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At least 91 records · Page 5

Mass Flux of ZnSe by Physical Vapor Transport

Mass fluxes of ZnSe by physical vapor transport (PVT) were measured in the temperature range of 1050 to 1160 C using an in-situ dynamic technique. The starting materials were either baked out or distilled under vacuum to obtain near-congruently subliming compositions. Using an optical absorption technique Zn and Se, were found to be the dominant vapor species. Partial pressures of Zn and Se, over the starting materials at temperatures between 960 and 1140 C were obtained by measuring the optical densities of the vapor phase at the wavelengths of 2138, 3405, 3508, 3613, and 3792 A. The amount and composition of the residual gas inside the experimental ampoules were measured after the run using a total pressure gauge. For the first time, the experimentally determined partial pressures of Zn and Se, and the amount and composition of the residual gas were used in a one-dimensional diffusion limited analysis of the mass transport rates for a PVT system. Reasonable agreement between the experimental and theoretical results was observed.

Sha, Yi-Gao↗

Dielectric Spectroscopy Study of ZnSe Grown by Physical Vapor Transport

The dielectric properties of ZnSe samples grown by physical vapor transport were measured as a function of frequency. Differences can be seen in the dielectric properties of samples grown under different conditions. The spectra of heat treated samples were also acquired and were found to exhibit significant deviations from those of the as grown crystals.

Kokan, J.↗

Simultaneous in situ Optical Monitoring Techniques during Crystal Growth of ZnSe by Physical Vapor Transport

ZnSe crystals grown in sealed ampoules by the physical vapor transport method were monitored in situ using three techniques, simultaneously. A Michelson interferometer was set-up to observe the growth rate and surface morphological evolution. An interference pattern (interferogram) is formed by the interaction between the reflection of a HeNe laser (632.8 nm wavelength) off the crystal-vapor interface and a reference beam from the same laser. Preliminary results indicate that the rate of growth/thermal-etching can be calculated using analog data acquisition and simple fringe counting techniques. Gross surface features may also be observed using a digital frame grabber and fringe analysis software. The second in situ technique uses optical absorption to determine the partial pressures of the vapor species. The Se2 and Zn vapor species present in the sealed ampoule absorb light at characteristic wavelengths. The optical absorption is determined by monitoring the light intensity difference between the sample and reference beams. The Se2 Partial pressure profile along the length of the ampoule was estimated from the vibronic absorption peaks at 340.5, 350.8, 361.3 and 379.2 nm using the Beer's law constants established in the calibration runs of pure Se. Finally, because the high temperature crystal growth furnace contains windows, in situ visual observation of the growing crystal is also possible. The use of these techniques not only permits in situ investigation of high temperature vapor growth of semiconductors, but also offers the potential for real time feed back on the growing crystal and allows the possibility of actively controlling the growth process.

Su, C.- H.↗

Simulation of Dynamics of PVT Growth: ZnSe

An unsteady model for the simulation of PVT growth process has been developed and applied to growth of ZnSe. The model is capable of tracking the unsteady aspects of the growth process caused by, for example, changes in the system temperature associated with growth, source-depletion, translation of the charge, out-gassing at high temperatures, as well as changes in the source composition during growth. The model predicts the evolution of growth interface morphology as well as the shape of source-gas interface. Thermo-fluid transport in the gas phase is handled by a Low-Mach number unsteady compressible flow formulation. Heat transfer in the crystal, source, and the quartz housing is calculated by the Monte-Carlo technique to capture the variations in the spectral transmittance and index of refraction of the participating media. Simulation results are presented for the growth interface morphology, thermal stresses in the crystal, and growth rate at various stages of growth. The influence of impurity gases on the growth process is also discussed, The simulation results are compared with the experimental observations. The capabilities of the developed tool in addressing other PVT growth processes such as SiC are discussed.

Worlikar, A.↗

Modeling Studies of PVT Growth of ZnSe: Current Status and Future Course

Bulk growth of wide band gap II-VI semiconductors by physical vapor transport (PVT) has been developed and refined over the past several years at NASA Marshall Space Flight Center. Results from a modeling study of PVT crystal growth of ZnSe are reported in this paper. The PVT process is numerically investigated using a two-dimensional formulation of the governing equations and associated boundary conditions. Both the incompressible Boussinesq approximation and a compressible model are tested to determine the influence of gravity on the process and to discern the differences between the two approaches. The influence of a residual gas is included in the models. The results show that both the incompressible and compressible approximations provide comparable results and the presence of a residual gas tends to measurably reduce the mass flux in the system. Detailed flow, thermal and concentration profiles are provided. The simulations show that the Stefan flux dominates the system flow field and the subtle gravitational effects can be gauged by subtracting this flux from the calculated profiles. Shear flows, due to solutal buoyancy, of the order of 50 microns/s for the liorizont,-d growth orientation and 10 microns/s for the vertical orientation are predicted. Whether these flows can fully account for the observed gravity related growth morphological effects and inhomogeneous solute and dopant distributions is a matter of conjecture. A template for future modeling efforts in this area is suggested which incorporates a mathematical approach to the tracking of the growth front based on energy of formation concepts.

Ramachandran, N.↗

Dielectric Spectroscopy Study of ZnSe Grown by Physical Vapor Transport

The dielectric properties of ZnSe samples grown by physical vapor transport were measured as a function of frequency. Differences can be seen in the dielectric properties of samples grown under different conditions. The spectra of heat treated samples were also acquired and were found to exhibit significant deviations from those of the as grown crystals.

Kokan, Julie L.↗

Numerical Modeling of Crystal of ZnSe by Physical Vapor Transport - Towards a more Comprehensive Formulations

Crystal growth from the vapor phase has various advantages over melt growth. The main advantage is from a lower processing temperature which makes the process more amenable in instances where the melting temperature of the crystal is high. Other benefits stem from the inherent purification mechanism in the process due to differences in the vapor pressures of the native elements and impurities, and the enhanced interfacial morphological stability during the growth process. Further, the implementation of PVT growth in closed ampoules affords experimental simplicity with minimal needs for complex process control which makes it an ideal candidate for space investigations in systems where gravity tends to have undesirable effects on the growth process. Bulk growth of wide band gap II-VI semiconductors by physical vapor transport has been developed and refined over the past several years at NASA MSFC. Results from a modeling study of PVT crystal growth of ZnSe are reported in this paper. The PVT process is numerically investigated using both two-dimensional and fully three-dimensional formulation of the governing equations and associated boundary conditions. Both the incompressible Boussinesq approximation and the compressible model are tested to determine the influence of gravity on the process and to discern the differences between the two approaches. The influence of a residual gas is included in the models. The results show that both the incompressible and compressible approximations provide comparable results and the presence of a residual gas tends to measurably reduce the mass flux in the system. Detailed flow, thermal and concentration profiles will be provided in the final manuscript along with computed heat and mass transfer rates. Comparisons with the 1-D model will also be provided. The effect of gravity on the process from numerical computations shows subtle effects although experimental evidence from vertically and horizontally grown samples show dramatic evidence of gravitational effects. The shortcomings of the problem formulation will be discussed and a framework will be provided leading up towards a more comprehensive model of PVT systems.

Ramachandran, N.↗

Crystal Growth of ZnSe by Physical Vapor Transport: A Modeling Study

Crystal growth from the vapor phase has various advantages over melt growth. The main advantage is from a lower processing temperature which makes the process more amenable in instances where the melting temperature of the crystal is high. Other benefits stem from the inherent purification mechanism in the process due to differences in the vapor pressures of the native elements and impurities, and the enhanced interfacial morphological stability during the growth process. Further, the implementation of Physical Vapor Transport (PVT) growth in closed ampoules affords experimental simplicity with minimal needs for complex process control which makes it an ideal candidate for space investigations in systems where gravity tends to have undesirable effects on the growth process. Bulk growth of wide band gap II-VI semiconductors by physical vapor transport has been developed and refined over the past several years at NASA MSFC. Results from a modeling study of PVT crystal growth of ZnSe arc reported in this paper. The PVI process is numerically investigated using both two-dimensional and fully three-dimensional formulation of the governing equations and associated boundary conditions. Both the incompressible Boussinesq approximation and the compressible model are tested to determine the influence of gravity on the process and to discern the differences between the two approaches. The influence of a residual gas is included in the models. The preliminary results show that both the incompressible and compressible approximations provide comparable results and the presence of a residual gas tends to measurably reduce the mass flux in the system. Detailed flow, thermal and concentration profiles will be provided in the final manuscript along with computed heat and mass transfer rates. Comparisons with the 1-D model will also be provided.

Ramachandran, Narayanan↗

In-Situ Optical Determination of Thermomechanical Properties of ZnSe and ZnTe Crystals

At temperatures above 1/2 T(sub m), the generation and movement of dislocations may result due to the load created by the weight of the crystal itself The deformation may be expected to increase the line defect density and may result in generation of low angle grain boundaries, especially in the regions of the crystal attached to the ampule. It has often been suspected that elimination of this effect in space can improve crystallinity of crystals grown under microgravity conditions, however, a direct experimental proof of such relation is still missing. In this work we have designed and built a system of in-situ optical detection and measurement of the mechanical deformations of a crystal wafer under its own weight, and studied the deformation effects as a function of temperature. The results of the measurements for ZnSe and ZnTe crystal wafers will be presented.

Burger, A.↗

Photoluminescence Studies of ZnSe Starting Materials and Vapor Grown Bulk Crystals

Low-temperature photoluminescence (PL) spectra and glow discharge mass spectroscopy (GDMS) were measured on ZnSe starting materials provided by various vendors and on bulk crystals grown from these starting materials by physical vapor transport (PVT) to study the effects of purification and contamination during crystal growth process. The purification effect of pre-growth heat treatments and the PVT process is evidenced from the GDMS results which showed orders of magnitude reduction in the Li and Na concentration and a factor of 3 reduction in the 0 content after growth. The PL spectra showed that the strong emissions associated with Li (or Na) in one of the starting materials disappeared after growth. To evaluate the contamination of the crystal during the high temperature growth process three growth runs were processed using similar growth parameters but with different furnace environments. The GDMS results showed orders of magnitude increase in the Al and Si contents after growth. The PL spectra suggest that the Al contamination was originated from the fused silica ampoule and the Inconel cartridge might have been the cause for the broad Cu green and Cu red bands observed in one of the grown crystal.

Su, Ching-Hua↗

In-Situ Partial Pressure Measurements and Visual Observation during Crystal Growth of ZnSe by Seeded Physical Vapor Transport

An in-situ monitoring furnace was constructed with side windows to perform partial pressure measurements by optical absorption and visual observation of the growing crystal. A fused silica -rowth ampoule with a 4.5 cm long square tube between the source and the seed was prepared for the optical absorption measurements. A ZnSe crystal was grown by the seeded physical vapor transport (PVT) technique in the horizontal configuration. The growth temperature was 1120 C and the furnace translation rate was 3nmVday. Partial pressures of Se2, P(sub Se2), at three locations along the length of the growth ampoule were measured at 90 min intervals during the growth process. The measured P (sub Se2) were in the range of 2.0 to 6.5 x 10(exp -3) atm. The P(sub Se2) results indicated that the partial pressure profile was inconsistent with the results of the one-dimensional diffusion mass transport model and that the source composition shifted toward Se-rich during the run, i.e. the grown crystal was more Zn-rich than the source. The visual observation showed that the seed crystal first etched back, with greater thermal etching occurring along the edges of the seed crystal. Once the growth started, the crystal crew in a predominately contactless mode and facets were evident during growth. The crystal did not grow symmetrically which is believed to be due to the unintentional asymmetry of the radial thermal profile in the furnace.

Su, Ching-Hua↗

The Preparation Conditions of Chromium Doped ZnSe and Their Effect on The Infrared Luminescence Properties

We report the investigation by photoluminescence lifetime measurements of the near-IR emissions from a series of chromium-doped ZnSe samples, correlated to their preparation conditions. The samples were polycrystalline or single crystals prepared by post growth diffusion doping or single crystals doped during growth by the Physical Vapor Transport method. Room temperature lifetime values between 6 and 8 microseconds were measured for samples with Cr (2+) concentrations from low 10 (exp 17) to high 10 (exp 18) per cubic centimeter range. Lifetime data taken down to 78 K was found to be rather temperature independent, reconfirming previous reports indicating a quantum yield of the corresponding emission of close to 100% at room temperature. A strong decrease in the room temperature lifetime was found for chromium concentrations higher than 10 (exp 19) per cubic centimeter.

Burger, A.↗

The Preparation Conditions of Chromium Doped ZnSe and Their Effect on the Infrared Luminescence Properties

We report the investigation by photoluminescence lifetime measurements of the near-IR emissions from a series of chromium-doped ZnSe samples, correlated to their preparation conditions. The samples were polycrystalline or single crystals prepared by post growth diffusion doping or single crystals doped during growth by the physical vapor transport method. Room temperature lifetime values between 6 and 8 micro seconds were measured for samples with Cr2+ from low 10(exp 17) to high 10(exp 18) / cubic cm range. Lifetime data taken down to 78 K was found to be rather temperature independent, reconfirming previous reports indicating a quantum yield of the corresponding emission of close to 100% at room temperature. A strong decrease in the room temperature lifetime was found for chromium concentrations higher than 10(exp 19) / cubic CM.

Burger, A.↗

Photoluminescence Studies of ZnSe Starting Materials and Vapor Grown Bulk Crystals

Low-temperature photoluminescence (PL) spectra were measured on ZnSe starting materials provided by various vendors and on bulk crystals grown from these starting materials by physical vapor transport (PVT) to study the effects of purification and contamination during PVT process. The impurity levels in one set of starting material/grown crystal were also measured by glow discharge mass spectroscopy (GDMS). The purification effect of pre-growth heat treatments and the PVT process is evidenced from the GDMS results which showed orders of magnitude reduction in the Li and Na concentration and a factor of 3 reduction in the O content after growth. The PL spectra showed that the strong emissions associated with Li (or Na) in one of the starting materials disappeared after growth. The GDMS results also showed increases in the At and Si contents by orders of magnitude after growth. To evaluate the contamination of the crystal during the high temperature growth process, three growth runs were processed using similar growth parameters but different furnace environments. The PL spectra suggest that the At contamination originated from the fused silica ampoule and that the Inconel cartridge might have been the cause of the broad Cu green and Cu red bands observed in one of the grown crystals.

Su, Ching-Hua↗

X-Ray Characterization of Structural Defects in Seeded and Self-Seeded ZnSe Crystal Grown by PVT in Horizontal and Vertical Configurations

As part of a pre-flight ground based investigation of crystal growth of II-VI compound semiconductors, a number of ZnSe boules have been grown by physical vapor transport (PVT) at Marshall Space Flight Center. Boules were grown in both horizontal and vertical configurations and seeded and self-seeded growth techniques were employed. As-grown and/or cleaved boules were examined by a combination of synchrotron white beam x-ray topography (SWBXT) and high resolution triple axis diffraction (HRTXD) to characterized the structural defects and correlate them with the growth conditions. Horizontal grown boules tend to grow away from the ampoule wall (contactless growth) and generally exhibit large (110) facets parallel to the gravity vector. Vertical grown boules grew to the full diameter of the ampoule and exhibited no faceting. X-ray topography combined with back reflection x-ray diffraction revealed the presence of lamellar twins (180 deg type about the [111] axis) in horizontal grown boules while vertically grown boules contain a few large grains, some of which are twinned. X-ray topographs and reciprocal space maps recorded from the boules show the better crystal quality of horizontal grown boules. The relationship between crystal quality and gravity vector is investigated. Further, an attempt is made to extend the Hurle theory of twin nucleation in Czochralski grown crystals to explain the twinning mechanisms in horizontal grown boules.

Raghothamachar, B.↗

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

The objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the crystals grown by vapor transport as results of buoyance-driven convection and growth interface fluctuations caused by irregular fluid-flows. ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, were grown by vapor transport technique with real time in-situ non-invasive monitoring techniques. The grown crystals were characterized extensively to correlate the grown crystal properties with the growth conditions.

Su, Ching-Hua↗

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

The objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the crystals grown by vapor transport as results of buoyancy-driven convection and growth interface fluctuations caused by irregular fluid-flows. ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, were grown by vapor transport technique with real time in situ non-invasive monitoring techniques. The grown crystals were characterized extensively to correlate the grown crystal properties with the growth conditions. Significant effects of gravity vector orientation on the growth crystal morphology and point defect distribution were observed.

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