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At least 37 records · Page 2

Low Temperature Unbalanced Magnetron Deposition of Hard, Wear-Resistant Coatings for Liquid-Film Bearing Applications

The original program for evaluating the tribological properties several different hard coatings for liquid film bearing applications was curtailed when the time for the program was reduced from 3 years to 1. Of the several different coatings originally planned for evaluation, we decided to concentrate on one coating, carbon nitride. At BIRL, we have been instrumental in the development of reactively sputtered carbon nitride coatings, and we have found that it is a very interesting new material with very good tribological properties. In this program, we found that the reactively sputtered carbon nitride does not bond well directly to hardened 440C stainless steel; but if an interlayer of titanium nitride is added between the carbon nitride and the 440C, the adhesion of the dual coating combination is very good. Statistically designed experiments were run with the dual layer combination, and 3 variables were chosen for the Box-Benken design, which were the titanium nitride interlayer thickness, the nitrogen partial pressure during the reactive sputtering of the carbon nitride, and the carbon nitride substrate bias voltage. Two responses were studied from these three variables; the adhesion of the dual coating combination to the 440C substrate and the friction coefficient of the carbon nitride in dry sliding contact with 52100 steel in air. The best adhesion came with the thickness interlayer thickness studied, which was 4 micrometers, and the lowest coefficient of friction was 0.1, which was achieved when the bias voltage was in the range of -80 to - 120 V and the nitrogen partial pressure was 3 mTorr.

Sproul, William D.↗

Low-Resistivity Zinc Selenide for Heterojunctions

Magnetron reactive sputtering enables doping of this semiconductor. Proposed method of reactive sputtering combined with doping shows potential for yielding low-resistivity zinc selenide films. Zinc selenide attractive material for forming heterojunctions with other semiconductor compounds as zinc phosphide, cadmium telluride, and gallium arsenide. Semiconductor junctions promising for future optoelectronic devices, including solar cells and electroluminescent displays. Resistivities of zinc selenide layers deposited by evaporation or chemical vapor deposition too high to form practical heterojunctions.

Stirn, R. J.↗

Tantalum Suboxide Films with Tunable Composition and Electrical Resistivity Deposited by Reactive Magnetron Sputtering

Tantalum-based films with tailored composition, density, and electrical resistivity are of interest for next generation hohlraums for magnetized indirect-drive inertial confinement fusion. Here, we use reactive direct-current magnetron sputtering to deposit tantalum suboxide films with O content in the range of 46–71 at.%. In contrast to a common approach involving varying reactive gas contents, compositional control is achieved kinetically by changing the total chamber pressure and the deposition rate, while keeping the working gas mix of Ar-5%O2 constant. The resultant films are X-ray amorphous with electrical resistivity varying by over seven orders of magnitude. The dominant conduction mechanism changes from metallic to activated tunneling above ∼55 at.% of O, which is characterized by a sharp increase in resistivity and a decrease in the carrier density at low temperatures.

36 MATERIALS SCIENCE↗

Isotopic study of oxygen diffusion in oxide coatings

Diffusion of oxygen in thin films of silicon dioxide was studied using oxygen isotopically enriched in oxygen of atomic mass 18 (O-18). This subject is of interest because thin films of dielectrics such as SiO2 are proposed for use as a protective coatings for solar mirrors in low Earth orbit, which is a strongly oxidizing environment. Films of this material were prepared with a direct current magnetron using reactive sputtering techniques. To produce (O-18)- enriched SiO2, a standard 3.5-in.-diameter silicon wafer was reactively sputtered using (O-18)-enriched (95 percent) oxygen as the plasma feed gas. The films were characterized using Rutherford backscattering and Secondary Ion Mass Spectrometer (SIMS) to establish stoichiometry and purity. Subsequently, the films were exposed to an air-derived oxygen plasma in a standard laboratory plasma reactor for durations of up to 10 hr. The concentration ratio of O-16 as a function of depth was determined using SIMS profiling and compared to a baseline, nonplasma exposed sample. A value for the diffusivity of oxygen near the surface of these films was obtained and found to be about 10(-15)sq cm/sec.

Gulino, Daniel A.↗

Preliminary results on CuInSe2/ZnSe solar cells using reactively sputter-deposited ZnSe

In this paper preliminary results on CuInSe2/ZnSe thin film heterojunction photovoltaic devices are presented. High-conductivity ZnSe films were reactively sutter-deposited onto CuInSe2 films and overcoated with ZnO to reduce the sheet resistance. The highest short-circuit current density, as determined from a spectral response weighted for air mass 1.5 global insolation, was 37.4 mA/sq cm. The highest pen-circuit voltage observed was 430 mV.

Nouhi, A.↗

Making AlN(x) Tunnel Barriers Using a Low-Energy Nitrogen-Ion Beam

A technique based on accelerating positive nitrogen ions onto an aluminum layer has been demonstrated to be effective in forming thin (<2 nm thick) layers of aluminum nitride (AlN(x)) for use as tunnel barriers in Nb/Al-AlN(x)/Nb superconductor/insulator/ superconductor (SIS) Josephson junctions. AlN(x) is the present material of choice for tunnel barriers because, to a degree greater than that of any other suitable material, it offers the required combination of low leakage current at high current density and greater thermal stability. While ultra-thin AlN films with good thickness and stoichiometry control are easily formed using techniques such as reactive molecular beam epitaxy and chemical vapor deposition, growth temperatures of 900 C are necessary for the dissociative adsorption of nitrogen from either nitrogen (N2) or ammonia (NH3). These growth temperatures are prohibitively high for the formation of tunnel barriers on Nb films because interfacial reactions at temperatures as low as 200 to 300 C degrade device properties. Heretofore, deposition by reactive sputtering and nitridation of thin Al layers with DC and RF nitrogen plasmas have been successfully used to form AlN barriers in SIS junctions. However, precise control over critical current density Jc has proven to be a challenge, as is attaining adequate process reproducibility from system to system. The present ion-beam technique is an alternative to the plasma or reactive sputtering techniques as it provides a highly controlled arrival of reactive species, independent of the electrical conditions of the substrate or vacuum chamber. Independent and accurate control of parameters such as ion energy, flux, species, and direction promises more precise control of film characteristics such as stoichiometry and thickness than is the case with typical plasma processes. In particular, the background pressure during ion-beam nitride growth is 2 or 3 orders of magnitude lower, minimizing the formation of compounds with contaminants, which is critical in devices the performance of which is dictated by interfacial characteristics. In addition, the flux of incoming species can be measured in situ using ion probes so that the dose can be controlled accurately. The apparatus used in the present ion-beam technique includes a vacuum chamber containing a commercial collimated- ion-beam source, a supply of nitrogen and argon, and an ion probe for measuring the ion dose. Either argon or nitrogen can be used as the feed gases for the ion source, depending on whether cleaning of the substrate or growth of the nitride, respectively, is desired. Once the Nb base electrode and Al proximity layer have been deposited, the N2 gas line to the ion beam is vented and purged, and the ion-source is turned on until a stable discharge is obtained. The substrate is moved over the ion-beam source to expose the Al surface layer to the ion beam (see figure) for a specified duration for the formation of the nitride tunnel barrier. Next, the Nb counter-electrode layer is deposited on the nitride surface layer. The Nb/Al- AlN(x)/Nb-trilayer-covered substrate is then patterned into individual devices by use of conventional integrated-circuit processing techniques.

Kaul, Anupama↗

Developing Multilayer Thin Film Strain Sensors With High Thermal Stability

A multilayer thin film strain sensor for large temperature range use is under development using a reactively-sputtered process. The sensor is capable of being fabricated in fine line widths utilizing the sacrificial-layer lift-off process that is used for micro-fabricated noble-metal sensors. Tantalum nitride films were optimized using reactive sputtering with an unbalanced magnetron source. A first approximation model of multilayer resistance and temperature coefficient of resistance was used to set the film thicknesses in the multilayer film sensor. Two multifunctional sensors were fabricated using multilayered films of tantalum nitride and palladium chromium, and tested for low temperature resistivity, TCR and strain response. The low temperature coefficient of resistance of the films will result in improved stability in thin film sensors for low to high temperature use.

Wrbanek, John D.↗

High temperature strain gages

A ceramic strain gage based on reactively sputtered indium-tin-oxide (ITO) thin films is used to monitor the structural integrity of components employed in aerospace propulsion systems operating at temperatures in excess of 1500.degree. C. A scanning electron microscopy (SEM) of the thick ITO sensors reveals a partially sintered microstructure comprising a contiguous network of submicron ITO particles with well defined necks and isolated nanoporosity. Densification of the ITO particles was retarded during high temperature exposure with nitrogen thus stabilizing the nanoporosity. ITO strain sensors were prepared by reactive sputtering in various nitrogen/oxygen/argon partial pressures to incorporate more nitrogen into the films. Under these conditions, sintering and densification of the ITO particles containing these nitrogen rich grain boundaries was retarded and a contiguous network of nano-sized ITO particles was established.

Gregory, Otto J.↗

CMOS-Compatible Ultrathin Superconducting NbN Thin Films Deposited by Reactive Ion Sputtering on 300 mm Si Wafer

We report a milestone in achieving large-scale, ultrathin (~5 nm) superconducting NbN thin films on 300 mm Si wafers using a high-volume manufacturing (HVM) industrial physical vapor deposition (PVD) system. The NbN thin films possess remarkable structural uniformity and consistently high superconducting quality across the entire 300 mm Si wafer, by incorporating an AlN buffer layer. High-resolution X-ray diffraction and transmission electron microscopy analyses unveiled enhanced crystallinity of (111)-oriented δ-phase NbN with the AlN buffer layer. Notably, NbN films deposited on AlN-buffered Si substrates exhibited a significantly elevated superconducting critical temperature (~2 K higher for the 10 nm NbN) and a higher upper critical magnetic field or H c2 (34.06 T boost in H c2 for the 50 nm NbN) in comparison with those without AlN. These findings present a promising pathway for the integration of quantum-grade superconducting NbN films with the existing 300 mm CMOS Si platform for quantum information applications.

36 MATERIALS SCIENCE↗

Combinatorial Synthesis of Oxysulfides in the Lanthanum–Bismuth-Copper System

Establishing synthesis approaches for a target material constitutes a grand challenge in materials research, which is compounded with use-inspired specifications on the format of the material. Solar photochemistry using thin film materials is a promising technology for which many complex materials are being proposed, and the present work describes application of combinatorial methods to explore the synthesis of predicted La–Bi–Cu oxysulfide photocathodes, in particular alloys of LaCuOS and BiCuOS. The variation in concentration of three cations and two anions in thin film materials, and crystallization thereof, is achieved by a combination of reactive sputtering and thermal processes including reactive annealing and rapid thermal processing. Composition and structural characterization establish composition-processing-structure relationships that highlight the breadth of processing conditions required for synthesis of LaCuOS and BiCuOS. The relative irreducibility of La oxides and limited diffusion indicate the need for high temperature processing, which conflicts with the temperature limits for mitigating evaporation of Bi and S. Collectively the findings indicate that alloys of these phases will require reactive annealing protocols that are uniquely tailored to each composition, motivating advancement of dynamic processing capabilities to further automate discovery of synthesis routes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deposition of reactively ion beam sputtered silicon nitride coatings

An ion beam source was used to deposit silicon nitride films by reactively sputtering a silicon target with beams of Ar + N2 mixtures. The nitrogen fraction in the sputtering gas was 0.05 to 0.80 at a total pressure of 6 to 2 millionth torr. The ion beam current was 50 mA at 500 V. The composition of the deposited films was investigated by auger electron spectroscopy and the rate of deposition was determined by interferometry. A relatively low rate of deposition of about 2 nm. one-tenth min. was found. AES spectra of films obtained with nitrogen fractions higher than 0.50 were consistent with a silicon to nitrogen ratio corresponding to Si3N4. However the AES spectra also indicated that the sputtered silicon nitride films were contaminated with oxygen and carbon and contained significant amounts of iron, nickel, and chromium, most probably sputtered from the holder of the substrate and target.

Grill, A.↗

Band-gap Engineering in Sputter Deposited Amorphous/Microcrystalline Sc(x)Ga(1-x)N

Reactive sputtering was used to grow thin films of Sc(x)Ga(1-x)N with scandium concentrations of 20%-70% on quartz substrates at temperatures of 300-675 K. X-ray diffraction (XRD) of the films showed either weak or no structure, suggesting the films are amorphous or microcrystalline. Optical absorption spectra were taken of each sample and the optical band gap was determined. The band gap varied linearly with increasing Ga concentration between 2.0 and 3.5 eV. Ellipsometry was used to confirm the band gap measurements and provide optical constants in the range 250-1200 nm. ScN and GaN have different crystal structures (rocksalt and wurzite, respectively), and thus may form a heterogeneous mixture as opposed to an alloy. Since the XRD data were inconclusive, bilayers of ScN/GaN were grown and optical absorption spectra taken. A fundamental difference in the spectra between the bilayer films and alloy films was seen, suggesting the films are alloys, not heterogeneous mixtures.

Little, Mark E.↗

Stable magnesium zinc oxide by reactive Co-Sputtering for CdTe-based solar cells

Magnesium zinc oxide (MZO) is a promising front contact material for CdTe solar cells. Due to its higher band gap than traditional CdS, MZO can reduce parasitic absorption to significantly increase short-circuit current density while also providing a benefit of conduction band offset tuning through Mg:Zn ratio optimization. MZO has been successfully implemented into CdTe devices, however its stability has been of concern. The MZO stability issue has been attributed to the presence of oxygen in the CdTe device processing ambient, leading to double-diode behavior (S-kink) in the current density-voltage curves. Here we report on MZO thin films deposited by reactive co-sputtering. The reactively co-sputtered MZO thin films have encouraging stability, show no significant variation in work function of the surface over a period of 6 months, as measured by Kelvin probe. Energy conversion efficiencies of around 16% have been achieved both with and without presence of oxygen in device processing ambients across multiple research facilities. Finally, these efficiencies should be possible to increase further by tuning of the thin film deposition and device processing parameters, especially through optimization of the back contact.

14 SOLAR ENERGY↗

Sputtered W-N diffusion barriers

The thermal stability of reactively sputtered tungsten-nitrogen alloy thin films is investigated for the application as diffusion barriers in silicon contact metallizations. The composition of W-N barriers is varied over a wide range including pure W. Aluminum, gold, and silver are used as low resistivity overlayers. Metallurgical interactions at temperatures ranging from 500 to 900 C are studied. Incorporating nitrogen into tungsten advantageously stabilizes all three systems. The overall failure takes place rapidly above critical temperatures that depend on both the metal overlayer and the microstructure of the barrier. In some cases, W-N alloys can effectively prevent interdiffusion at temperatures as high as 800 C for 30 min.

Kattelus, H. P.↗

Development of sputtering process to deposit stoichiometric zirconia coatings for the inside wall of regeneratively cooled rocket thrust chambers

Thermal barrier coatings of yttria stabilized zirconia and zirconia-ceria mixtures were deposited by RF reactive sputtering. Coatings were 1-2 mils thick, and were deposited on copper cylinders intended to simulate the inner wall of a regeneratively cooled thrust chamber. Coating stoichiometry and adherence were investigated as functions of deposition parameters. Modest deposition rates (approximately 0.15 mil/hr) and subambient sustrate temperatures (-80 C) resulted in nearly stoichiometric coatings which remained adherent through thermal cycles between -196 and 400 C. Coatings deposited at higher rates or substrates temperatures exhibited greater oxygen deficiences, while coatings deposited at lower temperatures were not adherent. Substrate bias resulted in structural changes in the coating and high krypton contents; no clear effect on stoichiometry was observed.

Busch, R.↗

Multi-cathode unbalanced magnetron sputtering systems

Ion bombardment of a growing film during deposition is necessary in many instances to ensure a fully dense coating, particularly for hard coatings. Until the recent advent of unbalanced magnetron (UBM) cathodes, reactive sputtering had not been able to achieve the same degree of ion bombardment as other physical vapor deposition processes. The amount of ion bombardment of the substrate depends on the plasma density at the substrate, and in a UBM system the amount of bombardment will depend on the degree of unbalance of the cathode. In multi-cathode systems, the magnetic fields between the cathodes must be linked to confine the fast electrons that collide with the gas atoms. Any break in this linkage results in electrons being lost and a low plasma density. Modeling of the magnetic fields in a UBM cathode using a finite element analysis program has provided great insight into the interaction between the magnetic fields in multi-cathode systems. Large multi-cathode systems will require very strong magnets or many cathodes in order to maintain the magnetic field strength needed to achieve a high plasma density. Electromagnets offer the possibility of independent control of the plasma density. Such a system would be a large-scale version of an ion beam enhanced deposition (IBED) system, but, for the UBM system where the plasma would completely surround the substrate, the acronym IBED might now stand for Ion Blanket Enhanced Deposition.

Sproul, William D.↗

Adherence of sputtered titanium carbides

Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited, in practice, by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium based alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

Brainard, W. A.↗

Improved adhesion of sputtered refractory carbides to metal substrates

Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited in practice by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium base alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

Wheeler, D. R.↗