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Scanning tunneling microscopy studies of diamond films and optoelectronic materials

In this report, we report on progress achieved from 12/1/92 to 10/1/93 under the grant entitled 'Scanning Tunneling Microscopy Studies of Diamond Films and Optoelectronic Materials'. We have set-up a chemical vapor deposition (CVD) diamond film growth system and a Raman spectroscopy system to study the nucleation and growth of diamond films with atomic resolution using scanning tunneling microscopy (STM). A unique feature of the diamond film growth system is that diamond films can be transferred directly to the ultrahigh vacuum (UHV) chamber of a scanning tunneling microscope without contaminating the films by exposure to air. The University of North Texas (UNT) provided $20,000 this year as matching funds for the NASA grant to purchase the diamond growth system. In addition, UNT provided a Coherent Innova 90S Argon ion laser, a Spex 1404 double spectrometer, and a Newport optical table costing $90,000 to set-up the Raman spectroscopy system. The CVD diamond growth system and Raman spectroscopy system will be used to grow and characterize diamond films with atomic resolution using STM as described in our proposal. One full-time graduate student and one full-time undergraduate student are supported under this grant. In addition, several graduate and undergraduate students were supported during the summer to assist in setting-up the diamond growth and Raman spectroscopy systems. We have obtained research results concerning STM of the structural and electronic properties of CVD grown diamond films, and STM and scanning tunneling spectroscopy of carbon nanotubes. In collaboration with the transmission electron microscopy (TEM) group at UNT, we have also obtained results concerning the optoelectronic material siloxene. These results were published in refereed scientific journals, submitted for publication, and presented as invited and contributed talks at scientific conferences.

Perez, Jose M.↗

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Thompson, David W.↗

Applications of Thin Film Thermocouples for Surface Temperature Measurement

Thin film thermocouples provide a minimally intrusive means of measuring surface temperature in hostile, high temperature environments. Unlike wire thermocouples, thin films do not necessitate any machining of the surface, therefore leaving intact its structural integrity. Thin films are many orders of magnitude thinner than wire, resulting in less disruption to the gas flow and thermal patterns that exist in the operating environment. Thin film thermocouples have been developed for surface temperature measurement on a variety of engine materials. The sensors are fabricated in the NASA Lewis Research Center's Thin Film Sensor Lab, which is a class 1000 clean room. The thermocouples are platinum-13 percent rhodium versus platinum and are fabricated by the sputtering process. Thin film-to-leadwire connections are made using the parallel-gap welding process. Thermocouples have been developed for use on superalloys, ceramics and ceramic composites, and intermetallics. Some applications of thin film thermocouples are: temperature measurement of space shuttle main engine turbine blade materials, temperature measurement in gas turbine engine testing of advanced materials, and temperature and heat flux measurements in a diesel engine. Fabrication of thin film thermocouples is described. Sensor durability, drift rate, and maximum temperature capabilities are addressed.

Martin, Lisa C.↗

Solid film lubricants and thermal control coatings flown aboard the EOIM-3 MDA sub-experiment

Additional experimental data were desired to support the selection of candidate thermal control coatings and solid film lubricants for the McDonnell Douglas Aerospace (MDA) Space Station hardware. The third Evaluation of Oxygen Interactions With Materials Mission (EOIM-3) flight experiment presented an opportunity to study the effects of the low Earth orbit environment on thermal control coatings and solid film lubricants. MDA provided five solid film lubricants and two anodic thermal control coatings for EOIM-3. The lubricant sample set consisted of three solid film lubricants with organic binders one solid film lubricant with an inorganic binder, and one solid film lubricant with no binder. The anodize coating sample set consisted of undyed sulfuric acid anodize and cobalt sulfide dyed sulfuric acid anodize, each on two different substrate aluminum alloys. The organic and inorganic binders in the solid film lubricants experienced erosion, and the lubricating pigments experienced oxidation. MDA is continuing to assess the effect of exposure to the low Earth orbit environment on the life and friction properties of the lubricants. Results to date support the design practice of shielding solid film lubricants from the low Earth orbit environment. Post-flight optical property analysis of the anodized specimens indicated that there were limited contamination effects and some atomic oxygen and ultraviolet radiation effects. These effects appeared to be within the values predicted by simulated ground testing and analysis of these materials, and they were different for each coating and substrate.

Murphy, Taylor J.↗

US/Russian Joint Film Test

A joint U.S./Russian film test was conducted during MIR Mission 18 to evaluate the effects of radiation on photographic film during long-duration space flights. Two duplicate sets of film were flown on this MIR mission: one set was processed and evaluated by the NASA/JSC Photographic Laboratory, and the other by the RKK Energia's Photographic Laboratory in Moscow. This preliminary report includes only the results of the JSC evaluation (excluding the SN-10 film which was not available for evaluation at the time this report was written). The final report will include an evaluation by JSC of the SN-10 film and an evaluation of the test data by the RKK Energia. ISC's evaluation of the test data showed the positive film flown was damaged very little when exposed to approximately 8 rads of radiation. Two of the three negative films were significantly damaged and the third film was damaged only moderately.

Slater, Richard↗

An Experimental Study of the Effect of Wake Passing on Turbine Blade Film Cooling

The effect of wake passing on the showerhead film cooling performance of a turbine blade has been investigated experimentally. The experiments were performed in an annular turbine cascade with an upstream rotating row of cylindrical rods. Nickel thin-film gauges were used to determine local film effectiveness and Nusselt number values for various injectants, blowing ratios, and Strouhal numbers. Results indicated a reduction in film effectiveness with increasing Strouhal number, as well as the expected increase in film effectiveness with blowing ratio. An equation was developed to correlate the span-average film effectiveness data. The primary effect of wake unsteadiness was found to be correlated by a streamwise-constant decrement of 0.094.St. Steady computations were found to be in excellent agreement with experimental Nusselt numbers, but to overpredict experimental film effectiveness values. This is likely due to the inability to match actual hole exit velocity profiles and the absence of a credible turbulence model for film cooling.

Heidmann, James D.↗

Thin Film Multilayer Conductor/Ferroelectric Tunable Microwave Components for Communication Applications

High Temperature Superconductor/Ferroelectric (HTS/FE ) thin film multilayered structures deposited onto dielectric substrates are currently being investigated for use in low loss, tunable microwave components for satellite and ground based communications. The main goal for this technology is to achieve maximum tunability while keeping the microwave losses as low as possible, so as to avoid performance degradation when replacing conventional technology (e.g., filters and oscillators) with HTS/FE components. Therefore, for HTS/FE components to be successfully integrated into current working systems, full optimization of the material and electrical properties of the ferroelectric films, without degrading those of the HTS film; is required. Hence, aspects such as the appropriate type of ferroelectric and optimization of the deposition conditions (e.g., deposition temperature) should be carefully considered. The tunability range as well as the microwave losses of the desired varactor (i.e., tunable component) are also dependent on the geometry chosen (e.g., parallel plate capacitor, interdigital capacitor, coplanar waveguide, etc.). In addition, the performance of the circuit is dependent on the location of the varactor in the circuit and the biasing circuitry. In this paper, we will present our results on the study of the SrTiO3/YBa2Cu3O(7-delta)/LaAl03 (STO/YBCO/LAO) and the Ba(x)Sr(1-x)TiO3/YBa2Cu3O(7-delta)/LaAl03(BSTO/YBCO/ILAO) HTS/FE multilayered structures. We have observed that the amount of variation of the dielectric constant upon the application of a dc electric field is closely related to the microstructure of the film. The largest tuning of the STO/YBCO/LAO structure corresponded to single-phased, epitaxial STO films deposited at 800 C and with a thickness of 500 nm. Higher temperatures resulted in interfacial degradation and poor film quality, while lower deposition temperatures resulted in films with lower dielectric constants, lower tunabilities, and higher losses. For STO/LAO multilayer structures having STO film of similar quality we have observed that interdigital capacitor configurations allow for higher tunabilities and lower losses than parallel plate configurations, but required higher dc voltage. Results on the use of these geometries in working microwave components such as filters and stabilizing resonators for local oscillators (LO) will be discussed.

Miranda, Felix A.↗

Nonlinear Optical Properties of Organic and Polymeric Thin Film Materials of Potential for Microgravity Processing Studies

In this paper, we will take a closer look at the state of the art of polydiacetylene, and metal-free phthalocyanine films, in view of the microgravity impact on their optical properties, their nonlinear optical properties and their potential advantages for integrated optics. These materials have many attractive features with regard to their use in integrated optical circuits and optical switching. Thin films of these materials processed in microgravity environment show enhanced optical quality and better molecular alignment than those processed in unit gravity. Our studies of these materials indicate that microgravity can play a major role in integrated optics technology. Polydiacetylene films are produced by UV irradiation of monomer solution through an optical window. This novel technique of forming polydiacetylene thin films has been modified for constructing sophisticated micro-structure integrated optical patterns using a pre-programmed UV-Laser beam. Wave guiding through these thin films by the prism coupler technique has been demonstrated. The third order nonlinear parameters of these films have been evaluated. Metal-free phthalocyanine films of good optical quality are processed in our laboratories by vapor deposition technique. Initial studies on these films indicate that they have excellent chemical, laser, and environmental stability. They have large nonlinear optical parameters and show intrinsic optical bistability. This bistability is essential for optical logic gates and optical switching applications. Waveguiding and device making investigations of these materials are underway.

Abdeldayem, Hossin↗

Fiber-Optic Temperature Sensor Using a Thin-Film Fabry-Perot Interferometer

A fiber-optic temperature sensor was developed that is rugged, compact, stable, and can be inexpensively fabricated. This thin-film interferometric temperature sensor was shown to be capable of providing a +/- 2 C accuracy over the range of -55 to 275 C, throughout a 5000 hr operating life. A temperature-sensitive thin-film Fabry-Perot interferometer can be deposited directly onto the end of a multimode optical fiber. This batch-fabricatable sensor can be manufactured at a much lower cost than can a presently available sensor, which requires the mechanical attachment of a Fabry-Perot interferometer to a fiber. The principal disadvantage of the thin-film sensor is its inherent instability, due to the low processing temperatures that must be used to prevent degradation of the optical fiber's buffer coating. The design of the stable thin-film temperature sensor considered the potential sources of both short and long term drifts. The temperature- sensitive Fabry-Perot interferometer was a silicon film with a thickness of approx. 2 microns. A laser-annealing process was developed which crystallized the silicon film without damaging the optical fiber. The silicon film was encapsulated with a thin layer of Si3N4 over coated with aluminum. Crystallization of the silicon and its encapsulation with a highly stable, impermeable thin-film structure were essential steps in producing a sensor with the required long-term stability.

Beheim, Glenn↗

Advances in Thin Film Thermocouple Durability Under High Temperature and Pressure Testing Conditions

Thin film thermocouples for measuring material surface temperature have been previously demonstrated on several material systems and in various hostile test environments. A well-developed thin film fabrication procedure utilizing shadow masking for patterning the sensors elements had produced thin films with sufficient durability for applications in high temperature and pressure environments that exist in air-breathing and hydrogen-fueled burner rig and engine test facilities. However, while shadow masking had been a reliable method for specimens with flat and gently curved surfaces, it had not been consistently reliable for use on test components with sharp contours. This work reports on the feasibility of utilizing photolithography processing for patterning thin film thermocouples. Because this patterning process required changes in the thin film deposition process from that developed for shadow masking, the effect of these changes on thin film adherence during burner rig testing was evaluated. In addition to the results of changing the patterning method, the effects on thin film adherence of other processes used in the thin film fabrication procedure is also presented.

Martin, Lisa C.↗

The Thin Oil Film Equation

A thin film of oil on a surface responds primarily to the wall shear stress generated on that surface by a three-dimensional flow. The oil film is also subject to wall pressure gradients, surface tension effects and gravity. The partial differential equation governing the oil film flow is shown to be related to Burgers' equation. Analytical and numerical methods for solving the thin oil film equation are presented. A direct numerical solver is developed where the wall shear stress variation on the surface is known and which solves for the oil film thickness spatial and time variation on the surface. An inverse numerical solver is also developed where the oil film thickness spatial variation over the surface at two discrete times is known and which solves for the wall shear stress variation over the test surface. A One-Time-Level inverse solver is also demonstrated. The inverse numerical solver provides a mathematically rigorous basis for an improved form of a wall shear stress instrument suitable for application to complex three-dimensional flows. To demonstrate the complexity of flows for which these oil film methods are now suitable, extensive examination is accomplished for these analytical and numerical methods as applied to a thin oil film in the vicinity of a three-dimensional saddle of separation.

Brown, James L.↗

Structure and Morphology of Phthalocyanine Films Grown in Electrical Fields by Vapor Deposition

Phthalocyanine is a very stable organic material in the atmosphere and has been used in numerous applications, such as optical switching and optical storage devices. Although this material has already been discovered for several decades and has had extensive studies conducted on it, many properties still need to be better understood, for example, the mechanisms of forming different solid phases and of changing film morphology by external forces. Phthalocyanine has two preferred solid phases (alpha and beta phases) for which the crystal structures, surface morphology and optical properties are different. In order to investigate these phenomena and the relationship among them, phthalocyanine films have been synthesized by vapor deposition on quartz substrates with and without an external electrical field. Some substrates were coated with a very thin gold film for the electrical field. These films have been characterized using x-ray diffraction, scanning electron microscopy, Fourier transfer infrared spectroscopy, and Z-scan technique. The films have excellent chemical and thermal stability. However, the surface of these films grown without the electrical field shows flower-like morphology. When films are deposited under an electrical field (approximately 3000 V/cm), an aligned structure is revealed on the surface. A comparison of the structure, morphology, optical properties, and the growth mechanism for these films with and without an electrical field will be discussed.

Zhu, Shen↗

Thin-Film Photovoltaic Solar Array Parametric Assessment

This paper summarizes a study that had the objective to develop a model and parametrically determine the circumstances for which lightweight thin-film photovoltaic solar arrays would be more beneficial, in terms of mass and cost, than arrays using high-efficiency crystalline solar cells. Previous studies considering arrays with near-term thin-film technology for Earth orbiting applications are briefly reviewed. The present study uses a parametric approach that evaluated the performance of lightweight thin-film arrays with cell efficiencies ranging from 5 to 20 percent. The model developed for this study is described in some detail. Similar mass and cost trends for each array option were found across eight missions of various power levels in locations ranging from Venus to Jupiter. The results for one specific mission, a main belt asteroid tour, indicate that only moderate thin-film cell efficiency (approx. 12 percent) is necessary to match the mass of arrays using crystalline cells with much greater efficiency (35 percent multi-junction GaAs based and 20 percent thin-silicon). Regarding cost, a 12 percent efficient thin-film array is projected to cost about half is much as a 4-junction GaAs array. While efficiency improvements beyond 12 percent did not significantly further improve the mass and cost benefits for thin-film arrays, higher efficiency will be needed to mitigate the spacecraft-level impacts associated with large deployed array areas. A low-temperature approach to depositing thin-film cells on lightweight, flexible plastic substrates is briefly described. The paper concludes with the observation that with the characteristics assumed for this study, ultra-lightweight arrays using efficient, thin-film cells on flexible substrates may become a leading alternative for a wide variety of space missions.

Hoffman, David J.↗

Synthesis of ZnO:As Films Using Off-Axis Sputtering Deposition

As a novel oxide semiconductor material, ZnO is interesting for use in many applications. For fabricating electronic devices, it is important to have n- and p- type ZnO materials. Arsenic has been proven to be one of the p-type dopants for ZnO materials. However, information in studying the ZnAsO ternary compound films has been scarce. In order to investigate the morphology, structure and electrical properties of ZnAsO ternary compounds, ZnO:As films have been synthesized using off-axis sputtering deposition on various substrates including (100) Si and (0001) sapphire crystals. Films are grown under various growth conditions. ZnO:As targets with the atomic weight ratios of arsenic to zinc from 0.01 to 0.10 are used for film synthesis. The growth temperatures and pressures range from 350 to 550C and 5 to 150 mTorr, respectively. Argon to oxygen gas ratio for film growth is varied to examine the film quality as well. Film surface morphology, crystal structure, and compositions, are characterized using atomic force microscopy, x-ray diffraction, and energy dispersive spectroscopy, respectively. The compositions of target material and ZnO:As films grown under various conditions are then assessed. The electrical properties were also measured. The detail of these measurements will be discussed in the presentation.

Zhu, Shen↗

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.↗

Improved Dielectric Properties of Heterostructured Ba2.5Sr0.5TiO3 Thin Film Composites for Microwave Dielectric Devices

In the present work we have deposited MgO and Ba(sub 0.5)Sr(sub 0.5)TiO(sub 3)(BST50) thin layers in different sequences to make MgO:BST50 hetero-structured thin films. These films were characterized by X-ray diffraction and Rutherford backscattering technique and found to be highly (100) textured. The figure of merit {(C(sub0)-C(sub v)/(C(sub0-tandelta)} of the hetero-structured films was found to be higher as compared to pure BST50 films measured at 1 MHz frequency with electric field of 25.3 kV/cm. These films were used to make eight element coupled micro-strip phase shifter and characterized in a frequency range of 13-15 GHz. The high frequency figure of merit (kappa factor, defined as the ratio of degree of phase shift per dB loss) measured at around 14 GHz with electric field of 333 kV/cm has been markedly improved (around 64.28 deg/dB for hetero-structured film as compared to 24.65 deg /dB for pure film). Improvement in dielectric properties in a wide frequency range in the MgO:BST are believed to be due to the higher densification of the hetero-structured films.

Jain, M.↗

Thin-Film Ferroelectric Tunable Microwave Devices Being Developed

Electronically tunable microwave components have become the subject of intense research efforts in recent years. Many new communications systems would greatly benefit from these components. For example, planned low Earth orbiting satellite networks have a need for electronically scanned antennas. Thin ferroelectric films are one of the major technologies competing to fill these applications. When a direct-current (dc) voltage is applied to ferroelectric film, the dielectric constant of the film can be decreased by nearly an order of magnitude, changing the high-frequency wavelength in the microwave device. Recent advances in film growth have demonstrated high-quality ferroelectric thin films. This technology may allow microwave devices that have very low power and are compact, lightweight, simple, robust, planar, voltage tunable, and affordable. The NASA Lewis Research Center has been designing, fabricating, and testing proof-of-concept tunable microwave devices. This work, which is being done in-house with funding from the Lewis Director's Discretionary Fund, is focusing on introducing better microwave designs to utilize these materials. We have demonstrated Ku- and K-band phase shifters, tunable local oscillators, tunable filters, and tunable diplexers. Many of our devices employ SrTiO3 as the ferroelectric. Although it is one of the more tunable and easily grown ferroelectrics, SrTiO3 must be used at cryogenic temperatures, usually below 100 K. At these temperatures, we frequently use high-temperature superconducting thin films of YBa2Cu3O7-8 to carry the microwave signals. However, much of our recent work has concentrated on inserting room-temperature ferroelectric thin films, such as BaxSr1- xTiO3 into these devices. The BaxSr1-xTiO3 films are used in conjuction with normal metal conductors, such as gold.

VanKeuls, Frederick W.↗

Wide-Bandgap CIAS Thin-film Photovoltaics with Transparent Back Contacts for Next-Generation Single and Multijunction Devices

Future spacecraft and high-altitude airship (HAA) technologies will require high array specific power (W/kg), which can be met using thin-film photovoltaics (PV) on lightweight and flexible substrates. It has been calculated that the thin-film array technology, including the array support structure, begins to exceed the specific power of crystalline multi-junction arrays when the thin-film device efficiencies begin to exceed 12%. Thin-film PV devices have other advantages in that they are more easily integrated into HAA s, and are projected to be much less costly than their crystalline PV counterparts. Furthermore, it is likely that only thin-film array technology will be able to meet device specific power requirements exceeding 1 kW/kg (photovoltaic and integrated substrate/blanket mass only). Of the various thin-film technologies, single junction and radiation resistant CuInSe2 (CIS) and associated alloys with gallium, aluminum and sulfur have achieved the highest levels of thin-film device performance, with the best efficiency, reaching 19.2% under AM1.5 illumination conditions and on thick glass substrates.(3) Thus, it is anticipated that single- and tandem-junction devices with flexible substrates and based on CIS and related alloys could achieve the highest levels of thin-film space and HAA solar array performance.

Woods, Lawrence M.↗