pubs.acs.

org/JPCC Article

Ion Migration in the All-Inorganic Perovskite CsPbBr3 and Its

Impacts on Photodetection
Jing Cai,∥ Tong Zhao,∥ Mingming Chen,* Jiayun Su, Xuemin Shen, Yuan Liu, and Dawei Cao*
Cite This: J. Phys. Chem. C 2022, 126, 10007−10013 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Ion migration has been widely investigated in the lead

halide perovskites, which severely deteriorates the performance of solar
cells. However, the impacts of ion migration on photodetection have
been rarely studied so far. In the current work, ion migration in the all-
inorganic perovskite CsPbBr3 and its impacts on photodetection have
Downloaded via ITMO UNIV on March 6, 2023 at 10:39:29 (UTC).

been investigated in detail. Electrical property studies showed that ion

migration has occurred under an external electric field poling, which led
to the formation of a pn-junction within the CsPbBr3 single crystals.
Density function theory calculations have shown that vacancy-assisted Br-
ion migration dominated the ion transportation processes. Accordingly,
the Au/CsPbBr3/Au metal−semiconductor−metal structured photo-
detectors showed a decreased performance in terms of a decreased
on−off ratio and decreased detectivity through a long-term operation under a bias voltage, although the photoresponsivity slightly
increased simultaneously. The results provided in this work verify the negative effects of ion migration in the all-inorganic perovskite
CsPbBr3, which may account for the instability of CsPbBr3-based optoelectronic devices reported in the literature.

1. INTRODUCTION their polycrystalline films.12−16 The ultralow concentration of

As emerging semiconductors, lead halide perovskites (LHPs)
with a typical formula of ABX3 (A = CH3NH3 (MA),
HC(NH2)2 (FA) or Cs; B = Pb; X = Cl, Br or I) have
attracted tremendous attention in recent years because of their
outstanding optoelectrical properties such as high charge
carrier diffusion length, long charge carrier lifetimes, high
optical absorption coefficients, and low-temperature solution-
processed ability.1 As a result of these advantages, the LHP
materials have achieved great success in the field of
photovoltaic technologies. 2−7 For example, the power
conversion efficiency (PCE) of LHP-based planar solar cells
has reached up to 25.7% very recently,7 which is comparable to
commercial silicon-based solar cells. Importantly, remarkable
high average external quantum efficiencies (EQEs) (∼90%) of
the LHP-based planar solar cells have been observed in the
visible spectra range,8 which suggests that the LHP materials
are promising candidates in the applications of visible light
photodetection.
In the past few years, various kinds of LHP materials such as
polycrystalline films, nanowires, microcrystals, and single
crystals (i.e., bulk materials) have been explored to fabricate
the visible light photodetectors (PDs).9−12 Among them, the
LHP single crystals are generally preferred because of their
improved crystalline quality and low density of defects, both of
which are fundamental for the fabrication of performance-
improved PDs. Notably, it showed that the density of defects
in the solution-grown LHP single crystals was only ∼109−1011
cm−3, which is about 6−7 orders of magnitude less than that in
defects guarantees the as-fabricated PDs with a low dark
current and produces a high photoresponsivity to the light
signal simultaneously. Very recently, we have demonstrated the
growth of high crystalline quality all-inorganic perovskite
CsPbBr3 single crystals via a modified low-temperature one-
step solution growth method, in which the defects were shown
as low as ∼109 cm−3.12,17 On this basis, Au/CsPbBr3/Au
metal−semiconductor−metal (MSM)-structured visible light
PDs have been fabricated with the photoresponsivity of 0.088
A/W.12 Notably, the photoresponsivity has increased to as
high as 0.61 A/W after the decoration of Au nanoparticles on
the CsPbBr3 single crystals.12 However, in the further study, it
has been noticed that both the dark current and the
photocurrent of the MSM-structured PDs increased through
a long-term operation under a bias voltage. Besides, photo-
voltaic phenomena with noticeable short-circuit current and
open-circuit voltage have further been observed (as will be
shown below). Such unexpected photoelectric properties have
rarely been investigated before but need to be studied in detail
Received: May 8, 2022
Revised: May 20, 2022
Published: June 6, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.jpcc.2c03175

10007 J. Phys. Chem. C 2022, 126, 10007−10013
The Journal of Physical Chemistry C
to fabricate the LHP-based PDs with an improved stability and
repeatability in the future.
Ion migration induced by external electric field poling in the
organic−inorganic hybrid LHP materials has attracted much
attention in earlier studies because it severely deteriorates the
performance including decreasing PCE and stability of the
LHP-based solar cells.18,19 In fact, ion migration was proposed
in the first place to understand the current−voltage (I−V)
hysteresis behaviors in the LHP-based solar cells.18 In recent
years, the ion migration behaviors have further been evidenced
both by experimental and theoretical investigations.20−23 It was
shown that halide species (Cl, Br, and I) have the lowest
migration barrier height and diffuse with the assistance of grain
boundaries and vacancy-type defects.21,24,25 This results in an
obvious energy band bending at both ends of the LHP film and
subsequently produces the typical I−V hysteresis. For the
LHP-based MSM-structured PDs, the effects of ion migration
on the photodetection performance have rarely been
concerned so far, although great efforts have been made
previously, but they mainly focused on improving the
photodetection performance of as-fabricated PDs and devel-
oping multifunctional (such as flexible, self-powered, and
narrow/broad-band detection) devices.26−29 In our opinion,
the effects of ion migration should be considered in the LHP-
based MSM-structured PDs because a bias voltage is
necessarily applied, especially for weak light detection. It is
worth noting that the ion migration has been observed in the
mixed halide CsPbX3-based light-emitting diodes recently.30
In this work, detailed experiments and density functional
theory (DFT) calculations have been performed to study ion
migration in the all-inorganic CsPbBr3 single crystals and its
impacts on the photodetection performance of MSM-
structured PDs. The preliminary results have shown that
vacancy-assisted Br-ion migration dominated the ion trans-
portation processes in the CsPbBr3 single crystals, which
substantially decreases the on−off ratio and detectivity in the
Au/CsPbBr3/Au MSM-structured PDs, although the photo
responsivity slightly increases.
2. EXPERIMENTS
2.1. Materials. Lead bromide (PbBr2, >99.5%), cesium
bromide (CsBr, >99.5%), dimethyl sulfoxide (DMSO,
anhydrous), dimethylformamide (DMF, anhydrous), and
silicone oil were used as received.
2.2. Preparation of CsPbBr3 Single Crystals and Au/
CsPbBr3/Au MSM-Structured PDs. The CsPbBr3 single
crystals were grown using a modified one-step solution growth
method. First, a precursor solution was prepared by dissolving
2.4 mmol PbBr2 and 1.2 mmol CsBr into 3 mL of anhydrous
dimethyl sulfoxide (DMSO). Then, the precursor solution was
filtered and heated at 140 °C in a silicone oil bath in sequence
(Figure S1, Supporting Information). The growth process
lasted ∼5 days. Finally, the as-grown CsPbBr3 single crystals
were washed by anhydrous DMF and dried in a vacuum for 2 h
in sequence and stored in a vacuum before they were further
characterized. The Au/CsPbBr3/Au MSM-structured PDs
were prepared by depositing interdigitated Au electrodes on
CsPbBr3 single crystals using a sputtering method with the
assistance of a mask. All experiments were carried out under
ambient conditions.
2.3. Characterization. The structural and optical proper-
ties of CsPbBr3 single crystals were studied by XRD (Bruker
D8 Advance diffractometer) and micro-PL spectroscopy. The
10008
pubs.acs.org/JPCC Article
steady-state PL spectroscopy was excited by a cw 405 nm laser.
The transient PL was excited by a 150 fs pulsed 400 nm laser.
The photoelectric properties of the Au/CsPbBr3/Au MSM-
structured PDs were studied by a photo response system
consisting of a Xe lamp (150 W), a monochromator, two
probers, an electronic shutter, and a Keithley 2401 source-
measure unit.
2.4. Calculation of Ion Migration. The first-principles
calculations were based on the DFT method using the Vienna
ab initio simulation package (VASP) within the projected
augmented wave (PAW) method and Perdew−Burke−
Ernzerhof revised for the solid (PBEsol) exchange-correlation
functional. According to ref 21, the PBEsol obtains accurate
migration barriers. The structure models were constructed by
using a 160-atom supercell consisting of 2 × 2 × 2
orthorhombic unit cells (Figure S2, Supporting Information).
The cutoff energy for the plane-wave basis set was 500 eV. K-
Points were sampled at the Γ-point. For structure relaxation,
forces were converged to 0.01 eV/Å. Vacancy-assisted ion
migration was investigated using climbing-image nudged
elastic band and constrained energy minimization methods.
Herein, only ionized vacancy defects (VBr+, VCs−, and VPb2−)
were considered in the calculation. The migration barrier
heights (i.e., activation energies) for proposed diffusion
processes were obtained from the total energy difference
between the diffusing species in their ground-state config-
uration and at the saddle point of the diffusion process.
3. RESULTS AND DISCUSSION
3.1. Evidence for Ion Migration in All-Inorganic
Perovskite CsPbBr3 Single Crystals. The all-inorganic
perovskite CsPbBr3 single crystals were prepared using a
modified low-temperature one-step solution growth method
according to a previous report (see Methods),17 where the
CsPbBr3 single crystals (Figure 1a inset) were obtained by
Figure 1. Typical features of as-grown CsPbBr3 single crystals. (a)
XRD pattern. (b) PL spectra. The inset in panel (a) is an optical
image of an as-grown CsPbBr3 single crystal. Scale bar: 5 mm. The
inset in panel (b) is a transient PL spectrum.
heating the precursor solution in an oil bath at 140 °C (Figure
S1, Supporting Information). It showed that the oil bath
heating was critical for the improvement of crystalline quality
and reduction of trap states (ntrap ∼ 5.1 × 109 cm−3) in the as-
grown CsPbBr3 single crystals.17 Figure 1a depicts the typical
X-ray diffraction (XRD) pattern of the as-grown CsPbBr3
single crystal. As shown, the XRD pattern is dominated by
the set of (0 0 l)/(h h 0) crystalline plane of orthorhombic
CsPbBr3. It is worth noting that the full width at half
maximums (FWHMs) of (002) and (004) XRD peaks are as
narrow as ∼0.09° (324 arcsec) and 0.13° (468 arcsec),
respectively (Figure S3, Supporting Information), showing an
https://doi.org/10.1021/acs.jpcc.2c03175
J. Phys. Chem. C 2022, 126, 10007−10013
The Journal of Physical Chemistry C
Figure 2. Electrical properties of Au/CsPbBr3/Au MSM-structured PD. (a,b) I−V curves. (c) Current at different I−V scan cycles extracted from
(a). (d) Degree of I−V hysteresis at different I−V scan cycles. The degree of I−V hysteresis is defined as H = IBackword/IForword. The inset in (a) is
the optical image of the Au/CsPbBr3/Au MSM-structured PD. The area of the PD is ∼0.38 mm2. The red line in (d) is a guide to the eye. The I−V
data were obtained in dark.
improved crystalline quality of the as-grown CsPbBr3 single
crystal. It is emphasized that our CsPbBr3 single crystals have a
higher crystalline quality compared to perovskite single crystals
reported before.31−33 Figure 1b shows the room-temperature
(RT) steady-state and transient photoluminescence (PL)
spectra of the CsPbBr3 single crystal. As shown, the RT PL
spectrum is centered at 532.5 nm (2.329 eV) with a narrow
FWHM of 18.2 nm (82.5 meV). In addition, the PL decay
curve can be well fitted with a bi-exponential function (Figure
1b inset), which yields the average PL lifetimes (τ̅) as long as
5.16 ns (Figure S4, Supporting Information). The above
results suggest that the as-grown CsPbBr3 single crystals
possess a high crystalline quality.
Figure 2a,b show the I−V curve loops of a typical Au/
CsPbBr3/Au MSM-structured PD (Figure 2a inset) at different
I−V scan cycles recorded under dark conditions. The voltage
range is [0 V, 5 V] with a scan rate of 0.855 V/s. Besides, an I−
V scan cycle was accomplished with the bias voltage starting
from 0 to 5 V and then back to 0 V. Meanwhile, the forward I−
V scan (labeled as “ ” in Figure 2a) is defined as the scan
starting from 0 to 5 V, and vice versa. The time delay between
two scan cycles is less than 0.2 s. As shown in Figure 2a, the I−
V curve loop exhibits a neglected hysteresis within the first
scan cycle. However, the I−V hysteresis becomes much more
noticeable with the increase of scan cycles (Figure 2b). Similar
to the case in the LHP-based solar cells, the backward I−V
scan shows a higher dark current than the forward one.34 It is
worth noting that the dark current shows a rapid increase
within the first 20 scan cycles but appears to saturate when
further increasing the I−V scan cycle (Figure 2c). Quantita-
tively, the degree of I−V hysteresis (H) is introduced as
follows: H = IBackword/IForword, in which IForword and IBackword are
10009
pubs.acs.org/JPCC Article
the dark current recorded under the forward and backward I−
V scan, respectively, to show the I−V hysteresis at different
scan cycles. The degree of I−V hysteresis (H) under the bias
voltage of 4 V is shown in Figure 2d. As can be seen, the
degree of I−V hysteresis shows a similar trend of evolution
with the dark current, which may suggest a potential
correlation between the dark current and I−V hysteresis.
The origin of I−V hysteresis behaviors is still under debate.
However, experimental and theoretical studies have shown that
the I−V hysteresis behaviors shown above are attributed to the
energy band bending of CsPbBr3, which may be caused by the
electric field poling induced ion migration and/or ferroelectric
polarization.35,36 In the former case, the energy band bending
is related to the accumulation of charged ions at the Au/
CsPbBr3 interface, while in the latter case, the energy band
bending is related to the remanent polarization. Herein, the
ferroelectric polarization of CsPbBr3 would be ruled out
because of the following reasons: first, the ferroelectric
polarization cannot be supported by the neglected I−V
hysteresis in the first scan cycle (Figure 2a) because the
response time of ferroelectric domain switching is as short as
∼0.1−1.0 ms scale,37 much faster than the time scale of I−V
hysteresis shown in Figure 2a,b. Meanwhile, no ferroelectric
polarization effects have been observed in the CsPbBr3 single
crystal (Figure S5, Supporting Information). As a result, the
energy band bending is reasonably attributed to the electric
field poling-induced ion migration, and the above I−V
hysteresis results (Figure 2) can be understood as follows.
Without prepoling treatment, the CsPbBr3 single crystal can be
regarded as a photoconductor (Figure 3a). Therefore, the dark
current is low in the forward I−V scan direction within the first
scan cycle because of the high crystalline quality and low
https://doi.org/10.1021/acs.jpcc.2c03175
J. Phys. Chem. C 2022, 126, 10007−10013
The Journal of Physical Chemistry C
Figure 3. Schemes of energy band diagrams of CsPbBr3 after (a)
without poling, (b) short-term poling, (c) long-term poling, (d) low-
voltage poling, and (e) high-voltage poling. The poling electric field is
denoted as “Eout”.
defects of the CsPbBr3 single crystal. However, charged species
(Cs+, Pb2+, and Br−) migrate under the positive poling voltages
(i.e., I−V scan with a positive bias voltage) with the positive
species (Cs+ and Pb2+) toward the cathode and the negative
ones (Br−) toward the anode, as schematically shown in Figure
3b. Because of unintentional doping effects, a pn-like junction
forms between the two Au electrodes.38 In detail, to keep the
material electrically neutral, the accumulated positively charged
ions should attract equivalent electrons, and therefore, n-
doping-like region forms at one end of CsPbBr3 near the
cathode and the band downward bends simultaneously (shown
by the red shaded area in Figure 3b). Similarly, the p-doping-
like region (shown by the blue shaded area in Figure 3b) forms
accompanied by an upward band bending at the other end of
CsPbBr3 near the anode. In addition, the n- and p-doping level
increases with the period of electric field poling (i.e., in the
long-term poling process, Figure 3c). It should be noted that
the pn-junction is forward-biased both in the forward and
backward I−V scan directions. As a result, I−V hysteresis with
a higher dark current under the backward I−V scan is observed
(Figure 2b). Meanwhile, the dark current increases with the
increase in I−V scan cycles, as shown in Figure 2d. However,
because of the limited available charged species, the ion
migration will be weakened when further increasing the scan
cycles, which slows down the evolution of dark current (Figure
2c) and I−V hysteresis (Figure 2d).
The formation of the pn-junction within the CsPbBr3 single
crystal after electric field poling was further verified by the
photovoltaic effects. Figure 4 shows the I−V curves of a fresh
Au/CsPbBr3/Au MSM-structured PDs captured under 540 nm
illumination after various electric field poling treatments. The
electric field poling was conducted under a positive bias voltage
of 0, 1, 2, 3, 4, and 5 V in dark with a poling time of 60 s. To
minimize the electric field poling effects during the I−V scan,
the voltage range is [0 V, 1 V]. As can be seen, typical
photovoltaic effects with noticeable short-circuit current (JSC)
and open-circuit voltage (VOP) can be observed after the
electric field poling treatment. This can be an indication of the
formation of the pn-junction within the CsPbBr3 single crystal.
It is worth noting that both the open-circuit voltage and short-
circuit current increase with the increase in the poling voltage
10010
pubs.acs.org/JPCC Article
Figure 4. I−V curves of Au/CsPbBr3/Au MSM-structured PD after
electric field poling treatment. The poling voltage is 0, 1, 2, 3, 4, and 5
V. The I−V curves were captured under 540 nm illumination with a
power of ∼50 nW.
(Figure 4), which further verifies the formation of the pn-
junction. Briefly, when increasing the poling voltage, more
charged ions accumulate at the Au/CsPbBr3 interface (Figure
3d,e), and therefore, more holes and electrons accumulate at
the ends of CsPbBr3 simultaneously because of the uninten-
tional doping effects. In other words, the corresponding n- and
p-doping level increases with the poling voltage. This leads to
an increased open-circuit voltage and short-circuit current
accordingly.
3.2. DFT Calculations on Ion Migration. To gain deep
insights into the ion transportation mechanism in the CsPbBr3
single crystal, the barrier heights (i.e., activation energy) for Cs,
Pb, and Br ions migration have been investigated using first-
principles calculations (see Methods). Owing to the single-
crystalline nature, the contributions of grain boundaries to ion
migration can be neglected. Herein, our theoretical calculations
were focused on vacancy transport involving Cs, Pb, and I
vacancy hopping between neighboring positions.21 The
minimum energy path and corresponding barrier height for
the Cs, Pb, and I ion transportation are illustrated in Figure
5a,b, respectively. As shown in Figure 5b, the obtained lowest
Figure 5. Mechanism of ion transportation in CsPbBr3. (a) Ion
transportation path. (b) Energy profile. Paths 1, 2, and 3 correspond
to Br, Cs, and Pb vacancy hopping processes.
migration barrier height is as low as 0.286 eV for Br vacancy
hopping, suggesting a significant vacancy-assisted Br-ion
migration in CsPbBr3. In contrast, higher migration barrier
heights of 0.692 and 1.663 eV are obtained for Cs and Pb ion
migration, respectively. The above results (Figure 5) suggest
that vacancy-assisted Br-ion migration dominates the ion
transportation processes in the all-inorganic CsPbBr3 single
crystal. Our results are consistent with previous calculations on
organic−inorganic hybrid perovskite MAPbI3, where vacancy-
https://doi.org/10.1021/acs.jpcc.2c03175
J. Phys. Chem. C 2022, 126, 10007−10013
The Journal of Physical Chemistry C
Figure 6. Photoelectric properties of Au/CsPbBr3/Au MSM-structured PD. (a) I−t curve recorded with incident light switched on and off. The red
dashed line is a guide to the eye. The inset shows the I−t curve in the first pulse. (b) On−off ratio, (c) responsivity, (d) detectivity at the rising
edge and falling edge. The responsivity (R) and detectivity (D) are obtained from followed equations: R =
where Iphoto is photocurrent, Idark is dark current, P is incident light power (∼50 nW), e is the electron charge, and S is the area of the PD (0.38 mm2
from Figure 2a inset).
assisted I ion migration dominates the ion transportation
processes.21 It is worth noting that the calculated migration
barrier height for Br ions in CsPbBr3 is lower than that for I
ions in MAPbI3 (0.58 eV), which may suggest a more
pronounced accumulation of charged ions and I−V hysteresis
in the CsPbBr3-based optoelectronic devices. Still, additional
studies are needed to further clarify the ion transportation
mechanism in the CsPbBr3 single crystal.
3.3. Impacts of Ion Migration on Photodetection.
Figure 6a shows the time-resolved photocurrent (I−t) of a
fresh Au/CsPbBr3/Au MSM-structured PD (Figure 2a inset)
captured with the incident light switched on and off under the
bias voltage of 3 V. As can be seen, the PD exhibits an efficient
photoresponse to visible light. Specifically, the on−off ratio,
which is defined as the ratio of photocurrent (defined as the
current captured under illumination) to dark current, is ∼55
under the 540 nm illumination with a power of ∼50 nW
(Figure 6b). As reported before, the efficient photoresponse of
the MSM-structured PDs is mainly associated with the high
optical absorption coefficient and efficient charge carrier
transport of the all-inorganic CsPbBr3.12,39 However, the
MSM-structured PD shows a poor stability. In detail, the dark
current rapidly increases with the increase in the pulse number
(a pulse means a cycle of switching on and off the incident
light, as shown in Figure 6a inset), as shown in Figures 6a and
S6 (Supporting Information).
As discussed above, the increased dark current with the
pulse number can be attributed to the ion migration-induced
formation of the pn-junction. It should be noted that both the
10011
pubs.acs.org/JPCC Article
Iphoto − Idark R
P
,D= , respectively,
2eIdark / S
photocurrent and net photocurrent (defined as the difference
between the photocurrent and dark current) slightly increase
with the pulse number (Figure S6, Supporting Information),
which suggests the enhancement of photoresponsivity (defined
as the ratio between the net photocurrent and incident light
power) when ion migration occurs (Figure 6c). However,
owing to the rapid increase in the dark current, both the on−
off ratio and detectivity of the MSM-structured PD
substantially decreases (Figure 6b,d), which should limit the
application of the MSM-structured PD. It is well known that
the photoresponsivity is associated with the photo-to-electric
conversion efficiency, while the detectivity is mainly
determined by the background noise current (which generally
equals to dark current in the radiation photodetector) of the
PDs. A high detectivity rather than high photoresponsivity is
critical to weak light detection.40,41 As a result, strategies for
suppressing the ion migration in the all-inorganic CsPbBr3 are
urgently explored to meet diverse application requirements of
PDs.
Interestingly, the response speed of the MSM-structured PD
seems to be improved when ion migration has occurred
(Figure S7, Supporting Information). Besides, transient
photocurrent peaks (highlighted by solid squares, as shown
in Figure 6a) have been observed when switching on and off
the incident light at a high pulse number. Herein, the transient
photocurrent peaks are believed to be associated with the trap-
state-related transient carrier accumulation and recombination
near the CsPbBr3/Au interface,42 which is owing to the defect
proliferation at the interface after a long-term electric field
https://doi.org/10.1021/acs.jpcc.2c03175
J. Phys. Chem. C 2022, 126, 10007−10013
The Journal of Physical Chemistry C
poling treatment.35 Such a phenomenon may further verify the
electric field-induced ion migration within the CsPbBr3 single
crystal.
4. CONCLUSIONS
In conclusion, electric field poling-induced ion migration has
been demonstrated in the all-inorganic CsPbBr3 single crystals.
DFT calculations have shown that vacancy-assisted Br-ion
migration dominated the ion transportation processes.
Electrical property investigations on Au/CsPbBr3/Au MSM-
structured PDs have shown that a pn-junction was formed
within the CsPbBr3, which was attributed to the accumulation
of charged ions at the Au/CsPbBr3 interface. Furthermore, the
formation of the pn-junction has shown negative impacts on
the photodetection in terms of a decreased on−off ratio and
decreased detectivity, although the photoresponsivity slightly
increased. The results reported in this work further verify the
negative effects of ion migration in the all-inorganic perovskite
CsPbBr3, which may account for the instability of CsPbBr3-
based optoelectronic devices reported in the literature.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.2c03175.
Growth setup, 160-atom supercell of orthorhombic
CsPbBr3 and minimum energy path of ion migration,
FWHMs of the XRD pattern, fitting of TRPL,
polarization-electric field hysteresis loop of CsPbBr3,
dark current and photocurrent, and response speed of
Au/CsPbBr3/Au MSM-structured PDs (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Mingming Chen − Guangdong-Hong Kong-Macao Joint
Laboratory for Intelligent Micro-Nano Optoelectronic
Technology and School of Physics and Optoelectronic
Engineering, Foshan University, Foshan, Guangdong 528225,
People’s Republic of China; Department of Microelectronics,
Jiangsu University, Zhenjiang, Jiangsu 212013, People’s
Republic of China; orcid.org/0000-0002-5352-8189;
Email: andychain@live.cn
Dawei Cao − Department of Microelectronics, Jiangsu
University, Zhenjiang, Jiangsu 212013, People’s Republic of
China; orcid.org/0000-0002-3134-3001;
Email: dwcao@ujs.edu.cn
Authors
Jing Cai − Guangdong-Hong Kong-Macao Joint Laboratory
for Intelligent Micro-Nano Optoelectronic Technology and
School of Physics and Optoelectronic Engineering, Foshan
University, Foshan, Guangdong 528225, People’s Republic of
China
Tong Zhao − Department of Microelectronics, Jiangsu
University, Zhenjiang, Jiangsu 212013, People’s Republic of
China
Jiayun Su − Guangdong-Hong Kong-Macao Joint Laboratory
for Intelligent Micro-Nano Optoelectronic Technology and
School of Physics and Optoelectronic Engineering, Foshan
University, Foshan, Guangdong 528225, People’s Republic of
China
10012
pubs.acs.org/JPCC Article
Xuemin Shen − Department of Microelectronics, Jiangsu
University, Zhenjiang, Jiangsu 212013, People’s Republic of
China
Yuan Liu − Department of Microelectronics, Jiangsu University,
Zhenjiang, Jiangsu 212013, People’s Republic of China;
orcid.org/0000-0002-5933-5281
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.2c03175
Author Contributions
∥
J.C. and T.Z. contributed equally to this work.
Notes
The authors declare no competing financial interest.
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
■ ACKNOWLEDGMENTS
This work was financially supported by the Research Fund of
Guangdong-Hong Kong-Macao Joint Laboratory for Intelli-
gent Micro-Nano Optoelectronic Technology (No.
2020B1212030010) and the Project of Faculty of Agricultural
Equipment of Jiangsu University (NZXB20210202,
NZXB20200215). D. C. appreciates support from the Jiangsu
Specially Appointed Professor Program.
■
REFERENCES
(1) Brenner, T. M.; Egger, D. A.; Kronik, L.; Hodes, G.; Cahen, D.
Hybrid organicinorganic perovskites: low-cost semiconductors with
intriguing charge-transport properties. Nat. Rev. Mater. 2016, 1,
15007.
(2) Zhou, H.; Chen, Q.; Li, G.; Luo, S.; Song, T.; Duan, H.; Hong,
Z.; You, J.; Liu, Y.; Yang, Y. Interface engineering of highly efficient
perovskite solar cells. Science 2014, 345, 542−546.
(3) Jeong, M.; Choi In, W.; Go Eun, M.; Cho, Y.; Kim, M.; Lee, B.;
Jeong, S.; Jo, Y.; Choi Hye, W.; Lee, J.; et al. Stable perovskite solar
cells with efficiency exceeding 24.8% and 0.3-V voltage loss. Science
2020, 369, 1615−1620.
(4) Yoo, J. J.; Seo, G.; Chua, M. R.; Park, T. G.; Lu, Y.; Rotermund,
F.; Kim, Y. K.; Moon, C. S.; Jeon, N. J.; Correa-Baena, J. P.; et al.
Efficient perovskite solar cells via improved carrier management.
Nature 2021, 590, 587−593.
(5) Min, H.; Lee, D. Y.; Kim, J.; Kim, G.; Lee, K. S.; Kim, J.; Paik, M.
J.; Kim, Y. K.; Kim, K. S.; Kim, M. G.; et al. Perovskite solar cells with
atomically coherent interlayers on SnO2 electrodes. Nature 2021,
598, 444−450.
(6) Liu, P.; Han, N.; Wang, W.; Ran, R.; Zhou, W.; Shao, Z. High-
Quality Ruddlesden−Popper Perovskite Film Formation for High-
Performance Perovskite Solar Cells. Adv. Mater. 2021, 33,
No. 2002582.
(7) Kim, M.; Jeong, J.; Lu, H.; Lee Tae, K.; Eickemeyer Felix, T.;
Liu, Y.; Choi In, W.; Choi Seung, J.; Jo, Y.; Kim, H. B.; et al.
Conformal quantum dot−SnO2 layers as electron transporters for
efficient perovskite solar cells. Science 2022, 375, 302−306.
(8) Nayak, P. K.; Mahesh, S.; Snaith, H. J.; Cahen, D. Photovoltaic
solar cell technologies: analysing the state of the art. Nat. Rev. Mater.
2019, 4, 269−285.
(9) Eze, V. O.; Adams, G. R.; Braga Carani, L.; Simpson, R. J.; Okoli,
O. I. Enhanced Inorganic CsPbIBr2 Perovskite Film for a Sensitive
and Rapid Response Self-Powered Photodetector. J. Phys. Chem. C
2020, 124, 20643−20653.
(10) Zeng, J.; Zhou, H.; Liu, R.; Wang, H. Combination of solution-
phase process and halide exchange for all-inorganic, highly stable
CsPbBr3 perovskite nanowire photodetector. Sci. China Mater. 2019,
62, 65−73.
(11) Zhou, H.; Zeng, J.; Song, Z.; Grice, C. R.; Chen, C.; Song, Z.;
Zhao, D.; Wang, H.; Yan, Y. Self-Powered All-Inorganic Perovskite
https://doi.org/10.1021/acs.jpcc.2c03175
J. Phys. Chem. C 2022, 126, 10007−10013
The Journal of Physical Chemistry C
Microcrystal Photodetectors with High Detectivity. J. Phys. Chem.
Lett. 2018, 9, 2043−2048.
(12) Yuan, Y.; Chen, M.; Yang, S.; Shen, X.; Liu, Y.; Cao, D.; Xing,
G.; Tang, Z. Improved CsPbBr3 visible light photodetectors via
decoration of sputtered au nanoparticles with synergistic benefits.
Nano Sel. 2022, 3, 178−187.
(13) Solanki, A.; Lim, S. S.; Mhaisalkar, S.; Sum, T. C. Role of Water
in Suppressing Recombination Pathways in CH3NH3PbI3 Perovskite
Solar Cells. ACS Appl. Mater. Interfaces 2019, 11, 25474−25482.
(14) Srimath Kandada, A. R.; Neutzner, S.; D’Innocenzo, V.;
Tassone, F.; Gandini, M.; Akkerman, Q. A.; Prato, M.; Manna, L.;
Petrozza, A.; Lanzani, G. Nonlinear Carrier Interactions in Lead
Halide Perovskites and the Role of Defects. J. Am. Chem. Soc. 2016,
138, 13604−13611.
(15) Jin, H.; Debroye, E.; Keshavarz, M.; Scheblykin, I. G.;
Roeffaers, M. B. J.; Hofkens, J.; Steele, J. A. It’s a trap! On the
nature of localised states and charge trapping in lead halide
perovskites. Mater. Horiz. 2020, 7, 397−410.
(16) Guo, J.; Liu, T.; Li, M.; Liang, C.; Wang, K.; Hong, G.; Tang,
Y.; Long, G.; Yu, S.; Lee, T.; et al. Ultrashort laser pulse doubling by
metal-halide perovskite multiple quantum wells. Nat. Commun. 2020,
11, 3361.
(17) Chen, M.; Yuan, Y.; Liu, Y.; Cao, D.; Xu, C. High-quality all-
inorganic CsPbBr3 single crystals prepared by a facile one-step
solution growth method. RSC Adv. 2022, 12, 14838−14843.
(18) Unger, E. L.; Hoke, E. T.; Bailie, C. D.; Nguyen, W. H.;
Bowring, A. R.; Heumüller, T.; Christoforo, M. G.; McGehee, M. D.
Hysteresis and transient behavior in current−voltage measurements of
hybrid-perovskite absorber solar cells. Energy Environ. Sci. 2014, 7,
3690−3698.
(19) Lan, D. The physics of ion migration in perovskite solar cells:
Insights into hysteresis, device performance, and characterization.
Prog. Photovoltaics 2020, 28, 533−537.
(20) Kumar, A. Numerical modelling of ion-migration caused
hysteresis in perovskite solar cells. Opt. Quantum Electron. 2021, 53,
166.
(21) Eames, C.; Frost, J. M.; Barnes, P. R. F.; O’Regan, B. C.; Walsh,
A.; Islam, M. S. Ionic transport in hybrid lead iodide perovskite solar
cells. Nat. Commun. 2015, 6, 7497.
(22) Zhao, Y. C.; Zhou, W. K.; Zhou, X.; Liu, K. H.; Yu, D. P.; Zhao,
Q. Quantification of light-enhanced ionic transport in lead iodide
perovskite thin films and its solar cell applications. Light: Sci. Appl.
2017, 6, e16243−e16243.
(23) Calado, P.; Telford, A. M.; Bryant, D.; Li, X.; Nelson, J.;
O’Regan, B. C.; Barnes, P. R. F. Evidence for ion migration in hybrid
perovskite solar cells with minimal hysteresis. Nat. Commun. 2016, 7,
13831.
(24) Yun, J. S.; Seidel, J.; Kim, J.; Soufiani, A. M.; Huang, S.; Lau, J.;
Jeon, N. J.; Seok, S.; Green, M. A.; Ho-Baillie, A. Critical Role of
Grain Boundaries for Ion Migration in Formamidinium and
Methylammonium Lead Halide Perovskite Solar Cells. Adv. Energy
Mater. 2016, 6, No. 1600330.
(25) Shao, Y.; Fang, Y.; Li, T.; Wang, Q.; Dong, Q.; Deng, Y.; Yuan,
Y.; Wei, H.; Wang, M.; Gruverman, A.; et al. Grain boundary
dominated ion migration in polycrystalline organic−inorganic halide
perovskite films. Energy Environ. Sci. 2016, 9, 1752−1759.
(26) Jing, H.; Peng, R.; Ma, R. M.; He, J.; Zhou, Y.; Yang, Z.; Li, C.
Y.; Liu, Y.; Guo, X.; Zhu, Y.; et al. Flexible Ultrathin Single-Crystalline
Perovskite Photodetector. Nano Lett. 2020, 20, 7144−7151.
(27) Yang, S.; Chen, M.; Shen, X.; Yuan, Y.; Liu, Y.; Wang, Q.; Cao,
D. Self-powered narrowband visible-light photodetection enabled by
organolead halide perovskite CH3NH3PbBr3/p-Si heterojunction.
Appl. Phys. Lett. 2021, 119, 121107.
(28) Liu, D.; Yu, B. B.; Liao, M.; Jin, Z.; Zhou, L.; Zhang, X.; Wang,
F.; He, H.; Gatti, T.; He, Z. Self-Powered and Broadband Lead-Free
Inorganic Perovskite Photodetector with High Stability. ACS Appl.
Mater. Interfaces 2020, 12, 30530−30537.
(29) Shen, X.; Yang, S.; Chen, M.; Su, J.; Cai, J.; Cheng, P.; Liu, Y.;
Wang, Q.; Cao, D. Interfacial Engineering with Aluminum Oxide
10013
pubs.acs.org/JPCC Article
toward an Improved Self-Powered Narrowband Visible-Light Photo-
detection in Lead Halide Perovskite CH3NH3PbBr3/p-Si Hetero-
junctions. Adv. Mater. Interfaces 2022, 9, No. 2102305.
(30) Vashishtha, P.; Halpert, J. E. Field-Driven Ion Migration and
Color Instability in Red-Emitting Mixed Halide Perovskite Nano-
crystal Light-Emitting Diodes. Chem. Mater. 2017, 29, 5965−5973.
(31) Rakita, Y.; Kedem, N.; Gupta, S.; Sadhanala, A.; Kalchenko, V.;
Böhm, M. L.; Kulbak, M.; Friend, R. H.; Cahen, D.; Hodes, G. Low-
Temperature Solution-Grown CsPbBr3 Single Crystals and Their
Characterization. Cryst. Growth Des. 2016, 16, 5717−5725.
(32) Zhang, M.; Zheng, Z.; Fu, Q.; Chen, Z.; He, J.; Zhang, S.;
Chen, C.; Luo, W. Synthesis and single crystal growth of perovskite
semiconductor CsPbBr3. J. Cryst. Growth 2018, 484, 37−42.
(33) Zhang, M.; Zheng, Z.; Fu, Q.; Chen, Z.; He, J.; Zhang, S.; Yan,
L.; Hu, Y.; Luo, W. Growth and characterization of all-inorganic lead
halide perovskite semiconductor CsPbBr3 single crystals. CrystEng-
Comm 2017, 19, 6797−6803.
(34) Snaith, H. J.; Abate, A.; Ball, J. M.; Eperon, G. E.; Leijtens, T.;
Noel, N. K.; Stranks, S. D.; Wang, J. T.; Wojciechowski, K.; Zhang, W.
Anomalous Hysteresis in Perovskite Solar Cells. J. Phys. Chem. Lett.
2014, 5, 1511−1515.
(35) Zhang, B. B.; Wang, F.; Zhang, H.; Xiao, B.; Sun, Q.; Guo, J.;
Hafsia, A. B.; Shao, A.; Xu, Y.; Zhou, J. Defect proliferation in
CsPbBr3 crystal induced by ion migration. Appl. Phys. Lett. 2020, 116,
No. 063505.
(36) Frost, J. M.; Butler, K. T.; Brivio, F.; Hendon, C. H.; van
Schilfgaarde, M.; Walsh, A. Atomistic Origins of High-Performance in
Hybrid Halide Perovskite Solar Cells. Nano Lett. 2014, 14, 2584−
2590.
(37) Leguy, A. M. A.; Frost, J. M.; McMahon, A. P.; Sakai, V. G.;
Kockelmann, W.; Law, C.; Li, X.; Foglia, F.; Walsh, A.; O’Regan, B.
C.; et al. The dynamics of methylammonium ions in hybrid organic−
inorganic perovskite solar cells. Nat. Commun. 2015, 6, 7124.
(38) Wu, D.; Li, W.; Liu, H.; Xiao, X.; Shi, K.; Tang, H.; Shan, C.;
Wang, K.; Sun, X. W.; Kyaw, A. K. K. Universal Strategy for
Improving Perovskite Photodiode Performance: Interfacial Built-In
Electric Field Manipulated by Unintentional Doping. Adv. Sci. 2021,
8, No. 2101729.
(39) Zeng, J.; Li, X.; Wu, Y.; Yang, D.; Sun, Z.; Song, Z.; Wang, H.;
Zeng, H. Space-Confined Growth of CsPbBr3 Film Achieving
Photodetectors with High Performance in All Figures of Merit. Adv.
Funct. Mater. 2018, 28, No. 1804394.
(40) Fang, Y.; Armin, A.; Meredith, P.; Huang, J. Accurate
characterization of next-generation thin-film photodetectors. Nat.
Photonics 2019, 13, 1−4.
(41) Zhou, Y.; Zhao, L.; Ni, Z.; Xu, S.; Zhao, J.; Xiao, X.; Huang, J.
Heterojunction structures for reduced noise in large-area and sensitive
perovskite x-ray detectors. Sci. Adv. 2021, 7, No. eabg6716.
(42) Shen, X.; Chen, S.; Liu, Y.; Chen, M.; Lei, H.; Cai, J.; Su, J.;
Yang, S.; Liu, Y.; Wang, Q.; et al. Realization of self-powered
bidirectional photoresponse in the ultraviolet/visible wavelength
region in ferroelectric heterojunctions. Appl. Phys. Lett. 2022, 120,
No. 091107.
https://doi.org/10.1021/acs.jpcc.2c03175
J. Phys. Chem. C 2022, 126, 10007−10013