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Debnam, W. J.

Publications and source records attributed to Debnam, W. J..

Growth of Compound Semiconductors in a Low Gravity Environment: Microgravity Growth of PbSnTe

The growth of the alloy compound semiconductor lead tin telluride (PbSnTe) was chosen for a microgravity flight experiment in the Advanced Automated Directional Solidification Furnace (AADSF), on the United States Microgravity Payload-3 (USNP-3) in February, 1996 and on USNW- 4 in November, 1997. The objective of these experiments was to determine the effect of the reduction in convection, during the growth process, brought about by the microgravity environment. The properties of devices made from PbSnTe, an alloy of PbTe and SnTe, are dependent on the ratio of the elemental components in the starting crystal. Compositional uniformity in the crystal is only obtained if there is no significant mixing in the liquid during growth. The technological importance of PbSnTe lies in its band gap versus composition diagram which has a zero energy crossing at approximately 40% SnTe. This facilitates the construction of long wavelength (greater than 6 gm) infrared detectors and lasers. The properties and utilization of PbSnTe are the subject of other papers. 1,2 PbSnTe is also interesting from a purely scientific point of view. It is, potentially, both solutally and thermally unstable due to the temperature and density gradients present during growth. Density gradients, through thermal expansion, are imposed in directional solidification because temperature gradients are required to extract heat. Solutal gradients occur in directional solidification of alloys due to segregation at the interface. Usually the gradients vary with both experiment design and inherent materials properties. In a simplified one dimensional analysis with the growth axis parallel to the gravity vector, only one of the two instabilities work at a time. During growth, the temperature in the liquid increases ahead of the interface. Therefore the density, due to thermal expansion, is decreasing in that direction. However, the phase diagram shows that the lighter SnTe is preferentially rejected at the interface. This causes the liquid density to increase with distance away from the interface.

Fripp, A. L.↗

The Effect of Microgravity Direction on the Growth of PbSnTe

The Space Shuttle Columbia was launched as STS-75 at 2018 GMT (Greenwich Mean Time) on February 22, 1996. One of the two major experiment packages was the Third United States Microgravity Payload (USMP-3), and one of the principal instruments on the USMP was the Advanced Automated Directional Solidification Furnace (AADSF). The AADSF is a multizone directional solidification furnace, and at the time of the USMP-3 flight was capable of processing only one sample per Shuttle mission which, for that flight, was a lead tin telluride (PbSnTe) crystal growth experiment. In the one year since the flight experiment the sample has been retrieved from the spacecraft and analysis has begun. After presenting introductory material on why PbSnTe was chosen as a test material, why microgravity processing was expected to produce desired results, and what we expected to find in conducting these tests, this report discusses the results to date which are far from complete.

Fripp, A. L.↗

Growth rates and interface shapes in germanium and lead tin telluride observed in-situ, real-time in vertical Bridgman furnaces

Using the advanced technology developed to visualize the melt-solid interface in low Prandtl number materials, crystal growth rates and interface shapes have been measured in germanium and lead tin telluride semiconductors grown in vertical Bridgman furnaces. The experimental importance of using in-situ, real time observations to determine interface shapes, to measure crystal growth rates, and to improve furnace and ampoule designs is demonstrated. The interface shapes observed in-situ, in real-time were verified by quenching and mechanically induced interface demarcation, and they were also confirmed using machined models to ascertain the absence of geometric distortions. Interface shapes depended upon the interface position in the furnace insulation zone, varied with the nature of the crystal being grown, and were dependent on the extent of transition zones at the ends of the ampoule. Actual growth rates varied significantly from the constant translation rate in response to the thermophysical properties of the crystal and its melt and the thermal conditions existing in the furnace at the interface. In the elemental semiconductor germanium the observed rates of crystal growth exceeded the imposed translation rate, but in the compound semiconductor lead tin telluride the observed rates of growth were less than the translation rate. Finally, the extent of ampoule thermal loading influenced the interface positions, the shapes, and the growth rates.

Barber, P. G.↗

Ground based preparation for microgravity growth of alloy semiconductors

Ground-based research conducted in order to prepare a microgravity space flight experiment is presented. The thermophysical properties of a PbSnTe alloy used for semiconductors are investigated, and furnace calibration and fluid-flow measurements are performed. The alloy has a zero energy crossing at approximately 40 percent SnTe in its band-gap vs composition diagram, which facilitates the design of long-wavelength IR detectors and lasers. The uniformity of devices made from this material depends on the ratio of PbTe and SnTe and requires the composition of the crystal growth to be closely controlled. The main obstacle to such control is the fact that liquid of this material is always solutally or thermally unstable, and, in a high-temperature gradient, the double convective instability cannot be made stable by balancing thermal and solutal expansion. In order to extend the science of crystal growth, the limits of suppression of convection have to be tested in low earth orbit.

Fripp, Archibald L.↗

Characterization of the Bridgman crystal growth process by radiographic imaging

Elemental (Ge) and alloy (PbSnTe) crystal growth that is monitored via radiography to reveal both the interface position and the shape in real time is discussed for both seeded and unseeded growth. It is concluded that the interface position and the actual growth rate of a Bridgman grown crystal is dependent on the growth conditions. The actual growth rate which is a strong function of the degree of supercooling exceeded the pull rate by a factor of greater than two. The interface shape changed from concave to flat to convex during the growth.

Fripp, Archibald L.↗

Radiographic instrumentation for DPM experiments

New developments in x-ray radiography that may be applicable to containerless experimentation are presented. The two features discussed are the use of radiography to determine the position and shape of the solid-liquid interface and, with the aid of appropriate markers, the flow patterns in either the surface or bulk of the liquid state. Both surface energy and fluid viscosity measurements can be made with the aid of the described radiographic system.

Fripp, Archie L.↗

Temperature profiles in high gradient furnaces

Accurate temperature measurement of the furnace environment is very important in both the science and technology of crystal growth as well as many other materials processing operations. A high degree of both accuracy and precision is acutely needed in the directional solidification of compound semiconductors in which the temperature profiles control the freezing isotherm which, in turn, affects the composition of the growth with a concomitant feedback perturbation on the temperature profile. Directional solidification requires a furnace configuration that will transport heat through the sample being grown. A common growth procedure is the Bridgman Stockbarger technique which basically consists of a hot zone and a cold zone separated by an insulator. In a normal growth procedure the material, contained in an ampoule, is melted in the hot zone and is then moved relative to the furnace toward the cold zone and solidification occurs in the insulated region. Since the primary path of heat between the hot and cold zones is through the sample, both axial and radial temperature gradients exist in the region of the growth interface. There is a need to know the temperature profile of the growth furnace with the crystal that is to be grown as the thermal load. However it is usually not feasible to insert thermocouples inside an ampoule and thermocouples attached to the outside wall of the ampoule have both a thermal and a mechanical contact problem as well as a view angle problem. The objective is to present a technique of calibrating a furnace with a thermal load that closely matches the sample to be grown and to describe procedures that circumvent both the thermal and mechanical contact problems.

Fripp, A. L.↗

Preparation for microgravity science investigation of compound semiconductor crystal growth

Preparatory work on Bridgman directional solidification (BDS) of PbSnTe crystals prior to microgravity crystal growth experiments on Shuttle flights are reported. Gravitational effects become important in crystal growth when density gradients are present. The situation is critical in BDS of PbSnTe because of the necessity of obtaining homogeneous compositional distributions, which can be disturbed when convective processes occur. Numerical models have been defined which quantify the effects of convection in the crystal growth solution. The models were verified by earth-based crystal-growth tests in a two-zone furnace using equal concentrations of each of the elements. Data are provided to demonstrate the differences in composition among crystals grown at different orientations to the gravitational field vector.

Fripp, A. L.↗

Experimental investigation of the effects of gravity on thermosolutal convection and compositional homogeneity in Bridgman grown, compound semiconductors

Lead-tin-telluride has been grown in a thermally stable mode (solutally unstable) and in a solutally stable (thermally unstable) mode in a Bridgman configuration. Significant differences in the crystal morphology and the compositional homogeneity have been found between the two configurations. In addition, for the solutally stable configuration, evidence has been found that the flow characteristics in the melt change drastically during the course of the run.

Crouch, R. K.↗

Characterization of the general purpose research furnace for low-G directional solidification experiments

Preliminary tests have shown that it is possible to control the temperature settings in NASA's General Purpose Research Furnace in such a manner as to obtain a constant rate of movement of a high temperature isotherm down the length of the furnace. These tests also showed that a temperature gradient on the order of 40 deg cm could be obtained in the furnace while moving the particular isotherm of interest, i.e., 900 C. This provides the possibility of performing directional solidification experiments in the furnace on a MEA flight in the low gravity environment provided by the Shuttle. A functional dependency of growth rate on perturbations during the the growth has been derived and shows the importance of avoiding non-steady growth rates and changing temperature gradients.

Crouch, R. K.↗

Experiment requirements and implementation plan (Erip) for semiconductor materials growth in low-G environment

The MEA-2 A facility was used to test the effect of the low gravity environment on suppressing convective mixing in the growth of Pb(1-x)Sn(x)Te crystals. The need to eliminate convection, the furnace characteristics and operation that will be required for successful experimental implementation, and to the level that is presently known, the measured physical properties of the Pb(1-x)Sn(x)Te system were discussed. In addition, a brief background of the present and potential utilization of Pb(1-x)Sn(x)Te is given. Additional experiments are anticipated in future MEA-A, improved MEA and other dedicated materials processing in space flight apparatus.

Crouch, R. K.↗

Vacuum Ampoule Isolates Corrosive Materials

Quartz vacuum ampoule confines corrosive sample wafer between two quartz plugs inserted in quartz tube. One quartz plug is window for measuring sample thermodynamic properties while laser pulse entering other quartz plug heats sample to molten state. Confinement of sample in vacuum prevents contamination of measurement system by hot corrosive vapors and any interference by preferential evaporation of melt.

Crouch, R. K.↗

Vacuum tight quartz ampoule for Bridgman growth of crystals with interface demarcation

A growth ampoule for protecting the furnace lining and to prevent a change in the composition of the melt during growth of Pb-T-Te or Ge semiconductors doped with Ga is described. Mo foil is inserted into a quartz tube and sealed at the ends. A vacuum pumping system collapses the tube onto the foil. Spotwelded Mo wires lead in two directions from the collapsed section through quartz capillaries, one of which is also collapsed, on the wire, which provides a contact point for seeded growth of the semiconductor. The ampoule has been used for Bridgeman growth of crystals using a hot zone of 1150 C, with a temperature gradient of 240 C/m, and with current pulses up to 40 A/sq cm.

Crouch, R. K.↗

Ground based studies for the space processing of lead-tin-telluride

This paper summarizes the results of a series of studies dealing with crystal growth from the melt and in particular, the growth of the narrow bandgap semiconductor PbSnTe by the Bridgman technique. Theoretical calculations have shown that for low Prandtl number fluids such as semiconductors, convection has no effect on the temperature field in the melt but has a significant effect on the compositional field. They also show that convective flow will exist in a Bridgman growth system on earth, even in the 'thermally stable' configuration. Measurements of the specific heat have been made up to temperatures of 722 C. The thermal diffusivity has been measured up to 1010 C which includes values for the melt. The interdiffusion coefficients for PbTe and SnTe in the melt have been determined. A technique has been developed and tested which provides a vacuum tight quartz ampoule with electrical feedthroughs for interface demarcation studies during the Bridgman growth. Analysis of crystals grown has indicated that the PbSnTe system is solutally unstable and the distribution of SnTe in the crystal, after an anomalous first to freeze region, follows that predicted by Pfann for convection controlled growth. Studies of the amount of supercooling in PbSnTe indicate that this may explain an anomalous composition distribution in the first to freeze region of an unseeded growth.

Crouch, R. K.↗

Thermophysical properties of germanium for thermal analysis of growth from the melt

The thermal diffusivity of Ge has been measured over a temperature range from 300 C to 1010 C which includes values for the melt. Specific heat has been measured from room temperature to 727 C. Thermal conductivity has been calculated over the same temperature range as the diffusivity measurements. These data are reported along with the best values from the literature for the other parameters which are required to calculate the temperature and convective fields for the growth of germanium by the Bridgman method. These parameters include the specific heat, the viscosity, the emissivity, and the density as a function of temperature.

Crouch, R. K.↗

Experiment Requirements and Implementation Plan (ERIP) for semiconductor materials growth in low-G environment experiment no. MPS-77F087

Crystals of the intermetallic compound Pb1-xSnxTe will be grown in furnaces on the Space Shuttle. The reasons for conducting this growth in space, the program of investigation to develop the space experiment and the requirements that are placed on the Space Shuttle furnace are discussed. Also included are relevent thermophysical properties of Pb1-xSnxTe to the degree which they are known.

Crouch, R. K.↗

The role of thermophysics in the design, optimization and understanding of semiconductor crystal growth in space

The compound semiconductor material PbSnTe has been investigated by NASA Langley Research Center as part of the Material Processing in Space (MPS) experiment in the framework of the Space Shuttle program. The long-range goal of the research is the improving of the performance of infrared detectors for use in remote sensing experiments. Three distinct techniques will be used in the low-g environment of space: two techniques involving bulk growth from melt and a vapor growth technique. In order to establish realistic estimates of the required time for experiments and to determine the thermal gradients that will be required to avoid constitutional supercooling, the diffusion coefficients must be accurately measured, however more data especially in the vapor-solid phase relations are needed.

Crouch, R. K.↗

Properties of GaN grown on sapphire substrates

Epitaxial growth of GaN on sapphire substrates using an open-tube growth furnace has been carried out to study the effects of substrate orientation and transfer gas upon the properties of the layers. It has been found that for the (0001) substrates, surface appearance was virtually independent of carrier gas and of doping levels. For the (1(-1)02) substrates surface faceting was greatly reduced when He was used as a transfer gas as opposed to H2. Faceting was also reduced when the GaN was doped with Zn, and the best surfaces for the (1(-1)02) substrates were obtained in a Zn-doped run using He as the transfer gas. The best sample in terms of electrical properties for the (1(-1)02) substrate had a mobility greater than 400 sq cm/V per sec and a carrier concentration of about 10 to the 17th per cu cm. This sample was undoped and used He as the transfer gas. The best (0001) sample was also grown undoped with He as the transfer gas and had a mobility of 300 sq cm/V per sec and a carrier concentration of 1 x 10 to the 18th per cu cm.

Crouch, R. K.↗