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The interaction of small particles and thin films of metals with gases. I - A brief review of the early stages of oxide formation

Existing work on gas-solid reactions making use of thin film technologies is reviewed. The discussion concentrates on two major areas of gas-metal interactions: chemisorption and the early stages of oxidation of metals (characterized by a non-volatile reaction product) and catalytic surface reactions (featuring volatile reaction products). A brief survey of oxide formation on metals is presented. Here it is of importance to distinguish between reactions on continuous thin film substrates and reactions on particulate deposits. Small particle-gas interactions also affect the nucleation, growth and sintering processes of thin films. It is shown that various combinations of UHV and high resolution electron microscopy techniques, which include in situ experimentation, can provide the appropriate tools for studying angstrom particle chemistry.

Poppa, H.↗

Patterning of Indium Tin Oxide Films

A relatively rapid, economical process has been devised for patterning a thin film of indium tin oxide (ITO) that has been deposited on a polyester film. ITO is a transparent, electrically conductive substance made from a mixture of indium oxide and tin oxide that is commonly used in touch panels, liquid-crystal and plasma display devices, gas sensors, and solar photovoltaic panels. In a typical application, the ITO film must be patterned to form electrodes, current collectors, and the like. Heretofore it has been common practice to pattern an ITO film by means of either a laser ablation process or a photolithography/etching process. The laser ablation process includes the use of expensive equipment to precisely position and focus a laser. The photolithography/etching process is time-consuming. The present process is a variant of the direct toner process an inexpensive but often highly effective process for patterning conductors for printed circuits. Relative to a conventional photolithography/ etching process, this process is simpler, takes less time, and is less expensive. This process involves equipment that costs less than $500 (at 2005 prices) and enables patterning of an ITO film in a process time of less than about a half hour.

Immer, Christopher↗

Metallic Thin-Film Bonding and Alloy Generation

Diffusion bonding a stack of aluminum thin films is particularly challenging due to a stable aluminum oxide coating that rapidly forms on the aluminum thin films when they are exposed to atmosphere and the relatively low meting temperature of aluminum. By plating the individual aluminum thin films with a metal that does not rapidly form a stable oxide coating, the individual aluminum thin films may be readily diffusion bonded together using heat and pressure. The resulting diffusion bonded structure can be an alloy of choice through the use of a carefully selected base and plating metals. The aluminum thin films may also be etched with distinct patterns that form a microfluidic fluid flow path through the stack of aluminum thin films when diffusion bonded together.

Fryer, Jack Merrill↗

Ceramic Composite Thin Films

A ceramic composite thin film or layer includes individual graphene oxide and/or electrically conductive graphene sheets dispersed in a ceramic (e.g. silica) matrix. The thin film or layer can be electrically conductive film or layer depending the amount of graphene sheets present. The composite films or layers are transparent, chemically inert and compatible with both glass and hydrophilic SiOx/silicon substrates. The composite film or layer can be produced by making a suspension of graphene oxide sheet fragments, introducing a silica-precursor or silica to the suspension to form a sol, depositing the sol on a substrate as thin film or layer, at least partially reducing the graphene oxide sheets to conductive graphene sheets, and thermally consolidating the thin film or layer to form a silica matrix in which the graphene oxide and/or graphene sheets are dispersed.

Ruoff, Rodney S.↗

A preliminary study of ester oxidation on an aluminum surface using chemiluminescence

The oxidation characteristics of a pure ester (trimethyolpropane triheptanoate) were studied by using a chemiluminescence technique. Tests were run in a thin-film micro-oxidation apparatus with an aluminum alloy catalyst. Conditions included a pure oxygen atmosphere and a temperature range of 176 to 206 C. Results indicated that oxidation of the ester (containing 10 to the minus 3 power M diphenylanthracene as an intensifier) was accompanied by emission of light. The maximum intensity of light emission (I sub max) was a function of the amount of ester, the concentration of intensifier, and the test temperature. The induction period or the time to reach one-half of maximum intensity (t sub 1/2) was an inverse function of test temperature. Decreases in light emission at the later stages of a test were caused by depletion of the intensifier.

Jones, W. R., Jr.↗

A preliminary study of ester oxidation on an aluminum surface using chemiluminescence

The oxidation characteristics of a pure ester (trimethyolpropane triheptanoate) were studied by using a chemiluminescence technique. Tests were run in a thin-film micro-oxidation apparatus with an aluminum alloy catalyst. Conditions included a pure oxygen atmosphere and a temperature range of 176 to 206 C. Results indicated that oxidation of the ester (containing 10 to the minus 3rd power M diphenylanthracene as an intensifier) was accompanied by emission of light. The maximum intensity of light emission (I sub max) was a function of the amount of ester, the concentration of intensifier, and the test temperature. The induction period or the time to reach one-half of maximum intensity (t sub 1/2) was an inverse function of test temperature. Decreases in light emission at the later stages of a test were caused by depletion of the intensifier.

Jones, William R., Jr.↗

Electrically Variable Resistive Memory Devices

Nonvolatile electronic memory devices that store data in the form of electrical- resistance values, and memory circuits based on such devices, have been invented. These devices and circuits exploit an electrically-variable-resistance phenomenon that occurs in thin films of certain oxides that exhibit the colossal magnetoresistive (CMR) effect. It is worth emphasizing that, as stated in the immediately preceding article, these devices function at room temperature and do not depend on externally applied magnetic fields. A device of this type is basically a thin film resistor: it consists of a thin film of a CMR material located between, and in contact with, two electrical conductors. The application of a short-duration, low-voltage current pulse via the terminals changes the electrical resistance of the film. The amount of the change in resistance depends on the size of the pulse. The direction of change (increase or decrease of resistance) depends on the polarity of the pulse. Hence, a datum can be written (or a prior datum overwritten) in the memory device by applying a pulse of size and polarity tailored to set the resistance at a value that represents a specific numerical value. To read the datum, one applies a smaller pulse - one that is large enough to enable accurate measurement of resistance, but small enough so as not to change the resistance. In writing, the resistance can be set to any value within the dynamic range of the CMR film. Typically, the value would be one of several discrete resistance values that represent logic levels or digits. Because the number of levels can exceed 2, a memory device of this type is not limited to binary data. Like other memory devices, devices of this type can be incorporated into a memory integrated circuit by laying them out on a substrate in rows and columns, along with row and column conductors for electrically addressing them individually or collectively.

Liu, Shangqing↗

Thin-film composite membranes based on hyperbranched poly(ethylene oxide) for CO 2 /N 2 separation

Cross-linked amorphous poly(ethylene oxide) (XLPEO) is one of the leading membrane materials for post-combustion CO 2 capture. For example, XLPEO prepared from poly(ethylene glycol) methyl ether acrylate (PEGMEA) exhibited CO 2 permeability of 570 Barrer and CO 2 /N 2 selectivity of 41 at 35 °C. However, these XLPEOs cannot be dissolved in coating solutions, making it impossible to be fabricated into thin-film composite (TFC) membranes using state-of-the-art manufacturing processes. In this study, we synthesized high molecular weight yet soluble HPEO via atom transfer radical polymerization (ATRP). These polymers were thoroughly characterized and compared with XLPEO, including thermal transitions, free volumes, and pure-gas sorption and permeation properties. A polymer with the best combination of CO 2 permeability (540 Barrer) and CO 2 /N 2 selectivity (43) was fabricated into defect-free TFC membranes with a thickness as thin as 506 ± 44 nm. When challenged with simulated flue gas containing water vapor at 35 °C for over 100 h, the membrane shows stable CO 2 permeance of 850 GPU and CO 2 /N 2 selectivity of 37, comparable to the leading commercial membranes for carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Density Functional Theory (DFT) Study on the Effect of Chlorine in the Magnesium Zinc Oxide (MZO) Front Interface for Cadmium Telluride (CdTe) Thin Film Solar Cells

Cadmium telluride photovoltaics has benefitted greatly from the cadmium chloride treatment which causes a remarkable improvement in cell efficiencies. This work investigates the effect of elemental chlorine at the interface between the magnesium zinc oxide front contact and the cadmium telluride absorber in such a device. Band alignment including band bending and interface states and its role in potential charge carrier transport is the key feature studied. It is seen that a small amount of chlorine is leads to a more desirable band alignment. Higher concentrations of chlorine result in unfavorable band characteristics.

14 SOLAR ENERGY↗

Topotactic Reduction‐Driven Crystal Field Excitations in Brownmillerite Manganite Thin Films

Topotactic reduction of perovskite oxides offers a powerful approach for discovering novel phenomena, such as superconducting infinite-layer nickelates and polar metallicity, and is commonly accompanied by the emergence of multiple valence states and/or complex crystal fields of transition metals. However, understanding the complex interplay between crystal chemistry, electronic structure, and physical properties at the spin- and orbital-resolved levels in these reduced systems remains elusive. Here, in this study, x-ray absorption spectroscopy, resonant inelastic x-ray scattering (RIXS), and density functional theory calculations are used to uncover topotactic metal-insulator transition and orbital-specific crystal field excitations in brownmillerite La 0.67 Ca 0.33 MnO 2.5 thin films. The Mn valence states are found to be Mn 2+ /Mn 3+ , along with their corresponding populations at octahedral and tetrahedral sites, which effectively weaken the Mn-O hybridization compared to the parent perovskite phase. As a result, La 0.67 Ca 0.33 MnO 2.5 films exhibit an antiferromagnetic insulating ground state. Moreover, by combining the RIXS measurements on selected single-valence manganites, specifically MnO, LaMnO 3 , and CaMnO 3 , with orbital- and spin-resolved density-of-states calculations, the study identifies the dd excitations of octahedrally and tetrahedrally coordinated Mn 2+ /Mn 3+ ions, directly linking the microscopic electronic structure to the macroscopic magnetic/electrical properties.

36 MATERIALS SCIENCE↗

Charging control techniques

Transparent conductive thin films of indium oxide and indium-tin oxide were evaluated for their properties to control charge buildup on satellite materials. Both oxide coatings were evaluated for their uniformity, stability, reproducibility and characteristics on various substrate materials such as FEP Teflon, Kapton, and glass. The process development toward optimization and characterization of these thin semiconductor oxide coatings and the evaluation on large sizes performed for qualification for use on thermal control satellite materials is described. The materials have been characterized in multiple energy electron plasma environment and at low temperatures. All radiation measurements of the coatings under simulated substorm conditions have exhibited the characteristics of stable charge control. Measurement of surface potential during and after irradiation by electrons up to 30 KeV and ionizing gamma radiation show an effective stable grounding surface.

Schmidt, R. E.↗

The Role of Cation Coordination in the Electrical and Optical Properties of Amorphous Transparent Conducting Oxides

Amorphous oxide semiconductor materials have demonstrated numerous advantages without compromise of electrical properties as compared to their crystalline counterparts, yet understanding of the fundamental principles allowing this has remained elusive. To study the origins of enhanced optoelectronic properties, we apply high-throughput, combinatorial sputtering, structural and spectral mapping, and computationally intensive ab initio molecular dynamics simulations with density functional theory to a ternary, post-transition metal oxide system, namely, zinc tin oxide. The deposited thin films exhibit a high figure of merit, achieving carrier densities in the range of 1019 to 1020 cm–3 and carrier mobilities up to 35 cm2/Vs. These results highlight the role of local distortions and cation coordination in determining the microscopic origins of carrier generation and transport. In particular, we identify the strong likelihood of Sn undercoordination in both Zn-poor and Zn-rich phases leading to the high carrier concentrations observed. This not only diverges from the still widespread historical indictment of oxygen vacancies controlling carrier population in crystalline oxides but also provides a comprehensive framework to describe the unique structure–property relationships using specific structural and electronic descriptors in disordered phase materials.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗

Electrified vapour deposition at ultrahigh temperature and atmospheric pressure for nanomaterials synthesis

Vapour-phase synthesis methods have shown promise for the scalable synthesis of nanomaterials and coatings. However, the vaporization of different precursors for the synthesis of a broad nanomaterial space, particularly at atmospheric pressure, while maintaining compositional and structural control of the final product is challenging. Here we report the generation of an ultrahigh-temperature atomic vapour at atmospheric pressure based on electrified heating, for the growth of multi-elemental nanomaterials and thin films. This process relies on a reactor design whereby solid-state precursors are vaporized within a semi-confined space beneath an electrified heater that can reach ~3,000 K. The proximity of the heater rapidly breaks down the bonds of metal salt precursors and decomposes them into an atomic vapour that expands into a high-temperature (>2,000 K), highly reactive and high-flux vapour (10 21 –10 22 atoms per cm 2 per second) that travels upwards in a directional flow. When mixed with entrained ambient gases, the highly reactive atomic species rapidly nucleate and grow into the desired final products, including alloys, oxides, sulfides and thin films, which can be deposited on a low-temperature substrate. This EVD approach can synthesize a broad range of functional nanomaterials at atmospheric pressure, including single-phase multi-elemental nanomaterials formed under thermodynamically non-equilibrium conditions.

36 MATERIALS SCIENCE↗

High efficiency thin-film GaAs solar cells

Several oxidation techniques are discussed which have been found to increase the open circuit (V sub oc) of metal-GaAs Schottky barrier solar cells, the oxide chemistry, attempts to measure surface state parameters, the evolving characteristics of the solar cell as background contamination (has been decreased, but not eliminated), results of focused Nd/YAG laser beam recrystallization of Ge films evaporated onto tungsten, and studies of AMOS solar cells fabricated on sliced polycrystalline GaAs wafers. Also discussed are projected materials availability and costs for GaAs thin-film solar cells.

Stirn, R. J.↗

The Mars oxidant experiment (MOx) for Mars '96

The MOx instrument was developed to characterize the reactive nature of the martian soil. The objectives of MOx were: (1) to measure the rate of degradation of organics in the martian environment; (2) to determine if the reactions seen by the Viking biology experiments were caused by a soil oxidant and measure the reactivity of the soil and atmosphere: (3) to monitor the degradation, when exposed to the martian environment, of materials of potential use in future missions; and, finally, (4) to develop technologies and approaches that can be part of future soil analysis instrumentation. The basic approach taken in the MOx instrument was to place a variety of materials composed as thin films in contact with the soil and monitor the physical and chemical changes that result. The optical reflectance of the thin films was the primary sensing-mode. Thin films of organic materials, metals, and semiconductors were prepared. Laboratory simulations demonstrated the response of thin films to active oxidants.

Flight Experiment↗

Optimization of La 2–x Sr x CuO 4 Single Crystal Film Growth via Molecular Beam Epitaxy

Atomic layer-by-layer molecular beam epitaxy (ALL-MBE) combined with ozone is one of the best methods to fabricate single-crystal thin films of complex oxides. Cuprate such as La 2-x Sr x CuO 4 (LSCO) is a representative complex-oxide high-temperature superconductor (HTS) material. Our group utilizes this method to produce high-quality single-crystal HTS films with atomically smooth surfaces and interfaces. In addition, ALL-MBE enables us to engineer multilayer heterostructures with atomic precision. This allows the fabrication of tunnel junctions, various nanostructures, and other HTS devices of interest for superconducting electronics. We have synthesized over three thousand LSCO thin films in the past two decades. These films’ structural and electronic properties have been studied and characterized by various methods. Here, we distill the extensive experience we accumulated into a step-by-step protocol to fabricate atomically perfect LSCO films. The recipe includes substrate preparation, ozone generation and distillation, source calibration, the in situ monitoring of the film synthesis, post-growth annealing, and ex situ characterization. It discloses a reproducible way to fabricate single-crystal LSCO films for basic research and HTS electronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Semi-Dirac and Weyl fermions in transition metal oxides

We illustrate that a class of compounds with I4/mcm crystalline symmetry hosts three-dimensional semi-Dirac fermions. Unlike the known two-dimensional semi-Dirac points, the degeneracy of these three-dimensional semi-Dirac points is not lifted by spin-orbit coupling due to the protection by a nonsymmorphic symmetry—mirror reflection in the a–b plane and a translation along the c axis. This crystalline symmetry is found in tetragonal perovskite oxides, realizable in thin films by epitaxial strain that results in a 0 a 0 c - -type octahedral rotation. Interestingly, with broken time-reversal symmetry, two pairs of Weyl points emerge from the semi-Dirac points within the Brillouin zone, and an additional lattice distortion leads to an enhanced intrinsic anomalous Hall effect. The ability to tune the Berry phase by epitaxial strain can be useful in novel oxide-based electronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗