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.

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.

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.

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.

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.

Palladium-catalyzed carbonylation of activated alkyl halides via radical intermediates

Palladium-catalyzed carbonylation is an efficient approach to prepare carbonyl-containing compounds with high atomic economy in synthetic organic chemistry.However,in comparison with aryl halides,carbonylation of alkyl halides is relatively challenging due to the decreased stability of the palladium intermediates.Carbonylation of activated alkyl halides is even more difficult,as nucleophilic substitution reactions with nucleophiles occur more easily with them.In this article,we summarize and discuss recent achievements in palladium-catalyzed carbonylative reactions of activated alkyl halides.The transformations proceed through radical intermediates which are generated in various manners.Under a relatively high pressure of carbon monoxide,the corresponding aliphatic carboxylic acid derivates were effectively prepared with various nucleophiles as the reaction partners.Besides alcohols,amines and organoboron reagents,four-component reactions in combination with alkenes or alkynes were also developed.Case-by-case reaction mechanisms are discussed as well and a personal outlook has also been provided.

A review of halide charge carriers for rocking-chair and dual-ion batteries

This review discusses how halide ion species have been used as charge carriers in both anion rocking-chair and dual-ion battery(DIB)systems.The anion rocking-chair batteries based on fluoride and chloride have emerged over the past decade and are garnering increased research interest due to their large theoretical energy density values and the natural abundance of halide-containing materials.Moreover,DIBs that use halide species as their anionic charge carrier are seen as one of the promising next-generation battery technologies due to their low cost and high working potentials.Although numerous polyatomic anions have been studied as charge carriers,the use of single halide ions(i.e.,F−and Cl−)and metal-based superhalides(e.g.,[MgCl_(3)]−)as anionic charge carriers in DIBs has been considerably less explored.Herein,we provide an overview of some of the key advances and recent progress that has been made with regard to halide ion charge carriers in electrochemical energy storage.We offer our perspectives on the current state of the field and provide a roadmap in hopes that it helps researchers toward making new advances in these promising and emerging areas.

Elucidating the effect of barium halide promoters on La_(2)O_(3)/CaO catalyst for oxidative coupling of methane

The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the reaction stability was poor due to the rapid loss of gas-phase halides or molten alkali halides.In this work,the barium salts,particularly barium halides(BaCl_(2)and BaF_(2)),were demonstrated to be efficient promoters to improve the OCM reactivity of La_(2)O_(3)/CaO catalyst by increasing both C_(2)selectivity and C_(2)H_(4)/C_(2)H_(6)ratio,and simultaneously achieving outstanding reaction stability.The promoting mechanism can be understood in two aspects.On the one hand,the introduction of barium salts increased the amount of surface electrophilic oxygen species,serving as the alkaline active sites for selective methane activation.On the other hand,the barium halide additives induced the in-situ formation of methyl halide intermediates facilitating C_(2)H_(6)dehydrogenation,and their intimate contact with catalyst substrate restricted the rapid halogen loss and thereby improved the catalytic stability.This work not only provides a class of efficient OCM catalyst,but also offers a highly stable halogen-assisted reaction strategy.

Enhanced efficiency and stability in Sn-based perovskite solar cells by trimethylsilyl halide surface passivation

Lead free tin perovskite solar cells(PKSCs)are the most suitable alternative candidate for conventional lead perovskite solar cells.However,the efficiency and the stability are insufficient,mainly because of the poor film quality and numerous defects.Here we introduce an efficient strategy based on a simple trimethylsilyl halide surface passivation to increase the film quality and reduce the defect density.At the same time,a hydrophobic protective layer on the perovskite surface is formed,which enhanced the PKSCs’stability.The efficiency of the solar cell after the passivation was enhanced from 10.05%to 12.22%with the improved open-circuit voltage from 0.57 V to 0.70 V.In addition,after 92 days of storage in N_(2) filled glovebox,the modified T-PKSCs demonstrated high stability maintaining 80%of its initial efficiency.This work provides a simple and widely used strategy to optimize the surface/interface optoelectronic properties of perovskites for giving more efficient and stable solar cells and other optoelectronic devices.

Influence of Halide Choice on Formation of Low-Dimensional Perovskite Interlayer in Efficient Perovskite Solar Cells

Recent advances in heterojunction and interfacial engineering of perovskite solar cells(PSCs)have enabled great progress in developing highly efficient and stable devices.Nevertheless,the effect of halide choice on the formation mechanism,crystallography,and photoelectric properties of the lowdimensional phase still requires further detailed study.In this work,we present key insights into the significance of halide choice when designing passivation strategies comprising large organic spacer salts,clarifying the effect of anions on the formation of quasi-2D/3D heterojunctions.To demonstrate the importance of halide influences,we employ novel neo-pentylammonium halide salts with different halide anions(neoPAX,X=I,Br,or Cl).We find that regardless of halide selection,iodide-based(neoPA)_(2)(FA)_((n-1))PbnI_((3n+1))phases are formed above the perovskite substrate,while the added halide anions diffuse and passivate the perovskite bulk.In addition,we also find the halide choice has an influence on the degree of dimensionality(n).Comparing the three halides,we find that chloride-based salts exhibit superior crystallographic,enhanced carrier transport,and extraction compared to the iodide and bromide analogs.As a result,we report high power conversion efficiency in quasi-2D/3D PSCs,which are optimal when using chloride salts,reaching up to 23.35%,and improving long-term stability.

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.

The influence of trapping centres on the photoelectron decay in silver halide

Photoelectron is the foundation of latent image formation, the decay process of photoelectrons is influenced by all kinds of trapping centres in silver halide. By analysing the mechanism of latent image formation it is found that electron trap, hole trap, and one kind of recombination centre where free electron and trapped hole recombine are the main trapping centres in silver halide. Different trapping centres have different influences on the photoelectron behaviour. The effects of all kinds of typical trapping centres on the decay of photoelectrons are systematically investigated by solving the photoelectron decay kinetic equations. The results are in agreement with those obtained in the microwave absorption dielectric spectrum experiment.

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.

Suppression of methane/air explosion by water mist with potassium halide additives driven by CO2

To enhance the explosion suppression effects of water mist, various potassium halide additives were tested in a confined vessel filled with a 10% mixture of methane/air. Air and CO2(0.7 MPa) were used as driver gases. The results revealed that halide additives exhibit considerable suppression effects on explosion overpressure. A30% KI mist decreased the explosion overpressure by 27.46% compared with the suppression by pure water mist under the same conditions. When CO2 is used as the driver gas, it will dissolve in water under high pressure.The synergistic effect of a CO2 solution with an effective additive afforded significant suppression. Under the same conditions, the overpressures suppressed by a mist of 30% KI + 0.7 MPa CO2 solution decreased by 33.53% compared with those suppressed by pure water mist driven by air. The synergistic suppression effect is much better than that of a 0.7 MPa CO2 solution mist or 30% KI mist alone. The multicomponent additives can be considered when suppressing methane/air explosions with pressure-formed water mist.

Pressure responses of halide perovskites with various compositions, dimensionalities, and morphologies

Metal halide perovskites(HPVs)have been greatly developed over the last decade,with various compositions,dimensionalities,and morphologies,leading to an emergence of high-performance photovoltaic and optoelectronic applications.Despite the tremendous progress made,challenges remain,which calls for a better understanding of the fundamental mechanisms.Pressure,a thermodynamic variable,provides a powerful tool to tune materials’structures and properties.In combination with in situ characterization methods,high-pressure research could provide a better fundamental understanding.In this review,we summarize the recent studies of the dramatic,pressure-induced changes that occur in HPVs,particularly the enhanced and emergent properties induced under high pressure and their structure-property relationships.We first introduce the characteristics of HPVs and the basic knowledge of high-pressure techniques,as well as in situ characterization methods.We then discuss the effects of pressure on HPVs with different compositions,dimensionalities,and morphologies,and underline their common features and anomalous behaviors.In the last section,we highlight the main challenges and provide suggestions for possible future research on high-pressure HPVs.

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.