Structure and properties of antimony-doped potassium titanyl phosphate single crystals

Antimony-doped potassium titanyl phosphate (KTP) crystals of the composition KTiOPO₄ are studied by X-ray diffraction analysis. It is shown that, with an increase of antimony content in KTP crystals, the occupancies of potassium positions change and new additional positions for potassium atoms arise. The formation of additional vacancies and splitting of the potassium-cation positions explain the considerable decrease in the temperature of the ferroelectric phase transition, enhancement of the relaxation phenomena, and an increase in electric conductivity of antimony-doped KTP crystals. Substitution of antimony atoms for titanium is accompanied by elongation of short and shortening of long Ti-O bonds in the TiO₆ octahedra, processes which result in lower intensity of second-harmonic generation in laser-irradiated KTP crystals.     

Structure and properties of niobium-doped potassium titanyl phosphate crystals

A series of potassium titanyl phosphate crystals, KTiOPO₄, with various concentrations of niobium dopant has been grown, and some of their physical properties and structural characteristics have been studied. The incorporation of a small amount of niobium results in considerable changes in the electrical conductivity of KTP: Nb crystals and the temperature of the ferroelectric phase transition. Thus, the presence of 3–4 at. % of niobium results in an increase of conductivity by more than an order of magnitude, whereas T _C decreases from 930 to 620°C. The X-ray diffraction study of the crystals has been performed at room temperature; the neutron diffraction analysis was made at temperatures of 20, 330, and 730°C. It was revealed that two crystallographically independent positions are statistically (by 90%) occupied by potassium cations, which results in the concentration of potassium atoms in the structure higher than it was expected from the condition of preservation of crystal electroneutrality. At high niobium concentrations, the monoclinic compound of the composition K₂TiNb₂P₂O₃ is formed.     

Structure and properties of potassium titanyl phosphate single crystals with 7 and 11 at. % Nb

This study is a continuation of research into the atomic structure and physical properties of niobium-doped potassium titanyl phosphate crystals, KTiOPO₄ (KTP: Nb). Crystals containing 7 and 11 at. % of niobium were grown and studied. With an increase in niobium content, the number of vacancies and additional potassium positions in the structure also increase. This fact accounts for an increase in both the intensities of relaxation peaks and the conductivity of KTP: Nb crystals.     

Structure and properties of crystals in the potassium titanyl phosphate family: A review

This paper presents an overview of the data available in the literature and the results obtained by the authors in the study of the influence of the chemical composition on the structure and properties of crystals in the potassium titanyl phosphate family. The structure and properties of phosphates in which univalent cations are substituted for potassium cations, as well as of crystals with isovalent or heterovalent substitutions for tetravalent titanium cations in the structure of potassium titanyl phosphate crystals, are considered.     

Synthesis,properties, and structure of potassium titanyl phosphate single crystals doped with hafnium

Single crystals of potassium titanyl phosphate doped with hafnium are grown by spontaneous flux crystallization. Their physical properties are studied, and the structure of three KTi_{1 − x} Hf _x OPO₄ crystals (x = 0.01, 0.03, and 0.12) is determined. In the crystals studied, hafnium mostly occupies the second titanium position. The doping of KTP crystals with hafnium results in an elongation of K-O bonds in the potassium polyhedra and, as a consequence, in a considerable (by approximately 180°C) decrease in the temperature of ferroelectric phase transition. The magnitude of anomalous permittivity substantially decreases. The electrical conduction in the specimens studied decreases by approximately half an order of magnitude in the low-temperature region but remains almost unchanged in the high-temperature region. Even at minor concentrations, the presence of a hafnium additive in the specimens considerably (by 35%) enhances the intensity of the second harmonic generation of laser radiation.     

Oriented inclusions in single crystals of potassium dihydrogen phosphate

Different forms of oriented inclusions in single crystals of potassium dihydrogen phosphate (KDP) grown by gel method and from aqueous solutions are reported. Small rod like chain and channel types of liquid inclusions are illustrated. These inclusions are oriented along 〈001〉, 〈011〉 and 〈010〉 directions and are attributed to mother liquor trapped in the body of the crystal during growth.     

Crystal structure of potassium titanyl phosphate doped with zirconium

This paper reports on the results of precision X-ray structural investigations of single crystals of the compounds KTi_0.96Zr_0.04OPO₄ (at 293 K) and KTi_0.97Zr_0.03OPO₄ (at 293 and 105 K). No significant splitting of the positions occupied by potassium atoms is revealed. This result is in agreement with a considerable decrease in the electrical conductivity of potassium titanyl phosphate KTiOPO₄ (KTP) crystals doped with zirconium (KTP: Zr) as compared to crystals of undoped potassium titanyl phosphate. It is established that the difference between the Ti-O bond lengths in chains formed by titanium octahedra is not a single structural parameter responsible for the nonlinear optical properties of crystals in this series.     

Growth and optical absorption studies on potassium dihydrogen phosphate single crystals

Growth of bulk nonlinear optical (NLO) single crystals gained new significance with the advent of solid‐state laser sources for opto‐electronic applications. An optically transparent crystal of potassium dihydrogen phosphate (KDP) has been grown from aqueous solution along (001) plane with the aid of modified growth assembly of Sankaranarayanan‐Ramasamy (SR) Method. The evaporation rate was controlled and single crystals of 5 mm diameter and 60 mm length with a growth rate 5 mm per day have been grown successfully. The improved transparency of grown crystal was investigated using DRS UV transmittance spectral analysis and the presence of functional groups in the grown crystal is confirmed using FTIR analysis. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bridgman growth and properties of potassium lithium niobate single crystals

Transparent KLN crystals 10mm in diameter and 25 to 45mm in length have been grown by the modified vertical Bridgman technique from different melts in the range of 3035mol% K₂O, 1723mol% Li₂O and 4350mol% Nb₂O₅. The growth conditions are a growth rate of less than 0.25 mm/hr, temperature gradient in solid-liquid interface of 23 °C/mm and growth direction of <110>. As-grown KLN crystals have tetragonal tungsten bronze structure. Most of the as-grown crystals do not crack when cooling through the paraelectric/ferroelectric phase transition. 180° domain structures are observed after the KLN crystal was etched in boiling 2HNO₃:Hf. Dielectric properties and transmission spectrum of the as-grown KLN crystals are measured.     

Growth and properties of ferroelectric potassium ferrocyanide trihydrate single crystals

Single crystals of potassium ferrocyanide trihydrate, K₄[Fe(CN)₆·3H₂O (KFCT), a ferroelectric material with Curie temperature 251K were grown in silica gel at room temperature for the first time by the solubility reduction method. Resorcinol and ethyl alcohol were used for the purpose of gel setting and supernatant liquid respectively. Optical and mechanical properties were studied for the grown crystal. The structure of the grown crystal was confirmed by X‐ray diffraction analysis. Fourier Transform Infrared (FTIR) and FT Raman spectral analysis of the crystalline samples reveal that the crystalline sample consist consists of all functional groups. Thermal analysis of the crystalline sample was performed by TGA and DTA methods. The Vicker's micro hardness value was measured for KFCT crystals. The square etch pits with a hopper‐like structure is an indicative of 2D nucleation mechanism. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrical conductivity and dielectric properties of potassium sulfamate single crystals

Single crystals of potassium sulfamate are grown by the method of slow evaporation at constant temperature. AC electrical conductivity of potassium sulfamate is measured in the temperature range 300–430 K and in the frequency region between 100 Hz and 3 MHz along the a, b and c‐axes. Complex impedance spectroscopy is used to investigate the frequency response of the electrical properties of the potassium sulfamate single crystal. Temperature variation of AC conductivity and dielectric measurements show a slope change around 345 K for both heating and cooling run and this anomaly is attributed as phase transition, which is well supported by the DSC measurements. Value of loss tangent in the temperature region 330–400 K is found to be very low. Activation energies for the conduction process are calculated along the a, b and c‐axes. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric properties of ferroelectric lead hydrogen phosphate single crystals

The ferroelectric lead hydrogen phosphate (LHP) single crystals have been grown by employing the gel technique. The controlled reaction between lead nitrate and orthophosphoric acid solutions by diffusion process in gel medium has been used. The dielectric constant (ϵ′) and the dielectric loss (ϵ″) have been measured for the first time as a function of frequency in the range 10² to 10⁴ Hz. They have also been determined as a function of temperatures in the range 300 to 680 K. The polarisation effect contributing to the dielectric constant has been studied. It has been observed that the mechanism of the dielectric behaviour is different in the lower and higher temperatur and frequency ranges. The activation energy of the oscillators has been calculated and found to be 1.12 eV. Attempt has been made to draw some qualitative conclusions, taking in view, the existing theories of various kinds of polarization and implications have been discussed.     

Electrolytic growth and dielectric properties of magnesium hydrogen phosphate single crystals

The growth of MgHPO₄, magnesium hydrogen phosphate, (MHP) single crystals in silica gels under the influence of an externally applied uniform electric field is described. A controlled reaction between magnesium chloride and orthophosphoric acid by a diffusion process in the gel medium is employed. The bright, transparent MHP crystals upto 4 × 2 × 1 mm³ in sizes are grown at room temperature. The dielectric measurements are carried out in the temperature range between 300 to 650 K. The effect of the applied frequency on the dielectric constants and the dielectric losses are investigated. It is observed that the mechanism of the dielectric behaviour is different in the lower and higher frequency and temperature ranges. The activation energy of the oscillators are calculated and found to be 1.105 eV. Attempt is made to draw some qualitative conclusions, taking in view the existing theories of various kinds of polarization, and implications are discussed.     

Microhardness investigations on potassium dihydrogen phosphate crystals

Vickers microhardness measurements are carried out on single crystals of potassium dihydrogen phosphate. Dependence of hardness on indentation load and anisotropy in hardness of (100) and (011) planes are described. Crack patterns around indentation are found to be dependent on indenter orientation. Also explained are the fracture at high indentation load and etch patterns obtained on indented surfaces.     

An analysis of flow and mass transfer during the solution growth of potassium titanyl phosphate

The first fully three-dimensional solution flow and solute transport simulations are performed to model the potassium titanyl phosphate (KTP) growth system of Bordui et al. Steady flows and supersaturation fields for two crystal mounting geometries are computed using a stabilized finite element method implemented on a data-parallel supercomputer. Our results present a mechanistic picture of solute transport which is consistent with inclusion formation patterns obtained in experiments. The simulations also explain beneficial outcomes, in terms of better global mixing and more uniform surface supersaturation, observed for a crystal mounting geometry which strongly breaks cylindrical symmetry in the system.     

EPR-spectrum of irradiated potassium dichromate single crystals

EPR-spectra of X-irradiated potassium dichromate crystals are studied at various temperatures from RT to LNT. The most intensive lines are interpreted as due to radicals CrO₄³⁻ (A-lines) and CrO₃⁻ (C-lines), resulting from Cr₂O₇ owing to X-irradiation. Hyperfine structure of C-line, due to interaction of unpaired electron with Cr⁵³ nucleus, occurs at low temperatures, and new unobserved earlier Q-lines appear near-by C-line. The spectrum may be described by usual spin Hamiltonian for S = 1/2 with following parameters: for A-line gz = 1.9841, gy = 1.9685, gx = 1.9592; for C-line gz = 1.9148, gy = 1.9671, gx = 1.9886, |Az| = 30.53 · 10⁻⁴ cm⁻¹, |Ax| = 10.62 · 10⁻⁴ cm⁻¹, |Ay| = 6.62 · 10⁻⁴ cm⁻¹.     

Study of potassium titanyl phosphate (KTP) flux growth by holographic phase-contrast interferometric microphotography

This paper describes a special set of equipment we designed, which is suitable to be used to study the high temperature solution growth process by optical method. The variation regularities of the solid-liquid interface boundary layer in the potassium titanyl phosphate (KTP) crystal growth and dissolution process have been investigated by holographic phase-contrast interferometric microphotography. It has been found that under the condition of free convection, the relation between the thickness of the boundary layer and supersaturation is linear. Moreover, the variation of refractive index caused by the change of solute concentration in the boundary layer will form an exponential function of the distance from the crystal face.     

X-ray diffraction topography study of defects in potassium dihydrogen phosphate (KDP) and ammonium dihydrogen phosphate (ADP) single crystals

The direct observation of dislocations in KH₂PO₄(KDP) and NH₄H₂PO₄ (ADP) single crystals has been performed by X-ray diffraction topography methods. Crystals were grown by slow cooling of stirred solutions on different types of seed crystals. It is demonstrated that the main sources of dislocation generation are the seed surface, inclusions of mother liquor and foreign particles. Space orientation of dislocations and their Burgers vector directions are found. In regions far from the seed the dislocation density did not exceed 10³ cm⁻² and a number of specimens with cross-sectional areas up to several cm² were free from dislocations. Dynamical phenomena characteristic of the diffraction in a weakly deformed lattice have been observed over a wide range of μ t at the boundaries between the {101} and {100} growth sectors having different impurity contents. Several crystals show also nonuniform impurity distribution in the form ot the layers parallel to growing face (growth layers).     

On the effect of structural and symmetrical features of potassium titanyl phosphate crystals with different contents of niobium,antimony, and zirconium on the second-harmonic intensity

A model is proposed, which shows that, at small deviations from the centrosymmetric state of the atomic structure, the quadratic nonlinear susceptibility of a crystal monotonically decreases with approach of the degree of central symmetry \(\eta _{\overline 1 } \)[φ(r)] of the electric potential function of the crystal structure to unity. The quadratic nonlinear susceptibility of K_{1 ? x} Ti_{1 ? x} Nb _x OPO₄ (x = 0, 0.02, 0.04, 0.11), K_{1 ? x} Ti_{1 ? x} Sb _x OPO₄ (x = 0.01, 0.07, 0.17), and KTi_{1 ? x} Zr _x OPO₄ (x = 0.03, 0.04) crystals has been measured. The degree of central symmetry \(\eta _{\overline 1 } \)[φ(r)] has been calculated for the structures of K_{1 ? x} Ti_{1 ? x} Nb _x OPO₄ (x = 0, 0.04, 0.11), K_{1 ? x} Ti_{1 ? x} Sb _x OPO₄ (x = 0.01, 0.07, 0.17), and KTi_{1 ? x} Zr _x OPO₄ (x = 0.03, 0.04) crystals. It is shown that, at \(\eta _{\overline 1 } \)[φ(r)] > 0.7, the relationship between the quadratic nonlinear susceptibility of the investigated crystals and the degree of their central symmetry \(\eta _{\overline 1 } \)[φ(r)] is in qualitative agreement with the proposed model.     

Dielectric studies of lead nitrate phosphate single crystals

Ferroelectric Lead Nitrogen Phosphate (LNP) single crystals have been synthesized using the controlled reaction between lead nitrate and orthophosphoric acid solutions by slow diffusion process in silicagel medium. The colourless transparent LNP crystals upto 6 × 4 × 3 mm³ in size have been grown at room temperature. The dielectric measurements have been carried out in the temperature range between 300 to 690 K. The effect of applied frequency on the dielectric constants and dielectric losses has been investigated. It has been observed that the mechanism of the dielectric behaviour is different in the lower and higher frequency and temperature ranges. The activation energy of the oscillators has been calculated and found to be 1.125 eV. Attempt has been made to draw some qualitative conclusions, taking in view, the existing theories of various kinds of polarizations and implications.