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At least 1,423 records · Page 79

Misfit layered Ca{sub 3}Co{sub 4}O{sub 9} as a high figure of merit p-type transparent conducting oxide film through solution processing

Ca{sub 3}Co{sub 4}O{sub 9} thin films synthesized through solution processing are shown to be high-performing, p-type transparent conducting oxides (TCOs). The synthesis method is a cost-effective and scalable process that consists of sol-gel chemistry, spin coating, and heat treatments. The process parameters can be varied to produce TCO thin films with sheet resistance as low as 5.7 kΩ/sq (ρ ≈ 57 mΩ cm) or with average visible range transparency as high as 67%. The most conductive Ca{sub 3}Co{sub 4}O{sub 9} TCO thin film has near infrared region optical transmission as high as 85%. The figure of merit (FOM) for the top-performing Ca{sub 3}Co{sub 4}O{sub 9} thin film (151 MΩ{sup −1}) is higher than FOM values reported in the literature for all other solution processed, p-type TCO thin films and higher than most others prepared by physical vapor deposition and chemical vapor deposition. Transparent conductivity in misfit layered oxides presents new opportunities for TCO compositions.

36 MATERIALS SCIENCE↗

Undercutting of defects in thin film protective coatings on polymer surfaces exposed to atomic oxygen

Protection for polymeric surfaces is needed to make them durable in the low Earth orbital environment, where oxidation by atomic oxygen is the predominant failure mechanism. Thin film coatings of oxides such as silicon dioxide are viable candidates to provide this protection, but concern has been voiced over the ability of these coatings to protect when defects are present in the coating due to surface anomalies occurring during the deposition process, handling, or micrometeoroid and debris bombardment in low Earth orbit. When a defected coating protecting a polymer substrate is exposed to atomic oxygen, the defect provides a pathway to the underlying polymer allowing oxidation and subsequent undercutting to occur. Defect undercutting was studied for sputter deposited coatings of silicon dioxide on polyimide Kapton. Preliminary results indicate that undercutting may be limited as long as the coating remains intact with the substrate. Therefore, coatings may not need to be defect free to give protection to the underlying surface.

Rutledge, Sharon K.↗

LPG ammonia and nitrogen dioxide gas sensing properties of nanostructured polypyrrole thin film

Nanostructured Polypyrrole thin film was synthesized by easy and economic chemical oxidative polymerization technique on glass at room temperature. The prepared thin film of Polypyrrole was characterized by optical absorbance study by UV-visible spectroscopy and electrical study by I-V measurement system. The optical absorbance spectrum of Polypyrrole shows two fundamental peaks in region of 420 and 890 nm, which confirms the formation of Polypyrrole on glass substrate. The I-V graph of nanostructured Polypyrrole represents the Ohmic nature. Furthermore, the thin film of Polypyrrole was investigated by Scanning electron microscopy for surface morphology study. The SEM micrograph represents spherical nanostructured morphology of Polypyrrole on glass substrate. In order to investigate gas sensing properties, 100 ppm of LPG, Ammonia and Nitrogen Dioxide were injected in the gas chamber and magnitude of resistance has been recorded as a function of time in second. It was observed that nanostructured Polypyrrole thin film shows good sensing behavior at room temperature.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

On fabrication procedures of Li-ion conducting garnets

Ceramic oxides exhibiting high lithium-ion mobility at room temperature receive broad attention as candidate electrolytes for lithium batteries. Lithium-stuffed garnets from the Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} group seem to be especially promising because of their high ionic conductivity at room temperature and their electrochemical stability. In this work, we discuss factors that affect formation of the garnet in its bulk form or in the form of thick and thin films. We demonstrate that zinc oxide can be applied as a sintering aid that facilitate the formation of the highly conducting cubic Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} garnet phase in a single-step sintering procedure. Based on our experience with the single-step sintering experiments, we successfully fabricated a thick-film membrane consisting of a garnet solid electrolyte using the tape casting technique. In order to reduce the thickness of the electrolyte even further we investigated the fabrication of a thin-film Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12} electrolyte by means of the pulsed laser deposition technique.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The composition of the Martian dark regions: Observations and analysis

Near infrared telescopic spectrophotometry for dark regions is present and interpreted using laboratory studies of iron bearing mineral mixtures and terrestrial oxidized and unoxidized basalts. Upon closer inspection (by spacecraft) the telescopic dark regions were found to consist of large scale intermixtures of bright soil (aeolian dust) and dark materials. The dark materials themselves consist of an intimate physical association of very fine grained ferric oxide bearing material with relatively high near infrared reflectance and darker, relatively unoxidized rocks or rock fragments. While these two components could exist finely intermixed in a soil, a number of lines of evidence indicate that the usual occurrence is probably a thin coating of physically bound oxidized material. The coated rocks are dark and generally clinopyroxene bearing. The shallow band depths and low overall reflectances indicate that opaque minerals such as magnetite are probably abundant.

Singer, R. B.↗

A Charge-Separated State that Lives for Almost a Second at a Conductive Metal Oxide Interface

Transparent conductive oxides (TCOs) are widely used commercially available materials for opto-electronic applications, yet they have received very little attention for dye-sensitization applications. Now, mesoporous thin films of conductive indium-doped tin oxide (ITO) nanocrystallites are shown to support long-lived charge separation with first-order recombination kinetics (k=1.5 s -1 ). A layer-by-layer technique was utilized to spatially arrange redox and/or chromophoric molecular components on ITO. Spectroelectrochemical measurements demonstrated that upon light absorption, each component provided a free-energy gradient to direct electron transfer at the conductive oxide interface. The long-lived nature of the photogenerated charge separated states provide favorable conditions for photocatalytic solar fuel production. Furthermore, the first-order recombination kinetics are most ideal for the fundamental understanding of interfacial charge separation dynamics.

catalysis (heterogeneous)↗

Design and evaluation of thin metal surface insulation for hypersonic flight

An all-metal insulation was studied as a thermal protection system for hypersonic vehicles. Key program goals included fabricating the insulation in thin packages which are optimized for high temperature insulation of an actively cooled aluminum structure, and the use of state-of-the-art alloys. The insulation was fabricated from 300 series stainless steel in thicknesses of 0.8 to 12 mm. The outer, 0.127 mm thick, skin was textured to accommodate thermal expansion and oxidized to increase emittance. The thin insulating package was achieved using an insulation concept consisting of foil radiation shields spaced within the package, and conical foil supports to carry loads from the skin and maintain package dimensions. Samples of the metal-insulation were tested to evaluate thermal insulation capability, rain and sand erosion resistance, high temperature oxidation resistance, applied load capability, and high temperature emittance.

Miller, R. C.↗

Accelerating Discovery of Solid‐State Thin‐Film Metal Dealloying for 3D Nanoarchitecture Materials Design through Laser Thermal Gradient Treatment

Thin‐film solid‐state metal dealloying (thin‐film SSMD) is a promising method for fabricating nanostructures with controlled morphology and efficiency, offering advantages over conventional bulk materials processing methods for integration into practical applications. Although machine learning (ML) has facilitated the design of dealloying systems, the selection of key thermal treatment parameters for nanostructure formation remains largely unknown and dependent on experimental trial and error. To overcome this challenge, a workflow enabling high‐throughput characterization of thermal treatment parameters is demonstrated using a laser‐based thermal treatment to create temperature gradients on single thin‐film samples of Nb‐Al/Sc and Nb‐Al/Cu. This continuous thermal space enables observation of dealloying transitions and the resulting nanostructures of interest. Through synchrotron X‐ray multimodal and high‐throughput characterization, critical transitions and nanostructures can be rapidly captured and subsequently verified using electron microscopy. The key temperatures driving chemical reactions and morphological evolutions are clearly identified. While the oxidation may influence nanostructure formation during thin‐film treatment, the dealloying process at the dealloying front involves interactions solely between the dealloying elements, highlighting the availability and viability of the selected systems. Further, this approach enables efficient exploration of the dealloying process and validation of ML predictions, thereby accelerating the discovery of thin‐film SSMD systems with targeted nanostructures.

36 MATERIALS SCIENCE↗

Electrodeposition synthesis of MnO{sub 2}/TiO{sub 2} nanotube arrays nanocomposites and their visible light photocatalytic activity

Highlights: • MnO{sub 2}/TiO{sub 2} nanotube arrays nanocomposites are prepared by electrodeposition. • MnO{sub 2}/TiO{sub 2} exhibits high visible light photocatalytic activity. • The results of XRD show the depositions are attributed to α-MnO{sub 2}. • A photocatalytic mechanism is discussed under visible light irradiation. - Abstract: MnO{sub 2}/TiO{sub 2} nanotube arrays nanocomposite photocatalysts have been synthesized through an electrodeposition method. X-ray powder diffraction analysis and X-ray photoelectron spectroscopy measurements reveal that the products of electrodeposition method are MnO{sub 2}. Scanning electron microscopy measurements suggest that the depositions are deposited on the surface or internal of the nanotube. UV–vis light absorbance spectra demonstrate the excellent adsorption properties of MnO{sub 2}/TiO{sub 2} over the whole region of visible light, which enables this novel photocatalytic material to possess remarkable activity in the photocatalytic degradation of acid Orange II under visible light radiation. Moreover, a possible photocatalytic mechanism is discussed.

36 MATERIALS SCIENCE↗

Multiferroic and magnetoelectric properties of CoFe{sub 2}O{sub 4}/Pb{sub 1−x}Sr{sub x}TiO{sub 3} composite films

To realize multiferroic and magnetoelectric properties, bi-layered nanocomposite films consisting of CoFe{sub 2}O{sub 4} (CFO)/Pb{sub 1−x}Sr{sub x}TiO{sub 3} (PST) phases (x = 0.1, 0.2, and 0.3) have been deposited on Pt/TiO{sub 2}/SiO{sub 2}/Si substrate by using a metallo-organic decomposition process. Both the PST perovskite and the CFO spinel phases are confirmed from X-ray diffraction patterns and Raman spectra of the composite films. The composite films exhibit room temperature multiferroic properties. The values of saturation magnetization (M{sub s}), remanent magnetization (M{sub r}), and coercive field (H{sub c}) of the composite films are in the range of 108–119 kA/m, 42–51 kA/m, and 44.5–64.1 kA/m, respectively. In addition, the saturation polarization (P{sub s}), remanent polarization (P{sub r}), and electrical coercive field (E{sub c}) are observed in the range of 11.3–14.4 μC/cm{sup 2}, 2.9–4.8 μC/cm{sup 2}, and 56–59.5 kV/cm, respectively. The dielectric response in the presence of applied magnetic field, H{sub dc} ∼ 238.6 kA/m shows a high magnetocapacitance value ∼385% at frequency 100 kHz for CFO/PST composite film with x = 0.1. The maximum magnetoelectric voltage co-efficient value, α{sub E} ∼ 380 kV/(m × T) has been achieved in the composite films with x = 0.1. The influence of elastic/and or interfacial strain on multiferroic magnetoelectric properties is evident from the results.

36 MATERIALS SCIENCE↗

Effect of structure on nonlinear optical properties in CaCu{sub 3}Ti{sub 4}O{sub 12} films

We report the third-order nonlinear optical properties of CaCu{sub 3}Ti{sub 4}O{sub 12} films with different preferred growth orientations on MgO and fused silica substrates. The films have (310)- and (220)-orientation on MgO and fused silica, respectively, due to the lattice-mismatch. Raman spectra further indicate different atom-bonding states in the films. The nonlinear optical measurements show the films possess the same self-defocusing behavior but with different values of nonlinear refraction, and changed signs of nonlinear absorption. The difference of optical nonlinearity in CaCu{sub 3}Ti{sub 4}O{sub 12} films is ascribed to different lattice parameters and intermediate levels induced by structure.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Thin-Film Selective Emitter

Direct conversion of thermal energy into electrical energy using a photovoltaic cell is called thermophotovoltaic energy conversion. One way to make this an efficient process is to have the thermal energy source be an efficient selective emitter of radiation. The emission must be near the band-gap energy of the photovoltaic cell. One possible method to achieve an efficient selective emitter is the use of a thin film of rare-earth oxides. The determination of the efficiency of such an emitter requires analysis of the spectral emittance of the thin film including scattering and reflectance at the vacuum-film and film-substrate interfaces. Emitter efficiencies (power emitted in emission band/total emitted power) in the range 0.35-0.7 are predicted. There is an optimum optical depth to obtain maximum efficiency. High emitter efficiencies are attained only for low (less than 0.05) substrate emittance values, both with and without scattering. The low substrate emittance required for high efficiency limits the choice of substrate materials to highly reflective metals or high-transmission materials such as sapphire.

Chubb, Donald L.↗

All-optical switching of an epsilon-near-zero plasmon resonance in indium tin oxide

Abstract Nonlinear optical devices and their implementation into modern nanophotonic architectures are constrained by their usually moderate nonlinear response. Recently, epsilon-near-zero (ENZ) materials have been found to have a strong optical nonlinearity, which can be enhanced through the use of cavities or nano-structuring. Here, we study the pump dependent properties of the plasmon resonance in the ENZ region in a thin layer of indium tin oxide (ITO). Exciting this mode using the Kretschmann-Raether configuration, we study reflection switching properties of a 60 nm layer close to the resonant plasmon frequency. We demonstrate a thermal switching mechanism, which results in a shift in the plasmon resonance frequency of 20 THz for a TM pump intensity of 70 GW cm −2 . For degenerate pump and probe frequencies, we highlight an additional two-beam coupling contribution, not previously isolated in ENZ nonlinear optics studies, which leads to an overall pump induced change in reflection from 1% to 45%.

36 MATERIALS SCIENCE↗

Reduced graphene oxide based silver sulfide hybrid films formed at a liquid/liquid interface

Free-standing, ultra-thin films of silver sulfide and reduced graphene oxide (RGO) based silver sulfide hybrids are prepared at a liquid/liquid interface employing in situ chemical reaction strategy. Ag{sub 2}S and RGO−Ag{sub 2}S hybrid films are characterized by various techniques such as UV-visible and photo luminescence spectroscopy, X-ray diffraction and scanning electron microscopy. The morphology of hybrid films consists of Ag{sub 2}S nanocrystals on RGO surface while Ag{sub 2}S films contains branched network of dendritic structures. RGO−Ag{sub 2}S exhibit interesting optical and electrical properties. The hybrid films absorb in the region 500–650 nm and show emission in the red region. A higher conductance is observed for the hybrid films arising from the RGO component. This simple low cost method can be extended to prepare other RGO based metal sulfides.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Thin‐Film Ferroelectrics

Abstract Over the last 30 years, the study of ferroelectric oxides has been revolutionized by the implementation of epitaxial‐thin‐film‐based studies, which have driven many advances in the understanding of ferroelectric physics and the realization of novel polar structures and functionalities. New questions have motivated the development of advanced synthesis, characterization, and simulations of epitaxial thin films and, in turn, have provided new insights and applications across the micro‐, meso‐, and macroscopic length scales. This review traces the evolution of ferroelectric thin‐film research through the early days developing understanding of the roles of size and strain on ferroelectrics to the present day, where such understanding is used to create complex hierarchical domain structures, novel polar topologies, and controlled chemical and defect profiles. The extension of epitaxial techniques, coupled with advances in high‐throughput simulations, now stands to accelerate the discovery and study of new ferroelectric materials. Coming hand‐in‐hand with these new materials is new understanding and control of ferroelectric functionalities. Today, researchers are actively working to apply these lessons in a number of applications, including novel memory and logic architectures, as well as a host of energy conversion devices.

Fernandez, Abel↗

Fractal analysis on Ag 2 O thin film using a data-driven approach

The synthesis of fractal Ag oxide (Ag 2 O) on the surface of Ag thin film has been achieved at room temperature by using Synchrotron X-ray irradiation. We have performed an automated quantitative analysis of a batch of 1879 fractal Ag 2 O patterns in a scanning electron microscopy (SEM) image within a radius of 2000 mm outward from the center of the X-ray beam. The morphology is similar to that of the diffusion-limited cluster aggregation (DLCA) model. The fractal dimension (D) of Ag 2 O is between 1.7 and 1.5 from the center to the edge. The area distribution density of fractal Ag 2 O follows a quadratic function with radius R. It is found that the branches’ number of fractal Ag 2 O is a key factor affecting the fractal dimension. The more branches the fractal has, the greater the D is. This is the first time that Ag fractal has been investigated by combining automated data analysis methods with batch experimental data. This data-driven approach provides a new research perspective for rationally regulating materials’ fractal morphology and performance.

36 MATERIALS SCIENCE↗

Multifunctional epitaxial systems on silicon substrates

Multifunctional heterostructures can exhibit a wide range of functional properties, including colossal magneto-resistance, magnetocaloric, and multiferroic behavior, and can display interesting physical phenomena including spin and charge ordering and strong spin-orbit coupling. However, putting this functionality to work remains a challenge. To date, most of the work reported in the literature has dealt with heterostructures deposited onto closely lattice matched insulating substrates such as DyScO{sub 3}, SrTiO{sub 3} (STO), or STO buffered Si(100) using concepts of lattice matching epitaxy (LME). However, strain in heterostructures grown by LME is typically not fully relaxed and the layers contain detrimental defects such as threading dislocations that can significantly degrade the physical properties of the films and adversely affect the device characteristics. In addition, most of the substrates are incompatible with existing CMOS-based technology, where Si (100) substrates dominate. This review discusses recent advances in the integration of multifunctional oxide and non-oxide materials onto silicon substrates. An alternative thin film growth approach, called “domain matching epitaxy,” is presented which identifies approaches for minimizing lattice strain and unwanted defects in large misfit systems (7%–25% and higher). This approach broadly allows for the integration of multifunctional materials onto silicon substrates, such that sensing, computation, and response functions can be combined to produce next generation “smart” devices. In general, pulsed laser deposition has been used to epitaxially grow these materials, although the concepts developed here can be extended to other deposition techniques, as well. It will be shown that TiN and yttria-stabilized zirconia template layers provide promising platforms for the integration of new functionality into silicon-based computer chips. This review paper reports on a number of thin-film heterostructure systems that span a variety of ferroelectric, multiferroic, magnetic, photocatalytic, and smart materials. Their properties have been extensively investigated and their functionality found to be comparable to films grown on single-crystal oxide substrates previously reported by researchers in this field. In addition, this review explores the utility of using laser processing to introduce stable defects in a controlled way and induce magnetism and engineer the optical and electrical properties of nonmagnetic oxides such as BaTiO{sub 3}, VO{sub 2}, NiO, and TiO{sub 2} as an alternative for incorporating additional magnetic and conducting layers into the structure. These significant materials advancements herald a flurry of exciting new advances in CMOS-compatible multifunctional devices.

36 MATERIALS SCIENCE↗