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).

First Principle Study of Cesium-based Lead-free Halide Double Perovskites

Inorganic halide double perovskites A_(2)B'B"X_(6) have gained significant interests for their diverse composition,stable physicochemical properties,and potential for photoelectric applications.The influences of trivalent and monovalent cations on the formation energy,decomposition energy,electronic structure and optical properties of cesium-based lead-free Cs^(+)_(2)B'B"Br_(6) (B'=Na^(+),In^(+)Cu^(+),or Ag^(+);B"=Bi^(3),Sb^(3+),In^(3+)) are systematically studied.In view of the analysis and results of the selected double perovskites,for the double perovskites with different B-site trivalent cation,the band gap increases in the order of Cs_(2)AgInBr_(6),Cs_(2)AgSbBr_(6) and Cs_(2)AgBiBr_(6),with Cs_(2)AgBiBr_(6) possessing the highest thermodynamic stability.Therefore,the Bi-based perovskites are further studied to elucidate the effect of monovalent cation on their stability and electronics.Results show that the thermodynamic stability rises in the sequence of Cs_(2)NaBiBr_(6),Cs_(2)InBiBr_(6),Cs_(2)AgBiBr_(6) and Cs_(2)CuBiBr_(6).Notably,Cs_(2)CuBiBr_(6) exhibits a relatively narrow and appropriate band gap of 1.4634 eV,together with the highest absorption coefficient than other compounds,suggesting that Cs_(2)CuBiBr_(6) is a promising light absorbing material that can be further explored experimentally and be applied to optoelectronic devices.Our research offers theoretical backing for the potential optoelectronic application of cesium-based lead-free halide double perovskites in solar energy conversion.

Hot carrier cooling in lead halide perovskites probed by two-pulse photovoltage correlation spectroscopy

The next-generation hot-carrier solar cells,which can overcome the Shockley-Queisser limit by harvesting excessenergy from hot carriers,are receiving increasing attention.Lead halide perovskite(LHP)materials are considered aspromising candidates due to their exceptional photovoltaic properties,good stability and low cost.The cooling rate of hotcarriers is a key parameter influencing the performance of hot-carrier solar cells.In this work,we successfully detected hotcarrier dynamics in operando LHP devices using the two-pulse photovoltage correlation technique.To enhance the signalto-noise ratio,we applied the delay-time modulation method instead of the traditional power modulation.This advancementallowed us to detect the intraband hot carrier cooling time for the organic LHP CH_(3)NH_(3)PbBr_(3),which is as short as 0.21 ps.In comparison,the inorganic Cs-based LHP CsPbBr_(3)exhibited a longer cooling time of around 0.59 ps due to differentphonon contributions.These results provide us new insights into the optimal design of hot-carrier solar cells and highlightthe potential of LHP materials in advancing solar cell technology.

First-Principles Calculations on Novel Rb-Based Halide Double Perovskites Alloys for Spintronics and Optoelectronic Applications

The outcomes of computational study of electronic, magnetic and optical spectra for A2BX6 (A = Rb;B = Tc, Pb, Pt, Sn, W, Ir, Ta, Sb, Te, Se, Mo, Mn, Ti, Zr and X = Cl, Br) materials have been proceeded utilizing Vanderbilt Ultra Soft Pseudo Potential (US-PP) process. The Rb2PbBr6 and Rb2PbCl6 are found to be a (Г-Г) semiconductors with energy gaps of 0.275 and 1.142 eV, respectively making them promising photovoltaic materials. The metallic behavior of the materials for Rb2BX6 (B = Tc, W, Ir, Ta, Mn, Sb, Mo) has been confirmed showing the attendance of conducting lineaments. The dielectric function is found to be large close to the ultraviolet districts (3.10 - 4.13 eV). The extinction coefficient of the Rb2BX6 has the ability to be used for implements. The band structures and density of states ensure the magnetic semiconductors’ nature of the Rb2Mn (Cl, Br)6 perovskites. The total calculated magnetic moment of Rb2MnCl6 and Rb2MnB6 is 3.00μβ. Advanced spintronic technology requires room-temperature ferromagnetism. The present work confirms that, bromine and chlorine-founded double perovskites are extremely attractive for photovoltaic and optoelectronic devices.

Lead-free halide perovskite Cs_(3)Bi_(2)Br_(9)single crystals for high-performance X-ray detection

All-inorganic lead-free halide perovskites have attracted interest owing to their high ambient and thermal stabilities,excellent optoelectronic properties,and environmental friendliness.Herein,the bismuth-based halide perovskite Cs_(3)Bi_(2)Br_(9)single crystals were successfully grown to a diameter of 12 mm and length of 40 mm using a modified Bridgman method for the first time.The resistivity and transmittance of transparent and crack-free Cs_(3)Bi_(2)Br_(9)single crystal are~6.8×10^(11)Ωcm and~80%,respectively.The carrier mobility of the(−120)plane is 0.17 cm^(2)V^(−1)s^(−1)along the[010]orientation(b axis),and the trap density is 9.7×10^(10)cm^(−3).Moreover,Cs_(3)Bi_(2)Br_(9)single crystals exhibit excellent potential for X-ray detection,including a high absorption coefficient,a superior X-ray sensitivity of~230.4μC Gyair^(−1)cm^(−2),and an ultra-low and no-drift dark current density of~17.8 pA mm−2,which enables lower noise and is also beneficial to the ultralow detection limit for X-ray detectors.Our study shows that Cs_(3)Bi_(2)Br_(9)is a promising candidate for X-ray detection applications.

Stability and optoelectronic property of lead-free halide double perovskite Cs_(2)B′BiI_(6)(B′=Li,Na and K)

Although lead-based perovskite solar cells have achieved more than 25%power conversion efficiency,the toxicity of lead and instability are still urgent problems faced in industrial application.Lead-free halide double perovskite(DP)materials are promising candidates to resolve these issues.Based on the density functional theory,we explore the geometric stability,thermodynamic stability,mechanical stability,electronic structures,and optical properties of theCs_(2)B 0BiI_(6)(B 0=Li,Na and K)DP materials.By analyzing the tolerance factor and octahedral factor,we find the geometric stabilities ofCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs are better thanCs_(2)LiBiI_(6).By calculating the total energy,formation energy and decomposition energy,we propose that the most favorable structure ofCs_(2)B 0BiI_(6) is the orthorhombic phase,andCs_(2)LiBiI_(6) is less stable relative to the other two counterparts from an energetic viewpoint.Mechanical stability evaluations reveal that the orthorhombicCs_(2)LiBiI_(6) material is less stable relative to the isostructuralCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs.The mechanical property calculations indicate that theCs_(2)B 0BiI_(6) DPs possess good ductility,which can be used as flexible materials.Electronic structures and optical property calculations show that the orthorhombicCs_(2)B 0BiI_(6) DPs have suitable band gap values,weaker exciton binding energies,and excellent optical absorption performance in the visible-light range.Based on the above comprehensive assessments,we can conclude that the orthorhombic Cs_(2)NaBiI_(6) and Cs_(2)KBiI_(6) DPs with good stability are promising candidates for solar cell applications.

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.

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.

Photo-and Electrocatalytic CO_(2)Reduction Based on Stable Lead-Free Perovskite Cs2PdBr6

All-inorganic lead-free palladium(Pd)halogen perovskites with prominent optoelectronic properties provide admirable potential for selective photo-and electroreduction of CO_(2).But it remains unachieved for effectively converting the CO_(2)to CO with high selectivity on Pd-based perovskites driven by solar light or electricity.Herein,high-quality Cs_(2)PdBr_(6)microcrystals and nanocrystals were synthesized through a facile antisolvent method.Among all the reported pure-phase perovskites,the Cs_(2)PdBr_(6)nanocrystals synthesized at 50℃performed the highest effectiveness on CO_(2)to CO conversion generating 73.8μmol g^(-1)of CO yield with 100%selectivity under visible light illumination(λ>420 nm)for 3 h.Meanwhile,for the first time,we report a new application of lead-free perovskites,in which they are applied to electrocatalysis of CO_(2)reduction reaction.Noticeably,they showed significant electrocatalytic activity(Faradaic yield:78%for CO)and operation stability(10 h).And the surface reaction intermediates were dynamically monitored and precisely unraveled according to the in situ diffuse reflectance infrared Fourier transform spectra investigation.In combination with the density functional theory calculation,the reaction mechanism and pathways were revealed.This work not only provides significant strategies to enhance the photocatalytic performance of perovskites,but also shows excellent potential for their application in electrocatalysis.

Direct drop-casting synthesis of all-inorganic lead and lead-free halide perovskite microcrystals for high-performance photodetectors

Due to the exciting photoelectric properties,better stability,and environmental-friendly nature,all-inorganic halide perovskites(AIHPs),especially the lead-free perovskites,have attracted worldwide attention.However,the film quality of AIHPs fabricated by typical spin-coating and subsequent high-temperature annealing is still not satisfactory,restricting their further development.Herein,we demonstrate a simple low-temperature solution-processed drop-casting method to achieve highly-crystalline cubic CsPbBr_(3)and lead-free layer-structured Cs_(3)Sb_(2)I_(9)microcrystals(MCs).This drop-casting technique not only consumes the less amount of precursor solution but also eliminates the high-temperature annealing as compared with those of spin coating.When these MCs are configured into photodetectors,they exhibit superior device performance,which is in distinct contrast to the one of spin-coated counterparts.Specifically,the responsivity of CsPbBr_(3)MCs is found to be as large as 8,990 mA/W,being 13 times larger than the spin-coated films and even better than many state-of-the-art solution-processed AIHPs devices.This device performance enhancement is attributed to the better film quality and phase purity obtained by the drop-casting method.All these results can evidently fill the“technology gap”for further enhancing the material quality of solution-processed AIHPs and breaking down the barriers that hinder the development of AIHPs based optoelectronic devices.

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.

Efficient Environment-friendly Lead-free Tin Perovskite Solar Cells Enabled by Incorporating 4-Fluorobenzylammonium Iodide Additives

Development of tin(Sn)-based perovskite solar cells(PSCs)largely lags behind that of lead counterparts due to fast crystallization process of Sn perovskite and numerous defects in both bulk and surface of Sn perovskite films.Herein,this work reports a facile strategy of introducing 4-fluorobenzylammonium iodide(FBZAI)as additives into Sn perovskite precursor to synergistically modulate the roles of benzylamine and fluorine in Sn-based PSCs.Incorporation of FBZAI can increase crystallinity,passivate defects,and inhibit the oxidation of Sn^(2+),leading to suppression of nonradiative recombination and enhancement of charge transport and collection in devices.As a result,the best-performing Sn-based PSC with the FBZAI additive achieves the maximum PCE of 13.85%with the enhanced fill factor of 77.8%and open-circuit voltage of 0.778 V.Our unencapsulated device exhibits good stability by maintaining 95%of its initial PCE after 160 days of storage.

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.

Stable yellow light emission from lead-free copper halides single crystals for visible light communication

Yellow light-emitting diodes(LEDs) as soft light have attracted abundant attention in lithography room, museum and art gallery. However, the development of efficient yellow LEDs lags behind green and blue LEDs, and the available perovskites yellow LEDs suffer from the instability. Herein, a pressure-assisted cooling method is proposed to grow lead-free CsCu2I3single crystals, which possess uniform surface morphology and enhanced photoluminescence quantum yield(PLQY) stability, with only 10% PLQY losses after being stored in air after 5000 h.Then, the single crystals used for yellow LEDs without encapsulation exhibit a decent Correlated Color Temperature(CCT) of 4290 K, a Commission Internationale de l’Eclairage(CIE) coordinate of(0.38, 0.41), and an excellent 570-h operating stability under heating temperature of 100°C. Finally, the yellow LEDs facilitate the application in wireless visible light communication(VLC), which show a-3 dB bandwidth of 21.5 MHz and a high achievable data rate of 219.2 Mbps by using orthogonal frequency division multiplexing(OFDM) modulation with adaptive bit loading. The present work not only promotes the development of lead-free single crystals, but also inspires the potential of CsCu2I3in the field of yellow illumination and wireless VLC.

Air-Stable,Eco-Friendly RRAMs Based on Lead-Free Cs_(3)Bi_(2)Br_(9)Perovskite Quantum Dots for High-Performance Information Storage

Development of lead-free halide perovskites that are innocuous and stable has become an attractive trend in resistive random access memory(RRAM)fields.However,their inferior memory properties compared with the lead-based analogs hinder their commercialization.Herein,the lead-free Cs_(3)Bi_(2)Br_(9)perovskite quantum dot(PQD)-based RRAMs are reported with outstanding memory performance,where Cs_(3)Bi_(2)Br_(9)quantum dots(QDs)are synthesized via a modified ligand-assisted recrystallization process.This is the first report of applying Cs_(3)Bi_(2)Br_(9)QDs as the switching layer for RRAM device.The Cs_(3)Bi_(2)Br_(9)QD device demonstrates nonvolatile resistive switching(RS)effect with large ON/OFF ratio of 105,low set voltage of-0.45 V,as well as good reliability,reproducibility,and flexibility.Concurrently,the device exhibits the notable tolerance toward moisture,heat and light illumination,and long-term stability of 200 days.More impressively,the device shows the reliable light-modulated RS behavior,and therefrom the logic gate operations including"AND"and"OR"are implemented,foreboding its prospect in logic circuits integrated with storage and computation.Such multifunctionality of device could be derived from the unique 2D layered crystal structure,small particle size,quantum confinement effect,and photoresponse of Cs_(3)Bi_(2)Br_(9)QDs.This work provides the strategy toward the high-performance RRAMs based on stable and eco-friendly perovskites for future applications.

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.

Phase transitions and degradation/oxidation mechanisms in lead-free CsSnI_(3) halide perovskites

Halide perovskites possess ultra-low thermal conductivity and show high potential for thermoelectric devices.The chemical properties and molecular structure of halide perovskite materials are not completely stable under ambient conditions,which hinders their use in thermoelectric generators.Changes in the properties of bulk halide perovskite thermoelectrics are accompanied by partial phase transitions and surface oxidation processes.In this paper,we conducted a comprehensive study of the transport and structural properties of CsSnI_(3),which were pristine by vacuum melting followed by spark plasma sintering.The research results on the electrical transport of these materials revealed that exposure to an inert atmosphere does not deteriorate stability and the properties of the materials remain unchanged.However,prolonged exposure to air leads to a significant degradation of the electrical transport properties.Contrary to thin-film samples,the shift to the double perovskite structure from the perovskite one is limited to a specific surface layer.This change significantly influences the electrical transport of the material while maintaining the essential properties of both perovskite types.

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.