Millimeter-sized Single Crystals Research Articles

The mechanical properties of Al3Sc single crystal investigated by nanoindentation using Hertzian elasticity theory method and Oliver-Pharr method

The crystal structure, orientation, reduced modulus, and hardness of Al3Sc single crystal were studied using X-ray diffraction (XRD), electron backscatter diffraction (EBSD) and nanoindentation techniques, combined with Hertzian elastic theory method (Hertz) and Oliver-Pharr method (O&P). Millimeter-sized Al3Sc single crystals were prepared using quasi-equilibrium solidification of hypereutectic Al-15(wt %) Sc alloy. The XRD results showed that the samples were composed of L12-Al3Sc and Al phases. The EBSD and nanoindentation results showed that for five Al3Sc single crystals with different orientations, the reduced moduli measured by Hertz method were 146.6 ± 0.4–148.3 ± 0.2 GPa; while measured by O&P method they were 147 ± 2–150 ± 3 GPa. The corresponding hardnesses were varied between 3.8 ± 0.1 and 3.9 ± 0.1 GPa. The Poisson's ratio and elastic constants were determined through iterative calculation based on the relationship between the reduced modulus and Young’s modulus at various orientations. The polycrystal elastic properties, bulk modulus, shear modulus and Young's modulus, were determined. The elastic constants c11, c12, and c44 were 179.2 ± 0.4, 44.1 ± 0.1, and 68.3 ± 0.3 GPa, respectively; the Poisson's ratio was 0.196 ± 0.001. The Young's modulus of five Al3Sc single crystals oriented in different directions was in the narrow range 161–164 GPa. The anisotropy factor of Al3Sc crystal was 1.011 ± 0.002, confirming that it is elastically isotropic. These results provide fundamental information for the research and development of the Al3Sc intermetallic compound and related alloys in future.

Single-Crystal Growth of a Cuprate Superconductor with the Highest Critical Temperature

Millimeter-sized single crystals of a trilayer cuprate superconductor (Hg,Re)Ba2Ca2Cu3O8+d, that exhibits the highest superconducting transition temperature under ambient pressure, were grown reproducibly and safely.

A zero-dimensional hybrid copper(I) bromide single crystal with highly efficient green emission.

Lead-free metal halides are considered as alternatives to lead-based perovskites due to their low toxicity, rich structural diversity, and high luminescence properties. We report millimeter-sized single crystals of a new zero-dimensional (0D) copper(I)-based hybrid material, (AEP)2Cu2Br6·2Br·2H2O (AEP = C6H18N33+), which exhibits bright broadband green photoluminescence (PL) at 510 nm with a Stokes shift of 220 nm and a PL lifetime of 121.1 μs. Density functional theory (DFT) calculations and experimental studies reveal that the green light can be attributed to self-trapping exciton (STE) emission. It is worth mentioning that this crystal has a high photoluminescence quantum yield (PLQY) of 90.5%, which is higher than most copper halides.

Nanoscale Study of the Polar and Electronic Properties of a Molecular Erbium(III) Complex Observed via Scanning Probe Microscopy

We successfully synthesized millimeter-sized single crystals of the molecular erbium(III) complex Er(acac)3(cphen), where acac = acetylacetonate and cphen = 5-chloro-1,10-phenanthroline. The novelty of this work stems from the exhaustive examination of the polar and electronic properties of the obtained samples at the macro-, micro-, and nanoscale levels. The single crystal X-ray diffraction method demonstrates the monoclinic (noncentrosymmetric space group P21) crystallographic structure of the synthesized samples and scanning electron microscopy exhibits the terrace–ledge morphology of the surface in erbium(III) crystals. By using the piezoelectric force microscopy mode, the origin of the polar properties and the hyperpolarizability in the synthesized samples were assigned to the internal domain structure framed by the characteristic terrace–ledge topography. The direct piezoelectric coefficient (~d33) was found to be intensely dependent on the local area and was measured in the range of 4–8 pm/V. A nanoscale study using the kelvin probe force and capacitance force (dC/dz) microscopy modes exposed the effect of the Er ions clustering in the erbium(III) complex. The PFM method applied solely to the Er ion revealed the corresponding direct piezoelectric coefficient (~d33) of about 4 pm/V. Given the maximum piezoelectric coefficient in the erbium(III) complex at 8 pm/V, we highlight the significant importance of the spatial coordination between the lanthanide ion and the ligands. The polar coordination between the lanthanide ion and the nitrogen and oxygen atoms was also corroborated by Raman spectroscopy supported by the density functional theory calculations. The obtained results can be of paramount importance for the application of molecular erbium(III) complex crystals in low-magnitude magnetic or electric field devices, which would reduce the energy consumption and speed up the processing switching in nonvolatile memory devices.

Growth of millimeter-sized high-quality CuFeSe2 single crystals by the molten salt method and study of their semiconducting behavior

An eutectic AlCl3/KCl molten salt method in a horizontal configuration was employed to grow millimeter-sized and composition homogeneous CuFeSe2 single crystals due to the continuous growth process in a temperature gradient induced solution convection. The typical as-grown CuFeSe2 single crystals in cubic forms are nearly 1.6 × 1.2 × 1.0 mm3 in size. The chemical composition and homogeneity of the crystals was examined by both inductively coupled plasma atomic emission spectroscopy and energy dispersive spectrometer with Cu:Fe:Se = 0.96:1.00:1.99 consistent with the stoichiometric composition of CuFeSe2. The magnetic measurements suggest a ferrimagnetic or weak ferromagnetic transition below TC = 146 K and the resistivity reveals a semiconducting behavior and an abrupt increase below TC.

Single Crystallization of Cs4PbBr6 Perovskite from Supersaturated Organic Solutions Optimized Through Solubility Studies.

We demonstrate the fabrication of millimeter-sized single crystals of 0D-Cs4PbBr6 grown in a supersaturated solution consisting of organic solvents without HBr (aq). One of the precursors, CsBr, was dissolved in ethylene glycol (EG) mixed with dimethyl sulfoxide, which is a good solvent for the other precursor, PbBr2. At a solvent ratio of 20 vol % EG, the solubility of cesium bromide decreased and the title compound, Cs4PbBr6, was selectively formed, whereas, with an EG ratio of 80 vol %, 3D-CsPbBr3 was formed. A phase diagram (solubility curve) of Cs4PbBr6 in the mixed solvent containing 20 vol % EG was obtained by visually observing dissolution and crystal precipitation while changing the temperature. Because the solubility was proportional to the temperature, the solubility curve demonstrated an upper critical solution phenomenon. The solubility near the boiling point of the solution (150 °C) was approximately 0.14 M. A single crystal of Cs4PbBr6 was formed by growing a seed crystal in a supersaturated solution on the low-temperature side of the solubility curve. X-ray analysis established the crystal structure; a fluorescence emission at 520 nm with a full width at half maximum of 20 nm confirms the composition of the single crystal to be Cs4PbBr6.

Terbium(iii)-based coordination polymer with millimeter-size single crystals and high selectivity and sensitivity for folic acid

Terbium(iii)-based coordination polymer with millimeter-size single crystals and high selectivity and sensitivity for folic acid.

RbCl·(H2SeO3)2: A Salt-Inclusion Selenite Featuring Short UV Cut-Off Edge and Large Birefringence

Birefringent materials are key components to control the light polarization in laser science and technology as well as optical communication. However, the performance of current commercial birefringent materials has been limited by the magnitude of birefringence, optical transparency range, or the attainability of large-scale single crystals. To explore new birefringent materials, we strategically incorporated a lone pair cation (Se4+) with large optical anisotropy, an alkali metal, and halogen ions (Rb+ and Cl-) with superior UV transparent capacity; thus a new compound, RbCl·(H2SeO3)2, was successfully discovered with the aid of the facile hydrothermal method. Interestingly, Rb-Cl chains locate in the [H2SeO3]∞ skeleton, which makes RbCl·(H2SeO3)2 a salt-inclusion selenite. Millimeter-sized single crystals (up to 4 × 2 × 1 mm3) were obtained, and the transmittance spectrum revealed that its UV cut-off edge can be as low as 230 nm. In addition, the calculated birefringence of RbCl·(H2SeO3)2 is 0.14 at 589 nm that is similar to the birefringent value of famous α-BaB2O4. Wide UV transparency, large birefringence, and feasible crystal growth make RbCl·(H2SeO3)2 a new member of birefringent materials for UV light applications.

Anisotropic Band-Edge Absorption of Millimeter-Sized Zn(3-ptz)2 Single-Crystal Metal-Organic Frameworks.

Metal–organic frameworks (MOFs) have emerged as promising tailor-designed materials for developing next-generation solid-state devices with applications in linear and nonlinear coherent optics. However, the implementation of functional devices is challenged by the notoriously difficult process of growing large MOF single crystals of high optical quality. By controlling the solvothermal synthesis conditions, we succeeded in producing large individual single crystals of the noncentrosymmetric MOF Zn(3-ptz)2 (MIRO-101) with a deformed octahedron habit and surface areas of up to 37 mm2. We measured the UV–vis absorption spectrum of individual Zn(3-ptz)2 single crystals across different lateral incidence planes. Millimeter-sized single crystals have a band gap of Eg = 3.32 eV and exhibit anisotropic absorption in the band-edge region near 350 nm, whereas polycrystalline samples are fully transparent in the same frequency range. Using solid-state density functional theory (DFT), the observed size dependence in the optical anisotropy is correlated with the preferred orientation adopted by pyridyl groups under conditions of slow crystal self-assembly. Our work thus paves the way for the development of optical polarization switches based on metal–organic frameworks.

Anisotropy of the magnetic and transport properties of EuZn2As2

Several recent studies have shown that the anisotropy in the magnetic structure of \ECA\ plays a significant role in stabilizing the Weyl nodes. To investigate the relationship between magnetic anisotropy and Weyl physics, we present a comparative study between EuZn$_2$As$_2$ and EuCd$_2$As$_2$ that are isostructural but with different magnetic anisotropy. We performed structural analysis, electronic transport, and magnetization experiments on millimeter-sized single crystals of EuZn$_2$As$_2$, and compared the results to those of EuCd$_2$As$_2$. By combining the first principle calculations and neutron diffraction experiment, we identify the magnetic ground state of EuZn$_2$As$_2$ as A-type antiferromagnetic order with a transition temperature ($T_\mathrm{N}$ = 19.6 K) twice that of EuCd$_2$As$_2$. Like EuCd$_2$As$_2$, the negative magnetoresistance of EuZn$_2$As$_2$ is observed after suppressing the resistivity peak at $T_\mathrm{N}$ with increasing fields. However, the anisotropy in both transport and magnetization are much reduced in EuZn$_2$As$_2$. The difference could be ascribed to the weaker spin-orbit coupling, more localized $d$-orbitals, and a larger contribution from the Eu $s$-orbitals in the zinc compound, as suggested by the electronic band calculations. The same band structure effect could be also responsible for the observation of a smaller non-linear anomalous Hall effect in EuZn$_2$As$_2$ compared to EuCd$_2$As$_2$.

Crystal structure, Raman characterization, and magnetic properties of the hydrate RbYb(MoO4)2, H2O

The millimeter-sized single crystals of RbYb(MoO4)2, H2O monohydrate were successfully grown using the high-temperature self-flux method. This colorless and shiny double molybdate crystallizes in the monoclinic system with space group C2/c. Its lamellar structure can be described with YbO8 regular square antiprisms sharing edges into chains aligned along the [001] direction. A layered arrangement occurs perpendicularly to the [010] direction with MoO4 tetrahedra and YbO8 polyhedra associated in complex anionic layers alternating with cationic layers made of Rb ​+ ​ions surrounded by eight oxygen atoms into flattened RbO8 square antiprisms. Raman investigation at room temperature shows a weak vibration at 737 ​cm−1 attributed to the existence of pseudo-double-bridges Mo-{O2}-Mo, while the absence of bands in the 500-700 ​cm−1 frequency range confirms the lack of covalent Mo–O–Mo single-bridge. Magnetic characterizations suggest that the title compound presents an antiferromagnetic coupling between the Yb3+ centers at T ​≤ ​10 ​K.

Liquid exfoliation of five-coordinate layered titanate K2Ti2O5 single crystals in water

Millimeter-sized K2Ti2O5 single crystals were grown from a KCl–KOH mixed flux using a flux-evaporation assisted method. H2O was found to be the best solvent for the liquid exfoliation of K2Ti2O5 crystals.

Real-Time Multiscale Monitoring and Tailoring of Graphene Growth on Liquid Copper.

The synthesis of large, defect-free two-dimensional materials (2DMs) such as graphene is a major challenge toward industrial applications. Chemical vapor deposition (CVD) on liquid metal catalysts (LMCats) is a recently developed process for the fast synthesis of high-quality single crystals of 2DMs. However, up to now, the lack of in situ techniques enabling direct feedback on the growth has limited our understanding of the process dynamics and primarily led to empirical growth recipes. Thus, an in situ multiscale monitoring of the 2DMs structure, coupled with a real-time control of the growth parameters, is necessary for efficient synthesis. Here we report real-time monitoring of graphene growth on liquid copper (at 1370 K under atmospheric pressure CVD conditions) via four complementary in situ methods: synchrotron X-ray diffraction and reflectivity, Raman spectroscopy, and radiation-mode optical microscopy. This has allowed us to control graphene growth parameters such as shape, dispersion, and the hexagonal supra-organization with very high accuracy. Furthermore, the switch from continuous polycrystalline film to the growth of millimeter-sized defect-free single crystals could also be accomplished. The presented results have far-reaching consequences for studying and tailoring 2D material formation processes on LMCats under CVD growth conditions. Finally, the experimental observations are supported by multiscale modeling that has thrown light into the underlying mechanisms of graphene growth.

Effect of crystallization of Ni catalyst on direct precipitation of multilayer graphene using W capping layer

In recent years, graphene growth technology has been greatly progressed, and it is possible to grow graphene with millimeter-size single crystals using metal-catalysis CVD. However, the transfer process is unavoidably which largely deteriorates the graphene. We have proposed direct precipitation method of graphene using a W capping layer. The method does not only require a transfer process, but also the introduction of wrinkles will be suppressed by optimizing the cooling rate at the graphene precipitation. The growth conditions such as thickness of amorphous carbon, annealing temperature, cooling rate and crystallinity of Ni catalyst were systematically changed to study the mechanism of the precipitation method using the W cap layer. By the optimization of the conditions, wrinkle-free multilayer graphene with D/G ratio of less than 0.1 were successfully obtained directly on a sapphire substrate.

Chemical Surface Reactivity and Morphological Changes of Bismuth Triiodide (BiI3) under Different Environmental Conditions.

Layered metal halides like BiI3 are of current interest in connection with both 2D materials and photovoltaics. Here, we present a facile new method for the preparation of millimeter-sized BiI3 single crystals. We use these crystals to study the surface reactivity of their (001) cleavage planes toward various environmental conditions by measuring morphological changes using atomic force microscopy and analyzing the formed species by means of X-ray photoelectron spectroscopy and X-ray diffraction methods. We find that freshly cleaved samples show atomically flat surface regions extending over several micrometers and reveal steps corresponding to single BiI3 layers. However, we also find that the surface deteriorates in air on a time scale of hours. By studying samples cleaved and stored under different conditions, we identify water as the agent initiating the changes in surface morphology, while under inert gas and dry oxygen, the surface stays intact. On the basis of the analysis of deteriorated long-term-stored samples we identify BiOI as the main product of hydrolysis. We also observe a second long-term decomposition route for samples stored under dynamic vacuum, where formation of BiI whiskers occurs. Overall, our findings emphasize the challenges associated with the surface reactivity of BiI3 but also demonstrate that well-ordered BiI3 surfaces can be obtained, which indicates that preparation of extended, atomically smooth BiI3 monolayers by exfoliation from bulk crystals should be possible.

Crystal Growth of Spin-frustrated Ba4Nb0.8Ir3.2O12: A Possible Spin Liquid Material

Polycrystalline Ba4NbIr3O12 has recently been shown to be a promising spin liquid candidate. We report an easy and reliable method to grow millimeter-sized single crystals of this trimer based spin liquid candidate material with the actual stoichiometry of Ba4Nb0.8Ir3.2O12. The growth of large crystals is achieved using BaCl2 as flux. The crystals show hexagonal plate-like habit with edges up to 3 mm in length. The structure is confirmed by single crystal X-ray diffraction and is found to be the same as of previously reported phase Ba12Nb2.4Ir9.6O36 [Ba4Nb0.8Ir3.2O12], indeed with a mixed occupancy of Nb/Ir at 3a site. The magnetic and calorimetric study on the individual single crystals confirms the possibility of a spin liquid state consistent with a recent report on a polycrystalline sample

Single crystal growth and physical property characterization of ternary phosphide chalcogenide ZrP1.49Se0.51

High-quality and sizable single crystals are essential for studying the intrinsic properties of a novel superconductor. Here for the first time we report the successful growth of millimeter-size single crystals of ZrP1.49Se0.51 with PbFCl-type structure by using a chemical vapor transport technique. Owing to the availability of the high-quality single crystals, intrinsic properties in both superconducting and normal states are systematically characterized by means of electrical transport, magnetization, and specific heat measurements. ZrP1.49Se0.51 single crystals show bulk superconductivity with a critical transition temperature Tc of 6.8 K. It is found that the temperature dependence of upper critical field μ0Hc2(T) deviates from the conventional Werthamer-Helfand-Hohenber (WHH) model. μ0Hc2(T) shows a moderate anisotropy (Γ = Hc2,ab(T)/Hc2,c(T)), which resides in the range 4.47–4.63 and shows a nonmonotonic temperature dependence, similar to the multiband iron-based superconductors. Moreover, the results of lower critical field and thermodynamic properties reveal that ZrP1.49Se0.51 is a weakly electron–phonon coupled type-II BCS superconductor.

Exploration of Multi-Component Vanadium and Titanium Pnictides Using Flux Growth and Conventional High-Temperature Methods.

The flux growth method was successfully employed to synthesize millimeter-sized single crystals of the ternary barium vanadium pnictides Ba5V12As19+x (x ≈ 0.02) and Ba5V12Sb19+x (x ≈ 0.36), using molten Pb and Sb, respectively. Both compositions crystallize in space group P3m and adopt a structure similar to those of the barium titanium pnictides Ba5Ti12Pn19+x (Pn = Sb, Bi), yet with a subtly different disorder, involving the pnictogen and barium atoms. Attempts to obtain an arsenide analog of Ba5Ti12Pn19+x using a Pb flux technique yielded binary arsenides. High-temperature treatment of the elements Ba, Ti, and As in Nb or Ta tubes resulted in side reactions with the crucible materials and produced two isostructural compositions Ba8Ti13−xMxAs21 (M = Nb, Ta; x ≈ 4), representing a new structure type. The latter structure displays fcc-type metal clusters comprised of statistically distributed Ti and M atoms (M = Nb, Ta) with multi-center and two-center bonding within the clusters, as suggested by our first-principle calculations.

Seeded growth of high-quality transition metal dichalcogenide single crystals via chemical vapor transport

Seeded chemical vapor transport growth gives high-quality and millimeter-sized transition metal dichalcogenide single crystals in a short period.

Magnetic Phase Diagram and Chiral Soliton Phase of Chiral Antiferromagnet [NH4][Mn(HCOO)3

We synthesize herein millimeter-sized single crystals of the molecule-based chiral antiferromagnet, [NH4][Mn(HCOO)3]. The crystal is optically transparent, and has a hexagonal crystal structure tha...