BM, where the
pristine CH3NH3PbI3 layer is sandwiched between the
PEDOT:PSS layer and the PC61BM ETL. In contrast, Fig. 9f shows
the CH3NH3PbI3:A10C60 composite layer sandwiched between
the PEDOT:PSS layer and the PC61BM ETL. The A10C60 domains
could be clearly seen in the CH3NH3PbI3:A10C60 composite
layer. This observation conrms that A10C60 was mixed with
CH3NH3PbI3 to form the CH3NH3PbI3:A10C60 BHJ composite
layer.
To further understand the underlying device performance of
both the PHJ and BHJ pero-HSCs, the PL of the CH3NH3PbI3,
CH3NH3PbI3/PC61BM, CH3NH3PbI3:A10C60 and (CH3NH3PbI3:A10C60)/PC61BM thin lms was investigated. Fig. 10a shows the
PL spectra of these thin lms. A more striking PL quenching
eect was seen with the CH3NH3PbI3:A10C60 BHJ composite thin
lms than with the pristine CH3NH3PbI3 thin lms, which
indicates that ecient electron extraction took place in the
H3NH3PbI3:A10C60 BHJ composite thin lms rather in the pristine CH3NH3PbI3 thin lms. The enlarged PL spectra of

Fig. 10 (a) PL spectra of CH3NH3PbI3, CH3NH3PbI3:A10C60, CH3NH3PbI3/PC61BM and CH3NH3PbI3:A10C60/PC61BM thin lms; insets, enlarged PL
spectra of CH3NH3PbI3/PC61BM and CH3NH3PbI3:A10C60/PC61BM thin lms. (b) Nyquist plots of PHJ and BHJ pero-HSCs measured in the dark
and at an applied voltage close to the open-circuit voltage of the pero-HSCs. (c) Recombination resistance resulting from impedance spectrometry measurements tted for dierent applied biases at 1 sun illumination.

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CH3NH3PbI3/PC61BM and CH3NH3PbI3:A10C60/PC61BM thin


lms in Fig. 10a (inset) clearly demonstrate that more PL
quenching took place in the (CH3NH3PbI3:A10C60)/PC61BM thin
lms than in the CH3NH3PbI3/PC61BM thin lms. These results
indicate that more ecient electron extraction occurred in the
(CH3NH3PbI3:A10C60)/PC61BM thin lms than in the CH3NH3PbI3/PC61BM thin lms. Therefore the PL spectra further
conrm that the high electron extraction eciency originated
from the enlarged interface between the CH3NH3PbI3 and
A10C60 in the CH3NH3PbI3:A10C60 BHJ composite.
To investigate the electrical properties of the interfaces,
impedance spectrometry was used to study the internal series
resistance (RS) of both the BHJ pero-HSCs and the PHJ peroHSCs. The impedance spectrometry analysis enabled us to
monitor the detailed electrical properties of the interfaces that
could not be determined by the direct current measurements.
The RS consists of the sheet resistance (RSHEET) of the electrodes,
the charge-transfer resistance (RCT) at the interfaces between
the electrode and the carrier selective layer and between the
carrier selective layer and the internal BHJ active layer.44 The
main dierence between the PHJ and BHJ pero-HSCs is the RCT
at the interface between CH3NH3PbI3 and A10C60. Fig. 10b
shows the Nyquist plots of both the PHJ and BHJ pero-HSCs in
the dark at an applied voltage close to the VOC of the pero-HSCs.
From the plots, RCT values of 0.85 and 0.66 kU were obtained for
the PHJ and BHJ pero-HSCs, respectively. In the PHJ pero-HSCs,
a large RCT value indicated that the large charge-transfer resistance resulted from the inferior contact at the interface with the
PC61BM/CH3NH3PbI3. For the BHJ pero-HSCs, a small RCT was
obtained as a result of the larger interfacial area between CH3NH3PbI3 and A10C60. Therefore a higher PCE is expected from
the BHJ pero-HSCs than from the PHJ pero-HSCs.
Fig. 10c shows the recombination resistance as a function of
the applied bias in the relevant voltage range. The recombination processes were associated with the feature observed in the
low-frequency region of the Nyquist plot of the pero-HSCs. The
recombination rate was inversely proportional to the recombination resistance. In this study, the major dierence in the
device structure was the introduction of A10C60 into CH3NH3PbI3 to form the CH3NH3PbI3:A10C60 BHJ composite. The
recombination resistance was signicantly enhanced at a low
applied bias, which was in good agreement with the large FF
observed for the BHJ pero-PSCs.45 On the other hand, at a high
applied bias, close to the VOC, both the PHJ and BHJ pero-HSCs
had a similar recombination resistance, indicating a similar VOC
for both cells.46 These observations were consistent with those
of the JV characteristics (Fig. 3a).

Conclusions
BHJ pero-HSCs were fabricated to address the fundamental
limitation of the unbalanced electronhole diusion length in
pero-HSCs. High-eciency BHJ pero-HSCs were fabricated by
solution-processing the BHJ composite from an ethanol solution consisting of CH3NH3PbI3 and A10C60 rather than from a
pristine CH3NH3PbI3 ethanol solution. XRD, AFM, TEM, PL and
impedance spectrometry studies showed that the high

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eciency of the BHJ pero-HSCs originated from the balanced


charge carrier extraction eciency and enlarged interfacial area
between the CH3NH3PbI3 and A10C60. The fabrication of these
BHJ pero-HSCs oers an ecient and simple way to increase the
eciency of pero-HSCs.

Acknowledgements
The authors thank the NSF (1351785) for nancial support.

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