Boron oxide encapsulated Bridgman growth of high-purity high-resistivity cadmium telluride crystals

High-purity semi-insulating CdTe crystals have been successfully grown by encapsulated (B₂O₃) Bridgman technique. The procedure strongly limits component losses allowing the achievement of stoichiometry control material and keeps a low level of impurity contamination as shown by mass spectroscopy analysis data. When strictly stoichiometry-controlled and high-purity polycrystalline source material has been used, high-resistivity crystals have been obtained without any intentional doping. EPD values in the range of 1–3×10⁴ cm⁻² have been observed in a wide region of the crystals. Luminescence spectroscopy confirms the purity and good structural quality of the material. The proposed method avoids the technical problems posed by the High Pressure Bridgman technique and fits the requirements for CdTe/CdZnTe crystals large-scale production.     

Defect characterization and composition distributions of mercury indium telluride single crystals

A mercury indium telluride (MIT) ingot was grown by the vertical Bridgman method. The defects in MIT crystals were characterized by the chemical etching method. A defect etchant for MIT crystals was developed. The etch pits of dislocations, microcracks and boundary was observed by scanning electron microscopy. It was elucidated that the etch pits density of dislocations of MIT wafers was about 4×10⁵ cm⁻². Te and In reduced at the grain boundaries, but were homogeneously distributed within the grains in the as-grown MIT crystals. The distribution of In in MIT crystals along the growth direction and radial direction was analyzed by electronic probe microscopy. It was found that In concentration was higher in the initial part and lower in the final part of the MIT ingot, which indicated that the segregation coefficient of In in MIT crystals was 1.15. The radial In concentration increased from the center to edge of the wafers and homogeneous in the middle part.     

Effect of lattice oxygen on optical absorption, radiation hardness and thermally stimulated luminescence of BaF2 crystal

The influence of the presence of BaO impurity on the optical absorption, radiation hardness and thermally stimulated luminescence of BaF₂ has been investigated. The presence of oxygen impurity gives rise to three absorption bands in the UV region, peaking around 220, 280 and 335 nm. Further, the impurity is found to be detrimental to crystal hardness against ionizing radiations. The thermally stimulated luminescence (TSL) has been studied from gamma-irradiated crystals containing different fractions of BaO impurity. Four prominent glow peaks around 100°C (peak I), 150°C (peak II), 220°C (peak III) and 290°C (peak IV) are observed for crystals containing BaO impurity concentrations lower than 0.5% (by wt). For crystals containing higher impurity concentrations, two additional peaks around 75°C and 260°C are also observed. The kinetics of TSL emission is observed to be of first order, implying that the absorption and the emission centers responsible for TSL are the same. The normalized TSL output for peak I is found to vary linearly with the concentration of oxide impurity. This fact can be utilized to detect the presence of minute amounts of oxygen in BaF₂ lattice, which is crucial to the growth of crystals exhibiting high radiation hardness.     

Growth and characterization of organic material 4-nitrobenzaldehyde single crystal using modified vertical Bridgman technique

The organic material 4-nitrobenzaldehyde single crystal has been grown using the single wall ampoule with nano-translation by modified vertical Bridgman technique. The grown crystal was confirmed by single and powder X-ray diffraction (XRD). Fourier transform infrared (FTIR) analysis was used to identify the functional groups present in the grown crystal. The optical property of the grown crystal was analyzed by UV–vis–NIR and photoluminescence (PL) spectral measurements. The thermal characteristics of the grown crystal were analyzed by thermogravimetric (TG) and differential thermal analyses (DTA). The dielectric measurements were carried out with four different frequencies and the results indicate an increase in dielectric and conductivity parameters with the increase of temperature at all frequencies. The microhardness measurements were used to analyze the mechanical property of the grown crystal.     

Effect of steady ampoule rotation on radial dopant segregation in vertical Bridgman growth of GaSe

For vertical Bridgman growth of the nonlinear optical material GaSe in an ampoule sufficiently long that flow and dopant transport are not significantly influenced by the upper free surface, we show computationally that steady rotation about the ampoule axis strongly affects the flow and radial solid-phase dopant segregation. Radial segregation depends strongly on both growth rate U and rotation rate Ω over the ranges 0.25 μms⁻¹U3.0 μms⁻¹ and 0Ω270 rpm. For each growth rate considered, the overall radial segregation passes through two local maxima as Ω increases, before ultimately decreasing at large Ω. Rotation has only modest effects on interface deflection. Radial segregation computed using a model with isotropic conductivity (one-third the trace of the conductivity tensor) predicts much less radial segregation than the “correct” model using the anisotropic conductivity, with the segregation decreasing monotonically with Ω. Consideration of a model in which centrifugal acceleration is deliberately omitted shows that, as Ω increases, diminution and ultimately disappearance of the “secondary” vortex lying immediately above the interface is due to centrifugal buoyancy, while axial distension of the larger “primary” vortex above is due to Coriolis effects. These results, which are qualitatively different from those accounting for centrifugal buoyancy, suggest that several earlier computational and analytical predictions of rotating vertical Bridgman growth are either limited to rotation rates sufficiently low that centrifugal buoyancy is unimportant, or are artifacts associated with its neglect. The overall radial segregation depends approximately linearly on the product of and the growth rate U for the conditions considered, where is the segregation coefficient.     

On favorable thermal fields for detached Bridgman growth

The thermal fields of two Bridgman-like configurations, representative of real systems used in prior experiments for the detached growth of CdTe and Ge crystals, are studied. These detailed heat transfer computations are performed using the CrysMAS code and expand upon our previous analysis [C. Stelian, A. Yeckel, J.J. Derby, Influence of thermal phenomena on crystal reattachment during the dewetted Bridgman growth, J. Cryst. Growth, in press] that posited a new mechanism involving the thermal field and meniscus position to explain stable conditions for dewetted Bridgman growth. Computational results indicate that heat transfer conditions that led to successful detached growth in both of these systems are in accordance with our prior assertion, namely that the prevention of crystal reattachment to the crucible wall requires the avoidance of any undercooling of the melt meniscus during the growth run. Significantly, relatively simple process modifications that promote favorable thermal conditions for detached growth may overcome detrimental factors associated with meniscus shape and crucible wetting. Thus, these ideas may be important to advance the practice of detached growth for many materials.     

X-ray characterization of detached-grown germanium crystals

Germanium (1 1 1)-oriented crystals have been grown by the vertical Bridgman technique, in both detached and attached configurations. Microstructural characterization of these crystals has been performed using synchrotron white beam X-ray topography (SWBXT) and double axis X-ray diffraction. Dislocation densities were measured from X-ray topographs obtained using the reflection geometry. For detached-grown crystals, the dislocation density is on the order of 10⁴ cm⁻² in the seed region, and decreases in the direction of growth to less than 10³ cm⁻², and in some crystals reaches less than 10² cm⁻². For crystals grown in the attached configuration, dislocation densities were on the order of 10⁴ cm⁻² in the middle of the crystals, increasing to greater than 10⁵ cm⁻² near the edge. The measured dislocation densities are in excellent agreement with etch pit density (EPD) results. Broadening and splitting of the rocking curve linewidths was observed in the vicinity of subgrain boundaries identified by X-ray topography in some of the attached-grown crystal wafers. The spatial distribution of rocking curve linewidths across the wafers corresponds to the spatial distribution of defect densities measured in the X-ray topographs and EPD micrographs.     

Growth and scintillation properties of the Na2W2O7 crystal

The growth and scintillation properties of the Na₂W₂O₇ crystal are reported. The solid reaction between Na₂CO₃ and WO₃ is used to synthesise the Na₂W₂O₇ material. The Na₂W₂O₇ single crystal has been grown by the Bridgman method. And the Na₂W₂O₇ single crystal with sizes 14×7×6 mm³ has been achieved. The transmission spectra, the Ultraviolet fluorescence spectra and the X-ray excited luminescence spectra of the Na₂W₂O₇ crystal are measured. The measurement results show that the Na₂W₂O₇ crystal is a promising intrinsic scintillator.     

Oriented growth of large size calcium fluoride single crystals for optical lithography

We report (1 1 1), (1 1 0) and (1 0 0) growth of CaF₂ by the vertical Bridgman method. Crystals up to 250 mm diameter were grown and various growth parameters such as growth rate, temperature gradient and post-growth cooling rate were studied. It was found that the growth rate and the cooling rate are slower for the larger diameter crystals with a fixed temperature gradient. These growth parameters were optimized for growing the crystals along specific orientation after realizing that CaF₂ has a tendency to grow along an orientation close to 1 1 0. Degradation in optical transmittance was evaluated by irradiating the crystal to γ-rays up to a dose of 10⁵ rad. Optimized scavenger addition resulted in crystals with better radiation resistance and excellent VUV transmittance.     

Crystal growth of PbFCl by modified Bridgman method

Lead fluoride chloride (PbFCl) crystal was grown by modified Bridgman method. The result of X-ray powder diffraction pattern (XRD) was well accordant with the data of JCPDS card. The transmittance spectrum was first reported without absorption band from 270 to 800 nm. Three emission bands were first observed at room temperature when excited by ultraviolet light.     

Optical property analysis of CZT:In single crystals after annealing by a two-step method

Indium-doped Cd_1−xZn_xTe (CZT:In) single crystals were annealed by a two-step method, including a high-temperature step and a low-temperature step in sequence. IR transmittance spectrum, I–V curve and PL spectrum were used to characterize the CZT single crystals. After annealing, the opto-electrical properties of the CZT:In crystals were improved obviously. The average IR transmittance was remarkably increased by about 23%, and the resistivity was enhanced by as high as four orders of magnitude. In the PL spectra, the intensity of the (D⁰, X) peak prominently increased, and the full-width-at-half-maximum was reduced. Meanwhile, the intensity of the DAP peak decreased greatly, and the structure became practically indistinguishable from the background. Moreover, the intensity of the D_complex peak also decreased. The investigation shows that these improvements in the physical properties after annealing are due to variations in the micro-structures. The two-step annealing method can eliminate precipitates/inclusions, remove impurities, compensate Cd vacancies, decrease dislocations and reduce internal stress.     

Extended defects in CdZnTe crystals: Effects on device performance

We explored some unique defects in a batch of cadmium zinc telluride (CdZnTe) crystals, along with dislocations and Te-rich decorated features, revealed by chemical etching. We extensively investigated these distinctive imperfections in the crystals to identify their origin, dimensions, and distribution in the bulk material. We estimated that these features ranged from 50 to 500 μm in diameter, and their depth was about ∼300 μm. The density of these features ranged between 2×10² and 1×10³ per cm³. We elaborated a model of them and projected their effect on charge collection and spectral response. In addition, we fabricated detectors with these defective crystals and acquired fine details of charge-transport phenomena over the detectors’ volume using a high-spatial resolution (25 μm) X-ray response mapping technique. We related the results to better understand the defects and their influence on the charge-transport properties of the devices. The role of the defects was identified by correlating their signatures with the findings from our theoretical model and our experimental data.     

Growth and properties of Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals directly from melt

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by a modified Bridgman method directly from melt using an allomeric Pb[(Mg_1/3Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal as a seed. X-ray diffraction (XRD) measurement confirmed that the as-grown PZNT91/9 single crystals are of pure perovskite structure. Electrical properties and thermal stabilization of PZNT91/9 crystals grown directly from melt exhibit different characters from those of PZNT91/9 crystals grown from flux, although segregation and the variation of chemical composition are not seriously confirmed by X-ray fluorescence analysis (XPS). The [0 0 1]-oriented PZNT91/9 crystals cut from the middle part of the as-grown crystal boules exhibit broad dielectric-response peaks at around 105 °C, accompanied by apparent frequency dispersion. The values of piezoelectric constant d₃₃, remnant polarization P_r, and induced strain are about 1800–2200 pC/N, 38.8 μC/cm², and 0.3%, respectively, indicating that the quality of PZNT crystals grown directly from melt can be comparable to those of PZNT91/9 single crystals grown from flux. However, further work deserves attention to improve the dielectric properties of PZNT crystals grown directly from melt. Such unusual characterizations of dielectric properties of PZNT crystals grown directly from melt are considered as correlating with defects, microinhomogeneities, and polar regions.     

Nucleation, growth and characterization of L-tartaric acid—nicotinamide NLO crystals

The solubility, metastable zone width and nucleation parameters of organic nonlinear optical material L-tartaric acid–nicotinamide (LTN) have been determined. The crystals of LTN are grown by the slow cooling method. The grown crystals are morphologically interpreted. The crystalline powder of the grown crystals has been examined by X-ray diffraction and thermogravimetric analysis. The different modes of vibrations present in the crystal are identified by the Fourier infrared spectroscopy analysis. The powder SHG efficiency of LTN is comparable with that of KDP.     

Production of high purity TeO2 single crystals for the study of neutrinoless double beta decay

High purity TeO₂ crystals are produced to be used for the search for the neutrinoless double beta decay of ¹³⁰Te. Dedicated production lines for raw material synthesis, crystal growth, and surface processing were built compliant with radio-purity constraints specific to rare event physics experiments. High sensitivity measurements of radio-isotope concentrations in raw materials, reactants, consumables, ancillaries, and intermediary products used for TeO₂ crystals production are reported. Indications are given on the crystals perfection and how it is achieved and maintained in a large scale production process. Production and certification protocols are presented and resulting ready-to-use TeO₂ crystals are described.     

Wet KOH etching of freestanding AlN single crystals

We investigated defect-selective wet chemical etching of freestanding aluminum nitride (AlN) single crystals and polished cuts in a molten NaOH–KOH eutectic at temperatures ranging from 240 to 400 °C. Due to the strong anisotropy of the AlN wurtzite structure, different AlN faces get etched at very different etching rates. On as-grown rhombohedral and prismatic facets, defect-related etching features could not be traced, as etching these facets was found to mainly emphasize features present already on the un-etched surface. On nitrogen polar basal planes, hexagonal pyramids/hillocks exceeding 100 μm in diameter may form within seconds of etching at 240 °C. They sometimes are arranged in lines and clusters, thus we attribute them to defects on the surface, presumably originating in the bulk material. On aluminum polar basal planes, the etch pit density which saturates after approx. 2–3 min of total etching time at 350 °C equals the density of a certain type of dislocations (presumably screw dislocations) threading the surface. Smaller etch pits form around annealed indentations, in the vicinity of some bigger etch pits after repeated etching, and sometimes also isolated on the surface area. Although alternate explanations exist, we attribute these etch pits to threading mixed and edge dislocations. This paper features etching parameters optimized for different planes and models on the formation of etching features especially on the polar faces. Finally, the issue of reliability and reproducibility of defect detection and evaluation by wet chemical etching is addressed.     

Vacancy defects in bulk ammonothermal GaN crystals

We have applied positron annihilation spectroscopy to study in-grown vacancy defects in bulk GaN crystals grown by the ammonothermal method. We observe a high concentration of Ga vacancy related defects in n-type samples in spite of the low growth temperature, suggesting that oxygen impurities promote the formation of vacancies also through other mechanisms than a mere reduction of thermodynamical formation enthalpy. On the other hand, no positron trapping at vacancy defects is observed in Mg-doped p-type samples, as expected when the Fermi level is close to the valence band and intrinsic defects are dominantly positively charged. Annealing of the samples at temperatures well above the growth temperature is found to change significantly the defect structure of the material.     

Inversion domains and parallel growth in ammonothermally grown GaN crystals

Macro-defects such as twins, inversion domains, crevices, and columnar growth occasionally appear in ammonothermally grown GaN crystals. Twinning mechanisms and parallel growth are proposed to explain the formation of these defects. As a polar crystal with wurtzite structure, GaN can have several different kinds of twins depending on the polarity arrangement of each individual twin. Inversion domains are formed in one of the twinning mechanisms. Parallel growth is used to explain the formation of pits on the nitrogen face and the columnar growth on the gallium face. Etching in hot H₃PO₄ is used to reveal the polarities and defects of GaN crystals when they are indistinguishable. Optical microscopy, scanning electron microscope, and cathodoluminescence are also employed to study these defects. In addition, seed quality, avoidance of macro-defect formation, and impurity effects are also discussed.     

Growth and properties of Nd:Lu3Ga5O12 laser crystal by floating-zone method

Neodymium (Nd) doped lutetium gallium garnet (Nd:Lu₃Ga₅O₁₂, Nd:LuGG) single crystal was successfully grown by the optical floating-zone method for the first time to our knowledge. Its absorption and luminescence spectra at room temperature were measured. By using the J–O theory, the spectral parameters of Nd:LuGG were calculated, which indicated that Nd:LuGG should possess comparable and even better laser properties than Nd:YAG. The maximum output power of 855 mW at 1062 nm was achieved with slope efficiency of 23.4% under a pump power of 5.2 W, and optical conversion efficiency of 16.4%. All the results show that Nd:LuGG is a potential laser material.