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NASA NTRS1987

Theoretical and material studies on thin-film electroluminescent devices

The effect of surface nucleation processes on the quality of ZnS layers grown on (001) GaAs substrates by molecular beam epitaxy is reported. Reflection high energy electron diffraction indicated that nucleation at high temperatures produced more planar surfaces than nucleation at low temperatures, but the crystalline quality as accessed by x ray double crystal diffractometry is relatively independent of nucleation temperature. A critical factor in layer quality was the initial roughness of the GaAs surfaces.

Summers, C. J.↗

NASA NTRS1986

Passivation of Si solar cells by hetero-epitaxial compound semiconductor coatings

A development status evaluation is made for high efficiency Si solar cells, with emphasis on the suppression of the deleterious effects of surface recombination. ZnS(0.9)Se(0.1) and GaP are identified as candidates for the reduction of surface recombination. Attention is given to methods developed for the deposition of heteroepitaxial compounds designed to block minority carrier transport to the Si solar cell surface without interfering with the majority carrier flow.

Vernon, S. M.↗

NASA NTRS1988

Theoretical and material studies on thin-film electroluminescent devices

During this report period work was performed on the modeling of High Field Electronic Transport in Bulk ZnS and ZnSe, and also on the surface cleaning of Si for MBE growth. Some MBE growth runs have also been performed in the Varian GEN II System. A brief outline of the experimental work is given. A complete summary will be done at the end of the next reporting period at the completion of the investigation. The theoretical studies are included.

Summers, C. J.↗

NASA NTRS1989

Ultra-thin, light-trapping silicon solar cells

Design concepts for ultra-thin (2 to 10 microns) high efficiency single-crystal silicon cells are discussed. Light trapping allows more light to be absorbed at a given thickness, or allows thinner cells of a given Jsc. Extremely thin cells require low surface recombination velocity at both surfaces, including the ohmic contacts. Reduction of surface recombination by growth of heterojunctions of ZnS and GaP on Si has been demonstrated. The effects of these improvements on AM0 efficiency is shown. The peak efficiency increases, and the optimum thickness decreases. Cells under 10 microns thickness can retain almost optimum power. The increase of absorptance due to light trapping is considered. This is not a problem if the light-trapping cells are sufficiently thin. Ultra-thin cells have high radiation tolerance. A 2 microns thick light-trapping cell remains over 18 percent efficient after the equivalent of 20 years in geosynchronous orbit. Including a 50 microns thick coverglass, the thin cells had specific power after irradiation over ten times higher than the baseline design.

Landis, Geoffrey A.↗

NASA NTRS1992

Post-flight analyses of the crystals from the M0003-14 quartz crystal microbalance experiment

Quartz Crystal Microbalances constructed by QCM Research were flown on the leading and trailing edges of the Long Duration Exposure Facility (LDEF) as one of the sub-experiments of M0003. Response of the crystals coated with 150 A of IN2O3ZnS was recorded during the first 424 days of the mission. A second QCM with crystals coated with 150 A was also flown but not monitored. The flight data and temperature profiles will be presented. After the flight, the QCM's were disassembled and analyzed. The samples included the crystals from the leading and trailing edge samples of both types of coatings along with the reference crystals which were inside the QCM housing. Analyses were performed by scanning electron microscopy, energy dispersive x ray analysis, x ray photoelectron spectroscopy, ion microprobe mass analysis, and reflectance spectroscopy in the infrared and ultraviolet/visible region. The crystals were contaminated predominantly with silicone compounds. The contamination is higher on the leading edge than on the trailing edge, and higher on the exposed crystal than on the reference crystals. No significant differences in composition of the In2O3 crystals were noted. Differences in the reflectance and surface analysis of the Zns crystals will be discussed.

Stuckey, W. K.↗

NASA NTRS1993

Post-flight analyses of the crystals from the M0003-14 quartz crystal microbalance experiment

Quartz Crystal Microbalances constructed by QCM Research were flown on the leading and trailing edges of LDEF as one of the sub-experiments of M0003. Response of the crystals coated with 150 A of In2O3 was recorded during the first 424 days of the mission. A second QCM with crystals coated with 150 A of ZnS was also flown but not monitored. After the flight, the QCM's were disassembled and analyzed in The Aerospace Corporation laboratories. The samples included the crystals from the leading and trailing edge samples of both types of coatings along with the reference crystals, which were inside the QCM housing. Analyses were performed by scanning electron microscopy, energy dispersive x-ray analyses, x-ray photoelectron spectroscopy, ion microprobe mass analysis, and reflectance spectroscopy in the infrared and UV/visible regions. The crystals are contaminated predominantly with silicone compounds. The contamination is higher on the leading edge than on the trailing edge and higher on the exposed crystals than on the reference crystals.

Stuckey, W. K.↗

NASA NTRS1993

Crystal growth of ZnSe and related ternary compound semiconductors by physical vapor transport

The materials to be investigated are ZnSe and related ternary semiconducting alloys (e.g., ZnS(x)Se(1-x), ZnTe(x)Se(1-x), and Zn(1-x)Cd(x)Se). These materials are useful for opto-electronic applications such as high efficient light emitting diodes and low power threshold and high temperature lasers in the blue-green region of the visible spectrum. The recent demonstration of its optical bistable properties also makes ZnSe a possible candidate material for digital optical computers. The investigation consists of an extensive ground-based study followed by flight experimentation, and involves both experimental and theoretical work. The objectives of the ground-based work are to establish the characteristics of the crystals grown on Earth as a basis for subsequent comparative evaluations of the crystals grown in a low gravity environment and to obtain the experimental data and perform the analyses required to define the optimum parameters for the flight experiments. During the six months of the Preliminary Definition Phase, the research efforts were concentrated on the binary compound ZnSe - the purification of starting materials of Se by zone refining, the synthesis of ZnSe starting materials, the heat treatments of the starting materials, the vapor transport rate measurements, the vapor partial pressure measurements of ZnSe, the crystal growth of ZnSe by physical vapor transport, and various characterization on the grown ZnSe crystals.

Su, Ching-Hua↗

NASA NTRS1995

Design of a three-layer antireflection coating for high efficiency indium phosphide solar cells using a chemical oxide as first layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 mu m of the surface of the illuminated cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3-layer AR coating for thermally diffused p+n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p+ emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as an efficient antireflective layer yielding a measured record high AMO open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3 and MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductors materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating should work well for all III-V compound-based solar cells.

Moulot, Jacques↗

NASA NTRS1995

Growth of Wide Band Gap II-VI Compound Semiconductors by Physical Vapor Transport

The studies on the crystal growth and characterization of II-VI wide band gap compound semiconductors, such as ZnTe, CdS, ZnSe and ZnS, have been conducted over the past three decades. The research was not quite as extensive as that on Si, III-V, or even narrow band gap II-VI semiconductors because of the high melting temperatures as well as the specialized applications associated with these wide band gap semiconductors. In the past several years, major advances in the thin film technology such as Molecular Beam Epitaxy (MBE) and Metal Organic Chemical Vapor Deposition (MOCVD) have demonstrated the applications of these materials for the important devices such as light-emitting diode, laser and ultraviolet detectors and the tunability of energy band gap by employing ternary or even quaternary systems of these compounds. At the same time, the development in the crystal growth of bulk materials has not advanced far enough to provide low price, high quality substrates needed for the thin film growth technology.

Su, Ching-Hua↗

NASA NTRS1998

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

Interest in optical devices which can operate in the visible spectrum has motivated research interest in the II-VI wide band gap semiconductor materials. The recent challenge for semiconductor opto-electronics is the development of a laser which can operate at short visible wavelengths, In the past several years, major advances in thin film technology such as molecular beam epitaxy and metal organic chemical vapor deposition have demonstrated the applicability of II-VI materials to important devices such as light-emitting diodes, lasers, and ultraviolet detectors.The demonstration of its optical bistable properties in bulk and thin film forms also make ZnSe a possible candidate material for the building blocks of a digital optical computer. Despite this, developments in the crystal growth of bulk II-VI semiconductor materials has not advanced far enough to provide the low price, high quality substrates needed for the thin film growth technology. The electrical and optical properties of semiconductor materials depend on the native point defects, (the deviation from stoichiometry), and the impurity or dopant distribution. To date, the bulk growth of ZnSe substrates has been plagued with problems related to defects such as non-uniform distributions of native defects, impurities and dopants, lattice strain, dislocations, grain boundaries, and second phase inclusions which greatly effect the device performance. In the bulk crystal growth of some technologically important semiconductors, such as ZnTe, CdS, ZnSe and ZnS, vapor growth techniques have significant advantages over melt growth techniques due to the high melting points of these materials.

Su, Ching-Hua↗

NASA NTRS2001

Vapor Growth of Binary and Ternary Chalcogenides in Preparation for Microgravity Experiments

In the bulk crystal growth of some technologically important semiconducting chalcopyrites, such as ZnTe, CdS, ZnSe and ZnS, vapor growth techniques have significant advantages over melt growth techniques due to the high melting points of these materials. The realization of routine production of high-quality single crystals of these semiconductors requires a fundamental, systematic and in-depth study on the PVT growth process and crystal growth by vapor transport in low gravity offers a set of unique conditions for this study. Previously, two reasons have been put forward to account for this. The first is weight-related reductions in crystal strain and defects. These are thought to be caused by the weight of the crystals during processing at elevated temperatures and retained on cooling, particularly for materials with a low yield strength. The second, and more general, reason is related to the reduction in density-gradient driven convection. The PVT crystal growth process consists of essentially three processes: sublimation of the source material, transport of the vapor species and condensation of the vapor species to form the crystal. The latter two processes can be affected by the convection caused by gravitational accelerations on Earth. Reductions in such convection in low gravity is expected to yield a nearly diffusion-limited growth condition which results in more uniform growth rates (on the microscopic scale) and hence greater crystalline perfection and compositional homogeneity. The reduction of convective contamination by performing flight experiments in a reduced gravity environment will help to understand the relation between fluid phase processes (growth parameters) and defect and impurity incorporation in grown crystals.

Su, C.↗

NASA NTRS2001

Vapor Growth of Binary and Ternary Chalcogenides in Preparation for Microgravity Experiments

Su, Ching-Hua↗

NASA NTRS2001

Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(x)V(1-x), alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(x),V(1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(x)Te(l-x) and ZnSe(Y)Te(1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(y)Te(1-y) alloys in the entire composition range, 0 less than or equal to y less than or equal to 1. The samples used in this study are bulk ZnSe(y)Te(1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the interaction between localized Se states and the conduction band. On the other hand we show that the large band gap reduction observed on the Se-rich side of the alloy system is a result of an interaction between the localized Te level and the valence bands. This interaction leads to the formation of a Te-like valence band edge that strongly interacts with the light hole valence band. Calculations based on a modified k p model account for the reduction of the band gap and the large increase of the spin-orbit splitting observed in Se-rich ZnSe(y)Te(l-y) alloys. We will also discuss the importance of these new results for understanding of the electronic structure and band offsets in other highly mismatched alloy systems.

Yu, Kin Man↗

NASA NTRS2001

Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(sub x)V(sub 1-x) alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(sub x)V(sub 1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(sub x)Te(sub 1-x) and ZnSe(sub y)Te(sub 1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(sub y)Te(sub 1-y) alloys in the entire composition range, y between 0 and 1. The samples used in this study are bulk ZnSe(sub y)Te(sub 1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the interaction between localized Se states and the conduction band. On the other hand we show that the large band gap reduction observed on the Se-rich side of the alloy system is a result of an interaction between the localized Te level and the valence bands. This interaction leads to the formation of a Te-like valence band edge that strongly interacts with the light hole valence band. Calculations based on a modified k(sup dot)p model account for the reduction of the band gap and the large increase of the spin-orbit splitting observed in Se-rich ZnSe(sub y)Te(sub 1-y) alloys. We will also discuss the importance of these new results for understanding of the electronic structure and band offsets in other highly mismatched alloy systems.

Yu, Kin Man↗

NASA NTRS2002

Ordered nanoparticle arrays formed on engineered chaperonin protein templates

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.

Chaperonins/chemistry/ultrastructure↗

NASA NTRS2014

Search for Fluid Inclusions in a Carbonaceous Chondrite Using a New X-Ray Micro-Tomography Technique Combined with FIB Sampling

Early solar system aqueous fluids are preserved in some H chondrites as aqueous fluid inclusions in halite (e.g., [1]). Although potential fluid inclusions are also expected in carbonaceous chondrites [2], they have not been surely confirmed. In order to search for these fluid inclusions, we have developped a new X-ray micro-tomography technique combined with FIB sampling and applied this techniqu to a carbanaceous chondrite. Experimental: A polished thin section of Sutter's Mill meteorite (CM) was observed with an optical microscope and FE-SEM (JEOL 7001F) for chosing mineral grains of carbonates (mainly calcite) and sulfides (FeS and ZnS) 20-50 microns in typical size, which may have aqueous fluid inclusions. Then, a "house" similar to a cube with a roof (20-30 microns in size) is sampled from the mineral grain by using FIB (FEI Quanta 200 3DS). Then, the house was atached to a thin W-needle by FIB and imaged by a SR-based imaging microtomography system with a Fresnel zone plate at beamline BL47XU, SPring-8, Japan. One sample was imaged at two X-ray energies, 7 and 8 keV, to identify mineral phases (dual-enegy microtomography: [3]). The size of voxel (pixel in 3D) was 50-80 nm, which gave the effective spatial resolution of approx. 200 nm. A terrestrial quartz sample with an aqueous fluid inclusion with a bubble was also examined as a test sample by the same method. Results and discussion: A fluid inclusion of 5-8 microns in quartz was clearly identified in a CT image. A bubble of approx. 4 microns was also identified as refraction contrast although the X-ray absorption difference between fluid and bubble is small. Volumes of the fluid and bubble were obtained from the 3D CT images. Fourteen grains of calcite, two grains of iron sulfide and one grain of (Zn,Fe)S were examined. Ten calcite, one iron sulfide and one (Zn,Fe)S grains have inclusions >1 micron in size (the maximum: approx. 5 microns). The shapes are spherical or irregular. Tiny inclusions (<1 micron) are also present in all the grains examined. These results show that mineral grains have more inclusions than expected from 2D observations. The X-ray absorption of the inclusions shows that they are not solid inclusions. No bubbles were observed inside, indicating that we cannot determine whether they are really aqueous fluids or merely voids. One calcite grain has an inclusion approx. 2 microns in size, which seems to have a bubble and a tiny solid daughter crystal inside (three-phase inclusion). As we know the exact 3D position of the inclusion, we will anlyze the inclusion by SIMS after freezing the sample as has been done for a halite sample [3]. The present technique is useful for finding small inclusions not only in carbonaceous chondrites but also for terrestrial materials.

Tsuchiyama, A.↗

NASA NTRS2015

Double-Diffusive Convection During Growth of Halides and Selenides

Heavy metal halides and selenides have unique properties which make them excellent materials for chemical, biological and radiological sensors. Recently it has been shown that selenohalides are even better materials than halides or selenides for gamma-ray detection. These materials also meet the strong needs of a wide band imaging technology to cover ultra-violet (UV), midwave infrared wavelength (MWIR) to very long wavelength infrared (VLWIR) region for hyperspectral imager components such as etalon filters and acousto-optic tunable filters (AO). In fact AOTF based imagers based on these materials have some superiority than imagers based on liquid crystals, FTIR, Fabry-Perot, grating, etalon, electro-optic modulation, piezoelectric and several other concepts. For example, broadband spectral and imagers have problems of processing large amount of information during real-time observation. Acousto-Optic Tunable Filter (AOTF) imagers are being developed to fill the need of reducing processing time of data, low cost operation and key to achieving the goal of covering long-wave infrared (LWIR). At the present time spectral imaging systems are based on the use of diffraction gratings are typically used in a pushbroom or whiskbroom mode. They are mostly used in systems and acquire large amounts of hyperspectral data that is processed off-line later. In contrast, acousto-optic tunable filter spectral imagers require very little image processing, providing new strategies for object recognition and tracking. They are ideally suited for tactical situations requiring immediate real-time image processing. But the performance of these imagers depends on the quality and homogeneity of acousto-optic materials. In addition for many systems requirements are so demanding that crystals up to sizes of 10 cm length are desired. We have studied several selenides and halide crystals for laser and AO imagers for MWIR and LWIR wavelength regions. We have grown and fabricated crystals of several materials such as mercurous chloride, mercurous bromide, mercurous iodide, lead chloride lead bromide, lead iodide, thallium arsenic selenide, gallium selenide, zince sulfide zinc selenide and several crystals into devices. We have used both Bridgman and physical vapor transport (PVT) crystal growth methods. In the past have examined PVT growth numerically for conditions where the boundary of the enclosure is subjected to a nonlinear thermal profile. Since past few months we have been working on binary and ternary materials such as selenoiodides, doped zinc sulfides and mercurous chloro bromide and mercurous bromoiodides. In the doped and ternary materials thermal and solutal convection play extremely important role during the growth. Very commonly striations and banding is observed. Our experiments have indicated that even in highly purified source materials, homogeneity in 1-g environment is very difficult. Some of our previous numerical studies have indicated that gravity level less than 10-4 (-g) helps in controlling the thermosolutal convection. We will discuss the ground based growth results of HgClxBr(1-x) and ZnSe growth results for the mm thick to large cm size crystals. These results will be compared with our microgravity experiments performed with this class of materials. For both HgCl-HgBr and ZnS-ZnSe the lattice parameters of the mixtures obey Vagard's law in the studied composition range. The study demonstrates that properties are very anisotropic with crystal orientation, and performance achievement requires extremely careful fabrication to utilize highest figure of merit. In addition, some parameters such as crystal growth fabrication, processing time, resolution, field of view and efficiency will be described based on novel solid solution materials. It was predicted that very similar to the pure compounds solid solutions also have very large anisotropy, and very precise oriented and homogeneous bulk and thin film crystals is required to achieve maximum performance of laser or imagers. Some of the parameters controlling the homogeneity such as thermos-solutal convection driven forces can be controlled in microgravity environments to utilize the benefits of these unique materials.

Singh, N. B.↗

NASA NTRS2017

Environmental Testing of Tritium-Phosphor Glass Vials for Use in Long-Life Radioisotope Power Conversion Units

Power generation in extreme environments, such as the outer solar system, the night side of planets, or other low-illumination environments, currently presents a technology gap that challenges NASA's ambitious scientific goals. We are developing a radioisotope power cell (RPC) that utilizes commercially available tritium light sources and standard 1.85 eV InGaP2 photovoltaic cells to convert beta particle energy to electric energy. In the test program described here, we perform environmental tests on commercially available borosilicate glass vials internally coated with a ZnS luminescent phosphor that are designed to contain gaseous tritium in our proposed power source. Such testing is necessary to ensure that the glass containing the radioactive tritium is capable of withstanding the extreme environments of launch and space for extended periods of time.

Zemcov, Michael↗