Effect of magnetic treatment of KDP and ADP crystals and solutions on their equilibrium temperature

The effect of magnetic treatment of KDP and ADP crystals and solutions on their equilibrium temperature has been revealed and studied. The change in the temperature reaches a maximum immediately after the magnetization. Then, the effect decreases monotonically, and the equilibrium temperature approaches the equilibrium value for 5 h. It has been found that the observed decrease in the solubility depends on the impurity concentration, and it is maximum in magnetically treated KDP crystals with a chromium impurity; then, it decreases in the series: KDP crystal, KDP-ADP crystals in KDP-ADP solution, KDP crystal in KDP-ADP solution, and KDP solution. For all five systems under study, the relaxation times have been determined. It has been revealed that the effect rapidly increases and reaches saturation at B = 0.02 T. The energy effects in the crystals and solutions have been estimated.     

Cation distribution by Rietveld,spectral and magnetic studies of chromium-substituted nickel ferrites

Ultrafine crystals of chromium-substituted nickel ferrite were prepared by wet chemical co-precipitation method using sulphates of respective metal ions. Formation of these materials has been confirmed by X-ray powder diffraction method. The fine crystal nature of these materials is evidenced from scanning electron microscope (SEM). Cation distribution has been investigated using X-ray diffraction technique. Cation distribution indicates that chromium occupy octahedral site for all the values of composition x. The saturation magnetization and magneton number both are decreasing with increase of chromium concentration x. The decrease in saturation magnetization and magneton number is attributed to the substitution of the Cr³⁺ ions. Curie temperature (T _C ) from susceptibility plot is found to decrease with Cr concentration x. Curie temperature of all the compositions are also obtained theoretically and it agrees with observed Curie temperature.     

Nucleation studies and characterization of potassium thiocyanate added KDP crystals grown by seed rotation technique

The effect of the addition of potassium thiocyanate on potassium dihydrogen phosphate (KDP) crystals, grown from aqueous solution by the temperature lowering method using a microcontroller based seed rotation technique has been studied. As part of nucleation studies, metastable zone width, induction period and crystal growth rate of additive added KDP are determined and analyzed with the pure system. Dielectric measurements were carried out on pure and doped crystals at various temperatures ranging from 313 to 423 K and compared. The crystalline perfection of the grown crystal was studied by the high resolution X-ray diffraction analysis. The crystal grown from additive added solution was subjected to structural, optical transmission, second harmonic generation and hardness studies and the effect of additive on pure system is investigated.     

Linear and nonlinear optical properties of dye-doped KDP crystals: Effect of thermal treatment

Potassium dihydrogen phosphate crystals (KDP, KH₂PO₄) doped with the organic xylenol orange (XO) dye are grown, the XO concentration in the crystal matrix is about 10 ppm. The spectral and luminescent properties of nominally pure, dye-doped and dye-doped/annealed at 150 °C crystals (KDP, KDP:XO and KDP:XO_an) were measured. The annealing temperature effect on the degree of dye protonation in the crystal matrix is established. Analysis of the IR-absorption spectra reveals a strong interaction between the incorporated dye molecules and the hydrogen subsystem of the matrix. The nonlinear optical (NLO) properties of KDP, KDP:XO and KDP:XO_an crystals are studied within the self-action effect of picosecond laser pulses at 532 nm. The mechanism of photoinduced bleaching and the effects of laser beam self-focusing (in KDP) and self-defocusing (in KDP:XO and KDP:XO_an) are supposed to be due to resonance excitation of the subsystems of intrinsic defects and dye molecules, correspondingly. For KDP:XO_an it is shown that thermal annealing of intrinsic crystal defects leads to domination of more effective NLO response of the subsystem of dye molecules that is correlated with photoluminescence data.     

硼酸对KDP晶体光学特性的影响

生长了不同硼酸掺杂浓度的KDP晶体,用超显微镜了晶体内部的散射颗粒,检测了晶体的光损耗和透过率特性。实验结果表明,较高浓度的硼酸对KDP晶体的光学均匀特性有较大影响,并使晶体具有显著的旋光性和波片效应。     

退火温度对KDP晶体光学均匀性的影响研究

 研究了磷酸二氢钾（KDP）晶体热退火前后光学均匀性的变化，发现适当温度下退火可以降低KDP晶体的内应力，提高晶体的消光比，从而提高晶体的光学均匀性。实验证明，50℃下退火即可消除部分内应力，110℃下退火可以消除生长鬼影和鬼线。但是,退火温度太高（如170℃）,也可能使晶体的均匀性降低。     

Effect of Mn(II) doping on crystalline perfection, nonlinear, optical and mechanical properties of KDP single crystals

The effect on crystalline perfection, second harmonic generation (SHG) efficiency, optical transparency and mechanical properties due to Mn(II) doping in KDP single crystals grown by slow evaporation solution technique by adding different quantities of MnCl₂ in the solution has been investigated. The actual incorporated quantity of Mn(II) in the crystals was evaluated by atomic absorption spectroscopy. Powder XRD study confirms the crystal system of KDP and found no additional phases at all doping levels (1 to 5 mol%). The influence of Mn(II) doping on the crystalline perfection has been assessed by high-resolution XRD and these studies revealed that the grown crystals could accommodate Mn(II) in the interstitial positions of the crystalline matrix of KDP only up to some critical concentration, above which the crystal developed structural grain boundaries. The relative SHG efficiency of the crystals was found to be increased sharply at low concentrations (1 mol%), and above this value it was decreased as the concentration increases though it is still higher than that of pure KDP. UV-Vis studies also revealed the same behavior with a significant enhancement at 1 mol% concentration and later gradually decreased. Good increment in the hardness values has been observed by increasing the doping concentrations.     

Effect of an organic dye on the ferroelectric phase transition in KH2PO4 (KDP)

This paper reports on the first measurement of the dielectric permittivity and heat capacity of a KDP crystal doped by Chicago Sky Blue organic dye within a temperature interval including the ferroelectric phase transition at T _c =122 K. Similar measurements were made on a pure KDP crystal under the same conditions for the sake of comparison. The heat capacities of the pure and doped crystals were shown to differ substantially within an interval 1 K wide in the vicinity of T _c , where an anomaly in the heat capacity of the doped crystal was observed to wash out without producing any change in the temperature position of its maximum. The doping reduces the permittivity in the polar phase markedly. The observed effects are associated with the influence of nonisomorphic defects on the ferroelectric phase transition in a piezoelectric crystal.     

KDP晶体微纳加工表层杂质对其激光损伤阈值影响的有限元分析

 根据KDP晶体杂质附近的温度场及热应力场理论,分析了微纳加工表层杂质影响下晶体温度场及热应力场的分布情况,发现杂质离子对激光的强吸收作用是造成KDP晶体损伤的主要原因之一,也是影响KDP晶体激光损伤阈值的最主要因素。通过分析还发现杂质半径对晶体的激光损伤阈值也有影响,并得到一个有害的杂质半径,使得杂质吸收能量最多,温度最高。另外杂质种类及杂质含量的不同也会对晶体的激光损伤阈值产生影响。     

Effect of organic dyes on the dielectric properties of KH<Subscript>2</Subscript>PO<Subscript>4</Subscript> crystals

The effect of organic dyes on the dielectric properties of KH₂PO₄ (KDP) crystals is studied over a wide range of temperatures. The dielectric properties of KDP crystals doped with molecules of the Chicago Sky Blue and Amaranth organic dyes are investigated for the first time. The dye molecules can be incorporated into the crystal lattice of KDP and selectively paint the pyramidal growth sectors of the crystal. The influence of dye organic impurities on the domain contribution to the permittivity is analyzed with due regard for the sectoral crystal structure. It is demonstrated that, upon doping of KDP crystals with organic dyes, the blocking effect of background impurities on domain walls is substantially weakened in the prismatic growth sector of the crystal in the polar phase. This leads to a noticeable change in the dielectric properties, specifically to an increase in the domain contribution to the permittivity of the crystal.     

杂质对KDP晶体光学质量的影响

 研究了几类可能出现在KDP晶体的生长溶液中的有机物杂质和无机阴离子杂质基团对KDP晶体散射、透过率、光损伤阈值等光学质量的影响，结果表明，不同种类的杂质的影响并不相同，造成这一结果的根本原因在于杂质离子的结构及其与晶体表面原子成键能力的不同。     

硫酸盐对KDP晶体质量的影响

 利用“点籽晶”快速生长技术生长了掺杂硫酸钾（K₂SO₄）的磷酸二氢钾（KDP）晶体，并对硫酸根类杂质离子对晶体的结构及光学质量的影响进行了研究。结果表明：在掺杂相对含量为50×10^-6条件下，K₂SO₄开始对KDP晶体产生一定影响，主要表现在不同扇形区域的结构略有改变，其原因主要在于硫酸根与KDP晶体各扇形结构有关；杂质粒子对晶体透过率、单轴性没有明显影响，但是热膨胀系数增大，光损伤阈值略有降低。     

The pH effects on the growth rate of KDP (KH2PO4) crystal by investigating Raman active lattice modes

We report on the dependence of the pH value on the growth rates of KDP single crystals. Extensive experimental work has been carried out in order to find the optimum pH ranges for growing KDP single crystals with suitable sizes and high optical quality. Different techniques including micro‐Raman back‐scattering spectroscopy, UV/vis/IR transmission spectroscopy and X‐ray diffraction have been employed for this investigation. Deuterated substituted single crystals of KDP and DKDP also have been grown for the investigation of growth rates and Raman active mode identification purposes. The molecular vibration modes of the grown crystals, including internal modes of PO₄ tetrahedrons molecular vibrations, external modes of optical phonons and hydrogen bonding modes have been determined exactly by micro‐Raman back‐scattering spectroscopy. The best pH values of the solution for the KDP crystal growth with reasonably higher growth rates from aqueous solutions that have been supersaturated ata temperature range of 30–50 °C have been found to be in the pH range of 3.2–5.4. Copyright © 2007 John Wiley & Sons, Ltd.     

不同波长三倍频DKDP晶体的激光损伤

采用传统降温法,利用高纯原料从氘化程度为80%的溶液生长了四方相磷酸二氘钾(DKDP)晶体,并按Ⅱ类三倍频方式切割晶体。三倍频用DKDP晶体的最大问题在于其抗光伤阈值低于KDP晶体,严重限制了激光输出的能量密度和晶体使用寿命。考察了不同波长下三倍频DKDP晶体的损伤阈值,以及激光退火效应。实验表明,激光退火对于DKDP晶体的损伤阈值有显著的提升作用,基频、倍频、三倍频的提升效果分别达到1.4,1.9,2.7倍,是改善DKDP晶体抗光伤能力的有效途径。     

Measurement of second-harmonic optical susceptibility using Rayleigh scattering

We report a simple method to measure relative second-harmonic optical susceptibilities of crystals by use of Rayleigh scattering. We use two crystals with fixed alignments: one is a phase-matched crystal with varying degrees of phase matching, which serves as a reference point of the phase relationship and a source for the second-harmonic beam to be incident on the sample crystal, and the other is a sample crystal for measurement. The second-harmonic signals generated from each of the two crystals are superposed in the sample crystal to give Rayleigh scattering at the second-harmonic frequency, the analysis of which can determine the relative values of the second-harmonic optical susceptibilities of the sample crystals. We have applied this method to obtain d ₁₄ (KDP)1.8 d ₃₆ (KDP), d ₃₆ (ADP)1.1 d ₃₆ (KDP), d ₃₁ (KTP)15 d ₃₆ (KDP), d ₃₂ (KTP)13 d ₃₆ (KDP), where d ₃₆ of KDP crystals was taken as a reference.     

Influence of l-alanine doping on crystalline perfection, SHG efficiency, optical and mechanical properties of KDP single crystals

Pure and l-alanine (LA) doped single crystals of potassium dihydrogen orthophosphate (KDP) were grown by slow evaporation solution technique (SEST) in aqueous solution at ambient temperature. Powder X-ray diffraction study was done to confirm the crystal system and lattice parameters of KDP. No additional phases were observed at all doping concentrations (1-7.5 mol%), which was further confirmed by FT-Raman spectroscopy analysis. The influence of LA doping on the crystalline perfection was assessed by high-resolution X-ray diffractometry (HRXRD) analysis. HRXRD studies revealed that the grown crystals could accommodate LA at the interstitial positions in the crystalline matrix of KDP up to some critical concentration without any deterioration in the crystalline perfection. Above this concentration, very low angle structural grain boundaries were developed and it seems that the excess LA above the critical concentration was segregated along the grain boundaries. The SHG efficiency was measured using the Kurtz powder technique. The relative SHG efficiency of the crystals was found to be increased with doping concentration up to 5 mol% and above this it decreases. Optical transmission study also revealed the same behavior with enhancement up to 5 mol% concentration and later decreased. The hardness values were found to be increased by increasing the doping concentration.     

X-ray diffraction in KDP crystal in the presence of temperature gradient

We investigate the effect of temperature gradient on the intensity of X-ray radiation reflected from different atomic planes of a KDP crystal, depending on the crystal thickness. We have studied the phenomenon of transfer of the X-ray beam intensity for x- and z-cuts of the KDP crystal in the presence and in the absence of temperature gradient. It is shown that the intensities of reflected radiations do not saturate because in conditions of the experiment the further increase in temperature gradient leads to destruction of the sample. It is revealed that in some cases at small values of temperature gradient the intensity of reflected radiation decreases initially by more than 10%, then increases monotonically with the increase in temperature gradient.     

Dielectric and polarization properties of KH<Subscript>2</Subscript>PO<Subscript>4</Subscript> single crystals doped with Li,Na, and NH<Subscript>4</Subscript> impurities

The dielectric and polarization properties of potassium dihydrogen phosphate (KDP) single crystals doped with Li, Na, and NH₄ impurities have been investigated in the temperature range 70–150 K. It is found that the domain freezing temperature in the lithium-containing sample exceeds that for nominally pure KDP. Disappearance of freezing is observed in the ammonium-doped crystal.     

Raman gains of ADP and KDP crystals

In this paper, the Raman gain coefficients of ammonium dihydrogen phosphate(ADP) and potassium dihydrogen phosphate(KDP) crystals are measured. By using a pump source of a 30-ps, 532-nm laser, the gain coefficients of ADP and KDP are 1.22 cm/GW, and 0.91 cm/GW, respectively. While for a 20-ps, 355-nm pump laser, the gain coefficients of these two crystals are similar, which are 1.95 cm/GW for ADP and 1.86 for KDP. The present results indicate that for ultra-violet frequency conversion, the problem of stimulated Raman scattering for ADP crystal will not be more serious than that for KDP crystal. Considering other advantages such the larger nonlinear optical coefficient, higher laser damage threshold,and lower noncritical phase-matching temperature, it can be anticipated that ADP will be a powerful competitor to KDP in large aperture, high energy third-harmonic generation or fourth-harmonic generation applications.     

Synthesis of manganese oxide nanocrystal by ultrasonic bath: effect of external magnetic field

A novel technique was used for the synthesis of manganese oxide nanocrystal by applying an external magnetic field (EMF) on the precursor solution before sonication with ultrasonic bath. The results were compared in the presence and absence of EMF. Manganese acetate solution as precursor was circulated by a pump at constant speed (7 rpm, equal to flow rate of 51.5 mL/min) in an EMF with intensity of 0.38 T in two exposure times (t_MF, 2 h and 24 h). Then, the magnetized solution was irradiated indirectly by ultrasonic bath in basic and neutral media. One experiment was designed for the effect of oxygen atmosphere in the case of magnetic treated solution in neutral medium. The as prepared samples were characterized with X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (HRTEM, TEM), energy-dispersive spectrum (EDS), and superconducting quantum interference device (SQUID) analysis. In neutral medium, the sonication of magnetized solution (t_MF, 24 h) led mainly to a mixture of Mn₃O₄ (hausmannite) and γ-MnOOH (manganite) and sonication of unmagnetized solution led to a pure Mn₃O₄. In point of particle size, the larger and smaller size of nanoparticles was obtained with and without magnetic treatment, respectively. In addition, the EMF was retarded the nucleation process, accelerated the growth of the crystal, and increased the amount of rod-like structure especially in oxygen atmosphere. In basic medium, a difference was observed on the composition of the products between magnetic treated and untreated solution. For these samples, the magnetic measurements as a function of temperature were exhibited a reduction in ferrimagnetic temperature to T_c = 39 K, and 40 K with and without magnetic treatment, respectively. The ferrimagnetic temperature was reported for the bulk at T_c = 43 K. A superparamagnetic behavior was observed at room temperature without any saturation magnetization and hysteresis in the measured field strength. The effect of EMF on the sample prepared in the basic medium was negligible but, in the case of neutral medium, the EMF affected the slope of the magnetization curves. The magnetization at room temperature was higher for the samples obtained in neutral medium without magnetic treatment. In addition, a horizontal shift loop was observed in neutral medium at low temperature.