High-quality Crystals Research Articles

Novel polymorph of 2-amino-6-methyl pyridinium-4-methyl benzoate (2A6MP4MB) single crystals: Synthesis, crystal structure, optical, spectroscopic and self-defocusing capabilities for nonlinear optical applications

By using the slow evaporation solution growth technique, the 2-amino 6-methyl pyridinium 4-methyl benzoate (2A6MP4MB) is crystallized in a single, high-quality crystal. Single crystal X-ray diffraction (SXRD) was used to determine the crystal structure. The different functional groups of the substances were identified using Fourier Transform Infrared Spectroscopy (FTIR) analysis. The 2A6MP4MB crystal exhibits a significant optical transmittance throughout the complete visible spectrum and a lowered UV cutoff wavelength, according to studies conducted using UV-Vis spectrometers. The optical band gap energy (Eg) of a single crystal of 2A6MP4MB is 4.768[Formula: see text]eV. The compound’s photoluminescence (PL) spectrum in the title illustrates the green emission technique. We analyze the produced single crystal’s dielectric tensorial behavior at various frequencies. The produced 2A6MP4MB crystal’s third-order susceptibility, nonlinear refraction, and nonlinear absorption coefficient were evaluated using the [Formula: see text]-scan technique. A Vickers hardness tester was used to assess the created crystal’s mechanical stability.

Oxygen-termination effect on the surface energy dissipation in diamond MEMS

Single-crystal diamond (SCD) microelectromechanical systems (MEMS) resonators with lower energy dissipation and higher quality (Q) factors have always been pursued for the development of high-sensitivity and high signal-to-noise ratio (SNR) MEMS sensors. The intrinsic loss such as the crystal quality and extrinsic loss of clamping loss have been examined to improve the Q factors of SCD MEMS resonators. Nevertheless, the surface termination induced energy dissipation has rarely been known due to the lack of high crystal quality diamond resonators and in-situ characterization. Here we examine the effect of oxygen-termination on the surface energy dissipation of SCD cantilevers by in-situ heating these cantilevers in a high vacuum chamber. After thermal treatment of the cantilevers at 933 K, the Q factor of the cantilever is improved from 2.8x105 to 3.3x105 (i.e. the 120 μm-long). The resonance frequency increase confirms the desorption of surface adsorbates. Compared to silicon, on which a native solid-state oxide exists, the surface oxygen-termination induced loss in diamond MEMS is much smaller. The non-existence of native oxides on diamond surface is an obvious merit toward ultra-high Q factor MEMS resonators.

Design and fabrication of 3D-printed in situ crystallization plates for probing microcrystals in an external electric field

X-ray crystallography is an established tool to probe the structure of macromolecules with atomic resolution. Compared with alternative techniques such as single-particle cryo-electron microscopy and micro-electron diffraction, X-ray crystallography is uniquely suited to room-temperature studies and for obtaining a detailed picture of macromolecules subjected to an external electric field (EEF). The impact of an EEF on proteins has been extensively explored through single-crystal X-ray crystallography, which works well with larger high-quality protein crystals. This article introduces a novel design for a 3D-printed in situ crystallization plate that serves a dual purpose: fostering crystal growth and allowing the concurrent examination of the effects of an EEF on crystals of varying sizes. The plate's compatibility with established X-ray crystallography techniques is evaluated.

Aminoazanium of A-site Cations in Metal-Free Halide Perovskite Single Crystals to Reduce Thermal Expansion for Efficient X-ray Detection.

Metal-free perovskites (MFPs) have recently become a newcomer in X-ray detection due to their flexibility and low toxicity characteristics. However, their photoelectronic properties and stability should be further improved mainly through materials design. Here, the aminoazanium of DABCO2+ was developed for the preparation of NDABCO-NH4Br3 (NDABCO = N-amino-N'-diazabicyclo[2.2.2]octonium) single crystals (SCs), and its physical properties, intermolecular interactions, and device performance were systematically explored. Notably, NDABCO-NH4Br3 can achieve improved stability by enlarging defect formation energy and inducing abundant intermolecular forces. Moreover, the slight lattice distortion could ensure the weakening electron-phonon coupling for improving carrier transport. In particular, the slight lattice distortion after the long-chain NDABCO2+ introduction could retard thermal expansion for the preparation of high-quality crystals. Finally, the corresponding X-ray detector delivered a moderate sensitivity of 623.3 μC Gyair-1 cm-2. This work provides a novel strategy through rationally designed organic cations to balance the material stability and device performance.

Study on subgrain boundaries in cast monocrystalline silicon

Cast monocrystalline silicon (mono-Si), also known as quasi-mono-Si, has been recognized for its potential as a high-performance crystalline silicon material due to its low manufacturing costs and high crystal quality. This study investigated the occurrence of high-density dislocation loops in cast mono-Si, which exhibited grid-like propagation caused mostly by subgrain boundaries. The study looked at the fundamental properties of these subgrain boundaries as well as the mechanisms that allow them to propagate in a grid-like pattern within cast mono-Si. Observations revealed differences in the crystallographic misorientation of subgrain boundaries across the ingot, ranging from 1 to 3°. Electron Beam Induced Current (EBIC) tests revealed strong recombination activity at these boundaries under typical conditions. As the temperature gradually decreases from 300 K to 80 K during EBIC testing, subgrain boundaries with shallower energy states emerge, which become more apparent in photoluminescence (PL) tests conducted on Si wafers cut from different heights of the ingot.

Influence of an Overshoot Layer on the Morphological, Structural, Strain, and Transport Properties of InAs Quantum Wells.

InAs quantum wells (QWs) are promising material systems due to their small effective mass, narrow bandgap, strong spin-orbit coupling, large g-factor, and transparent interface to superconductors. Therefore, they are promising candidates for the implementation of topological superconducting states. Despite this potential, the growth of InAs QWs with high crystal quality and well-controlled morphology remains challenging. Adding an overshoot layer at the end of the metamorphic buffer layer, i.e., a layer with a slightly larger lattice constant than the active region of the device, helps to overcome the residual strain and provides optimally relaxed lattice parameters for the QW. In this work, we systematically investigated the influence of overshoot layer thickness on the morphological, structural, strain, and transport properties of undoped InAs QWs on GaAs(100) substrates. Transmission electron microscopy reveals that the metamorphic buffer layer, which includes the overshoot layer, provides a misfit dislocation-free InAs QW active region. Moreover, the residual strain in the active region is compressive in the sample with a 200 nm-thick overshoot layer but tensile in samples with an overshoot layer thicker than 200 nm, and it saturates to a constant value for overshoot layer thicknesses above 350 nm. We found that electron mobility does not depend on the crystallographic directions. A maximum electron mobility of 6.07 × 105 cm2/Vs at 2.6 K with a carrier concentration of 2.31 × 1011 cm-2 in the sample with a 400 nm-thick overshoot layer has been obtained.

Fabrication of Tungsten Oxide Nanowalls through HFCVD for Improved Electrochemical Detection of Methylamine.

In this study, well-defined tungsten oxide (WO3) nanowall (NW) thin films were synthesized via a controlled hot filament chemical vapor deposition (HFCVD) technique and applied for electrochemical detection of methylamine toxic substances. Herein, for the thin-film growth by HFCVD, the temperature of tungsten (W) wire was held constant at ~1450 °C and gasification was performed by heating of W wire using varied substrate temperatures ranging from 350 °C to 450 °C. At an optimized growth temperature of 400 °C, well-defined and extremely dense WO3 nanowall-like structures were developed on a Si substrate. Structural, crystallographic, and compositional characterizations confirmed that the deposited WO3 thin films possessed monoclinic crystal structures of high crystal quality. For electrochemical sensing applications, WO3 NW thin film was used as an electrode, and cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were measured with a wide concentration range of 20 μM~1 mM of methylamine. The fabricated electrochemical sensor achieved a sensitivity of ~183.65 μA mM-1 cm-2, a limit of detection (LOD) of ~20 μM and a quick response time of 10 s. Thus, the fabricated electrochemical sensor exhibited promising detection of methylamine with considerable stability and reproducibility.

Crystal growth, structure, spectral and thermal properties of ScxY1-xCOB single crystals

Yttrium calcium oxyborate (YCOB) crystals are excellent nonlinear optical crystals. To enhance the thermal properties of YCOB crystal, Sc-doped YCOB crystals, denoted as ScxY1-xCa4O(BO3)3 (x = 0.1 and 0.2) were grown using the Czochralski method along the b-direction. Various measurements, including X-ray powder diffraction, rocking curve analysis, inductively coupled plasma-optical emission spectroscopy (ICP-OES), transmission spectroscopy, density measurements, and thermal property assessments, were conducted to evaluate the characteristics of the ScxY1-xCOB crystals. The results indicated that ScxY1-xCOB crystals have an isostructural arrangement like YCOB, with segregation coefficients of approximately 0.2. The full width at half maximum (FWHM) values of the rocking curves of the ScxY1-xCOB (x = 0.1 and 0.2) crystals are 33.9″ and 29.3″, respectively. Furthermore, the specific heat, thermal diffusion coefficients and thermal conductivity of the ScxY1-xCOB crystals were examined in the temperature range of 298–573 K, which were found to be higher than those of pure YCOB. These high-quality ScxY1-xCOB crystals are expected to serve as suitable nonlinear optical crystals media for optical parametric chirped pulse amplification (OPCPA) applications.

Design and characterization of type-II superlattice-based InAs/AlSb/GaSb detector structure

In this study, N-Structured based InAs/AlSb/GaSb Type-II Superlattice pbin type detector structures are investigated. These systems make absorption in the infrared region in the electromagnetic spectrum as detectors. Structural characterization of these systems is aimed. n-type GaSb is used as the substrate. InAs/AlSb/GaSb-based repetitive SL layers are formed as n-layer, i-layer, p-layer, and p-contact layer from the bottom InAsSb layer to the top GaSb cap layer for 120, 300, 15, and 80 periods, respectively. Structural characterization of all layers is made by using SIMS and XRD systems analyses. The structural depth profile of the SL layers has been presented comparatively through SIMS analysis. The interfacial transitions observed in the depth profile are consistent with the designed T2SL layers. By using XRD characterization, crystal quality parameters, lattice constants, periodicity, and deviation of superlattice peak from the substrate are determined. Such dislocation density and strain are measured AS 7.85x107cm−2 and 6.4x10-3 nm, respectively. AFM analysis technic is used to examine the surface morphology of the structure. Also, SEM analysis is used to examine the cross-section of the structure. The cross-sectional measurements allowed the observation of interfacial transitions within the SL structure. In this study, super lattice with high crystal quality is achieved and results show that T2SL detector structures have succeeded.

Room Temperature Crystallized Phase-Pure α-FAPbI3 Perovskite with In-Situ Grain-Boundary Passivation.

Energy loss in perovskite grain boundaries (GBs) is a primary limitation toward high-efficiency perovskite solar cells (PSCs). Two critical strategies to address this issue are high-quality crystallization and passivation of GBs. However, the established methods are generally carried out discretely due to the complicated mechanisms of grain growth and defect formation. In this study, a combined method is proposed by introducing 3,4,5-Trifluoroaniline iodide (TFAI) into the perovskite precursor. The TFAI triggers the union of nano-sized colloids into microclusters and facilitates the complete phase transition of α-FAPbI3 at room temperature. The controlled chemical reactivity and strong steric hindrance effect enable the fixed location of TFAI and suppress defects at GBs. This combination of well-crystallized perovskite grains and effectively passivated GBs leads to an improvement in the open circuit voltage (Voc) of PSCs from 1.08V to 1.17V, which is one of the highest recorded Voc without interface modification. The TFAI-incorporated device achieved a champion PCE of 24.81%. The device maintained a steady power output near its maximum power output point, showing almost no decay over 280h testing without pre-processing.

Scalable Synthesis of High-Quality Ultrathin Ferroelectric Magnesium Molybdenum Oxide.

The development of ultrathin, stable ferroelectric materials is crucial for advancing high-density, low-power electronic devices. Nonetheless, ultrathin ferroelectric materials are rare due to the critical size effect. Here, a novel ferroelectric material, magnesium molybdenum oxide (Mg2Mo3O8) is presented. High-quality ultrathin Mg2Mo3O8 crystals are synthesized using chemical vapor deposition (CVD). Ultrathin Mg2Mo3O8 has a wide bandgap (≈4.4eV) and nonlinear optical response. Mg2Mo3O8 crystals of varying thicknesses exhibit out-of-plane ferroelectric properties at room temperature, with ferroelectricity retained even at a 2nm thickness. The Mg2Mo3O8 exhibits a relatively large remanent polarization ranging from 33 to 52µCcm- 2, which is tunable by changing its thickness. Notably, Mg2Mo3O8 possesses a high Curie temperature (>980°C) across various thicknesses. Moreover, the as-grown Mg2Mo3O8 crystals display remarkable stability under harsh environments. This work introduces nolanites-type crystal into ultrathin ferroelectrics. The scalable synthesis of stable ultrathin ferroelectric Mg2Mo3O8 expands the scope of ferroelectric materials and may prosper applications of ferroelectrics.

Superior Phonon-Limited Exciton Mobility in Lead-Free Two-Dimensional Perovskites.

Tin-based two-dimensional (2D) perovskites are emerging as lead-free alternatives in halide perovskite materials, yet their exciton dynamics and transport remain less understood due to defect scattering. Addressing this, we employed temperature-dependent transient photoluminescence (PL) microscopy to investigate intrinsic exciton transport in three structurally analogous Sn- and Pb-based 2D perovskites. Employing conjugated ligands, we synthesized high-quality crystals with enhanced phase stability at various temperatures. Our results revealed phonon-limited exciton transport in Sn perovskites, with diffusion constants increasing from 0.2 cm2 s-1 at room temperature to 0.6 cm2 s-1 at 40 K, and a narrowing PL line width. Notably, Sn-based perovskites exhibited greater exciton mobility than their Pb-based equivalents, which is attributed to lighter effective masses. Thermally activated optical phonon scattering was observed in Sn-based compounds but was absent in Pb-based materials. These findings, supported by molecular dynamics simulations, demonstrate that the phonon scattering mechanism in Sn-based halide perovskites can be distinct from their Pb counterparts.

Strain Engineering: Perfecting Freestanding Perovskite Oxide Fabrication.

Freestanding oxide membranes provide a promising path for integrating devices on silicon and flexible platforms. To ensure optimal device performance, these membranes must be of high crystal quality, stoichiometric, and their morphology free from cracks and wrinkles. Often, layers transferred on substrates show wrinkles and cracks due to a lattice relaxation from an epitaxial mismatch. Doping the sacrificial layer of Sr3Al2O6 (SAO) with Ca or Ba offers a promising solution to overcome these challenges, yet its effects remain critically underexplored. A systematic study of doping Ca into SAO is presented, optimizing the pulsed laser deposition (PLD) conditions, and adjusting the supporting polymer type and thickness, demonstrating that strain engineering can effectively eliminate these imperfections. Using SrTiO3 as a case study, it is found that Ca1.5Sr1.5Al2O6 offers a near-perfect match and a defect-free freestanding membrane. This approach, using the water-soluble Bax/CaxSr3-xAl2O6 family, paves the way for producing high-quality, large freestanding membranes for functional oxide devices.

Strain and optical characteristics analyses of three-dimentional self-ordered multilayered SiGe nanodots by photoluminescence and Raman spectroscopy

The strain state, optical properties, and band structure of the self-ordered multilayered silicon-germanium (SiGe) nanodots, which are staggered and dot-on-dot alignment and embedded by Si spacer, were evaluated by Raman spectroscopy and low-temperature photoluminescence (PL). These results suggest that the compressive strain applied to the staggered nanodots is smaller than that of the dot-on-dot nanodots, which contributes to the shrinking of the bandgap of the staggered nanodots. Strong PL intensity was observed from the nanodots compared to the single crystalline bulk SiGe due to the carrier confinement and high crystal quality of the nanodots. The stack-controlled nanodots showed a redshift of the PL peaks compared to the bulk SiGe and the effect of strain induced in SiGe nanodots might not be enough to explain this phenomenon. The cause of the redshift was clarified by considering the hetero band structure of the nanodots and the tensile strained spacer.

Dehydroxylation and structural transition in α-GaOOH investigated by in situ X-ray diffraction

Ga2O3 is an ultra-wide-bandgap semiconductor that is receiving considerable attention due to its promising applications in high-frequency, high-power and high-temperature settings. It can be prepared by calcinating the α-GaOOH phase at high temperatures. Understanding the significance of hydroxyl groups in α-GaOOH, dehydroxylation and the structural transition at high temperatures has become a key aspect of preparing high-quality α-Ga2O3 crystals, but the underlying mechanism remains unknown. In this research, α-GaOOH nanorods were hydrothermally synthesized and the structural evolution of α-GaOOH investigated at high temperatures by in situ X-ray diffraction. The hydroxyl group in α-GaOOH squeezes Ga3+ from the center of the [GaO6] octahedron, resulting in deformed [GaO6] octahedra and significant microstrain in α-GaOOH. The hydroxyl groups are peeled off from α-GaOOH when the temperature exceeds 200°C, resulting in contraction along the c-axis direction and expansion along the a-axis direction of α-GaOOH. When the temperature exceeds 300°C, the Ga—O bond inside the double chains preferentially breaks to generate square-wave-like octahedron chains, and the neighboring chains repack to form hexagonal-like octahedron layers. The octahedron layers are packed up and down by electrostatic interaction to generate the α-Ga2O3 structure. This work highlights the role of hydroxyl groups in α-GaOOH, dehydroxylation and the structural transition on the atomic scale, providing valuable guidelines for the fabrication of high-quality α-Ga2O3 crystals.

Molecular Symmetry of Small-Molecule Passivating Agents Improves Crystal Quality of Perovskite Solar Cells.

Direct interaction with the defect sites of perovskite, functional groups have become the focal point of attention as passivating agents. However, the molecular parent nucleus determines the overall physical properties of the molecule, including the push-pull electronic characteristics of the functional groups, which poses significant challenges in terms of selectivity. Here, we discovered that the binary acid structure based on thiophene as the parent nucleus, due to changes in molecular symmetry, caused significant changes in the molecular dipole moment, resulting in significant changes in the passivation effects on under-coordinated Pb2+ in perovskite solar cells. For the axially symmetric thiophen-2,5-dicarboxylic acid (TPDC), the high dipole moment formed a concentrated surface negative potential on the carboxyl group, showing significant superiority over the centrally symmetric thieno[3,2-b] thiophene-2,5-dicarboxylic acid (TTDC) in forming high-quality perovskite crystals, suppressing charge recombination, enhancing effective charge transport, and raising internal electric fields. The power conversion efficiencies of the fully printable mesoscopic perovskite solar cells based on TPDC and TTDC were 17.15 % and 14.79 %, respectively, exhibiting important research value in the field of small molecule passivation mechanism research.

Refolding, Crystallization, and Crystal Structure Analysis of a Scavenger Receptor Cysteine-Rich Domain of Human Salivary Agglutinin Expressed in Escherichia coli

Scavenger receptors are a protein superfamily that typically consists of one or more repeats of the scavenger receptor cysteine-rich structural domain (SRCRD), which is an ancient and highly conserved protein module. The expression and purification of eukaryotic proteins containing multiple disulfide bonds has always been challenging. The expression systems that are commonly used to express SRCRD proteins mainly consist of eukaryotic protein expression systems. Herein, we established a high-level expression strategy of a Type B SRCRD unit from human salivary agglutinin using the Escherichia coli expression system, followed by a refolding and purification process. The untagged recombinant SRCRD was expressed in E. coli using the pET-32a vector, which was followed by a refolding process using the GSH/GSSG redox system. The SRCRD expressed in E. coli SHuffle T7 showed better solubility after refolding than that expressed in E. coli BL21(DE3), suggesting the importance of the disulfide bond content prior to refolding. The quality of the refolded protein was finally assessed using crystallization and crystal structure analysis. As proteins refolded from inclusion bodies exhibit a high crystal quality and reproducibility, this method is considered a reliable strategy for SRCRD protein expression and purification. To further confirm the structural integrity of the refolded SRCRD protein, the purified protein was subjected to crystallization using sitting-drop vapor diffusion method. The obtained crystals of SRCRD diffracted X-rays to a resolution of 1.47 Å. The solved crystal structure appeared to be highly conserved, with four disulfide bonds appropriately formed. The surface charge distribution of homologous SRCRD proteins indicates that the negatively charged region at the surface is associated with their calcium-dependent ligand recognition. These results suggest that a high-quality SRCRD protein expressed by E. coli SHuffle T7 can be successfully folded and purified, providing new options for the expression of members of the scavenger receptor superfamily.

Metalorganic Chemical Vapor Deposition of AlN on High Degree Roughness Vertical Surfaces for MEMS Fabrication

AbstractAluminum nitride (AlN) grown on vertical surfaces can be utilized for the fabrication of advanced piezoelectric microelectromechanical systems (MEMS). The in‐plane motion of the parts of a MEMS element is possible when AlN is deposited on the vertical surfaces of the moving structure. For the best device performance, AlN must have high crystal quality, uniform coverage of the vertical sidewalls, and c‐axis crystalline orientation perpendicular to the plane of a vertical surface. The impact of the surface roughness (Rq) of the vertical sidewalls formed in Si using wet and dry etching methods on the crystal quality, crystallographic orientation, and uniformity of the metalorganic chemical vapor deposited (MOCVD) AlN thin films is studied in this paper. In both cases, AlN films demonstrated full sidewall coverage and grew crystalline in the c‐axis direction. AlN films grown on vertical Si surfaces achieved using anisotropic wet etching are highly crystalline and oriented in [0001] direction, while the films grown on vertical surfaces achieved using dry etching displayed a lower level of alignment with the Si sidewalls.

Narrowing band gap and enhanced optoelectronic properties in methylammonium lead chloride perovskite under pressure

In this study, we explore the impact of hydrostatic pressure on the structural stability, elastic properties, mechanical behavior, thermodynamics, and optoelectronic characteristics of lead halide perovskite, specifically focusing on CH3NH3PbCl3. Through high-level ab initio simulation techniques, we investigate the lattice squeezing effects on this methylammonium lead chloride perovskite. Our findings reveal that applying hydrostatic pressure squeezes lattice parameters, influences the electronic profile, and results in spin-split band edges. The band gaps in compressed perovskites are observed to be narrower, with the potential for pressure-induced closures, offering new electronic features under various thermodynamic conditions. Because of the high-quality crystal and its optimal optical band gap, we successfully construct an efficient UV-photodetector, highlighting its promising applications in optoelectronics. This work contributes to a deeper atomistic understanding of inorganic halide perovskite behavior under external pressure and demonstrates the potential for realizing enhanced electronic functionalities through pressure conditions.

Ag-LSPR and molecular additive: A collaborative approach to improve the photovoltaic performance of perovskite solar cells

The development of multi-functional synergetic strategy with defect passivation and optical management is expected to further improve the photovoltaic performance of perovskite solar cells (PSCs). Herein, the small organic molecule of 4-trifluoromethyl pyridine (TFP) and Ag nanoparticle modified by TFP (Ag@TFP) with local surface plasmon resonance (LSPR) effects were introduced into PSCs. After investigating their different intervention ways in PSCs, a novel technique has been proved to own the ability to achieve the best photovoltaic performance of PSCs, i.e. TFP was introduced into the perovskite layer by anti-solvent method, and then a layer of Ag@TFP was deposited on the perovskite layer. The TFP can both coordinate with Pb related defects and form hydrogen bonds with MA+ and FA+ to effectively inhibit ion migration, so that the perovskite films with high crystal quality and improved stability can be obtained. The further deposition of Ag@TFP enhances the light absorption of perovskite via far-field light scattering effects and produces hot electrons for injection, so that the Jsc and Voc can be greatly increased. Meanwhile, an enhanced near-field electromagnetic field of Ag@TFP increases the build-in field of device, and a more matched energy level alignment has been formed, which greatly accelerates the charge transfer from perovskite to HTL. As a result, the highest PCE of 23.86 % has been achieved in the Ag@TFP-TFP based Cs0.069FA0.826MA0.105Pb(I0.955Br0.045)3 PSCs. This work not only provides an effective approach to improve the photovoltaic performance of PSCs, but also open a new gate to design synergetic strategy with multifunction for prompting the development of PSCs.