Preparation and promising optoelectronic applications of lead halide perovskite patterned structures:A review

Lead halide perovskites have received considerable attention from researchers over the past several years due to their superior optical and optoelectronic properties,because of which they can be a versatile platform for fundamental science research and applications.Patterned structures based on lead halide perovskites have much more novel properties compared with their more commonly seen bulk-,micro-,and nano-crystals,such as improvement in antireflection,light-scattering effects,and light absorption,as a result of their adjustability of spatial distributions.However,there are many challenges yet to be resolved in this field,such as insufficient patterned resolution,imperfect crystal quality,complicated preparation process,and so on.To pave the way to solve these problems,we provide a systematic presentation of current methods for fabricating lead halide perovskite patterned structures,including thermal imprint,use of etching films,two-step vapor-phase growth,template-confined solution growth,and seed-assisted growth.Furthermore,the advantages and disadvantages of these methods are elaborated in detail.In addition,thanks to the extraordinary properties of lead halide perovskite patterned structures,a variety of potential applications in optics and optoelectronics of these structures are described.Lastly,we put forward existing challenges and prospects in this exciting field.

Close-loop recyclable and flexible halide perovskite@wool keratin sensor with piezoelectric property

Halide perovskites with excellent piezoelectric properties,but their poor stability hinders their largescale application.Herein,a sandwich-structured halide perovskite flexible sensor with good stability was developed according to a three-step procedure as follows:(ⅰ) in-situ growth of wool keratinCsPbBr_(3)(WK-CsPbBr_(3)) using wool keratin in interfacial passivation and coating,(ⅱ) electrospinning of a wool keratin-CsPbBr_(3)/polyacrylonitrile(WCP) nanofiber film,and(ⅲ) coating of the WCP nanofiber with polydimethylsiloxane(PDMS) to obtain a sensor(WCPP).The sensor could generate a piezoelectric voltage of 7.8 V at a pressure of 6 kPa in the stages of pressing and releasing,and the output characteristics did not decline even after 10,000 cycles.Compared to the 4-month stability of the perovskite sensor,WCPP sensor exhibited the output performance even after 16 months,which indicated that wool keratin as a multidentate improved the stability of the halide perovskite.Additionally,the sensor displayed a self-cleaning property and could also light up 14 commercial LEDs.The close-loop recycling of the lead halide perovskite was achieved by dissolving the WCP nanofiber film in DMF and then reelectrospinning.Therefore,the method proposed is a step forward for achieving the commercialization of WK-CsPbBr_(3) and providing new avenues for further utilization of wool waste.

Infrared optical absorption of Fr?hlich polarons in metal halide perovskites

The formation of Frohlich polarons in metal halide perovskites,arising from the charge carrier-longitudinal optical(LO)phonon coupling,has been proposed to explain their exceptional properties,but the effective identification of polarons in these materials is still a challenging task.Herein,we theoretically present the infrared optical absorption of Frohlich polarons based on the Huang-Rhys model.We find that multiphonon overtones appear as the energy of the incident photons matches the multiple LO phonons,wherein the average phonon number of a polaron can be directly evaluated by the order of the strongest overtone.These multiphonon structures sensitively depend on the scale of electronic distribution in the ground state and the dimensionality of the perovskite materials,revealing the effective modulation of competing processes between polaron formation and carrier cooling.Moreover,the order of the strongest overtone shifts to higher ones with temperature,providing a potential proof that the carrier mobility is affected by LO phonon scattering.The present model not only suggests a direct way to verify Frohlich polarons but also enriches our understanding of the properties of polarons in metal halide perovskites.

Stretchable alkenamides terminated Ti_(3)C_(2)T_(x)MXenes to release strain for lattice-stable mixed-halide perovskite solar cells with suppressed halide segregation

Bandgap-tunable mixed-halide perovskite materials have attracted considerable interest because of their indispensability as top counterparts in tandem solar cells.However,the soft and disordered lattice always suffers from severe phase segregation under illumination,which is particularly susceptible to residual lattice strain.Herein,we report a strain regulation strategy by using alkenamides terminated Ti_(3)C_(2)T_(x)MXenes as an additive into perovskite precursor.Apart from the role of a template for grain growth to obtain high-quality films,the stretchable alkyl chain promotes lattice shrinkage or expansion to form an elastic grain boundary to eliminate the spatially distributed stain and shut down ion migration channels.As a result,the all-inorganic perovskite solar cells based on CsPbIBr_(2)and CsPbI_(2)Br halides achieve prolonged device stability under harsh conditions and the best power conversion efficiencies up to 11.06%and 14.30%,respectively.

Organic-inorganic halide perovskites for memristors

Organic-inorganic halides perovskites(OHPs)have drawn the attention of many researchers owing to their astonishing and unique optoelectronic properties.They have been extensively used for photovoltaic applications,achieving higher than 26%power conversion efficiency to date.These materials have potential to be deployed for many other applications beyond photovoltaics like photodetectors,sensors,light-emitting diodes(LEDs),and resistors.To address the looming challenge of Moore’s law and the Von Neumann bottleneck,many new technologies regarding the computation of architectures and storage of information are being extensively researched.Since the discovery of the memristor as a fourth component of the circuit,many materials are explored for memristive applications.Lately,researchers have advanced the exploration of OHPs for memristive applications.These materials possess promising memristive properties and various kinds of halide perovskites have been used for different applications that are not only limited to data storage but expand towards artificial synapses,and neuromorphic computing.Herein we summarize the recent advancements of OHPs for memristive applications,their unique electronic properties,fabrication of materials,and current progress in this field with some future perspectives and outlooks.

Temperature-dependent photoluminescence of lead-free cesium tin halide perovskite microplates

Tin halide perovskites recently have attracted extensive research attention due to their similar electronic and band structures but non-toxicity compared with their lead analogues. In this work, we prepare high-quality CsSnX_(3)(X=Br,I) microplates with lateral sizes of around 1–4 μm by chemical vapor deposition and investigate their low-temperature photoluminescence(PL) properties. A remarkable splitting of PL peaks of the CsSnBr_(3)microplate is observed at low temperatures. Besides the possible structural phase transition at below 70 K, the multi-peak fittings using Gauss functions and the power-dependent saturation phenomenon suggest that the PL could also be influenced by the conversion from the emission of bound excitons into free excitons. With the increase of temperature, the peak position shows a blueshift tendency for CsSnI_(3), which is governed by thermal expansion. However, the peak position of the CsSnBr3microplate exhibits a transition from redshift to blueshift at ~160 K. The full width at half maximum of CsSnX_(3)broadens with increasing temperature, and the fitting results imply that longitudinal optical phonons dominate the electron–phonon coupling and the coupling strength is much more robust in CsSnBr3than in CsSnI_(3). The PL intensity of CsSnX_(3)microplates is suppressed due to the enhanced non-radiative relaxation and exciton dissociation competing with radiative recombination. According to the Arrhenius law, the exciton binding energy of CsSnBr_(3)is ~38.4 meV, slightly smaller than that of CsSnI_(3).

Self-polarized RGB device realized by semipolar micro-LEDs and perovskite-in-polymer films for backlight applications

In backlighting systems for liquid crystal displays,conventional red,green,and blue(RGB)light sources that lack polarization properties can result in a significant optical loss of up to 50%when passing through a polarizer.To address this inefficiency and optimize energy utilization,this study presents a high-performance device designed for RGB polarized emissions.The device employs an array of semipolar blueμLEDs with inherent polarization capabilities,coupled with mechanically stretched films of green-emitting CsPbBr3 nanorods and red-emitting CsPbI3-Cs4PbI6 hybrid nanocrystals.The CsPbBr3 nanorods in the polymer film offer intrinsic polarization emission,while the aligned-wire structures formed by the stable CsPbI3-Cs4PbI6 hybrid nanocrystals contribute to substantial anisotropic emissions,due to their high dielectric constant.The resulting device achieved RGB polarization degrees of 0.26,0.48,and 0.38,respectively,and exhibited a broad color gamut,reaching 137.2%of the NTSC standard and 102.5%of the Rec.2020 standard.When compared to a device utilizing c-plane LEDs for excitation,the current approach increased the intensity of light transmitted through the polarizer by 73.6%.This novel fabrication approach for polarized devices containing RGB components holds considerable promise for advancing next-generation display technologies.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Flexible perovskite light-emitting diodes for display applications and beyond

The flexible perovskite light-emitting diodes(FPeLEDs),which can be expediently integrated to portable and wearable devices,have shown great potential in various applications.The FPeLEDs inherit the unique optical properties of metal halide perovskites,such as tunable bandgap,narrow emission linewidth,high photoluminescence quantum yield,and particularly,the soft nature of lattice.At present,substantial efforts have been made for FPeLEDs with encouraging external quantum efficiency(EQE)of 24.5%.Herein,we summarize the recent progress in FPeLEDs,focusing on the strategy developed for perovskite emission layers and flexible electrodes to facilitate the optoelectrical and mechanical performance.In addition,we present relevant applications of FPeLEDs in displays and beyond.Finally,perspective toward the future development and applications of flexible PeLEDs are also discussed.

Lead?Free Halide Double Perovskite Materials: A New Superstar Toward Green and Stable Optoelectronic Applications

Lead-based halide perovskites have emerged as excellent semiconductors for a broad range of optoelectronic applications, such as photovoltaics, lighting, lasing and photon detection. However, toxicity of lead and poor stability still represent significant challenges. Fortunately, halide double perovskite materials with formula of A_2M(I)M(III)X_6 or A_2M(IV)X_6 could be potentially regarded as stable and green alternatives for optoelectronic applications, where two divalent lead ions are substituted by combining one monovalent and one trivalent ions, or one tetravalent ion. Here, the article provides an up-to-date review on the developments of halide double perovskite materials and their related optoelectronic applications including photodetectors, X-ray detectors, photocatalyst, light-emitting diodes and solar cells. The synthesized halide double perovskite materials exhibit exceptional stability, and a few possess superior optoelectronic properties. However, the number of synthesized halide double perovskites is limited, and more limited materials have been developed for optoelectronic applications to date. In addition, the band structures and carrier transport properties of the materials are still not desired, and the films still manifest low quality for photovoltaic applications. Therefore, we propose that continuing e orts are needed to develop more halide double perovskites, modulate the properties and grow high-quality films, with the aim of opening the wild practical applications.

Low-Dimensional Halide Perovskites and Their Advanced Optoelectronic Applications

Metal halide perovskites are crystalline materials originally developed out of scientific curiosity. They have shown great potential as active materials in optoelectronic applications. In the last 6 years, their certified photovoltaic efficiencies have reached 22.1%. Compared to bulk halide perovskites, low-dimensional ones exhibited novel physical properties. The photoluminescence quantum yields of perovskite quantum dots are close to 100%. The external quantum efficiencies and current efficiencies of perovskite quantum dot light-emitting diodes have reached 8% and 43 cd A^(-1),respectively, and their nanowire lasers show ultralow-threshold room-temperature lasing with emission tunability and ease of synthesis. Perovskite nanowire photodetectors reached a responsivity of 10 A W^(-1)and a specific normalized detectivity of the order of 10^(12 )Jones. Different from most reported reviews focusing on photovoltaic applications, we summarize the rapid progress in the study of low-dimensional perovskite materials, as well as their promising applications in optoelectronic devices. In particular, we review the wide tunability of fabrication methods and the state-of-the-art research outputs of low-dimensional perovskite optoelectronic devices. Finally, the anticipated challenges and potential for this exciting research are proposed.

Metal halide perovskite photodetectors: Material features and device engineering

In recent years, the rapid progress of metal halide perovskite solar cells has been witnessed by the rocketing power conversion efficiency. In addition, perovskites have opened up a great opportunity for high performance photodetectors(PDs), due to their attractive optical and electrical properties. This review summarizes the latest progress of perovskitebased PDs, aiming to give a comprehensive understanding of the material design and device engineering in perovskite PDs.To begin with, the performance parameters and device configurations of perovskite PDs are introduced, which are the basis for the next discussion. Next, various PDs based on perovskites in different morphologies are discussed from two aspects:the preparation method, and device performance. Then, several device engineering strategies to enhance the performance of perovskite-based PDs are highlighted, followed by the introduction of flexible and narrow-band perovskite PDs. Finally,key issues and major challenges of perovskite PDs that need to be addressed in the future are outlined.

Origin of Luminescent Centers and Edge States in Low-Dimensional Lead Halide Perovskites:Controversies,Challenges and Instructive Approaches

With only a few deep-level defect states having a high formation energy and dominance of shallow carrier non-trapping defects,the defect-tolerant electronic and optical properties of lead halide perovskites have made them appealing materials for high-efficiency,low-cost,solar cells and light-emitting devices.As such,recent observations of apparently deep-level and highly luminescent states in low-dimensional perovskites have attracted enormous attention as well as intensive debates.The observed green emission in 2D CsPb2Br5 and 0 D Cs4PbBr6 poses an enigma over whether it is originated from intrinsic point defects or simply from highly luminescent CsPbBr3 nanocrystals embedded in the otherwise transparent wide band gap semiconductors.The nature of deep-level edge emission in 2D Ruddlesden–Popper perovskites is also not well understood.In this mini review,the experimental evidences that support the opposing interpretations are analyzed,and challenges and root causes forthe controversy are discussed.Shortcomings in the current density functional theory approaches to modeling of properties and intrinsic point defects in lead halide perovskites are also noted.Selected experimental approaches are suggested to better correlate property with structure of a material and help resolve the controversies.Understanding and identification of the origin of luminescent centers will help design and engineer perovskites for wide device applications.

Influence of defect states on the performances of planar tin halide perovskite solar cells

Although tin halide perovskite has shown excellent photoelectric performance, its efficiency of solar cell is low compared with that of lead halide. In order to enhance the efficiency of tin halide perovskite solar cell, a deep understanding of the role of the defects in the perovskite absorption layer and at the electron transport layer(ETL)/absorber or absorber/hole transport layer(HTL) interface is very necessary. In this work, the planar heterojunction-based CH_3NH_3SnI_3 perovskite solar cells were simulated with the SCAPS-1D program. Simulation results revealed a great dependence of device efficiency on defect density and interface quality of the perovskite absorber. The defect density at the front interface is critical for high efficiency, and the polarity of the interface charge has a different impact on the device efficiency. Strikingly, an efficiency over 29% was obtained under the moderate simulation conditions.

Light-emitting diodes based on all-inorganic copper halide perovskite with self-trapped excitons

Light-emitting diodes based on lead halide perovskite have attracted great attention due to their outstanding performance.However,their application is plagued by the toxicity of Pb and the poor stability.Herein novel copper-based all inorganic perovskite CsCu2I3 with much enhanced stability has been reported with a potential photoluminescence quantum yield(PLQY)over 20%and self-trapped excitons(STE).By taking advantage of its extraordinary thermal stability,we successfully fabricate high-quality CsCu2I3 film through direct vacuum-based deposition(VBD)of CsCu2I3 powder.The resulting film shows almost the same PLQY with the synthesized powder,as well as excellent uniformity and stability.The perovskite light-emitting diodes(Pe-LED)based on the evaporated CsCu2I3 emitting layer achieve a luminescence of 10 cd/m2 and an external quantum efficiency(EQE)of 0.02%.To the best of our knowledge,this is the first CsCu2I3 Pe-LED fabricated by VBD with STE property,which offers a new avenue for lead-free Pe-LED.

The application of halide perovskites in memristors

New neuromorphic architectures and memory technologies with low power consumption,scalability and high-speed are in the spotlight due to the von Neumann bottleneck and limitations of Moore’s law.The memristor,a two-terminal synaptic device,shows powerful capabilities in neuromorphic computing and information storage applications.Active materials with high defect migration speed and low defect migration barrier are highly promising for high-performance memristors.Halide perovskite(HP)materials with point defects(such as gaps,vacancies,and inversions)have strong application potential in memristors.In this article,we review recent advances on HP memristors with exceptional performances.First,the working mechanisms of memristors are described.Then,the structures and properties of HPs are explained.Both electrical and photonic HP-based memristors are overviewed and discussed.Different fabrication methods of HP memristor devices and arrays are described and compared.Finally,the challenges in integrating HP memristors with complementary metal oxide semiconductors(CMOS)are briefly discussed.This review can assist in developing HP memristors for the next-generation information technology.

Progress on the controllable synthesis of all-inorganic halide perovskite nanocrystals and their optoelectronic applications

In the past five years,all-inorganic metal halide perovskite(CsPbX3,X=Cl,Br,I)nanocrystals have been intensely studied due to their outstanding optical properties and facile synthesis,which endow them with potential optoelectronic applications.In order to optimize their physical and chemical properties,different strategies have been developed to realize the controllable synthesis of CsPbX3 nanocrystals.In this short review,we firstly present a comprehensive and detailed summary of existed synthesis strategies of CsPbX3 nanocrystals and their analogues.Then,we introduce the regulations of several reaction parameters and their effects on the morphologies of CsPbX3 nanocrystals.At the same time,we provide stability improvement methods and representative applications.Finally,we propose the current challenges and future perspectives of the promising materials.

Stability of mixed-halide wide bandgap perovskite solar cells: Strategies and progress

Benefiting from the superior optoelectronic properties and low-cost manufacturing techniques,mixedhalide wide bandgap(WBG)perovskite solar cells(PSCs)are currently considered as ideal top cells for fabricating multi-junction or tandem solar cells,which are designed to beyond the Shockley-Queisser(S-Q)limit of single-junction solar cells.However,the poor long-term operational stability of WBG PSCs limits their further employment and hinders the marketization of multi-junction or tandem solar cells.In this review,recent progresses on improving environmental stability of mixed-halide WBG PSCs through different strategies,including compositional engineering,additive engineering,interface engineering,and other strategies,are summarized.Then,the outlook and potential direction are discussed and explored to promote the further development of WBG PSCs and their applications in multijunction or tandem solar cells.

Doped all-inorganic cesium zirconium halide perovskites with high-efficiency and tunable emission

Doping enables manipulation of both the electrical and optical properties of halide perovskites.Herein,we incorporated Te^(4+) into Cs_(2)ZrCl_(6) single crystal,simultaneously preserving the vacancy-ordered structure,to obtain an efficient yellow-emitting perovskite with a near-unity photoluminescence quantum yield(PLQY≈97.6%).Te^(4+) doping modifies the hue and emission color of pristine Cs_(2)ZrCl_(6),generates new absorption channels,and successfully extends the excitation energy from<280 nm to 360-450 nm range.Detailed spectral characterizations,including ultrafast femtosecond transient absorption measurements,reveal that the bright yellow light is derived from triplet self-trapped excitons.Moreover,further tuning doping concentration enables Te-doped Cs_(2)ZrCl_(6) single crystals to exhibit efficient warm white light emission.This work provides a new perspective for the development and design of stable lead-free perovskites with highly efficient luminescence.

Comprehensive first-principles studies on phase stability of copper-based halide perovskite derivatives A_lCu_mX_n(A = Rb and Cs;X = Cl, Br, and I)

Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.