In Situ Observation of Skeletal Shape Transition during BaB2O4 Crystal Growth in High-Temperature Solution

The transition from a fiat solid-liquid interface to a skeletal shape during BaB2O4 （BBO） single crystal growth in Li2B4O7 flux is observed in real time by an optical high-temperature in-situ observation system. The movement of crystal step is also investigated. The observation results demonstrate that the steps propagate along and parallel to the fiat interface when the crystal size is small. Nevertheless, they will ‘bend＇ close to the face centre if the crystal size becomes greater. Atomic force microscopy reveals that more deposition places near the face centre give rise to the bending of advancing steps and thus the formation of a vicinal interface structure. Measurements of step velocity show that the velocity keeps nearly constant at different moments for one specific step, whereas the step on a newly formed layer advanced faster than that on a previously formed one when the crystal size is larger than 210μm or so. Thus interracial morphological instability occurs and a skeletal interface is obtained.     

Effects of Al and Ti/Cu on Synthesis of Type-IIa Diamond Crystals in Ni70Mn25Co5-C System at HPHT

High-quality type-Ⅱa gem diamond crystals are successfully synthesized in a NiToMn25Co5-C system by temperature gradient method （TGM） at about 5.5 GPa and 1560 K. Al and Ti/Cu are used as nitrogen getters respectively. While nitrogen getter Al or Ti/Cu is added into the synthesis system, some inclusions and caves tend to be introduced into the crystals. When Al is added into the solvent alloy, we would hardly gain high-quality type-Ⅱa diamond crystals with nitrogen concentration Nc 〈 1 ppm because of the reversible reaction of Al and N at high pressure and high temperature （HPHT）. Piowever, when Ti/Cu is added into the solvent alloy, high-quality type-Ⅱa diamond crystals with Nc 〈 1 ppm can be grown by decreasing the growth rate of diamonds.     

Synthesis of Cubic Boron Nitride by the Reaction of Li3N and B2O3

Cubic boron nitride is synthesized by the reaction of Li3N and B203 under high pressure and high temperature （4.0-5.0 GPa, 1350-1500℃）. The minimum pressure of cBN formation is 4.0 GPa. The present condition of cBN formation is clearly lower than the eutectic temperature of Li3BN2 and BN in the Li3N-hBN system （5.5 GPa, 1610℃）. The content of cBN in the sample increases, while the content of hBN decreases with the temperature and pressure. The maximum conversion rate （5.0 GPa, 1500℃） is about 34%, which is higher than that in the hBN-Li3N system. The cBN crystals are octahedral or tetrahedral in shape and approximately 20 μm in diameter.     

Effect of Carbon Source with Different Graphitization Degrees on the Synthesis of Diamond

Using three kinds of graphites with different graphitization degrees as carbon source and Fe-Ni alloy powder as catalyst, the synthesis of diamond crystals is performed in a cubic anvil high-pressure and high-temperature apparatus （SPD-6 × 1200）. Diamond crystals with perfect hexoctahedron shape are successfully synthesized at pressure from 5.0 to 5.5GPa and at temperature from 1570 to 1770K. The synthetic conditions, nucleation, morphology, inclusion and granularity of diamond crystals are studied. The temperature and pressure increase with the increase of the graphitization degree of graphite. The quantity of nucleation and granularity ofdiamonds decreases with the increase of graphitization degree of graphite under the same synthesis conditions. Moreover, according to the results of the M6ssbauer spectrum, the composition of inclusions is mainly Fe3 C and Fe-Ni alloy phases in diamond crystals synthesized with three kinds of graphites.     

Crystal growth and dielectric, piezoelectric and elastic properties of Ca3TaGa3Si2O14 single crystal

Single crystals of Ca₃TaGa₃Si₂O₁₄ (CTGS) were successfully grown from stoichiometric melts by the conventional Czochralski technique. The relative dielectric constants, the piezoelectric strain constants and the elastic compliance constants of CTGS single crystal have been determined by an electric bridge and resonance-antiresonance method. At room temperature, the two piezoelectric strain constants d₁₁ and d₁₄ are −4.58×10⁻¹² coulombs per newton (C/N) and 10.43×10⁻¹² coulombs per newton (C/N), respectively. The velocities of the bulk acoustic wave are also calculated.     

HPHT Synthesis of Micron Grade Boron-Doped Diamond Single Crystal in Fe-Ni-C-B Systems

Micron grade boron-doped diamond crystals with octahedral morphology are successfully synthesized in a Fe-Ni- C-B system under high pressure and high temperature （HPHT）. The effects of the additive boron on synthesis conditions, nucleation and growth, crystal morphology of diamond are studied. The synthesized micron grade diamond crystals were characterized by optical microscope （OM）, scanning electron microscope （SEM）, x-ray diffraction （XRD） and Raman spectroscopy. The research results show that the V-shaped section of synthetic diamond moves downwards to the utmost extent due to 0.3a wt% （a is a constant.） boron added in the synthesis system. The crystal colour is black, and the average crystal size is about 25μm. The crystal faces of synthetic diamond are mainly （111） face. The synthesis of this kind of diamond is few reported, and it will have important and widely applications.     

HPHT Synthesis of Different Shape Coarse-Grain Diamond Single Crystals

Synthesis of coarse-grain diamond crystals is studied in a China-type SPD6× 1670T cubic high-pressure apparatus with high exact control system. To synthesize high quality coarse-grain diamond crystals, advanced indirect heat assembly, powder catalyst technology and optimized synthesis craft are used. At last, three kinds of coarse- grain diamond （about 0.85 mm） single crystals with hexahedron, hex-octahedron and octahedron are synthesized successfully under HPHT （about 5.4 GPa, 1300-1450℃）. The growth characters of different shape crystals are discussed. The results and techniques might be useful for the production of coarse-grain diamonds.     

Dependence of Limited Growth Rate of High-Quality Gem Diamond on Growth Conditions

The growth rate of diamond has been investigated for a long time and researchers have been attempting to enhance the growth rate of high-quality gem diamond infinitely. However, it has been found according to previous research results that the quality of diamond is debased with the increase of growth rate. Thus, under specific conditions, the growth rate of high-quality diamond cannot exceed a limited value that is called the limited growth rate of diamond. We synthesize a series of type Ib gem diamonds by temperature gradient method under high pressure and high temperature （HPHT） using the as-grown {100} face. The dependence of limited growth rate on growth conditions is studied. The results show that the limited growth rate increases when synthetic temperature decreases, also when growth time is prolonged.     

Finite Element Analysis of Convection in Growth Cell for Diamond Growth Using Ni-Based Solvent

Thermal-electricaJ-fluid coupled finite element analyses are performed in the model of the growth cell in a high-pressure and high-temperature （HPHT） cubic apparatus in which the large diamond crystal can be grown by using Ni-based solvent with temperature gradient method （TGM）. The convection in the Ni-based solvent with different thicknesses at 1700-1800 K is simulated by finite element method （FEM）. The experiments of diamond crystal growth are also carried out by using Ni-based solvent at 5.7GPa and 1700-1800K in a China-type cubic high pressure apparatus （CHPA）. The simulation results show that the Rayleigh number in the solvent is enhanced obviously with the increasing solvent thickness. Good quality diamond single crystal cannot be grown if the Rayleigh number in the solvent is too high.     

Single-crystalline Zn2SnO4 hexangular microprisms: Fabrication, characterization and optical properties

Large-scale Zn₂SnO₄ hexangular microprisms were successfully synthesized through a simple thermal evaporation method by heating metal Zn and Sn powders under varying temperatures. The synthesized microprisms are single-crystalline, tens of micrometers in length. And their surfaces have many nano-scale skewed steps along the axial direction. Structurally, we supposed that the hexangular prism could be described as a row of inlaid octahedron of Zn₂SnO₄ crystals. A broad asymmetrical emission band was observed in the PL spectrum of these Zn₂SnO₄ microprisms, which was discussed in detail in the paper.     

SrTiO3 homoepitaxy by the pulsed laser deposition method: island, layer-by-layer, and step-flow growth

SrTiO₃ homoepitaxy was investigated under various conditions using the pulsed laser deposition method. The growth mode was determined by in-situ reflection high-energy electron diffraction, and the surface of the films was characterized by ex-situ atomic force microscopy. At the laser fluence of 0.68 J/cm², island growth was observed below 500 °C substrate temperature, while the growth mode turned into layer-by-layer growth above 500 °C. On further raising the substrate temperature, the step-flow growth mode prevailed above 800 °C. We thus demonstrated that step-flow growth in SrTiO₃ homoepitaxy is possible at a temperature as low as 800 °C.     

Influence of niobium doping on the electrical properties of 0.58Pb(Sc1/2Nb1/2)O3-0.42PbTiO3 single crystal

Piezoelectric single crystals of 0.58Pb(Sc_1/2Nb_1/2)-0.42PbTiO₃ and Nb⁵⁺-doped PSN-PT have been grown using flux technique. It is believed that the addition of Nb⁵⁺ creates lead vacancy in order to compensate charge neutrality. The structural distortion that occured in the doped crystals has been revealed through broadening of some peaks in X-ray diffraction studies. Niobium content that increased from 0.50 to 1.00 mol% might have induced more defect dipoles associated with . This plays a significant role in improving the ferroelectric, dielectric and piezoelectric properties. Our observations clearly show an increase in the spontaneous polarization (P_r), dielectric constant at room temperature, degree of diffuseness and transition temperature (T_c) and also a decrease in coercive field. The reasons behind these enhanced electrical properties are discussed in detail.     

Formation of Mixture of A and C Centres in Diamond Synthesized with Fe90Ni10-C-High-Content Additive NaN3 by HPHT

Very rich nitrogen concentration with the dominant C centres and some A centres are found in diamonds grown from a Fe90Ni10-C-high-content NaN3 additive system. The concentrations of C centres rapidly increase with increasing content of NaN3 additive, while the concentrations of A centres increase slowly. The total nitrogen concentration tends to increase rapidly with increasing content of NaN3 additive when the content of NaN3 is below 0.7 wt%. However, the total concentration of nitrogen in the diamonds increases slowly when the content of NaN3 is further increased up to 1.0 wt%, and the total nitrogen average concentration are calculated to be around 2230ppm for most of the analysed synthetic diamonds. Eurthermore, the nitrogen impurities in different crystal sectors of the diamonds are inhomogeneously distributed. The nitrogen impurities in the diamonds in [111] zones are incorporated more easily than that in [100].     

Raman Spectrum Analysis on the Solid-Liquid Boundary Layer of BGO Crystal Growth

We study the Raman spectra of Bi4GeO12 crystal at different temperatures, as well as its melt. The structure characters of the single crystal, melt and growth solid-liquid boundary layer of BGO are investigated by their high-temperature Raman spectra for the first time. The rule of structure change of BGO crystal with increasing temperature is analysed. The results show that there exists [GeO4] polyhedral structure and Bi ion independently in BGO melt. The bridge bonds Bi-O-Bi and Bi-O-Ge appear in the crystal and at the boundary layer, but disappear in the melt. The structure of the growth solid-liquid boundary layer is similar to that of BGO crystal. In the melt, the long-range order structure of the crystal disappears. The thickness of the growth solid-liquid boundary layer of BGO crystal is about 50 μm.     

A New Dopant of NaN3 for High-Concentration-Nitrogen Diamond Synthesized by HPHT

Nitrogen is successfully doped in diamond by adding sodium azide （NaN3 ） as the source of nitrogen to the graphite and iron powders. The diamond crystals with high nitrogen concentration, 1000-2200ppm, which contain the same concentrations of nitrogen with natural diamond, have been synthesized by using the system of iron-carbon- additive NAN3. The nitrogen concentrations in diamond increase with the increasing content of NAN3. When the content of NaN3 is increased to 0.7-1.3 wt. %, the nitrogen concentration in the diamond almost remains in a nitrogen concentration range from 1250ppm to 2200ppm, which is the highest value and several times higher than that in the diamond synthesized by a conventional method without additive NaN3 under high pressure and high temperature （HPHT） conditions.     

GaN/LiNbO3 (0 0 0 1) interface formation calculated from first-principles

The stable adsorption sites for both Ga and N ions on the ideal and on the reconstructed LiNbO₃ (0 0 0 1) surface are determined by means of first-principle total energy calculations. A single N layer is found to be more strongly bound to the substrate than a single Ga layer. The adsorption of a GaN monolayer on the polar substrate within different orientations is then modeled. On the basis of our results, we propose a microscopic model for the GaN/LiNbO₃ interface. The GaN and LiNbO₃ (0 0 0 1) planes are parallel, but rotated by 30° each other, with in-plane epitaxial relationship [1 0 0]_GaN‖ [1 1  0]_LiNbO3. In this way the (0 0 0 1) plane lattice mismatch between GaN and LiNbO₃ is minimal and equal to 6.9% of the GaN lattice constant. The adsorbed GaN and the underlying LiNbO₃ substrate have parallel c-axes.     

Hetero-Epitaxial Diamond Single Crystal Growth on Surface of cBN Single Crystals at High Pressure and High Temperature

We report a new diamond synthesis process in which cubic boron nitride single crystals are used as seeds, FesoNi20 alloy powder is used as catalyst/solvent and natural flake-like graphite is used as the carbon source. The samples are investigated using laser Raman spectra and x-ray diffraction （XRD）. Morphology of the sample is observed by a scanning electron microscope （SEM）. Based on the measurement results, we conclude that diamond single crystals have grown on the cBN crystal seeds under the conditions of high temperature 1230℃ and high pressure 4.8 GPa. This work provides an original method for synthesis of high quality hereto-semiconductor with cBN and diamond single crystals, and paves the way for future development.     

Structure and electrical conductivity of a novel inorganic solid electrolyte: Na14.5[Al(PO4)2F2]2.5[Ti(PO4)2F2]0.5 (NATP)

A novel inorganic solid electrolyte with a layered framework structure stable up to 1043 K, Na_14.5[Al(PO₄)₂F₂]_2.5[Ti(PO₄)₂F₂]_0.5 (NATP), has been hydrothermally prepared and characterized by single-crystal and powder X-ray diffraction techniques, X-ray fluorescence (XRF) analysis, IR spectroscopic measurement, thermogravimetric and differential thermal analysis (TGA and DTA). NATP crystallizes in the acentric hexagonal space group P3 with a=10.448(2), b=10.448(2), , Z=1, containing a large number of Na⁺ cations in the interlamellar space and the cavities of its framework. There are six different crystallographic Na⁺ cationic sites, in which 8% Na(5) and 12% Na(6) sites are vacant. Electrical conductivity measurements show that Na⁺ cations exhibit a high mobility with two domains for the electrical conductivity versus temperature.     

HPHT Synthesis of High-Quality Diamond Single Crystals with Micron Grain Size

High-quality diamond single crystals with micron grain size are synthesized with a new high-pressure and high-temperature （HPHT） synthesis technique in a cubic anvil high pressure apparatus. Morphology of the synthesized diamonds is observed by a scanning electron microscope （SEM）. The samples are characterized using laser Raman spectra. The results show that the new synthesis technique improves the nucleation of diamond greatly, and diamond single crystals with perfect morphology and micron grain size are successfully synthesized, with the average grain size of about 6μm. This work provides a new synthesis technique to implement industrialization of high-quality diamond single crystals with super-fine grain size, and paves the way for future development.     

Effects of NaN3 Added in Fe-C System on Inclusion and Impurity of Diamond Synthesized at High Pressure and High Temperature

Effects of NaN3 added in Fe-C system to synthesize nitric diamond at high pressure and high temperature are investigated. Diamond crystals with high nitrogen concentration are synthesized by the system of Fe-C and NaN3 additive at pressure 5.8 GPa and at temperatures 1750-1780 K for 15 min. The synthetic diamond crystals have a cubo-octahedral or octahedral shape with yellowish green or green colour. Some disfigurements are observed on the surfaces of most diamond crystals. The composition and content of inclusions formed by iron in diamond are changed and iron nitride is detected in diamond crystals synthesized with Fe-C-NaN3 additive. As the amount of NaN3 additive increases, Fe3C decreases and iron nitride increases with α-Fe being nearly constant. Moreover, the nitrogen concentrations in diamond crystals synthesized with 1.5 wt% NaN3 additive is up to 2250ppm in substitutional form.