Achieving Narrowed Bandgaps and Blue-Light Excitability in Zero-Dimensional Hybrid Metal Halide Phosphors via Introducing Cation-Cation Bonding

Zero-dimensional(0D)hybrid metal halides,which consist of organic cations and isolated inorganic metal halide anions,have emerged as phosphors with efficient broadband emissions.However,these materials generally have too wide bandgaps and thus cannot be excited by blue light,which hinders their applications for efficient white light-emitting diodes(WLEDs).The key to achieving a blue-light-excitable 0D hybrid metal halide phosphor is to reduce the fundamental bandgap by rational chemical design.In this work,we report two designed hybrid copper(I)iodides,(Ph_(3)MeP)_(2)Cu_(4)I_(6)and(Cy_(3)MeP)_(2)Cu_(4)I_(6),as blue-light-excitable yellow phosphors with ultrabroadband emission.In these compounds,the[Cu_(4)I_(6)]^(2-)anion forms an I6 octahedron centered on a cationic Cu_(4)tetrahedron.The strong cation-cation bonding within the unique cationic Cu_(4)tetrahedra enables significantly lowered conduction band minimums and thus narrowed bandgaps,as compared to other reported hybrid copper(I)iodides.The ultrabroadband emission is attributed to the coexistence of free and self-trapped excitons.The WLED using the[Cu_(4)I_(6)]^(2-)anion-based single phosphor shows warm white light emission,with a high luminous efficiency of 65 Im W^(-1)and a high color rendering index of 88.This work provides strategies to design narrow-bandgap 0D hybrid metal halides and presents two first examples of blue-light-excitable 0D hybrid metal halide phosphors for efficient WLEDs.

Deep Extractive Desulfurization of Gasoline with Ionic Liquids Based on Metal Halide

Ionic liquid [Et3NH]C1-FeCl3/CuCl was synthesized by mixing [Et3NH]Cl, anhydrous FeCl3 and anhydrous CuCl, and the desulfurization activity of this ionic liquid was tested. It exhibited remarkable ability in effective desulfurization of model gasoline （thiophene in n-octane） and fluid catalytic cracking （FCC） gasoline, and the sulfur removal of thiophene in model oil （V（IL）： V（oil）=0.08） could reach 93.9% in 50 min at 50 ℃. Low-sulfur （〈10 μg/g） FCC gasoline could be obtained after three extraction runs at an ionic liquid/oil volume ratio of 0.1, with the yield of FCC gasoline reaching 94.3%. The ionic liquid could be recycled 5 times with merely a slight decrease in activity.

Recent advances in metal halide perovskite photocatalysts:Properties,synthesis and applications

As a class of new emerged semiconductors,MHPs exhibit many excellent photoelectronic properties,which are superior to most conventional semiconductor nanocrystals(NCs).Particularly,MHPs have received extensive attention and brought new opportunities for the development of photocatalysis.Over the past few years,numerous efforts have been made to design and prepare MHP-based materials for a wide range of applications in photocatalysis,ranging from photocatalytic H_(2) generation,photocatalytic CO_(2) reduction,photocatalytic organic synthesis and pollutant degradation.In this review,recent advances in the development of MHP-based materials are summarized from the standpoint of photocatalysis.A brief outlook of this field has been proposed to point out some important challenges and possible solutions.This review suggests that the new family of MHP photocatalysts provide a new paradigm in efficient artificial photosynthesis.

Strategies and methods for fabricating high quality metal halide perovskite thin films for solar cells

With the development of human society,the problems of environmental deterioration and energy shortage have become increasingly prominent.In order to solve these problems,metal halide perovskite solar cells(PSCs)stand out because of their excellent properties(i.e.,high optical absorption coefficient,long carrier lifetime and carrier diffusion length,adjustable band gap)and have been widely studied.PSCs with low cost,high power conversion efficiency and high stability are the future development trend.The quality of perovskite film is essential for fabricating PSCs with high performance.To provide a full picture of realizing high performance PSCs,this review focuses on the strategies for preparing high quality perovskite films(including antisolvent,Lewis acid-base,additive engineering,scaleable fabrication,strain engineering and band gap adjustment),and therefore to fabricate high performance PSCs and to accelerate the commercialization.

Study on Thermal Expansion Coefficient of Sealing Materials for Ceramic Metal Halide Lamps

With Al2O3, Dy2O3, and SiO2 as starting materials, the basic glass of Al2O3-Dy2O3-SiO2 system was prepared by conventional melting technology, and their thermal expansion coefficients （TECs） at different anneal time were investigated. TECs of the basic glass, which were heat-treated under different temperature, were also investigated. The result showed that TECs of the basic glass gradually approached a fixed value as the anneal time was extended, which suggested that most of the inner stress had been eliminated. After heat treatment, the contents of Dy2O3, Dy2Si2O7, and a new crystal increased up to 1200 ℃ and decreased below 1250 ℃, which was consistent with the TEC change of crystallized samples. This suggests that the crystal has a direct effect on TECs of the crystallized samples.

Ionic Interactions in Molecular and Liquid States ofPolyvalent Metal Halides

Progress in the development of phenomenological models for the microscoplc interactions in the halides of polyvalent metals is reviewed, with main attention to neutral and ionized molecular states and to the melts of these materials. The following physical problems are discussed: (1)bond bending in the molecules of the alkaline-earth halides, (2) binding of molecular dimers and halogen transfer reactions relevant to the melts of trivalent metal halides, (3) stability of molecular ions in liquid mixtures of polyvalent metal halides and alkali halides, and (4) stabilityof molecular ions and reduced-valence states in molten cryolite under addition of sodium metal.

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.

Temperature-dependent self-trapped exciton emission in Cu(I) doped zinc-based metal halides from well-resolved excited state structures

Zero-dimensional metal halides are of unique structures and tunable photoluminescence properties,showing great potential applications such as light-emitting diodes(LEDs)and sensing.Herein,we successfully synthesized Cu^(+)doped(MA)_(2)ZnCl_(4)metal halides by a slow evaporation solvent method.The introduction of Cu^(+)results in sky-blue self-trapped exciton emission in(MA)_(2)ZnCl_(4) at 486 nm at room temperature,and a photoluminescence quantum yield is as high as 54.9%.Interestingly,at low temperatures,Cu^(+)-doped(MA)_(2)ZnCl_(4) exhibits two emission peaks located at 482 and 605 nm,respectively.This temperaturedependent dual emission indicates two excited state structures that exist on the triplet excited-state potential energy surface.In addition,the temperature sensor we fitted has good performance(Sr=1.65%·K^(−1)),which is the first attempt in Cu^(+) doped Znbased metal halides.Our work enriches the family of sky-blue metal halides and provides a promising strategy for building skyblue LEDs.

Near-infrared emitting metal halide materials:Luminescence design and applications

Near-infrared(NIR)luminescent metal halide(LMH)materials have attracted great attention in various optoelectronic applications due to their low-temperature solution-processable synthesis,abundant crystallographic/electronic structures,and unique optoelectronic properties.However,some challenges still remain in their luminescence design,performance improvement,and application assign-ments.This review systematically summarizes the development of NIR LMHs through classifying NIR luminescent origins into four major categories:band-edge emission,self-trapped exciton(STE)emission,ion emission,and defect-related emission.The luminescence mechanisms of different types of NIR LMHs are discussed in detail by analyzing typical examples.Reasonable strategies for design-ing and optimizing luminescence/optoelectronic properties of NIR LMHs are summarized,including bandgap engineering,self-trapping state engineering,chemical composition modification,energy transfer,and other auxiliary strategies such as improvement of synthesis scheme and post-processing.Furthermore,application prospects based on the optoelectronic devices are revealed,including phosphor-converted light-emitting diodes(LEDs),electroluminescent LEDs,pho-todetectors,solar cells,and x-ray scintillators,as well as demonstrations of some related practical applications.Finally,the existing challenges and future perspec-tives on the development of NIR LMH materials are critically proposed.This review aims to provide general understanding and guidance for the design of high-performance NIR LMHs materials.

Realizing efficient emission and triple-mode photoluminescence switching in air-stable tin(IV)-based metal halides via antimony doping and rational structural modulation

Recently,many lead-free metal halides with diverse structures and highly efficient emission have been reported.However,their poor stability and single-mode emission color severely limit their applications.Herein,three homologous Sb^(3+)-doped zero-dimensional(0D)air-stable Sn(IV)-based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl_(4)lattice,which brings different optical properties.Under photoexcitation,(C_(25)H_(22)P)SnC_(l5)@Sb⋅CH_(4O)(Sb^(3+)−1)does not emit light,(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-α(Sb^(3+)−2α)shines bright yellow emission with a photoluminescence quantum yield(PLQY)of 92%,and(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-β(Sb^(3+)−2β)exhibits intense red emission with a PLQY of 78%.The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions.Particularly,Sb^(3+)−1 can be successfully converted into Sb^(3+)−2αunder the treatment of C_(25)H_(22)PCl solution,accompanied by a transition from nonemission to efficient yellow emission,serving as a“turn-on”photoluminescence(PL)switching.Parallelly,a reversible structure conversion between Sb^(3+)−2αand Sb^(3+)−2βwas witnessed after dichloromethane or volatilization treatment,accompanied by yellow and red emission switching.Thereby,a triple-mode tunable PL switching of off-onI-onII can be constructed in Sb^(3+)-doped Sn(IV)-based compounds.Finally,we demonstrated the as-synthesized compounds in fluorescent anticounterfeiting,information encryption,and optical logic gates.

Ion migration in 3D metal halide perovskite field effect transistors

3D perovskite materials are advancing rapidly in the field of photovoltaics and light-emitting diodes,but the development in field effect transistors(FETs)is limited due to their intrinsic ion migration.Ion migration in perovskite FETs can screen the electric field of the gate and affect its modulation,as well as influence the charge carriers transport,leading to non-ideal device characteristics and lower device stability.Here,we provide a concise review that explains the mechanism of ion migration,summarizes the strategies for suppressing ion migration,and concludes with a discussion of the future prospects for 3D perovskite FETs.

Space-confined growth of metal halide perovskite crystal films

Metal halide perovskites,as a new generation of optoelectronic materials,have attracted a great deal of interest due to their remarkable intrinsic properties.Due to the excellent optoelectronic properties,the perovskite crystals are widely used in lasers,photodetectors,X-ray detectors and solar cells.Considering the device performance and fabrication requirements,proper thickness of the crystal is required to avoid carrier loss and simultaneously ensure sufficient light absorption,which can realize the full potential of its excellent carrier transport property.Thus,the fabrication of perovskite crystal in a thin film with an adjustable thickness is highly desirable.The space-confined method has been demonstrated to be an effective way of preparing perovskite with controlled thickness.In this method,the thickness of perovskite can be regulated flexibly in a geometric confined space.Moreover,the size,quality and architecture of perovskite crystal films are also major concerns for practical photoelectric devices,which can also be optimized by the space-confined method owing to its good adaptability towards various modified strategies.In a word,the space-confined method is not only a simple and conventional way to adjust the thickness of perovskite crystal films,but also provides a platform to optimize their size,quality and architecture through applying appropriate strategies to the confined space.Herein,we review the space-confined growth of perovskite crystal films.Particularly,various modified strategies based on the space-confined method applied to the optimization of thickness,size,quality and architecture are highlighted.Then the stability investigating and component regulating of perovskite crystal films would be also mentioned.Furthermore,the correlation between the perovskite thickness and the device performance is discussed.Finally,several key challenges and proposed solutions of perovskite thin films based on the space-confined method are discussed.

Metal Halide Perovskite for next-generation optoelectronics:progresses and prospects

Metal halide perovskites(MHPs),emerging as innovative and promising semiconductor materials with prominent optoelectronic properties,has been pioneering a new era of light management(ranging from emission,absorption,modulation,to transmission)for next-generation optoelectronic technology.Notably,the exploration of fundamental characteristics of MHPs and their devices is the main research theme during the past decade,while in the next decade,it will be primarily critical to promote their implantation in the next-generation optoelectronics.In this review,we first retrospect the historical research milestones of MHPs and their optoelectronic devices.Thereafter,we introduce the origin of the unique optoelectronic features of MHPs,based on which we highlight the tunability of these features via regulating the phase,dimensionality,composition,and geometry of MHPs.Then,we show that owing to the convenient property control of MHPs,various optoelectronic devices with target performance can be designed.At last,we emphasize on the revolutionary applications of MHPs-based devices on the existing optoelectronic systems.This review demonstrates the key role of MHPs played in the development of modern optoelectronics,which is expected to inspire the novel research directions of MHPs and promote the widespread applications of MHPs in the next-generation optoelectronics.

Chemical regulation of metal halide perovskite nanomaterials for efficient light-emitting diodes

Metal halide perovskite nanomaterials emerged as attractive emitting materials for light-emitting diodes(LEDs) devices due to their high photoluminescence quantum yield(PLQY), narrow bandwidth, high charge-carrier mobility, bandgap tunability, and facile synthesis. In the past few years, it has been witnessed an unprecedented advance in the field of metal halide perovskite nanomaterials based LEDs(Pe LEDs) with a rapid external quantum efficiency(EQE) increase from 0.1% to 14.36%. From the viewpoint of material chemistry, the chemical regulation of metal halide perovskite nanomaterials made a great contribution to the efficiency improvement of Pe LEDs. In this review, we categorize the strategies of chemical regulation as A-site cation engineering, B-site ion doping, X-site ion exchange, dimensional confinement, ligand exchange, surface passivation and interface optimization of transport layers for improving the EQEs of Pe LEDs. We also show the potentials of chemical regulation strategies to enhance the stability of Pe LEDs. Finally, we present insight toward future research directions and an outlook to further improve EQEs and stabilities of Pe LEDs aiming to practical applications.

Recent advances and perspective on the synthesis and photocatalytic application of metal halide perovskite nanocrystals

Metal halide perovskite nanocrystals have attracted great attention of researchers due to their unique optoelectronic properties such as high photoluminescence quantum yield (PLQY), narrow full width at half-maximum (FWHM), long exciton diffusion length and high carrier mobility, which have been widely used in diverse fields including solar cells, photodetectors, light-emitting diodes, and lasers. Very recently, metal halide perovskites have emerged as a new class of materials in photocatalysis due to their promising photocatalytic performance. In this review, we summarize the recent advances on synthesis, modification and functionalization, with a specific focus on the photocatalytic application of metal halide perovskite nanocrystals. Finally, a brief outlook is proposed to point out the challenges in this emerging area. The goal of this view is to introduce the photocatalytic application of the metal halide perovskites and motivate researchers from different fields to explore more potentials in catalysis.

Low-dimensional metal halide perovskites and related optoelectronic applications

Low-dimensional materials have pivotal significance in modern photonic,electronic,and optoelectronic areas due to their unique properties of the scale effect.Metal halide perovskites have revived in the optoelectronic fields recently,drawing intensive attention in photovoltaic devices,light-emitting diodes,lasers,photodetectors,and so on.Compared to their three-dimensional counterparts,the role of low-dimensional perovskites is becoming crucial,requiring a comprehensive understanding and exploration unceasingly.In this review,we examine low-dimensional perovskite of different forms and clarify various synthesis methods with morphological and dimensional control.Additionally,we also summarize potential optoelectronic applications based on their advantageous optical/electrical properties and enhanced mechanical integrity and stability.Finally,we propose a future perspective and possible developing directions in the exploration of novel perovskite-derived materials,new physics,and promising applications.

Recent developments in flexible photodetectors based on metal halide perovskite

Flexible photodetectors(FPDs)have been receiving increasing attention in recent years because of their potential applications in electronic eyes,bioinspired sensing,smart textiles,and wearable devices.Moreover,metal halide perovskites(MHPs)with outstanding optical and electrical properties,good mechanical flexibility,lowcost and low-temperature solution-processed fabrication have become promising candidates as light harvesting materials in FPDs.Herein,we comprehensively review the developments of FPDs based on MHPs reported recently.This review firstly provides an introduction with respect to the performance parameters and device configurations of perovskite photodetectors,followed by the specific requirements of FPDs including substrate and electrode materials.Next,chemical compositions,structures and preparation methods of MHPs are presented.Then,the FPDs on the basis of single-component perovskite and hybrid structure perovskite are discussed,subsequently,self-powered flexible perovskite photodetectors were presented.In the end,conclusions and challenges are put forward in the field of FPDs based on perovskites.

Wafer-scale heterogeneous integration of self-powered lead-free metal halide UV photodetectors with ultrahigh stability and homogeneity

Large-scale growth and heterogeneous integration with existing semiconductors are the main obstacles to the application of metal halide perovskites in optoelectronics.Herein,a universal vacuum evaporation strategy is presented to prepare copper halide films with wafer-scale spatial homogeneity.Benefiting from the electric field manipulation method,the built-in electric fields are optimized and further boost the self-powered UV photodetecting performances of common wide-bandgap semiconductors by more than three orders of magnitude.Furthermore,with effective modulation of the interfacial charge dynamics,the as-fabricated GaN-substrate heterojunction photodetector demonstrates an ultrahigh on/off ratio exceeding 107,an impressive responsivity of up to 256 mA W^(-1),and a remarkable detectivity of 2.16×10^(13) Jones at 350 nm,0 V bias.Additionally,the device exhibits an ultrafast response speed(t r/t d=716 ns/1.30 ms),an ultra-narrow photoresponse spectrum with an FWHM of 18 nm and outstanding continuous operational stability as well as long-term stability.Subsequently,a 372-pixel light-powered imaging sensor array with the coefficient of variation of photocurrents reducing to 5.20%is constructed,which demonstrates exceptional electrical homogeneity,operational reliability,and UV imaging capability.This strategy provides an efficient way for large-scale integration of metal halide perovskites with commercial semiconductors for miniature optoelectronic devices.

Copper‑based metal halides for X‑ray and photodetection

Copper-based metal halides have become important materials in the feld of X-ray and photodetection due to their excellent optical properties,good environmental stability and low toxicity.This review presents the progress of research on crystal structure/morphology,photophysics/optical properties and applications of copper-based metal halides.We also discuss the challenges of copper-based metal halides with a perspective of their future research directions.

Carbon dots embedded in lead-free luminescent metal halide crystals toward single-component white emitters

The development of single-component white emitters for white light-emitting diodes(WLEDs)remains challenging.Herein,a rare earth-free white light-emitting composite is developed by assembling blue-emitting carbon dots(CDs)and yellow-emitting Cs_(2)InCl_(5)·H_(2)O:Sb^(3+)metal halide crystals via a facile liquid-liquid diffusion-assisted crystallization approach.The encapsulation mechanism is then analyzed.Depending on the ratios of blue/yellow emitters,these luminescent composites exhibit white light emission with tunable cold and warm hues.The composites also possess prominent ultraviolet resistance,thermal tolerance,and good stability at about 200°C.By employing such“CDs in metal halide”composites as a converter,a WLED is successfully fabricated with a high color rendering index of 93.6,benefiting from the assembled blue and yellow broadband emission.With this strategy,the developed composites show great promise in next-generation WLED lighting.