Effect of urea and thiourea on nonlinear optical hippuric acid crystals

Pure, urea and thiourea doped hippuric acid (HA) single crystals have been grown in acetone using slow evaporation technique at a constant temperature, with the vision to improve the properties of the crystals. The crystal systems and the unit cell parameters of the grown crystals were identified from single crystal X-ray diffraction. The crystalline nature of the grown crystals was confirmed by powder X-ray diffraction and the diffraction peaks were indexed. The variations in composition due to the addition of dopants were identified by CHNS analysis. FT-IR studies reveal the presence of different vibrational bands. The optical characteristics were assessed by UV–vis analysis and it indicates the transmission in the visible region. TGA and DSC studies indicate the thermal behavior of pure and doped crystals. The Second Harmonic Generation (SHG) has been tested using Kurtz Powder Technique for the pure and doped crystals. It is found that the thiourea doped hippuric acid crystals have SHG efficiency of 2.08 times higher than that of potassium dihydrogen phosphate (KDP) single crystal. The dielectric studies were carried out, and the variations of dielectric constant and dielectric loss with temperature have been studied.     

Growth and characterization of a pure and doped nonlinear optical l-histidine acetate single crystals

Single crystals of pure, Cu²⁺and Mg²⁺ doped l-histidine acetate (LHA) were grown successfully by slow evaporation technique. The X-ray diffraction (XRD) studies were carried out for the pure and doped grown crystals. Absorption of these grown crystals was analyzed using UV-vis-NIR studies, and it was found that these crystals possess minimum absorption from 200 nm to 1500 nm. The pure and doped crystals are characterized by Fourier transform Raman (FT-Raman), thermal and photoconductivity studies. Vickers microhardness tests were carried out for the pure and doped crystals and the mechanical strengths were found. The dielectric constant and the dielectric loss with frequency were also studied.     

Spectral,Optical and Mechanical studies on pure and thiourea doped ammonium di-hydrogen phosphate NLO single crystals

Pure and thiourea substituted single crystals of ammonium di-hydrogen phosphate have been grown from aqueous solution by isothermal solvent evaporation technique. Doped crystal exhibits prominent changes in physical and chemical properties. Single crystal XRD analyses of the samples are carried out and the results are compared. FTIR and UV–vis–NIR spectral analyses have been employed to identify the presence of various functional groups and the UV cut-off range in the grown crystals. Density measurements have been made and Photoconductivity studies revealed the negative photo conducting nature. Hardness measurement shows that the mechanical strength of the doped crystal is high when compared to pure ammonium di-hydrogen phosphate. The dielectric response of the samples has been studied in the frequency range 100 Hz–5 MHz at room temperature and the results are discussed.     

Crystal growth and dielectric, mechanical, electrical and ferroelectric characterization of n-bromo succinimide doped triglycine sulphate crystals

Single crystals of triglycine sulphate (TGS) doped with n-bromo succinimide (NBS) were grown at ambient temperature by the slow evaporation technique. An aqueous solution containing 1-20 mol% of n-bromo succinimide as dopant was used for the growth of NBSTGS crystals. The incorporation of NBS in TGS crystals has been qualitatively confirmed by FTIR spectral data. The effect of the dopant on morphology and crystal properties was investigated. The cell parameters of the doped crystal were determined by the powder X-ray diffraction technique. The dielectric constant of NBS doped TGS crystal was calculated along the ferroelectric direction over the temperature range of 30-60 °C. The dielectric constant of NBSTGS crystals decrease with the increase in NBS concentration and considerable shift in the phase transition temperature (T_C) towards the higher temperature observed. Pyroelectric studies on doped TGS were carried out to determine the pyroelectric coefficient. The emergence of internal bias field due to doping was studied by collecting P-E hysteresis data. Temperature dependence of DC conductivity of the doped crystals was studied and gradual increase in the conductivity with the increase of dopant concentration was observed. The activation energy (ΔE) calculated was found to be lower in both the ferroelectric and the paraelectric phases for doped crystals compared to that of pure TGS. The micro-hardness studies were carried out at room temperature on thin plates cut perpendicular to the b-axis. Less doped TGS crystals show higher hardness values compared to pure TGS. Piezoelectric measurements were also carried out on 010 plates of doped TGS crystals at room temperature.     

Effect of Co2+ on the growth,optical properties and laser damage threshold of potential nonlinear optical l-alanine single crystal

Good transparent bulk single crystals of pure l-alanine (LA) and cobalt doped LA crystals have been synthesized and successfully grown by slow-cooling method from their aqueous solutions. The concentration of metal dopants in the mother solution with 0.5 mol% for cobalt was carried out individually and crystals were obtained with well defined morphology. The as grown metal doped and pure single crystals were characterized by single crystal XRD studies which confirm that the incorporation of metallic dopants has not changed the basic structure of the parent crystal. The absorption of these crystals was analyzed and the result confirms that they possess low absorption in the range 230–1100 nm. Fourier transform infrared (FTIR) spectroscopy was carried out to investigate the molecular vibrations of these crystals and to confirm the incorporation of the dopants. The thermal properties have been studied by TGA/DTA curves. The EDAX measurement and surface morphology were studied for pure and metal doped LA crystals. The second harmonic generation (SHG) signals were observed using Nd: YAG laser with fundamental wavelength of 1064 nm in pure and metal doped crystals. The laser damage threshold was measured for pure and metal doped LA crystals and also tested by using a Q-switched Nd: YAG laser showed enhanced LDT value for metal (Co²⁺) doped LA crystal compared to pure LA crystal due to the metallic substitutions thus proving their useful candidature for nonlinear optical applications.     

Growth and comparison of physicochemical properties of pure,Ca and Sr doped NH4Sb3F10 single crystals for electro optic applications

Single crystals of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ are grown by slow evaporation technique. The effect of dopants on the growth and physicochemical properties also have been investigated and reported for the first time. The grown crystals are characterized with the aid of single crystal X-ray diffractometry to confirm the crystal structure. EDAX studies are done to confirm the presence of dopants in the crystal lattice. The vibrational frequencies of various group ligands in the crystals have been derived from the Fourier transform infrared (FT-IR) spectrum. From the optical absorption spectrum the band gap energy was calculated and it was found to be 5.76, 6.29 and 6.35 eV for pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals respectively. Thermal stability of the sample has been analysed using TG-DTA analysis. The activation energy of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals were calculated from the dc conductivity measurements and it is found to be 0.2728, 0.2816 and 0.3622 eV Experimental results shows improved physicochemical properties when the dopant is added to the pure material.     

Growth and characterization of pure and potassium iodide-doped zinc tris-thiourea sulphate (ZTS) single crystals

Single crystals of pure and potassium iodide (KI)-doped zinc tris-thiourea sulphate (ZTS) were grown from aqueous solutions by the slow evaporation method. The grown crystals were transparent. The lattice parameters of the grown crystals were determined by the single-crystal X-ray diffraction technique. The grown crystals were also characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. The FT-IR spectrum was recorded in the range 400-4500 cm⁻¹. Second harmonic generation (SHG) was confirmed by the Kurtz powder method. The thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) studies reveal that the materials have good thermal stability. Atomic absorption studies confirm the presence of dopant in ZTS crystals. The electrical measurements were made in the frequency range 10²-10⁶ Hz and in the temperature range 40-130 °C along a-, b- and c-directions of the grown crystals. The present study shows that the electrical parameters viz. dc conductivity, dielectric constant, dielectric loss factor and ac conductivity increase with increase in temperature. Activation energy values were also determined for the ac conduction process in grown crystals. The dc conductivity, dielectric constant, dielectric loss factor and ac conductivity of KI-doped ZTS crystal were found to be more than those of pure ZTS crystals.     

Growth of 4-(dimethylamino) benzaldehyde doped triglycine sulphate single crystals and its characterization

Single crystals of triglycine sulphate (TGS) doped with 1 mol% of 4-(dimethylamino) benzaldehyde (DB) have been grown from aqueous solution at ambient temperature by slow evaporation technique. The effect of dopant on the crystal growth and dielectric, pyroelectric and mechanical properties of TGS crystal have been investigated. X-ray powder diffraction pattern for pure and doped TGS was collected to determine the lattice parameters. FTIR spectra were employed to confirm the presence of 4-(dimethylamino) benzaldehyde in TGS crystal, qualitatively. The dielectric permittivity has been studied as a function of temperature by cooling the sample at a rate of 1 °C/min. An increase in the Curie temperature T_c=51 °C (for pure TGS, T_c=48.5 °C) and decrease in maximum permittivity has been observed for doped TGS when compared to pure TGS crystal. Pyroelectric studies on doped TGS were carried out to determine pyroelectric coefficient. The Vickers's hardness of the doped TGS crystals along (0 1 0) face is higher than that of pure TGS crystal for the same face. Domain patterns on b-cut plates were observed using scanning electron microscope. The low dielectric constant, higher pyroelectric coefficient and higher value of hardness suggest that doped TGS crystals could be a potential material for IR detectors.     

Iminodiacetic acid doped ferroelectric triglycine sulphate crystal: Crystal growth and characterization

Single crystals of iminodiacetic acid (HN(CH₂COOH)₂) doped triglycine sulphate (IDATGS) crystals have been grown from aqueous solution containing 1-10 mol% of iminodiacetic acid at constant temperature by slow evaporation technique. The effects of different amounts of doping entities on the growth habit have been investigated. X-ray powder diffraction pattern for pure and doped TGS was collected to determine the lattice parameters. The grown crystals were subjected to Fourier transform infrared (FTIR) spectroscopy studies to find the presence of various functional groups qualitatively. The dielectric permittivity has been studied as a function of temperature. An increase in the transition temperature (49.2-49.7 °C) of IDATGS crystals is observed. The dielectric constant (ε′_max) of IDATGS crystals vary in the range 922-2410 compared to pure TGS (T_c=49.12 °C and ε′_max=3050). Curie Weiss constants C_p and C_f in the paraelectric and ferroelectric phases were determined. The transition temperature (T_c) is found to decrease with increase in dopant concentration. P-E hysteresis studies show the presence of internal bias field in the crystal. Piezoelectric measurements were also carried out at room temperature. Domain patterns on b-cut plates were observed using scanning electron microscope. The micro hardness studies reveal that the doped crystals are harder than the pure TGS crystals. The low dielectric constant, higher transition temperature, internal bias field and hardness suggest that IDATGS crystals could be a potential material for IR detectors.     

Structural, optical and dielectric studies of glycinium trifluoroacetate single crystal

An organic material glycinium trifluoroacetate (GTFA) has been re-synthesized and large single crystals have been grown by solution technique. Complete structure of GTFA has been redetermined from single crystal XRD data. FTIR confirmed the presence of various functional groups. Melting point (152.44 °C), thermal stability and specific heat were studied from TG/ DTA and DSC. In UV absorption spectra, a lower cutoff value as 220 nm and a wide band gap as 4.86 eV for GTFA were observed. The dielectric studies, dielectric constant and loss were measured at different temperatures (30-90 °C) in the frequency range 100 Hz-2 MHz.     

Growth, optical, mechanical and dielectric studies on NLO active pure and metal ion doped single crystals of bis-thiourea zinc chloride

Good quality single crystals of pure and metal ion (Ni²⁺) doped bis-thiourea zinc chloride (BTZC) possessing excellent nonlinear optical properties have been grown from aqueous solution by the slow solvent evaporation technique. The lattice parameters of the grown crystals are determined by single crystal X-ray analysis. The well defined sharp peaks in the powder X-ray diffraction pattern reveals the crystalline perfection and the EDAX spectrum confirms the presence of dopant in the lattice of the parent crystal. The DRS UV-visible spectral study reveals improved transparency for the doped crystal, ascertaining the inclusion of metal ion in the lattice. The optical band gap of the pure and doped crystals was calculated to be 4.8 and 5.2 eV respectively from the UV transmission spectrum. The vickers hardness test brings forth higher hardness value for Ni²⁺doped BTZC as compared to pure BTZC crystal. The dielectric measurement exhibits very low dielectric constant and dielectric loss at higher frequencies for both the pure and Ni²⁺doped BTZC. The existence of second harmonic generation signals in the crystal also has been confirmed by performing the Kurtz powder test.     

Solid solutions on the base of bismuth vanadate: Preparation, structure, phase transitions, dielectric and transport properties

Ceramic solid solutions (Bi_1-yLa_y)₄(V_1-xMe_x)₂O_11-y with x, y < 0.2, Me-Zr, Ga, Fe, Cu, have been prepared by the solid state reaction method. Crystal structure parameters, phase transitions, dielectric and transport properties of ceramic samples have been studied. Concentration and temperature stability regions of monoclinic α-, orthorhombic β- and tetragonal γ- or γ’- polymorph modifications have been determined.Annealing of samples, containing large amount of Cu and/or La dopants, at 973 K in the reducing atmosphere resulted in their decomposition, though compositions containing low content of La, Ga or Zr dopants, remained pretty stable.     

Conductivity in Nd+K doped ferroelectric lead germanate single crystals

Nd⁺³+K⁺ doped ferroelectric lead germanate (LG) single crystals were grown to study the influence of the double dopants on ferroelectric behavior of LG. The crystals were grown by controlled cooling of the melt. Temperature variation of d.c. conductivity of the grown samples was studied in temperature range of 40-400 °C. Room temperature conductivity was enhanced as a result of doping. The existence of two activation energies, one in the ferroelectric phase (0.61 eV) and another in the paraelectric phase (0.77 eV) in the results, were revealed. The increase in conductivity due to doping is attributed to the generation of charge carriers due to double doping and the existence of two activation energies is attributed to the structural changes taking place at the ferroelectric transition 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.     

Synthesis, growth and characterization of novel semiorganic nonlinear optical potassium boro-succinate (KBS) single crystals

Single crystals of novel semiorganic material, potassium boro-succinate (KBS) have been grown from aqueous solution by slow evaporation technique. The lattice parameters for the grown crystals were determined by the single crystal X-ray diffraction analysis. The presence of functional groups was estimated qualitatively by using fourier transform infrared (FTIR) analysis. The optical absorption spectrum shows that the UV cut-off wavelength for the grown crystal is at 240 nm. The thermal stability of the KBS crystal was studied by using TG/DTA analysis. The dielectric constant and loss were studied as a function of frequency. Nonlinear optical properties (NLO) test was performed by using Kurtz powder technique.     

The lithium- and sodium-enhanced transformation of Ba-exchanged zeolite LTA into celsian phase

The Li⁺- and Na⁺-doped hexacelsians (HC) synthesized from Ba-LTA synthetic zeolite as precursors were used for preparation of monoclinic celsians (MC). The doped pure MC and mixture HC/MC species were obtained by thermally induced polymorphous transformation at 1200 °C. Synthesized-doped MC have been characterized by X-ray powder diffraction and spectroscopic (infrared, Raman and ²⁹Si magic angle spinning nuclear magnetic resonance) methods. The obtained results suggest that in all investigated samples Na⁺ or Li⁺ dopants were incorporated in MC crystal structures during thermal transformation of a zeolite. It has been shown that HC→MC transformation depends on molar fractions of alkali cations. These findings combined with used temperature/time conditions could help in optimization of MC synthesis route.     

High-conductive nanocrystalline silicon with phosphorous and boron doping

Intrinsic, P- and B-doped hydrogenated amorphous silicon thin films were prepared by plasma-enhanced chemical vapor deposition technique. As-deposited samples were thermally annealed at the temperature of 800 °C to obtain the doped nanocrystalline silicon (nc-Si) films. The microstructures, optical and electronic properties have been evaluated for the undoped and doped nanocrystalline films. X-ray photoelectron spectroscopy (XPS) measurements demonstrated the presence of the substitutional boron and phosphorous in the doped films. It was found that thermal annealing can efficiently activate the dopants in films accompanying with formation of nc-Si grains. Based on the temperature-dependent conductivity measurements, it was shown that the activation of dopant by annealing increased the room temperature dark conductivity from 3.4 × 10⁻⁴ S cm⁻¹ to 5.3 S cm⁻¹ for the P-doped films and from 1.28 × 10⁻³ S cm⁻¹ to 130 S cm⁻¹ for the B-doped films. Meanwhile, the corresponding value of conductivity activation energies was decreased from 0.29 eV to 0.03 eV for the P-doped films and from 0.3 eV to 5.6 × 10⁻⁵ eV for the B-doped films, which indicated the doped nc-Si films with high conductivity can be achieved with the present approach.     

Localized and long-distance charge hopping in fresh and thermally aged conductive copolymers of polypyrrole and polyaniline studied by combined TSDC and dc conductivity

The charge trapping centers in fresh and thermally aged conductive polyaniline-polypyrrole copolymers (starting from pure polyaniline and ending in pure polypyrrole by steps of 10 wt%) were studied by thermally stimulated depolarization current (TSDC) spectroscopy and dc conductivity measurements. One low temperature (115-135 K) relaxation mechanism appears in polyaniline-rich copolymers and disappears after thermal anneal. It is attributed to polaron trapping in the vicinity of chlorine anion dopants. Another relaxation mechanism operates close to room temperature and is related to conformational relaxation, which corresponds to the influence of the annihilation of the conformons on the conduction mechanism. The relaxation is sensitive to thermal aging as a result of the thermal annealing on the conductivity. The temperature derivative of the dc conductivity supports the latter assertion. The activation energy values were obtained as a function of composition for both fresh and heated samples. The TSDC spectroscopy is a sensitive tool which is an alternative to the standard conductivity studies for the characterization of polypyrrole-polyaniline conductive copolymers and the study of the thermal degradation.     

Calorimetric, optical and catalytic activity studies of europium chloride-polyvinyl alcohol composite system

Polyvinyl alcohol (PVA) films doped with europium chloride (EuCl₃) have been prepared by casting from their aqueous solutions. The phase transitions and thermal decomposition behavior of the prepared samples were investigated by thermal analysis and the interactions between the host PVA and Eu³⁺ were examined by FTIR spectroscopy. The optical absorption was recorded at room temperature in the range of 190-1000 nm. From the absorption edge studies, the values of the Urbach energy (E_e) were found to be 0.56 eV in case of the pure polymer; however, its value increased to be in the range of 1.21-1.75 eV. These energy values indicate that the model based on electronic transitions between localized states is not preferable and transitions are made between band tails. Optical parameters such as refractive index and complex dielectric constant have been determined. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. Color properties of the prepared samples are discussed in the framework of CIE L?u*v* color space. The prepared samples have been used as catalysts in the photocatalytic degradation of p-nitrophenol (PNP) in aqueous solution under UV light irradiation using H₂O₂ as oxidizing agent. The catalytic activity of the Eu-polymer towards the photodegradation of PNP greatly increased after doping with Eu³⁺ ions. The highest catalytic activity was noticed at the optimum pH value of 5.5.