Nonmetallic crystals with high thermal conductivity

Nonmetallic crystals transport heat primarily by phonons at room temperature and below. There are only a few nonmetallic crystals which can be classed as high thermal conductivity solids, in the sense of having a thermal conductivity of > 1 W/cmK at 300K. Thermal conductivity measurements on natural and synthetic diamond, cubic BN, BP and AIN confirm that all of them are high thermal conductivity solids. Studies have been made of the effect on the thermal conductivity of nitrogen impurities in diamond, and oxygen impurities in AIN. The nitrogen impurities scatter phonons mostly from the strain field, the oxygen impurities scatter phonons mostly from the mass defects caused by aluminum vacancies. Pure A1N as well as pure SiC, BeO, BP and BeS conduct heat almost as well as does copper at room temperature, while pure natural and synthetic diamonds conduct heat five times better than copper.All of the nonmetallic solids that are known to possess high thermal conductivity have either the diamond-like, boron carbide, or graphite crystal structure. There are twelve different diamond-like crystals, a few boron carbide-type crystals, and two graphite structure crystals that have high thermal conductivity. Analyses of the rock-salt, fluorite, quartz, corundum and other structures show no candidates for this class. The four rules for finding crystals with high thermal conductivity are that the crystal should have (1) low atomic mass, (2) strong bonding, (3) simple crystal structure, and (4) low anharmonicity. The prime example of such a solid is diamond, which has the highest known thermal conductivity at 300K.     

Growth and characterization of pure and doped organic nonlinear optical single crystal: l-Alanine alaninium nitrate (LAAN)

The pure l-alanine alaninium nitrate (LAAN) single crystals and LAAN crystals doped with lanthanum oxide (La₂O₃), sodium chloride (NaCl), urea (CH₄N₂O), glycine (C₂H₅NO₂) and thiourea (CH₄N₂S) were grown by slow evaporation method. The X-ray diffraction analysis, scanning electron microscopy (SEM), energy dispersive X-ray (EDAX) analysis, UV–vis spectral analysis, dielectric studies and powder SHG measurement are studied systematically. The slight changes in the lattice parameters were observed for the doped crystals compared to pure LAAN crystal. The incorporation of doping into the crystal lattice was confirmed by energy dispersive X-ray analysis. There is no change in the transmission window due to doping and the percentage of transmission in doped samples was found to increase as compared to that of pure LAAN crystal. The dielectric constant of pure crystal was found to be less than that of doped crystals. The AC conductivity was found to increase after doping and with the increase in temperature. A green radiation of 532 nm was observed from the pure and doped LAAN crystals confirming the second harmonic generation (SHG) of the crystals.     

AgGaS2- and Al-doped GaSe Crystals for IR Applications

We report a systematic study of AgGaS₂- and Al-doped GaSe crystals in comparison with pure GaSe and S-doped GaSe crystals. AgGaS₂-doped GaSe (GaSe:AgGaS₂) crystal was grown by Bridgman technique from the melt of GaSe:AgGaS₂ (10.6 wt.%). Its real composition was identified as GaSe:S (2 wt.%). Al-doped GaSe (GaSe:Al) crystals were grown from the melt of GaSe and 0.01, 0.05, 0.1, 0.5, 1, 2 mass % of aluminium. Al content in the grown crystals is too small to be measured. The hardness of GaSe:S (2 wt.%) crystal grown from the melt of GaSe:AgGaS₂ is 25% higher than that of GaSe:S (2 wt.%) crystal grown by a conventional S-doping technique and 1.5- to 1.9-times higher than that of pure GaSe. GaSe:Al crystals are characterized by 2.5- to 3-times higher hardness than that of pure GaSe and by extremely low conductivity of ≤ 10^− 7 Om^− 1 cm^− 1. A comparative experiment on SHG in AgGaS₂-, Al-, S-doped GaSe and pure GaSe is carried out under the pumps of 2.12-2.9 μm fs OPA and 9.2−10.8 μm ns CO₂ laser. It was found that GaSe:S crystals possess the best physical properties for mid-IR applications among these doped GaSe crystals. GaSe:Al crystals have relatively low conductivity which have strong potential for THz application.     

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.     

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.     

Conductivity tensor and scattering of carriers in isotropic crystals with parabolic bands

The conductivity tensor for isotropic crystals with parabolic bands is evaluated for mixed scattering by phonons and charged centers and for various values of the reduced Fermi level. The evaluated tensor elements are shown as a function of magnetic field in reduced scales, which makes it easy to compare widely different characteristics of any crystal. The effect of mixing is important in discussing the scattering mechanism-the galvanomagnetic effects for mixed scattering by acoustic phonons and charged centers resemble, in a certain range of mixing, those for pure optical phonon scattering rather than for acoustic.     

First stage f centre formation in pure and doped KCl crystals by room temperaure X-irradiation

The electrical conductivity and optical absorption of potassium chloride crystals, pure and doped with divalent cation impurities, have been measured before and after X-irradiation at room temperature. The concentration of free positive ion vacancies at room temperature has been calculated from conductivity for each crystal before irradiation and is found to be much less than the first stage F centre concentration. This shows that both free and associated positive ion vacancies are the latent source of F centres in the first stage colouration. Pb^{+ +} ions trap electrons producing Pb^{+ +} and Pb⁰ centres and making free the associated cation vacancies. Such centres are not produced in Ca-doped crystals where impurity-vacancy complexes trap F centres producing Z centres. The higher ratio of F centres to positive ion vacancies in Pb-doped crystals indicates that free cation vacancies are more effective in producing F centres. However, the concentration of divalent cations is found to decrease in both the crystals after irradiation, the decrease being more in Ca-doped crystals.The author is indebted to Prof. H. N. Bose for helpful discussions. Thanks are also due to Dr. M. L. Mukherjee for providing the crystals.     

Anisotropie der elektrischen Leitfähigkeit in diglycinselenat-einkristallen

The d.c. electrical conductivity of very pure diglycine selenate single crystals has been studied in the temperature range of 20–110°C. The samples were grown from a solution. The measurements were performed at an applied electric field below 50 V/cm and the results show an anisotropic behaviour of the conductivity in this organic crystal. A dependence of the activation energy on the direction of the applied field is shown. Crystallographic and dielectric constant data are also included in this report.     

Electrical and nonlinear optical studies of flux grown Mo and Fe doped KTP crystals

The molybdenum (Mo) and ferric (Fe) doped potassium titanyl phosphate (KTP) crystals were grown by high temperature solution growth (HTSG) technique. The concentration of Mo and Fe in grown crystals was measured by EDX analysis. The SHG efficiencies of the Mo and Fe doped KTP crystals were measured and it was found to be 1.77 and 1.38 times respectively higher than that of pure KTP crystal. The frequency dependence of dielectric constant, loss and ac conductivity was studied at room temperature. The phase matching measurements were made using a Q-switched Nd:YAG laser operating at 1064 nm and the measured phase matching angles are 44.2° and 87.88° for Mo and Fe doped KTP crystals respectively.     

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 doped L-Lysine monohydrochloride dihydrate (L-LMHCl) nonlinear optical single crystals

Semi-organic nonlinear optical single crystals of pure, Ni²⁺ and Cd²⁺ doped L-Lysine monohydrochloride dihydrate (L-LMHCl) were grown from aqueous solution by slow evaporation technique. Single crystal X-ray diffraction analysis reveal that the pure and doped L-LMHCl crystals belong to monoclinic system with the space group P2₁. The presence of functional groups present in the pure and doped crystals was determined qualitatively by using Fourier Transform Infrared (FTIR) spectroscopy. Optical absorption studies reveal very low absorption for the doped crystal than that of the pure crystal. Dielectric studies have been carried out for the grown crystals and the results were discussed in detail.     

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.     

Effects of doping and preliminary processing on the magnetically stimulated mobility of dislocations in InSb single crystals

The effect of the type of conductivity and the doping level of InSb single crystals on the mobility of fast 60° dislocations in a magnetic field is discovered. It is found that doping of a pure InSb crystal with tellurium (n-type impurity) to 10¹⁸ cm^?3 reduces the mobility of dislocations to the background level. At the same time, in p-type InSb crystals doped with Ge with the same carrier concentration (10¹⁸ cm^?3), the magnetoplastic effect is manifested clearly. It is shown that preliminary mechanical loading and, hence, internal stresses in the crystal affect not only the mean path length of dislocations in a magnetic field but also the magnitude of the threshold magnetic field below which the magnetoplastic effect is not observed. Possible reasons for these phenomena are discussed.     

Growth and characterization of pure and picric acid doped ADP single crystals

Ammonium dihydrogen phosphate (ADP) is a pioneer kind of nonlinear optical crystal. It can be used in various electro-optical, nonlinear optical applications. The pure and different weight percentage of Picric acid doped ADP single crystals are grown using the slow solvent evaporation technique at room temperature. The powder XRD study shows single phasic nature of all the grown crystals. The photoluminescence study suggests that the dopant causes defect in structure of ADP by virtue of vibration relaxation and self trapping exciton. The dielectric constant and the dielectric loss of all the grown crystals exhibited universal behaviour over frequency range considered. The Correlation Barrier Hopping and the Non Overlapping Small Polaron Tunnelling kind of conductivity mechanism are observed. The grain and grain boundary is indentified using the complex Impedance and the complex modulus spectroscopy. The third order nonlinear optical susceptibility is increased on doping the Picric acid in ADP crystals. The results are discussed here.     

Electrical conductivity and colour centres in Tl-doped KCl crystal

The electrical conductivity and optical absorption of potassium chloride crystals doped with different concentrations of thallium have been measured before and after X-irradiation. The optical absorption spectrum exhibits the characteristic Tl⁺ ion band at 247 nm. The extrinsic conductivity and the absorption coefficient at 247 nm increase with impurity addition upto a certain concentration. Further increase in impurities decreases them. Room temperature X-irradiation decreases the Tl⁺ ion band and produces the F band. F centre concentration is higher in lightly doped crystal compared to pure or heavily doped KCl. These results have been interpreted in terms of formation of interstitial potassium ions and positive ion vacancies in the Tl-doped KCl lattice due to large ionic radius of Tl⁺ ions. The impurity ions precipitate into TlCl phase when the doping is heavy.     

Growth and Characterization of Pure and Thiourea-Doped L-Alanine Single Crystals for NLO Devices

We successfully grow single crystals of pure and thiourea-doped glycyl-L-alanine hydrochloride (GLAH and TU-GLAH) from aqueous solutions by the slow evaporation technique. We study the effect of thiourea dopant on the crystal properties. Single-crystal X-ray techniques confirm the crystal structure and change in the lattice-parameter values for the doped crystals. We analyze the doped crystals quantitatively by energy-dispersive X-ray analysis (EDAX) and confirm the presence of thiourea in the pure samples. We obtain the second-harmonic generations for the grown crystals using a Nd:YAG laser. We determine values of the work hardening coefficient from the microhardness study. We measure the values of the dielectric constant and dielectric losses in order to understand the electrical phenomena taking place in pure and TU-GLAH crystals.     

The effect of normal phonon-phonon scattering processes on the maximum thermal conductivity of isotopically pure silicon crystals

The effect of normal phonon-phonon scattering processes on the thermal conductivity of silicon crystals with various degrees of isotope disorder is considered. The redistribution of phonon momentum in normal scattering processes is taken into account within each oscillation branch (the Callaway generalized model), as well as between different oscillation branches of the phonon spectrum (the Herring mechanism). The values of the parameters are obtained that determine the phonon momentum relaxation in anharmonic scattering processes. The contributions of the drift motion of longitudinal and transverse phonons to the thermal conductivity are analyzed. It is shown that the momentum redistribution between longitudinal and transverse phonons in the Herring relaxation model represents an efficient mechanism that limits the maximum thermal conductivity in isotopically pure silicon crystals. The dependence of the maximum thermal conductivity on the degree of isotope disorder is calculated. The maximum thermal conductivity of isotopically pure silicon crystals is estimated for two variants of phonon momentum relaxation in normal phonon-phonon scattering processes.     

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.     

EPR and optical absorption studies of X-irradiated cobalt doped sodium chloride crystals

Sodium chloride crystals containing small concentrations of cobalt (< 10 ppm) do not show any EPR line. A thick block of crystal containing ～25 ppm of Co showed two partially resolved lines, with approximate g-values 2.036 and 2.011. These g-values are not close to those of Co⁺⁺ (4.0 to 4.5) in other crystals. On X-irradiation, pure NaCl crystals show a complex EPR spectrum. X-irradiated Co doped NaCl crystals showed an EPR line superimposed on the complex EPR spectrum. Cobalt doped highly pure crystals, on X-irradiation, showed an EPR line superimposed on the F center EPR line. The g-value of the former is 2.049±0.002 and half width is 62±3 gauss. These results combined with those of dielectric loss and optical studies show that X-irradiation of Co doped crystals produces new centers, labelled as S centers, which produce a dielectric loss peak, a decrease in electrical conductivity, an optical band at 210 nm and the EPR line. Possible models of the S centers are discussed.