Conduction Band Research Articles

The significant role of Z-scheme band alignment at the heterojunction for the enhanced photocatalytic H2 production in TiO2/BiNbO4/rGO nanocomposite

An efficient ternary TiO2/BiNbO4/rGO nanocomposite was prepared by a simple wet impregnation process. PXRD confirmed the tetragonal and orthorhombic crystalline natures of titanium dioxide (TiO2) and bismuth niobate (BiNbO4) respectively. The loading of BiNbO4 and reduced graphene oxide (rGO) shifted the light absorption of TiO2 to a longer wavelength from 400 to 430 nm. The suitable conduction band position of BiNbO4 facilitated a favourable band alignment to suppress the electron/hole (e−/h+) recombination in TiO2 via the Z scheme mechanism at the heterojunction. The excited electrons at the CB of TiO2 were easily transported via the fast electron accepting and conducting rGO matrix for the surface redox reactions with the improved charge transfer efficiency, which was confirmed by EIS and PL studies respectively. BiNbO4 and rGO synergistically improved the specific surface area and solar light absorption. EPR analysis confirmed the presence of increased oxygen vacancies at the heterojunction. Hence, the ternary TiO2/BiNbO4/rGO nanocomposite demonstrated an enhanced hydrogen evolution (8910 μ mol h−1 gcat−1) than bare TiO2 (4820 μ mol h−1 gcat−1), bare BiNbO4 (950 μ mol h−1 gcat−1) and TiO2/BiNbO4 (6730 μ mol h−1 gcat−1) under direct solar light. The optimum of 1 wt % BiNbO4 and rGO loaded TiO2 nanocomposite produced twice the H2 production than the bare TiO2. This also further confirms that rGO played a major role during the photocatalytic process by highlighting the potential of metal oxides combined with carbon material as an efficient photocatalyst which prominently enhances the H2 evolution.

Band alignments, conduction band edges and intralayer bandgap renormalisation in MoSe2/WSe2 heterobilayers

Abstract Stacking two semiconducting transition metal dichalcogenide (MX2) monolayers to form a heterobilayer creates a new variety of semiconductor junction with unique optoelectronic features, such as hosting long-lived dipolar interlayer excitons. Despite many optical, transport, and theoretical studies, there have been few direct electronic structure measurements of these junctions. Here, we apply angle-resolved photoemission spectroscopy with micron-scale spatial resolution (µARPES) to determine the band alignments in MoSe2/WSe2 heterobilayers, using in-situ electrostatic gating to electron-dope and thus probe the conduction band edges. By comparing spectra from heterobilayers with opposite stacking orders, that is, with either MoSe2 or WSe2 on top, we confirm that the band alignment is type II, with the valence band maximum in the WSe2 and the conduction band minimum in the MoSe2. The overall band gap is EG = 1.43 ± 0.03 eV, and to within experimental uncertainty it is unaffected by electron doping. However, the offset between the WSe2 and MoSe2 valence bands clearly decreases with increasing electron doping, implying band renormalisation only in the MoSe2, the layer in which the electrons accumulate. In contrast, µARPES spectra from a WS2/MoSe2 heterobilayer indicate type I band alignment, with both band edges in the MoSe2. These insights into the doping-dependent band alignments and gaps of MX2 heterobilayers will be useful for properly understanding and ultimately utilizing their optoelectronic properties.

WSe2/n-GaN and WSe2/p-GaN heterojunction band alignment

Abstract In this work, we measured the band alignment of 2D/3D heterostructures of WSe2 on n-doped, pdoped, and intrinsic GaN by X-ray photoelectron spectroscopy (XPS). The WSe2/n-GaN heterojunction exhibits type-II band alignment, with measured valence band offset (VBO) and conduction band offset (CBO) values of 2.28±0.15 eV and 0.96±0.15 eV, respectively. On the other hand, the WSe2/p-GaN heterojunction shows type-I band alignment, with measured VBO and CBO values of 0.1±0.15 eV and 1.22±0.15 eV, respectively. The results show that doping has a significant effect on the arrangement of the energy bands of the heterostructure, and provides a reference for device applications based on heterojunctions.

Fe-N Co-Doped BiVO4 Photoanode with Record Photocurrent for Water Oxidation.

Bismuth vanadate ranks among the most promising photoanodes for photoelectrochemical water splitting. Nonetheless, slow charge separation and transportare key barriers to its photoefficiency. Here, we present a co-doping strategy that significantly improves the charge separation performance of BVO. Under standard one sun illumination, the Fe-N co-doped BVO photoanode (Fe-N-BVO) by N-coordinated Fe precursor reaches a record photocurrent density of 7.01 mA cm-2 at 1.23 V vs RHE after modified a surface co-catalyst. By contrast, much lower photocurrent density is obtained for the N-doped and Fe-doped BVO with separated N and Fe precursors. The detailed characterizations show that the high activity of the Fe-N-BVO is attributed to the enhanced photo-induced bulk charge separation and the accelerated surface water oxidation kinetics. XPS, EXAFS and DFT calculations clearly show that, instead of formation of deep trapping state in the individually doped BVO, the co-doping of Fe-N into BVO generates Fe-based electronic states just below the bottom of conduction band and N-derived states just above the top of valence band. Such modulations in electronic structure enable the efficient trap of the electrons and holes to enhance the separation of photo-induced carriers, but hinder the charge recombination originated from the deep trapping sites.

Annealing influence on stoichiometry and band alignment of 4H-SiC/SiO2 interface evaluated by x-ray photoelectron spectroscopy

Abstract Post oxidation annealing (POA) is a crucial technique for enhancing the performance of SiC Metal-Oxide-Semiconductor Field Effect Transistors (MOSFETs). This study investigates the impact of nitrogen-based POA on the 4H-SiC/SiO2 interface, utilizing X-ray photoelectron spectroscopy (XPS) to assess changes in stoichiometry and band alignment. We discovered that high-temperature nitrogen POA significantly refines the interface quality, shifting the SiOxCy binding energy from 101.3 eV (at 400°C) to 102.1 eV (at 1150°C) and reducing the C:Si ratio from 1.120 (at 400°C) to 0.972 (at 1150°C), indicating reoxidation and transition from C-rich interface to Si-rich interface. Despite improvements, the conduction band offset at the interface, decreases from 2.59 eV to 1.62 eV with increasing annealing temperature, suggesting a higher likelihood of electron tunneling. This finding underscores the necessity of evaluating band offsets introduced by POA to ensure the reliability of SiC MOSFETs. Additionally, excessive Ar ion etching introduces residual Ar and surface charges, causing band bending and an increased density of states in the valence band of the 4H-SiC substrate.

Graphdiyne surface-modified CuS-GDY/LaCoO3 S-scheme heterojunctions for enhanced photocatalytic hydrogen evolution

An effective strategy to enhance the photocatalytic hydrogen evolution activity is to rationally guide the photogenerated carrier migration. In this work, a novel carbon-based material CuS/Graphdiyne (CuS-GDY), was synthesized via a Cu-surface mediated method. Subsequently, the peanut-shaped LaCoO3 is distributed uniformly on the surface of the layered CuS-GDY via electrostatic self-assembly, forming stepped heterojunctions that accelerate the transfer of photogenerated carriers. The modified CuS-GDY facilitated further optimization of the electrical conductivity and electron transfer capabilities of GDY. Furthermore, the formation of a Schottky junction between CuS and LaCoO3 facilitates electron egress from the conduction band of LaCoO3, thereby enriching the catalyst with active sites. The combined effect of the S-scheme and Schottky junctions within the composite catalysts facilitates the separation and transfer of photogenerated carriers, as evidenced by in situ XPS, DFT theoretical calculations, and complementary characterization techniques. This study presents novel insights into the modification of GDY and a deeper comprehension of the heterojunction dynamics in catalyst systems.

Sulfur vacancies-engineered CaIn2S4 microspheres for enhanced photocatalytic organic pollutant and antibiotic removal

It is an interesting research topic on construction of defect- rich structures to enhance the performance of photocatalysts. In this study, CaIn2S4 photocatalyst containing sulfur vacancy was successfully synthesized using a straightforward solvothermal method. The sulfur vacancy concentration in CaIn2S4 was controlled by adjusting the amount of thioacetamide added during preparation. Among the prepared samples, CaIn2S4-10 sample with excellent photocatalytic performance exhibits superior degradation efficiency (98.2 %) within 50 minutes when the initial methyl orange (MO) concentration was 20 mg/L. Similarly, it shows the highest degradation performance (94 %) against the antibiotic tetracycline hydrochloride (TCH) (20 mg/L). The phase structure, surface element composition, optical properties and other characteristics of the prepared samples were systematically investigated. The findings demonstrate that the CaIn2S4-10 sample exhibits a decreased band gap width and a negatively shifted conduction band position, which enhances its reduction ability and improves its photocatalytic activity.

Carrier scattering and temperature characteristics of mobility and resistivity of Fe-doped GaN

Abstract The electron mobility and dark resistivity of Fe-doped semi-insulating GaN (GaN:Fe) are calculated over the temperature range from 10 K to 500 K by considering the impurities compensation mechanism and majority carrier scattering. The temperature characteristic curve of the mobility exhibits unimodality and the curve of resistivity decreases monotonically with rising temperature. The carrier scatterings induced by ionized impurities, acoustic deformation potential, piezoelectric, and polar optical phonons are analyzed. It is found that the mobility is determined by ionized impurity scattering, piezoelectric scattering, and polar optical phonon scattering in different temperature ranges, and the contribution of acoustic deformation potential scattering is negligible over the entire temperature range. Furthermore, the effects of concentrations of shallow donors and deep acceptors on the temperature characteristic curves of mobility and resistivity, the peak mobility and its corresponding temperature (peak temperature), and the mobility and resistivity at room temperature are discussed. Our simulation shows the calculation results agree very well with the reported experimental and theoretical results when the Fe-related level is selected as 0.58 eV below the conduction band edge. Understanding of thermal properties of dark resistivity and mobility can be useful for optimizing GaN:Fe-based electronic and photonic devices performance in different temperature regimes.

Ab-initio investigation of structural, electronic, thermoelectric and optical properties of Full-Heusler X2MnB (X = Ti, Zr) for energy harvesting applications

In this manuscript comprehensive first-principles calculations have been presented for Full-Heusler X2MnB (X = Ti, Zr) compounds. This work includes detailed observations of the structural stability, origin of the transport phenomenon, optical properties, and electronic response. Structural parameters support the previous findings by confirming structural stability in the non-magnetic phase. Ti2MnB (Zr2MnB) valence band maxima and conduction band minima have bandgaps of 0.217 (0.301) eV and 0.181 (0.209) eV for PBE-GGA (mBJ) approximations which lie between L-L symmetry points. Due to the comparative measurements of the two states, the DOS results show that the Ti1/Zr1, Ti2/Zr2 Mn eg, and t2g states mainly contribute to the valence band region for Ti2MnB and Zr2MnB alloys, confirming their ionic nature. The computation of the overall electronic parameters’ reveals semiconducting nature. Thermoelectric properties have been calculated as a function of temperature in the 100–1200 K range. The positive values of Seebeck coefficients specify p-type character of X2MnB While at 300 K, Zr2MnB and Ti2MnB showed the highest Seebeck coefficients, measuring roughly values of 268 (µK/V) and 243 (µK/V), respectively. These values suggest that the material exhibits high thermoelectric performance. Though high optical absorption coefficient and low reflectivity in the visible and ultra violet regions, confirms use of these materials in solar cell applications. These findings suggest that material holds great potential for use in thermoelectrical applications which can support in upcoming experimental considerations.

Conduction band electronic states of ultrathin furan-phenylene co-oligomer on the surfaces of oxidized silicon and of layer-by-layer grown zinc oxide

The paper reports on results of an investigation of the electronic states of the conduction band of ultrathin films of furan-phenylene co-oligomer 1,4-bis(5-phenylfuran-2-yl)benzene (FP5) and the results of an investigation of the interfacial potential barrier upon the formation of these films on the surfaces of (SiO2)n-Si and of layer-by-layer deposited ZnO. Upon deposition of an 8–10 nm thick FP5 film, the total current spectroscopy (TCS) technique was used for investigation within the energy range from 5 eV to 20 eV above EF. FP5 films on the (SiO2)n-Si surface showed a domain structure with a characteristic domain size of the order of 1 micro.m × 1 micro.m and a surface roughness within the domain under 1 nm. In contrast, FP5 on the ZnO surface showed a granular structure with a grain height of 40–50 nm.

Accounting for the energy dispersion of free carriers induced by powerful femtosecond laser radiation in dielectrics

Dynamics of free carriers in the conduction band of dielectrics induced by femtosecond near infrared laser radiation is analyzed. It is stressed the importance of accounting for the energy dispersion term in the Fokker-Planck equation describing such dynamics.

Fundamental Understanding of Interface Chemistry and Electrical Contact Properties of Bi and MoS2.

The interface properties and thermal stability of bismuth (Bi) contacts on molybdenum disulfide (MoS2) shed light on their behavior under various deposition conditions and temperatures. The examination involves extensive techniques including X-ray photoelectron spectroscopy, scanning tunneling microscopy (STM), and scanning tunneling spectroscopy (STS). Bi contacts formed a van der Waals interface on MoS2 regardless of deposition conditions, such as ultrahigh vacuum (UHV, 3 × 10-11 mbar) and high vacuum (HV, 4 × 10-6 mbar), while the oxidation on MoS2 has been observed. However, the semimetallic properties of Bi suppress the impact of defect states, including oxidized-MoS2 and vacancies. Notably, the n-type characteristic of Bi/MoS2 remains unaffected, and no significant changes in the local density of states near the conduction band minimum are observed despite the presence of defects detected by STM and STS. As a result, the Fermi level (EF) resides below the conduction band of MoS2. The study also examines the impact of annealing on the contact interface, revealing no interface reaction between Bi and MoS2 up to 300 °C. These findings enhance our understanding of semimetal (Bi) contacts on MoS2, with implications for improving the performance and reliability of electronic devices.

Insights into the structural, dielectric, optical and electrochemical characteristics reveal the limiting parameters toward efficient OER catalysts in the perovskite solid solution Sr1-xLaxTi1-xFexO3 (0.2 ≤ x ≤ 0.8)

Due to their structural stability and flexibility, perovskite oxides have paved their way as oxygen evolution reaction (OER) electrocatalysts. The in-depth understanding of the limiting factors toward good activity and fast charge transfer are still considered as major challenges for highly active OER perovskite catalysts. In this work, we disclose the changes in the perovskite structure and properties that influence the activity as we introduce new criteria to be considered for perovskites electrocatalysts design. The activity test of the series Sr1-xLaxTi1-xFexO3 (0.2 ≤ x ≤ 0.8) reveals the overpotential of 300 mV @ 10 mA.cm−1, and Tafel slop of 57.6 mV dec−1, as the lowest values corresponding to the composition x = 0.4. As function of the composition, the dielectric constant is found to decrease from 3000 (x = 0.2) to 953 (x = 0.4), and increases up to 5497 (x = 0.8). This variation of the dielectric constant is found to influence the activity of the catalysts where lowest overpotential of 300 mV @ 10 mA.cm−1 is found for x = 0.4 with the smallest dielectric constant. The phase transition detected in the perovskite series upon substitution has induced a distortion in the unit cell, which is found to be in alignment with the evolution of the overpotential in the perovskites series. The distortion has induced a preferable octahedra orientation for efficient OER reaction, this orientation correspond to the interatomic distance <Ti/Fe-O2> (1) = 1.89 Å and <Ti/Fe-O2> (2) = 2.04 Å (x=0.4) with the condition of <Ti/Fe-O2> (1) remains shorter than <Ti/Fe-O2> (2). The band gap, thus the conduction and valence bands edges, is found to decrease with the increase of the interatomic distance (Fe/Ti-O) and with the deviation of the Bond angle (B)-O2-(B) from the ideal value of 180°. These findings put light on the limiting factors of the perovskites activity by linking the structural parameters and the physical properties with the objective of accurately designing highly-efficient perovskite OER electrocatalysts.

Understanding oxidation potential and degradation mechanism of acid-treated TiO2 coupled g-C3N4 S-scheme heterojunction photocatalyst for the removal of gaseous formaldehyde

In this work, a step (S)-scheme heterojunction catalyst is synthesized by coupling acid-treated TiO2 (ATT) with graphitic carbon nitride nanosheet (g-C3N4: GCN) and used for adsorption-photocatalytic removal of gaseous formaldehyde (FA: 100 - 500 ppm). The acid treatment of TiO2 proves to be an effective approach for improving the surface porosity of ATT with more abundant active sites for efficient catalytic reactions. Similarly, the S-scheme heterojunction displays superior redox potential (i.e., availability of free e- at conduction band of GCN (reduction potential of −0.485 eV/NHE) and free h+ at valance band of ATT (oxidation potential 2.79 eV/NHE)). As such, in a dynamic packed-bed flow reactor, the improved textural and optical properties of ATT-GCN (bed mass = 10 mg) offer outstanding adsorption and photocatalytic oxidation potential, effectively removing 86% of 200 ppm FA vapor at a reaction rate of 70.2 nmole mg−1 min−1 under slightly humidified conditions (e.g., 20% relative humidity (RH) and 21% O2) when exposed to 32-W UV-A light source. Under these operational conditions, the ATT-GCN achieves the superior performance metrics (e.g., quantum yield of 5.1E-02 molec. photon-1, space–time yield of 5.1E-03 molec. photon-1 mg−1, and specific clean air delivery rate of 515.4 L g-1 h−1). In-situ Kelvin probe microscope analysis of ATT-GCN postulates the formation of a strong built-in electric field to improve the separation of charge carriers. Considerations on the degradation pathway and intermediate dynamics with the aid of in-situ DRIFTS analysis suggest that the presence of water molecules (e.g., 20% RH) is beneficial for accelerating the oxidation and mineralization of FA molecules relative to a dry gas stream. The overall outcomes of this work are expected to help deliver new paths for the construction of advanced photocatalytic systems for upscaled applications toward air quality management.

The electronic structure and optical properties of BaBiBO4, a promising compound with high birefringence

Birefringence is a crucial parameter for various advanced optical devices like birefringent crystals, and nonlinear optical materials. In this paper, the electronic structures and optical properties of centrosymmetric BaBiBO4 are investigated using the first-principles method. The results show that BaBiBO4 could be a good birefringent compound whose birefringence is 0.195 @ 1064 nm and 0.266 @ 532 nm. The spin–orbit-coupling effect plays an important role in electronic structures, leading to downshift and band splitting of the conduction band, resulting in a reduced bandgap of 3.32 eV and enhanced birefringence. The projected density of states and real-space atom-cutting results reveal that BiO5 groups with asymmetric distribution of stereochemical active lone pairs and the staggered parallel arrangement of the BO3 groups give the main contribution to birefringence.

Synthesis and characterization of the doped/co‐doped SnO2 nanoparticles by the sol–gel method

AbstractTin oxide (SnO2) is one of the important semiconductors used in the application of solar cells because of its chemical–mechanical stability and wide band gap. These properties are very important for the performance development and photoanode optimization of a dye‐sensitized solar cell (DSSC). However, the low conduction band value of SnO2 reduces the photovoltaic efficiency, which limits the application of DSSC. Therefore, the doping strategy was used to increase the sensitivity to the visible light spectrum and change the light absorption properties of SnO2. In this paper, pure SnO2, Ag/SnO2, Pt/SnO2, and Pt/Ag/SnO2 nanoparticles were synthesized at the nanoscale by a simple chemical sol–gel method. To characterize the structure, morphological/chemical properties, optical properties, and surface properties of the synthesized SnO2 nanoparticles, X‐Ray Diffraction (XRD), ultraviolet–visible, Brunauer–Emmett–Teller, Scanning Electron Microscopy (SEM)/Energy Dispersive X‐Ray Spectroscopy (EDX), Transmission Electron Microscopy (TEM), and particle size analysis were respectively used. XRD results showed that the crystal sizes varied between 8.8 and 12.2 nm depending on the doping. Doping processes resulted in reductions in particle sizes. Optical studies resulted in decreases in the band gap with the doping process. The conclusions obtained have shown that Ag doping, and Pt–Ag co‐doping can be promising for use as photoanode materials in semiconductor technology and especially in DSSC applications.

Novel CoFe2O4 / LaAlO3 nanocomposites: An impressive photocatalyst with p-n hetero-junction for improved H2 generation under visible exposure

The present work is devoted to the synthesis of perovskite LaAlO3 by Sol-Gel approach and its application for the photo-evolution of H2 in conjunction with cobalt ferrite CoFe2O4 prepared by nitrate route. The thermal analysis (TG/DSC) showed that the formation is completed at 600 °C. The X-ray diffraction (XRD) pattern is characteristic of a single phase, crystallizing in a rhombohedral symmetry with a crystallite size of 36 nm. The SEM micrographs revealed a homogeneous structure with an agglomeration of shaped grains (40–80 nm). The forbidden band (3.39 eV), calculated from diffuse reflectance data, is assigned to the ligand charge transfer O2−: 2p → Al3+: 3s orbital. As prepared, LaAlO3 is an n-type semiconductor as demonstrated from the capacitance - potential (C−2 - E) graph with an electron density of 9.4 × 1014 cm−3 due to oxygen under-stoichiometry. Attention was directed to photo-electrochemistry in connection with water reduction into hydrogen. With a negative conduction band potential (−0.11 VSCE), H2 generation can be synergized over the hetero-system by visible light. The photocatalytic capability of CoFe2O4 25%/LaAlO3 revealed a high H2 generation of 963 μmol g−1 in the alkaline electrolyte (NaOH, 0.1 M) with a catalyst dose of 1 mg mL−1, which is 1.3 times more than CoFe2O4 under similar conditions. Photoactivity is significantly improved by 60%, up to 2400 μmol g−1 in the presence of oxalate C2O42− as a hole scavenger in the hetero-junction, two hydrogen release tests were successfully recorded. The higher H2 production in the hetero-junction system is attributed to the lower recombination rate of electron/hole (e−/h+) in the material, due to the large band bending at the solid interfacial.

Achieving Tunable Band Structure and Photocarrier Dynamics by Regulating 2D Atomic Layer Stacking Toward High‐Performance Self‐Powered Broadband and Deep‐UV Photodetection

Abstract2D materials with unique layer‐dependent electronic structure can bring precise control to their photocarrier dynamics for optimizing and expanding optoelectronic applications, while the challenge of controlling layer stacking makes the layer dependency law still underexplored in emerging 2D ternary metal chalcogenides. Herein, 2D rhombohedral‐phase ZnIn2S4 (R‐ZIS) with controllable layer thickness is achieved by confined‐growth strategy in high yield, exhibiting continuously tunable direct bandgap (2.39–2.77 eV) with evident upshift of conduction band minimum (CBM) and Fermi level (EF), demonstrated arising from the synergistic effect of reduced interlayer interaction with inevitably increasing Zn defects. Remarkably, the carrier dynamics of R‐ZIS in photoelectrochemical (PEC) device is successfully regulated by adjusted CBM and EF, resulting in continuously tunable optical absorption band, photocarrier separation efficiency, self‐powered capability, and dark current noise. Beneficial from tailored band structure and carrier dynamics, self‐powered PEC‐type photodetector with broadband photoresponse (254–765 nm), is achieved fast response speed (12.3/5.3 ms) and high responsivity (90.29 mA W−1) in multilayer R‐ZIS, while deep‐UV photodetector with ultra‐high specific detectivity (1.62 × 1012 Jones) at 254 nm in monolayer R‐ZIS, exhibiting the record performance in both fields. This work motivates the development of tailored band structure for 2D‐materials‐based optoelectronic devices in strategy and mechanism.

The structural, mechanical, electronic, and optical properties of monolayer and bilayer ABC3(A [dbnd] Ga, In; B [dbnd] Si, Ge; C [dbnd] S, Se, Te)

This paper studies the structural, mechanical, optical, and electronic characteristics of monolayer and bilayer ABC3 (AGa, In; BSi, Ge; CS, Se, Te). Their characteristics are obtained using the density functional theory with van der Waals (vdW) correction. The stability is confirmed by examining Born’s criterion, cohesive energy, phonon dispersions, and COHP analysis. In addition, the stability of these monolayers against tensile strain is explored. The electronic properties are extensively studied through band structure, PDOS, and effective masses. The optical properties are investigated for possible applications in optoelectronic devices. In the following, bilayer ABC3 with three different stacking orders is investigated. Most of the monolayers and bilayers ABC3 show an indirect bandgap. The contributions of each element at the valence and conduction bands are explored through the projected density of the state. The effective mass is derived for the valence and conduction band valleys, whereas the Γ-valley shows the lowest effective mass. Additionally, both real and imaginary parts of the dielectric constant, electron energy loss spectra, and optical absorption are studied, which might lead to intriguing usages in photovoltaic and electroluminescent systems. The analysis of the optical properties reveals that the studied monolayers and bilayers have acceptable visible-range absorption characteristics. Furthermore, the monolayer and bilayer ABC3 dielectric function and absorption coefficient spectra display prominent optical peaks in the UV light range. Due to their distinct band gaps and optical characteristics, monolayer and bilayer ABC3 materials are good prospects for upcoming electrical and optoelectronic applications.

Full-shell d-orbitals of interstitial Ni and anomalous electrical transport in Ni-based half-Heusler thermoelectric semiconductors

We systematically investigate the anomalous electronic properties and electrical transport induced by full-shell d10-orbitals of the extra interstitial Nii in Ni-based half-Heusler XNi1+xZ semiconductors. The orbitals from the interstitial Nii have the unique d10 configuration, split into high-energy eg4 orbitals and low-energy t2g6 orbitals under the octahedral crystal field. In XIVNi1+xZIV (XIV=Ti, Zr, Hf; ZIV=Sn, Pb), the localized Nii-eg4 states fall within the intrinsic bandgap leading to a reduced bandgap. In XIIINi1+xZV (XIII=Sc, Y; ZV=Sb, Bi), the Nii-eg4 states overlap with the intrinsic valence bands. Additionally, the interstitial Nii perturb the nearest neighbor X atomic coordination, leading to the splitting of degenerate conduction band minimum, which is stronger in XIIINi1+xZV than XIVNi1+xZIV. Trace amounts of interstitial Nii significantly impact the electrical transport properties. The introduction of the extra interstitial Nii reduces the density of states effective mass, the electron group velocity, and the relaxation time, leading to a decrease of the Seebeck coefficient and electrical conductivity at low and medium temperatures. Nevertheless, the introduction of localized Nii-eg4 states within the bandgap as new valence band maximum attenuate the high-temperature bipolar effect at low carrier concentration intervals, thus maintaining a high thermopower at elevated temperatures. Furthermore, the tuning of the Nii-d10 orbitals by solid solution of both XIVNi1+xZIV and XIIINi1+xZV is expected to further optimize the electrical transport.