First-principles study on structural,electronic and optical properties of perovskite solid solutions KB1−xMgxI3 (B = Ge,Sn) toward water splitting photocatalysis

Perovskite materials have been recently attracting a great amount of attention as new potential photocatalysts for water splitting hydrogen evolution. Here, we propose lead-free potassium iodide perovskite solid solutions KBI₃ with B-site mixing between Ge/Sn and Mg as potential candidates for photocatalysts based on systematic first-principles calculations. Our calculations demonstrate that these solid solutions, with proper Goldschmidt and octahedral factors for the perovskite structure, become stable by configurational entropy at finite temperature and follow Vegard’s law in terms of lattice constant, bond length and elastic constants. We calculate their band gaps with different levels of theory with and without spin–orbit coupling, revealing that the hybrid HSE06 method yields band gaps increasing along the quadratic function of Mg content x. Moreover, we show that the solid solutions with 0.25 ≤ x ≤ 0.5 have appropriate band gaps between 1.5 and 2.2 eV, reasonable effective masses of charge carriers, and suitable photoabsorption coefficients for absorbing sunlight. Among the solid solutions, KB_0.5Mg_0.5I₃ (B = Ge, Sn) is found to have the most promising band edge alignment with respect to the water redox potentials with different pH values, motivating experimentalists to synthesize them.

We propose lead-free potassium iodide perovskite solid solutions KBI₃ with B-site mixing between Ge/Sn and Mg as potential candidates for photocatalysts based on systematic first-principles calculations.     

Computational prediction of structural,electronic, and optical properties and phase stability of double perovskites K2SnX6 (X = I,Br, Cl)

The vacancy-ordered double perovskites K₂SnX₆ (X = I, Br, Cl) attract significant research interest due to their potential applications as light absorbing materials in perovskite solar cells. However, deeper insight into their material properties at the atomic scale is currently lacking. Here we present a systematic investigation of the structural, electronic, and optical properties and phase stabilities of the cubic, tetragonal, and monoclinic phases based on density functional theory calculations. Quantitatively reliable predictions of lattice constants, band gaps, effective masses of charge carriers, and exciton binding energies are provided and compared with the available experimental data, revealing the tendency of the band gap and exciton binding energy to increase on lowering the crystallographic symmetry from cubic to monoclinic and on moving from I to Cl. We highlight that cubic K₂SnBr₆ and monoclinic K₂SnI₆ are suitable for applications as light absorbers for solar cell devices due to their appropriate band gaps of 1.65 and 1.16 eV and low exciton binding energies of 59.4 and 15.3 meV, respectively. The constant-volume Helmholtz free energies are determined through phonon calculations, which predict phase transition temperatures of 449, 433 and 281 K for cubic–tetragonal and 345, 301 and 210 K for tetragonal–monoclinic transitions for X = I, Br and Cl, respectively. Our calculations provide an understanding of the material properties of the vacancy-ordered double perovskites K₂SnX₆, which could help in devising a low-cost and high performance perovskite solar cell.

HSE + SOC were used to calculate the band structures of the cubic, tetragonal, and monoclinic phases of the double perovskites K₂SnX₆ (X = I, Br, Cl).     

RbSnX3 (X = Cl,Br, I): promising lead-free metal halide perovskites for photovoltaics and optoelectronics

Lead (Pb) free metal halide perovskites by atomistic design are of strong interest to photovoltaics and optoelectronics industries because of the pressing need to resolve Pb-related toxicity and instability challenges. In this study, structural, mechanical, electronic, and optical properties of Pb-free RbSnX₃ (X = Cl, Br, I) perovskites have been evaluated by using ab initio density functional theory (DFT) calculations. The computed elastic constants suggest that the Rb-based halide perovskites are mechanically stable and highly ductile, making them suitable as flexible thin films in optoelectronic devices. Besides, the investigated electronic band structures reveal that the RbSnX₃ compounds are direct bandgap semiconductors, suitable for photovoltaic and optoelectronic applications. Furthermore, several optical parameters such as dielectric functions, reflectivity, photon absorptions, refractive index, optical conductivity, and loss functions have been investigated and the results predict the excellent optoelectronic efficiency of RbSnX₃. Also, the computed mechanical and optical properties of RbSnX₃ (X = Cl, Br, I) have been compared with the previously studied CsBX₃ (B = Ge, Sn, Pb; X = Cl, Br, I) phases, revealing that the Rb-based perovskites are extremely ductile and possess excellent light absorption and optical conductivity compared to the Cs-based perovskites. Importantly, RbSnI₃ shows superior ductility, absorption coefficient, and optical conductivity compared to the CsBX₃ (B = Ge, Sn, Pb; X = Cl, Br, I) perovskites. Superior absorption at the ultraviolet region of RbSnI₃ holds great promise of this perovskite to be used in next-generation ultraviolet photodetectors.

This work summarizes that RbSnX₃ (X = Cl, Br, I) exhibits remarkable ductility and absorption in the ultraviolet (UV) region of the electromagnetic spectrum compared to those of CsBX₃ (B = Ge, Sn, Pb; X = Cl, Br, I) metal halide perovskites.     

Structural,elastic and optoelectronic properties of inorganic cubic FrBX3 (B = Ge,Sn; X = Cl,Br, I) perovskite: the density functional theory approach

Inorganic metal-halide cubic perovskite semiconductors have become more popular in industrial applications of photovoltaic and optoelectronic devices. Among various perovskites, lead-free materials are currently most explored due to their non-toxic effect on the environment. In this study, the structural, electronic, optical, and mechanical properties of lead-free cubic perovskite materials FrBX₃ (B = Ge, Sn; X = Cl, Br, I) are investigated through first-principles density-functional theory (DFT) calculations. These materials are found to exhibit semiconducting behavior with direct bandgap energy and mechanical phase stability. The observed variation in the bandgap is explained based on the substitutions of cations and anions sitting over B and X-sites of the FrBX₃ compounds. The high absorption coefficient, low reflectivity, and high optical conductivity make these materials suitable for photovoltaic and other optoelectronic device applications. It is observed that the material containing Ge (germanium) in the B-site has higher optical absorption and conductivity than Sn containing materials. A systematic analysis of the electronic, optical, and mechanical properties suggests that among all the perovskite materials, FrGeI₃ would be a potential candidate for optoelectronic applications. The radioactive element Fr-containing perovskite FrGeI₃ may have applications in nuclear medicine and diagnosis such as X-ray imaging technology.

Inorganic metal-halide cubic perovskite semiconductors have become more popular in industrial applications of photovoltaic and optoelectronic devices.     

Role of metal and anions in organo-metal halide perovskites CH3NH3MX3 (M: Cu,Zn, Ga,Ge, Sn,Pb; X: Cl,Br, I) on structural and optoelectronic properties for photovoltaic applications

Methylammonium metal halide perovskites have recently been explored for new uses due to their unique and exciting optoelectronic properties. Their exceptional electronic properties have often been attributed to the overlap between the metal cation s and halogen p states. In this study, density functional theory calculations have been carried out based on the orthorhombic phase of the organometal trihalide perovskite CH₃NH₃MX₃ (M: Cu, Zn, Ga, Ge, Sn, Pb; X: Cl, Br, I) to systematically investigate the effects of the metal cation and halogen anion on the structural, electronic, and optical properties for solar cell applications. The calculated lattice parameters agree well with previously obtained experimental and theoretical results. All of these perovskites are direct band gap compounds at the G symmetry point, except CH₃NH₃GaX₃. The band gap increases from iodide to chloride and also with the metal cation size, from Ge to Pb or Cu to Zn. Furthermore, metal halide perovskites show blue shifts in their optical absorption spectra with an increase in metal cation size. Among the studied examples, CH₃NH₃GaBr₃ and CH₃NH₃CuCl₃ absorb a wide range of light, from UV to the visible region, and possess very unusual high dielectric constants and refractive indices. Our calculations reveal that CH₃NH₃SnI₃, CH₃NH₃GeI₃, and CH₃NH₃ZnI₃ are favorable candidates for lead-free photovoltaic applications.

Varying the metal and halide in a perovskite can significantly change the resulting properties.     

Direct hybridization gap from intersite and onsite electronic interactions in CeAg2Ge2

Electronic and crystal structure studies are presented to describe the role of intersite and onsite interactions for antiferromagnetic ordering in CeAg₂Ge₂. The crystal structure showed a prominent magnetovolume effect with anomalous negative thermal expansion at low temperature as a consequence of itinerant electron magnetism. The direct hybridization gap with a V-shaped band observed in the angle resolved photoemission data at room temperature, indicates that spin polarized quasiparticle states exist in the gapped region. Valence band broadening and enhanced localization effects at low temperature indicate strong hybridization of the valence orbitals of Ce atoms with the near neighbor Ge atoms. We find that the intersite interaction between the Ce atoms at high temperature stabilizes the onsite interaction at low temperature that leads to the spin density wave type antiferromagnetism in CeAg₂Ge₂.

Electronic and crystal structure studies are presented to describe the role of intersite and onsite interactions for the itinerant electron magnetism in CeAg₂Ge₂.Magnetovolume effect and hybridization gap opening have been observed at low temperature.     

Half-metallicity in new Heusler alloys Mn2ScZ (Z = Si,Ge, Sn)

Study of half-metallicity has been performed in a new series of Mn₂ScZ (Z = Si, Ge and Sn) full Heusler alloys using density functional theory with the calculation and implementation of a Hubbard correction term (U). Volume optimization in magnetic and non-magnetic phases for both the Cu₂MnAl and Hg₂CuTi type structures was done to predict the stable ground state configuration. The stability was determined by calculating their formation energy as well as from elastic constants under ambient conditions. A half-metal is predicted for Mn₂ScSi and Mn₂ScGe with a narrow band gap in the minority spin whereas Mn₂ScSn shows a metallic nature. The magnetic moments of Mn and Sc are coupled in opposite directions with different strengths indicating that the ferrimagnetic order and the total magnetic moment per formula unit for half-metals follows the Slater Pauling rule. And a strong effect was shown by the size of the Z element in the electronic and magnetic properties.

Study of half-metallicity has been performed in a new series of Mn₂ScZ (Z = Si, Ge and Sn) full Heusler alloys using density functional theory with the calculation and implementation of a Hubbard correction term (U).     

Modulation of the electronic property of hydrogenated 2D tetragonal Ge by applying external strain

Inspired by the novel properties of a newly predicted two-dimensional (2D) tetragonal allotrope of Ge called 2D tetragonal Ge, first-principles calculations have been performed to explore the stability, and structural and electronic properties of 2D tetragonal Ge via hydrogenation, and the effect of external strain on structural and electronic properties of hydrogenated 2D tetragonal Ge is considered. Our calculations reveal that the hydrogenated 2D tetragonal Ge, α-GeH and β-GeH, are proved to be dynamically and thermally stable. Both α-GeH and β-GeH are semiconductors with a direct band gap of 0.953 eV and indirect band gap of 2.616 eV, respectively. When applying external strain from −7% to 7%, α-GeH is more energetically stable than β-GeH around the equilibrium geometry, β-GeH is more stable than α-GeH when external strains exceed a certain critical value, respectively. The direct band gap of α-GeH reduces rapidly from 2.008 eV to 0.036 eV as external strain increases from −7% to 7%, while the indirect band gap of β-GeH is changed slightly. Our results reveal that α-GeH and β-GeH can offer an intriguing platform for nanoscale device applications and spintronics.

α- and β-GeH are semiconductors with direct band gap of 0.953 eV and indirect gap of 2.616 eV, respectively. Direct band gap of α-GeH reduces from 2.008 to 0.036 eV as strain increase from −7 to 7%, indirect band gap of β-GeH is changed slightly.     

A first-principles study of electronic structure and photocatalytic performance of GaN–MX2 (M = Mo,W; X= S,Se) van der Waals heterostructures

Modeling novel van der Waals (vdW) heterostructures is an emerging field to achieve materials with exciting properties for various devices. In this paper, we report a theoretical investigation of GaN–MX₂ (M = Mo, W; X= S, Se) van der Waals heterostructures by hybrid density functional theory calculations. Our results predicted that GaN–MoS₂, GaN–MoSe₂, GaN–WS₂ and GaN–WSe₂ van der Waals heterostructures are energetically stable. Furthermore, we find that GaN–MoS₂, GaN–MoSe₂ and GaN–WSe₂ are direct semiconductors, whereas GaN–WS₂ is an indirect band gap semiconductor. Type-II band alignment is observed through PBE, PBE + SOC and HSE calculations in all heterostructures, except GaN–WSe₂ having type-I. The photocatalytic behavior of these systems, based on Bader charge analysis, work function and valence and conduction band edge potentials, shows that these heterostructures are energetically favorable for water splitting.

Modeling novel van der Waals (vdW) heterostructures is an emerging field to achieve materials with exciting properties for various devices.     

Two-dimensional topological insulators of Pb/Sb honeycombs on a Ge(111) semiconductor surface

Based on first-principles hybrid functional calculations, we demonstrate the formation of two-dimensional (2D) topological insulators (TIs) of Pb/Sb honeycombs on Ge(111) semiconductor surface. We show that 1/3 Cl-covered Ge(111) surface offers an ideal template for metal deposition. When Pb and Sb atoms are deposited on Cl–Ge(111) surface, they spontaneously form a hexagonal lattice (Pb/Sb@Cl–Ge(111)). The Pb/Sb@Cl–Ge(111) exhibits a 2D TI state with large bulk gap of 0.27 eV for Pb@Cl–Ge(111) and 0.81 eV for Sb@Cl–Ge(111). The mechanism of 2D TI state is the substrate orbital-filtering effect that effectively removes the p_z bands of Pb(Sb) away from the Fermi level, leaving behind only the p_x and p_y orbitals at the Fermi level. Our findings pave another way for future design of 2D topological insulators on conventional semiconductor surface, which promotes the application of 2D TIs in spintronics and quantum computing devices at room-temperature.

Based on first-principles hybrid functional calculations, we demonstrate the formation of two-dimensional (2D) topological insulators (TIs) of Pb/Sb honeycombs on Ge(111) semiconductor surface.     

Electronic and optical properties of orthorhombic (CH3NH3)BX3 (B = Sn,Pb; X = F,Cl, Br,I) perovskites: a first-principles investigation

Lead halide perovskites have generated considerable interest in solar cell, sensor, and electronics applications. While great focus has been placed on (CH₃NH₃)PbI₃, an organic–inorganic hybrid perovskite, comparatively little work has been done to understand some of its existing crystal phases and analogous materials after substituting with Sn and/or other halogens in the framework. Here, first-principles density functional theory calculations are performed to comprehensively evaluate the electronic and optical properties of (CH₃NH₃)BX₃ (B = Sn, Pb; X = F, Cl, Br, I) in a low-temperature orthorhombic phase. Bulk modulus, electronic structures, and several optical properties of these perovskite systems are further calculated. The obtained results are first confirmed by comparing with existing perovskite systems in literature. The shifting trends on those physical properties when extending to other barely studied systems of (CH₃NH₃)BX₃ is further revealed. The band gap of these perovskites is found to decrease when varying halogen anion in “X” sites from F to I, and/or substituting Pb cations with Sn in “B” sites. Notably, the less toxic Sn-containing perovskites, (CH₃NH₃)SnI₃ in particular, display higher absorption coefficients in the visible light range than their Pb-containing counterparts. An orthorhombic (CH₃NH₃)PbF₃ is predicted to exist at low temperature, and adsorb strongly UV energy. Our systematical examination efforts on the two groups of perovskites provide valuable physical insights in these materials, and the accompanied new findings warrant further investigation on such subjects.

The electronic and optical properties of orthorhombic (CH₃NH₃)BX₃ (B = Sn, Pb; X = F, Cl, Br, I) were investigated by first-principles density functional theory.     

The mechanical,electronic, optical and thermoelectric properties of two-dimensional honeycomb-like of XSb (X = Si,Ge, Sn) monolayers: a first-principles calculations

Herein, by using first-principles calculations, we demonstrate a two-dimensional (2D) of XSb (X = Si, Ge, and Sn) monolayers that have a honey-like crystal structure. The structural, mechanical, electronic, thermoelectric efficiency, and optical properties of XSb monolayers are studied. Ab initio molecular dynamic simulations and phonon dispersion calculations suggests their good thermal and dynamical stabilities. The mechanical properties of XSb monolayers shows that the monolayers are considerably softer than graphene, and their in-plane stiffness decreases from SiSb to SnSb. Our results shows that the single layers of SiSb, GeSb and SnSb are semiconductor with band gap of 1.48, 0.77 and 0.73 eV, respectively. The optical analysis illustrate that the first absorption peaks of the SiSb, GeSb and SnSb monolayers along the in-plane polarization are located in visible range of light which may serve as a promising candidate to design advanced optoelectronic devices. Thermoelectric properties of the XSb monolayers, including Seebeck coefficient, electrical conductivity, electronic thermal conductivity, power factor and figure of merit are calculated as a function of doping level at temperatures of 300 K and 800 K. Between the studied two-dimensional materials (2DM), SiSb single layer may be the most promising candidate for application in the thermoelectric generators.

Herein, by using first-principles calculations, we demonstrate a two-dimensional (2D) of XSb (X = Si, Ge, and Sn) monolayers that have a honey-like crystal structure.     

Electronic,mechanical and piezoelectric properties of glass-like complex Na2Si1−xGexO3 (x = 0.0, 0.25, 0.50, 0.75, 1.0)

Motivated by our previous work on pristine Na₂SiO₃, we proceeded with calculations on the structural, electronic, mechanical and piezoelectric properties of complex glass-like Na₂Si_1−xGe_xO₃ (x = 0.0, 0.25, 0.50, 0.75, 1.0) by using density functional theory (DFT). Interestingly, the optimized bond lengths and bond angles of Na₂SiO₃ and Na₂GeO₃ resemble each other with high similarity. On doping we report the negative formation energy and feasibility of transition of Na₂SiO₃ → Na₂GeO₃ while the structural symmetry is preserved. Analyzing the electronic profile, we have observed a reduced band gap on increasing x = Ge concentration at Si-sites. All the systems are indirect band gap (Z–Γ) semiconductors. The studied systems have shown mechanical stabilities by satisfying the Born criteria for mechanical stability. The calculated results have shown highly anisotropic behaviour and high melting temperature, which are a signature of glass materials. The piezoelectric tensor (both direct and converse) is computed. The results thus obtained predict that the systems under investigation are potential piezoelectric materials for energy harvesting.

Motivated by our previous work on pristine Na₂SiO₃, we proceeded with calculations on the structural, electronic, mechanical and piezoelectric properties of complex glass-like Na₂Si_1−xGe_xO₃ (x = 0.0, 0.25, 0.50, 0.75, 1.0) by using density functional theory (DFT).     

Tunable spin-polarized band gap in Si2/NiI2 vdW heterostructure

Using density functional theory (DFT) calculations we investigate the structural and electronic properties of a heterogeneous van der Waals (vdW) structure consisting of silicene and NiI₂ single layers. We observe an interaction between the two layers with a net charge transfer from the ferromagnetic semiconductor NiI₂ to silicene, breaking the inversion symmetry of the silicene structure. However, the charges flow in opposite directions for the two spin channels, which leads to a vdW heterostructure with a spin-polarized band gap between the π and π* states. The band gap can be tuned by controlling the vertical distance between the layers. The features shown by this vdW heterostructure are new, and we believe that silicene on a NiI₂ layer can be used to construct heterostructures which have appropriate properties to be used in nanodevices where control of the spin-dependent carrier mobility is necessary and can be incorporated into silicon based electronics.

Using density functional theory (DFT) calculations we investigate the structural and electronic properties of a heterogeneous van der Waals (vdW) structure consisting of silicene and NiI₂ single layers.     

Structural exploration of AuxM− (M = Si,Ge, Sn; x = 9–12) clusters with a revised genetic algorithm

We used a revised genetic algorithm (GA) to explore the potential energy surface (PES) of Au_xM⁻ (x = 9–12; M = Si, Ge, Sn) clusters. The most interesting finding in the structural study of Au_xSi⁻ (x = 9–12) is the 3D (Au₉Si⁻ and Au₁₀Si⁻) → quasi-planar 2D (Au₁₁Si⁻ and Au₁₂Si⁻) structural evolution of the Si-doped clusters, which reflects the competition of Au–Au interactions (forming a 2D structure) and Au–Si interactions (forming a 3D structure). The Au_xM⁻ (x = 9–12; M = Ge, Sn) clusters have quasi-planar structures, which suggests a lower tendency of sp³ hybridization and a similarity of electronic structure for the Ge or Sn atom. Au₉Si⁻ and Au₁₀Si⁻ have a 3D structure, which can be viewed as being built from Au₈Si⁻ and Au₉Si⁻ with an extra Au atom bonded to a terminal gold atom, respectively. In contrast, the quasi-planar structures of Au_xM⁻ (x = 9–12; M = Ge, Sn) reflect the domination of the Au–Au interactions. Including the spin–orbit (SO) effects is very important to calculate the simulated spectrum (structural fingerprint information) in order to obtain quantitative agreement between theoretical and future experimental PES spectra.

We used a revised genetic algorithm (GA) to explore the potential energy surface (PES) of Au_xM⁻ (x = 9–12; M = Si, Ge, Sn) clusters.     

HfS2/MoTe2 vdW heterostructure: bandstructure and strain engineering based on first-principles calculation

In this study, a multilayered van der Waals (vdW) heterostructure, HfS₂/MoTe₂, was modeled and simulated using density functional theory (DFT). It was found that the multilayers (up to 7 layers) are typical indirect bandgap semiconductors with an indirect band gap varying from 0.35 eV to 0.51 eV. The maximum energy value of the valence band (VBM) and the minimum energy value of the conduction band (CBM) of the heterostructure were found to be dominated by the MoTe₂ layer and the HfS₂ layer, respectively, characterized as type-II band alignment, leading to potential photovoltaic applications. Optical spectra analysis also revealed that the materials have strong absorption coefficients in the visible and ultraviolet regions, which can be used in the detection of visible and ultraviolet light. Under an external strain perpendicular to the layer plane, the heterostructure exhibits a general transition from semiconductor to metal at a critical interlayer-distance of 2.54 Å. The carrier effective mass and optical properties of the heterostructures can also be modulated under external strain, indicating a good piezoelectric effect in the heterostructure.

In this study, a multilayered van der Waals (vdW) heterostructure, HfS₂/MoTe₂, was modeled and simulated using density functional theory (DFT).     

Theoretical and experimental study on the electronic and optical properties of K0.5Rb0.5Pb2Br5: a promising laser host material

The data on the electronic structure and optical properties of bromide K_0.5Rb_0.5Pb₂Br₅ achieved by first-principle calculations and verified by X-ray spectroscopy measurements are reported. The kinetic energy, the Coulomb potential induced by the exchange hole, spin-orbital effects, and Coulomb repulsion were taken into account by applying the Tran and Blaha modified Becke–Johnson function (TB-mBJ), Hubbard U parameter, and spin-orbital coupling effect (SOC) in the TB-mBJ + U + SOC technique. The band gap was for the first time defined to be 3.23 eV. The partial density of state (PDOS) curves of K_0.5Rb_0.5Pb₂Br₅ agree well with XES K Ll and Br Kβ₂, and XPS spectra. The valence band (VB) is characterized by the Pb-5d_3/2 and Pb-5d_5/2 sub-states locating in the vicinities of −20 eV and −18 eV, respectively. The VB middle part is mainly formed by K-3p, Rb-4p and Br-4s states, in which the separation of Rb-4p_3/2 and Rb-4p_1/2 was also observed. The strong hybridization of Br-p and Pb-s/p states near −6.5 eV reveals a major covalent part in the Br–Pb bonding. With a large band gap of 3.23 eV, and the remarkably high possibility of inter-band transition in energy ranges of 4–7 eV, and 10–12 eV, the bromide K_0.5Rb_0.5Pb₂Br₅ is expected to be a very promising active host material for core valence luminescence and mid-infrared rare-earth doped laser materials. The anisotropy of optical properties in K_0.5Rb_0.5Pb₂Br₅ is not significant, and it occurs at the extrema in the optical spectra. The absorption coefficient α(ω) is in the order of magnitude of 10⁶ cm⁻¹ for an energy range of 5–25 eV.

The data on the electronic structure and optical properties of bromide K_0.5Rb_0.5Pb₂Br₅ achieved by first-principle calculations and verified by X-ray spectroscopy measurements are reported.     

Intriguing electronic,optical and photocatalytic performance of BSe,M2CO2 monolayers and BSe–M2CO2 (M = Ti,Zr, Hf) van der Waals heterostructures

Using density functional (DFT) theory calculations, we have investigated the electronic band structure, optical and photocatalytic response of BSe, M₂CO₂ (M = Ti, Zr, Hf) monolayers and their corresponding BSe–M₂CO₂ (M = Ti, Zr, Hf) van der Waals (vdW) heterostructures. Optimized lattice constant, bond length, band structure and bandgap values, effective mass of electrons and holes, work function and conduction and valence band edge potentials of BSe and M₂CO₂ (M = Ti, Zr, Hf) monolayers are in agreement with previously available data. Binding energies, interlayer distance and Ab initio molecular dynamic simulations (AIMD) calculations show that BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures are stable with specific stacking and demonstrate that these heterostructures might be synthesized in the laboratory. The electronic band structure shows that all the studied vdW heterostructures have indirect bandgap nature – with the CBM and VBM at the Γ–K and Γ-point of BZ for BSe–Ti₂CO₂, respectively; while for BSe–Zr₂CO₂ and BSe–Hf₂CO₂ vdW heterostructures the CBM and VBM lie at the K-point and Γ-point of BZ, respectively. Type-II band alignment in BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures prevent the recombination of electron–hole pairs, and hence are crucial for light harvesting and detection. Absorption spectra are investigated to understand the optical behavior of BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures, where the lowest energy transitions are dominated by excitons. Furthermore, BSe–M₂CO₂ (M = Ti, Zr, Hf) vdW heterostructures are found to be potential photocatalysts for water splitting at pH = 0, and exhibit enhanced optical properties in the visible light zones.

Using density functional theory calculations, we have investigated the electronic band structure, optical and photocatalytic response of BSe, M₂CO₂ (M = Ti, Zr, Hf) monolayers and their corresponding BSe–M₂CO₂ (M = Ti, Zr, Hf) van der Waals heterostructures.     

Electronic,magnetic, optical and thermoelectric properties of Ca2Cr1−xNixOsO6 double perovskites

With the help of density functional theory calculations, we explored the recently synthesized double perovskite material Ca₂CrOsO₆ and found it to be a ferrimagnetic insulator with a band gap of ∼0.6 eV. Its effective magnetic moment is found to be ∼0.23 μ_B per unit cell. The proposed behavior arises from the cooperative effect of spin–orbit coupling and Coulomb correlation of Cr-3d and Os-5d electrons along with the crystal field. Within the ferrimagnetic configuration, doping with 50% Ni in the Cr-sites resulted in a half-metallic state with a total moment of nearly zero, a characteristic of spintronic materials. Meanwhile, the optical study reveals that both ε₁^xx and ε₁^zz decrease first and then increase rapidly with increasing photon energy up to 1.055 eV. We also found optical anisotropy up to ∼14 eV, where the material becomes almost optically isotropic. This material has a plateau like region in the σ_xx and σ_zz parts of the optical conductivity due to a strong 3d–5d interband transition between Cr and Os. In addition, we performed thermoelectric calculations whose results predict that the material might not be good as a thermoelectric device due to its small power factor.

With the help of density functional theory calculations, we explored the recently synthesized double perovskite material Ca₂CrOsO₆ and found it to be a ferrimagnetic insulator with a band gap of ∼0.6 eV.     

Ge nanowires on top of a Ge substrate for applications in anodes of Li and Na ion batteries: a first-principles study

In this study, density functional theory (DFT) was used to research the adsorption and diffusion features of Li and Na on Ge nanowires on top of a Ge substrate. The adsorption energies at different positions are 0.71–1.28 eV for Na and −2.96–−2.13 eV for Li. The adsorption energies can be further reduced by surface modification with one or two P atoms. In particular, the sidewall of the Ge nanowire modified by two P atoms is most favorable to adsorb Li/Na. In addition, we used the nudged elastic band (NEB) method to study the diffusion pathways of Li/Na on the sidewall of Ge NW and the Ge substrate and computed their energy barriers. When Li or Na diffuses across the Ge NW, the energy barrier is 0.65 or 0.79 eV, indicating that the Ge NW can be applied to anodes in lithium and sodium ion batteries. Finally, the insertion of more lithium and sodium atoms into the Ge NW would cause volume expansion and the average length of Ge–Ge bonds to increase. This work will contribute to studying the adsorption and diffusion of Li and Na on nanowires with a substrate and the volume expansion caused by the insertion of Li/Na into the nanowires. Additionally, it provides guidance for designing Ge anodes for sodium ion batteries.

(a) The energy curves along the D–E pathway for the Li/Na diffusion; the side-view of the trajectories of (b) Li and (c) Na diffusion across the Ge NW.