Estimation of the chemical compatibility of alloys with lead telluride and tin telluride thermoelectric materials.
Chemical compatibility estimation of lead and tin tellurides thermoelectric materials with metallic alloys
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Chemical compatibility estimation of lead and tin tellurides thermoelectric materials with metallic alloys
A modified Bridgman-Stockbarger furnace was constructed for a study of the solidification of silver, germanium and lead-tin-telluride. The melt-solid interface position with respect to the furnace and its temperature profile was determined by measuring the discontinuity in the slope of temperature as a function of position in the melt and in the solid. The results show that the interface position of the semiconductors germanium and lead-tin-telluride was essentially constant with respect to the furnace and hence the growth rate was constant and equal to the sample translation rate of 0.046 cm/min and 0.178 cm/min in each case. The metal, silver, on the other hand showed a continuous interface migration toward the hot zone of the furnace and always exhibited a growth rate which was higher than the ampoule translation rate. The K sub L/K sub S ratio of lead-tin-telluride was determined to be 2.33 + or - 0.06 where K sub L,S denotes the thermal conductivity of the liquid, solid respectively. The value of K sub L was calculated to be about 0.054 Watt 0.1 cm 0.1 K. The diffusion boundary layer thickness was calculated for lead-tin-telluride to be about 0.05 cm using a liquid diffusivity of .00007 sq cm/sec.
Compatibility of lead and tin tellurides with metals evaluated for chemical stability of interfaces in ternary systems
The main objective of this research was to present a model for the prediction of the effect of the microgravity environment on the growth of Lead Tin Telluride. The attitude change and its relation to the experimental objectives: The main objective for the AADSF experiment on USMP 3 involving LTT growth was to estimate the effect of ampoule orientation on the axial and radial segregation of tin telluride. As the furnace was not situated on a gimbal there was no possibility to reorient the ampoule during the flight. Instead the only way to change the growth orientation was to change the attitude of the orbiter. This was accomplished by vernier rocket firings. In what follows it must be noted that the orbiter body coordinates are such that the positive z axis points outward from the 'belly', the positive 'x' axis points outwards from the nose and the positive 'y' axis points outwards from the starboard side. The furnace which was in the pay load had its axis aligned with the orbiter's 'z' axis with the hot end closest to the shuttle body. There were basically three orientations that were desired. These corresponded to the ampoule being seen as a heated from above (thermally stable-solutally unstable) configuration, the heated from below (where the instabilities were reversed from the first orientation) configuration and an 'in between' case where the ampoule axis was misaligned with respect to the orbiters 'g(sub z)' axis.
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.
High resolution X-ray diffraction images of two directly comparable crystals of lead tin telluride, one Bridgman-grown on Space Shuttle STS 61A and the other terrestrially Bridgman-grown under similar conditions from identical material, present different subgrain structure. In the terrestrial, sample 1 the appearance of an elaborate array of subgrains is closely associated with the intrusion of regions that are out of diffraction in all of the various images. The formation of this elaborate subgrain structure is inhibited by growth in microgravity.
An X-ray and gamma-ray analysis technique has been developed which makes it possible to observe the melt solid interface during semiconductor crystal growth in a Bridgman furnace. Experiments have been carried out to observe the interface movement and shape in germanium as well as in lead tin telluride by means of the new method, and the results are discussed in detail. X-ray and gamma-ray radiographs of the melt-solid interfaces in the two semiconductor crystal specimens, are provided.
Convective currents during the Bridgman growth of a compound semiconductor lead to temperature fluctuations at the solid-liquid interface. These temperature fluctuations in turn lead to microscopic compositional variations in the solid. Electrochemical principles have been applied to develop three etches which delineate the variations in the compound semiconductor, lead tin telluride, and allow optical studies of the growth kinetics of this material. Use of these etches has shown periodic lines during the initial growth, with indications of oscillatory instabilities developing in later stages of growth, and, finally, complete breakdown of the interface.
The goals outlined for the research project for this year have been completed, and the following supporting documentation is attached: 1. A copy of the proposal outlining the principal goals: (a) Improve the characterization of semiconductor crystals through new etches and etching procedures. (b) Developed a novel voltammetric method to characterize semiconductor crystals as a result of searching for improved etches for lead-tin-telluride. (c) Presented paper at ACCG- 10. (d) Prepared manuscripts for publication. Completed additional testing suggested by reviewers and re-submitted manuscripts. (e) Worked with an undergraduate student on this project to provide her an opportunity to have a significant research experience prior to graduation. 2. In addition to the anticipated goals the following were also accomplished: (a) Submitted the newly developed procedures for consideration as a patent or a NASA Tech Brief. (b) Submitted a paper for presentation at the forthcoming ICCG- 12 conference. 3. A copy of the final draft of the publication as submitted to the editors of the Journal of Crystal Growth.
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.
Improved gels and several geometries were investigated for use in growing crystals. The use of lead sulfide test crystals proved workable, but it was impossible to obtain and maintain a sufficiently concentrated telluride ion solution to successfully grow lead telluride crystals. It appears that oxygen in the solution is capable of oxidizing the telluride ion up to tellurium metal. The method may still be successful, but only if precautions are taken to eliminate dissolved oxygen from the gels and aqueous solutions and to maintain a suitable concentration of telluride, Te(2)-(aq.).
The solutal diffusion coefficient has been determined for liquid lead telluride-tin telluride using a modified shear cell technique. Postdiffusion concentration profiles are presented for several diffusion couples. The best analytical curve fit to the data gives a composition-dependent diffusion coefficient of (/3/7/ to the C power) x 0.00014 sq cm/sec, where C is the PbTe concentration. In addition, data are presented to show the importance of solutal convection in the lead-tin-telluride system.
High pressure effect on metallurgical phenomena of thallium-lead alloys, and high pressure effects on lead telluride, tin telluride, and lead-tin- tellurium system
Diffusion and braze bonding of tungsten and tantalum to lead telluride and lead telluride- tin telluride thermoelectric alloys
Low resistance, high strength, nonmagnetic electrode bonding to lead telluride and lead- telluride-tin telluride alloys
Solid-state diffusion process bonds lead telluride and lead telluride-tin telluride thermoelectric elements to tungsten electrodes. The resulting bond is nonmagnetic and has high strength and low electrical and thermal resistance. This method is also used with tantalum electrodes.
The tuning of the Fermi level in tin telluride, a topological crystalline insulator, is essential for accessing its unique surface states and optimizing its electronic properties for applications such as spintronics and quantum computing. In this study, we demonstrate that the Fermi level in tin telluride can be effectively modulated by controlling the tin concentration during chemical vapor deposition synthesis. By introducing tin-rich conditions, we observed a blue shift in the x-ray photoelectron spectroscopy core-level peaks of both tin and tellurium, indicating an upward shift in the Fermi level. Further, this shift is corroborated by a decrease in work function values measured via ultraviolet photoelectron spectroscopy, confirming the suppression of Sn vacancies. Our findings provide a low-cost, scalable method to achieve tunable Fermi levels in tin telluride, offering a significant advancement in the development of materials with tailored electronic properties for next-generation technological applications.
Evaporation rates of lead telluride and lead tin telluride in pressed and sintered thermoelement form