Crystal Flakes Research Articles

Structural and weak antilocalization analysis of topological single-crystal SnSb2Te4

Here, we report successful single crystal growth of SnSb2Te4 using the self-flux method. Unidirectional crystal growth is confirmed through X-ray Diffraction (XRD) pattern taken on mechanically cleaved crystal flake while the rietveld refined Powder XRD (PXRD) pattern confirms the phase purity of the grown crystal. Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) image and Energy Dispersive X-Ray analysis (EDAX) confirm crystalline morphology and exact stoichiometry of constituent elements. Vibrational Modes observed in Raman spectra also confirm the formation of the SnSb2Te4 phase. DC resistivity (ρ-T) measurements confirm the metallic character of the grown crystal. Magneto-transport measurements up to±5T show a non-saturating low magneto-resistance percentage (MR%). V-type cusp and Hikami Larkin Nagaoka (HLN) fitting at lower field confirms the Weak Anti-localization (WAL) effect in SnSb2Te4. Density Functional Theory (DFT) calculations were showing topological non-trivial electronic band structure. It is the first-ever report on MR study and WAL analysis of SnSb2Te4 single crystal.

Anisotropic magnetoresistance in room temperature ferromagnetic single crystal CrTe flake

Chromium tellurides have triggered tremendous investigations in physics and materials science, where their unique properties offer excellent opportunities for spintronic applications. Here, we report anisotropic magnetoresistance (AMR) of ferromagnetic CrTe single crystal flake grown by chemical vapor deposition. An individual hexagonal flake exhibits an easy magnetization axis along its normal direction, and cooling from room temperature to low temperature, its electrical resistance measured with the magnetization parallel to current geometry is larger than that for the perpendicular to the current geometry, indicating the presence of an AMR behavior. The AMR ratio has been found to increase with decreasing temperature and is 5.2% at 5 K, comparable with general magnetic transition metal and alloy. This suggests CrTe single crystal flake to be a promising magnetic material for spintronics applications.

Switching ferroelectricity in SnSe across phase transition

We experimentally investigate transport properties of a hybrid structure, which consists of a thin single crystal SnSe flake on a top of 5 μm spaced Au leads. The structure initially is in highly conductive state, while it can be switched to the low-conductive one at high currents due to the Joule heating of the sample, which should be identified as phase transition to the symmetric β-Cmcm phase in SnSe. For the highly conductive state, there is significant hysteresis in curves at low biases, so the sample conductance depends on the sign of the applied bias change. This hysteretic behavior reflects slow relaxation due to additional polarization current in the ferroelectric SnSe phase, which we confirm by direct measurement of time-dependent relaxation curves. In contrast, we observe no noticeable relaxation or low-bias hysteresis for the quenched low-conductive phase. Thus, the ferroelectric behavior can be switched on or off in transport through hybrid SnSe structure by controllable phase transition to the symmetric β-Cmcm phase. This result can also be important for nonvolatile memory development, e.g., phase change memory for neuromorphic computations or other applications in artificial intelligence and modern electronics.

Dependence of the polycarbonate mechanical performances on boron nitride flakes morphology

A key requirement for the exploitation of two-dimensional (2D)-crystals in the field of composites relies on their large-scale production. In this respect, liquid phase exfoliation of layered-crystals is emerging as one of the most promising approaches for the scalable production of high-quality 2D-crystals. However, the dependence of the 2D crystal flakes morphology, i.e. thickness and lateral size, on the mechanical properties of the polymer composites is not fully understood yet. Herein, we tackle this issue by designing an environmentally friendly approach, based on the exfoliation of bulk hexagonal-boron nitride (h-BN), widely used as filler in polymer composites for its high intrinsic stiffness, i.e. approaching 1 TPa, in a water/surfactant solution with controlled thickness and lateral size by using cascade ultra-centrifugation. Our approach allows us to obtain two populations of flakes with aspect ratio, i.e. lateral size over thickness, equal to 250 and 350, respectively. The h-BN flakes with tuned aspect ratio are subsequently used as filler in a polycarbonate (PC) matrix by exploiting solution blending in 1,3-dioxolane, a solvent with Hansen’s solubility parameters matching the ones of h-BN, thus enhancing the dispersion of the filler inside the matrix, as evaluated by Raman mapping. We tested the composite mechanical properties finding that flakes with higher aspect ratio show superior reinforcements in terms of both ultimate tensile strength and Young’s modulus, compared with their lower aspect ratio counterparts. As example, at 0.1 wt% of loading, the difference in reinforcement in terms of Young’s Modulus is of 56 MPa, being the increment, compared to pristine PC, of ∼22% for composites produced with higher aspect ratio fillers, whereas it is instead of only ∼17% for lower aspect ratio fillers.

Thermoelectric response as a tool to observe electrocaloric effect in a thin conducting ferroelectric SnSe flake

We experimentally investigate thermoelectric response of a 100~nm thick SnSe single crystal flake under the current-induced dc electric field. Thermoelectric response appears as a second-harmonic transverse voltage $V_{xy}^{2\omega}$, which reflects temperature gradient across the sample due to the Joule heating by harmonic ac excitation current $I_{ac}$. In addition to strongly non-monotonous dependence $V_{xy}^{2\omega}$, we observe that dc field direction controls the sign of the temperature gradient in the SnSe flake. We provide arguments, that electrocaloric effect is the mostly probable reason for the results obtained. Thus, our experiment can be understood as demonstration of the possibility to induce electrocaloric effect by in-plane electric field in conducting ferroelectric crystals and to detect it by thermoelectric response.

Observation of the Out‐of‐Plane Polarized Spin Current from CVD Grown WTe2

AbstractWeyl semimetal Td‐phase WTe2 possesses the spin‐resolved band structure with strong spin–orbit coupling, holding promises as a useful spin source material. The noncentrosymmetric crystalline structure of Td‐WTe2 endows the generation of the out‐of‐plane polarized spin, which is of great interest in magnetic memory applications. Previously, WTe2 was explored in spin devices based on mechanically exfoliated single crystal flakes with a size of micrometers. For practical spintronics applications, it is highly desirable to implement wafer‐scale thin films. In this work, centimeter‐scale chemical vapor deposition (CVD) grown Td‐WTe2 thin films are used and the spin current generation is studied by the spin torque ferromagnetic resonance (ST‐FMR) technique. The in‐plane and out‐of‐plane spin conductivities of 7.36 × 103 () (Ωm)–1 and 1.76 × 103 () (Ωm)–1, respectively, are found in CVD‐growth 5 nm‐WTe2. The current‐induced magnetization switching in WTe2/NiFe is demonstrated at room temperature in the domain wall motion regime, which may invigorate potential spintronic device innovations based on Weyl semimetals.

Inhomogeneous Broadening of Photoluminescence Spectra and Kinetics of Nanometer-Thick (Phenethylammonium)2PbI4 Perovskite Thin Films: Implications for Optoelectronics.

An outstanding potentiality of layered two-dimensional (2D) organic–inorganic hybrid perovskites (2DHPs) is in the development of solar cells, photodetectors, and light-emitting diodes. In 2DHPs, an exciton is localized in an atomically thin lead(II) halide inorganic layer of sub-nanometer thickness as in a quantum well sandwiched between organic layers as energetic and dielectric barriers. In previous years, versatile optical characterization of 2DHPs has been carried out mainly for thin flakes of single crystals and ultrathin (of the order of 20 nm) polycrystalline films, whereas there is a lack of optical characterization of thick (hundreds of nanometers) polycrystalline films, fundamentals for fabrication of devices. Here, with the use of photoluminescence (PL) and absorption spectroscopies, we studied the exciton behavior in ∼200 nm polycrystalline thin films of 2D perovskite (PEA)2PbI4, where PEA is phenethylammonium. Contrary to the case of ultrathin films, we have found that peak energies and line width of the excitonic bands in our films demonstrate unusual extremely weak sensitivity to temperature in 20–300 K diapason. The excitonic PL band is characterized by a significant (∼30 meV) Stokes shift with respect to the corresponding absorption band as well as by a full absence of the exciton fine structure at cryogenic temperatures. We suggest that the observed effects are due to the large inhomogeneous broadening of the excitonic PL and absorption bands resulting from the (PEA)2PbI4 band gap energy dependence on the number of lead(II) halide layers of individual crystallites. The characteristic time of the exciton energy funneling from higher- to lower-energy crystallites within (PEA)2PbI4 polycrystalline thin films is about 100 ps.

Inhibitory effect of antioxidants on biodiesel crystallization: Revealing the role of antioxidants

Effect of six antioxidants (butylated hydroxytoluene, butyl hydroxyanisole, di-tert-butylhydroquinone, tert-butyl hydroquinone, propyl gallate, and pyrogallic acid) on crystallization properties of biodiesel was systematically investigated. Results showed that all the six antioxidants effectively inhibited biodiesel crystallization at low temperatures as reflected by the decrease of cold filter plugging point by 1 ~ 3℃, solid fat content by 0.01 ~ 2.30%, crystallization rate from 10-4 to 10-5 ~ 10-6 k/min, crystal size from 214 × 14 ~ 357 × 43 to 71 × 14 ~ 286 × 29 (length × width, μm × μm), the absolute values of crystallization enthalpy changes by 1.5 ~ 5.5 J/g. The minimum concentrations of antioxidants for biodiesel to reach the induction period (8 h) regulated by the European Union standard were 500 mg/kg for TBHQ, PG, and PY, 1000 mg/kg for BHA and DBHQ, and 2000 mg/kg for BHT, respectively. Antioxidants were inserted between initial crystal nucleuses through hydrogen bonds. The large steric hindrance of antioxidants inhibited the clustering of initial crystal nucleuses, thus inhibiting the growth of methyl ester crystals. Biodiesel with the six antioxidants all had the same crystalline form (two-dimensional flake crystals). The weaker inhibitory effect of BHA than the other five antioxidants which didn’t present significant difference in inhibiting biodiesel crystallization was because the methoxy group of BHA cannot form a hydrogen bond well with the carbonyl group of methyl ester molecule.

Bioinspired Reactive Interfaces Based on Layered Double Hydroxides-Zn Rich Hydroxyapatite with Antibacterial Activity

This work is focused on the preparation and multi-technique characterization of potentially biocompatible reactive interfaces obtained by combining layered double hydroxides (LDHs) and hydroxyapatite (HA). Antimicrobial and osteoinductive metallic ions as Zn2+ and Ga3+ were chosen as intralayer constituents of LDH to obtain ZnAl and ZnAlGa systems. These LDHs, exchanged with dihydrogenphosphate anions, promoted the precipitation of HA on the LDH surface yielding HA@LDH composites. X-ray diffraction quantitative analysis, through the Rietveld refinement method, coupled with elemental analysis and micro-Raman spectroscopy showed the formation of a mixed Ca-Zn HA phase. Scanning electron microscopy revealed that HA, in the presence of LDH, grew preferentially along its a-axis, thus crystallizing mainly in the form of flake crystals. LDH and HA@LDH composites showed antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa at not cytotoxic concentrations for human osteoblasts (hFob 1.19), especially when Ga cations were present in the LDH structure. The effect of the presence of HA in the composites on the bone-bonding ability and on human osteoblast proliferation was also investigated. The HA seemed to reduce the toxicity of the LDH toward human osteoblast while did not affect the bone-bonding ability. This multidisciplinary study provides the bio-chemical, structural characterization of new LDH and HA@LDH composites, evaluating also their bioactivity to be potentially applicable to titanium-based prostheses.

Ultrasonic-assisted top-down preparation of NbSe2 micro/nanoparticles and hybrid material as solid lubricant for sliding electrical contact

2H-NbSe2 single crystal flake (ca. 2 × 2 × 0.5 mm in size) by chemical vapor transport is employed as the precursor for a top-down preparation of NbSe2 micro/nanoparticles by two kinds of processes, i.e. (1) mechanical exfoliation; (2) ultrasonic-assisted exfoliation in ethanol without ageing and with ageing for 210 days. NbSe2 micro/nanoparticles are applied on top of a Cu disk by a drop-casting process and the tribological property in sliding against a Cu pin under sliding electrical contact is investigated at room temperature. Mechanical exfoliation produces NbSe2 microplatets with typical sizes of 1 μm to 30 μ m with a thickness less than 2 μm. Ultrasonic-assisted exfoliation without aging facilitates the formation of NbSe2 micro/nanoplatets with sizes of 0.1 μm to 25 μm and nano-whiskers with 100 nm in diameter and 1 ~ 3 μm in length, but Nb2O5 and Se are also found on the basis of XPS results. Prolonged aging of the suspensions modifies the morphology by converting platets and whiskers into corrugated floccules (hybrid material), which are composed of Nb2O5, Se, NbSe2, and graphene. Notably, NbSe2 micro/nanoparticles by ultrasonic-assisted exfoliation without ageing exhibit an excellent lubricating property with low friction coefficient (0.3), mild wear, and longer wear lifetime (120 min) than that of mechanical exfoliated NbSe2 microplatets (10 min). The wear lifetime for the aged NbSe2 micro/nanoparticles can be as long as 504 min and are 4.2 times of the sample without aging, which can be a good solid lubricant for sliding electrical contact

Photoelectrochemical performance of TiO2 photoanodes: Nanotube versus nanoflake electrodes

In the present work, we compare the photoresponse of vertically erected (VE) single crystal anatase layers with that of widely used TiO2 nanotube layers. These VE-anatase layers were grown hydrothermally, directly on fluorine-doped tin oxide (FTO) glass, and consist of an array of anatase single crystal flakes with preferred (001) facets. As formed, these single crystal layers are fluorine terminated – this termination can be removed by a thermal treatment in air. We compare the photocurrent magnitude and photocurrent transients using intensity-modulated photocurrent spectroscopy (IMPS). We find that the “de-fluorinated” VE-anatase layers show significantly higher photocurrents than the comparable nanotube layers. This high efficiency of the VE-anatase layers is due to the electron transport being 100 times faster in these single crystal electrodes, provided that the blocking fluorine termination is removed.

Fabrication of Bi$_{2}$Sr$_{2}$CaCu$_{2}$O$_{8+x}$ ab-Plane Josephson Junctions by a Focused Helium Ion Beam

We report the fabrication and measurement of an ab-plane Josephson junction created in an 80-nm thick thin-film-like exfoliated Bi <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> Sr <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> CaCu <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">8+x</sub> $ single crystal flake. The junctions are formed using ion irradiation from a focused helium ion beam which locally converts the material from a superconductor to an insulator. Current-voltage characteristics show the device to be a weak link with I <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">C</sub> R <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">N</sub> product of 40 μA. The critical current exhibits a well-behaved Fraunhofer pattern with magnetic field applied perpendicular to the film confirming the DC Josephson effect. Simulations reveal a large amount of ion straggle deep into the film which is likely influencing the electrical properties. Combination of these devices with the intrinsic junctions could provide a method for multi-dimensional Josephson devices.

Purification of carbazole by solvent crystallization under two forced cooling modes

• Gradual cooling mode is favorable to the purification of carbazole. • Anthracene can promote the growth of carbazole in solution. • Chlorobenzene is an ideal solvent for carbazole refining. To identify the effect of solvents and anthracene on the purification of carbazole, the solvent crystallization of carbazole was investigated with xylene, chlorobenzene and tetrachloroethylene (TCE) as solvents under two forced circulation cooling (FCC) modes. The co-crystalline experimental data were obtained from runs carried out at different anthracene levels between 1% (mass) and 10% (mass). The results showed that a uniform flake carbazole crystal obtained when using xylene and chlorobenzene under the FCC-1 mode with gradual cooling rate. Nevertheless, fine flake crystals grown under shock cooling of FCC-2 mode. It is beneficial to improving the purity of carbazole with chlorobenzene as solvent under cooling mode of FCC-1. Anthracene could promote the growth of carbazole in solution, and it has a significant influence on the purification of carbazole.

Experimental setup for the Seebeck and Nernst coefficient measurements.

A new experimental setup is designed for the measurement of Seebeck and Nernst coefficients on the single crystal flakes and polycrystalline samples. The setup utilizes the multifunctional probe assembly of the physical property measurement system by Quantum Design, Inc. and can measure in the temperature range of 1.8 K-380 K up to 8 T magnetic fields. The experimental measurement was fully automated through a computer using the code written in LabVIEW software. The setup is capable of measurements on samples as small as 2 × 1 mm2 in size and thickness as small as a few micrometers, which is quite important for the crystal flakes grown using the vapor transport method. The determination of the coefficients is based on the quasi-static approach, with the thermal gradient of 0.2 K-1.2 K across the sample in the measured temperature range of 1.8 K-300 K. The sensitivity of the instrument is better than 0.1 µV/K, and the accuracy is better than ∼0.5 µV/K, which can be further improved with the better quality of electrical contacts on the sample. The Seebeck and Nernst coefficient measurements performed on some well-studied semimetallic (bismuth), thermoelectric (Bi2Se3), and superconducting (FeTe0.5Se0.5) systems are also presented.

Single crystal flake parameters of MoS2 and MoSe2 exfoliated using anodic bonding technique and its potential in rapid prototyping

Rapid prototyping of devices using exfoliated Molybednum di-Sulphide (MoS2) and Molybdenum di-Selenide (MoSe2) requires an experimental protocol for maximizing the probability of realizing flakes with desired physical dimension and properties. In this work, we analyzed the size and thickness distribution of MoS2 and MoSe2 single crystalline flakes exfoliated using anodic bonding technique and established a correlation between physical dimension of the flakes and the bonding parameters. Anodic bonding was carried out by applying a fixed voltage of 200 V with a set temperature of 150 °C for four different bonding time intervals. On analyzing the flake parameters from the four anodic bonded substrates using the optical and atomic force microscopy, it is found that the probability of getting flakes with large lateral size (>200 μm) increases as the bonding time interval is increased. Most of these large sized flakes have thickness of more than one hundred mono-layers and a tiny fraction of them have thickness of the order of few monolayers. A similar trend was also observed for MoSe2 single crystals. To demonstrate the feasibility of this technique in rapid prototyping, ultra thin MoS2 flakes was directly bridged between two ITO electrodes and their transport properties was investigated. Micro-Raman and photoluminescence studies were taken on selected regions of the thicker and thinner exfoliated flakes and their physical properties are compared.

Carbon Dioxide Conversion with High-Performance Photocatalysis into Methanol on NiSe2/WSe2

Climate change has been recognized as a threatening environmental problem around the world. CO2 is considered to be the main component of greenhouse gas. By using solar energy (light energy) as the energy source, photocatalytic conversion is one of the most effective technologies to reveal the clean utilization of CO2. Herein, using sodium tungstate, nickel nitrate, and selenium powder as the main raw materials, the high absorption and utilization of WSe2 for light energy and the high intrinsic conductivity of NiSe2 were combined by a hydrothermal method to prepare NiSe2/WSe2 and hydrazine hydrate as the reductant. Then, high-performance NiSe2/WSe2 photocatalytic material was prepared. The characterization results of XRD, XPS, SEM, specific surface area, and UV-visible spectroscopy show that the main diffraction peak of synthesized NiSe2/WSe2 is sharp, which basically coincides with the standard card. After doping NiSe2, the morphology of WSe2 was changed from a flake shape to smaller and more trivial crystal flakes, which demonstrates richer exposed edges and more active sites; the specific surface area increased from 3.01 m2 g−1 to 8.52 m2 g−1, and the band gap becomes wider, increasing from 1.66 eV to 1.68 eV. The results of a photocatalytic experiment show that when the prepared NiSe2/WSe2 catalyst is used to conduct photocatalytic reduction of CO2, the yield of CH3OH is significantly increased. After reaction for 10 h, the maximum yield could reach 3.80 mmol g−1, which presents great photocatalytic activity.

Spontaneous Growth of CaBi4Ti4O15 Piezoelectric Crystal Using Mixed Flux Agents

The bismuth layer-structured ferroelectrics (BLSFs) materials have potential for high-temperature piezoelectric applications. Among these piezoelectric materials, the CaBi4Ti4O15 (CBT) piezoelectric ceramic with a high decomposition temperature of about 1250 °C attracts a lot of attention. Achieving a CBT single crystal is a significant way to improve its piezoelectric properties. For this purpose, the flux system for growing CBT crystal was explored in this study. The optimum flux composition ratio was found to be PbO:B2O3:CBT = 3:3:1 in mol%, where the PbO–B2O3 mixtures were used as a flux system. Millimeter size flake-shaped CBT crystals were obtained using the spontaneous growth process for the first time. The relationship between the crystal structure and flake growth habit was analyzed. In addition, the bandgap was evaluated by the combination of transmittance spectrum and first-principle calculations. Besides, the piezoelectric property was predicted from the perspective of polyhedral distortion, which indicated the potential of CBT crystal for piezoelectric applications.

Tailoring the phase transition and electron-phonon coupling in 1T′−MoTe2 by charge doping: A Raman study

Transition metal dichalcogenides (TMDs) are a class of widely studied 2D layered materials which exist in various polymorphs. The 1T' phase of MoTe2 is of prime importance as it has been reported to show quantum spin hall (QSH) behavior with a fairly large band-gap of ~ 60 meV, in contrast to most QSH materials known. It is noteworthy that though the monolayer 1T'-MoTe2 was initially predicted to show the QSH behavior, recent theoretical studies claim that the few-layered counterparts also exhibit higher order topological behavior. Besides, 1T'-MoTe2 also undergoes a hysteretic phase transition to the Td phase (which is a type-II Weyl semimetal) by breaking the inversion symmetry of the crystal. While the phase transition between these two topological phases is of utmost importance, its study has been mostly restricted to bulk single crystal flakes, thereby not sufficiently exploring the effect of dimensionality. We have studied the phase transition in 1T'-MoTe2 as a function of flake-thickness. Though our Raman studies show a suppression of the phase transition in the thin (thickness <10 nm) flakes [similar to the report Phys. Rev. B 97, 041410 (2018)], we have experimentally demonstrated the possibility of stabilizing the desired phase (1T' or Td) at room temperature by charge doping. Further, we have observed clear signatures of electron-phonon coupling in MoTe2, which evolves as a function of flake-thickness and charge doping.

Crystal structure of ClA1, a type of chlorinase from soil bacteria

Halogenated compounds are widely discovered in nature, and many of them exhibit biological activities, such as an important chlorinated natural product salinosporamide A serving as a potential anticancer agent. Compared with bromination, iodination and fluorination, chlorination is the mainly important modification. To shed light on the mechanism of SAM-dependent chlorinases, a recombinant chlorinase ClA1 was expressed in Escherichia coli and further purified for crystallization and X-ray diffraction experiments. The flake crystals of ClA1 were able to diffract to a resolution of 1.85 Å. The crystals belonged to space group R3, with unit-cell parameters α = β = 90.0°, γ = 120.0°. By determining the structure of ClA1, it is revealed that the side chain of Arg242 in ClA1 may have contacts with the L-Met. However, in SalL the equivalent Arg243’s side chain is far from L-Met. Considering the ClA1 and SalL are from different environments and their enzyme kinetics are quite different, it is suggested that the side chain conformation differences of the conserved arginine are possibly related with the enzyme activity differences of the two chlorinases.

Resistive memory based on single-crystalline black phosphorus flake/HfOx structure

Two-dimensional materials are gaining more and more attention in the field of electronic devices because of their unique advantages, such as high crystalline quality and clean and flat contact planes; compared to traditional materials, the use of two-dimensional materials as the working layer of a resistive random-access memory (RRAM) has the potential to further reduce the device size and enhance its performance. Herein, a black phosphorus (BP) single crystal flake passivated by hafnium oxide is used as the working layer for an RRAM. The devices show a switching on/off ratio of 102 in more than 100 cycles, and others can even be as high as 106. We speculated the working mechanism of the BP RRAM based on the results of serial experiments and transport analysis.