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Cite this: Energy Environ. Sci., 2015, 8,

1256
Received 24th December 2014
Accepted 12th February 2015

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Anomalously large interface charge in polarityswitchable photovoltaic devices: an indication of

mobile ions in organicinorganic halide
perovskites
Yong Zhao,a Chunjun Liang,*a Huimin Zhang,a Dan Li,a Ding Tian,b Guobao Li,c
Xiping Jing,c Wenguan Zhang,d Weikang Xiao,a Qian Liu,a Fujun Zhanga
and Zhiqun He*a

DOI: 10.1039/c4ee04064c
www.rsc.org/ees

It is proved that a large amount of mobile ions exist in organicinorganic halide perovskites. The accumulated ions at the interface change
the band bending of the semiconductor, leading to polarity-switchable photovoltaic devices. The interface charge signicantly inuences
the function and performance of perovskite devices. The discovery of
the interface charge has important implications for currentvoltage
hysteresis in perovskite solar cells.

The power conversion eciency (PCE) of perovskite solar cells

(PSCs) has been increasing rapidly since the emergence of solar
cell-based organicinorganic halide perovskites.110 PSCs
display diversied device architectures, such as distributed
heterojunctions with mesoporous TiO2, ZrO2, and Al2O3 nanostructures1014 as well as thin-lm planar heterojunctions
(TPHJs).3,5,15 The solar cells in the TPHJ structure are composed
of a perovskite layer (abbreviated as PRV) and carrier-selective
layers, such as an n-type electron transport layer (abbreviated as
N) and a p-type hole transport layer (abbreviated as P). Layer
combinations, such as NPRVP,16,17 NPRV18 and PRVP19
display remarkable photovoltaic performance. In addition, a
wide range of carrier-selective (TiO2, ZnO, PCBM, spiro-OMeTAD, and P3HT) and electrode materials (Au,18,20 PEDOT:PSS
and carbon14) have been used. Other solar-energy materials do
not show the same wide range of device architecture and electrode materials as organicinorganic perovskites. PSCs exhibit
currentvoltage (JV) hysteresis in all architectures. The shape
of the JV curve varies depending on the scan direction, range,

Key Laboratory of Luminescence and Optical Information, Ministry of Education,

School of Science, Beijing Jiaotong University, Beijing 100044, China. E-mail:
chjliang@bjtu.edu.cn; zhqhe@bjtu.edu.cn

School of Science, China University of Geosciences, Beijing 100083, China

College of Chemistry and Molecular Engineering, Peking University, Beijing 100871,

China
d

Lab of Printing & Packaging Material and Technology-Beijing Area Major Laboratory,
Beijing Institute of Graphic Communication, Beijing 102600, China
Electronic supplementary
10.1039/c4ee04064c

information

(ESI)

1256 | Energy Environ. Sci., 2015, 8, 12561260

available.

See

DOI:

Broader context
The development of organicinorganic halide perovskite solar cells (PSCs)
has been very fast, recently. PSCs display diversied device architectures
and anomalous currentvoltage hysteresis. These features imply that the
organicinorganic halide perovskites possess some unique properties.
Here we report an unusual polarity-switchable photovoltaic device in the
structure of ITO/PEDOT:PSS/CH3NH3PbI3/MoO3/Al. The polarity of the
device is switchable with a preset voltage. An unusually large quantity of
interface charge is observed. The accumulation of the interface charge
converts the device from a hole-only device to a functional photovoltaic
device in a time scale of
10 s. The interface charge has been proved to
mainly originate from mobile ions in the hybrid perovskite. The discovery
of the interface charge reveals a unique device mechanism in perovskite
photovoltaics. The interface charge changes the band bending near the
interface and thus leads to a wide range of device architectures, current
voltage hysteresis, and polarity switch. The results suggest that manipulating the interface charge is key to controlling the performance of PSCs.
The discovery of the mobile ions indicates an unexpected, unique property
of the hybrid perovskites. Future studies should investigate the origin and
the related eects of the mobile ions.

and rate of the applied voltage during measurements. Hysteresis becomes prominent when the n-type or p-type carrierselective layer is absent. The unusually wide range of device
architectures and the JV hysteresis imply that the organic
inorganic halide perovskites possess a unique property, which
is unknown, although several mechanisms have been proposed
to address the hysteresis.21
In this work, we report an unusual perovskite device, i.e., a
polarity-switchable photovoltaic device. Its polarity switches
with changing bias, thus suggesting a unique device mechanism. A large quantity of electric charge at the interfaces
between the perovskite and the electrodes, which leads to the
polarity switch, is observed. Finally, we prove that high-density
mobile ions, which are the origin of the interface charge, exist in
the hybrid perovskite.
PbI2 (99.999%, Sigma-Aldrich) and MAI (>99.9%, HeptaChroma) were dissolved in DMF and 2-propanol, respectively. To
ensure MAI and PbI2 were fully dissolved, both solutions were

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heated at 70  C for 30 min before use. Samples were prepared on

glass substrates with indium tin oxide (ITO). The device architecture is ITO/PEDOT:PSS/MAPbI3/MoO3/Al, and the active area
is 0.038 cm2. PEDOT:PSS (Baytron-P4083) was spin-cast onto the
clean surface of the ITO substrates at 3000 rpm for 40 s and then
thermally annealed on a hot plate at 120  C for 30 min in air. In a
nitrogen-lled glove box, the PbI2 solution in DMF (460 mg ml1)
was spin-coated onto the PEDOT:PSS layer at 4000 rpm for 15 s
and then annealed at 70  C for 15 min. Aer drying, the MAI
solution in 2-propanol (20 mg ml1) was spin-coated onto the
PbI2 layer at 3000 rpm for 5 s and then annealed at 70  C for
45 min to form the perovskite MAPbI3. The samples were moved
to a thermal evaporator for MoO3 (8 nm) and aluminium
(100 nm) deposition. The resulting thickness of the perovskite
was
480 nm, as measured with an Ambios XP-2 prolometer.
The JV characteristics were recorded by a Keithley (and Agilent)
source meter under an illumination of AM 1.5G 100 mW cm2
from an Abet 2000 solar simulator. Ferroelectric hysteresis loops
were measured using a Radiant ferroelectric tester Premier II.
Impedance spectroscopy was conducted on a ZAHNER ZENNIUM electrochemical workstation.
The crystal structure of CH3NH3PbI3 (MAPbI3) is illustrated
in Fig. 1a. The perovskite MAPbI3 is sandwiched between two
conventional hole-injection electrodes, ITO/PEDOT:PSS and
MoO3/Al (Fig. 1b), which have close work functions of 5.0 and
5.3 eV, respectively. The polarity of the device is switchable with
a preset voltage (Fig. 2). Tempering the device at +2.0 V for 10 s
before the forward scan and at 2.0 V for 10 s before the

Energy & Environmental Science

Fig. 2 Currentvoltage characteristics of the polarity-switchable

photovoltaic device under one sun illumination. A preset voltage of
2.0 V (2.0 V) is applied on the device for 10 s before the forward
(backward) scan. The open circuit voltage (Voc), short circuit current
(Jsc), ll factor (FF) and power conversion eciency (PCE) indicate the
photovoltaic performance.

backward scan yields an impressive PCE of 10.6% in the forward

scan and 4.8% in the backward scan (we dene ITO/PEDOT:PSS
as ground, the scan from positive to negative as the forward
scan, and that from negative to positive as the backward scan).
Moreover, the observed Voc of 0.95 V in the forward scan and
0.88 V in the backward scan cannot be understood with a

Fig. 1 Material, device and mechanism of polarity-switchable perovskite photovoltaic devices. (a) Crystal structure of CH3NH3PbI3. (b) Device
structure. (c) Energy-level diagram of the materials. (df) Schematic energy band diagrams under equilibrium (dark and short circuits) conditions.
(d) Without interface charge the device is a hole-only device. (e) The device is a forward diode due to positive charges near the ITO/PEDOT:PSS
electrode. (f) The device is a reversed diode due to positive charges near the MoO3/Al electrode. Interface charge and screen charge are
represented in red and black, respectively.

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conventional view because the symmetric electrodes ITO/

PEDOT:PSS and MoO3/Al can provide neither sucient nor
direction-switchable built-in elds. Therefore, the unusual
performances suggest a unique photovoltaic mechanism in the
device. We found that large interface charge exists in the device
and leads to the mechanism.
Changeable interface charge near the electrode, which originates from mobile ions22,23 or ferroelectric polarization,24 leads
to polarity switch in diodes. We propose that a very strong
electric eld is formed between the interface charge in the
perovskite and the screen charge on the electrode (Fig. S1). The
strong eld changes the band bending near the interface and
thus modulates the barrier height of the contact. Consequently,
the same electrode material can form an Ohmic contact with
the perovskite semiconductor for either electron injection or
hole injection, depending on the nature of the interface charge.
In the virgin state (no interface charge), the device acts as a holeonly device (Fig. 1d), in which the JV curve obeys the power law
(typically V2 for space charge limited current). If a positive
charge is accumulated near the ITO/PEDOT:PSS electrode
(Fig. 1e), the positive charge changes the band bending and
reduces the barrier height between Ec and the electrode, thus
forming an Ohmic contact for electron injection. As a result,
the device would be a diode with ITO/PEDOT:PSS as the
cathode and MoO3/Al as the anode. Similarly, if the positive
charge is accumulated near the other electrode (MoO3/Al), the
resulting diode will switch its polarity, i.e., ITO/PEDOT:PSS
would serve as the anode and MoO3/Al as the cathode (Fig. 1f).
The JV curve of diodes obeys the exponential law (diode
equation: J J0(exp(qV/nkT)  1)). The interface charge can be
controlled by a preset voltage, leading to the polarity-controllable photovoltaics.
A constant bias (including the preset voltage) induces and
accumulates the interface charge and thus changes the device
from a hole-only device to a diode and functional photovoltaic

device. The transition is displayed in Fig. 3. As indicated in

Fig. 3a, the current decreases and eventually stabilizes aer tens
of seconds when the constant bias is lower than
1.1 V. When
the applied voltage is higher than
1.1 V, the current increases
and stabilizes in the time scale of
10 s. A higher bias leads to a
shorter transition time. Fig. 3b indicates the JV curves of the
device before and aer the transition. At the beginning (0 s) the
JV curve can be tted with a power law, indicating that the
device is a hole-only device at this moment. At the time of 30 s
the JV curve is consistent with an exponential law, indicating
that the device becomes a diode.
Relaxation (decline) of the interface charge was observed
(Fig. 4). A bias of 2.0 (2.0) V was applied on the device for 12 s
to accumulate the charge. The device was then kept at a short
circuit condition to observe the relaxation current. Aer
removal of the 2.0 (2.0) V bias (Fig. 4a), a small reverse current
appears and decays in a time scale of
20 s (Fig. 4a, inset),
indicating the relaxation process. Assuming that the perovskite
nally relaxes to the virgin state, the time integral of the relaxation current is an indication of the interface charge density
before the relaxation, which is 56 mC cm2 for 2.0 V bias and
53 mC cm2 for 2.0 V bias.
The density of the accumulated interface charge varies with
dierent bias (Fig. 4b). In the lower voltage range, the density of

Transition of the device from a hole-only device to a diode. (a)

Under constant bias the dark current changes with time, indicating that
the transition is underway. (b) At the beginning (0 s) the JV curve
obeys the power law, but after the transition (30 s) the JV curve obeys
the exponential law. The current densities in panel (b) are the current
densities in panel (a) at the measurement times of 0 s (blue triangle)
and 30 s (red circle), respectively.

Fig. 4 Relaxation of the interface charge. (a) A bias of 2.0 (2.0) V was

Fig. 3

1258 | Energy Environ. Sci., 2015, 8, 12561260

applied on the device for 12 s. The device was then kept at a short
circuit condition to observe the relaxation. The inset shows the
relaxation current and the time integral of the current density. (b)
Interface charge density measured at dierent bias. The interface
charge density was calculated from the time integral of the relaxation
current.

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the interface charge continuously increases with the rising bias

until a peak value of 284 mC cm2 is reached at a voltage of 3.6 V.
The anomalously large interface charge is consistent with the
very high dielectric constant (over 10 000) observed from
impedance spectroscopy (Fig. S2).
The observed interface charge mainly originates from mobile
ions in the perovskite layer because of the following reasons: (i)
the transition time
10 s is consistent with moving ions
(seconds to hours),25,26 whereas the switching time of typical
ferroelectric polarization is much faster (sub-microsecond);27
(ii) the relaxation indicates the gradual vanishing of the interface charge aer the removal of the applied voltage, which does
not support ferroelectric polarization because permanent
polarization is a necessary condition for ferroelectricity; (iii) no
ferroelectric hysteresis was observed in the device at room
temperature and at a low temperature of 77 K (Fig. S3); and (iv)
even if ferroelectric polarization occurs in the material, a
maximum polarization of 71 mC cm2 is estimated in MAPbI3
(Fig. S4), which is much smaller than the observed interface
charge density (D) 284 mC cm2.
Point defects, such as interstitial atoms and/or methylammonium (iodine) vacancies, possibly exist and act as mobile
ions. The density of ions (defects) is estimated as N D/qL 3.7
 1019 cm3, where q is the elementary charge and L is the
thickness of the perovskite. This value is unacceptably high for
most solar cells because high-density defects severely reduce
the carrier collection eciency.28 This value indicates that PSCs
have very high tolerance to defects.

further explored to develop ecient, low-cost, and long-life

devices (Fig. S5). Secondly, the polarity switch is actually an
exaggerated JV hysteresis. Our results indicate that the
dierent polarities of the interface charge during the scans
cause the exaggerated JV hysteresis, thus implying that the
dynamic change of the interface charge is an important cause of
JV hysteresis. The results also suggest that manipulating the
interface charge is key to controlling the performance of
perovskite photovoltaic devices.
The discovered high-density mobile ions indicate a unique
property of the hybrid perovskite. These ions signicantly
inuence the function and performance of perovskite devices.
Very likely they would aect the stability of PSCs as well.
Therefore the origin and the related eect of the mobile ions
should be investigated extensively in the future. We note that in
the submission period of this manuscript an ion dri in hybrid
perovskites was observed with an optical microscopic image.29

Conclusions

Acknowledgements

It is found that a large amount of mobile ions exist in organic

inorganic halide perovskites. Under an electric eld these ions
accumulate at the interfaces of the device. The existence of the
interface charge changes the band bending near the interface
and modulates the barrier height of the contact, thus forming
an Ohmic contact for either electron injection or hole injection
depending on the polarity of the charge. This unique mechanism leads to the polarity-switchable photovoltaic device. The
device ITO/PEDOT:PSS/MAPbI3/MoO3/Al is a switchable photovoltaic device, of which the performance is determined by the
dynamics of the interface charge (Fig. S8). The simple device
structure and the impressive photovoltaic response suggest that
it can be used as a special photodetector, of which the sensitivity and the polarity can be controlled by interface charge.
The above results have important implications for perovskite
photovoltaic devices. Firstly, the results indicate that photovoltaics from the hybrid perovskites can be achieved in a very
simple device structure with even symmetric electrodes. The
existence of the interface charge leads to band bending of the
semiconductor and thus conventional PN junctions or asymmetric electrodes are not a necessary condition for perovskite
photovoltaics. This nding suggests that various electrode
materials can be used, and explains the wide range of device
architectures and the wide variety of electrode materials in
perovskite photovoltaics. It also suggests that more carrierselective and non-selective electrode materials should be

The authors acknowledge the nancial support from the

National Natural Science Foundation of China (no. 11474017,
21174016 and 60776039), the Research Fund for the Doctoral
Program of Higher Education of China (no. 20120009110031),
and the Fundamental Research Funds for the Central Universities (no. 2013JBZ004, 2013JBM102).

This journal is The Royal Society of Chemistry 2015

Author contributions
Z.Q.H. and C.J.L. contributed to the conception and analysis of
the data. Y.Z. and H.M.Z. carried out the device fabrication and
measurement. D.L., D.T., X.P.J. and F.J.Z. contributed to the
data calculation and analysis. G.B.L. performed the ferroelectric
hysteresis measurement. W.G.Z. obtained the impedance
spectroscopy. W.K.X. and Q.L. contributed to material synthesis
and device fabrication. C.J.L. wrote the manuscript with the
assistance of Y.Z.

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