Crystal growth,optical, mechanical and electrical properties of organic NLO material γ‐glycine

Single crystals of organic non‐linear optical material, γ‐glycine have been grown by gel method for the first time. The γ‐phase is confirmed by single crystal XRD. The presence of various functional groups of γ‐glycine are confirmed by FTIR. The UV‐Vis‐NIR spectrum reveals the high percentage of transmission of the sample in the entire visible region. The SHG of γ‐glycine is confirmed by Kurtz powder technique. TGA‐DTA studies indicate that the crystal is structurally stable upto 170 °C. Microhardness investigations are conducted on the grown crystals. The dielectric constant measurements are carried out and the nature of variation of dielectric constant ε′ and dielectric loss D in the frequency range of 50 Hz to 5 MHz is studied and reported. Photoconductivity studies of γ‐glycine crystals revealed the negative photoconducting nature. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Impact of malonic acid on the segregation of glycine polymorphs – Analytical assisted molecular approach

Proton dissociation assisted negative polarity of malonic acid molecules admist glycine zwitterions leads to orgination of γ nucleation in the solution. Alteration in the nucleation behaviour and segregation of glycine polymorphs in the presence of malonic acid over a wide range of concentrations has been investigated both by experimental and analytical approaches. Complete changeover in the nucleation behaviour from 100% α to 100% γ is observed at the critical concentration of the additive. Shifting in the overall charge environment of the system towards cationic in the presence of malonic acid favours the nucleation of γ through induced charge compensation in the solution. Tuning of merohedral twinning in γ nucleation by the additive concentration has been well revealed in the present work. CNT based analytical approach employed elucidates well the experimental observations through the estimated interfacial energy, volume excess free energy, critical radius, activation energy barrier and nucleation rates of α and γ polymorphs. Structural affirmation of the nucleated polymorphs was carried out by powder x‐ray diffraction.     

Effect of strontium chloride on the optical and mechanical properties of γ–glycine crystals

Single crystals of γ‐glycine have been grown from aqueous solution in the presence of small amount of strontium chloride. Single crystal X‐Ray diffraction analysis was used to measure the unit cell parameters and to confirm the crystal structure. The grown crystals have also been subjected to powder X‐Ray diffraction study to identify the crystalline nature. The presence of all the functional groups of the γ‐glycine has been confirmed by Fourier Transform Infrared (FTIR) spectral analysis. The presence of hydrogen and carbon in the glycine molecules was confirmed by using proton and carbon nuclear magnetic resonance (NMR) spectral analyses. Optical behavior of the crystal was studied using UV – Visible absorbance spectroscopy and second harmonic generation (SHG) studies. The SHG efficiency of γ‐glycine is greater than that of standard potassium dihydrogen phosphate (KDP). Mechanical strength of the γ‐glycine crystal has been determined by microhardness studies. Thermal stability of the grown crystal is probed using thermo gravimetric analysis and differential thermal analysis. Laser damage threshold value has been determined using Q‐switched Nd:YAG laser operating at 1064 nm and with 13 ns pulse width in single shot mode. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

XRD,thermal, FTIR and SEM studies on gel grown γ‐glycine crystals

Glycine is the smallest among amino acids. The polymorphs, α‐ and γ‐forms of glycine were crystallized in silica gel by reduction of solubility method. The grown crystals were characterized by single crystal X‐ray diffraction studies and density determination. Fourier transform infrared spectroscopic studies and thermogravimetric analysis of γ‐glycine were also conducted. Morphological and scanning electron microscopic (SEM) studies were also made and compared with the crystal packing. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization of β‐glycine by spray drying

Glycine crystallization during spray drying has been investigated on a laboratory scale. In order to obtain different polymorphs the experiments have been performed at different hot air temperatures, concentrations, different flow of the solution and spraying air. The obtained crystals were analyzed by means of X‐ray powder diffractometry, differential scanning calorimetry and the Fourier transform infrared spectrometry. Crystallization mostly resulted with a mixture of α‐ and β‐glycine with a small amount of γ‐glycine. The glycine polymorphism is affected by the drying air temperature, concentration and the flow of the solution, as well as the spraying air flow. Decrease of the drying air temperature and increase of the solution flow rate causes the increase of the quantity of β‐glycine. At room conditions, β‐glycine spontaneously transforms into thermodynamically more stable α‐glycine. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of α and γ polymorphs of glycine crystallized from water‐ammonia solution

Crystallization of metastable α and stable γ polymorphs of glycine was carried out from aqueous solution in the presence of ammonia. Pure aqueous solution and solution with lower concentration of ammonia yield α nucleation and solution with a critical concentration of ammonia yield γ nucleation. Variation in the solubility of glycine in double distilled water and pH of the resulting solution due to the ammonia incorporation was studied in a range of temperatures. The induction period for the α and γ nucleation in the solution was determined and its variation due to the ammonia incorporation was also studied. Single crystals of both the polymorphs were grown by slow evaporation method. Effect of ammonia concentration and the resultant pH of the solution on the nucleation, growth and morphology of the grown polymorphs were investigated. The unidirectional growth of the γ polymorph along the polar axis was revealed. X‐ray powder diffraction method was employed to distinguish both the polymorphs structurally. Their thermal stability above room temperature was studied by differential scanning calorimetry which revealed that the as‐grown γ polymorph transforms to α at 179.6 °C while the as‐grown α retains its phase until melting. The optical transmittance of the grown γ polymorph was studied in the UV‐Vis‐Near IR region. The second harmonic generation (SHG) efficiency of the grown γ polymorph was studied with a Nd:YAG laser source and is about 6.8% higher than that of the inorganic standard KDP. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of 4,4′‐dihydroxy‐α‐methylstilbene crystal

4,4′‐dihydroxy‐α‐methylstilbene (DHAMS) was synthesized by condensation reaction with chloroacetone and phenol in the presence of concentrated sulfuric acid, and has been successfully grown by solution growth technique. This is the first report in the literature on the crystallization of DHAMS and exhibited the birefringent melt (liquid crystal property) of the optical properties. FTIR and FTNMR studies are in accordance with the structure. Good quality crystals were grown by slow evaporation technique by acetone as solvent. A transmission spectrum of the crystal was obtained in the region of 285 nm. The structural and optical properties were studied. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth Habit and Habit Variation of γ‐CuI Crystallites under Hydrothermal Conditions

The octahedra were observed in the γ CuI crystallites synthesized by hydrothermal method using 1.6g (C₂H₅OO)₂Cu and 2.66g KI as precursors at 200 °C for 12 hours in the de‐ionized water. The effect of additives on the morphology of γ‐CuI crystallites was investigated. Results show that the morphology of γ‐CuI crystallites prepared in the mixed solution of de‐ionized water and alcohol at 200 °C for 12 hours is the tetrahedron. In order to disclose the effect of the additive on the growth habit of γ‐CuI crystallites, the microcosmic growth mechanism of γ‐CuI crystal is investigated from the complex of I^‐ and Cu⁺ ions to each other. It is concluded that the effect of alcohol on the morphology of γ‐CuI crystallites is carried out through changing the relative rate of complex of anion and cation to each other at the interface. Based on the above analysis, the growth habit of γ‐CuI crystallites and the habit variation under hydrothermal conditions are explained reasonably.     

Recharging processes of Cr ions in Mg2SiO4 and Y3Al5O12 crystals under influence of annealing and γ ‐ irradiation

Recharging processes of chromium ions were investigated for Mg₂SiO₄:Mg, Cr single crystals using annealing in O₂ and in air and γ‐irradiation, as compare to YAG :Ca, Cr single crystals. The formation of tetravalent Cr ions in the Mg₂SiO₄ :Mg, Cr is related not only to the initial Cr content in the melt, oxygen partial pressure and O₂‐ vacancy existing in the crystal, but also to the external field such as γ‐irradiation. The additional absorption after γ‐irradiation shows the decrease in intensity of the absorption of Cr³⁺ and Cr⁴⁺ ions in some part of the spectrum and increase in the other giving evidence on recharging effects between Cr³⁺ and Cr⁴⁺. There arises also color centers observed between 380 nm and 570 nm that may participate in energy transfer of any excitation to Cr⁴⁺ giving rise to Cr⁴⁺ emission. Opposite to forsterite crystal, absorption spectrum of YAG:Ca, Cr crystal after γ‐irradiation reveals only increase in the absorption of the Cr bands. The observed behavior of the absorption spectrum of YAG:Ca, Cr crystal under influence of γ‐irradiation suggests that γ‐irradiation ionizes only Cr ions. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical and Luminescence Properties of YAlO3 ‐Tm Crystals

The results on optical absorption, photoluminescence and thermoluminescence of YAP‐Tm crystals of 1 at.% and 4 at.% of Tm are presented as well as influence of UV‐, γ‐radiation and thermal treatments on optical and luminescence properties of the crystals. The blue‐green luminescence of defect centers was observed in YAP‐Tm crystals at Ar⁺‐laser excitation. The possibility of energy transfer processes between defect centers and Tm³⁺ ions was shown.     

A detailed study of gold single crystal growth in a silica gel

Gold single microcrystals have been fabricated by electrochemical growth in a silica gel. Structural characterization of the single crystals by backscatter electron diffraction showed a preferred orientation of Au (1 1 1) and a minor orientation of Au (1 0 0). In addition, the influence of additives on the nucleation and growth of gold microcrystals has been studied. It was found that the inclusion of chemical additives in the growth solutions altered the characteristics of the gold crystals. Possible mechanisms for nucleation and growth of these crystals are discussed.     

Microscopic study of polymorphism of a photographic coupler

Polymorphism and polymorphic transformation of a photographic coupler have been examined using hot stage optical microscopy (HSOM). Two different polymorphs, metastable needle-like crystals and stable cubic-like crystals, were identified on heating. A solid-state transformation was found to occur from the metastable form to the stable form. Both polymorphs can precipitate from coupler solutions. The needle-like crystals appear in all cases examined; the cubic-like crystals precipitate only with higher concentrations and lower cooling rates. The solution-mediated transformation occurs in an organic solvent through dissolution of the metastable polymorph and growth of the stable polymorph. The growth rate of the stable polymorph is dependent on temperature as well as concentration. The activation energy of the growth is estimated for coupler solutions with different concentrations.     

基于钠助熔剂法的GaN单晶生长研究进展

宽禁带氮化镓(GaN)材料以其独特的性质和应用前景成为国内外研究的热点,高质量GaN单晶衬底的制备是获得性能优异的光电子器件和功率器件的基础。钠助熔剂法生长条件温和,易获得高质量、大尺寸的GaN单晶,是一种具有广阔商业化前景的GaN单晶生长方法。钠助熔剂法自20世纪90年代末期被发明以来,经过20多年的发展,钠助熔剂法生长的晶体在尺寸与质量上都取得了长足的进步。本文从晶体生长原理和关键工艺(籽晶选择、温度梯度以及添加剂)等方面综述了钠助熔剂法生长GaN单晶研究进展,并对其面临的挑战和未来发展趋势进行了展望。     

Self-selecting vapour growth of bulk crystals – Principles and applicability

A method of self-selecting vapour growth (SSVG) for bulk binary and multernary crystals of semiconducting materials is reviewed comprehensively for the first time. Although it has been developed over three decades, the method is less well known – even though it is physically distinct from the more widely used ‘Piper–Polich’ and ‘Markov–Davydov’ vapour transport bulk growth methods. The means by which growth takes place on a polycrystalline source to form a crystal free from the walls is described. Modelling and empirical observations have been used to establish the characteristics of the almost isothermal temperature fields that drive the transport in SSVG. It is demonstrated that precise control of thermal radiation is a fundamental requirement for tailoring the temperature distribution—a fact that has been used well in the design of horizontal tube furnace growth rigs. Achievements in the growth of useful PbS, PbSe, PbTe, CdTe and ZnTe compound crystals are described. The SSVG method has proved to be particularly well suited to the growth of solid solutions, and the results of growth experiments, and of compositional and structural analysis, are presented for Pb(Se,S), (Pb,Sn)Se, (Pb,Sn)Te, (Pb,Ge)Te, Cd(Te,Se), Cd(Te,S) and (Cd,Zn)Te. The excellent compositional uniformity delivered is attributed to entropy driven mixing in the low thermal gradients present in SSVG.

To date, most SSVG has been done at the <50 g level for research or small scale production use. Prospects for scaling up the growth are considered, there being no barriers identified in principle. However, there is a limitation in that the shape of the grown crystals is not accurately controlled at present. To overcome this, and to offer an alternative method of scaling up, the use of vertical tube systems is explored. A significant additional advantage of the vertical configuration is that it allows for continuous recycling of the source/crystal mass so as to continuously self-refine the increasingly uniform – and crystalline – product. Achievements to date in growing II–VI and IV–VI crystals are described for prototype vertical SSVG systems. Finally, future prospects for the SSVG method in terms of further developments to the method, and the specific materials that will benefit from it are highlighted.     

Investigations on the nucleation kinetics of bis glycine sodium nitrate

The nucleation parameters such as, energy per unit volume, radius of critical nucleus, critical free energy barrier, number of molecules in the critical nucleus and nucleation rate have been evaluated for bis glycine sodium nitrate single crystals. The interfacial energy of the solution at various temperatures has been estimated from existing solubility data. The metastable zone width and induction period measurements have been carried out experimentally.     

Spherulitic crystallization of β‐In2Te3 by physical vapour deposition

Different morphologies of indium telluride (In₂Te₃) including novel spherulites were crystallized using the physical vapour deposition (PVD) method, by varying the difference in the growth and source zone temperature (ΔT) of a dual zone horizontal furnace assembled indigenously. Whiskers and kinked needles of In₂Te₃were grown at ΔT = 250 K and 300 K respectively, maintaining the growth zone at 500 °C. At high supersaturation (Δ T = 400 K), spherulitic crystals were obtained. The stoichiometric composition of these crystals has been confirmed using energy dispersive analysis by x‐rays (EDAX). The structure of β‐In₂Te₃ spherulitic crystals is identified as zinc blende with lattice parameter a = 6.159 Å, from x‐ray diffraction (XRD) studies. The scanning electron microscope (SEM) images revealed the radial structure of the grown spherulites. The growth mechanism for the spherulitic crystallization of β‐In₂Te₃ crystals has been discussed based on the theoretical models. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Oberflächenstörungen und Hohlwachstum bei der Züchtung von β-Kupferphthalocyanin-Einkristallen aus der Gasphase

Hollow crystals are obtained frequently during the growth of copper phthalocyanine single crystals from the vapour phase. This appearance makes some physical investigations impossible. To overcome these difficulties some ways are discussed. The reasons for hollow growth are instabilities in the growth caused by diffusion controlled inhomogeneities in supersaturation on the growth front. This was found by observations of surface defects and by defined growth experiments. By introduction of special methods of growth and use of defined parameters one obtains bulk crystals of larger extent up to 1 mm in cross direction. References are given in the field of hollow crystal growth in the vapour phase of other substances.     

Effect of citric acid and 1,2‐dihydroxybenzene 3,5‐disulfonic acid on crystallization of calcium sulfate dihydrate under simulated conditions of phosphoric acid production

The effect of citric acid and 1,2‐dihydroxybenzene 3,5‐disulfonic acid (DHBDSA), as additives, on the crystallization of gypsum was studied under simulated conditions of the of phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 °C, and the turbidity of the reaction mixture was measured at different time periods to calculate the induction time of gypsum crystals formation. Addition of citric acid increased the induction time and decreased the growth efficiency while addition of DHBDSA decreased the induction time and increased the growth efficiency compared with in absence of additives. The crystals mean and median diameters were found to decrease in the presence of citric acid and increased in the presence of DHBDSA. The surface energy decreased with citric acid and increased with DHBDSA compared to the baseline (without additives). Interestingly, the majority of the formed crystals are tabular with DHBDSA and needle‐like type with citric acid and baseline     

Growth and characterization of 4‐(2‐hydroxyphenylamino)‐pent‐3‐en‐2‐one single crystals

4‐(2‐hydroxyphenylamino)‐pent‐3‐en‐2‐one (HPAP) was synthesized and single crystals were grown by the solution growth technique using methanol as a solvent. The crystals having orthorhombic symmetry were characterized by single crystal XRD, FTIR spectroscopy, NMR spectroscopy, TGA, DSC and dielectric studies. Very less variation in the value of dielectric constant is found for different frequencies of applied field. The crystals were exhibiting positive photoconductivity and poor NLO responses. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Zur Gleichgewichts- und Wachstumsform von β-Kupferphthalocyanin-Einkristallen

The equilibrium shape of β-copper-phthalocyanine single crystals is obtained by the method of the PBC-vectors according to HARTMAN and PERDOK . These results agree well with the experimentally found growth shape of single crystals grown in the vapour phase. The crystals are of needle-like shape. The crystal surfaces are lattice planes of the kind {001}, {201 }, {100}, {101 } and {110}. The ratio of length to width of the crystals is influenced by the inert gas pressure during the growth process. This dependence is caused by the diffusion of the nutrient.