As-grown Crystals Research Articles

Synthesis and Characterization of 2D Ternary Compound TMD Materials Ta3VSe8

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are garnering considerable scientific interest, prompting discussion regarding their prospective applications in the fields of nanoelectronics and spintronics while also fueling groundbreaking discoveries in phenomena such as the fractional quantum anomalous Hall effect (FQAHE) and exciton dynamics. The abundance of binary compound TMDs, such as MX2 (M = Mo, W; X = S, Se, Te), has unlocked myriad avenues of exploration. However, the exploration of ternary compound TMDs remains relatively limited, with notable examples being Ta2NiS5 and Ta2NiSe5. In this study, we report the synthesis of a new 2D ternary compound TMD materials, Ta3VSe8, employing the chemical vapor transport (CVT) method. The as-grown bulk crystal is shiny and can be easily exfoliated. The crystal quality and structure are verified by X-ray diffraction (XRD), while the surface morphology, stoichiometric ratio, and uniformity are determined by scanning electron microscopy (SEM). Although the phonon property is found stable at different temperatures, magneto-resistivity evolves. These findings provide a possible approach for the realization and exploration of ternary compound TMDs.

Effects of rare earth codoping on the optical and scintillation properties of Cs3Cu2I5:Tl single crystals

In this work, the effects of rare earth ion codoping on the optical and scintillation performance of Cs3Cu2I5:Tl single crystals were studied. Cs3Cu2I5:Tl single crystals codoped with different concentrations of Sc3+, Y3+, and La3+ ions were grown by the Bridgman method. It was found that rare earth ion codoping reduces the optical transmittance of the as-grown crystals, in particular the coloring caused by Sc3+codoping. The luminescence mechanism associated with self-trapped exciton (STE) and Tl-related emissions has not been affected by the introduction of rare earth ion. The gamma scintillation yield and energy resolution are degraded after rare earth ion codoping.

Nonsymmorphic symmetry protected nodal lines in layered topological semimetal Ta3GeTe6

Topological semimetals have garnered significant attention due to their distinctive physical properties. However, the ideal material platforms for studying these phenomena remain limited. Here, we report the synthesis and nontrivial topological properties of high-quality van der Waals material Ta3GeTe6. Angle-resolved photoemission spectroscopy studies performed systematically on the as-grown Ta3GeTe6 single crystal along different high-symmetry directions reveal the formation of two nodal lines located near 0.07 and 0.55 eV below EF along the loop X-U-R-S, which arises from band crossings protected by nonsymmorphic symmetry. Furthermore, the nodal lines near the Fermi level along the S-R and S-X directions exhibit a flat feature. The discovery of this material enriches the family of topological nodal line semimetals and provides a promising platform for future investigations into exotic electronic correlation phenomena and potential device applications.

Growth of Spontaneous Nucleation AlN Crystals by Al-Base Alloy Evaporation in Nitrogen Atmosphere

Aluminum nitride (AlN) crystals with areas ranging from 1 mm2 to 2 mm2 were successfully grown through spontaneous nucleation at 1700 °C using a modified vapor transport method. In this approach, Cu–Al alloy served as the source of aluminum (Al), and nitrogen (N2) was employed as the nitrogen source. The morphology and crystalline quality of the AlN crystals were characterized by a stereo microscope, Raman spectrometer, photoluminescence (PL) and secondary-ion mass spectrometry (SIMS). Deposited on the graphite lid, the as-grown AlN crystals exhibited both rectangular and hexagonal shapes, identified as m-plane and c-plane AlN, respectively, based on Raman spectroscopy. The full width half maximum (FWHM) values of E2 (high) for the rectangular and hexagonal grains were measured to be 6.00 cm−1 and 6.06 cm−1, respectively, indicating high crystalline quality. However, PL and SIMS analysis indicated the presence of impurities associated with oxygen in the crystals. This paper elucidates the growth mechanism of the modified vapor transport method and highlights the role of the Cu–Al alloy in sustaining reactions at lower temperatures. The addition of copper (Cu) not only facilitates sustainable reactions, but also provides a novel perspective for the growth of AlN single crystals.

Single Crystal Growth and X-ray Diffraction Characterization of a Quasi-Spin Chain Compound, Li2CuO2

We report the growth of single crystals and X-ray diffraction characterization of the quasi-one-dimensional spin chain compound, Li2CuO2. The single crystals were grown using the high-temperature solution growth technique. The resulting blade-shaped crystals exhibit a shiny black color, with dimensions reaching several millimeters along the crystallographic b-axis. The as-grown crystals were characterized using powder X-ray diffraction and Laue back reflection. The I-centered orthorhombic, Immm, structure was confirmed. Crystal structure parameters were determined to be a = 3.6744 Å, b = 2.8600 Å, and c = 9.4257 Å from Rietveld analysis. Our work helps to remove obstacles to the synthesis and study of a model cuprate system, Li2CuO2, facilitating the use of experimental probes that require sizable crystals.

Ba6RE2Ti4O17 (RE = Nd, Sm, Gd, Dy-Yb): A Family of Rare-Earth-Based Layered Triangular Lattice Magnets.

The exploration of new rare-earth (RE)-based triangular-lattice materials plays a significant role in motivating the discovery of exotic magnetic states. Herein, we report a family of hexagonal perovskite compounds Ba6RE2Ti4O17 (RE = Nd, Sm, Gd, Dy-Yb) with a space group of P63/mmc, where magnetic RE3+ ions are distributed on the parallel triangular-lattice layers within the ab-plane and stacked in an 'AA'-type fashion along the c-axis. The low-temperature magnetic characterizations indicate that all synthesized Ba6RE2Ti4O17 compounds exhibit dominant antiferromagnetic (AFM) interactions and the absence of magnetic order down to 1.8 K. The isothermal magnetization and electron spin resonance results reveal the distinct magnetic anisotropy for the compounds with different RE ions. Moreover, the as-grown Ba6Nd2Ti4O17 single crystals exhibit Ising-like magnetic anisotropy with a magnetic easy-axis perpendicular to the triangle-lattice plane and no long-range magnetic order down to 80 mK, as the quantum spin liquid candidate with dominant Ising-type interactions.

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 (Mg2 Mo3 O8 ) is presented. High-quality ultrathin Mg2 Mo3 O8 crystals are synthesized using chemical vapor deposition (CVD). Ultrathin Mg2 Mo3 O8 has a wide bandgap (≈4.4eV) and nonlinear optical response. Mg2 Mo3 O8 crystals of varying thicknesses exhibit out-of-plane ferroelectric properties at room temperature, with ferroelectricity retained even at a 2nm thickness. The Mg2 Mo3 O8 exhibits a relatively large remanent polarization ranging from 33 to 52µCcm- 2 , which is tunable by changing its thickness. Notably, Mg2 Mo3 O8 possesses a high Curie temperature (>980°C) across various thicknesses. Moreover, the as-grown Mg2 Mo3 O8 crystals display remarkable stability under harsh environments. This work introduces nolanites-type crystal into ultrathin ferroelectrics. The scalable synthesis of stable ultrathin ferroelectric Mg2 Mo3 O8 expands the scope of ferroelectric materials and may prosper applications of ferroelectrics.

Growth of a Sub-Centimeter-Sized CsPbBr3 Bulk Single Crystal Using an Anti-Solvent Precipitation Method

A facile and low-cost strategy to fabricate CsPbBr3 single crystals is essential for developing perovskite optoelectronic devices. Herein, we have presented a room temperature anti-solvent precipitate method for growing sub-centimeter-sized CsPbBr3 single crystals. The as-prepared CsPbBr3 single crystal has an orthorhombic structure, and phase transition occurs as the measured temperature increases. The as-grown CsPbBr3 single crystal also shows abundant surface morphologies including footsteps, precipitated crystals, cracks, and pits. Subsequently, a metal–semiconductor–metal (MSM)-structured photodetector was fabricated based on the CsPbBr3 single crystal. Under 525 nm green light illumination, the photodetector exhibits an obvious response and the photocurrent linearly increases with the increase in the light intensity. The rise time of the photodetector increases from 0.82 s to 2.19 s as the light intensity is enhanced from 15 mW/cm2 to 160 mW/cm2, indicating that more time is required to reach to a stable photocurrent. However, the decay time is as fast as ~0.82 ms, irrelevant of the light intensity. The photocurrent, under continuous light illumination, was further studied and this indicates that a stronger light intensity can accelerate the attenuation of the device.

Structural and resistivity properties of Fe1-xCoxSe single crystals grown by the molten salt method

A series of tetragonal Fe1-xCoxSe single crystals with a complete Co doping range (0 ≤ x ≤ 0.52) up to its solid solubility limit in FeSe have been grown by an eutectic AlCl3/KCl molten salt method. The typical lateral size of as-grown Fe1-xCoxSe single crystals is 1–5 mm. The chemical composition and homogeneity of the crystals was examined by both inductively coupled plasma atomic emission spectroscopy and energy dispersive spectrometer. X-ray diffraction analysis demonstrates that the crystal lattice parameters a and c are both linearly decreased with increasing Co doping level x. In the whole doping range, all the samples show metallic behaviour in contrast to a metal insulator transition of Cu-doped FeSe according to the resistivity measurements.

Crystal growth, luminescence, and scintillation properties of Er-doped La2Hf2O7 single crystal

The growth of Er-doped La2Hf2O7 (LHO:Er) single crystals with a high mp of 2413 °C was achieved by the melt-growth method using a tungsten (W) crucible. Polished LHO:Er specimens were obtained from the as-grown crystals. The full width at half maximum of the X-ray Rocking curve on the (222) diffraction peak was 599 arcsec, and the crystals have relatively low crystallinity. The photoluminescence spectra of the polished LHO:Er specimen showed emission peaks originating from the Er3+ ions in both the visible and IR wavelength ranges. It also exhibited scintillation light under X-ray irradiation.

Anisotropy of Anion Diffusion in All-Inorganic Perovskite Single Crystals.

Ion diffusion is a fundamentally important process in understanding and manipulating the optoelectronic properties of semiconductors. Most current studies on ionic diffusion have been focusing on perovskite polycrystalline thin films and nanocrystals. However, the random orientation and grain boundaries can heavily interfere with the kinetics of ion diffusion, where the experimental results only reveal the average ion exchange kinetics and the actual ion diffusion mechanisms perpendicular to the direction of individual crystal facets remain unclear. Here, the anion (Cl, I) diffusion anisotropy on (111) and (100) facets of CsPbBr3 single crystals is demonstrated. The as-grown single crystals with (111) and (100) facets exhibit anisotropic growth with different halide incorporation, which lead to different resulting optoelectronic properties. Combined experimental characterizations and theoretical calculations reveal that the (111) CsPbBr3 shows a faster anion diffusion behavior compared with that of the (100) CsPbBr3 , with a lower diffusion energy barrier, a larger built-in electric field, and lower inverse defect formation energy. The work highlights the anion diffusion anisotropic mechanisms perpendicular to the direction of individual crystal facets for optimizing and designing perovskite optoelectronic devices.

Zn1−xMgxTe and P:Zn1−xMgxTe (x = 0.06–0.25) bulk crystals grown by travelling Te solution method

Zn1−xMgxTe and P:Zn1−xMgxTe (x = 0.06–0.25) bulk crystals were successfully grown by travelling Te solution method. The segregation of Mg with the growth of crystal is weaken and the as-grown crystal has high homogeneity.

Scattering-free Ce:LYBO single crystals for thermal neutron detection

Ce:Li6Y(BO3)3 (LYBO) is a well-known candidate for thermal neutron detection with a very high Li concentration (3.06 × 1022/cm3). So far, as-grown crystals exhibit a milky appearance that compromises their performance as scintillators. Current work demonstrates, for the first time, the growth of scattering-free undoped and Ce-doped LYBO by a thermal quenching process. The origin and features of the scattering centers are investigated in detail. Furthermore, the annealing treatment for the scintillation activation is studied, finding that the reduction in oxygen vacancies is mandatory. Under thermal neutron irradiation, the annealed scattering-free Ce:LYBO single crystal achieves a record-high light yield of 6200 ph/n in a single decay with a lifetime as short as 24 ns.

Solution-grown millimeter-scale Mn-doped CsPbBr3/Cs4PbBr6 crystals with enhanced photoluminescence and stability for light-emitting applications.

Metal halide perovskites are particularly emerging for optoelectronic applications in light-emitting diodes, photodetectors, and solar cells due to their flourishing photophysical properties. However, the poor stability of three-dimensional (3D) lead halide perovskite nanocrystals (NCs) significantly hampers their optoelectronics and photovoltaics applications. Embedding 3D perovskites into zero-dimensional (0D) perovskite crystals and doping ions of appropriate elements into host lattices provide effective approaches to improve the stability and optical-electronic performance. In this study, millimeter-scale Mn-doped and undoped CsPbBr3/Cs4PbBr6 perovskite crystals were successfully fabricated by a one-step slow cooling method. We systematically investigated the effects of Mn2+ ion doping on the PL performance and stability of CsPbBr3/Cs4PbBr6 crystals. Compared with undoped crystals, the existence of Mn2+ ions not only blue-shifted the PL peak but also improved the luminescence performance and stability of the prepared millimeter-sized crystals. Moreover, doping Mn2+ ions can increase the proportion of radiative recombination at low temperature, which may be because Mn2+ ions can effectively accelerate the decay of a dark exciton by the magnetic mixing of bright and dark excitons. In addition, green LED devices with high efficiency packaged as-grown crystals are explored, which promises further application in display backlights.

Single Crystal Growth and Nano-Structure Study in a Topological Dirac Metal, CoTe2-δ

A single crystal of a topological material, CoTe2-δ, has been grown via the chemical vapor transport method for a structural and electronic transport study. Single-crystal X-ray diffraction, powder X-ray diffraction, and high-resolution scanning electron microscope measurements confirm the high quality of the as-grown single crystals. In a high-resolution scanning electron microscopy study, a clear layered feature of the trigonal CoTe2-δ crystal was observed. Fractal features and mosaic-type nanostructures were observed on the as-grown surface and cleaved surface, respectively. The trigonal CoTe2-δ demonstrates a metallic ground state in transport measurements, with a typical carrier’s concentration in a 1021 cm−3 magnitude and a residual resistivity ratio of 1.6. Below 10 K, trigonal CoTe2-δ contains quite complicated magnetoresistance behavior as a result of the competing effect between Dirac states and possible spin fluctuations.

Broadened and enhanced ∼ 2.9 μm mid-infrared emission in Dy3+/Er3+: Na5Y9F32 single crystals by Gd3+ co-doping

A series of Er3+, Dy3+ and Gd3+ doped Na5Y9F32 single crystals for laser output at ∼ 2.9 μm have been fabricated via a reformative Bridgman technique. The impacts of optically active ions of Dy3+ and Er3+ and non-optically active ion of Gd3+ on the emission spectra at ∼ 2.9 μm were investigated. The patterns of X-ray diffraction (XRD) of the obtained crystals indicated that the doping level of rare earth (RE) ions had inconspicuous effects on the lattice structure of Na5Y9F32. The emission spectra at ∼ 2.9 μm of the as-grown single crystals as change of various Er3+/Dy3+/Gd3+ contents were measured systematically excited by 974 nm light. A strong and wide emission band at ∼ 2.9 μm could be obtained in Er3+/Dy3+ co-doped crystal by utilizing Er3+ as sensitizer for Dy3+ ions. Meanwhile, the introduction of Gd3+ ions into Er3+/Dy3+ doped Na5Y9F32 single crystal could further widen the emission band at ∼ 2.9 μm due to the lattice distortion and variation of the crystal fields around Er3+ and Dy3+. Furthermore, the effective ∼ 2.9 μm emission bandwidth (Δλeff) of the Er3+/ Dy3+/ Gd3+ triply incorporated crystal was approximately 255.65 nm, which was nearly 3.4 times that of the 0.5 mol% Er ion singly doped sample (74.86 nm) and 1.4 times that of the 0.5 mol% Er/0.3 mol% Dy ions doubly incorporated sample (182.25 nm). The results unveiled that the introduction of Gd3+ was conducive to the generation of level population inversion of 6H13/2 and 6H15/2 of Dy3+ ions to help the output of ∼ 2.9 μm laser.

Optical and scintillation properties of modified LSO crystals with different ions doping grown by a rapid CZ system

LSO:Ce is a well-known scintillation crystal that is widely used in nuclear medicine, security checks, and high-energy physics. The scintillation properties of LSO can be modified by doping to meet the ever-growing requirements of radiation detection. However, exploring new doping techniques for LSO crystals with self-designed scintillation features remains time-consuming, especially by the Czochralski (CZ) method. In this paper, we established a high-efficiency crystal growth system based on the CZ method for the rapid growth of LSO crystals. The system is regulated by a high-accuracy auto-diameter controller to grow small boules of ϕ 20 mm × 100 mm. By incorporating an arc bottom crucible and optimizing the temperature field, the crystallization fraction of the as-grown crystal can be increased to 95% with the growth period compressed to 48 h. With the aid of the growth system, LSO crystals with Lu3+ partially substituted by optical inertia RE ions (Sc3+, Y3+, La3+, Gd3+), metal cations co-doping (Ca2＋, Li1+, Yb3+), and different luminescent ions doping (Pr3+, Nd3+, Eu3+, Tb3+, Dy3+, Yb3+) are grown. Comparative analysis shows that the Ca co-doped LSO:Ce exhibits the best scintillation performance, taking into account both light output and decay time, among our samples. Moreover, Tb-doped LSO features relatively good scintillation efficiency with various wavelengths of visible light emission.

Effects of processing parameters and grinding direction on the material removal mechanism of (100) surface single crystal diamond in self-rotating mechanical grinding

The current commonly used method for diamond processing is mechanical polishing using the cast iron grinding wheel (Scaife). However, this method is challenging to meet the processing requirements of semiconductor applications. This study proposes a more efficient grinding method that employs a high-speed self-rotating grinding device, coupled with a bonded abrasive diamond grinding wheel with high self-sharpening properties, to achieve high precision grinding of single crystal diamonds. Different cutting depths, grit sizes, and linear velocities are employed in the processing, and the material removal mechanism is studied through morphology characterization, element content, and other detection methods. The experimental results indicate that the material removal method of diamond (100) crystal surface is influenced by the cutting depth. It is a collaborative removal process in the 〈110〉 and 〈100〉 directions, and the brittle-ductile transition in the <110> direction significantly affects the machining quality. Surface fractures and subsurface cracks primarily occur through cleavage along the (111) plane, so a method to distinguish the orientation of the (100) crystal plane is proposed. Additionally, this study demonstrates the influence of different processing directions on the surface of the diamond within the same plane. By using this method, the surface roughness of the 7 × 7 mm as-grown crystal can be reduced to Ra 0.523 nm within 10 min, with a material removal rate of 32.4 μm/h.

The Growth and Spectroscopic Properties of Er, Nd: YSGG Single Crystal Fibers

Single crystal fiber (SCF) is a novel solid gain medium and technique which combines the advantages of glass fiber and single crystal, showing great potential in the field of high-power lasers. In this paper, Er, Nd: YSGG single crystals with diameters of 2 mm and lengths of 80 mm were successfully grown using the micro-pulling-down method for the first time. Then, the measurements of Laue spots and Er3+ distribution indicated that the as-grown crystals were of a high quality. The effect of co-doped Nd3+ on the Er: YSGG was systematically discussed, which demonstrated that Nd3+ can decrease the fluorescence lifetime of Er: 4I13/2 that solve the self-termination bottleneck accordingly. These results demonstrate that Er, Nd: YSGG SCFs are promising materials for the further 3 μm laser generations.

Influence of heat treatment on the structure and mechanical properties of zirconium dioxide crystals partially stabilized by samarium oxide

The effect of high-temperature treatment in different media on the phase composition, microhardness and fracture toughness of (ZrO2)1-х(Sm2O3)х crystals with x = 0.02÷0.06 has been studied. The crystals have been grown using direction melt crystallization in a cold skull. The crystals have been heat treated at 1600 °C for 2 h in air and in vacuum. The phase composition of the crystals has been studied using X-ray diffraction and Raman scattering. We show that samarium cations enter the ZrO2 lattice mainly in a trivalent charge state and do not change their charge after air or vacuum annealing. The as-annealed phase composition has changed in all the test crystals except for the (ZrO2)0.94(Sm2O3)0.06 composition. After air or vacuum annealing the (ZrO2)1-x(Sm2O3)x crystals with 0.002 ≤ x ≤ 0.05 contain a monoclinic phase. The (ZrO2)0.94(Sm2O3)0.06 crystals contain two tetragonal phases (t and t´) with different tetragonality degrees. After air or vacuum annealing of the (ZrO2)0.94(Sm2O3)0.06 crystals the lattice parameters of the t and t´ phases change in opposite manners, suggesting that the tetragonality degree of the t phase increases whereas the tetragonality degree of the t´ phase decreases. The microhardness and fracture toughness of the as-annealed crystals depend on the Sm2O3 concentration in the solid solutions. The formation of the monoclinic phase in the (ZrO2)1-х(Sm2O3)х crystals with 0.037 ≤ x ≤ 0.05 significantly reduces the microhardness and fracture toughness of the crystals. Annealing of the (ZrO2)0.94(Sm2O3)0.06 crystals triggers more efficient hardening mechanisms and thus increases the fracture toughness of the crystals. We show that air or vacuum annealing of the (ZrO2)0.94(Sm2O3)0.06 crystals increases the fracture toughness of the crystals by 1.5 times as compared with that of the as-grown crystals.