Semiconductor-metal Transition Research Articles

Formation of vanadium dioxide nanocrystal arrays via post-growth annealing for stable and energy-efficient switches

The abrupt and reversible semiconductor-metal phase transition in vanadium dioxide nanocrystals has attracted considerable attention for potential applications in oxide electronics, including neuromorphic systems. This study presents a systematic investigation of post-growth annealing conditions for the formation of single VO2 M-phase nanocrystals arrays from VOx films synthesized by atomic layer deposition. The composition of the initial VOx films and the annealing parameters were found to significantly affect the morphology, phase composition and electrical properties of the obtained single nanocrystal arrays. Our results demonstrate that the formation of VO2 M-phase nanocrystal arrays occurs at annealing temperatures of 650 °C and above, irrespective of the initial film composition. More homogeneous in size nanocrystals are formed from initial VOx films with higher V+4 content. The structures with the initial V+4 content of 60 % annealed at 650 °C for 2 h demonstrates the resistive switching with an energy less than 150 fJ, and a total number of stable switching cycles more than 101⁰. Our results pave the way for the novel energy-efficient nanoelectronic and nanophotonic devices based on VO₂ nanoparticles.

Pressure-induced superconductivity and phase transition in PbSe and PbTe

Abstract The IV-VI semiconducting chalcogenides are a large material family with distinct physical behavior. Here, we systematically investigate the effect of pressure on the electronic and crystal structure in PbSe and PbTe by combining high-pressure electrical transport and synchrotron x-ray diffraction (XRD) measurements. The resistivity of PbSe and PbTe changes dramatically under high pressure and a non-monotonic evolution of ρ(T) is observed. Both PbSe and PbTe are found to undergo semiconductor-metal transition upon compression and show superconductivity under higher pressure. The structural evolutions from the Fm-3m to Pnma phase and then to the Pm-3m phase in PbSe are verified by the x-ray diffraction. The present findings reveal the internal correlation between the structural evolution and the physical properties in lead chalcogenides.

Comprehensive approach on La1-xPbxMnO3 (0.2 ≤ x ≤ 0.5) perovskites synthesized by solid state reaction technique

We have synthesized Pb concentrated La manganites La1-xPbxMnO3 (0.2 ≤ x ≤ 0.5) using solid state reaction route to investigate several physical properties such as structural, thermal, magnetic, electronic and elastic properties via both the experimental characterizations and the first principles calculations under the framework of density functional theory (DFT). The structures of the studied perovskites are examined by X-ray diffraction (XRD) pattern and also compared with the crystallographic data obtained by computations. The crystallization and formation of the studied phase of manganites are confirmed by analyzing the thermogravimetric (TG) curve. The temperature dependence of magnetization of all the samples exhibits a ferromagnetic metal phase with the Curie temperatures TC ranging from 334 to 338 K. Although a metal-semiconductor transition is expected at around TC for the measurement of electrical resistivity with temperature but we observe semiconducting behavior because of the resistivity data started from room temperature. The calculated energy dispersion of all the manganites shows metallic conduction in conformity with the available experimental results. All the studied perovskites under investigation possess mechanical stability, malleability as well as anisotropy. The calculated Debye temperatures of all the Pb-doped La manganites show excellent correspondence with the other thermophysical parameters like melting point, phonon thermal conductivity and hardness as well.

The tunable electronic and optical properties of WS2/PtO2 heterojunctions are calculated by first principles

In this paper, the optical and electrical characteristics of WS2/PtO2 heterojunction are calculated by first principles method. The results show that WS2/PtO2 heterojunction is a semiconductor heterojunction with an indirect bandgap of 0.7 eV and a Type-Ⅱ band distribution, which can achieve rapid division and transport of photogenerated carriers. Its narrow band gap has a unique electronic structure and tunability, which shows great application potential in high-performance optoelectronic devices and solar cells. When we apply biaxial strain and electric field, the WS2/PtO2 heterojunction has semiconductor–metal transition. This transformation can be used in electronic devices to regulate the carrier concentration and transport characteristics in electronic devices. It also shows excellent properties in optics. The above shows that the stable structure and tunable electronic properties make WS2/PtO2 heterojunctions hold significant promise for future optoelectronic devices and other applications.

Strain-modulation of electronic and optical properties of two-dimensional GeTe/SnSe van der Waals heterostructure

By first-principles method, the electronic and optical properties of stable GeTe/SnSe van der Waals heterostructure under strain have been investigated. By applying uniaxial and biaxial strain, the bandgap and band alignment of this heterostructure can be controlled, and semiconductor-metal phase transition is observed. By applying biaxial strain, the optical absorption of the heterostructure can be improved, and the power conversion efficiency can be improved from 13% to 19%. The easily controlled electronic properties and good optical properties make GeTe/SnSe van der Waals heterostructure to be a promising material in optoelectronic and solar energy conversion devices.

Evolution of ferromagnetism and electrical resistivity in Sb-doped Cr4PtGa17

We describe the doping effects on a metallic breathing pyrochlore compound, Cr4PtGa17. Upon doping with Sb, i.e., Cr4Pt(Ga1-xSbx)17, it was found that a selective doping on one of the seven Ga sites occurs. With increasing dopant level, the ferromagnetism in the parent compound is gradually suppressed, along with a decrease in fitted Curie-Weiss temperature (from 61 (1) K to −1.8 (1) K) and effective moment (from ∼2.26 μB/f.u. to ∼0.68 μB/f.u.). Low-temperature heat capacity measurements confirm the absence of magnetic ordering above 0.4 K for the three most doped samples. Meanwhile, electrical resistivity measurements display a metal-semiconductor transition with increasing Sb contents, which is attributed to an increase of Fermi energy based on the calculations of electronic band structure and density of states. Moreover, we have speculated that the ferromagnetism in Cr4PtGa17 is governed by itinerant electrons according to our observations. This study of Sb-doping effect on Cr4PtGa17 provides deeper understanding of magnetism of this system and possibilities for future modifications.

Semiconductor-metal transition in TlPbF3 under isotropic pressure and its impact on optical, elastic and mechanical properties: a DFT computation with HSE06

This research aims to comprehensively evaluate the structure, elasticity, mechanics, anisotropy, electrical properties, and optical attributes of TlPbF3 at pressures from 0 to 60 GPa. A cubic structure of the material remains same without any phase changes, but there is a reduction in the lattice parameters. The material is determined to be mechanically secure by doing calculations on a variety of mechanical and elastic characteristics, including bulk, shear, and Young’s modulus, stiff, and not particularly flexible. It also shows a significant resistance to shear force. The material’s ability to withstand high pressures, its metallic bond nature, and ductility have been shown by the Kleinman’s parameter, Poisson’s ratio, Cauchy pressure, and Pugh ratio. Anisotropy can be confirmed by activating specific anisotropy factors. When we consider the electronic band structure, we observe a transition from a broad gap in the band (3.719 eV) comparable with a small band distance (0.65 eV), and converts to a metal (0 eV). To explore this, we have estimated the total, partial and elemental partial density of states. Additionally, we have computed the real and imaginary functions of dielectric, absorption factor, refractive index, extinction coefficient, loss function, reflectivity and real/imaginary conductivity to assess the material’s applicability. As pressure is applied, the static values of ε1(ω) and n(ω) increase. This material is also well-suited for optoelectronic devices due to its high conductivity, reflectivity, absorption, and refractive index.

Electronic and magnetic properties of graphene-fluorographene nanoribbons: Controllable semiconductor-metal transition

Electronic and magnetic properties of graphene-fluorographene nanoribbons: Controllable semiconductor-metal transition

Nature of electrically detected magnetic resonance in highly nitrogen-doped 6H -SiC single crystals

This work focuses on unraveling electron paramagnetic resonance (EPR) and electrically detected magnetic resonance (EDMR) properties of n-type 6H silicon carbide (SiC) single crystals with high concentrations of uncompensated nitrogen (N) donors, which is essential for fundamental understanding of spin-related phenomena, developing spin-based devices, optimizing materials and devices, and advancing research in quantum information and spintronics. Utilizing low-temperature multifrequency EPR spectroscopy (9.4–395.12 GHz), we identified two intense signals labeled as S line and S1 line in the 6H-SiC crystals with ND–NA≈8×1018 and 4×1019cm−3. In addition, in 6H-SiC crystals with ND–NA≈8×1018cm−3, a low-intensity triplet from N donors substituting the quasicubic “k2” nonequivalent position (Nk2) was observed. The S line [g⊥=2.0029(2),g∥=2.0038(2)] was assigned to the exchange interaction of conduction electrons and Nk2, while the S1 line [g⊥=2.0030(2),g∥=2.0040(2)] is caused by the exchange spin coupling of localized N donors at the “k1” and “k2” positions. The S1 line was observed in high-frequency EDMR spectra of 6H-SiC with ND–NA≈8×1018cm−3, and its emergence was explained by an enhancement of the hopping conductivity due to the EPR-induced temperature increase mechanism. No EDMR spectra were found to occur in the 6H-SiC crystals with ND–NA≈4×1019cm−3, which is close to the critical donor concentration value for a semiconductor-metal transition. Thus it can be concluded that this N donor concentration is too high for the appearance of spin-dependent scattering and too low for the emergence of EPR-induced hopping mechanisms in 6H-SiC. Published by the American Physical Society 2024

Investigation into the role of MoS2 in the composite of Cu-Cu2O/MoS2 in catalytic aerobic oxidation of benzylic alcohols

Cuprous oxide (Cu2O), as a common transition metal semiconductor material, has found extensive applications and research in the field of catalysis due to its unique physicochemical properties. To improve its catalytic performance, introducing carriers to form composite materials with Cu2O has proven to be a promising strategy for enhancing its stability, activity, and selectivity. In this study, we introduced MoS2 to form a composite material with Cu-Cu2O, investigating the impact of MoS2 on the activity of Cu-Cu2O in selective alcohol oxidation. The results demonstrate a significant improvement in the catalytic activity of Cu-Cu2O upon the introduction of MoS2. Further investigations substantiate the close correlation between the enhanced activity of Cu-Cu2O and the interaction with thin layered MoS2 flakes. The quantity of the thin layered MoS2 is small but its impact on the catalytic activity is significant. It induces changes in the band and electronic structures of Cu-Cu2O, and the changes facilitate the activation of O2 and electron transfer in the oxidation, and thus promote the catalysis.

Understanding vapor phase growth of hexagonal boron nitride.

Hexagonal boron nitride (hBN), with its atomically flat structure, excellent chemical stability, and large band gap energy (∼6 eV), serves as an exemplary 2D insulator in electronics. Additionally, it offers exceptional attributes for the growth and encapsulation of semiconductor transition metal dichalcogenides (TMDCs). Current methodologies for producing hBN thin films primarily involve exfoliating multi-layer or bulk crystals and thin film growth via chemical vapor deposition (CVD), which entails the thermal decomposition and surface reaction of molecular precursors like ammonia boranes (NH3BH3) and borazine (B3N3H6). These molecular precursors contain pre-existing B-N bonds, thus promoting the nucleation of BN. However, the quality and phase purity of resulting BN films are greatly influenced by the film preparation and deposition process conditions that remain a substantial concern. This study aims to comprehensively investigate the impact of varied CVD systems, parameters, and precursor chemistry on the synthesis of high-quality, large scale hBN on both catalytic and non-catalytic substrates. The comparative analysis provided new insights into most effective approaches concerning both quality and scalability of vapor phase grown hBN films.

Advancements in Manganese-Based Cathode for Sustainable Energy Utilization.

Manganese-based compounds, especially manganese oxides, are one of the most exceptional electrode materials. Specifically, manganese oxides have gained significant interest owing to their unique crystal structures, high theoretical capacity, abundant natural availability and eco-friendly nature. However, as transition metal semiconductors, manganese oxide possess low electrical conductivity, limited rate capacity, and suboptical cycle stability. Thus, combining manganese oxides with carbon or other metallic materials can significantly improve their electrochemical performance. These composites increase active sites and conductivity, thereby improving electrode reaction kinetics, cycle stability, and lifespan of supercapacitors (SCs) and batteries. This paper reviews the latest applications of Mn-based cathodes in SCs and advanced batteries. Moreover, the energy storage mechanisms were also proposed. In this review, the development prospects and challenges for advanced energy storage applications of Mn-based cathodes are summarized.

Pressure-induced metallization in Pb3Mn7O15

The multiferroic material Pb3Mn7O15 exhibits a high resistivity arising from the orbital electrons localized around the manganese ions, which hinders its potential applications. Previous studies indicated that the resistivity of Pb3Mn7O15 was influenced by its crystal structure and the distribution of Mn ions. Consequently, pressure-induced structural change are expected to represent a viable method for tuning the resistivity and other properties of this compound. In the present study, the pressure effect on the resistivity of Pb3Mn7O15 was investigated up to 42 GPa. Furthermore, the X-ray diffraction and Raman spectroscopy techniques, along with the density functional theory calculations were employed to study the crystal structure evolution of Pb3Mn7O15 under pressure. The results demonstrate an electronic semiconductor-metal phase transition in Pb3Mn7O15, accompanying an irreversible orthorhombic to monoclinic phase transition. Additionally, within the orthorhombic phase, an iso-structural phase transition is observed, originating from the magnetic moments collapse of manganese cations. This study provides compelling evidence that high-pressure processing can be employed to modulate the crystal structure and functional properties of multifunctional materials.

Strain and orientation modulated optoelectronic properties of La-doped SrSnO3 epitaxial films

We have studied the structural, electrical, and optical properties of La0.05Sr0.95SnO3 thin films, which exhibited a strong dependence upon the substrate’s orientation and strain. X-ray diffraction results show that the LSSO films grow epitaxially on (001) and (011)-oriented LaAlO3 substrates, and the in-plane compressive strain decreases gradually upon increasing film thickness. Room-temperature resistivity varies from 4.23 (13.0) to 1.37 (4.76) mΩ cm as the film thickness increases for (001) orientation ((011) orientation). Temperature dependent resistivity curves of all the samples show a metal–semiconductor transition (MST), which can be explained by the electron–electron interactions below MST rather than weak localization. Both reducing the in-plane compressive strain and transferring the orientation from (011) to (001) can drive the MST point shifts toward lower temperature, indicative of the enhancement of the metallic transport in the films. The band gap increases upon increasing film thickness due to Burstein-Moss effect. The charge distributions of Sn and O from density functional theory (DFT) calculations illustrate that (001)-plane has a better conductivity. Furthermore, our DFT results also demonstrate that decreasing the in-plane strain will lead to a smaller electron effective mass, thus the increased carrier mobility can be obtained. These comprehensive investigations advance our knowledge of the optoelectronic characteristics and provide valuable insights for future research in related transparent materials.

The electrical properties of nitrogen-doped vanadium dioxide thin films grown by magnetron sputtering

Abstract Vanadium dioxide (VO2) undergoes a reversible semiconductor-metal phase transition near 68°C, and the optical and electrical properties could be changed in femtoseconds. These unique characteristics meet the electro-optic switch applications. In this work, to improve the intrinsic characteristics of VO2, a series of nitrogen-doped vanadium dioxide thin films were prepared by reactive magnetron sputtering. Moreover, the effects of different nitrogen flow rates on the microstructure, surface morphology, electrical properties and phase transition properties of the samples were investigated. The samples are characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), four-point probe system, and Hall effect et al. Sheet resistance variation at room temperature and high temperatures indicates remarkable semiconductor-metal transition characteristics. According to results of Hall effect measurement, when nitrogen flow rate is less than 1 sccm, the samples exhibits p-type semiconductor characteristics. However, while nitrogen flow rate reaches 1 sccm, n-type semiconductor characteristics appear. What’s more, Carrier mobility reaches a maximum at a nitrogen to oxygen flow ratio of 0.3. The results reveal that the samples have a great potential on electro-optic switching applications.

Single atom intercalation in 2D triazine-based (g-C6N6) and boroxine-based (B6O6) porous covalent organic framework bilayers and heterostructures

Covalent organic frameworks (COFs) are new class of organic porous materials with tunable pore size and low weight density, demonstrating remarkable potential applications in gas storage, gas separation, and catalysis. The inherent periodic porosity of COF monolayers (MLs) establishes anchoring sites for single atoms. Using first-principles calculations, we study the structural and electronic properties of atom-embedded C6N6 and B6O6 MLs. Subsequently, the intercalation of atoms between C6N6 and B6O6 bilayers (BLs) and their heterostructure (HTS) are investigated. Our findings show the significant effects of embedded atoms on the structural parameters of the host material. Notably, the Li atom anchors within the pore region of C6N6 ML without forming bonds, while it establishes two σ bonds with O atoms in B6O6 ML. The Cs atom forms six bonds in both MLs and resides between layers in BLs. In the HTS, the Cs atom forms six bonds with N atoms of the C6N6 layer, positioning in the middle of the layers. Calculations reveal that Li and Cs atoms induce a red shift in energy, leading to a semiconductor–metal transition. Conversely, the insertion of an F atom induces a blue shift in energy, creating a midgap state at the Fermi energy.

The external electric field induces Rashba and Zeeman spin splitting in non-polar MXene Lu2CF2 monolayers for spintronics application

For the application of the spintronics devices, large Rashba spin splitting and Zeeman spin splitting are required. However, the absence of spin splitting in the non-polar MXene Lu2CT2 (T = F, OH) with mirror symmetry limits the functionality of the spintronics applications. In this paper, by the density functional theory calculation, the effect of the electric field on the electronic properties along with the spin polarization of MXene Lu2CT2 (T = F, OH) are investigated. For Lu2CF2, the electric field can effectively regulate the energy band structures resulting in the indirect-direct band gap transition and semiconductor-metal transition. The spin splitting and spin polarization that are not observed in the situation of the intrinsic systems are established due to the breaking of the mirror symmetry by a suitable external electric field, which is sufficient to support the spintronics functionality. Furthermore, the electric field can effectively control the in-plane Rashba spin splitting and out-of-plane Zeeman spin splitting. The parameters of Rashba and the warping coefficients are comprehensively studied by using the effective k·p model. Therefore, our results provide a possible way to induce and tune Rashba spin splitting and Zeeman spin splitting in the MXene by an external electric field, which is useful for spintronic devices.

Exploring optoelectronic and thermal characteristics of Janus MoSeTe and WSeTe monolayers under mechanical strain

This paper reveals the effect of external strain on the electronic, thermal and optical properties of Janus MSeTe (M=Mo, W) using first principles. Phonon spectrum calculations confirm the dynamic stability of the system. Biaxial stretching can effectively modulate its thermal properties. Uniaxial, biaxial and shear strains modulate the band structure, structural parameters, averaged differential charge density and optical properties of the MSeTe system to different degrees. The increase of compressive and shear strains leads to a gradual decrease of the band gap and triggers a semiconductor-metal phase transition at the critical point. The intrinsic system exhibits strong light absorption in the visible and ultraviolet regions, while strain induces a redshift of the light-absorbing edge, which enhances the response to the infrared and visible wavelength bands. These findings provide a theoretical basis and application potential for the design of optoelectronic devices and thermoelectric materials.

First-principles calculation of the tunable electronic and optical properties of the BP/ZrS2 heterojunction

s: The first principles of density functional theory (DFT) were used to calculate the geometrical structure, as well as the optical and electrical properties of BP/ZrS2 heterojunctions in this study. The analysis indicates that the BP/ZrS2 heterostructure demonstrates a Z-scheme electron transfer mechanism as a type II heterostructure, and possesses an indirect band gap of 0.19 eV. Under the effect of applied extra electric field and biaxial strain, the BP/ZrS2 heterojunction could undergo a transition from type II to type I and a semiconductor-metal transition. The heterojunction demonstrates markedly enhanced light absorption compared to the two individual monolayers within a specific range of visible light. These features suggest that BP/ZrS2 heterojunctions have a wide range of applications in areas such as photodetectors.

Metal–semiconductor transition in bilayer graphene by bowl inversion of monofluorosumanene

The bowl-shaped hydrocarbon molecule, monofluorosumanene (C21H11F), can act as a molecular switch to control the carrier density of bilayer graphene by flipping its conformation. Our calculations indicate that monofluorosumanene, in which F atom is located outside the curved C–C network (exo-F molecular conformation), induces electron and hole co-doping of 1.5 × 1013 cm−2 in monofluorosumanene-intercalated bilayer graphene because of a large dipole moment normal to the molecular plane of the monofluorosumanene. The intercalated monofluorosumanene does not affect the electronic structure of bilayer graphene when the F atom is located inside the curved C–C network (endo-F conformation) owing to a small out-of-plane dipole moment. The application of an external electric field across the graphene layers promotes bowl inversion between endo-F and exo-F molecular conformations because of the low activation barrier (approximately 800 meV) between these two conformations and the dipole moment normal to the molecular plane of the exo-F conformation.