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Highly Efficient Multilayer Thermoelectric Devices

Multilayer thermoelectric devices now at the prototype stage of development exhibit a combination of desirable characteristics, including high figures of merit and high performance/cost ratios. These devices are capable of producing temperature differences of the order of 50 K in operation at or near room temperature. A solvent-free batch process for mass production of these state-of-the-art thermoelectric devices has also been developed. Like prior thermoelectric devices, the present ones have commercial potential mainly by virtue of their utility as means of controlled cooling (and/or, in some cases, heating) of sensors, integrated circuits, and temperature-critical components of scientific instruments. The advantages of thermoelectric devices for such uses include no need for circulating working fluids through or within the devices, generation of little if any noise, and high reliability. The disadvantages of prior thermoelectric devices include high power consumption and relatively low coefficients of performance. The present development program was undertaken in the hope of reducing the magnitudes of the aforementioned disadvantages and, especially, obtaining higher figures of merit for operation at and near room temperature. Accomplishments of the program thus far include development of an algorithm to estimate the heat extracted by, and the maximum temperature drop produced by, a thermoelectric device; solution of the problem of exchange of heat between a thermoelectric cooler and a water-cooled copper block; retrofitting of a vacuum chamber for depositing materials by sputtering; design of masks; and fabrication of multilayer thermoelectric devices of two different designs, denoted I and II. For both the I and II designs, the thicknesses of layers are of the order of nanometers. In devices of design I, nonconsecutive semiconductor layers are electrically connected in series. Devices of design II contain superlattices comprising alternating electron-acceptor (p)-doped and electron-donor (n)-doped, nanometer- thick semiconductor layers.

Boufelfel, Ali↗

Sputter process investigation: Material and environment interaction processes investigation

The multilayer Ellipsometry program has been developed with which the thickness and the optical properties of top layer can be determined with the additional information obtained from other measurement such as the optical constant of the middle layer film. Once the proper parameters are input into the program, the multilayer Ellipsometry program which was developed by H. Kim and Dr. Fromhold gives the best possible set of the solutions for the top layer thickness or its optical index graphically on a PC screen. In this report the basic two layer Ellipsometry theory will be summarized briefly as well as the one layer case. All the code is written in Microsoft Quickbasic version 4.5 for IBM PC with a VGA color graphics monitor so that the measurement could be cross-checked out graphically on the screen.

Williams, John R.↗

Development of sputter coatings for the gravity probe B gyroscope housings

Cu/Ti coatings have been applied by sputter deposition to fused quartz housings to serve as the electrodes and lands of electrostatically supported gyroscopes. Niobium-coated fused quartz gyro rotors have been successfully suspended and spun up in those housings. The Cu/Ti bilayer coating and alternative multilayer coatings (Cu/Mo, Mo/Cu/Ti and Mo/Cu/Mo) with 2-micron thickness produced by sputter deposition on flat, fused quartz substrates have been examined with scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and four-point resistivity measurement techniques. The multilayer coatings with a molybdenum bonding layer appear to produce smoother surfaces than those with a titanium bonding layer. All multilayer coatings survived thermal cycling to 77 K without adhesion failure.

Zhou, P.↗

Molybdenum-silicon multilayer mirrors for the extreme ultraviolet

Multilayer structures of molybdenum and silicon have been synthesized by sputter deposition onto flat silicon single-crystal silicon substrates and spherically ground (0.5and 22.0-m radii) fused silica substrates; and the reflectivities for 170.4-A (72.8-eV), 160.1-A (77.4-eV), and 228-A (54.4-eV) light measured at near normal incidence. Observed peak values ranged from 26.2 to 78 percent, the highest reflectivities occurring closest to normal incidence. Energy resolutions were about 10 in all cases. Model calculations were performed using optical constants and experimentally determined multilayer structural parameters. In all cases the measured reflectivities were equal to or larger (by up to a factor of 2) than the calculated values, a result attributed to uncertainty in the optical constants used in the calculations. Experimental and calculated angular-peak positions and energy resolutions were in good agreement. The high reflectivities of these molybdenum-silicon structures will make possible application of traditional optics approaches in the EUV and support new developments including free-electron lasers.

Barbee, T. W., Jr.↗

High-temperature /1100 degrees F/ capacitors operate without supplement cooling

Multilayered capacitor with one-mil thick pyrolytic boron nitride and wrap around sputtered electrodes achieves parallel electrical interconnections in a stacked configuration of 3 to 9 wafers. These capacitors are compact, lightweight, and suitable for operation in high temperatures without supplemental cooling.

Stapleton, R. E.↗

Reflection Properties of Metallic Gratings on ZnO Films over GaAs Substrates

A potential application for piezoelectric film deposited on GaAs substrates is the monolithic integration of surface acoustic wave (SAW) devices with GaAs electronics. Metallic gratings are basic elements required for the construction of such devices, and analyzing the reflectivity and the velocity change due to metallic gratings is often a critical design parameter. In this article, Datta and Hunsinger technique is extended to the case of a multilayered structure, and the developed technique is applied to analyze shorted and open gratings on ZnO films sputtered over (001)-cut (110)-propagating GaAs substrates. The analysis shows that zero reflectivity of shorted gratings can be obtained by a combination of the ZnO film and the metal thickness and the metalization ratio of the grating. Experiments are performed on shorted and an open gratings (with the center frequency of about 180 MHz) for three different metal thicknesses over ZnO films which are 0.8 and 2.6 micrometers thick. From the experiments, zero reflectivity at the resonant frequency of the grating is observed for a reasonable thickness (h/Alpha = 0.5%) of aluminum metalization. The velocity shift between the shorted and the open grating is also measured to be 0.18 MHz and 0.25 MHz for 0.8 and 1.6 micrometers respectively. The measured data show relatively good agreement with theoretical predictions.

Hickernell, Fred S.↗

Development of Ni-based Multilayer Coatings for Extended Broadband X-ray Imaging

Next-generation astronomical hard x-ray telescopes require new multilayer coating designs to extend the current imaging capabilities into the 100’s of keV. W/Si and Pt/C demonstrate excellent reflectivity response and effective area up to approximately 70 and 80 keV but are severely limited beyond this due to Kα absorption lines. Lower-density metals provide a promising alternative to Pt and W for broader energy bands as their K-edges occur at significantly lower energies. Ni/C is such a low-density pairing that through modeling can achieve the desired energy responses. However, Ni is a notoriously difficult metal to sputter, often resulting is relatively low deposition rates and rough coating surfaces. The goal of this work is to characterize Ni/C multilayers using a custom deposition chamber at GSFC and determine the feasibility of these designs for future hard x-ray missions such as HEX-P.

Danielle N. Gurgew↗

Collaboration of the NASA Glenn Research Center and Rolls-Royce Developed Thin Film Multilayered Dielectrics for Harsh Environments

The use of thin films to electrically insulate thin film sensors on engine components minimizes the intrusiveness of the sensors and allows a more accurate measurement of the environment. A variety of insulating films were investigated for preventing electrical shorting caused by insulator failure between the sensor and the component. By alternating layers of sputtered high-temperature ceramics, a sequence of insulating layers was devised that (1) prevents pinholes from forming completely through the insulator and (2) maintains high electrical resistivity at high temperatures. The total thickness is only a fraction of that needed for conventional insulating techniques. The Sensors and Electronics Technology Branch of the NASA Glenn Research Center has an in-house effort to develop thin film sensors for surface measurement in propulsion system research. Thin film sensors do not require special machining of the components on which they are mounted, and they are considerably thinner (less than 10 mm thick) than wire or foil sensors. The thin film sensors are thus much less disturbing to the operating environment and have a minimal impact on the physical characteristics of the supporting component. To further this research, NASA Glenn and Rolls-Royce (Derby, UK), with assistance from the Ohio Aerospace Institute (OAI) and the Akima Corporation, pursued a joint investigation using multilayered thin film dielectrics as a reliable insulator in harsh environments. The use of a multilayered scheme is thought to be promising for the fabrication of electrically insulating thin films. A major cause of conduction in thin film dielectrics is the presence of defects, such as pinholes, that propagate through the film to the underlying substrate surface. By alternating the insulating material, each new growth pattern would deviate from the previous one, eliminating direct pathways for conduction to the substrate. The film depositions and testing were conducted in the Instrument Research Laboratory at Glenn. The multilayered insulator test samples were made from alumina and stainless steel shims that were first covered with a sputtered underlayer of either yttria-stabilized zirconia or chromium carbide, and then overcoated with a sputtered top layer of alumina. An example of a test sample is shown in the following photograph. Each multilayered insulator sample was 5 mm thick, at least an order of magnitude thinner than conventional insulators. The insulating properties of the samples were tested in a high-temperature air oven to determine their suitability. The multilayer insulators tested showed a stabilized film at temperatures in excess of 800 C (1472 F). The underlying materials in these multilayers allow thermal expansion stresses produced during the heating to be graded. The chromium carbide-alumina multilayer had the best adhesion at high temperatures, presumably from the induced chemical bonding between the substrate and the chromium carbide underlayer. However, the zirconia-alumina multilayer proved to have slightly better insulating properties when adhering. The application of the zirconia-alumina insulator has been demonstrated on a nickel-alloy fan blade, as shown. The insulators using thin film sensors still need to be tested in a relevant high-temperature combustion environment.

Wrbanek, John D.↗

Multifunction Vacuum Chamber for IC Metallization

Vacuum system chamber processing multilayer metallization on integrated circuits (IC's) performs four operations ordinarily done in separated equipment. Chamber etches holes, removes photoresist, cleans by sputter etching, and deposits final layer of metal. Combinedfunction chamber costs less than separate equipment. Chamber avoids exposing integrated circuits to room air and, to oxidation and dust, between steps. Eliminates time spent in transferring circuits from one apparatus to next.

Routh, D. E.↗

Low Energy Ionizing Radiation and Plasma Contributions to Radiation Dose in Materials at Sun-Earth Lagrange Points

- High energy radiation environments responsible for radiation damage to thick materials are well characterized and modeled: - Galactic cosmic rays — Badhwar-O’Neil 2020, CREME96, Nymmik - Solar particle events — Emission of Solar Protons, SAPPHIRE, JPL, King 1972 - Trapped radiation belts — AE8/AP8, AE9/AP9/IRENE - Low energy radiation environments responsible for radiation damage to thin materials relevant to Lagrange points and interplanetary missions have not been treated as comprehensively to date: - Solar wind - Magnetosheath - Magnetotail - Concern to spacecraft design and operations is radiation damage to surfaces and thin materials with mission critical applications on exterior of spacecraft - Applications: thermal control coatings, sunshields, multilayer insulation, optical thin film coatings, solar sails, thermo-optical properties of space exposed materials - Damage processes: radiation degradation (total dose), light ion sputtering, proton blistering of soft metals, modification of optical properties (α/ε), modification of charging properties (SEY, surface conductivity)

Joseph I. Minow↗

Ion mixing

Recent experimental studies of the ion-mixing phenomenon are summarized. Ion mixing is differentiated from ion implantation and shown to be a useful technique for overcoming the sputter-dependent limitations of implantation processes. The fundamental physical principles of ion/solid interactions are explored. The basic experimental configurations currently in use are characterized: bilayered samples, multilayered samples, and samples with a thin marker layer. A table listing the binary systems (metal-semiconductor or metal-metal) which have been investigated using each configuration is presented. Results are discussed, and some sample data are plotted. The prospects for future application of ion mixing to the alteration of solid surface properties are considered. Practical applications are seen as restricted by economic considerations to the production of small, expensive components or to fields (such as the semiconductor industry) which already have facilities for ion implantation.

Matteson, S.↗

Reaction of amorphous Ni-W and Ni-N-W films with substrate silicon

Wiley et al. (1982) have studied sputtered amorphous films of Nb-Ni, Mo-Ni, Si-W, and Si-Mo. Kung et al. (1984) have found that amorphous Ni-Mo films as diffusion barriers between multilayer metallizations on silicon demonstrate good electrical and thermal stability. In the present investigation, the Ni-W system was selected because it is similar to the Ni-Mo system. However, W has a higher silicide formation temperature than Mo. Attention is given to aspects of sample preparation, sample characterization, the interaction between amorphous Ni-W films and Si, the crystallization of amorphous Ni(36)W(64) films on SiO2, amorphous Ni-N-W films, silicide formation and phase separation, and the crystallization of amorphous Ni(36)W(64) and Ni(30)N(21)W(49) layers.

Zhu, M. F.↗

Hard X-Ray and Wide Focusing Telescopes

Studies are being carried out to compare the performance of several different separation materials used in the replication process. This report presents the results obtained during the second year of a program which consists of replicating smooth, thin substrates, depositing multilayer coatings upon them, and evaluating their performance. Replication and multilayer coatings are both critically important to the development of focussing hard X-ray telescopes that function up to 100 keV. The activities of the current year include extending the comparison between sputtered amorphous carbon and evaporated gold to include sputtered as well as evaporated gold. The figure of merit being the smoothness of the replica which has a direct effect on the specular reflectivity. These results were obtained with epoxy replication, but they should be applicable to electroformed nickel, the process we expect to use for the ultimate replicated optics.

Gorenstein, Paul↗

Directed Growth of Carbon Nanotubes Across Gaps

An experiment has shown that when single-walled carbon nanotubes (SWNTs) are grown by chemical vapor deposition in the presence of an electric field of suitable strength, the nanotubes become aligned along the electric field. In an important class of contemplated applications, one would exploit this finding in fabricating nanotube transistors; one would grow SWNTs across gaps between electrodes that would serve, subsequently, as source and drain contacts during operation of the transistors. In preparation for the experiment, a multilayer catalyst comprising a 20-nmthick underlayer of iridium (platinum group), a 1-nm-thick middle layer of iron, and a 0.2-nm-thick outer layer of molybdenum was ion-beam sputtered onto a quartz substrate. A 25 micrometers-diameter iron wire was used as a shadow mask during the sputtering to create a 25 micrometers gap in the catalyst. Then electrical leads were connected to the catalyst areas separated by the gap so that these catalyst areas would also serve as electrodes. The substrate as thus prepared was placed in a growth chamber that consisted of a quartz tube of 1-in. (2.54-cm) diameter enclosed in a furnace. SWNTs of acceptably high quantity and quality were grown in 10 minutes with methane at atmospheric pressure flowing through the chamber at a rate of 1,000 standard cubic centimeters per minute at a temperature of 900 C. To prevent oxidation of the SWNTs, the chamber was purged with 99.999-percent pure argon before and after growth, and the chamber was cooled to less than 300 C before opening it to the atmosphere after growth. When no voltage was applied across the gap, the SWNTs grew in random directions extending out from the edges of the catalyst at the gap. When a potential of 10 V was applied between the catalyst/electrode areas to create an electric field across the gap, the SWNTs grew across the gap, as shown in the figure.

Delzeit, Lance↗

Characterization of ZrO2 buffer layers for sequentially evaporated Y-Ba-CuO on Si and Al2O3 substrates

Thin film high temperature superconductors have the potential to change the microwave technology for space communications systems. For such applications it is desirable that the films be formed on substrates such as Al2O3 which have good microwave properties. The use of ZrO2 buffer layers between Y-Ba-Cu-O and the substrate has been investigated. These superconducting films have been formed by multilayer sequential electron beam evaporation of Cu, BaF2 and Y with subsequent annealing. The three layer sequence of Y/BaF2/Cu is repeated four times for a total of twelve layers. Such a multilayer film, approximately 1 micron thick, deposited directly on SrTiO3 and annealed at 900 C for 45 min produces a film with a superconducting onset of 93 K and critical temperature of 85 K. Auger electron spectroscopy in conjunction with argon ion sputtering was used to obtain the distribution of each element as a function of depth for an unannealed film, the annealed film on SrTiO3 and annealed films on ZrO2 buffer layers. The individual layers were apparent. After annealing, the bulk of the film on SrTiO3 is observed to be fairly uniform while films on the substrates with buffer layers are less uniform. The Y-Ba-Cu-O/ZrO2 interface is broad with a long Ba tail into the ZrO2, suggesting interaction between the film and the buffer layer. The underlying ZrO2/Si interface is sharper. The detailed Auger results are presented and compared with samples annealed at different temperatures and durations.

Valco, George J.↗

Growth and micro structural studies on Yittria Stabilized Zirconia (YSZ) and Strontium Titanate (STO) buffer layers

Microstructure of Yittria Stabilized Zirconia (YSZ) and Strontium Titanate (STO) of radio frequency magnetron sputtered buffer layers was studied at various sputtering conditions on Si (100), Sapphire and LaAlO3 (100) substrates. The effect of substrate temperatures up to 800 C and sputtering gas pressures in the range of 50 mTorr. of growth conditions was studied. The buffer layers of YSZ and STO showed a strong tendency for columnar growth was observed above 15 mTorr sputtering gas pressure and at high substrate temperatures. Post annealing of these films in oxygen atmosphere reduced the oxygen deficiency and strain generated during growth of the films. Strong c-axis oriented superconducting YBa2Cu3O7-x (YBCO) thin films were obtained on these buffer layers using pulsed laser ablation technique. YBCO films deposited on multilayers of YSZ and STO were shown to have better superconducting properties.

Srinivas, S.↗

A Multilayered Thin Film Insulator for Harsh Environments

The status of work to develop a reliable high temperature dielectric thin film for use with thin film sensors is presented. The use of thin films to electrically insulate thin film sensors on engine components minimizes the intrusiveness of the sensor and allows a more accurate measurement of the environment. A variety of insulating films were investigated for preventing electrical shorting caused by insulator failure between the sensor and the component. By alternating layers of sputtered high temperature ceramics, a sequence of insulating layers was devised that prevents pinholes from forming completely through the insulator and maintains high electrical resistivity at high temperatures. The major technical challenge remaining is to optimize the fabrication of the insulator with respect to composition to achieve a reliable high temperature insulating film. Data from the testing of various potentially insulating thin film systems is presented and their application to thin film sensors is also discussed.

Wrbanek, John D.↗

Multi-Dimensional Damage Detection for Surfaces and Structures

Current designs for inflatable or semi-rigidized structures for habitats and space applications use a multiple-layer construction, alternating thin layers with thicker, stronger layers, which produces a layered composite structure that is much better at resisting damage. Even though such composite structures or layered systems are robust, they can still be susceptible to penetration damage. The ability to detect damage to surfaces of inflatable or semi-rigid habitat structures is of great interest to NASA. Damage caused by impacts of foreign objects such as micrometeorites can rupture the shell of these structures, causing loss of critical hardware and/or the life of the crew. While not all impacts will have a catastrophic result, it will be very important to identify and locate areas of the exterior shell that have been damaged by impacts so that repairs (or other provisions) can be made to reduce the probability of shell wall rupture. This disclosure describes a system that will provide real-time data regarding the health of the inflatable shell or rigidized structures, and information related to the location and depth of impact damage. The innovation described here is a method of determining the size, location, and direction of damage in a multilayered structure. In the multi-dimensional damage detection system, layers of two-dimensional thin film detection layers are used to form a layered composite, with non-detection layers separating the detection layers. The non-detection layers may be either thicker or thinner than the detection layers. The thin-film damage detection layers are thin films of materials with a conductive grid or striped pattern. The conductive pattern may be applied by several methods, including printing, plating, sputtering, photolithography, and etching, and can include as many detection layers that are necessary for the structure construction or to afford the detection detail level required. The damage is detected using a detector or sensory system, which may include a time domain reflectometer, resistivity monitoring hardware, or other resistance-based systems. To begin, a layered composite consisting of thin-film damage detection layers separated by non-damage detection layers is fabricated. The damage detection layers are attached to a detector that provides details regarding the physical health of each detection layer individually. If damage occurs to any of the detection layers, a change in the electrical properties of the detection layers damaged occurs, and a response is generated. Real-time analysis of these responses will provide details regarding the depth, location, and size estimation of the damage. Multiple damages can be detected, and the extent (depth) of the damage can be used to generate prognostic information related to the expected lifetime of the layered composite system. The detection system can be fabricated very easily using off-the-shelf equipment, and the detection algorithms can be written and updated (as needed) to provide the level of detail needed based on the system being monitored. Connecting to the thin film detection layers is very easy as well. The truly unique feature of the system is its flexibility; the system can be designed to gather as much (or as little) information as the end user feels necessary. Individual detection layers can be turned on or off as necessary, and algorithms can be used to optimize performance. The system can be used to generate both diagnostic and prognostic information related to the health of layer composite structures, which will be essential if such systems are utilized for space exploration. The technology is also applicable to other in-situ health monitoring systems for structure integrity.

Williams, Martha↗