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org/acsaelm Article

Two-Dimensional Ruddlesden−Popper Perovskite Cs2PbI2Cl2

Nanostructures for Self-Powered Visible−Blind Ultraviolet
Photodetectors
Yanshuang Ba, Weidong Zhu,* Zeyulin Zhang, Zhuangjie Xu, Fuhui Bai, He Xi, Dazheng Chen,
Jincheng Zhang, Chunfu Zhang,* and Yue Hao
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ABSTRACT: All-inorganic two-dimensional Ruddlesden−Popper

perovskite Cs2PbI2Cl2 nanostructures with excellent thermal stability,
tunability, and carrier mobility have great potential to be utilized as
functional layers in visible−blind ultraviolet photodetectors. In order
to achieve efficient devices, we prepare herein Cs 2 PbI 2 Cl 2
nanostructures using a two-step dipping method and reveal the
growth process of the nanostructures from nanowires to films. The
morphologies of the intermediate nanosheets and nanosheet/film
structures are characterized to investigate their microstructural
characteristics and crystallization processes. Furthermore, typical
Cs2PbI2Cl2 nanostructures are utilized to construct low cost, simple-
structured, self-powered photodetectors. The self-powered champion
device based on a Cs2PbI2Cl2 nanosheet/film nanostructure exhibits
a peak responsivity of 35.01 mA/W, a specific detectivity of 2.45 × 1012 Jones, and a short response time of 80 μs, together with
exceptional operational stability in ambient air. The favorable electronic performance is strongly related to the suppressed carrier
recombination and enhanced built-in potential.
KEYWORDS: Ruddlesden−Popper perovskite, two-step dipping, Cs2PbI2Cl2, nanostructures, self-powered photodetector

■ INTRODUCTION
Visible−blind ultraviolet (UV) photodetectors (PDs) are of
of strong optical absorption, tunable band gap, and bipolar
transport with large carrier diffusion length, high mobility, and
considerable importance in the fields of optical communica- low-temperature solution preparation.14−17 Two-dimensional
tion, imaging, environmental monitoring, biological sensing, (2D) Ruddlesden−Popper (RP) perovskites have received
military warning, etc.1−4 Compared with bulk semiconductors, extensive attention because of their high tunability, good
such as Si, GaN, and ZnO, solution-processed semiconductor quantum confinement effects, high exciton binding energies,
materials are considered better candidates for visible−blind and excellent stability.18−20 Xiao et al. developed high-quality
UV PDs.5−7 They offer advantages in the integration of quasi-2D RP perovskite films for fabricating flexible self-
miniaturized and functionalized devices with read-out inte- powered UV PDs, demonstrating a device with a detectivity of
grated circuits.8 Furthermore, PDs that rely on external power 2.59 × 1012 Jones and excellent mechanical stability for flexible
sources can be cumbersome to operate in certain environ- applications.21 Zou et al. grew large-area and high-quality 2D
ments, leading to additional costs and maintenance issues.9,10 perovskite single-crystal thin films using the gas−liquid
In this context, solvent-prepared, self-powered, and visible− interface crystallization method and used the as-prepared
blind UV PDs have attracted substantial research attention thin films to prepare UV PDs with a detectivity of ∼1012
owing to their compact size, sustainability, and remote Jones.22 Zhai et al. demonstrated the development of a high-
controllability.11−13 An essential part of research on these performance UV PD based on a hybrid heterojunction of 2D
exceptional PDs involves the exploration of new functional
materials that possess high carrier mobilities, large carrier Received: November 18, 2024
diffusion lengths, selective, and strong UV light absorption, Revised: December 17, 2024
easy fabrication, and reliable stability. Accepted: December 26, 2024
In the past decade, metal halide perovskites (MHPs) have Published: January 3, 2025
emerged as promising semiconductor materials for visible−
blind UV PDs, offering promising advantageous characteristics

© 2025 American Chemical Society https://doi.org/10.1021/acsaelm.4c02064

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Figure 1. (A) Schematic of the preparation process of Cs2PbI2Cl2 nanostructures. (B−D) Scanning electron microscopy (SEM) images of the
Cs2PbI2Cl2 nanostructure samples prepared using (B) 6, (C) 8, and (D) 10 mg/mL CsCl−methanol solution (CsCl/MeOH).

Figure 2. (A) Ultraviolet−visible absorption spectra, (B) XRD patterns, and (C) SEM images of the Cs2PbI2Cl2 nanostructure samples prepared
using (C1) 6, (C2) 7, (C3) 8, (C4) 9, (C5) 10, and (C6) 11 mg/mL CsCl/MeOH.

RP perovskite (PEA)2PbI4 and SnP2S6, achieving a responsivity methanol (MeOH)/isopropanol treatment to enhance the
(R) of 239.4 A/W and excellent photoelectric imaging crystallization kinetics of Cs2PbI2Cl2/CsPbI2.5Br0.5 perovskite
capabilities.23 In particular, all-inorganic 2D RP perovskite films, improving device performance by increasing the power
Cs2PbI2Cl2, with a band gap of ∼2.95 eV, is promising for conversion efficiency from 13.44% to 14.10%.29 Chen et al.
application in visible−blind UV PDs.24 It exhibits several introduced Cs2PbI2Cl2 nanosheets and effectively passivated
desirable characteristics, including high carrier mobility, direct CsPbI3 quantum-dot-based solar cells, achieving a champion
band gap, small carrier effective masses, low exciton binding efficiency of 14.73% with excellent stability.30 Various studies
energy, and excellent ambient/thermal stability.25−27 However, have demonstrated favorable electronic characteristics of
state-of-the-art research has mainly focused on application of Cs2PbI2Cl2 nanostructures. However, studies focusing on the
Cs2PbI2Cl2 in the transport and passivation layers and application of these nanostructures in the absorption layer of
heterojunction compositions, and the studied Cs2PbI2Cl2 visible−blind UV PDs are scarce. Moreover, to the best of our
materials possess a microstructure comprising nanowires, knowledge, precise control of the morphology of Cs2PbI2Cl2
nanosheets, and films. In our previous study, we fabricated a nanostructures has not yet been achieved. Furthermore, the
Cs2PbI2Cl2 nanowire/PbI2 heterojunction for applications in a electronic performance of different Cs2PbI2Cl2 nanostructures
self-powered PD, demonstrating favorable performance with a remains unexplored.
peak responsivity and specific detectivity (D*) of 0.17 A/W Herein, for the first time, we fabricated Cs 2 PbI 2 Cl 2
and 3.02 × 1012 Jones, respectively.28 Xu et al. utilized a nanostructures with different morphologies (nanowires, nano-
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Figure 3. (A−C) Low- and high-resolution TEM images, (D) SAED pattern, and (E) elemental mapping results for the Cs2PbI2Cl2 nanostructures
prepared using 8 mg/mL CsCl/MeOH. Core-level (F) I 3d, (G) Pb 4f, (H) Cs 3d, and (I) Cl 2p X-ray photoelectron spectra of the PbI2 film and
Cs2PbI2Cl2 nanostructures prepared using 8 mg/mL CsCl/MeOH.

sheets, and films) using a two-step dipping method, in which a composed of nanowires. When the CsCl/MeOH concen-
solution-prepared PbI2 film was directly dipped into a CsCl− tration was increased to 8 and 10 mg/mL, the nanowires
MeOH solution (CsCl/MeOH). We demonstrated a typical extended to form incomplete nanosheets and grew into
growth process of Cs2PbI2Cl2 nanostructures from nanowires Cs2PbI2Cl2 films. In addition, the dipping duration clearly
to films by adjusting the CsCl/MeOH concentration. An affected the crystal morphology of the Cs2PbI2Cl2 nanostruc-
intermediate nanosheet/film mixed structure was observed, ture. Figure S1 shows the SEM images of the samples prepared
which defined the growth process. Representative Cs2PbI2Cl2 by using 8 mg/mL CsCl/MeOH and dipping durations of 20,
nanostructures were utilized to construct visible−blind UV 30, and 40 s. Approximated with the concentration, the
PDs comprising a simple layered structure of FTO/TiO2/ dipping duration endows the Cs2PbI2Cl2 nanostructure with a
PbI2/Cs2PbI2Cl2/carbon. The self-powered champion device completely different growth consequence, revealing a morpho-
fabricated using the nanosheet/film mixed structure yielded a logical change from nanowires to films. Accordingly, a mezzo-
peak responsivity of 35.01 mA/W, a specific detectivity of 2.45 growth duration of 30 s was confirmed to achieve precise
× 1012 Jones, and a short response time of 80 μs, together with control of the growth process.
exceptional operational stability in ambient air. To further investigate the crystallization process and

■ RESULTS AND DISCUSSION

Typical procedures for preparing Cs2PbI2Cl2 nanostructures
components of Cs2PbI2Cl2 nanostructures, the CsCl/MeOH
concentration was refined to 6, 7, 8, 9, 10, and 11 mg/mL.
UV−visible spectra in Figure 2A demonstrate that Cs2PbI2Cl2
using a two-step dipping method are shown in Figure 1A. First, nanostructures exhibit a clear onset wavelength of 420 nm,
100 μL of the PbI2 precursor was spin-coated onto the FTO/ which is consistent with the band gap of Cs2PbI2Cl2 materials
TiO2 substrate at 2000 rpm for 30 s, followed by thermal reported earlier.24,31 Figure 2B shows the X-ray diffraction
treatment at 200 °C for 5 min to complete the preparation of (XRD) patterns of the Cs2PbI2Cl2 nanostructures prepared
the PbI2 film. The PbI2 precursor was prepared by dissolving using 6, 7, 8, 9, 10, and 11 mg/mL CsCl/MeOH. The XRD
461 mg of PbI2 in 1 mL of dimethyl sulfoxide at room peaks at 15.95, 22.54, and 32.08° were assigned to the (101),
temperature. The as-prepared PbI2 films were then dipped in 6, (110), and (200) planes of Cs2PbI2Cl2, respectively.26,32 With
8, or 10 mg/mL of CsCl/MeOH for 30 s. increasing CsCl/MeOH concentrations, the XRD peaks of
Finally, the dipped samples were annealed at 250 °C for 10 Cs2PbI2Cl2 were clearly enhanced, indicating a higher
min to promote the crystallization of the Cs 2 PbI 2 Cl 2 crystallinity of Cs2PbI2Cl2. When the CsCl/MeOH concen-
nanostructures. Figure 1B−D shows the SEM images of the tration increased to 9 mg/mL, an XRD peak was detected at
above-mentioned Cs2PbI2Cl2 nanostructure samples. The 12.71°, corresponding to the (001) plane of PbI2.33 In
sample prepared by dipping in 6 mg/mL CsCl/MeOH was addition, as the CsCl/MeOH concentration increased, the
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Figure 4. (A) Schematic structure of the self-powered photodetector (PD) based on Cs2PbI2Cl2 nanostructures. (B) Light current density−voltage
(J−V) curves, (C) dark J−V curves, (D) EQE profiles, (E) R profiles, and (F) D* profiles for the self-powered PDs fabricated with Cs2PbI2Cl2
nanostructures formed using 6, 8, and 10 mg/mL CsCl/MeOH. (G) Transient photovoltage curves and (H) response characteristics of the self-
powered PDs based on the Cs2PbI2Cl2 nanostructures prepared using 8 mg/mL CsCl/MeOH toward a 405 nm on/off modulated laser for a test
period of 4 h.

PbI2 component exhibited a considerable increase in the nanosheets into films. The high-resolution TEM image in
crystallinity. We infer that an excessive CsCl/MeOH Figure 3C reveals the characteristic lattice spacing of
concentration will result in the rapid growth of Cs2PbI2Cl2 continuous lattice fringes with an interplanar spacing of
nanostructures on the surface and hinder the reactions 0.295 nm, providing further evidence of the crystallinity and
between CsCl and PbI2 inside of the PbI2 films. SEM images the preferential [200] growth characteristics of Cs2PbI2Cl2
of the studied Cs2PbI2Cl2 nanostructures are shown in Figure nanostructures. The corresponding SAED pattern, as depicted
2C1−C6. With increasing CsCl/MeOH concentrations, in Figure 3D, consist of sharp diffraction spots, revealing the
Cs2PbI2Cl2 nanowires gradually expanded into complete high crystallinity and monocrystalline characteristics of the
Cs2PbI2Cl2 nanosheets, and subsequently, the bottom of the nanosheet. Moreover, the SEAD yields the typical (101),
nanosheets grew into Cs2PbI2Cl2 films. At this point, (110), and (200) facets, indicating that Cs2PbI2Cl2 belongs to
Cs2PbI2Cl2 nanostructures consisted of a nanosheet/film the tetragonal phase. The elemental mapping results in Figure
mixed structure, and finally, these nanostructures grew into 3E reveal a uniform elemental distribution of Cs, Pb, I, and Cl
Cs2PbI2Cl2 films. Moreover, the low-resolution SEM images of in the incomplete Cs2PbI2Cl2 nanosheets with a composition
Cs2PbI2Cl2 nanostructures with the characteristic morphology ratio of approximately 2:1:2:2, which is consistent with the
of nanowires, nanosheets, nanosheets/film mixed structure, stoichiometric ratio of Cs2PbI2Cl2.
and film are provided in Figure S2. It is seen that the The element distribution was unaffected by the spotty
nanostructures prepared by two-step dipping method show pattern inside the Cs2PbI2Cl2 nanosheet, which further
favorable uniformity. Notably, the Cs2PbI2Cl2 nanosheet/film confirmed that the nanosheet comprised pure phase
mixed structures appeared semitransparent, as shown in Figure Cs2PbI2Cl2. In addition, the surface compositions of the
S3. The objects located behind the Cs2PbI2Cl2 nanosheet/film pristine PbI2 film and Cs2PbI2Cl2 nanostructures prepared
mixed structure were clearly visible, demonstrating the using 8 mg/mL CsCl/MeOH and a dipping duration of 30 s
potential applicability of the as-prepared nanostructures in were studied via X-ray photoelectron spectroscopy. As
visible−blind UV PDs. illustrated in Figures 3F−I and S4, clear signals of Pb 4f and
Furthermore, to investigate the microstructural character- I 3d were detected for both samples. Furthermore, additional
istics and crystallization process of the Cs2PbI2Cl2 nanostruc- Cs 3d and Cl 2p peaks are observed for the Cs2PbI2Cl2
ture, an incomplete nanosheet was studied via transmission nanostructures.
electron microscopy (TEM) in conjunction with selected area These results demonstrate that the nanostructures comprise
electron diffraction (SAED) and energy-dispersive spectrom- components of Cs2PbI2Cl2. Next, the as-obtained Cs2PbI2Cl2
etry (EDS) (Figure 3A−D). As shown in Figure 3A,B, the nanostructures were utilized to fabricate PDs with a simple
interior of the nanosheet has an uneven spotty pattern, which device structure of the FTO/TiO2/Cs2PbI2Cl2 nanostructure/
can be attributed to mass transfer during the transformation of carbon, as illustrated in Figure 4A. Notably, the functional
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Table 1. Summary of the Performance Parameters of the Visible−Blind UV PDs Based on MHPs
materials self-powered bias (V) R (mA/W) D* (Jones) rising/falling time wavelength range (nm) refs
Cs2PbI2Cl2 nanostructure yes 0 35.01 2.45 × 1012 -/80 μs 350−550 this work
Cs3BiBr6 single crystal (SC) no 6 0.025 0.8 × 109 50/60 ms 400 37
Cs3Cu2I5 quantum dots no 4 0.08 1.09 × 109 0.35/0.41 s 250−900 38
Cs2PbI2Cl2 nanosheets yes 0 17.3 1.85 × 1012 -/0.2 ms 250−450 39
Rb2TeI6 films no 5 1.4 1010 16.4/19.2 ms 450 40
(PEA)2PbBr4 SC films no 10 28.6 2.4 × 1011 32/85 ms 365 41
Sr2Nb3O10 nanosheets yes 5 10.8 3.39 × 1011 -/67.3 ms 270 42
CsPbCl3 SC no 5 4.52 3.3 × 1010 1.651/0.104 s 254−365 43
Cs2AgBiCl6 films Yes 0 9.68 1.11 × 1012 365 44
Cs2NaBiCl6 nanocrystals No 15 11.13 2 × 1010 440 45
CsPbBr3 nanowires No 5 7.26 1.7 × 1011 10/22 ms 463 46

layers of PDs are prepared via solution methods, which endow decrease in R at 395 nm can be observed for the PDs prepared
the device with the advantages of low cost, facile fabrication, using 6 and 8 mg/mL CsCl/MeOH, corresponding to the
easy scaling, etc.34,35 Figure 4B shows the light current density absorption onsets of the Cs2PbI2Cl2 nanostructures. In
versus voltage (J−V) curves of the PDs prepared using 6, 8, comparison, a different characteristic was observed for the
and 10 mg/mL CsCl/MeOH, which were measured under PD prepared using 10 mg/mL CsCl/MeOH, which can be
continuous illumination from a xenon lamp with an intensity of attributed to the absorption onset of the unreacted PbI2 film.
100 mW cm−2. The photovoltage characteristics demonstrate Notably, the PD prepared using 8 mg/mL CsCl/MeOH
the self-powered functionality of the PDs. The open-circuit demonstrated consistently higher R and D* values within the
voltages of PDs prepared by using 6, 8, and 10 mg/mL CsCl/ entire response range, indicating a favorable capability for
MeOH were estimated to be 0.61, 0.80, and 0.77 V, visible−blind UV detection.
respectively. Meanwhile, the device fabricated using 8 mg/ In this case, the maximum R and D* values are 35.01 mA/W
mL CsCl/MeOH exhibits a higher light current density (0.44 and 2.45 × 1012 Jones, respectively, which are better than those
mA cm−2) than the devices formed using 6 and 10 mg/mL of the previously reported visible−blind UV PDs based on
CsCl/MeOH. The linear-coordinate and logarithmic-coordi- MHPs, as presented in Table 1. The response time of a typical
nates dark J−V curves of the studied devices are shown in PD prepared using 8 mg/mL CsCl/MeOH was studied using
Figures 4C and S5. The dark J−V curves exhibit asymmetry, transient photovoltage (TPV) measurement equipment,
indicating that the PDs possess rectification characteristics, following a previously reported method.47 The TPV results
which lead to the generation of a built-in field in the PDs.36 PD obtained at a bias of 0 V are shown in Figure 4G, and the
prepared using 8 mg/mL CsCl/MeOH exhibited a relatively response time is estimated at 80 μs by fitting the TPV curve
lower dark current density. At a bias of 0.5 V, the devices with a single-exponential decay function. Furthermore, the
prepared using 6, 8, and 10 mg/mL CsCl/MeOH were response time of our device based on 8 mg/mL CsCl/MeOH
estimated to possess current densities of 2.99 × 10−5, 1.74 × was comparable to the data presented in Table 1. The
10−5, and 2.34 × 10−5 A/cm2, respectively. The device operational stability of the PD prepared using 8 mg/mL CsCl/
prepared using 8 mg/mL CsCl/MeOH produced low dark and MeOH is further studied in an ambient air atmosphere with a
light current densities, providing a device with low noise and relative humidity of 40%−50% and a temperature of ∼25 °C.
good photoelectric conversion capacity. Notably, the device As demonstrated in Figure 4H, under the irradiation of a 405
with such favorable electric characteristics consisted of a nm on/off modulated laser, the device exhibited minimal dark
nanosheet/film mixed structure, demonstrating the potential and light current variations over the test period of 5 h,
for producing high-performance PDs. For comparison, the PD indicating its favorable operational stability. Meanwhile, the
based on Cs2PbI2Cl2 nanosheets is also prepared using a two- response curves of the studied PD to a 405 nm on/off
step dipping method, which yields an obvious response to modulated laser of one PD after being preserved in ambient air
illumination (Figure S6). Figure 4D presents the external for about 1 month is measured. As shown in Figure S7, the
quantum efficiency (EQE) profiles of the fabricated PDs at a current decay is only about 7%, indicating its excellent stability.
bias of 0 V. The apparent response to light at different Herein, we investigated the growth process of Cs2PbI2Cl2
wavelengths further confirms the self-powered functionality of nanostructures formed using a two-step dipping method and
the PDs. The devices prepared using 6 and 8 mg/mL CsCl/ their application in self-powered visible−blind UV PDs. The
MeOH exhibited an onset wavelength of 420 nm, which CsCl/MeOH concentration was adjusted to optimize the
corresponds to Cs2PbI2Cl2. However, the device fabricated electronic characteristics of Cs2PbI2Cl2 nanostructures and the
with 10 mg/mL CsCl/MeOH exhibited an onset wavelength device performance parameters of PDs, including EQE, R, and
of 515 nm. This response characteristic was attributed to the D*. To deeply understand the dependence between the
unreacted PbI2 component present in the Cs2PbI2Cl2 film.28 electronic characteristics of Cs2PbI2Cl2 nanostructures and the
Furthermore, the device prepared using 8 mg/mL CsCl/ performance of PDs, electrochemical analyses, including
MeOH demonstrated a substantially higher EQE, and its peak electrochemical impedance spectroscopy and Mott−Schottky
EQE is as high as 11.1%. measurements, were conducted. Figure 5A shows the Nyquist
To further explore the detection capability of the PDs based plots of the Cs2PbI2Cl2 nanostructures prepared using 6, 8, and
on Cs2PbI2Cl2 nanostructures, the responsivity and specific 10 mg/mL CsCl/MeOH. The Nyquist plots are fitted with the
detectivity of the PDs were evaluated using the dark J−V and equivalent circuit model in Figure S8. The arc is related to the
EQE results. As depicted in Figure 4E,F, a considerable recombination of photogenerated carriers near the interface of
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trations for 30 s, respectively. Finally, the dipped samples were

annealed at 250 °C for 5 min to fulfill the crystallization of Cs2PbI2Cl2
nanostructures.
Fabrication of Self-Powered PDs. PD with a carbon electrode
was prepared by a screen-printing method, which was followed by
baking at 120 °C for 15 mim.
Characterizations. The characterization part is in accordance
with our previous work.28

Figure 5. (A) Nyquist plots and (B) Mott−Schottky analysis results

■
*
ASSOCIATED CONTENT
sı Supporting Information
for the self-powered PDs fabricated with the Cs2PbI2Cl2 nanostruc- The Supporting Information is available free of charge at
tures produced using 6 and 8 mg/mL CsCl/MeOH. https://pubs.acs.org/doi/10.1021/acsaelm.4c02064.
SEM images of Cs2PbI2Cl2 nanostructure prepared by 8
the TiO2/Cs2PbI2Cl2 nanostructures, which is characterized by mg/mL CsCl/MeOH solution with dipping duration of
recombination resistance (Rrec). The sample prepared using 8 20, 30, and 40 s; photograph of the Cs 2PbI2Cl2
mg/mL CsCl/MeOH had a higher Rrec, indicating a decrease nanosheets/film mixed-structures; and XPS survey
in photogenerated carrier recombination.48,49 As shown in spectra of Cs2PbI2Cl2 nanostructure prepared using 8
Figure 5B, the sample prepared using 8 mg/mL CsCl/MeOH mg/mL CsCl/MeOH solution with a dipping duration
exhibited a higher built-in potential (Vbi), which was estimated of 30 s (PDF)
at 1.37 V, than the other tested samples. Generally, a high Vbi is
beneficial for carrier transportation and the suppression of
carrier recombination.50 The excellent performance of the
device prepared using 8 mg/mL CsCl/MeOH (nanosheet/film
■ AUTHOR INFORMATION
Corresponding Authors
mixed structures) is strongly related to the suppressed carrier Weidong Zhu − State Key Laboratory of Wide-Bandgap
recombination and enhanced Vbi. Semiconductor Devices and Integrated Technology, Shaanxi

■ CONCLUSIONS
In summary, we successfully fabricated Cs2PbI2Cl2 nanostruc-
Joint Key Laboratory of Graphene, School of Microelectronics,
Xidian University, Xi’an 710071, China; Guangzhou Wide
Bandgap Semiconductor Innovation Center, Guangzhou
tures with different morphologies, including nanowires, Institute of Technology, Xidian University, Guangzhou
nanosheets, and films, by using a two-step dipping method. 510555, China; orcid.org/0000-0002-3872-7323;
By adjusting the CsCl/MeOH concentration, we observed the Email: [email protected]
growth process of the nanostructures from nanowires to films, Chunfu Zhang − State Key Laboratory of Wide-Bandgap
with the formation of an intermediate structure of nanosheets Semiconductor Devices and Integrated Technology, Shaanxi
and nanosheet/film. These nanostructures were subsequently Joint Key Laboratory of Graphene, School of Microelectronics,
utilized to construct visible−blind UV PDs with a simple layer Xidian University, Xi’an 710071, China; Guangzhou Wide
structure. The champion device fabricated using the nano- Bandgap Semiconductor Innovation Center, Guangzhou
sheet/film mixed structure demonstrated excellent perform- Institute of Technology, Xidian University, Guangzhou
ance, including a peak responsivity of 35.01 mA/W, specific 510555, China; orcid.org/0000-0001-9555-3377;
detectivity of 2.45 × 1012 Jones, and short response time of 80 Email: [email protected]
μs, together with exceptional operational stability in ambient
Authors
air. The improved electronic performance was attributed to
suppressed carrier recombination and an enhanced built-in Yanshuang Ba − State Key Laboratory of Wide-Bandgap
potential. This study provides a facile approach for fabricating Semiconductor Devices and Integrated Technology, Shaanxi
Cs2PbI2Cl2 nanostructures with the desired morphologies and Joint Key Laboratory of Graphene, School of Microelectronics,
paves the way for the development of low cost, simple- Xidian University, Xi’an 710071, China
structured, and self-powered PDs with excellent performances. Zeyulin Zhang − State Key Laboratory of Wide-Bandgap
Semiconductor Devices and Integrated Technology, Shaanxi
■ EXPERIMENTAL SECTION
Materials. Ultradry PbI2 (≥99.998%, Alfa-Aesar), ultradry CsCl
Joint Key Laboratory of Graphene, School of Microelectronics,
Xidian University, Xi’an 710071, China
Zhuangjie Xu − State Key Laboratory of Wide-Bandgap
(≥99.5%, Alfa-Aesar), anhydrous DMSO (≥99.9%, Sigma-Aldrich),
absolute MeOH (99.8%, Sigma-Aldrich), conductive carbon paste Semiconductor Devices and Integrated Technology, Shaanxi
(Shanghai MaterWin New Materials Co., Ltd.), and FTO glass (8 Ω Joint Key Laboratory of Graphene, School of Microelectronics,
sq−1, Pilkington TEC Glass) were purchased without further Xidian University, Xi’an 710071, China
purification. Fuhui Bai − State Key Laboratory of Wide-Bandgap
Preparation of Cs2PbI2Cl2 Nanostructures. First, 461 mg PbI2 Semiconductor Devices and Integrated Technology, Shaanxi
was dissolved in 1 mL DMSO and stirred at 80 °C to prepare the Joint Key Laboratory of Graphene, School of Microelectronics,
precursor of PbI2. The CsCl/MeOH solution with concentrations 6, Xidian University, Xi’an 710071, China
7, 8, 9, 10, and 11 mg/mL was obtained by the same method at room
temperature. We utilized a spin-coating method at 3000 rpm on He Xi − State Key Laboratory of Wide-Bandgap
FTO/TiO2 substrates and annealed the sample at 200 °C for 10 min Semiconductor Devices and Integrated Technology, Shaanxi
to prepare the PbI2 film. The FTO/TiO2 substrates are prepared as Joint Key Laboratory of Graphene, School of Microelectronics,
we reported earlier.28 Next, as-prepared FTO/TiO2/PbI2 substrates Xidian University, Xi’an 710071, China; orcid.org/0000-
were dipped into a CsCl/MeOH solution with different concen- 0003-0684-4979
587 https://doi.org/10.1021/acsaelm.4c02064
ACS Appl. Electron. Mater. 2025, 7, 582−589
ACS Applied Electronic Materials pubs.acs.org/acsaelm Article

Dazheng Chen − State Key Laboratory of Wide-Bandgap Perovskite-Based Photodetectors for Optical Communication Appli-
Semiconductor Devices and Integrated Technology, Shaanxi cations. Adv. Mater. 2018, 30, 1803422.
Joint Key Laboratory of Graphene, School of Microelectronics, (9) Liu, D.; Yu, B.-B.; Liao, M.; Jin, Z.; Zhou, L.; Zhang, X.; Wang,
Xidian University, Xi’an 710071, China; Guangzhou Wide F.; He, H.; Gatti, T.; He, Z. Self-Powered and Broadband Lead-Free
Inorganic Perovskite Photodetector with High Stability. ACS Appl.
Bandgap Semiconductor Innovation Center, Guangzhou
Mater. Interfaces 2020, 12, 30530−30537.
Institute of Technology, Xidian University, Guangzhou (10) Fang, H.; Zheng, C.; Wu, L.; Li, Y.; Cai, J.; Hu, M.; Fang, X.;
510555, China; orcid.org/0000-0001-8152-4313 Ma, R.; Wang, Q.; Wang, H. Solution-Processed Self-Powered
Jincheng Zhang − State Key Laboratory of Wide-Bandgap Transparent Ultraviolet Photodetectors with Ultrafast Response
Semiconductor Devices and Integrated Technology, Shaanxi Speed for High-Performance Communication System. Adv. Funct.
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https://pubs.acs.org/10.1021/acsaelm.4c02064 Powered Wide-Narrow Bandgap-Laminated Perovskite Photodetector
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and devices, wrote the draft of the manuscript. W. Zhu and C.
(15) Dou, L.; Yang, Y.; You, J.; Hong, Z.; Chang, W.-H.; Li, G.;
Zhang: designed and supervised the research. Z. Zhang, Z. Xu, Yang, Y. Solution-Processed Hybrid Perovskite Photodetectors with
F. Bai, H. Xi, D. Chen, J. Zhang, and Y. Hao: contributed High Detectivity. Nat. Commun. 2014, 5, 5404.
useful comments to the manuscript. (16) Min, L.; Sun, H.; Guo, L.; Wang, M.; Cao, F.; Zhong, J.; Li, L.
Notes Frequency-Selective Perovskite Photodetector for Anti-Interference
The authors declare no competing financial interest. Optical Communications. Nat. Commun. 2024, 15, 2066.
(17) Chai, W.; Zhu, W.; Ma, J.; Huangfu, S.; Zhang, Z.; Chen, D.;

■ ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support from
Zhang, J.; Zhang, C.; Hao, Y. Charge-Selective-Contact-Dependent
Halide Phase Segregation in CsPbIBr2 Perovskite Solar Cells and Its
Correlation to Device Degradation. Appl. Surf. Sci. 2022, 595, 153544.
the National Key R&D Program of China (2022YFB3204101, (18) Fu, P.; Liu, Y.; Yu, S.; Yin, H.; Yang, B.; Ahmad, S.; Guo, X.; Li,
2021YFF0500504, 2022YFB3605402, and 2021YFF0500501), C. Dion-Jacobson and Ruddlesden-Popper Double-Phase 2D Perov-
the Fundamental Research Funds for the Central Universities skites for Solar Cells. Nano Energy 2021, 88, 106249.
(YJSJ24020), the National Natural Science Foundation of (19) Liu, P.; Han, N.; Wang, W.; Ran, R.; Zhou, W.; Shao, Z. High-
Quality Ruddlesden−Popper Perovskite Film Formation for High-
China (62274132, 61804113, and 62204189), and the Natural
Performance Perovskite Solar Cells. Adv. Mater. 2021, 33, 2002582.
Science Basic Research Program of Shaanxi (2021JC-24). (20) Righetto, M.; Giovanni, D.; Lim, S. S.; Sum, T. C. The

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