www.acsami.

org Research Article

PbS/CsPbBr3 Heterojunction for Broadband Neuromorphic Vision

Sensing
Kangmin Leng, Zhiqiang Guo, Junming Chen, Yao Fu, Ruihua Ma, Xuechao Yu,* Li Wang,*
and Qisheng Wang*
Cite This: ACS Appl. Mater. Interfaces 2024, 16, 7470−7479 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.
Downloaded via IISER THIRUVANANTHAPURAM on August 23, 2024 at 21:58:13 (UTC).

ABSTRACT: Neuromorphic light sensors with analogue-domain image processing capability hold promise for overcoming the
energy efficiency limitations and latency of von Neumann architecture-based vision chips. Recently, metal halide perovskites, with
strong light−matter interaction, long carrier diffusion length, and exceptional photoelectric conversion efficiencies, exhibit
reconfigurable photoresponsivity due to their intrinsic ion migration effect, which is expected to advance the development of visual
sensors. However, suffering from a large bandgap, it is challenging to achieve highly tunable responsivity simultaneously with a wide-
spectrum response in perovskites, which will significantly enhance the image recognition accuracy through the machine learning
algorithm. Herein, we demonstrate a broadband neuromorphic visual sensor from visible (Vis) to near-infrared (NIR) by coupling
all-inorganic metal halide perovskites (CsPbBr3) with narrow-bandgap lead sulfide (PbS). The PbS/CsPbBr3 heterostructure is
composed of high-quality single crystals of PbS and CsPbBr3. Interestingly, the ion migration of CsPbBr3 with the implementation of
an electric field induces the energy band dynamic bending at the interface of the PbS/CsPbBr3 heterojunction, leading to reversible,
multilevel, and linearly tunable photoresponsivity. Furthermore, the reconfigurable and broadband photoresponse in the PbS/
CsPbBr3 heterojunction allows convolutional neuronal network processing for pattern recognition and edge enhancements from the
Vis to the NIR waveband, suggesting the great potential of the PbS/CsPbBr3 heterostructure in artificial intelligent vision sensing.
KEYWORDS: reconfigurable photoresponsivity, broadband photoresponse, perovskites, ion migration, heterojunction

1. INTRODUCTION light−matter interaction, high mobility, long carrier diffusion

Optical image sensing and processing are separated in a length, and exceptional photoelectric conversion efficien-
traditional sensory computing architecture (i.e., von Neumann cies.7−11 Additionally, the intrinsic ion migration in perov-
computing). Consequently, a large amount of unstructured skites, which directly alters the local chemical ratio, is desirable
data is transferred between front-end photodetectors and back- for mimicking neurotransmitter transport in biological
end postprocessors, which leads to high latency and power synapses.12−14 Moreover, with the growing adoption of
consumption.1−4 In contrast, the superiority of the human machine vision, in which image analysis is performed by
vision system in cognitive abilities, response speed, and energy computational algorithms, a vast amount of input data is
efficiency has been well recognized for its capability of
simultaneously sensing and preprocessing visual information.5,6 Received: November 29, 2023
In this regard, photodetectors that possess the capability to Revised: January 11, 2024
mimic human vision are considered promising avenues for Accepted: January 18, 2024
analog-domain sensing and computing. Published: February 1, 2024
Metal halide perovskites have recently emerged as robust
platforms for neuromorphic vision sensors due to their strong

© 2024 American Chemical Society https://doi.org/10.1021/acsami.3c17935

7470 ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

Figure 1. Characterization of the PbS/CsPbBr3 heterostructure. (a) Cross-sectional SEM image of the heterojunction showing the CsPbBr3 and
PbS layers. Scale bar: 5 μm. (b) OM image of the CsPbBr3 (top panel) and PbS films (bottom panel) Scale bar: 10 μm. (c) Photos of the CsPbBr3
(top panel) and PbS films (bottom panel). (d) XRD patterns. (e) photoluminescence (PL) spectra of the CsPbBr3 and PbS/CsPbBr3
heterostructures under 405 nm excitation. (f) Normalized time-resolved PL decay spectra of the CsPbBr3 and PbS/CsPbBr3 heterostructures.

required to establish correlations that can facilitate object the implementation of advanced neural network vision chips in
identification and classification. Consequently, acquiring the future.
optical information across a diverse wavelength range becomes
highly advantageous.15−20 Nevertheless, the large bandgap of 2. RESULTS AND DISCUSSION
metal halide perovskite semiconductors restricts their response
range to not extend beyond visible light.21−24 Despite 2.1. Design and Characterization of the PbS/CsPbBr3
heterojunctions promising to broaden the response spectral Heterojunction. For fabricating the perovskite broadband
of perovskite, it remains a big challenge to simultaneously and responsivity tunable photodetector, one of the solutions is
achieve highly tunable photoresponsivity and wide-spectrum to design the heterojunction with suitable band alignment,
response due to lattice, energy band, and mechanism which is however extremely challenging due to lattice and
mismatch.25−32 energy band mismatch. For this purpose, we chose a large-scale
Herein, by combining the narrow bandgap (0.4 eV) and PbS single-crystalline thin film, as developed in our previous
nearly identical lattice constant (a = 5.90 Å) of PbS with work35,36 as the epitaxy layer to fabricate the PbS/CsPbBr3
CsPbBr3,33,34 we present a broadband neuromorphic vision heterostructure. More details regarding material growth are
sensor based on PbS/CsPbBr3 heterojunction, extending the shown in Materials and Methods. The PbS has the same cubic
response spectrum from Vis to near-infrared (NIR). The crystal structure as CsPbBr3, with a small lattice mismatch
migration of ions within the CsPbBr3 layer, induced by electric (∼0.5%) between the PbS (200) crystal plane and the CsPbBr3
field poling, controls the doping profile and energy band (200) crystal plane.19,37 As a result, a clean cross-section
bending at the interface. This feature allows for adjusting interface and shiny surface are obtained, as shown by the
multiple polarization states in the sensor and enables a bipolar scanning electron microscope (SEM) image in Figure 1a and
self-powered photoresponse. The device also demonstrates the optical microscopy (OM) image in Figure 1 b with the
reversible and multilevel photoresponsivity by modulating the centimeter-scale (5 × 5 mm) area (Figure 1c). The X-ray
electric field. Inspired by the neural networks in the human diffraction (XRD) (Figure 1d) shows distinct peaks at (200)
retina, we show that a neuromorphic vision sensor can be and (400) crystal planes for both SrTiO3/PbS and SrTiO3/
trained for pattern recognition. Furthermore, the sensor’s PbS/CsPbBr3, which further demonstrates the perfectly
broad linear voltage-dependennt photoresponsivity enables matched crystal orientation along the (200) crystal planes for
simultaneous image sensing and edge enhancement using the heterostructure.13,26,38,39 The excellent crystalline quality of
different kernels. This study provides new insights into metal- PbS and CsPbBr3 without any additional phase is critical for
halide perovskite broadband neuromorphic vision sensors for photoexcited carrier transport at the interface.
7471 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

Figure 2. Polarization switching behavior and broadband photoresponse in the PbS/CsPbBr3 heterostructure. (a) Schematic of the device
structure. (b) Typical I−V scan hysteresis. I−V characteristics measured after applying different negative pulses (c) and positive pulses (d) to the
device initialized by +6 V and −6 V preset bias, respectively. (e) Illuminated I−V characteristics of the heterostructure device under different
wavelengths (520, 780, and 980 nm). (f) Illuminated I−V characteristics measured after applying different negative pulses and positive pulses to the
device with λ = 780 nm.

Next, we demonstrate PL spectral analyses to investigate the the distinct bandgaps of the components enables the structure
interfacial charge dynamics behavior of the heterostructure. to be a promising candidate for a broadband photodetector.
Steady-state PL spectra (Figure 1e) for SrTiO3/CsPbBr3 2.2. Switchable Polarization and Broadband Photo-
exhibit two emission bands at 527 and 540 nm, partially response. To investigate the electrical properties of the
contributed by a surface/defect-related excitation state derived vertically stacked PbS/CsPbBr3 heterostructure, an individual
from a large lattice mismatch with the SrTiO3 substrate.13,40−43 image sensor with a simple two-terminal structure, as
In comparison, the emission peak of the SrTiO3/PbS/CsPbBr3 schematically illustrated in Figure 2a, was fabricated (see
heterostructure at 527 nm is less intense, about ten times that Methods for more details about the fabrication process). A
of SrTiO3/CsPbBr3, indicating a strong PL quenching typical hysteresis loop as a function of voltage under dark
occurred in the PbS/CsPbBr3 heterostructure. In addition, conditions is shown in Figure 2b. As indicated by the green
the only presence of a single emission peak (Figure S1, dashed arrow, the logarithmic scale of the backward current−
Supporting Information) of SrTiO3/PbS/CsPbBr3 at 527 nm voltage (I−V) scan (blue line) exhibits a lower dark current at
(corresponding to the band edge emission of the CsPbBr3 zero bias compared to the forward scan (red line). The
layer) further confirms defects-related excitation at 540 nm and evolution of dark current suggests a potential correlation
the negligible defect density in SrTiO3/PbS/CsPbBr3. To between dark current and voltage polarity, as reported by
elucidate the origin of PL quenching, time-resolved emission previous research. This can be ascribed to the inherent ion
spectra for both heterostructures are shown in Figure 1f, which migration in CsPbBr3 perovskite after electric field poling,
exhibits a nonradiative recombination time constant (10.3 ns) leading to a remanent polarization.12,13,44 Accordingly, it can
for SrTiO3/CsPbBr3 and a significantly decreased value (0.8 be speculated that the dark current is also influenced by the
ns) for SrTiO3/PbS/CsPbBr3. As a result, the heterojunction voltage amplitude, potentially resulting in multiple intermedi-
formed by adding a PbS layer accelerates the PL decay of ate polarization states. To verify this, monopolar triangular
CsPbBr3, which could be related to the interfacial charge pulses with varying amplitudes were applied to modulate the
transfer from CsPbBr3 to PbS for the built-in electric field, polarization states. It is important to note that prior to applying
hindering the recombination of photoexcited electron−hole each monopolar pulse, a preset bias of +6 or −6 V was applied
pairs. Furthermore, with the application of an external electric to establish the polarization in the down (Pdown) or up (Pup)
field, the transfer of photogenerated electrons and holes can be state, respectively. As illustrated in Figure 2c,d, I−V scans were
regulated and result in multilevel and bipolar photovoltaic performed from −0.4 to +0.4 V in each polarization state. It
responses, which will be discussed later. The result mentioned can be observed that the dark current undergoes significant
above indicates the active interfacial charge transfer involved in changes across different polarization states. As mentioned
the construction of the heterojunction. Combining this with above, the ion migration occurred in the CsPbBr3 perovskite
7472 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

Figure 3. Switching mechanism and broadband neuromorphic sensing of the PbS/CsPbBr3 heterostructure device. Schematic crystal structure and
energy band diagrams of the heterojunction after positive poling (a) and negative poling (b). (c) Extracted photoresponsivity varies for 520, 780,
and 980 nm, with applied voltages ranging from −6 to 6 V, and demonstrates a linear dependence. (d) Duration-tunable positive and negative
photoresponse under illumination at 520, 780, and 980 nm. (e) One-cycle LTD and LTP characteristics, where the photoresponsivity represents
the synaptic weight along with the evolution of polarization during pulse application. The upper panel shows the schematics of the positive and
negative pulses applied in succession, while the preset pulse applied at the very beginning is not shown. (f) Multicycle LTD and LTP
characteristics.

layer as an external electric field was applied, leading to the positive value. This phenomenon indicates a reversal of the
variation of dark current, which derives from the potential band bending direction at the interface of the heterojunction,
barrier change at the interface of the heterojunction, which will leading to a reverse photocurrent and polarization state (Pup).
be discussed later. When starting from the same Pdown state, Additionally, there is a notable enhancement in the positive Isc
applying negative pulses ranging from 0 to −5 V leads to the as the poling voltage was increased, which suggests the
evolution of the polarization state from Pdown to Pup. This enhancement of the degree of band bending at the interface.
process reveals the existence of six distinct and well-separated Accordingly, the positive photovoltaic effect can switch back to
states, indicating the presence of multiple incomplete polar- negative after positive poling treatment, which is consistent
ization states. Likewise, by applying positive pulses ranging with the revolution of the dark current in Figure 2c,d.
from 0 to 5 V, Pup is switched back to Pdown. The Apparently, these photocurrents show almost a one-to-one
distinguishable intermediate polarization states and the correlation with the polarization states.
reversible transition between Pup and Pdown manifest the 2.3. Principle of Reconfigurable Photoresponse. To
reconfigurable electrical properties of the image sensor.45 gain deep insights into the correlation between switchable
We then proceeded to characterize the broadband photo- photoresponse and bias-induced polarization states, we now
response under irradiation at different wavelengths (520, 780, discuss the ion transportation mechanism in CsPbBr3 and the
and 980 nm), as depicted in Figure 2e. It was observed that a corresponding energy band bending at the interface. To date,
higher incident photon energy correlates with a higher experimental and theoretical studies have shown that the
response current. The negative short-circuit current (Isc) at hysteresis loop of the I−V scan shown above can be attributed
different wavelengths in linear curves (Figure S2, Supporting to the energy band bending of CsPbBr3, which may be caused
Information) indicates the inherent broadband negative by the electric field poling-induced ion migration and/or
photovoltaic effect from Vis to NIR, which derives from the ferroelectric polarization.12,13 To the best of our knowledge, no
initial band alignment at the interface of the as-fabricated ferroelectric polarization effects have been reported in the PbS
heterojunction. In other words, the negative photocurrent and CsPbBr3 single crystals; thus, the ferroelectric polarization
corresponds to the initial band alignment. Nevertheless, as can be ruled out. A detailed examination has shown that the
shown in Figure 2f, following the negative electric field poling energy band bending is related to the accumulation of charged
treatment, a change in the photovoltaic effect from negative to ions at the CsPbBr3 interface, and ion transportation can be
positive conditions was observed. Specifically, the initially ascribed to Cs, Pb, and Br vacancy hopping between
negative short-circuit current (Isc) underwent a transition to a neighboring positions. Previous studies have provided
7473 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

important information on calculations of barrier heights,13 modulate the migration direction and accumulation of Br−
where the migration barrier height of Br vacancy hopping is the ions, which influence the band bending direction at the
lowest, suggesting a significant vacancy-assisted Br− ion interface of the heterojunction. As a result, the collection of
migration in CsPbBr3, which dominates the ion transportation photogenerated carriers is different, which presents bipolar and
processes in CsPbBr3. As depicted in Figure S3, the I−V scan switchable photocurrent. In addition, the further accumulation
of the PbS/CsPbBr3 heterostructure with different electrode of charged species results in a higher potential barrier and
materials was compared, and it was shown that there is a large built-in electric field at the interface with an increase in the
on/off ratio when electrodes such as Ag and Al are chosen, amplitude of the bias voltage, leading to an enhanced
which can be ascribed to the mobile cation of those active photocurrent.
metals. In contrast, there is still a small on/off ratio when an 2.4. Linearly Tunable Photoresponsivity and Synap-
Au electrode is chosen, but the mobile cation of the metal tic Behavior. Given the correlation between photoresponse
electrode can be ruled out for the chemical inertness of Au. In and polarization states, we then characterize the polarization-
addition, it is shown that a lower work function corresponds to modulated reconfigurable photoresponsivity for broadband
a higher current for the device. Therefore, the hysteresis loop sensing. The relationship between the photocurrent, photo-
of the I−V scan and energy band bending are reasonably responsivity, and optical power of the device is shown in Figure
attributed to the bias-induced Br− ion migration. According to S4. The photocurrent increases as the optical power increases,
the previous reports, the bandgap energy of CsPbBr3 (100) while the photoresponsivity decreases with increasing optical
single-crystal is estimated to be 2.33 eV, the valence band power. This decrease in photoresponsivity can be attributed to
maximum (VBM) is calculated to be −5.81 eV, and the Fermi trap states caused by defects or impurities at the hetero-
level of CsPbBr3 (100) is calculated to be 4.65 eV, which junction. When exposed to light, the trap states can capture the
indicates the epitaxial CsPbBr3 in our work is a weak p-type photogenerated charges, resulting in a reduced recombination
semiconductor. As for the typical n-type PbS single-crystal, the rate and an increased lifetime of photogenerated charge
bandgap energy is approximately 0.37 eV, the conduction band carriers. As the light power increases, the captured charges
minimum (CBM) is calculated to be −4.74 eV, and the Fermi become saturated due to the limited number of trap states,
level of PbS is approximately 4.86 eV. As a result, the interface leading to a decrease in photoresponsivity. The photo-
features type-I band alignment with both the CBM and the responsivity of the device measured at wavelengths of 520,
VBM on the PbS side. The reconfigurable electrical properties 780, and 980 nm is shown in Figure 3c, respectively. A
and switchable photoresponse mentioned above can be constant preset voltage with different polarities and amplitudes
understood as follows. Under the positive poling voltage is applied to the top electrode for 60 s. Unless otherwise
(i.e., the positive bias voltage on the top electrode), negatively specified, the photoresponsivity was measured at zero bias after
charged species (Br−) migrate toward the anode, as schemati- electric field poling, the applied light intensity was 58 mW, and
cally shown in the left panel of Figure 3a. To keep the material the photosensitive area is 2.296 mm2. The six distinguishable
electrically neutral, the accumulated positively charged Br photoresponse states induced by the preset voltage correspond
vacancies should attract equivalent electrons, and conse- to different polarization states. We replot the experimental data
quently, an n doping-like region forms at one end of CsPbBr3 for the voltage-dependent positive and negative photo-
near the interface of heterojunction. The band downward responsivities at different wavelengths and fit these data to
bends simultaneously (shown by the red-shaded area in the linear equations. The fitting results indicate that for the given
right panel of Figure 3a). Meanwhile, the p-doping region wavelengths and light intensities, the photoresponsivity can be
(shown by the blue-shaded area in the right panel of Figure 3a) linearly varied by the applied voltage, suggesting that the
forms accompanied by an upward band bending at the other photoresponsivity is well controlled by the polarization. In
end of CsPbBr3 near the anode. As a result, a PN-like junction addition, the photoresponsivity changes from positive to
forms in the CsPbBr3 layer, and the device is programmed into negative as the voltage increases, which is consistent with the
the Pdown state. In addition, the loss of electrons results in an up-to-down polarization switching in Figure 2f, further
upward band bending at the end of PbS near the interface. confirming the reversible polarization control of the photo-
Under 780 or 980 nm monochromatic NIR light irradiation, voltaic response, which indicates its potential as a self-powered
excess electrons and holes generated in the PbS layer are reconfigurable photosensor. It is assumed that the accumu-
separated by the built-in electric field at the interface. The lation of charged species and energy band bending at the
photogenerated electrons are collected by the bottom interface increases with the period of electric field poling.
electrode and exhibit a negative electron photocurrent at Figure 3d shows the photoresponsivity of the device captured
zero bias, which is consistent with the result at the Pdown state under 520, 780, and 980 nm illumination after various electric
in Figure 2f. In contrast, negative electric field poling pushes field poling duration treatments. The electric field poling was
the Br− back from the anode, as schematically shown in the left conducted under −6 and +6 V in the dark, respectively.
panel of Figure 3b, which results in a NP-like junction in the Similarly, the fitted results show that the photoresponsivity
CsPbBr3 layer for the opposite doping region (right panel of increases linearly in both polarities after the electric field poling
Figure 3b). The photogenerated holes are collected by the treatment, which further verifies the ion migration-induced
bottom electrode due to the built-in electric field and exhibit a photovoltaic effect. Briefly, when increasing the duration of
positive hole photocurrent at zero bias, which is consistent poling voltage, more charged ions are pushed and accumulate
with the result at the Pup state in Figure 2f. Under 520 nm at the interface, the built-in electric field is strengthened, and
monochromatic visible light irradiation, excess electrons and therefore, a higher carrier collection efficiency is obtained,
holes generated in both PbS and CsPbBr3 layers, the transfer of leading to an increased photoresponsivity accordingly. As a
photogenerated carriers, and the direction of electron and hole comparison, the photoresponsivity of the device measured at
current are identical with those under 780 or 980 nm light nonzero bias demonstrates a significant enhancement after
irradiation. Hence, external electric field poling is expected to electric field poling treatment (Figure S5), which further
7474 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

Figure 4. Implementation of image recognition and broadband convolutional processing with the neuromorphic vision sensor. (a) Experimental
setup used for transmission imaging of patterns involved a lock-in amplifier with modulation frequency input from a chopper, which recorded the
photocurrent. (b) Demonstration of patterns obtained after electric field poling treatments with different polarity and amplitude. (c) Schematic of
the convolution calculation process, which derives a weighted electrical output from optical inputs. The kernel values can be represented by
theoretical dimensionless weights and converted to applied voltage. The input layer (original image) is represented by the incident light, and the
pixel values correspond to optical power. (d) From left to right: Theoretical photoresponsivity obtained from linear dependence under illumination
at 520, 780, and 980 nm. (e) Images obtained using distinct photoresponsivity matrices at 520, 780, and 980 nm. The output photocurrent can be
represented by the convolution operation between optical power and photoresponsivity. The result obtained at 980 nm is magnified three times for
clarity.

confirms the regulation of ion migration-induced polarization. image sensors with reconfigurable photoresponsivity and self-
Moreover, unlike previous photovoltaic-type reconfigurable powered features.
photosensors,46 the heterojunction in our study eliminates the The polarization control of photovoltaic behavior with high
need for gate voltage to maintain the photoresponsivity. linearity promises our device to be a superior optoelectrical
Instead, it utilizes ion migration-induced remanent polarization synaptic device (the photoresponsivity can be seen as the
as the control mechanism, thereby significantly reducing power synaptic weight).45,47 To verify the continuous regulation
consumption. As established, Br− ions migrate in the direction capability of spikes, typical synaptic behaviors, i.e., long-term
of the external electric field, resulting in a distinct poling state potentiation and depression (LTP and LTD, respectively), are
and enhanced photoresponsivity. Subsequently, these Br− ions demonstrated in Figure 3e. In the measurement, the device was
return when the external electric field is removed. Con- initialized in the Pup state by applying an −3 V/1 ms preset
sequently, the residual polarization induced by ion migration spike. Then, 5 positive rectangular spikes (amplitude: from 0.5
gradually diminishes over time. To examine the evolution of to 2.5 V in increments of 0.5 V; width: 1 s) and 5 negative
remanent polarization induced by ion migration, a current− rectangular spikes (amplitude: from −0.5 to −2.5 V in
time curve of the photoresponse is displayed in Figure S6a. decrements of 0.5 V; width: 1 s) were applied successively
Following electric field poling at 5 V for 100 s, when subjected without preset spikes inserted between them (see top panel of
to monochromatic visible light irradiation at 520 nm, the inset Figure 3e). The spike voltages increased in magnitude so that
shows the photoresponse for the initial 20 s, clearly the polarization could be switched gradually to produce four
demonstrating the attenuation of the photoresponse. In intermediate states. After each positive or negative pulse, Isc
general, the evolution of enhanced photoresponsivity is a was measured, and photoresponsivity was calculated (see
gradual process that can persist for at least 10 min. The bottom panel of Figure 3e), which is defined as R = Iph/P,
photoresponse current values are extracted for clarification, where R is the photoresponsivity, Iph is the photocurrent, and P
clearly indicating the beginning of stabilization of the is the input optical power. The value of the photoresponsivity
photoresponse and remanent polarization (Figure S6b). To R is extracted from the temporal response curve, where the
assess the reproducibility, the measurements were repeated 30 portion that has not yet decayed. In this case, once a
times using the same method. After applying an electric field of photoresponse period is over, the subsequent voltage pulse is
5 V for 100 s, when exposed to monochromatic visible light applied to the device immediately, which is different from the
irradiation at 780 nm, the responsivity−time curves were previous measurement, where another bias voltage was applied
almost overlapped (Figure S6c), indicating excellent reprodu- until the photoresponsivity recovered to near-zero. As can be
cibility. These results allow for the construction of broadband seen, R decreases gradually from ∼4.42 nA/W to ∼ −21.08
7475 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

nA/W with increasing the number of positive spikes, exhibiting configuration of different convolution kernels to achieve
the LTD behavior. By contrast, R increases from ∼ −21.08 to different operations on remote sensing images.15 As a proof
∼5.8 nA/W under the stimulation of consecutive negative of concept, we have used a single device to receive each pixel
spikes, demonstrating the LTP behavior. Indeed, the limited image one by one to perform the convolutional processing. As
voltage pulses will not fully set or reset those Br− ions, but the a demonstration, Figure 4c illustrates the mapping of the
increased accumulation of charged species will further Difference-of-Gaussian kernel (3 × 3) into our vision sensor,
strengthen the unintentional doping effects, leading to a showcasing the edge enhancement of the letter “N”. The
higher/lower potential barrier at the interface of the theoretical dimensionless weights of the simulated kernels in
heterojunction. As a result, the direction and magnitude of Figure 4c determine the experimental fixed voltage kernel. As
the photocurrent undergo corresponding changes, which shown in Figure 4d, the actual weight matrices of three
present a bipolar and switchable photoresponsivity R. Addi- different wavelengths (520, 780, and 980 nm) are calculated by
tionally, similar LTD and LTP characteristics in Figure 3f show quasi-linear dependence in Figure 3c. Then, reconstructing the
reproducible switching with identical amplitude-increasing data of the photocurrent produced by our device, Figure 4e
pulses. In the intermediate polarization states, the upward or shows gray images of the letter “N” with three different
downward energy band bending determines the magnitude and wavelengths. The experimental results are in good agreement
direction of the overall photocurrent, and hence multilevel with the simulation results in Figure 4c, which indicate that the
photoresponsivity is accessible. As a result, polarization heterostructure photosensor is advantageous for broadband
modulation can, therefore, well explain the bias-induced neuromorphic vision processing. Besides, the photocurrent
reconfigurable photoresponse. The multiple and reproducible contrast of the letter “N” decreases with the incident photon
photoresponsivity states in the LTD or LTP process allow the energies, which is consistent with the slope of quasi-linear
construction of a device with broadband neuromorphic vision dependence. The characteristic not only allows for tuning the
processing capability. convolution kernels for various types of convolutional
2.5. Image Recognition Via Broadband Convolutional processing but also enables the implementation of weight
Processing. With the integrated optical signal detection, updates in the training process of the convolutional neural
processing, and memorizing functions, the sensor has been network.
demonstrated to be feasible for the mimicry of human visual The low latency of the heterojunction-based image sensor
sensing. Experimentally, the device is integrated into a home- can be attributed to effective control of the built-in electric
built transmission imaging system and serves as an imaging field at the interface through polarization. Due to the
sensor for recognition of a simple pattern. Figure 4a presents a limitations in the time resolution of our measurement system,
schematic with a continuous point-scanning mode imple- we can confirm that the photovoltaic response time is below
mented by a piezo-driven x−y stage. Under monochromatic 2.9 ms (Figure S7), which is shorter than that of previously
light irradiation, the photodetector captures the transmitted reported perovskite-based broadband photodetectors.19,21,26
pattern point-by-point and outputs the photocurrent matrix via Regarding energy consumption, the device operates based on
a lock-in amplifier. The input images consisted of 5 × 3 pixels, the photovoltaic effect (i.e., self-powered), resulting in zero
and each was stimulated by a fixed period of 0.3 s. Figure 4b energy being consumed during inference in machine learning.
shows the obtained results for different polarities of electric Energy consumption occurs only when the device is
field poling treatments. Apparently, the input image has been programmed to achieve polarization modulation, as demon-
well recognized through the photocurrent contrast. Besides, for strated previously. Applying ±0.5 V/1 s programming pulses to
the same input image, a longer treatment time leads to an our device yields an average change of R of 6 nA/W,
enhanced photocurrent. According to the bias-induced considering the energy consumption during set and reset
reconfigurable photoresponse, as explained above, the different process together, the total energy consumption is approx-
polarity of external electric field will reverse the direction of imately 1.5 nJ. Besides, a single device can represent both
built-in electric field at the interface of the heterojunction. positive and negative photoresponsivity for the reversible ion
Therefore, the signs of corresponding photocurrent changes. migration, making it unnecessary to use a pair of devices to
Furthermore, as the poling treatment time increased, the represent a signed synaptic weight in neuromorphic comput-
strengthened unintentional doping effects result in a higher/ ing.45,48 Beyond the proof-of-concept demonstration presented
lower potential barrier at the interface of the heterojunction, in this work, further advancements in device structure
which increase the contrast of the recognized images. In other optimization and array integration are necessary to propel
words, the photoresponse efficiency can be modulated by the the proposed concept toward practical applications. For
duration of electric field poling, which is consistent with the example, the adjustment of the perovskite precursor ratio can
result in Figure 3d. The modulation of image recognition is achieve improved optoelectronic performance; the ease of
derived from switchable photoresponsivity, which indicates the manufacturability and good scalability of PbS epitaxy layer
excellent synaptic plasticity that is crucial for neuromorphic allows the construction of a large-scale PbS/CsPbBr 3
vision processing. heterojunction sensor array in a small area, which could
The PbS/CsPbBr3 heterojunction-based broadband neuro- further decrease the energy consumption. Additionally, the
morphic vision sensor shows the functionality of simultaneous ionic relaxation following electric field poling can be extended
sensing and processing with a tunable linear broadband through defect engineering or interface passivation techniques,
photovoltaic effect, which allows the implementation of various enabling the creation of intelligent devices capable of in-sensor
types of convolutional processing. Under a fixed gate voltage, computing with nonvolatile memory capabilities. Moreover, by
the photoresponse modulation under different photon energies combining with narrower bandgap semiconductors, such as
determines the wavelength-dependent convolution character- PbSe49 and PbTe,50 it holds promise to develop a broader
istics. In addition, the photoresponse depends on the applied range of multiwavelength processing strategies, expanding the
voltage, and modulation of voltage can be used to realize the applications to hyperspectral sensing and processing. Given the
7476 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

outstanding crystalline quality and the epitaxial growth method 4.4. Implementation of Convolutional Processing. The linear
employed, it should be possible in the future to achieve large- relationship between the bias voltage and the photoresponsivity of the
scale integration of devices for practical convolution processing PbS/CsPbBr3 heterojunction devices demonstrates their programm-
implementation. ability and convolutional characteristics. By adjusting the bias voltage,
various convolutional kernels can be configured. We apply a 3 × 3
array simulated by PbS/CsPbBr3 heterojunction devices to an image,
3. CONCLUSIONS and its output current is determined by the equation
In conclusion, we present a prototype broadband neuro- 3,3
morphic vision sensor employing a PbS/CsPbBr3 hetero- Im , n = R i , j × Pim, j , n
junction. The sensor encompasses a wide range of colors from i,j
visible to NIR. Its photosensitivity is self-powered and
where Ri,j represents the photoresponsivity matrix of the pixel, and
adjustable due to ion migration induced by electric field Pi,jm,n is the light signal vector of the input image. Specific bias voltages
poling in CsPbBr3, which modulates the bending of energy are assigned to each element of the 3 × 3 array to map the difference-
bands. Moreover, the sensor can simulate the learning and of-Gaussian kernel onto the sensor for edge-enhancement processing
forgetting behaviors of artificial synapses through its multilevel of an 8 × 8 letter “N”. The pixel values in the input image of the letter
photosensitivity. Furthermore, it allows for the processing of “N” are converted into binary units using the incident light power as
wide-spectrum images and edge enhancement through linearly the input. The 3 × 3 convolutional kernel slides with a stride of 1 on
tunable photosensitivity. This research highlights the potential the input image with padding applied to the edges of the “N” to
of metal halide perovskites for achieving broadband and ensure input and output images of the same size. Figure 4e presents
the edge-enhancement effect of the letter “N” at different wavelengths
neuromorphic image sensing capabilities, which are vital for
(520, 780, and 980 nm).
complex optical recognition tasks such as remote sensing and
environmental monitoring.

4. EXPERIMENTAL METHODS
■ ASSOCIATED CONTENT
Data Availability Statement
All data needed to evaluate the conclusions in the paper are
4.1. Preparation of the PbS/CsPbBr3 Heterojunction. The present in the paper and/or the Supporting Information.
PbS thin film was first grown on the SrTiO3 substrate by chemical
vapor deposition, as described in our previous work. 0.1 g of PbS
Additional data related to this paper may be requested from
powder (Maeklin 99.99%) was placed in the middle of the furnace, the authors.
which was heated to 800 °C. The SrTiO3 substrates were placed in *
sı Supporting Information
the downstream region. The quartz tube was vacuumed to 1 Pa The Supporting Information is available free of charge at
through a mechanical pump. The furnace was kept at 800 °C for 6 https://pubs.acs.org/doi/10.1021/acsami.3c17935.
min, and then it was naturally cooled to room temperature. 0.3 g of
CsBr (Maeklin 99.99%) and 0.255 g of PbBr2 (Maeklin 99.99%) Steady-state PL spectra, illuminated I−V characteristics
powder were mixed (in a 2:1 molar ratio) and placed in the middle of of the heterostructure device under different wave-
the furnace. Before the SrTiO3/PbS substrate was pushed into the lengths, I−V characteristics of the PbS/CsPbBr 3
downstream region of the furnace, half of the exposed area of PbS was heterostructure with different electrode materials, photo-
covered by a piece of quartz glass to avoid the complete coverage of current and photoresponsivity of the device depending
CsPbBr3. Similarly, the quartz tube was vacuumed into 1 Pa, and then
on the optical power, photoresponsivity of the device
the furnace was heated to 570 °C and kept for 40 min; then, the
sample was naturally cooled to room temperature. The PbS/CsPbBr3 before and after electric field poling, current-time and
heterojunction-based vision sensor was fabricated with 10 nm Ti/100 photoresponse current-time curves of the device, and
nm Au as electrodes, which were deposited via thermal evaporation photovoltaic response time of the heterojunction-based
(YAN HUA, 610L) with a custom stainless-steel mask. The image sensor (PDF)
morphologies of PbS and PbS/CsPbBr3 films were characterized by
OM (Olympus BX53M). The single-crystalline nature of PbS and
PbS/CsPbBr3 thin films was characterized by an XRD analyzer
(Philips Xʼpert PRO) and SEM (Zeiss Merlin). The SrTiO3/CsPbBr3
■ AUTHOR INFORMATION
Corresponding Authors
and SrTiO3/PbS/CsPbBr3 heterostructures were characterized by a Xuechao Yu − Key Laboratory of Multifunctional
fluorescence spectrometer (PicoQuant, FlouTime 300) under 405 nm
laser irradiation; the power intensity of the incident laser is 3.84 mW,
Nanomaterials and Smart Systems, Suzhou Institute of
and the frequency is 40 MHz. Lifetime measurement was performed Nano-Tech and Nano-Bionics, Chinese Academy of Sciences,
using a picosecond pulsed laser head with a 405 nm excitation Suzhou 215123 Jiangsu, China; Email: xcyu2022@
wavelength as the excitation source. sinano.ac.cn
4.2. Electrical and Photoresponse Measurements. The I−V Li Wang − Department of Physics, School of Physics and
curve and transient photocurrent signals were measured by a PAD Materials Science, Nanchang University, Nanchang 330031,
semiconductor analyzer (Fs-Pro). The 520, 780, and 980 nm lasers China; orcid.org/0000-0001-6919-1712;
were focused on the sample, which was mounted on a homemade Email: [email protected]
stage. The modulated signals of these monochromatic lasers were Qisheng Wang − Department of Physics, School of Physics and
output by a waveform generator (RIGOL DG5000).
Materials Science, Nanchang University, Nanchang 330031,
4.3. Scanning Photocurrent Microscopy. The results are
characterized by the photocurrent system (TuoTuo Technology). China; orcid.org/0000-0002-9913-7693;
The heterojunction-based device and the stainless-steel mask were Email: [email protected]
mounted to a piezo stage that moves in the x−y plane. The 520 nm
laser was focused on the sample through the confocal optical Authors
microscope with a 20× objective lens (numerical aperture NA ∼ Kangmin Leng − Department of Physics, School of Physics and
0.42). The photocurrent signals were recorded by a lock-in amplifier Materials Science, Nanchang University, Nanchang 330031,
(Stanford SR830) with a chopper frequency of 211 Hz. China
7477 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

Zhiqiang Guo − Department of Physics, School of Physics and C. A.; De Angelis, F.; et al. Ionotronic Halide Perovskite Drift-
Materials Science, Nanchang University, Nanchang 330031, Diffusive Synapses for Low-Power Neuromorphic Computation. Adv.
China Mater. 2018, 30, 1805454.
Junming Chen − Department of Physics, School of Physics and (9) Xiao, M.; Shen, D.; Musselman, K. P.; Duley, W. W.; Zhou, Y. N.
Materials Science, Nanchang University, Nanchang 330031, Oxygen Vacancy Migration/diffusion Induced Synaptic Plasticity in A
Single Titanate Nanobelt. Nanoscale 2018, 10, 6069−6079.
China
(10) Wang, Y.; Lv, Z.; Chen, J.; Wang, Z.; Zhou, Y.; Zhou, L.; Chen,
Yao Fu − Department of Materials, School of Physics and X.; Han, S. Photonic Synapses based on Inorganic Perovskite
Materials Science, Nanchang University, Nanchang 330031, Quantum Dots for Neuromorphic Computing. Adv. Mater. 2018,
China 30, 1802883.
Ruihua Ma − Department of Physics, School of Physics and (11) Wang, Y.; Gong, Y.; Huang, S.; Xing, X.; Lv, Z.; Wang, J.; Yang,
Materials Science, Nanchang University, Nanchang 330031, J.-Q.; Zhang, G.; Zhou, Y.; Han, S.-T. Memristor-based Biomimetic
China Compound Eye for Real-time Collision Detection. Nat. Commun.
Complete contact information is available at: 2021, 12, 5979.
(12) Eames, C.; Frost, J. M.; Barnes, P. R.; O’regan, B. C.; Walsh, A.;
https://pubs.acs.org/10.1021/acsami.3c17935
Islam, M. S. Ionic Transport in Hybrid Lead Iodide Perovskite Solar
Cells. Nat. Commun. 2015, 6, 7497.
Author Contributions (13) Cai, J.; Zhao, T.; Chen, M.; Su, J.; Shen, X.; Liu, Y.; Cao, D. Ion
These authors contributed equally: K.L., Z.G., K.M.L., L.W., Migration in the All-Inorganic Perovskite CsPbBr3 and Its Impacts on
and Q.S.W. conceived the idea and supervised the projects. Photodetection. J. Phys. Chem. C 2022, 126, 10007−10013.
K.M.L., X.C.Y., and Q.S.W. wrote and reviewed the manu- (14) Kong, Q.; Obliger, A.; Lai, M.; Gao, M.; Limmer, D. T.; Yang,
script. Q.S.W. was associated with formal analysis and funding P. Solid-State Ionic Rectification in Perovskite Nanowire Hetero-
acquisition. Z.Q.G. synthesized the material, fabricated the structures. Nano Lett. 2020, 20, 8151−8156.
devices, and carried out the optical and optoelectronic (15) Pi, L.; Wang, P.; Liang, S.-J.; Luo, P.; Wang, H.; Li, D.; Li, Z.;
measurements. K.M.L., Z.Q.G., J.M.C., and R.H.M. analyzed Chen, P.; Zhou, X.; Miao, F.; et al. Broadband Convolutional
the data. J.M.C. provided the simulations. Y.F. helped with the Processing Using Band-alignment-tunable Heterostructures. Nat.
drawing and modeling. All authors discussed the results and Electron. 2022, 5, 248−254.
commented on the manuscript. K.M.L. and Z.Q.G. contributed (16) Wu, D.; Guo, J.; Wang, C.; Ren, X.; Chen, Y.; Lin, P.; Zeng, L.;
equally to this work. Shi, Z.; Li, X. J.; Shan, C.-X.; et al. Ultrabroadband and High-
Detectivity Photodetector based on WS2/Ge Heterojunction through
Notes Defect Engineering and Interface Passivation. ACS Nano 2021, 15,
The authors declare no competing financial interest. 10119−10129.

■ ACKNOWLEDGMENTS
This work was financially supported by the National Natural
(17) Wu, E.; Wu, D.; Jia, C.; Wang, Y.; Yuan, H.; Zeng, L.; Xu, T.;
Shi, Z.; Tian, Y.; Li, X. In Situ Fabrication of 2D WS2/Si Type-II
Heterojunction for Self-Powered Broadband Photodetector with
Science Foundation of China (no. 61904055, no. 62375279), Response up to Mid-Infrared. ACS Photonics 2019, 6, 565−572.
(18) Wang, X.; Wang, P.; Wang, J.; Hu, W.; Zhou, X.; Guo, N.;
the China Baowu Low Carbon Metallurgy Innovation
Huang, H.; Sun, S.; Shen, H.; Lin, T.; et al. Ultrasensitive and
Foudation (BWLCF202209), the National Young Talents Broadband MoS2 Photodetector Driven by Ferroelectrics. Adv. Mater.
Project of China, the Jiangxi Provincial Natural Science 2015, 27, 6575−6581.
Foundation (no. 20232ACB201010), the Jiangxi Double- (19) Liu, Q.; Liang, L.; Shen, H.; Li, D.; Zhou, H. Epitaxial growth
Thousand Plan, Jiangxi, and the National Introduction of of CsPbBr3-PbS vertical and lateral heterostructures for visible to
Overseas Talent Innovation and Entrepreneurship Projects. infrared broadband photodetection. Nano Res. 2021, 14, 3879−3885.
The authors are grateful for the technical support from the (20) Li, T.; Miao, J.; Fu, X.; Song, B.; Cai, B.; Ge, X.; Zhou, X.;
Nano-X from the Suzhou Institute of Nano-Tech and Nano- Zhou, P.; Wang, X.; Jariwala, D.; et al. Reconfigurable, Non-volatile
Bionics, Chinese Academy of Sciences (SINANO). Neuromorphic Photovoltaics. Nat. Nanotechnol. 2023, 18 (11),

■ REFERENCES
(1) Zhou, F.; Chai, Y. Near-sensor and In-sensor Computing. Nat.
1303−1310.
(21) Liu, S.; Chen, Y.; Gao, W.; Li, W.; Yang, X.; Li, Z.; Xiao, Z.;
Liu, Y.; Wang, Y. Epitaxy of a Monocrystalline CsPbBr3-SrTiO3
Halide-Oxide Perovskite p-n Heterojunction with High Stability for
Electron. 2020, 3, 664−671.
(2) Liao, F.; Zhou, F.; Chai, Y. Neuromorphic Vision Sensors: Photodetection. Adv. Mater. 2023, 35, 2303544.
Principle, Progress and Perspectives. J. Semicond. 2021, 42, 013105. (22) Tian, C.; Wang, F.; Wang, Y.; Yang, Z.; Chen, X.; Mei, J.; Liu,
(3) Chai, Y. In-sensor Computing for Machine Vision. Nature 2020, H.; Zhao, D. Chemical Vapor Deposition Method Grown All-
579, 32−33. Inorganic Perovskite Microcrystals for Self-Powered Photodetectors.
(4) Wan, T.; Ma, S.; Liao, F.; Fan, L.; Chai, Y. Neuromorphic ACS Appl. Mater. Interfaces 2019, 11, 15804−15812.
Sensory Computing. Sci. China Inf. Sci. 2022, 65, 141401. (23) Yi, L.; Hou, B.; Zhao, H.; Liu, X. X-ray-to-visible Light-field
(5) Gollisch, T.; Meister, M. Eye Smarter than Scientists Believed: Detection Through Pixelated Colour Conversion. Nature 2023, 618,
Neural Computations in Circuits of the Retina. Neuron 2010, 65, 281−286.
150−164. (24) Huang, C.; Li, H.; Wu, Y.; Lin, C.; Guan, X.; Hu, L.; Kim, J.;
(6) Boyun, V. P.; Voznenko, L. O.; Malkush, I. F. Principles of Zhu, X.; Zeng, H.; Wu, T. Inorganic Halide Perovskite Quantum
Organization of the Human Eye Retina and Their Use in Computer Dots: A Versatile Nanomaterial Platform for Electronic Applications.
Vision Systems. Cybern. Syst. Anal. 2019, 55, 701−713. Nano-Micro Lett. 2023, 15, 16.
(7) Kim, S. G.; Van Le, Q.; Han, J. S.; Kim, H.; Choi, M.-J.; Lee, S. (25) Cong, H.; Chu, X.; Wan, F.; Chu, Z.; Wang, X.; Ma, Y.; Jiang,
A.; Kim, T. L.; Kim, S. B.; Kim, S. Y.; Jang, H. W. Dual-Phase All- J.; Shen, L.; You, J.; Xue, C. Broadband Photodetector based on
Inorganic Cesium Halide Perovskites for Conducting-Bridge Memo- Inorganic Perovskite CsPbBr3/GeSn Heterojunction. Small Methods
ry-based Artificial Synapses. Adv. Funct. Mater. 2019, 29, 1906686. 2021, 5, 2100517.
(8) John, R. A.; Yantara, N.; Ng, Y. F.; Narasimman, G.; Mosconi, (26) Zhang, Y.; Xu, W.; Xu, X.; Cai, J.; Yang, W.; Fang, X. Self-
E.; Meggiolaro, D.; Kulkarni, M. R.; Gopalakrishnan, P. K.; Nguyen, Powered Dual-Color UV-Green Photodetectors based on SnO2

7478 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479
ACS Applied Materials & Interfaces www.acsami.org Research Article

Millimeter Wire and Microwires/CsPbBr3 Particle Heterojunctions. J. (44) Tress, W.; Marinova, N.; Moehl, T.; Zakeeruddin, S. M.;
Phys. Chem. Lett. 2019, 10, 836−841. Nazeeruddin, M. K.; Gratzel, M. Understanding the Rate-dependent
(27) Zhao, X.; Fang, Y.; Dong, J.; Song, X.; Yu, H.; Wang, P.; Yan, Z. J-V Hysteresis, Slow Time Component, and Aging in CH3NH3PbI3
Synergistically Enhanced Wide Spectrum Photodetection of A Perovskite Solar Cells: The Role of A Compensated Electric Field.
Heterogeneous Trilayer CsPbI3/PbS/ZnO Architecture. J. Mater. Energy Environ. Sci. 2015, 8, 995−1004.
Chem. C 2022, 10, 15168−15176. (45) Cui, B.; Fan, Z.; Li, W.; Chen, Y.; Dong, S.; Tan, Z.; Cheng, S.;
(28) Cao, M.; Tian, J.; Cai, Z.; Peng, L.; Yang, L.; Wei, D. Perovskite Tian, B.; Tao, R.; Tian, G.; et al. Ferroelectric Photosensor Network:
Heterojunction based on CH3NH3PbBr3 Single Crystal for High- An Advanced Hardware Solution to Real-time Machine Vision. Nat.
sensitive Self-powered Photodetector. Appl. Phys. Lett. 2016, 109, Commun. 2022, 13, 1707.
233303. (46) Zeng, P.; Wang, W.; Han, D.; Zhang, J.; Yu, Z.; He, J.; Zheng,
(29) Hu, W.; Cong, H.; Huang, W.; Huang, Y.; Chen, L.; Pan, A.; P.; Zheng, H.; Zheng, L.; Su, W.; et al. MoS 2/WSe 2 vdW
Xue, C. Germanium/perovskite Heterostructure for High-perform- Heterostructures Decorated with PbS Quantum Dots for the
ance and Broadband Photodetector from Visible to Infrared Development of High-Performance Photovoltaic and Broadband
Telecommunication Band. Light Sci. Appl. 2019, 8, 106. Photodiodes. ACS Nano 2022, 16, 9329−9338.
(30) Peng, Y.; Jiang, D.; Zhao, M.; Duan, Y.; Wei, H.; Li, H.; Liang, (47) Wang, C.-Y.; Liang, S.-J.; Wang, S.; Wang, P.; Li, Z.; Wang, Z.;
Q.; Wang, S. High-Performance UV-visible Photodetectors based on Gao, A.; Pan, C.; Liu, C.; Liu, J.; et al. Gate-tunable Van der Waals
ZnO/perovskite Heterostructures. J. Alloys Compd. 2023, 965, Heterostructure for Reconfigurable Neural Network Vision Sensor.
171372. Sci. Adv. 2020, 6, No. eaba6173.
(31) Chen, S.; Teng, C.; Zhang, M.; Li, Y.; Xie, D.; Shi, G. A Flexible (48) Fu, X.; Li, T.; Cai, B.; Miao, J.; Panin, G. N.; Ma, X.; Wang, J.;
UV-Vis-NIR Photodetector based on a Perovskite/Conjugated- Jiang, X.; Li, Q.; Dong, Y.; et al. Graphene/MoS2‑xOx/graphene
Photomemristor with Tunable Non-volatile Responsivities for Neuro-
Polymer Composite. Adv. Mater. 2016, 28 (28), 5969−5974.
morphic Vision Processing. Light Sci. Appl. 2023, 12, 39.
(32) Zeng, L.-H.; Chen, Q.-M.; Zhang, Z.-X.; Wu, D.; Yuan, H.; Li,
(49) Cheng, Z.; Wu, S.; Jiang, Y.; Wu, X.; Qiu, M.; Li, Q.; Shen, Y.;
Y.-Y.; Qarony, W.; Lau, S. P.; Luo, L.-B.; Tsang, Y. H. Multilayered
Yu, K.; Wang, L.; Wang, Q. Long-distance Transport of Hot Carriers
PdSe2/Perovskite Schottky Junction for Fast, Self-Powered, Polar-
Due to Acoustic Phonon Bottleneck in PbSe with Room-temperature
ization-Sensitive, Broadband Photodetectors, and Image Sensor Sensitive Mid-infrared Sensing. Appl. Phys. Lett. 2023, 122, 242102.
Application. Adv. Sci. 2019, 6, 1901134. (50) Ma, S.; Li, K.; Xu, H.; Zhu, J.; Zhu, H.; Wu, H. Lattice-
(33) Miller, E. M.; Kroupa, D. M.; Zhang, J.; Schulz, P.; Marshall, A. Mismatched PbTe/ZnTe Heterostructure with High-Speed Midin-
R.; Kahn, A.; Lany, S.; Luther, J. M.; Beard, M. C.; Perkins, C. L.; frared Photoresponses. ACS Appl. Mater. Interfaces 2019, 11, 39342−
et al. Revisiting the Valence and Conduction Band Size Dependence 39350.
of PbS Quantum Dot Thin Films. ACS Nano 2016, 10, 3302−3311.
(34) Wang, Q.; Wen, Y.; Cai, K.; Cheng, R.; Yin, L.; Zhang, Y.; Li, J.;
Wang, Z.; Wang, F.; Wang, F.; et al. Nonvolatile Infrared Memory in
MoS2/PbS Van der Waals Heterostructures. Sci. Adv. 2018, 4 (4),
No. eaap7916.
(35) Qin, L.; Wu, S.; Gan Wang, J.; Li, Q.; Yuan, C.; Wang, Z.;
Wang, J.; Hu, Z.; Wang, L.; Wang, Q. Enhancement of Infrared
Response Speed via Modulating Crystallinity of Highly-oriented PbS
Polycrystalline Thin Films. Infrared Phys. Technol. 2022, 121, 104033.
(36) Wu, S.; Qin, L.; Li, Q.; Wu, Z.; Nie, Z.; Jiang, Y.; Wang, J.;
Wang, Z.; Zhou, Y.; Yu, K.; et al. Hot-carrier Infrared Detection in
PbS with Ultrafast and Highly Sensitive Responses. Appl. Phys. Lett.
2022, 120, 042101.
(37) Jung, Y.-K.; Butler, K. T.; Walsh, A. Halide Perovskite
Heteroepitaxy: Bond Formation and Carrier Confinement at the PbS-
CsPbBr3 Interface. J. Phys. Chem. C 2017, 121, 27351−27356.
(38) Han, Q.-F.; Jin, F.; Yang, W.-J.; Sun, D.-P.; Wang, X. Liquid-
liquid Interfacial Synthesis of Single-crystalline PbS Nanoplates and
Nanocube-based Microspheres. Mater. Lett. 2012, 69, 10−12.
(39) Kumar, D.; Agarwal, G.; Tripathi, B.; Vyas, D.; Kulshrestha, V.
Characterization of PbS Nanoparticles Synthesized by Chemical Bath
Deposition. J. Alloys Compd. 2009, 484, 463−466.
(40) Mo, X.; Li, X.; Dai, G.; He, P.; Sun, J.; Huang, H.; Yang, J. All-
inorganic Perovskite CsPbBr3 Microstructures Growth via Chemical
Vapor Deposition for High-performance Photodetectors. Nanoscale
2019, 11, 21386−21393.
(41) Cen, G.; Liu, Y.; Zhao, C.; Wang, G.; Fu, Y.; Yan, G.; Yuan, Y.;
Su, C.; Zhao, Z.; Mai, W. Atomic-Layer Deposition-Assisted Double-
Side Interfacial Engineering for High-Performance Flexible and Stable
CsPbBr3 Perovskite Photodetectors toward Visible Light Communi-
cation Applications. Small 2019, 15, 1902135.
(42) Wang, Y.; Li, X.; Liu, P.; Xia, J.; Meng, X. Epitaxial Growth of
CsPbBr3/PbS Single-crystal Film Heterostructures for Photodetec-
tion. J. Semicond. 2021, 42, 112001.
(43) Yang, Z.; Xu, Q.; Wang, X.; Lu, J.; Wang, H.; Li, F.; Zhang, L.;
Hu, G.; Pan, C. Large and Ultrastable All-Inorganic CsPbBr3
Monocrystalline Films: Low-Temperature Growth and Application
for High-Performance Photodetectors. Adv. Mater. 2018, 30,
1802110.

7479 https://doi.org/10.1021/acsami.3c17935
ACS Appl. Mater. Interfaces 2024, 16, 7470−7479