Crystallization Growth of Single Crystal Cu by Continuous Casting

Crystallization growth of single-crystal Cu by continuous casting has been investigated using self-designed horizontal continuous casting equipment and XRD. Experimental results showed that the crystallization plane of (311), (220) and (ill) were eliminated sequentially in evolutionary process. The final growth plane of crystal was (200), the direction of crystallization was [100], the growth direction of both sides of the rod inclined to axis, and the degree of deviation of direction [100] from the crystal axis was less than 10°. In order to produce high quality single crystal, the solid-liquid interface morphology must be smooth, even be planar.

Enhanced efficiency and stability in Sn-based perovskite solar cells with secondary crystallization growth

The conversion efficiencies reported for Tin(Sn)halide-based perovskite solar cells(PSCs)fall a large gap behind those of lead halide-based PSCs,mainly because of poor film quality of the former.Here we report an efficient strategy based on a simple secondary crystallization growth(SCG)technique to improve film quality for tin halide-based PSCs by applying a series of functional amine chlorides on the perovskite surface.They were discovered to enhance the film crystallinity and suppress the oxidation of Sn^(2+)remarkably,hence reduce trap state density and non-irradiative recombination in the absorber films.Furthermore,the SCG film holds the band levels matching better with carrier transport layers and herein favoring charge extraction at the device interfaces.Consequently,a champion device efficiency of 8.07% was achieved alo ng with significant enhancements in VOC and JSC,in contrast to 5.35% of the control device value.Moreover,the SCG film-based devices also exhibit superior stability comparing with the control one.This work explicitly paves a novel and general strategy for developing high performance lead-free PSCs.

Stability of Crystal Growth Face and Dissolution Face in Crystallization from Solution under Microgravity

The stability of the shapes of crystal growth face and dissolution face in a two-dimensional mathematical model of crystal growth from solution under microgravity is studied. It is proved that the stable shapes of crystal growth face and dissolution face do exist, which are suitably shaped curves with their upper parts inclined backward properly.The stable shapes of crystal growth faces and dissolution faces are calculated for various values of parameters, Ra, Pr and Sc. It is shown that the stronger the convection relative to the diffusion in solution is, the more backward the upperparts of the stable crystal growth face and dissolution face are inclined. The orientation and the shape of dissolution face hardly affect the stable shape of crystal growth face and vice versa.

A MATHEMATICAL EXPRESSION OF CRYSTAL GROWTH RATE DURING CRYSTALLIZATION OF AMORPHOUS ALLOYS

A mathematical expression of the crystal growth rate during crystallization of the amorphous alloys was derived from the micromechanism of crystallization newly developed by the authors. Thus, the satisfactory explanation of the experimental results obtained by Nunogaki et al., Heimendahl et al. and the authors might be found. It seems also to be modelled with the expression for the crystal growth and the crystal size influenced by time during the crystallization of amorphous Ni-P alloy foil at in situ heating. Based on the expression, the factors influencing the crystal growth rate, such as temperature, time and microstructure of amorphous alloys have been discussed.

Single crystal growth and transport properties of narrow-bandgap semiconductor RhP_(2)

We report the growth of high-quality single crystals of RhP_(2),and systematically study its structure and physical properties by transport,magnetism,and heat capacity measurements.Single-crystal x-ray diffraction reveals that RhP_(2) adopts a monoclinic structure with the cell parameters a=5.7347(10)A,b=5.7804(11)A,and c=5.8222(11)A,space group P2_(1)/c(No.14).The electrical resistivityρ(T)measurements indicate that RhP_(2) exhibits narrow-bandgap behavior with the activation energies of 223.1 meV and 27.4 meV for two distinct regions,respectively.The temperaturedependent Hall effect measurements show electron domain transport behavior with a low charge carrier concentration.We find that RhP_(2) has a high mobilityμ_(e)~210 cm^(2)·V^(-1)·s^(-1)with carrier concentrations n_(e)~3.3×10^(18)cm^(3) at 300 K with a narrow-bandgap feature.The high mobilityμ_(e) reaches the maximum of approximately 340 cm^(2)·V^(-1)·s^(-1)with carrier concentrations n_^(e)~2×10^(18)cm^(-3)at 100 K.No magnetic phase transitions are observed from the susceptibilityχ(T)and specific heat C_(p)(T)measurements of RhP_(2).Our results not only provide effective potential as a material platform for studying exotic physical properties and electron band structures but also motivate further exploration of their potential photovoltaic and optoelectronic applications.

Single crystal growth and characterization of 166-type magnetic kagome metals

Kagome magnets were predicted to be a good platform to investigate correlated topology band structure,Chern quantum phase,and geometrical frustration due to their unique lattice geometry.Here we reported single crystal growth of 166-type kagome magnetic materials,including HfMn_(6)Sn_(6),ZrMn_(6)Sn_(6),GdMn_(6)Sn_(6)and GdV_(6)Sn_(6),by using the flux method with Sn as the flux.Among them,HfMn_(6)Sn_(6)and ZrMn_(6)Sn_(6)single crystals were grown for the first time.X-ray diffraction measurements reveal that all four samples crystallize in HfFe6Ge6-type hexagonal structure with space group P6/mmm.All samples show metallic behavior from temperature dependence of resistivity measurements,and the dominant carrier is hole,except for GdV6Sn6 which is electron dominated.All samples have magnetic order with different transition temperatures,HfMn_(6)Sn_(6),ZrMn_(6)Sn_(6)and GdV_(6)Sn_(6)are antiferromagnetic with TN of 541 K,466 K and 4 K respectively,while GdMn_(6)Sn_(6)is ferrimagnetic with the critical temperature of about 470 K.This study will enrich the research platform of magnetic kagome materials and help explore the novel quantum phenomena in these interesting materials.The dataset of specific crystal structure parameters for HfMn_(6)Sn_(6)are available in Science Data Bank,with the link.

Probing the Nucleation and Growth Kinetics of Bismuth Nanoparticles via In-situ Transmission Electron Microscopy

The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.

Control of GaN inverted pyramids growth on c-plane patterned sapphire substrates

Growth of gallium nitride(GaN)inverted pyramids on c-plane sapphire substrates is benefit for fabricating novel devices as it forms the semipolar facets.In this work,GaN inverted pyramids are directly grown on c-plane patterned sapphire substrates(PSS)by metal organic vapor phase epitaxy(MOVPE).The influences of growth conditions on the surface morphol-ogy are experimentally studied and explained by Wulff constructions.The competition of growth rate among{0001},{1011},and{1122}facets results in the various surface morphologies of GaN.A higher growth temperature of 985 ℃ and a lowerⅤ/Ⅲratio of 25 can expand the area of{}facets in GaN inverted pyramids.On the other hand,GaN inverted pyramids with almost pure{}facets are obtained by using a lower growth temperature of 930℃,a higherⅤ/Ⅲratio of 100,and PSS with pattern arrangement perpendicular to the substrate primary flat.

Role of Crystal Seed in Aluminum Hydroxide Crystallization from Ammonia System with Added NH_(4)Al(SO_(4))_(2)·12H_(2)O

A method to promote aluminum hydroxide crystal growth through pickling Al(OH)_(3)as seed in the ammonia system was proposed to overcome these defects.The experimental results show that,under the conditions of pickling time of 15 min,the acid concentration of 10%,the addition of 70 g/L pickling-Al(OH)_(3)seed,and the coarse granular Al(OH)_(3)products(d0.5=85.667)can be obtained.The characterization results show that the phase of the product is gibbsite,consistent with the seed.Moreover,the steps and ledges can be formed on pickling Al(OH)_(3)seed surface under the ammonia system,effectively promoting crystal growth.During crystal growth,the roughness of the crystal surface was first increased and then decreased,and the lamellar structure was deposited on the crystal seed surface.The final particles are approximately round,the surface is compact and dense.The growth of the product is surface reaction controlled.In addition,the content of the AlO_(6)unit is increased and contributed to Al(OH)_(3)crystal growth.

Growth mechanism of primary silicon in cast hypoeutectic Al-Si alloys

The microstructural features of hypoeutectic AI-10%Si alloy were observed using optical microscopy and electron backscatter diffraction. The results show that primary silicon particles are frequently found in hypoeutectic alloys. Hence, the nucleation and growth mechanisms of the precipitation of primary silicon of hypoeutectic Al-10%Si alloy melts were investigated. It was discovered that Si atoms are easy to segregate and form Si-Si clusters, which results in the formation of primary silicon even in eutectic or hypoeutectic Al-Si alloys. In addition, solute redistribution caused by chemical driving force and large pile-ups or micro-segregation of the solute play an important role in the formation of the primary silicon, and the solute redistribution equations were derived from Jackson-Chalmers equations. Once Si solute concentration exceeds eutectic composition, primary silicon precipitates are formed at the front of solid/liquid interface.

Anisotropic and temperature-dependent growth mechanism of S-phase precipitates in Al-Cu-Mg alloy in relation with GPB zones

By employing atomic-resolution imaging and first principles energy calculations, the growth behavior of S-phase precipitates in a high strength A1-Cu-Mg alloy was investigated. It is demonstrated that the nucleation and growth of the S-phase precipitate are rather anisotropic and temperature-dependent companying with low dimensional phase transformation. There are actually two types of Guinier-Preston （GP） zones that determine the formation mechanism of S-phase at high aging temperatures higher than 180 ℃. One is the precursors of the S-phase itself, the other is the structural units or the precursors of the well-known Guinier-Preston-Bagaryatsky （GPB） zones. At high temperatures the later GPB zone units may form around S-phase precipitate and cease its growth in the width direction, leading to the formation of rod-like S-phase crystals; whereas at low temperatures the S-phase precipitates develop without the interference with GPB zones, resulting in S-phase orecioitates with lath-like momhology.

Precipitates identification in R_2PdSi_3(R= Pr,Tb and Gd) single crystal growth

Floating zone method with optical radiation heating was applied to growing a class of R2PdSi3（R=Pr,Tb and Gd） single crystals due to its containerless melting and high stability of the floating zone.One serious problem during the single crystal growth,precipitates of secondary phases,was discussed from the following four parts：precipitates from the raw materials and preparation process,precipitates formed during the growing process,precipitates in the melts and precipitates in the grown crystals.Annealing treatment and composition shift can effectively reduce the precipitates which are not formed during the crystallization but precipitated on post-solidification cooling from the as-grown crystal matrix because of the retrograde solubility of Si.

Microstructure and crystal growth direction of Al-Cu alloy

The microstructures and crystal growth directions of permanent mould casting（PMC） and directionally solidified（DS） Al-Cu alloys with different contents of Cu were investigated. Simultaneously, the effects of pouring temperature on the microstructure and crystal growth direction of permanent mould casting pure Al were also discussed. The results indicate that the α（Al） crystals in the pure Al do not always keep common columnar grains, but change from the columnar grains to columnar dendrites with developed arms as the pouring temperature rises. The growth direction also varies with the change of pouring temperature. Cu element has similar effects on the microstructures of the PMC and DS casting Al-Cu alloys and the α（Al） crystals gradually change from columnar crystals in turn to columnar dendrites and developed equiaxed dendrites as the Cu content increases. The crystal growth direction in the PMC alloys gradually approaches （110） orientation with increasing Cu content. But the resulting crystals with growth direction of （110） do not belong to feathery grains. There are also no feathery grains to form in all of the DS Al-Cu alloys.

Low-Temperature Growth and Photoluminescence of SnO_2 Nanowires

SnO2 nanowires with a diameter of 25nm are synthesized at 550~C by Au-Ag catalyst assisted thermal evapora- tion of SnO powders. The room-temperature photoluminescence spectra （PL） of the prepared nanowires are measured. Among the four PL peaks,the peak of 418nm is newly observed. This peak is caused by the plane defects of the twinned crystal nanowires. The formation of SnO2 nanowires at low temperature is pursued on the basis of the VLS mechanism and application of the reaction source of SnO. We suggest that the chemical reactions of the low temperature and low concen- tration of the vaporized species are responsible for the thinner size of the SnO2 nanowires.

Crystal growth of Gd_2PdSi_3 intermetallic compound

Gd2PdSi3 single crystals were grown by a vertical floating zone method with radiation heating at a zone traveling rate of 3 mm/h. The compound exhibited congruent melting behavior at a liquidus temperature of about 1700 ＆#176;C. The slightly Pd-depleted composition of the crystal, with respect to the nominal Gd2PdSi3 stoichiometry, led to gradual accumulation of Pd in the traveling zone and to a decreasing operating temperature during the growth process. Thin platelet-like precipitates of a GdSi phase were detected in the stoichiometric feed rod growth crystal matrix which can be reduced by annealing treatment. Feed rod composition shift crystal growth was proved to be a better way of getting high quality of Gd2PdSi3 single crystal.

Crystal Growth of Nitrogenase CrFe Protein and MnFe Protein in Space

Nitrogenase CrFe protein and MnFe protein were purified from a mutant strain UW3 of Azotobacter vinelandii Lipmann grown on a medium containing Cr and Mn, respectively. In order to meet the requirement for crystal growth Of O-2-susceptible proteins including nitrogenase in space, crystallization conditions were optimized for the proteins using a simple and suitable device, as a replacement for the cumbersome anaerobic box (dry box), for anaerobic addition of the protein samples. In all used precipitant and protein solutions added in the simplified plexi glass box, CrFe protein and MnFe protein could be crystallized on the spacecraft in one week by the liquid/liquid diffusion method and vapor diffusion by the sitting drop method, respectively. All formed crystals were single on the spacecraft, but under the same condition twin crystals appeared on the ground. The size of the largest crystal grown in space from CrFe protein was 2-fold larger than that on the ground. But the size of the largest crystal grown in space from MnFe protein was not larger than that on the ground. The difference in crystal growth in space between CrFe protein and MnFe protein could be resulted from the crystallization method, rather than the kind of protein.

Growth of Large Single Crystals of Nitrogenase CrFe Protein and MnFe Protein

By using the liquid/liquid diffusion method at a suitable crystallization conditions, large single and dark brown crystals (the sides of the largest crystals were 0.20 mm x 0.20 mm x 0.07 min and 0.18 mm x 0.18 mm x 0.05 mm, respectively) could be obtained from the solutions of nitrogenase CrFe protein and MnFe protein purified from a mutant UW3 of Azotobacter vinelandii Lipmarm grown in Cr- or Mn-containing but NH3-free medium. The time of crystal formation, as well as the number, size, shape and quality of crystals obviously depended on the concentrations of PEG, MgCl2 and NaCl. The liquid/liquid diffusion method seems to benefit CrFe protein and MnFe protein for the growth of large single crystals for X-ray diffraction analysis.

Simulation aided hot zone design for faster growth of CZ silicon mono crystals

Computer simulation was used for optimizing a hot zone for Czochralski （CZ） silicon crystal growth. The heater structure and heat shield material were investigated. With this optimized hot zone, the temperature gradient near the crystal/melt interface increased and the CZ crystal could be grown at a faster rate. It is a great contribution for saving power consumption.

Recent advances of pharmaceutical crystallization theories

As a technology of separation and purification,crystallization plays a vital role in diverse industries such as inorganic salt,pharmaceutical,and food industries,which has a huge impact on purity,crystal polymorph,crystal morphology,and particle size distribution of final products.In the past few decades,with the rapid advancement of experimental approaches and molecular simulation methods,considerable advances in the interpretation of crystallization mechanisms have been obtained,promoting the investigation and understanding of crystallization theories greatly.In this review,the advances of pharmaceutical crystallization theories in recent years from the perspectives of nucleation and crystal growth are summarized and discussed.Two thermodynamic models that are helpful in the study of the crystallization mechanisms will be introduced.In this section,the perturbed-chain statistical associating fluid theory(PC-SAFT)and a chemical-potential-gradient model will be introduced,which have been successfully applied in pharmaceutical solubility prediction,the research of dissolution mechanism as well as dissolution kinetics analysis.These two models are expected to be applied to the study of pharmaceutical crystallization process and mechanism.Furthermore,molecular simulation based on the interaction between particles can provide structural information,thermodynamics,and dynamics properties of complex systems at the molecular level,like intermolecular interaction and surface adsorption energies.Application and some shortcomings of molecular simulation,especially molecular dynamics simulation,in the field of pharmaceutical crystallization will be expounded.

Effect of Additive EDTA on Crystallization Process of Magnesium Hydroxide Precipitation

The effects of additive ethylenediaminetetraacetic acid (EDTA) on crystallization process were investigated by the induction time of MgSO 4-NaOH system. Nucleation and growth rates, growth mechanism and particle size distribution of magnesium hydroxide precipitation were involved with. The induction time in unseeded and seeded precipitation of magnesium hydroxide with and without additive EDTA was measured. The conductivity method was used to determine the induction period. Theoretical relations of the induction time and supersaturation ratio for different growth mechanisms and a combined analysis on the induction time were applied to determine nucleation and growth rates. The growth mechanism of magnesium hydroxide precipitation was disclosed by analyzing the experimental data with and without additive. The analysis on induction time indicated that additive EDTA had a significant influence on both nucleation and growth of magnesium hydroxide precipitation. The mechanism underlying the effect of EDTA on crystal growth was 2-dimension nucleation-mediated growth model.