硫酸盐掺杂导致KDP晶体开裂的研究

采用传统降温法生长了掺杂不同浓度的SO42-离子KDP晶体,研究分析了晶体的宏观缺陷及开裂形式,从晶体生长角度初步分析了硫酸盐掺杂导致KDP晶体开裂的主要原因。实验表明,随着SO42-离子掺杂浓度的增大,KDP晶体的主要开裂形式是垂直于生长层{101}面的裂纹;晶体中裂纹存在的区域都分布有大量层层平行于生长层的母液包藏。随着SO42-离子掺杂浓度的进一步增大,晶体内包藏呈云雾状分布,裂纹不规则,晶体质量严重下降,透明度降低。     

Investigating optical,electrical, and mechanical traits of thiourea admixtured KDP single crystals to explore NLO device applications

The 0.5 and 1 mol% thiourea “mixed” potassium dihydrogen phosphate (KDP) crystals have been developed by conventional slow solution evaporation method. The crystallographic parameters of grown crystals have been determined by employing single crystal X-ray diffraction technique. The functional groups of grown crystals were successfully identified by means of FTIR spectral analysis. The optical transmittance is 79%, 84%, and 89% for KDP, 0.5 mol thiourea mixed KDP, and 1 mol thiourea mixed KDP crystal. The energy band gap (E_g) of KDP, 0.5 mol thiourea mixed KDP, and 1 mol thiourea mixed KDP crystal is 3.71 eV, 3.61 eV, and 3.75 eV, respectively. The Kurtz–Perry test has been employed to determine the SHG efficiency and SHG efficiency of 0.5 and 1 mol thiourea mixed KDP crystal is 2.09 and 2.22 times superior to KDP crystal. Effect of thiourea mixing on hardness properties of KDP crystal have been scrutinized using the Vickers microhardness studies. The frequency dependent dielectric behavior of grown crystals has been analyzed at room temperature.

     

Solution growth of KDP single crystals doped with titanium dioxide nanoparticles

Pure KDP single crystals and KDP crystals doped with TiO₂ nanocrystals were grown by the method of temperature reduction from aqueous solutions. Adsorption of the phosphate-ions on the surface of TiO₂ particles was studied by FTIR spectroscopy. It was shown that the nanoparticles with adsorbed H₂PO₄^– and (H₂PO₄)₂^2–anions were incorporated predominantly into the positively charged face (1 0 1) of the pyramidal sector of KDP. High-resolution X-ray three-crystal diffractometry (TCD) investigation of the as grown samples of KDP + TiO₂ revealed the presence of the turns of the growth layer “stacks” up to 3 arcsec in the growth sectors {1 0 0} and {1 0 1}. The observed thickness of these “stacks” was of the order of 20–30 μm. For KDP + TiO₂ crystals there was found a relative change of the crystal lattice parameter (Δd/d) caused by incorporation of TiO₂ nanoparticles into the boundaries of the growth layers. This gave rise to the formation of a semicoherent binding on the interface between the captured TiO₂ and the matrix. No essential influence of the nanoparticles on the laser damage threshold of KDP with 10⁻⁵ wt.% of TiO₂ was established.     

Synthesis,growth, optical,mechanical and electrical properties of <Emphasis Type="Italic">L</Emphasis>-lysine <Emphasis Type="Italic">L</Emphasis>-lysinium dichloride nitrate (<Emphasis Type="Italic">L</Emphasis>-LLDN) single crystal

Semi-organic nonlinear optical material, L-lysine L-lysinium dichloride nitrate (2C₆H₁₅N₂O₂⁺_{2}^{+} · H⁺ · NO₃^-_{3}^{-} · 2Cl⁻) was synthesized at room temperature. Single crystals of L-LLDN were grown by slow cooling solution growth technique. The grown crystal was confirmed by powder X-ray diffraction analysis. The crystalline perfection of the grown single crystal was characterized by high-resolution X-ray diffraction (HRXRD) studies. The cut-off wavelength was determined by UV-vis transmission spectral analysis. The frequency doubling of the grown crystal was confirmed by powder second harmonic generation (SHG) measurement. The refractive index and birefringence of the crystal were determined using He–Ne laser source. Mechanical property of the crystal was determined by Vickers hardness tester. The frequency and temperature dependence of dielectric constant (ε _r), dielectric loss (tan δ) and a.c. conductivity (σ _ac) were also measured.     

Effective Distribution Coefficients of Cation Impurities in KDP Crystals

The effective distribution coefficients of 19 elements are measured in the {100} and {101} sectors of KDP single crystals grown from stoichiometric solutions. The results indicate that, at low impurity concentrations in the solution, depends on the mechanism of the incorporation of cations (which form three types of defect centers in the structure of KDP) and their ionic radius. Increasing the concentrations of several divalent cations in solution may reduce their distribution coefficients because of the competition between the cations for interstitial sites in KDP.     

Studies on lithium l-ascorbate dihydrate: An interesting chiral nonlinear optical crystal

Lithium l-Ascorbate dihydrate (LLA) is a new metal organic nonlinear optical crystal belonging to the saccharide family. Single crystals of LLA were grown from aqueous solution. Solubility of the crystal has a positive temperature coefficient facilitating growth by slow cooling. Rietveld refinement was used to confirm the phase formation. The crystal has prismatic habit with (010), (001) and (10−1) prominent faces. Thermal analysis shows that the crystal is stable up to 102 °C. Transmission spectrum of the crystal extends from 302 nm to 1600 nm. Dielectric spectroscopic analysis revealed Cole–Cole behaviour and prominent piezoelectric resonance peaks were observed in the range of 100–200 kHz. Second harmonic generation (SHG) conversion efficiency of up to 2.56 times that of a phase matched KDP crystal was achieved when the (010) plate of LLA single crystal was rotated about the +ve c axis, by 9.4° in the clockwise direction. We also observed SHG conical sections which were attributed to noncollinear phase matching. The observation of the third conical section suggests very high birefringence and large nonlinear coefficients. A detailed study of surface laser damage showed that the crystal has high multiple damage thresholds of 9.7 GW cm⁻² and 4.2 GW cm⁻² at 1064 nm and 532 nm radiation respectively.     

Melt growth of novel organic nonlinear optical material and its characterization

Ethyl P-amino benzoate (EPAB) is also known as benzocaine was recently identified as new organic non linear optical (NLO) material which is having nearly six times higher SHG efficiency than that of KDP. Hence, growth of unidirectional EPAB crystal gains importance for phase matching studies and this is the first melt growth report of EPAB single crystal. Seeding with the microtube in the present technique eliminates the need for pre-grown seed and has more probability to grow bulk single crystal. Growth direction of the μT-Cz grown EPAB single crystals was identified as <100> using X-ray powder diffraction studies. Thermal properties and optical transparency of the grown material were analyzed by TG and DTA and UV-VIS spectroscopic studies respectively. Laser damage threshold study shows nearly five times high damage threshold than KDP.     

TiO2和O-Al2O3晶体的生长习性

通过水热法制备粉体的实验观察到金红石、锐钛矿和α-Al2O3晶体的生长习性．采用配位多面体生长习性法则合理地解释了Ti O2和α-Al2O3的生长习性．其主要结果为α-Al2O3晶体的生长习性为平板{0001}，其各晶面的生长速度为：V｛0001 }＜V｛1123}；锐钛矿的生长习性为四面体，其各晶面的生长速度为V<010>=V<001>>V<010>>V<111>．而PBC理论很难合理地解释α-Al2 O3晶体的生长习性．     

Controlling the Nonlinear Optical Behavior and Structural Transformation with A-Site Cation in α-AZnPO4 (A = Li,K)

Regulating the crystal structure by A-site cation substitution is one of the effective methods to explore high-performance nonlinear optical (NLO) materials. Herein, two non-centrosymmetric (NCS) compounds, α-MZnPO₄ (M = Li, K) with short UV absorption edges 221 and 225 nm, are obtained by performing A-site cation substitution method. It is noteworthy that α-LiZnPO₄ (α-LZPO) achieves >10 times second harmonic generation (SHG) response (2.3 × KDP) enhancement compared with that of α-KZnPO₄ (α-KZPO) (0.2 × KDP), which is the only case among phosphates with different A-site cations. By structural comparison, it is found that the A-site cations play important roles for anion rearrangements, and further the structure features of the two compounds by designing two suppositional crystal models as well as performing other theoretical calculations are analyzed. The study confirms the feasibility to design promising NLO materials with strengthen SHG response and structural stability in orthophosphate system.     

Orientation of silicon particles in a binary Al–Si alloy

The orientations Si-crystals take in aluminium, in an alloy with composition Al–1.3at%Si, were investigated by transmission electron microscopy. Hardness was measured for isothermal heat-treatments at 175 °C and 260 °C. Conditions analysed by TEM were 17 h at 175 °C and an additional 3 h at 260 °C, both containing a high density of small Si-crystals, the finest corresponding to 175 °C. Two main orientation relationships were found: The first accounted for approximately 60% of Si precipitates in condition 17 h_175 °C. Despite a high number density and well-aligned interfaces, the Si precipitates have negligible influence on hardness. Findings are consistent with Ge particles in Al–Ge alloys.     

Experimental and theoretical characterization of semiorganic nonlinear optical material l-leucine hydrobromide

Semiorganic nonlinear optical material l-leucine hydrobromide (LEHBr) has been synthesized and single crystals were grown by solvent evaporation method at a constant temperature of 35 °C. CHN test, FTIR and XRD analysis were performed for identification of the material. Thermal and mechanical stability of the grown crystal were investigated by DTA-TGA analysis and microhardness measurement respectively. Suitability of LEHBr for NLO application was studied by optical transmission study and second harmonic generation (SHG) efficiency measurement. SHG efficiency was found to be 4 times of KDP. First hyperpolarizability, dipole moment and polarizability of LEHBr were calculated at the framework of Hartree–Fock (HF) with 6-311G(d) basis set. First order hyperpolarizability was found to be 3.233 × 10⁻³³ esu which is 4.9 times of urea.     

Investigations of structural defects,crystalline perfection,metallic impurity concentration and optical quality of flat-top KDP crystal

KDP crystal grown using flat-top technique has been characterized using X-ray and optical techniques with the aim of correlating the defects structure and impurity concentration in the crystal with its optical properties. Crystallographic defects were investigated using X-ray topography revealing linear and arc like chains of dislocations and to conclude that defects do not originate from the flat-top part of the crystal. Etching was performed to quantify dislocation defects density. The crystalline perfection of the crystal was found to be high as the FWHM of the rocking curves measured at several locations was consistently low 6–9 arc s. The concentration of Fe metallic impurity quantified using X-ray fluorescence technique was approximately 5 times lower in the flat-top part which falls in pyramidal growth sector as compared to the region near to the seed which lies in prismatic sector. The spectrophotometric characterization for plates cut normal to different crystallographic directions in the flat-top potassium dihydrogen phosphate (FT-KDP) crystal was performed to understand the influence of metallic impurity distribution and growth sectors on the optical transmittance. The transmittance of the FT-KDP crystal at 1064 nm and its higher harmonics (2nd, 3rd, 4th and 5th) was determined from the measured spectra and the lower transmission in the UV region was attributed to increased absorption by Fe metallic impurity at these wavelengths. The results are in agreement with the results obtained using X-ray fluorescence and X-ray topography. Birefringence and Mach–Zehnder interferometry show that except for the region near to the seed crystal the optical homogeneity of the entire crystal was good. The laser-induced damage threshold (LDT) values are in the range 2.4–3.9 GW/cm². The LDT of the plate taken from the flat-top region is higher than that from the bottom of the crystal, indicating that the flat-top technique has good optical quality and is comparable to those reported using rapid growth technique. The results indicate that the structural defects, crystalline quality and impurity concentration have a correlation with the optical properties of the FT-KDP crystal.     

The equilibrium orientation relationship between Pt and SrTiO3 and its implication on Pt films deposited by physical vapor phase deposition

The equilibrium orientation of Pt in contact with (100)-SrTiO₃, at 1050 °C and in an Ar/2 % O₂ environment, was determined by solid-state dewetting of continuous Pt films on single crystal SrTiO₃ substrates. Given the similar lattice parameters between Pt and SrTiO₃, a simple cube-on-cube orientation relationship was expected to form at equilibrium. However, only a preferred orientation of Pt {111} parallel to the SrTiO₃ (100) surface formed, without a low-index orientation relationship. It was found that reconstruction of the SrTiO₃ surface (a complexion) was responsible for the Pt particle texture. The equilibrium crystal shape of the Pt particles was analyzed and it was found to contain the following facets: {111}, {100}, {110}, and {113}.     

Epitaxial growth of CoSi2 on Si(001) by reactive deposition epitaxy: Island growth and coalescence

Epitaxial CoSi₂ layers, which are phase pure but contain {111} twins, are grown on Si(001) at 700 °C by reactive deposition epitaxy. Transmission electron microscopy analyses show that the initial formation of CoSi₂(001) follows the Volmer-Weber mode characterized by the independent nucleation and growth of three-dimensional islands whose evolution we follow as a function of deposited Co thickness t_Co in order to understand the origin of the observed twin density. We find that there are two families of island shapes: inverse pyramids and platelets. The rectangular-based pyramidal islands extend along orthogonal 〈110〉 directions, bounded by four {111} CoSi₂/Si interfaces, and grow with a cube-on-cube orientation with respect to the substrate: (001)_CoSi2||(001)_Si and [100]_CoSi2||[100]_Si. Platelet-shaped CoSi₂ islands are bounded across their long 〈110〉 directions by {111} twin planes (i.e. {111}(001)_CoSi2||{111}_Si) and their narrow 〈110〉 directions by {511}_CoSi2||{111}_Si interfaces. The top and bottom surfaces are {22¯1}, with {22¯1}_CoSi2||(001)_Si, and {1¯1¯1}, with {1¯1¯1}_CoSi2||{11¯1}_Si, respectively. The early stages of film growth (t_Co ≤ 13 Å) are dominated by the twinned platelets due to a combination of higher nucleation rates resulting from a larger number of favorable adsorption sites in the Si(001)2 × 1 surface unit cell and rapid elongation of the platelets along preferred 〈110〉 directions. However, at t_Co ≥ 13 Å island coalescence becomes significant as orthogonal platelets intersect and block elongation along fast growth directions. In this regime, where both twinned and untwinned island number densities have saturated, further island growth becomes dominated by the untwinned islands. A continuous epitaxial CoSi₂(001) layer, with a twin density of 2.8 × 10¹⁰ cm^− 2, is obtained at t_Co = 50 Å.     

Etch pits in flux-grown corundum

Procedures have been developed for chemically polishing and etching {0001}, {10¯11}, {10¯12}, {11¯20}, and {1¯100} planes in crystals of ruby and sapphire grown from a PbF₂ flux. The shape and the orientation of the etch pits were found to be characteristic for each plane and the density of the pits was 10² to 10⁴/cm². Similar pits were produced in flame-fusion material, but the density was 10⁶ to 10⁸/cm². Ruby and sapphire crystals grown by the same process behaved similarly. There is evidence that etch pits reveal dislocations which emerge normally to the basal or to the prismatic planes, since similar patterns of pits were produced after the removal of successive layers of material parallel to these planes, and a correlation was found between the pit patterns on opposite {0001} faces. Inconclusive evidence on this point was obtained for the rhombohedral planes.     

升华再结晶法制备AIN晶须及其生长特性

以AIN粉体为原料，加入适量的CaO-B2O3矿化剂，采用升华再结晶法制备AIN晶须．初步探讨了反应器及其合成温度对产物种类的影响，研究了晶须的结构特征及其生长机理．结果表明，初期的合成产物包括AIN晶柱、晶须和非晶AIN纤维，以VLS机制生长：后期产物为AIN晶须，表现为VS生长机制：XRD及TEM分析表明，晶须大多呈现沿｛2110｝、｛101l｝和｛0001｝，l＝0、1、2、3的晶面生长．多数晶须宏观生长轴向平行于这些晶面的法线，而部分晶须由于发生斜生长，导致宏观生长轴向与这些晶面的法线斜交．     

Site preferences for Nd in YAG films grown by LPE

We have made spin-resonance measurements of the concentration on different, though crystallographically equivalent, sites, of Nd³⁺ dilutely incorporated into thin films of yttrium aluminum garnet (YAG). The films were grown on {001}, {110}, and {111} substrates of pure YAG by liquid phase epitaxy (LPE). Sites which differ only in the orientation of their local axes relative to the growth direction are found to be unequally populated. The site preferences found for {110} films are close to, though larger than, those found previously for {110} facets of bulk crystals grown from the flux. This result supports the view that the growth-induced magnetic anisotropy of LPE films of mixed rare earth iron garnets arises from the same site preference mechanism as the anisotropy found under natural facets of bulk crystals. Very large site preferences, up to 4.5:1, are found in {001} films; but for {111} films they are only slight. Site preferences are not greatly affected by changes in growth temperature (850°C to 1044°C) or in overall concentration (0.1% to 5% atomic). The effective distribution coefficient varies with concentration and substrate orientation.     

Crystalline perfection and optical properties of rapid grown KH2PO4 crystal with chromate additive

Potassium dihydrogen phosphate (KDP) crystals were grown in the presence of a series of chromate (CrO $_{4}^{2-}$ ) additive concentrations via rapid growth method. CrO $_{4}^{2-}$ made KDP crystals were coloured by yellow-green, suggesting CrO $_{4}^{2-}$ had entered into the crystal lattice. The elemental analysis indicated that Cr element in KDP crystal was at ppm level. High resolution X-ray diffraction data revealed that the crystalline perfection of these as-grown KDP crystals was destroyed after CrO $_{4}^{2-}$ entered into crystal lattice, embedded in the full width at half maximum was broadened and satellite peaks appeared. Additionally, the extinction ratio was decreased with rise of CrO $_{4}^{2-}$ concentration. CrO $_{4}^{2-}$ introduced two absorption peaks centred at 360 and 280 nm and enhanced the intrinsic absorption near 220 nm, which were at the same band positions compared with the CrO $_{4}^{2-}$ or HCrO $_{4}^{-}$ transmittance spectra. Additionally, CrO $_{4}^{2-}$ could increase the size of light scattering, which was attributed to the point defects and microscopic defects by the replacement by CrO $_{4}^{2-}$ at PO $_{4}^{3-}$ position.     

A comparative analysis on growth aspects and characterization of novel benzophenone derivatives

The growth aspects of two benzophenone derivatives such as 4-4′ dimethylbenzophenone (4-4′ DMBP) and 4-amino benzophenone (4-ABP) were investigated based on solute–solvent interactions in the growth medium. The structural, mechanical and optical properties of the two derivatives were comparatively investigated. It was found that the 4-ABP crystal was relatively harder compared to 4-4′ DMBP. The optical transmission study showed that the 4-4′ DMBP sample has high transparency especially in the UV region as it had the cut-off wavelength of 331 nm. On the other hand, the 4-ABP crystal has relatively low transparency in the visible region with the cut-off wavelength of 400 nm. The 4-4′ DMBP sample exhibited the SHG efficiency of 1.5 times that of KDP whereas the 4-ABP sample exhibited the SHG efficiency of 161 times that of KDP. The optical properties of the derivatives were discussed in relation with the molecular structure of the materials.     

Impact of nickel doping on structural,optical, electrical,and third-order NLO behavior of piperazinium L-tartrate single crystals

Slow evaporation technique was used to grow single crystals of pure and nickel (Ni)-doped piperazinium L-tartrate (PPLT). Powder crystal X-ray diffraction was used to characterize the structural properties of the grown crystals. Fourier transform infrared spectroscopy was used to determine the functional groups. In the visible band, both pure and Ni-doped PPLT crystals have low absorbance, indicating their utility in nonlinear optical (NLO) applications. PPLT crystals, both pure and Ni doped, have bandgap energies that indicate their insulating nature, indicating their utility in electronic applications. The growth pattern and dislocation density of the crystal are revealed by etching analysis. The electric field response of generated single crystals was investigated in terms of dielectric constant and dielectric loss as a function of the frequency and temperature, with the findings described. The efficiency of nickel-doped PPLT crystal is 2.86 times larger than potassium dihydrogen phosphate (KDP), whereas the efficiency of pure PPLT is 1.38 times greater than KDP, according to NLO testing measured by Kurtz powder method. Because metal ions were incorporated into the crystal lattice, the SHG efficiency of nickel-doped PPLT was somewhat improved.