Bulk Crystal Growth Research Articles

Halogen-Bonded Hole-Transport Material Enhances Open-Circuit Voltage of Inverted Perovskite Solar Cells.

Interfacial properties of a hole-transport material (HTM) and a perovskite layer are of high importance, which can influence the interfacial charge transfer dynamics as well as the growth of perovskite bulk crystals particularly in inverted structure. The halogen bonding (XB) has been recognized as a powerful functional group to be integrated with new small molecule HTMs. Herein, a carbazole-based halo (iodine)-functional HTM (O1), is synthesized for the first time, demonstrating a high hole mobility and suitable energy levels that align well with those of perovskites. The strong interaction between O1 and perovskite, i.e., I···I-, induces the formation of an ordered interlayer, which are verified by both theoretical and experimental studies. Compared to the reference HTM (O2) without any halo-function, the XB-induced interlayer effectively enhances the interfacial charge extraction efficiency, while significantly hindering the non-radiative charge recombination by reducing the surface traps upon the strong passivation effect. This is reflected as a big increase in the open-circuit voltage by up to 114mV in the fabrication of inverted devices with the highest power conversion efficiency of 22.34%. Moreover, the ordered XB-driven interlayer at the interface of O1 and perovskite is mainly responsible for the extended lifespan under the operational conditions.

Host-guest charge transfer for scalable single crystal epitaxy of a metal-organic framework

Methods to grow large crystals provide the foundation for material science and technology. Here we demonstrate single crystal homoepitaxy of a metal-organic framework (MOF) built of zinc, acetate and terephthalate ions, that encapsulate arrays of octahedral zinc dimethyl sulfoxide (DMSO) complex cations within its one-dimensional (1D) channels. The three-dimensional framework is built of two-dimensional Zn-terephthalate square lattices interconnected by anionic acetate pillars through diatomic zinc nodes. The charge of the anionic framework is neutralized by the 1D arrays of Zn(DMSO)62+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\rm{Zn}}}{({{\\rm{DMSO}}})}_{6}^{2+}$$\\end{document} cations that fill every second 1D channel of the framework. It is demonstrated that the repeatable and scalable epitaxy allows square cuboids of this charge-transfer MOF to grow stepwise to sizes in the centimeter range. The continuous growth with no size limits can be attributed to the ionic nature of the anionic framework with cationic 1D molecular fillers. These findings pave the way for epitaxial growth of bulk crystals of MOFs.

Comments on recently published papers reporting on the growth of bulk crystals based on aromatic amines or optically active forms of ascorbic acid

Comments on recently published papers reporting on the growth of bulk crystals based on aromatic amines or optically active forms of ascorbic acid

Growth of Ba2CoWO6 single crystals and their magnetic, thermodynamic and electronic properties

This study explores the bulk crystal growth, structural characterization, and physical property measurements of the cubic double perovskite Ba2CoWO6(BCWO). In BCWO, Co2+ions form a face-centred cubic lattice with non-distorted cobalt octahedra. The compound exhibits long-range antiferromagnetic order belowTN= 14 K. Magnetization data indicated a slight anisotropy along with a spin-flop transition at 10 kOe, a saturation field of 310 kOe and an ordered moment of 2.17µB atT= 1.6 K. Heat capacity measurements indicate an effectivej= 1/2 ground state configuration, resulting from the combined effects of the crystal electric field and spin-orbit interaction. Surface photovoltage analysis reveals two optical gaps in the UV-Visible region, suggesting potential applications in photocatalysis and photovoltaics. The magnetic and optical properties highlight the significant role of orbital contributions within BCWO, indicating various other potential applications.

Hydrostatic Pressure as a Tool for the Study of Semiconductor Properties-An Example of III-V Nitrides.

Using the example of III-V nitrides crystallizing in a wurtzite structure (GaN, AlN, and InN), this review presents the special role of hydrostatic pressure in studying semiconductor properties. Starting with a brief description of high-pressure techniques for growing bulk crystals of nitride compounds, we focus on the use of hydrostatic pressure techniques in both experimental and theoretical investigations of the special properties of nitride compounds, their alloys, and quantum structures. The bandgap pressure coefficient is one of the most important parameters in semiconductor physics. Trends in its behavior in nitride structures, together with trends in pressure-induced phase transitions, are discussed in the context of the behavior of other typical semiconductors. Using InN as an example, the pressure-dependent effects typical of very narrow bandgap materials, such as conduction band filling or effective mass behavior, are described. Interesting aspects of bandgap bowing in In-containing nitride alloys, including pressure and clustering effects, are discussed. Hydrostatic pressure also plays an important role in the study of native defects and impurities, as illustrated by the example of nitride compounds and their quantum structures. Experiments and theoretical studies on this topic are reviewed. Special attention is given to hydrostatic pressure and strain effects in short periods of nitride superlattices. The explanation of the discrepancies between theory and experiment in optical emission and its pressure dependence from InN/GaN superlattices led to the well-documented conclusion that InN growth on the GaN substrate is not possible. The built-in electric field present in InGaN/GaN and AlGaN/GaN heterostructures crystallizing in a wurtzite lattice can reach several MV/cm, leading to drastic changes in the physical properties of these structures and related devices. It is shown how hydrostatic pressure modifies these effects and helps to understand their origin.

A library of 2D electronic material inks synthesized by liquid-metal-assisted intercalation of crystal powders

Solution-processable 2D semiconductor inks based on electrochemical molecular intercalation and exfoliation of bulk layered crystals using organic cations has offered an alternative pathway to low-cost fabrication of large-area flexible and wearable electronic devices. However, the growth of large-piece bulk crystals as starting material relies on costly and prolonged high-temperature process, representing a critical roadblock towards practical and large-scale applications. Here we report a general liquid-metal-assisted approach that enables the electrochemical molecular intercalation of low-cost and readily available crystal powders. The resulted solution-processable MoS2 nanosheets are of comparable quality to those exfoliated from bulk crystals. Furthermore, this method can create a rich library of functional 2D electronic inks ( >50 types), including 2D wide-bandgap semiconductors of low electrical conductivity. Lastly, we demonstrated the all-solution-processable integration of 2D semiconductors with 2D conductors and 2D dielectrics for the fabrication of large-area thin-film transistors and memristors at a greatly reduced cost.

The bulk crystal growth and yellow–orange spectral performances of Pr3+: BaF2 and Pr3+/RE3+(RE3+ = Gd3+, Y3+, Lu3+, Ce3+): BaF2 crystals

The bulk crystal growth and yellow–orange spectral performances of Pr3+: BaF2 and Pr3+/RE3+(RE3+ = Gd3+, Y3+, Lu3+, Ce3+): BaF2 crystals

Advances in fast 4H–SiC crystal growth and defect reduction by high-temperature gas-source method

This paper reviews recent progress in the development of high-speed 4H–SiC bulk crystal growth technology using the high-temperature gas-source method (high-temperature chemical vapor deposition). Vertical-type reactors capable of growing SiC bulk crystals of 50–75 and 100–150 mm in diameter have been developed, as have reactor configurations and growth conditions to achieve a high growth rate and material quality. Using the reactors, high growth rates up to or exceeding 3 mm/h have been achieved by employing an H2–SiH4–C3H8 gas system with high partial pressures of source gases and high growth temperature of 2500–2550 °C. It is also confirmed that the dislocation densities decline significantly in the direction of growth under proper growth conditions. Key factors for enhancing growth rate and improving crystal quality in the growth process are discussed.

Bulk crystal growth and characterization of non-centrosymmetric single crystal CaTa4O11

For the first time, high-quality bulk single crystals of CaTa4O11 were grown by the floating-zone method, and thus the current phase-diagram was revised for the stoichiometry CaO·2Ta2O5, showing a congruent melting behavior.

Enhanced near-infrared optical transmission in zinc germanium phosphide crystals via precise magnesium doping.

A zinc germanium phosphorus (ZnGeP2) crystal with a chalcopyrite structure is an efficient frequency converter in the mid-infrared region. However, point defect-induced optical absorption at the pumping wavelength (near infrared region) blocked the further application of ZnGeP2. To alleviate the absorption losses caused by point defects, in situ magnesium doping compensation was presented during the ZnGeP2 bulk crystal growth process via the vertical Bridgman method. Combined with theoretical calculations, the structural distortion of the magnesium-doped ZnGeP2 crystals in different orientations was illustrated. The thermodynamic and kinetic stability of the magnesium-doped ZnGeP2 structure were demonstrated. The transmission results indicated the improvement of transmittance within a wavelength range of 1.8-2.4 μm when doped with magnesium, which revealed the powerful ability of the appropriate dopant in optimizing near-infrared optical properties. Thus, the introduction of magnesium is a practical approach to improve the transmittance performance and extend the pumping source wavelengths of ZnGeP2 crystals.

Thin Films of α-Quartz GeO2 on TiO2-Buffered Quartz Substrates.

α-Quartz (SiO2) is one of the most widely used piezoelectric materials. However, the challenges associated with the control of the crystallization and the growth process limit its production to the hydrothermal growth of bulk crystals. GeO2 can also crystallize into the α-quartz phase, with a higher piezoelectric response and better thermal stability than SiO2. In a previous study, we have found that GeO2 crystallization on nonquartz substrates shows a tendency to form spherulites with a randomized orientation; while epitaxial growth of crystalline GeO2 thin films can take place on quartz (SiO2) substrates. However, in the latter case, the α-β phase transition that takes place in both substrates and thin films during heating deteriorates the long-range order and, thus, the piezoelectric properties. Here, we report the ousting of spherulitic growth by using a buffer layer. Using TiO2 as a buffer layer, the epitaxial strain of the substrates can be transferred to the growing films, leading to the oriented crystallization of GeO2 in the α-quartz phase. Moreover, since the TiO2 separates the substrates and the thin films, the thermal stability of the GeO2 is kept across the substrate's phase transitions. Our findings reveal the complexity of the crystallization process of quartz thin films and present a way to eliminate the tendency for spherulitic growth of quartz thin films by epitaxial strain.

Bulk Crystal Growth and Properties of a (K,Na)NbO3 Single Crystal by the Czochralski Method

Bulk Crystal Growth and Properties of a (K,Na)NbO₃ Single Crystal by the Czochralski Method

Design of High-Performance Organic Nonlinear Optical and Terahertz Crystals by Controlling the van der Waals Volume.

In the development of new organic crystals for nonlinear optical and terahertz (THz) applications, it is very challenging to achieve the essentially required non-centrosymmetric molecular arrangement. Moreover, the resulting crystal structure is mostly unpredictable due to highly dipolar molecular components with complex functional substituents. In this work, new organic salt crystals with top-level macroscopic optical nonlinearity by controlling the van der Waals volume (VvdW ), rather than by trial and error, are logically designed. When the VvdW of molecular ionic components varies, the corresponding crystal symmetry shows an observable trend: change from centrosymmetric to non-centrosymmetric and back to centrosymmetric. All non-centrosymmetric crystals exhibit an isomorphic P1 crystal structure with an excellent macroscopic second-order nonlinear optical response. Apart from the top-level macroscopic optical nonlinearity, new organic crystals introducing highly electronegative fluorinated substituents with strong secondary bonding ability show excellent performance in efficient and broadband THz wave generation, high crystal density, high thermal stability, and good bulk crystal growth ability.

A Self-Powered UV Photodetector With Ultrahigh Responsivity Based on 2D Perovskite Ferroelectric Films With Mixed Spacer Cations.

Self-powered photodetectors (PDs) have the advantages of no external power requirement, wireless operation, and long life. Spontaneous ferroelectric polarizations can significantly increase built-in electric field intensity, showing great potential in self-powered photodetection. Moreover, ferroelectrics possess pyroelectric and piezoelectric properties, beneficial for enhancing self-powered PDs. 2D metal halide perovskites (MHPs), which have ferroelectric properties, are suitable for fabricating high-performance self-powered PDs. However, the research on 2D metal halide perovskites ferroelectrics focuses on growing bulk crystals. Herein, 2D ferroelectric perovskite films with mixed spacer cations for self-powered PDs are demonstrated by mixing Ruddlesden-Popper (RP)-type and Dion-Jacobson (DJ)-type perovskite. The (BDA0.7 (BA2 )0.3 )(EA)2 Pb3 Br10 film possesses, overall, the best film qualities with the best crystalline quality, lowest trap density, good phase purity, and obvious ferroelectricity. Based on the ferro-pyro-phototronic effect, the PD at 360nm exhibits excellent photoelectric properties, with an ultrahigh peak responsivity greater than 93 A W-1 and a detectivity of 2.5 × 1015 Jones, together with excellent reproducibility and stability. The maximum responsivities can be modulated by piezo-phototronic effect with an effective enhancement ratio of 480%. This work will open up a new route of designing MHP ferroelectric films for high-performance PDs and offers the opportunity to utilize it for various optoelectronics applications.

Bulk crystal growth of materials with possible novel quantum states with RMX structure type

Bulk crystal growth of materials with possible novel quantum states with <i>RMX</i> structure type

Improved figure of merit (z) at low temperatures for superior thermoelectric cooling in Mg3(Bi,Sb)2

The low-temperature thermoelectric performance of Bi-rich n-type Mg3(Bi,Sb)2 was limited by the electron transport scattering at grain boundaries, while removing grain boundaries and bulk crystal growth of Mg-based Zintl phases are challenging due to the volatilities of elemental reactants and their severe corrosions to crucibles at elevated temperatures. Herein, for the first time, we reported a facile growth of coarse-grained Mg3Bi2-xSbx crystals with an average grain size of ~800 μm, leading to a high carrier mobility of 210 cm2 · V−1 · s−1 and a high z of 2.9 × 10−3 K−1 at 300 K. A DeltaT of 68 K at Th of 300 K, and a power generation efficiency of 5.8% below 450 K have been demonstrated for Mg3Bi1.5Sb0.5- and Mg3Bi1.25Sb0.75-based thermoelectric modules, respectively, which represent the cutting-edge advances in the near-room temperature thermoelectrics. In addition, the developed grain growth approach can be potentially extended to broad Zintl phases and other Mg-based alloys and compounds.

Direct comparison of surface crystal growth kinetics in chalcogenide glass measured by microscopy and DSC

AbstractSurface crystallization in fine powder Se70Te30 chalcogenide glass was studied by differential scanning calorimetry (DSC) and optical microscopy. A complex kinetic analysis of these experimental data reveals that the contracting sphere mechanism (R3 model) is the rate determining step of crystal growth, and the conventional Johnson–Mehl–Avrami–Kolmogorov model cannot be used in this case. Moreover, it is clearly shown that the particle size distribution should be considered in crystallization studies. Actually, when the particle size effect is taken into account, the simulated DSC curves for the R3 model agree very well with the experimental data over the entire temperature range. The crystallization kinetics determined from the nonisothermal DSC data are consistent with previously reported isothermal crystallization data for the same powder fraction. The crystal growth rate calculated from isothermal and nonisothermal DSC data agrees very well with the microscopically measured surface and bulk crystal growth rate.

Nonlinear Optical Sulfides LiMGa8 S14 (M=Rb/Ba, Cs/Ba) Created by Li+ Driven 2D Centrosymmetric to 3D Noncentrosymmetric Transformation.

Cations that can regulate the configuration of anion group are greatly important but regularly unheeded. Herein, the structural transformation from 2D CS to 3D noncentrosymmetric (NCS, which is the prerequisite for second-order NLO effect) is rationally designed to newly afford two sulfides LiMGa8 S14 (M = Rb/Ba, 1; Cs/Ba, 2) by introducing the smallest alkali metal Li+ cation into the interlamination of 2D centrosymmetric (CS) RbGaS2 . The unusual frameworks of 1 and 2 are constructed from C2 -type [Ga4 S11 ] supertetrahedrons in a highly parallel arrangement. 1 and 2 display distinguished NLO performances, including strong phase-matchable second-harmonic generation (SHG) intensities (0.8 and 0.9 × AgGaS2 at 1910 nm), wide optical band gaps (3.24 and 3.32 eV), and low coefficient of thermal expansion for favorable laser-induced damage thresholds (LIDTs, 4.7, and 7.6 × AgGaS2 at 1064nm), which fulfill the criteria of superior NLO candidates (SHG intensity >0.5 × AGS and band gap >3.0 eV). Remarkably, 1 and 2 melt congruently at 873.8 and 870.5°C, respectively, which endows them with the potential of growing bulk crystals by the Bridgeman-Stockbarge method. This investigated system provides a new avenue for the structural evolution from layered CS to 3D NCS of NLO materials.

Crystallization of Amorphous Nimesulide: The Relationship between Crystal Growth Kinetics and Liquid Dynamics.

Understanding crystallization and its correlations with liquid dynamics is relevant for developing robust amorphous pharmaceutical solids. Herein, nimesulide, a classical anti-inflammatory agent, was used as a model system for studying the correlations between crystallization kinetics and molecular dynamics. Kinetic parts of crystal growth (ukin) of nimesulide exhibited a power law dependence upon the liquid viscosity (η) as ukin~η-0.61. Bulk molecular diffusivities (DBulk) of nimesulide were predicted by a force-level statistical-mechanical model from the α-relaxation times, which revealed the relationship as ukin~Dbulk0.65. Bulk crystal growth kinetics of nimesulide in deeply supercooled liquid exhibited a fragility-dependent decoupling from τα. The correlations between growth kinetics and α-relaxation times predicted by the Adam-Gibbs-Vogel equation in a glassy state were also explored, for both the freshly made and fully equilibrated glass. These findings are relevant for the in-depth understanding and prediction of the physical stability of amorphous pharmaceutical solids.

Real-time in situ X-ray micro-computed tomography study of the effect of impurities on the crystallization of amorphous nifedipine

Controlling the physical stability of noncrystalline active pharmaceutical ingredients remains a major challenge in the development of amorphous formulations such as amorphous solid-dispersion (ASD) formulations. To establish new evaluation and formulation strategies, the spatial distribution of the crystal phase in bulk amorphous nifedipine (NFD) was investigated as a model. The crystallization of amorphous NFD and the effect of a deliberately added impurity were investigated using powder X-ray diffraction (PXRD), differential scanning calorimetry and real-time in situ X-ray micro-computed tomography (X-ray CT). The stability data of amorphous samples, i.e., NFD and a mixture of NFD with an oxidative degradation product of NFD, impurity A (Imp A), at a weight ratio of 90:10, presented as percent amorphous remaining, suggests that Imp A accelerates the bulk crystal growth of NFD. Real-time in situ X-ray CT results showed surface-enhanced crystal growth and cavity formation in solid NFD samples. Moreover, the crystals were heterogeneous in density. These results suggest that Imp A affects the physical stability of the amorphous NFD. X-ray CT equipped with a heating unit can aid in-situ evaluation and assessment of physicochemical properties and physical stability of amorphous samples and formulations.