Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Non-volatile dynamically switchable color display via chalcogenide stepwise cavity resonators

High-resolution multi-color printing relies upon pixelated optical nanostructures,which is crucial to promote color display by producing nonbleaching colors,yet requires simplicity in fabrication and dynamic switching.Antimony trisulfide(Sb_(2)S_(3))is a newly rising chalcogenide material that possesses prompt and significant transition of its optical characteristics in the visible region between amorphous and crystalline phases,which holds the key to color-varying devices.Herein,we proposed a dynamically switchable color printing method using Sb_(2)S_(3)-based stepwise pixelated Fabry-Pérot(FP)cavities with various cavity lengths.The device was fabricated by employing a direct laser patterning that is a less timeconsuming,more approachable,and low-cost technique.As switching the state of Sb_(2)S_(3) between amorphous and crystalline,the multi-color of stepwise pixelated FP cavities can be actively changed.The color variation is due to the profound change in the refractive index of Sb_(2)S_(3) over the visible spectrum during its phase transition.Moreover,we directly fabricated sub-50 nm nano-grating on ultrathin Sb_(2)S_(3) laminate via microsphere 800-nm femtosecond laser irradiation in far field.The minimum feature size can be further decreased down to~45 nm(λ/17)by varying the thickness of Sb_(2)S_(3) film.Ultrafast switchable Sb_(2)S_(3) photonic devices can take one step toward the next generation of inkless erasable papers or displays and enable information encryption,camouflaging surfaces,anticounterfeiting,etc.Importantly,our work explores the prospects of rapid and rewritable fabrication of periodic structures with nano-scale resolution and can serve as a guideline for further development of chalcogenide-based photonics components.

Chalcogenide-based S-scheme heterojunction photocatalysts

The unique photocatalytic mechanism of S-scheme heterojunction can be used to study new and efficient photocatalysts.By carefully selecting semiconductors for S-scheme heterojunction photocatalysts,it is possible to reduce the rate of photogenerated carrier recombination and increase the conversion efficiency of light into energy.Chalcogenides are a group of compounds that include sulfides and selenides(e.g.,CdS,ZnS,Bi_(2)S_(3),MoS_(2),ZnSe,CdSe,and CuSe).Chalcogenides have attracted considerable attention as heterojunction photocatalysts owing to their narrow bandgap,wide light absorption range,and excellent photoreduction properties.This paper presents a thorough analysis of S-scheme heterojunction photocatalysts based on chalcogenides.Following an introduction to the fundamental characteristics and benefits of S-scheme heterojunction photocatalysts,various chalcogenide-based S-scheme heterojunction photocatalyst synthesis techniques are summarized.These photocatalysts are used in numerous significant photocatalytic reactions,in-cluding the reduction of carbon dioxide,synthesis of hydrogen peroxide,conversion of organic matter,generation of hydrogen from water,nitrogen fixation,degradation of organic pollutants,and sterilization.In addition,cutting-edge characterization techniques,including in situ characterization techniques,are discussed to validate the steady and transient states of photocatalysts with an S-scheme heterojunction.Finally,the design and challenges of chalcogenide-based S-scheme heterojunction photocatalysts are explored and recommended in light of state-of-the-art research.

Chalcogenide Ovonic Threshold Switching Selector

Today’s explosion of data urgently requires memory technologies capable of storing large volumes of data in shorter time frames,a feat unattain-able with Flash or DRAM.Intel Optane,commonly referred to as three-dimensional phase change memory,stands out as one of the most promising candidates.The Optane with cross-point architecture is constructed through layering a storage element and a selector known as the ovonic threshold switch(OTS).The OTS device,which employs chalcogenide film,has thereby gathered increased attention in recent years.In this paper,we begin by providing a brief introduction to the discovery process of the OTS phenomenon.Subsequently,we summarize the key elec-trical parameters of OTS devices and delve into recent explorations of OTS materials,which are categorized as Se-based,Te-based,and S-based material systems.Furthermore,we discuss various models for the OTS switching mechanism,including field-induced nucleation model,as well as several carrier injection models.Additionally,we review the progress and innovations in OTS mechanism research.Finally,we highlight the successful application of OTS devices in three-dimensional high-density memory and offer insights into their promising performance and extensive prospects in emerging applications,such as self-selecting memory and neuromorphic computing.

Third-order nonlinear wavelength conversion in chalcogenide glass waveguides towards mid-infrared photonics

The increasing demand in spectroscopy and sensing calls for infrared(mid-IR)light sources.Here,we theoretically investigate nonlinear wavelength conversion of Ge_(28)Sb_(12)Se_(60)chalcogenide glass waveguide in the mid-IR spectral regime.With waveguide dispersion engineering,we predict generation of over an octave wavelength(2.8μm-5.9μm)tuning range Raman soliton self-frequency shift,over 2.5 octaves wavelength cover range supercontinuum(1.2μm-8.0μm),as well as single soliton Kerr comb generated in suspended Ge_(28)Sb_(12)Se_(60)waveguide.Our findings evidenced that Ge_(28)Sb_(12)Se_(60)chalcogenide glass waveguides can simultaneously satisfy the generation of Raman soliton self-frequency shift,supercontinuum spectrum,and Kerr frequency comb generation through dispersion engineering towards mid-IR on chip.

Design of a coated thinly clad chalcogenide long-period fiber grating refractive index sensor based on dual-peak resonance near the phase matching turning point

A novel method for designing chalcogenide long-period fiber grating(LPFG) sensors based on the dual-peak resonance effect of the LPFG near the phase matching turning point(PMTP) is presented. Refractive index sensing in a high-refractive-index chalcogenide fiber is achieved with a coated thinly clad film. The dual-peak resonant characteristics near the PMTP and the refractive index sensing properties of the LPFG are analyzed first by the phase-matching condition of the LPFG. The effects of film parameters and cladding radius on the sensitivity of refractive index sensing are further discussed. The sensor is optimized by selecting the appropriate film parameters and cladding radius. Simulation results show that the ambient refractive index sensitivity of a dual-peak coated thinly clad chalcogenide LPFG at the PMTP can be 2400 nm/RIU, which is significantly higher than that of non-optimized gratings. It has great application potential in the field of chemical sensing and biosensors.

Optical properties and local structure of Dy^(3+)-doped chalcogenide and chalcohalide glasses

Dy^3＋-doped Ge-Ga-Se chalcogenide glasses and GeSe2-Ga2Se3-CsI chalcohalide glasses were prepared. The absorption, emission properties, and local structure of the glasses were investigated. When excited at 808 nm diode laser, intense 1.32 and 1.55 μm near-infrared luminescence were observed with full width at half maximum （FWHM） of about 90 and 50 nm, respectively. The lifetime of the 1.32 μm emission varied due to changes in the local structure surrounding Dy^3＋ ions. The longest lifetime was over 2.5 ms, and the value was significantly higher than that in other Dy^3＋-doped glasses. Some other spectroscopic parameters were calculated by using Judd-Ofelt theory. Meanwhile, Ge-Ga-Se and GeSe2-Ga2Se3-CsI glasses showed good infrared transmittance. As a result, Dy^3＋-doped Ge-Ga-Se and GeSe2-Ga2Se3-CsI glasses were believed to be useful hosts for 1.3 μm optical fiber amplifier.

Flexible and stretchable photodetectors and gas sensors for wearable healthcare based on solution-processable metal chalcogenides

Wearable smart sensors are considered to be the new generation of personal portable devices for health monitoring.By attaching to the skin surface,these sensors are closely related to body signals(such as heart rate,blood oxygen saturation,breath markers,etc.)and ambient signals(such as ultraviolet radiation,inflammable and explosive,toxic and harmful gases),thus providing new opportunities for human activity monitoring and personal telemedicine care.Here we focus on photodetectors and gas sensors built from metal chalcogenide,which have made great progress in recent years.Firstly,we present an overview of healthcare applications based on photodetectors and gas sensors,and discuss the requirement associated with these applications in detail.We then discuss advantages and properties of solution-processable metal chalcogenides,followed by some recent achievements in health monitoring with photodetectors and gas sensors based on metal chalcogenides.Last we present further research directions and challenges to develop an integrated wearable platform for monitoring human activity and personal healthcare.

Facile synthesis of free-standing nickel chalcogenide electrodes for overall water splitting

Developing high-performance noble metal-free and free-standing catalytic electrodes are crucial for overall water splitting. Here, nickel sulfide（NiS） and nickel selenide（Ni Se） are synthesized on nickel foam（NF） with a one-pot solvothermal method and directly used as free-standing electrodes for efficiently catalyzing hydrogen evolution reaction（HER） and oxygen evolution reaction（OER） in alkaline solution.In virtue of abundant active sites, the NiS/NF and the NiS e/NF electrodes can deliver a current density of 10 m A cmat only 123 m V, 137 m V for HER and 222 m V, 271 m V for OER. Both of the hierarchical NiS/NF and Ni Se/NF electrodes can serve as anodes and cathodes in electrocatalytic overall watersplitting and can achieve a current density of 10 m A cmwith an applied voltage of.59 V and 1.69 V,respectively. The performance of as-obtained NiS/NF||NiS/NF is even close to that of the noble metalbased Pt/C/NF||IrO/NF system.

A perspective of chalcogenide semiconductor-noble metal nanocomposites through structural transformations

Intense efforts have been devoted to the synthesis of heterogeneous nanocomposites consisting of chalcogenide semiconductors and noble metals,which usually exhibit enhanced properties owing to the synergistic effect between their different material domains.Tailoring the structure of the metal domains in the nanocomposites may lead to further improvements of its performance for a given application.This review therefore highlights the strategies based on a structural conversion process for the fabrication of nanocomposites consisting of chalcogenide semiconductors and noble metals with various internal structures,e.g.,hollow or cage-bell.This strategy relies on a unique inside-out diffusion phenomenon of Ag in core-shell nanoparticles with Ag residing at core or inner shell region.In the presence of sulfur or selenium precursors,the diffused Ag are converted into Ag2S or Ag2Se,which is connected with the remaining noble metal parts,forming nanocomposites consisting of silver chalcogenide and noble metal nanoparticles with hollow or cage-bell structures.We would focus on the introduction of the fundamentals,principles,electrocatalytic applications as well as perspectives of the chalcogenide semiconductor-noble metal nanocomposites derived from their core-shell precursors so as to provide the readers insights in designing efficient nanocomposites for electrocatalysis.

Near-infrared lead chalcogenide quantum dots:Synthesis and applications in light emitting diodes

This paper reviews the recent progress in the synthesis of near-infrared(NIR) lead chalcogenide(PbX;PbX = PbS,PbSe, PbTe) quantum dots(QDs) and their applications in NIR QDs based light emitting diodes(NIR-QLEDs). It summarizes the strategies of how to synthesize high efficiency PbX QDs and how to realize high performance Pb X based NIR-QLEDs.

Memristive Devices Based on Two-Dimensional Transition Metal Chalcogenides for Neuromorphic Computing

Two-dimensional(2D)transition metal chalcogenides(TMC)and their heterostructures are appealing as building blocks in a wide range of electronic and optoelectronic devices,particularly futuristic memristive and synaptic devices for brain-inspired neuromorphic computing systems.The distinct properties such as high durability,electrical and optical tunability,clean surface,flexibility,and LEGO-staking capability enable simple fabrication with high integration density,energy-efficient operation,and high scalability.This review provides a thorough examination of high-performance memristors based on 2D TMCs for neuromorphic computing applications,including the promise of 2D TMC materials and heterostructures,as well as the state-of-the-art demonstration of memristive devices.The challenges and future prospects for the development of these emerging materials and devices are also discussed.The purpose of this review is to provide an outlook on the fabrication and characterization of neuromorphic memristors based on 2D TMCs.

Homopolar bonds in Se-rich Ge-As-Se chalcogenide glasses

We have prepared three groups of Ge–As–Se glasses in which the Se content is 5.5 mol%, 10 mol%, and 20 mol%rich, respectively. We explored the possibility of suppressing the formation of the Ge–Ge and As–As homopolar bonds in the glasses. Thermal kinetics analysis indicated that the 5.5 mol% Se-rich Ge_（11.5）As_（24）Se_（64.5） glass exhibits the minimum fragility and thus is most stable against structural relaxation. Analysis of the Raman spectra of the glasses indicated that the Ge–Ge and As–As homopolar bonds could be almost completely suppressed in 20 mol% Se-rich Ge_（15）As_（14）Se_（71） glass.

Si1Sb2Te3 phase change material for chalcogenide random access memory

This paper investigated phase change Si1Sb2Te3 material for application of chalcogenide random access memory. Current-voltage performance was conducted to determine threshold current of phase change from amorphous phase to polycrystalline phase. The film holds a threshold current about 0.155 mA, which is smaller than the value 0.31 mA of Ge2Sb2Te5 film. Amorphous Si1Sb2Te3 changes to face-centred-cubic structure at ~ 180℃ and changes to hexagonal structure at ~ 270℃. Annealing temperature dependent electric resistivity of Si1Sb2Te3 film was studied by four-point probe method. Data retention of the films was characterized as well.

Experimental and numerical investigation of mid-infrared laser in Pr^(3+)-doped chalcogenide fiber

We report on a chalcogenide glass fiber doped with Pr^(3+) that can be used for commercialized 1.5-μm and 2-μm laser excitations by emitting broadband 3 μm–5.5 μm fluorescence, which is extruded into a preform and then drawn into a step-index fiber. The spectroscopic properties of the fiber and glass are reported, and the mid-infrared fiber lasers are also numerically investigated. Cascade lasing is employed to increase the inversion population of the upper laser level. The particle swarm approach is applied to optimize the fiber laser parameters. The output power can reach 1.28 W at 4.89-μm wavelength, with a pump power of 5 W, excitation wavelength at 2.04 μm, Pr^(3+) ion concentration at 4.22 × 10^(25) ions/m^3,fiber length at 0.94 m, and fiber background loss at 3 dB/m.

Rational design of multinary copper chalcogenide nanocrystals for photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution is one of the most promising ways to solve environmental problems and produce a sustainable energy source.To date,different types of photocatalysts have been developed and widely used in photocatalytic hydrogen evolution.Recently,multinary copper chalcogenides have attracted much attention and exhibited potential applications in photocatalytic hydrogen evolution due to their composition-tunable band gaps,diverse structures and environmental-benign characteristics.In this review,some progress on the synthesis and photocatalytic hydrogen evolution of multinary copper chalcogenide nanocrystals(NCs)was summarized.In particular,considerable attention was paid to the rational design and dimensional or structural regulation of multinary copper chalcogenide NCs.Importantly,the photocatalytic hydrogen evolution of multinary copper chalcogenide NCs were reviewed from the aspects of energy level structures,crystal facets,morphology as well as composition.Finally,the current challenges and future perspectives of copper chalcogenide were proposed.

Two Ternary Europium Chalcogenides Eu(1-x)Ga2Te4(x≈0.19) and EuY2Se4, Experimental and Theoretical Investigations

Two ternary europium chalcogenides, Eu1-xGa2Te4（x ≈ 0.19）（1） and EuY2Se4（2）, have been synthesized by a facile solid-state route using boron as the reducing reagent. Eu1-xGa2Te4 crystallizes in the tetragonal space group I4/mcm with a = 8.2880（9）, c = 6.7439（12） A, V = 463.24（13） A^3, and Z = 2. EuY2Se4 crystallizes in the orthorhombic space group Pnma with a = 12.4726（16）, b = 4.1204（6）, c = 14.849（2） A, V = 763.11（19） A^3, and Z = 4. Eu1-xGa2Te4 belongs to the Tl Se-type 3D closed structure, while EuY2Se4 adopts the CaFe2O4-type 3D channel structure. The optical band gap of Eu1-xGa2Te4 is determined to be 0.48 Ev. Electronic structures of 1 and 2 are calculated using TB-LMTO software.

Recent advances in the electrochemistry of layered post-transition metal chalcogenide nanomaterials for hydrogen evolution reaction

Layered two-dimensional(2 D)materials have received tremendous attention due to their unique physical and chemical properties when downsized to single or few layers.Several types of layered materials,especially transition metal dichalcogenides(TMDs)have been demonstrated to be good electrode materials due to their interesting physical and chemical properties.Apart from TMDs,post-transition metal chalcogenides(PTMCs)recently have emerged as a family of important semiconducting materials for electrochemical studies.PTMCs are layered materials which are composed of post-transition metals raging from main group IIIA to group VA(Ga,In,Ge,Sn,Sb and Bi)and group VI chalcogen atoms(S,selenium(Se)and tellurium(Te)).Although a large number of literatures have reviewed the electrochemical and electrocatalytic applications of TMDs,less attention has been focused on PTMCs.In this review,we focus our attention on PTMCs with the aim to provide a summary to describe their fundamental electrochemical properties and electrocatalytic activity towards hydrogen evolution reaction(HER).The characteristic chemical compositions and crystal structures of PTMCs are firstly discussed,which are different from TMDs.Then,inherent electrochemistry of PTMCs is discussed to unveil the well-defined redox behaviors of PTMCs,which could potentially affect their efficiency when applied as electrode materials.Following,we focus our attention on electrocatalytic activity of PTMCs towards HER including novel synthetic strategies developed for the optimization of their HER activity.This review ends with the perspectives for the future research direction in the field of PTMC based electrocatalysts.

Rare-Earth Chalcogenides:A Large Family of Triangular Lattice Spin Liquid Candidates

Frustrated quantum magnets are expected to host many exotic quantum spin states like quantum spin liquid（QSL）, and have attracted numerous interest in modern condensed matter physics. The discovery of the triangular lattice spin liquid candidate YbMgGaO_4 stimulated an increasing attention on the rare-earth-based frustrated magnets with strong spin-orbit coupling. Here we report the synthesis and characterization of a large family of rare-earth chalcogenides AReCh_2（A = alkali or monovalent ions, Re = rare earth, Ch = O,S,Se）. The family compounds share the same structure（R3 m） as YbMgGaO_4,and antiferromagnetically coupled rare-earth ions form perfect triangular layers that are well separated along the c-axis. Specific heat and magnetic susceptibility measurements on NaYbO_2,NaYbS_2 and NaYbSe_2 single crystals and polycrystals, reveal no structural or magnetic transition down to 50 mK. The family, having the simplest structure and chemical formula among the known QSL candidates, removes the issue on possible exchange disorders in YbMgGaO_4. More excitingly, the rich diversity of the family members allows tunable charge gaps, variable exchange coupling, and many other advantages.This makes the family an ideal platform for fundamental research of QSLs and its promising applications.

Longitudinal Magnetoresistance and ＂Chirar＇ Coupling in Silver Chalcogenides

A complex longitudinal magnetoresistance （MR//） effect in the non-stoichiometric silver chaJcogenides （include the silver selenide and telluride） has been found, however the mechanism for the MR// effect is not clear now. In this work, a new random resistor network for MR// effect is proposed based on the experimental observation. The network is constructed from six-terminal resistor units and the mobility of carries within the network has a Gaussian distribution. Considering the non-zero transverse-longitudinal coupling in materials, the resistance matrix of the six- terminal resistor unit is modified. It is found that the material has the ＂chiral＂ transverse-longitudinal couplings, which is suggested a main reason for the complex MR//effect. The model predictions are compared with the experimental results. A three dimension （3D） visualization of current flow within the network demonstrates the ＂current jets＂ phenomenon in the thickness of materials dearly.