Metastable Wurtzite Research Articles

High temperature decomposition and age hardening of single-phase wurtzite Ti1−xAlxN thin films grown by cathodic arc deposition

Wurtzite TmAlN (Tm=transition metal) themselves are of interest as semiconductors with tunable band gap, insulating motifs to superconductors, and piezoelectric crystals. Characterization of wurtzite TmAlN is challenging because of the difficulty to synthesize them as single-phase solid solution and such thermodynamic, elastic properties, and high temperature behavior of wurtzite Ti1−xAlxN is unknown. Here, we investigated the high temperature decomposition behavior of wurtzite Ti1−xAlxN films using experimental methods combined with first-principles calculations. We have developed a method to grow single-phase metastable wurtzite Ti1−xAlxN (x=0.65, 0.75, 085, and 0.95) solid-solution films by cathodic arc deposition using low duty-cycle pulsed substrate-bias voltage. We report the full elasticity tensor for wurtzite Ti1−xAlxN as a function of Al content and predict a phase diagram including a miscibility gap and spinodals for both cubic and wurtzite Ti1−xAlxN. Complementary high-resolution scanning transmission electron microscopy and chemical mapping demonstrate decomposition of the films after high temperature annealing (950∘C), which resulted in nanoscale chemical compositional modulations containing Ti-rich and Al-rich regions with coherent or semicoherent interfaces. This spinodal decomposition of the wurtzite film causes age hardening of 1–2 GPa. Published by the American Physical Society 2024

Wurtzite InAs Nanocrystals with Short-Wavelength Infrared Emission Synthesized through the Cation Exchange of Cu3As Nanocrystals

Colloidal InAs nanocrystals (NCs) are among the most promising light emitters in the short-wavelength infrared (SWIR) range. These InAs NCs are eligible to crystalize into two distinct phases, i.e., cubic zinc-blende phase and metastable hexagonal wurtzite phase. However, InAs NCs directly produced through molecular precursors unanimously exhibited zinc-blende structure, and the synthesis of their wurtzite counterparts has never been achieved. Herein, we report the first successful synthesis of high-quality wurtzite InAs NCs, which show bright SWIR photoluminescence with a tunable emission peak and high quantum yield of up to ∼37%. This is achieved by the cation exchange of Cu3As NCs with controllable size and morphology, followed by the growth of inorganic passivation layers to eliminate the possible surface trap centers. We further expand the synthesis route to wurtzite ternary InAs0.5P0.5 NCs with quasi-one dimensional confinement, which exhibit polarized SWIR emission, exploring the potential of these anisotropic NCs as efficient polarized light emitters.

Single‐precursor phase‐controlled synthesis of copper selenide nanocrystals and their conversion to amorphous hollow nanostructures

AbstractThe crystal phases are essential to the physicochemical properties and functionalities of materials. Copper selenide has emerged as an important and appealing semiconductor, which can exist in a variety of polymorphic phases. However, the richness of polymorphs also makes it a challenge to the direct preparation of copper selenide nanocrystals with tunable phases. Herein, two polymorphs, that is, quasi‐tetragonal Cu2−xSe nanocubes and metastable wurtzite Cu2Se nanodisks, are successfully synthesized by using a single precursor, copper(I) selenocyanate (CuSeCN), as the Cu and Se sources. The key to phase modulation is the optimal choice of the ligand in the synthesis. The as‐prepared nanocrystals possess different morphologies and compositions, giving rise to distinct optical properties and electrical conductivities. Interestingly, the copper selenide nanocrystals can provide a platform for the rational construction of two types of amorphous hollow Au─Cu─Se nanostructures by reaction with Au(I) precursor, in which their final shapes are well kept as that of the original nanocrystal templates. This work provides an easy strategy for the phase‐controlled synthesis of copper selenide nanocrystals and enables the design of new materials for broad applications.

Snowflake-like Metastable Wurtzite CuGaS2/MoS2 Composite with Superior Electrochemical HER Activity.

In the present work, we report the synthesis of wurtzite CuGaS2 and its composite with MoS2 and explored their efficacy toward two important applications, viz. electrocatalytic hydrogen evolution reaction (HER) and adsorption of Rhodamine B dye. The CuGaS2 was synthesized via a low-temperature ethylenediamine-mediated solvothermal method. The obtained products were characterized by various techniques such as X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy to ascertain the phase formation, surface morphology, and elemental oxidation states. The electrocatalytic activity of the wurtzite CuGaS2 and CuGaS2/MoS2 composites toward HER was investigated, wherein the CuGaS2/MoS2 composite exhibited superior activity when compared to the pristine sample with a small Tafel slope of 56.2 mV dec-1 and an overpotential value of -464 mV at the current density of 10 mA cm-2. On the other hand, the synthesized CuGaS2 also showed an impressive adsorption behavior toward Rhodamine B dye with 99% adsorption in 60 min, which is relatively better than that observed with the composite material.

Wurtzite Gallium Phosphide via Chemical Beam Epitaxy: Impurity-Related Luminescence vs Growth Conditions.

The metastable wurtzite crystal phase in gallium phosphide (WZ GaP) is a relatively new structure with little available information about its emission properties compared to the most stable zinc-blend phase. Here, the effect of growth conditions of WZ GaP nano- and microstructures obtained via chemical beam epitaxy on the optical properties was studied using power- and temperature-dependent photoluminescence (PL). We showed that the PL spectra are dominated by two strong broad emission bands at 1.68 and 1.88 eV and two relatively narrow peaks at 2.04 and 2.09 eV. The broad emissions are associated with the presence of carbon and a small number of extended crystal defects, respectively. For the sharp emissions, two main radiative recombination channels were observed with ionization energies estimated in the range of 50-80 meV and lower than 10 meV. No variation of the low-temperature PL spectra was observed for samples grown at different P precursor flows, while increasing Ga content enhanced the dominant broad emission at around 1.68 eV, suggesting that the group III organometallic precursor is the main source of impurities. Finally, Be-doped samples were grown, and their characteristic optical emission at 2.03 eV was identified. These results contribute to the understanding of impurity-related luminescence in hexagonal GaP, being useful for further crystal growth optimization required for the fabrication of optoelectronic devices.

First-principles investigation of polytypic defects in InP

In this paper we study polytypic defects in Indium Phosphide (InP) using the complementary first-principles methods of density functional theory and non-equilibrium Greens functions. Specifically we study interfaces between the ground state Zincblende crystal structure and the meta-stable Wurtzite phase, with an emphasis on the rotational twin plane defect, which forms due to the polytypic nature of InP. We found that the transition of the band structure across the interface is anisotropic and lasts 7 nm (3.5 nm). Due to this, a crystal-phase quantum well would require a minimal width of 10 nm, which eliminates rotational twin planes as possible quantum wells. We also found that for conducting current, the interfaces increase conductivity along the defect-plane ([11bar{2}]), whereas due to real growth limitations, despite the interfaces reducing conductivity across the defect-plane ([111]), we found that a high degree of polytypic defects are still desirable. This was argued to be the case, due to a higher fraction of Wurtzite segments in a highly phase-intermixed system.

Revealing an elusive metastable wurtzite CuFeS2 and the phase switching between wurtzite and chalcopyrite for thermoelectric thin films

As the alternative for the high-performance thermoelectric semiconductors such as GeTe, PbTe, and other compounds with rare and expensive elements, the cost-effective and abundant sulfides have been considered as one of the promising materials and garnered intensive interest. In this study, a rarely reported metastable wurtzite-type phase of CuFeS2 has been successfully obtained as thin film grown on quartz substrates via magnetron sputtering. Subsequent temperature-dependent depositions were performed to establish a phase transition between the metastable wurtzite and the chalcopyrite phase in the temperature range between room temperature and 473 K while maintaining the nominal composition ratio of CuFeS2. The wurtzite metastable analogue can be recovered and stabilized when the temperature reached 573 K and above. Thermoelectric properties were evaluated and constituted the first experimental result of the inorganic CuFeS2 thin film for thermoelectrics. The phase change between the wurtzite and chalcopyrite structure induced a significant effect on the thermoelectric properties associated with the lattice disorder and carrier scattering. The reduced thermal conductivity compared with bulk was demonstrated by the picosecond time-domain thermoreflectance method, which was found to be well correlated with the polycrystal sizes. The work provides new insight into synthesizing and manipulating the metastable wurtzite phase of the ternary I-III-VI for future applications in thermoelectrics, solar cells, and other electronic applications.

Growth‐Related Formation Mechanism of I3‐Type Basal Stacking Fault in Epitaxially Grown Hexagonal Ge‐2H

AbstractThe hexagonal‐2H crystal phase of Ge has recently emerged as a promising direct bandgap semiconductor in the mid‐infrared range providing new prospects of additional opto‐electronic functionalities of group‐IV semiconductors (Ge and SiGe). The controlled synthesis of such hexagonal‐2H Ge phase is a challenge that can be overcome by using wurtzite GaAs nanowires as a template. However, depending on growth conditions, unusual basal stacking faults (BSFs) of I3‐type are formed in the metastable 2H structure. The growth of such core/shell heterostructures is observed in situ and in real time by means of environmental transmission electron microscopy using chemical vapor deposition. The observations provide the first direct evidence of a step‐flow growth of Ge‐2H epilayers and reveal the growth‐related formation of I3‐BSFs during unstable growth. Their formation conditions are dynamically investigated. Through these in situ observations, a scenario can be proposed for the nucleation of I3‐type BSFs that is likely valid for any metastable hexagonal 2H or wurtzite structures grown on m‐plane substrates. Conditions are identified to avoid their formation for perfect crystalline synthesis of SiGe‐2H.

Insight into the Growth Mechanism of Mixed Phase CZTS and the Photocatalytic Performance.

In this work, CZTS particles with a mixed phase of wurtzite and kesterite were synthesized by the solvothermal method. The time-dependent XRD patterns, Raman spectra, SEM, and EDS analysis were employed to study the growth mechanism of CZTS. The results revealed that the formation of CZTS started from the nucleation of monoclinic Cu7S4 seeds, followed by the successive incorporation of Zn2+ and Sn4+ ions. Additionally, the diffusion of Zn2+ into Cu7S4 crystal lattice is much faster than that of Sn4+. With increasing time, CZTS undergoes a phase transformation from metastable wurtzite to steady kesterite. The morphology of CZTS tends to change from spherical-like to flower-like architecture. The mixed-phase CZTS with a bandgap of 1.5 eV exhibited strong visible light absorption, good capability for photoelectric conversion, and suitable band alignment, which makes it capable to produce H2 production and degrade RhB under simulated solar illumination.

Quantitative analysis of metastable wurtzite phase into the self-catalyzed GaP NWs

In this letter, we report the growth of the self-catalyzed GaP nanowires with a high concentration of wurtzite phase by molecular beam epitaxy. Formation of rotational twins and wurtzite polymorph in vertical nanowires was observed by the developed a complex approach based on the transmission electron microscopy and X-ray diffraction method. Microstructural analysis performed by high resolution transmission electron microscopy and micro-Raman spectroscopy gives us insights on the nanowire formation mechanism and vibrational properties of nanowires with mixed crystal phase. We obtained wurtzite polytype segments with thicknesses lying in the range from several tens up to 500 nm. The results of the work open new perspectives for high phase purity phosphide NWs synthesis and its fast investigation with XRD technique using a laboratory X-Ray source.

Bias-Enhanced Formation of Metastable and Multiphase Boron Nitride Coating in Microwave Plasma Chemical Vapor Deposition.

Boron nitride (BN) is primarily a synthetically produced advanced ceramic material. It is isoelectronic to carbon and, like carbon, can exist as several polymorphic modifications. Microwave plasma chemical vapor deposition (MPCVD) of metastable wurtzite boron nitride is reported for the first time and found to be facilitated by the application of direct current (DC) bias to the substrate. The applied negative DC bias was found to yield a higher content of sp3 bonded BN in both cubic and metastable wurtzite structural forms. This is confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Nano-indentation measurements reveal an average coating hardness of 25 GPa with some measurements as high as 31 GPa, consistent with a substantial fraction of sp3 bonding mixed with the hexagonal sp2 bonded BN phase.

First-principles calculation of electroacoustic properties of wurtzite (Al,Sc)N

We study the electroacoustic properties of aluminum scandium nitride crystals ${\mathrm{Al}}_{1\ensuremath{-}x}{\mathrm{Sc}}_{x}\mathrm{N}$ with the metastable wurtzite structure by means of first-principles calculations based on density functional theory. We extract the material property data relevant for electroacoustic device design, namely, the full tensors of elastic and piezoelectric constants. Atomistic models were constructed and analyzed for a variety of Sc concentrations $0\ensuremath{\le}x\ensuremath{\le}50$%. The functional dependence of the material properties on the scandium concentration was extracted by fitting the data obtained from an averaging procedure for different disordered atomic configurations. We give an explanation of the observed elastic softening and the extraordinary increase in piezoelectric response as a function of Sc content in terms of an element-specific analysis of bond lengths and bond angles.

Wurtzite InP microdisks: from epitaxy to room-temperature lasing

Metastable wurtzite crystal phases of conventional semiconductors comprise enormous potential for high-performance electro-optical devices, owed to their extended tunable direct band gap range. However, synthesizing these materials in good quality and beyond nanowire size constraints has remained elusive. In this work, the epitaxy of wurtzite InP microdisks and related geometries on insulator for advanced optical applications is explored. This is achieved by an elaborate combination of selective area growth of fins and a zipper-induced epitaxial lateral overgrowth, which enables co-integration of diversely shaped crystals at precise position. The grown material possesses high phase purity and excellent optical quality characterized by STEM and µ-PL. Optically pumped lasing at room temperature is achieved in microdisks with a lasing threshold of 365 µJ cm−2. Our platform could provide novel geometries for photonic applications.

Hydrothermal synthesis of tetragonal and wurtzite Cu2MnSnS4 nanostructures for multiple applications: Influence of different sulfur reactants on growth and properties

The present article reports the hydrothermal synthesis of quaternary Cu2MnSnS4 (CMTS) nanostructures under subcritical reaction conditions. The effect of different chalcogen (sulfur) precursor sources (l-cysteine, elemental sulfur and sodium sulfide) on the growth and properties of the nanostructures is studied. The sulfur precursors showed prominent influence on the structural and morphological properties of the nanostructures. Structural properties indicated the growth of single phase crystalline materials. The crystal phase was controlled and determined by the reactivity of the sulfur sources. Metastable wurtzite phase was achieved with the mildly reactive precursor while tetragonal phase was obtained in the case of highly reactive precursors. Morphological studies showed formation of nanoflakes and anisotropic two-dimensional irregular nanostructures. Surface area analysis indicated that the nanoflakes are mesoporous in nature and exhibited a high specific surface area of 32.24 m2/g. The electrical studies demonstrated p-type conductivity of the material. Optical properties revealed optimum energy band gap value (~1.7 eV) of the nanostructures, suitable for the solar energy conversion applications. The magnetic properties indicated ferromagnetic behavior of the CMTS nanoflakes. The nanostructures were investigated as catalysts for photocatalytic decolaration of malachite green (MG) dye under UV–Visible light illumination. The nanoflakes showed good activity against the dye and photodegraded 95% of the dye in an illumination duration of 140 min. The photocatalysts exhibited good stability during the photocatalytic processes.

Pressure dependence of the interlayer and intralayer E2g Raman-active modes of hexagonal BN up to the wurtzite phase transition

We present a Raman-scattering study of the interlayer and intralayer ${E}_{2g}$ Raman-active modes of hexagonal boron nitride $(h\ensuremath{-}\mathrm{BN})$ under hydrostatic pressure for pressures up to the transition to the wurtzite phase (10.5 GPa). Pressure coefficients and Gr\uneisen parameters are determined for both modes, and are compared to ab initio calculations based on density functional perturbation theory. The pressure coefficient of the low-energy interlayer mode is higher than that of the high-energy intralayer mode owing to the large compressibility of the $h\ensuremath{-}\mathrm{BN}$ crystal along the $c$ direction. Both modes exhibit a sublinear phonon frequency increase with pressure, which is more marked in the case of the low-energy mode. The intensity of the low-energy mode increases with pressure, suggesting an enhancement of the mode polarizability as the honeycomb layers become closer. The Raman spectrum of the metastable wurtzite phase is observed at ambient pressure in the transited sample after decompression.

Templated Growth of Metastable Polymorphs on Amorphous Substrates with Seed Layers

Metastable inorganic materials with unique properties are important in many practical applications, but their synthesis is often challenging. In physics, epitaxial stabilization, also known as pseudomorphic growth, is used to synthesize metastable polymorphs, but usually only as very thin films and on expensive single-crystal substrates. In chemistry, the templated growth of inorganic solid-state materials on self-assembled monolayers of organic molecules is reported. Bridging these two fields, here, we show that the synthesis of metastable polymorphs is possible up to large film thickness on amorphous substrates covered with thin inorganic seed layers that serve as templates. The stabilization of a 500-nm-thick metastable wurtzite (WZ) $\mathrm{Mn}\mathrm{Te}$ film by a 5-nm-thick $\mathrm{Zn}\mathrm{Te}$ seed layer sputtered on amorphous glass substrates is experimentally demonstrated. Theoretical calculations explain this experimental observation by the small WZ polymorph energy relative to that of the ground-state nickeline (NC) structure of $\mathrm{Mn}\mathrm{Te}$ and a large lattice constant difference of the two. The resulting metastable WZ-$\mathrm{Mn}\mathrm{Te}$ polymorph exhibits a wide band gap of 2.7 eV and a low hole density of ${10}^{12}\phantom{\rule{0.25em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}3}$, which is relevant to optoelectronic applications. These properties are in sharp contrast to those of the narrow-band-gap highly doped NC-$\mathrm{Mn}\mathrm{Te}$ with 1.3 eV band gap and ${10}^{19}\phantom{\rule{0.25em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}3}$ hole density. The difference in hole density is due to the calculated difference in the formation energy of manganese vacancy acceptor defects. Overall, these results suggest that templated growth on amorphous substrates with seed layers can be used to synthesize metastable polymorphs of other materials, without the need for expensive single-crystal substrates.

Impact of Elastic Stress on Crystal Phase of GaP Nanowires

In most cases, III–V compounds form a crystal structure, which is stable under certain experimental conditions. Meantime crystal phase of III–V nanowires may differ from the stable phase of bulk structures. In this work, we show that the elastic stress could be the sole factor responsible for nanowire growth in the metastable phase. Depending on the experimental conditions of GaP nanowire growth, the elastic stress contribution to nucleation barrier can be greater than the difference in the energy of the formation of the cubic and hexagonal phase, and thus, it causes the growth in metastable wurtzite crystal phase.

Combinatorial Tuning of Structural and Optoelectronic Properties in CuxZn1−xS

Summary P-type transparent conductors (TCs) are important enabling materials for optoelectronics and photovoltaics, but their performance still lags behind n-type counterparts. Recently, semiconductor CuxZn1−xS has demonstrated potential as a p-type TC, but it remains unclear how properties vary with composition. Here, we investigate CuxZn1−xS across the entire alloy space (0 ≤ x ≤ 1) using combinatorial sputtering and high-throughput characterization. First, we find a metastable wurtzite alloy at an intermediate composition between cubic endpoint compounds, contrasting with solid solutions or cubic composites (ZnS:CuyS) from the literature. Second, structural transformations correlate with shifts in hole conductivity and absorption; specifically, conductivity increases at the wurtzite phase transformation (x ≈ 0.19). Third, conductivity and optical transparency are optimized within a "TC regime" of 0.10

Direct Synthesis of Novel Cu2–xSe Wurtzite Phase

Herein, we report the unprecedented direct synthesis of a recently discovered metastable wurtzite phase of Cu2–xSe. Nanocrystals of Cu2–xSe were synthesized employing dodecyl diselenide as the selenium source and ligand. Optical characterization performed with UV–vis–NIR spectroscopy in solution showed a broad plasmonic band in the NIR. Structural characterization was performed with X-ray diffraction (XRD) and transmission electron microscopy. Variable-temperature XRD analysis revealed that the wurtzite nanocrystals irreversibly transform into the thermodynamic cubic phase at 151 °C. Replacement of dodecyl diselenide with dodecyl selenol yielded cubic phase Cu2–xSe, allowing for polymorphic phase control. An aliquot study was performed to gain insight into the mechanism of phase selectivity. The direct synthesis of this novel wurtzite phase could enable the discovery of new phenomena and expand the vast application space of CuxSey compounds.

Stabilizing the metastable superhard material wurtzite boron nitride by three-dimensional networks of planar defects

Wurtzite boron nitride (w-BN) is a metastable superhard material that is a high-pressure polymorph of BN. Clarifying how the metastable high-pressure material can be stabilized at atmospheric pressure is a challenging issue of fundamental scientific importance and promising technological value. Here, we fabricate millimeter-size w-BN bulk crystals via the hexagonal-to-wurtzite phase transformation at high pressure and high temperature. By combining transmission electron microscopy and ab initio molecular dynamics simulations, we reveal a stabilization mechanism for w-BN, i.e., the metastable high-pressure phase can be stabilized by 3D networks of planar defects which are constructed by a high density of intersecting (0001) stacking faults and {10[Formula: see text]0} inversion domain boundaries. The 3D networks of planar defects segment the w-BN bulk crystal into numerous nanometer-size prismatic domains with the reverse crystallographic polarities. Our findings unambiguously demonstrate the retarding effect of crystal defects on the phase transformations of metastable materials, which is in contrast to the common knowledge that the crystal defects in materials will facilitate the occurrence of phase transformations.