Dielectric properties of rapidly grown KDP crystals

The dielectric properties of rapidly grown potassium dihydrogen phosphate KH₂PO₄ (KDP) crystals have been studied over a wide temperature range and compared with the properties of traditionally grown KDP crystals. It was found that the contribution of domains to permittivity in rapidly grown crystals is considerably less than in conventionally grown ones. The dielectric properties in various growth sectors of KDP crystals are determined.     

Structural and mechanical properties of KН2PО4 single crystals with embedded nanoparticles and organic molecules

Single crystals of KDP crystals with embedded Urea molecules and TiO₂ nanoparticles have been grown from aqueous solution by the temperature lowering method. The effect of the organic molecules and nanoparticles on the structural and mechanical properties has been studied. It has been observed that addition of Urea molecules improves laser induced damage threshold and mechanical strength of the crystal, while TiO₂ nanoparticles have the opposite effect. The structure and composition of KDP:Urea crystal are studied by three‐crystal X‐ray diffraction analysis, which reveals the existence of a correlation between the increase of the microhardness value and the change of the crystal lattice parameter. The surface features of KDP:TiO₂ crystals are analyzed by scanning electron microscopy that reveals the presence of quasi‐equidistant growth bands caused by capture of the nanoparticles. It is shown that the rise of TiO₂ nanoparticles concentration up to 10⁻⁴ wt.% and higher resulted in 3‐fold reduction of the laser damage threshold of KDP:TiO₂ relative to pure KDP in [001] and [100] crystallographic directions. It is found that microhardness and fracture toughness decrease at the nanoparticles concentration of 10⁻³ wt.% due to crack formation at crystal lattice discontinuities. The grown crystals also have been subjected to dielectric studies.     

Study on rapid growth of KH2PO4 and its characterization

Large size crystals of KH₂PO₄ (KDP) were grown by adopting rapid growth technique from point seeds in a 1500‐liter crystallizer which is used to grow KDP crystals by conventional method. The grown KDP crystal size can reach to 310 × 310 × 320 mm³ and the average growth rate was 8mm/day. The optic properties of the rapidly grown KDP crystals were characterized comparing with the KDP crystals grown by the traditional temperature reduction method. We found it that the optical quality of the KDP crystals we grown rapidly are not significantly different from those of KDP crystals grown by traditional method. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and thermal studies on pure ADP,KDP and mixed K1‐x(NH4)xH2PO4 crystals

The investigations on the formation of mixed crystals of ammonium dihydrogen orthophosphate (ADP) and potassium dihydrogen orthophosphate (KDP) i.e. potassium ammonium dihydrogen phosphate, K_1‐x(NH₄)_xH₂PO₄ have been presented in this paper. Pure and mixed crystals of ADP and KDP have been grown by slow evaporation technique from the supersaturated solution at an ambient temperature 26±1 °C for ammonium concentration x in the range 0.0 ≤ x ≤ 1.0 in the case of mixed crystals. Crystal compositions were determined by flame atomic absorption spectroscopy and chemical analysis. The results of the X‐ray analysis of the grown crystals are also reported. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the kinetic process of dehydration and the high temperature phase behaviour. DTA showed the distinct thermal events attributed to dehydration of ADP, KDP and K_1‐x(NH₄)_xH₂PO₄. The results of thermal analysis and chemical analysis are consistent with each other. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman Study of Lattice Vibration Modes and Growth Mechanism of KDP Single Crystals

The space group theoretical analyses and assignment of the lattice modes of the KDP crystal have been made, and the Raman spectra of their growth solution have been observed in different growth regions. The attention is focused on the analysis of the 912 cm^‐1 band arising from the H₂PO₄^‐ anions in the interface between the KDP crystals and their growth solution. This has been assigned to the asymmetrical stretching mode of the deformation P(OH)₂ . From these results, the growth units of KDP crystal has been concluded to be the dimers of H₂PO₄^‐ anions. We consider that the result presented here is an important step towards the development of more complete crystal growth theories.     

Enhancement of stability of growth,structural and NLO properties of KDP crystals due to additive along with seed rotation

Potassium Acetate (CH₃COOK) and Potassium Citrate (K₃C₆H₅O₇) as new additives were added into the potassium dihydrogen phosphate (KDP) solutions in different molar ratios. The metastable zone width and induction period with and without these additives were determined and compared. Dielectric measurements on pure and doped KDP crystals at various temperatures ranging from 313 to 423 K were carried out by the conventional parallel plate capacitor method which results low dielectric constant value dielectrics in doped crystals. The high resolution XRD studies show that CH₃COOK doped KDP crystal and K₃C₆H₅O₇ doped KDP crystal do not contain any internal structural grain boundaries and indicates that the crystalline perfection is very good. Moreover, the addition of these potassium additives improves the quality of the crystal and yields highly transparent crystals with well defined features. The effect of additives on the growth, nucleation kinetics, structural, NLO and optical properties has been investigated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Doping of KDP single crystals with cerium: Growth and optical properties

The features of doping of KDP crystals with cerium ions and organocerium complexes with alizarin complexon and arsenazo III have been investigated. It is established that “direct” doping by introducing cerium salts into the initial solution cannot be implemented. The effect of organometallic complexes of cerium on the crystal growth has been studied. Organocerium complexes predominantly enter the prismatic or pyramidal growth sectors. It is shown that the complex arsenazo III + Ce blocks the growth of the prismatic sector. Cerium-doped KDP crystals exhibit a photoluminescence band peaking at the wavelength λ_max= 350 nm.     

Synthesis and Size Optimization of Crystals Grown by the Mixed Gel-Solution Technique

Two experimental devices have been used with the aim to optimize the synthesis of single crystals by means of the mixed gel-solution technique. These consist of a gel source-reservoir saturated at T₀ and a vessel of aqueous solution saturated at T_f. T₀ > T_f. In such devices, the evlution of the supersaturation in the vessel of aqeous solutions allows that the grwoth process to be controlled by such a source-reservoir and the crystal itself. Average growth rates of 3 and 4 mm/day have been found for KDP crystals.     

The combined effects of supersaturation and Ba2+ on the batch cooling crystallization of potassium dihydrogen phosphate

The combined effects of supersaturation and Ba²⁺ on potassium dihydrogen phosphate (KDP) were investigated in batch cooling suspension crystallization. Growth size, morphology, and impurity Ba²⁺ adsorbed in the KDP crystals were measured with changing Ba²⁺ concentration and supersaturation. Significant changes in shapes and volume of the grown crystals have been observed. The results further confirmed that the size and shape of crystals were greatly determined by supersaturation. Ba²⁺ ions significantly modified the growth habit of KDP crystals. The concentration of Ba²⁺ ions adsorbed in the crystals increases with the increasing Ba²⁺ ions in the solutions and supersaturation. The foggy phenomena caused by the addition of Ba to the KDP solution were also described. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and physical properties of a new chiral open-framework crystal for NLO applications: Cesium hydrogen l-malate monohydrate

Cesium hydrogen l-malate monohydrate, CsH(C₄H₄O₅)·H₂O, is a new chiral open-framework semi-organic crystalline material with a second-harmonic generation efficiency one order of magnitude greater than KDP. Single crystals of this new material have been grown by the conventional slow cooling technique from aqueous solution. Grown crystals display both platy and prismatic morphologies depending on the imposed supersaturation. Hardness values measured using Vickers hardness indenter show considerable anisotropy. The resistivity behavior at room temperature and above, places the crystal between an ionic conductor and a dielectric. The single-crystal SHG efficiency estimated through Maker fringes experiment gives d_eff which is 4.24 times that of KDP. Single and multiple shot experiments performed on the grown crystals for the fundamental and second harmonic of pulsed Nd:YAG laser (1064 and 532 nm) show that it exhibits a high laser damage threshold which is a favorable property for nonlinear optical applications.     

Influence of SiO32‐ impurity on growth habit of potassium dihydrogen phosphate crystal

By altering the concentration of silicate (SiO₃^2‐) impurity in the solution, a series of potassium dihydrogen phosphate (KDP) crystals was obtained by the conventional temperature cooling and the rapid growth methods, respectively. It was observed that the presence of SiO₃^2‐ made KDP crystals tapering in conventional cooling method, while more SiO₃^2‐ induced inclusions at prismatic sectors in the rapid growth method. Laser‐polarization‐interference results showed that SiO₃^2‐ extended the dead zone and reduced the growth rate of (100) face of KDP crystals. The negative influence of SiO₃^2‐on the growth was considered absolutely similar to the effect of cations. It was also suggested that the stability of solution doped with SiO₃^2‐ was improved without seed crystals, while it was destructed with seed crystals. The inhibition mechanism was analyzed in terms of SiO₃^2‐ absorption on (100) face. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Crystallizer for Growing Large Singe Crystals from Solution under Steady-State Concentration Convection Conditions

A crystallizer for growing large single crystals from solution under steady-state concentration convection conditions is described. The crystallizer has only one vessel divided by a drilled plate in two compartments kept at different temperatures. The convection of concentration occurs through the dividing plate between the compartments. The crystallizer was used for growing KDP and TGS single crystals. Mass- and heat transfer equations are derived. Growth rate calculations may be carried out using the derived equations. Growth rate measurements of KDP crystals have been performed. The overall heat transfer coefficient for the transfer of heat through the dividing plate is also experimentally determined. Light absorption, ESR and Mössbauer spectra have shown the presence of Fe⁺², Cr⁺³ and Mn⁺² ions in the (100) greenish zones of KDP crystals.     

Single crystal growth,structural, optical,mechanical, dielectric and thermal studies of formic acid doped potassium dihydrogen phosphate crystal for NLO applications

Optically transparent formic acid (FA) doped potassium dihydrogen phosphate (KDP) crystal of dimension 21×15×9 mm³ has been grown by slow evaporation solution technique (SEST). The X‐ray diffraction (XRD) technique was used to confirm the cell parameters and the shifts in peak positions of identified reflecting planes. The incorporation of FA in KDP has been qualitatively analyzed by fourier transform infrared analysis. The UV‐visible absorption spectrum of crystals has been recorded in the range of 200 to 900 nm and the doped KDP crystal is found to have improved optical parameters than pure KDP. The color centered photoluminescence emission spectrum of grown crystal has been illustrated in visible region. The mechanical behavior of pure and doped KDP crystal has been investigated using the Vicker's microhardness analyzer and hardness parameters have been calculated. The effect of FA on thermal stability of KDP crystal was examined by means of thermogravimetric and differential thermal analysis. The temperature dependent dielectric behavior of crystals was studied.     

A new nonlinear optical crystal: Bi2O2(OH)(NO3)

The nonlinear optical (NLO) properties of Bi₂O₂(OH)(NO₃) crystals have been reported for the first time. Bi₂O₂(OH)(NO₃) crystals with dimensions of 1.3×1.2×0.1 mm³ have been grown by hydrothermal method, and the crystals characterized by X‐ray powder diffraction (XRD), SEM and IR. The measured second harmonic generation (SHG) effect of Bi₂O₂(OH)(NO₃) was about 7 times that of KDP. The mechanism responsible for the large SHG of Bi₂O₂(OH)(NO₃) was explained according to its structure. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of l-Tartaric acid,an NLO material

Single crystals of l-Tartaric acid (C₄H₆O₆), an organic nonlinear optical (NLO) material, have been grown by hanging seed solution and submerged seed solution techniques at room temperature. The crystal system has been confirmed from the single crystal X-ray diffraction analysis. The crystalline perfection was evaluated using high-resolution X-ray diffractometry (HRXRD). From this analysis, it was found that the quality of the crystal is quite good. The functional groups were identified using FTIR spectroscopy. UV–vis–NIR spectrum showed the absence of absorption in the wavelength region of 220–900 nm. The second harmonic generation efficiency is 89% compared to that of standard potassium dihydrogen phosphate (KDP). The laser damage threshold value is much higher than that of KDP and closer to that of β-barium borate.     

Potassium and ammonium dihydrogen phosphates activated with thallium: Growth and luminescence and scintillation properties

The conditions for the growth of potassium dihydrogen phosphate (KDP) and ammonium dihydrogen phosphate (ADP) crystals with concentrations of the thallium activator in the initial solution of 0.01, 0.1, and 1.0 wt % are investigated. It is shown that the character of incorporation and distribution of thallium in the KDP and ADP lattices is limited, apparently, by the difference in the ionic radii of K⁺, NH ₄ ⁺ , and Tl⁺ cations and the charge state of prismatic {100} and pyramidal {101} growth planes. Doping of KDP and ADP with thallium (to 0.1 and 1.0 wt %, respectively) does not deteriorate the structural quality of these crystals. The dependence of the lattice parameters a and c on the thallium impurity concentration is investigated. The absorption bands of thallium in the KDP:Tl⁺ and ADP:Tl⁺ crystals peak at 218 and 215 nm, respectively, while the photoluminescence band peaks at 280 nm for both types of crystals. The relative light yield upon excitation of scintillations by α particles (Pu²³⁹) and β particles (Bi²⁰⁷) is measured.     

Influence of La3+ ions on growth and NLO properties of KDP single crystals

Single crystals of pure and Lanthanum added KDP crystals were grown from aqueous solution. The influence of La³⁺ ions in KDP crystals is studied. Isolated centers are formed by La³⁺ ions in KDP structure along (100) plane. La³⁺ ions incorporated into superficial crystal growth layer and slightly affect the growth process as they generate weak lattice stresses. The creation of these weak lattice stress is confirmed by Vickers's micro hardness test. The HRXRD analysis showed reduced structural defects in the La added KDP in the (100) plane than pure KDP. The incorporation of La in the crystal was confirmed by EDAX analysis. The Kurtz's powder SHG efficiency was found to be 1.5 times that of pure KDP. The UV‐Vis transmission spectra of La added KDP showed excellent transmittance from 1100 nm to 340 nm and did not show any change in lower cutoff wavelength with respect to pure KDP. Laser damage threshold value has been determined using Q‐switched Nd:YAG laser operating at 1064 nm and with 65 ns pulses in single shot mode. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microscopic investigations of morphological structures on the pyramidal faces of KDP and DKDP single crystals

Studying a number of {101} faces of KDP and DKDP single crystals in the as-grown state we found in most cases one, rarely few, clearly stepped growth hillocks covering the whole face. The geometry of these growth hillocks was determined from photomicrographs; the step heights were measured with a profilometer. To prove our results we carried out X-ray topographic investigations and in-situ observations on KDP crystals. In addition we studied the as-grown faces of ADP and LiJO₃ single crystals.     

The effect of material,thermal and laser conditioning on the damage threshold of type II tripler‐cut DKDP crystals

By using the traditional temperature‐reduction method, KD₂PO₄ (DKDP) crystals were grown from 85%‐deuterated aqueous solution synthesized by different kind of KH₂PO₄ (KDP) raw materials. An experimental technique was employed to measure the variation of bulk damage threshold in plates of DKDP crystals. Bulk laser damage in unconditioned, thermal‐conditioned and laser‐conditioned type II tripler‐cut DKDP crystals has been studied using 1064 nm (ω) and 355 nm (3ω) laser at pulse lengths of 5ns, 5ns respectively. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Single crystal growth and properties of semiorganic nonlinear optical L‐arginine hydrochloride monohydrate crystals

L‐arginine hydrochloride monohydrate (LAHCl.H₂O) has been synthesized and single crystals have been grown from its aqueous solution by slow evaporation and slow cooling methods. The solubility of the material was measured at various temperatures and bulk crystals of size 26×13×11 mm³ have been grown by optimizing the growth parameters. The grown crystals have been subjected to single crystal XRD studies to confirm the structure and to estimate the lattice parameters. FTIR analysis indicate the mode of vibrations of different molecular groups present in LAHCl and confirm the protonation of guanidyl, amino groups and deprotonation of COO^‐ groups. UV‐Vis transmission spectrum revealed the linear optical properties of the grown crystals with a transparency of 65% over the entire visible range upto 300 nm. Thermal behavior of the grown crystal was investigated from DTA and TGA measurements. Dielectric studies have been carried out on the grown crystals. Kurtz and Perry powder SHG technique confirms the NLO property of the grown crystal. The SHG efficiency of LAHCl was found to be 0.38 with respect to KDP. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)