Sequestration of helium and xenon via iron-halide compounds in early Earth

The terrestrial abundance anomalies of helium and xenon suggest the presence of deep-Earth reservoirs of these elements,which has led to great interest in searching for materials that can host these usually unreactive elements.Here,using an advanced crystal structure search approach in conjunction with first-principles calculations,we show that several Xe/He-bearing iron halides are thermodynamically stable in a broad region of P–T phase space below 60 GPa.Our results present a compelling case for sequestration of He and Xe in the early Earth and may suggest their much wider distribution in the present Earth than previously believed.These findings offer insights into key material-based and physical mechanisms for elucidating major geological phenomena.

Photochemical Production of Methyl Halides with Guaiacol as the Precursor

Methyl halides are crucial trace greenhouse gases in the atmosphere,playing a significant role in global climate change and the atmospheric environment.This study investigated the photochemical production of methyl halides in an artificial seawater system using guaiacol as a precursor through laboratory simulation experiments.The influences of various environmental factors,including illumination time,radiation wavebands,illumination intensity,concentrations of guaiacol and halide ions(X^(-)),Fe^(3+),salinity,dissolved oxygen(DO),and pH value on the photochemical production of methyl halides were examined.We demonstrated that increased illumination intensity and duration promote the photochemical production of methyl halides,with a notable enhancement under UV-B radiation.Guaiacol and halide ions were identified as key precursors,and their high concentrations facilitated the formation of methyl halides.Additionally,different types of halide ions exhibited a competitive relationship in producing methyl halides.The study found that an increase in pH inhibited the photochemical formation of CH_(3)I due to the reaction between OH^(-)and·CH_(3).Dissolved oxygen was found to inhibit the photochemical formation of CH3I while promoting the formation of CH_(3)Cl.Conversely,an appropriate concentration of Fe^(3+)enhanced the photochemical production of methyl halides.Field observations indicated a high photochemical production of methyl halides in the natural waters near Qingdao’s coastal area,likely due to the high concentration of dissolved organic matter(DOM),which supports photochemical reactions.Furthermore,the photochemical production of methyl halides in natural seawater was significantly higher than in dark conditions,underscoring the importance of illumination in promoting these photochemical processes in seawater.

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.

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.

Light emission from multiple self-trapped excitons in one-dimensional Ag-based ternary halides

Ternary metal halides based on Cu(I)and Ag(I)have attracted intensive attention in optoelectronic applications due to their excellent luminescent properties,low toxicity,and robust stability.While the self-trapped excitons(STEs)emission mechanisms of Cu(I)halides are well understood,the STEs in Ag(I)halides remain less thoroughly explored.This study explores the STE emission efficiency within the A_(2)AgX_(3)(A=Rb,Cs;X=Cl,Br,I)system by identifying three distinct STE states in each material and calculating their configuration coordinate diagrams.We find that the STE emission efficiency in this system is mainly determined by STE stability and influenced by self-trapping and quenching barriers.Moreover,we investigate the impact of structural compactness on emission efficiency and find that the excessive electron–phonon coupling in this system can be reduced by increasing the structural compactness.The atomic packing factor is identified as a low-cost and effective descriptor for predicting STE emission efficiency in both Cs_(2)AgX_(3) and Rb_(2)AgX_(3) systems.These findings can deepen our understanding of STE behavior in metal halide materials and offer valuable insights for the design of efficient STE luminescent materials.The datasets presented in this paper are openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.12094.

Luminescence regulation of Sb^(3+)in 0D hybrid metal halides by hydrogen bond network for optical anti-counterfeiting

The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) ions in OIHMHs is primarily confined to the low energy region,resulting in yellow or red emissions.To date,there are few reports about green emission of Sb^(3+)-doped OIHMHs.Here,we present a novel approach for regulating the luminescence of Sb^(3+) ions in 0D C_(10)H_(2)_(2)N_(6)InCl_(7)·H_(2)O via hydrogen bond network,in which water molecules act as agents for hydrogen bonding.Sb^(3+)-doped C_(10)H_(2)2N_(6)InCl_(7)·H_(2)O shows a broadband green emission peaking at 540 nm and a high photoluminescence quantum yield(PLQY)of 80%.It is found that the intense green emission stems from the radiative recombination of the self-trapped excitons(STEs).Upon removal of water molecules with heat,C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7) generates yellow emis-sion,attributed to the breaking of the hydrogen bond network and large structural distortions of excited state.Once water molecules are adsorbed by C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7),it can subsequently emit green light.This water-induced reversible emission switching is successfully used for optical security and information encryption.Our findings expand the under-standing of how the local coordination structure influences the photophysical mechanism in Sb^(3+)-doped metal halides and provide a novel method to control the STEs emission.

Stimuli-responsive photoluminescent copper(Ⅰ) halides for scintillation, anticounterfeiting, and light-emitting diode applications

Highly sensitive stimuli-responsive luminescent materials are crucial for appli-cations in optical sensing,security,and anticounterfeiting.Here,we report two zero-dimensional(0D)copper(I)halides,(TEP)_(2)Cu_(2)Br_(4),(TEP)_(2)Cu_(4)Br_(6),and 1D(TEP)_(3)Ag_(6)Br_(9),which are comprised of isolated[Cu_(2)Br_(4)]^(2-),[Cu_(4)Br_(6)]^(2-),and[Ag_(6)Br_(9)]3-polyanions,respectively,separated by TEP^(+)(tetraethylphosphonium[TEP])cations.(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) demonstrate greenish-white and orange-red emissions,respectively,with near unity photoluminescence quantum yields,while(TEP)_(3)Ag_(6)Br_(9) is a poor light emitter.Optical spectroscopy mea-surements and density-functional theory calculations reveal that photoemissions of these compounds originate from self-trapped excitons due to the excited-state distor-tions in the copper(I)halide units.Crystals of Cu(I)halides are radioluminescence active at room temperature under both X-andγ-rays exposure.The light yields up to 15,800 ph/MeV under 662 keVγ-rays of ^(137)Cs suggesting their potential for scintillation applications.Remarkably,(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) are inter-convertible through chemical stimuli or reverse crystallization.In addition,both compounds demonstrate luminescence on-off switching upon thermal stimuli.The sensitivity of(TEP)_(2)Cu_(2)Br_(4) and(TEP)_(2)Cu_(4)Br_(6) to the chemical and thermal stimuli coupled with their ultrabright emission allows their consideration for applications such as solid-state lighting,sensing,information storage,and anticounterfeiting.

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.

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.

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.

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.

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.

Elucidating the diffusion pathway of lithium ions in superionic halide solid electrolytes Li_(2+x)Hf_(1-x)In_(x)Cl_(6) for all-solid-state lithium-metal based batteries

All-solid-state batteries(ASSBs) with inorganic solid-state-electrolytes(SSEs) have been regarded as the promising candidate for next-generation energy storage due to their high energy density and outstanding safety performance.However,the representative oxide and sulfide electrolytes suffer from low ionic conductivity and poor(electro)chemical stability,respectively.Herein,we report a series of new halide superionic conductors Li_(2+x)Hf_(1-x)In_(x)Cl_(6) with high ionic conductivity up to 1.05 mS cm^(-1) at 30 ℃ that are simultaneously stable to high voltage.By means of the characterization techniques and bond-valence site energy(BVSE) calculation,insights into the effect of the phase transformation and underlying ionic transport mechanism by In substitution for Hf in Li_(2)HfCl_(6) are provided.Importantly,with the increased amount of aliovalent substitution in Li_(2+x)Hf_(1-x)In_(x)Cl_(6) microcrystal framework,a gradual structure evolution from trigonal to monoclinic phase has been observed,which is accompanied by the redistribution of Li-ions to generate two dimensionally(2D) preferable diffusion pathways through octahedral-tetrahe dral-octahedral sites in In^(3+)-substituted Li_(2)HfCl_(6).Additionally,due to the oxidative stability of Insubstituted Li_(2)HfCl_(6),the bulk-type ASSBs with bare LiCoO_(2) deliver distinguished electrochemical performance.

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 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).

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.

Glass-compatible and self-powered temperature alarm system by temperature-responsive organic manganese halides via backward energy transfer process

A pioneering glass-compatible transparent temperature alarm system self-powered by luminescent solar concentrators(LSCs) is reported.Single green-emitted organic manganese halides(OMHs) of PEA_(2)MnBr_(2)I_(2),which has a unique temperature-dependent backward energy transfer process from selftrapped state to^(4)T_(1)energy level of Mn,is used for triggering the temperature alarm.The LSC with redemitted CsPbI_(3)perovskite-polymer composite films on the glass substrate is used for power supply.The spectrally separated nature between the green-emitted OMHs for temperature alarm and red-emitted CsPbI3in LSC for power supply allows for probing the signal light of temperature-responsive OMHs without the interference of LSCs,making it possible to calibrate the temperature visually just by a self-powered brightness detection circuit with LED indicators.Taking advantage of LSC without hot spot effects plaguing the solar cells,as-prepared temperature alarm system can operate well on both sunny and cloudy day.

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.

Application of halide vapor phase epitaxy for the growth of ultrawide band gap Ga_2O_3

Halide vapor phase epitaxy(HVPE) is widely used in the semiconductor industry for the growth of Si, GaAs, GaN, etc.HVPE is a non-organic chemical vapor deposition(CVD) technique, characterized by high quality growth of epitaxial layers with fast growth rate, which is versatile for the fabrication of both substrates and devices with wide applications. In this paper, we review the usage of HVPE for the growth and device applications of Ga_2O_3, with detailed discussions on a variety of technological aspects of HVPE. It is concluded that HVPE is a promising candidate for the epitaxy of large-area Ga_2O_3 substrates and for the fabrication of high power β-Ga_2O_3 devices.