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ZnSe has been a great choice for the rare-earth and transition metal doping to develop lasers. It is an excellent material for variety of optical applications due to wide transparency range, good fabricability and very low optical absorption similar to other selenides. NASA Marshall Space Flight Center has developed large crystals using physical vapor deposition (PVD) doped with transition metals for lasing. GaAs based quasi-phase matched structures have a lot of limitations including difficulty of frequency conversion from available high-power lasers. We are developing Si- and GaAs- based templates and using microfabrication process to deposit ZnSe using physical vapor transport (PVT) method. Experimental results of the fabrication of templates and growth of ZnSe on templates will be presented.

During the past several decades physical vapor transport (PVT) method has been extensively used for developing laser and electronic and optical sensor materials especially for incongruent and high vapor materials. Extensive careful studies of the NASA Marshall Space Flight Center on ZnSe growth by PVT has demonstrated that both thermal and solutal convection play very important roles on the quality of crystals and can be controlled by microgravity experiments. In case, the growth is performed by sputtering or systems such as DENTON, it is very difficult to control fluid flow and both thermal and solutal convective flows. We have demonstrated that by controlling the transport path, temperature of substrate and source and using purified source micron size thick ness can be achieved. We will present the experimental results of pure and doped lead selenide (PbSe) which demonstrated various morphologies and bandgap based on size of particles based on growth condition.

Synthesis and crystal growth of scintillators and semiconductor materials for radiation detectors have been proven to be time consuming and very costly. Several alternative crystals such as Tl3ASSe3, TlGaSe2, Tl4HgI6, PbSe(1-x)Ix have developed in our laboratory. These heavy metal and high Z based compounds have shown great promise. We have been working on some innovative approaches based on Cerenkov radiation and nanocomposites of ionizing organics for faster and efficient sensors. By combining some metallic oxides with an organic material, it should be possible to both extend the energy range of particles capable of being detected while also providing more discrimination for high energy gamma-rays, based on local secondary effects in the surrounding organic matrix. We have been working with a highly ionizing organic compound p-chloranil (2,3,5,6-Tetrachloro-1,4-benzoquinone) matrix. In addition, we have determined effect of oxidizing compounds MnO2 on urea-based composites. We use metal oxide as active ingredient in this matrix. We will present effect of morphology and processing on the performance of nanocomposite for sensing gamma-rays.

There are several mechanisms which have been proposed for the existence of colossal dielectric constant in the class of perovskite calcium copper titanate (CaCu3Ti4O12 or CCTO) materials. Researches indicate that existence of twinning parallel to (100) (001) and (010) planes causes planar defects and causes changes in local electronic structure. This change can cause insulating barriers locally which contribute to the large dielectric values irrespective of processing. The combination of insulating barriers, defects and displacements caused by twinning have been attributed to the generation of large dielectric constant in CCTO. To examine some of these arguments some researchers replaced Ca with other elements and evaluated this concept. In this study we present the synthesis and characterization of Ga2/3Cu3Ti4O12-xNx (GCTON) material. This provides both distortion due to atomic size difference and defects due to insertion of nitrogen. The morphology of the compound was determined to show that processing has tremendous effect on the dielectric values. The resistivity of GCTON was several order higher than CCTO and dielectric constant was higher than 10,000.

There is a strong need for rad hard and high operating temperature IR detectors for space environment. Heavy metal Selenides (high Z and large density) have been investigated for more than half century for high operating temperature mid wave infrared (MWIR) applications. Most of the efforts have been devoted to make detector arrays on high-resistivity Si substrates for operating wavelengths in the 1.5 to 5.0 μm region using physical vapor transport grown poly crystalline materials. For most of the biological spectral and imaging applications, short wave infrared (SWIR) detectors have shown better performance. Recent growth materials have shown variation in morphology with slight change in growth conditions and hence variation in performance parameters such as bandgap, mobility and resistivity from sample to sample. We have performed growth and optical characterization of binary materials CdSe-PbSe to determine the suitability for IR detector. We have determined bandgap using several theoretical models for different morphologies observed during growth on silicon wafers.

Recent studies on multinary oxides for applications as laser hosts and high dielectric capacitors have shown that processing at high temperature provides glassy or crystalline materials based on thermal treatments and cooling rates. Since hydroxyapatites are now subject of great interests due to their bioactivity, interest in producing soft and hard materials with glassy and crystalline nature by processing parameters has become very important. Crystalline materials by using Bridgman, Czochralski and flux growth methods are costly and require huge investment. We have observed that even low temperature solidification in organic flux produced oriented fibers. This organic treated material has different characteristics than in situ oxide materials prepared by sintering and grain growth. Examples of phosphate and silicate-based systems will be presented to demonstrate soft and hard materials. Effect of TiO2 and other hardening elements will be also reported.

The transition metal oxide embodied organic composites have great promise for high energy radiation detection. The interaction of high energy radiation such as γ-rays with the organic composite can generate photoelectric responses, Compton scattering and electron hole pairs, which can provide favorable properties to enhance the radiation detectivity of the composite. These effects along with changes of oxidation state of metal oxides, provide significant change in the electrical characteristics of composites due to radiation exposure. We have developed nickel oxide (NiO2) nanoparticles embodied urea composite (urea-NiO2), and determined effect of γ-radiation on the current – voltage characteristics in the frequency range of 100 Hz to 100,000Hz. In this paper, we describe the results of effect of additional oxidizing agent MnO2 (urea-NiO2-MnO2) on the morphology, processing and current voltage characteristics due to exposure of Cs-137 γ-radiation. It was observed that addition of MnO2 in urea-NiO2 composite decreases the sensitivity of detection. However, urea-NiO2-MnO2 composite recovers to original properties after irradiation much faster than urea-NiO2 composite.

This study provides excellent method to create large surface area and morphologies which can be used in drug delivery and for absorption of drugs. In addition provides knowledge about morphological transition

Recently there is a big thrust on bio-inspired sensors and there has been a large rise in the investment and expectations for nanotechnology to meet these goals. For in situ sensor development materials deposition on substrate is essential part of device development. Physical vapor deposition (PVD), chemical vapor deposition (CVD) and molecular organic vapor deposition methods have developed for growth of semiconductor bulk and thin film growth with some modifications have been used for these materials. Oxides and other elements of the VI group such as sulfides and selenides are key components in the skins of many species. Growth of ordered structures containing these elements have been achieved by using PVD method. This paper describes effect of growth parameters during PVD growth on the quality of materials. Growth kinetics and mechanism will be discussed for the vertical and horizontal growth reactors. Since most of the efficient materials systems are multinary and in many cases non-congruent, PVD provides a pathway to grow materials below melting temperature.

Thin film and nanocrystalline materials of oxides have been very attractive choice as low cost option for γ-ray detection and have shown great promise. Our studies on pure oxide films indicated that thickness and microstructure have pronounced effect on sensitivity. Since the interaction of γ-ray with composites involves all three interaction processes; photoelectric effect, Compton scattering, and pair production, composites containing ionic organics have better chance for enhancing sensitivity. In the composites of ionizing organics oxidation effect of unusual oxides changes much faster and hence increases the sensitivity of radiation. In this study, we have used nickel oxide and titanium oxide in ionic organics to develop composite materials for low energy γ-ray sensing. We prepared composites containing ethylene carbonate and evaluated the effect of commercial Cs-137 radiation source by studying current-voltage relationship at several frequencies. Radiated samples showed higher resistivity compared to as prepared composites.

Semiconductor nanowires exhibit very exciting optical and electrical properties including high transparency and a several order of magnitude better photocurrent than thin film and bulk materials. We present here the mechanism of nanowire growth from the melt-liquid-vapor medium. We describe preliminary results of binary and ternary selenide materials in light of recent theories. Experiments were performed with lead selenide and thallium arsenic selenide systems which are multifunctional material and have been used for detectors, acousto-optical, nonlinear and radiation detection applications. We observed that small units of nanocubes and elongated nanoparticles arrange and rearrange at moderate melt undercooling to form the building block of a nanowire. Since we avoided the catalyst, we observed self-nucleation and uncontrolled growth of wires from different places. Growth of lead selenide nanowires was performed by physical vapor transport method and thallium arsenic selenide nanowire by vapor-liquid-solid (VLS) method. In some cases very long wires (>mm) are formed. To achieve this goal experiments were performed to create situation where nanowires grew on the surface of solid thallium arsenic selenide itself.

The process for the formation of kidney stone is very complex phenomena and has some similarity to the crystal growth from a solution. It is very much dependent on the acidity pH of the fluids. This pH variation affects the content and amount of filtering residue and its morphology. In this study we have performed experiments using carbonate, oxides and urea to simulate and understand the morphologies of the residue filtered and coarsened in different conditions. We observed that different of morphologies of kidney stones can be explained on the basis of acidity and hydration conditions. At lower pH fat prism crystals are observed and as pH increases, long fat needle crystals with large aspect ratio are observed. The coarsening experiments showed further growth of crystals. The remelting experiments showed that during dissolution of kidney stones the joining material breaks first leaving the large faceted crystals undissolved when attempts are made to dissolve into small crystallites. However, the morphology did not change. It was also observed that impurities such as magnesium oxide (MgO) affect the morphology significantly.

Increasing threats of radiological weapons have revitalized the researches for low cost large volume γ-ray and neutron ray sensors In the past few years we have designed and grown ternary and quaternary lead and thallium chalcogenides and lead selenoiodides for detectors to meet these challenges. These materials are congruent, can be tailored to enhance the parameters required for radiation sensors. In addition, this class of compounds can be grown by Bridgman method which promises for large volume productions. We have single crystals of several compounds from the melt including Tl 3 AsSe 3 , Tl 3 AsSe 3-x S x , TlGaSe 2 , AgGaGe 3 Se 8 , Ag x Li 1-x AgGaGe 3 Se 8 and PbTlI 5-x Se x compounds. Experimental studies indicate that these have very low absorption coefficient, low defect density and can be fabricated in any shape and sizes. These crystals do not require post growth annealing and do not show any second phase precipitates when processed for electrode bonding and other fabrication steps. In this paper we report purification, growth and fabrication of large Tl 3 AsSe 3 (TAS) crystals. We observed that TAS crystals grown by using further purification of as supplied high purity source materials followed by directionally solidified charge showed higher resistivity than previously reported values. TAS also showed constant value as the function of voltage.

ZnO is a wide-band-gap oxide material that has many applications. A new potential application of ZnO material is for light emitting devices since its structure and electrical properties are similar to that of the GaN material (a blue laser candidate). It also is a good substrate for fabricating GaN-based devices. Off-axis sputtering technique has revealed great potential in synthesizing excellent oxide materials because the negative ion bombardment is greatly reduced when adatoms condense on substrates. The surface of films grown by off-axis sputtering will be much smoother than that produced in a regular sputtering configuration. A growth mechanism is studied by investigating the morphology and structure of ZnO films under different growth conditions and orientations. ZnO films are deposited on (0001) sapphire and quartz substrates by off- axis sputtering deposition at various oxygen/argon mixture ratios and pressures and at different temperatures. All films reveal highly textured structures on quartz substrates and epitaxial growth on sapphire substrates. Two off-axis configurations, vertical and horizontal orientations are conducted to study the process of film growth, surface morphology, and film structure. X-ray diffraction, scanning probe microscopy, and electrical measurements are used to characterize these films. Detailed results will be discussed in the presentation. Keywords: ZnO, Photonic material, Off-axis sputtering, Growth mechanism

Infrared detector materials, such as Hg(1-x)Cd(x)Te, Hg(1-x)Zn(x)Te have energy gaps almost linearly proportional to its composition. Due to the wide separation of liquidus and solidus curves of their phase diagram, there are compositional segregations in both of axial and radial directions of these crystals grown in the Bridgman system unidirectionally with constant growth rate. It is important to understand the mechanisms which affect lateral segregation such that large uniform radial composition crystal is possible. Following Coriell, etc's treatment, we have developed a theory to study the effect of a curved melt-solid interface shape on the lateral composition distribution. The system is considered to be cylindrical system with azimuthal symmetric with a curved melt-solid interface shape which can be expressed as a linear combination of a series of Bessell's functions. The results show that melt-solid interface shape has a dominate effect on lateral composition distribution of these systems. For small values of b, the solute concentration at the melt-solid interface scales linearly with interface shape with a proportional constant of the product of b and (1 - k), where b = VR/D, with V as growth velocity, R as sample radius, D as diffusion constant and k as distribution constant. A detailed theory will be presented. A computer code has been developed and simulations have been performed and compared with experimental results. These will be published in another paper.

Crystal growth kinetics from the vapor phase or from solution can be described by the diffusion of growth species to the echelon of equidistant steps present at vicinal surfaces. Diffusion takes place in a thin boundary layer adjacent to the interface. Present theories of this process neglect a convective transport mechanism in the boundary layer. In this work, we reexamine this zero-flow assumption. We consider the difference in the densities between the mother phase and the growing crystalline phase as the driving force for the flow. This force is localized at the step positions when only lateral growth of the steps is permitted. In such a case a highly nonuniform flow pattern is obtained. It consists of two vortices with the line between these vortices corresponding to a flow directed towards the step. This nonuniform part of the flow is found to extend into the mother phase up to an inter- step distance. This is the region where diffusion in the horizontal direction takes place. Consequently, the results suggest the importance of convective transport in the boundary layer. Finally, a constant horizontal flow, far from the surface, is predicted.© (1997) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

Undoped and doped CdS0.8 Se0.2 crystals were grown by physical vapor transport (PVT). The selected dopant was vanadium at a nominal concentration of 150 ppm creating for photorefractive effect. The as-grown crystal has a large crystal size, 1.1 cm in diameter and 6 cm in length, with a medium resistivity of 104 - 107 (Omega) -cm. The results from low temperature photoluminescence (PL) show that the undoped crystal has only one emission band at 2.31 eV and its phonon replicas. The vanadium doped crystal not only show the similar emission band but also has an additional broad band center at 1.95 eV due to the effect of doping. Low temperature (16 K) and room temperature IR transmittance spectra of vanadium doped crystal revealed a broad absorption band between 0.8 and 1.3 eV which may be due to vanadium dopant. Etch pitch density (EPD) measurements were performed, and the results showed EPD in the range of 104/cm2 for both types of crystals. Precipitate/inclusion were also found in both crystal, and their distribution patterns may be related to gravity-induced convection during growth process.© (1997) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

Experiments were performed in controlled conditions to understand both morphological and convective instabilities and results were compared with the theoretical calculations. The sharp contrast between the solid (yellow) and the liquid (bright red) phases makes this transparent lead bromide a very suitable material for such an investigation. Crystals doped with 5000 ppm silver bromide were grown. The experimental observations agree with the preliminary results of the numerical prediction. Further, toroidal instabilities resulting from double diffusive convection were observed during crystal growth. Crystals for these interfacial observations were grown in a two zone vertical Bridgman furnace. The acoustic properties were better in doped rather than undoped crystals. Crystals were characterized by x-ray rocking curves and contour scans. Crystals grown at lower Rayleigh numbers showed better quality than crystals grown at higher Rayleigh numbers.

The mechanism of physical vapor transport of II-VI semiconducting compounds was studied both theoretically, using a one-dimensional diffusion model, as well as experimentally. It was found that the vapor phase stoichiometry is critical in determining the vapor transport rate. The experimental heat treatment methods to control the vapor composition over the starting materials were investigated and the effectiveness of the heat treatments was confirmed by partial pressure measurements using an optical absorption technique. The effect of residual (foreign) gas on the transport rate was also studies theoretically by the diffusion model and confirmed experimentally by the measurements of total pressure and compositions of the residual gas. An in-situ dynamic technique for the transport rate measurements and a further extension of the technique that simultaneously measured the partial pressures and transport rates were performed and, for the first time, the experimentally determined mass fluxes were compared with those calculated, without any adjustable parameters, from the diffusion model. Using the information obtained from the experimental transport rate measurements as guideline high quality bulk crystal of wide band gap II-VI semiconductor were grown from the source materials which undergone the same heat treatment methods. The grown crystals were then extensively characterized with emphasis on the analysis of the crystalline structural defects.

The Universal Multizone Crystallizator (UMC) is a special apparatus for crystal growth under terrestrial and microgravity conditions. The use of twenty-five zones allows the UMC to be used for several normal freezing growth techniques. The thermal profile is electronically translated along the stationary sample by systematically reducing the power to the control zones. Elimination of mechanical translation devices increases the systems reliability while simultaneously reducing the size and weight. This paper addresses the UMC furnace design, sample cartridge and typical thermal profiles and corresponding power requirements necessary for the dynamic gradient freeze crystal growth technique. Results from physical vapor transport and traveling heater method crystal growth experiments are also discussed.

The first United States Microgravity Laboratory Mission (USML- 1) flew in June 1992 on the Space Shuttle Columbia. An important part of this SpaceLab mission was the debut of the Crystal Growth Furnace (CGF). Of the seven samples grown in the furnace, three were bulk grown 2-6 compounds, two of a cadmium zinc telluride alloy, and one of a mercury zinc telluride alloy. Ground based results are presented, together with the results of computer simulated growths of these experimental conditions. Preliminary characterization results for the three USML-1 growth runs are also presented and the flight sample characteristics are compared to the equivalent ground truth samples. Of particular interest are the effect of the containment vessel on surface features, and especially on the nucleation, and the effect of the gravity vector on radial and axial compositional variations and stress and defect levels.

In preparation for anticipated microgravity space missions carrying the Advanced Automated Directional Solidification Furnace, experiments were conducted to determine growth of interface in growing crystals of cadmium-doped germanium (test case), cadmium telluride, and mercury zinc telluride, using three different techniques. It was found that compositional variations detectable by microprobe and EDS techniques were most successful for detecting interfaces in materials with extensive transient regions, large segregation coefficients, and high alloy content.