The rectified bulk photovoltaic effect (BPVE) in noncentrosymmetric semiconductors, also called shift current, is considered promising for optoelectronic devices, terahertz emission and possibly solar energy harvesting. A clear understanding of the shift current mechanism and search for materials with large shift current is, therefore, of immense interest. $ABC$ semiconductors LiZn$X$ ($X$ = N, P, As, and Sb) can be stabilized in cubic as well as hexagonal morphologies lacking inversion symmetry$-$an ideal platform to investigate the significant contributing factors to shift current, such as the role of structure and chemical species. Using density-functional calculations properly accounting for the electronic bandgaps, the shift current conductivities in LiZn$X$ ($X$ = P, As, Sb) are found to be approximately an order of magnitude larger than the well-known counterparts and peak close to the maximum solar radiation intensity. Notably, hexagonal LiZnSb shows a peak shift current conductivity of $\sim -75 ~\rm{\rmμ}$A/V$^2$ and Glass coefficient of $ -20$ $\times$ 10$^{-8}$ cm/V, comparable to the highest predicted values in literature. Our comparative analysis reveals a quantitative relationship between the shift current response and the electronic polarization. These findings not only posit Li-Zn-based $ABC$ semiconductors as viable material candidates for potential applications but also elucidates key aspects of the structure-BPVE relationship.
Based on first-principles calculations, we find that LiZnBi, a metallic hexagonal $ABC$ compound, can be driven into a Dirac semimetal with a pair of Dirac points by strain. The nontrivial topological nature of the strained LiZnBi is directly demonstrated by calculating its $\mathbb{Z}_2$ index and the surface states, where the Fermi arcs are clearly observed. The low-energy states as well as topological properties are shown to be sensitive to the strain configurations. The finding of Dirac semimetal phase in LiZnBi may intrigue further researches on the topological properties of hexagonal $AB…
In principle thermoelectricity is a viable route of converting waste heat into electricity, but the commercialization of the technology is limited by its present efficiency. In quest of improved materials, utilizing an \textit{ab initio} approach, we report polytypism induced improved thermoelectric performance in Li based Nowotny-Juza phases LiZn\textit{X} (\textit{X} = N, P, As, Sb, and Bi). In addition to LiZnSb, we find that cubic LiZnBi is energetically more favorable than the hitherto explored hexagonal phase whereas the hexagonal polytypes of cubic LiZnP, and LiZnAs are likely to be sta…
We use extensive first-principles quantum mechanical calculations to show that, although the static lattice and harmonic vibrational energies are almost identical, the anharmonic vibrational energy of hexagonal ice is significantly lower than that of cubic ice. This difference in anharmonicity is crucial, stabilising hexagonal ice compared with cubic ice by at least 1.4 meV/H2O, in agreement with experimental estimates. The difference in anharmonicity arises predominantly from molecular O-H bond stretching vibrational modes and is related to the different stacking of atomic layers.
Hexagonal diamond has been predicted computationally to display extraordinary physical properties including a hardness that exceeds cubic diamond. However, a recent electron microscopy study has shown that so-called hexagonal diamond samples are in fact not discrete materials but faulted and twinned cubic diamond. We now provide a quantitative analysis of cubic and hexagonal stacking in diamond samples by analysing X-ray diffraction data with the DIFFaX software package. The highest fractions of hexagonal stacking we find in materials which were previously referred to as hexagonal diamond are …
BaTiO3 appears in cubic and hexagonal variants, both of which are centrosymmetric. Samples of cubic BaTiO3 are known to exhibit breaking of the centric symmetry locally and globally. It has been proposed that the local symmetry breaking originates in polar regions, the precursors of the ferroelectric phase. Origins of the macroscopic symmetry breaking, which are not well understood, have been previously tentatively correlated with inhomogeneities in the samples, such as strain gradients that may align or redistribute objects such as charged point defects or polar regions making material macros…
Electron-phonon coupling in hexagonal and cubic water ice is studied using first-principles quantum mechanical methods. We consider 29 distinct hexagonal and cubic ice proton-orderings with up to 192 molecules in the simulation cell to account for proton-disorder. We find quantum zero-point vibrational corrections to the minimum electronic band gaps ranging from -1.5 to -1.7 eV, which leads to improved agreement between calculated and experimental band gaps. Anharmonic nuclear vibrations play a negligible role in determining the gaps. Deuterated ice has a smaller band-gap correction at zero-te…
The lighter group-V element phosphorus forms the As-type (hR2) structure under pressure, above 5 GPa, and at 10 GPa transforms to the simple cubic structure (cP1), similar to arsenic. Despite of its low packing density, the simple cubic structure is stable in phosphorus over a very wide pressure range up to 103 GPa. On further pressure increase, the simple cubic structure transforms to a simple hexagonal structure (hP1) via a complex phase that was solved recently as incommensurately modulated. Structural transformations of phosphorus are connected with the changes of physical properties. Abov…
We have performed ab-initio molecular dynamics simulations to elucidate the mechanism of the phase transition at high pressure from hexagonal graphite (HG) to hexagonal diamond (HD) or to cubic diamond (CD). The transition from HG to HD is found to occur swiftly in very small time of 0.2 ps, with large cooperative displacements of all the atoms. We observe that alternate layers of atoms in HG slide in opposite directions by (1/3, 1/6, 0) and (-1/3, -1/6, 0), respectively, which is about 0.7 Å along the pm[2, 1, 0] direction, while simultaneously puckering by about pm0.25 Å perpendicular to the…
Using ab-initio density functional theory we study the role of interstitial hydrogen on the energetics of the phase transformation of iron from bcc to hcp along Bain's pathway. The impurity creates an internal stress field that can be released through a tetragonal distortion of the lattice, promoting the bcc (ferromagnetic) $\rightarrow$ fcc (frustrated antiferromagnetic) $\rightarrow$ hcp (ferromagnetic) transition. The transformation between crystal systems is accompanied by a drastic magnetic reorganization and sudden variations of the unit cell volume, that can be one of the reasons for em…
Periodic structures of GdN particles encapsulated in a single crystalline GaN matrix were prepared by plasma assisted molecular beam epitaxy. High resolution X-ray diffractometery shows that GdN islands, with rock salt structure are epitaxially oriented to the wurtzite GaN matrix. Scanning transmission electron microscopy combined with in-situ reflection high energy electron diffraction allows for the study of island formation dynamics, which occurs after 1.2 monolayers of GdN coverage. Magnetometry reveals two ferromagnetic phases, one due to GdN particles with Curie temperature of 70K and a …
Analytical formulae are derived for the zero-point vibrational energy and anharmonicity corrections of the cohesive energy and the mode Grüneisen parameter within the Einstein model for the cubic lattices (sc, bcc and fcc) and for the hexagonal close-packed structure. This extends the work done by Lennard Jones and Ingham in 1924, Corner in 1939 and Wallace in 1965. The formulae are based on the description of two-body energy contributions by an inverse power expansion (extended Lennard-Jones potential). These make use of three-dimensional lattice sums, which can be transformed to fast converg…
Superstructures of cubic and hexagonal diamonds (h- and c-diamond) comprising a family of stable diamond-like $sp^3$ hybridized novel carbon allotropes are proposed, which are referred to as U$_n$-carbon where $n \geq 2$ denotes the number of structural layers in a unit cell. The conventional h- and c-diamond are included in this family as members with $n=2$ and 3, respectively. U$_n$-carbon ($n=4-6$), which are unveiled energetically and thermodynamically more stable than h-diamond and possess remarkable kinetic stabilities, are shown to be insulators with indirect gaps of $5.6 \sim 5.8$ eV, …
The density of states and the band diagrams were computed for diamond, cubic boron nitrde (cBN), and hexagonal boron nitride (hBN) using a Korringa-Kohn-Rostoker (KKR) scheme to investigate the shift of the Fermi level by impurity-atom doping below 10 at.%. The dopant atoms were B and N for diamond, Be, Si, and C for cBN, and Be and C for hBN. It was found that the Fermi level was located at the valence band maximum or the conduction band minimum in the following seven cases: (i) the B concentration was 0.3 at.% in B-doped diamond, (ii) the N concentration was 0.4 at.% in N-doped diamond, (iii…
We investigate the structural stability and magnetic properties of cubic, tetragonal and hexagonal phases of Mn3Z (Z=Ga, Sn and Ge) Heusler compounds using first-principles density-functional theory. We propose that the cubic phase plays an important role as an intermediate state in the phase transition from the hexagonal to the tetragonal phases. Consequently, Mn3Ga and Mn3Ge behave differently from Mn3Sn, because the relative energies of the cubic and hexagonal phases are different. This result agrees with experimental observations from these three compounds. The weak ferromagnetism of the h…
RF plasma assisted MBE growth of Scandium Nitride (ScN) thin films on GaN (0001)/SiC, AlN (0001)/Al2O3 and on 6H-SiC (0001) hexagonal substrates is found to lead to a face centered cubic (rock-salt) crystal structure with (111) out-of-plane orientation instead of hexagonal orientation. For the first time, cubic (111) twinned patterns in ScN are observed by in-situ electron diffraction during epitaxy, and the twin domains in ScN are detected by electron backscattered diffraction, and further corroborated with X-ray diffraction. The epitaxial ScN films display very smooth, sub nanometer surface …
We explore the structural evolution of highly oriented pyrolytic graphite (HOPG) under detonation-induced shock conditions using in-situ synchrotron X-ray diffraction in the ns time scale. We observe the formation of hexagonal diamond (lonsdaleite) at pressures above 50 GPa, in qualitative agreement with recent gas gun experiments. First-principles density functional calculations reveal that under uniaxial compression the energy barrier for the transition towards hexagonal diamond is lower than cubic diamond. Finally, no indication of cubic diamond formation was observed up to >70 GPa.
Among the over eighteen different forms of water ice, only the common hexagonal phase and a cubic phase are present in nature on Earth. The existence of these two polytypes, almost degenerate in energy, represents one of the most important and unresolved topics in the physics of ice. It is now widely recognised that all the samples of "cubic ice" obtained so far are instead a stacking-disordered form of ice I (i.e. ice Isd), in which both hexagonal and cubic stacking sequences of hydrogen-bonded water molecules are present. Here we describe a new method to obtain cubic ice Ic in large quantiti…
MASnI$_3$, an organometallic halide, has great potential in the field of lead-free perovskite solar cells. Ultraviolet photons have been shown to generate deep trapping electronic defects in mesoporous TiO$_2$-based perovskite, affecting its performance and stability. In this study, the structure, electronic properties, and optical properties of the cubic, tetragonal, and hexagonal phases of MASnI$_3$ were studied using first-principles calculations. The results indicate that the hexagonal phase of MASnI$_3$ possesses a larger indirect band gap and larger carrier effective mass along the \emph…
In succession to the first paper (arXiv 1406.6204v5), the impurity-atom concentrations when the Fermi levels are either at the valence band maximum (VBM) or the conduction band minimum (CBM) were identified for diamond, cubic boron nitride (cBN), and hexagonal boron nitride (hBN) using the Korringa-Kohn-Rostoker (KKR) scheme using the local density approximation (LDA). In the present paper, the generalized gradient approximation (GGA) was used instead of the LDA for exchange-correlation. The impurity atoms were B and N for diamond, Be, Si, and C for cBN, and Be for hBN; these impurity atoms we…
In nanostructure electronic devices, it is well-known that the optical lattice waves in the constituent semiconductor crystals have to obey both mechanical and electrical boundary conditions at an interface. The theory of hybrid optical modes, established for cubic crystals, is here applied to hexagonal crystals. In general, the hybrid is a linear combination of a longitudinally-polarized (LO) mode, an interface mode (IF), and an interface TO mode. It is noted that the dielectric and elastic anisotropy of these crystals add significant complications to the assessment of the electro-phonon inte…
Skyrmions are disk-like objects that typically form triangular crystals in two dimensional systems. This situation is analogous to the so-called "pancake vortices" of quasi-two dimensional superconductors. The way in which skyrmion disks or pancake skyrmions pile up in layered centro-symmetric materials is dictated by the inter-layer exchange. Unbiased Monte Carlo simulations and simple stabilization arguments reveal face centered cubic and hexagonal close packed skyrmion crystals for different choices of the inter-layer exchange, in addition to the conventional triangular crystal of skyrmion …
We calculate the lattice thermal conductivity ($κ$) for cubic (zinc-blende) and hexagonal (wurtzite) phases for 8 semiconductors using $\textit{ab initio}$ calculations and solving the Phonon Boltzmann Transport Equation, explaining the different behavior of the ratio $κ_{\rm hex}/κ_{\rm cub}$ between the two phases. We show that this behavior depends on the relative importance of two antagonistic factors: anharmonicity, which we find to be always higher in the cubic phase; and the accessible phase space, which is higher for the less symmetric hexagonal phase. Based on that, we develop a metho…
DFT modelling of stacking faults in hexagonal and cubic GaN
University College London（伦敦大学学院）；London Centre for Nanotechnology, University College London（伦敦大学学院纳米技术伦敦中心）；Research Centre for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS)（国立材料研究所（NIMS）材料纳米结构研究中心（WPI-MANA)）
We investigate the phase diagram of the heterostructural solid solution (InxGa1-x)2O3 both computationally, by combining cluster expansion and density functional theory, and experimentally, by means of TEM measurements of pulsed laser deposited (PLD) heteroepitaxial thin films. The shapes of the Gibbs free energy curves for the monoclinic, hexagonal and cubic bixbyite alloy as a function of composition can be explained in terms of the preferred cation coordination environments of indium and gallium. We show by atomically resolved STEM that the strong preference of indium for six-fold coordinat…
In the paper "Andrew D.P. Smith, Peter T. Haugen, Boyd F. Edwards: Hysteretic transition between states of a filled hexagonal magnetic dipole cluster, Journal of Magnetism and Magnetic Materials 549 (2022): 168991" a hysteretic transition between two stable arrangements of a cluster of seven dipoles is presented. The relative strength of the center dipole in a hexagonal arrangement serves as the bifurcation parameter. The authors clearly demonstrate the existence of two instabilities accompanied by discontinuous jumps of the dipole arrangement, but leave the question about the nature of these …
In this paper, we show how to incorporate cubic and hexagonal anisotropies in interfacial energies in phase field models; this incorporation is achieved by including upto sixth rank tensor terms in the free energy expansion, assuming that the free energy is only a function of coarse grained composition, its gradient, curvature and aberration. We derive the number of non-zero and independent components of these tensors. Further, by demanding that the resultant interfacial energy is positive definite for inclusion of each of the tensor terms individually, we identify the constraints imposed on t…
ZnSe nanowire growth has been successfully achieved on ZnSe (100) and (111)B buffer layers deposited on GaAs substrates. Cubic [100] oriented ZnSe nanowires or [0001] oriented hexagonal NWs are obtained on (100) substrates while [111] oriented cubic mixed with [0001] oriented hexagonal regions are obtained on (111)B substrates. Most of the NWs are perpendicular to the surface in the last case. CdSe quantum dots were successfully incorporated in the ZnSe NWs as demonstrated by transmission electron microscopy, energy filtered TEM and high angle annular dark field scanning TEM measurements.
Enhanced Hydrogen Evolution Catalysis of Pentlandite due to the Increases in Coordination Number and Sulfur Vacancy during Cubic-Hexagonal Phase Transition
We present a comprehensive computational study on the properties of face-centered cubic and hexagonal chalcogenide Ge2Sb2Te5. We calculate the electronic structure using density functional theory (DFT); the obtained density of states (DOS) compares favorably with experiments, also looking suitable for transport analysis. Optical constants including refraction index and absorption coefficient capture major experimental features, aside from an energy shift owed to an underestimate of the band gap that is typical of DFT calculations. We also compute the phonon DOS for the hexagonal phase, obtaini…
The metastable hexagonal-diamond phase of Si and Ge (and of SiGe alloys) displays superior optical properties with respect to the cubic-diamond one. The latter is the most stable and popular one: growing hexagonal-diamond Si or Ge without working at extreme conditions proved not to be trivial. Recently, however, the possibility of growing hexagonal-diamond group-IV nanowires has been demonstrated, attracting attention on such systems. Based on first-principle calculations we show that the surface energy of the typical facets exposed in Si and Ge nanowires is lower in the hexagonal-diamond phas…
Thermodynamic Phase Stability, Structural, Mechanical, Optoelectronic, and Thermoelectric Properties of the III-V Semiconductor AlSb for Energy Conversion Applications
S.U. Umarov Physical-Technical Institute of NAST（纳兹尔科学院苏·乌马尔物理技术研究所）；School of Optoelectronic Engineering & CQUPT-BUL Innovation Institute, Chongqing University of Posts and Telecommunications（重庆邮电大学光电工程学院与CQUPT-BUL创新学院）
Growth of two-dimensional metals has eluded materials scientists since the discovery of the atomically thin graphene and other covalently bound 2D materials. Here, we report a two-atom-thick hexagonal copper-gold alloy, grown through thermal evaporation on freestanding graphene and hexagonal boron nitride. The structures are imaged at atomic resolution with scanning transmission electron microscopy and further characterized with spectroscopic techniques. Electron irradiation in the microscope provides sufficient energy for a phase transformation of the 2D structure--atoms are released from the…
Binary alloy phases of the noble metals with main group elements are analyzed in relation to body centered cubic structure with orthorhombic and hexagonal distortions. Stability of these distorted phases is considered on the base of the Fermi sphere - Brillouin zone interaction to understand the important part of the band structure energy contribution to the overall crystal energy. Examination of Brillouin zone - Fermi sphere configurations for several representative phases has shown significance of the electron energy contribution in the formation of distorted structures with superlattices an…
Optoelectronic and Thermoelectric Properties of High-Performance AlSb Semiconductors
S.U. Umarov Physical-Technical Institute of NAST（S.U. 乌马罗夫物理技术研究所 (NAST)）；School of Optoelectronic Engineering & CQUPT-BUL Innovation Institute, Chongqing University of Posts and Telecommunications（重庆邮电大学光电工程学院及CQUPT-BUL创新学院）；Tajik National University（塔吉克斯坦国立大学）
We have utilised a high spatial resolution imaging method, Differential Phase Contrast (DPC) performed in a scanning transmission electron microscope (STEM), for precise measurement of the magnetic induction distribution in skyrmion states in noncentrosymmetric magnetically ordered materials. Applied to investigate the internal structure of hexagonal skyrmion lattice cells, stabilised by an out-plane applied magnetic field in an FeGe nanowedge specimen, mapping of the in-plane component of magnetic induction has yielded "average" skyrmion profiles and observation of internal six-fold symmetry.…
High-quality defect-free lonsdaleite Si and Ge can now be grown on hexagonal nanowire substrates. These hexagonal phases of group-IV semiconductors have been predicted to exhibit improved electronic and optical properties for optoelectronic applications. While lonsdaleite Si is a well-characterized indirect semiconductor, experimental data and reliable calculations on lonsdaleite Ge are scarce and not consistent regarding the nature of its gap. Using ab initio density-functional theory, we calculate accurate structural, electronic, and optical properties for hexagonal Ge. Given the well-known …
