4H Polytype Research Articles

Atomic-scale deformation behavior of SiC polytypes using molecular dynamics simulation

The atomic-scale deformation behavior of the Silicon carbide (SiC) polytypes, including 3 C-SiC and 4 H-SiC, during the nanoindentation with different square-based pyramid indenter angles was investigated by molecular dynamics (MD) simulations. Detailed analyses were conducted on atomic displacement magnitude, atomic structure, radial distribution function and dislocation distribution were analyzed in-depth in both loading and unloading processes. The results show that the indentation deformation phenomenon of ‘‘pile-up’’ occurs with indenter angles below 120°. Maximum load shows a non-linear increase trend as the indenter angles increase. The residual depth of the 3 C polytype has insignificant fluctuations while that of the 4 H polytype generally increases as the angle decreases and fluctuates at the indenter angles of 100° ∼ 110°. The number of amorphous atoms in 4 H is greater than that of 3 C polytype. Most of the amorphous atoms recover to their original structure after the indenter is fully withdrawn. Dislocation analysis indicates that the total length of dislocation lines increases with larger indenter angles. The length of the 3 C dislocation line is greater than that of 4 H. At the same indenter angle, the dislocation slip depth of 3 C polytype is greater than that of 4 H polytype due to the different lattice stacking order of 3 C polytype is greater than that of 4 H polytype due to the different lattice stacking order.

Energetics and Structural Transitions of Nonequivalent Polytypes for FCC and HCP Metals

AbstractAlthough metal nanomaterials with unconventional phases have attracted extensive attention, the lack of information on the characteristics of metal polytypes hinders the development of related research. In this work, the energetics of nonequivalent polytypes for bulk face‐centered cubic (Li, Al, Ca, Cu, Sr, Rh, Pd, Ag, Ir, Pt, Au, and Pb) and hexagonal close‐packed metals (Be, Na, Mg, Sc, Ti, Zn, Cd, Y, Zr, Tc, Ru, Hf, Re, Os, and Tl) is systematically reported. For each metal, the structural properties and energies for its polytypes with up to the periodic stacking length of L = 10 is obtained by DFT calculation. The variation tendency of the energy differences between 3C and 2H polytypes is summarized in the Periodic Table of Elements. Generally, the ratio c/(La) increases when metal crystals except Ir, Rh, Zn, and Cd leave away from their ground‐state structure. It is found that the energy difference between polytypes originates from various interactions between the two types of atomic layers: the k layer and the h layer. The work is helpful to understand not only the structural transitions in bulk metals, such as Li, Na, Sr, Ti, Al, Pb, Y, Re, and Tl, but also the evolutions of Au nanomaterials.

Thermochromic Properties of 3C-, 6H- and 4H-SiC Polytypes up to 500°C

The thermochromic properties (color change with temperature) of n type doped SiC wafers of different polytypes (3C, 4H and 6H) have been investigated up to 500°C under air. It was found that 3C-SiC color passes from bright yellow at room temperature to deep orangeat 500°C leading to a color contrast (ΔE) as high as 64. The hexagonal polytypes undergo also a color change upon heating but far less pronounced, with ΔE values <20. All these semiconductors undergo band gap shrinkage upon heating which effect largely participated to the observed color change. This effect is very sensitive for 3C polytypesince its bandgap is already in the visible energy range at room temperature. The thermochromicity of 3C-SiC was found to be reversible thanks to its thermal stability and its resistance towards oxidation.

Analysis of Defect Structures during the Early-Stages of PVT Growth of 4H-SiC Crystals

To better understand the effects of various growth parameters during the early-stages of PVT growth of 4H-SiC on resulting defect structures, multiple short duration growths have been carried out under varying conditions of seed quality, nucleation rate, thermal gradients, and N incorporation. Besides the replication of TSDs/TMDs and TEDs as well as the deflection of TSDs/TMDs into Frank dislocations, synchrotron monochromatic beam x-ray topography (SMBXT) studies also reveal the formation of stacking faults bounded by Frank dislocations. Using ray tracing simulations to characterize the Frank dislocations, three types of stacking faults are revealed: Type 1 stacking fault resulting from 2D nucleation of 6H polytype on terraces; Type 2 stacking fault resulting from macrostep overgrowth of the surface growth spiral steps of TSDs/TMDs which separate into c/2 or c/4 increments; Type 3 stacking fault resulting from vicinal step overgrowth of surface growth spiral steps of TSDs/TMDs which separate into c/4 and 3c/4 increments. Analysis of atomic resolution scanning transmission electron microscopy (STEM) images reveals the mechanism of the Type 3 fault.

Unveiling Novel Direct Bandgap Allotropes of Germanium: A Computational Exploration

Germanium crystallizes in a cubic diamond structure, which restricts its applications in optoelectronics due to its indirect band gap. However, the slight energy difference between the direct and indirect band gaps in germanium presents a promising opportunity to engineer its structure into a direct band gap material, with the hexagonal diamond (lonsdaleite) phase being a notable example. In this study, we conducted an extensive computational search to find germanium allotropes with a direct band gap and low energy using a sensible random structure search approach informed by data-derived interatomic potentials. Among the predicted allotropes, we identified a hexagonal 8H structure with the lowest energy compared to all known germanium allotropes and only 5 meV/atom above the ground state cubic diamond structure. Compared to the cubic diamond phase, which has complete cubicity, the 8H phase consists of 3/4 cubicity and 1/4 hexagonality. This structural motif, coupled with band structure back folding in the hexagonal Brillouin zone, results in a direct band gap of 0.25 eV. Given the prior experimental discovery of 2H and 4H polytypes, the experimental synthesis of the 8H allotrope in germanium is highly feasible. Future research could explore alloying 8H germanium with silicon to optimize the bandgap energy and optical transitions, potentially achieving lifetimes comparable to those of group III-V semiconductors like GaAs.

Two-dimensional electrons at mirror and twistronic twin boundaries in van der Waals ferroelectrics

Semiconducting transition metal dichalcogenides (MX2) occur in 2H and rhombohedral (3R) polytypes, respectively distinguished by anti-parallel and parallel orientation of consecutive monolayer lattices. In its bulk form, 3R-MX2 is ferroelectric, hosting an out-of-plane electric polarisation, the direction of which is dictated by stacking. Here, we predict that twin boundaries, separating adjacent polarisation domains with reversed built-in electric fields, are able to host two-dimensional electrons and holes with an areal density reaching ~ 1013cm−2. Our modelling suggests that n-doped twin boundaries have a more promising binding energy than p-doped ones, whereas hole accumulation is stable at external surfaces of a twinned film. We also propose that assembling pairs of mono-twin films with a ‘magic’ twist angle θ* that provides commensurability between the moiré pattern at the interface and the accumulated carrier density, should promote a regime of strongly correlated states of electrons, such as Wigner crystals, and we specify the values of θ* for homo- and heterostructures of various TMDs.

X-ray Characterizations of Exfoliated MoS2 Produced by Microwave-Assisted Liquid-Phase Exfoliation.

An X-ray analysis of exfoliated MoS2, produced by means of microwave-assisted liquid-phase exfoliation (LPE) from bulk powder in 1-methyl-2-pyrrolidone (NMP) or acetonitrile (ACN) + 1-methyl-2-pyrrolidone (NMP) solvents, has revealed distinct structural differences between the bulk powder and the microwave-exfoliated samples. Specifically, we performed X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements to identify the elements of our exfoliated sample deposited on a Si substrate by drop-casting, as well as their chemical state and its structural crystalline phase. In the exfoliated sample, the peaks pattern only partially resemble the theoretical Miller indices for MoS2. In contrast, the bulk powder's spectrum shows the characteristic peaks of the 2H polytype of MoS2, but with some broadening. Notable is the retention of partial crystallinity in the post-exfoliation phases, specifically in the normal-to-plane orientation, thus demonstrating the effectiveness of microwave-assisted techniques in producing 2D MoS2 and attaining desirable properties for the material. XPS measurements confirm the success of the exfoliation procedure and that the exfoliated sample retains its original structure. The exfoliation process has been optimized to maintain the structural integrity of MoS2 while enhancing its surface area and electrochemical performance, thereby making it a promising material for advanced electronic and optoelectronic applications ranging from energy storage to sensing devices under ambient conditions.

Shallow-level defect passivation by 6H perovskite polytype for highly efficient and stable perovskite solar cells

The power conversion efficiency of perovskite solar cells continues to increase. However, defects in perovskite materials are detrimental to their carrier dynamics and structural stability, ultimately limiting the photovoltaic characteristics and stability of perovskite solar cells. Herein, we report that 6H polytype perovskite effectively engineers defects at the interface with cubic polytype FAPbI3, which facilitates radiative recombination and improves the stability of the polycrystalline film. We particularly show the detrimental effects of shallow-level defect that originates from the formation of the most dominant iodide vacancy (VI+) in FAPbI3. Furthermore, additional surface passivation on top of the hetero-polytypic perovskite film results in an ultra-long carrier lifetime exceeding 18 μs, affords power conversion efficiencies of 24.13% for perovskite solar cells, 21.92% (certified power conversion efficiency: 21.44%) for a module, and long-term stability. The hetero-polytypic perovskite configuration may be considered as close to the ideal polycrystalline structure in terms of charge carrier dynamics and stability.

Exploring High-Spin Color Centers in Wide Band Gap Semiconductors SiC: A Comprehensive Magnetic Resonance Investigation (EPR and ENDOR Analysis).

High-spin defects (color centers) in wide-gap semiconductors are considered as a basis for the implementation of quantum technologies due to the unique combination of their spin, optical, charge, and coherent properties. A silicon carbide (SiC) crystal can act as a matrix for a wide variety of optically active vacancy-type defects, which manifest themselves as single-photon sources or spin qubits. Among the defects, the nitrogen-vacancy centers (NV) are of particular importance. This paper is devoted to the application of the photoinduced electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) techniques at a high-frequency range (94 GHz) to obtain unique information about the nature and properties of NV defects in SiC crystal of the hexagonal 4H and 6H polytypes. Selective excitation by microwave and radio frequency pulses makes it possible to determine the microscopic structure of the color center, the zero-field splitting constant (D = 1.2-1.3 GHz), the phase coherence time (T2), and the values of hyperfine (≈1.1 MHz) and quadrupole (Cq ≈ 2.45 MHz) interactions and to define the isotropic (a = -1.2 MHz) and anisotropic (b = 10-20 kHz) contributions of the electron-nuclear interaction. The obtained data are essential for the implementation of the NV defects in SiC as quantum registers, enabling the optical initialization of the electron spin to establish spin-photon interfaces. Moreover, the combination of optical, microwave, and radio frequency resonant effects on spin centers within a SiC crystal shows the potential for employing pulse EPR and ENDOR sequences to implement protocols for quantum computing algorithms and gates.

4H silicon carbide bulk acoustic wave gyroscope with ultra-high Q-factor for on-chip inertial navigation

Inertial navigation on a chip has long been constrained by the noise and stability issues of micromechanical Coriolis gyroscopes, as silicon, the dominant material for microelectromechanical system devices, has reached the physical limits of its material properties. To address these challenges, this study explores silicon carbide, specifically its monocrystalline 4H polytype, as a substrate to improve gyroscope performance due to its low phonon Akhiezer dissipation and its isotropic hexagonal crystal lattice. We report on low-noise electrostatic acoustic resonant gyroscopes with mechanical quality factors exceeding several millions, fabricated on bonded 4H silicon carbide-on-insulator wafers. These gyroscopes operate using megahertz frequency bulk acoustic wave modes for large open-loop bandwidth and are tuned electrostatically using capacitive transducers created by wafer-level deep reactive ion etching. Experimental results show these gyroscopes achieve superior performance under various conditions and demonstrate higher quality factors at increased temperatures, enabling enhanced performance in an ovenized or high-temperature stabilized configuration.

Formation and stability of point defect color centers in 6H silicon carbide

Point defect color centers acting as single-photon emitters are promising for quantum technology applications and have been extensively studied, e.g., in the 4H polytype of silicon carbide (SiC). However, the physics of such color centers in other SiC polytypes is much less explored. Herein, we study the formation and thermal stability of such color centers in 6H-SiC using photoluminescence spectroscopy. The emissions from typical single-photon emitters, such as silicon vacancies, divacancies, and carbon antisite-vacancy pairs in 6H-SiC, were monitored as a function of the proton irradiation fluence and post-irradiation annealing, and compared to that in 4H-SiC. Overall, at the background of similarities between the emission behavior in 4H- and 6H-SiC polytypes, we observed prominent differences; e.g., for the thermal stability of the carbon antisite-vacancy pair, which exhibited maximized emissions upon 300 and 900 °C anneals in 4H- and 6H-SiC, respectively. Moreover, we observed a range of defect emission signatures not previously reported for 6H-SiC in the literature and discussed their potential origin in the context of the thermal stability. For example, among the PL-lines in 6H-SiC, we detected periodically repeatable emission signatures, resembling the so-called L-lines recently reported in 4H-SiC, even though their exact origin has not yet been settled in the literature. Thus, we use color centers comparison in different polytypes to better understand the nature of the single-photon emitters in SiC.

The crystal structure of charmarite – the first case of a 11 × 11 Å superstructure mesh in layered double hydroxides

Abstract Charmarite, Mn4Al2(OH)12CO3⋅3H2O, is a hydrotalcite supergroup member (or layered double hydroxide, LDH) with a previously unknown crystal structure and a Mn2+-analogue of quintinite (commonly erroneously reported as ‘2:1 hydrotalcite’). The single-crystal X-ray diffraction (XRD) data were obtained from the specimen from Mont Saint-Hilaire, Québec, Canada and are best processed in the space group P $\bar{3}$ , a = 10.9630(4), c = 15.0732(5) Å and V = 1568.89(12) Å3. The crystal structure has been solved by direct methods and refined to R1 = 0.0750 for 3801 unique reflections with Fo > 2σ(Fo). The charmarite structure has long-range periodicity in the xy plane due to $2\sqrt 3$ a’ × $2\sqrt 3$ a’ scheme (or 11 × 11 Å) determined for LDHs for the first time (where a’ is a subcell parameter ≈ 3.2 Å). This periodicity is produced by the combination of two superstructures formed by: (1) Mn2+ and Al3+ ordering in the metal-hydroxide layers [Mn4Al2(OH)12]2+ according to the $\sqrt 3$ a’ × $\sqrt 3$ a’ pattern and (2) the (CO3)2– ordering according to the 2a’ × 2a’ pattern in the [CO3(H2O)3]2– interlayer sheet in order to avoid close contacts between adjacent carbonate groups. The $2\sqrt 3$ a’ × $2\sqrt 3$ a’ superstructure is an example of the adaptability of the components of the interlayer space to the charge distribution of the metal-hydroxyl layers. The Mn2+ and Al3+ cations have a large difference in size, which apparently leads to the considerable degree of their order as di- and trivalent cations resulting in a higher degree of statistical order of the interlayer components. Both powder and single-crystal XRD data show that the samples studied belong to the hexagonal branch of two-layer polytypes (2T or 2H) with d00n ≈ 7.57 Å. The chemical composition of the samples studied is close to the ideal formula. The Raman spectrum of charmarite is reported and the band assignment is provided.

A new path towards ultra-high efficient laser power converters: Silicon carbide-based multijunction devices

Current high power laser transmission technology faces two major limitations to improve the efficiency of the photovoltaic receivers: the intrinsic entropic losses associated to low bandgap materials (such as GaAs) and the series resistance losses that degrade the device performance at high power densities. The use of high bandgap materials and new architectures for laser power converters (LPC) have been pointed out as alternatives to overcome these limitations. In this work, three silicon carbide polytypes (3C, 4H and 6H) are proposed as base materials for the standard horizontal laser power converter (hLPC) architecture and the Vertical Epitaxial Hetero-Structure Architecture (VEHSA). 3C SiC based hLPCs outperform the power converters based on the other two polytypes, achieving a maximum efficiency of 84.6% at ▪, but suffer from series resistance losses, that deteriorate their efficiency, at higher laser power densities. This issue is solved with 3C SiC 4 cells VEHSAs that demonstrated increasing efficiency with the input power, reaching a maximum of 87.4% at ▪. The VEHSA reduced number of cells minimize the risks of efficiency losses due to current mismatch between cells. These results support the feasibility of a new generation of LPCs capable of efficiently convert ultra-high laser power densities.

Influence of Different Hydrocarbons on Chemical Vapor Deposition Growth and Surface Morphological Defects in 4H‐SiC Epitaxial Layers

Controlled epitaxial growth of 4H‐SiC is essential for advancing both power electronics and quantum technologies. This study explores how different carbon sources—methane and propane—affect the surface morphology of these epitaxial layers. By varying C/Si ratios and using the two mentioned hydrocarbons as the carbon source in chloride‐based epitaxial growth of 4H‐SiC layers, it is unveiled that methane results in an exceptionally smooth surface. However, it pronounces surface irregularities such as short step bunching and dislocation‐related etch pits. Moreover, methane amplifies the overgrowth of triangular defects with the 4H polytype. In contrast, the introduction of propane causes a step‐bunched surface together with inclined line‐like surface morphological defects. Notably, a majority of the triangular defects exhibit a pure 3C character without an overgrown 4H polytype. It is shown that these outcomes could be attributed to different sticking coefficients and diffusivity of the molecular species resulting from different carbon sources on the 4H‐SiC surface during the epitaxial growth. This research also uncovers the underlying origins and mechanisms responsible for various surface morphological defects.

Thermal expansion of 4H and 6H SiC from 5 K to 340 K

The first thermal expansion measurements of the 4H and 6H polytypes of SiC below room temperature are reported. The measurements were carried out on single-crystal specimens using high-resolution capacitive-based dilatometry. For both polytypes, the thermal expansion coefficient is below 2.4 × 10−6 1/K near room temperature. No phase transitions are observed over the 5 K to 340 K temperature range of the measurements. The thermal expansion coefficient α of 4H SiC is slightly anisotropic for measurements parallel and perpendicular to the crystallographic c axis with α|| about 2.2 × 10−7 1/K larger than α⊥ near room temperature. For 6H SiC no discernible anisotropy is observed. The differences in anisotropy can be understood by considering the ratio of hexagonal to cubic bonds of each polytype. Narrow regions with negative thermal expansion that are within the limits of our resolution (∼1×10−8) are observed in the vicinity of 30 K for both specimens. Tabulated data, polynomial fits, fit parameters, and comparison to data based on lattice-parameter measurements are provided.

Computationally guided epitaxial synthesis of (Sr/Ba)MnO[formula omitted] films on (Sr/Ba)TiO[formula omitted] substrates

Density functional theory (DFT) was used in the computation of thermodynamic terms relevant to the competition between epitaxial polytypes during nucleation of (Sr/Ba)MnO3 on (100), (110), and (111) cubic (Sr/Ba)TiO3 substrates. Values for volumetric formation energies, volumetric strain energies, and area-specific interface energies were computed for different polytypes (3C, 4H, and 2H) and were incorporated in a standard (capillarity) model for epitaxial nucleation. Experimental orientation relationships (ORs) for SrMnO3 were used in the construction of strained and interface cells for (Sr/Ba)MnO3. For 3C polytypes, the OR is simply cube-on-cube, or (111)[11̄0]3C,film||(111)[11̄0]3C,sub, and is isostructural with cubic (Sr/Ba)TiO3. For 4H/2H polytypes, the orientation relationship is (001)[100]4H/2H,film||(111)[11̄0]3C,sub, which can only be modeled with a coherent interface on the (111) substrate. Results indicate that 3C SrMnO3 has increased energies (becomes less stable) on moving from SrTiO3 substrate orientations (100) to (110) to (111), consistent with experimental observations. For BaMnO3, similar trends are predicted, although no experimental data is available for comparison. We use the DFT results to discuss the different thermodynamic contributions to polytype stability, and assess the feasibility of stabilizing a 3C BaMnO3 film on (Sr/Ba)TiO3 substrates.

Synthesis of Hexagonal Nanophases in the La2O3–MO3 (M = Mo, W) Systems

We report a study of nanophases in the La2O3–MO3 (M = Mo, W) systems, which are known to contain a variety of good oxygen-ion and proton conductors. Mechanically activated La2O3 + MO3 (M = Mo, W) mixtures and the final ceramics have been characterized by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) with Rietveld refinement. The microstructure of the materials has been examined by scanning electron microscopy (SEM), and their conductivity in dry and wet air has been determined using impedance spectroscopy. In both systems, the formation of hexagonal La15M8.5O48 (phase II, 5H polytype) (M = Mo, W) nanophases is observed for the composition 1:1, with exothermic peaks in the DSC curve in the range ~480–520 °C for La15Mo8.5O48 and ~685–760 °C for La15W8.5O48, respectively. The crystallite size of the nanocrystalline tungstates is ~40 nm, and that of the nanocrystalline molybdates is ~50 nm. At higher temperatures (~630–690 and ~1000 °C), we observe irreversible reconstructive phase transitions of hexagonal La15Mo8.5O48 to tetragonal γ-La2MoO6 and of hexagonal La15W8.5O48 to orthorhombic β-La2WO6. We compare the temperature dependences of conductivity for nanoparticulate and microcrystalline hexagonal phases and high-temperature phases differing in density. Above 600 °C, oxygen ion conduction prevails in the coarse-grained La18W10O57 (phase I, 6H polytype) ceramic. Low-density La15W8.5O48 and La15Mo8.5O48 (phase II, 5H polytype) nanoceramics exhibit predominantly electron conduction with an activation energy of 1.36 and 1.35 eV, respectively, in dry air.

Structural, Optical, and Chemical Characteristics of High‐Quality PbI2 Thin Films via Chemical Solution Deposition with Thermal Annealing

Herein, a synthesis method for obtaining lead iodide through chemical bath deposition, a type of chemical solution deposition without the use of organic solvents, is presented; the process consists of three stages. In the first stage, tin hydroxide films are produced which act as a seed layer allowing for a better adherence of the film that is to be deposited. The second stage consists of the synthesis of the lead iodide films. Finally, annealing is done (100, 150, and 200 °C) with the purpose of promoting the polytypic transitions of the material and to study the effect of these structures on the properties of the material. Assessment of the structural and optical properties of the films is done by means of scanning electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, optical spectroscopy, Raman spectroscopy, and transmission electron microscopy, where a direct influence of the annealing in the induction of polytypes is observed. The resultant PbI2 films have a large‐area coverage across the substrate, wide‐bandgap (2.38 eV), and a structure that belongs to the 2H and 4H polytypes. Hence, it is suggested from these results that the chemically deposited PbI2 thin films are promising candidates for large‐area optoelectronic applications.

REDUCTION OF CRACK FORMATION DURING ABRASIVE TREATMENT WITH DIAMOND PASTES OF SILICON CARBIDE SEMICONDUCTOR PLATES

The results of diamond-abrasive treatment of the reverse side of silicon carbide semiconductor plates of polytypes 4H and 6H are presented. Dimensions of surface microcracks of ceramic plates after abrasive treatment with pastes with diamond powder of different grain size are investigated, and also relationship between length of surface microcrack and rate of material removal depending on technological modes of diamond-abrasive treatment is established. As a result, a new method of single-sided abrasion treatment of thin ceramic plates is proposed, which ensures reduction of crack formation.

Formation of Ba3Nb0.75Mn2.25O9-6H during thermo-chemical reduction of Ba4NbMn3O12-12R.

The resurgence of inter-est in hydrogen-related technologies has stimulated new studies aimed at advancing lesser-developed water-splitting processes, such as solar thermochemical hydrogen production (STCH). Progress in STCH has been largely hindered by a lack of new materials able to efficiently split water at a rate comparable to ceria under identical experimental conditions. BaCe0.25Mn0.75O3 (BCM) recently demonstrated enhanced hydrogen production over ceria and has the potential to further our understanding of two-step thermochemical cycles. A significant feature of the 12R hexa-gonal perovskite structure of BCM is the tendency to, in part, form a 6H polytype at high temperatures and reducing environments (i.e., during the first step of the thermochemical cycle), which may serve to mitigate degradation of the complex oxide. An analogous compound, namely BaNb0.25Mn0.75O3 (BNM) with a 12R structure was synthesized and displays nearly complete conversion to the 6H structure under identical reaction conditions as BCM. The structure of the BNM-6H polytype was determined from Rietveld refinement of synchrotron powder X-ray diffraction data and is presented within the context of the previously established BCM-6H structure.