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Semiconductor- Metal Graded Index Composite Thin Films for Infrared Applications

Theoretical/experimental studies have been carried out on Germanium:Silver (Ge:Ag) graded index composite thin films, which demonstrate that graded coatings, consisting of varied concentrations of Ag with respect to the Ge film thickness, exhibit different optica properties ranging from selective infrared (IR) reflectance to broadband IR absorptance.

Inhomogeneous

Semiconductor-metal graded-index composite thin films for infrared applications

Theoretical/experimental studies have been carried out on germanium:silver (Ge:Ag) graded-index composite thin films which demonstrate that graded coatings, consisting of varied concentrations of Ag with respect to the Ge film thickness, exhibit different optical properties ranging from selective infrared (IR) reflectance to broadband IR absorptance. The graded coatings have been produced by dc magnetron cosputtering of Ge and Ag and the spectral properties are found to be stable against temperature. The coatings have been applied to an infrared tunnel sensor (micro-Golay cell) to improve the device performance.

Lamb, James L.

Compositionally-Graded Shape Memory Film for Self-Deployment of Membrane Reflectors and Optics

The next generation of space systems will require large apertures in order to image faint targets or cover large areas of Earth. These large apertures must be able to fit inside a launch vehicle fairing, be light enough for launch into orbit, and deploy on orbit with repeatability and reliability. The current state-of-the-art in flight optics is represented by the 4 meter LAMP telescope, with an areal density of 10 km sq m. Development of a Beryllium mirror demonstration article for NGST (Next Generation Space Telescope) at the University of Arizona indicate areal densities of 0.5 kg sq m with flight hardware in the 12 meter range. With progressive improvements in existing deployment, packaging, and structural technologies, the size of optics and reflectors will continue to increase, while mass is reduced. However, without a breakthrough in materials, packaging and/or deployment technologies, the goal for Gossamer structures of 0.1 kg sq m is unachievable for the near and mid-term NASA missions. Membrane technology provides the best hope of achieving such low areal densities. In combination with advances in membrane materials and structures, development of revolutionary techniques for deployment systems can provide significant improvements in large aperture technology. In this paper, the results of a six-month Phase I research effort to demonstrate the application of thin film NiTi to aerospace-qualified membrane and mesh materials are presented. Deposition of shape memory thin film was achieved Astromesh (trademark) metal mesh and CP-1, and optical-quality polymer membrane. Not only was full-coating deposition demonstrated, but also small segment deposition which holds potential for local surface control. Deployment of these materials was also demonstrated, setting the stage for the development of a larger test article.

Hill, Lisa

Automatic chemical vapor deposition

Report reviews chemical vapor deposition (CVD) for processing integrated circuits and describes fully automatic machine for CVD. CVD proceeds at relatively low temperature, allows wide choice of film compositions (including graded or abruptly changing compositions), and deposits uniform films of controllable thickness at fairly high growth rate. Report gives overview of hardware, reactants, and temperature ranges used with CVD machine.

Kennedy, B. W.

Tribological characteristics of gold films deposited on metals by ion plating and vapor deposition

The graded interface between an ion-plated film and a substrate is discussed as well as the friction and wear properties of ion-plated gold. X-ray photoelectron spectroscopy (XPS) depth profiling and microhardness depth profiling were used to investigate the interface. The friction and wear properties of ion-plated and vapor-deposited gold films were studied both in an ultra high vacuum system to maximize adhesion and in oil to minimize adhesion. The results indicate that the solubility of gold on the substrate material controls the depth of the graded interface. Thermal diffusion and chemical diffusion mechanisms are thought to be involved in the formation of the gold-nickel interface. In iron-gold graded interfaces the gold was primarily dispersed in the iron and thus formed a physically bonded interface. The hardness of the gold film was influenced by its depth and was also related to the composition gradient between the gold and the substrate. The graded nickel-gold interface exhibited the highest hardness because of an alloy hardening effect. The effects of film thickness on adhesion and friction were established.

Miyoshi, K.

Tribological characteristics of gold films deposited on metals by ion plating and vapor deposition

The graded interface between an ion-plated film and a substrate is discussed as well as the friction and wear properties of ion-plated gold. X-ray photoelectron spectroscopy (XPS) depth profiling and microhardness depth profiling were used to investigate the interface. The friction and wear properties of ion-plated and vapor-deposited gold films were studied both in an ultra high vacuum system to maximize adhesion and in oil to minimize adhesion. The results indicate that the solubility of gold on the substrate material controls the depth of the graded interface. Thermal diffusion and chemical diffusion mechanisms are thought to be involved in the formation of the gold-nickel interface. In iron-gold graded interfaces the gold was primarily dispersed in the iron and thus formed a physically bonded interface. The hardness of the gold film was influenced by its depth and was also related to the composition gradient between the gold and the substrate. The graded nickel-gold interface exhibited the highest hardness because of an alloy hardening effect. The effects of film thickness on adhesion and friction were established.

Miyoshi, K.

X-Ray photoelectron spectroscopy study of radiofrequency-sputtered titanium, carbide, molybdenum carbide, and titanium boride coatings and their friction properties

Radiofrequency sputtered coatings of titanium carbide, molybdenum carbide and titanium boride were tested as wear resistant coatings on stainless steel in a pin on disk apparatus. X-ray photoelectron spectroscopy (XPS) was used to analyze the sputtered films with regard to both bulk and interface composition in order to obtain maximum film performance. Significant improvements in friction behavior were obtained when properly biased films were deposited on deliberately preoxidized substrates. XPS depth profile data showed thick graded interfaces for bias deposited films even when adherence was poor. The addition of 10 percent hydrogen to the sputtering gas produced coatings with thin poorly adherent interfaces. Results suggest that some of the common practices in the field of sputtering may be detrimental to achieving maximum adherence and optimum composition for these refractory compounds.

Brainard, W. A.

X-ray photoelectron spectroscopy study of radiofrequency-sputtered refractory compound steel interfaces

Radiofrequency sputtering was used to deposit Mo2C, Mo2B5, and MoSi2 coatings on 440C steel substrates. Both sputter etched and preoxidized substrates were used, and the films were deposited with and without a substrate bias of -300 V. The composition of the coatings was measured as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. In the interfacial region there was evidence that bias produced a graded interface in Mo2B5 but not in Mo2C. Oxides of iron and of all film constituents except carbon were presented in all cases but the iron oxide concentration was higher and the layer thicker on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 film. The presence of mixed oxides correlates with enhanced film adhesion.

Wheeler, D. R.

An XPS study of the adherence of refractory carbide, silicide, and boride RF-sputtered wear-resistant coatings

Radio frequency sputtering was used to deposit refractory carbide, silicide, and boride coatings on 440-C steel substrates. Both sputter etched and pre-oxidized substrates were used and the films were deposited with and without a substrate bias. The composition of the coatings was determined as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. Friction and wear tests were conducted to evaluate coating adherence. In the interfacial region there was evidence that bias may produce a graded interface for some compounds. Biasing, while generally improving bulk film stoichiometry, can adversely affect adherence by removing interfacial oxide layers. Oxides of all film constituents except carbon and iron were present in all cases but the iron oxide coverage was only complete on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 films. In the case of mixed oxides, preoxidation enhanced film adherence. In the layered case it did not.

Brainard, W. A.

High-efficiency heteroepitaxial InP solar cells

High-efficiency, thin-film InP solar cells grown heteroepitaxially on GaAs and Si single-crystal bulk substrates are being developed as a means of eliminating the problems associated with using single-crystal InP substrates. A novel device structure employing a compositionally graded Ga(x)In(1-x)As layer between the bulk substrate and the InP cell layers is used to reduce the dislocation density and improve the minority carrier properties in the InP. The structures are grown in a continuous sequence of steps using computer-controlled atmospheric pressure metalorganic vapor phase epitaxy (APMOVPE). Dislocation densities as low as 3 x 10(exp 7) sq cm and minority carrier lifetimes as high as 3.3 ns are achieved in the InP layers with this method using both GaAs or Si substrates. Structures prepared in this fashion are also completely free of microcracks. These results represent a substantial improvement in InP layer quality when compared to heteroepitaxial InP prepared using conventional techniques such as thermally cycled growth and post-growth annealing. The present work is is concerned with the fabrication and characterization of high-efficiency, thin-film InP solar cells. Both one-sun and concentrator cells were prepared for device structures grown on GaAs substrates. One-cell cells have efficiencies as high as 13.7 percent at 25 C. However, results for the concentrator cells are emphasized. The concentrator cell performance is characterized as a function of the air mass zero (AM0) solar concentration ratio and operating temperature. From these data, the temperature coefficients of the cell performance parameters are derived as a function of the concentration ratio. Under concentration, the cells exhibit a dramatic increase in efficiency and an improved temperature coefficient of efficiency. At 25 C, a peak conversion efficiency of 18.9 percent is reported. At 80 C, the peak AM0 efficiency is 15.7 percent at 75.6 suns. These are the highest efficiencies yet reported for InP heteroepitaxial cells. Approaches for further improving the cell performance are discussed.

Wanlass, M. W.

Optimization of solar cells for air mass zero operation and a study of solar cells at high temperatures, phase 3

The etch-back epitaxy process is described for producing thin, graded composition GaAlAs layers. The palladium-aluminum contact system is discussed along with its associated problems. Recent solar cell results under simulated air mass zero light and at elevated temperatures are reported and the growth of thin polycrystalline GaAs films on foreign substrates is developed.

Blakeslee, A. E.

Mechanism of incipient oxidation of bulk chemical vapor deposited Si3N4

X-ray photoelectron spectroscopy was employed, in conjunction with ion bombardment, to analyze the chemical composition profile across thin (less than 50 nm) oxide films on chemically vapor deposited Si3N4. The thermal oxides were grown in dry oxygen at 1100 C on samples with or without native oxide film (formed in room air). The results show that the thermal oxidation product was silicon oxynitride of graded N:O ratio, and that the presence of a native oxide film promotes the formation of a SiO2 crust over the oxynitride. It is proposed that the fundamental mechanism of Si3N4 oxidation is progressive O-for-N substitution in the silicon oxynitride unit tetrahedron, which is best designated SiN(2-x)O(2+x), where x is also an index of depth. The corresponding equation for nonstoichiometric oxidation of Si3N4 describes a bulk (rather than an interface) reaction process, with significant implications for O2 and N2 fluxes and diffusivities.

Ogbuji, L. U. T.

Non-destructive Evaluation of Bonds Between Fiberglass Composite and Metal

To assess the integrity and reliability of an adhesive joint in an automotive composite component, several non-destructive evaluation (NDE) methodologies are correlated to lap shear bond strengths. A glass-fabric-reinforced composite structure was bonded to a metallic structure with a two-part epoxy adhesive. Samples were subsequently cut and tested in shear, and flaws were found in some areas. This study aims to develop a reliable and portable NDE system for service-level adhesive inspection in the automotive industry. The results of the experimental investigation using several NDE methods are presented and discussed. Fiberglass-to-metal bonding is the ideal configuration for NDE via thermography using excitation with induction heating, due to the conductive metal and non-conductive glass-fiber-reinforced composites. Excitation can be either by a research-grade induction heater of highly defined frequency and intensity, or by a service-level heater, such as would be used for sealing windshields in a body shop. The thermographs thus produced can be captured via a high-resolution infrared camera, with principal component analysis and 2D spatial Laplacian processing. Alternatively, the thermographs can be captured by low resolution thermochromic microencapsulated liquid crystal film imaging, which needs no post-processing and can be very inexpensive. These samples were also examined with phased-array ultrasound. The NDE methods are compared to the lap shear values and to each other for approximate cost, accuracy, and time and level of expertise needed.

Zhao, Selina

Friction and hardness of gold films deposited by ion plating and evaporation

Sliding friction experiments were conducted with ion-plated and vapor-deposited gold films on various substrates in contact with a 0.025-mm-radius spherical silicon carbide rider in mineral oil. Hardness measurements were also made to examine the hardness depth profile of the coated gold on the substrate. The results indicate that the hardness is influenced by the depth of the gold coating from the surface. The hardness increases with an increase in the depth. The hardness is also related to the composition gradient in the graded interface between the gold coating and the substrate. The graded interface exhibited the highest hardness resulting from an alloy hardening effect. The coefficient of friction is inversely related to the hardness, namely, the load carrying capacity of the surface. The greater the hardness that the metal surface possesses, the lower is the coefficient of friction. The graded interface exhibited the lowest coefficient of friction.

Miyoshi, K.

Beyond Melting: Amorphous Bonding for Joining and Consolidation

Crystallization may be the hidden constraint in thermoplastic composite manufacturing. It requires tightly controlled cooling, induces residual stresses through shrinkage, and introduces path-dependent behavior that complicates predictive modeling yet remains essential for structural performance. This work asks: can bonding be achieved without relying on melt-driven crystallization? To address this, thin (5–20 μm) polyetherimide (PEI) interlayers are pre-healed to slow-cooled polyaryletherketone (PAEK) in two contexts. The first, Thermabond®, is sub-melt joining of low melt-PAEK laminates. Results show that bond quality is governed primarily by processing (i.e., adequate healing and film handling) rather than modest changes in interlayer thickness. This concept is then extended to laminate-scale manufacturing through an architecture known as OATMEAL (Out-of-autoclave Amorphous/semicrystalline Thermoplastic Material for Energy-efficient Aerospace-grade Laminates). PEI is healed to carbon fiber reinforced polyetheretherketone (PEEK) at the prepreg and excess PEI is then ablated from the surface. Crystallinity is developed off-line during prepreg fabrication, while subsequent consolidation occurs below the melt temperature to preserve it. Cross-ply warpage experiments show that, contrary to intuition, repeated amorphous interfaces reduce global curvature by lowering the effective stress lock-in temperature and eliminating crystallization shrinkage from the lamina response. Correspondingly, laminate behavior is accurately predicted using classical laminate theory (CLT) with a single effective stress-free temperature, whereas conventional CF/PEEK requires accounting for crystallization-driven effects. By decoupling interfacial healing from crystallization, OATMEAL enables sub-melt consolidation, reduces energy consumption by up to 75%, and increases manufacturing throughput by fivefold. These results demonstrate that amorphous bonding is not only a joining strategy, but a pathway to more predictable and scalable thermoplastic composite manufacturing.

solidification

Thermal barrier coatings for heat engine components

A comprehensive NASA-Lewis program of coating development for aircraft gas turbine blades and vanes is presented. Improved ceramic layer compositions are investigated, along the MCrAlY bond films and the methods of uniform deposition of the coatings; the thermomechanical and fuel impurity tolerance limits of the coatings are being studied. Materials include the ZrO2-Y2O3/NiCrAlY system; the effects of the bond coat and zirconia composition on coating life and Mach 1 burner rig test results are discussed. It is concluded that Diesel engines can also utilize thermal barrier coatings; they have been used successfully on piston crowns and exhaust valves of shipboard engines to combat lower grade fuel combustion corrosion.

Levine, S. R.

Optical Properties of Thin Film Molecular Mixtures

Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling the degree of molecular mixing, the solar selective coatings can be tailored to have the combined properties of high solar absorptance, alpha, and low infrared emittance, epsilon. On orbit, these combined properties would simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. Mini-satellites equipped with solar collectors coated with these cermet coatings may utilize the captured heat energy to power a heat engine to generate electricity, or to power a thermal bus that directs heat to remote regions of the spacecraft. Early work in this area identified the theoretical boundary conditions needed to operate a Carnot cycle in space, including the need for a solar concentrator, a solar selective coating at the heat inlet of the engine, and a radiator. A solar concentrator that can concentrate sunlight by a factor of 100 is ideal. At lower values, the temperature of the solar absorbing surface becomes too low for efficient heat engine operation, and at higher values, cavity type heat receivers become attractive. In designing the solar selective coating, the wavelength region yielding high solar absorptance must be separated from the wavelength region yielding low infrared emittance by establishing a sharp transition in optical properties. In particular, a sharp transition in reflectance is desired in the infrared to achieve the desired optical performance. For a heat engine operating at 450C, a sharp transition at 1.8 micrometers is desired. The radiator completes the heat flow through the Carnot cycle. Additional work has been done supporting the use of molecular mixtures for terrestrial applications. Sputter deposition provides a means to apply coatings to the tubes that carry a working fluid at the focus of trough-style collectors. Sputtering offers considerable flexibility in coating conditions, including a wide variety of metal and dielectric targets. Coating designs range from simple two or three layer coatings to complex coatings that are purposely graded to be metal-rich at their base and oxide-rich at their surface in order to yield the desired solar selective properties. In these cermet coatings, molecular islands of metal are thought to be embedded in a three dimensional matrix of dielectric. Recent work has identified the use of custom made ion beam sputter deposition targets to produce coatings containing molecular mixtures of metal and dielectric. The targets are cylindrical and the surface consists of a gradually changing composition of metal and dielectric. Rotating the cylinder under the beam during ion beam sputter deposition yields a coating that is a molecular mixture of metal and dielectric, with the composition changing through the thickness of the coating. The optical properties of these coatings are not only dependent on their thickness and chemical composition, but are also dependent on the extent of the through thickness gradient established during deposition. This paper presents a summary of the optical properties of several thin film molecular mixtures designed as solar selective coatings. Optical performance is first identified as a function of wavelength, from the ultraviolet to the visible and infrared. Coating composition, thickness, and gradient from metal to dielectric also play an important role. Additional work for future activities is also identified.

Jaworske, Donald A.

The growth of low band-gap InAs on (111)B GaAs substrates

The use of low band-gap materials is of interest for a number of photovoltaic and optoelectronic applications, such as bottom cells of optimized multijunction solar cell designs, long wavelength light sources, detectors, and thermophotovoltaics. However, low band-gap materials are generally mismatched with respect to lattice constant, thermal expansion coefficient, and chemical bonding to the most appropriate commercially available substrates (Si, Ge, and GaAs). For the specific case of III-V semiconductor heteroepitaxy, one must contend with the strain induced by both lattice constant mismatch at the growth temperature and differences in the rates of mechanical deformation during the cool down cycle. Several experimental techniques have been developed to minimize the impact of these phenomena (i.e., compositional grading, strained layer superlattices, and high-temperature annealing). However, in highly strained systems such as InAs-on-GaAs, three-dimensional island formation and large defect densities (greater than or equal to 10(exp 8)/ cm(exp -2)) tend to limit their applicability. In these particular cases, the surface morphology and defect density must be controlled during the initial stages of nucleation and growth. At the last SPRAT conference, we reported on a study of the evolution of InAs islands on (100) and (111)B GaAs substrates. Growth on the (111)B orientation exhibits a number of advantageous properties as compared to the (100) during these early stages of strained-layer epitaxy. In accordance with a developing model of nucleation and growth, we have deposited thin (60 A - 2500 A), fully relaxed InAs films on (111)B GaAs substrates. Although thicker InAs films are subject to the formation of twin defects common to epitaxy on the (111)B orientation, appropriate control of the growth parameters can greatly minimize their density. Using this knowledge base, InAs films up to 2 microns in thickness with improved morphology and structural quality have been grown on (111)B GaAs substrates, thereby enabling the measurement of electronic and optical properties.

Welser, R. E.