Transforming a Two-Dimensional Layered Insulator into a Semiconductor or a Highly Conductive Metal through Transition Metal Ion Intercalation

Atomically thin two-dimensional(2D) materials are the building bricks for next-generation electronics and optoelectronics, which demand plentiful functional properties in mechanics, transport, magnetism and photoresponse.For electronic devices, not only metals and high-performance semiconductors but also insulators and dielectric materials are highly desirable. Layered structures composed of 2D materials of different properties can be delicately designed as various useful heterojunction or homojunction devices, in which the designs on the same material(namely homojunction) are of special interest because preparation techniques can be greatly simplified and atomically seamless interfaces can be achieved. We demonstrate that the insulating pristine ZnPS_3, a ternary transition-metal phosphorus trichalcogenide, can be transformed into a highly conductive metal and an n-type semiconductor by intercalating Co and Cu atoms, respectively. The field-effect-transistor(FET) devices are prepared via an ultraviolet exposure lithography technique. The Co-ZnPS_3 device exhibits an electrical conductivity of 8 × 10^(4) S/m, which is comparable to the conductivity of graphene. The Cu-ZnPS_3 FET reveals a current ON/OFF ratio of 1-05 and a mobility of 3 × 10^(-2 )cm^(2)·V^(-1)·s^(-1). The realization of an insulator, a typical semiconductor and a metallic state in the same 2D material provides an opportunity to fabricate n-metal homojunctions and other in-plane electronic functional devices.

Comparative coherence between layered and traditional semiconductors: unique opportunities for heterogeneous integration

As Moore’s law deteriorates,the research and development of new materials system are crucial for transitioning into the post Moore era.Traditional semiconductor materials,such as silicon,have served as the cornerstone of modern technologies for over half a century.This has been due to extensive research and engineering on new techniques to continuously enrich silicon-based materials system and,subsequently,to develop better performed silicon-based devices.Meanwhile,in the emerging post Moore era,layered semiconductor materials,such as transition metal dichalcogenides(TMDs),have garnered considerable research interest due to their unique electronic and optoelectronic properties,which hold great promise for powering the new era of next generation electronics.As a result,techniques for engineering the properties of layered semiconductors have expanded the possibilities of layered semiconductor-based devices.However,there remain significant limitations in the synthesis and engineering of layered semiconductors,impeding the utilization of layered semiconductor-based devices for mass applications.As a practical alternative,heterogeneous integration between layered and traditional semiconductors provides valuable opportunities to combine the distinctive properties of layered semiconductors with well-developed traditional semiconductors materials system.Here,we provide an overview of the comparative coherence between layered and traditional semiconductors,starting with TMDs as the representation of layered semiconductors.We highlight the meaningful opportunities presented by the heterogeneous integration of layered semiconductors with traditional semiconductors,representing an optimal strategy poised to propel the emerging semiconductor research community and chip industry towards unprecedented advancements in the coming decades.

Effective Qubit Emerging from the Nanoheterointerface Two-Dimensional Electron Gas Photodynamics

An “Eigenstate Adjustment Autonomy” Model, permeated by the Nanosystem’s Fermi Level Pinning along with its rigid Conduction Band Discontinuity, compatible with pertinent Experimental Measurements, is being employed for studying how the Functional Eigenstate of the Two-Dimensional Electron Gas (2DEG) dwelling within the Quantum Well of a typical Semiconductor Nanoheterointerface evolves versus (cryptographically) selectable consecutive Cumulative Photon Dose values. Thus, it is ultimately discussed that the experimentally observed (after a Critical Cumulative Photon Dose) Phenomenon of 2DEG Negative Differential Mobility allows for the Nanosystem to exhibit an Effective Qubit Specific Functionality potentially conducive to (Telecommunication) Quantum Information Registering.

Li_(2)NiSe_(2):A new-type intrinsic two-dimensional ferromagnetic semiconductor above 200 K

By using first-principles electronic structure calculations,we propose a two-dimensional ferromagnetic semiconductor Li_(2)NiSe_(2)with a Curie temperature above 200 K.The structure of monolayer Li_(2)NiSe_(2)is dynamically stable,which is derived from the synthesized prototype compound Li_(2)Ni O_(2)and can be denoted as Li-decorated 1T-type NiSe_(2).The Ni–Se–Ni ferromagnetic superexchange dominates the magnetic couplings between the Ni atoms,which can be understood in the frame of the Goodenough–Kanamori–Anderson(GKA)rules.Our systematic study of monolayer Li_(2)NiSe_(2)enables its promising applications in spintronics and suggests a new choice to design two-dimensional ferromagnetic semiconductors.

Valley polarization in transition metal dichalcogenide layered semiconductors:Generation,relaxation,manipulation and transport

In recent years,valleytronics researches based on 2D semiconducting transition metal dichalcogenides have attracted considerable attention.On the one hand,strong spin–orbit interaction allows the presence of spin–valley coupling in this system,which provides spin addressable valley degrees of freedom for information storage and processing.On the other hand,large exciton binding energy up to hundreds of me V enables excitons to be stable carriers of valley information.Valley polarization,marked by an imbalanced exciton population in two inequivalent valleys(+K and-K),is the core of valleytronics as it can be utilized to store binary information.Motivated by the potential applications,we present a thorough overview of the recent advancements in the generation,relaxation,manipulation,and transport of the valley polarization in nonmagnetic transition metal dichalcogenide layered semiconductors.We also discuss the development of valleytronic devices and future challenges in this field.

A family of flexible two-dimensional semiconductors:MgMX2Y6(M=Ti/Zr/Hf;X=Si/Ge;Y=S/Se/Te)

Inspired by the recently predicted 2D MX_(2)Y_(6)(M=metal element;X=Si/Ge/Sn;Y=S/Se/Te),we explore the possible applications of alkaline earth metal(using magnesium as example)in this family based on the idea of element replacement and valence electron balance.Herein,we report a new family of 2D quaternary compounds,namely MgMX_(2)Y_(6)(M=Ti/Zr/Hf;X=Si/Ge;Y=S/Se/Te)monolayers,with superior kinetic,thermodynamic and mechanical stability.In addition,our results indicate that MgMX_(2)Y_(6)monolayers are all indirect band gap semiconductors with band gap values ranging from 0.870 to 2.500 eV.Moreover,the band edges and optical properties of 2D MgMX_(2)Y_(6)are suitable for constructing multifunctional optoelectronic devices.Furthermore,for comparison,the mechanical,electronic and optical properties of In_(2)X_(2)Y_(6)monolayers have been discussed in detail.The success of introducing Mg into the 2D MX_(2)Y_(6)family indicates that more potential materials,such as Caand Sr-based 2D MX_(2)Y_(6)monolayers,may be discovered in the future.Therefore,this work not only broadens the existing family of 2D semiconductors,but it also provides beneficial results for the future.

Room temperature synthesis of two-dimensional multi layer magnets based on α-Co^(Ⅱ) layered hydroxides

Research on two-dimensional(2D) materials is one of the most active fields in materials science and nanotechnology. Among the members of the 2D family, layered hydroxides(LHs) represent an exceptional case of study due to their unparalleled chemical versatility which allows the modulation of their physicochemical properties at will. Nowadays, LHs based on earth-abundant metals are key materials in the areas of energy storage and conversion, hybrid materials or magnetism. α-Co hydroxides(Simonkolleite-like structures) are promising phases with tuneable electronic and magnetic properties by ligand modification. However, even in the simple case of α-Co^(Ⅱ) hydroxychlorides, the preparation of well-defined large 2D crystals is not straightforward, hindering the development of fundamental studies. Herein, we present the synthesis of 2D hexagonal crystals with outstanding sizethickness relationship(diameter > 5 μm and thickness of 20 ± 7 nm) by a simple homogeneous synthesis taking place at room temperature. In structural terms, no differences are observed between our layered materials and those obtained hydrothermally. However, dynamic susceptibility measurements alert about different arrangements of the magnetic sublattices, which have been rationalized with structural DFT calculations. This work provides an extremely easy bottom-up method to obtain high-quality 2D crystals based on α-CoIIhydroxides,paving the way for the development of fundamental studies and applications.

Layered coordination polymer with two-dimensional covalent bismuth-organic networks:Semiconductor and lithium ion storage

Single crystals of a bismuth-based coordination polymer(CP)with carboxyl-thiol ligands,[Bi(C_(8)H_(2)O_(4)S_(2))(C2H8N)]n(Bi-DSBDC-DMA,DMBDC=2,5-disulfur-1,4-dicarboxylate,DMA=dimethylamine),have been successfully synthesized.X-ray diffraction analysis reveals that Bi-DSBDC-DMA possesses a layered structure,with two-dimensional(2D)Bi-DSBDC networks alternating with layers composed of dimethylamine ions.This material demonstrates semiconducting properties,featuring an optical bandgap of 2.2 eV and an electrical conductivity of 2×10^(-8) S/cm.Furthermore,electrodes based on this material exhibit a capacity of 250 mAh/g after 200 cycles for lithium-ion storage.

Atomic layer deposition for nanoscale oxide semiconductor thin film transistors:review and outlook

Since the first report of amorphous In–Ga–Zn–O based thin film transistors,interest in oxide semiconductors has grown.They offer high mobility,low off-current,low process temperature,and wide flexibility for compositions and processes.Unfortunately,depositing oxide semiconductors using conventional processes like physical vapor deposition leads to problematic issues,especially for high-resolution displays and highly integrated memory devices.Conventional approaches have limited process flexibility and poor conformality on structured surfaces.Atomic layer deposition(ALD)is an advanced technique which can provide conformal,thickness-controlled,and high-quality thin film deposition.Accordingly,studies on ALD based oxide semiconductors have dramatically increased recently.Even so,the relationships between the film properties of ALD-oxide semiconductors and the main variables associated with deposition are still poorly understood,as are many issues related to applications.In this review,to introduce ALD-oxide semiconductors,we provide:(a)a brief summary of the history and importance of ALD-based oxide semiconductors in industry,(b)a discussion of the benefits of ALD for oxide semiconductor deposition(in-situ composition control in vertical distribution/vertical structure engineering/chemical reaction and film properties/insulator and interface engineering),and(c)an explanation of the challenging issues of scaling oxide semiconductors and ALD for industrial applications.This review provides valuable perspectives for researchers who have interest in semiconductor materials and electronic device applications,and the reasons ALD is important to applications of oxide semiconductors.

Fundamental band gap and alignment of two-dimensional semiconductors explored by machine learning

Two-dimensional(2D)semiconductors isoelectronic to phosphorene have been drawing much attention recently due to their promising applications for next-generation(opt)electronics.This family of 2D materials contains more than 400members,including(a)elemental group-V materials,(b)binary III–VII and IV–VI compounds,(c)ternary III–VI–VII and IV–V–VII compounds,making materials design with targeted functionality unprecedentedly rich and extremely challenging.To shed light on rational functionality design with this family of materials,we systemically explore their fundamental band gaps and alignments using hybrid density functional theory(DFT)in combination with machine learning.First,calculations are performed using both the Perdew–Burke–Ernzerhof exchange–correlation functional within the generalgradient-density approximation(GGA-PBE)and Heyd–Scuseria–Ernzerhof hybrid functional(HSE)as a reference.We find this family of materials share similar crystalline structures,but possess largely distributed band-gap values ranging approximately from 0 eV to 8 eV.Then,we apply machine learning methods,including linear regression(LR),random forest regression(RFR),and support vector machine regression(SVR),to build models for the prediction of electronic properties.Among these models,SVR is found to have the best performance,yielding the root mean square error(RMSE)less than 0.15 eV for the predicted band gaps,valence-band maximums(VBMs),and conduction-band minimums(CBMs)when both PBE results and elemental information are used as features.Thus,we demonstrate that the machine learning models are universally suitable for screening 2D isoelectronic systems with targeted functionality,and especially valuable for the design of alloys and heterogeneous systems.

Temperature-induced phase transition of two-dimensional semiconductor GaTe

GaTe is a two-dimensional Ⅲ-Ⅵ semiconductor with suitable direct bandgap of~1.65 eV and high photoresponsivity,which makes it a promising candidate for optoelectronic applications.GaTe exists in two crystalline phases:monoclinic(m-GaTe,with space group C2/m) and hexagonal(h-GaTe,with space group P63/mmc).The phase transition between the two phases was reported under temperature-varying conditions,such as annealing,laser irradiation,etc.The explicit phase transition temperature and energy barrier during the temperature-induced phase transition have not been explored.In this work,we present a comprehensive study of the phase transition process by using first-principles energetic and phonon calculations within the quasi-harmonic approximation framework.We predicted that the phase transition from h-GaTe to m-GaTe occurs at the temperature decreasing to 261 K.This is in qualitative agreement with the experimental observations.It is a two-step transition process with energy barriers 199 meV and 288 meV,respectively.The relatively high energy barriers demonstrate the irreversible nature of the phase transition.The electronic and phonon properties of the two phases were further investigated by comparison with available experimental and theoretical results.Our results provide insightful understanding on the process of temperature-induced phase transition of GaTe.

Vertical two-dimensional non-hydrostatic pressure model with single layer

The vertical two-dimensional non-hydrostatic pressure models with multiple layers can make prediction more accurate than those obtained by the hydrostatic pres- sure assumption. However, they are time-consuming and unstable, which makes them unsuitable for wider application. In this study, an efficient model with a single layer is developed. Decomposing the pressure into the hydrostatic and dynamic components and integrating the x-momentum equation from the bottom to the free surface can yield a horizontal momentum equation, in which the terms relevant to the dynamic pressure are discretized semi-implicitly. The convective terms in the vertical momentum equation are ignored, and the rest of the equation is approximated with the Keller-box scheme. The velocities expressed as the unknown dynamic pressure are substituted into the continuity equation, resulting in a tri-diagonal linear system solved by the Thomas algorithm. The validation of solitary and sinusoidal waves indicates that the present model can provide comparable results to the models with multiple layers but at much lower computation cost.

Express Methods for Measurement of Electroconductivity of Semiconductor Layered Crystal

We describe theoretically the grounded method of measuring the conductivity of anisotropic layered semiconductor materials. The suggested method implies the use of a four-probe testing device with a linear arrangement of probes. The final expressions for identifying the electrical conductivity are presented in the form of a series of analytic functions. The suggested method is experimentally verified, and practical recommendations of how to apply it are also provided.

Universal transfer of full-class metal electrodes for barrier-free two-dimensional semiconductor contacts

Metal–semiconductor contacts are crucial components in semiconductor devices.Ultrathin two-dimensional transition-metal dichalcogenide semiconductors can sustain transistor scaling for next-generation integrated circuits.However,their performance is often degraded by conventional metal deposition,which results in a high barrier due to chemical disorder and Fermi-level pinning(FLP).Although,transferring electrodes can address these issues,they are limited in achieving universal transfer of full-class metals due to strong adhesion between pre-deposited metals and substrates.Here,we propose a nanobelt-assisted transfer strategy that can avoid the adhesion limitation and enables the universal transfer of over 20 different types of electrodes.Our contacts obey the Schottky–Mott rule and exhibit a FLP of S=0.99.Both the electron and hole contacts show record-low Schottky barriers of 4.2 and 11.2 meV,respectively.As a demonstration,we construct a doping-free WSe_(2) inverter with these high-performance contacts,which exhibits a static power consumption of only 58 pW.This strategy provides a universal method of electrode preparation for building high-performance post-Moore electronic devices.

Two-dimensional semiconductor heterostructures for photocatalytic CO_(2)conversion

The CO_(2)reduction into carbon-contained fuel via solar energy offers the powerful tools to realize the zero-emission carbon cycle.Owing to the intriguing features of the two-dimensional(2D)heterostructures,it is susceptible to modulate the electronic structure as well as the surface geometry for optimizing the photocatalytic CO_(2)reactivity.From this perspective,we surveyed the fundamental insights of 2D semiconductor heterostructures,involving the fabrication strategies and classification of the 2D semiconductor heterostructure.Also,we have detailly discussed the overview of 2D semiconductor heterostructure for optimizing CO_(2)photocatalytic influenced factors,including the solar energy utilization,photogenerated carriers separation,and redox reaction kinetics.Afterwards,we showed the significant advantages of 2D heterostructures in elevating CO_(2)photoreduction performance,focusing on activity,selectivity and photostability.By analyzing the limitations and developments,we ended by putting forward insights into the further researches about the CO_(2)photocatalysts and reactor design,even industrial applications.

Synergistic cerium doping and MXene coupling in layered double hydroxides as efficient electrocatalysts for oxygen evolution

Oxygen evolution reaction(OER) is a bottle-neck process in many sustainable energy conversion systems due to its sluggish kinetics.The development of cost-effective yet efficient electrocatalysts towards OER is highly desirable but still a great challenge at current stage.Herein,a new type of hybrid nanostructure,consisting of two-dimensional(2D) Cerium-doped NiFe-layered double hydroxide nanoflakes directly grown on the 2D Ti3C2Tx MXene surface(denoted as NiFeCe-LDH/MXene),is designed using a facile insitu coprecipitation method.The resultant NiFeCe-LDH/MXene hybrid presents a hierarchical nanoporous structure,high electrical conductivity and strong interfacial junction because of the synergistic effect of Ce doping and MXene coupling.As a result,the hybrid catalyst exhibits an excellent catalytic activity for OER,delivering a low onset overpotential of 197 mV and an overpotential of 260 mV at a current density of 10 mA·cm-2 in the alkaline medium,much lower than its pure LDH counterparts and IrO2 catalyst.Besides,the hybrid catalyst also displays a fast reaction kinetics and a remarkable stable durability.Further theoretic studies using density function theory(DFT) methods reveal that Ce doping could effectively narrow the bandgap of NiFe-LDH and reduce the overpotential in OER process.This work may shed light on the exploration of advanced electrocatalysts for renewable energy conversion and storage systems.

Research on quantum well intermixing of 680 nm AlGaInP/GaInP semiconductor lasers induced by composited Si-Si_(3)N_(4) dielectric layer

The optical catastrophic damage that usually occurs at the cavity surface of semiconductor lasers has become the main bottleneck affecting the improvement of laser output power and long-term reliability.To improve the output power of 680 nm AlGaInP/GaInP quantum well red semiconductor lasers,Si-Si_(3)N_(4)composited dielectric layers are used to induce its quantum wells to be intermixed at the cavity surface to make a non-absorption window.Si with a thickness of 100 nm and Si_(3)N_(4)with a thickness of 100 nm were grown on the surface of the epitaxial wafer by magnetron sputtering and PECVD as diffusion source and driving source,respectively.Compared with traditional Si impurity induced quantum well intermixing,this paper realizes the blue shift of 54.8 nm in the nonabsorbent window region at a lower annealing temperature of 600 ℃ and annealing time of 10 min.Under this annealing condition,the wavelength of the gain luminescence region basically does not shift to short wavelength,and the surface morphology of the whole epitaxial wafer remains fine after annealing.The application of this process condition can reduce the difficulty of production and save cost,which provides an effective method for upcoming fabrication.

Measurement of residual stress in a multi-layer semiconductor heterostructure by micro-Raman spectroscopy

Si-based multilayer structures are widely used in current microelectronics. During their preparation, some inhomogeneous residual stress is induced, resulting in competition between interface mismatching and surface energy and even leading to structure failure. This work presents a methodological study on the measurement of residual stress in a multi-layer semiconductor heterostructure. Scanning electron microscopy（SEM）, micro-Raman spectroscopy（MRS）, and transmission electron microscopy（TEM） were applied to measure the geometric parameters of the multilayer structure. The relationship between the Raman spectrum and the stress/strain on the [100] and [110] crystal orientations was determined to enable surface and crosssection residual stress analyses, respectively. Based on the Raman mapping results, the distribution of residual stress along the depth of the multi-layer heterostructure was successfully obtained.