Antimonides T2SL Mid-Wave and Long-Wave Infrared Focal Plane Arrays for Earth Remote Sensing Applications
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A radioisotope thermophotovoltaic generator space power system (RTPV) is lightweight, low-cost alternative to the present radioisotope thermoelectric generator system (RTG). The fabrication of such an RTPV generator has recently become feasible as the result of the invention of the GaSb infrared sensitive photovoltaic cell. Herein, we present the results of a parametric study of emitters and optical filters in conjuction with existing data on gallium antimonide cells. We compare a polished tungsten emitter with an Erbia selective emitter for use in combination with a simple dielectric filter and a gallium antimonide cell array. We find that the polished tungsten emitter is by itself a very selective emitter with low emissivity beyond 4 microns. Given a gallium antimonide cell and a tungsten emitter, a simple dielectric filter can be designed to transmit radiant energy below 1.7 microns and to reflect radiant energy between 1.7 and 4 microns back to the emitter. Because of the low long wavelength emissivity associated with the polished tungsten emitter, this simple dielectric filter then yields very respectable system performance. Also as a result of the longer wavelength fall-off in the tungsten emissivity curve, the radiation energy peak for a polished tungsten emitter operating at 1300 K shifts to shorter wavelengths relative to the blackbody spectrum so that the radiated energy peak falls right at the gallium antimonide cell bandedge. The result is that the response of the gallium antimonide cell is well matched to a polished tungsten emitter. We propose, therefore, to fabricate an operating prototype of a near term radioisotope thermophotovoltaic generator design consisting of a polished tungsten emitter, standard gallium antimonide cells, and a near-term dielectric filter. The Jet Propulsion Laboratory will design and build the thermal cavity, and JX Crystals will fabricate the gallium antimonide cells, dielectric filters, and resultant receiver panels. With 250 Watts of heat input, we expect this prototype to produce over 300 Watts of electrical energy output for a system energy conversion efficiency of over 12%. This low risk, near term design provides advances relative to present radioisotope thermophotovoltaic generators and has the additional advantage of allowing component and system development and testing to begin immediately. Improved cells and filters can easily be incorporated in this baseline system if they should become available in the future.
A technique for suppressing sublimation of key elements from skutterudite compounds in advanced thermoelectric devices has been demonstrated. The essence of the technique is to cover what would otherwise be the exposed skutterudite surface of such a device with a thin, continuous film of a chemically and physically compatible metal. Although similar to other sublimation-suppression techniques, this technique has been specifically tailored for application to skutterudite antimonides. The primary cause of deterioration of most thermoelectric materials is thermal decomposition or sublimation - one or more elements sublime from the hot side of a thermoelectric couple, changing the stoichiometry of the device. Examples of elements that sublime from their respective thermoelectric materials are Ge from SiGe, Te from Pb/Te, and now Sb from skutterudite antimonides. The skutterudite antimonides of primary interest are CoSb3 [electron-donor (n) type] and CeFe(3-x)Co(x)Sb12 [electron-acceptor (p) type]. When these compounds are subjected to typical operating conditions [temperature of 700 C and pressure <10(exp -5) torr (0.0013 Pa)], Sb sublimes from their surfaces, with the result that Sb depletion layers form and advance toward their interiors. As the depletion layer advances in a given device, the change in stoichiometry diminishes the thermal-to-electric conversion efficiency of the device. The problem, then, is to prevent sublimation, or at least reduce it to an acceptably low level. In preparation for an experiment on suppression of sublimation, a specimen of CoSb3 was tightly wrapped in a foil of niobium, which was selected for its chemical stability. In the experiment, the wrapped specimen was heated to a temperature of 700 C in a vacuum of residual pressure <10(exp -5) torr (0.0013 Pa), then cooled and sectioned. Examination of the sectioned specimen revealed that no depletion layer had formed, indicating the niobium foil prevented sublimation of antimony at 700 C. This was a considerable improvement, considering that uncoated CoSb3 had been found to decompose to form the lowest antimonide at the surface at only 600 C. Evidently, because the mean free path of Sb at the given temperature and pressure was of the order of tens of centimeters, any barrier closer than tens of centimeters (as was the niobium foil) would have suppressed transport of Sb vapor, thereby suppressing sublimation of Sb
Alkali antimonides are well established as high efficiency, low intrinsic emittance photocathodes for accelerators and photon detectors. However, conventionally grown alkali antimonide films are polycrystalline with surface disorder and roughness that can limit achievable beam brightness. Ordering the crystalline structure of alkali antimonides has the potential to deliver higher brightness electron beams by reducing surface disorder and enabling the engineering of material properties at the level of atomic layers. In this report, we demonstrate the growth of ordered Cs3Sb films on single crystal substrates 3C-SiC and graphene-coated 4H-SiC using pulsed laser deposition and conventional thermal evaporation growth techniques. The crystalline structures of the Cs3Sb films were examined using reflection high energy electron diffraction and x-ray diffraction diagnostics, while film thickness and roughness estimates were made using x-ray reflectivity. With these tools, we observed ordered domains in less than 10 nm thick films with quantum efficiencies greater than 1% at 530 nm. Moreover, we identify structural features such as Laue oscillations indicative of highly ordered films. We found that Cs3Sb films grew with flat, fiber-textured surfaces on 3C-SiC and with multiple ordered domains and sub-nanometer surface roughness on graphene-coated 4H-SiC under our growth conditions. We identify the crystallographic orientations of Cs3Sb grown on graphene-coated 4H-SiC substrates and discuss the significance of examining the crystal structure of these films for growing epitaxial heterostructures in future experiments.
The binary antimonide compounds of the skutterudite family have a good potential for thermoelectric applications as recent results at JPL have shown. However, the room temperature thermal conductivity of these materials is about 10 Wm(sup -1)K(sup -1) with an 80 % contribution from the lattice. To achieve maximum ZT values, the lattice thermal conductivity needs to be lowered. Because the lattice thermal conductivity of solid solutions can substantially decrease due to the addition of point defect phonon scattering (all state-of-the-art thermoelectric materials are solid solutions), a study of the formation of solid solutions between the antimonide skutterudite compounds is of interest. The preparation and characterization of both p-type and n-type CoSb(sub 3)-IrSb(sub 3) solid solutions by several techniques is reviewed in this paper. Experimental results showed that solid solutions were successfully formed in a wide range of compositions. The changes in the thermoelectric properties indicated the influence of a strong point defect scattering, resulting in large decreases in Hall mobility and thermal conductivity. The potential for high ZT values in CoSb(sub 3)-IrSb(sub 3) solid solutions is discussed.
Synthesis, crystal structure, thermal stability, and electronic band structure of four new metal antimonides AMSb (A = Rb, Cs; M = Zn, Cd) are reported. CsZnSb and RbZnSb crystallize in the hexagonal ZrBeSi structure type, in a P6 3 /mmc space group (no. 194, Z = 2) and unit cell dimensions of a = 4.5588(2)/4.5466(4) Å and c = 11.9246(6)/11.0999(10) Å. CsCdSb and RbCdSb crystallize in the tetragonal PbFCl structure type in a P4/nmm space group (no. 129; Z = 2) and unit cell parameters of a = 4.8884(5)/4.8227(3) Å and c = 8.8897(9)/8.5492(7) Å. All four compounds are air- and water-sensitive and are shown through DSC measurements to decompose between 975 K and 1060 K. Analysis of the calculated electronic band structure shows that the Zn-containing antimonides are topologically trivial narrow bandgap semiconductors, whereas Cd-containing compounds exhibit a band inversion along Γ-Z direction.
Five novel Zintl phase solid solutions in the Ba 1–x Sr x Zn 2–y Cd y Sb 2 (0 ≤ x ≤ 0.13(1); 0 ≤ y ≤ 0.32(2)) system were successfully synthesized by the molten Pb metal-flux method, and the powder X-ray diffraction and single-crystal X-ray diffraction analyses proved that all five title compounds adopted the BaCu 2 S 2 -type phase having the orthorhombic Pnma space group (Z = 4, Pearson code oP20) with five crystallographically independent atomic sites. The previously studied BaCu 2 S 2 -type antimonides demonstrated a limited tolerance for doping in contrast to the CaAl 2 Si 2 -type antimonides. To understand the relatively narrower phase width and limited dopability of the title BaCu 2 S 2 -type phase than the CaAl 2 Si 2 -type phase in the overall Ba 1–x Sr x Zn 2–y Cd y Sb 2 system, the radius ratio of cations and anionic elements r + /r – for two structure types were thoroughly investigated. For the first time, the r + /r – ratio was identified as a critical factor for the phase selectivity: (1) r + /r – > 1 favored the BaCu 2 S 2 -type phase, and (2) r + /r – < 1 favored the CaAl 2 Si 2 -type phase. Further, we also revealed the structural transformation mechanism from the more widely observed CaAl 2 Si 2 -type phase to the title BaCu 2 S 2 -type phase as the relatively larger cationic elements were introduced to the system. A series of DFT calculations using the three hypothetical models indicated that a resonance peak near EF in the density of states curves was descended from the relatively flat band structure at several special symmetry points rationalizing the enhanced Seebeck coefficients of Ba 0.94(1) Sr 0.06 Zn 1.86(3) Cd 0.14 Sb 2 and Ba 0.96(1) Sr 0.04 Zn 1.68(2) Cd 0.32 Sb 2 . Electron localization function analysis rationalized the correlation between the polarity change of anionic Zn/Cd–Sb bonds and the charge carrier mobility on the anionic frameworks. Temperature-dependent thermoelectric properties were studied for the four title compounds, and the results proved that the Sr and Cd doping in the title Ba 1–x Sr x Zn 2–y Cd y Sb 2 system successfully enhanced the ZT values through the increased Seebeck coefficients and the reduced total thermal conductivities.
Three new antimonide Zintl phases, RbGaSb 2 , CsGaSb 2 , and CsInSb 2 , were discovered during exploration of corresponding A–M–Sb (A = Rb, Cs; M = Ga, In) ternary systems while searching for new clathrates. The AGaSb 2 phases crystallize in the tetragonal space group P4 2 /nmc (No. 137) in the LiBS 2 structure type, while CsInSb 2 crystallizes in lower symmetry in the orthorhombic space group Cmce (No. 64) in the KGaSb 2 structure type with additional disorder of one of the Cs sites. The crystal structures of all three reported AMSb 2 compounds are composed of two-dimensional [MSb 2 ] – tetrahedral layers separated by Rb + or Cs + cations. [MSb 2 ] – layers are built from fused M–Sb pentagons and hexagons, which are also the main structural units for A 8 M 27 Sb 19 clathrate cages. The semiconductor nature of AMSb 2 was suggested by band structure calculations and confirmed by transport property characterization. CsGaSb 2 is a rare example of an n-type pnictide Zintl phase. Finally, all reported compounds exhibit low thermal conductivity typical for complex antimonides of heavy elements.
Photocathode (alkali antimonides & tellurides) thin film growth state of the art remains largely an art of “cooking” instead of a controlled technological process. Our technology is a method of growing thin films by molecular beam deposition, that applies specifically to photoemissive films. We discovered that some of the photoemissive properties of Cs3Sb (easily measurable) strongly depend on the film’s stoichiometry (very difficult to measure, especially in real time). Such correlation allows to implement a feedback loop that adjusts the ratio of Cs and Sb fluxes in real time and thus maintains the same stoichiometric composition of the film during the whole growth cycle that may last for hours/days. Proposed scheme constitutes true, robust and versatile process control for the growth of alkali antimonide thin films.
Research on the growth of single crystals of the III-V compound indium antimonide was pursued in order to gain a firsthand knowledge of some factors which govern the growth of single crystals of this compound. These studies were conducted using a standard Czochralski crystal pulling furnace. This type of furnace allows crystals to be formed without being constrained to a crucible. Several factors were found to have a large detrimental effect on the growth of single crystals of indium antimonide, the most important of which seems to be the degree to which the environment surrounding the crystal during growth can be controlled. Ways to overcome these effects were determined and are outlined.
A postflight preliminary technical evaluation is presented of the returned samples of aluminum antimonide (AlSb) syntectic compound and lead-zinc (PbZn) monotectic immiscible processed during the Apollo-Soyuz Test Project (ASTP) mission. The returned cartridges, extracted ampoules, and removed samples were examined in detail. A genesis of the experiment is given along with a summary of the efforts and various scheduled tests up to the ASTP mission. A tentative characterization plan is developed from the postflight preliminary examination which makes use of the limited number of available samples and is based on the initial observations. It is indicated that a higher degree of compositional homogeneity in aluminum antimonide was achieved under flight test conditions.
An analysis was performed of the convection which existed on ground tests and during skylab processing of two experiments: vapor growth of IV-VI compounds growth of spherical crystals. A parallel analysis was also performed on Skylab experiment indium antimonide crystals because indium antimonide (InSb) was used and a free surface existed in the tellurium-doped Skylab III sample. In addition, brief analyses were also performed of the microsegregation in germanium experiment because the Skylab crystals indicated turbulent convection effects. Simple dimensional analysis calculations and a more accurate, but complex, convection computer model, were used in the analysis.
The flight test furnace run of the monotectic and syntectic alloys experiment was successfully performed during the Apollo-Soyuz Test Project mission in July 1975. Examination of the returned sample cartridges and the formal comparative characterization of the low-g and one-g processed samples of lead-zinc and aluminum antimonide were completed. The results for aluminum antimonide show that polycrystalline and multiphased material can be homogenize in space under low-g conditions. Microstructural study on the lead-zinc flight samples shows that complete interdiffusion of lead and zinc had not been achieved, even though the flight data indicated a soak temperature in the miscible region that was 40 K above the published consolute temperature.
Assessment of available IR sensor technology showed that the four aerothermodynamic conditions of interest during the entry trajectory of space shuttle can be accommodated by an aircraft flying parallel to the orbiter reentry ground track. Thermal information from the sides of the vehicle can be obtained with degraded performance (temperatures below 800 K) by flying the C-141 aircraft on the opposite side of the shuttle ground track and in the direction opposite that which is optimum for lower surface viewing. An acquisition system using a 6.25-cm aperture telescope and a single indium antimonide detector were designed to meet the acquisition requirements and interface with the 91.5-cm telescope with minimum modification. An image plane system using 600 indium antimonide detectors in two arrays which requires no modification to the existing telescope was also designed. Currently available components were used in a data handling system with interfaces with the experimentors station and the HP2100 computer.
An improved understanding of the phenomena of importance to directional solidification is attempted to enable explanation and prediction of differences in behavior between solidification on Earth and in space. Emphasis is now on experimentally determining the influence of convection and freezing rate fluctuations on compositional homogeneity and crystalline perfection. A correlation is sought between heater temperature profiles, buoyancy-driven convection, and doping inhomogeneities using naphthalene doped with anthracene. The influence of spin-up/spin-down is determined on compositional homogeneity and microstructure of indium gallium antimonide. The effect is determined of imposed melting - freezing cycles on indium gallium antimonide. The mechanism behind the increase of grain size caused by using spin-up/spin-down in directional solidification of mercury cadimum telluride is sought.
Indium antimonide has been epitaxially grown directly on sapphire. Reflection high-energy electron diffraction, TEM, and SEM data are presented to show that the indium antimonide layer is epitaxial, has an abrupt interface with the sapphire, and grows in the 111-line direction. Mobility data show room-temperature mobilities as high as 10,000 sq cm/V s from some regions on the wafer.