Reduced Size Carbon Energy - 2023 - Lan - Preparation and Promising Optoelectronic Applications of Lead Halide Perovskite Patterned

Received: 30 October 2022 | Revised: 22 November 2022 | Accepted: 29 November 2022
DOI: 10.1002/cey2.318
REVIEW
Preparation and promising optoelectronic applications

of lead halide perovskite patterned structures: A review
Shangui Lan1,2 | Baojun Pan2 | Ying Liu1,2 | Zhixiang Zhang2 |

Lijie Zhang3 | Bin Yu2,4 | Yanjun Fang1 | Peijian Wang2,4
1
State Key Laboratory of Silicon
Materials, School of Materials Science Abstract
and Engineering, Zhejiang University, Lead halide perovskites have received considerable attention from researchers
Hangzhou, Zhejiang, China
2
over the past several years due to their superior optical and optoelectronic
ZJU‐Hangzhou Global Scientific and
Technological Innovation Center, Future properties, because of which they can be a versatile platform for fundamental
Science Research Institute, Zhejiang science research and applications. Patterned structures based on lead halide
University, Hangzhou, Zhejiang, China
perovskites have much more novel properties compared with their more
3
Key Laboratory of Carbon Materials of
commonly seen bulk‐, micro‐, and nano‐crystals, such as improvement in
Zhejiang Province, Institute of New
Materials and Industrial Technologies, antireflection, light‐scattering effects, and light absorption, as a result of their
College of Chemistry and Materials adjustability of spatial distributions. However, there are many challenges yet
Engineering, Wenzhou University,
Wenzhou, Zhejiang, China
to be resolved in this field, such as insufficient patterned resolution, imperfect
4
School of Micro‐Nano Electronics, crystal quality, complicated preparation process, and so on. To pave the way to
Zhejiang University, Hangzhou, Zhejiang, solve these problems, we provide a systematic presentation of current methods
China
for fabricating lead halide perovskite patterned structures, including thermal
Correspondence imprint, use of etching films, two‐step vapor‐phase growth, template‐confined
Peijian Wang, ZJU‐Hangzhou Global solution growth, and seed‐assisted growth. Furthermore, the advantages and
Scientific and Technological Innovation
disadvantages of these methods are elaborated in detail. In addition, thanks to
Center, Future Science Research
Institute, Zhejiang University, Hangzhou, the extraordinary properties of lead halide perovskite patterned structures, a
311215 Zhejiang, China. variety of potential applications in optics and optoelectronics of these
Email: pjwang@zju.edu.cn
structures are described. Lastly, we put forward existing challenges and
Yanjun Fang, State Key Laboratory of
Silicon Materials and School of Materials,
prospects in this exciting field.
Science and Engineering, Zhejiang
University, Hangzhou, 310007 Zhejiang, KEYWORDS
China. fabrication, lead halide perovskites, optics, optoelectronics, patterned structures,
Email: jkfang@zju.edu.cn photovoltaics
1 | INTRODUCTION formula of perovskite is AMX3, where A and M are

cations and X represents the anion.6–8 The M cation and
Perovskite is a class of material with a CaTiO3‐like crystal the X anion form an octahedron, and the A cation
structure1–3 that was first discovered by Gustav Ross in the occupies the cubic octahedron cavity to maintain the
18th century and later named “perovskite” by a Russian electrical neutrality of the system.9,10 When Pb2+ and a
mineralogist L. A. Perovski.4,5 The general chemical halogen ion occupy the M location and the X location,
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2023 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.
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2 of 25 | LAN ET AL.
respectively, they form lead halide perovskites.11–13 The the optoelectronic applications.35,48 Their unique
past several decades have witnessed progress in research shallow defect energy levels have little effect on optical
on perovskites and their applications in optics and and optoelectronic properties compared with usual
optoelectronics.2,8,14–16 In the past few years, the number deep defect energy levels in other materials.49–51
of articles has increased to more than 10,000 per year Furthermore, lead halide perovskite single crystals
according to the Web of Science. Impressively, in the mere can exist in various forms including three‐dimensional
past ten years, the resarchers have improved the power (3D) (bulk crystals), 2D (film), or 1D (nanowires)
conversion efficiency of lead halide perovskite solar cells forms.52–54 Their micro‐crystals or nano‐crystals are
from less than 4% to 25.2%, while counterpart silicon solar usually randomly distributed.55 Compared with bulk‐,
cell has used almost more than 60 years for improvement micro‐, and nano‐crystals, lead halide perovskite pat-
for the same efficacy.14,17–19 The development of perov- terned structures have much more novel optical and
skite solar cells is in line with the current social demand optoelectronic properties resulting from their periodicity
for high energy‐efficiency and low‐carbon emission.20,21 and adjustability of spatial distributions, which attracts
Lead halide perovskites have attracted extensive extensive attention of research communities.56–58 For
attention of scientists due to their superior optical and example, the metasurfaces based on lead halide perov-
optoelectronic properties.22–25 We have divided their skite patterned structures take advantage of the interfer-
properties into two classes. One class focuses on the ence of visible light to tune the wavelength, intensity, or
ability of radiative recombination of carriers, including nonlinear optical effect.44,59,60 Besides, they can also be
large exciton binding energy (for CsPbBr3, ~72 meV) applied to lasing, photodetectors, phototransistors, solar
(Figure 1A,B) and high photoluminescence quantum cells, and LEDs with better uniformity and higher
yields (PLQYs) (nearly 100%) (Figure 1C).26–28,36–39 efficiency.61–64 The practical scalable applications such
Because of this, lead halide perovskites are considered as photodetectors and solar cells usually require that the
promising candidates for high‐efficiency light‐emitting perovskites are a patterned array instead of merely a
devices. For instance, Jianhai Li and coauthors single piece of material.65,66 Thus, effective fabrication of
achieved a 50‐fold improvement in the external perovskite patterned structures is useful. In spite of their
quantum efficiency (EQE) (up to 6.27%) for solution‐ superior optical and optoelectronic properties, research
processed CsPbBr3 quantum‐dot light‐emitting diodes on their patterned structures is still in its infancy.67,68 At
(LEDs) through balancing surface passivation and present, the methods of preparing perovskite patterned
effective carrier injection via ligand density control.40 structures can be divided into two categories: top‐down
Their ultra‐stable amplified spontaneous emission at and bottom‐up processes. The top‐down method repro-
strikingly low thresholds has been demonstrated, cesses perovskite thin films, usually by etching or
indicating the potential of lead halide perovskites to imprinting, to prepare their patterned structures, includ-
be used as electrically operated coherent light sources ing etching film and thermal imprinting.63,69 The top‐
with high energy efficiency, taking into account their down approach such as etching includes photoresists and
charge transport characteristics.41 The other class of lift‐off, which can have negative effects on the material
properties of lead halide perovskites focuses their properties. Moreover, the top‐down methods usually
ability to lead to improvements of carrier separation result in partial loss of materials, reducing the utilization
and transport, including long carrier lifetime (>80 μs) efficiency of materials. On the other hand, the bottom‐up
(Figure 1D) and high carrier mobility (tens of cm2/V s) method involves direct growth of perovskite patterned
(Figure 1E), making them suitable for photodetectors structures via a solution or vapor‐phase process, includ-
and photovoltaic devices.30,31,42,43 Figure 1F shows the ing template‐confined solution growth, two‐step vapor‐
photoresponsivity of a perovskite photodetector with phase growth, and seed‐assisted growth.34,70,71 The
varying light intensity (> several hundred mA/W).32,33 contamination of the material is less and the additive
Moreover, the band gap of lead halide perovskites can process results in higher utilization efficiency of material.
be continuously adjusted in the visible light range by However, morphology control in terms of precision is
doping different halogen atoms, rendering them more difficult and there is less uniformity.
tailorable emission or detection wavelength range Although researchers have developed various methods
(Figure 1G).27,34,44–47 On the other hand, the high to fabricate lead halide perovskite patterned structures,
defect tolerance overall sets lead halide perovskites there is still a long way to go for in terms of their
apart, and may provide a physical explanation for their widespread commercial use.34,67,69–71 First, toxicity to
long carrier lifetime because defects act as carrier humans and the intrinsic low stability of perovskite
recombination centers, reducing the carrier lifetime, patterned structures against oxygen and moisture markedly
and thus are very significant and highly conducive for impede their use in commercial applications. Second, there
LAN ET AL. | 3 of 25
F I G U R E 1 Optical and optoelectronic properties of lead halide perovskites. (A) The FWHM of CsPbBr3 (pink) and CsPbCl3 (navy) exciton
peak dependent on the temperature. A single‐exponential decrease function (lines) is used to fit the experimental data (dots) to evaluate the
exciton binding energy of CsPbBr3 (38 meV) and CsPbCl3 (72 meV). (B) Optical absorption and PL spectra of CsPbCl3 (blue lines), CsPbBr3
(green lines), and CsPbI3 (red lines) nanoplatelets. The insets show fluorescence images of CsPbCl3 (left), CsPbBr3 (middle), and CsPbI3 (right).
Reproduced with permission: Copyright 2016, Wiley‐VCH.26 (C) Absolute PLQY variations with the change of the Cs to Pb precursor molar
ratio taken in the reaction system for the synthesis of CsPbCl3 and CsPbBr3 nanocrystals. Reproduced with permission: Copyright 2019,
Wiley‐VCH.27,28 (D) Transient photovoltaic curves of the MAPbI3 single‐crystal devices under 1 sun and 0.1 sun illumination, respectively, with
incident light from the semitransparent Au anode. The transient photovoltaic decay curves were fitted by a single‐exponential decay function.
Reproduced with permission: Copyright 2015, American Association for the Advancement of Science.29 (E) Effective THz carrier mobility for
perovskite films on quartz slides. Reproduced with permission: Copyright 2018, The Royal Society of Chemistry.30,31 (F) Photocurrent and
responsivity of the perovskite photodetectors under various intensities of light. Reproduced with permission: Copyright 2018, Wiley‐VCH.32,33
(G) PL spectra of CsPbX3 perovskite submicron plates with different halide ions. Reproduced with permission: Copyright 2021, Wiley‐VCH.27,34
(H) The calculated defect charge‐transition levels. Reproduced with permission: Copyright 2017, American Chemical Society.35
are two key parameters for perovskite patterned structures, create strong diffraction and interference; simultaneously,
namely, crystal quality and patterned resolution, which are high crystal quality for better uniformity is also called for.
important for practical arrayed applications. For example, Both these two factors are necessary. However, for the top‐
for metasurfaces, a patterened resolution of several down process involving high temperatures, high pressures,
hundred nanometers is requred for that the length scale or etching, the crystal quality of patterned structures can be
is able to reach down to the wavelength of visible light to considerably affected, which can hamper their subsequent
applications. For bottom‐up growth commonly involving a existing challenges in this field and also propose some
solution, in spite of the good crystal quality due to the direct possible solutions to these problems from our own
growth, their patterned resolution can only reach microm- perspective.
eter size due to the tension of the liquid surface. Currently,
there are few methods that can simultaneously realize high
patterned resolution and good crystal quality. Last but not 2 | FABRICATION METHODS OF
the least, for optimal manufacturing scaling‐up that is LEAD HALIDE PEROVS KITE
necessary for widespread commercial implementation, the P A T T E R N ED ST R U C T U R E S
repeatability, production efficiency, and manufacturing cost
of the fabrication methods are important factors. However, 2.1 | Thermal imprint
existing methods usually involve very complicated opera-
tion processes, such as high‐temperature heating, high Thermal imprint is a typical top‐down method of
pressure, photolithography, and some other complicated preparing lead halide perovskite patterned structures.
semiconductor processing technologies. Therefore, control- The thermal imprint process involves pressing a hard
lable fabrication of lead halide perovskite patterned template with patterned structures on a lead halide
structures is an emerging but promising field, and a review perovskite film at a certain temperature and pressure. As
of the lead halide perovskite patterned structures and their shown in Figure 3A, Neda and coauthors pressed a stamp
applications is timely and necessary. with a periodic line pattern (3600 lines mm−1) on a film
To pave the way for solving these problems, in this to prepare lead halide perovskite patterned structures.61
review, we provide a detailed summary of some current The film was synthesized by a solution process. The
common methods for fabricating lead halide perovskite stamp was a commercially available diffraction grating
patterned structures, including thermal imprinting, purchased from Thorlabs. The pressure applied to the
etching film, two‐step vapor‐phase growth, template‐ diffraction grating was 100 bar and the film was heated to
confined solution‐growth, and seed‐assisted growth 150°C using a hot plate. The cross‐section of the
(Figure 2). Operation steps and examples are introduced imprinted perovskite layer was a sinusoidal grating
for each method. Furthermore, we evaluate in detail the structure as shown in the scanning electron microscopy
patterned resolution, crystal quality, repeatability, pro- (SEM) image (inserted in Figure 3A). Honglei and
duction efficiency, and manufacturing cost for each coauthors reported the use of a thermal imprint to
fabrication method. In addition, due to the extraordinary define ordered perovskite patterned structures
properties of lead halide perovskite patterned structures, (Figure 3B).63 Three different Si molds (flat surface,
a variety of potential applications in optics and opto- nanopillar, and nanograting) were used to prepare
electronics of these structures are described, including different structures. The Si molds were first pretreated
lasing emission, metasurfaces, photodetectors, photo- with an antiadhesion monolayer of 1H,1H,2H,2H‐
transistors, solar cells, and LEDs. Lastly, we analyze the perfluorodecyltrichlorosilane to reduce the surface
FIGURE 2 Framework of this review, including fabrication and applications of lead halide perovskite patterned structures
hundreds of nanometers. In spite of their high patterned

resolution, due to the high temperature and high
pressure required in the preparation process, the crystal
quality of patterned structures fabricated by thermal
imprint is adversely affected compared with a pretreated
film, which is clear from the irregular shape of the cross‐
section shown in the inset of Figure 3B‐ⅶ. On the other
hand, the production process is relatively complicated
due to the high‐temperature heating and high pressure,
increasing the manufacturing cost and reducing the
production efficiency.
2.2 | Etching film
To avoid the use of high temperature and pressure, an

etching film has been put forward as another alternative
top‐down process for preparing lead halide perovskite
patterned structures. In this method, a lead halide
perovskite film is etched into patterned structures by
focused ion beam (FIB) treatment, inductively coupled
plasma (ICP) etching, or direct laser writing using
appropriate templates in general.72 Yisheng and coau-
thors fabricated 1D MAPbBr3 gratings by ICP etching.73
They could vary the periodicity of MAPbBr3 gratings by
changing the periodicity of the templates (Figure 4A).
F I G U R E 3 Thermal imprint. (A) The direct thermal imprint of With increasing periodicity, the peaks of the experi-
a linear grating into the CsPbBr3 layer. Glass is used as a substrate. mental (solid lines) and simulated (dashed lines) reflec-
The periodicity of the linear grating is 278 nm. (i) Schematic tion spectra red shift, covering most of the visible
illustration of the direct thermal imprint. (ⅱ) SEM image of the spectrum (left panel in Figure 4A). Characterizations
cross‐section of the patterned CsPbBr3. Reproduced with
including OM images, SEM images, and simulated colors
permission: Copyright 2019, Wiley‐VCH.61 (B) The NIL process for
based on the optical grating periodicity in the right panel
fabricating MAPbI3 patterned structures. Schematic illustration of
the NIL process with (ⅰ) a Si flat mold, (ⅱ) a Si nanopillar mold, and
of Figure 4A show their tidy grating structures and the
(ⅲ) a Si nanograting mold. SEM images of (ⅳ) a nonimprinted tunable periodicity and color. In addition, Benzheng Xia
MAPbI3 thin film and a film imprinted with (ⅴ) a Si flat mold, (ⅵ) a and coauthors fabricated MAPbI3 dot patterns on Si
Si nanopillar mold, and (ⅶ) a Si nanograting mold. Reproduced substrates by etching, as shown in Figure 4B,C.74 Besides
with permission: Copyright 2016, American Chemical Society.63 ICP etching, Yangguang and coauthors obtained regular‐
shaped high‐quality CsPbBr3 disk arrays processed by
FIB treatment of a CsPbBr3 film.69 The single‐crystalline
CsPbBr3 was grown by the chemical vapor deposition
energy of the interface between the Si molds and the (CVD) process, whose schematic setup is shown in
perovskite film. The molds were then pressed on Figure 4D. CsBr and PbBr2 powder were heated to the
the different areas of the same perovskite thin film at gas phase and reacted to form a CsPbBr3 deposition on
the same time to ensure that the same conditions were the surface of a downstream sapphire substrate under an
applied for all Si molds. The pressure applied to Si molds Ar carrier gas atmosphere. The optical image of the
was 7 MPa and the film was heated to 100°C using a hot CsPbBr3 single‐crystal film shows its smooth surface
plate for 20 min. SEM was used to characterize the (Figure 4E). The thickness of the film was about 300 nm,
morphology of both the nonimprinted and imprinted as shown in the line profile shown in the inset of
films (Figure 3B). Due to the in situ imprinting, the Figure 4E. Figure 4F,G shows the SEM and fluorescent
perovskite nanohole structures and nanograting struc- images of CsPbBr3 arrays fabricated by FIB treatment,
tures were well defined (Figure 3B). They were negative respectively, highlighting the regular microdisk array
replications of the Si molds. The SEM images also show structures. However, this method has the common
that the printing resolution of thermal imprint can reach disadvantage of the top‐down process. The crystal quality
F I G U R E 4 Etching film. (A) The left panel shows the experimental (solid lines) and simulated (dashed lines) reflection spectra, while
the right panel shows the corresponding OM images, SEM images, and calculated colors. Here, the period and gap increase in panels
I–VIII. All scale bars are 1 μm. Reproduced with permission: Copyright 2018, American Chemical Society.73 MAPbI3 dot patterns: (B)
10 μm‐diameter circles and (C) 5 μm‐diameter circles on Si. Reproduced with permission: Copyright 2022, Wiley.74 (D–G) CsPbBr3
microdisk arrays fabricated by FIB treatment. (D) Schematic illustration of the CVD setup for growing a CsPbBr3 single‐crystal film.
(E) Optical image of a CsPbBr3 single‐crystal film. The scale bar is 50 μm. The line profile in the inset shows the thickness of the film.
(F) SEM and (G) fluorescent images of CsPbBr3 microdisk arrays fabricated by FIB treatment. The scale bar is 5 μm. Reproduced with
permission: Copyright 2020, American Chemical Society.69
is reduced due to the arbitrary etching process. More- two‐step vapor‐phase growth was developed to grow
over, the etching methods that require FIB bombardment their patterned structures. This growth process
cannot be performed with sufficient throughput as to be converts a Pb precursor into lead halide perovskites.
economically viable. Gongming and coauthors fabricated MAPbI3 micro-
plate arrays by converting PbI2 microplate arrays into
perovskite arrays.71 Figure 5A shows the schematic
2.3 | Two‐step vapor‐phase growth illustration of the two‐step vapor‐phase procedure.
The SiO2 /Si substrate was first treated with OTS vapor
The bottom‐up method involves direct growth of to produce a hydrophobic surface. Then, periodic
perovskite crystals, which is thought to possess the hydrophilic area arrays were created on the substrate
feasibility to grow their patterned structures with by lithography and oxygen plasma treatment. PbI 2
high crystal quality. CVD growth is a widely used arrays on the substrate were fabricated using the
method to synthesize high‐quality lead halide perov- cooling crystallization method and were finally
skites crystals.75–78 Recently, as a bottom‐up method, converted into MAPbI3 arrays by intercalating
F I G U R E 5 Two‐step vapor‐phase growth. (A–D) MAPbI3 microplate arrays fabricated by converting PbI2 microplate arrays into
perovskite arrays. (A) Schematic illustration of the procedure for preparing MAPbI3 perovskite plate arrays on a patterned substrate.
SEM images of (B) PbI2 microplates and (C) MAPbI3 microplates in a hexagonal lattice pattern. The scale bar is 20 μm. (D) Dark‐field optical
microscopy image (top panel) and SEM image (bottom panel) of PbI2 microplates forming a “CLA” pattern. The scale bar is 100 μm.
Reproduced with permission: Copyright 2015, AAAS.71 (E) CsPbI3 perovskite nanowire arrays synthesized inside an anodic alumina
membrane using the CVD method. Precursors are Pb metal and CsI powder. The right panel: Pb metal nanoclusters deposited at the bottom
of nanopores on an anodic alumina membrane template. The middle panel: schematic illustration of the CVD setup in which arrows show
the transport direction of CsI vapors. The left panel: CsPbI3 nanowire arrays inside nanopores. Top image: magnified crystal view of a CsPbI3
nanowire. Reproduced with permission: Copyright 2017, American Chemical Society.79 Two‐step vapor‐phase growth of 2D organic–
inorganic perovskite patterned structure: (F) SEM image, (G) optical image, and (H) corresponding PL mapping of the converted (BA)2Pbl4‐
xClx patterned structures. The scale bars in (F) and (G,H) are 50 and 20 μm, respectively. Reproduced with permission: Copyright 2018,
American Chemical Society.80
methylammonium iodide (MAI) vapor in a homebuilt anodic alumina membrane template transformed into
CVD system. Figure 5B,C shows the SEM images of CsPbI3 nanowire arrays with CsI vapors.
PbI2 arrays and MAPbI 3 arrays with a hexagonal Besides 3D perovskites, 2D layered organic–inorganic
lattice pattern, respectively. They could even form a perovskite patterned structures were fabricated by two‐
“CLA” pattern based on PbI 2 microplates by designing step vapor‐phase growth by intercalating butyl ammo-
an appropriate template (Figure 5D). Aashir and nium iodide vapor to PbI2 microplate arrays.80 2D layered
coauthors synthesized CsPbI3 perovskite nanowire perovskites are a series of perovskite materials with the
arrays inside an anodic alumina membrane using the chemical formula (RNH3)2An−1MnX3n+1, where RNH3 is
CVD method (Figure 5E). 79 Anodic alumina mem- an aliphatic or aromatic alkylammonium spacer cation,
branes were used as nanoengineering templates, A is a monovalent organic cation, M is a divalent metal
where the nanowires were grown using a facile vapor cation (Pb in general), X is a halide anion, and n
growth method from Pb metal nanoclusters. Pb metal represents the number of [MX6]4− octahedral structures
nanoclusters deposited at the bottom of nanopores on sandwiched between two layers of spacer cations.81,82
They have inherent multiple quantum well structures fluorescence image of these nanowires, wherein each
with a very large exciton binding energy and tunable nanowire emits bright green light, which is coincident
quantum well thickness by simply changing the number with their PL spectra. Additionally, Zheng Yang and
of n in the above‐mentioned chemical formula. These coauthors successfully synthesized monocrystalline
properties made 2D layered perovskites a convenient CsPbBr3 microwire arrays with tunable widths, lengths,
platform to investigate the exciton‐polaritons and explore and locations using the PDMS template‐confined anti-
for novel photonic devices.80,83 Figure 5F–H shows SEM solvent crystallization method.70 Figure 6D shows the
images, optical images, and corresponding PL mapping schematic diagram of the entire preparation procedure.
of the converted (BA)2Pbl4‐xClx patterned structures, CsPbBr3 microwires with different widths and heights
respectively. However, the two‐step vapor‐phase growth could be prepared by changing the size of the PDMS
inserts another precursor into the lattice of one precur- template (Figure 6E). Besides, Xianxiong He and
sor, which destroys the crystal structure of the original coauthors reported PDMS cylindrical‐hole‐template
precursor, reducing the crystal quality of the samples. (CHT)‐confined solution growth of large‐area microdisk
Figure 5G shows the optical image of perovskite arrays of CsPbCl3 up to 1 × 1 cm2.57 Figure 6F shows the
patterned structures, indicating the polycrystalline prop- schematic illustration of the preparation procedures.
erties reflected by the rough surface of the samples. Figure 6G–J shows the in situ monitoring of the growth
Moreover, the repeatability of this method is poor process of CsPbCl3 microdisks, which includes four
because it prepares PbI2 arrays utilizing hydrophilic procedures: solution confinement, edge nucleation,
and hydrophobic arrays of substrates. The hydrophobic- confined growth, and finally, square microdisks.
ity of substrates can easily change when the substrates Besides 3D perovskites, template‐confined solu-
are exposed to ambient atmosphere, reducing the tion growth can be used to synthesize 2D layered
production efficiency. perovskite patterned structures. For example, Shun‐
Xin Li and coauthors reported 2D layered perovskite
microwire arrays grown by template‐confined growth
2.4 | Template‐confined solution (Figure 7A). 67 Figure 7B–E shows the SEM images of
growth microwires with different widths, ranging from 8 to
100 μm. In addition, Haihua Zhang and coauthors
Besides vapor‐phase growth, template‐confined solution reported 2D Ruddlesden–Popper (R‐P) perovskites of
growth is also widely used to prepare perovskite (BA)2 (MA) n−1 Pbn Br 3n+1 micro‐ring arrays by
86
patterned structures. Peng Liu and coauthors placed a template‐confined solution growth. Figure 7F shows
polydimethylsiloxane (PDMS) rectangular groove tem- the schematic illustration of the preparation proce-
plate (RGT) in a perovskite solution to prepare large‐ dures of (BA) 2 (MA)5 Pb6 Br 19 micro‐ring arrays.
scale perovskite nanowire arrays.84 Figure 6A shows the Figure 7G,H shows the fluorescence image and the
schematic illustration of the growth procedure, which SEM image of the as‐grown (BA) 2 (MA) 5Pb6 Br 19
includes four steps: solution confinement in RGTs, micro‐ring arrays, respectively. Although the repeat-
nucleation at RGT ends, 1D growth along RGTs, and ability of template‐confined solution growth is good,
nanowire arrays after detachment of RGTs. PDMS‐RGTs the crystal quality is not good enough due to the
with a width of ∼1 μm, a height (or depth) of ∼5 μm, and mechanical force. On the other hand, since the
a length varying between 10 and 50 μm were fabricated process involves a solution, its patterned resolution
by soft lithography.85 In a typical synthesis of perovskite can only reach micrometer scale due to the tension of
nanowire arrays, a PDMS‐RGT pad was placed on top of the liquid surface.
a stock solution of MABr·PbBr2 (0.1 M, 20 μL) in N,N‐
dimethylformamide spreading on a hydrophilic sub-
strate. Upon mild pressure on the PDMS pad, the stock 2.5 | Seed‐assisted growth
solution of MABr·PbBr2 was driven into the void space of
PDMS‐RGTs. Once these primary nuclei were formed at Seed‐assisted growth utilizes the epitaxial growth of
the end positions, they grew along the direction of the preprepared seeds arrays to fabricate lead halide perov-
length of PDMS‐RGTs. After the solvent volatilized skite patterned structures, which is a method for
completely, the PDMS‐RGTs were peeled off to leave preparing patterned structures with high crystal quality
PNW arrays on the substrate. Figure 6B shows the SEM (Figure 8). For instance, Zhenkun Gu and coauthors
image of the MAPbBr3 nanowire arrays, indicating that reported an effective strategy to synthesize high‐quality
each nanowire has a rectangular cross section with a cesium lead bromide perovskite (CsPbBr3) microplate
smooth surface and a sharp edge. Figure 6C shows the arrays by seed‐assisted vapor‐phase growth, which shows
F I G U R E 6 Template‐confined solution‐grown 3D perovskite patterned structures. MAPbBr3 nanowire arrays grown using the template‐
confined method. (A) Schematic illustration of the growth procedures, including four steps: solution confinement in RGTs, nucleation at RGT
ends, one‐dimensional growth along RGTs, and nanowire arrays after detachment of RGTs. (B) SEM image and (C) fluorescence image of
MAPbBr3 nanowire arrays. The scale bars in (B) and (C) are 50 and 10 μm, respectively. Reproduced with permission: Copyright 2017, American
Chemical Society.84 CsPbBr3 microwire arrays grown using the PDMS template‐confined antisolvent crystallization method. (D) Schematic
diagram showing the entire preparation procedure. (E) SEM images showing CsPbBr3 microwires with different widths and heights. The scale bar
is 5 μm. Reproduced with permission: Copyright 2019, Wiley‐VCH.70 CsPbCl3 microdisk arrays grown using the PDMS‐CHT‐confined solution‐
growth method. (F) Schematic illustration of the preparation procedures including three processes: press sealing, CHT‐confined growth, and
removing template. (G‐J) Specific details of procedures i and ii of (F), including corresponding in‐situ monitoring of the growth process of CsPbCl3
microdisks on a quartz glass slide using bright‐field fluorescence microscopy under ultraviolet light (360–380 nm) irradiation, revealing the
evolution from non‐luminescent precursor seeds to luminescent perovskite. Reproduced with permission: Copyright 2017, Wiley‐VCH.57
F I G U R E 7 Template‐confined solution‐grown 2D layered perovskite patterned structures. Template‐confined growth of 2D layered

perovskite microwire arrays. (A) Schematic illustration of the growth procedures. SEM images of microwires with different widths: (B) 8 μm,
(C) 15 μm, (D) 30 μm, and (E) 100 μm. Reproduced with permission: Copyright 2019, Royal Society of Chemistry.67
Template‐confined solution growth of (BA)2(MA)5Pb6Br19 micro‐ring arrays. (F) Schematic illustration of the preparation procedures of
micro‐ring arrays. (G) Fluorescence image and (H) SEM image of as‐grown micro‐ring arrays. The scale bars in (G) and (H) are 20 μm.
Reproduced with permission: Copyright 2018, Wiley‐VCH.86
uniform morphology as well as controlled location and fabricated seeded silicon by fabricating a silicon substrate
size.87 Figure 8A shows the schematic illustration of with a hydrophilic array and spin‐coating the perovskite
vapor‐phase synthesis of CsPbBr3 microplate arrays. precursor solution onto the substrate (Figure 8C).
They first fabricated CsPbBr3 crystal seeds on a silicon Subsequently, the seeded substrate was introduced into
substrate using their previously reported inkjet printing the tube furnace to grow perovskite submicron plate
method.88 Consequently, the desired patterned CsPbBr3 arrays. Figure 8D shows the schematic diagram of the
seeds were prepared by printing a dilute perovskite space‐confined vapor‐phase‐growth setup with a mica
precursor solution on a silicon wafer. Finally, perovskite covering on the seeded substrate, which ensures the
microplate arrays were obtained by introducing seeded growth of submicron plate arrays. Figure 8E,F shows the
silicon into a CVD tube furnace to modulate the epitaxial SEM images of the as‐grown CsPbBr3 and CsPbI3
growth of these crystal seeds. The growth process was submicron plate arrays, respectively, showing their
tracked by fluorescence images, which shows the rather smooth surface and a very sharp edge, suggesting
evolution process from seeds to microplate arrays. their excellent crystalline quality. In spite of their good
Moreover, Shangui Lan and coauthors reported the crystal quality, the patterned resolution can be only tens
seed‐assisted space‐confined vapor‐phase growth of all‐ of microns. In addition, the whole process involves
inorganic perovskite submicron plate arrays.34 They photolithography, preparation of a hydrophilic array of a
F I G U R E 8 Seed‐assisted growth.
Seed‐assisted vapor‐phase growth of CsPbBr3
microplate arrays. (A) Schematic illustration of
vapor‐phase synthesis of CsPbBr3 microplate
arrays. (B) Fluorescence images of the CsPbBr3
microplate growth process. The scale bar is
50 μm. Reproduced with permission: Copyright
2020, Wiley‐VCH.87 Seed‐assisted growth of
all‐inorganic perovskite patterned structures.
(C) Seeded substrate fabrication. (D) Schematic
diagram of the space‐confined vapor‐phase‐
growth setup. SEM images of (E) CsPbBr3 and
(F) CsPbI3 submicron plate arrays. The scale
bars for (E) and (F) are 3 μm. Reproduced with
permission: Copyright 2020, Wiley‐VCH.34
substrate, synthesis of perovskite arrays, and epitaxial In two‐step vapor‐phase growth, the crystal quality of
growth of CVD. The complicated process reduces the samples can decrease because another precursor is
repeatability and production efficiency and increases the inserted into the lattice of the original precursor. For
manufacturing cost. template‐confined solution growth, the crystal quality is
Each of these methods for fabricating lead halide not good due to the mechanical force. In addition, since
perovskite patterned structures has advantages and these two patterned processes involve a solution, the
disadvantages in crystal quality and patterned resolution. patterned resolution can only reach micrometers due to
For comparison of crystal quality, we list the patterned the tension of the liquid surface. For seed‐assisted
resolution and full width at half maximum (FWHM) of growth, the same problem occurs (low patterned
PL spectra based on various fabrication methods resolution, ~ micron scale) in spite of the good crystal
(Table 1). For the same perovskite material, the FWHM quality due to the epitaxial growth of crystal seeds. The
of PL spectra can partly reflect crystal quality because PL advantages and disadvantages of these fabrication
spectra can broaden when crystal quality is decreased. methods are schematically illustrated in Figure 9.
For thermal imprint and etching film, the pattern
resolution can decrease to nanometers. It should be
noted that the resolution of hundreds of nanometers 3 | APPLICATIONS IN OPTICS
(visible wavelength) is adequate based on their optic and A N D OP T O E L E C T RO N I CS
optoelectronic applications, because the emission wave-
length of lead halide perovskites is in the range of visible 3.1 | Applications in optics
light. For example, the metasurfaces based on lead halide
perovskite patterned structures take advantage of inter- Due to their novel properties, lead halide perovskite
ference of visible light to tune the wavelength, the patterned structures are used in a variety of optical
intensity, or the nonlinear optical effect, so the resolution applications. The Fabry–Perot (F–P) cavity consists of two
of hundreds of nanometers is adequate. However, their parallel plane reflectors, in which the light with specific
preparation process involves high temperatures or wavelength can stably form a standing wave.90 Lasing
etching; the crystal quality of patterned structures arrays can be attained when the optical gain of lead halide
fabricated using these methods can be adversely affected. perovskite arrays is greater than loss.91 As shown in
TABLE 1 Summary of various fabrication methods

Fabrication Patterned FWHM of
methods Materials resolution (μm) PL (nm) Advantages Disadvantages
Thermal imprint CsPbBr361 0.2 25 High pattern Relatively low crystal
resolution quality
MAPbI363 0.5 42
Etching film MAPbBr373 0.28 20 High pattern Relatively low crystal
resolution quality
MAPbBr389 0.8 ‐
CsPbBr369 10 15
Two‐step vapor‐ MAPbI371 40 40 Easy operation Relatively low crystal
phase growth quality, low
CsPbI379 1 75
pattern resolution
BA2PbI480 40 20
template‐confined MAPbBr384 10 25 Easy operation Relatively low crystal
solution growth quality, low
CsPbBr370 200 20
pattern resolution
57
CsPbCl3 20 23
67
(BA)2(MA)n−1PbnBr3n+1 20 35
(BA)2(MA)5Pb6Br1986 20 30
Seed‐assisted growth CsPbBr387 100 18 Good crystal Low pattern
quality resolution
CsPbBr334 10 12
Note: High patterned resolution means that it reaches nanoscale and low patterned resolution is in micron scale.
F I G U R E 9 Evaluation and comparison of crystal quality and patterned resolution for various fabrication methods. We distinguish the
positive and negative properties of various methods in patterned resolution and crystal quality by different quadrants. The positive direction
implies that the corresponding properties have some advantages and the negative direction implies that the corresponding properties have
some disadvantages. For example, seed‐assisted growth is located at quadrant Ⅳ, which means that the crystal quality is good but patterned
resolution is low. The question mark in the first quadrant indicates that realization of both high patterned resolution and good crystal
quality simultaneously remains a problem.
Figure 10, it has been demonstrated that F–P mode lasing nanowire versus pump density at 400 nm. The insets
arrays can be achieved based on lead halide perovskite show fluorescence microscopy images recorded below
patterned structures. Peng Liu and coauthors reported (left) and above (right) the lasing threshold, respectively.
F–P mode lasing arrays based on MAPbBr3 nanowires.84 When the pump density is above the lasing threshold, the
Figure 10A shows the PL spectra of a single MAPbBr3 luminescence at both ends of the nanowire is brighter
F I G U R E 10 F–P mode lasing arrays. MAPbBr3 nanowires for F–P lasing arrays. (A) PL spectra versus pump density at 400 nm of a
single MAPbBr3 nanowire. The insets show fluorescence microscopy images recorded below (left) and above (right) the lasing threshold.
The scale bar is 10 μm. (B) PL intensity as a function of pump density. (C) Time‐resolved PL intensity of a single MAPbBr3 nanowire,
suggesting the evolution from spontaneous emission to lasing emission with increasing pump density. (D) Fluorescence microscopy image
of a 2 × 5 MAPbBr3 nanowire array above the lasing threshold. The scale bar is 10 μm. (E) PL spectra collected from MAPbBr3 nanowires
labeled 1−10 in (D). (F) Mode spacing Δλ around λ = 543 nm versus reciprocal of length of MAPbBr3 nanowires. Inset: schematic
illustration of the F–P cavity. Reproduced with permission: Copyright 2017, American Chemical Society.84 F–P lasing arrays based on 2D
layered R–P perovskite nanowires. (G) Fluorescence images of n = 3 R–P perovskite nanowire arrays collected above the lasing threshold.
(H) PL spectra recorded from nanowire 6 labeled in (G) as a function of pump density. The inset shows the plot of PL intensity as a function
of pump density. (I) Mode spacing versus reciprocal of lengths of nanowires. Reproduced with permission: Copyright 2018, Wiley‐VCH.92
than that in the middle, indicating that the nanowire pump density. Figure 10D shows the fluorescence
forms an F–P mode cavity. Figure 10B shows the PL microscopy image of a 2 × 5 MAPbBr3 nanowire array
intensity as a function of pump density, showing a typical above the lasing threshold. Figure 10E shows the PL
S‐shaped curve, demonstrating the formation of lasing. spectra collected from MAPbBr3 nanowires labeled 1−10
Figure 10C shows the time‐resolved PL intensity of a in Figure 10D, indicating that all nanowires yielded
single MAPbBr3 nanowire, indicating the evolution from almost consistent mode characteristics. The mode spacing
spontaneous emission to lasing emission with increasing Δλ around λ = 543 nm was inversely proportional to the
length of the MAPbBr3 nanowires (Figure 10F), demon- function of pump density with a typical S‐shaped curve.
strating the F–P mode lasing whose schematic illustration Mode spacing versus reciprocal of lengths of nanowires
is shown in the inset of Figure 10F. Moreover, Haihua demonstrates F–P mode lasing.
Zhang and coauthors achieved room‐temperature ampli- Besides the F–P mode, whispering gallery mode (WGM)
fied spontaneous emission and nanowire lasing based on microcavities can achieve 3D confinement of light due to the
the 2D R–P perovskites of (BA)2(FA)n‐1PbnBr3n+1.92 total internal reflection and there are no such corner optical
Figure 10G shows the fluorescence images of n = 3 R‐P losses.93,94 It has been reported that WGM lasing arrays can
perovskite nanowire arrays collected above the lasing be achieved based on perovskite patterned structures
threshold, showing bright emission of green light. (Figure 11). Xinfeng Liu and coauthors realized room‐
Figure 10H shows the PL spectra recorded from nanowire temperature high‐quality factor WGM lasing (Q ≈ 1210)
6 labeled in Figure 10G as a function of pump density. The arrays from patterned lead halide perovskite microplatelets.68
inset of Figure 10H shows the plot of PL intensity as a Figure 11A shows the SEM image of the as‐prepared
F I G U R E 11 WGM lasing arrays. WGM lasing arrays from MAPbI3 platelets. (A) SEM image of the as‐prepared MAPbI3 platelet arrays.
The scale bar is 100 μm. (B) Emission spectra with the pump fluences increasing at around the lasing threshold. (C) Lasing spectra of
MAPbI3 platelets with different edge lengths. The edge lengths from top to bottom are 8.3, 13.1, 16.8, and 19.6 μm, respectively. The
thickness of the platelet is ≈180 nm. (D) Mode spacing of the lasing peaks versus the reciprocal edge length. The experimental data can be
well fitted linearly (green line). (E) Logarithmic plot of the experimental lasing intensity with increasing pump fluence, showing a “kink”
region between spontaneous emission and lasing. (F) (ⅰ) Optical image of a representative perovskite platelet, (ⅱ) scattering image excited by
a 400 nm laser, (ⅲ) fluorescence image of perovskite above threshold, and (ⅳ) simulated field distribution of the resonant cavity mode. All
images have the same scale bar (i.e., 5 μm). Reproduced with permission: Copyright 2016, Wiley‐VCH.69 CsPbBr3 WGM micro‐laser arrays.
(G) Fluorescence image of the CsPbBr3 micro‐ring arrays. The scale bar is 20 μm. (H) Laser spectra recorded from nine micro‐rings in arrays
when the pump density is above the lasing threshold. Reproduced with permission: Copyright 2020, Royal Society of Chemistry.95
2D Ruddlesden–Popper perovskite micro‐ring laser arrays. (I) Fluorescence image of nine micro‐rings when the pump density is above the
lasing threshold. (J) Room‐temperature PL spectra collected from micro‐ring 8 labeled in panel (I) as a function of pump density. The inset
shows a laser spectrum above the threshold with a Gaussian fitting. Reproduced with permission: Copyright 2018, Wiley‐VCH.87
MAPbI3 microplatelet arrays, suggesting that the edge length spin‐coated film of MAPbI3 perovskite with a thickness of
of a single MAPbI3 hexagonal platelet is about 15 μm and the 200 nm, respectively. Figure 12D,E show the reflection
gap distance between two adjacent platelets is about 50 μm. spectra of asymmetric nanograting and nano slit metasur-
Figure 11B shows the emission spectra when the pump faces, with different etch depths from d ≈ 200 nm (fully
fluences increase around the tipping point of lasing etched) to d ≈ 20 nm. The peak position of the reflection
threshold. A broad spontaneous emission is observed below spectrum shifts with the change of the etching parameters.
the threshold, and narrow lasing peaks can be seen when the Figure 12F shows the corresponding optical microscope
pump fluence is above the threshold. Figure 11C shows the image of nanograting metasurfaces (period = 350 nm) with
lasing spectra of MAPbI3 platelets with different edge 19 different etch depths varying from d ≈ 200 nm (I) to
lengths. The edge lengths from top to bottom are 8.3, 13.1, d ≈ 20 nm (XVI), demonstrating the varying colors.
16.8, and 19.6 μm, respectively. The thickness of the platelet Figure 12G shows the marked points on the Commission
is about 180 nm. The lasing wavelength red shifts and mode International de L'Eclairage color palette created by the
spacing decreases with increasing hexagonal cavity edge nanograting metasurfaces, covering the three primary colors
length. Figure 11D shows the mode spacing of the lasing of red, green, and blue. Besides color manipulation,
peaks versus the reciprocal edge length. The experimental metasurfaces based on lead halide perovskite patterned
data can be fitted well linearly (green line), demonstrating structures can be used for enhancing emission and
the WGM cavities. Figure 11E shows the logarithmic plot absorption intensity.96 Figure 12H shows the absorption,
of the experimental lasing intensity with increasing transmission, and reflection spectra of nano‐hole perovskite
pump fluence, showing a typical S‐shaped curve with a metasurfaces (solid line) and an unpatterned perovskite film
‘kink' region between spontaneous emission and lasing. (dashed line), showing enhanced absorption. Figure 12I
Figure 11F‐ⅰ–iii shows the optical image and the fluorescence shows the PL spectra of a metasurface (blue line) and a
image of a MAPbI3 platelet when the pump fluence is below planar perovskite film (orange line). The inset of Figure 12I
and above the lasing threshold, respectively. When the pump shows PL mapping of the boundary between the metasurface
fluence is above the lasing threshold, the field distribution is (yellow region) and the planar film (red region), implying
consistent with the simulated one (Figure 11F‐ⅳ), implying enhanced PL emission intensity. The PL emission enhance-
the formation of WGM cavities. Moreover, Haihua Zhang ment of perovskite metasurfaces can be tuned by varying the
and coauthors reported WGM micro‐laser arrays with hole radius (Figure 12J). Additionally, Yubin Fan and
CsPbBr3 micro‐ring arrays.95 Figure 11G shows the fluores- coauthors found that the three‐photon luminescence was
cence image of the CsPbBr3 micro‐ring arrays with a more efficient and showed greater enhancement on lead
homogeneous size and a precise position. Figure 11H shows halide perovskite metasurfaces.58 Figure 12K shows the tilt‐
the laser spectra recorded from nine micro‐rings in arrays view SEM image of the MAPbBr3 perovskite metasurface.
when the pump density is above the lasing threshold. Their Figure 12L shows the enhancement factor of three‐photon
lasing modes and peak positions are very similar. Their emission (orange dots) and third harmonic generation (blue
research group also demonstrated WGM micro‐laser arrays dots) as a function of excitation wavelength, which is
with 2D R‐P perovskites micro‐ring arrays.86 Figure 11I consistent with the corresponding numerically calculated
shows the fluorescence image of nine micro‐rings when the resonant enhancement (the red dashed line in Figure 12L).
pump density is above the lasing threshold. Spatial Last but not the least, importantly, Guankui Long and
interference patterns of all nine micro‐rings show their coauthors used a planar nanostructure design to realize all‐
coherent lasing emission. Figure 11J shows the room‐ dielectric perovskite metasurfaces with giant superstructural
temperature PL spectra collected from micro‐ring 8 labeled chirality (Figure 12M).60 They obtained a large anisotropy
in Figure 11I as a function of pump density. The inset shows factor of 0.49 and circular dichroism of 6350 mdeg, giving
a laser spectrum above the threshold with a Gaussian fitting. rise to the potential application of chiral light detection.60
The FWHM is approximately 0.21 nm, corresponding to a Q
factor of approximately 2600 for Q ≈ λ/Δλ with the emission
wavelength of 546 nm. 3.2 | Applications in optoelectronics
In addition, lead halide perovskite patterned structures
can be used as metasurfaces as a result of their periodicity Perovskite patterned structures facilitate their applica-
and adjustability of spatial distributions at wavelength scale. tions in integrated optoelectronic devices. For example,
Behrad Gholipour and coauthors demonstrated tunable photodetectors based on perovskite patterned structures
structural color and radiative emission properties with provide alternative candidates for next‐generation high‐
perovskite metasurfaces.59 Figure 12A–C show the corre- performance and flexible imaging systems. Hui Deng and
sponding SEM images of unpatterned, asymmetric nano- coauthors reported photodetectors based on perovskite
grating, and nano slit metasurfaces fabricated in a patterned structures used for spatial intensity distribution
F I G U R E 12 Perovskite metasurfaces. Tunable structural color and radiative emission properties with perovskite metasurfaces.
Corresponding SEM images of (A) unpatterned, (B) asymmetric nanograting, and (C) nano slit metasurfaces fabricated in a spin‐coated film of
MAPbI3 perovskite with a thickness of 200 nm. Reflection spectra of (D) asymmetric nanograting and (E) nano slit metasurfaces, with different
etch depths from d ≈ 200 nm (fully etched) to d ≈ 20 nm. (F) Corresponding optical microscope image of nanograting metasurfaces (period =
350 nm) with 19 different etch depths varying from d ≈ 200 nm (I) to d ≈ 20 nm (XVI). (G) The marked points on the Commission International
de L'Eclairage color palette are created by the nanograting metasurfaces. Reproduced with permission: Copyright 2017, Wiley‐VCH.59
Perovskite metasurfaces for enhanced emission and absorption. (H) Absorption, transmission, and reflection spectra of nano‐hole perovskite
metasurfaces (solid line) and an unpatterned perovskite film (dashed line); letters A, T, and R represent absorption, transmission, and
reflection, respectively. (I) PL spectra of a metasurface (blue line) and a planar perovskite film (orange line). The inset shows a PL mapping of
the boundary between the metasurface (yellow region) and the planar film (red region). The scale bar is 10 μm. The samples are excited by a
514 nm laser. (J) PL emission enhancement of perovskite metasurfaces with varying hole radii. Reproduced with permission: Copyright 2020,
Wiley‐VCH.96 Resonance‐enhanced three‐photon emission with lead halide perovskite metasurfaces. (K) Tilt‐view SEM image of the MAPbBr3
perovskite metasurface. The scale bar is 2 μm. (L) Enhancement factor of three‐photon emission (orange dots) and third harmonic generation
(blue dots) as a function of excitation wavelength. Here, the pump density is maintained at 30 mJ cm−2. The red dashed line shows the
corresponding numerically calculated resonant enhancement of excited laser by considering the actual size and morphology of the fabricated
perovskite metasurfaces. Reproduced with permission: Copyright 2019, Nature Publishing Group.58 (M) Experimental circular dichroism of
unpatterned MAPbI3 film, right‐, and left‐handed perovskite chiral metasurfaces, illuminated over a solid angle with a numerical aperture of 0.
1. The insets show scanning electron microscopy images of 3 × 3 unit cells of left‐ and right‐handed perovskite chiral metasurfaces. Reproduced
with permission: Copyright 2022, Nature Publishing Group.60
F I G U R E 13 Perovskite patterned structures for photodetectors. Photodetectors based on perovskite patterned structures used for spatial
intensity distribution mapping of light sources. (A) Schematic illustration of one photodetector (top) and photograph of network
photodetector arrays (bottom). The length, width, and thickness of the channel between two adjacent square pads are 200, 500, and 100 nm,
respectively. (B) Spatial intensity distribution of a light source. The four colors denote the four light power densities of 10, 40, 80, and
100 μW/cm2, respectively. (C) Photocurrent mapping obtained from the network photodetector arrays. (D) Current statistic values of 49
network photodetectors excited by a 650 nm light at various power densities (0–100 μW/cm2) at a 10 V bias voltage. Reproduced with
permission: Copyright 2015, American Chemical Society.65 MAPbI3 microwire arrays used for a flexible photodetector. (E) Schematic
illustration of the flexible photodetector. The inset shows a photograph of the as‐fabricated flexible devices under bending conditions.
(F) Current of the flexible photodetector without bending and after 5, 10, 100, 150, and 200 cycles of bending with a bending radius of 18 mm
in the dark (OFF) and illuminated by a 520 nm light source (ON). (G) Current of the flexible photodetector bent to different radii under OFF
and ON states. Reproduced with permission: Copyright 2019, Wiley‐VCH.97 Perovskite nanowire array photodetectors mounted in alumina
templates yield improved environmental stability. Light current decay for (H) a perovskite nanowire device inside a porous alumina
template and (I) a thin‐film device. The inset images in (H) and (I) show the schematic of a nanowire device and a thin‐film device with a
circular Au electrode on top, respectively. Reproduced with permission: Copyright 2016, American Chemical Society.98
mapping of light sources.65 Figure 13A shows the network photodetector arrays. The obtained photocurrent
schematic illustration of one photodetector (top) and mapping is generally consistent with the spatial intensity
the photograph of network photodetector arrays (bot- distribution of the light source. Figure 13D shows the
tom). Figure 13B shows the spatial intensity distribution current statistic values of 49 network photodetectors
of a light source. Figure 13C shows the photocurrent excited by a 650 nm light in various power densities,
mapping of the light source, which is obtained from the indicating the good stability of photocurrent.
Furthermore, Chun‐Yan Wu and coauthors reported

MAPbI3 microwire arrays used for flexible photodetec-
tors.97 Figure 13E shows the schematic illustration of the
flexible photodetectors. The inset shows the photograph
of as‐fabricated flexible devices under bending conditions.
Figure 13F shows the current of the flexible photo-
detector without bending and after various cycles of
bending with a bending radius of 18 mm in the dark
(OFF) and under the illumination of a 520 nm light
source (ON). The almost constant photocurrent and dark
current imply the excellent stability of the flexible
photodetector under bending conditions, which is also
proved by the current of the flexible photodetector bent to
different radii under OFF and ON states (Figure 13G).
The environmental stability of photodetectors is a critical
property for practical applications. In addition, Aashir
Waleed and coauthors reported perovskite nanowire
array photodetectors mounted in alumina templates
yielding improved environmental stability.98 The inserted
images in Figure 13H,I show the schematic of a nanowire F I G U R E 14 Perovskite patterned structures for
device and a thin‐film device with a circular Au electrode phototransistors. (A) OM image of the MAPbI3 nanoparticles on
on top, respectively. Light current decay over time for the the surfaces of the C8‐BTBT single‐crystal array. (B) Four
perovskite nanowire device inside the porous alumina representative programming and erasing cycles of the device.
template (Figure 13H) versus the thin‐film device (C) Transfer characteristics of the hybrid phototransistor during
(Figure 13I) shows the significantly improved environ- programming and erasing cycles. (D) Long‐term stability of the
mental stability (7 days compared with 30 min). hybrid phototransistor. Reproduced with permission: Copyright
Moreover, perovskite patterned structures represent 2019, American Chemical Society.64
promising candidates for use in integrated high‐
performance phototransistors. A phototransistor is a kind
of device with both photodetection and field effect transistor cells.8 However, a single perovskite crystal generates
characteristics.99,100 For instance, Xiuzhen Xu and coau- photogenerated current only depending on the intrinsic
thors reported the fabrication of high‐performance photo- light absorption of a single piece.104 In contrast, their
transistors based on a hybrid structure of a 2,7‐dioctyl1 patterned structures have been considered to improve power
benzothieno[3,2‐b]1 benzothiophene (C8‐BTBT) single‐ conversion efficiency greatly due to the improved light
crystal array coated with MAPbI3 nanoparticles absorption efficiency caused by the interference of light.66
(Figure 14A).64 Figure 14B shows four representative Figure 15A,B shows the simulation of improving the power
programming and erasing cycles of the device, showing conversion efficiency of a perovskite solar cell by introducing
that the ON/OFF ratio is high, above 105. Figure 14C shows two kinds of nano textures on it: column‐shaped nano
the transfer characteristics of the hybrid phototransistor hollow (CLNH) arrays (Figure 15A) and cone‐shaped nano
during programming and erasing cycles. After 50 days, the hollow (CNNH) arrays (Figure 15B).66 Figure 15C shows the
Ids–Vg curve of the device showed almost no change ultimate power conversion efficiencies η0 for the CLNH and
(Figure 14D). The phototransistor shows good long‐term CNNH textured MAPbI3 solar cells, which are, respectively,
stability, which is critical for practical applications. two to three times higher compared with those of a
On the other hand, lead halide perovskites show superior nontextured planar film. Integration with silicon is of great
performance on photovoltaic devices due to their relatively significance for practical applications due to the dominant
long carrier lifetime, high carrier mobility, and high role of silicon in current electronic circuits. Figure 15D
photogenerated carrier efficiency, which is conducive to shows the schematic illustration of fabrication of a four‐
meeting the needs of modern society for low‐carbon terminal solar cell based on perovskite nanopillar arrays and
emission and environmental protection.101 Initially manu- single‐crystalline silicon.105 Additionally, it has been experi-
factured with a power conversion efficiency of 3.8%, mentally proven that the performance of solar cells based on
perovskite solar cells have now achieved a lab‐scale power perovskite patterned structures is better than that based on
conversion efficiency of over 25%,102,103 comparable with the their film.106 Figure 15E shows that the open‐circuit voltage
performance of commercial multicrystalline silicon solar (VOC) of a target (assisted by perovskite crystal array) device
F I G U R E 15 Perovskite patterned structures for solar cells. Simulation of improving the power conversion efficiency of a perovskite
solar cell by introducing nano textures. Two kinds of nano texture arrays are simulatively introduced on a MAPbI3 perovskite film:
(A) column‐shaped nano hollow (CLNH) arrays and (B) cone‐shaped nano hollow (CNNH) arrays. (C) Optimized ultimate power
conversion efficiencies η0 for the CLNH and CNNH textured MAPbI3 solar cells, compared with those of a nontextured planar film.
Reproduced with permission: Copyright 2018, Elsevier.66 (D) Schematic illustration of a four‐terminal solar cell based on perovskite
nanopillar arrays and single‐crystalline silicon. The system consists of a top sub cell composed of periodically arranged MAPbI3 perovskite
nanopillars and a single‐crystalline silicon heterojunction bottom sub‐cell. Reproduced with permission: Copyright 2017, American
Chemical Society.105 (E) Light intensity‐dependent VOC using a range of background illumination intensities for the control (film) and the
target (assisted by perovskite crystal array) device. (F) EQE curves of a 0.0784 cm2 perovskite solar cell over 300 to 850 nm wavelengths and
integrated JSC under 1 sun illumination of control and target devices. Reproduced with permission: Copyright 2022, The Royal Society of
Chemistry.106
with an area of 0.0784 cm2 is around 25 meV larger than that connections can improve this margin.106 Therefore, perov-
of a film device under the same light intensity.106 Figure 15F skite patterned structures show excellent potential for use in
shows that the EQE and short‐circuit current (JSC) of a target energy harvesting.
device are almost 10% and 1.5 mA cm−2 higher than those of Besides conversion from light energy into electric energy,
a film device under the same wavelength of illumination lead halide perovskite patterned structures can also be
light, respectively. Further enhancement of crystallinity, applied to devices that convert electric energy into light
lowering of defect density, and series and parallel energy, for example, LED arrays.107,108 Their patterned
F I G U R E 16 Perovskite patterned structures for LEDs. (A) J–L–V and (B) EQE–CE–V curves of the LEDs. The inset in (B) shows an EL
image of eight devices. Every single device has a size of 2.0 mm × 2.8 mm. EL scalability demonstration: (C) a 3 cm × 5 cm display pattern
and a four‐inch wafer‐scale device (D) without and (E) with a current distribution gridline electrode. Reproduced with permission:
Copyright 2022, Nature Publishing Group.109
structures can be accomodate for large‐scale LED arrays to new optical phenomena or significant applications in
rather than a single LED, which makes them the candidate optoelectronic devices. Above, we introduce some
for integrated and energy‐efficient display devices.109 For current common methods for fabricating lead halide
instance, Figure 16A,B shows the J–L–V and EQE–current perovskite patterned structures, including thermal
efficiency (CE)–V curves of the LED arrays fabricated by imprint, etching film, two‐step vapor‐phase growth,
space‐confined growth.109 The luminance can reach over 104 template‐confined solution‐growth, and seed‐assisted
cd m−2 at 8 V, while an iPad Air 3 tablet screen can only growth. Their advantages and disadvantages in terms of
reach a luminance of around 170 cd m−2.110 The EQE maxes crystal quality and patterned resolution are discussed in
at 7.3% on applying a voltage of about 5 V, which is 90 times detail. Finally, we discuss a variety of potential applica-
higher than the value reported in a metal–insulator– tions in optics and optoelectronics of lead halide
semiconductor junction that injects carriers into a perovskite patterned structures, including lasing emission, meta-
polycrystalline film.111 Specifically, a 3.5 cm × 5.0 cm electro- surfaces, photodetectors, phototransistors, solar cells,
luminescence (EL) pattern and a two four‐inch wafer‐scale and LEDs. The various fabrication methods and the
EL patterned array without and with extra current distribu- diversity of properties and applications of lead halide
tion gridlines are shown in Figure 16C–E, respectively, perovskite patterned structures presented in this review
demonstrating their high potential for use in an integrated demonstrate that they have the potential for use in the
and energy‐efficient display device.109 manufacture of high‐performance on‐chip optoelectronic
devices. They can be combined with 2D materials. We
are about to carry out research in this aspect. In
4 | SUMMARY AND O UTLOOK particular, perovskite patterned structures, which we
have made efforts to grow and presented in our previous
Lead halide perovskite patterned structures provide a papers, are important for fabrication of integrated
platform for theoretical research and experiments in chips.34 Although experiments of optical properties and
fundamental physics and optical and optoelectronic optoelectronic applications have been reported and
applications. Due to the periodicity and adjustability of demonstrated on lead halide perovskite patterned struc-
spatial distributions, they yield novel properties that tures, studies on thee are still in the early stage. There are
bulk‐, micro‐, and nano‐crystals do not possess, leading still some challenges in both fundamental science and
device applications in terms of lead halide perovskite for perovskites with commonly cubic phase, it is likely to
patterned structures. These issues need to be addressed be etched to square shape arrays by the self‐etching. We
and more efforts should be devoted to ensure further believe that the self‐etching along the crystal structure by
practical applications. adequate etchant such as tentatively hydrogen halides is
First, for their practical applications in solar cells and also a promising process for patterned lead halide
photodetectors, toxicity to humans and the low stability perovskites. In addition, with the improved resolution
of perovskite patterned structures against oxygen and of printers, printing may be a promising method to
moisture are issues that need to be resolved urgently. For synthesize perovskite patterned structures with high
toxicity, although lead‐free perovskites are becoming patterned resolution and good crystal quality. Theoreti-
increasingly more popular and their patterned structures cally, the resolution of laser printers is only limited by
have been studied, their optical and optoelectronic the laser wavelength.
properties are not so attractive compared with lead Moreover, lead halide perovskite patterned struc-
halide perovskite patterned structures.62,112 Thus, ex- tures with periodicity or adjustability in 3D spatial
ploration of nontoxic perovskite patterned structures distributions are important. For instance, as a unique
with excellent optical and optoelectronic properties is photonic band gap material, 3D photonic crystals have
necessary. Besides, development of advanced packaging excellent photonic propagation characteristics in 3D
technology on devices is a feasible approach for tackling space.120 Therefore, they have extensive potential
the problem of toxicity to humans and improving application in optical physical devices, electromagnetic
stability against oxygen and moisture.113,114 For example, wave regulation, intelligent infrared stealth technology,
conductive glass (such as indium tin oxide) can be and other fields.121,122 However, using most existing
utilized as a packaging material to maintain the methods, only 2D planar patterned structures can be
optoelectronic performance of perovskites. prepared. Recently, ion‐exchange‐mediated self‐
Second, at present, there is no method that can assembly was considered to synthesize FAPbBr3 3D
simultaneously yield high patterned resolution and good photonic crystals.123 Continuous tuning of the FAPbBr3
crystal quality. Currently no existing methods can be emission in the narrow range of 525–535 nm can be
positioned in the first quadrant in the plot in the achieved.123 However, self‐assembled photonic crystals
Figure 9. Microfluidic confining the perovskite precursor can easily decompose in a dilute solution during
solution to the PDMS template may be a feasible method subsequent device preparation, limiting their practical
to achieve high pattern resolution and good crystal applications.124 In addition, 3D printing is a technology
quality.115,116 The pattern resolution, in other words, the used to construct objects by layer printing based on
resolution of the PDMS template, is only limited by the digital model files and has intrinsic adaptability for fast
resolution of lithography, which can decrease to hun- fabrication of patterned structures.125 Therefore, as
dreds of nanometers (wavelength of visible light).117,118 long as suitable digital model files are constructed and
On the other hand, microfluidic confining can help to appropriate precursor materials are developed, high‐
promote the natural growth of perovskite crystals and quality and stable 3D perovskite patterned structures
reduce the influence of external mechanical forces, can be prepared by 3D printing.
improving the crystal quality of lead halide perovskite Last but not the least, existing fabrication methods
patterned structures. We can focus on other materials for of patterned perovskite structures generally involve a
use in new preparation methods, and self‐etching is one complicated operation process, which reduces the
example, which may be a promising process to achieve repeatability and production efficiency and increases
high resolution and high crystal quality simultaneously the cost of manufacture. How to simplify the prepara-
and can be positioned in the first quadrant in Figure 9. tion process to reduce the cost in large‐scale preparation
Self‐etching is a kind of orderly etching with a confined is a significant research topic in this field. For example,
etching direction, which is related to the intrinsic crystal most methods for synthesizing perovskite patterned
structure of the material and has been demonstrated in structures involve high‐temperature heating at present,
2D materials. Because etching occurs along the crystal which limits higher scalability and increases the
structure, self‐etching can maintain good crystal quality energy cost of their patterned structures for practical
after a high‐resolution patterning process.119 Ya Deng applications.126–129 Thus, development of a low‐
and coauthors reported CVD‐grown single‐crystalline temperature growth method with higher energy effi-
MoTe2 nanoribbon arrays whose resolution was about ciency of lead halide perovskite patterned structures is
100 nm.119 The as‐grown MoTe2 film can be self‐etched necessary and anticipated. Exploration of efficient
to rectangles by doubling the hydrogen content according catalyzers for low‐temperature, low energy‐cost fabrica-
to its crystal structure, ensuring good quality. Similarly, tion could also be a promising research topic.
ACKNOWLEDGMENTS 17. Sahli F, Werner J, Kamino BA, et al. Fully textured

The authors acknowledge support from the National monolithic perovskite/silicon tandem solar cells with 25.2%
Natural Science Foundation of China (Grant Nos. power conversion efficiency. Nat Mater. 2018;17(9):820‐826.
18. Park N‐G, Zhu K. Scalable fabrication and coating methods
51902061 and 62090031).
for perovskite solar cells and solar modules. Nat Rev Mater.
2020;5(5):333‐350.
C O N F LI C T S OF IN T E R E ST 19. He R, Huang X, Chee M, Hao F, Dong P. Carbon‐based
The authors declare no conflicts of interest. perovskite solar cells: from single‐junction to modules.
Carbon Energy. 2019;1(1):109‐123.
ORCID 20. Yuan Y, Lu J. Demanding energy from carbon. Carbon
Peijian Wang http://orcid.org/0000-0002-6201-7284 Energy. 2019;1(1):8‐12.
21. Liang C, Gu H, Xia J, et al. High‐performance flexible perovskite
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Reduced Size Carbon Energy - 2023 - Lan - Preparation and Promising Optoelectronic Applications of Lead Halide Perovskite Patterned

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Received: 30 October 2022 | Revised: 22 November 2022 | Accepted: 29 November 2022

Preparation and promising optoelectronic applications

Shangui Lan1,2 | Baojun Pan2 | Ying Liu1,2 | Zhixiang Zhang2 |

1 | INTRODUCTION formula of perovskite is AMX3, where A and M are

Carbon Energy. 2023;5:e318. wileyonlinelibrary.com/journal/cey2 | 1 of 25

hundreds of nanometers. In spite of their high patterned

2.2 | Etching film

To avoid the use of high temperature and pressure, an

F I G U R E 7 Template‐confined solution‐grown 2D layered perovskite patterned structures. Template‐confined growth of 2D layered

TABLE 1 Summary of various fabrication methods

Furthermore, Chun‐Yan Wu and coauthors reported

ACKNOWLEDGMENTS 17. Sahli F, Werner J, Kamino BA, et al. Fully textured

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