Alternating current properties of bulk- and nanosheet-graphitic carbon nitride compacts at elevated temperatures.

The investigations of temperature-dependent electrical properties in graphitic carbon nitride (g-C3N4) have been largely performed at/below room temperature on devices commonly fabricated by vacuum techniques, leaving the gap to further explore its behaviors at high-temperature. We reported herein the temperature dependence (400 → 35 °C) of alternating current (AC) electrical properties in bulk- and nanosheet-g-C3N4 compacts simply prepared by pelletizing the powder. The bulk sample was synthesized via the direct heating of urea, and the subsequent HNO3-assisted thermal exfoliation yielded the nanosheet counterpart. Their thermal stability was confirmed by variable-temperature X-ray diffraction, demonstrating reversible interlayer expansion/contraction upon heating/cooling with the thermal expansion coefficient of 2.2 × 10-5-3.1 × 10-5 K-1. It is found that bulk- and nanosheet-g-C3N4 were highly insulating (resistivity ρ ∼ 108 Ω cm unchanged with temperature), resembling layered van der Waals materials such as graphite fluoride but unlike electronically insulating oxides. Likewise, the dielectric permittivity ε', loss tangent tan δ, refractive index n, dielectric heating coefficient J, and attenuation coefficient α, were weakly temperature- and frequency-dependent (103-105 Hz). The experimentally determined ε' of bulk-g-C3N4 was reasonably close to the in-plane static dielectric permittivity (8 vs. 5.1) deduced from first-principles calculation, consistent with the anisotropic structure. The nanosheet-g-C3N4 exhibited a higher ε' ∼ 15 while keeping similar tan δ (∼0.09) compared to the bulk counterpart, demonstrating its potential as a highly insulating, stable dielectrics at elevated temperatures.

The role of native point defects and donor impurities in the electrical properties of ZnSb2O4: a hybrid density-functional study.

The ceramic material zinc antimony oxide ZnSb2O4 has promising electrical and magnetic properties, making it suitable for various applications such as electrochemical and energy storage. However, the effects of point defects and impurities on its electrical properties have never been revealed. Here, we employ hybrid density-functional calculations to investigate the energetics and electronic properties of native point defects and donor impurities in ZnSb2O4. The energetically favorable configurations of native point defects under selected growth conditions (O-rich and O-poor) are identified based on the calculated formation energies. The study finds no shallow donor and shallow acceptor defects with low formation energies. Still, the oxygen vacancy (VO) has the lowest formation energy among the donor-type defects under O-rich and O-poor conditions. However, it acts as a very deep acceptor, making it unlikely to provide free electron carriers to the conduction band. Moreover, electron carriers are likely to be compensated by the formation of zinc vacancies (VZn) and the zinc substituted for antimony (ZnSb), which behave as dominant acceptors. Our analysis of the charge neutrality conditions estimates that the Fermi level of undoped ZnSb2O4 would be pinned in a range that is 2.60 eV to 3.12 eV above the VBM for O-rich to O-poor growth conditions, respectively, suggesting that this material is semi-insulating. The possibility of enhancing free electron carriers by doping with Al, Ga, In, and F impurities is also investigated. Our results, however, indicate that high n-type conductivity is hindered by self-compensation in which the impurities additionally act as electron killers. Our results suggest that other impurity candidates and approaches may need to be considered to efficiently dope this material into n-type. Overall, this work paves the way for point defect engineering in this class of ternary oxides.

Ternary pentagonal BXN (X = C, Si, Ge, and Sn) sheets with high piezoelectricity.

The discovery of new and stable two-dimensional pentagonal materials with piezoelectric properties is essential for technological advancement. Inspired by recently reported piezoelectric materials penta-BCN and penta-BSiN, we proposed penta-BGeN and penta-BSnN as new members of the penta-family based on first-principles calculations. Comprehensive analyses indicated that both penta-BGeN and penta-BSnN are thermodynamically, dynamically, mechanically, and thermally stable. In terms of mechanical stability, the elastic constant decreased as lower elements in group 4A of the periodic table were used. Therefore, penta-BGeN and penta-BSnN are softer than penta-BCN and penta-BSiN. In terms of piezoelectric properties, piezoelectric stress and strain tensors increase following the same pattern. In group 4A, penta-BSnN had the highest intrinsic piezoelectricity, especially the e 22 piezoelectric stress. Typically, the piezoelectric strain d ij coefficient increases with material softness; penta-BSnN possessed the highest d ij . Thus, due to its inherent piezoelectricity, penta-BSnN has tremendous potential as a nanoscale piezoelectric material.

Theoretically proposed stable polymorph of two-dimensional pentagonal ß-PdPSe.

The theoretical discovery of new and stable 2D penta materials based on first-principles calculations has stimulated technological advances due to the anticipated exotic properties of such structures, which include the α and ß phases of penta-NiPS. Inspired by the similarity between the theoretically proposed penta-NiPS and the experimentally synthesized (α phase) of penta-PdPSe, we propose herein the ß phase of penta-PdPSe as a new penta-2D material. Comprehensive analyses indicated that ß phase penta-PdPSe is thermodynamically, dynamically, mechanically, and thermally stable, similar to its NiPS analogue. It was found that ß penta-PdPSe is a wide band gap semiconductor with an indirect band gap of 1.58 eV, significantly lower than 2.15 eV for the α phase. Moreover, the two polymorphs of penta-PdPSe are soft materials with 2D Young's modului of Ea = 151 N m-1 and Eb = 123 N m-1 for the ß phase, compared with Ea = 155 N m-1 and Eb = 113 N m-1 for the α phase. The calculated absorption coefficient showed that ß phase penta-PdPSe is acceptable for electronic and optical nanodevices.

Effects of oxygen pressure on the morphology and surface energetics of ß-PbO2: insight from DFT calculations.

For over a century, lead dioxide (PbO2) has been investigated in lead-acid batteries and extensively utilized in a variety of applications. Identifying the surface properties and equilibrium morphology of ß-PbO2 (rutile phase) particles is mandatory for industrial utilization and surface engineering. Using density-functional calculations within the generalized gradient approximation revised for solids (PBEsol), we investigate a variety of surface properties of ß-PbO2. The surface energies of low-Miller-index stoichiometric surfaces are firstly determined, and the (110) surface is found to be the most thermodynamically stable. The relative energetics of these surfaces are represented by a Wulff construction which shows an acicular shape, mostly dominated by the (110) and (100) surfaces. Besides, we investigate the surface chemistry of ß-PbO2 under reduction and oxidation conditions as a function of oxygen pressure, finding that most surfaces except for (100) and (110) are likely to be oxidized. Under oxygen pressure at 1 atm and oxygen-rich limit, the (101) surface is the most thermodynamically stable, dominating the Wulff construction with pyramidal shapes. Our results indicate that the growth conditions that cause non-stoichiometry of the surface could modify the equilibrium Wulff shape of ß-PbO2. Our predicted Wulff shapes and dominant facets agree with the experimental results in which the pyramidal shape of the ß-PbO2 grains has often been observed with the (101) preferred orientation.

Towards a new packing pattern of Li adsorption in two-dimensional pentagonal BCN.

Two-dimensional (2D) materials with a penta-atomic-configuration, such as penta-graphene and penta-B2C, have received great attention as anodes in Li-ion batteries (LIBs). Recently, penta-BCN has been demonstrated to exhibit the highest theoretical capacity to date of 2183 mA h g-1, corresponding to the composition Li3BCN. Herein, we study the layer-by-layer Li adsorption on penta-BCN by explicitly and comprehensively considering its structure. We discover a new, more energetically favorable Li adsorption site that is distinct from the latest report by Chen et al. (Phys. Chem. Chem. Phys., 2021, 23, 17693). The possible migration pathway and the accompanying activation energy are also investigated. Full lithium adsorption leads to the formula Li2BCN and the reduced theoretical capacity of 1455 mA h g-1. Still, penta-BCN exhibits metallic conductivity during Li adsorption, and has a low open-circuit voltage, and a low ion-diffusion barrier, all being beneficial for anode materials. These observations imply that penta-BCN remains one of the most effective anode materials for LIBs with a quick charge/discharge rate.

Author Correction: Stacking stability of C2N bilayer nanosheet.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Energetics and optical properties of carbon impurities in rutile TiO2.

Titanium dioxide is one of the most promising materials for many applications such as photovoltaics and photocatalysis. Non-metal doping of TiO2 is widely used to improve the photoconversion efficiency by shifting the absorption edge from the UV to visible-light region. Here, we employ hybrid density-functional calculations to investigate the energetics and optical properties of carbon (C) impurities in rutile TiO2. The predominant configurations of the C impurities are identified through the calculated formation energies under O-poor and O-rich growth conditions. Under the O-poor condition, we find that C occupying the oxygen site (CO) is energetically favorable for Fermi-level values near the conduction band minimum (n-type TiO2), and acts as a double acceptor. Under the O-rich condition, the Ci-VTi complex is energetically favorable, and is exclusively stable in the neutral charge state. We also find that interstitial hydrogen (Hi) can bind to CO, forming a CO-Hi complex. Our results suggest that CO and CO-Hi are a cause of visible-light absorption under oxygen deficient growth conditions.

Stacking stability of C2N bilayer nanosheet.

In recent years, a 2D graphene-like sheet: monolayer C2N was synthesized via a simple wet-chemical reaction. Here, we studied the stability and electronic properties of bilayer C2N. According to a previous study, a bilayer may exist in one of three highly symmetric stacking configurations, namely as AA, AB and AB'-stacking. For the AA-stacking, the top layer is directly stacked on the bottom layer. Furthermore, AB- and AB'-stacking can be obtained by shifting the top layer of AA-stacking by a/3-b/3 along zigzag direction and by a/2 along armchair direction, respectively, where a and b are translation vectors of the unit cell. By using first-principles calculations, we calculated the stability of AA, AB and AB'-stacking C2N and their electronic band structure. We found that the AB-stacking is the most favorable structure and has the highest band gap, which appeared to agree with previous study. Nevertheless, we furthermore examine the energy landscape and translation sliding barriers between stacking layers. From energy profiles, we interestingly found that the most stable positions are shifted from the high symmetry AB-stacking. In electronic band structure details, band characteristic can be modified according to the shift. The interlayer shear mode close to local minimum point was determined to be roughly 2.02 × 1012 rad/s.

Energetics of native defects in anatase TiO2: a hybrid density functional study.

The energetics and electronic structures of native defects in anatase TiO2 are comprehensively studied using hybrid density functional calculations. We demonstrate that oxygen vacancies (VO) and titanium interstitials (Tii) act as shallow donors, and can form at substantial concentrations, giving rise to free electrons with carrier densities from 1011 to 1019 cm-3 under oxygen-rich and oxygen-poor conditions, respectively. The titanium vacancies (VTi), identified as deep acceptors and induced hole carriers, are incapable of fully compensating for the free electrons originating from the donor-type defects at any oxygen chemical potential. Even under extreme oxygen-rich conditions, the Fermi level, which is determined from the charge neutrality condition among charge defects, electron and hole carriers, is located 2.34 eV above the valence band maximum, indicating that p-type conductivity can never be realized under any growth conditions without external doping. This is consistent with common observations of intrinsic n-type conductivity of TiO2. At a typical annealing temperature and under a typical oxygen partial pressure, the carrier concentration is found to be approximately 5 × 1013 cm-3.

Electronic properties of highly-active Ag3AsO4 photocatalyst and its band gap modulation: an insight from hybrid-density functional calculations.

The electronic structures of highly active Ag-based oxide photocatalysts Ag3AsO4 and Ag3PO4 are studied by hybrid-density functional calculations. It is revealed that Ag3AsO4 and Ag3PO4 are indirect band gap semiconductors. The Hartree-Fock mixing parameters are fitted for experimental band gaps of Ag3AsO4 (1.88 eV) and Ag3PO4 (2.43 eV). The smaller electron effective mass and the lower valence band edge of Ag3AsO4 are likely to be responsible for the superior photocatalytic oxidation reaction to Ag3PO4. The comparable lattice constant and analogous crystal structure between the two materials allow the opportunities of fine-tuning the band gap of Ag3AsxP1-xO4 using a solid-solution approach. The development of Ag3AsxP1-xO4 should be promising for the discovery of novel visible-light sensitized photocatalysts.