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Introducing Cu 2 O Thin-Films as a Hole-Transport Layer in Efficient Planar

Perovskite Solar Cell Structures

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DOI: 10.1021/acs.jpcc.5b11540

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Introducing Cu2O Thin Films as a Hole-Transport Layer in Efficient

Planar Perovskite Solar Cell Structures
Soumyo Chatterjee and Amlan J. Pal*
Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, West Bengal 700032, India
*
S Supporting Information

ABSTRACT: In this work, we introduce Cu2O thin films as a

hole-transport layer in planar perovskite solar cells. Here, a
Cu2O layer was formed through successive ionic layer
adsorption and reaction (SILAR) method. With methylammo-
nium lead triiodide (MAPbI3) we form a direct structure (p−
i−n), where the perovskite layer is sandwiched between a layer
of p-type Cu2O and another layer of n-type PCBM (phenyl-
C61-butyric acid methyl ester), which acted as hole- and
electron-transport materials, respectively. We locate band
edges of the materials with respect to their Fermi energy by recording scanning tunneling spectroscopy that has correspondence
to their density of states (DOS). We observe that the energy levels of the materials form type II band alignments at each of the
two interfaces (p−i and i−n) for charge separation and uninterrupted carrier transport upon illumination. Such a band alignment
enabled charge transfer from MAPbI3 as evidenced from quenching of its photoluminescence emission when the perovskite was
in contact with either the hole- or the electron-transport layer. With the direct p−i−n structure having appropriate energy levels
for carrier separation, the planar perovskite solar cell (Cu2O/MAPbI3/PCBM) yielded an energy conversion efficiency (η) of
8.23% under 1 sun illumination.

1. INTRODUCTION hole mobility apart from energy levels remaining compatible

In recent years, research on solar cells received a quantum jump
with the introduction of organometal halides.1 This unique
class of perovskites, namely, methylammonium lead triiodide
(CH3NH3PbI3, MAPbI3) and its derivatives, is sandwiched
between a hole-transport layer and an electron-transport layer
in the form of n−i−p structures to form mesoscopic or planar
(thin-film) perovskite solar cells having an inverted device
geometry.1−5 After light absorption, charge generation as well
as charge extraction occurs in the perovskite layer, followed by
transport of holes and electrons through the hole- and electron-
transport layers (HTL and ETL), respectively. Due to such a 2-
fold role played by the perovskite in solar cells, the devices have
produced promisingly high power conversion efficiency. The
high output is consistent with its ambipolar transport property
and long-range electron−hole diffusion lengths in addition to
high carrier mobility of the material.6,7 In consideration of the
band edges of the perovskite material, either TiO2 or ZnO was
used as an ETL.2−4,8,9 2,2′,7,7′-Tetrakis(N,N-di-4-methoxyphe-
nylamino)-9,9′-spirobifluorene (commonly known as spiro-
MeOTAD) has so far been the only major choice as the HTL
so that holes did not face any energy barrier at the MAPbI3/
HTL and HTL/gold interfaces.1,4,8 In efforts to replace spiro-
MeOTAD with a more stable and less expensive suitable
material, such as CuI,2 CuSCN,3,10,11 carbazole,9 or copper
phthalocyanine,5 the efficiency of solar cells had to be
compromised. To obtain high photovoltaic performance, it is
of critical importance that the HTL should also possess high
with the valence band edge of the perovskite.
A direct structure (p−i−n) is always preferred in thin-film
solar cells, since an expensive and high work-function metal
(5.1 eV for gold) used as a top electrode in an inverted
geometry often creates pinholes. In perovskite solar cells, a p−
i−n structure is more advantageous, since with a lower work-
function metal as a hole-collecting electrode we may then have
further choice in replacing spiro-MeOTAD. With indium tin
oxide (ITO) as a hole-collecting electrode, the HOMO (or
valence band) of the HTL can then be extended up to 4.7 eV
without any barrier for holes to be transported through the
ITO/HTL interface (4.7 eV is the well-known work-function of
ITO). Here HOMO represents the highest occupied molecular
orbitals of conjugated organics. In such direct structures, while
PCBM remained the only ETL,12 nickel oxide (NiO),10,13
copper-doped NiO (Cu@NiO), 14 CuSCN, 10 and PE-
DOT:PSS12 have so far been used as HTL in ITO/HTL/
MAPbI3/PCBM/Al structures. Here, PCBM and PEDOT:PSS
represent phenyl-C61-butyric acid methyl ester and poly(3,4-
ethylenedioxythiophene) polystyrenesulfonate, respectively.
In our quest for a suitable HTL in such direct thin-film
structures, we report introduction of Cu2O in perovskite solar
cells. The HTL has been grown through a successive ionic layer
adsorption and reaction (SILAR) method.15,16 In a very recent
Received: November 26, 2015
Revised: December 24, 2015
Published: January 7, 2016

© 2016 American Chemical Society 1428 DOI: 10.1021/acs.jpcc.5b11540

J. Phys. Chem. C 2016, 120, 1428−1437
The Journal of Physical Chemistry C
Figure 1. (a) UV−visible absorption spectrum, (b) Tauc plot estimating the optical band gap, (c) XRD pattern, and (d) Raman spectrum of MAPbI3
thin film. Insets show (a) d[(αhν)2]/d(hν) versus energy plot of the material and (b) lattice structure of the perovskite.
report, which came to our attention during manuscript review,
solution-processed Cu2O (and CuO) were used as hole-
transport materials in perovskite solar cells.17 Apart from its
natural p-type conductivity, Cu2O also possesses a high carrier
mobility of about 100 cm2/(V·s) and a long carrier diffusion
length ranging up to several micrometers.18−20 Since light
enters through the HTL in a direct (p−i−n) structure, a band
gap of 2.16 eV21 moreover would allow Cu2O to absorb higher-
energy photons while remaining transparent to the perovskite.
In this work, we report fabrication and characterization of
planar perovskite solar cells based on Cu2O and MAPbI3.
2. RESULTS AND DISCUSSION
2.1. Characterization of Perovskite Material. To ensure
formation of the perovskite, the material was characterized by
conventional techniques. In Figure 1, we present the optical
absorption spectrum of a MAPbI3 thin film deposited on a
quartz substrate. The spectrum that extends until the near-IR
region has features characteristic of the perovskite material,
indicating that MAPbI3 indeed formed during the reaction.22
The spectrum shows two dominant and distinct photoinduced
peaks located at around 490 and 740 nm and a decrease in the
absorbance in the 500−520 nm region, which are characteristics
of MAPbI3 films deposited from N,N-dimethylformamide
(DMF) solvent.23,24 The peaks have been assigned to
transitions arising due to a dual valence band structure (VB1
and VB2) of methylammonium-based perovskites.25 The peak
at 740 nm has been attributed to a direct gap transition from
the first valence band maximum (VB1) to the conduction band
(CB) minimum, representing that the photogeneration in the
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material begins at that wavelength. The shouldered peak at 490
nm was similarly assigned to the transition from the lower
valence band (VB2) to the CB in the two-valence-band model;
an iodide-to-lead charge-transfer transition has also been
assigned to the higher-energy peak. A better view of these
two photoinduced peaks can be obtained from d[(αhν)2]/
d(hν) versus hν plots as shown in the inset of Figure 1a. The
plot shows two distinct peaks at energy values 1.67 and 2.49 eV,
which correspond to 742 and 498 nm, respectively. The
positions match the peaks appearing in the absorption
spectrum.
In Figure 1b, we show a plot of (αhν)2 versus energy (Tauc
plot) to obtain the optical gap of the perovskite. From
extrapolation of the linear part of rgw Tauc plot (Kubelka−
Munk theory26), the optical gap of MAPbI3 could be estimated
as 1.54 eV, which is in close agreement with previous reports.27
Here, the optical gap inferred the low-energy transition
between VB1 and CB.
Since the crystalline nature of semiconductors is an
important parameter in forming solar cells, we have recorded
X-ray diffraction (XRD) patterns of the perovskite thin films.
The patterns moreover infer formation of the material when
they are compared with reported results in this direction.8,28 In
Figure 1c, we show XRD patterns of MAPbI3 that yielded
intense and sharp peaks at appropriate diffraction angles,
ensuring formation of the corresponding material in a single
phase. The material adopted a typical tetragonal structure for
CH3NH3MX3 hybrid perovskites (M = Pb, Sn; X = halogen)
formed by a three-dimensional anionic framework of PbI6
octahedron with methylammonium cations in the interstitial
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space (inset of Figure 1b). A closer look of the patterns reveals
that in the region of the (110) diffraction peak at 14.12° there is
only a small signature of a peak at 12.65° (marked with an
asterisk) that corresponds to the (001) diffraction peak for
unreacted PbI2. In the spectrum of MAPbI3−xClx, the peak at
12.65° did not appear, implying absence of PbI2 in the material.
(It may be recalled that PbI2 was not required to form
MAPbI3−xClx.) The representative peak of MAPbCl3 that in
general appears at 15.68° was also absent in the spectrum,
implying formation of MAPbI3−xClx with a high level of phase
purity. The optical absorption spectrum and XRD pattern of
MAPbI3−xClx are presented in Figure S1 (Supporting
Information).
We have further characterized the perovskite by recording its
Raman spectrum. The films appeared to be very sensitive to
laser power. We therefore used a low laser power that was just
sufficient to obtain adequate Raman signal; when the power
was a little higher, the material was found to be affected by the
laser beam, as evidenced by a change in its color. In the Raman
spectrum, as presented in Figure 1d, a couple of modes in the
low-frequency range were observed at 67.2 and 86.4 cm−1. The
former could be assigned to the inorganic component of the
perovskite, arising out of bending vibrations of the I−Pb−I
bonds and a consequent libration of the cations due to
deformation of the inorganic cage. The latter mode at 86.4
cm−1 also represents the inorganic component of the material
and is known to be associated with both Pb−I stretching and
libration modes of the cations. The sharp peak at 143.2 cm−1
appears due to the motion of the organic cations (methyl-
ammonium). Modes in the 200−400 cm−1 range could be
attributed to torsional vibration frequencies of the organic
cations. Quarti et al.29 have proposed these modes as possible
markers of orientation order of the organic cations in the
material, and thus of the whole crystal. The Raman spectrum
hence substantiated the formation of CH3NH3PbI3 for use in
perovskite solar cells. When we analyzed the elemental
composition of the perovskites through energy-dispersive X-
ray (EDX) analysis (Figure S2 in Supporting Information), the
spectra matched the reported results and were reproducible
over the whole scan region, implying homogeneity of the
synthesized material.30
We characterized the layers of NiO and Cu@NiO and of
Cu2O also through optical absorption, Tauc plots, and XRD
patterns. The characteristics matched the reported results of the
respective materials.16,21,31,32 In Figures S3 and S4 (Supporting
Information), we present such plots of the materials.
2.2. Estimation of Band Edges by Scanning Tunneling
Spectroscopy. Since energy levels of a p−i−n heterojunction
must form a type II band alignment at both interfaces for
uninterrupted carrier transport, we aimed to locate the CB and
VB of the individual materials with respect to their Fermi
energy. In order to do so, we recorded tunneling current versus
tip voltage characteristics of ultrathin films of the materials
formed separately on n-type highly doped Si ⟨111⟩ substrates.
From the obtained data, we have calculated the differential
conductance (dI/dV) of the materials that has correspondence
to their density of states (DOS). In the DOS spectra, which are
shown in Figure 2a, since tip voltage was applied with respect
to the substrate, the peaks in the positive and negative voltages
denoted VB and CB of the semiconductors, respectively. For
PCBM, the peaks represented HOMO and lowest unoccupied
molecular orbital (LUMO) levels, respectively. The work-
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Figure 2. (a) Differential conductance (dI/dV) plots of NiO, Cu@
NiO, Cu2O, MAPbI3, and PCBM thin films. VB and CB edges of the
materials and HOMO and LUMO levels of PCBM with respect to the
Fermi energy are marked with vertical continuous and broken straight
bars in the positive and negative voltage regions, respectively. (b)
Schematic energy level diagram of Cu2O/MAPbI3/PCBM hetero-
junction. The dashed line represents the Fermi energy after contact.
function of the substrate electrode is set to be aligned to the
Fermi energy of the semiconductors.
The DOS spectrum of MAPbI3 shows that while the CB
edge was located at 0.69 eV above the Fermi energy, the first
valence band maximum (VB1) could be located at 0.75 eV
below. Location of the lower VB (VB2) could not be seen in
the DOS spectrum, since tunneling to VB1 remained efficient
also at higher positive voltages. The DOS spectrum moreover
evidenced that the Fermi energy was mostly at the middle of
CB and first VB edges, inferring the intrinsic nature of the
semiconductor in pristine thin films.
The DOS spectra of NiO, Cu@NiO, and Cu2O show that
the Fermi energy was closer to the valence band edge, implying
the p-type nature of the materials. Similarly, PCBM can be seen
to act as an electron-acceptor material (n-type semiconductor).
Transport gap of the semiconductors can be estimated by
calculating the difference between CB and VB edges in the
DOS spectra. The results show that the transport gap was lower
than the optical gap of each of the materials. This is expected
since trap states also contribute to tunneling current and hence
appear in the DOS spectrum. From the VB and CB edges of
the semiconductors, we have formulated the energy band
diagram of the proposed device architectures that are shown in
Figure 2b and Figure S5 (Supporting Information). The band
diagram implied that the heterojunctions formed a p−i−n
architecture, which is appropriate for carrier separation and to
act as solar cells.
The expected carrier separation at the HTL/MAPbI3 and
MAPbI3/ETL interfaces can be monitored also by recording PL
spectrum of the heterojunctions. It may be recalled that in case
of TiO2/MAPbI3/Spiro-MeOTAD n−i−p structures, when PL
of MAPbI3/Spiro-MeOTAD and TiO2/MAPbI3 heterojunc-
tions were recorded, PL of the perovskite that appeared at
around 763 nm was found to be quenched due to a hole-
transfer to Spiro-MeOTAD and an electron-transfer to TiO2,
respectively.33 In our Cu2O/MAPbI3/PCBM p−i−n structures,
we accordingly went on to record PL emission of the perovskite
in the Cu2O/MAPbI3 and MAPbI3/PCBM heterojunctions. In
Figure 3, we present photoluminescence (PL) spectra of such
heterojunctions in addition to a spectrum of the perovskite film
in its pristine form. PL emission of MAPbI3 appeared at 763
nm, representing transition from the VB1 edge. The emission
of the perovskite quenched in the heterojunctions with HTL
and ETL separately. Quenching of PL emission in the two
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that the sandwiched structures may act as solar cells under

illumination. For each type of devices, we characterized at least
20 cells; a typical I−V of each of the devices under 1 sun
condition is shown in the corresponding panel. All the devices
acted as solar cells, the parameters of which are listed in Table
1. While the VOC was high and ranged between 0.89 and 1.03 V,

Table 1. Photovoltaic Parameters of HTL/MAPbI3/PCBM

Heterojunctions with Different HTLsa
ISC VOC fill factor
device structure (mA/cm2) (V) (%) η (%)
NiO/MAPbI3/PCBM 9.75 0.91 43 3.81
Cu@NiO/MAPbI3/PCBM 14.90 1.03 51 7.80
Cu2O/MAPbI3/PCBM 16.52 0.89 56 8.23
Cu2O/MAPbI3−xClx 15.60 0.92 58 8.30
Figure 3. PL emission spectra of MAPbI3 thin films and Cu2O/ /PCBM
MAPbI3 (p−i) and MAPbI3/PCBM (i−n) heterostructures. Excitation a
wavelength of the PL measurements was 600 nm. Parameters of device based on MAPbI3−xClx are shown in the last
row.
heterojunctions occurred due to hole transfer to Cu2O and
electron transfer to PCBM from the perovskite, respectively. the fill factor was moderate (up to 56%). The ISC in Cu2O-
Scanning tunneling spectroscopy (STS) results also inferred based devices exhibited a higher value. Although the fill factor
that such transfers were energetically possible. Photolumines- of Cu2O-based devices was not high enough, the energy
cence of MAPbI3 in Cu2O/MAPbI3 heterojunction was conversion efficiency (η) reached up to 8.23% in such devices.
quenched the most. The quenching process in Cu2O/ Such efficiency in a direct planar structure is indeed worth
MAPbI3 was efficient, presumably due to a higher hole mobility reporting in perovskite solar cell research. Histograms of VOC,
of the oxide that would result in efficient charge extraction. The ISC, η, and fill factor of the solar cells, as measured in 20 cells,
other HTLs, namely NiO and Cu@NiO, also quenched PL are presented in Figure S6 in Supporting Information.
emission of the perovskite. The results hence support the Excelling in energy conversion efficiency with Cu2O as the
inference of carrier separation at the two interfaces of the p−i− HTL occurs primarily due to a near-perfect alignment of its VB
n heterojunctions that is necessary for solar cell applications. edge with that of the perovskite. In addition, a high degree of
2.3. Photovoltaic Performance. We hence proceeded to crystallinity of Cu2O formed through a SILAR method, as
characterize the p−i−n heterojunctions under dark and evidenced from XRD patterns, led to an improved hole-
illumination conditions. In Figure 4a−c, we present I−V extraction efficiency of the material. When the performances of
characteristics of the heterojunctions with a layer of (a) NiO, devices based on NiO and Cu@NiO as HTL are compared,
(b) Cu@NiO, and (c) Cu2O as separate HTL, respectively. V OC and correspondingly η could be found to show
The dark characteristics were rectifying in nature, indicating improvement upon inclusion of copper in the NiO layer. The

Figure 4. Current−voltage characteristics of (a) NiO/MAPbI3/PCBM, (b) Cu@NiO/MAPbI3/PCBM, and (c) Cu2O/MAPbI3/PCBM
heterojunctions under dark and white light illumination conditions.

1431 DOI: 10.1021/acs.jpcc.5b11540

J. Phys. Chem. C 2016, 120, 1428−1437
The Journal of Physical Chemistry C
presence of copper, which is known to occupy vacant metal
sites, led to a decrease in carrier concentration (as evidenced by
a shift in Fermi energy away from the VB edge); in the band
diagram of Cu@NiO/MAPbI3/PCBM (Figure S5b in Support-
ing Information), upon alignment of Fermi energy, a large
energy difference hence existed between VB of Cu@NiO and
CB of MAPbI3. Since the energy difference is known to
contribute to VOC, this parameter excelled in Cu@NiO/
MAPbI3/PCBM heterojunction, exceeding 1 V.
We introduced Cu2O also with MAPbI3−xClx, that is, as a
Cu2O/MAPbI3−xClx/PCBM p−i−n heterojunction device. I−V
characteristics under dark and white light are shown in Figure 5.
Figure 5. Current−voltage characteristics of Cu2O/MAPbI3−xClx/
PCBM heterojunctions under dark and white light illumination
conditions.
Here also, the dark characteristics were rectifying in nature;
under illumination, the device acted as a solar cell, the η of
Figure 6. (a) −dV/dI vs (ISC − I)−1, (b) ln (ISC − I) vs (V + IRseries), and (c) dI/dV vs V plots of the heterojunctions with a range of HTLs as stated
in the legend. In the former two plots, broken lines represent linear fits to the experimental points.
1432
Article
which reached up to 8.30%. Solar cell parameters of Cu2O/
MAPbI3−xClx/PCBM heterojunction have been appended in
Table 1. Since the efficiencies of MAPbI3−xClx- and MAPbI3-
based devices were comparable, we continued further character-
ization of the Cu2O/MAPbI3/PCBM heterojunction.
We may add here that we did not target to use CuO as a
HTL that can be formed through high-temperature annealing
of Cu2O layer, since such annealing reduces carrier mobility
and hence also the conductivity.34 Moreover, as compared to
Cu2O, cupric oxide has a smaller band gap (∼1.4 eV);21 CuO
would hence form an opaque layer in front of the perovskite,
reducing its light-absorbing capability drastically.
In the case of a planar junction perovskite solar cell, it is of
critical importance that the layers are uniform and smooth for
better contact with the next material. For example, a smooth
MAPbI3 film would lead to better contact between the
perovskite and PCBM layers, enabling efficient electron
extraction in the devices. To compare the morphology of
HTL and MAPbI3 films deposited on different HTLs, we
recorded their atomic force microscopic (AFM) images (Figure
S7 in Supporting Information). When we compared surface
morphology of NiO, Cu@NiO, and Cu2O layers, we observed
that the root-mean-square (RMS) roughness (RRMS) of the
Cu2O layer was the least. This implied that the Cu2O/MAPbI3
interface will facilitate hole extraction in the devices. To
compare morphology of MAPbI3 films deposited on different
HTLs, we recorded AFM images of HTL/MAPbI3 films. While
RRMS of the perovskite film deposited on bare glass substrate
was around 62 nm, the smoothness of the MAPbI3 film
improved by a large extent when the perovskite layer was
formed on a HTL, implying a more compact and denser nature
of the film with less voids and traps. With a layer of NiO, Cu@
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Table 2. Diode Parameters of Different Device Structures

device structure Rseries (Ω·cm2) ideality factor (n) I0 (mA/cm2) calcd VOC (V) Rshunt (kΩ·cm2)
−2
NiO/MAPbI3/PCBM 18.2 7.9 9.2 × 10 0.93 132
Cu@NiO/MAPbI3/PCBM 9.4 7.0 5.2 × 10−2 1.06 165
Cu2O/MAPbI3/PCBM 9.1 3.8 8.0 × 10−4 0.97 380

Figure 7. Photocurrent hysteresis behavior of Cu2O/MAPbI3/PCBM heterojunction with different (a) voltage sweep directions and (b) delay times.
Symbols have the same meaning in the two plots. (c) Photovoltaic parameters of the heterojunction measured over a span of 15 days.

NiO, or Cu2O beneath, the RRMS of MAPbI3 layer was 19.4, ⎡ q ⎤ ⎛ V + IR series ⎞
15.0, and 5.3 nm, respectively. Such a smooth surface of Cu2O/ I = ISC − I0 exp⎢ (V + IR series)⎥ − ⎜ ⎟
⎣ nKBT ⎦ ⎝ R shunt ⎠
MAPbI3 heterojunction would allow formation of a uniform
(1)
PCBM layer leading to better contact between these two layers
and hence unhindered electron extraction in the devices. where I is current flowing through the external load, ISC is light-
Improved η in Cu2O/MAPbI3/PCBM could therefore be due induced current, I0 is dark saturation current density, V is
applied voltage, n is the ideality factor, KB is the Boltzmann
to efficient hole and electron extractions at the two interfaces. A constant, T is temperature, and q is electron charge. Equation 1
homogeneous ETL would furthermore allow deposition of a reduces to
smooth top Al electrode, ensuring reflection of unabsorbed
q
photons. ln(ISC − I ) = ln I0 + (V + IR series)
2.4. Junction Properties. Apart from the solar cell nKBT (2)
parameters, such as VOC, ISC, fill factor, and η, we have
when the contribution of Rshunt is neglected. From the first
analyzed the I−V characteristics further. It is imperative that an derivative of eq 2, Rseries of the devices can be evaluated as
efficient solar cell structure would possess low series resistance
and high shunt resistance. While low series resistance (Rseries) dV nKBT 1
− = R series +
improves charge extraction possibilities, large shunt resistance dI q (ISC − I ) (3)
(Rshunt) would reduce recombination losses. We therefore
Equation 3 allowed us to determine the series resistances of our
analyzed the I−V curves to evaluate the resistances (Rseries and
devices, based on the three HTLs, when we plotted −dV/dI
Rshunt) of the solar cells. versus (ISC − I)−1 (Figure 6a). Equation 3 in addition yielded
Planar-structured solar cells can in general be treated as a the ideality factor (n) from the slope of the linear fit. When
single-junction diode; I−V characteristics of such diodes can be Rseries of the device is available, it may be used in eq 2 to
expressed as determine I0 as intercept, with the ordinate of the linear fit to ln
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(ISC − I) versus (V + IRseries) plots in the higher ISC − I region
(Figure 6b).
Rshunt of devices could also be evaluated from eq 1 as
q presumably due to a morphologically superior Cu2O layer on
dI 1
− = + I0eqV / nKBT
dV R shunt nKBT (4)
Here, the contribution of Rseries was neglected. From plots of
dI/dV versus V (Figure 6c), Rshunt could be estimated from the
reciprocal of the ordinate at V = 0. The other term, namely (q/
nKBT)I0, could be neglected due to a low value of I0. The values
of Rseries, Rshunt, I0, and n, as obtained from the above analysis,
are listed in Table 2. The values show that Rseries was the lowest
and Rshunt was the highest in the Cu2O/MAPbI3/PCBM
heterojunction as compared to the corresponding resistances of
the devices based on the other two hole-transport materials.
The improved fill factor strongly indicates a reduction in
recombination loss as a result of Cu2O incorporation. However,
the value is still lower than the reported results and thus may
have limited the η of the devices. The value of I0 was at least 2
orders of magnitude lower in the Cu2O/MAPbI3/PCBM
heterojunction. The ideality factor was also substantially
lower in the Cu2O based devices. The junction properties are
hence favorable in the Cu2O/MAPbI3/PCBM heterojunction,
and the analyses are in concurrence with the superior solar cell
parameters that we observed in this device.
In a heterojunction solar cell, the value of the ideality factor
represents junction quality and the carrier recombination
mechanism. For such a solar cell, the ideality factor (n) is
typically between 1 and 2. The value of n approaches unity
when the diode current of a pn junction is dominated by carrier
diffusion in the neutral region of the semiconductors. When
carrier recombination in the depleted region dominates the
diode current, the ideality factor approaches 2. In most cases,
both phenomena take place simultaneously and hence n lies
between 1 and 2. In our efforts, the ideality factor was higher
than 2 in all the devices. Such a value meant that recombination
of trapped charges was prevalent in those devices.35
From eq 1, VOC of the devices could be derived as
nKBT ⎛ ISC ⎞
VOC = ln⎜ ⎟
q ⎝ I0 ⎠ (5)
With the values of n and I0 being available, we went on to
evaluate VOC of the devices, and these values are listed in Table
2. The values matched reasonably well with VOC values
observed in the I−V characteristics under illumination,
implying correctness of the device parameters, such as Rseries,
Rshunt, I0, and n.
2.5. Hysteresis in Current−Voltage Characteristics.
Perovskite solar cells having mesoscopic36 or planar junction37
structure have both been reported to show anomalous
hysteresis in their I−V characteristics, making it difficult to
accurately represent the device performance. The hysteresis
behavior has been reported to depend on the voltage sweep
direction, sweep speed or delay time, and light soaking of the
devices.38 These effects led to either over- or underestimation
of the device performance. To ensure a high degree of accuracy
of our I−V measurements, we characterized the devices under
two voltage sweep directions and at various sweep rates or
delay times. As can be seen in Figure 7a,b, the Cu2O-based
device exhibited a not-so-significant amount of hysteresis in the
I−V characteristics under illumination conditions. The
deviations in ISC and VOC with a range of delay times were
1434
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0.35 mA/cm2 and 0.01 V, which amounted to 2% and 1% with
respect to the magnitude of the parameters, respectively. A low
hysteresis effect in Cu2O/MAPbI3/PCBM could be achieved,
which the perovskite film was deposited. The low hysteresis in
these devices moreover implied that the parameters achieved in
the solar cells appeared truly due to efficient charge separation
at p−i and i−n interfaces of the direct p−i−n heterojunctions.
2.6. Stability. In perovskite solar cells, stability has
remained an issue since their inception.39,40 The instability
apparently occurs due to degradation of the perovskite (and
also spiroMeOTED) upon exposure to oxygen, moisture, UV
radiation, temperature, and the solvents and additives used
during processing of the materials. In order to protect the
materials and the devices from oxygen and moisture, we
fabricated the devices and characterized them in a glovebox. We
did not use any additives; neither did we use any encapsulation.
No special effort was undertaken to protect the devices from
UV radiation or from normal indoor illumination. Parameters
of the solar cell recorded once a day over a fortnight are shown
in Figure 7c. The devices were found to possess about 60% of
their initial performance after a fortnight.
3. CONCLUSION
In conclusion, we have introduced Cu2O as a hole-transport
material in perovskite solar cells having a direct p−i−n
structure. When we determined the band edges of Cu2O and
the perovskite (MAPbI3) and the energy levels of PCBM from
dI/dV spectra that have correspondence to the material’s DOS,
we observed that p−i and i−n interfaces formed type II band
alignment, enabling charge separation at both of them. Due to
such an appropriate band diagram, the Cu2O/MAPbI3/PCBM
heterojunction when sandwiched between ITO and aluminum
electrodes yielded an efficiency of 8.23%. The value excelled
when compared to heterojunctions based on other HTLs, such
as NiO and copper-doped NiO. In the rest of the paper, we
present our results on diode parameters. Such parameters
showed that the higher efficiency in Cu2O/MAPbI3/PCBM
devices was due to low series resistance, high shunt resistance,
and low ideality factor, leading to a low recombination loss as a
result of Cu2O incorporation in a direct-structured perovskite
solar cell.
4. EXPERIMENTAL DETAILS
4.1. Materials. Methylamine (MA, CH3NH2), hydrogen
iodide (HI), anhydrous lead iodide (PbI2) and lead chloride
(PbCl2), N,N-dimethylformamide, anhydrous, 99.8% (DMF),
copper(II) chloride dihydrate (CuCl2·2H2O), and chloroben-
zene (99.5%) were purchased from Sigma−Aldrich Chemical
Co. Phenyl-C61-butyric acid methyl ester (PCBM) (99%) was
purchased from M/s SES Research, Houston, TX.
4.2. Synthesis of Perovskites. We synthesized
CH3NH3PbI3 and CH3NH3PbI3−xClx following a reported
route that contained a couple of steps. 23,27 At first,
methylammonium iodide (CH3NH3I) was synthesized by
reacting methylamine (CH3NH2) (13.5 mL, 40 wt % in
aqueous solution) and hydroiodic acid (15.0 mL, 57 wt % in
water) in an ice bath for 2 h. When the reaction that produced
CH3NH3I in the form of white powder was complete, the
solvent was evaporated by use of a rotary evaporator at 50 °C
for 1 h. The precipitate was then collected, washed with diethyl
ether (99.7% Merck) three times, dried at 60 °C in a nitrogen-
DOI: 10.1021/acs.jpcc.5b11540
J. Phys. Chem. C 2016, 120, 1428−1437
The Journal of Physical Chemistry C
filled glovebox overnight, and finally stored in the glovebox for
further use.
To prepare thin films of CH3NH3PbI3 and
CH3NH3PbI3−xClx, a one-step process was followed in both
cases. A solution of CH3NH3PbI3 was prepared by mixing
CH3NH3I and PbI2 at 1:1 equimolar ratio in DMF. The
solution was allowed to stir overnight at 70 °C in the glovebox
that had oxygen and moisture levels below 0.1 ppm each to
obtain a yellow homogeneous and transparent solution of
CH3NH3PbI3 perovskite. To form CH3NH3PbI3−xClx, the
reactants, composed of 3:1 molar ratio of CH3NH3I and
PbCl2 in DMF, underwent the same reaction protocol in the
glovebox.
PbI 2 + CH3NH3I → CH3NH3PbI3
PbCl 2 + 3CH3NH3I → CH3NH3PbI3 − xCl x + CH3NH3Cl
Upon heating, methylamine hydrochloride decomposed into
hydrochloric acid and methylamine as
CH3NH3Cl → HCl( ↑ ) + CH3NH 2( ↑ )
4.3. Characterization of Materials. The materials were
characterized by optical absorption and photoluminescence
(PL) spectroscopy, X-ray diffraction (XRD) patterns, and
Raman spectroscopy. The measurements were carried out with
a Shimadzu UV-2550 spectrophotometer and Spex Fluoromax
4P emission spectrophotometer, Bruker D8 advanced X-ray
powder diffractometer (Cu Kα radiation, λ = 1.54 Å), and a
Horiba Jobin-Yvon triple-grating Raman spectrometer system
(model number T64000) using 514 nm excitation of an argon-
ion laser source (Stabilite 2017, Spectra Physics), respectively.
In addition, the materials were characterized with a scanning
tunneling microscope (STM). We used a Nanosurf Easyscan2
STM in ambient conditions to record tunneling current
through ultrathin films of Cu2O and other HTLs, perovskites,
and PCBM. From the tunneling current, we determined
differential conductance (dI/dV) that is known to have a
correspondence to the density of states (DOS) of semi-
conductor materials.41 This enabled us to locate conduction
and valence band edges (CB and VB, respectively) of the
inorganic semiconductors with respective to their Fermi energy.
For PCBM, the dI/dV spectrum located its highest occupied
molecular orbitals (HOMO) and lowest unoccupied molecular
orbitals (LUMO), respectively. For STM measurements, tip
voltage was applied with respect to the substrate. At a positive
voltage, the tip therefore withdrew electrons from the
semiconductor; the peaks in the positive voltage of DOS
spectrum hence denoted the VB (or HOMO) of the
semiconductors. Similarly, the peaks at negative voltages, at
which electrons could be injected from the tip to a
semiconductor, provided the location of the CB (or LUMO).
4.4. Device Fabrication. All the planar perovskite solar
cells were built on patterned ITO-coated glass substrates (sheet
resistance = 15 Ω/square). Prior to deposition of a HTL, the
substrates were cleaned following a usual protocol, followed by
UV−ozone treatment for 20 min that ensured better contact
with the layer. NiO and copper-doped NiO (5 at. %, Cu@NiO)
layers were formed via spin-coating from their respective
solutions. Both pristine and copper-doped NiO thin films were
also formed by spin-coating their corresponding hydroxide
solutions at 3000 rpm for 30 s, followed by annealing at 425 °C
for 15 min. The reported method followed to form NiO and
Cu@NiO layers31,32 is also briefly stated in Supporting
1435
Article
Information. Thickness of NiO and Cu@NiO thin films was
around 40 nm each.
Cu2O thin films were grown on ITO substrates by the SILAR
technique, in which highly pure copper(II) chloride dihydrate
(CuCl2·2H2O), ammonium hydroxide (NH4OH), and hydro-
gen peroxide (H2O2) were used as copper precursor,
complexing agent, and oxidizing agent, respectively. Dehy-
drated methanol acted as a solvent during the film formation
process. The cationic precursor was prepared by dissolving 0.1
M of the copper salt (∼341 mg) in 20 mL of methanol,
followed by complexation with 25% NH4OH at pH 11.8. In
doing so, the light green homogeneous solution of the copper
salt turned deep blue. The film formation process was carried
out at room temperature in an automated multivessel dip-
coating unit (Apex Instruments Co. Pvt. Ltd.). The substrates
were dipped in (i) copper precursor, (ii) methanol, (iii) H2O2
solution (1%, diluted in methanol) for 10 s to oxidize the
adsorbed copper ions that could be inferred from formation of
bubbles, and (iv) methanol, all kept in separate beakers, in
sequence for the growth of Cu2O films. The steps were cycled
to obtain a desired thickness of Cu2O thin films (40 nm), which
were finally annealed at 170 °C for 20 min.
Following a transfer of HTL-coated ITO substrates to the
glovebox, thin films of the perovskites were spun on such
substrates at 2500 rpm for 60 s. The films were left in the
glovebox for 30 min for slow evaporation of the solvent,
preceded by annealing at 100 °C for 30 min (45 min for
CH3NH3PbI3−xClx) to promote crystallization of the perov-
skites. Thickness of CH3NH3PbI3 and CH3NH3PbI3−xClx layers
was 270 nm for both. As the n-type ETL layer, PCBM was spun
from a 17 mg/mL chlorobenzene solution followed by further
annealing at 100 °C for 15 min. Thickness of the ETL was 15
nm, which was measured by forming its separate film on a
substrate. The device fabrication process was completed by
thermal evaporation of aluminum at a pressure below 5 × 10−6
Torr as the top electrode. Here, the evaporation chamber was
attached to the glovebox, allowing easy transfer of the films
from the glovebox to the chamber. Thermal evaporation
through a shadow mask was carried out at 0.2 Å/s until a
thickness of 100 nm was achieved. With the widths of ITO and
Al strips being 1/8 in. each and orthogonal to each other, this
completed the device fabrication process of four cells, each one
having an area of 10 mm2, on a single glass substrate.
4.5. Device Characterization. Current−voltage (I−V)
characteristics of the devices under dark and illumination
conditions were recorded with a Keithley 2636 electrometer
using LabTracer software. Electrodes of the devices, which were
kept in the glovebox, were connected to the electrometer via
pressure-loaded spring contacts. A 300 W solar simulator
(Newport-Stratfort model 76500) attached with an AM1.5 filter
placed outside the glovebox acted as a source for illumination.
Intensity of the simulated solar light on the device was 100
mW/cm2. While I−V characteristics were recorded under
illumination conditions, regions outside the cell area were
masked to avoid any contribution from neighboring areas or
cells. Bias was swept toward both directions and also in loops.
To study stability of the devices, the cells, shelved in the
glovebox, were characterized once per day for a fortnight. The
cells were neither encapsulated nor protected from exposure to
usual room light.
DOI: 10.1021/acs.jpcc.5b11540
J. Phys. Chem. C 2016, 120, 1428−1437
The Journal of Physical Chemistry C
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.5b11540.
Additional text describing growth of NiO and Cu@NiO
thin films and seven figures showing optical absorption
and XRD of CH3NH3PbI3−xClx perovskites; EDX of
perovskites; optical absorption, Tauc plots, and XRD of
NiO and Cu@NiO thin films and of Cu2O thin film
formed through SILAR technique; energy band diagrams
of NiO/MAPbI 3 /PCBM and Cu@NiO/MAPbI 3 /
PCBM; histogram of VOC, ISC, η, and fill factor of
Cu2O/MAPbI3/PCBM solar cells; and surface morphol-
ogies of perovskite films (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*Telephone +91-33-24734971; fax +91-33-24732805; e-mail
sspajp@iacs.res.in.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
SC acknowledges DST INSPIRE Fellowship [IF 140158]. The
authors acknowledge financial assistance from DeitY, SERIIUS,
and Nano Mission (DST) projects.
■
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1437 DOI: 10.1021/acs.jpcc.5b11540

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