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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
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
Experimental
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Materials
Characterization of perovskite lm
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.
(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.
HSCs
Device
VOC
(V)
JSC
RS
RSH
PCE
(mA cm2) FF (%) (kU cm2) (kU cm2) (%)
77.2
81.6
0.92
0.75
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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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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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
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
Device
BHJ pero-HSC
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
0.43
0.29
0.32
0.35
0.42
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
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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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.
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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Acknowledgements
The authors thank the NSF (1351785) for nancial support.
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