Electronic Properties Of Metals Research Articles

Semiconducting Properties of Delaminated Titanium Nitride Ti4N3Tx MXene with Gate-Tunable Electrical Conductivity.

MXenes have garnered significant attention due to their atomically thin two-dimensional structure with metallic electronic properties. However, it has not yet been fully achieved to discover semiconducting MXenes to implement them into gate-tunable electronics such as field-effect transistors and phototransistors. Here, a semiconducting Ti4N3Tx MXene synthesized by using a modified oxygen-assisted molten salt etching method under ambient conditions, is reported. The oxygen-rich synthesis environment significantly enhances the etching reaction rate and selectivity of Al from a Ti4AlN3 MAX phase, resulting in well-delaminated and highly crystalline Ti4N3Tx MXene with minimal defects and high content of F and O, which led to its improved hydrophobicity and thermal stability. Notably, the synthesized Ti4N3Tx MXene exhibited p-type semiconducting characteristics, including gate-tunable electrical conductivity, with a current on-off ratio of 5 × 103 and a hole mobility of ∼0.008 cm2 V-1 s-1 at 243 K. The semiconducting property crucial for thin-film transistor applications is evidently associated with the surface terminations and the partial substitution of oxygen in the nitrogen lattice, as corroborated by density functional theory (DFT) calculations. Furthermore, the synthesized Ti4N3Tx exhibits strong light absorption characteristics and photocurrent generation. These findings highlight the delaminated Ti4N3Tx as an emerging two-dimensional semiconducting material for potential electronic and optoelectronic applications.

Synthesis, physico-chemical characterization, DFT simulation, and field electron behaviour of 2D layered Ti3C2Tx MXene nanosheets

Nanostructures of Ti3C2Tx, one of the members of the MXenes family, have been successfully prepared by chemical etching of Al from Ti3AlC2 (MAX phase) using Hydrofluoric Acid (HF) for various etching durations at room temperature. The phase, morphological, structural, and chemical analysis was performed using XRD, FESEM, TEM, Raman, and x-ray photoelectron spectroscopy. The surface morphology of as-synthesized Ti3C2Tx (MXene) phase is characterized by stacks of layered sheets like structures. Field electron emission (FEE) behaviour was investigated at the base pressure of 1 × 10−8 mbar. The pristine Ti3AlC2 (MAX) and Ti3C2Tx (MXene) nanosheets emitters showed values of turn-on field (defined at current density ∼ 1 μA cm−2) as 4.18 and 1.67 V μm−1, respectively. Furthermore, maximum emission current density of ∼ 825 μA cm−2 was extracted from the MXene nanosheets emitter at an applied field of 3.60 V μm−1, in contrast to ∼71 μA cm−2 drawn at 7.31 V μm−1 from the pristine MAX emitter. The MXene nanosheets emitter exhibited good emission current stabilities at pre-set values ∼ 10 and 100 μA over 3 h duration. Work function values of the MAX and MXene nanosheets emitters were measured using a retarding field analyzer, and found to be 4.4 and 3.6 eV, respectively. Extensive ab-initio simulations have been performed to provide structural and electronic properties, as well as for estimating the work function of Ti3C2 layered material. The estimated electronic density of states revealed its metallic character. The improved FEE performance exhibited by the 2D layered Ti3C2Tx (MXene) nanosheets emitter is attributed to its unique morphology characterized by high aspect ratio, metallic electronic properties and relatively lower work function.

Regulating the Hydrodeoxygenation Activity of Molybdenum Carbide with Different Diamines as Carbon Sources

The hydrodeoxygenation (HDO) of renewable fats or fatty acids into alkanes is a powerful measure to address energy and environmental crises. Molybdenum carbide-based catalysts are promising due to their platinum-like noble metal electronic properties. In this paper, Mo2C catalysts were prepared by one-step carbonization of amine molybdenum oxide (AMO) precursors using diamines with different carbon chain lengths as ligands. The physical and chemical properties and the HDO catalytic activity of the catalysts were investigated. The results indicate that as the carbon chain of diamines in the precursor increases, the carbon content of the catalysts in the surface and bulk phase increases. The Mo2C-12 catalyst exhibited excellent catalytic performance, with a palmitic acid conversion rate of 100% and an alkane selectivity of 96.6%, which are attributed to the smallest particle size, largest pore size, and synergistic effect of carbon. This work provides a simple and safe method for regulating the surface properties of Mo2C catalysts.

Electrically Conductive Polymers for Additive Manufacturing.

The use of electrically conductive polymers (CPs) in the development of electronic devices has attracted significant interest due to their unique intrinsic properties, which result from the synergistic combination of physicochemical properties in conventional polymers with the electronic properties of metals or semiconductors. Most conventional methods adopted for the fabrication of devices with nonplanar morphologies are still challenged by the poor ionic/electronic mobility of end products. Additive manufacturing (AM) brings about exciting prospects to the realm of CPs by enabling greater design freedom, more elaborate structures, quicker prototyping, relatively low cost, and more environmentally friendly electronic device creation. A growing variety of AM technologies are becoming available for three-dimensional (3D) printing of conductive devices, i.e., vat photopolymerization (VP), material extrusion (ME), powder bed fusion (PBF), material jetting (MJ), and lamination object manufacturing (LOM). In this review, we provide an overview of the recent research progress in the area of CPs developed for AM, which advances the design and development of future electronic devices. We consider different AM techniques, vis-à-vis, their development progress and respective challenges in printing CPs. We also discuss the material requirements and notable advances in 3D printing of CPs, as well as their potential electronic applications including wearable electronics, sensors, energy storage and conversion devices, etc. This review concludes with an outlook on AM of CPs.

Investigation of the physical properties of the metal (Co, Cr, Mn, Sc) doped TiAl3 compounds: A DFT study

In this paper, the elastic and electronic properties of Metal (M = Co, Cr, Mn, Ni, Sc) - TiAl3 are compared based on the first-principles calculation method based on density functional theory, and the Metal-TiAl3 Mechanical, thermodynamic and electronic properties of TiAl3 intermetallic compounds. The results of mechanical property calculations show that the structures of Sc-TiAl3 and V-TiAl3 are the most stable. The ability of Sc-TiAl3 to resist volume deformation and shear deformation is larger. The Poisson's ratio ν is less than 0.33, and it can be determined that the calculated compounds are brittle materials (except Ni-TiAl3). Cr-TiAl3 has the largest intrinsic Vickers hardness, while Ni-TiAl3 has the smallest intrinsic Vickers hardness. This study has a significant impact on adjusting the mechanical properties of TiAl3.

Coupling Borophene to Graphene in Air‐Stable Heterostructures

AbstractArtificial 2D van der Waals heterostructures with controllable vertical stacking and rotational orientation exhibit multifaceted electronic properties that are appealing for applications in fields ranging from optoelectronics to energy storage. Along with transition metal dichalcogenides and graphene, borophene has recently emerged as a promising building block for 2D devices due to its conductive nature as well as its exceptional mechanical and electronic properties. Here, it is demonstrated that the combination of the dissolution‐segregation process and chemical vapor deposition allows for the synthesis of graphene/borophene heterostructures of the highest crystalline and chemical quality, in which graphene sits on top of the borophene layer with metallic character. The formation of laterally distinct micron‐sized areas allows a comparative study of borophene, graphene, and the graphene–borophene heterostack in terms of their electronic properties and stability in a reactive environment. Whereas pristine borophene is particularly prone to oxidation, the graphene–borophene heterostack is chemically inert and enables the conservation of borophene's character even after exposure to air. This study opens up new perspectives for the scalable synthesis of graphene–borophene heterostacks with enhanced ability to preserve the metallic character and electronic properties of borophene.

Theoretical prediction of the influence of defects and atomic occupation on the elastic and electronic properties of NbSi2 form the first-principles calculations

In now days, the transition metal silicides are one of the promising materials for making high-temperature materials. To improve the inherent brittleness of the transition metal silicides, the elastic and electronic properties of the C40-type NbSi2 disilicides have been predicted using first-principles calculations. Six defect models (V-Va, Si-Va, N-V, N-Si, O-V, O-Si) were chosen to evaluate the elastic properties of transition metal silicides. According to the data of thermodynamic parameters, NbSi2 with the different defect and doping models shows the phase stability. The introduction of different defects and doping models changes the mechanical behavior. The defect and doping models lead to the decrease in the deformation resistance and hardness of the perfect NbSi2. Additionally, the defect and doping models result in the perfect NbSi2 to actualize the brittle-to-ductile transition. The Nb defects resulted in NbSi2 having the greatest degree of anisotropy. The electronic structures are calculated to discuss the brittle-to- ductile transition for NbSi2 with defects.

Sidechain Metallopolymers with Precisely Controlled Structures: Synthesis and Application in Catalysis.

Inspired by the cooperative multi-metallic activation in metalloenzyme catalysis, artificial enzymes as multi-metallic catalysts have been developed for improved kinetics and higher selectivity. Previous models about multi-metallic catalysts, such as cross-linked polymer-supported catalysts, failed to precisely control the number and location of their active sites, leading to low activity and selectivity. In recent years, metallopolymers with metals in the sidechain, also named as sidechain metallopolymers (SMPs), have attracted much attention because of their combination of the catalytic, magnetic, and electronic properties of metals with desirable mechanical and processing properties of polymeric backbones. Living and controlled polymerization techniques provide access to SMPs with precisely controlled structures, for example, controlled degree of polymerization (DP) and molecular weight dispersity (Đ), which may have excellent performance as multi-metallic catalysts in a variety of catalytic reactions. This review will cover the recent advances about SMPs, especially on their synthesis and application in catalysis. These tailor-made SMPs with metallic catalytic centers can precisely control the number and location of their active sites, exhibiting high catalytic efficiency.

Strong Second- and Third-Harmonic Generation in 1D Chiral Hybrid Bismuth Halides.

Breaking the symmetry of a crystal structure can enable even-order nonlinear activities, including second-harmonic generation (SHG). The emerging chiral hybrid organic-inorganic metal halides feature unique optical and electronic properties and flexible crystal structures, making them a class of promising nonlinear optical materials. However, their nonlinear response performances are currently inferior to traditional nonlinear crystals, because of the lack of research on resonant enhancement and third-harmonic generation (THG). Herein, we designed chiral hybrid bismuth halides with naturally nonsymmetrical structure to enable SHG. Simultaneously, these chiral compounds preserve 1D crystal structures to create strong free exciton, broad self-trapped exciton (STE), and discrete band energy levels, which facilitate the resonant enhancement of SHG and THG susceptibilities. These new chiral films showcase superior effective SHG susceptibility (χ(2) ∼ 130.5 pm V-1 at an interesting wavelength of 1550 nm), exceeding that of the reference, a commercial LiNbO3 (χ(2) ∼ 83.4 pm V-1) single-crystal film. Furthermore, their THG intensities are even higher than their SHG intensities, with effective THG susceptibility (χ(3)) being ∼9.0 × 106 pm2 V-2 at 1550 nm (37 times that of the reference monolayer WS2). Their high SHG and THG performances indicate the promising future of these 1D chiral hybrid bismuth halides toward nonlinear optical applications.

Monitoring Dynamics, Structure, and Magnetism of Switchable Metal-Organic Frameworks via 1 H-Detected MAS NMR.

We present a toolbox for the rapid characterisation of powdered samples of paramagnetic metal–organic frameworks at natural abundance by 1H‐detected solid‐state NMR. Very fast MAS rates at room and cryogenic temperatures and a set of tailored radiofrequency irradiation schemes help overcome the sensitivity and resolution limits often associated with the characterisation of MOF materials. We demonstrate the approach on DUT‐8(Ni), a framework containing Ni2+ paddle‐wheel units which can exist in two markedly different architectures. Resolved 1H and 13C resonances of organic linkers are detected and assigned in few hours with only 1–2 mg of sample at natural isotopic abundance, and used to rapidly extract information on structure and local internal dynamics of the assemblies, as well as to elucidate the metal electronic properties over an extended temperature range. The experiments disclose new possibilities for describing local and global structural changes and correlating them to electronic and magnetic properties of the assemblies.

Exchange interactions, half metallic ferromagnetism, mechanical, thermal and magneto-electronic properties of full Heusler alloys Co2YGe(Y= Mn, Fe) for acoustical and spintronic devices

The focal point of this article is to pay attention on the half metallic ferromagnetism, structural, elastic, thermal, electronic and magnetic properties of Co2YGe (YMn, Fe) Heusler compounds with Fm-3m crystal structure involving the density functional theory within the framework of full potential linearized augmented plane wave method as integrated in the Wien2k package. The structural optimizations plots confirm that both alloys are in the lower energy state in ferromagnetic order. Moreover the structural parameters are consistent with experiment. The computed elastic properties show the ductile nature of these alloys. Based on the thermal properties of these alloys, Co2MnGe is more favorable for the fabrication of elevated temperature acoustical devices as compared to Co2FeGe. For the calculation of electronic and magnetic properties of Co2YGe (YMn, Fe) alloys in addition to GGA functional, the GGA + U (U= Hubbard parameters) were also adopted. Both alloys are HMF in nature. It is also observed that the values of the compound's magnetic-moments fit excellent with Slater Pauling law. Furthermore we have calculated the formation energy and Curie temperature of these alloys. The negative values of the formation energy of both compounds represent their thermodynamic stability and strong bonding. Higher values of thermal parameters, half metallic nature and ferromagnetism of Co2YGe (YMn, Fe) predict the importance of these compounds in acoustical and spintronic devices respectively.

Magnetic and Electronic Properties of Heavy Lanthanides (Gd, Tb, Dy, Er, Ho, Tm)

Rare earth metals (REM) occupy a special and important place in our lives. This became especially noticeable during the rapid development of industry in the industrial era of the twentieth century. The tendency of development of the rare-earth metals market certainly remains in the XXI century. According to experts estimates the industry demand for chemical compounds based on them will tend to grow during the nearest years until it reaches the market balance. At the same time, the practical use of high-purity rare-earth metals requires the most accurate understanding of the physical properties of metals, especially magnetic ones. Despite a certain decline in interest in the study of high-purity REM single crystals during the last decade, a number of scientific groups (Ames Lab, Lomonosov Moscow State University (MSU), Baikov Institute of Metallurgy and Materials Science Russian Academy of Science (RAS)) are still conducting high-purity studies on high-purity metal samples. The present article is a combination of a review work covering the analysis of the main works devoted to the study of heavy REMs from gadolinium to thulium, as well as original results obtained at MSU. The paper considers the electronic properties of metals in terms of calculating the density of states, analyzes the regularities of the magnetic phase diagrams of metals, gives the original dependences of the Neel temperature and tricritical temperatures for Gd, Tb, Dy, Er, Ho, Tm, and also introduces a phenomenological parameter that would serve as an indicator of the phase transformation in heavy REMs.

Surface functionalization of the honeycomb structure of zinc antimonide (ZnSb) monolayer: A first-Principles study

Structural, electronic, optic and vibrational properties of Zinc antimonide (ZnSb) monolayers and their functionalized (semi-fluorinated and fully chlorinated) structures are investigated by means of the first-principles calculations. The phonon dispersion curves reveal the presence of imaginary frequencies and thus confirm the dynamical instability of ZnSb monolayer. The calculated electronic band structure corroborates the metallic character with fully-relativistic calculations. Moreover, we analyze the surface functionalization effect on the structural, vibrational, and electronic properties of the pristine ZnSb monolayer. The semi-fluorinated and fully-chlorinated ZnSb monolayers are shown to be dynamically stable in contrast to the ZnSb monolayer. At the same time, semi-fluorination and fully-chlorination of ZnSb monolayer could effectively modulate the metallic electronic properties of pristine ZnSb. In addition, a magnetic metal to a nonmagnetic semiconductor transition with a band gap of 1 eV is achieved via fluorination, whereas a transition to a semiconducting state with 1.4 eV band gap is found via chlorination of the ZnSb monolayer. According to the optical properties analysis, the first absorption peaks of the fluorinated- and chlorinated-ZnSb monolayers along the in-plane polarization are placed in the infrared range of spectrum, while they are in the middle ultraviolet for the out-of-plane polarization. Interestingly, the optically anisotropic behavior of these novel monolayers along the in-plane polarizations is highly desirable for design of polarization-sensitive photodetectors. The results of the calculations clearly proved that the tunable electronic properties of the ZnSb monolayer can be realized by chemical functionalization for application in the next generation nanoelectronic devices.

Ab initio simulation of functionalized β12 borophene

In this work we evaluated the structural and electronic properties of C-doped and COOH-functionalized β12 borophene through ab initio simulations using the density functional theory (DFT). β12 borophene is a stable 2D nanomaterial and composed only by B atoms, with promising applications specially for the electronic industry. The substitutional C-doped β12 borophene is chemically favorable with a strong hybridization of carbon-boron energy levels. The COOH-functionalization on β12 borophene presents high energy adsorption (around 3.2 eV). The studied functionalizations show metallic electronic properties in the resulting systems, as well as observed for pristine β12 borophene.

Supermetal

Large density of states may have competing effects on electronic properties of metals: enhanced susceptibility towards ordering and strong screening of electron repulsion. This work investigates electron interaction effects near a high-order Van Hove singularity, where the density of states shows a power-law divergence. By combining the mean-field and renormalization-group studies, the authors reveal a supermetal, a non-Fermi liquid metal with various divergent susceptibilities but no long range order due to scale invariance.

Analysis of Transport Properties of the Randomly Moving Electrons in Metals

In this critical analysis on the base of randomly moving (RM) electrons, presented the resistivity dependence on temperature for elemental metals both above and below the Debye’s temperatures. There also are presented the general relationships for estimation of the average diffusion coefficient, the average velocity, mean free path and average relaxation time of RM electrons on the Fermi surface at mentioned temperature range. It is shown that the scattering of RM electrons mainly is due to electronic defects associated with distortion of the periodic potential distribution in the periodic lattice, and accounting the exchange of the thermal energies between phonon and RM electron. The calculation results of resistivity dependence on temperature in the temperature range from 1 K to 900 K are demonstrated for Au and W and compared with the experimental data. There also is presented the simple method for determination of the basic kinetic characteristic dependences on temperature only from the resistivity dependence on temperature. It is at first time determined for Au and W the temperature dependences of the mean free path, average diffusion coefficient, average relaxation time of RM electrons from 1 K to 900 K.

Plasmonics of Diffused Silver Nanoparticles in Silver/Nitride Optical Thin Films

Metal-dielectric multilayers are versatile optical devices that can be designed to combine the visible transmittance of dielectrics with the electronic properties of metals for plasmonic and meta-material applications. However, their performances are limited by an interfacial optical absorption often attributed entirely to the metal surface roughness. Here, we show that during deposition of AlN/Ag/AlN and SiNx/Ag/SiNx multilayers, significant diffusion of Ag into the top dielectric layer form Ag nanoparticles which excite localized surface plasmon resonances that are primarily responsible for the interfacial optical absorption. Based on experimental depth profiles, we model the multilayer’s silver concentration profile as two complementary error functions: one for the diffused Ag nanoparticles and one for the interface roughness. We apply the Maxwell-Garnett and Bruggeman effective medium theories to determine that diffusion characteristics dominate the experimental absorption spectra. The newfound metal nanoparticle diffusion phenomenon effectively creates a hybrid structure characteristic of both metal-dielectric multilayer and metal-dielectric composite.

Hot Electrons Modulation of Third-Harmonic Generation in Graphene

Hot electrons dominate the ultrafast ($\sim$fs-ps) optical and electronic properties of metals and semiconductors and they are exploited in a variety of applications including photovoltaics and photodetection. We perform power-dependent third harmonic generation measurements on gated single-layer graphene and detect a significant deviation from the cubic power-law expected for a third harmonic generation process. We assign this to the presence of hot electrons. Our results indicate that the performance of nonlinear photonics devices based on graphene, such as optical modulators and frequency converters, can be affected by changes in the electronic temperature, which might occur due to increase of absorbed optical power or Joule heating.

Quadratic contact point semimetal: Theory and material realization

Most electronic properties of metals are determined solely by the low-energy states around the Fermi level, and for topological metals/semimetals, these low-energy states become distinct because of their unusual energy dispersion and emergent pseudospin degree of freedom. Here, we propose a class of materials which are termed as quadratic contact point (QCP) semimetals. In these materials, the conduction and valence bands contact at isolated points in the Brillouin zone, around which the band dispersions are quadratic along all three directions. We show that in the absence/presence of spin-orbit coupling, there may exist triply/quadruply-degenerate QCPs that are protected by the crystalline symmetry. We construct effective models to characterize the low-energy fermions near these QCPs. Under strong magnetic field, unlike the usual 3D electron gas, there appear unconventional features in the Landau spectrum. The QCP semimetal phase is adjacent to a variety of topological phases. For example, by breaking symmetries via Zeeman field or lattice strain, it can be transformed into a Weyl semimetal with Weyl and double Weyl points, a Z2 topological insulator/metal, or a Dirac semimetal. Via first-principles calculations, we identify realistic materials Cu2Se and RhAs3 as candidates for QCP semimetals.

A novel hybrid sp-sp2 metallic carbon allotrope

In this paper, we propose a novel hybrid sp-sp2 monoclinic carbon allotrope mC12. This allotrope is a promising light metallic material, the mechanical and electronic properties of which are studied based on first-principles calculations. The structure of this new mC12 is mechanically and dynamically stable at ambient pressure and has a low equilibrium density due to its large cell volume. Furthermore, calculations of the elastic constants and moduli reveal that mC12 has a rigid mechanical property. Finally, it exhibits metallic characteristics, owing to the mixture of sp-sp2 hybrid carbon atoms.