Growth and characterization of pure and doped NLO L-arginine acetate single crystals

Single crystals of pure, Cu²⁺ and Mg²⁺ doped L-arginine acetate (LAA) were grown successfully by slow evaporation technique. In order to improve the device characteristics of LAA crystals, metal dopants of Cu²⁺ and Mg²⁺ were incorporated into the parent crystals. The grown pure and doped crystals were confirmed by X-ray powder diffraction studies. The pure and doped crystals were characterized by Fourier transform Raman (FT-Raman) and thermal studies. Absorptions of these grown crystals were analysed using UV-Vis-NIR studies, and it was found that these crystals possess minimum absorption in the entire visible region. Nonlinear optical studies of pure and doped crystals were carried out and it reveals that the dopants have increased the efficiency of LAA crystals.     

Investigation of SR method grown 0 0 1 directed KDP single crystal and its characterization by high-resolution X-ray diffractometry (HRXRD), laser damage threshold, dielectric, thermal analysis, optical and hardness studies

0 0 1 directed potassium dihydrogen orthophosphate (KDP) single crystal was grown by Sankaranarayanan–Ramasamy (SR) method. The 0 0 1 oriented seed crystals were mounted at the bottom of the platform and the size of the crystals were 10 mm diameter, 110 mm height. Two different growths were tried, in one the crystal diameter was the ampoule's inner diameter and in the other the crystal thickness was less than the ampoule diameter. In the first case only the top four pyramidal faces were existing whereas in the second case the top four pyramidal faces and four prismatic faces were existing through out the growth. The crystals were grown using same stoichiometric solution. The results of the two growths are discussed in this paper. The grown crystals were characterized by high-resolution X-ray diffractometry (HRXRD), laser damage threshold, dielectric, thermal analysis, UV–vis spectroscopy and microhardness studies. The HRXRD analysis indicates that the crystalline perfection is excellent without having any very low angle internal structural grain boundaries. Laser damage threshold value has been determined using Nd:glass laser operating at 1054 nm. The damage threshold for the KDP crystal is greater than 4.55 GW cm⁻². The dielectric constant was higher and the dielectric loss was less in SR method grown crystal as against conventional method grown crystal. In thermal analysis, the starting of decomposition nature is similar in SR method grown KDP crystal and conventional method grown crystal. The SR method grown KDP has higher transmittance and higher hardness value compared to conventional method grown crystals.     

Effect of cobalt (Co<Superscript>2+</Superscript>) concentration on structural,optical, thermal and mechanical properties of potassium acid phthalate (KAP) crystals

Single crystals of pure and Co²⁺ (0.2, 0.4 and 0.6 mol%) doped KAP crystals were grown by low temperature slow evaporation method. The grown crystals were subjected to various characterization techniques such as X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), UV–visible spectroscopy and Second Harmonic Generation studies. The XRD profile confirms that Co²⁺ ions incorporated into the KAP crystal lattice. The existence of functional groups in the grown crystals have been studied by FTIR analysis. Optical transmission is decreased when doping Co²⁺ concentration increase. After melting point, no decomposition is found in the pure crystal. Vickers micro hardness studies revealed that the doped crystals possess very high hardness values. The dielectric constant, dielectric loss and thermal stability values have been measured as a function of frequency and temperature respectively for the doped crystals.     

Growth, thermal, dielectric and mechanical studies of triglycine zinc chloride, a semiorganic nonlinear optical material

Triglycine zinc chloride, a semiorganic material, has been grown by slow solvent evaporation technique from a mixture of aqueous solution of glycine and zinc chloride in 2:1 molar ratio at room temperature. The grown crystal is up to the dimension of 45 × 23 × 18 mm³. Characterization of the crystals was made using single-crystal X-ray diffraction for obtaining unit cell parameters. Powder X-ray diffraction was recorded and the major peaks were indexed. Simultaneous thermogravimetric analysis and differential thermal analysis were carried out for the as grown crystals to determine the thermal stability of the crystal. The crystals were further characterized by UV-Vis-NIR transmission spectrum in the range of 200 to 1100 nm. Dielectric constant and dielectric loss measurements were carried out at different temperatures and frequencies. Mechanical studies were carried out on the as grown crystal.     

Thermal decomposition studies of CuInS2

Single crystals of copper indium disulphide (CuInS₂) have been successfully grown by the chemical vapour transport (CVT) technique using iodine as the transporting agent. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out for the CVT grown CuInS₂ single crystals. It was revealed that the crystals are thermally stable between the ambient temperature (300 K) and 845 K and that the decomposition occurs sequentially in three steps. The kinetic parameters, e.g., activation energy, order of reaction, and frequency factor were evaluated using non-mechanistic equations for thermal decomposition.     

Crystal growth, thermal and optical studies of semiorganic nonlinear optical material: l-lysine hydrochloride dihydrate

Single crystals of l-lysine hydrochloride dihydrate (LLHCD), a nonlinear optical material, have been grown by slow cooling technique from its aqueous solution. LLHCD was found to be highly soluble in water. The grown crystals have been subjected to single crystal X-ray diffraction to confirm the structure and to estimate the lattice parameters. The vibrational structure of the molecule is elucidated from FTIR spectra. Thermal analysis revealed the thermal stability of the grown crystals. The optical transmittance spectrum shows that the material possesses good optical transparency in the entire visible region with a UV cut-off wavelength at 228 nm. The mechanical properties of the grown crystal have been studied using Vicker's microhardness test. The laser damage threshold of 52.25 MW/cm² has been measured by irradiating Q-switched Nd:YAG laser (1064 nm).     

Crystal growth of Bi2Sr2CuO6 from flux system KCl-KF and its superconductivity

Single crystals of Bi₂Sr₂CuO₆ (BSCO) were grown from high-temperature solution using KCl-KF as flux. Differential thermal analysis (DTA) of the starting materials enabled an appropriate temperature programme to be introduced for crystal growth by spontaneous nucleation. By means of the improved thermogravimetric (TG) method, Bi₂Sr₂CuO₆ crystals were grown after determination of the crystallization temperature. A single crystal in the form of a thin rectangular platelet up to 6×4 mm² was obtained and was identified by X-ray powder pattern and by scanning electron microscopy (SEM). Analyses were performed by using high-resolution electron probe microanalysis (EPMA), which indicated that it is the nonstoichiometric compound Bi_2+xSr_2–xCuO₆. The superconducting properties are strongly dependent on the composition of Bi and Sr in the crystals and on heat treatment. The transition temperature of 7 K with 0.5 K width for as-grown crystals, has been obtained.     

Synthesis,growth and characterization of π conjugated organic nonlinear optical chalcone derivative

A new potentially useful nonlinear optical organic material, 1-(5-chlorothiophen-2-yl)-3-(2,3-dimethoxyphenyl)prop-2-en-1-one, has been synthesized and grown as a high-quality single crystal by the slow evaporation technique. The grown crystals were characterized by FT-IR, NMR, thermal analysis, and UV–visible spectroscopy. The material is thermally stabile up to 111 °C. The mechanical property of the grown crystals was studied using Vickers microhardness tester and the load dependence hardness was observed. The third order nonlinear optical properties of the material such as real and imaginary part of χ⁽³⁾, nonlinear absorption coefficient and nonlinear refractive index were determined using nanosecond laser pulses at 532 nm wavelength by employing Z-scan technique. The nonlinear refractive index is found to be of the order of 10⁻¹¹ cm² W⁻¹. The magnitude of third order susceptibility is of the order of 10⁻¹³ esu. The observed increase in the third order nonlinearity in these molecules clearly indicates the electronic origin. The compounds exhibit good optical limiting at 532 nm. The best optical limiting behavior of this molecule is due to the substituted strong electron donor.     

Crystal growth and thermal neutron scintillation response of Ce doped KLiYF5

K⁶Li(Y_1−xCe_x)F₅ (x = 0.003, 0.02) single crystals were grown from the melt using the precise atmosphere control type Micro-Pulling-Down (μ-PD) method to examine their potential as a new thermal neutron scintillators. The grown crystals were single-phase materials as confirmed by XRD. The crystals demonstrated 40-60% transmittance above 320 nm and Ce³⁺ 5d-4f luminescence observed around 340 nm when exited by α-ray. The radio luminescence measurements under thermal neutron excitation (²⁵²Cf) demonstrated the light yield of 890 (Ph/neutron) and the decay time excited by α-ray exhibited 20 and 259 ns.     

Growth and characterization of l-phenylalanine nitric acid, a new organic nonlinear optical material

A new organic nonlinear optical material L-phenylalanine nitric acid [2C₉H₁₁NO₂.H⁺. NO₃⁻] (LPN), was synthesized in mixed solvent of deionised water and methanol and single crystals of LPN was grown by slow evaporation method. Transparent crystals upto 2.9 × 0.3 × 0.05 cm³ were obtained. The grown crystals have been subjected to powder X-ray diffraction studies to identify the crystalline nature. Single crystal X-ray diffractometer was utilized to measure unit cell parameters and to confirm the crystal structure. The modes of vibration of different molecular groups present in LPN were identified by FTIR spectral analysis. Transmission spectra reveals that the crystal has low UV cutoff of 295 nm and has a good transmittance in the entire visible region enabling its use in optical applications. Thermal properties of the crystals have been investigated using thermogravimetric (TG) and differential thermal analyses (DTA), which indicate that the material does not decompose before melting. The existence of second harmonic generation signals was observed using Nd:YAG laser with fundamental wavelength of 1064 nm.     

Optical investigations on Tb3+ doped l-Histidine hydrochloride mono hydrate single crystals grown by low temperature solution techniques

The potential nonlinear optical material of Terbium (Tb³⁺) ion doped l-Histidine hydrochloride monohydrate (LHHC) single crystals were successfully grown. Tb³⁺:LHHC crystals of 7 mm × 5 mm × 3 mm and 59 mm length and 15 mm diameter have been grown by the slow solvent evaporation and Sankaranarayanan-Ramasamy (SR) techniques respectively. The grown crystals were characterized by single crystal X-ray diffraction analysis to confirm the crystalline structure and morphology. High resolution X-ray diffraction (HRXRD) studies revealed that the SR grown sample shows relatively good crystalline nature with 9″ full-width at half-maximum (FWHM) for the diffraction curve. Functional groups were identified by Fourier transform infra-red spectroscopy (FTIR). The optical transparency and band gaps of grown crystals were measured by UV–Vis spectroscopy. Thermogravimetric and differential thermal analysis (TG/DTA) studies reveal that the crystal was thermally stable up to 155 °C in SR grown crystal. Surface morphology of the growth plane was observed using scanning electron microscopy (SEM). The incorporation of Tb ion was estimated by EDAX. The frequency-dependent dielectric properties of the crystals were carried out for different temperatures. Vickers hardness study carried out on (1 0 0) face at room temperature shows increased hardness of the SR method grown crystal. Second harmonic generation efficiency of SEST and SR grown crystals are 3.2 and 3.5 times greater than that of pure KDP. The Photoluminescence (PL) studies of Tb³⁺ ions result from the radiative intra-configurational f-f transitions that occur from the ⁵D₄ excited state to the ⁷F_j (j = 6, 5, 4, 3) ground states. The decay curve of the ⁵D₄ level of emission was observed with a long life time of 319.2041 μs for the SR grown Tb³⁺:LHHC crystal.     

Growth of Cu2+ and Mg2+ doped nonlinear optical LATF crystals and their characterization

Single crystals of pure, Cu²⁺ and Mg²⁺ doped l-arginine trifluoroacetate (LATF) have been grown by the temperature lowering method. The presence of Cu²⁺ and Mg²⁺ was determined by atomic absorption spectroscopy (AAS). Single crystal X-ray diffraction studies were performed to calculate the lattice parameters of the pure and doped crystals. Absorption of these crystals was analyzed and the result confirms that they possess low absorption in the range 230–1100 nm. Thermal analysis (TGA, DTA) and Fourier transform infrared (FTIR) spectroscopy were carried out to investigate the thermal behavior and molecular vibrations of these crystals, respectively. The second harmonic generation (SHG) measurement reveals the NLO properties of pure and doped crystal. Surface morphologies of these crystals were also observed and studied in detail by atomic force microscopy.     

Thermal stability and annealing behavior of photoluminescence from Eu doped YAG

Eu₂O₃ doped Y₃Al₅O₁₂ (YAG) crystals have been grown using a floating zone technique and evaluated thermal stability and annealing behavior of PL for a fluorescence thermo-sensor application. Color of the crystals grown varies from deep purple to colorless with O₂ concentration of the growth atmosphere and annealing in air. Photoluminescence (PL) peaking at λ = 590, 607, 624, 647 and 709 nm due to Eu³⁺ ions are observed from the crystals under UV excitation. Anomalous temperature dependence of PL intensity, which is observed in as-grown crystals, is improved greatly by annealing through the heat cycle. From annealing behavior of optical absorption spectra, residual Eu²⁺ ions are suggested to be responsible for the de-coloration and the improvement of anomalous temperature dependence of Eu doped YAG crystals.     

Epitaxial growth of Ag on Ag-doped NaCl

NaCl crystals doped with AgSO₄ have been grown in the laboratory and pure silver films of different thicknesses have been grown on the cleavages of doped and undoped crystals in a vacuum of the order of 10^-5 torr at room temperature by thermal evaporation. The films have been examined in an electron microscope and the nucleation and growth processes have been studied and compared. It is observed that: (i) preferential nucleation occurs on doped cleavages whereas uniform nucleation occurs on the undoped cleavages; (ii) coalescence of nuclei takes place earlier in films grown on doped substrates than on undoped ones; and (iii) films on doped substrates grow epitaxially with (100) orientation. The implications are discussed.     

Single crystalline β-FeSi2 grown using high-purity FeSi2 source

We have investigated the effect of FeSi₂ source purity on the electrical property of β-FeSi₂ grown from solution. A high-purity FeSi₂ source avoided a contamination of Cu and W metals was synthesized by melting a high-purity Fe (5N) and Si (5N-up) in a quartz ampoule. Glow discharge mass spectrometry revealed that the purity of the FeSi₂ source synthesized using 5N-Fe and a quartz-ampoule-melting process is one order of magnitude higher than that of the conventional arc-melted FeSi₂ source using 4N-Fe. The β-FeSi₂ crystals grown using the high-purity FeSi₂ and Zn solvent showed n-type conduction, whereas those grown using the arc-melted FeSi₂ showed p-type. The carrier concentration of the n-type crystals was (4.9-6.3) × 10¹⁸ cm^− 3, which was more than 10 times higher than that of the p-type crystals (5.2 × 10¹⁷ cm^− 3). From the ICP-MS and SIMS analysis of the grown crystals, we found that dominant impurity concentrations (Cr, Mn, Co, Ni, Cu, Zn and W) in the p-type crystals were higher than those in the n-type ones. Therefore, the p-type conductivity of undoped crystals grown using Zn solvent results from unintentional doping by the high impurity level of the used FeSi₂ source.     

Effect of hollow pores on the detection characteristics of trans-stilbene crystals grown by vertical Bridgman technique

Bulk crystals of trans-stilbene were grown using Vertical Bridgman Technique with progressive modification of growth parameters. The grown crystals were studied for their performance in time resolution setup with two anti collinear gamma rays from ²²Na sources. The crystals were subjected to optical microscopic and Scanning Electron Microscopic (SEM) studies. The microscopic defects (hollow pores) in the grown crystals and their effect on the detection characteristics are reported.     

Growth and characteristics of near-stoichiometric Zn:LiNbO3 crystals grown by TSSG method

A series of near-stoichiometric Zn:LiNbO₃ (Zn:NSLN) crystals were grown by the top seed solution growth (TSSG) method using K₂O as flux. Defect structures and Zn²⁺ occupation mechanism were analyzed and discussed by X-ray powder diffraction (XRD), differential thermal analysis (DTA), ultraviolet-visible (UV) absorption and infrared (IR) spectrum measurement. Moreover, we also found that the threshold concentration of ZnO in NSLN were between 2 and 3 mol%.     

Studies on the synthesis, structure, growth and physical properties of an organic NLO crystal: 2-Amino-5-nitropyridinium Phenolsulfonate

A noncentrosymmetric crystal was prepared from 2-amino-5-nitropyridine (2A5NP) and p-Phenolsulfonic acid, which was designed for second harmonic generation. Good quality single crystals of 2-amino-5-nitropyridinium Phenolsulfonate (2A5NPP) were successfully grown by the slow evaporation method with dimensions 10 × 4 × 3 mm³. The unit cell dimensions were determined from single crystal X-ray diffraction studies. The structural perfection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. Fourier transform infrared (FTIR) spectral studies have been performed to identify the functional groups. The optical transmittance window and the lower cutoff wavelength of the 2A5NPP have been identified by UV-vis-NIR studies. Thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study its thermal properties. Powder test with Nd:YAG laser radiation shows a high second harmonic generation. The laser induced surface damage threshold for the grown crystal was measured using Nd:YAG laser.     

Investigation on certain optical,thermal, and Z-scan studies of nonlinear optical tris–sarcosine calcium chloride single crystal

Slow solvent evaporation was used to produce single crystals of Tris–Sarcosine Calcium Chloride (TSCC) from aqueous solution. The cell parameters of the grown crystals were determined using the single-crystal X-ray diffraction analysis. The existence of functional groups in TSCC was confirmed using the Fourier Transform Infrared spectrum analysis. Energy-Dispersive X-ray Analysis verified the chemical composition of the TSCC crystal. The optical transmittance of TSCC was greater than 90%, according to the UV–Vis–NIR transmittance spectrum measurements. This indicates TSCC is an appropriate material for NLO applications. The optical characteristics of the grown crystal, including band gap energy, were determined. The photoluminescence characteristics of TSCC crystal were also studied in order to better understand its optical device manufacturing. The thermal behavior of TSCC was investigated using the TGA/DTA and DSC studies. For various temperatures, the fluctuation of the dielectric constant and dielectric loss with regard to frequency variation was examined and the results were described in depth. The TSCC susceptibility χ⁽³⁾ and nonlinear refractive index n₂ values were evaluated. The saturation absorption of TSCC was revealed by open aperture Z-scan technique, and the self-defocusing performance was revealed by closed aperture Z-scan measurements.

     

Growth and physical properties of ZnGeAs2

Single-phase poly crystalline chalcopyrite-structure ZnGeAs₂ ingots with an average grain size of 70 μm have been grown using a modified vertical Bridgman apparatus. The melting point of the compound was determined by differential thermal analysis (DTA) to be 860°C and corrected X-ray diffraction (XRD) peak positions were obtained. The crystals were p type with a room-temperature carrier concentration of 1.1 × 10¹⁹ cm^?3 and a corresponding mobility of 15 cm²/V s. A possible chalcopyrite-to-sphalerite phase transition, reported previously to occur to 812°C, was not observed either by DTA or by XRD of quenched samples.