Microstructure and Oxidation of (La,Sr)CrO3-Added Ti3SiC2 Composites.

PubMed

Lee, Dong Bok

2015-11-01

Composites of Ti3SiC2-(10, 20, 40)wt% La0.8Sr0.2CrO3 were synthesized by hot pressing powders of Ti3SiC2 and La0.8Sr0.2CrO3. These powders reacted to form stable TiC carbides and LaTiO3, Cr2Ti4O11, La2O3, and SrCrO4 oxides during hot pressing. The composites consisted primarily of a fine TiC-rich matrix phase and coarse Ti3SiC2 dispersoids. The addition of oxidation-immune La0.8Sr0.2CrO3 into Ti3SiC2 increased the oxidation rate because TiC formed during hot pressing. During oxidation of the composites at 800-1000 degrees C for 100 h in air, Ti diffused outward to form an outer rutile-TiO2 layer, and oxygen transported inward to form an inner oxide layer.

Initial oxidation of pure and K doped NiTi shape memory alloys

NASA Astrophysics Data System (ADS)

Tollefsen, H.; Raaen, S.

2009-06-01

Initial oxidation of pure and K doped nitinol has been studied by photoelectron spectroscopy. The composition of the TiOx layer that forms on the surface is found to depend on the temperature during oxidation. The oxidation at high temperatures results in enhanced formation of lower oxides, whereas TiO2 predominates for oxidation at lower temperatures, e.g., 70 °C. Submonolayer coverage of K on NiTi enhances the formation of TiO2 on the expense of lower oxides, which is of consequence for formation of a protective oxide layer and biocompatibility. Oxidation in the martensitic phase was found to be independent of temperature for temperatures between -40 and 10 °C, whereas in the austenitic phase the oxide growth is thermally activated.

Oxidation characteristics of Ti-25Al-10Nb-3V-1Mo intermetallic alloy

NASA Technical Reports Server (NTRS)

Wallace, Terryl A.; Clark, Ronald K.; Sankaran, Sankara N.; Wiedemann, Karl E.

1990-01-01

Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x ray diffraction techniques, electron microprobe analysis, and energy dispersive x ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.

Influences of Indium Tin Oxide Layer on the Properties of RF Magnetron-Sputtered (BaSr)TiO3 Thin Films on Indium Tin Oxide-Coated Glass Substrate

NASA Astrophysics Data System (ADS)

Kim, Tae Song; Oh, Myung Hwan; Kim, Chong Hee

1993-06-01

Nearly stoichiometric ((Ba+Sr)/Ti=1.08-1.09) and optically transparent (BaSr)TiO3 thin films were deposited on an indium tin oxide (ITO)-coated glass substrate by means of rf magnetron sputtering for their application to the insulating layer of an electroluminescent flat panel display. The influence of the ITO layer on the properties of (BaSr)TiO3 thin films deposited on the ITO-coated substrate was investigated. The ITO layer did not affect the crystallographic orientation of (BaSr)TiO3 thin film, but enhanced the grain growth. Another effect of the ITO layer on (BaSr)TiO3 thin films was the interdiffusion phenomenon, which was studied by means of secondary ion mass spectrometry (SIMS). As the substrate temperature increased, interdiffusion intensified at the interface not only between the grown film and ITO layer but also between the ITO layer and base glass substrate. The refractive index (nf) of (BaSr)TiO3 thin film deposited on a bare glass substrate was 2.138-2.286, as a function of substrate temperature.

Ternary Oxides in the TiO2-ZnO System as Efficient Electron-Transport Layers for Perovskite Solar Cells with Efficiency over 15.

PubMed

Yin, Xiong; Xu, Zhongzhong; Guo, Yanjun; Xu, Peng; He, Meng

2016-11-02

Perovskite solar cells, which utilize organometal-halide perovskites as light-harvesting materials, have attracted great attention due to their high power conversion efficiency (PCE) and potentially low cost in fabrication. A compact layer of TiO 2 or ZnO is generally applied as electron-transport layer (ETL) in a typical perovskite solar cell. In this study, we explored ternary oxides in the TiO 2 -ZnO system to find new materials for the ETL. Compact layers of titanium zinc oxides were readily prepared on the conducting substrate via spray pyrolysis method. The optical band gap, valence band maximum and conduction band minimum of the ternary oxides varied significantly with the ratio of Ti to Zn, surprisingly, in a nonmonotonic way. When a zinc-rich ternary oxide was applied as ETL for the device, a PCE of 15.10% was achieved, comparable to that of the device using conventional TiO 2 ETL. Interestingly, the perovskite layer deposited on the zinc-rich ternary oxide is stable, in sharp contrast with that fabricated on a ZnO layer, which will turn into PbI 2 readily when heated. These results indicate that potentially new materials with better performance can be found for ETL of perovskite solar cells in ternary oxides, which deserve more exploration.

Enhancing antimicrobial activity of TiO2/Ti by torularhodin bioinspired surface modification.

PubMed

Ungureanu, Camelia; Dumitriu, Cristina; Popescu, Simona; Enculescu, Monica; Tofan, Vlad; Popescu, Marian; Pirvu, Cristian

2016-02-01

Implant-associated infections are a major cause of morbidity and mortality. This study was performed using titanium samples coated by anodization with a titanium dioxide (TiO2) shielded nanotube layer. TiO2/Ti surface was modified by simple immersion in torularhodin solution and by using a mussel-inspired method based on polydopamine as bio adhesive for torularhodin immobilization. SEM analysis revealed tubular microstructures of torularhodin and the PDA ability to function as a catchy anchor between torularhodin and TiO2 surface. Corrosion resistance was associated with TiO2 barrier oxide layer and nano-organized oxide layer and the torularhodin surface modification does not bring significant changes in resistance of the oxide layer. Our results demonstrated that the torularhodin modified TiO2/Ti surface could effectively prevent adhesion and proliferation of Escherichia coli, Staphylococcus aureus, Enterococcus faecalis, Bacillus subtilis, and Pseudomonas aeruginosa. The new modified titanium surface showed good biocompatibility and well-behaved haemocompatibility. This biomaterial with enhanced antimicrobial activity holds great potential for future biomedical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

TiO2/ZnO and ZnO/TiO2 core/shell nanofibers prepared by electrospinning and atomic layer deposition for photocatalysis and gas sensing

NASA Astrophysics Data System (ADS)

Boyadjiev, Stefan I.; Kéri, Orsolya; Bárdos, Péter; Firkala, Tamás; Gáber, Fanni; Nagy, Zsombor K.; Baji, Zsófia; Takács, Máté; Szilágyi, Imre M.

2017-12-01

In the present work, core TiO2 and ZnO oxide nanofibers were prepared by electrospinning, then shell oxide (ZnO, TiO2) layers were deposited on them by atomic layer deposition (ALD). The aim of preparing ZnO and TiO2 nanofibers, as well as ZnO/TiO2 and TiO2/ZnO nanocomposites is to study the interaction between the oxide materials when a pure oxide fiber is covered with thin film of the other oxide, and explore the influence of exchanging the core and shell materials on their photocatalytic and gas sensing properties. The composition, structure and morphology of the pure and composite nanofibers were studied by SEM-EDX, TEM, XRD, FTIR, UV-vis and Raman. The photocatalytic activity of the as-prepared materials was analyzed by UV-vis spectroscopy through decomposing aqueous methyl orange under UV irradiation. The gas sensing of the nanofibers was investigated by detecting 100 ppm NH3 at 150 and 220 °C using interdigital electrode based sensors.

Porous TiO₂ surface formed on nickel-titanium alloy by plasma electrolytic oxidation: a prospective polymer-free reservoir for drug eluting stent applications.

PubMed

Huan, Zhiguang; Fratila-Apachitei, Lidy E; Apachitei, Iulian; Duszczyk, Jurek

2013-07-01

In this study, a porous oxide layer was formed on the surface of nickel-titanium alloy (NiTi) by plasma electrolytic oxidation (PEO) with the aim to produce a polymer-free drug carrier for drug eluting stent (DES) applications. The oxidation was performed galvanostatically in concentrated phosphoric acid electrolyte at low temperature. It was found that the response of NiTi substrate during the PEO process was different from that of bulk Ti, since the presence of large amount of Ni delayed the initial formation of a compact oxide layer that is essential for the PEO to take place. Under optimized PEO conditions, the resultant surface showed porosity, pore density and oxide layer thickness of 14.11%, 2.40 × 10⁵ pores/mm² and 0.8 μm, respectively. It was additionally noted that surface roughness after PEO did not significantly increase as compared with that of original NiTi substrate and the EDS analyses revealed a decrease in Ni/Ti ratio on the surface after PEO. The cross-section morphology showed no discontinuity between the PEO layer and the NiTi substrate. Furthermore, wettability and surface free energy of the NiTi substrate increased significantly after PEO treatment. The PEO process could be successfully translated to NiTi stent configuration proving for the first time its feasibility for such a medical device and offering potential for development of alternative, polymer-free drug carriers for NiTi DES. Copyright © 2013 Wiley Periodicals, Inc.

Surface oxidation of NiTi shape memory alloy.

PubMed

Firstov, G S; Vitchev, R G; Kumar, H; Blanpain, B; Van Humbeeck, J

2002-12-01

Mechanically polished NiTi alloy (50 at% Ni) was subjected to heat treatment in air in the temperature range 300-800 degrees C and characterised by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. Thermogravimetry measurements were carried out to investigate the kinetics of oxidation. The results of thermodynamic calculations were compared to the experimental observations. It was found that NiTi alloy exhibits different oxidation behaviour at temperatures below and above 500 degrees C. A Ni-free zone was found in the oxide layer for oxidation temperatures of 500 degrees C and 600 degrees C. The oxidation at 500 degrees C produces a smooth protective nickel-free oxide layer with a relatively small amount of Ni species at the air/oxide interface, which is in favour of good biocompatibility of NiTi implants. The oxidation mechanism for the NiTi shape memory alloy is discussed. Copyright 2002 Elsevier Science Ltd.

Ultra-fine structural characterization and bioactivity evaluation of TiO2 nanotube layers.

PubMed

Jang, JaeMyung; Kwon, TaeYub; Kim, KyoHan

2008-10-01

For an application as biomedical materials of high performance with a good biocompatibility, the TiO2 nanotube-type oxide film on Ti substrate has been fabricated by electrochemical method, and the effects of surface characteristics of TiO2 naotube layer have been investigated. The surface morphology of TiO2 nanotube layer depends on factors such as anodizing time, current density, and electrolyte temperature. Moreover, the cell and pore size gradually were increased with the passage of anodizing time. X-ray diffraction (XRD) results indicated that the TiO2 nanotube layer formed in acidic electrolytes was mainly composed of anatase structure containing rutile. From the analysis of chemical states of TiO2 nanotube layer using X-ray photoelectron spectroscopy (XPS), Ti2p, P2p and O1s were observed in the nanotubes layer, which were penetrated from the electrolyte into the oxide layer during anodic process. The incorporated phosphate species were found mostly in the forms of HPO4-, PO4-, and PO3-. From the result of biological evaluation in simulated body fluid (SBF) the TiO2 nanotube layer was effective for bioactive property.

Enhancement of wear and corrosion resistance of low modulus β-type Zr-20Nb-xTi (x=0, 3) dental alloys through thermal oxidation treatment.

PubMed

Zhang, Jianfeng; Gan, Xiaxia; Tang, Hongqun; Zhan, Yongzhong

2017-07-01

In order to obtain material with low elastic modulus, good abrasion resistance and high corrosion stability as screw for dental implant, the biomedical Zr-20Nb and Zr-20Nb-3Ti alloy with low elastic modulus were thermal oxidized respectively at 700°C for 1h and 600°C for 1.25h to obtain the compact oxidized layer to improve its wear resistance and corrosion resistance. The results show that smooth compact oxidized layer (composed of monoclinic ZrO 2 , tetragonal ZrO 2 and 6ZrO 2 -Nb 2 O 5 ) with 22.6μm-43.5μm thickness and 1252-1306HV hardness can be in-situ formed on the surface of the Zr-20Nb-xTi (x=0, 3). The adhesion of oxidized layers to the substrates is determined to be 58.35-66.25N. The oxidized Zr-20Nb-xTi alloys reveal great improvement of the pitting corrosion resistance in comparison with the un-oxidized alloys. In addition, the oxidized Zr-20Nb-3Ti exhibits sharply reduction of the corrosion rates and the oxidized Zr-20Nb shows higher corrosion rates than un-oxidized alloys, which is relevant with the content of the t-ZrO 2 . Wear test in artificial saliva demonstrates that the wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) are superior to pure Ti. All of the un-oxidized Zr-20Nb-xTi (x=0, 3) alloys suffer from serious adhesive wear due to its high plasticity. Because of the protection from compact oxide layer with high adhesion and high hardness, the coefficients of friction and wear losses of the oxidized Zr-20Nb-xTi (x=0, 3) alloys decrease 50% and 95%, respectively. The defects on the oxidized Zr-20Nb have a negative effect on the friction and wear properties. In addition, after the thermal oxidation, compression test show that elastic modulus and strength of Zr-20Nb-xTi (x=0, 3) increase slightly with plastic deformation after 40% of transformation. Furthermore, stripping of the oxidized layer from the alloy matrix did not occur during the whole experiments. As the surface oxidized Zr-20Nb-3Ti alloy has a combination of excellent performance such as high chemical stability, good wear resistance performance and low elastic modulus, moderate strength, it is considered an alternative material as dental implant. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrical level of defects in single-layer two-dimensional TiO2

NASA Astrophysics Data System (ADS)

Song, X. F.; Hu, L. F.; Li, D. H.; Chen, L.; Sun, Q. Q.; Zhou, P.; Zhang, D. W.

2015-11-01

The remarkable properties of graphene and transition metal dichalcogenides (TMDCs) have attracted increasing attention on two-dimensional materials, but the gate oxide, one of the key components of two-dimensional electronic devices, has rarely reported. We found the single-layer oxide can be used as the two dimensional gate oxide in 2D electronic structure, such as TiO2. However, the electrical performance is seriously influenced by the defects existing in the single-layer oxide. In this paper, a nondestructive and noncontact solution based on spectroscopic ellipsometry has been used to detect the defect states and energy level of single-layer TiO2 films. By fitting the Lorentz oscillator model, the results indicate the exact position of defect energy levels depends on the estimated band gap and the charge state of the point defects of TiO2.

Oxidation behavior of Al/Cr coating on Ti2AlNb alloy at 900 °C

NASA Astrophysics Data System (ADS)

Yang, Zhengang; Liang, Wenping; Miao, Qiang; Chen, Bowen; Ding, Zheng; Roy, Nipon

2018-04-01

In this paper, the Al/Cr coating was fabricated on the surface of Ti2AlNb alloy via rf magnetron sputtering and double glow treatment to enhance oxidation resistance. The protective coating with an outer layer of Al and inner layer of Cr has great bonding strength due to the in-diffusion of Cr and the inter-diffusion between Al and Cr to form Al-Cr alloyed layer which has great hardness. Acoustic emission curve which was detected via WS-2005 scratch tester indicates the bonding strength between Al/Cr coating and substrate is great. Morphology of Ti2AlNb alloy with Al/Cr coating after scratch test shows that the scratch is smooth without disbanding, and the depth and breadth of scratch are changed uniformly. The mass change was reduced after oxidation test due to the Al/Cr protective coating. Isothermal oxidation test at 900 °C was researched. Results indicate that Al/Cr coating provided oxidation resistance of Ti2AlNb alloy with prolonged air exposure at 900 °C. Al2O3 was detected by XRD patterns and SEM images, and was formed on the surface of Ti2AlNb alloy to protect substrate during oxidation test. A certain content of Cr is beneficial for the formation of Al2O3. Besides, Cr2O3 was produced under Al2O3 by outward diffusion of Cr to protect substrate sequentially, no cracks were discovered on Al/Cr protective coating. The process of Ti outward diffusion into surface was suppressive due to integration of Cr-Ti and Al-Ti intermetallics. A steady, adherent and continuous coated layer of Al/Cr on Ti2AlNb alloy increases oxidation resistance.

Growth of aluminum-free porous oxide layers on titanium and its alloys Ti-6Al-4V and Ti-6Al-7Nb by micro-arc oxidation.

PubMed

Duarte, Laís T; Bolfarini, Claudemiro; Biaggio, Sonia R; Rocha-Filho, Romeu C; Nascente, Pedro A P

2014-08-01

The growth of oxides on the surfaces of pure Ti and two of its ternary alloys, Ti-6Al-4V and Ti-6Al-7Nb, by micro-arc oxidation (MAO) in a pH 5 phosphate buffer was investigated. The primary aim was to form thick, porous, and aluminum-free oxide layers, because these characteristics favor bonding between bone and metal when the latter is implanted in the human body. On Ti, Ti-6Al-4 V, and Ti-6Al-7Nb, the oxides exhibited breakdown potentials of about 200 V, 130 V, and 140 V, respectively, indicating that the oxide formed on the pure metal is the most stable. The use of the MAO procedure led to the formation of highly porous oxides, with a uniform distribution of pores; the pores varied in size, depending on the anodizing applied voltage and time. Irrespective of the material being anodized, Raman analyses allowed us to determine that the oxide films consisted mainly of the anatase phase of TiO2, and XPS results indicated that this oxide is free of Al and any other alloying element. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of Functional Inorganic Materials by Soft Chemical Process Using Ion-Exchange Reactions

NASA Astrophysics Data System (ADS)

Feng, Qi

Our study on soft chemical process using the metal oxide and metal hydroxide nanosheets obtained by exfoliation their layered compounds were reviewed. Ni(OH)2⁄MnO2 sandwich layered nanostructure can be prepared by layer by-layer stacking of exfoliated manganese oxide nanosheets and nickel hydroxide layers. Manganese oxide nanotubes can be obtained by curling the manganese oxide nanosheets using the cationic surfactants as the template. The layered titanate oriented thin film can be prepared by restacking the titanate nanosheets on a polycrystalline substrate, and transformed to the oriented BaTiO3 and TiO2 thin films by the topotactic structural transformation reactions, respectively. The titanate nanosheets can be transformed anatase-type TiO2 nanocrystals under hydrothermal conditions. The TiO2 nanocrystals are formed by a topotactic structural transformation reaction. The TiO2 nanocrystals prepared by this method expose specific crystal plane on their surfaces, and show high photocatalytic activity and high dye adsorption capacity for high performance dye-sensitized solar cell. A series of layered basic metal salt (LBMS) compounds were prepared by hydrothermal reactions of transition metal hydroxides and organic acids. We succeeded in the exfoliation of these LBMS compounds in alcohol solvents, and obtained the transition metal hydroxide nanosheets for the first time.

Understanding the mechanisms of interfacial reactions during TiO{sub 2} layer growth on RuO{sub 2} by atomic layer deposition with O{sub 2} plasma or H{sub 2}O as oxygen source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaker, A.; Szkutnik, P. D.; Pointet, J.

2016-08-28

In this paper, TiO{sub 2} layers grown on RuO{sub 2} by atomic layer deposition (ALD) using tetrakis (dimethyla-mino) titanium (TDMAT) and either oxygen plasma or H{sub 2}O as oxygen source were analyzed using X-ray diffraction (XRD), Raman spectroscopy, and depth-resolved X-ray Photoelectron spectroscopy (XPS). The main objective is to investigate the surface chemical reactions mechanisms and their influence on the TiO{sub 2} film properties. The experimental results using XRD show that ALD deposition using H{sub 2}O leads to anatase TiO{sub 2} whereas a rutile TiO{sub 2} is obtained when oxygen-plasma is used as oxygen source. Depth-resolved XPS analysis allows tomore » determine the reaction mechanisms at the RuO{sub 2} substrate surface after growth of thin TiO{sub 2} layers. Indeed, the XPS analysis shows that when H{sub 2}O assisted ALD process is used, intermediate Ti{sub 2}O{sub 3} layer is obtained and RuO{sub 2} is reduced into Ru as evidenced by high resolution transmission electron microscopy. In this case, there is no possibility to re-oxidize the Ru surface into RuO{sub 2} due to the weak oxidation character of H{sub 2}O and an anatase TiO{sub 2} layer is therefore grown on Ti{sub 2}O{sub 3}. In contrast, when oxygen plasma is used in the ALD process, its strong oxidation character leads to the re-oxidation of the partially reduced RuO{sub 2} following the first Ti deposition step. Consequently, the RuO{sub 2} surface is regenerated, allowing the growth of rutile TiO{sub 2}. A surface chemical reaction scheme is proposed that well accounts for the observed experimental results.« less

Composition of low-strength solder joints in solar-concentrator-cell arrays

NASA Astrophysics Data System (ADS)

Chamberlain, M. B.; Nordstrom, T. V.

Bond strengths of Cu strips soldered to the backside metallization of solar concentrator cells were found to be unacceptably low. To determine whether contaminants in the cell metallization caused these low strengths, unsoldered cells and soldered cells were characterized by scanning Auger microscopy. The backside metallization consisted of a 5 micrometers Ag conductor layer, a 150 nm Pd diffusion barrier and a 150 nm Ti adhesion layer next to an Al ohmic contact layer on the Si cell. The analysis showed that the Ti layer are partially oxidized during soldering, that Pb from the Pb-5 wt % Sn - 2.5 wt % Ag solder segregated during soldering to the Pd-oxidized Ti interface, and that low strength fractures occurred in this Pb layer at the Pd-oxidized Ti interface. The problem was solved by changing the ambient gas used during soldering from N2 to forming gas (80% N2 + 20% H2).

Peculiarities of structure formation of layered metal-oxide system Ti-Ta-(Ti,Ta)xOy during electro-spark alloying and thermally stimulated modification

NASA Astrophysics Data System (ADS)

Fomina, Marina A.; Koshuro, Vladimir A.; Fomin, Aleksandr A.; Rodionov, Igor V.; Skaptsov, Aleksandr A.; Zakharevich, Andrey M.; Aman, Alexander; Oseev, Aleksandr; Hirsch, Soeren; Majcherek, Soeren

2016-04-01

The study focuses on high-performance combined electro-spark alloying of titanium and titanium alloy (VT1-0, VT16) surface and porous matrix structure oxidation. The metal-oxide coatings morphology is the result of melt drop transfer, heat treatment, and oxidation. The study establishes the influence of technological regimes of alloying and oxidation on morphological heterogeneity of biocompatible layered metal-oxide system Ti-Ta-(Ti,Ta)xOy. It was found that during electro-spark alloying the concentration of tantalum on the titanium surface ranges from 0.1 to 3.2 at.%. Morphology of the deposited splats is represented by uniformly grown crystals of titanium and tantalum oxides, which increase from nano- to submicron size.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, S. K.; Mohan, S.; Bysakh, S.

The formation of surface oxide layer as well as compositional changes along the thickness for NiTi shape memory alloy thin films deposited by direct current magnetron sputtering at substrate temperature of 300 °C in the as-deposited condition as well as in the postannealed (at 600 °C) condition have been thoroughly studied by using secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, and scanning transmission electron microscopy-energy dispersive x-ray spectroscopy techniques. Formation of titanium oxide (predominantly titanium dioxide) layer was observed in both as-deposited and postannealed NiTi films, although the oxide layer was much thinner (8 nm) in as-deposited condition. The depletionmore » of Ti and enrichment of Ni below the oxide layer in postannealed films also resulted in the formation of a graded microstructure consisting of titanium oxide, Ni{sub 3}Ti, and B2 NiTi. A uniform composition of B2 NiTi was obtained in the postannealed film only below a depth of 200–250 nm from the surface. Postannealed film also exhibited formation of a ternary silicide (Ni{sub x}Ti{sub y}Si) at the film–substrate interface, whereas no silicide was seen in the as-deposited film. The formation of silicide also caused a depletion of Ni in the film in a region ∼250–300 nm just above the film substrate interface.« less

Investigations into the structure of PEO-layers for understanding of layer formation

NASA Astrophysics Data System (ADS)

Friedemann, A. E. R.; Thiel, K.; Haßlinger, U.; Ritter, M.; Gesing, Th. M.; Plagemann, P.

2018-06-01

Plasma electrolytic oxidation (PEO) is a type of high-voltage anodic oxidation process capable of producing a thick oxide layer with a wide variety of structural and chemical properties influenced by the electrolytic system. This process enables the combined adjustment of various characteristics, i.e. the morphology and chemical composition. The procedure facilitates the possibility of generating an individual structure as well as forming a crystalline surface in a single step. A highly porous surface with a high crystalline content consisting of titanium dioxide phases is ensured through the process of plasma electrolytic oxidizing pure titanium. In the present study plasma electrolytic oxidized TiO2-layers were investigated regarding their crystallinity through the layer thickness. The layers were prepared with a high applied voltage of 280 V to obtain a PEO-layer with highly crystalline anatase and rutile amounts. Raman spectroscopy and electron backscatter diffraction (EBSD) were selected to clarify the structure of the oxide layer with regard to its crystallinity and phase composition. The composition of the TiO2-phases is more or less irregularly distributed as a result of the higher energy input on the uppermost side of the layer. Scanning transmission electron microscopy (STEM) provided a deeper understanding of the structure and the effects of plasma discharges on the layer. It was observed that the plasma discharges have a strong influence on crystallite formation on top of the oxide layer and also at the boundary layer to the titanium substrate. Therefore, small crystallites of TiO2 could be detected in these regions. In addition, it was shown that amorphous TiO2 phases are formed around the characteristic pore structures, which allows the conclusion to be drawn that a rapid cooling from the gas phase had to take place in these areas.

Microstructure and high temperature oxidation resistance of Ti-Ni gradient coating on TA2 titanium alloy fabricated by laser cladding

NASA Astrophysics Data System (ADS)

Liu, Fencheng; Mao, Yuqing; Lin, Xin; Zhou, Baosheng; Qian, Tao

2016-09-01

To improve the high temperature oxidation resistance of TA2 titanium alloy, a gradient Ni-Ti coating was laser cladded on the surface of the TA2 titanium alloy substrate, and the microstructure and oxidation behavior of the laser cladded coating were investigated experimentally. The gradient coating with a thickness of about 420-490 μm contains two different layers, e.g. a bright layer with coarse equiaxed grain and a dark layer with fine and columnar dendrites, and a transition layer with a thickness of about 10 μm exists between the substrate and the cladded coating. NiTi, NiTi2 and Ni3Ti intermetallic compounds are the main constructive phases of the laser cladded coating. The appearance of these phases enhances the microhardness, and the dense structure of the coating improves its oxidation resistance. The solidification procedure of the gradient coating is analyzed and different kinds of solidification processes occur due to the heat dissipation during the laser cladding process.

High temperature solar selective coatings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, Cheryl E

Improved solar collectors (40) comprising glass tubing (42) attached to bellows (44) by airtight seals (56) enclose solar absorber tubes (50) inside an annular evacuated space (54. The exterior surfaces of the solar absorber tubes (50) are coated with improved solar selective coatings {48} which provide higher absorbance, lower emittance and resistance to atmospheric oxidation at elevated temperatures. The coatings are multilayered structures comprising solar absorbent layers (26) applied to the meta surface of the absorber tubes (50), typically stainless steel, topped with antireflective Savers (28) comprising at least two layers 30, 32) of refractory metal or metalloid oxides (suchmore » as titania and silica) with substantially differing indices of refraction in adjacent layers. Optionally, at least one layer of a noble metal such as platinum can be included between some of the layers. The absorbent layers cars include cermet materials comprising particles of metal compounds is a matrix, which can contain oxides of refractory metals or metalloids such as silicon. Reflective layers within the coating layers can comprise refractory metal silicides and related compounds characterized by the formulas TiSi. Ti.sub.3SiC.sub.2, TiAlSi, TiAN and similar compounds for Zr and Hf. The titania can be characterized by the formulas TiO.sub.2, Ti.sub.3O.sub.5. TiOx or TiO.sub.xN.sub.1-x with x 0 to 1. The silica can be at least one of SiO.sub.2, SiO.sub.2x or SiO.sub.2xN.sub.1-x with x=0 to 1.« less

Improved out-coupling efficiency of organic light emitting diodes fabricated on a TiO2 planarization layer with embedded Si oxide nanostructures

NASA Astrophysics Data System (ADS)

Sung, Young Hoon; Jung, Pil-Hoon; Han, Kyung-Hoon; Kim, Yang Doo; Kim, Jang-Joo; Lee, Heon

2017-10-01

In order to increase the out-coupling efficiency of organic light emitting diodes, conical Si oxide nanostructures were formed on a glass substrate using nanoimprint lithography with hydrogen silsesquioxane. Then, the substrate was planarized with TiO2 nanoparticles. Since TiO2 nanoparticles have a higher refractive index than Si oxide, the surface of substrate is physically flat, but optically undulated in a manner that enables optical scattering and suppression of total internal reflection. Subsequently, OLEDs formed on a substrate with nanostructured Si oxide and a TiO2 planarization layer exhibit a 25% increase in out-coupling efficiency by suppressing total internal reflection.

Two-dimensional electron gas in tricolor oxide interfaces

NASA Astrophysics Data System (ADS)

Cao, Yanwei; Kareev, Michael; Liu, Xiaoran; Middey, Srimanta; Meyers, Derek; Tchakhalian, Jak

2014-03-01

Understanding and manipulating spin of electrons in nanometer scale is the main challenge of current spintronics, recent emergent two-dimensional electron gas in oxide interface provides a good platform to investigate the spin behavior by covering an insulating magnetic oxide layer. In this work, take titanates as an example, ultra-thin tricolor (tri-compound) titanate superlattices ([LaTiO3/SrTiO3/YTiO3]) were grown in a layer-by-layer way by pulsed laser deposition. High sample quality and their electronic structures were characterized by the combination of in-situ photoelectron and ex-situ structure and surface morphology probes. Temperature-dependent sheet resistance indicates the presence of metallic interfaces in both [LaTiO3 /SrTiO3 ] and all the tricolor structures, whereas a [YTiO3 /SrTiO3] bi-layer shows insulating behavior. The tricolor titanate superlattices provide an opportunity to induce tunable spin-polarization into the two-dimensional electron gas (2DEG) with Mott carriers.

Novel Combination of Efficient Perovskite Solar Cells with Low Temperature Processed Compact TiO2 Layer via Anodic Oxidation.

PubMed

Du, Yangyang; Cai, Hongkun; Wen, Hongbin; Wu, Yuxiang; Huang, Like; Ni, Jian; Li, Juan; Zhang, Jianjun

2016-05-25

In this work, a facile and low temperature processed anodic oxidation approach is proposed for fabricating compact and homogeneous titanium dioxide film (AO-TiO2). In order to realize morphology and thickness control of AO-TiO2, the theory concerning anodic oxidation (AO) is unveiled and the influence of relevant parameters during the process of AO such as electrolyte ingredient and oxidation voltage on AO-TiO2 formation is observed as well. Meanwhile, we demonstrate that the planar perovskite solar cells (p-PSCs) fabricated in ambient air and utilizing optimized AO-TiO2 as electron transport layer (ETL) can deliver repeatable power conversion efficiency (PCE) over 13%, which possess superior open-circuit voltage (Voc) and higher fill factor (FF) compared to its counterpart utilizing conventional high temperature processed compact TiO2 (c-TiO2) as ETL. Through a further comparative study, it is indicated that the improvement of device performance should be attributed to more effective electron collection from perovskite layer to AO-TiO2 and the decrease of device series resistance. Furthermore, hysteresis effect about current density-voltage (J-V) curves in TiO2-based p-PSCs is also unveiled.

Fabrication of hydroxyapatite and TiO 2 nanorods on microarc-oxidized titanium surface using hydrothermal treatment

NASA Astrophysics Data System (ADS)

Song, Ho-Jun; Kim, Ji-Woo; Kook, Min-Suk; Moon, Won-Jin; Park, Yeong-Joon

2010-09-01

AC-type microarc oxidation (MAO) and hydrothermal treatment techniques were used to enhance the bioactivity of commercially pure titanium (CP-Ti). The porous TiO 2 layer fabricated by the MAO treatment had a dominant anatase structure and contained Ca and P ions. The MAO-treated specimens were treated hydrothermally to form HAp crystallites on the titanium oxide layer in an alkaline aqueous solution (OH-solution) or phosphorous-containing alkaline solution (POH-solution). A small number of micro-sized hydroxyapatite (HAp) crystallites and a thin layer composed of nano-sized HAps were formed on the Ti-MAO-OH group treated hydrothermally in an OH-solution, whereas a large number of micro-sized HAp crystallites and dense anatase TiO 2 nanorods were formed on the Ti-MAO-POH group treated hydrothermally in a POH-solution. The layer of bone-like apatite that formed on the surface of the POH-treated sample after soaking in a modified simulated body fluid was thicker than that on the OH-treated samples.

Periodic oxidation for fabricating titanium oxynitride thin films via atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iwashita, Shinya, E-mail: shinya.iwashita@tel.com; Aoyama, Shintaro; Nasu, Masayuki

2016-01-15

This paper demonstrates thermal atomic layer deposition (ALD) combined with periodic oxidation for synthesizing titanium oxynitride (TiON) thin films. The process used a typical ALD reactor for the synthesis of titanium nitride (TiN) films wherein oxygen was supplied periodically between the ALD-TiN cycles. The great advantage of the process proposed here was that it allowed the TiN films to be oxidized efficiently. Also, a uniform depth profile of the oxygen concentration in the films could be obtained by tuning the oxidation conditions, allowing the process to produce a wide variety of TiON films. The resistivity measurement is a convenient methodmore » to confirm the reproducibility of metal film fabrication but may not be applicable for TiON films depending upon the oxidation condition because the films can easily turn into insulators when subjected to periodic oxidation. Therefore, an alternative reproducibility confirmation method was required. In this study, spectroscopic ellipsometry was applied to monitor the variation of TiON films and was able to detect changes in film structures such as conductor–insulator transitions in the TiON films.« less

Origin of Fe-Ti Oxide Mineralization in the Middle Paleoproterozoic Elet'ozero Syenite-Gabbro Intrusive Complex (Northern Karelia, Russia)

NASA Astrophysics Data System (ADS)

Sharkov, E. V.; Chistyakov, A. V.; Shchiptsov, V. V.; Bogina, M. M.; Frolov, P. V.

2018-03-01

Magmatic oxide mineralization widely developed in syenite-gabbro intrusive complexes is an important Fe and Ti resource. However, its origin is hotly debatable. Some researchers believe that the oxide ores were formed through precipitation of dense Ti-magnetite in an initial ferrogabbroic magma (Bai et al., 2012), whereas others consider them as a product of immiscible splitting of Fe-rich liquid during crystallization of Fe-Ti basaltic magma (Zhou et al., 2013). We consider this problem with a study of the Middle Paleoproterozoic (2086 ± 30 Ma) Elet'ozero Ti-bearing layered intrusive complex in northern Karelia (Baltic Shield). The first ore-bearing phase of the complex is mainly made up of diverse ferrogabbros, with subordinate clinopyroxenites and peridotites. Fe-Ti oxides (magnetite, Ti-magnetite, and ilmenite) usually account for 10-15 vol %, reaching 30-70% in ore varieties. The second intrusive phase is formed by alkaline and nepheline syenites. Petrographical, mineralogical, and geochemical data indicate that the first phase of the intrusion was derived from a moderately alkaline Fe-Ti basaltic melt, while the parental melt of the second phase was close in composition to alkaline trachyte. The orebodies comprise disseminated and massive ores. The disseminated Fe-Ti oxide ores make up lenses and layers conformable to general layering. Massive ores occur in subordinate amounts as layers and lenses, as well as cross-cutting veins. Elevated Nb and Ta contents in Fe-Ti oxides makes it possible to consider them complex ores. It is shown that the Fe-Ti oxide mineralization is related to the formation of a residual (Fe,Ti)-rich liquid, which lasted for the entire solidification history of the first intrusive phase. The liquid originated through multiple enrichment of Fe and Ti in the crystallization zone of the intrusion owing to the following processes: (1) precipitation of silicate minerals in the crystallization zone with a corresponding increase in the Fe and Ti contents in an interstitial melt; and (2) periodic accumulation of the residual melt in front of this zone. Unlike liquid immiscibility leading to melt splitting into two phases, this liquid dissolved the residual components of the melt. Correspondingly, such an Fe-rich liquid has unusual properties and requires further study.

The influence of titanium adhesion layer oxygen stoichiometry on thermal boundary conductance at gold contacts

NASA Astrophysics Data System (ADS)

Olson, David H.; Freedy, Keren M.; McDonnell, Stephen J.; Hopkins, Patrick E.

2018-04-01

We experimentally demonstrate the role of oxygen stoichiometry on the thermal boundary conductance across Au/TiOx/substrate interfaces. By evaporating two different sets of Au/TiOx/substrate samples under both high vacuum and ultrahigh vacuum conditions, we vary the oxygen composition in the TiOx layer from 0 ≤ x ≤ 2.85. We measure the thermal boundary conductance across the Au/TiOx/substrate interfaces with time-domain thermoreflectance and characterize the interfacial chemistry with x-ray photoemission spectroscopy. Under high vacuum conditions, we speculate that the environment provides a sufficient flux of oxidizing species to the sample surface such that one essentially co-deposits Ti and these oxidizing species. We show that slower deposition rates correspond to a higher oxygen content in the TiOx layer, which results in a lower thermal boundary conductance across the Au/TiOx/substrate interfacial region. Under the ultrahigh vacuum evaporation conditions, pure metallic Ti is deposited on the substrate surface. In the case of quartz substrates, the metallic Ti reacts with the substrate and getters oxygen, leading to a TiOx layer. Our results suggest that Ti layers with relatively low oxygen compositions are best suited to maximize the thermal boundary conductance.

Corrosion resistance of titanium ion implanted AZ91 magnesium alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Chenglong; Xin Yunchang; Tian Xiubo

2007-03-15

Degradable metal alloys constitute a new class of materials for load-bearing biomedical implants. Owing to their good mechanical properties and biocompatibility, magnesium alloys are promising in degradable prosthetic implants. The objective of this study is to improve the corrosion behavior of surgical AZ91 magnesium alloy by titanium ion implantation. The surface characteristics of the ion implanted layer in the magnesium alloys are examined. The authors' results disclose that an intermixed layer is produced and the surface oxidized films are mainly composed of titanium oxide with a lesser amount of magnesium oxide. X-ray photoelectron spectroscopy reveals that the oxide has threemore » layers. The outer layer which is 10 nm thick is mainly composed of MgO and TiO{sub 2} with some Mg(OH){sub 2}. The middle layer that is 50 nm thick comprises predominantly TiO{sub 2} and MgO with minor contributions from MgAl{sub 2}O{sub 4} and TiO. The third layer from the surface is rich in metallic Mg, Ti, Al, and Ti{sub 3}Al. The effects of Ti ion implantation on the corrosion resistance and electrochemical behavior of the magnesium alloys are investigated in simulated body fluids at 37{+-}1 deg. C using electrochemical impedance spectroscopy and open circuit potential techniques. Compared to the unimplanted AZ91 alloy, titanium ion implantation significantly shifts the open circuit potential (OCP) to a more positive potential and improves the corrosion resistance at OCP. This phenomenon can be ascribed to the more compact surface oxide film, enhanced reoxidation on the implanted surface, as well as the increased {beta}-Mg{sub 12}Al{sub 17} phase.« less

Preparation of titanium dioxide films on etched aluminum foil by vacuum infiltration and anodizing

NASA Astrophysics Data System (ADS)

Xiang, Lian; Park, Sang-Shik

2016-12-01

Al2O3-TiO2 (Al-Ti) composite oxide films are a promising dielectric material for future use in capacitors. In this study, TiO2 films were prepared on etched Al foils by vacuum infiltration. TiO2 films prepared using a sol-gel process were annealed at various temperatures (450, 500, and 550 °C) for different time durations (10, 30, and 60 min) for 4 cycles, and then anodized at 100 V. The specimens were characterized using X-ray diffraction, field emission scanning electron microscopy, and field emission transmission electron microscopy. The results show that the tunnels of the specimens feature a multi-layer structure consisting of an Al2O3 outer layer, an Al-Ti composite oxide middle layer, and an aluminum hydrate inner layer. The electrical properties of the specimens, such as the withstanding voltage and specific capacitance, were also measured. Compared to specimens without TiO2 coating, the specific capacitances of the TiO2-coated specimens are increased. The specific capacitance of the anode Al foil with TiO2 coating increased by 42% compared to that of a specimen without TiO2 coating when annealed at 550 °C for 10 min. These composite oxide films could enhance the specific capacitance of anode Al foils used in dielectric materials.

NiTi shape-memory alloy oxidized in low-temperature plasma with carbon coating: Characteristic and a potential for cardiovascular applications

NASA Astrophysics Data System (ADS)

Witkowska, Justyna; Sowińska, Agnieszka; Czarnowska, Elżbieta; Płociński, Tomasz; Borowski, Tomasz; Wierzchoń, Tadeusz

2017-11-01

Surface layers currently produced on NiTi alloys do not meet all the requirements for materials intended for use in cardiology. Plasma surface treatments of titanium and its alloys under glow discharge conditions make it possible to produce surface layers, such as TiN or TiO2, which increases corrosion resistance and biocompatibility. The production of layers on NiTi alloys with the same properties, and maintaining their shape memory and superelasticity features, requires the use of low-temperature processes. At the same time, since it is known that the carbon-based layers could prevent excessive adhesion and aggregation of platelets, we examined the composite a-CNH + TiO2 type surface layer produced by means of a hybrid method combining oxidation in low-temperature plasma and Radio Frequency Chemical Vapor Deposition (RFCVD) processes. Investigations have shown that this composite layer increases the corrosion resistance of the material, and both the low degree of roughness and the chemical composition of the surface produced lead to decreased platelet adhesion and aggregation and proper endothelialization, which could extend the range of applications of NiTi shape memory alloys.

Investigation of the Dissolution-Reformation Cycle of the Passive Oxide Layer on NiTi Orthodontic Archwires

NASA Astrophysics Data System (ADS)

Uzer, B.; Birer, O.; Canadinc, D.

2017-09-01

Dissolution-reformation cycle of the passive oxide layer on the nickel-titanium (NiTi) orthodontic archwires was investigated, which has recently been recognized as one of the key parameters dictating the biocompatibility of archwires. Specifically, commercially available NiTi orthodontic archwires were immersed in artificial saliva solutions of different pH values (2.3, 3.3, and 4.3) for four different immersion periods: 1, 7, 14, and 30 days. Characterization of the virgin and tested samples revealed that the titanium oxide layer on the NiTi archwire surfaces exhibit a dissolution-reformation cycle within the first 14 days of the immersion period: the largest amount of Ni ion release occurred within the first week of immersion, while it significantly decreased during the reformation period from day 7 to day 14. Furthermore, the oxide layer reformation was catalyzed on the grooves within the peaks and valleys due to relatively larger surface energy of these regions, which eventually decreased the surface roughness significantly within the reformation period. Overall, the current results clearly demonstrate that the analyses of dissolution-reformation cycle of the oxide layer in orthodontic archwires, surface roughness, and ion release behavior constitute utmost importance in order to ensure both the highest degree of biocompatibility and an efficient medical treatment.

Functionalization of Ti99.2 substrates surface by hybrid treatment investigated with spectroscopic methods

NASA Astrophysics Data System (ADS)

Jasinski, Jaroslaw Jan; Lubas, Malgorzata; Kurpaska, Lukasz; Napadlek, Wojciech; Sitarz, Maciej

2018-07-01

The article presents spectroscopic investigation of Ti 99.2 based functional substrates formed by hybrid oxidation process. Surface treatments were performed by combining methods of fluidized bed atmospheric diffusion treatment (FADT) with physical vapor deposition (PVD) - magnetron sputtering and laser surface texturing (LST) treatments. The processes were implemented to form a titanium diffusive layer saturated with oxygen in the substrate and a tight homogeneous oxide coating on Ti surface deposited with magnetron sputtering or laser texturing technique. The hybrid treatment was realized in Al2O3 fluidized bed reactor with air atmosphere, at 640 °C for 8 h and 12 h. At the same time, magnetron sputtering with the use of TiO2 target at a pressure of 3 × 102 mbar and laser surface texturing treatment with Nd:YAG λ = 1064 nm was performed. In order to investigate the effects of hybrid oxidation, microscopic (AFM, CLSM, SEM/SEM-EDX), spectroscopic (RS) and X-ray investigations (GID-XRD) were performed. Applied hybrid technique made possible to combine the effects of the generated layers and to reduce the stresses in the area of the PVD coating/oxidized Ti substrate interface. Furthermore, Raman spectroscopy results obtained at oxide layers manufactured with different variants of oxidation allowed detailed analysis of the created oxides. The coatings have shown structure with a Tiα(O) diffusion zone, a TiO2 rutile and anatase oxide zone deposited and textured on the substrate. Phase composition and morphology of these oxides is essential for the osseointegration process i.e. intensity of hydroxyapatite growing on the implant surface. Performed processes influenced the surface roughness parameter and cause the increase of substrate functional properties, which are important for biomedical applications.

A comparative study of TiN and TiC: Oxidation resistance and retention of xenon at high temperature and under degraded vacuum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavarini, S.; Bes, R.; Millard-Pinard, N.

2011-01-01

Dense TiN and TiC samples were prepared by hot pressing using micrometric powders. Xenon species (simulating rare gas fission products) were then implanted into the ceramics. The samples were annealed for 1 h at 1500 deg. C under several degraded vacuums with P{sub O{sub 2}} varying from 10{sup -6} to 2x10{sup -4} mbars. The oxidation resistance of the samples and their retention properties with respect to preimplanted xenon species were analyzed using scanning electron microscopy, grazing incidence x-ray diffraction, Rutherford backscattering spectrometry, and nuclear backscattering spectrometry. Results indicate that TiC is resistant to oxidation and does not release xenon formore » P{sub O{sub 2{<=}}}6x10{sup -6} mbars. When P{sub O{sub 2}} increases, geometric oxide crystallites appear at the surface depending on the orientation and size of TiC grains. These oxide phases are Ti{sub 2}O{sub 3}, Ti{sub 3}O{sub 5}, and TiO{sub 2}. Apparition of oxide crystallites is associated with the beginning of xenon release. TiC surface is completely covered by the oxide phases at P{sub O{sub 2}}=2x10{sup -4} mbars up to a depth of 3 {mu}m and the xenon is then completely released. For TiN samples, the results show a progressive apparition of oxide crystallites (Ti{sub 3}O{sub 5} mainly) at the surface when P{sub O{sub 2}} increases. The presence of the oxide crystallites is also directly correlated with xenon release, the more oxide crystallites are growing the more xenon is released. TiN surface is completely covered by an oxide layer at P{sub O{sub 2}}=2x10{sup -4} mbars up to 1 {mu}m. A correlation between the initial fine microstructure of TiN and the properties of the growing layer is suggested.« less

Effect of modification of oxide layer on NiTi stent corrosion resistance.

PubMed

Trépanier, C; Tabrizian, M; Yahia, L H; Bilodeau, L; Piron, D L

1998-01-01

Because of its good radiopacity, superelasticity, and shape memory properties, nickel-titanium (NiTi) is a potential material for fabrication of stents because these properties can facilitate their implantation and precise positioning. However, in vitro studies of NiTi alloys report the dependence of alloy biocompatibility and corrosion behavior on surface conditions. Surface oxidation seems to be very promising for improving the corrosion resistance and biocompatibility of NiTi. In this work, we studied the effect on corrosion resistance and surface characteristics of electropolishing, heat treatment, and nitric acid passivation of NiTi stents. Characterization techniques such as potentiodynamic polarization tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to relate corrosion behavior to surface characteristics and surface treatments. Results show that all of these surface treatments improve the corrosion resistance of the alloy. This improvement is attributed to the plastically deformed native oxide layer removal and replacement by a newly grown, more uniform one. The uniformity of the oxide layer, rather than its thickness and composition, seems to be the predominant factor to explain the corrosion resistance improvement.

Constructing oxide interfaces and heterostructures by atomic layer-by-layer laser molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Lei, Qingyu; Golalikhani, Maryam; Davidson, Bruce A.; Liu, Guozhen; Schlom, Darrell G.; Qiao, Qiao; Zhu, Yimei; Chandrasena, Ravini U.; Yang, Weibing; Gray, Alexander X.; Arenholz, Elke; Farrar, Andrew K.; Tenne, Dmitri A.; Hu, Minhui; Guo, Jiandong; Singh, Rakesh K.; Xi, Xiaoxing

2017-12-01

Advancements in nanoscale engineering of oxide interfaces and heterostructures have led to discoveries of emergent phenomena and new artificial materials. Combining the strengths of reactive molecular-beam epitaxy and pulsed-laser deposition, we show here, with examples of Sr1+xTi1-xO3+δ, Ruddlesden-Popper phase Lan+1NinO3n+1 (n = 4), and LaAl1+yO3(1+0.5y)/SrTiO3 interfaces, that atomic layer-by-layer laser molecular-beam epitaxy significantly advances the state of the art in constructing oxide materials with atomic layer precision and control over stoichiometry. With atomic layer-by-layer laser molecular-beam epitaxy we have produced conducting LaAlO3/SrTiO3 interfaces at high oxygen pressures that show no evidence of oxygen vacancies, a capability not accessible by existing techniques. The carrier density of the interfacial two-dimensional electron gas thus obtained agrees quantitatively with the electronic reconstruction mechanism.

Efficiency Enhancement of Nanotextured Black Silicon Solar Cells Using Al2O3/TiO2 Dual-Layer Passivation Stack Prepared by Atomic Layer Deposition.

PubMed

Wang, Wei-Cheng; Tsai, Meng-Chen; Yang, Jason; Hsu, Chuck; Chen, Miin-Jang

2015-05-20

In this study, efficient nanotextured black silicon (NBSi) solar cells composed of silicon nanowire arrays and an Al2O3/TiO2 dual-layer passivation stack on the n(+) emitter were fabricated. The highly conformal Al2O3 and TiO2 surface passivation layers were deposited on the high-aspect-ratio surface of the NBSi wafers using atomic layer deposition. Instead of the single Al2O3 passivation layer with a negative oxide charge density, the Al2O3/TiO2 dual-layer passivation stack treated with forming gas annealing provides a high positive oxide charge density and a low interfacial state density, which are essential for the effective field-effect and chemical passivation of the n(+) emitter. In addition, the Al2O3/TiO2 dual-layer passivation stack suppresses the total reflectance over a broad range of wavelengths (400-1000 nm). Therefore, with the Al2O3/TiO2 dual-layer passivation stack, the short-circuit current density and efficiency of the NBSi solar cell were increased by 11% and 20%, respectively. In conclusion, a high efficiency of 18.5% was achieved with the NBSi solar cells by using the n(+)-emitter/p-base structure passivated with the Al2O3/TiO2 stack.

Investigation of TiN thin film oxidation depending on the substrate temperature at vacuum break

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piallat, Fabien, E-mail: fabien.piallat@gmail.com; CEA, LETI, Campus Minatec, F-38054 Grenoble; LTM-CNRS, 17 rue des Martyrs, 38054 Grenoble

2016-09-15

Due to the reduction of the thickness of the layers used in the advanced technology nodes, there is a growing importance of the surface phenomena in the definition of the general properties of the materials. One of the least controlled and understood phenomenon is the oxidation of metals after deposition, at the vacuum break. In this study, the influence of the sample temperature at vacuum break on the oxidation level of TiN deposited by metalorganic chemical vapor deposition is investigated. TiN resistivity appears to be lower for samples which underwent vacuum break at high temperature. Using X-ray photoelectron spectrometry analysis,more » this change is correlated to the higher oxidation of the TiN layer. Moreover, angle resolved XPS analysis reveals that higher is the temperature at the vacuum break, higher is the surface oxidation of the sample. This surface oxidation is in turn limiting the diffusion of oxygen in the volume of the layer. Additionally, evolution of TiN layers resistivity was monitored in time and it shows that resistivity increases until a plateau is reached after about 10 days, with the lowest temperature at vacuum break resulting in the highest increase, i.e., the resistivity of the sample released to atmosphere at high temperature increased by a factor 1.7 whereas the resistivity of the sample cooled down under vacuum temperature increased by a factor 2.7.« less

Osteoblast responses to different oxide coatings produced by the sol-gel process on titanium substrates.

PubMed

Ochsenbein, Anne; Chai, Feng; Winter, Stefan; Traisnel, Michel; Breme, Jürgen; Hildebrand, Hartmut F

2008-09-01

In order to improve the osseointegration of endosseous implants made from titanium, the structure and composition of the surface were modified. Mirror-polished commercially pure (cp) titanium substrates were coated by the sol-gel process with different oxides: TiO(2), SiO(2), Nb(2)O(5) and SiO(2)-TiO(2). The coatings were physically and biologically characterized. Infrared spectroscopy confirmed the absence of organic residues. Ellipsometry determined the thickness of layers to be approximately 100nm. High resolution scanning electron microscopy (SEM) and atomice force microscopy revealed a nanoporous structure in the TiO(2) and Nb(2)O(5) layers, whereas the SiO(2) and SiO(2)-TiO(2) layers appeared almost smooth. The R(a) values, as determined by white-light interferometry, ranged from 20 to 50nm. The surface energy determined by the sessile-drop contact angle method revealed the highest polar component for SiO(2) (30.7mJm(-2)) and the lowest for cp-Ti and 316L stainless steel (6.7mJm(-2)). Cytocompatibility of the oxide layers was investigated with MC3T3-E1 osteoblasts in vitro (proliferation, vitality, morphology and cytochemical/immunolabelling of actin and vinculin). Higher cell proliferation rates were found in SiO(2)-TiO(2) and TiO(2), and lower in Nb(2)O(5) and SiO(2); whereas the vitality rates increased for cp-Ti and Nb(2)O(5). Cytochemical assays showed that all substrates induced a normal cytoskeleton and well-developed focal adhesion contacts. SEM revealed good cell attachment for all coating layers. In conclusion, the sol-gel-derived oxide layers were thin, pure and nanostructured; consequent different osteoblast responses to those coatings are explained by the mutual action and coadjustment of different interrelated surface parameters.

Structural & oxidation behavior of TiN & AlxTi1-xN coatings deposited by CA-PVD technique

NASA Astrophysics Data System (ADS)

Thorat, Nirmala; Mundotia, Rajesh; Varma, Ranjana; Kale, Ashwin; Mhatre, Umesh; Patel, Nainesh

2018-04-01

Coatings with thermal stability at elevated temperatures are prerequisite for various high speed machining and high temperature applications. The present work compares the oxidation behavior of the AlxTi1-xN coating prepared with different Al composition. Coated samples were tested at different temperatures in the range of 400 - 800 C to study their oxidation behavior. Percentage weight gain of all the samples were evaluated using high accuracy weighing balance. The depth of oxide layers were studied using Calo-test instrument. The XRD analysis was carried out to specify the phase structure. Higher oxidation rate was observed for TiN coating at all the oxidation temperatures. Oxidation rate was higher for Al13Ti87N and Al70Ti30N coatings compared to Al60Ti40N and Al50Ti50N coatings which exhibits better oxygen diffusion barrier at all the temperature.

Tuning the Phase and Microstructural Properties of TiO2 Films Through Pulsed Laser Deposition and Exploring Their Role as Buffer Layers for Conductive Films

NASA Astrophysics Data System (ADS)

Agarwal, S.; Haseman, M. S.; Leedy, K. D.; Winarski, D. J.; Saadatkia, P.; Doyle, E.; Zhang, L.; Dang, T.; Vasilyev, V. S.; Selim, F. A.

2018-04-01

Titanium oxide (TiO2) is a semiconducting oxide of increasing interest due to its chemical and thermal stability and broad applicability. In this study, thin films of TiO2 were deposited by pulsed laser deposition on sapphire and silicon substrates under various growth conditions, and characterized by x-ray diffraction (XRD), atomic force microscopy (AFM), optical absorption spectroscopy and Hall-effect measurements. XRD patterns revealed that a sapphire substrate is more suitable for the formation of the rutile phase in TiO2, while a silicon substrate yields a pure anatase phase, even at high-temperature growth. AFM images showed that the rutile TiO2 films grown at 805°C on a sapphire substrate have a smoother surface than anatase films grown at 620°C. Optical absorption spectra confirmed the band gap energy of 3.08 eV for the rutile phase and 3.29 eV for the anatase phase. All the deposited films exhibited the usual high resistivity of TiO2; however, when employed as a buffer layer, anatase TiO2 deposited on sapphire significantly improves the conductivity of indium gallium zinc oxide thin films. The study illustrates how to control the formation of TiO2 phases and reveals another interesting application for TiO2 as a buffer layer for transparent conducting oxides.

Influence of silicon oxide on the performance of TiN bottom electrode in phase change memory

NASA Astrophysics Data System (ADS)

Gao, Dan; Liu, Bo; Xu, Zhen; Wang, Heng; Xia, Yangyang; Wang, Lei; Zhu, Nanfei; Li, Ying; Zhan, Yipeng; Song, Zhitang; Feng, Songlin

2016-10-01

The stability of TiN which is the preferred bottom electrode contact (BEC) of phase change memory (PCM) due to its low thermal conductivity and suitable electrical conductivity, is very essential to the reliability of PCM devices. In this work, in order to investigate the effect of high aspect ratio process (HARP) SiO2 on the performance of TiN, both TiN/SiO2, TiN/SiN thin films and TiN BEC device structures are analyzed. By combining transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS), we found that the TiN would be oxidized after the deposition of HARP SiO2 and there exist a thin ( 4 nm) oxidation interfacial layer between TiN and SiO2. Electrical measurements were performed on the 1R PCM test-key die with 7 nm and 10 nm BEC-only cells. The statistical initial resistances of BEC have wide distribution and it is confirmed that the non-uniform oxidation of TiN BEC affects the astringency of the resistance of TiN BEC. The experimental results help to optimize the process of TiN BEC, and SiN is recommended as a better choice as the linear layer.

Microstructure and antibacterial property of in situ TiO(2) nanotube layers/titanium biocomposites.

PubMed

Cui, C X; Gao, X; Qi, Y M; Liu, S J; Sun, J B

2012-04-01

The TiO(2) nanotube layer was in situ synthesized on the surface of pure titanium by the electrochemical anodic oxidation. The diameter of nano- TiO(2) nanotubes was about 70~100 nm. The surface morphology and phase compositions of TiO(2) nanotube layers were observed and analyzed using the scanning electron microscope (SEM). The important processing parameters, including anodizing voltage, reaction time, concentration of electrolyte, were optimized in more detail. The photocatalytic activity of the nano- TiO(2) nanotube layers prepared with optimal conditions was evaluated via the photodegradation of methylthionine in aqueous solution. The antibacterial property of TiO(2) nanotube layers prepared with optimal conditions was evaluated by inoculating Streptococcus mutans on the TiO(2) nanotube layers in vitro. The results showed that TiO(2) nanotube layers/Ti biocomposites had very good antibacterial activity to resist Streptococcus mutans. As a dental implant biomaterial, in situ TiO(2) nanotube layer/Ti biocomposite has better and wider application prospects. Copyright © 2012 Elsevier Ltd. All rights reserved.

Issues Concerning the Oxidation of Ni(Pt)Ti Shape Memory Alloys

NASA Technical Reports Server (NTRS)

Smialek, James

2011-01-01

The oxidation behavior of the Ni-30Pt-50Ti high temperature shape memory alloy is compared to that of conventional NiTi nitinol SMAs. The oxidation rates were 1/4 those of NiTi under identical conditions. Ni-Ti-X SMAs are dominated by TiO2 scales, but, in some cases, the activation energy diverges for unexplained reasons. Typically, islands of metallic Ni or Pt(Ni) particles are embedded in lower scale layers due to rapid selective growth of TiO2 and low oxygen potential within the scale. The blocking effect of Pt-rich particles and lower diffusivity of Pt-rich depletion zones are proposed to account for the reduction in oxidation rates.

Properties of epitaxial BaTiO{sub 3} deposited on GaAs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Contreras-Guerrero, R.; Droopad, R.; Veazey, J. P.

2013-01-07

Single crystal BaTiO{sub 3} (BTO) has been grown epitaxially on GaAs using molecular beam epitaxy with a 2 unit cell SrTiO{sub 3} nucleation layer. The oxide film is lattice-matched to GaAs through an in-plane rotation of 45 Degree-Sign relative to the (100) surface leading to c-axis orientation of the BaTiO{sub 3}. X-ray diffraction confirmed the crystallinity and orientation of the oxide film with a full width half maximum of 0.58 Degree-Sign for a 7.5 nm thick layer. Piezoresponse force microscopy was used to characterize the ferroelectric domains in the BaTiO{sub 3} layer, and a coercive voltage of 1-2 V andmore » piezoresponse amplitude {approx}5 pm/V was measured.« less

Optimization of Al2O3/TiO2 nanolaminate thin films prepared with different oxide ratios, for use in organic light-emitting diode encapsulation, via plasma-enhanced atomic layer deposition.

PubMed

Kim, Lae Ho; Jeong, Yong Jin; An, Tae Kyu; Park, Seonuk; Jang, Jin Hyuk; Nam, Sooji; Jang, Jaeyoung; Kim, Se Hyun; Park, Chan Eon

2016-01-14

Encapsulation is essential for protecting the air-sensitive components of organic light-emitting diodes (OLEDs), such as the active layers and cathode electrodes. Thin film encapsulation approaches based on an oxide layer are suitable for flexible electronics, including OLEDs, because they provide mechanical flexibility, the layers are thin, and they are easy to prepare. This study examined the effects of the oxide ratio on the water permeation barrier properties of Al2O3/TiO2 nanolaminate films prepared by plasma-enhanced atomic layer deposition. We found that the Al2O3/TiO2 nanolaminate film exhibited optimal properties for a 1 : 1 atomic ratio of Al2O3/TiO2 with the lowest water vapor transmission rate of 9.16 × 10(-5) g m(-2) day(-1) at 60 °C and 90% RH. OLED devices that incorporated Al2O3/TiO2 nanolaminate films prepared with a 1 : 1 atomic ratio showed the longest shelf-life, in excess of 2000 hours under 60 °C and 90% RH conditions, without forming dark spots or displaying edge shrinkage.

TiOx thin films grown on Pd(100) and Pd(111) by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Farstad, M. H.; Ragazzon, D.; Grönbeck, H.; Strømsheim, M. D.; Stavrakas, C.; Gustafson, J.; Sandell, A.; Borg, A.

2016-07-01

The growth of ultrathin TiOx (0≤x≤2) films on Pd(100) and Pd(111) surfaces by chemical vapor deposition (CVD), using Titanium(IV)isopropoxide (TTIP) as precursor, has been investigated by high resolution photoelectron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. Three different TiOx phases and one Pd-Ti alloy phase have been identified for both surfaces. The Pd-Ti alloy phase is observed at the initial stages of film growth. Density functional theory (DFT) calculations for Pd(100) and Pd(111) suggest that Ti is alloyed into the second layer of the substrate. Increasing the TTIP dose yields a wetting layer comprising Ti2 + species (TiOx, x ∼0.75). On Pd(100), this phase exhibits a mixture of structures with (3 × 5) and (4 × 5) periodicity with respect to the Pd(100) substrate, while an incommensurate structure is formed on Pd(111). Most importantly, on both surfaces this phase consists of a zigzag pattern similar to observations on other reactive metal surfaces. Further increase in coverage results in growth of a fully oxidized (TiO2) phase on top of the partially oxidized layer. Preliminary investigations indicate that the fully oxidized phase on both Pd(100) and Pd(111) may be the TiO2(B) phase.

Electrical and band structural analyses of Ti1-x Al x O y films grown by atomic layer deposition on p-type GaAs

NASA Astrophysics Data System (ADS)

An, Youngseo; Mahata, Chandreswar; Lee, Changmin; Choi, Sungho; Byun, Young-Chul; Kang, Yu-Seon; Lee, Taeyoon; Kim, Jiyoung; Cho, Mann-Ho; Kim, Hyoungsub

2015-10-01

Amorphous Ti1-x Al x O y films in the Ti-oxide-rich regime (x  <  0.5) were deposited on p-type GaAs via atomic layer deposition with titanium isopropoxide, trimethylaluminum, and H2O precursor chemistry. The electrical properties and energy band alignments were examined for the resulting materials with their underlying substrates, and significant frequency dispersion was observed in the accumulation region of the Ti-oxide-rich Ti1-x Al x O y films. Although a further reduction in the frequency dispersion and leakage current (under gate electron injection) could be somewhat achieved through a greater addition of Al-oxide in the Ti1-x Al x O y film, the simultaneous decrease in the dielectric constant proved problematic in finding an optimal composition for application as a gate dielectric on GaAs. The spectroscopic band alignment measurements of the Ti-oxide-rich Ti1-x Al x O y films indicated that the band gaps had a rather slow increase with the addition of Al-oxide, which was primarily compensated for by an increase in the valance band offset, while a nearly-constant conduction band offset with a negative electron barrier height was maintained.

The role of titanium aluminide in n-gallium nitride ohmic contact technology

NASA Astrophysics Data System (ADS)

Pelto, Christopher M.

Ohmic contacts are essential to the realization of efficient and affordable nitride-based electronic and optoelectronic devices. Currently, the most successful ohmic contact schemes to n-GaN are based on the Al/Ti bilayer structure, although the mechanism responsible for the low resistance in these contacts is not sufficiently understood. In this work, the intermetallic TiAl3 has been employed both as a model ohmic contact system to help understand the essential features of the Al/Ti standard contact, as well as a thermally stable oxidation cap for the bilayer structure. A quaternary isotherm of the Al-Ti-Ga-N system was calculated at 600°C, which showed that a sufficient phase topology was present to apply the exchange mechanism to the TiAl 3/GaN couple. The exchange mechanism rationalized the selection of the TiAl3 intermetallic by predicting that an Al-rich AlGaN layer will form at the metal/semiconductor interface. As part of the investigation of these novel contact systems, a thorough characterization was undertaken on both a standard Al/Ti and Au/Ni/Al/Ti contact to n-GaN in which the essential processing parameters and metallurgical properties were identified. The TiAl 3 contact was found to exhibit inferior electrical behavior compared to the Al/Ti bilayer, requiring significantly higher annealing temperatures to achieve comparable specific contact resistance. It is conjectured that this is due to the early formation of a TiN layer at the metal/semiconductor interface of the bilayer contact, even though both contacts are suspected to form the Al-rich nitride layer at higher temperature. As an oxidation cap, the TiAl3 metallization was found to provide much improved performance characteristics compared to the four-layer Au/Al/Ni/Ti standard. The TiAl 3/Al/Ti contact proved to achieve optimal performance at a much lower temperature than the standard, and furthermore showed complete insensitivity to the oxidation content of the annealing ambient. Reaction mechanisms for the TiAl3-capped and the four-layer contact metallizations are suggested that account for both the morphology and the expected interfacial phases of each system.

Effects of substrate microstructure on the formation of oriented oxide nanotube arrays on Ti and Ti alloys

NASA Astrophysics Data System (ADS)

Ferreira, C. P.; Gonçalves, M. C.; Caram, R.; Bertazzoli, R.; Rodrigues, C. A.

2013-11-01

The formation of nanotubular oxide layers on Ti and Ti alloys has been widely investigated for the photocatalytic degradation of organic compounds due to their excellent catalytic efficiency, chemical stability, and low cost and toxicity. Aiming to improve the photocatalytic efficiency of this nanostructured oxide, this work investigated the influence of substrate grain size on the growth of nanotubular oxide layers. Ti and Ti alloys (Ti-6Al, Ti-6Al-7Nb) were produced by arc melting with non-consumable tungsten electrode and water-cooled copper hearth under argon atmosphere. Some of the ingots were heat-treated at 1000 °C for 12 and 24 h in argon atmosphere, followed by slow cooling rates to reduce crystalline defects and increase the grain size of their microstructures. Three types of samples were anodized: commercial substrate, as-prepared and heat-treated samples. The anodization was performed using fluoride solution and a cell potential of 20 V. The samples were characterized by optical microscopy, field-emission scanning electron microscopy and X-ray diffraction. The heat treatment preceding the anodization process increased the grain size of pure Ti and Ti alloys and promoted the formation of Widmanstätten structures in Ti6Al7Nb. The nanotubes layers grown on smaller grain and thermally untreated samples were more regular and homogeneous. In the case of Ti-6Al-7Nb alloy, which presents a α + β phase microstructure, the morphology of nanotubes nucleated on α matrix was more regular than those of nanotubes nucleated on β phase. After the annealing process, the Ti-6Al-7Nb alloy presented full diffusion process and the growth of equilibrium phases resulting in the appearance of regions containing higher concentrations of Nb, i.e. beta phase. In those regions the dissolution rate of Nb2O5 is lower than that of TiO2, resulting in a nanoporous layer. In general, heat treating reduces crystalline defects and promotes the increasing of the grain sizes, not favoring the process of nanotube nucleation and growth on the metallic surface.

Thin TiOx layer as a voltage divider layer located at the quasi-Ohmic junction in the Pt/Ta2O5/Ta resistance switching memory.

PubMed

Li, Xiang Yuan; Shao, Xing Long; Wang, Yi Chuan; Jiang, Hao; Hwang, Cheol Seong; Zhao, Jin Shi

2017-02-09

Ta 2 O 5 has been an appealing contender for the resistance switching random access memory (ReRAM). The resistance switching (RS) in this material is induced by the repeated formation and rupture of the conducting filaments (CFs) in the oxide layer, which are accompanied by the almost inevitable randomness of the switching parameters. In this work, a 1 to 2 nm-thick Ti layer was deposited on the 10 nm-thick Ta 2 O 5 RS layer, which greatly improved the RS performances, including the much-improved switching uniformity. The Ti metal layer was naturally oxidized to TiO x (x < 2) and played the role of a series resistor, whose resistance value was comparable to the on-state resistance of the Ta 2 O 5 RS layer. The series resistor TiO x efficiently suppressed the adverse effects of the voltage (or current) overshooting at the moment of switching by the appropriate voltage partake effect, which increased the controllability of the CF formation and rupture. The switching cycle endurance was increased by two orders of magnitude even during the severe current-voltage sweep tests compared with the samples without the thin TiO x layer. The Ti deposition did not induce any significant overhead to the fabrication process, making the process highly promising for the mass production of a reliable ReRAM.

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Golden, D. C.

2004-01-01

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE PAGES

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.; ...

2017-03-20

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

All-nanoparticle self-assembly ZnO/TiO₂ heterojunction thin films with remarkably enhanced photoelectrochemical activity.

PubMed

Yuan, Sujun; Mu, Jiuke; Mao, Ruiyi; Li, Yaogang; Zhang, Qinghong; Wang, Hongzhi

2014-04-23

The multilaminated ZnO/TiO2 heterojunction films were successfully deposited on conductive substrates including fluorine-doped tin oxide (FTO) glass and flexible indium tin oxide coated poly(ethylene terephthalate) via the layer-by-layer (LBL) self assembly method from the oxide colloids without using any polyelectrolytes. The positively charged ZnO nanoparticles and the negatively charged TiO2 nanoparticles were directly used as the components in the consecutive deposition process to prepare the heterojunction thin films by varying the thicknesses. Moreover, the crystal growth of both oxides could be efficiently inhibited by the good connection between ZnO and TiO2 nanoparticles even after calcination at 500 °C, especially for ZnO which was able to keep the crystallite size under 25 nm. The as-prepared films were used as the working electrodes in the three-electrode photoelectrochemical cells. Because the well-contacted nanoscale heterojunctions were formed during the LBL self-assembling process, the ZnO/TiO2 all-nanoparticle films deposited on both substrates showed remarkably enhanced photoelectrochemical properties compared to that of the well-established TiO2 LBL thin films with similar thicknesses. The photocurrent response collected from the ZnO/TiO2 electrode on the FTO glass substrate was about five times higher than that collected from the TiO2 electrode. Owing to the absence of the insulating layer of dried polyelectrolytes, the ZnO/TiO2 all-nanoparticle heterojunction films were expected to be used in the photoelectrochemical device before calcination.

TiO2-graphene oxide nanocomposite as advanced photocatalytic materials.

PubMed

Stengl, Václav; Bakardjieva, Snejana; Grygar, Tomáš Matys; Bludská, Jana; Kormunda, Martin

2013-02-27

Graphene oxide composites with photocatalysts may exhibit better properties than pure photocatalysts via improvement of their textural and electronic properties. TiO2-Graphene Oxide (TiO2 - GO) nanocomposite was prepared by thermal hydrolysis of suspension with graphene oxide (GO) nanosheets and titania peroxo-complex. The characterization of graphene oxide nanosheets was provided by using an atomic force microscope and Raman spectroscopy. The prepared nanocomposites samples were characterized by Brunauer-Emmett-Teller surface area and Barrett-Joiner-Halenda porosity, X-ray Diffraction, Infrared Spectroscopy, Raman Spectroscopy and Transmission Electron Microscopy. UV/VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies. From the TiO2 - GO samples, a 300 μm thin layer on a piece of glass 10×15 cm was created. The photocatalytic activity of the prepared layers was assessed from the kinetics of the photocatalytic degradation of butane in the gas phase. The best photocatalytic activity under UV was observed for sample denoted TiGO_100 (k = 0.03012 h-1), while sample labeled TiGO_075 (k = 0.00774 h-1) demonstrated the best activity under visible light.

TiO2-graphene oxide nanocomposite as advanced photocatalytic materials

PubMed Central

2013-01-01

Background Graphene oxide composites with photocatalysts may exhibit better properties than pure photocatalysts via improvement of their textural and electronic properties. Results TiO2-Graphene Oxide (TiO2 - GO) nanocomposite was prepared by thermal hydrolysis of suspension with graphene oxide (GO) nanosheets and titania peroxo-complex. The characterization of graphene oxide nanosheets was provided by using an atomic force microscope and Raman spectroscopy. The prepared nanocomposites samples were characterized by Brunauer–Emmett–Teller surface area and Barrett–Joiner–Halenda porosity, X-ray Diffraction, Infrared Spectroscopy, Raman Spectroscopy and Transmission Electron Microscopy. UV/VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies. From the TiO2 - GO samples, a 300 μm thin layer on a piece of glass 10×15 cm was created. The photocatalytic activity of the prepared layers was assessed from the kinetics of the photocatalytic degradation of butane in the gas phase. Conclusions The best photocatalytic activity under UV was observed for sample denoted TiGO_100 (k = 0.03012 h-1), while sample labeled TiGO_075 (k = 0.00774 h-1) demonstrated the best activity under visible light. PMID:23445868

In-depth evolution of chemical states and sub-10-nm-resolution crystal orientation mapping of nanograins in Ti(5 nm)/Au(20 nm)/Cr(3 nm) tri-layer thin films

NASA Astrophysics Data System (ADS)

Zhu, Xiaoli; Todeschini, Matteo; Bastos da Silva Fanta, Alice; Liu, Lintao; Jensen, Flemming; Hübner, Jörg; Jansen, Henri; Han, Anpan; Shi, Peixiong; Ming, Anjie; Xie, Changqing

2018-09-01

The applications of Au thin films and their adhesion layers often suffer from a lack of sufficient information about the chemical states of adhesion layers and about the high-lateral-resolution crystallographic morphology of Au nanograins. Here, we demonstrate the in-depth evolution of the chemical states of adhesive layers at the interfaces and the crystal orientation mapping of gold nanograins with a lateral resolution of less than 10 nm in a Ti/Au/Cr tri-layer thin film system. Using transmission electron microscopy, the variation in the interdiffusion at Cr/Au and Ti/Au interfaces was confirmed. From X-ray photoelectron spectroscopy (XPS) depth profiling, the chemical states of Cr, Au and Ti were characterized layer by layer, suggesting the insufficient oxidation of the adhesive layers. At the interfaces the Au 4f peaks shift to higher binding energies and this behavior can be described by a proposed model based on electron reorganization and substrate-induced final-state neutralization in small Au clusters supported by the partially oxidized Ti layer. Utilizing transmission Kikuchi diffraction (TKD) in a scanning electron microscope, the crystal orientation of Au nanograins between two adhesion layers was non-destructively characterized with sub-10 nm spatial resolution. The results provide nanoscale insights into the Ti/Au/Cr thin film system and contribute to our understanding of its behavior in nano-optic and nano-electronic devices.

Oxide Scales Formed on NiTi and NiPtTi Shape Memory Alloys

NASA Technical Reports Server (NTRS)

Smialek, James L.; Garg, Anita; Rogers, Richard B.; Noebe, Ronald D.

2011-01-01

Ni-49Ti and Ni-30Pt-50Ti (at.%) shape memory alloys were oxidized isothermally in air over the temperature range of 500 to 900 C. The microstructure, composition, and phase content of the scales were studied by SEM, EDS, XRD, and metallography. Extensive plan view SEM/EDS identified various features of intact or spalled scale surfaces. The outer surface of the scale was a relatively pure TiO2 rutile structure, typified by a distinct highly striated and faceted crystal morphology. Crystal size increased significantly with temperature. Spalled regions exhibited some porosity and less distinct features. More detailed information was obtained by correlation of SEM/EDS studies of 700 C/100 hr cross-sections with XRD analyses of serial or taper-polishing of plan surfaces. Overall, multiple layers exhibited graded mixtures of NiO, TiO2, NiTiO3, Ni(Ti) or Pt(Ni,Ti) metal dispersoids, Ni3Ti or Pt3Ti depletion zones, and substrate, in that order. The NiTi alloy contained a 3 at.% Fe impurity that appeared in embedded localized Fe-Ti-rich oxides, while the NiPtTi alloy contained a 2 v/o dispersion of TiC that appeared in lower layers. The oxidation kinetics of both alloys (in a previous report) indicated parabolic growth and an activation energy (250 kJ/mole) near those reported in other Ti and NiTi studies. This is generally consistent with TiO2 existing as the primary scale constituent, as described here.

Tuning SPT-3G Transition-Edge-Sensor Electrical Properties with a Four-Layer Ti-Au-Ti-Au Thin-Film Stack

NASA Astrophysics Data System (ADS)

Carter, F. W.; Ade, P. A. R.; Ahmed, Z.; Anderson, A. J.; Austermann, J. E.; Avva, J. S.; Thakur, R. Basu; Bender, A. N.; Benson, B. A.; Carlstrom, J. E.; Cecil, T.; Chang, C. L.; Cliche, J. F.; Cukierman, A.; Denison, E. V.; de Haan, T.; Ding, J.; Divan, R.; Dobbs, M. A.; Dutcher, D.; Everett, W.; Foster, A.; Gannon, R. N.; Gilbert, A.; Groh, J. C.; Halverson, N. W.; Harke-Hosemann, A. H.; Harrington, N. L.; Henning, J. W.; Hilton, G. C.; Holzapfel, W. L.; Huang, N.; Irwin, K. D.; Jeong, O. B.; Jonas, M.; Khaire, T.; Kofman, A. M.; Korman, M.; Kubik, D.; Kuhlmann, S.; Kuo, C. L.; Kutepova, V.; Lee, A. T.; Lowitz, A. E.; Meyer, S. S.; Michalik, D.; Miller, C. S.; Montgomery, J.; Nadolski, A.; Natoli, T.; Nguyen, H.; Noble, G. I.; Novosad, V.; Padin, S.; Pan, Z.; Pearson, J.; Posada, C. M.; Rahlin, A.; Ruhl, J. E.; Saunders, L. J.; Sayre, J. T.; Shirley, I.; Shirokoff, E.; Smecher, G.; Sobrin, J. A.; Stan, L.; Stark, A. A.; Story, K. T.; Suzuki, A.; Tang, Q. Y.; Thompson, K. L.; Tucker, C.; Vale, L. R.; Vanderlinde, K.; Vieira, J. D.; Wang, G.; Whitehorn, N.; Yefremenko, V.; Yoon, K. W.; Young, M. R.

2018-04-01

We have developed superconducting Ti transition-edge sensors with Au protection layers on the top and bottom for the South Pole Telescope's third-generation receiver (a cosmic microwave background polarimeter, due to be upgraded this austral summer of 2017/2018). The base Au layer (deposited on a thin Ti glue layer) isolates the Ti from any substrate effects; the top Au layer protects the Ti from oxidation during processing and subsequent use of the sensors. We control the transition temperature and normal resistance of the sensors by varying the sensor width and the relative thicknesses of the Ti and Au layers. The transition temperature is roughly six times more sensitive to the thickness of the base Au layer than to that of the top Au layer. The normal resistance is inversely proportional to sensor width for any given film configuration. For widths greater than five micrometers, the critical temperature is independent of width.

A critical study of the role of the surface oxide layer in titanium bonding

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1983-01-01

Scanning electron microscope/X-ray photoelectron spectroscopy (SEM/XPS) analysis of fractured adhesively bonded Ti 6-4 samples is discussed. The text adhesives incuded NR 056X polyimide, polypheylquinoxaline (PPQ), and LARC-13 polyimide. Differentiation between cohesive and interfacial failure was based on the absence of presence of a Ti 2p XPS photopeak. In addition, the surface oxide layer on Ti-(6A1-4V) adherends is characterized and bond strength and durability are addressed. Bond durability in various environmental conditions is discussed.

A Strategy to Enhance the Efficiency of Quantum Dot-Sensitized Solar Cells by Decreasing Electron Recombination with Polyoxometalate/TiO2 as the Electronic Interface Layer.

PubMed

Chen, Li; Chen, Weilin; Li, Jianping; Wang, Jiabo; Wang, Enbo

2017-07-21

Electron recombination occurring at the TiO 2 /quantum dot sensitizer/electrolyte interface is the key reason for hindering further efficiency improvements to quantum dot sensitized solar cells (QDSCs). Polyoxometalate (POM) can act as an electron-transfer medium to decrease electron recombination in a photoelectric device owing to its excellent oxidation/reduction properties and thermostability. A POM/TiO 2 electronic interface layer prepared by a simple layer-by-layer self-assembly method was added between fluorine-doped tin oxide (FTO) and mesoporous TiO 2 in the photoanode of QDSCs, and the effect on the photovoltaic performance was systematically investigated. Photovoltaic experimental results and the electron transmission mechanism show that the POM/TiO 2 electronic interface layer in the QDSCs can clearly suppress electron recombination, increase the electron lifetime, and result in smoother electron transmission. In summary, the best conversion efficiency of QDSCs with POM/TiO 2 electronic interface layers increases to 8.02 %, which is an improvement of 25.1 % compared with QDSCs without POM/TiO 2 . This work first builds an electron-transfer bridge between FTO and the quantum dot sensitizer and paves the way for further improved efficiency of QDSCs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silyukov, Oleg I., E-mail: olegsilyukov@yandex.ru; Abdulaeva, Liliia D.; Burovikhina, Alena A.

2015-03-15

Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}

Effect of titanium oxide compact layer in dye-sensitized solar cell prepared by liquid-phase deposition

NASA Astrophysics Data System (ADS)

Huang, Jung-Jie; Chiu, Shih-Ping; Wu, Menq-Jion; Hsu, Chun-Fa

2016-11-01

In this study, titanium dioxide films were deposited on indium tin oxide glass substrates by liquid-phase deposition (LPD) for application as the compact layer in dye-sensitized solar cells (DSSCs). A deposition solution of ammonium hexafluorotitanate and boric acid was used for TiO2 deposition. Compact layer passivation can improve DSSC performance by decreasing carrier losses from recombination at the ITO/electrolyte interface and improving the electrical contact between the ITO and the TiO2 photo-electrode. The optimum thickness of the compact layer was found to be 48 nm, which resulted in a 50 % increase in the conversion efficiency compared with cells without compact layers. The conversion efficiency can be increased from 3.55 to 5.26 %. Therefore, the LPD-TiO2 compact layer inhibits the dark current and increases the short-circuit current density effectively.

Semi-rechargeable Aluminum-Air Battery with a TiO2 Internal Layer with Plain Salt Water as an Electrolyte

NASA Astrophysics Data System (ADS)

Mori, Ryohei

2016-07-01

To develop a semi-rechargeable aluminum-air battery, we attempted to insert various kinds of ceramic oxides between an aqueous NaCl electrolyte and an aluminum anode. From cyclic voltammetry experiments, we found that some of the ceramic oxide materials underwent an oxidation-reduction reaction, which indicates the occurrence of a faradaic electrochemical reaction. Using a TiO2 film as an internal layer, we successfully prepared an aluminum-air battery with secondary battery behavior. However, cell impedance increased as the charge/discharge reactions proceeded probably because of accumulation of byproducts in the cell components and the air cathode. Results of quantum calculations and x-ray photoelectron spectroscopy suggest the possibility of developing an aluminum rechargeable battery using TiO2 as an internal layer.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

PubMed Central

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-01-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I–V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later. PMID:28252106

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

NASA Astrophysics Data System (ADS)

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers.

PubMed

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-02

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO 2 /nanoporous-Si and the TiO 2 /nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO 2 /nanoporous Si are lower than that of the HfO 2 /nanoporous Si, the former is more stable than the later.

Diffusion and interface evolution during the atomic layer deposition of TiO{sub 2} on GaAs(100) and InAs(100) surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Liwang; Gougousi, Theodosia, E-mail: gougousi@umbc.edu

2016-01-15

Atomic layer deposition is used to form TiO{sub 2} films from tetrakis dimethyl amino titanium and H{sub 2}O on native oxide GaAs(100) and InAs(100) surfaces. The evolution of the film/substrate interface is examined as a function of the deposition temperature (100–325 °C) using ex situ x-ray photoelectron spectroscopy. An increase in the deposition temperature up to 250 °C leads to enhancement of the native oxide removal. For depositions at 300 °C and above, interface reoxidation is observed during the initial deposition cycles but when the films are thicker than 3 nm, the surface oxides are removed steadily. Based on these observations, two distinct filmmore » growth regimes are identified; up to 250 °C, layer-by-layer dominates while at higher temperatures island growth takes over. Angle resolved x-ray photoelectron spectroscopy measurements performed on 3 nm TiO{sub 2} film deposited at 325 °C on both surfaces demonstrates a very important difference between the two substrates: for GaAs the native oxides remaining in the stack are localized at the interface, while for InAs(100), the indium oxides are mixed in the TiO{sub 2} film.« less

Evaluation of passive oxide layer formation-biocompatibility relationship in NiTi shape memory alloys: geometry and body location dependency.

PubMed

Toker, S M; Canadinc, D; Maier, H J; Birer, O

2014-03-01

A systematic set of ex-situ experiments were carried out on Nickel-Titanium (NiTi) shape memory alloy (SMA) in order to identify the dependence of its biocompatibility on sample geometry and body location. NiTi samples with three different geometries were immersed into three different fluids simulating different body parts. The changes observed in alloy surface and chemical content of fluids upon immersion experiments designed for four different time periods were analyzed in terms of ion release, oxide layer formation, and chemical composition of the surface layer. The results indicate that both sample geometry and immersion fluid significantly affect the alloy biocompatibility, as evidenced by the passive oxide layer formation on the alloy surface and ion release from the samples. Upon a 30 day immersion period, all three types of NiTi samples exhibited lower ion release than the critical value for clinic applications. However; a significant amount of ion release was detected in the case of gastric fluid, warranting a thorough investigation prior to utility of NiTi in gastrointestinal treatments involving long-time contact with tissue. Furthermore, certain geometries appear to be safer than the others for each fluid, providing a new set of guidelines to follow while designing implants making use of NiTi SMAs to be employed in treatments targeting specific body parts. Copyright © 2013 Elsevier B.V. All rights reserved.

Solution-deposited F:SnO₂/TiO₂ as a base-stable protective layer and antireflective coating for microtextured buried-junction H₂-evolving Si photocathodes.

PubMed

Kast, Matthew G; Enman, Lisa J; Gurnon, Nicholas J; Nadarajah, Athavan; Boettcher, Shannon W

2014-12-24

Protecting Si photocathodes from corrosion is important for developing tandem water-splitting devices operating in basic media. We show that textured commercial Si-pn(+) photovoltaics protected by solution-processed semiconducting/conducting oxides (plausibly suitable for scalable manufacturing) and coupled to thin layers of Ir yield high-performance H2-evolving photocathodes in base. They also serve as excellent test structures to understand corrosion mechanisms and optimize interfacial electrical contacts between various functional layers. Solution-deposited TiO2 protects Si-pn(+) junctions from corrosion for ∼24 h in base, whereas junctions protected by F:SnO2 fail after only 1 h of electrochemical cycling. Interface layers consisting of Ti metal and/or the highly doped F:SnO2 between the Si and TiO2 reduce Si-emitter/oxide/catalyst contact resistance and thus increase fill factor and efficiency. Controlling the oxide thickness led to record photocurrents near 35 mA cm(-2) at 0 V vs RHE and photocathode efficiencies up to 10.9% in the best cells. Degradation, however, was not completely suppressed. We demonstrate that performance degrades by two mechanisms, (1) deposition of impurities onto the thin catalyst layers, even from high-purity base, and (2) catastrophic failure via pinholes in the oxide layers after several days of operation. These results provide insight into the design of hydrogen-evolving photoelectrodes in basic conditions, and highlight challenges.

Comparative Study of Surface Chemical Composition and Oxide Layer Modification upon Oxygen Plasma Cleaning and Piranha Etching on a Novel Low Elastic Modulus Ti25Nb21Hf Alloy

NASA Astrophysics Data System (ADS)

Paredes, Virginia; Salvagni, Emiliano; Rodríguez-Castellón, Enrique; Manero, José María

2017-08-01

Metals are widely employed for many biological artificial replacements, and it is known that the quality and the physical/chemical properties of the surface are crucial for the success of the implant. Therefore, control over surface implant materials and their elastic moduli may be crucial to avoid undesired effects. In this study, surface modification upon cleaning and activation of a low elastic modulus Ti alloy (Ti25Hf21Nb) was investigated. Two different methods, oxygen plasma (OP) cleaning and piranha (PI) solution, were studied and compared. Both surface treatments were effective for organic contaminant removal and to increase the Ti-oxide layer thickness rather than other metal-oxides present at the surface, which is beneficial for biocompatibility of the material. Furthermore, both techniques drastically increased hydrophilicity and introduced oxidation and hydroxylation (OH)-functional groups at the surface that may be beneficial for further chemical modifications. However, these treatments did not alter the surface roughness and bulk material properties. The surfaces were fully characterized in terms of surface roughness, wettability, oxide layer composition, and hydroxyl surface density through analytical techniques (interferometry, X-ray photoelectron spectroscopy (XPS), contact angle, and zinc complexation). These findings provide essential information when planning surface modifications for cleanliness, oxide layer thickness, and surface hydroxyl density, as control over these factors is essential for many applications, especially in biomaterials.

Fabrication of free standing anodic titanium oxide membranes with clean surface using recycling process.

PubMed

Meng, Xianhui; Lee, Tae-Young; Chen, Huiyu; Shin, Dong-Wook; Kwon, Kee-Won; Kwon, Sang Jik; Yoo, Ji-Beom

2010-07-01

Large area of self-organized, free standing anodic titanium oxide (ATO) nanotube membranes with clean surfaces were facilely prepared to desired lengths via electrochemical anodization of highly pure Ti sheets in an ethylene glycol electrolyte, with a small amount of NH4F and H2O at 50 V, followed by self-detachment of the ATO membrane from the Ti substrate using recycling processes. In the first anodization step, the nanowire oxide layer existed over the well-arranged ATO nanotube. After sufficiently rinsing with water, the whole ATO layer was removed from the Ti sheet by high pressure N2 gas, and a well-patterned dimple layer with a thickness of about 30 nm existed on the Ti substrate. By using these naturally formed nano-scale pits as templates, in the second and third anodization process, highly ordered, vertically aligned, and free standing ATO membranes with the anodic aluminum oxide (AAO)-like clean surface were obtained. The inter-pore distance and diameter was 154 +/- 2 nm and 91+/- 2 nm, the tube arrays lengths for 25 and 46 hours were 44 and 70 microm, respectively. The present study demonstrates a simple approach to producing high quality, length controllable, large area TiO2 membrane.

Plasmonic engineering of metal-oxide nanowire heterojunctions in integrated nanowire rectification units

NASA Astrophysics Data System (ADS)

Lin, Luchan; Zou, Guisheng; Liu, Lei; Duley, Walt W.; Zhou, Y. Norman

2016-05-01

We show that irradiation with femtosecond laser pulses can produce robust nanowire heterojunctions in coupled non-wetting metal-oxide Ag-TiO2 structures. Simulations indicate that joining arises from the effect of strong plasmonic localization in the region of the junction. Strong electric field effects occur in both Ag and TiO2 resulting in the modification of both surfaces and an increase in wettability of TiO2, facilitating the interconnection of Ag and TiO2 nanowires. Irradiation leads to the creation of a thin layer of highly defected TiO2 in the contact region between the Ag and TiO2 nanowires. The presence of this layer allows the formation of a heterojunction and offers the possibility of engineering the electronic characteristics of interfacial structures. Rectifying junctions with single and bipolar properties have been generated in Ag-TiO2 nanowire circuits incorporating asymmetrical and symmetrical interfacial structures, respectively. This fabrication technique should be applicable for the interconnection of other heterogeneous metal-oxide nanowire components and demonstrates that femtosecond laser irradiation enables interfacial engineering for electronic applications of integrated nanowire structures.

Facile synthesis of 3D few-layered MoS2 coated TiO2 nanosheet core-shell nanostructures for stable and high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Chen, Biao; Zhao, Naiqin; Guo, Lichao; He, Fang; Shi, Chunsheng; He, Chunnian; Li, Jiajun; Liu, Enzuo

2015-07-01

Uniform transition metal sulfide deposition on a smooth TiO2 surface to form a coating structure is a well-known challenge, caused mainly due to their poor affinities. Herein, we report a facile strategy for fabricating mesoporous 3D few-layered (<4 layers) MoS2 coated TiO2 nanosheet core-shell nanocomposites (denoted as 3D FL-MoS2@TiO2) by a novel two-step method using a smooth TiO2 nanosheet as a template and glucose as a binder. The core-shell structure has been systematically examined and corroborated by transmission electron microscopy, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy analyses. It is found that the resultant 3D FL-MoS2@TiO2 as a lithium-ion battery anode delivers an outstanding high-rate capability with an excellent cycling performance, relating to the unique structure of 3D FL-MoS2@TiO2. The 3D uniform coverage of few-layered (<4 layers) MoS2 onto the TiO2 can remarkably enhance the structure stability and effectively shortens the transfer paths of both lithium ions and electrons, while the strong synergistic effect between MoS2 and TiO2 can significantly facilitate the transport of ions and electrons across the interfaces, especially in the high-rate charge-discharge process. Moreover, the facile fabrication strategy can be easily extended to design other oxide/carbon-sulfide/oxide core-shell materials for extensive applications.Uniform transition metal sulfide deposition on a smooth TiO2 surface to form a coating structure is a well-known challenge, caused mainly due to their poor affinities. Herein, we report a facile strategy for fabricating mesoporous 3D few-layered (<4 layers) MoS2 coated TiO2 nanosheet core-shell nanocomposites (denoted as 3D FL-MoS2@TiO2) by a novel two-step method using a smooth TiO2 nanosheet as a template and glucose as a binder. The core-shell structure has been systematically examined and corroborated by transmission electron microscopy, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy analyses. It is found that the resultant 3D FL-MoS2@TiO2 as a lithium-ion battery anode delivers an outstanding high-rate capability with an excellent cycling performance, relating to the unique structure of 3D FL-MoS2@TiO2. The 3D uniform coverage of few-layered (<4 layers) MoS2 onto the TiO2 can remarkably enhance the structure stability and effectively shortens the transfer paths of both lithium ions and electrons, while the strong synergistic effect between MoS2 and TiO2 can significantly facilitate the transport of ions and electrons across the interfaces, especially in the high-rate charge-discharge process. Moreover, the facile fabrication strategy can be easily extended to design other oxide/carbon-sulfide/oxide core-shell materials for extensive applications. Electronic supplementary information (ESI) available: Supplementary SEM, TEM, XPS and EIS analyses. See DOI: 10.1039/c5nr03334a

A new bimetallic plasmonic photocatalyst consisting of gold(core)-copper(shell) nanoparticle and titanium(IV) oxide support

NASA Astrophysics Data System (ADS)

Sato, Yuichi; Naya, Shin-ichi; Tada, Hiroaki

2015-10-01

Ultrathin Cu layers (˜2 atomic layers) have been selectively formed on the Au surfaces of Au nanoparticle-loaded rutile TiO2 (Au@Cu/TiO2) by a deposition precipitation-photodeposition technique. Cyclic voltammetry and photochronopotentiometry measurements indicate that the reaction proceeds via the underpotential deposition. The ultrathin Cu shell drastically increases the activity of Au/TiO2 for the selective oxidation of amines to the corresponding aldehydes under visible-light irradiation (λ > 430 nm). Photochronoamperometry measurements strongly suggest that the striking Cu shell effect stems from the enhancement of the charge separation in the localized surface plasmon resonance-excited Au/TiO2.

Multilayer (TiN, TiAlN) ceramic coatings for nuclear fuel cladding

NASA Astrophysics Data System (ADS)

Alat, Ece; Motta, Arthur T.; Comstock, Robert J.; Partezana, Jonna M.; Wolfe, Douglas E.

2016-09-01

In an attempt to develop an accident-tolerant fuel (ATF) that can delay the deleterious consequences of loss-of-coolant-accidents (LOCA), multilayer coatings were deposited onto ZIRLO® coupon substrates by cathodic arc physical vapor deposition (CA-PVD). Coatings were composed of alternating TiN (top) and Ti1-xAlxN (2-layer, 4-layer, 8-layer and 16-layer) layers. The minimum TiN top coating thickness and coating architecture were optimized for good corrosion and oxidation resistance. Corrosion tests were performed in static pure water at 360 °C and 18.7 MPa for up to 90 days. The optimized coatings showed no spallation/delamination and had a maximum of 6 mg/dm2 weight gain, which is 6 times smaller than that of a control sample of uncoated ZIRLO® which showed a weight gain of 40.2 mg/dm2. The optimized architecture features a ∼1 μm TiN top layer to prevent boehmite phase formation during corrosion and a TiN/TiAlN 8-layer architecture which provides the best corrosion performance.

Photocatalytic hollow TiO2 and ZnO nanospheres prepared by atomic layer deposition.

PubMed

Justh, Nóra; Bakos, László Péter; Hernádi, Klára; Kiss, Gabriella; Réti, Balázs; Erdélyi, Zoltán; Parditka, Bence; Szilágyi, Imre Miklós

2017-06-28

Carbon nanospheres (CNSs) were prepared by hydrothermal synthesis, and coated with TiO 2 and ZnO nanofilms by atomic layer deposition. Subsequently, through burning out the carbon core templates hollow metal oxide nanospheres were obtained. The substrates, the carbon-metal oxide composites and the hollow nanospheres were characterized with TG/DTA-MS, FTIR, Raman, XRD, SEM-EDX, TEM-SAED and their photocatalytic activity was also investigated. The results indicate that CNSs are not beneficial for photocatalysis, but the crystalline hollow metal oxide nanospheres have considerable photocatalytic activity.

Study the formation of porous surface layer for a new biomedical titanium alloy

NASA Astrophysics Data System (ADS)

Talib Mohammed, Mohsin; Diwan, Abass Ali; Ali, Osamah Ihsan

2018-03-01

In the present work, chemical treatment using hydrogen peroxide (H2O2) oxidation and subsequent thermal treatment was applied to create a uniform porous layer over the surface of a new metastable β-Ti alloy. The results revealed that this oxidation treatment can create a stable ultrafine porous film over the oxidized surface. This promoted the electrochemical characteristics of H2O2-treated Ti-Zr-Nb (TZN) alloy system, presenting nobler corrosion behavior in simulated body fluid (SBF) comparing with untreated sample.

Impact of ultra-thin Al2O3-y layers on TiO2-x ReRAM switching characteristics

NASA Astrophysics Data System (ADS)

Trapatseli, Maria; Cortese, Simone; Serb, Alexander; Khiat, Ali; Prodromakis, Themistoklis

2017-05-01

Transition metal-oxide resistive random access memory devices have demonstrated excellent performance in switching speed, versatility of switching and low-power operation. However, this technology still faces challenges like poor cycling endurance, degradation due to high electroforming (EF) switching voltages and low yields. Approaches such as engineering of the active layer by doping or addition of thin oxide buffer layers have been often adopted to tackle these problems. Here, we have followed a strategy that combines the two; we have used ultra-thin Al2O3-y buffer layers incorporated between TiO2-x thin films taking into account both 3+/4+ oxidation states of Al/Ti cations. Our devices were tested by DC and pulsed voltage sweeping and in both cases demonstrated improved switching voltages. We believe that the Al2O3-y layers act as reservoirs of oxygen vacancies which are injected during EF, facilitate a filamentary switching mechanism and provide enhanced filament stability, as shown by the cycling endurance measurements.

Preparation and characterization of TiO2 coated Fe nanofibers for electromagnetic wave absorber.

PubMed

Jang, Dae-Hwan; Song, Hanbok; Lee, Young-In; Lee, Kun-Jae; Kim, Ki Hyeon; Oh, Sung-Tag; Lee, Sang-Kwan; Choa, Yong-Ho

2011-01-01

Recently, electromagnetic interference (EMI) and electromagnetic compatibility (EMC) have become serious problems due to the growth of electronic device and next generation telecommunication. It is necessary to develop new electromagnetic wave absorbing material to overcome the limitation of electromagnetic wave shielding materials. The EMI attenuation is normally related to magnetic loss and dielectric loss. Therefore, magnetic material coating dielectric materials are required in this reason. In this study, TiO2 coated Fe nanofibers were prepared to improve their properties for electromagnetic wave absorption. Poly(vinylpyrrolidone) (PVP) and Iron (III) nitrate nonahydrate (Fe(NO3)3 x 9H2O) were used as starting materials for the synthesis of Fe oxide nanofibers. Fe oxide nanofibers were prepared by electrospinning in an electric field and heat treatment. TiO2 layer was coated on the surface of Fe oxide nanofibers using sol-gel process. After the reduction of TiO2 coated Fe oxide nanofibers, Fe nanofibers with a TiO2 coating layer of about 10 nm were successfully obtained. The morphology and structure of fibers were characterized by SEM, TEM, and XRD. In addition, the absorption properties of TiO2 coated Fe nanofibers were measured by network analyzer.

Surface XPS characterization of NiTi shape memory alloy after advanced oxidation processes in UV/H 2O 2 photocatalytic system

NASA Astrophysics Data System (ADS)

Wang, R. M.; Chu, C. L.; Hu, T.; Dong, Y. S.; Guo, C.; Sheng, X. B.; Lin, P. H.; Chung, C. Y.; Chu, P. K.

2007-08-01

Surface structure of NiTi shape memory alloy (SMA) was modified by advanced oxidation processes (AOP) in an ultraviolet (UV)/H 2O 2 photocatalytic system, and then systematically characterized with x-ray photoelectron spectroscopy (XPS). It is found that the AOP in UV/H 2O 2 photocatalytic system leads to formation of titanium oxides film on NiTi substrate. Depth profiles of O, Ni and Ti show such a film possesses a graded interface structure to NiTi substrate and there is no intermediate Ni-rich layer like that produced in conventional high temperature oxidation. Except TiO 2 phase, some titanium suboxides (TiO, Ti 2O 3) may also exist in the titanium oxides film. Oxygen mainly presents in metal oxides and some chemisorbed water and OH - are found in titanium oxides film. Ni nearly reaches zero on the upper surface and relatively depleted in the whole titanium oxides film. The work indicates the AOP in UV/H 2O 2 photocatalytic system is a promising way to favor the widespread application of biomedical NiTi SMA by improving its biocompatibility.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Byungsu; Samsung Display Co. Ltd., Tangjeong, Chungcheongnam-Do 336-741; Choi, Yonghyuk

We demonstrate an enhanced electrical stability through a Ti oxide (TiO{sub x}) layer on the amorphous InGaZnO (a-IGZO) back-channel; this layer acts as a surface polarity modifier. Ultrathin Ti deposited on the a-IGZO existed as a TiO{sub x} thin film, resulting in oxygen cross-binding with a-IGZO surface. The electrical properties of a-IGZO thin film transistors (TFTs) with TiO{sub x} depend on the surface polarity change and electronic band structure evolution. This result indicates that TiO{sub x} on the back-channel serves as not only a passivation layer protecting the channel from ambient molecules or process variables but also a control layermore » of TFT device parameters.« less

Stressor-layer-induced elastic strain sharing in SrTiO 3 complex oxide sheets

DOE PAGES

Tilka, J. A.; Park, J.; Ahn, Y.; ...

2018-02-26

A precisely selected elastic strain can be introduced in submicron-thick single-crystal SrTiO 3 sheets using a silicon nitride stressor layer. A conformal stressor layer deposited using plasma-enhanced chemical vapor deposition produces an elastic strain in the sheet consistent with the magnitude of the nitride residual stress. Synchrotron x-ray nanodiffraction reveals that the strain introduced in the SrTiO 3 sheets is on the order of 10 -4, matching the predictions of an elastic model. Using this approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect notmore » achievable in heteroepitaxy on rigid substrates.« less

Stressor-layer-induced elastic strain sharing in SrTiO 3 complex oxide sheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tilka, J. A.; Park, J.; Ahn, Y.

A precisely selected elastic strain can be introduced in submicron-thick single-crystal SrTiO 3 sheets using a silicon nitride stressor layer. A conformal stressor layer deposited using plasma-enhanced chemical vapor deposition produces an elastic strain in the sheet consistent with the magnitude of the nitride residual stress. Synchrotron x-ray nanodiffraction reveals that the strain introduced in the SrTiO 3 sheets is on the order of 10 -4, matching the predictions of an elastic model. Using this approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect notmore » achievable in heteroepitaxy on rigid substrates.« less

Transparent-conductive-oxide (TCO) buffer layer effect on the resistive switching process in metal/TiO2/TCO/metal assemblies

NASA Astrophysics Data System (ADS)

Filatova, E. O.; Baraban, A. P.; Konashuk, A. S.; Konyushenko, M. A.; Selivanov, A. A.; Sokolov, A. A.; Schaefers, F.; Drozd, V. E.

2014-11-01

The effect of a transparent conductive oxide (TCO) buffer layer on the insulator matrix and on the resistive switching process in the metal/TiO2/TCO/metal assembly was studied depending on the material of the TCO (ITO-(In2O3)0.9(SnO2)0.1 or SnO2 or ZnO). For the first time electro-physical studies and near edge x-ray absorption fine structure (NEXAFS) studies were carried out jointly and at the same point of the sample, providing direct experimental evidence that the switching process strongly influences the lowest unoccupied bands and the local atomic structure of the TiO2 layers. It was established that a TCO layer in a metal/TiO2/TCO/metal assembly is an additional source of oxygen vacancies for the TiO2 film. The RL (RH) states are achieved presumably with the formation (rupture) of the electrically conductive path of oxygen vacancies. Inserting an Al2O3 thin layer between the TiO2 and TCO layers to some extent restricts the processes of migration of the oxygen ions and vacancies, and does not allow the anti-clockwise bipolar resistive switching in a Au/TiO2/Al2O3/ITO/Au assembly. The greatest value of the ratio RH/RL is observed for the assembly with a SnO2 buffer layer that will provide the maximum set of intermediate states (recording analog data) and increase the density of information recording in this case.

Defect-rich Ni-Ti layered double hydroxide as a highly efficient support for Au nanoparticles in base-free and solvent-free selective oxidation of benzyl alcohol.

PubMed

Liu, Mengran; Fan, Guoli; Yu, Jiaying; Yang, Lan; Li, Feng

2018-04-17

Tuning the surface properties of supported metal catalysts is of vital importance for governing their catalytic performances in nanocatalysis. Here, we report highly dispersed nanometric gold nanoparticles (NPs) supported on Ni-Ti layered double hydroxides (NiTi-LDHs), which were employed in solvent-free and base-free selective oxidation of benzyl alcohol. A series of characterization techniques demonstrated that defect-rich NiTi-LDHs could efficiently stabilize Au NPs and decrease surface electron density of Au NPs. The as-formed Au/NiTi-LDH catalyst with a Ni/Ti molar ratio of 3 : 1 and an Au loading of 0.71 wt% yielded the highest turnover frequency value of ∼4981 h-1 at 120 °C among tested Au/NiTi-LDH catalysts with different Ni/Ti molar ratios, along with a high benzaldehyde selectivity of 98%. High catalytic efficiency of the catalyst was mainly correlated with surface cooperation between unique defects (i.e. defective Ti3+ species and oxygen vacancies) and abundant hydroxyl groups on the brucite-like layers of the NiTi-LDH support, which could lead to the preferential adsorption and activation of an alcohol hydroxyl moiety in benzyl alcohol and oxygen molecule, as well as the formation of more electron-deficient Ni3+ and Au0 species on the catalyst surface. Furthermore, the present Au/NiTi-LDH catalyst tolerated the oxidation of a wide variety of substrate structures into the corresponding aldehydes, acids or ketones. Our primary results illustrate that defect-rich NiTi-LDHs are promising supports which can efficiently modify surface structure and electronic properties of supported metal catalysts and consequently improve their catalytic performances.

Smooth Interfacial Scavenging for Resistive Switching Oxide via the Formation of Highly Uniform Layers of Amorphous TaOx.

PubMed

Tsurumaki-Fukuchi, Atsushi; Nakagawa, Ryosuke; Arita, Masashi; Takahashi, Yasuo

2018-02-14

We demonstrate that the inclusion of a Ta interfacial layer is a remarkably effective strategy for forming interfacial oxygen defects at metal/oxide junctions. The insertion of an interfacial layer of a reactive metal, that is, a "scavenging" layer, has been recently proposed as a way to create a high concentration of oxygen defects at an interface in redox-based resistive switching devices, and growing interest has been given to the underlying mechanism. Through structural and chemical analyses of Pt/metal/SrTiO 3 /Pt structures, we reveal that the rate and amount of oxygen scavenging are not directly determined by the formation free energies in the oxidation reactions of the scavenging metal and unveil the important roles of oxygen diffusibility. Active oxygen scavenging and highly uniform oxidation via scavenging are revealed for a Ta interfacial layer with high oxygen diffusibility. In addition, the Ta scavenging layer is shown to exhibit a highly uniform structure and to form a very flat interface with SrTiO 3 , which are advantageous for the fabrication of a steep metal/oxide contact.

Nanoparticle-induced oxidation of corona proteins initiates an oxidative stress response in cells†

PubMed Central

Jayaram, Dhanya T.; Runa, Sabiha; Kemp, Melissa L.

2017-01-01

Titanium dioxide nanoparticles (TiO2 NPs), used as pigments and photocatalysts, are ubiquitous in our daily lives. Previous work has observed cellular oxidative stress in response to the UV-excitation of photocatalytic TiO2 NPs. In comparison, most human exposure to TiO2 NPs takes place in the dark, in the lung following inhalation or in the gut following consumption of TiO2 NP food pigment. Our spectroscopic characterization shows that both photocatalytic and food grade TiO2 NPs, in the dark, generate low levels of reactive oxygen species (ROS), specifically hydroxyl radicals and superoxides. These ROS oxidize serum proteins that form a corona of proteins on the NP surface. This protein layer is the interface between the NP and the cell. An oxidized protein corona triggers an oxidative stress response, detected with PCR and western blotting. Surface modification of TiO2 NPs to increase or decrease surface defects correlates with ROS generation and oxidative stress, suggesting that NP surface defects, likely oxygen vacancies, are the underlying cause of TiO2 NP-induced oxidative stress. PMID:28537609

Engineering of highly ordered TiO2 nanopore arrays by anodization

NASA Astrophysics Data System (ADS)

Wang, Huijie; Huang, Zhennan; Zhang, Li; Ding, Jie; Ma, Zhaoxia; Liu, Yong; Kou, Shengzhong; Yang, Hangsheng

2016-07-01

Finite element analysis was used to simulate the current density distributions in the TiO2 barrier layer formed at the initial stage of Ti anodization. The morphology modification of the barrier layer was found to induce current density distribution change. By starting the anodization with proper TiO2 barrier layer morphology, the current density distribution can be adjusted to favor the formation of either nanotube arrays or nanopore arrays of anodic TiO2. We also found that the addition of sodium acetate into the electrolyte suppressed both the field-assisted chemical dissolution of TiO2 and the TiF62- hydrolysis induced TiO2 deposition during anodization, and thus further favored the nanopore formation. Accordingly, highly ordered anodic TiO2 nanopore arrays, similar to anodic aluminum oxide nanopore arrays, were successfully prepared.

Process for growing a film epitaxially upon a MgO surface

DOEpatents

McKee, Rodney Allen; Walker, Frederick Joseph

1997-01-01

A process and structure wherein optical quality perovskites, such as BaTiO.sub.3 or SrTiO.sub.3, are grown upon a single crystal MgO substrate involves the epitaxial build up of alternating planes of TiO.sub.2 and metal oxide wherein the first plane grown upon the MgO substrate is a plane of TiO.sub.2. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Interdiffusion-driven synthesis of tetragonal chromium (III) oxide on BaTi O3

NASA Astrophysics Data System (ADS)

Asa, M.; Vinai, G.; Hart, J. L.; Autieri, C.; Rinaldi, C.; Torelli, P.; Panaccione, G.; Taheri, M. L.; Picozzi, S.; Cantoni, M.

2018-03-01

Interfaces play a crucial role in the study of novel phenomena emerging at heterostructures comprising metals and functional oxides. For this reason, attention should be paid to the interface chemistry, which can favor the interdiffusion of atomic species and, under certain conditions, lead to the formation of radically different compounds with respect to the original constituents. In this work, we consider Cr/BaTi O3 heterostructures grown on SrTi O3 (100) substrates. Chromium thin films (1-2 nm thickness) are deposited by molecular beam epitaxy on the BaTi O3 layer, and subsequently annealed in vacuum at temperatures ranging from 473 to 773 K. A disordered metallic layer is detected for annealing temperatures up to 573 K, whereas, at higher temperatures, we observe a progressive oxidation of chromium, which we relate to the thermally activated migration of oxygen from the substrate. The chromium oxidation state is +3 and the film shows a defective rocksalt structure, which grows lattice matched on the underlying BaTi O3 layer. One out of every three atoms of chromium is missing, producing an uncommon tetragonal phase with C r2O3 stoichiometry. Despite the structural difference with respect to the ordinary corundum α-C r2O3 phase, we demonstrate both experimentally and theoretically that the electronic properties of the two phases are, to a large extent, equivalent.

The effect of thermal pre-treatment of titanium hydride (TiH2) powder in argon condition

NASA Astrophysics Data System (ADS)

Franciska P., L.; Erryani, Aprilia; Annur, Dhyah; Kartika, Ika

2018-04-01

Titanium hydride (TiH2) powders are used to enhance the foaming process in the formation of a highly porous metallic material with a cellular structure. But, the low temperature of hydrogen release is one of its problems. The present study, different thermal pre-treatment temperatures were employed to investigate the decomposition behavior of TiH2 to retard or delay a hydrogen gas release process during foaming. As a foaming agent, TiH2 was subjected to various heat treatments prior at 450 and 500°C during 2 hours in argon condition. To study the formation mechanism, the thermal behavior of titanium hydride and hydrogen release are investigated by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The morphology of pre-treated titanium hydride powders were examined using Scanning Electron Microscope (SEM) while unsure mapping and elemental composition of the pre-treated powders processed by Energy Dispersive Spectroscopy (EDS). To study the phase formation was characterized by X-ray diffraction analysis (XRD). In accordance with the results, an increase in pre-treatment temperature of TiH2 to higher degrees are changing the process of releasing hydrogen from titanium hydride powder. DTA/TGA results showed that thermal pre-treatment TiH2 at 450°C, released the hydrogen gas at 560°C in heat treatment when foaming process. Meanwhile, thermal pre-treatment in TiH2 at 500°C, released the hydrogen gas at 670°C when foaming process. There is plenty of direct evidence for the existence of oxide layers that showed by EDS analysis obtained in SEM. As oxygen is a light element and qualitative proof shows that the higher pre-treatment temperature produces more and thicker oxygen layers on the surface of the TiH2 powder particles. It might the thickness of oxide layer are different from different pre-treatment temperatures, which leading to the differences in the decomposition temperature. But from SEM result that oxidation of the powder does not change the powder morphology. The oxidation process also confirmed by XRD result, which showed higher thermal pre-treatment TiH2, more oxide higher peak is formed. The oxide layer of TiH2 particles is responsible for the observed shift in decomposition temperature and can prepare the stable foam that stabilizes forming of cell walls and avoid their collapse at higher temperatures.

Atomic-scale analysis of cation ordering in reduced calcium titanate.

PubMed

Li, Luying; Hu, Xiaokang; Jiang, Fan; Jing, Wenkui; Guo, Cong; Jia, Shuangfeng; Gao, Yihua; Wang, Jianbo

2017-11-03

The phenomenon of cation ordering is closely related to certain physical properties of complex oxides, which necessitates the search of underlying structure-property relationship at atomic resolution. Here we study the superlattices within reduced calcium titanate single crystal micro-pillars, which are unexpected from the originally proposed atomic model. Bright and dark contrasts at alternating Ti double layers perpendicular to b axis are clearly observed, but show no signs in corresponding image simulations based on the proposed atomic model. The multi-dimensional chemical analyses at atomic resolution reveal periodic lower Ti concentrations at alternating Ti double layers perpendicular to b axis. The following in-situ heating experiment shows no phase transition at the reported T c and temperature independence of the superlattices. The dimerization of the Ti-Ti bonds at neighboring double rutile-type chains within Ti puckered sheets are directly observed, which is found to be not disturbed by the cation ordering at alternating Ti double layers. The characterization of cation ordering of complex oxides from chemical and structural point of view at atomic resolution, and its reaction to temperature variations are important for further understanding their basic physical properties and exploiting potential applications.

Tunable Orbital-Selective Magnetic Interaction in Tricolor Oxide Interfaces

NASA Astrophysics Data System (ADS)

Cao, Yanwei; Kareev, Michael; Liu, Xiaoran; Choudhury, Debraj; Middey, Srimanta; Meyers, Derek; Chakhalian, Jak

2015-03-01

Recently, several theoretical scenarios of orbital-selective magnetic interactions were proposed to understand the emergence of the unexpected interfacial magnetism in the archetypical SrTiO3-based two-dimensional electron gas systems, the origin of which is still intriguing and not an entirely understood phenomenon in oxide interface physics. Experimentally, however, there thus far lacks a material system to directly demonstrate the magnetic interaction with orbital-selection (dxy vs. dxz/dyz) and eventually manipulate this magnetic interaction. To address this, here we induced 2DEG and localized magnetism into the same SrTiO3 layer by devising the heterostructure LaTiO3/SrTiO3/YTiO3. Combined electrical transport and atomic-resolved scanning transmission electron microscope with electron energy loss spectroscopy revealed that the magnetic localized electrons are formed by the spin transfer from the YTiO3 layer into 2DEG formed at the LaTiO3 /SrTiO3 interface, with the orbital occupancy and strength of the magnetic interaction controlled by the SrTiO3 layer thickness. Our work provides an ideal platform to explore the orbital physics driven by the interfacial magnetism with prospects for exciting spintronic applications.

Growth and Stability of Titanium Dioxide Nanoclusters on Graphene/Ru(0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frederick, Ryan T.; Novotny, Zbynek; Netzer, Falko P.

Titanium dioxide/graphene composites have recently been demonstrated to improve the photocatalytic activity of TiO2 in visible light. To better understand the interactions of TiO2 with graphene we have investigated the growth of TiO2 nanoclusters on single-layer graphene/Ru(0001) using scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES). Deposition of Ti in the O2 background at 300 K resulted in the formation of nanoclusters nucleating on intrinsic defects in the graphene (Gr) layer. The saturation nanocluster density decreased as the substrate temperature was increased from 300 to 650 K, while deposition at 700 K resulted in the significant etching of themore » Gr layer. We have also prepared nanoclusters with Ti2O3 stoichiometry using lower O2 pressures at 650 K. Thermal stability of the TiO2 nanoclusters prepared at 300 K was evaluated with AES and STM. No change in oxidation state for the TiO2 nanoclusters or etching of the Gr layer was observed up to ~900 K. Annealing studies characterized using STM revealed that cluster ripening proceeds via a Smoluchowski mechanism below 800 K and that Ostwald ripening dominates above 800 K. At even higher temperatures, the nanoclusters undergo reduction to TiOx (x ≈ 1 - 1.5) which is accompanied by oxidation and etching of the Gr. Our studies demonstrate that highly thermally stable TiOx nanoclusters of controlled composition and morphology can be prepared on Gr supports.« less

Air Oxidation Behavior of Two Ti-Base Alloys Synthesized by HIP

NASA Astrophysics Data System (ADS)

Liu, S.; Guo, Q. Q.; Liu, L. L.; Xu, L.; Liu, Y. Y.

2016-04-01

The oxidation behavior of Ti-5Al-2.5Sn and Ti-6Al-4V produced by hot isostatic pressing (HIP) has been studied at 650-850°C in air for 24 h. The oxidation kinetics of both alloys followed the parabolic law with good approximation, except for Ti-5Al-2.5Sn oxidized at 850°C. Multi-layered scales formed on both alloys at 750°C and 850°C. Ternary additions of Sn and V accounted for the different morphology of the scales formed on these two alloys. In addition, the oxidation behavior of HIP alloys is compared with that of the corresponding cast alloys and the scaling mechanism is discussed.

Single and multi-layered core-shell structures based on ZnO nanorods obtained by aerosol assisted chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sáenz-Trevizo, A.; Amézaga-Madrid, P.; Pizá-Ruiz, P.

2015-07-15

Core–shell nanorod structures were prepared by a sequential synthesis using an aerosol assisted chemical vapor deposition technique. Several samples consisting of ZnO nanorods were initially grown over TiO{sub 2} film-coated borosilicate glass substrates, following the synthesis conditions reported elsewhere. Later on, a uniform layer consisting of individual Al, Ni, Ti or Fe oxides was grown onto ZnO nanorod samples forming the so-called single MO{sub x}/ZnO nanorod core–shell structures, where MO{sub x} was the metal oxide shell. Additionally, a three-layer core–shell sample was developed by growing Fe, Ti and Fe oxides alternately, onto the ZnO nanorods. The microstructure of the core–shellmore » materials was characterized by grazing incidence X-ray diffraction, scanning and transmission electron microscopy. Energy dispersive X-ray spectroscopy was employed to corroborate the formation of different metal oxides. X-ray diffraction outcomes for single core–shell structures showed solely the presence of ZnO as wurtzite and TiO{sub 2} as anatase. For the multi-layered shell sample, the existence of Fe{sub 2}O{sub 3} as hematite was also detected. Morphological observations suggested the existence of an outer material grown onto the nanorods and further microstructural analysis by HR-STEM confirmed the development of core–shell structures in all cases. These studies also showed that the individual Al, Fe, Ni and Ti oxide layers are amorphous; an observation that matched with X-ray diffraction analysis where no apparent extra oxides were detected. For the multi-layered sample, the development of a shell consisting of three different oxide layers onto the nanorods was found. Overall results showed that no alteration in the primary ZnO core was produced during the growth of the shells, indicating that the deposition technique used herein was and it is suitable for the synthesis of homogeneous and complex nanomaterials high in quality and purity. In addition, materials absorptance determined from the total transmittance and reflectance spectra revealed a broader absorption interval including visible light, indicating potential uses of these nanostructures on solar energy appliances. - Graphical abstract: Display Omitted - Highlights: • Uniform ZnO nanorods (core)–metal oxide (shell) were obtained sequentially by AACVD. • Shells were structured of homogeneous single or multi-layered non-mixed metal oxides. • ZnO nanorod core was preserved during the shell synthesis. • Optical absorptance revealed visible interval absorption for FeO{sub x} shell samples. • Materials can be suitable for photocatalytic or photovoltaic applications.« less

Layered CU-based electrode for high-dielectric constant oxide thin film-based devices

DOEpatents

Auciello, Orlando

2010-05-11

A layered device including a substrate; an adhering layer thereon. An electrical conducting layer such as copper is deposited on the adhering layer and then a barrier layer of an amorphous oxide of TiAl followed by a high dielectric layer are deposited to form one or more of an electrical device such as a capacitor or a transistor or MEMS and/or a magnetic device.

Optimization of Oxidation Temperature for Commercially Pure Titanium to Achieve Improved Corrosion Resistance

NASA Astrophysics Data System (ADS)

Bansal, Rajesh; Singh, J. K.; Singh, Vakil; Singh, D. D. N.; Das, Parimal

2017-03-01

Thermal oxidation of commercially pure titanium (cp-Ti) was carried out at different temperatures, ranging from 200 to 900 °C to achieve optimum corrosion resistance of the thermally treated surface in simulated body fluid. Scanning electron microscopy, x-ray diffraction, Raman spectroscopy and electrochemical impedance spectroscopy techniques were used to characterize the oxides and assess their protective properties exposed in the test electrolyte. Maximum resistance toward corrosion was observed for samples oxidized at 500 °C. This was attributed to the formation of a composite layer of oxides at this temperature comprising Ti2O3 (titanium sesquioxide), anatase and rutile phases of TiO2 on the surface of cp-Ti. Formation of an intact and pore-free oxide-substrate interface also improved its corrosion resistance.

Dry-spray deposition of TiO2 for a flexible dye-sensitized solar cell (DSSC) using a nanoparticle deposition system (NPDS).

PubMed

Kim, Min-Saeng; Chun, Doo-Man; Choi, Jung-Oh; Lee, Jong-Cheon; Kim, Yang Hee; Kim, Kwang-Su; Lee, Caroline Sunyong; Ahn, Sung-Hoon

2012-04-01

TiO2 powders were deposited on indium tin oxide (ITO) coated polyethylene terephthalate (PET) substrates for application to the photoelectrode of a dye-sensitized solar cell (DSSC). In the conventional DSSC manufacturing process, a semiconductor oxide such as TiO2 powder requires a sintering process at higher temperature than the glass transition temperature (T(g)) of polymers, and thus utilization of flexible polymer substrates in DSSC research has been constrained. To overcome this restriction related to sintering, we used a nanoparticle deposition system (NPDS) that could produce a thin coating layer through a dry-spray method under atmospheric pressure at room temperature. The powder was sprayed through a slit-type nozzle having a 0.4 x 10 mm2 rectangular outlet. In order to determine the deposited TiO2 thickness, five kinds of TiO2 layered specimens were prepared, where the specimens have single and double layer structures. Deposited powders on the ITO coated PET substrates were observed using FE-SEM and a scan profiler The thicker TiO2 photoelectrode with a DSSC having a double layer structure showed higher energy efficiency than the single layer case. The highest fabricated flexible DSSC displayed a short circuit current density J(sc) = 1.99 mA cm(-2), open circuit voltage V(oc) = 0.71 V, and energy efficiency eta = 0.94%. These results demonstrate the possibility of utilizing the dry-spray method to fabricate a TiO2 layer on flexible polymer substrates at room temperature under atmospheric pressure.

Novel Magnetic Phenomena in Oxide Thin Films, Interfaces and Heterostructures

NASA Astrophysics Data System (ADS)

Venkatesan, Thirumalai

2015-03-01

Oxide films, heterostructures and interfaces present wonderful opportunities for exploring novel magnetic phenomena. The idea of cationic vacancy induced ferromagnetism was demonstrated by observing ferromagnetism in TaxTi1-xO2(x = 2 - 6%). Using XAS, XPS and XMCD, the magnetism was mainly located at the Ti sites and was shown to arise from Ti vacancies as opposed to Ti3+. The substrate-film interface was crucial for observing the ferromagnetism, as the required concentration of Ti vacancies could only be maintained close to the interface. With electron transport we were able to see with increasing thickness the emerging role of Kondo scattering (mediated by Ti3+) and at larger thickness impurity scattering. The polar LaAlO3/non-polar SrTiO3 interface exhibits a mixture of magnetic phases most likely arising from cationic defects and selective electron occupancy in Ti t2g levels. Using XMCD ferromagnetism was seen at these interfaces even at room temperature. Unlike LaAlO3, polar LaMnO3 is an insulator exhibiting orbital order that has a smaller band gap than SrTiO3. It is a traditional antiferromagnetic material, but when grown on SrTiO3, LaMnO3 exhibits ferromagnetism for film thicknesses exceeding 5 unit cells. This is discussed in terms of electronic reconstruction with polar charge transfer to the LaMnO3 side of the interface and also to the surface of the over layer. Novel magnetic coupling effects are seen in perovskite ferromagnets separated by a polar oxide layer such as LaAlO3 or NdGaO3, whereas non-polar oxides do not show the same effect. The coupling between the ferromagnetic layers oscillates in sign between FM and AFM, depending on the barrier thickness. Such coupling is totally unexpected in the absence of any itinerary electrons, with insulating barriers that are too thick for tunneling. The novel magnetic coupling is shown to be mediated by spin-orbit coupling and also magnetic excitation of defect levels in the polar oxide planes.

Conducting interface in oxide homojunction: Understanding of superior properties in black TiO 2

DOE PAGES

Lu, Xujie; Chen, Aiping; Luo, Yongkang; ...

2016-09-14

Black TiO 2 nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO 2. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO 2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO 2 nanoparticles. Metallic conduction is achieved at the crystalline–amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO 2.more » As a result, this work not only achieves an unprecedented understanding of black TiO 2 but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest.« less

Improving the efficiency of cadmium sulfide-sensitized titanium dioxide/indium tin oxide glass photoelectrodes using silver sulfide as an energy barrier layer and a light absorber

PubMed Central

2014-01-01

Cadmium sulfide (CdS) and silver sulfide (Ag2S) nanocrystals are deposited on the titanium dioxide (TiO2) nanocrystalline film on indium tin oxide (ITO) substrate to prepare CdS/Ag2S/TiO2/ITO photoelectrodes through a new method known as the molecular precursor decomposition method. The Ag2S is interposed between the TiO2 nanocrystal film and CdS nanocrystals as an energy barrier layer and a light absorber. As a consequence, the energy conversion efficiency of the CdS/Ag2S/TiO2/ITO electrodes is significantly improved. Under AM 1.5 G sunlight irradiation, the maximum efficiency achieved for the CdS(4)/Ag2S/TiO2/ITO electrode is 3.46%, corresponding to an increase of about 150% as compared to the CdS(4)/TiO2/ITO electrode without the Ag2S layer. Our experimental results show that the improved efficiency is mainly due to the formation of Ag2S layer that may increase the light absorbance and reduce the recombination of photogenerated electrons with redox ions from the electrolyte. PMID:25411566

Magnetoresistance of oxygen concentration-modulated Co-Ti-O films

NASA Astrophysics Data System (ADS)

Nakano, Masatoshi; Wan, Fuxing; Wang, Jian; Sannomiya, Takumi; Muraishi, Shinji; Harumoto, Takashi; Nakamura, Yoshio; Shi, Ji

2018-06-01

Co-Ti-O films have been prepared by a sputtering method in an Ar- and O2-mixed atmosphere. The O2 flow rate was modulated during the deposition to optimize the oxygen concentration and the microstructure of the films. For the as-deposited film, negligible magnetization and magnetoresistance (MR) were observed. The structure of the layers with lower O2 flow rate is basically amorphous alloy with Ti-O and Co-Ti bonds. On the other hand, in the layers with high O2 flow rate, both Ti and Co are oxidized. Upon thermal annealing in a vacuum, significant enhancements in both magnetization and MR in Co-Ti-O films were observed. It is found that granular structure of Co particles embedded in insulating TiO2 matrix is formed due to the oxygen diffusion and further oxidization of Ti as a result of the heat treatment. The significantly enhanced magnetization and MR ratio have been ascribed to the formation of nano-sized Co particles and the tunneling conduction between these Co particles across the TiO2 interlayers, respectively.

Optimization of chemical structure of Schottky-type selection diode for crossbar resistive memory.

PubMed

Kim, Gun Hwan; Lee, Jong Ho; Jeon, Woojin; Song, Seul Ji; Seok, Jun Yeong; Yoon, Jung Ho; Yoon, Kyung Jean; Park, Tae Joo; Hwang, Cheol Seong

2012-10-24

The electrical performances of Pt/TiO(2)/Ti/Pt stacked Schottky-type diode (SD) was systematically examined, and this performance is dependent on the chemical structures of the each layer and their interfaces. The Ti layers containing a tolerable amount of oxygen showed metallic electrical conduction characteristics, which was confirmed by sheet resistance measurement with elevating the temperature, transmission line measurement (TLM), and Auger electron spectroscopy (AES) analysis. However, the chemical structure of SD stack and resulting electrical properties were crucially affected by the dissolved oxygen concentration in the Ti layers. The lower oxidation potential of the Ti layer with initially higher oxygen concentration suppressed the oxygen deficiency of the overlying TiO(2) layer induced by consumption of the oxygen from TiO(2) layer. This structure results in the lower reverse current of SDs without significant degradation of forward-state current. Conductive atomic force microscopy (CAFM) analysis showed the current conduction through the local conduction paths in the presented SDs, which guarantees a sufficient forward-current density as a selection device for highly integrated crossbar array resistive memory.

Micro-arc oxidation treatment to improve the hard-tissue compatibility of Ti-29Nb-13Ta-4.6Zr alloy

NASA Astrophysics Data System (ADS)

Tsutsumi, Yusuke; Niinomi, Mitsuo; Nakai, Masaaki; Tsutsumi, Harumi; Doi, Hisashi; Nomura, Naoyuki; Hanawa, Takao

2012-12-01

Micro-arc oxidation (MAO) was performed on a β-type Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) in this study to improve its bioactivity in a body fluid and its hard-tissue compatibility. The surface oxide layer formed on TNTZ by MAO treatment in a mixture of calcium glycerophosphate and magnesium acetate was characterized using various surface analyses. The oxide layer was mainly composed of two types of TiO2 (rutile and anatase), and it also contained Ca, P, and Mg, which were incorporated from the electrolyte during the treatment. The calcium phosphate formation on the surface of the specimens after immersion in Hanks' solution was evaluated to determine the bioactivity of TNTZ with and without MAO treatment. As a result, thick calcium phosphate layers formed on the TNTZ specimen that underwent MAO treatment, whereas only a small amount of precipitate was observed on TNTZ without treatment. Thus, the MAO treatment is a promising method to improve the bioactivity and hard-tissue compatibility of TNTZ.

Effect of Ti3SiC2 on Tribological Properties of M50 Matrix Self-Lubricating Composites from 25 to 450 °C

NASA Astrophysics Data System (ADS)

Deng, Xiaobin; Shi, Xiaoliang; Liu, Xiyao; Huang, Yuchun; Yan, Zhao; Yang, Kang; Wang, Yufu

2017-09-01

The tribological performance is a key factor for M50 steel that is widely used in aero-engine main-shaft bearings. In this study, the tribological properties of M50 matrix self-lubricating composites with different contents of Ti3SiC2 against Si3N4 ceramic counterpart are investigated at 15 N-0.2 m/s from 25 to 450 °C. The results showed that M50 with 10 wt.% Ti3SiC2 (MT10) exhibits the lower friction coefficients (0.21-0.78) and less wear rates (1.78-3.14 × 10-6 mm3 N-1 m-1) at 25-450 °C. Especially at 350 °C, MT10 shows the lowest friction coefficient and wear rate owing to the formation of smooth lubricating layer containing Ti3SiC2 and oxides. Ti3SiC2 and compacted Ti-Si-oxides are uniformly distributed in the lubricating layer, which can well improve the anti-friction and anti-wear performance of MT10. The mechanically mixed layer containing massive Ti3SiC2 can sustain the lubricating layer, resulting in the increase of anti-wear performance of MT10. MT10 could be applied under the practical conditions of friction and wear for its outstanding anti-friction and anti-wear performance.

The Interface Structure of High-Temperature Oxidation-Resistant Aluminum-Based Coatings on Titanium Billet Surface

NASA Astrophysics Data System (ADS)

Xu, Zhefeng; Rong, Ju; Yu, Xiaohua; Kun, Meng; Zhan, Zhaolin; Wang, Xiao; Zhang, Yannan

2017-10-01

A new type of high-temperature oxidation-resistant aluminum-based coating, on a titanium billet surface, was fabricated by the cold spray method, at a high temperature of 1050°C, for 8 h, under atmospheric pressure. The microstructure of the exposed surface was analyzed via optical microscopy, the microstructure of the coating and elemental diffusion was analyzed via field emission scanning electron microscopy, and the interfacial phases were identified via x-ray diffraction. The Ti-Al binary phase diagram and Gibbs free energy of the stable phase were calculated by Thermo-calc. The results revealed that good oxidation resistant 50-μm-thick coatings were successfully obtained after 8 h at 1050°C. Two layers were obtained after the coating process: an Al2O3 oxidation layer and a TiAl3 transition layer on the Ti-based substrate. The large and brittle Al2O3 grains on the surface, which can be easily spalled off from the surface after thermal processing, protected the substrate against oxidation during processing. In addition, the thermodynamic calculation results were in good agreement with the experimental data.

Strain-induced phenomenon in complex oxide thin films

NASA Astrophysics Data System (ADS)

Haislmaier, Ryan

Complex oxide materials wield an immense spectrum of functional properties such as ferroelectricity, ferromagnetism, magnetoelectricity, optoelectricity, optomechanical, magnetoresistance, superconductivity, etc. The rich coupling between charge, spin, strain, and orbital degrees of freedom makes this material class extremely desirable and relevant for next generation electronic devices and technologies which are trending towards nanoscale dimensions. Development of complex oxide thin film materials is essential for realizing their integration into nanoscale electronic devices, where theoretically predicted multifunctional capabilities of oxides could add tremendous value. Employing thin film growth strategies such as epitaxial strain and heterostructure interface engineering can greatly enhance and even unlock novel material properties in complex oxides, which will be the main focus of this work. However, physically incorporating oxide materials into devices remains a challenge. While advancements in molecular beam epitaxy (MBE) of thin film oxide materials has led to the ability to grow oxide materials with atomic layer precision, there are still major limitations such as controlling stoichiometric compositions during growth as well as creating abrupt interfaces in multi-component layered oxide structures. The work done in this thesis addresses ways to overcome these limitations in order to harness intrinsic material phenomena. The development of adsorption-controlled stoichiometric growth windows of CaTiO3 and SrTiO3 thin film materials grown by hybrid MBE where Ti is supplied using metal-organic titanium tetraisopropoxide material is thoroughly outlined. These growth windows enable superior epitaxial strain-induced ferroelectric and dielectric properties to be accessed as demonstrated by chemical, structural, electrical, and optical characterization techniques. For tensile strained CaTiO3 and compressive strained SrTiO 3 films, the critical effects of nonstoichiometry on ferroelectric properties are investigated, where enhanced ferroelectric responses are only found for stoichiometric films grown inside of the growth windows, whereas outside of the optimal growth window conditions, ferroelectric properties are greatly deteriorated and eventually disappear for highly nonstoichiometric film compositions. Utilizing these stoichiometric growth windows, high temperature polar phase transitions are discovered for compressively strained CaTiO3 films with transition temperatures in excess of 700 K, rendering this material as a strong candidate for high temperature electronic applications. Beyond the synthesis of single phase materials using hybrid MBE, a methodology is presented for constructing layered (SrTiO3)n/(CaTiO 3)n superlattice structures, where precise control over the unit cell layering thickness (n) is demonstrated using in-situ reflection high energy electron diffraction. The effects of interface roughness and layering periodicity (n) on the strain-induced ferroelectric properties for a series of n=1-10 (SrTiO3)n/(CaTiO3) n superlattice films are investigated. It is found that the stabilization of a ferroelectric phase is independent of n, but is however strongly dominated by the degree of interface roughness which is quantified by measuring the highest nth order X-ray diffraction peak splitting of each superlattice film. A counter-intuitive realization is made whereby a critical amount of interface roughness is required in order to enable the formation of the predicted strain-stabilized ferroelectric phase, whereas sharp interfaces actually suppress this ferroelectric phase from manifesting. It is shown how high-quality complex oxide superlattices can be constructed using hybrid MBE technique, allowing the ability to control layered materials at the atomic scale. Furthermore, a detailed growth methodology is provided for constructing a layered n=4 SrO(SrTiO3)n Ruddlesden-Popper (RP) phase by hybrid MBE, where the ability to deposit single monolayers of SrO and TiO2 is utilized to build the RP film structure over a time period of 5 hours. This is the first time that a thin film RP phase has been grown using hybrid MBE, where an a stable control over the fluxes is demonstrated during relatively long time periods of growth, which advantageously facilitates the synthesis of high-quality RP materials with excellent structural and chemical homogeneity. Additionally, this work demonstrates some major advancements in optical second harmonic generation (SHG) characterization techniques of ferroelectric thin film materials. The SHG characterization techniques developed here proved to be the 'bread-and-butter' for most of the work performed in this thesis, providing a powerful tool for identifying the existence of strain-induced ferroelectric phases, including their temperature dependence and polar symmetry. The work presented in this dissertation will hopefully provide a preliminary road map for future hybrid MBE growers, scientists and researchers, to develop and investigate epitaxial strain and heterostructure layering induced phenomena in other complex oxide systems.

Mo/Si multilayers with enhanced TiO II- and RuO II-capping layers

NASA Astrophysics Data System (ADS)

Yulin, Sergiy; Benoit, Nicolas; Feigl, Torsten; Kaiser, Norbert; Fang, Ming; Chandhok, Manish

2008-03-01

The lifetime of Mo/Si multilayer-coated projection optics is one of the outstanding issues on the road of commercialization of extreme-ultraviolet lithography (EUVL). The application of Mo/Si multilayer optics in EUVL requires both sufficient radiation stability and also the highest possible normal-incidence reflectivity. A serious problem of conventional high-reflective Mo/Si multilayers capped by silicon is the considerable degradation of reflective properties due to carbonization and oxidation of the silicon surface layer under exposure by EUV radiation. In this study, we focus on titanium dioxide (TiO II) and ruthenium dioxide (RuO II) as promising capping layer materials for EUVL multilayer coatings. The multilayer designs as well as the deposition parameters of the Mo/Si systems with different capping layers were optimized in terms of maximum peak reflectivity at the wavelength of 13.5 nm and longterm stability under high-intensive irradiation. Optimized TiO II-capped Mo/Si multilayer mirrors with an initial reflectivity of 67.0% presented a reflectivity drop of 0.6% after an irradiation dose of 760 J/mm2. The reflectivity drop was explained by the partial oxidation of the silicon sub-layer. No reflectivity loss after similar irradiation dose was found for RuO II-capped Mo/Si multilayer mirrors having initial peak reflectivity of 66%. In this paper we present data on improved reflectivity of interface-engineered TiO II- and RuO II-capped Mo/Si multilayer mirrors due to the minimization of both interdiffusion processes inside the multilayer stack and absorption loss in the oxide layer. Reflectivities of 68.5% at the wavelength of 13.4 nm were achieved for both TiO II- and RuO II-capped Mo/Si multilayer mirrors.

Superconductivity-induced magnetization depletion in a ferromagnet through an insulator in a ferromagnet-insulator-superconductor hybrid oxide heterostructure.

PubMed

Prajapat, C L; Singh, Surendra; Paul, Amitesh; Bhattacharya, D; Singh, M R; Mattauch, S; Ravikumar, G; Basu, S

2016-05-21

Coupling between superconducting and ferromagnetic states in hybrid oxide heterostructures is presently a topic of intense research. Such a coupling is due to the leakage of the Cooper pairs into the ferromagnet. However, tunneling of the Cooper pairs though an insulator was never considered plausible. Using depth sensitive polarized neutron reflectivity we demonstrate the coupling between superconductor and magnetic layers in epitaxial La2/3Ca1/3MnO3 (LCMO)/SrTiO3/YBa2Cu3O7-δ (YBCO) hybrid heterostructures, with SrTiO3 as an intervening oxide insulator layer between the ferromagnet and the superconductor. Measurements above and below the superconducting transition temperature (TSC) of YBCO demonstrate a large modulation of magnetization in the ferromagnetic layer below the TSC of YBCO in these heterostructures. This work highlights a unique tunneling phenomenon between the epitaxial layers of an oxide superconductor (YBCO) and a magnetic layer (LCMO) through an insulating layer. Our work would inspire further investigations on the fundamental aspect of a long range order of the triplet spin-pairing in hybrid structures.

Butanol Dehydration over V₂O₅-TiO₂/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition.

PubMed

Choi, Hyeonhee; Bae, Jung-Hyun; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki

2013-04-29

MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

Process for growing a film epitaxially upon a MGO surface and structures formed with the process

DOEpatents

McKee, Rodney Allen; Walker, Frederick Joseph

1998-01-01

A process and structure wherein optical quality perovskites, such as BaTiO.sub.3 or SrTiO.sub.3, are grown upon a single crystal MgO substrate involves the epitaxial build up of alternating planes of TiO.sub.2 and metal oxide wherein the first plane grown upon the MgO substrate is a plane of TiO.sub.2. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Studies of surface modified NiTi alloy

NASA Astrophysics Data System (ADS)

Shevchenko, N.; Pham, M.-T.; Maitz, M. F.

2004-07-01

A corrosion resistant and nickel free surface on NiTi (nitinol) for biomedical applications should be produced by ion implantation. Ar + and/or N + implantation in NiTi alloy was performed at energies of 20-40 keV and fluences of (3-5) × 10 17 cm -2 by means of plasma immersion ion implantation. The modification of the NiTi alloy and its biocompatibility properties were studied. The near surface layers were analysed by Auger electron spectroscopy (AES), grazing incidence X-ray diffraction (GIXRD) and cell culture tests, and electrochemical corrosion analysis of these layers was performed. A nickel depleted surface layer is produced by the implantation, which was sealed by the formation of TiN or Ti oxide layers at the different implantation regimes, respectively. No differences in biocompatibility were seen on the modified compared with the initial surfaces. The corrosion stability increased by this treatment.

Biocompatilibity-related surface characteristics of oxidized NiTi.

PubMed

Danilov, Anatoli; Tuukkanen, Tuomas; Tuukkanen, Juha; Jämsä, Timo

2007-09-15

In the present study, we examined the effect of NiTi oxidation on material surface characteristics related to biocompatibility. Correspondence between electron work function (EWF) and adhesive force predicted by electron theory of adsorption as well as the effect of surface mechanical stress on the adhesive force were studied on the nonoxidized and oxidized at 350, 450, and 600 degrees C NiTi alloy for medical application. The adhesive force generated by the material surface towards the drops of alpha-minimal essential medium (alpha-MEM) was used as a characteristic of NiTi adsorption properties. The study showed that variations in EWF and mechanical stress caused by surface treatment were accompanied by variations in adhesive force. NiTi oxidation at all temperatures used gave rise to decrease in adhesive force and surface stress values in comparison to the nonoxidized state. In contrary, the EWF value revealed increase under the same condition. Variations in surface oxide layer thickness and its phase composition were also followed. The important role of oxide crystallite size in EWF values within the range of crystallite dimensions typical for NiTi surface oxide as an instrument for the fine regulation of NiTi adsorption properties was demonstrated. The comparative oxidation of pure titanium and NiTi showed that the effect of Ni on the EWF value of NiTi surface oxide is negligible. Copyright 2007 Wiley Periodicals, Inc.

Chemical variations in the Triple Group of the Skaergaard intrusion: insights for the mineralization and crystallization process

NASA Astrophysics Data System (ADS)

Nielsen, T. F.; Bernstein, S.

2009-12-01

The 54 Ma. old Skaergaard intrusion ( East Greenland) is a type example for fractionation of basaltic melt along the Fenner Trend. The Triple Group is the upper most 100 m of the Middle Zone and consists of FeTi-oxide rich layered gabbro with three distinct leugabbro layers 2-5 m thick ( L-layers; L1-L3, 2-5m thick) and a less marked layer (L0) c.20 m below L1. These are the most marked of many such layers. Apart from the pronounced layering the lower part of the Triple Group also hosts a world class Au-PGE mineralization. The mineralization is perfectly concordant with the L-layers, and the Triple Group invites investigation of the relationship between host and mineralization. The mineralization includes 5 main levels defined by palladium concentration. The chemical variation across the mineralization is covered by ca. 250 bulk major and trace element compositions, each representing 25cm of stratigraphy giving a continuum of ca. 60m. Proportions of normative plagioclase (plag) and pyroxene (px, including cpx and opx) are complementary, except in mineralized gabbro which is rich in FeTi-oxides. Cumulus ilmenite (ilm) is strongly enriched in layers (7m apart). They occur in both plag- and px-rich gabbro, whereas magnetite (mt) shows no simple correlation with ilm and is mainly a poikilitic intercumulus phase. The L-layers are composed of an upper part rich in plag and px and poor in FeTi-oxides, and a lower part rich in plag and FeTi-oxides and poor in px. The marked breaks in the mineralogy in the L-layers separate one layered succession from the next. The layered successions consist of a lower oxide-poor px-plag adcumulate, followed by complex mesocratic orthocumulate with poikilitic interstitial FeTi-oxide, and an upper part of increasingly simple plag-rich adcumulate with decreasing content of interstitial mt. The Au-PGE mineralized levels are found in the complex FeTi-rich gabbros at and in the base of the leucogabbro layers. The stratigraphic variation in density and densities of melt and liquidus phases suggest plag to have neutral buoyancy (floating), whereas all other phases would sink. The repeated successions are suggested to be the result of repeated “self-stratification” in the mush zone at the crystallization front, characterized by separation of px and plag leaving a transitional zone enriched in Fe-rich melt. In this melt, crystallization of mt led to S-saturation and formation of immiscible sulfide globules (30µm) in which PGE-minerals crystallize. During solidification, residual or immiscible Si-rich melt and volatiles rose from the transitional zone and took Au, Ag, Pt, Te, As, Pb, Sb, Sn, a.o. along to the main magma above and at late stage to granophyric veins. The Fe-enriched gabbros in the transitional zone are commonly accepted as average gabbros, but are in the Triple Group mixes of cumulus phases and evolved Fe-rich melt and should be used with care in the modeling of lines of liquid descent.

Efficient Performance of Electrostatic Spray-Deposited TiO2 Blocking Layers in Dye-Sensitized Solar Cells after Swift Heavy Ion Beam Irradiation.

PubMed

Sudhagar, P; Asokan, K; Jung, June Hyuk; Lee, Yong-Gun; Park, Suil; Kang, Yong Soo

2011-12-01

A compact TiO2 layer (~1.1 μm) prepared by electrostatic spray deposition (ESD) and swift heavy ion beam (SHI) irradiation using oxygen ions onto a fluorinated tin oxide (FTO) conducting substrate showed enhancement of photovoltaic performance in dye-sensitized solar cells (DSSCs). The short circuit current density (Jsc = 12.2 mA cm(-2)) of DSSCs was found to increase significantly when an ESD technique was applied for fabrication of the TiO2 blocking layer, compared to a conventional spin-coated layer (Jsc = 8.9 mA cm(-2)). When SHI irradiation of oxygen ions of fluence 1 × 10(13) ions/cm(2) was carried out on the ESD TiO2, it was found that the energy conversion efficiency improved mainly due to the increase in open circuit voltage of DSSCs. This increased energy conversion efficiency seems to be associated with improved electronic energy transfer by increasing the densification of the blocking layer and improving the adhesion between the blocking layer and the FTO substrate. The adhesion results from instantaneous local melting of the TiO2 particles. An increase in the electron transport from the blocking layer may also retard the electron recombination process due to the oxidized species present in the electrolyte. These findings from novel treatments using ESD and SHI irradiation techniques may provide a new tool to improve the photovoltaic performance of DSSCs.

Efficient Performance of Electrostatic Spray-Deposited TiO2 Blocking Layers in Dye-Sensitized Solar Cells after Swift Heavy Ion Beam Irradiation

PubMed Central

2011-01-01

A compact TiO2 layer (~1.1 μm) prepared by electrostatic spray deposition (ESD) and swift heavy ion beam (SHI) irradiation using oxygen ions onto a fluorinated tin oxide (FTO) conducting substrate showed enhancement of photovoltaic performance in dye-sensitized solar cells (DSSCs). The short circuit current density (Jsc = 12.2 mA cm-2) of DSSCs was found to increase significantly when an ESD technique was applied for fabrication of the TiO2 blocking layer, compared to a conventional spin-coated layer (Jsc = 8.9 mA cm-2). When SHI irradiation of oxygen ions of fluence 1 × 1013 ions/cm2 was carried out on the ESD TiO2, it was found that the energy conversion efficiency improved mainly due to the increase in open circuit voltage of DSSCs. This increased energy conversion efficiency seems to be associated with improved electronic energy transfer by increasing the densification of the blocking layer and improving the adhesion between the blocking layer and the FTO substrate. The adhesion results from instantaneous local melting of the TiO2 particles. An increase in the electron transport from the blocking layer may also retard the electron recombination process due to the oxidized species present in the electrolyte. These findings from novel treatments using ESD and SHI irradiation techniques may provide a new tool to improve the photovoltaic performance of DSSCs. PMID:27502653

Corrosion behavior of ceramic-coated ZIRLO™ exposed to supercritical water

NASA Astrophysics Data System (ADS)

Mandapaka, Kiran K.; Cahyadi, Rico S.; Yalisove, Steven; Kuang, Wenjun; Sickafus, K.; Patel, Maulik K.; Was, Gary S.

2018-01-01

The corrosion behavior of ceramic coated ZIRLO™ tubing was evaluated in a supercritical water (SCW) environment to determine its behavior in high temperature water. Two coating architectures were analyzed; a 4 bi-layer TiAlN/TiN coating with Ti bond coat, and a TiN monolithic coating with Ti bond layer on ZIRLO™ tubes using cathodic arc physical vapor deposition (CA-PVD) technique. Femtosecond laser ablation was used to introduce reproducible defects in some of the coated tubes. On exposure to deaerated supercritical water at 542 °C for 48 h, coated tubes exhibited significantly higher weight gain compared to uncoated ZIRLO™. Examination revealed formation of a uniform ZrO2 layer beneath the coating of a thickness similar to that on the uncoated tube inner surface. The defects generated during the coating process acted as preferential paths for diffusion of oxygen resulting in the oxidation of substrate ZIRLO™. However, there was no delamination of the coating. There were insignificant differences in the oxidation weight gain between laser ablated and non-ablated tubes and the laser induced defects did not spread beyond their original size.

Effect of niobium alloying level on the oxidation behavior of titanium aluminides at 850°C

NASA Astrophysics Data System (ADS)

Banu, Alexandra; Marcu, Maria; Petrescu, Simona; Ionescu, Nicolae; Paraschiv, Alexandru

2016-12-01

This work addresses the alloying of titanium aluminides used in aircraft engine applications and automobiles. The oxidation resistance behavior of two titanium aluminides of α2 + γ(Ti3Al + TiAl) and orthorhombic Ti2NbAl, recognized as candidates for high-temperature applications, was investigated by exposure of the alloys for 100 h in air. Thus, oxidation resistance was expressed as the mass gain rate, whereas surface aspects were analyzed using scanning electron microscopy in conjunction with energy-dispersive X-ray spectroscopy, and the type of oxidation products was analyzed by X-ray diffraction and Raman spectroscopy. The orthorhombic Ti2NbAl alloy was embrittled, and pores and microcracks were formed as a result of oxygen diffusion through the external oxide layer formed during thermal oxidation for 100 h.

Toward optimizing dental implant performance: Surface characterization of Ti and TiZr implant materials.

PubMed

Murphy, M; Walczak, M S; Thomas, A G; Silikas, N; Berner, S; Lindsay, R

2017-01-01

Targeting understanding enhanced osseointegration kinetics, the goal of this study was to characterize the surface morphology and composition of Ti and TiZr dental implant substrates subjected to one of two surface treatments developed by Straumann. These two treatments are typically known as SLA and SLActive, with the latter resulting in more rapid osseointegration. A range of techniques was applied to characterize four different substrate/surface treatment combinations (Ti SLA , Ti SLActive , TiZr SLA , and TiZr SLActive ). Contact angle measurements established their hydrophilic/hydrophobic nature. Surface morphology was probed with scanning electron microscopy. X-ray diffraction, Raman μ-spectroscopy, and X-ray photoelectron spectroscopy were used to elucidate the composition of the near-surface region. Consistent with previous work, surface morphology was found to differ only at the nanoscale, with both SLActive substrates displaying nano-protrusions. Spectroscopic data indicate that all substrates exhibit surface films of titanium oxide displaying near TiO 2 stoichiometry. Raman μ-spectroscopy reveals that amorphous TiO 2 is most likely the only phase present on Ti SL A , whilst rutile-TiO 2 is also evidenced on Ti SLActive , TiZr SLA , and TiZr SLActive . For TiZr alloy substrates, there is no evidence of discrete phases of oxidized Zr. X-ray photoelectron spectra demonstrate that all samples are terminated by adventitious carbon, with it being somewhat thicker (∼1nm) on Ti SL A and TiZr SLA . Given previous in vivo studies, acquired data suggest that both nanoscale protrusions, and a thinner layer of adventitious carbon contribute to the more rapid osseointegration of SLActive dental implants. Composition of the surface oxide layer is apparently less important in determining osseointegration kinetics. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Control of Interfacial Phenomena in Artificial Oxide Heterostructures

DTIC Science & Technology

2015-09-01

heterostructures using the field effect to control superconductivity, magnetism, and metal‐insulator transitions. We also identify the existence of double TiO2 ...double TiO2 layers play a crucial role in determining the superconducting states of monolayer FeSe/SrTiO3. 15. SUBJECT TERMS Thin films, conductor...development of oxide‐based electronic devices.  We also identify the existence of double  TiO2   layers at the surface of SrTiO3 in the recently

Resistance change effect in SrTiO3/Si (001) isotype heterojunction

NASA Astrophysics Data System (ADS)

Huang, Xiushi; Gao, Zhaomeng; Li, Pei; Wang, Longfei; Liu, Xiansheng; Zhang, Weifeng; Guo, Haizhong

2018-02-01

Resistance switching has been observed in double and multi-layer structures of ferroelectric films. The higher switching ratio opens up a vast path for emerging ferroelectric semiconductor devices. An n-n+ isotype heterojunction has been fabricated by depositing an oxide SrTiO3 layer on a conventional n-type Si (001) substrate (SrTiO3/Si) by pulsed laser disposition. Rectification and resistive switching behaviors in the n-n+ SrTiO3/Si heterojunction were observed by a conductive atomic force microscopy, and the n-n+ SrTiO3/Si heterojunction exhibits excellent endurance and retention characteristics. The possible mechanism was proposed based on the band structure of the n-n+ SrTiO3/Si heterojunction, and the observed electrical behaviors could be attributed to the modulation effect of the electric field reversal on the width of accumulation and the depletion region, as well as the height of potential of the n-n+ junction formed at the STO/Si interface. Moreover, oxygen vacancies are also indicated to play a crucial role in causing insulator to semiconductor transition. These results open the way to potential application in future microelectronic devices based on perovskite oxide layers on conventional semiconductors.

Growth and Electronic Structure Characterization of (SrCoOx)n :(SrTiO3)1 Superlattices

NASA Astrophysics Data System (ADS)

Cook, Say Young; Andersen, Tassie; Rosenberg, Richard; Hong, Hawoong; Marks, Laurence; Fong, Dillon

We report on the synthesis of a (SrCoOx)1 :(SrTiO3)1 superlattice by oxide molecular beam epitaxy and the characterization of its electronic structure by soft x-ray spectroscopy. X-ray photoelectron and absorption spectroscopy reveal that Ti remains octahedrally coordinated with a 4 + oxidation state, while the Co oxidation state is intermediate of 3 + and 4 +. Despite having the same half an oxygen vacancy per Co atom found in brownmillerite SrCoO2.5, which consists of alternating tetrahedral and octahedral layers of Co, the confinement of oxygen vacancies to isolated single atomic layers of SrCoOx stabilizes square pyramidal coordination of Co, as observed by the linear dichroism in the Co 2p-3d x-ray absorption. The corresponding stabilization of Co4+ along with Co3 + within the square pyramidal SrCoO2.5 layers gives rise to a Fermi-edge step observed at strong Co 2p-3d resonance in the resonant photoemission spectroscopy of the valence band, and reveals a band gap of 1.7 eV. Comparisons with a Sr(Co,Ti)Ox alloy and a (SrCoOx)2 :(SrTiO3)1 superlattice also will also be presented. The obtained results demonstrate artificial superlattices as effective means to defect engineer complex oxides by harnessing the confinement of oxygen vacancies to control the oxygen coordination environment of the transition metal.

Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Wenjing; Vannucci, Aaron K.; Farnum, Byron H.

2014-06-27

Light-driven dehydrogenation of benzyl alcohol (BnOH) to benzaldehyde and hydrogen has been shown to occur in a dye-sensitized photoelectrosynthesis cell (DSPEC). In the DSPEC, the photoanode consists of mesoporous films of TiO2 nanoparticles or of core/shell nanoparticles with tin-doped In2O3 nanoparticle (nanoITO) cores and thin layers of TiO2 deposited by atomic layer deposition (nanoITO/TiO2). Metal oxide surfaces were coderivatized with both a ruthenium polypyridyl chromophore in excess and an oxidation catalyst. Chromophore excitation and electron injection were followed by cross-surface electron-transfer activation of the catalyst to RuIV=O2+, which then oxidizes benzyl alcohol to benzaldehyde. The injected electrons are transferred tomore » a Pt electrode for H2 production. The nanoITO/TiO2 core/shell structure causes a decrease of up to 2 orders of magnitude in back electron-transfer rate compared to TiO2. At the optimized shell thickness, sustained absorbed photon to current efficiency of 3.7% was achieved for BnOH dehydrogenation, an enhancement of ~10 compared to TiO2.« less

Mechanical writing of n-type conductive layers on the SrTiO3 surface in nanoscale

PubMed Central

Wang, Yuhang; Zhao, Kehan; Shi, Xiaolan; Li, Geng; Xie, Guanlin; Lai, Xubo; Ni, Jun; Zhang, Liuwan

2015-01-01

The fabrication and control of the conductive surface and interface on insulating SrTiO3 bulk provide a pathway for oxide electronics. The controllable manipulation of local doping concentration in semiconductors is an important step for nano-electronics. Here we show that conductive patterns can be written on bare SrTiO3 surface by controllable doping in nanoscale using the mechanical interactions of atomic force microscopy tip without applying external electric field. The conductivity of the layer is n-type, oxygen sensitive, and can be effectively tuned by the gate voltage. Hence, our findings have potential applications in oxide nano-circuits and oxygen sensors. PMID:26042679

Investigation of atomic-layer-deposited TiO x as selective electron and hole contacts to crystalline silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsui, Takuya; Bivour, Martin; Ndione, Paul F.

Here, the applicability of atomic-layer-deposited titanium oxide (TiO x) thin films for the formation of carrier selective contacts to crystalline silicon (c-Si) is investigated. While relatively good electron selectivity was presented recently by other groups, we show that carrier selectivity can be engineered from electron to hole selective depending on the deposition conditions, post deposition annealing and the contact material covering the TiOx layer. For both the electron and hole contacts, an open-circuit voltage (Voc) of ~ >650 mV is obtained. The fact that the Voc is correlated with the (asymmetric) induced c-Si band bending suggests that carrier selectivity ismore » mainly governed by the effective work function and/or the fixed charge rather than by the asymmetric band offsets at the Si/TiOx interface, which provides important insight into the basic function of metal-oxide-based contact systems.« less

Investigation of atomic-layer-deposited TiO x as selective electron and hole contacts to crystalline silicon

DOE PAGES

Matsui, Takuya; Bivour, Martin; Ndione, Paul F.; ...

2017-09-21

Here, the applicability of atomic-layer-deposited titanium oxide (TiO x) thin films for the formation of carrier selective contacts to crystalline silicon (c-Si) is investigated. While relatively good electron selectivity was presented recently by other groups, we show that carrier selectivity can be engineered from electron to hole selective depending on the deposition conditions, post deposition annealing and the contact material covering the TiOx layer. For both the electron and hole contacts, an open-circuit voltage (Voc) of ~ >650 mV is obtained. The fact that the Voc is correlated with the (asymmetric) induced c-Si band bending suggests that carrier selectivity ismore » mainly governed by the effective work function and/or the fixed charge rather than by the asymmetric band offsets at the Si/TiOx interface, which provides important insight into the basic function of metal-oxide-based contact systems.« less

Processing of catalysts by atomic layer epitaxy: modification of supports

NASA Astrophysics Data System (ADS)

Lindblad, Marina; Haukka, Suvi; Kytökivi, Arla; Lakomaa, Eeva-Liisa; Rautiainen, Aimo; Suntola, Tuomo

1997-11-01

Different supports were modified with titania, zirconia and chromia by the atomic layer epitaxy technique (ALE). In ALE, a metal precursor is bound to the support in saturating gas-solid reactions. Surface oxides are grown by alternating reactions of the metal precursor and an oxidizing agent. Growth mechanisms differ depending on the precursor-support pair and the processing conditions. In this work, the influences of the support, precursor and reaction temperature were investigated by comparing the growth of titania from Ti(OCH(CH 3) 2) 4 on silica and alumina, titania from TiCl 4 and Ti(OCH(CH 3) 2) 4 on silica, and zirconia from ZrCl 4 on silica and alumina. The modification of porous oxides supported on metal substrates (monoliths) was demonstrated for the growth of chromia from Cr(acac) 3.

Influence of substrates and rutile seed layers on the assembly of hydrothermally grown rutile TiO2 nanorod arrays

NASA Astrophysics Data System (ADS)

Kalb, Julian; Dorman, James A.; Folger, Alena; Gerigk, Melanie; Knittel, Vanessa; Plüisch, Claudia S.; Trepka, Bastian; Lehr, Daniela; Chua, Emily; Goodge, Berit H.; Wittemann, Alexander; Scheu, Christina; Polarz, Sebastian; Schmidt-Mende, Lukas

2018-07-01

Rutile TiO2 nanorod arrays (NRAs) are applicable in various prospective technologies. Hydrothermal methods present a simple technique to fabricate such NRAs. In this report, we present the fabrication of seed layers for the hydrothermal growth of rutile TiO2 nanorods via sputter deposition, electron-beam evaporation, and sol-gel method and study the influence of each on the growth behavior. To satisfy the requirements of numerous applications, p-type silicon, platinum, levitating carbon membranes, a template made of polystyrene spheres, and commercial fluorine tin oxide (FTO) were employed as substrates. We document the structural properties of the TiO2 seed layers and describe the relationship between the characteristics of the seed crystals, the growth evolution, and the appearance of as-grown nanorods. Various growth stages of rutile TiO2 nanorods are compared depending on whether they are grown on polycrystalline TiO2 or FTO seed layers. In both cases, a homogenous TiO2 bottom layer is formed at the seed layer/substrate interface, which is essential for electronic applications such as hybrid solar cells. Detached NRAs illustrate the effect of rutile FTO and TiO2 on the porosity of this bottom layer. Further details about the formation process of this layer are obtained from the growth on confined seed layers fabricated by electron-beam lithography.

Microstructure and high-temperature oxidation resistance of TiN/Ti3Al intermetallic matrix composite coatings on Ti6Al4V alloy surface by laser cladding

NASA Astrophysics Data System (ADS)

Zhang, Xiaowei; Liu, Hongxi; Wang, Chuanqi; Zeng, Weihua; Jiang, Yehua

2010-11-01

A high-temperature oxidation resistant TiN embedded in Ti3Al intermetallic matrix composite coating was fabricated on titanium alloy Ti6Al4V surface by 6kW transverse-flow CO2 laser apparatus. The composition, morphology and microstructure of the laser clad TiN/Ti3Al intermetallic matrix composite coating were characterized by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectrometer (EDS). In order to evaluate the high-temperature oxidation resistance of the composite coatings and the titanium alloy substrate, isothermal oxidation test was performed in a conventional high-temperature resistance furnace at 600°C and 800°C respectively. The result shows that the laser clad intermetallic composite coating has a rapidly solidified fine microstructure consisting of TiN primary phase (granular-like, flake-like, and dendrites), and uniformly distributed in the Ti3Al matrix. It indicates that a physical and chemical reaction between the Ti powder and AlN powder occurred completely under the laser irradiation. In addition, the microhardness of the TiN/Ti3Al intermetallic matrix composite coating is 844HV0.2, 3.4 times higher than that of the titanium alloy substrate. The high-temperature oxidation resistance test reveals that TiN/Ti3Al intermetallic matrix composite coating results in the better modification of high-temperature oxidation behavior than the titanium substrate. The excellent high-temperature oxidation resistance of the laser cladding layer is attributed to the formation of the reinforced phase TiN and Al2O3, TiO2 hybrid oxide. Therefore, the laser cladding TiN/Ti3Al intermetallic matrix composite coating is anticipated to be a promising oxidation resistance surface modification technique for Ti6Al4V alloy.

New oxidation treatment of NiTi shape memory alloys to obtain Ni-free surfaces and to improve biocompatibility.

PubMed

Michiardi, A; Aparicio, C; Planell, J A; Gil, F J

2006-05-01

Various oxidation treatments were applied to nearly equiatomic NiTi alloys so as to form a Ni-free protective oxide on the surface. Sample surfaces were analyzed by X-ray Photoelectron Spectroscopy, and NiTi transformation temperatures were determined by differential scanning calorimetry (DSC) before and after the surface treatment. An ion release experiment was carried out up to one month of immersion in SBF for both oxidized and untreated surfaces. The results show that oxidation treatment in a low-oxygen pressure atmosphere leads to a high surface Ti/Ni ratio, a very low Ni surface concentration and a thick oxide layer. This oxidation treatment does not significantly affect the shape memory properties of the alloy. Moreover, the oxide formed significantly decreases Ni release into exterior medium comparing with untreated surfaces. As a consequence, this new oxidation treatment could be of great interest for biomedical applications, as it could minimize sensitization and allergies and improve biocompatibility and corrosion resistance of NiTi shape memory alloys. (c) 2005 Wiley Periodicals, Inc.

Improvements of anti-corrosion and mechanical properties of NiTi orthopedic materials by acetylene, nitrogen and oxygen plasma immersion ion implantation

NASA Astrophysics Data System (ADS)

Poon, Ray W. Y.; Ho, Joan P. Y.; Liu, Xuanyong; Chung, C. Y.; Chu, Paul K.; Yeung, Kelvin W. K.; Lu, William W.; Cheung, Kenneth M. C.

2005-08-01

Nickel-titanium shape memory alloys (NiTi) are useful materials in orthopedics and orthodontics due to their unique super-elasticity and shape memory effects. However, the problem associated with the release of harmful Ni ions to human tissues and fluids has been raising safety concern. Hence, it is necessary to produce a surface barrier to impede the out-diffusion of Ni ions from the materials. We have conducted acetylene, nitrogen and oxygen plasma immersion ion implantation (PIII) into NiTi alloys in an attempt to improve the surface properties. All the implanted and annealed samples surfaces exhibit outstanding corrosion and Ni out-diffusion resistance. Besides, the implanted layers are mechanically stronger than the substrate underneath. XPS analyses disclose that the layer formed by C2H2 PIII is composed of mainly TiCx with increasing Ti to C concentration ratios towards the bulk. The nitrogen PIII layer is observed to be TiN, whereas the oxygen PIII layer is composed of oxides of Ti4+, Ti3+ and Ti2+.

Interface engineering in epitaxial growth of layered oxides via a conducting layer insertion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yun, Yu; Meng, Dechao; Wang, Jianlin

2015-07-06

There is a long-standing challenge in the fabrication of layered oxide epitaxial films due to their thermodynamic phase-instability and the large stacking layer number. Recently, the demand for high-quality thin films is strongly pushed by their promising room-temperature multiferroic properties. Here, we find that by inserting a conducting and lattice matched LaNiO{sub 3} buffer layer, high quality m = 5 Bi{sub 6}FeCoTi{sub 3}O{sub 18} epitaxial films can be fabricated using the laser molecular beam epitaxy, in which the atomic-scale sharp interface between the film and the metallic buffer layer explains the enhanced quality. The magnetic and ferroelectric properties of the high qualitymore » Bi{sub 6}FeCoTi{sub 3}O{sub 18} films are studied. This study demonstrates that insertion of the conducting layer is a powerful method in achieving high quality layered oxide thin films, which opens the door to further understand the underline physics and to develop new devices.« less

Ultra-fine structures of Pd-Ag-HAp nanoparticle deposition on protruded TiO2 barrier layer for dental implant

NASA Astrophysics Data System (ADS)

Jang, Jae-Myung; Kim, Seung-Dai; Park, Tae-Eon; Choe, Han-Cheol

2018-02-01

The biocompatibility structure of an implant surface is of great importance to the formation of new bone tissue around the dental implant and also has a significant chemical reaction in the osseointegration process. Thus, ultra-fine Pd-Ag-HAp nanoparticles have been electrodeposited on protruded TiO2 barrier layer in mixed electrolyte solutions. Unusual protrusions patterns, which are assigned to Pd-Ag-HAp nanoparticles, can be clearly differentiated from a TiO2 nanotube oxide layer formed by an anodizing process. In the chemical bonding state, the surface characteristics of Pd/Ag/HAp compounds have been investigated by FE-SEM, EDS mapping analysis, and XPS analysis. The mapping dots of the elements including Ti, Ca, Pd, Ag, and P showed a homogeneous distribution throughout the entire surface when deposited onto the protruded TiO2 barrier layer. The XPS spectra of Ti-2p, O-1S, Pd-3d, and Ag-3d have been investigated, with the major XPS peak indicating Pd-3d. The Ag-3d level was clearly observed with further scanning of the Ca-2p region. Based on the results of the chemical states, the structural properties of the protrusion patterns were also examined after being deposited onto the barrier oxide film, resulting in the representative protrusion patterns being mainly composed of Pd-Ag-HAp compounds. The results of the soaking evaluation showed that the protrusion patterns and the protruded TiO2 barrier layer were all effective in regards to biocompatibility.

Nanocrystallized SrHA/SrHA SrTiO3/SrTiO3 TiO2 multilayer coatings formed by micro-arc oxidation for photocatalytic application

NASA Astrophysics Data System (ADS)

Han, Y.; Chen, D. H.; Zhang, L.

2008-08-01

Novel photocatalytic coatings containing strontium hydroxyapatite (SrHA), strontium titanate (SrTiO3), and TiO2 were formed by micro-arc oxidation (MAO) in an aqueous electrolyte containing strontium acetate and β-glycerophosphate disodium at 530 V for 0.1-5 min. The structure evolution of the coatings was investigated as a function of processing time, and the photocatalytic activity of the coatings was evaluated by measuring the decomposition rate of methyl orange under ultraviolet irradiation. During the MAO processing of the coatings, it was observed that some granules appeared in the electrolyte adjacent to the anode and they increased in amount as the processing time was prolonged. The obtained results show that the granules are amorphous and poorly crystallized SrHA with negative charges. The coating prepared for 5 min presents a microporous structure of SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayers, in which the SrHA outermost layer and the SrHA-SrTiO3 intermediate layer are nanocrystallized. It is suggested that formation of the granules, electro-migration of the granules onto the pre-formed layer, and crystallization of the adhered granules are possible mechanisms for the formation of a SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayer coating. This coating shows much higher photocatalytic decomposition efficiency relative to the MAO-formed TiO2 coating, and is expected to have an important photocatalytic application.

Phase inversion and frequency doubling of reflection high-energy electron diffraction intensity oscillations in the layer-by-layer growth of complex oxides

NASA Astrophysics Data System (ADS)

Mao, Zhangwen; Guo, Wei; Ji, Dianxiang; Zhang, Tianwei; Gu, Chenyi; Tang, Chao; Gu, Zhengbin; Nie*, Yuefeng; Pan, Xiaoqing

In situ reflection high-energy electron diffraction (RHEED) and its intensity oscillations are extremely important for the growth of epitaxial thin films with atomic precision. The RHEED intensity oscillations of complex oxides are, however, rather complicated and a general model is still lacking. Here, we report the unusual phase inversion and frequency doubling of RHEED intensity oscillations observed in the layer-by-layer growth of SrTiO3 using oxide molecular beam epitaxy. In contacts to the common understanding that the maximum(minimum) intensity occurs at SrO(TiO2) termination, respectively, we found that both maximum or minimum intensities can occur at SrO, TiO2, or even incomplete terminations depending on the incident angle of the electron beam, which raises a fundamental question if one can rely on the RHEED intensity oscillations to precisely control the growth of thin films. A general model including surface roughness and termination dependent mean inner potential qualitatively explains the observed phenomena, and provides the answer to the question how to prepare atomically and chemically precise surface/interfaces using RHEED oscillations for complex oxides. We thank National Basic Research Program of China (No. 11574135, 2015CB654901) and the National Thousand-Young-Talents Program.

Micro-arc oxidation as a tool to develop multifunctional calcium-rich surfaces for dental implant applications.

PubMed

Ribeiro, A R; Oliveira, F; Boldrini, L C; Leite, P E; Falagan-Lotsch, P; Linhares, A B R; Zambuzzi, W F; Fragneaud, B; Campos, A P C; Gouvêa, C P; Archanjo, B S; Achete, C A; Marcantonio, E; Rocha, L A; Granjeiro, J M

2015-09-01

Titanium (Ti) is commonly used in dental implant applications. Surface modification strategies are being followed in last years in order to build Ti oxide-based surfaces that can fulfill, simultaneously, the following requirements: induced cell attachment and adhesion, while providing a superior corrosion and tribocorrosion performance. In this work micro-arc oxidation (MAO) was used as a tool for the growth of a nanostructured bioactive titanium oxide layer aimed to enhance cell attachment and adhesion for dental implant applications. Characterization of the surfaces was performed, in terms of morphology, topography, chemical composition and crystalline structure. Primary human osteoblast adhesion on the developed surfaces was investigated in detail by electronic and atomic force microscopy as well as immunocytochemistry. Also an investigation on the early cytokine production was performed. Results show that a relatively thick hybrid and graded oxide layer was produced on the Ti surface, being constituted by a mixture of anatase, rutile and amorphous phases where calcium (Ca) and phosphorous (P) were incorporated. An outermost nanometric-thick amorphous oxide layer rich in Ca was present in the film. This amorphous layer, rich in Ca, improved fibroblast viability and metabolic activity as well as osteoblast adhesion. High-resolution techniques allowed to understand that osteoblasts adhered less in the crystalline-rich regions while they preferentially adhere and spread over in the Ca-rich amorphous oxide layer. Also, these surfaces induce higher amounts of IFN-γ cytokine secretion, which is known to regulate inflammatory responses, bone microarchitecture as well as cytoskeleton reorganization and cellular spreading. These surfaces are promising in the context of dental implants, since they might lead to faster osseointegration. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrical and morphological characterization of transfer-printed Au/Ti/TiO{sub x}/p{sup +}-Si nano- and microstructures with plasma-grown titanium oxide layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weiler, Benedikt, E-mail: benedikt.weiler@nano.ei.tum.de; Nagel, Robin; Albes, Tim

2016-04-14

Highly-ordered, sub-70 nm-MOS-junctions of Au/Ti/TiO{sub x}/p{sup +}-Si were efficiently and reliably fabricated by nanotransfer-printing (nTP) over large areas and their functionality was investigated with respect to their application as MOS-devices. First, we used a temperature-enhanced nTP process and integrated the plasma-oxidation of a nm-thin titanium film being e-beam evaporated directly on the stamp before the printing step without affecting the p{sup +}-Si substrate. Second, morphological investigations (scanning electron microscopy) of the nanostructures confirm the reliable transfer of Au/Ti/TiO{sub x}-pillars of 50 nm, 75 nm, and 100 nm size of superior quality on p{sup +}-Si by our transfer protocol. Third, the fabricated nanodevices are alsomore » characterized electrically by conductive AFM. Fourth, the results are compared to probe station measurements on identically processed, i.e., transfer-printed μm-MOS-structures including a systematic investigation of the oxide formation. The jV-characteristics of these MOS-junctions demonstrate the electrical functionality as plasma-grown tunneling oxides and the effectivity of the transfer-printing process for their large-scale fabrication. Next, our findings are supported by fits to the jV-curves of the plasma-grown titanium oxide by kinetic-Monte-Carlo simulations. These fits allowed us to determine the dominant conduction mechanisms, the material parameters of the oxides and, in particular, a calibration of the thickness depending on applied plasma time and power. Finally, also a relative dielectric permittivity of 12 was found for such plasma-grown TiO{sub x}-layers.« less

Stability of Y-Ti-O nanoparticles during laser deposition of oxide dispersion strengthened steel powder

NASA Astrophysics Data System (ADS)

Euh, Kwangjun; Arkhurst, Barton; Kim, Il Hyun; Kim, Hyun-Gil; Kim, Jeoung Han

2017-11-01

This study investigated the feasibility of a direct energy deposition process for fabrication of oxide dispersion strengthened steel cladding. The effect of the laser working power and scan speed on the microstructural stability of oxide nanoparticles in the deposition layer was examined. Y-Ti-O type oxide nanoparticles with a mean diameter of 45 nm were successfully dispersed by the laser deposition process. The laser working power significantly affected nanoparticle size and number density. A high laser power with a low scan speed seriously induced particle coarsening and agglomeration. Compared with bulk oxide dispersion strengthened steel, the hardness of the laser deposition layer was much lower because of a relatively coarse particle and grain size. Formation mechanism of nanoparticles during laser deposition was discussed.

Surface Characterization, Corrosion Resistance and in Vitro Biocompatibility of a New Ti-Hf-Mo-Sn Alloy

PubMed Central

Ion, Raluca; Drob, Silviu Iulian; Ijaz, Muhammad Farzik; Vasilescu, Cora; Osiceanu, Petre; Gordin, Doina-Margareta; Cimpean, Anisoara; Gloriant, Thierry

2016-01-01

A new superelastic Ti-23Hf-3Mo-4Sn biomedical alloy displaying a particularly large recovery strain was synthesized and characterized in this study. Its native passive film is very thick (18 nm) and contains very protective TiO2, Ti2O3, HfO2, MoO2, and SnO2 oxides (XPS analysis). This alloy revealed nobler electrochemical behavior, more favorable values of the corrosion parameters and open circuit potentials in simulated body fluid in comparison with commercially pure titanium (CP-Ti) and Ti-6Al-4V alloy taken as reference biomaterials in this study. This is due to the favorable influence of the alloying elements Hf, Sn, Mo, which enhance the protective properties of the native passive film on alloy surface. Impedance spectra showed a passive film with two layers, an inner, capacitive, barrier, dense layer and an outer, less insulating, porous layer that confer both high corrosion resistance and bioactivity to the alloy. In vitro tests were carried out in order to evaluate the response of Human Umbilical Vein Endothelial Cells (HUVECs) to Ti-23Hf-3Mo-4Sn alloy in terms of cell viability, cell proliferation, phenotypic marker expression and nitric oxide release. The results indicate a similar level of cytocompatibility with HUVEC cells cultured on Ti-23Hf-3Mo-4Sn substrate and those cultured on the conventional CP-Ti and Ti-6Al-4V metallic materials. PMID:28773939

Characteristics of zinc oxide nanorod array/titanium oxide film heterojunction prepared by aqueous solution deposition

NASA Astrophysics Data System (ADS)

Lee, Ming-Kwei; Hong, Min-Hsuan; Li, Bo-Wei

2016-07-01

The characteristics of a ZnO nanorod array/TiO2 film heterojunction were investigated. A TiO2 film was prepared on glass by aqueous solution deposition with precursors of ammonium hexafluorotitanate and boric acid at 40 °C. Then, a ZnO seed layer was prepared on a TiO2 film/glass substrate by RF sputtering. A vertically oriented ZnO nanorod array was grown on a ZnO seed layer/TiO2 film/glass substrate by aqueous solution deposition with precursors of zinc nitrate and hexamethylenetetramine (HMT) at 70 °C. After thermal annealing in N2O ambient at 300 °C, this heterojunction used as an oxygen gas sensor shows much better rise time, decay time, and on/off current ratio than as-grown and annealed ZnO nanorods.

Electronic and Optical Properties of Atomic Layer-Deposited ZnO and TiO2

NASA Astrophysics Data System (ADS)

Ates, H.; Bolat, S.; Oruc, F.; Okyay, A. K.

2018-05-01

Metal oxides are attractive for thin film optoelectronic applications. Due to their wide energy bandgaps, ZnO and TiO2 are being investigated by many researchers. Here, we have studied the electrical and optical properties of ZnO and TiO2 as a function of deposition and post-annealing conditions. Atomic layer deposition (ALD) is a novel thin film deposition technique where the growth conditions can be controlled down to atomic precision. ALD-grown ZnO films are shown to exhibit tunable optical absorption properties in the visible and infrared region. Furthermore, the growth temperature and post-annealing conditions of ZnO and TiO2 affect the electrical properties which are investigated using ALD-grown metal oxide as the electron transport channel on thin film field-effect devices.

Effect of thermal oxidation on corrosion and corrosion-wear behaviour of a Ti-6Al-4V alloy.

PubMed

Güleryüz, Hasan; Cimenoğlu, Hüseyin

2004-07-01

In this study, comparative investigation of thermal oxidation treatment for Ti-6Al-4V was carried out to determine the optimum oxidation conditions for further evaluation of corrosion-wear performance. Characterization of modified surface layers was made by means of microscopic examinations, hardness measurements and X-ray diffraction analysis. Optimum oxidation condition was determined according to the results of accelerated corrosion tests made in 5m HCl solution The examined Ti-6Al-4V alloy exhibited excellent resistance to corrosion after oxidation at 600 degrees C for 60 h. This oxidation condition achieved 25 times higher wear resistance than the untreated alloy during reciprocating wear test conducted in a 0.9% NaCl solution.

The role of surface oxides on hydrogen sorption kinetics in titanium thin films

NASA Astrophysics Data System (ADS)

Hadjixenophontos, Efi; Michalek, Lukas; Roussel, Manuel; Hirscher, Michael; Schmitz, Guido

2018-05-01

Titanium is presently discussed as a catalyst to accelerate the hydrogenation kinetics of hydrogen storage materials. It is however known that H absorption in Ti decisively depends on the surface conditions (presence or absence of the natural surface oxide). In this work, we use Ti thin films of controlled thickness (50-800 nm) as a convenient tool for quantifying the atomic transport. XRD and TEM investigations allow us to follow the hydrogenation progress inside the film. Hydrogenation of TiO2/Ti bi-layers is studied at 300 °C, for different durations (10 s to 600 min) and at varying pressures of pure H2 atmosphere. Under these conditions, the hydrogenation is found to be linear in time. By comparing films with and without TiO2, as well as by studying the pressure dependence of hydrogenation, it is demonstrated that hydrogen transport across the oxide represents the decisive kinetic barrier rather than the splitting of H2 molecules at the surface. Hydrogenation appears by a layer-like reaction initiated by heterogeneous nucleation at the backside interface to the substrate. The linear growth constant and the H diffusion coefficient inside the oxide are quantified, as well as a reliable lower bound to the hydrogen diffusion coefficient in Ti is derived. The pressure dependence of hydrogen absorption is quantitatively modelled.

Oxygen ion irradiation effect on corrosion behavior of titanium in nitric acid medium

NASA Astrophysics Data System (ADS)

Ningshen, S.; Kamachi Mudali, U.; Mukherjee, P.; Barat, P.; Raj, Baldev

2011-01-01

The corrosion assessment and surface layer properties after O 5+ ion irradiation of commercially pure titanium (CP-Ti) has been studied in 11.5 N HNO 3. CP-Ti specimen was irradiated at different fluences of 1 × 10 13, 1 × 10 14 and 1 × 10 15 ions/cm 2 below 313 K, using 116 MeV O 5+ ions source. The corrosion resistance and surface layer were evaluated by using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and glancing-angle X-ray diffraction (GXRD) methods. The potentiodynamic anodic polarization results of CP-Ti revealed that increased in ion fluence (1 × 10 13-1 × 10 15 ions/cm 2) resulted in increased passive current density due to higher anodic dissolution. SEM micrographs and GXRD analysis corroborated these results showing irradiation damage after corrosion test and modified oxide layer by O 5+ ion irradiation was observed. The EIS studies revealed that the stability and passive film resistance varied depending on the fluence of ion irradiation. The GXRD patterns of O 5+ ion irradiated CP-Ti revealed the oxides formed are mostly TiO 2, Ti 2O 3 and TiO. In this paper, the effects of O 5+ ion irradiation on material integrity and corrosion behavior of CP-Ti in nitric acid are described.

A double Fe-Ti oxide and Fe-sulphide liquid immiscibility in the Itsindro Gabbro Complex, Madagascar

NASA Astrophysics Data System (ADS)

Augé, Thierry; Bailly, Laurent; Roig, Jean-Yves

2017-11-01

The petrology and mineralogy of the Itsindro complex in south-central Madagascar has been investigated through samples obtained from the 320.7 m-deep Lanjanina borehole. The section consists of a 254 m-thick pyroxenite unit with interbedded gabbro layers that overlies a gabbro unit and is itself overlain by a 19 m-thick granite unit. Most of the structures are sub-horizontal. A weak magmatic layering is locally observed but at the scale of the core, the intrusion does not appear to be a layered complex. Pyroxenite and gabbro show a systematic disseminated mineralization consisting of Fe-Ti-P oxides and Fe-(Cu-Ni) sulphides that takes the form of ilmenite-titanomagnetite ± apatite and pyrrhotite ± chalcopyrite ± pentlandite. In the upper zone, from 90 to 72 m, sub-massive centimetre-to decimetre-sized layers of oxides and sulphides comprise a total of 16 m of sub-massive sulphide (the main mineralized zone). In this mineralized zone the oxide/sulphide ratio is close to 1/1. The sulphide is strongly dominated by pyrrhotite, which may locally contain inclusions of molybdenite crystals with the Re sulphide rheniite (ReS2). Oxides are generally euhedral, included in or attached to the Fe-sulphide, and also locally form sub-massive centimetre-sized bands. Apatite as a cumulus phase is ubiquitous. Locally it may account for 30% of the ore-rich samples and some samples consist of apatite-Fe-Ti oxides-Fe-Cu-Ni sulphides with virtually no silicate. Apatite is the main REE carrier but the total REE content remains low (<90 ppm). Mineral compositions and whole rock geochemistry indicate that the rocks are highly differentiated, and in spite of a relatively limited thickness, the differentiation process is observed. Two zones can be distinguished: from the bottom to 162.8 m we see a decrease in the Mg number of olivine and pyroxene, and a drop in TiO2 and Al2O3 for the latter. A reverse trend is then observed within the pyroxenite unit from the 162.8 m level upwards. The main mineralized zone is located in the upper part of this unit, about 70 m above this discontinuity. The highly differentiated Fe-Ti-P facies of the Lanjanina series in the Itsindro Gabbro Complex have been interpreted as corresponding to the Fe-Ti-P rich, Si-poor member remaining after an immiscible segregation of an evolved mafic magma. The granite dykes and the overlying granite unit represent the second, Si-rich member of the immiscibility process. The presence of large amounts of sulphide is attributed to sulphur contamination of the Fe-Ti-rich liquid. Fe-Ti oxides will tend to crystallize on the sulphide droplets and the accumulation of dense Fe-sulphides (liquid) and associated Fe-Ti oxides (solid) will result in this complex and unusual association taking the form of a net texture.

A bioactive coating with submicron-sized titania crystallites fabricated by induction heating of titanium after tensile deformations.

PubMed

Li, Ning-Bo; Xu, Wen-Hua; Xiao, Gui-Yong; Zhao, Jun-Han; Lu, Yu-Peng

2017-11-01

Thermal oxidation technology was widely investigated as one of effective surface modification method for improving the bioactivity and biocompatibility of titanium and its alloys. In this work, the induction heat oxidization method, a fast, efficient, economical and environmental protective technology, was applied to prepare the submicron-morphological oxide coating with variable rutile TiO 2 equiaxed crystallites on the surface of pure Ti substrates after cold-drawing with 10-20% deformations. The results showed the plastic-deformed Ti cylinders recrystallized during induction heating treatment (IHT) for 10-20s which resulted in evolution of microstructures as well as slight improvement of microhardness. The surface characteristics of TiO 2 crystallites in oxidation layers were determined by the microstructural evolutions of Ti substrate in terms of the nucleation and growth of TiO 2 crystallites. Specially, the oxidized surface with 50-75nm roughness and more uniform and finer equiaxed oxide grains remarkablely improved the apatite deposition after bioactive evaluation in 1.5 × SBF for 7 days. This work provided a potential method to create controlled bioactive oxide coatings with submicro-/nano-scaled TiO 2 crystallites on titanium substrate in terms of the role of metallographic microstructure in the formation process of titanium oxides. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation of grape-like Bi{sub 2}O{sub 3}/Ti photoanode and its visible light activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Guoting; Department of Biology, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong SAR; Yip, H.Y.

2011-02-15

Graphical abstract: Compact and grape-like bismuth oxide (Bi{sub 2}O{sub 3}) coated titania (Ti) anode was prepared by oxalic acid (H{sub 2}C{sub 2}O{sub 4}) etching, electrodeposition and calcination in order to explore its photoelectrocatalytic activities. The Bi{sub 2}O{sub 3} coating was demonstrated to be full of pores, and a good combination between Bi{sub 2}O{sub 3} layer and honeycomb-like Ti substrate was observed by scanning electron microscopy. A synergy was found between electrolysis and photocatalysis using the prepared Bi{sub 2}O{sub 3}/Ti anode for photoelectrocatalytic oxidation of azo dye Acid Orange 7 under visible light irradiation (420 nm). Research highlights: {yields} Bi{sub 2}O{submore » 3}/Ti anode was prepared by H{sub 2}C{sub 2}O{sub 4} etching, electrodeposition and calcination. {yields} A compact and grape-like Bi{sub 2}O{sub 3} coated Ti anode was obtained. {yields} Bi{sub 2}O{sub 3} coating was full of pores, and have a good combination with Ti substrate. {yields} A synergy was observed in photoelectrocatalytic oxidation under visible light. -- Abstract: Compact and grape-like bismuth oxide (Bi{sub 2}O{sub 3}) coated titania (Ti) anode was prepared by oxalic acid (H{sub 2}C{sub 2}O{sub 4}) etching, electrodeposition and calcination in order to explore its photoelectrocatalytic activities. The Bi{sub 2}O{sub 3} coating was demonstrated to be full of pores, and a good combination between Bi{sub 2}O{sub 3} layer and honeycomb-like Ti substrate was observed by scanning electron microscopy. The characteristic morphology of Bi{sub 2}O{sub 3} coating indicated that the electrode is stable during degradation. The Bi{sub 2}O{sub 3}/Ti electrode was used in oxidative degradation of Acid Orange 7 by electrolysis, photocatalytic oxidation and photoelectrocatalytic oxidation processes. The pseudo-first order kinetics parameter (K{sub app}) of photoelectrocatalytic process was 1.15 times of the sum of electrolysis and photocatalytic oxidation under visible light irradiation at 420 nm. The results indicated that the synergy of electrolysis and photocatalysis lead to an excellent photoelectrocatalytic property of the Bi{sub 2}O{sub 3}/Ti electrode.« less

A high density two-dimensional electron gas in an oxide heterostructure on Si (001)

NASA Astrophysics Data System (ADS)

Jin, E. N.; Kornblum, L.; Kumah, D. P.; Zou, K.; Broadbridge, C. C.; Ngai, J. H.; Ahn, C. H.; Walker, F. J.

2014-11-01

We present the growth and characterization of layered heterostructures comprised of LaTiO3 and SrTiO3 epitaxially grown on Si (001). Magnetotransport measurements show that the sheet carrier densities of the heterostructures scale with the number of LaTiO3/SrTiO3 interfaces, consistent with the presence of an interfacial 2-dimensional electron gas (2DEG) at each interface. Sheet carrier densities of 8.9 × 1014 cm-2 per interface are observed. Integration of such high density oxide 2DEGs on silicon provides a bridge between the exceptional properties and functionalities of oxide 2DEGs and microelectronic technologies.

Photocatalysis of zinc oxide nanotip array/titanium oxide film heterojunction prepared by aqueous solution deposition

NASA Astrophysics Data System (ADS)

Lee, Ming-Kwei; Lee, Bo-Wei; Kao, Chen-Yu

2017-05-01

A TiO2 film was prepared on indium tin oxide (ITO)/glass by aqueous solution deposition (ASD) with precursors of ammonium hexafluoro-titanate and boric acid at 40 °C. The photocatalysis of annealed TiO2 film increases with increasing growth time and decreases with increasing growth times longer than 60 min. A ZnO nanotip array was prepared on ZnO seed layer/TiO2 film/glass by aqueous solution deposition with precursors of zinc nitrate and ammonium hydroxide at 70 °C. The photocatalysis of ASD-ZnO/ASD-TiO2 film/ITO glass can be better than that of P25.

AES study on the chemical composition of ferroelectric BaTiO3 thin films RF sputter-deposited on silicon

NASA Technical Reports Server (NTRS)

Dharmadhikari, V. S.; Grannemann, W. W.

1983-01-01

AES depth profiling data are presented for thin films of BaTiO3 deposited on silicon by RF sputtering. By profiling the sputtered BaTiO3/silicon structures, it was possible to study the chemical composition and the interface characteristics of thin films deposited on silicon at different substrate temperatures. All the films showed that external surface layers were present, up to a few tens of angstroms thick, the chemical composition of which differed from that of the main layer. The main layer had stable composition, whereas the intermediate film-substrate interface consisted of reduced TiO(2-x) oxides. The thickness of this intermediate layer was a function of substrate temperature. All the films showed an excess of barium at the interface. These results are important in the context of ferroelectric phenomena observed in BaTiO3 thin films.

Effect of nanostructured titanium on anodization growth of self-organized TiO2 nanotubes

NASA Astrophysics Data System (ADS)

Zhang, Lan; Han, Yong

2010-02-01

To understand the effect of substrate microstructure on the formation of TiO2 nanotubes, anodic oxidizations of commercially pure titanium subjected to surface mechanical attrition treatment (SMATed-Ti) and unSMATed-Ti in a glycol solution containing NH4F and small amounts of water were investigated. The SMATed-Ti exhibit a nanocrystallized surface layer containing a high density of grain boundaries compared with unSMATed-Ti. The anodization results show that the formed TiO2 nanotube layer on the SMATed-Ti is much thicker than that on the unSMATed-Ti. It is indicated that nanocrystallized Ti is propitious to the growth of TiO2 nanotubes; grain boundaries and dislocations play the leading role in accelerating the reaction rate and ion diffusion coefficient during anodization. In addition, nanocrystallization of Ti does not change surface morphologies and phase components of the TiO2 nanotubes.

Effect of yttrium on martensite-austenite phase transformation temperatures and high temperature oxidation kinetics of Ti-Ni-Hf high-temperature shape memory alloys

NASA Astrophysics Data System (ADS)

Kim, Jeoung Han; Kim, Kyong Min; Yeom, Jong Taek; Young, Sung

2016-03-01

The effect of yttrium (< 5.5 at%) on the martensite-austenite phase transformation temperatures, microstructural evolution, and hot workability of Ti-Ni-Hf high-temperature shape memory alloys is investigated. For these purposes, differential scanning calorimetry, hot compression, and thermo-gravimetric tests are conducted. The phase transformation temperatures are not noticeably influenced by the addition of yttrium up to 4.5 at%. Furthermore, the hot workability is not significantly affected by the yttrium addition up to 1.0 at%. However, when the amount of yttrium addition exceeds 1.0 at%, the hot workability deteriorates significantly. In contrast, remarkable improvement in the high temperature oxidation resistance due to the yttrium addition is demonstrated. The total thickness of the oxide layers is substantially thinner in the Y-added specimen. In particular, the thickness of (Ti,Hf) oxide layer is reduced from 200 µm to 120 µm by the addition of 0.3 at% Y.

Influence of Ti Content on the Partial Oxidation of TixFeCoNi Thin Films in Vacuum Annealing

PubMed Central

Yang, Ya-Chu; Yeh, Jien-Wei; Tsau, Chun-Huei

2017-01-01

This study investigated the effects of Ti content and vacuum annealing on the microstructure evolution of TixFeCoNi (x = 0, 0.5, and 1) thin films and the underlying mechanisms. The as-deposited thin film transformed from an FCC (face center cubic) structure at x = 0 into an amorphous structure at x = 1, which can be explained by determining topological instability and a hard ball model. After annealing was performed at 1000 °C for 30 min, the films presented a layered structure comprising metal solid solutions and oxygen-deficient oxides, which can be major attributed to oxygen traces in the vacuum furnace. Different Ti contents provided various phase separation and layered structures. The underlying mechanism is mainly related to the competition among possible oxides in terms of free energy production at 1000 °C. PMID:28953244

Fabrication of Highly Ordered and Well-Aligned PbTiO 3/TiN Core–Shell Nanotube Arrays

DOE PAGES

Yoon, Jaesung; Kim, Sangjoon; Kim, Dongjin; ...

2015-04-30

Highly ordered and well-aligned PbTiO 3/TiN core–shell nanotubes are fabricated in this paper via an anodic aluminum oxide templating route followed by TiN and TiO 2 atomic layer deposition deposition and a subsequent PbO vapor reaction. Finally, PbTiO 3/TiN nanotubes keep their original shape after the vapor phase reaction, and they display well-defined piezoresponse hysteresis curves with remnant piezoresponse of 38 pm V -1.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bharadwaja, S. S. N., E-mail: s.s.n.bharadwaja@gmail.com; Ko, S. W.; Qu, W.

Excimer laser assisted re-oxidation for reduced, crystallized BaTiO{sub 3} thin films on Ni-foils was investigated. It was found that the BaTiO{sub 3} can be re-oxidized at an oxygen partial pressure of ∼50 mTorr and substrate temperature of 350 °C without forming a NiO{sub x} interface layer between the film and base metal foil. The dielectric permittivity of re-oxidized films was >1000 with loss tangent values <2% at 100 Hz, 30 mV{sub rms} excitation signal. Electron Energy Loss Spectroscopy indicated that BaTiO{sub 3} thin films can be re-oxidized to an oxygen stoichiometry close to ∼3 (e.g., stoichiometric). High resolution cross sectional transmission electronmore » microscopy showed no evidence of NiO{sub x} formation between the BaTiO{sub 3} and the Ni foil upon excimer laser re-oxidation. Spectroscopic ellipsometry studies on laser re-oxidized [001]{sub C} and [111]{sub C} BaTiO{sub 3} single crystals indicate that the re-oxidation of BaTiO{sub 3} single crystals is augmented by photo-excitation of the ozone, as well as laser pulse induced temperature and local stress gradients.« less

Experimental Study of Acid Treatment Toward Characterization of Structural, Optical, and Morphological Properties of TiO2-SnO2 Composite Thin Film

NASA Astrophysics Data System (ADS)

Fajar, M. N.; Hidayat, R.; Triwikantoro; Endarko

2018-04-01

The TiO2-SnO2 thin film with single and double-layer structure has successfully synthesized on FTO (Fluorine-doped Tin Oxide) substrate using the screen printing technique. The structural, optical, and morphological properties of the film were investigated by XRD, UV-Vis, and SEM, respectively. The results showed that the single and double-layer structure of TiO2-SnO2 thin film has mixed phase with a strong formation of casseritte phase. The acid treatment effect on TiO2-SnO2 thin film decreases the peak intensity of anatase phase formation and thin film’s absorbance values. The morphological study is also revealed that the single layer TiO2-SnO2 thin film had a more porous nature and decreased particle size distribution after acid treatment, while the double-layer TiO2-SnO2 thin film Eroded due to acid treatment.

Enhanced photovoltaic performance of inverted hybrid bulk-heterojunction solar cells using TiO2/reduced graphene oxide films as electron transport layers

NASA Astrophysics Data System (ADS)

Morais, Andreia; Alves, João Paulo C.; Lima, Francisco Anderson S.; Lira-Cantu, Monica; Nogueira, Ana Flavia

2015-01-01

In this study, we investigated inverted hybrid bulk-heterojunction solar cells with the following configuration: fluorine-doped tin oxide (FTO) |TiO2/RGO|P3HT:PC61BM|V2O5 or PEDOT:PSS|Ag. The TiO2/GO dispersions were prepared by sol-gel method, employing titanium isopropoxide and graphene oxide (GO) as starting materials. The GO concentration was varied from 0.1 to 4.0 wt%. The corresponding dispersions were spin-coated onto FTO substrates and a thermal treatment was performed to remove organic materials and to reduce GO to reduced graphene oxide (RGO). The TiO2/RGO films were characterized by x-ray diffraction, Raman spectroscopy, and microscopy techniques. Atomic force microscopy (AFM) images showed that the addition of RGO significantly changes the morphology of the TiO2 films, with loss of uniformity and increase in surface roughness. Independent of the use of V2O5 or PEDOT: PSS films as the hole transport layer, the incorporation of 2.0 wt% of RGO into TiO2 films was the optimal concentration for the best organic photovoltaic performance. The solar cells based on TiO2/RGO (2.0 wt%) electrode exhibited a ˜22.3% and ˜28.9% short circuit current density (Jsc) and a power conversion efficiency enhancement, respectively, if compared with the devices based on pure TiO2 films. Kelvin probe force microscopy images suggest that the incorporation of RGO into TiO2 films can promote the appearance of regions with different charge dissipation capacities.

Effect of Surface Alloying by Silicon on the Corrosion Resistance and Biocompatibility of the Binary NiTi

NASA Astrophysics Data System (ADS)

Psakhie, S. G.; Meisner, S. N.; Lotkov, A. I.; Meisner, L. L.; Tverdokhlebova, A. V.

2014-07-01

This paper presents the study on changes in element and phase compositions in the near-surface layer and on surface topography of the NiTi specimens after the silicon ion-beam treatment. The effect of these parameters of the near-surface layer on corrosion properties in biochemical solutions and biocompatibility with mesenchymal stem cells of rat marrow is studied. Ion-beam surface modification of the specimens was performed by a DIANA-3 implanter (Tomsk, Russia), using single-ion-beam pulses under oil-free pumping and high vacuum (10-4 Pa) conditions in a high-dose ion implantation regime. The fluence made 2 × 1017 cm-2, at an average accelerating voltage of 60 kV, and pulse repetition frequency of 50 Hz. The silicon ion-beam treatment of specimen surfaces is shown to bring about a nearly twofold improvement in the corrosion resistance of the material to attack by aqueous solutions of NaCl (artificial body fluid) and human plasma and a drastic decrease in the nickel concentration after immersion of the specimens into the solutions for ~3400 and ~6000 h, respectively (for the artificial plasma solution, a nearly 20-fold decrease in the Ni concentration is observed). It is shown that improvement of NiTi corrosion resistance after treatment by Si ions occurs mainly due to the formation of two-layer composite coating based on Ti oxides (outer layer) on the NiTi surface and adjacent inner layer of oxides, carbides, and silicides of the NiTi alloy components. Inner layer with high silicon concentration serves as a barrier layer preventing nickel penetration into biomedium. This, in our opinion, is the main reason why the NiTi alloy exhibits no cytotoxic properties after ion modification of its surface and leads to the biocompatibility improvement at the cellular level, respectively.

Strong polarization enhancement in asymmetric three-component ferroelectric superlattices

NASA Astrophysics Data System (ADS)

Lee, Ho Nyung; Christen, Hans M.; Chisholm, Matthew F.; Rouleau, Christopher M.; Lowndes, Douglas H.

2005-01-01

Theoretical predictions-motivated by recent advances in epitaxial engineering-indicate a wealth of complex behaviour arising in superlattices of perovskite-type metal oxides. These include the enhancement of polarization by strain and the possibility of asymmetric properties in three-component superlattices. Here we fabricate superlattices consisting of barium titanate (BaTiO3), strontium titanate (SrTiO3) and calcium titanate (CaTiO3) with atomic-scale control by high-pressure pulsed laser deposition on conducting, atomically flat strontium ruthenate (SrRuO3) layers. The strain in BaTiO3 layers is fully maintained as long as the BaTiO3 thickness does not exceed the combined thicknesses of the CaTiO3 and SrTiO3 layers. By preserving full strain and combining heterointerfacial couplings, we find an overall 50% enhancement of the superlattice global polarization with respect to similarly grown pure BaTiO3, despite the fact that half the layers in the superlattice are nominally non-ferroelectric. We further show that even superlattices containing only single-unit-cell layers of BaTiO3 in a paraelectric matrix remain ferroelectric. Our data reveal that the specific interface structure and local asymmetries play an unexpected role in the polarization enhancement.

Highly Oriented Growth of Piezoelectric Thin Films on Silicon Using Two-Dimensional Nanosheets as Growth Template Layer.

PubMed

Nguyen, Minh D; Yuan, Huiyu; Houwman, Evert P; Dekkers, Matthijn; Koster, Gertjan; Ten Elshof, Johan E; Rijnders, Guus

2016-11-16

Ca 2 Nb 3 O 10 (CNOns) and Ti 0.87 O 2 (TiOns) metal oxide nanosheets (ns) are used as a buffer layer for epitaxial growth of piezoelectric capacitor stacks on Si and Pt/Ti/SiO 2 /Si (Pt/Si) substrates. Highly (001)- and (110)-oriented Pb(Zr 0.52 Ti 0.48 )O 3 (PZT) films are achieved by utilizing CNOns and TiOns, respectively. The piezoelectric capacitors are characterized by polarization and piezoelectric hysteresis loops and by fatigue measurements. The devices fabricated with SrRuO 3 top and bottom electrodes directly on nanosheets/Si have ferroelectric and piezoelectric properties well comparable with devices that use more conventional oxide buffer layers (stacks) such as YSZ, CeO 2 /YSZ, or SrTiO 3 on Si. The devices grown on nanosheets/Pt/Si with Pt top electrodes show significantly improved polarization fatigue properties over those of similar devices grown directly on Pt/Si. The differences in properties are ascribed to differences in the crystalline structures and the density of the films. These results show a route toward the fabrication of single crystal piezoelectric thin films and devices with high quality, long-lifetime piezoelectric capacitor structures on nonperovskite and even noncrystalline substrates such as glass or polished metal surfaces.

A novel rotating electrochemically anodizing process to fabricate titanium oxide surface nanostructures enhancing the bioactivity of osteoblastic cells.

PubMed

Chang, Chih-Hung; Lee, Hsin-Chun; Chen, Chia-Chun; Wu, Yi-Hau; Hsu, Yuan-Ming; Chang, Yin-Pen; Yang, Ta-I; Fang, Hsu-Wei

2012-07-01

Titanium oxide (TiO(2) ) surface layers with various surface nanostructures (nanotubes and nanowires) have been developed using an anodizing technique. The pore size and length of TiO(2) nanotubes can be tailored by changing the anodizing time and applied voltage. We developed a novel method to transform the upper part of the formed TiO(2) nanotubes into a nanowire-like structure by rotating the titanium anode during anodizing process. The transformation of nanotubes contributed to the preferential chemical dissolution of TiO(2) on the areas with intense interface tension stress. Furthermore, we further compared the effect of various TiO(2) surface nanostructures including flat, nanotubes, and nanowires on bioactive applications. The MG-63 osteoblastic cells cultured on the TiO(2) nanowires exhibited a polygonal shape with extending filopodia and showed highest levels of cell viability and alkaline phosphatase activity (ALP). The TiO(2) nanowire structure formed by our novel method can provide beneficial effects for MG-63 osteoblastic cells in attachment, proliferation, and secretion of ALP on the TiO(2) surface layer. Copyright © 2012 Wiley Periodicals, Inc.

Dual functional reduced graphene oxide as photoanode and counter electrode in dye-sensitized solar cells and its exceptional efficiency enhancement

NASA Astrophysics Data System (ADS)

Jumeri, F. A.; Lim, H. N.; Zainal, Z.; Huang, N. M.; Pandikumar, A.; Lim, S. P.

2015-10-01

The dual functionalities of reduced graphene oxide (rGO) as photoanode and counter electrode in dye-sensitized solar cells (DSSCs) is explored. A titanium dioxide (TiO2) film is deposited on an indium tin oxide (ITO) glass using an in-house aerosol-assisted chemical vapor deposition method. Graphene oxide (GO) is then introduced onto the TiO2-ITO substrate, and the GO layer is successively thermally treated to rGO. The TiO2-rGO film is used as a compact layer for the photoanode of the DSSC. A layer of zinc oxide-silver (ZnO-Ag) is introduced on top of the compact layer as an active material. Its highly porous flower-shaped morphology is advantageous for the adsorption of dye. The in-situ electrochemical polymerization method used for the fabrication of polypyrrole incorporated with rGO and p-toluenesulfonate (pTS) (Ppy-rGO-pTS) on an ITO glass is used as a counter electrode for the DSSC. The DSSC assembled with the Ppy-rGO-1.0pTS counter electrode exhibites an enhanced conversion efficiency of 1.99% under solar illumination, which is better than that using conventional Pt as a counter electrode (0.08%). This is attributed to the increased contact area between the Ppy-rGO-pTS counter electrode and electrolyte, which subsequently improves the conductivity and high electrocatalytic activities of the Ppy-rGO-pTS counter electrode.

TiOx-based thin-film transistors prepared by femtosecond laser pre-annealing

NASA Astrophysics Data System (ADS)

Shan, Fei; Kim, Sung-Jin

2018-02-01

We report on thin-film transistors (TFTs) based on titanium oxide (TiOx) prepared using femtosecond laser pre-annealing for electrical application of n-type channel oxide transparent TFTs. Amorphous TFTs using TiOx semiconductors as an active layer have a low-temperature process and show remarkable electrical performance. And the femtosecond laser pre-annealing process has greater flexibility and development space for semiconductor production activity, with a fast preparation method. TFTs with a TiOx semiconductor pre-annealed via femtosecond laser at 3 W have a pinhole-free and smooth surface without crystal grains.

Impact of Film Thickness of Ultrathin Dip-Coated Compact TiO2 Layers on the Performance of Mesoscopic Perovskite Solar Cells.

PubMed

Masood, Muhammad Talha; Weinberger, Christian; Sarfraz, Jawad; Rosqvist, Emil; Sandén, Simon; Sandberg, Oskar J; Vivo, Paola; Hashmi, Ghufran; Lund, Peter D; Österbacka, Ronald; Smått, Jan-Henrik

2017-05-31

Uniform and pinhole-free electron-selective TiO 2 layers are of utmost importance for efficient perovskite solar cells. Here we used a scalable and low-cost dip-coating method to prepare uniform and ultrathin (5-50 nm) compact TiO 2 films on fluorine-doped tin oxide (FTO) glass substrates. The thickness of the film was tuned by changing the TiCl 4 precursor concentration. The formed TiO 2 follows the texture of the underlying FTO substrates, but at higher TiCl 4 concentrations, the surface roughness is substantially decreased. This change occurs at a film thickness close to 20-30 nm. A similar TiCl 4 concentration is needed to produce crystalline TiO 2 films. Furthermore, below this film thickness, the underlying FTO might be exposed resulting in pinholes in the compact TiO 2 layer. When integrated into mesoscopic perovskite solar cells there appears to be a similar critical compact TiO 2 layer thickness above which the devices perform more optimally. The power conversion efficiency was improved by more than 50% (from 5.5% to ∼8.6%) when inserting a compact TiO 2 layer. Devices without or with very thin compact TiO 2 layers display J-V curves with an "s-shaped" feature in the negative voltage range, which could be attributed to immobilized negative ions at the electron-extracting interface. A strong correlation between the magnitude of the s-shaped feature and the exposed FTO seen in the X-ray photoelectron spectroscopy measurements indicates that the s-shape is related to pinholes in the compact TiO 2 layer when it is too thin.

Direct Low-Temperature Growth of Single-Crystalline Anatase TiO2 Nanorod Arrays on Transparent Conducting Oxide Substrates for Use in PbS Quantum-Dot Solar Cells.

PubMed

Chung, Hyun Suk; Han, Gill Sang; Park, So Yeon; Shin, Hee-Won; Ahn, Tae Kyu; Jeong, Sohee; Cho, In Sun; Jung, Hyun Suk

2015-05-20

We report on the direct growth of anatase TiO2 nanorod arrays (A-NRs) on transparent conducting oxide (TCO) substrates that can be directly applied to various photovoltaic devices via a seed layer mediated epitaxial growth using a facile low-temperature hydrothermal method. We found that the crystallinity of the seed layer and the addition of an amine functional group play crucial roles in the A-NR growth process. The A-NRs exhibit a pure anatase phase with a high crystallinity and preferred growth orientation in the [001] direction. Importantly, for depleted heterojunction solar cells (TiO2/PbS), the A-NRs improve both electron transport and injection properties, thereby largely increasing the short-circuit current density and doubling their efficiency compared to TiO2 nanoparticle-based solar cells.

Characterization of N3 dye adsorption on TiO2 using quartz-crystal microbalance with dissipation monitoring

NASA Astrophysics Data System (ADS)

Wayment-Steele, Hannah K.; Johnson, Lewis E.; Dixon, Matthew C.; Johal, Malkiat S.

2013-09-01

Understanding the kinetics of dye adsorption on semiconductors is crucial for designing dye-sensitized solar cells (DSSCs) with enhanced efficiency. Harms et al. recently applied the Quartz-Crystal Microbalance with Dissipation Monitoring (QCM-D) to study in situ dye adsorption on flat TiO2 surfaces. QCM-D measures adsorption in real time and therefore allows one to determine the kinetics of the process. In this work, we characterize the adsorption of N3, a commercial RuBipy dye, using the native oxide layer of a titanium sensor to simulate the TiO2 substrate of a DSSC. We report equilibrium constants that are in agreement with previous absorbance studies of N3 adsorption, and therefore demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption.

Strain relaxation in single crystal SrTiO3 grown on Si (001) by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Choi, Miri; Posadas, Agham; Dargis, Rytis; Shih, Chih-Kang; Demkov, Alexander A.; Triyoso, Dina H.; David Theodore, N.; Dubourdieu, Catherine; Bruley, John; Jordan-Sweet, Jean

2012-03-01

An epitaxial layer of SrTiO3 grown directly on Si may be used as a pseudo-substrate for the integration of perovskite oxides onto silicon. When SrTiO3 is initially grown on Si (001), it is nominally compressively strained. However, by subsequent annealing in oxygen at elevated temperature, an SiOx interlayer can be formed which alters the strain state of SrTiO3. We report a study of strain relaxation in SrTiO3 films grown on Si by molecular beam epitaxy as a function of annealing time and oxygen partial pressure. Using a combination of x-ray diffraction, reflection high energy electron diffraction, and transmission electron microscopy, we describe the process of interfacial oxidation and strain relaxation of SrTiO3 on Si (001). Understanding the process of strain relaxation of SrTiO3 on silicon will be useful for controlling the SrTiO3 lattice constant for lattice matching with functional oxide overlayers.

Effect of laser parameters on the microstructure of bonding porcelain layer fused on titanium

NASA Astrophysics Data System (ADS)

Chen, Xiaoyuan; Guo, Litong; Liu, Xuemei; Feng, Wei; Li, Baoe; Tao, Xueyu; Qiang, Yinghuai

2017-09-01

Bonding porcelain layer was fused on Ti surface by laser cladding process using a 400 W pulse CO2 laser. The specimens were studied by field-emission scanning electron microscopy, X-ray diffraction and bonding tests. During the laser fusion process, the porcelain powders were heated by laser energy and melted on Ti to form a chemical bond with the substrate. When the laser scanning speed decreased, the sintering temperature and the extent of the oxidation of Ti surface increased accordingly. When the laser scanning speed is 12.5 mm/s, the bonding porcelain layers were still incomplete sintered and there were some micro-cracks in the porcelain. When the laser scanning speed decreased to 7.5 mm/s, vitrified bonding porcelain layers with few pores were synthesized on Ti.

In vitro apatite formation on nano-crystalline titania layer aligned parallel to Ti6Al4V alloy substrates with sub-millimeter gap.

PubMed

Hayakawa, Satoshi; Matsumoto, Yuko; Uetsuki, Keita; Shirosaki, Yuki; Osaka, Akiyoshi

2015-06-01

Pure titanium substrates were chemically oxidized with H2O2 and subsequent thermally oxidized at 400 °C in air to form anatase-type titania layer on their surface. The chemically and thermally oxidized titanium substrate (CHT) was aligned parallel to the counter specimen such as commercially pure titanium (cpTi), titanium alloy (Ti6Al4V) popularly used as implant materials or Al substrate with 0.3-mm gap. Then, they were soaked in Kokubo's simulated body fluid (SBF, pH 7.4, 36.5 °C) for 7 days. XRD and SEM analysis showed that the in vitro apatite-forming ability of the contact surface of the CHT specimen decreased in the order: cpTi > Ti6Al4V > Al. EDX and XPS surface analysis showed that aluminum species were present on the contact surface of the CHT specimen aligned parallel to the counter specimen such as Ti6Al4V and Al. This result indicated that Ti6Al4V or Al specimens released the aluminum species into the SBF under the spatial gap. The released aluminum species might be positively or negatively charged in the SBF and thus can interact with calcium or phosphate species as well as titania layer, causing the suppression of the primary heterogeneous nucleation and growth of apatite on the contact surface of the CHT specimen under the spatial gap. The diffusion and adsorption of aluminum species derived from the half-sized counter specimen under the spatial gap resulted in two dimensionally area-selective deposition of apatite particles on the contact surfaces of the CHT specimen.

Influence of source and drain contacts on the properties of indium-gallium-zinc-oxide thin-film transistors based on amorphous carbon nanofilm as barrier layer.

PubMed

Luo, Dongxiang; Xu, Hua; Zhao, Mingjie; Li, Min; Xu, Miao; Zou, Jianhua; Tao, Hong; Wang, Lei; Peng, Junbiao

2015-02-18

Amorphous indium-gallium-zinc-oxide thin film transistors (α-IGZO TFTs) with damage-free back channel wet-etch (BCE) process were achieved by introducing a carbon nanofilm as a barrier layer. We investigate the effects of different source-and-drain (S/D) materials on TFT performance. We find the TFT with Ti/C S/D electrodes exhibits a superior performance with higher output current, lower threshold voltage, and higher effective electron mobility compared to that of Mo/C S/D electrodes. Transmittance electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) are employed to analysis the interfacial interaction between S/D metal/C/α-IGZO layers. The results indicate that the better performance of TFTs with Ti/C electrodes should be attributed to the formations of Ti-C and Ti-O at the Ti/C-contact regions, which lead to a lower contact resistance, whereas Mo film is relatively stable and does not react easily with C nanofilm, resulting in a nonohmic contact behavior between Mo/C and α-IGZO layer. However, both kinds of α-IGZO TFTs show good stability under thermal bias stress, indicating that the inserted C nanofilms could avoid the impact on the α-IGZO channel regions during S/D electrodes formation. Finally, we successfully fabricated a high-definition active-matrix organic lighting emitting diode prototype driven by α-IGZO TFTs with Ti/C electrodes in a pilot line.

Preparation of well-distributed titania nanopillar arrays on Ti6Al4V surface by induction heating for enhancing osteogenic differentiation of stem cells

NASA Astrophysics Data System (ADS)

Li, Ning-Bo; Sun, Sheng-Jun; Bai, Han-Ying; Xiao, Gui-Yong; Xu, Wen-Hua; Zhao, Jun-Han; Chen, Xin; Lu, Yu-Peng; Zhang, Yi-Lin

2018-01-01

Great effort has recently been devoted to the preparation of nanoscale surfaces on titanium-based implants to achieve clinically fast osteoinduction and osseointegration, which relies on the unique characteristics of the nanostructure. In this work, we used induction heating treatment (IHT) as a rapid oxidation method to fabricate a porous nanoscale oxide layer on the Ti6Al4V surface for better medical application. Well-distributed vertical nanopillars were yielded by IHT for 20-35 s on the alloy surface. The composition of the oxides contained rutile/anatase TiO2 and a small amount of Al2O3 between the TiO2 grain boundaries (GBs). This technology resulted in a reduction and subsequent increase of surface roughness of 26-32 nm when upregulating the heating time, followed by the successive enhancement of the thickness, wettability and adhesion strength of the oxidation layer to the matrix. The surface hardness also distinctly rose to 554 HV in the IHT-35 s group compared with the 350 HV of bare Ti6Al4V. The massive small-angle GBs in the bare alloy promoted the formation of nanosized oxide crystallites. The grain refinement and deformation texture reduction further improved the mechanical properties of the matrix after IHT. Moreover, in vitro experiments on a mesenchymal stem cell (BMSC) culture derived from human bone marrow for 1-7 days indicated that the nanoscale layers did not cause cytotoxicity, and facilitated cell differentiation in osteoblasts by enhancing the gene and osteogenesis-related protein expressions after 1-3 weeks of culturing. The increase of the IHT time slightly advanced the BMSC proliferation and differentiation, especially during long-term culture. Our findings provide strong evidence that IHT oxidation technology is a novel nanosurface modification technology, which is potentially promising for further clinical development.

Studies of surface morphology and optical properties of ZnO nanostructures grown on different molarities of TiO{sub 2} seed layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asib, N. A. M., E-mail: amierahasib@yahoo.com; Afaah, A. N.; Aadila, A.

Titanium dioxide (TiO{sub 2}) seed layer was prepared by using sol-gel spin-coating technique, followed by growth of 0.01 M of Zinc oxide (ZnO) nanostructures by solution-immersion. The molarities of TiO{sub 2} seed layer were varied from 1.1 M to 0.100 M on glass substrates. The nanostructures thin films were characterized by Field Emission Scanning Electrons Microscope (FESEM), Photoluminescence (PL) spectroscopy and Ultraviolet-Visible (UV-Vis) spectroscopy. FESEM images demonstrate that needle-like ZnO nanostructures are formed on all TiO{sub 2} seed layer. The smallest diameter of needle-like ZnO nanostructures (90.3 nm) were deposited on TiO{sub 2} seed layer of 0.100 M. PL spectramore » of the TiO{sub 2}: ZnO nanostructures thin films show the blue shifted emissions in the UV regions compared to the ZnO thin film. Meanwhile, UV-vis spectra of films display high absorption in the UV region and high trasparency in the visible region. The highest absorbance at UV region was recorded for sample which has 0.100 M of TiO{sub 2} seed layer.« less

Effect of Sn addition on the corrosion behavior of Ti-7Cu-Sn cast alloys for biomedical applications.

PubMed

Tsao, L C

2015-01-01

The aim of this study was to investigate the effects of Sn content on the microstructure and corrosion resistance of Ti7CuXSn (x=0-5 wt.%) samples. The corrosion tests were carried out in 0.9 wt.% NaCl solution at 25 °C. The electrochemical corrosion behavior of the Ti7CuXSn alloy samples was evaluated using potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and equivalent circuit analysis. The resulting impedance parameters and polarization curves showed that adding Sn improved the electrochemical corrosion behavior of the Ti7CuXSn alloy. The Ti7CuXSn alloy samples were composed of a dual-layer oxide consisting of an inner barrier layer and an outer porous layer. Copyright © 2014 Elsevier B.V. All rights reserved.

Excellent c-Si surface passivation by low-temperature atomic layer deposited titanium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Baochen, E-mail: liaobaochen@nus.edu.sg; Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Singapore 117576; A*STAR Institute of Materials Research and Engineering

2014-06-23

In this work, we demonstrate that thermal atomic layer deposited (ALD) titanium oxide (TiO{sub x}) films are able to provide a—up to now unprecedented—level of surface passivation on undiffused low-resistivity crystalline silicon (c-Si). The surface passivation provided by the ALD TiO{sub x} films is activated by a post-deposition anneal and subsequent light soaking treatment. Ultralow effective surface recombination velocities down to 2.8 cm/s and 8.3 cm/s, respectively, are achieved on n-type and p-type float-zone c-Si wafers. Detailed analysis confirms that the TiO{sub x} films are nearly stoichiometric, have no significant level of contaminants, and are of amorphous nature. The passivation is foundmore » to be stable after storage in the dark for eight months. These results demonstrate that TiO{sub x} films are also capable of providing excellent passivation of undiffused c-Si surfaces on a comparable level to thermal silicon oxide, silicon nitride, and aluminum oxide. In addition, it is well known that TiO{sub x} has an optimal refractive index of 2.4 in the visible range for glass encapsulated solar cells, as well as a low extinction coefficient. Thus, the results presented in this work could facilitate the re-emergence of TiO{sub x} in the field of high-efficiency silicon wafer solar cells.« less

Facile decoration of TiO2 nanoparticles on graphene for solar degradation of organic dye

NASA Astrophysics Data System (ADS)

Salem, Shiva; Salem, Amin; Rezaei, Mostafa

2016-11-01

The reduced graphene oxide is interesting material for the synthesis of TiO2-based photocatalyst. In the present investigation, blackberry fruit, which contains high levels of anthocyanins and other phenolic compounds, was employed as a reducing agent mainly due to its high antioxidant capacity. The nano-crystalline TiO2 was decorated on different amounts of graphene oxide with sol-gel method and then the photocatalytic activity for degradation of cationic dye was evaluated by UV spectroscopy to achieve the optimum content of graphene oxide. The decoration of anatase nanoparticles on prepared reduced graphene oxide was investigated by X-ray diffraction, scanning and transmission electron microscopy techniques. The new composite gives significantly higher activity when is compared to the compositions fabricated by graphene oxide. The compact layer provides a large TiO2-graphene contact area and reduces the electron recombination. The decoration of TiO2 nanoparticles, 5-10 nm, on the graphene oxide reduced by blackberry juice further improves the dye removal. The results imply that the nanoparticle decoration is the key strategy to increase the degradation capacity.

Visible-light-responsive photocatalysts toward water oxidation based on NiTi-layered double hydroxide/reduced graphene oxide composite materials.

PubMed

Li, Bei; Zhao, Yufei; Zhang, Shitong; Gao, Wa; Wei, Min

2013-10-23

A visible-light responsive photocatalyst was fabricated by anchoring NiTi-layered double hydroxide (NiTi-LDH) nanosheets to the surface of reduced graphene oxide sheets (RGO) via an in situ growth method; the resulting NiTi-LDH/RGO composite displays excellent photocatalytic activity toward water splitting into oxygen with a rate of 1.968 mmol g(-1) h(-1) and a quantum efficiency as high as 61.2% at 500 nm, which is among the most effective visible-light photocatalysts. XRD patterns and SEM images indicate that the NiTi-LDH nanosheets (diameter: 100-200 nm) are highly dispersed on the surface of RGO. UV-vis absorption spectroscopy exhibits that the introduction of RGO enhances the visible-light absorption range of photocatalysts, which is further verified by the largely decreased band gap (∼1.78 eV) studied by cyclic voltammetry measurements. Moreover, photoluminescence (PL) measurements indicate a more efficient separation of electron-hole pairs; electron spin resonance (ESR) and Raman scattering spectroscopy confirm the electrons transfer from NiTi-LDH nanosheets to RGO, accounting for the largely enhanced carrier mobility and the resulting photocatalytic activity in comparison with pristine NiTi-LDH material. Therefore, this work demonstrates a facile approach for the fabrication of visible-light responsive NiTi-LDH/RGO composite photocatalysts, which can be used as a promising candidate in solar energy conversion and environmental science.

Elaboration and Characterization of TiO2 and Study of the Influence of The Number of Thin Films on the Methylene Blue Adsorption Rate

NASA Astrophysics Data System (ADS)

Madoui, Karima; Medjahed, Aicha; Hamici, Melia; Djamila, Abdi; Boudissa, Mokhtar

2018-05-01

Thin films of titanium oxide (TiO2) deposited on glass substrates were fabricated by using the sol-gel route. The realization of these thin layers was made using the dip-coating technique with a solution of titanium isopropoxyde as a precursor. The samples prepared with different numbers of deposited layers were annealed at 400 ° C for 2 hours. The main purposes of this work were investigations of both the effect of the number of thin TiO2 layers on the crystal structure of the anatase form first and, their ability to adsorb the solution of methylene blue in order to make colored filters from a photocatalytic process. The deposited titanium-oxide layers were characterized by using various techniques: namely, X-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM) and UV-Visible spectrometry. The result obtained by using the XRD technique showed the appearance of an anatase phase, as was confirmed by using Raman spectroscopy. The AFM surface analysis allowed the surface topography to be characterized and the surface roughness to be measured, which increased with increasing number of layers. The UV-Visible spectra showed that the TiO2 films had a good transmittance varying from 65% to 95% according to the number of layers. The gap energy varied as a function of the number of deposited layers. The as deposited TiO2 layers were tested as a photocatalyst towards the adsorption of methylene blue dye. The results obtained during this study showed that the adsorption capacity varied according to the number of deposited thin layers and the exposing duration to ultraviolet (UV) light. The maximum absorption rate of the dye was obtained for the two-layer sample. Seventy-two hours of irradiation allowed the adsorption intensity of the dye to be maximized for two-layer films.

Effect of Aluminum Coating on the Surface Properties of Ti-(~49 at. pct) Ni Alloy

NASA Astrophysics Data System (ADS)

Sinha, Arijit; Khan, Gobinda Gopal; Mondal, Bholanath; Majumdar, Jyotsna Dutta; Chattopadhyay, Partha Protim

2015-08-01

Stable porous layer of mixed Al2O3 and TiO2 has been formed on the Ti-(~49 at. pct) Ni alloy surface with an aim to suppress leaching of Ni from the alloy surface in contact with bio-fluid and to enhance the process of osseointegration. Aluminum coating on the Ni-Ti alloy surface prior to the anodization treatment has resulted in enhancement of depth and uniformity of pores. Thermal oxidation of the anodized aluminum-coated Ni-Ti samples has exhibited the formation of Al2O3 and TiO2 phases with dense porous structure. The nanoindentation and nanoscratch measurements have indicated a remarkable improvement in the hardness, wear resistance, and adhesiveness of the porous aluminum-coated Ni-Ti sample after thermal oxidation.

The Otto Aufranc Award: enhanced biocompatibility of stainless steel implants by titanium coating and microarc oxidation.

PubMed

Lim, Young Wook; Kwon, Soon Yong; Sun, Doo Hoon; Kim, Yong Sik

2011-02-01

Stainless steel is one of the most widely used biomaterials for internal fixation devices, but is not used in cementless arthroplasty implants because a stable oxide layer essential for biocompatibility cannot be formed on the surface. We applied a Ti electron beam coating, to form oxide layer on the stainless steel surface. To form a thicker oxide layer, we used a microarc oxidation process on the surface of Ti coated stainless steel. Modification of the surface using Ti electron beam coating and microarc oxidation could improve the ability of stainless steel implants to osseointegrate. The ability of cells to adhere to grit-blasted, titanium-coated, microarc-oxidated stainless steel in vitro was compared with that of two different types of surface modifications, machined and titanium-coated, and microarc-oxidated. We performed energy-dispersive x-ray spectroscopy and scanning electron microscopy investigations to assess the chemical composition and structure of the stainless steel surfaces and cell morphology. The biologic responses of an osteoblastlike cell line (SaOS-2) were examined by measuring proliferation (cell proliferation assay), differentiation (alkaline phosphatase activity), and attraction ability (cell migration assay). Cell proliferation, alkaline phosphatase activity, migration, and adhesion were increased in the grit-blasted, titanium-coated, microarc-oxidated group compared to the two other groups. Osteoblastlike cells on the grit-blasted, titanium-coated, microarc-oxidated surface were strongly adhered, and proliferated well compared to those on the other surfaces. The surface modifications we used (grit blasting, titanium coating, microarc oxidation) enhanced the biocompatibility (proliferation and migration of osteoblastlike cells) of stainless steel. This process is not unique to stainless steel; it can be applied to many metals to improve their biocompatibility, thus allowing a broad range of materials to be used for cementless implants.

Investigation of embedded perovskite nanoparticles for enhanced capacitor permittivities.

PubMed

Krause, Andreas; Weber, Walter M; Pohl, Darius; Rellinghaus, Bernd; Verheijen, Marcel; Mikolajick, Thomas

2014-11-26

Growth experiments show significant differences in the crystallization of ultrathin CaTiO3 layers on polycrystalline Pt surfaces. While the deposition of ultrathin layers below crystallization temperature inhibits the full layer crystallization, local epitaxial growth of CaTiO3 crystals on top of specific oriented Pt crystals occurs. The result is a formation of crystals embedded in an amorphous matrix. An epitaxial alignment of the cubic CaTiO3 ⟨111⟩ direction on top of the underlying Pt {111} surface has been observed. A reduced forming energy is attributed to an interplay of surface energies at the {111} interface of both materials and CaTiO3 nanocrystallites facets. The preferential texturing of CaTiO3 layers on top of Pt has been used in the preparation of ultrathin metal-insulator-metal capacitors with 5-30 nm oxide thickness. The effective CaTiO3 permittivity in the capacitor stack increases to 55 compared to capacitors with amorphous layers and a permittivity of 28. The isolated CaTiO3 crystals exhibit a passivation of the CaTiO3 grain surfaces by the surrounding amorphous matrix, which keeps the capacitor leakage current at ideally low values comparable for those of amorphous thin film capacitors.

Protecting hydrogenation-generated oxygen vacancies in BiVO4 photoanode for enhanced water oxidation with conformal ultrathin amorphous TiO2 layer

NASA Astrophysics Data System (ADS)

Zhang, Yang; Zhang, Xintong; Wang, Dan; Wan, Fangxu; Liu, Yichun

2017-05-01

Introducing appropriate amount of oxygen vacancies by hydrogenation treatment is a simple and efficient way to improve the photoelectrochemical performance of nanostructured oxide photoanodes. However, the hydrogenation effect is often not durable due to the gradual healing of oxygen vacancies at or close to surface of photoanodes. Herein, we tackled the problem by conformal coating the hydrogenated nanoporous BiVO4 (H-BiVO4) photoanode with an ultrathin layer of amorphous TiO2. Photoelectrochemical measurements showed that a 4 nm-thick TiO2 layer could significantly improve the stability of H-BiVO4 photoanode for repeated working test, with negligible influence on the initial photocurrent compared to the uncoated one. Mott-Schottky and linear sweep voltammetry measurements showed that donor density and photocurrent density of the H-BiVO4 electrode almost decayed to the values of pristine BiVO4 electrode after 3 h test, while the amorphous TiO2-coated electrode only degraded by 6% and 5% of the initial values respectively in the same period. The investigation thus suggested that the amorphous TiO2 layer did protect the oxygen vacancies in H-BiVO4 photoanode by isolating these oxygen vacancies from environmental oxygen, while at the same time not impeding the interfacial charge transfer to water molecules due to its leaky nature.

Dual functional passivating layer of graphene/TiO2 for improved performance of dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Shahid, Muhammad Umair; Mohamed, Norani Muti; Muhsan, Ali Samer; Khatani, Mehboob; Bashiri, Robabeh; Zaine, Siti Nur Azella; Shamsudin, Adel Eskandar

2018-02-01

The FTO/TiO2 interface plays a crucial role in the performance of dye-sensitized solar cells (DSSCs). The uneven microstructure morphology of FTO (fluorine-doped tin oxide) glass surface and high porosity of TiO2 layer produce tiny gaps and voids at the FTO/TiO2 interface that breaks the connectivity, leading to an increase in the recombination process. In the current work, a dual functional passivating layer is introduced by the combination of the graphene/TiO2 compact layer. The excellent mobility and flexibility of graphene is capitalized using its layer to fill the voids in the FTO surface, which can consequently reduce the charge transfer resistance at the interface, while the added TiO2 compact layer avoids direct contact with the electrolyte thus reducing the recombination. Graphene was synthesized by the facile solvent exfoliation method with the assistance of the probe sonication process. The parameters of sonication were optimized to achieve high-quality concentrated graphene inks (0.177-0.51 mg/ml). Raman spectroscopy and transmission electron microscopy (TEM) revealed that the graphene obtained is of a few-layer type. Electrochemical impedance spectroscopy (EIS) analysis indicated that the incorporated compact layer of graphene/TiO2 was capable of accelerating the charge transfer and reducing the recombination process at the FTO/TiO2 interface. Consequently, the photoconversion efficiency (PCE) for the device (1 cm2 active area) with double-coated graphene layer under one sun irradiation (AM 1.5) was found to be 49.49% higher than the conventional one.

Transparent conducting oxides: A δ-doped superlattice approach

PubMed Central

Cooper, Valentino R.; Seo, Sung S. Ambrose; Lee, Suyoun; Kim, Jun Sung; Choi, Woo Seok; Okamoto, Satoshi; Lee, Ho Nyung

2014-01-01

Metallic states appearing at interfaces between dissimilar insulating oxides exhibit intriguing phenomena such as superconductivity and magnetism. Despite tremendous progress in understanding their origins, very little is known about how to control the conduction pathways and the distribution of charge carriers. Using optical spectroscopic measurements and density-functional theory (DFT) simulations, we examine the effect of SrTiO3 (STO) spacer layer thickness on the optical transparency and carrier distribution in La δ-doped STO superlattices. We experimentally observe that these metallic superlattices remain highly transparent to visible light; a direct consequence of the appropriately large gap between the O 2p and Ti 3d states. In superlattices with relatively thin STO layers, we predict that three-dimensional conduction would occur due to appreciable overlap of quantum mechanical wavefunctions between neighboring δ-doped layers. These results highlight the potential for using oxide heterostructures in optoelectronic devices by providing a unique route for creating novel transparent conducting oxides. PMID:25109668

In vitro corrosion behaviour of Ti-Nb-Sn shape memory alloys in Ringer's physiological solution.

PubMed

Rosalbino, F; Macciò, D; Scavino, G; Saccone, A

2012-04-01

The nearly equiatomic Ni-Ti alloy (Nitinol) has been widely employed in the medical and dental fields owing to its shape memory or superelastic properties. The main concern about the use of this alloy derives form the fact that it contains a large amount of nickel (55% by mass), which is suspected responsible for allergic, toxic and carcinogenic reactions. In this work, the in vitro corrosion behavior of two Ti-Nb-Sn shape memory alloys, Ti-16Nb-5Sn and Ti-18Nb-4Sn (mass%) has been investigated and compared with that of Nitinol. The in vitro corrosion resistance was assessed in naturally aerated Ringer's physiological solution at 37°C by corrosion potential and electrochemical impedance spectroscopy (EIS) measurements as a function of exposure time, and potentiodynamic polarization curves. Corrosion potential values indicated that both Ni-Ti and Ti-Nb-Sn alloys undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Ti-18Nb-5Sn alloy. Significantly low anodic current density values were obtained from the polarization curves, indicating a typical passive behaviour for all investigated alloys, but Nitinol exhibited breakdown of passivity at potentials above approximately 450 mV(SCE), suggesting lower corrosion protection characteristics of its oxide film compared to the Ti-Nb-Sn alloys. EIS studies showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The obtained EIS spectra were analyzed using an equivalent electrical circuit representing a duplex structure oxide film, composed by an outer and porous layer (low resistance), and an inner barrier layer (high resistance) mainly responsible for the alloys corrosion resistance. The resistance of passive film present on the metals' surface increases with exposure time displaying the highest values to Ti-18Nb-4Sn alloy. All these electrochemical results suggest that Ti-Nb-Sn alloys are promising materials for biomedical applications.

Formation of Cr-modified silicide coatings on a Ti-Nb-Si based ultrahigh-temperature alloy by pack cementation process

NASA Astrophysics Data System (ADS)

Qiao, Yanqiang; Guo, Xiping

2010-10-01

Cr-modified silicide coatings were prepared on a Ti-Nb-Si based ultrahigh temperature alloy by Si-Cr co-deposition at 1250 °C, 1350 °C and 1400 °C for 5-20 h respectively. It was found that both coating structure and phase constituents changed significantly with increase in the co-deposition temperature and holding time. The outer layers in all coatings prepared at 1250 °C for 5-20 h consisted of (Ti,X) 5Si 3 (X represents Nb, Cr and Hf elements). (Ti,X) 5Si 4 was found as the only phase constituent in the intermediate layers in both coatings prepared at 1250 °C for 5 and 10 h, but the intermediate layers in the coatings prepared at 1250 °C for 15 and 20 h were mainly composed of (Ti,X) 5Si 3 phase that was derived from the decomposition of (Ti,X) 5Si 4 phase. In the coating prepared at 1350 °C for 5 h, single (Ti,X) 5Si 3 phase was found in its outmost layer, the same as that in the outer layers in the coatings prepared at 1250 °C; but in the coatings prepared at 1350 °C for 10-20 h, (Nb 1.95Cr 1.05)Cr 2Si 3 ternary phase was found in the outmost layers besides (Ti,X) 5Si 3 phase. In the coatings prepared at 1400 °C for 5-20 h, (Nb 1.95Cr 1.05)Cr 2Si 3 ternary phase was the single phase constituent in their outmost layers. The phase transformation (Ti,X) 5Si 4 → (Ti,X) 5Si 3 + Si occurred in the intermediate layers of the coatings prepared at 1350 and 1400 °C with prolonging co-deposition time, similar to the situation in the coatings prepared at 1250 °C for 15 and 20 h, but this transformation has been speeded up by increase in the co-deposition temperature. The transitional layers were mainly composed of (Ti,X) 5Si 3 phase in all coatings. The influence of co-deposition temperature on the diffusion ability of Cr atoms was greater than that of Si atoms in the Si-Cr co-deposition processes investigated. The growth of coatings obeyed inverse logarithmic laws at all three co-deposition temperatures. The Si-Cr co-deposition coating prepared at 1350 °C for 10 h showed a good oxidation resistance due to the formation of SiO 2 and Nb, Cr-doped TiO 2 scale after oxidation at 1250 °C for 10 h.

Low-temperature liquid precursors of crystalline metal oxides assisted by heterogeneous photocatalysis.

PubMed

Bretos, Iñigo; Jiménez, Ricardo; Pérez-Mezcua, Dulce; Salazar, Norberto; Ricote, Jesús; Calzada, M Lourdes

2015-04-24

The photocatalytically assisted decomposition of liquid precursors of metal oxides incorporating TiO2 particles enables the preparation of functional layers from the ferroelectric Pb(Zr,Ti)O3 and multiferroic BiFeO3 perovskite systems at temperatures not exceeding 350 ºC. This enables direct deposition on flexible plastic, where the multifunctionality provided by these complex-oxide materials guarantees their potential use in next-generation flexible electronics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface characterization of implant materials c.p. Ti, Ti-6Al-7Nb and Ti-6Al-4V with different pretreatments.

PubMed

Sittig, C; Textor, M; Spencer, N D; Wieland, M; Vallotton, P H

1999-01-01

The biocompatibility of commercially pure titanium and its alloys is closely related to their surface properties, with both the composition of the protecting oxide film and the surface topography playing an important role. Surfaces of commercially pure titanium and of the two alloys Ti-6Al-7Nb and Ti-6Al-4V (wt %) have been investigated following three different pretreatments: polishing, nitric acid passivation and pickling in nitric acid-hydrogen fluoride. Nitric acid treatment is found to substantially reduce the concentration of surface contaminants present after polishing. The natural 4-6 nm thick oxide layer on commercially pure titanium is composed of titanium oxide in different oxidation states (TiO2, Ti2O3 and TiO), while for the alloys, aluminium and niobium or vanadium are additionally present in oxidized form (Al2O3, Nb2O5 or V-oxides). The concentrations of the alloying elements at the surface are shown to be strongly dependent on the pretreatment process. While pickling increases the surface roughness of both commercially pure titanium and the alloys, different mechanisms appear to be involved. In the case of commercially pure titanium, the dissolution rate depends on grain orientation, whereas in the case of the two alloys, selective alpha-phase dissolution and enrichment of the beta-phase appears to occur. Copyright 1999 Kluwer Academic Publishers

Analysis of dispersive interactions at polymer/TiAlN interfaces by means of dynamic force spectroscopy.

PubMed

Wiesing, M; de Los Arcos, T; Gebhard, M; Devi, A; Grundmeier, G

2017-12-20

The structural and electronic origins of the interactions between polycarbonate and sputter deposited TiAlN were analysed using a combined electron and force spectroscopic approach. Interaction forces were measured by means of dynamic force spectroscopy and the surface polarizability was analysed by X-ray photoelectron valence band spectroscopy. It could be shown that the adhesive interactions between polycarbonate and TiAlN are governed by van der Waals forces. Different surface cleansing and oxidizing treatments were investigated and the effect of the surface chemistry on the force interactions was analysed. Intense surface oxidation resulted in a decreased adhesion force by a factor of two due to the formation of a 2 nm thick Ti 0.21 Al 0.45 O surface oxide layer. The origin of the residual adhesion forces caused by the mixed Ti 0.21 Al 0.45 O surface oxide was clarified by considering the non-retarded Hamaker coefficients as calculated by Lifshitz theory, based on optical data from Reflection Electron Energy Loss Spectroscopy. This disclosed increased dispersion forces of Ti 0.21 Al 0.45 O due to the presence of Ti(iv) ions and related Ti 3d band optical transitions.

Thermal conductivity of SrVO3-SrTiO3 thin films: Evidence of intrinsic thermal resistance at the interface between oxide layers

NASA Astrophysics Data System (ADS)

Katsufuji, T.; Saiki, T.; Okubo, S.; Katayama, Y.; Ueno, K.

2018-05-01

By using a technique of thermoreflectance that can precisely measure the thermal conductivity of thin films, we found that the thermal conductivity of SrVO3-SrTiO3 multilayer thin films normal to the surface was substantially reduced by decreasing the thickness of each layer. This indicates that a large intrinsic thermal resistance exists at the interface between SrVO3 and SrTiO3 in spite of the similar phononic properties for these two compounds.

Resistance switching mode transformation in SrRuO3/Cr-doped SrZrO3/Pt frameworks via a thermally activated Ti out-diffusion process

PubMed Central

Jo, Yongcheol; Jung, Kyooho; Kim, Jongmin; Woo, Hyeonseok; Han, Jaeseok; Kim, Hyungsang; Hong, Jinpyo; Lee, Jeon-Kook; Im, Hyunsik

2014-01-01

This work reports on a mechanism for irreversible resistive switching (RS) transformation from bipolar to unipolar RS behavior in SrRuO3 (SRO)/Cr-doped SrZrO3 (SZO:Cr)/Pt capacitor structures prepared on a Ti/SiO2/Si substrate. Counter-clockwise bipolar RS memory current-voltage (I–V) characteristics are observed within the RS voltage window of −2.5 to +1.9 V, with good endurance and retention properties. As the bias voltage increases further beyond 4 V under a forward bias, a forming process occurs resulting in irreversible RS mode transformation from bipolar to unipolar mode. This switching mode transformation is a direct consequence of thermally activated Ti out-diffusion from a Ti adhesion layer. Transition metal Ti effectively out-diffuses through the loose Pt electrode layer at high substrate temperatures, leading to the unintended formation of a thin titanium oxide (TiOx where x < 2) layer between the Pt electrode and the SZO:Cr layer as well as additional Ti atoms in the SZO:Cr layer. Cross-sectional scanning electron microscopy, transmission electron microscopy and Auger electron spectroscopy depth-profile measurements provided apparent evidence of the Ti out-diffusion phenomenon. We propose that the out-diffusion-induced additional Ti atoms in the SZO:Cr layer contributes to the creation of the metallic filamentary channels. PMID:25483325

The influence of coating solution and calcination condition on the durability of Ir1-xSnxO2/Ti anodes for oxygen evolution

NASA Astrophysics Data System (ADS)

Kato, Zenta; Kashima, Ryo; Tatsumi, Kohei; Fukuyama, Shinnosuke; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2016-12-01

For oxygen formation without forming chlorine in seawater electrolysis for hydrogen production we have been using the anode consisting of three layers of MnO2-type multiple oxide catalyst, intermediate layer and titanium substrate. The intermediate layer was used for prevention of oxidation of the titanium substrate during anodic polarization for oxygen evolution and was prepared by calcination of butanol solutions of H2IrCl6 and SnCl4 coated on titanium. The protectiveness of Ir1-xSnxO2 layer formed was directly examined using Ir1-xSnxO2/Ti anodes in H2SO4 solution changing the preparation conditions of the layer. When the sum of Ir4+ and Sn4+ was 0.1 M, the highest protectiveness was observed at 0.06 M Sn4+. Although an increase in calcination temperature led to the formation of Ir1-x-ySnxTiyO2 triple oxide with a slightly lower catalytic activity for oxygen evolution, the anode calcined at 450 °C showed the highest protectiveness.

Structure and Formation Mechanism of Black TiO 2 Nanoparticles

DOE PAGES

Tian, Mengkun; Mahjouri-Samani, Masoud; Eres, Gyula; ...

2015-10-27

The remarkable properties of black TiO 2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO 2 nanoparticles consists of a disordered Ti 2O 3 shell. The measurements show a transition region that connects the disordered Ti 2O 3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitialmore » atoms, followed by an ordered reconstruction layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti 2O 3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO 2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti 2O 3, which is a narrow-band-gap semiconductor. In conclusion, as a stoichiometric compound of the lower oxidation state Ti 3+ it is expected to be a more robust atomic structure than oxygen-deficient TiO 2 for preserving and stabilizing Ti 3+ surface species that are the key to the enhanced photocatalytic activity of black TiO 2.« less

Mechanical and tribological property of single layer graphene oxide reinforced titanium matrix composite coating

NASA Astrophysics Data System (ADS)

Hu, Zengrong; Li, Yue; Fan, Xueliang; Chen, Feng; Xu, Jiale

2018-04-01

Single layer grapheme oxide Nano sheets and Nano titanium powder were dispersed in deionized water by ultrasonic dispersion. Then the mixed solution was pre-coating on AISI4140 substrate. Using laser sintering process to fabricated grapheme oxide and Ti composite coating. Microstructures and composition of the composite coating was studied by Scanning Electron Microscopy (SEM), x-ray diffract meter (XRD) and Raman spectroscopy. Raman spectrum, XRD pattern and SEM results proved that grapheme oxide sheets were dispersed in the composite coating. The composite coating had much higher average Vickers hardness values than that of pure Ti coating. The tribological performance of the composite coatings became better while the suitable GO content was selected. For the 2.5wt. % GO content coating, the friction coefficient was reduced to near 0.1.

Effect of chemical composition of Ni-Cr dental casting alloys on the bonding characterization between porcelain and metal.

PubMed

Huang, H-H; Lin, M-C; Lee, T-H; Yang, H-W; Chen, F-L; Wu, S-C; Hsu, C-C

2005-03-01

The purpose of this study was to investigate the influence of chemical composition of Ni-Cr dental casting alloys on the bonding behaviour between porcelain and metal. A three-point bending test was used to measure the fracture load of alloy after porcelain firing. A scanning electron microscope, accompanied by an energy dispersion spectrometer, was used to analyse the morphology and chemical composition of the fracture surface. An X-ray photoelectron spectrometer and glow discharge spectrometer were used to identify the structure and cross-sectional chemical composition, respectively, of oxide layers on Ni-Cr alloys after heat treatment at 990 degrees C for 5 min. Results showed that the oxide layers formed on all Ni-Cr alloys contained mainly Cr2O3, NiO, and trace MoO3. The Ni-Cr alloy with a higher Cr content had a thicker oxide layer, as well as a weaker bonding behaviour of porcelain/metal interface. The presence of Al (as Al2O3) and Be (as BeO) on the oxide layer suppressed the growth of the oxide layer, leading to a better porcelain/metal bonding behaviour. However, the presence of a small amount of Ti (as TiO2) on the oxide layer did not have any influence on the bonding behaviour. The fracture propagated along the interface between the opaque porcelain and metal, and exhibited an adhesive type of fracture morphology.

Improved attachment of mesenchymal stem cells on super-hydrophobic TiO2 nanotubes.

PubMed

Bauer, Sebastian; Park, Jung; von der Mark, Klaus; Schmuki, Patrik

2008-09-01

Self-organized layers of vertically orientated TiO(2) nanotubes providing defined diameters ranging from 15 up to 100nm were grown on titanium by anodic oxidation. These TiO(2) nanotube layers show super-hydrophilic behavior. After coating TiO(2) nanotube layers with a self-assembled monolayer (octadecylphosphonic acid) they showed a diameter-dependent wetting behavior ranging from hydrophobic (108+/-2 degrees ) up to super-hydrophobic (167+/-2 degrees ). Cell adhesion, spreading and growth of mesenchymal stem cells on the unmodified and modified nanotube layers were investigated and compared. We show that cell adhesion and proliferation are strongly affected in the super-hydrophobic range. Adsorption of extracellular matrix proteins as fibronectin, type I collagen and laminin, as well as bovine serum albumin, on the coated and uncoated surfaces showed a strong influence on wetting behavior and dependence on tube diameter.

Nanoscale Multigate TiN Metal Nanocrystal Memory Using High-k Blocking Dielectric and High-Work-Function Gate Electrode Integrated on Silcon-on-Insulator Substrate

NASA Astrophysics Data System (ADS)

Lu, Chi-Pei; Luo, Cheng-Kei; Tsui, Bing-Yue; Lin, Cha-Hsin; Tzeng, Pei-Jer; Wang, Ching-Chiun; Tsai, Ming-Jinn

2009-04-01

In this study, a charge-trapping-layer-engineered nanoscale n-channel trigate TiN nanocrystal nonvolatile memory was successfully fabricated on silicon-on-insulator (SOI) wafer. An Al2O3 high-k blocking dielectric layer and a P+ polycrystalline silicon gate electrode were used to obtain low operation voltage and suppress the back-side injection effect, respectively. TiN nanocrystals were formed by annealing TiN/Al2O3 nanolaminates deposited by an atomic layer deposition system. The memory characteristics of various samples with different TiN wetting layer thicknesses, post-deposition annealing times, and blocking oxide thicknesses were also investigated. The sample with a thicker wetting layer exhibited a much larger memory window than other samples owing to its larger nanocrystal size. Good retention with a mere 12% charge loss for up to 10 years and high endurance were also obtained. Furthermore, gate disturbance and read disturbance were measured with very small charge migrations after a 103 s stressing bias.

Resistive switching in TiO2 nanocolumn arrays electrochemically grown

NASA Astrophysics Data System (ADS)

Marik, M.; Mozalev, A.; Hubalek, J.; Bendova, M.

2017-04-01

Resistive switching in metal oxides, especially in TiO2, has been intensively investigated for potential application in non-volatile memory microdevices. As one of the working mechanisms, a conducting filament consisting of a substoichiometric oxide phase is created within the oxide layer. With the aim of investigating the filament formation in spatially confined elements, we fabricate arrays of self-ordered TiO2 nanocolumns by porous-anodic-alumina (PAA)-assisted anodizing, incorporate them into solid-state microdevices, study their electron transport properties, and reveal that this anodizing approach is suitable for growing TiO2 nanostructures exhibiting resistive switching. The electrical properties and resistive switching behavior are both dependent on the electrolytic formation conditions, influencing the concentration and distribution of oxygen vacancies in the nanocolumn material during the film growth. Therefore, the PAA-assisted TiO2 nanocolumn arrays can be considered as a platform for investigating various phenomena related to resistive switching in valve metal oxides at the nanoscale.

Plasmonically sensitized metal-oxide electron extraction layers for organic solar cells.

PubMed

Trost, S; Becker, T; Zilberberg, K; Behrendt, A; Polywka, A; Heiderhoff, R; Görrn, P; Riedl, T

2015-01-16

ZnO and TiOx are commonly used as electron extraction layers (EELs) in organic solar cells (OSCs). A general phenomenon of OSCs incorporating these metal-oxides is the requirement to illuminate the devices with UV light in order to improve device characteristics. This may cause severe problems if UV to VIS down-conversion is applied or if the UV spectral range (λ < 400 nm) is blocked to achieve an improved device lifetime. In this work, silver nanoparticles (AgNP) are used to plasmonically sensitize metal-oxide based EELs in the vicinity (1-20 nm) of the metal-oxide/organic interface. We evidence that plasmonically sensitized metal-oxide layers facilitate electron extraction and afford well-behaved highly efficient OSCs, even without the typical requirement of UV exposure. It is shown that in the plasmonically sensitized metal-oxides the illumination with visible light lowers the WF due to desorption of previously ionosorbed oxygen, in analogy to the process found in neat metal oxides upon UV exposure, only. As underlying mechanism the transfer of hot holes from the metal to the oxide upon illumination with hν < Eg is verified. The general applicability of this concept to most common metal-oxides (e.g. TiOx and ZnO) in combination with different photoactive organic materials is demonstrated.

Plasmonically sensitized metal-oxide electron extraction layers for organic solar cells

PubMed Central

Trost, S.; Becker, T.; Zilberberg, K.; Behrendt, A.; Polywka, A.; Heiderhoff, R.; Görrn, P.; Riedl, T.

2015-01-01

ZnO and TiOx are commonly used as electron extraction layers (EELs) in organic solar cells (OSCs). A general phenomenon of OSCs incorporating these metal-oxides is the requirement to illuminate the devices with UV light in order to improve device characteristics. This may cause severe problems if UV to VIS down-conversion is applied or if the UV spectral range (λ < 400 nm) is blocked to achieve an improved device lifetime. In this work, silver nanoparticles (AgNP) are used to plasmonically sensitize metal-oxide based EELs in the vicinity (1–20 nm) of the metal-oxide/organic interface. We evidence that plasmonically sensitized metal-oxide layers facilitate electron extraction and afford well-behaved highly efficient OSCs, even without the typical requirement of UV exposure. It is shown that in the plasmonically sensitized metal-oxides the illumination with visible light lowers the WF due to desorption of previously ionosorbed oxygen, in analogy to the process found in neat metal oxides upon UV exposure, only. As underlying mechanism the transfer of hot holes from the metal to the oxide upon illumination with hν < Eg is verified. The general applicability of this concept to most common metal-oxides (e.g. TiOx and ZnO) in combination with different photoactive organic materials is demonstrated. PMID:25592174

Nanoporous Aluminum Oxide Membranes Coated with Atomic Layer Deposition-Grown Titanium Dioxide for Biomedical Applications: An In Vitro Evaluation.

PubMed

Petrochenko, Peter E; Kumar, Girish; Fu, Wujun; Zhang, Qin; Zheng, Jiwen; Liang, Chengdu; Goering, Peter L; Narayan, Roger J

2015-12-01

The surface topographies of nanoporous anodic aluminum oxide (AAO) and titanium dioxide (TiO2) membranes have been shown to modulate cell response in orthopedic and skin wound repair applications. In this study, we: (1) demonstrate an improved atomic layer deposition (ALD) method for coating the porous structures of 20, 100, and 200 nm pore diameter AAO with nanometer-thick layers of TiO2 and (2) evaluate the effects of uncoated AAO and TiO2-coated AAO on cellular responses. The TiO2 coatings were deposited on the AAO membranes without compromising the openings of the nanoscale pores. The 20 nm TiO2-coated membranes showed the highest amount of initial protein adsorption via the micro bicinchoninic acid (micro-BCA) assay; all of the TiO2-coated membranes showed slightly higher protein adsorption than the uncoated control materials. Cell viability, proliferation, and inflammatory responses on the TiO2-coated AAO membranes showed no adverse outcomes. For all of the tested surfaces, normal increases in proliferation (DNA content) of L929 fibroblasts were observed over from 4 hours to 72 hours. No increases in TNF-alpha production were seen in RAW 264.7 macrophages grown on TiO2-coated AAO membranes compared to uncoated AAO membranes and tissue culture polystyrene (TCPS) surfaces. Both uncoated AAO membranes and TiO2-coated AAO membranes showed no significant effects on cell growth and inflammatory responses. The results suggest that TiO2-coated AAO may serve as a reasonable prototype material for the development of nanostructured wound repair devices and orthopedic implants.

The Role of Nano-TiO2 Lubricating Fluid on the Hot Rolled Surface and Metallographic Structure of SS41 Steel

PubMed Central

Meng, Yanan; Sun, Jianlin; Wu, Ping; Dong, Chang; Yan, Xudong

2018-01-01

In this paper, nano-TiO2lubricating fluid was chosen as an advanced rolling lubricant to investigate its effect on the hot rolled surface and metallographic structure of SS41 steel strips. The tribological performances of nano-TiO2 lubricating fluid were measured by a four-ball tribotester. The hot rolling experiments under different lubrication conditions were carried out by a four-high rolling mill. The surface morphology, oxide scales and metallographic structure after hot rolling were observed using a confocal laser scanning microscope and scanning electron microscope (SEM), respectively. The composition of surface attachments was analyzed with X-ray photoelectron spectroscopy (XPS). The results indicate that the nano-TiO2 lubricating fluid has a better tribological performance. The surface defects on the hot rolled surface could be decreased. The phase composition of the surface still appears as a mixture of ferrite and pearlite. The surface of steel strips is not micro-alloyed with titanium as predicted. Additionally, the grain size of rolled steel strips which were lubricated with the nano-TiO2lubricating fluid decreased by nearly 50%, compared with traditional lubricating fluid. Furthermore, it was found that the thickness of the oxide layers on the surface reduced, whilst the Rockwell hardness of the oxide layers was enhanced as nano-TiO2 lubricating fluid was applied. PMID:29462937

The Role of Nano-TiO2 Lubricating Fluid on the Hot Rolled Surface and Metallographic Structure of SS41 Steel.

PubMed

Meng, Yanan; Sun, Jianlin; Wu, Ping; Dong, Chang; Yan, Xudong

2018-02-16

In this paper, nano-TiO2lubricating fluid was chosen as an advanced rolling lubricant to investigate its effect on the hot rolled surface and metallographic structure of SS41 steel strips. The tribological performances of nano-TiO2 lubricating fluid were measured by a four-ball tribotester. The hot rolling experiments under different lubrication conditions were carried out by a four-high rolling mill. The surface morphology, oxide scales and metallographic structure after hot rolling were observed using a confocal laser scanning microscope and scanning electron microscope (SEM), respectively. The composition of surface attachments was analyzed with X-ray photoelectron spectroscopy (XPS). The results indicate that the nano-TiO2 lubricating fluid has a better tribological performance. The surface defects on the hot rolled surface could be decreased. The phase composition of the surface still appears as a mixture of ferrite and pearlite. The surface of steel strips is not micro-alloyed with titanium as predicted. Additionally, the grain size of rolled steel strips which were lubricated with the nano-TiO2lubricating fluid decreased by nearly 50%, compared with traditional lubricating fluid. Furthermore, it was found that the thickness of the oxide layers on the surface reduced, whilst the Rockwell hardness of the oxide layers was enhanced as nano-TiO2 lubricating fluid was applied.

Improving the electrical contact at a Pt/TiO2 nanowire interface by selective application of focused femtosecond laser irradiation

NASA Astrophysics Data System (ADS)

Xing, Songling; Lin, Luchan; Zou, Guisheng; Liu, Lei; Peng, Peng; Wu, Aiping; Duley, Walter W.; Zhou, Y. Norman

2017-10-01

In this paper, we show that tightly focused femtosecond laser irradiation is effective in improving nanojoining of an oxide nanowire (NW) (TiO2) to a metal electrode (Pt), and how this process can be used to modify contact states. Enhanced chemical bondings are created due to localized plasmonically enhanced optical absorption at the Pt/TiO2 interface as confirmed by finite element simulations of the localized field distribution during irradiation. Nano Auger electron spectroscopy shows that the resulting heterojunction is depleted in oxygen, suggesting that a TiO2-x layer is formed between the Pt electrode and the TiO2 NW. The presence of this redox layer at the metal/oxide interface plays an important role in decreasing the Schottky barrier height and in facilitating chemical bonding. After laser irradiation at the cathode for 10 s at a fluence of 5.02 mJ cm-2, the Pt/TiO2 NW/Pt structure displays different electrical properties under forward and reverse bias voltage, respectively. The creation of this asymmetric electrical characteristic shows the way in which modification of the electronic interface by laser engineering can replace the electroforming process in resistive switching devices and how it can be used to control contact states in a metal/oxide interface.

Improving the electrical contact at a Pt/TiO2 nanowire interface by selective application of focused femtosecond laser irradiation.

PubMed

Xing, Songling; Lin, Luchan; Zou, Guisheng; Liu, Lei; Peng, Peng; Wu, Aiping; Duley, Walter W; Zhou, Y Norman

2017-10-06

In this paper, we show that tightly focused femtosecond laser irradiation is effective in improving nanojoining of an oxide nanowire (NW) (TiO 2 ) to a metal electrode (Pt), and how this process can be used to modify contact states. Enhanced chemical bondings are created due to localized plasmonically enhanced optical absorption at the Pt/TiO 2 interface as confirmed by finite element simulations of the localized field distribution during irradiation. Nano Auger electron spectroscopy shows that the resulting heterojunction is depleted in oxygen, suggesting that a TiO 2-x layer is formed between the Pt electrode and the TiO 2 NW. The presence of this redox layer at the metal/oxide interface plays an important role in decreasing the Schottky barrier height and in facilitating chemical bonding. After laser irradiation at the cathode for 10 s at a fluence of 5.02 mJ cm -2 , the Pt/TiO 2 NW/Pt structure displays different electrical properties under forward and reverse bias voltage, respectively. The creation of this asymmetric electrical characteristic shows the way in which modification of the electronic interface by laser engineering can replace the electroforming process in resistive switching devices and how it can be used to control contact states in a metal/oxide interface.

Polydopamine-Coated TiO2 Nanotubes for Selective Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde Under Visible Light.

PubMed

Tripathy, Jyotsna; Loget, Gabriel; Altomare, Marco; Schmuki, Patrik

2016-05-01

TiO2 nanotube arrays grown by anodization were coated with thin layers of polydopamine as visible light sensitizer. The PDA-coated TiO2 scaffolds were used as photocatalyst for selective oxidation of benzyl alcohol under monochromatic irradiation at 473 nm. Benzaldehyde was selectively formed and no by-products could be detected. A maximized reaction yield was obtained in O2-saturated acetonitrile. A mechanism is proposed that implies firstly the charge carrier generation in polydopamine as a consequence of visible light absorption. Secondly, photo-promoted electrons are injected in TiO2 conduction band, and subsequently transferred to dissolved O2 to form O*2- radicals. These radicals react with benzyl alcohol and lead to its selective dehydrogenation oxidation towards benzaldehyde.

Corrosion behavior and surface structure of orthodontic Ni-Ti alloy wires.

PubMed

Iijima, M; Endo, K; Ohno, H; Yonekura, Y; Mizoguchi, I

2001-03-01

The corrosion behaviors of a commercial Ni-Ti alloy orthodontic wire and a polished plate with same composition in 0.9% NaCl and 1% lactic acid solutions were examined using an electrochemical technique, an analysis of released ions, and a surface analysis by X-ray photoelectron spectroscopy (XPS). The effect of polishing the wire on the corrosion was also examined. The XPS analysis demonstrated the presence of a thick oxide film mainly composed of TiO2 with trace amounts of Ni hydroxide, which had formed on the wire surface during the heat treatment and subsequent pickling processes. This oxide layer contributed to the higher resistance of the as-received wire to both general and localized corrosion in 0.9% NaCl solution, compared with that of the polished plate and the polished wire. The thick oxide layer, however, was not stable and did not protect the orthodontic wire from corrosion in 0.1% lactic acid solution.

The structure feature of layered M1/3TiNbO5 (M=Fe, Ce) and their photocatalytic oxidization performance for ethyl mercaptan

NASA Astrophysics Data System (ADS)

Dong, Rui; Wang, Yuan; Wang, Ningning; Xu, Lei; He, Jie; Wu, Shanshan; Lan, Yunxiang; Hu, Jinsong

2016-09-01

Layered photocatalytic materials M1/3TiNbO5 (M = Fe, Ce) were prepared by ion-exchange of KTiNbO5 with M(NO3)3. The parent KTiNbO5 was synthesized with titanium (IV) isopropoxide and niobium oxalate by a novel polymerized complex (PC) method. The micro-structures and spectral response features of the as-prepared samples were characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), laser Raman spectroscopy (LRS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The results revealed that there was a significant interaction between the interlayer cation and the terminal Nbdbnd O (Tidbnd O) bond in the NbO6 (TiO6) unit of the laminates. Photocatalytic performance was evaluated in oxidation of ethyl mercaptan under natural and UV light irradiation. It can be deduced that the photocatalytic oxidization performance can be directly affected by the characteristics of the interlayer cations.

Influence of different TiO2 blocking films on the photovoltaic performance of perovskite solar cells

NASA Astrophysics Data System (ADS)

Zhang, Chenxi; Luo, Yudan; Chen, Xiaohong; Ou-Yang, Wei; Chen, Yiwei; Sun, Zhuo; Huang, Sumei

2016-12-01

Organolead trihalide perovskite materials have been successfully used as light absorbers in efficient photovoltaic (PV) cells. Cell structures based on mesoscopic metal oxides and planar heterojunctions have already demonstrated very impressive and brisk advances, holding great potential to grow into a mature PV technology. High power conversion efficiency (PCE) values have been obtained from the mesoscopic configuration in which a few hundred nano-meter thick mesoporous scaffold (e.g. TiO2 or Al2O3) infiltrated by perovskite absorber was sandwiched between the electron and hole transport layers. A uniform and compact hole-blocking layer is necessary for high efficient perovskite-based thin film solar cells. In this study, we investigated the characteristics of TiO2 compact layer using various methods and its effects on the PV performance of perovskite solar cells. TiO2 compact layer was prepared by a sol-gel method based on titanium isopropoxide and HCl, spin-coating of titanium diisopropoxide bis (acetylacetonate), screen-printing of Dyesol's bocking layer titania paste, and a chemical bath deposition (CBD) technique via hydrolysis of TiCl4, respectively. The morphological and micro-structural properties of the formed compact TiO2 layers were characterized by scanning electronic microscopy and X-ray diffraction. The analyses of devices performance characteristics showed that surface morphologies of TiO2 compact films played a critical role in affecting the efficiencies. The nanocrystalline TiO2 film deposited via the CBD route acts as the most efficient hole-blocking layer and achieves the best performance in perovskite solar cells. The CBD-based TiO2 compact and dense layer offers a small series resistance and a large recombination resistance inside the device, and makes it possible to achieve a high power conversion efficiency of 12.80%.

Thermal Shock and Oxidation Behavior of HiPIMS TiAlN Coatings Grown on Ti-48Al-2Cr-2Nb Intermetallic Alloy

PubMed Central

Badini, Claudio; Deambrosis, Silvia M.; Padovano, Elisa; Fabrizio, Monica; Ostrovskaya, Oxana; Miorin, Enrico; D’Amico, Giuseppe C.; Montagner, Francesco; Biamino, Sara; Zin, Valentina

2016-01-01

A High Power Impulse Magnetron Sputtering (HiPIMS) method for depositing TiAlN environmental barrier coatings on the surface of Ti-48Al-2Cr-2Nb alloy was developed in view of their exploitation in turbine engines. Three differently engineered TiAlN films were processed and their performance compared. Bare intermetallic alloy coupons and coated specimens were submitted to thermal cycling under oxidizing atmosphere up to 850 °C or 950 °C, at high heating and cooling rates. For this purpose, a burner rig able to simulate the operating conditions of the different stages of turbine engines was used. Microstructures of the samples were compared before and after each test using several techniques (microscopy, XRD, and XPS). Coating-intermetallic substrate adhesion and tribological properties were investigated too. All the TiAlN films provided a remarkable increase in oxidation resistance. Good adhesion properties were observed even after repeated thermal shocks. HiPIMS pretreatments of the substrate surfaces performed before the coating deposition significantly affected the oxidation rate, the oxide layer composition and the coating/substrate adhesion. PMID:28774082

Toward improved mechanical, tribological, corrosion and in-vitro bioactivity properties of mixed oxide nanotubes on Ti-6Al-7Nb implant using multi-objective PSO.

PubMed

Rafieerad, A R; Bushroa, A R; Nasiri-Tabrizi, B; Kaboli, S H A; Khanahmadi, S; Amiri, Ahmad; Vadivelu, J; Yusof, F; Basirun, W J; Wasa, K

2017-05-01

Recently, the robust optimization and prediction models have been highly noticed in district of surface engineering and coating techniques to obtain the highest possible output values through least trial and error experiments. Besides, due to necessity of finding the optimum value of dependent variables, the multi-objective metaheuristic models have been proposed to optimize various processes. Herein, oriented mixed oxide nanotubular arrays were grown on Ti-6Al-7Nb (Ti67) implant using physical vapor deposition magnetron sputtering (PVDMS) designed by Taguchi and following electrochemical anodization. The obtained adhesion strength and hardness of Ti67/Nb were modeled by particle swarm optimization (PSO) to predict the outputs performance. According to developed models, multi-objective PSO (MOPSO) run aimed at finding PVDMS inputs to maximize current outputs simultaneously. The provided sputtering parameters were applied as validation experiment and resulted in higher adhesion strength and hardness of interfaced layer with Ti67. The as-deposited Nb layer before and after optimization were anodized in fluoride-base electrolyte for 300min. To crystallize the coatings, the anodically grown mixed oxide TiO 2 -Nb 2 O 5 -Al 2 O 3 nanotubes were annealed at 440°C for 30min. From the FESEM observations, the optimized adhesive Nb interlayer led to further homogeneity of mixed nanotube arrays. As a result of this surface modification, the anodized sample after annealing showed the highest mechanical, tribological, corrosion resistant and in-vitro bioactivity properties, where a thick bone-like apatite layer was formed on the mixed oxide nanotubes surface within 10 days immersion in simulated body fluid (SBF) after applied MOPSO. The novel results of this study can be effective in optimizing a variety of the surface properties of the nanostructured implants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of shot-peening and atmospheric-pressure plasma on aesthetic improvement of Ti-Nb-Ta-Zr alloy for dental applications

NASA Astrophysics Data System (ADS)

Miura-Fujiwara, Eri; Suzuki, Yuu; Ito, Michiko; Yamada, Motoko; Matsutake, Sinpei; Takashima, Seigo; Sato, Hisashi; Watanabe, Yoshimi

2018-01-01

Ti and Ti alloys are widely used for biomedical applications such as artificial joints and dental devices because of their good mechanical properties and biochemical compatibility. However, dental devices made of Ti and Ti alloys do not have the same color as teeth, so they are inferior to ceramics and polymers in terms of aesthetic properties. In a previous study, Ti-29Nb-13Ta-4.6Zr was coated with a white Ti oxide layer by heat treatment to improve its aesthetic properties. Shot-peening is a severe plastic deformation process and can introduce a large shear strain on the peened surface. In this study, the effects of shot-peening and atmospheric-pressure plasma on Ti-29Nb-13Ta-4.6Zr were investigated to form a white layer on the surface for dental applications.

Atomic Layer Deposition of TiO2 for a High-Efficiency Hole-Blocking Layer in Hole-Conductor-Free Perovskite Solar Cells Processed in Ambient Air.

PubMed

Hu, Hang; Dong, Binghai; Hu, Huating; Chen, Fengxiang; Kong, Mengqin; Zhang, Qiuping; Luo, Tianyue; Zhao, Li; Guo, Zhiguang; Li, Jing; Xu, Zuxun; Wang, Shimin; Eder, Dominik; Wan, Li

2016-07-20

In this study we design and construct high-efficiency, low-cost, highly stable, hole-conductor-free, solid-state perovskite solar cells, with TiO2 as the electron transport layer (ETL) and carbon as the hole collection layer, in ambient air. First, uniform, pinhole-free TiO2 films of various thicknesses were deposited on fluorine-doped tin oxide (FTO) electrodes by atomic layer deposition (ALD) technology. Based on these TiO2 films, a series of hole-conductor-free perovskite solar cells (PSCs) with carbon as the counter electrode were fabricated in ambient air, and the effect of thickness of TiO2 compact film on the device performance was investigated in detail. It was found that the performance of PSCs depends on the thickness of the compact layer due to the difference in surface roughness, transmittance, charge transport resistance, electron-hole recombination rate, and the charge lifetime. The best-performance devices based on optimized TiO2 compact film (by 2000 cycles ALD) can achieve power conversion efficiencies (PCEs) of as high as 7.82%. Furthermore, they can maintain over 96% of their initial PCE after 651 h (about 1 month) storage in ambient air, thus exhibiting excellent long-term stability.

First-principles many-body investigation of δ-doped titanates

NASA Astrophysics Data System (ADS)

Lechermann, Frank; Obermeyer, Michael

2015-03-01

Studying oxide heterostructures provides the possibility for exploring novel composite materials beyond nature's original conception. In this respect, the doping of Mott-insulating distorted-perovskite titanates such as LaTiO3 and GdTiO3 with a single SrO layer gives rise to a very rich correlated electronic structure. A realistic superlattice survey by means of the charge self-consistent combination of density functional theory (DFT) with dynamical mean-field theory (DMFT) reveals layer- and temperature-dependent multi-orbital metal-insulator transitions. In [001] stacking, an orbital-selective metallic layer at the interface dissolves via an orbital-polarized doped-Mott state into an orbital-ordered insulating regime beyond the two conducting TiO2 layers. We find large differences in the scattering behavior within the latter. Breaking the spin symmetry in δ-doped GdTiO3 results in blocks of ferromagnetic itinerant and ferromagnetic Mott-insulating layers which are coupled antiferromagnetically. Support from the DFG-FOR1346 is acknowledged.

Oxygen-implanted induced formation of oxide layer enhances blood compatibility on titanium for biomedical applications.

PubMed

Hung, Wei-Chiang; Chang, Fang-Mo; Yang, Tzu-Sen; Ou, Keng-Liang; Lin, Che-Tong; Peng, Pei-Wen

2016-11-01

Titanium dioxide (TiO2) layers were prepared on a Ti substrate by using oxygen plasma immersion ion implantation (oxygen PIII). The surface chemical states, structure, and morphology of the layers were studied using X-ray photoelectron spectroscopy, X-ray diffraction, Raman microscopy, atomic force microscopy and scanning electron microscope. The mechanical properties, such as the Young's modulus and hardness, of the layers were investigated using nanoindentation testing. The Ti(4+) chemical state was determined to be present on oxygen-PIII-treated surfaces, which consisted of nanocrystalline TiO2 with a rutile structure. Compared with Ti substrates, the oxygen-PIII-treated surfaces exhibited decreased Young's moduli and hardness. Parameters indicating the blood compatibility of the oxygen-PIII-treated surfaces, including the clotting time and platelet adhesion and activation, were studied in vitro. Clotting time assays indicated that the clotting time of oxygen-PIII-treated surfaces was longer than that of the Ti substrate, which was associated with decreased fibrinogen adsorption. In conclusion, the surface characteristics and the blood compatibility of Ti implants can be modified and improved using oxygen PIII. Copyright © 2016 Elsevier B.V. All rights reserved.

Weaving a two-dimensional fishing net from titanoniobate nanosheets embedded with Fe3O4 nanocrystals for highly efficient capture and isotope labeling of phosphopeptides

NASA Astrophysics Data System (ADS)

Chen, Xueqin; Li, Siyuan; Zhang, Xiaoxia; Min, Qianhao; Zhu, Jun-Jie

2015-03-01

Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3O4 nanocrystals (Fe3O4-TiNbNS) is constructed via a facile cation-exchange approach, and adopted for the capture and isotope labeling of phosphopeptides. In this nanoarchitecture, the 2D titanoniobate nanosheets offer enlarged surface area and a spacious microenvironment for capturing phosphopeptides, while the Fe3O4 nanocrystals not only incorporate a magnetic response into the composite but, more importantly, also disrupt the restacking process between the titanoniobate nanosheets and thus preserve a greater specific surface for binding phosphopeptides. Owing to the extended active surface, abundant Lewis acid sites and excellent magnetic controllability, Fe3O4-TiNbNS demonstrates superior sensitivity, selectivity and capacity over homogeneous bulk metal oxides, layered oxides, and even restacked nanosheets in phosphopeptide enrichment, and further allows in situ isotope labeling to quantify aberrantly-regulated phosphopeptides from sera of leukemia patients. This composite nanosheet greatly contributes to the MS analysis of phosphopeptides and gives inspiration in the pursuit of 2D structured materials for separation of other biological molecules of interests.Qualitative and quantitative characterization of phosphopeptides by means of mass spectrometry (MS) is the main goal of MS-based phosphoproteomics, but suffers from their low abundance in the large haystack of various biological molecules. Herein, we introduce two-dimensional (2D) metal oxides to tackle this biological separation issue. A nanocomposite composed of titanoniobate nanosheets embedded with Fe3O4 nanocrystals (Fe3O4-TiNbNS) is constructed via a facile cation-exchange approach, and adopted for the capture and isotope labeling of phosphopeptides. In this nanoarchitecture, the 2D titanoniobate nanosheets offer enlarged surface area and a spacious microenvironment for capturing phosphopeptides, while the Fe3O4 nanocrystals not only incorporate a magnetic response into the composite but, more importantly, also disrupt the restacking process between the titanoniobate nanosheets and thus preserve a greater specific surface for binding phosphopeptides. Owing to the extended active surface, abundant Lewis acid sites and excellent magnetic controllability, Fe3O4-TiNbNS demonstrates superior sensitivity, selectivity and capacity over homogeneous bulk metal oxides, layered oxides, and even restacked nanosheets in phosphopeptide enrichment, and further allows in situ isotope labeling to quantify aberrantly-regulated phosphopeptides from sera of leukemia patients. This composite nanosheet greatly contributes to the MS analysis of phosphopeptides and gives inspiration in the pursuit of 2D structured materials for separation of other biological molecules of interests. Electronic supplementary information (ESI) available: Sequence of phosphopeptides from the digests of α- and β-casein percentages of the 4 methylated products from peptide β1 at different labeling reaction times; sequence of serum phosphopeptides; XPS spectra of Nb 3d and Ti 2p in layered oxides and H+-stacked nanosheets; phosphopeptide enrichment sensitivity of bulk oxides, layered oxides and H+-stacked nanosheets; AFM image of TiNbNS; saturated adsorption isotherm for pNPP adsorbed on bulk oxides, layered oxides and H+-stacked nanosheets; XPS spectra of Fe3O4-TiNbNS nitrogen adsorption-desorption isotherms and pore size distribution curves for the Fe3O4 nanocrystals; phosphopeptide enrichment sensitivity, capacity and selectivity of the Fe3O4-TiNbNS composites; MS/MS spectra of phosphopeptides enriched from serum; linear relationship between the logarithms of peak area ratio and loading volume ratio. See DOI: 10.1039/c4nr07041k

Atomic Layer Deposition of Titanium Oxide on Single-Layer Graphene: An Atomic-Scale Study toward Understanding Nucleation and Growth

PubMed Central

2017-01-01

Controlled synthesis of a hybrid nanomaterial based on titanium oxide and single-layer graphene (SLG) using atomic layer deposition (ALD) is reported here. The morphology and crystallinity of the oxide layer on SLG can be tuned mainly with the deposition temperature, achieving either a uniform amorphous layer at 60 °C or ∼2 nm individual nanocrystals on the SLG at 200 °C after only 20 ALD cycles. A continuous and uniform amorphous layer formed on the SLG after 180 cycles at 60 °C can be converted to a polycrystalline layer containing domains of anatase TiO2 after a postdeposition annealing at 400 °C under vacuum. Using aberration-corrected transmission electron microscopy (AC-TEM), characterization of the structure and chemistry was performed on an atomic scale and provided insight into understanding the nucleation and growth. AC-TEM imaging and electron energy loss spectroscopy revealed that rocksalt TiO nanocrystals were occasionally formed at the early stage of nucleation after only 20 ALD cycles. Understanding and controlling nucleation and growth of the hybrid nanomaterial are crucial to achieving novel properties and enhanced performance for a wide range of applications that exploit the synergetic functionalities of the ensemble. PMID:28356613

Synthesis of layered perovskite oxides, ACa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10] (A = K, Rb, Cs), and characterization of new solid acids, HCa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10] (O < x [le] 2), exhibiting variable Bronsted acidity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gopalakrishnan, J.; Uma, S.; Bhat, V.

1993-01-01

Layered perovskite oxides of the formula ACa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10] (A = K, Rb, Cs and 0 , x [le] 2) have been prepared. The members adopt the structures of the parent ACa[sub 2]Nb[sub 3]O[sub 10]. Interlayer alkali cations in the niobium-titanium oxide series can be ion-exchanged with Li[sup +], Na[sup +], NG[sub 4][sup +], of H[sup +] to give new derivatives. Intercalation of the protonated derivatives with organic bases reveals that the Bronsted acidity of the solid solution series, HCa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10], depends on the titanium content. While the x = 1 member (HCaLaNb[submore » 2]TiO[sub 10]) is nearly as acidic as the parent HCa[sub 2]Nb[sub 3]O[sub 10], the x = 2 member (HLA[sub 2]NbTi[sub 2]O[sub 10]) is a weak acid hardly intercalating organic bases with pK[sub a] [approximately] 11.3. The variation of acidity is probably due to an ordering of Nb/Ti atoms in the triple octahedral perovskite slabs, [Ca[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10

Structural changes of anodic layer on titanium in sulfate solution as a function of anodization duration in constant current mode

NASA Astrophysics Data System (ADS)

Komiya, Shinji; Sakamoto, Kouta; Ohtsu, Naofumi

2014-03-01

The present study investigated the effect of anodization time, in constant current mode, on the anodic oxide layer formed on titanium (Ti). Anodization of the Ti substrate was　carried out in a 0.1 M (NH4)2SO4 aqueous solution with reaction times of various durations, after which the characteristics and photocatalytic activity were investigated in detail. The TiO2 layer fabricated in a short duration exhibited comparatively flat surface morphology and an anatase-type crystal structure. This layer acted as a photocatalyst only under ultraviolet light (UV) illumination. Upon prolonging the anodization, the layer structure changed drastically. The surface morphology became rough, and the crystal structure changed to rutile-type TiO2. Furthermore, the layer showed photocatalytic activity both under UV and visible light illumination. Further anodization increased the amount of methylene blue (MB) adsorbed on the surface, but did not cause additional change to the structure of the anodic layer. The surface morphology and crystal structure of the anodic layer were predominantly controlled by the anodization time; thus, the anodization time is an important parameter for controlling the characteristics of the anodic layer.

Optical properties of Na2O-TiO2-SiO2 glass films prepared by the sol-gel method

NASA Astrophysics Data System (ADS)

Barton, Ivo; Matejec, Vlastimil; Mrazek, Jan; Predoana, Luminita; Zaharescu, Maria

2017-12-01

Layers based on TiO2-SiO2 systems fabricated by sol-gel method have been investigated for the preparation of planar waveguides, antireflective coatings, Bragg mirrors, etc. However, at high titania contents such materials exhibit high viscosities and tendency to phase separation. In this paper we present optical properties of films containing TiO2 which are prepared via a novel approach sol-gel on the basis of ternary Na2O-TiO2-SiO2 glasses and which can exhibit lower viscosities. Films of Na2O-TiO2-SiO2 systems were prepared from input sols mixed of silica, titania and sodium oxide sols. The silica sol was prepared from tetraethyl orthosilicate (TEOS), ethanol, hydrochloric acid and water, with a TEOS c= 2 mol/l and water/alkoxide ratio 1.75. The titania sol was mixed from titanium tetraisopropoxide (TiPr), propan-2-ol, nitric acid and water, c= 0.5 mol/l, RW= 0.42. The sodium oxide sols with c= 0.474 mol/l were prepared from sodium ethoxide and ethanol. Input sols were prepared by mixing the silica and titania sols first and then the sodium sol was added. The input sols were aged for one hour. Stable input sols were obtained. The input sols were deposited on glass and silica slides by dip-coating technique at a withdrawing speeds of 200 mm/min. Applied gel layers were thermally treated at temperatures of 450 and 900°C. Layers containing sodium oxide and titania in concentration ranges of 0-20 mol.% and 0-30 mol.% respectively have been fabricated. Optical properties of layers were determined by UV-VIS-NIR transmission and reflection spectrophotometry. Refractive indices of layers were determined by spectral ellipsometry and from transmission spectra. Optical properties were correlated with results of XRD spectroscopy, optical microscopy, and atomic force microscopy. Transparent homogenous films with a maximum refractive index of 1.61 at a wavelength of 600 nm have been obtained.

Simulation of the effect of photoprotective titanium dioxide (TiO2) and zinc oxide (ZnO) nanoparticles on the thermal response and optical characteristics of skin

NASA Astrophysics Data System (ADS)

Krasnikov, I. V.; Seteikin, A. Yu.; Popov, A. P.

2015-04-01

The thermal response of skin covered with a mixture of titanium dioxide (TiO2) and zinc oxide (ZnO) nanoparticles of optimal sizes and irradiated by sunlight has been calculated. The nanoparticles were rubbed into the skin for maximum protection against the incident radiation. The dependences of the temperature dynamics in different skin layers (corneal layer, epidermis, dermis) have been obtained and analyzed upon skin irradiation with light at a wavelength of 310-800 nm. It has been found that increasing light scattering and absorption due to the nanoparticles introduced into the corneal layer resulted in a decrease in the thermal load and penetration depth of the incident radiation.

Surface characteristics of sterilized electropolished NiTi shape memory alloy as biomaterials

NASA Astrophysics Data System (ADS)

Tabrizian, Maryam; Thierry, Benjamin; Savadogo, Omarou; Yahia, L'Hocine

1999-05-01

As a potential biomaterial for many medical applications, NiTi alloy derives its good biocompatibility and corrosion resistance from a homogeneous and protective oxide layer, mainly composed of TiO2, with little concentration of nickel. However, during corrosion testing at high potential, NiTi is susceptible to pitting corrosion, which may affect the amount of ions (nickel and titanium) released by the alloy and thus, may affect its biocompatibility. As a passivating treatment, electropolishing (EP) was demonstrated to decrease the amount of nickel on the surface and to remarkably improve the corrosion behavior of the alloy. After sterilization by ethylene oxide (EO), no modification of the promising corrosion behavior of electropolished NiTi were observed, although some surface modifications were reported. The corrosion resistance of ethylene oxide sterilized and electropolished samples ranked between that of the commonly used Ti6A14V and 316L (0.4 less than 1 less than 1.4 mV/SCE) implant alloys.

Influence of Different Defects in Vertically Aligned Carbon Nanotubes on TiO2 Nanoparticle Formation through Atomic Layer Deposition.

PubMed

Acauan, Luiz; Dias, Anna C; Pereira, Marcelo B; Horowitz, Flavio; Bergmann, Carlos P

2016-06-29

The chemical inertness of carbon nanotubes (CNT) requires some degree of "defect engineering" for controlled deposition of metal oxides through atomic layer deposition (ALD). The type, quantity, and distribution of such defects rules the deposition rate and defines the growth behavior. In this work, we employed ALD to grow titanium oxide (TiO2) on vertically aligned carbon nanotubes (VACNT). The effects of nitrogen doping and oxygen plasma pretreatment of the CNT on the morphology and total amount of TiO2 were systematically studied using transmission electron microscopy, Raman spectroscopy, and thermogravimetric analysis. The induced chemical changes for each functionalization route were identified by X-ray photoelectron and Raman spectroscopies. The TiO2 mass fraction deposited with the same number of cycles for the pristine CNT, nitrogen-doped CNT, and plasma-treated CNT were 8, 47, and 80%, respectively. We demonstrate that TiO2 nucleation is dependent mainly on surface incorporation of heteroatoms and their distribution rather than structural defects that govern the growth behavior. Therefore, selecting the best way to functionalize CNT will allow us to tailor TiO2 distribution and hence fabricate complex heterostructures.

A comparative study of the mechanical behaviour of thermally oxidised commercially pure titanium and zirconium.

PubMed

Alansari, A; Sun, Y

2017-10-01

The objective of this study is to compare the mechanical behaviour of thermally oxidised commercially pure titanium (CP-Ti) and commercially pure zirconium (CP-Zr). For this purpose, these two bio-metals were thermally oxidised under the same condition (650°C for 6h) and the oxidised specimens were characterised using various analytical and experimental techniques, including oxygen uptake analysis, layer thickness and hardness measurements, scratch tests, dry sliding friction and wear tests and tribocorrosion tests in Ringer's solution. The results show that under the present thermal oxidation condition, 4 times more oxygen is introduced into CP-Zr than into CP-Ti and the oxide layer produced on CP-Zr is nearly 6 times thicker than that on CP-Ti. Thermally oxidised CP-Zr possesses a higher hardness, a deeper hardening depth and better scratch resistance than thermally oxidised CP-Ti. Under dry sliding and tribocorrosion conditions, thermally oxidised CP-Zr also possesses much better resistance to material removal and a higher load bearing capacity than thermally oxidised CP-Ti. Thus, thermally oxidised Zr possesses much better mechanical behaviour than thermally oxidised Ti. Copyright © 2017 Elsevier Ltd. All rights reserved.

One-Step to Prepare Self-Organized Nanoporous NiO/TiO2 Layers and its Use in Non-Enzymatic Glucose Sensing

PubMed Central

Gao, Zhi-Da; Han, Yuyao; Wang, Yongmei; Xu, Jingwen; Song, Yan-Yan

2013-01-01

A highly ordered nanoporous NiTi oxide layers were fabricated on Ti alloys with high Ni contents (50.6 at.%) by a combination of self-organizing anodization at 0°C and subsequent selective etching in H2O2. The key for successful formation of such layers is to sufficiently suppress the dissolve of NiO by applying lower temperature during anodization. The resulting nanoporous structure is connected and well-adhered, which exhibits a much higher electrochemical cycling stability in 0.1 M NaOH. Without further surface modification or the use of polymer binders, the layers can be behave as a low-cost, stable and sensitive platform in non-enzymatic glucose sensing. PMID:24270125

The role of yttrium and titanium during the development of ODS ferritic steels obtained through the STARS route: TEM and XAS study

NASA Astrophysics Data System (ADS)

Ordás, Nerea; Gil, Emma; Cintins, Arturs; de Castro, Vanessa; Leguey, Teresa; Iturriza, Iñigo; Purans, Juris; Anspoks, Andris; Kuzmin, Alexei; Kalinko, Alexandr

2018-06-01

Oxide Dispersion Strengthened Ferritic Steels (ODS FS) are candidate materials for structural components in future fusion reactors. Their high strength and creep resistance at elevated temperatures and their good resistance to neutron radiation damage is obtained through extremely fine microstructures containing a high density of nanometric precipitates, generally yttrium and titanium oxides. This work shows transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS) characterization of Fe-14Cr-2W-0.3Ti-0.24Y ODS FS obtained by the STARS route (Surface Treatment of gas Atomized powder followed by Reactive Synthesis), an alternative method to obtain ODS alloys that avoids the mechanical alloying to introduce Y2O3 powder particles. In this route, FS powders already containing Ti and Y, precursors of the nanometric oxides, are obtained by gas atomization. Then, a metastable Cr- and Fe-rich oxide layer is formed on the surface of the powder particles. During consolidation by HIP at elevated temperatures, and post-HIP heat treatments above the HIP temperature, this oxide layer at Prior Particle Boundaries (PPBs) dissociates, the oxygen diffuses, and Y-Ti-O nano-oxides precipitate in the ferritic matrix. TEM characterization combined with XAFS and XANES analyses have proven to be suitable tools to follow the evolution of the nature of the different oxides present in the material during the whole processing route and select appropriate HIP and post-HIP parameters to promote profuse and fine Y-Ti-O nanometric precipitates.

Waterless TiO{sub 2} atomic layer deposition using titanium tetrachloride and titanium tetraisopropoxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Virginia R.; Cavanagh, Andrew S.; Abdulagatov, Aziz I.

2014-01-15

The surface chemistry for TiO{sub 2} atomic layer deposition (ALD) typically utilizes water or other oxidants that can oxidize underlying substrates such as magnetic disks or semiconductors. To avoid this oxidation, waterless or oxidant-free surface chemistry can be used that involves titanium halides and titanium alkoxides. In this study, waterless TiO{sub 2} ALD was accomplished using titanium tetrachloride (TiCl{sub 4}) and titanium tetraisopropoxide (TTIP). In situ transmission Fourier transform infrared (FTIR) studies were employed to study the surface species and the reactions during waterless TiO{sub 2} ALD. At low temperatures between 125 and 225  °C, the FTIR absorbance spectra revealed thatmore » the isopropoxide species remained on the surface after TTIP exposures. The TiCl{sub 4} exposures then removed the isopropoxide species and deposited additional titanium species. At high temperatures between 250 and 300  °C, the isopropoxide species were converted to hydroxyl species by β-hydride elimination. The observation of propene gaseous reaction product by quadrupole mass spectrometry (QMS) confirmed the β-hydride elimination reaction pathway. The TiCl{sub 4} exposures then easily reacted with the hydroxyl species. QMS studies also observed the 2-chloropropane and HCl gaseous reaction products and monitored the self-limiting nature of the TTIP reaction. Additional studies examined the waterless TiO{sub 2} ALD growth at low and high temperature. Quartz crystal microbalance measurements observed growth rates of ∼3 ng/cm{sup 2} at a low temperature of 150  °C. Much higher growth rates of ∼15 ng/cm{sup 2} were measured at a higher temperature of 250  °C under similar reaction conditions. X-ray reflectivity analysis measured a growth rate of 0.55 ± 0.05 Å/cycle at 250  °C. X-ray photoelectron depth-profile studies showed that the TiO{sub 2} films contained low Cl concentrations <1 at. %. This waterless TiO{sub 2} ALD process using TiCl{sub 4} and TTIP should be valuable to prevent substrate oxidation during TiO{sub 2} ALD on oxygen-sensitive substrates.« less

Pseudocapacitive Electrodes Produced by Oxidant-Free Polymerization of Pyrrole between the Layers of 2D Titanium Carbide (MXene)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boota, Muhammad; Anasori, Babak; Voigt, Cooper

Heterocyclic pyrrole molecules are in situ aligned and polymerized in the ­absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25 000 cycles at a 100 mV s-1 scan rate.

Well-crystallized mesoporous TiO2 shells for enhanced photocatalytic activity: prepared by carbon coating and silica-protected calcination.

PubMed

Zhang, Zewu; Zhou, Yuming; Zhang, Yiwei; Zhou, Shijian; Shi, Junjun; Kong, Jie; Zhang, Sicheng

2013-04-14

Mesoporous anatase-phase TiO2 hollow shells were successfully fabricated by the solvothermal and calcination process. This method involves preparation of SiO2@TiO2 core-shell colloidal templates, sequential deposition of carbon and then silica layers through solvothermal and sol-gel processes, crystallization of TiO2 by calcination and finally removal of the inner and outer silica to produce hollow anatase TiO2 shells. The prepared samples were characterized by transmission electron microscopy, X-ray diffraction, N2 adsorption-desorption isotherms and UV-vis absorption spectroscopy. The results show that a uniform carbon layer is coated on the core-shell particles through the solvothermal process. The combustion of carbon offers the space for the TiO2 to further grow into large crystal grains, and the outer silica layer serves as a barrier against the excessive growth of anatase TiO2 nanocrystals. Furthermore, the initial crystallization of TiO2 generated in the carbon coating step and the heat generated by the combustion of the carbon layer allow the crystallization of TiO2 at a relatively low temperature without changing the uniform structure. When used as photocatalysts for the oxidation decomposition of Rhodamine B in aqueous solution under UV irradiation, the hollow TiO2 shells showed enhanced catalytic activity. Moreover, the TiO2 hollow shells prepared with optimal crystallinity by this method showed a higher performance than commercial P25 TiO2.

Nitridation-driven conductive Li4Ti5O12 for lithium ion batteries.

PubMed

Park, Kyu-Sung; Benayad, Anass; Kang, Dae-Joon; Doo, Seok-Gwang

2008-11-12

To modify oxide structure and introduce a thin conductive film on Li4Ti5O12, thermal nitridation was adopted for the first time. NH3 decomposes surface Li4Ti5O12 to conductive TiN at high temperature, and surprisingly, it also modifies the surface structure in a way to accommodate the single phase Li insertion and extraction. The electrochemically induced Li4+deltaTi5O12 with a TiN coating layer shows great electrochemical properties at high current densities.

Transport Properties of Anatase-TiO2 Polycrystalline-Thin-Film Field-Effect Transistors with Electrolyte Gate Layers

NASA Astrophysics Data System (ADS)

Horita, Ryohei; Ohtani, Kyosuke; Kai, Takahiro; Murao, Yusuke; Nishida, Hiroya; Toya, Taku; Seo, Kentaro; Sakai, Mio; Okuda, Tetsuji

2013-11-01

We have fabricated anatase-TiO2 polycrystalline-thin-film field-effect transistors (FETs) with poly(vinyl alcohol) (PVA), ion-liquid (IL), and ion-gel (IG) gate layers, and have tried to improve the response to gate voltage by varying the concentration of mobile ions in these electrolyte gate layers. The increase in the concentration of mobile ions by doping NaOH into the PVA gate layer or reducing the gelator in the IG gate layer markedly increases the drain-source current and reduces the driving gate voltage, which show that the mobile ions in the PVA, IL, and IG gate layers cause the formation of electric double layers (EDLs), which act as nanogap capacitors. In these TiO2-EDL-FETs, the slow formation of EDLs and the oxidation reaction at the interface between the surface of the TiO2 film and the electrolytes cause unideal FET properties. In the optimized IL and IG TiO2-EDL-FETs, the driving gate voltage is less than 1 V and the ON/OFF ratios of the transfer characteristics are about 1×104 at RT, and the nearly metallic state is realized at the interface purely by applying a gate voltage.

Enhanced performance of dye-sensitized solar cells with layered structure graphitic carbon nitride and reduced graphene oxide modified TiO2 photoanodes

NASA Astrophysics Data System (ADS)

Lv, Huiru; Hu, Haihua; Cui, Can; Lin, Ping; Wang, Peng; Wang, Hao; Xu, Lingbo; Pan, Jiaqi; Li, Chaorong

2017-11-01

TiO2/reduced graphene oxide (TiO2/rGO) composite has been widely exploited as the photoanode material for high efficient dye-sensitized solar cells (DSSCs). However, the power conversion efficiency (PCE) is limited due to the charge recombination between the rGO and electrolyte. In this paper, we incorporate 5.5 wt% layered structure graphitic carbon nitride (g-C3N4) and 0.25 wt% rGO into TiO2 nanoparticle (NP) film to form a triple-component TiO2/rGO/g-C3N4 (TGC) photoanode for DSSCs. The TGC photoanode significantly increased the dye absorption and thus to improve the light harvesting efficiency. Furthermore, the electrochemical impedance spectroscopy (EIS) analysis of the DSSCs based on TGC photoanode demonstrates that the incorporation of the rGO and g-C3N4 into TiO2 effectively accelerates the electron transfer and reduces the charge recombination. As a result, the DSSCs based on TGC film show PCE of 5.83%, enhanced by 50.1% compared with that of pure TiO2 photoanodes. This result strongly suggests a facile strategy to improve the photovoltaic performance of DSSCs.

Tuning the Seebeck effect in C60-based hybrid thermoelectric devices through temperature-dependent surface polarization and thermally-modulated interface dipoles.

PubMed

Liu, Yuchun; Xu, Ling; Zhao, Chen; Shao, Ming; Hu, Bin

2017-06-07

Fullerene (C 60 ) is an important n-type organic semiconductor with high electron mobility and low thermal conductivity. In this work, we report the experimental results on the tunable Seebeck effect of C 60 hybrid thin-film devices by adopting different oxide layers. After inserting n-type high-dielectric constant titanium oxide (TiO x ) and zinc oxide (ZnO) layers, we observed a significantly enhanced n-type Seebeck effect in oxide/C 60 hybrid devices with Seebeck coefficients of -5.8 mV K -1 for TiO x /C 60 and -2.08 mV K -1 for ZnO/C 60 devices at 100 °C, compared with the value of -400 μV K -1 for the pristine C 60 device. However, when a p-type nickel oxide (NiO) layer is inserted, the C 60 hybrid devices show a p-type to n-type Seebeck effect transition when the temperature increases. The remarkable Seebeck effect and change in Seebeck coefficient in different oxide/C 60 hybrid devices can be attributed to two reasons: the temperature-dependent surface polarization difference and thermally-dependent interface dipoles. Firstly, the surface polarization difference due to temperature-dependent electron-phonon coupling can be enhanced by inserting an oxide layer and functions as an additional driving force for the Seebeck effect development. Secondly, thermally-dependent interface dipoles formed at the electrode/oxide interface play an important role in modifying the density of interface states and affecting the charge diffusion in hybrid devices. The surface polarization difference and interface dipoles function in the same direction in hybrid devices with TiO x and ZnO dielectric layers, leading to enhanced n-type Seebeck effect, while the surface polarization difference and interface dipoles generate the opposite impact on electron diffusion in ITO/NiO/C 60 /Al, leading to a p-type to n-type transition in the Seebeck effect. Therefore, inserting different oxide layers could effectively modulate the Seebeck effect of C 60 -based hybrid devices through the surface polarization difference and thermally-dependent interface dipoles, which represents an effective approach to tune the vertical Seebeck effect in organic functional devices.

X-ray analyses of thermally grown and reactively sputtered tantalum oxide films on NiTi alloy

NASA Astrophysics Data System (ADS)

McNamara, Karrina; Tofail, Syed A. M.; Conroy, Derek; Butler, James; Gandhi, Abbasi A.; Redington, Wynette

2012-08-01

Sputter deposition of tantalum (Ta) on the surface of NiTi alloy is expected to improve the alloy's corrosion resistance and biocompatibility. Tantalum is a well-known biomaterial which is not affected by body fluids and is not irritating to human tissue. Here we compare the oxidation chemistry crystal structure evolution of tantalum oxide films grown on NiTi by reactive O2 sputtering and by thermal oxidation of sputter deposited Ta films. The effect of sputtering parameters and post-sputtering treatments on the morphology, oxidation state and crystal structure of the tantalum oxide layer have been investigated by field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The study has found that it may be better to avoid oxidation at and above 600 °C. The study establishes that reactive sputtering in presence of low oxygen mixture yields thicker film with better control of the film quality except that the surface oxidation state of Ta is slightly lower.

Corrosion behavior of heat-treated intermetallic titanium-nickel in hydrochloric acid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Starosvetsky, D.; Khaselev, O.; Yahalom, J.

1998-07-01

Samples of 45% Ti-55% Ni alloy (Ti-Ni) were heat-treated in air at 450 C, and their anodic behavior in 0.3 M, 1 M, 2 M, and 4 M hydrochloric acid (HCl) solutions was studied. In 0.3 M HCl, heat-treated Ti-Ni was passive, and very low anodic currents were observed. In 1 M and 2 M HCl, heat-treated Ti-Ni was dissolved actively, while heat-treated and surface-ground Ti-Ni became passive. The effect was explained by selective oxidation of Ti-Ni and formation of a layered structure on its surface with discontinuous titanium oxide and a nickel-enriched zone underneath. The latter was dissolved inmore » the HCl solutions, thus accelerating failure of the Ti-Ni samples. In 4 M HCl, heat-treated and heat-treated/ground samples were dissolved readily.« less

Bi-functional anodic TiO2 oxide: Nanotubes for wettability control and barrier oxide for uniform coloring

NASA Astrophysics Data System (ADS)

Kim, Sunkyu; Jung, Minkyeong; Kim, Moonsu; Choi, Jinsub

2017-06-01

A uniformly colored TiO2, on which the surface is functionalized with nanotubes to control wettability, was prepared by a two-step anodization; the first anodization was carried out to prepare nanotubes for a super-hydrophilic or -hydrophobic surface and the second anodization was performed to fabricate a thin film barrier oxide to ensure uniform coloring. The effect of the nanotubes on barrier oxide coloring was examined by spectrophotometry and UV-vis-IR spectroscopy. We found four different regimes governing the color changes in terms of anodization voltage, indicating that the color of the duplex TiO2 was primarily determined by the thickness of the barrier oxide layer formed during the second anodization step. The surface wettability, as confirmed by the water contact angle, revealed that the single barrier TiO2 yielded 74.6° ± 2.1, whereas the nanotubes on the barrier oxide imparted super-hydrophilic properties as a result of increasing surface roughness as well as imparting a higher hydrophobicity after organic acid treatment.

Characterization of ion beam modified ceramic wear surfaces using Auger electron spectroscopy

NASA Technical Reports Server (NTRS)

Wei, W.; Lankford, J.

1987-01-01

An investigation of the surface chemistry and morphology of the wear surfaces of ceramic material surfaces modified by ion beam mixing has been conducted using Auger electron spectroscopy and secondary electron microscopy. Studies have been conducted on ceramic/ceramic friction and wear couples made up of TiC and NiMo-bonded TiC cermet pins run against Si3N4 and partially stabilized zirconia disc surfaces modified by the ion beam mixing of titanium and nickel, as well as ummodified ceramic/ceramic couples in order to determine the types of surface changes leading to the improved friction and wear behavior of the surface modified ceramics in simulated diesel environments. The results of the surface analyses indicate that the formation of a lubricating oxide layer of titanium and nickel, is responsible for the improvement in ceramic friction and wear behavior. The beneficial effect of this oxide layer depends on several factors, including the adherence of the surface modified layer or subsequently formed oxide layer to the disc substrate, the substrate materials, the conditions of ion beam mixing, and the environmental conditions.

Apatite-forming PEEK with TiO2 surface layer coating.

PubMed

Kizuki, Takashi; Matsushita, Tomiharu; Kokubo, Tadashi

2015-01-01

Polyetheretherketone (PEEK) is widely used in orthopedic implants, such as spinal fusion devices, because of its moderate elastic modulus, as well as relatively high mechanical strength. However, it does not bond to living bone, and hence it needs autograft to be fixed to the bone. In this study, we attempted to add bone-bonding properties to PEEK by coating with TiO2 synthesized by the sol-gel process. When a TiO2 sol solution consisting of titanium isopropoxide, water, ethanol, and nitric acid was deposited on a PEEK substrate without any pretreatment, the formed TiO2 gel layer was easily peeled off after subsequent treatments. However, when the same solution was deposited on PEEK that was preliminarily subjected to UV or O2 plasma treatment, the deposited TiO2 gel layer strongly adhered to the substrate even after subsequent treatments. The strong adhesion was attributed to the interaction among the C-O, C=O, and O-C=O groups on the PEEK owing to the UV or O2 plasma treatment and the Ti-O bond of the TiO2 gel. Apatite did not form on the as-formed TiO2 gel layer in a simulated body fluid (SBF) even within 3 days; however, apatite formed after soaking in 0.1 M HCl solution at 80 °C for 24 h. This apatite formation was attributed to positive surface charge of the TiO2 gel layer induced by the acid treatment. The PEEK with the TiO2 gel layer coating formed by the proposed process is expected to bond to living bone, because a positively charged titanium oxide which facilitates the formation of apatite in SBF within a short period is known to bond to living bone.

Preparation of ceramic coating on Ti substrate by Plasma electrolytic oxidation in different electrolytes and evaluation of its corrosion resistance

NASA Astrophysics Data System (ADS)

Shokouhfar, M.; Dehghanian, C.; Baradaran, A.

2011-01-01

Ceramic oxide coatings (titania) were produced on Ti by micro-arc oxidation in different aluminate and carbonate based electrolytes. This process was conducted under constant pulsed DC voltage condition. The effect of KOH and NaF in aluminate based solution was also studied. The surface morphology, growth and phase composition of coatings were investigated using scanning electron microscope and X-ray diffraction. Corrosion behavior of the coatings was also examined by potentiodynamic polarization and electrochemical impedance spectroscopy. It was found that the sparking initiation voltage (spark voltage) had a significant effect on the form and properties of coatings. Coatings obtained from potassium aluminate based solution had a lower spark voltage, higher surface homogeneity and a better corrosion resistance than the carbonate based solution. Addition of NaF instead of KOH had improper effects on the homogeneity and adhesion of coatings which in turn caused a poor corrosion protection behavior of the oxide layer. AC impedance curves showed two time constants which is an indication of the coatings with an outer porous layer and an inner compact layer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moddeman, W.E.; Foose, D.S.; Bowling, W.C.

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface chemistry of three BORAZON* materials: Type I, 510, and 550. Samples were examined in the ``as-received`` condition and following heat treatments in air. Boron oxides were found on the Type I and 550 BORAZON crystals; oxide thicknesses were estimated to be 15A. The titanium-coated product, 510, was found to have a discontinuous titanium coating with a TiO{sub 2} layer that was approximately 20A thick. Following heat treatment at 800{degrees}C for 1 hr in air, the boron oxide layer on the Type I crystals was foundmore » to increase in thickness to approximately 30A. The same heat treatment on the 510 crystals yielded a multi-layered structure consisting of an enriched outer layer of B{sub 2}O{sub 3} over a predominantly TiO{sub 2} one. The entire initial titanium coating was oxidized, and segregated patches of B{sub 2}O{sub 3} (``islands``) were observed. The segregated patches can be explained in terms of the coalescence of liquid B{sub 2}O{sub 3} (melting point = 450{degrees}C). The 550 crystals were oxidized at 500{degrees}C. The oxide formed at this temperature was B{sub x}O (x > 0.67). These results were interpreted in terms of their potential use in sealing BORAZON to glass in vitreous bonding.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moddeman, W.E.; Foose, D.S.; Bowling, W.C.

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface chemistry of three BORAZON* materials: Type I, 510, and 550. Samples were examined in the as-received'' condition and following heat treatments in air. Boron oxides were found on the Type I and 550 BORAZON crystals; oxide thicknesses were estimated to be 15A. The titanium-coated product, 510, was found to have a discontinuous titanium coating with a TiO{sub 2} layer that was approximately 20A thick. Following heat treatment at 800{degrees}C for 1 hr in air, the boron oxide layer on the Type I crystals was foundmore » to increase in thickness to approximately 30A. The same heat treatment on the 510 crystals yielded a multi-layered structure consisting of an enriched outer layer of B{sub 2}O{sub 3} over a predominantly TiO{sub 2} one. The entire initial titanium coating was oxidized, and segregated patches of B{sub 2}O{sub 3} ( islands'') were observed. The segregated patches can be explained in terms of the coalescence of liquid B{sub 2}O{sub 3} (melting point = 450{degrees}C). The 550 crystals were oxidized at 500{degrees}C. The oxide formed at this temperature was B{sub x}O (x > 0.67). These results were interpreted in terms of their potential use in sealing BORAZON to glass in vitreous bonding.« less

Synthesis, characterization, and performance evaluation of multilayered photoanodes by introducing mesoporous carbon and TiO2 for humic acid adsorption.

PubMed

Hosseini, Soraya; Jahangirian, Hossein; Webster, Thomas J; Soltani, Salman Masoudi; Aroua, Mohamed Kheireddine

2016-01-01

Nanostructured photoanodes were prepared via a novel combination of titanium dioxide (TiO2) nanoparticles and mesoporous carbon (C). Four different photoanodes were synthesized by sol-gel spin coating onto a glassy substrate of fluorine-doped tin oxide. The photocatalytic activities of TiO2, TiO2/C/TiO2, TiO2/C/C/TiO2, and TiO2/C/TiO2/C/TiO2 photoanodes were evaluated by exposing the synthesized photoanodes to UV-visible light. The photocurrent density observed in these photoanodes confirmed that an additional layer of mesoporous carbon could successfully increase the photocurrent density. The highest photocurrent density of ~1.022 mA cm(-2) at 1 V/saturated calomel electrode was achieved with TiO2/C/C/TiO2 under an illumination intensity of 100 mW cm(-2) from a solar simulator. The highest value of surface roughness was measured for a TiO2/C/C/TiO2 combination owing to the presence of two continuous layers of mesoporous carbon. The resulting films had a thickness ranging from 1.605 µm to 5.165 µm after the calcination process. The presence of double-layer mesoporous carbon resulted in a 20% increase in the photocurrent density compared with the TiO2/C/TiO2 combination when only a single mesoporous carbon layer was employed. The improved performance of these photoanodes can be attributed to the enhanced porosity and increased void space due to the presence of mesoporous carbon. For the first time, it has been demonstrated here that the photoelectrochemical performance of TiO2 can be improved by integrating several layers of mesoporous carbon. Comparison of the rate of removal of humic acid by the prepared photoanodes showed that the highest performance from TiO2/C/C/TiO2 was due to the highest photocurrent density generated. Therefore, this study showed that optimizing the sequence of mesoporous carbon layers can be a viable and inexpensive method for enhanced humic acid removal.

Synthesis, characterization, and performance evaluation of multilayered photoanodes by introducing mesoporous carbon and TiO2 for humic acid adsorption

PubMed Central

Hosseini, Soraya; Jahangirian, Hossein; Webster, Thomas J; Soltani, Salman Masoudi; Aroua, Mohamed Kheireddine

2016-01-01

Nanostructured photoanodes were prepared via a novel combination of titanium dioxide (TiO2) nanoparticles and mesoporous carbon (C). Four different photoanodes were synthesized by sol–gel spin coating onto a glassy substrate of fluorine-doped tin oxide. The photocatalytic activities of TiO2, TiO2/C/TiO2, TiO2/C/C/TiO2, and TiO2/C/TiO2/C/TiO2 photoanodes were evaluated by exposing the synthesized photoanodes to UV–visible light. The photocurrent density observed in these photoanodes confirmed that an additional layer of mesoporous carbon could successfully increase the photocurrent density. The highest photocurrent density of ~1.022 mA cm−2 at 1 V/saturated calomel electrode was achieved with TiO2/C/C/TiO2 under an illumination intensity of 100 mW cm−2 from a solar simulator. The highest value of surface roughness was measured for a TiO2/C/C/TiO2 combination owing to the presence of two continuous layers of mesoporous carbon. The resulting films had a thickness ranging from 1.605 µm to 5.165 µm after the calcination process. The presence of double-layer mesoporous carbon resulted in a 20% increase in the photocurrent density compared with the TiO2/C/TiO2 combination when only a single mesoporous carbon layer was employed. The improved performance of these photoanodes can be attributed to the enhanced porosity and increased void space due to the presence of mesoporous carbon. For the first time, it has been demonstrated here that the photoelectrochemical performance of TiO2 can be improved by integrating several layers of mesoporous carbon. Comparison of the rate of removal of humic acid by the prepared photoanodes showed that the highest performance from TiO2/C/C/TiO2 was due to the highest photocurrent density generated. Therefore, this study showed that optimizing the sequence of mesoporous carbon layers can be a viable and inexpensive method for enhanced humic acid removal. PMID:27574426

In situ study of electric field controlled ion transport in the Fe/BaTiO3 interface

NASA Astrophysics Data System (ADS)

Merkel, D. G.; Bessas, D.; Bazsó, G.; Jafari, A.; Rüffer, R.; Chumakov, A. I.; Khanh, N. Q.; Sajti, Sz; Celse, J.-P.; Nagy, D. L.

2018-01-01

Electric field controlled ion transport and interface formation of iron thin films on a BaTiO3 substrate have been investigated by in situ nuclear resonance scattering and x-ray reflectometry techniques. At early stage of deposition, an iron-II oxide interface layer was observed. The hyperfine parameters of the interface layer were found insensitive to the evaporated layer thickness. When an electric field was applied during growth, a 10 Å increase of the nonmagnetic/magnetic thickness threshold and an extended magnetic transition region was measured compared to the case where no field was applied. The interface layer was found stable under this threshold when further evaporation occurred, contrary to the magnetic layer where the magnitude and orientation of the hyperfine magnetic field vary continuously. The obtained results of the growth mechanism and of the electric field effect of the Fe/BTO system will allow the design of novel applications by creating custom oxide/metallic nanopatterns using laterally inhomogeneous electric fields during sample preparation.

Multifunctional organized mesoporous tin oxide films templated by graft copolymers for dye-sensitized solar cells.

PubMed

Park, Jung Tae; Ahn, Sung Hoon; Roh, Dong Kyu; Lee, Chang Soo; Kim, Jong Hak

2014-07-01

The synthesis of organized mesoporous SnO2 films with high porosity, larger pores, and good interconnectivity, obtained by sol-gel templating with an amphiphilic graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate), is reported. An improved performance of dye-sensitized solar cells (DSSCs) is demonstrated by the introduction of a 400 nm thick organized mesoporous SnO2 interfacial (om-SnO2 IF) layer between nanocrystalline TiO2 (nc-TiO2 ) and a fluorine-doped tin oxide substrate. To elucidate the improved efficiency, the structural, optical, and electrochemical properties of the devices were characterized by SEM, UV/Vis spectroscopy, noncontact 3D surface profilometry, intensity-modulated photocurrent/voltage spectroscopy, incident photon-to-electron conversion efficiency, and electrochemical impedance spectroscopy measurements. The energy-conversion efficiency of the solid polymerized ionic liquid based DSSC fabricated with the om-SnO2 IF/nc-TiO2 photoanode reached 5.9% at 100 mW cm(-2) ; this is higher than those of neat nc-TiO2 (3.5%) and organized mesoporous TiO2 interfacial/nc-TiO2 layer (5.4%) photoanodes. The improved efficiency is attributed to the antireflective property, cascadal energy band gap, good interconnectivity, and high electrical conductivity of the om-SnO2 IF layer, which results in enhanced light harvesting, increased electron transport, reduced charge recombination, and decreased interfacial/internal resistance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and electrical properties of Pb(Zr ,Ti)O3 grown on (0001) GaN using a double PbTiO3/PbO bridge layer

NASA Astrophysics Data System (ADS)

Xiao, Bo; Gu, Xing; Izyumskaya, Natalia; Avrutin, Vitaliy; Xie, Jinqiao; Liu, Huiyong; Morkoç, Hadis

2007-10-01

Pb(Zr0.52Ti0.48)O3 films were deposited by rf magnetron sputtering on silicon-doped GaN(0001)/c-sapphire with a PbTiO3/PbO oxide bridge layer grown by molecular beam epitaxy. X-ray diffraction data showed the highly (111)-oriented perovskite phase in lead zirconate titanate (PZT) films with PbTiO3/PbO bridge layers, compared to the pyrochlore phase grown directly on GaN. The in-plane epitaxial relationships were found from x-ray pole figures to be PZT[112¯]‖GaN[11¯00] and PZT[11¯0]‖GaN[112¯0]. The polarization-electric field measurements revealed the ferroelectric behavior with remanent polarization of 30-40μC /cm2 and asymmetric hysteresis loops due to the depletion layer formed in GaN under reverse bias which resulted in a high negative coercive electric field (950kV/cm).

Electrochemical impedance spectroscopy investigation on the clinical lifetime of ProTaper rotary file system.

PubMed

Penta, Virgil; Pirvu, Cristian; Demetrescu, Ioana

2014-01-01

The main objective of the current paper is to show that electrochemical impedance spectroscopy (EIS) could be a method for evaluating and predicting of ProTaper rotary file system clinical lifespan. This particular aspect of everyday use of the endodontic files is of great importance in each dental practice and has profound clinical implications. The method used for quantification resides in the electrochemical impedance spectroscopy theory and has in its main focus the characteristics of the surface titanium oxide layer. This electrochemical technique has been adapted successfully to identify the quality of the Ni-Ti files oxide layer. The modification of this protective layer induces changes in corrosion behavior of the alloy modifying the impedance value of the file. In order to assess the method, 14 ProTaper sets utilized on different patients in a dental clinic have been submitted for testing using EIS. The information obtained in regard to the surface oxide layer has offered an indication of use and proves that the said layer evolves with each clinical application. The novelty of this research is related to an electrochemical technique successfully adapted for Ni-Ti file investigation and correlation with surface and clinical aspects.

[INVITED] Laser gas assisted treatment of Ti-alloy: Analysis of surface characteristics

NASA Astrophysics Data System (ADS)

Yilbas, B. S.; Ali, H.; Karatas, C.

2016-04-01

Laser gas assisted treatment of Ti6Al4V alloy surface is carried out and nitrogen/oxygen mixture with partial pressure of PO2/PN2=1/3 is introduced during the surface treatment process. Analytical tools are used to characterize the laser treated surfaces. The fracture toughness at the surface and the residual stress in the surface region of the laser treated layer are measured. Scratch tests are carried out to determine the friction coefficient of the treated surface. It is found that closely spaced regular laser scanning tracks generates a self-annealing effect in the laser treated layer while lowering the stress levels in the treated region. Introducing high pressure gas mixture impingement at the surface results in formation of oxide and nitride species including, TiO, TiO2, TiN and TiOxNy in the surface region. A dense layer consisting of fine size grains are formed in the surface region of the laser treated layer, which enhances the microhardness at the surface. The fracture toughness reduces after the laser treatment process because of the microhardness enhancement at the surface. The residual stress formed is comprehensive, which is in the order of -350 MPa.

Rapid degradation of methylene blue in a novel heterogeneous Fe3O4 @rGO@TiO2-catalyzed photo-Fenton system.

PubMed

Yang, Xiaoling; Chen, Wei; Huang, Jianfei; Zhou, Ying; Zhu, Yihua; Li, Chunzhong

2015-05-22

Herein, a ternary nanocomposite with TiO2 nanoparticles anchored on reduced graphene oxide (rGO)-encapsulated Fe3O4 spheres (Fe3O4@rGO@TiO2) is presented as a high efficient heterogeneous catalyst for photo-Fenton degradation of recalcitrant pollutants under neutral pH. Fe3O4@rGO@TiO2 was synthesized by depositing TiO2 nanoparticles on the surface of the Fe3O4 spheres wrapped by graphene oxide (GO) which was obtained by an electrostatic layer-by-layer method. This as-prepared catalyst reflected good ferromagnetism and superior stability which makes it convenient to be separated and recycled. Due to the synergic effects between the different components composed the catalyst, swift reduction of Fe(3+) can be achieved to regenerate Fe(2+). Fe3O4@rGO@TiO2 exhibited enhancing catalytic activity for the degradation of azo-dyes compared with Fe3O4, Fe3O4@SiO2@TiO2 or SiO2@rGO@TiO2, further conforming the rapid redox reaction between Fe(2+) and Fe(3+). All these merits indicate that the composite catalyst possesses great potential for visible-light driven destruction of organic compounds.

Rapid degradation of methylene blue in a novel heterogeneous Fe3O4 @rGO@TiO2-catalyzed photo-Fenton system

PubMed Central

Yang, Xiaoling; Chen, Wei; Huang, Jianfei; Zhou, Ying; Zhu, Yihua; Li, Chunzhong

2015-01-01

Herein, a ternary nanocomposite with TiO2 nanoparticles anchored on reduced graphene oxide (rGO)-encapsulated Fe3O4 spheres (Fe3O4@rGO@TiO2) is presented as a high efficient heterogeneous catalyst for photo-Fenton degradation of recalcitrant pollutants under neutral pH. Fe3O4@rGO@TiO2 was synthesized by depositing TiO2 nanoparticles on the surface of the Fe3O4 spheres wrapped by graphene oxide (GO) which was obtained by an electrostatic layer-by-layer method. This as-prepared catalyst reflected good ferromagnetism and superior stability which makes it convenient to be separated and recycled. Due to the synergic effects between the different components composed the catalyst, swift reduction of Fe3+ can be achieved to regenerate Fe2+. Fe3O4@rGO@TiO2 exhibited enhancing catalytic activity for the degradation of azo-dyes compared with Fe3O4, Fe3O4@SiO2@TiO2 or SiO2@rGO@TiO2, further conforming the rapid redox reaction between Fe2+ and Fe3+. All these merits indicate that the composite catalyst possesses great potential for visible-light driven destruction of organic compounds. PMID:26000975

Ultrathin epitaxial barrier layer to avoid thermally induced phase transformation in oxide heterostructures

DOE PAGES

Baek, David J.; Lu, Di; Hikita, Yasuyuki; ...

2016-12-22

Incorporating oxides with radically different physical and chemical properties into heterostructures offers tantalizing possibilities to derive new functions and structures. Recently, we have fabricated freestanding 2D oxide membranes using the water-soluble perovskite Sr 3Al 2O 6 as a sacrificial buffer layer. Here, with atomic-resolution spectroscopic imaging, we observe that direct growth of oxide thin films on Sr 3Al 2O 6 can cause complete phase transformation of the buffer layer, rendering it water-insoluble. More importantly, we demonstrate that an ultrathin SrTiO 3 layer can be employed as an effective barrier to preserve Sr 3Al 2O 6 during subsequent growth, thus allowingmore » its integration in a wider range of oxide heterostructures.« less

Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment.

PubMed

Esquivel, K; Arriaga, L G; Rodríguez, F J; Martínez, L; Godínez, Luis A

2009-08-01

Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO2 semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO2 based photoanode using an optic fiber support. The novel arrangement of a TiO2 layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 microm thickness SnO2:Sb films on which the photoactive TiO2 layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO2:Sb and TiO2 showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H(2)O(2) close to 50% as compared to different types of TiO2 films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L(-1)) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.

Condensation in Supernova Ejecta at High Spatial Resolution

NASA Astrophysics Data System (ADS)

Fedkin, A. V.; Meyer, B. S.; Grossman, L.; Desch, S. J.

2009-03-01

^44Ti-rich TiC condenses before graphite in SN ejecta only if thin sub-layers of the main burning zones mix together; such mixing is also needed to form Fe-olivine. High-T phases change from carbides to oxides along composition gradients within the He/N zone.

One-Pot Synthesis of Reduced Graphene Oxide/Anatase Titanium Dioxide Composites for Photocatalytic Degradation of Methylene Blue.

PubMed

Lee, Hyo In; Park, Soo-Jin

2018-09-01

In this work, highly ordered TiO2-reduced graphene oxide sheets (TGS) were successfully fabricated via a one-pot solvothermal method with different amounts of graphene oxide (0.01, 0.03, 0.05, and 0.07 g). This was achieved by reacting graphene oxide (GO) layers with titanium isopropoxide as the TiO2 precursor. The TGS exhibited superior efficiency compared to pristine TiO2 and the best results were recorded for the TGS-0.05 sample. The presence of the reduced graphene oxide (rGO) component was determined to be an important factor governing the separation of the photogenerated electron-hole pair via interfacial charge transfer. The significantly increased activity of the TGS under simulated solar light in the degradation of methylene blue (MB) indicates that these materials are promising photocatalysts for efficient water purification.

FeOx-TiO2 Film with Different Microstructures Leading to Femtosecond Transients with Different Properties: Biological Implications under Visible Light

PubMed Central

Rtimi, Sami; Pulgarin, Cesar; Nadtochenko, Victor A.; Gostev, Fedor E.; Shelaev, Ivan V.; Kiwi, John

2016-01-01

This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx:TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be ~1.4 in the film bulk and by XPS-etching a ratio of 4:1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation. PMID:27443505

FeOx-TiO2 Film with Different Microstructures Leading to Femtosecond Transients with Different Properties: Biological Implications under Visible Light.

PubMed

Rtimi, Sami; Pulgarin, Cesar; Nadtochenko, Victor A; Gostev, Fedor E; Shelaev, Ivan V; Kiwi, John

2016-07-22

This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx:TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be ~1.4 in the film bulk and by XPS-etching a ratio of 4:1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation.

FeOx-TiO2 Film with Different Microstructures Leading to Femtosecond Transients with Different Properties: Biological Implications under Visible Light

NASA Astrophysics Data System (ADS)

Rtimi, Sami; Pulgarin, Cesar; Nadtochenko, Victor A.; Gostev, Fedor E.; Shelaev, Ivan V.; Kiwi, John

2016-07-01

This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx:TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be ~1.4 in the film bulk and by XPS-etching a ratio of 4:1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation.

The Otto Aufranc Award: Enhanced Biocompatibility of Stainless Steel Implants by Titanium Coating and Microarc Oxidation

PubMed Central

Lim, Young Wook; Kwon, Soon Yong; Sun, Doo Hoon

2010-01-01

Background Stainless steel is one of the most widely used biomaterials for internal fixation devices, but is not used in cementless arthroplasty implants because a stable oxide layer essential for biocompatibility cannot be formed on the surface. We applied a Ti electron beam coating, to form oxide layer on the stainless steel surface. To form a thicker oxide layer, we used a microarc oxidation process on the surface of Ti coated stainless steel. Modification of the surface using Ti electron beam coating and microarc oxidation could improve the ability of stainless steel implants to osseointegrate. Questions/purposes The ability of cells to adhere to grit-blasted, titanium-coated, microarc-oxidated stainless steel in vitro was compared with that of two different types of surface modifications, machined and titanium-coated, and microarc-oxidated. Methods We performed energy-dispersive x-ray spectroscopy and scanning electron microscopy investigations to assess the chemical composition and structure of the stainless steel surfaces and cell morphology. The biologic responses of an osteoblastlike cell line (SaOS-2) were examined by measuring proliferation (cell proliferation assay), differentiation (alkaline phosphatase activity), and attraction ability (cell migration assay). Results Cell proliferation, alkaline phosphatase activity, migration, and adhesion were increased in the grit-blasted, titanium-coated, microarc-oxidated group compared to the two other groups. Osteoblastlike cells on the grit-blasted, titanium-coated, microarc-oxidated surface were strongly adhered, and proliferated well compared to those on the other surfaces. Conclusions The surface modifications we used (grit blasting, titanium coating, microarc oxidation) enhanced the biocompatibility (proliferation and migration of osteoblastlike cells) of stainless steel. Clinical Relevance This process is not unique to stainless steel; it can be applied to many metals to improve their biocompatibility, thus allowing a broad range of materials to be used for cementless implants. PMID:20936386

High temperature volatility and oxidation measurements of titanium and silicon containing ceramic materials

NASA Astrophysics Data System (ADS)

Nguyen, Quynhgiao N.

Titanium (Ti) containing materials are of high interest to the aerospace industry due to its high temperature capability, strength, and light weight. As with most metals an exterior oxide layer naturally exists in environments that contain oxygen (i.e. air). At high temperatures, water vapor plays a key role in the volatility of materials including oxide surfaces. This study first evaluates several hot-pressed Ti-containing compositions at high temperatures as a function of oxidation resistance. This study will also evaluate cold pressed titanium dioxide (TiO2) powder pellets at a temperature range of 1400°C--1200°C in water containing environments to determine the volatile hydoxyl species using the transpiration method. The water content ranged from 0-76 mole % and the oxygen content range was 0-100 mole % during the 20-250 hour exposure times. Preliminary results indicate that oxygen is not a key contributor at these temperatures and the following reaction is the primary volatile equation at all three temperatures: TiO 2 (s) + H2O (g) = TiO(OH)2 (g).

Thermally oxidized titania nanotubes enhance the corrosion resistance of Ti6Al4V.

PubMed

Grotberg, John; Hamlekhan, Azhang; Butt, Arman; Patel, Sweetu; Royhman, Dmitry; Shokuhfar, Tolou; Sukotjo, Cortino; Takoudis, Christos; Mathew, Mathew T

2016-02-01

The negative impact of in vivo corrosion of metallic biomedical implants remains a complex problem in the medical field. We aimed to determine the effects of electrochemical anodization (60V, 2h) and thermal oxidation (600°C) on the corrosive behavior of Ti-6Al-4V, with serum proteins, at physiological temperature. Anodization produced a mixture of anatase and amorphous TiO2 nanopores and nanotubes, while the annealing process yielded an anatase/rutile mixture of TiO2 nanopores and nanotubes. The surface area was analyzed by the Brunauer-Emmett-Teller method and was estimated to be 3 orders of magnitude higher than that of polished control samples. Corrosion resistance was evaluated on the parameters of open circuit potential, corrosion potential, corrosion current density, passivation current density, polarization resistance and equivalent circuit modeling. Samples both anodized and thermally oxidized exhibited shifts of open circuit potential and corrosion potential in the noble direction, indicating a more stable nanoporous/nanotube layer, as well as lower corrosion current densities and passivation current densities than the smooth control. They also showed increased polarization resistance and diffusion limited charge transfer within the bulk oxide layer. The treatment groups studied can be ordered from greatest corrosion resistance to least as Anodized+Thermally Oxidized > Anodized > Smooth > Thermally Oxidized for the conditions investigated. This study concludes that anodized surface has a potential to prevent long term implant failure due to corrosion in a complex in-vivo environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Fatigue in artificially layered Pb(Zr,Ti)O3 ferroelectric films

NASA Astrophysics Data System (ADS)

Jiang, A. Q.; Scott, J. F.; Dawber, M.; Wang, C.

2002-12-01

We have performed fatigue tests on lead zirconate titanate (PZT) multilayers having stacks of Pb(Zr0.8Ti0.2)O3/Pb(Zr0.2Ti0.8)O3 with repeated distances of 12 formula groups. The results are compared with single-layer n-type (0.5 at. % Ta-doped) PZT films. We conclude that fatigue is dominated by space-charge layers in each case, but that in the multilayer such space charge accumulates at the layer interfaces, rather than at the electrode-dielectric interface. The model, which includes both drift and diffusion, is quantitative and yields a rate-limiting mobility of 6.9±0.9×10-12 cm2/V s, in excellent agreement with the oxygen vacancy mobility for perovskite oxides obtained from Zafar et al.

Hybrid SnO2/TiO2 Nanocomposites for Selective Detection of Ultra-Low Hydrogen Sulfide Concentrations in Complex Backgrounds

PubMed Central

Larin, Alexander; Womble, Phillip C.; Dobrokhotov, Vladimir

2016-01-01

In this paper, we present a chemiresistive metal oxide (MOX) sensor for detection of hydrogen sulfide. Compared to the previous reports, the overall sensor performance was improved in multiple characteristics, including: sensitivity, selectivity, stability, activation time, response time, recovery time, and activation temperature. The superior sensor performance was attributed to the utilization of hybrid SnO2/TiO2 oxides as interactive catalytic layers deposited using a magnetron radio frequency (RF) sputtering technique. The unique advantage of the RF sputtering for sensor fabrication is the ability to create ultra-thin films with precise control of geometry, morphology and chemical composition of the product of synthesis. Chemiresistive films down to several nanometers can be fabricated as sensing elements. The RF sputtering technique was found to be very robust for bilayer and multilayer oxide structure fabrication. The geometry, morphology, chemical composition and electronic structure of interactive layers were evaluated in relation to their gas sensing performance, using scanning electron microscopy (SEM), X-ray diffraction technique (XRD), atomic force microscopy (AFM), Energy Dispersive X-ray Spectroscopy (EDAX), UV visible spectroscopy, and Kelvin probe measurements. A sensor based on multilayer SnO2/TiO2 catalytic layer with 10% vol. content of TiO2 demonstrated the best gas sensing performance in all characteristics. Based on the pattern relating material’s characteristics to gas sensing performance, the optimization strategy for hydrogen sulfide sensor fabrication was suggested. PMID:27618900

Single-layer graphene/titanium oxide cubic nanorods array/FTO heterojunction for sensitive ultraviolet light detection

NASA Astrophysics Data System (ADS)

Liang, Feng-Xia; Wang, Jiu-Zhen; Wang, Yi; Lin, Yi; Liang, Lin; Gao, Yang; Luo, Lin-Bao

2017-12-01

In this study, we report on the fabrication of a sensitive ultraviolet photodetector (UVPD) by simply transferring single-layer graphene (SLG) on rutile titanium oxide cubic nanorod (TiO2NRs) array. The cubic TiO2NRs array with strong light trapping effect was grown on fluorine-doped tin oxide (FTO) glass through a hydrothermal approach. The as-assembled UVPD was very sensitive to UV light illumination, but virtually blind to white light illumination. The responsivity and specific detectivity were estimated to be 52.1 A/W and 4.3 × 1012 Jones, respectively. What is more, in order to optimize device performance of UVPD, a wet-chemistry treatment was then employed to reduce the high concentration of defects in TiO2NRs during hydrothermal growth. It was found that the UVPD after treatment showed obvious decrease in sensitivity, but the response speed (rise time: 80 ms, fall time: 160 ms) and specific detectivity were substantially increased. It is also found that the speicific detectivity was imporoved by six-fold to 3.2 × 1013 Jones, which was the best result in comparison with previously reported TiO2 nanostructures or thin film based UVPDs. This totality of this study shows that the present SLG/TiO2NR/FTO UVPD may find potential application in future optoelectronic devices and systems.

On the Ni-Ion release rate from surfaces of binary NiTi shape memory alloys

NASA Astrophysics Data System (ADS)

Ševčíková, Jana; Bártková, Denisa; Goldbergová, Monika; Kuběnová, Monika; Čermák, Jiří; Frenzel, Jan; Weiser, Adam; Dlouhý, Antonín

2018-01-01

The study is focused on Ni-ion release rates from NiTi surfaces exposed in the cell culture media and human vascular endothelial cell (HUVEC) culture environments. The NiTi surface layers situated in the depth of 70 μm below a NiTi oxide scale are affected by interactions between the NiTi alloys and the bio-environments. The finding was proved with use of inductively coupled plasma mass spectrometry and electron microscopy experiments. As the exclusive factor controlling the Ni-ion release rates was not only thicknesses of the oxide scale, but also the passivation depth, which was two-fold larger. Our experimental data strongly suggested that some other factors, in addition to the Ni concentration in the oxide scale, admittedly hydrogen soaking deep below the oxide scale, must be taken into account in order to rationalize the concentrations of Ni-ions released into the bio-environments. The suggested role of hydrogen as the surface passivation agent is also in line with the fact that the Ni-ion release rates considerably decrease in NiTi samples that were annealed in controlled hydrogen atmospheres prior to bio-environmental exposures.

Characterization of the Alumina Scale formed on Coated and Uncoated Doped Superalloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Unocic, Kinga A; Parish, Chad M; Pint, Bruce A

2011-01-01

To investigate the mechanisms by which Y and La dopants affect the oxidation behavior of Ni base single crystal superalloys, the oxide scales formed on two variants of a commercial X4 alloy, each with and without a MCrAlYHfSi coating were characterized. The alloy systems were oxidized for 100h at 1100 C and then examined using analytical transmission electron microscopy. Without a coating, a duplex scale was formed on the superalloy surface comprised of an outer Ni rich spinel type layer and an inner columnar Al2O3 layer. In this case, Hf and Ti were found segregated to the alumina grain boundariesmore » in the outer part of the scale on both alloys but only Hf was detected near the metal alumina interface. There was no evidence of Ta, Y or La segregation to the scale grain boundaries after this exposure. The scale formed on the alloys with the thermally sprayed coating was primarily alumina, and Y and Hf segregated to the alumina grain boundaries for both alloys. There was evidence of Ti rich oxides in the outer part of the scale indicating that Ti had diffused through the coating into the thermally grown oxide but La was not found.« less

Low temperature perovskite solar cells with an evaporated TiO 2 compact layer for perovskite silicon tandem solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bett, Alexander J.; Schulze, Patricia S. C.; Winkler, Kristina

Silicon-based tandem solar cells can overcome the efficiency limit of single junction silicon solar cells. Perovskite solar cells are particularly promising as a top cell in monolithic tandem devices due to their rapid development towards high efficiencies, a tunable band gap with a sharp optical absorption edge and a simple production process. In monolithic tandem devices, the perovskite solar cell is deposited directly on the silicon cell, requiring low-temperature processes (< 200 °C) to maintain functionality of under-lying layers of the silicon cell in case of highly efficient silicon hetero-junction (SHJ) bottom solar cell. In this work, we present amore » complete low-temperature process for perovskite solar cells including a mesoporous titanium oxide (TiO 2) scaffold - a structure yielding the highest efficiencies for single-junction perovskite solar cells. We show that evaporation of the compact TiO 2 hole blocking layer and ultra-violet (UV) curing for the mesoporous TiO 2 layer allows for good performance, comparable to high-temperature (> 500 °C) processes. With both manufacturing routes, we obtain short-circuit current densities (J SC) of about 20 mA/cm 2, open-circuit voltages (V OC) over 1 V, fill factors (FF) between 0.7 and 0.8 and efficiencies (n) of more than 15%. We further show that the evaporated TiO 2 layer is suitable for the application in tandem devices. The series resistance of the layer itself and the contact resistance to an indium doped tin oxide (ITO) interconnection layer between the two sub-cells are low. Additionally, the low parasitic absorption for wavelengths above the perovskite band gap allow a higher absorption in the silicon bottom solar cell, which is essential to achieve high tandem efficiencies.« less

Low temperature perovskite solar cells with an evaporated TiO 2 compact layer for perovskite silicon tandem solar cells

DOE PAGES

Bett, Alexander J.; Schulze, Patricia S. C.; Winkler, Kristina; ...

2017-09-21

Silicon-based tandem solar cells can overcome the efficiency limit of single junction silicon solar cells. Perovskite solar cells are particularly promising as a top cell in monolithic tandem devices due to their rapid development towards high efficiencies, a tunable band gap with a sharp optical absorption edge and a simple production process. In monolithic tandem devices, the perovskite solar cell is deposited directly on the silicon cell, requiring low-temperature processes (< 200 °C) to maintain functionality of under-lying layers of the silicon cell in case of highly efficient silicon hetero-junction (SHJ) bottom solar cell. In this work, we present amore » complete low-temperature process for perovskite solar cells including a mesoporous titanium oxide (TiO 2) scaffold - a structure yielding the highest efficiencies for single-junction perovskite solar cells. We show that evaporation of the compact TiO 2 hole blocking layer and ultra-violet (UV) curing for the mesoporous TiO 2 layer allows for good performance, comparable to high-temperature (> 500 °C) processes. With both manufacturing routes, we obtain short-circuit current densities (J SC) of about 20 mA/cm 2, open-circuit voltages (V OC) over 1 V, fill factors (FF) between 0.7 and 0.8 and efficiencies (n) of more than 15%. We further show that the evaporated TiO 2 layer is suitable for the application in tandem devices. The series resistance of the layer itself and the contact resistance to an indium doped tin oxide (ITO) interconnection layer between the two sub-cells are low. Additionally, the low parasitic absorption for wavelengths above the perovskite band gap allow a higher absorption in the silicon bottom solar cell, which is essential to achieve high tandem efficiencies.« less

Synthesis, characterization and photocatalytic activity of mixed oxides derived from ZnAlTi ternary layered double hydroxides

NASA Astrophysics Data System (ADS)

Sahu, R. K.; Mohanta, B. S.; Das, N. N.

2013-09-01

A new series of Ti4+ containing ZnAl-LDHs with varying Zn:Al:Ti (~3:1:0-3:0.5:0.5) ratio were prepared by coprecipitation of homogeneous solution metal salts and characterized by various physicochemical methods. Powder XRD revealed the formation of well crystallized LDH even at the highest Ti4+ content. On thermal treatment at 450 °C, the well crystallized LDH precursors yielded mixed oxides with BET surface area in the range 92-118 m2/g. UV-vis diffuse reflection spectroscopy (DRS) showed a marginal decrease of band gap energy for calcined ZnAlTi-LDHs in comparison to either ZnO or TiO2-P25. The TEM analyses of a representative sample (as-synthesized and calcined) indicated more or less uniform distribution of titanium species. The derived mixed oxides from titanium containing LDH precursors demonstrated better activity toward photodegradation of methylene blue and rhodamine B than those of a physical mixture of ZnO and TiO2. Moreover, the present work not only provided a first hand understanding about semiconductor properties of ZnAlTi-LDHs but also demonstrated their potential as photocatalysts for degradation of organic pollutants.

Stable Water Oxidation in Acid Using Manganese-Modified TiO2 Protective Coatings.

PubMed

Siddiqi, Georges; Luo, Zhenya; Xie, Yujun; Pan, Zhenhua; Zhu, Qianhong; Röhr, Jason A; Cha, Judy J; Hu, Shu

2018-06-06

Accomplishing acid-stable water oxidation is a critical matter for achieving both long-lasting water-splitting devices and other fuel-forming electro- and photocatalytic processes. Because water oxidation releases protons into the local electrolytic environment, it becomes increasingly acidic during device operation, which leads to corrosion of the photoactive component and hence loss in device performance and lifetime. In this work, we show that thin films of manganese-modified titania, (Ti,Mn)O x , topped with an iridium catalyst, can be used in a coating stabilization scheme for acid-stable water oxidation. We achieved a device lifetime of more than 100 h in pH = 0 acid. We successfully grew (Ti,Mn)O x coatings with uniform elemental distributions over a wide range of manganese compositions using atomic layer deposition (ALD), and using X-ray photoelectron spectroscopy, we show that (Ti,Mn)O x films grown in this manner give rise to closer-to-valence-band Fermi levels, which can be further tuned with annealing. In contrast to the normally n-type or intrinsic TiO 2 coatings, annealed (Ti,Mn)O x films can make direct charge transfer to a Fe(CN) 6 3-/4- redox couple dissolved in aqueous electrolytes. Using the Fe(CN) 6 3-/4- redox, we further demonstrated anodic charge transfer through the (Ti,Mn)O x films to high work function metals, such as iridium and gold, which is not previously possible with ALD-grown TiO 2 . We correlated changes in the crystallinity (amorphous to rutile TiO 2 ) and oxidation state (2+ to 3+) of the annealed (Ti,Mn)O x films to their hole conductivity and electrochemical stability in acid. Finally, by combining (Ti,Mn)O x coatings with iridium, an acid-stable water-oxidation anode, using acid-sensitive conductive fluorine-doped tin oxides, was achieved.

The plasma electrolytic oxidation micro-discharge channel model and its microstructure characteristic based on Ti tracer

NASA Astrophysics Data System (ADS)

Gao, Fangyuan; Hao, Li; Li, Guang; Xia, Yuan

2018-02-01

This study focuses on the individual discharge channel of ceramic coating prepared by plasma electrolytic oxidation (PEO), and attempts to reveal the mechanism of breakdown discharge at low voltage. Titanium (Ti) was employed as a substrate with the layer of aluminum deposited on it (aluminized Ti). The shape and microstructure of the discharge channels in PEO coatings were investigated using transmission electron microscope (TEM) and scanning electron microscopy (SEM). A schematic model of the individual discharge channel was proposed based on Ti tracer method. The shape of the discharge channel was mainly cylinder-shaped in the compact coating, with a groove-like oxidation region existed at the coating/substrate interface. In the groove-like oxidation region, the phase composition mainly composed of amorphous and mixed polycrystalline (aluminum titanate and mullite). β-Al2O3 was found in the ceramic coating. TEM morphology showed that nanometer sized micro channels existed in the ceramic coatings.

High performance GaN-based LEDs on patterned sapphire substrate with patterned composite SiO2/Al2O3 passivation layers and TiO2/Al2O3 DBR backside reflector.

PubMed

Guo, Hao; Zhang, Xiong; Chen, Hongjun; Zhang, Peiyuan; Liu, Honggang; Chang, Hudong; Zhao, Wei; Liao, Qinghua; Cui, Yiping

2013-09-09

GaN-based light-emitting diodes (LEDs) on patterned sapphire substrate (PSS) with patterned composite SiO(2)/Al(2)O(3) passivation layers and TiO(2)/Al(2)O(3) distributed Bragg reflector (DBR) backside reflector have been proposed and fabricated. Highly passivated Al(2)O(3) layer deposited on indium tin oxide (ITO) layer with excellent uniformity and quality has been achieved with atomic layer deposition (ALD) technology. With a 60 mA current injection, an enhancement of 21.6%, 59.7%, and 63.4% in the light output power (LOP) at 460 nm wavelength was realized for the LED with the patterned composite SiO(2)/Al(2)O(3) passivation layers, the LED with the patterned composite SiO(2)/Al(2)O(3) passivation layers and Ag mirror + 3-pair TiO(2)/SiO(2) DBR backside reflector, and the LED with the patterned composite SiO(2)/Al(2)O(3) passivation layer and Ag mirror + 3-pair ALD-grown TiO(2)/Al(2)O(3) DBR backside reflector as compared with the conventional LED only with a single SiO(2) passivation layer, respectively.

Evaluation of Ti-48Al-2Nb Under Fretting Conditions

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Lerch, Bradley A.; Draper, Susan L.; Raj, Sai V.

2001-01-01

An investigation was conducted to examine the fretting behavior of lambda-TiAl (Ti-48Al-2Cr-2Nb) in contact with a nickel-base superalloy (Inconel 718) in air at temperatures from 23 to 550 C. Fretting wear experiments were conducted with 9.4-mm-diameter hemispherical Inconel (IN) 718 pins in contact with Ti-48Al-2Cr-2Nb flats (and the reverse) at loads from 1 to 40 N and fretting frequencies from 50 to 160 Hz with slip amplitudes from 50 to 200 microns for 1 to 20 million fretting cycles. The results were similar for both combinations of pin and flat. Reference fretting wear experiments were also conducted with 9.4-mm-diameter hemispherical Ti-6Al-4V pins in contact with IN718 flats. The interfacial adhesive bonds between Ti-48Al-2Cr-2Nb and IN718 in contact were generally stronger than the cohesive bonds in the cohesively weaker Ti-48Al-2Cr-2Nb. The failed Ti-48Al-2Cr-2Nb subsequently transferred to the IN718 surface at any fretting condition. The wear scars produced on Ti-48Al-2Cr-2Nb contained metallic and oxide wear debris, scratches, plastically deformed asperities, cracks, and fracture pits. Oxide layers readily formed on the Ti-48Al-2Cr-2Nb surface at 550 C, but cracks easily occurred in the oxide layers. Factors including fretting frequency, temperature, slip amplitude, and load influenced the fretting behavior of Ti-48Al-2Cr-2Nb in contact with IN718. The wear volume loss of Ti-48Al-2Cr-2Nb generally decreased with increasing fretting frequency. The increasing rate of oxidation at elevated temperatures up to 200 C led to a drop in wear volume loss at 200 C. However, the fretting wear increased as the temperature was increased from 200 to 550 C. The highest temperatures of 450 and 550 C resulted in oxide film disruption with generation of cracks, loose wear debris, and pits on the Ti-48Al-2Cr-2Nb wear surface. The wear volume loss generally increased as the slip amplitude increased. The wear volume loss also generally increased as the load increased. Increasing slip amplitude and increasing load both tended to produce more metallic wear debris, causing severe abrasive wear in the contacting metals.

Dimensional crossover of electron weak localization in ZnO/TiO{sub x} stacked layers grown by atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saha, D., E-mail: sahaphys@gmail.com, E-mail: pmisra@rrcat.gov.in; Misra, P., E-mail: sahaphys@gmail.com, E-mail: pmisra@rrcat.gov.in; Joshi, M. P.

2016-01-25

We report on the dimensional crossover of electron weak localization in ZnO/TiO{sub x} stacked layers having well-defined and spatially-localized Ti dopant profiles along film thickness. These films were grown by in situ incorporation of sub-monolayer TiO{sub x} on the growing ZnO film surface and subsequent overgrowth of thin conducting ZnO spacer layer using atomic layer deposition. Film thickness was varied in the range of ∼6–65 nm by vertically stacking different numbers (n = 1–7) of ZnO/TiO{sub x} layers of nearly identical dopant-profiles. The evolution of zero-field sheet resistance (R{sub ◻}) versus temperature with decreasing film thickness showed a metal to insulator transition. Onmore » the metallic side of the metal-insulator transition, R{sub ◻}(T) and magnetoresistance data were found to be well corroborated with the theoretical framework of electron weak localization in the diffusive transport regime. The temperature dependence of both R{sub ◻} and inelastic scattering length provided strong evidence for a smooth crossover from 2D to 3D weak localization behaviour. Results of this study provide deeper insight into the electron transport in low-dimensional n-type ZnO/TiO{sub x} stacked layers which have potential applications in the field of transparent oxide electronics.« less

Effect of intermediate layers on atomic layer deposition-aluminum oxide protected silver mirrors

NASA Astrophysics Data System (ADS)

Fryauf, David M.; Diaz Leon, Juan J.; Phillips, Andrew C.; Kobayashi, Nobuhiko P.

2017-07-01

This work investigates intermediate materials deposited between silver (Ag) thin-film mirrors and an aluminum oxide (AlOx) barrier overlayer and compares the effects on mirror durability to environmental stresses. Physical vapor deposition of various fluorides, oxides, and nitrides in combination with AlOx by atomic layer deposition (ALD) is used to develop several coating recipes. Ag-AlOx samples with different intermediate materials undergo aggressive high-temperature (80°C), high-humidity (80%) (HTHH) testing for 10 days. Reflectivity of mirror samples is measured before and after HTHH testing, and image processing techniques are used to analyze the specular surface of the samples after HTHH testing. Among the seven intermediate materials used in this work, TiN, MgAl2O4, NiO, and Al2O3 intermediate layers offer more robust protection against chemical corrosion and moisture when compared with samples with no intermediate layer. In addition, results show that the performance of the ALD-AlOx barrier overlayer depends significantly on the ALD-growth process temperature. Because higher durability is observed in samples with less transparent TiN and NiO layers, we propose a figure of merit based on post-HTHH testing reflectivity change and specular reflective mirror surface area remaining after HTHH testing to judge overall barrier performance.

A Tandem Catalyst with Multiple Metal Oxide Interfaces Produced by Atomic Layer Deposition.

PubMed

Ge, Huibin; Zhang, Bin; Gu, Xiaomin; Liang, Haojie; Yang, Huimin; Gao, Zhe; Wang, Jianguo; Qin, Yong

2016-06-13

Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal-oxide interfaces based on a tube-in-tube nanostructure using template-assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al2 O3 nanotube (Ni/Al2 O3 interface) and Pt nanoparticles are attached to the inner surface of the outer TiO2 nanotube (Pt/TiO2 interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO2 interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al2 O3 interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube-in-tube tandem catalyst with multiple metal-oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of diffusing species from marker experiments in the system Ni Ti O

NASA Astrophysics Data System (ADS)

Schirmer, S.; Lindner, J. K. N.; Mändl, S.

2007-04-01

Surface modification of NiTi for improved biocompatibility is a pressing issue. Using oxygen plasma immersion ion implantation (PIII), it is possible to form closed TiO2 layers on NiTi3 on NiTi. Using 60Ni marker ions implanted at 180 keV, it is shown conclusively that mobile Ni are the diffusing species, with the onset of diffusion occurring between 300 and 400 °C. Additionally, Ni is selectively removed from the oxide by preferential sputtering from the surface.

Controllable synthesis of graphene-based titanium dioxide nanocomposites by atomic layer deposition.

PubMed

Meng, Xiangbo; Geng, Dongsheng; Liu, Jian; Li, Ruying; Sun, Xueliang

2011-04-22

Atomic layer deposition (ALD) was used to synthesize graphene-based metal oxide nanocomposites. This strategy was fulfilled on the preparation of TiO(2)-graphene nanosheet (TiO(2)-GNS) nanocomposites using titanium isopropoxide and water as precursors. The synthesized nanocomposites demonstrated that ALD exhibited many benefits in a controllable means. It was found that the as-deposited TiO(2) was tunable not only in its morphologies but also in its structural phases. As for the former, TiO(2) was transferable from nanoparticles to nanofilms with increased cycles. With regard to the latter, TiO(2) was changeable from amorphous to crystalline phase, and even a mixture of the two with increased growth temperatures (up to 250 °C). The underlying growth mechanisms were discussed and the resultant TiO(2)-GNS nanocomposites have great potentials for many applications, such as photocatalysis, lithium-ion batteries, fuel cells, and sensors.

Improved Optical Transmittance and Crystal Characteristics of ZnS:TbOF Thin Film on Bi4Ti3O12/Indium Tin Oxide/Glass Substrate by Using a SiO2 Buffer Layer

NASA Astrophysics Data System (ADS)

Chia, Wei‑Kuo; Yokoyama, Meiso; Yang, Cheng‑Fu; Chiang, Wang‑Ta; Chen, Ying‑Chung

2006-07-01

Bi4Ti3O12 thin films are deposited on indium tin oxide (ITO)/glass substrates using RF magnetron sputtering technology and are annealed at 675 °C in a rapid thermal annealing furnace in an oxygen atmosphere. The resulting films have high optical transmittances and good crystalline characteristics. ZnS:TbOF films are then deposited on the Bi4Ti3O12 films, causing the originally highly transparent specimens to blacken and to resemble a glass surface coated with carbon powder. The optical transmittance of the specimen is less than 15% under the visible wavelength range, and neither a crystalline phase nor a distinct ZnS grain structure is evident in X-ray diffractometer (XRD) and scanning electronic microscope (SEM). Secondary ion mass spectrometer (SIMS) analysis reveals the occurrence of interdiffusion between the ZnS and Bi4Ti3O12 layers. This suggests that one or more unknown chemical reactions take place among the elements Bi, S, and O at the interface during the deposition of ZnS:TbOF film on a Bi4Ti3O12/ITO/glass substrate. These reactions cause the visible transmittance of the specimens to deteriorate dramatically. To prevent interdiffusion, a silicon dioxide (SiO2) buffer layer 100 nm thick was grown on the Bi4Ti3O12/ITO/glass substrate using plasma-enhanced chemical vapor deposition (PECVD), then the ZnS:TbOF film was grown on the SiO2 buffer layer. The transmittance of the resulting specimen is enhanced approximately 8-fold in the visible region. XRD patterns reveal the ZnS(111)-oriented phase is dominant. Furthermore, dense, crack-free ZnS:TbOF grains are observed by SEM. The results imply that the SiO2 buffer layer sandwiched between the ZnS:TbOF and Bi4Ti3O2 layers effectively separates the two layers. Therefore, interdiffusion and chemical reactions are prevented at the interface of the two layers, and the crystalline characteristics of the ZnS:TbOF layer and the optical transmittance of the specimen are improved as a result. Finally, the dielectric constant of the stacked structure is lower than that of the single layer structure without SiO2, but the dielectric breakdown strength is enhanced.

On the effect of Ti on the stability of amorphous indium zinc oxide used in thin film transistor applications

NASA Astrophysics Data System (ADS)

Lee, Sunghwan; Paine, David C.

2011-06-01

In2O3-based amorphous oxide channel materials are of increasing interest for thin film transisitor applications due, in part, to the remarkable stability of this class of materials amorphous structure and electronic properties. We report that this stability is degraded in the presence of Ti, which is widely used as a contact and/or adhesion layer. A cross-sectional transmission electron microscopy analysis, supported by glancing incident angle x-ray and selected area diffraction examination, shows that amorphous indium zinc oxide in contact with Ti undergoes crystallization to the bixbyite phase and reacts to form the rutile phase of TiO2 at a temperature of 200 °C. A basic thermodynamic analysis is presented and forms the basis of a model that describes both the crystallization and the resistivity decrease.

Control of crystallographic texture and surface morphology of Pt/Tio2 templates for enhanced PZT thin film texture.

PubMed

Fox, Austin J; Drawl, Bill; Fox, Glen R; Gibbons, Brady J; Trolier-McKinstry, Susan

2015-01-01

Optimized processing conditions for Pt/TiO2/SiO2/Si templating electrodes were investigated. These electrodes are used to obtain [111] textured thin film lead zirconate titanate (Pb[ZrxTi1-x ]O3 0 ≤ x ≤ 1) (PZT). Titanium deposited by dc magnetron sputtering yields [0001] texture on a thermally oxidized Si wafer. It was found that by optimizing deposition time, pressure, power, and the chamber pre-conditioning, the Ti texture could be maximized while maintaining low surface roughness. When oxidized, titanium yields [100]-oriented rutile. This seed layer has as low as a 4.6% lattice mismatch with [111] Pt; thus, it is possible to achieve strongly oriented [111] Pt. The quality of the orientation and surface roughness of the TiO2 and the Ti directly affect the achievable Pt texture and surface morphology. A transition between optimal crystallographic texture and the smoothest templating surface occurs at approximately 30 nm of original Ti thickness (45 nm TiO2). This corresponds to 0.5 nm (2 nm for TiO2) rms roughness as determined by atomic force microscopy and a full-width at half-maximum (FWHM) of the rocking curve 0002 (200) peak of 5.5/spl degrees/ (3.1/spl degrees/ for TiO2). A Pb[Zr0.52Ti 0.48]O3 layer was deposited and shown to template from the textured Pt electrode, with a maximum [111] Lotgering factor of 87% and a minimum 111 FWHM of 2.4/spl degrees/ at approximately 30 nm of original Ti.

Fabrication of TiO2 Crystalline Coatings by Combining Ti-6Al-4V Anodic Oxidation and Heat Treatments

PubMed Central

Schvezov, Carlos Enrique; Ares, Alicia Esther

2015-01-01

The bio- and hemocompatibility of titanium alloys are due to the formation of a TiO2 layer. This natural oxide may have fissures which are detrimental to its properties. Anodic oxidation is used to obtain thicker films. By means of this technique, at low voltages oxidation, amorphous and low roughness coatings are obtained, while, above a certain voltage, crystalline and porous coatings are obtained. According to the literature, the crystalline phases of TiO2, anatase, and rutile would present greater biocompatibility than the amorphous phase. On the other hand, for hemocompatible applications, smooth and homogeneous surfaces are required. One way to obtain crystalline and homogeneous coatings is by heat treatments after anodic oxidation. The aim of this study is to evaluate the influence of heat treatments on the thickness, morphology, and crystalline structure of the TiO2 anodic coatings. The characterization was performed by optical and scanning electron microscopy, X-ray diffraction, and X-ray reflectometry. Coatings with different colors of interference were obtained. There were no significant changes in the surface morphology and roughness after heat treatment of 500°C. Heat treated coatings have different proportions of the crystalline phases, depending on the voltage of anodic oxidation and the temperature of the heat treatment. PMID:25784939

Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Altman, Eric I.

2015-10-06

The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractablemore » for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO 2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO 2 surfaces. Building on this work on anatase, the mechanism by which TiO 2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO 2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce catalytic properties not seen for the individual binary oxides and to the structure and properties of transition metal oxide clusters. For the latter, surprising results were found including the observation that small clusters can actually be orders of magnitude more difficult than bulk materials to oxidize and that even weak substrate interactions can dictate the structure and reactivity of the oxide clusters. It was shown that these results could be explained in terms of simple thermodynamic arguments that extend to materials beyond the Co oxide system studied.« less

Layer-by-Layer Evolution of a Two-Dimensional Electron Gas Near an Oxide Interface

NASA Astrophysics Data System (ADS)

Chang, Young Jun; Moreschini, Luca; Bostwick, Aaron; Gaines, Geoffrey A.; Kim, Yong Su; Walter, Andrew L.; Freelon, Byron; Tebano, Antonello; Horn, Karsten; Rotenberg, Eli

2013-09-01

We report the momentum-resolved measurement of a two-dimensional electron gas at the LaTiO3/SrTiO3 interface by angle-resolved photoemission spectroscopy (ARPES). Thanks to an advanced sample preparation technique, the orbital character of the conduction electrons and the electronic correlations can be accessed quantitatively as each unit cell layer is added. We find that all of these quantities change dramatically with distance from the interface. These findings open the way to analogous studies on other heterostructures, which are traditionally a forbidden field for ARPES.

Low modulus and bioactive Ti/α-TCP/Ti-mesh composite prepared by spark plasma sintering.

PubMed

Guo, Yu; Tan, Yanni; Liu, Yong; Liu, Shifeng; Zhou, Rui; Tang, Hanchun

2017-11-01

A titanium mesh scaffold composite filled with Ti/α-TCP particles was prepared by spark plasma sintering (SPS). The microstructures and interfacial reactions of the composites were investigated by scanning electron microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) analyses. The compressive strength and elastic modulus were also measured. In vitro bioactivity and biocompatibility was evaluated by using simulated body fluid and cells culture, respectively. After high temperature sintering, Ti oxides, Ti x P y and CaTiO 3 were formed. The formation of Ti oxides and Ti x P y were resulted from the diffusion of O and P elements from α-TCP to Ti. CaTiO 3 was the reaction product of Ti and α-TCP. The composite of 70Ti/α-TCP incorporated with Ti mesh showed a high compressive strength of 589MPa and a low compressive modulus of 30GPa. The bioactivity test showed the formation of a thick apatite layer on the composite and well-spread cells attachment. A good combination of mechanical properties and bioactivity indicated a high potential application of Ti/α-TCP/Ti-mesh composite for orthopedic implants. Copyright © 2017. Published by Elsevier B.V.

CdS Nanoparticle-Modified α-Fe2O3/TiO2 Nanorod Array Photoanode for Efficient Photoelectrochemical Water Oxidation.

PubMed

Yin, Ruiyang; Liu, Mingyang; Tang, Rui; Yin, Longwei

2017-09-02

In this work, we demonstrate a facile successive ionic layer adsorption and reaction process accompanied by hydrothermal method to synthesize CdS nanoparticle-modified α-Fe 2 O 3 /TiO 2 nanorod array for efficient photoelectrochemical (PEC) water oxidation. By integrating CdS/α-Fe 2 O 3 /TiO 2 ternary system, light absorption ability of the photoanode can be effectively improved with an obviously broadened optical-response to visible light region, greatly facilitates the separation of photogenerated carriers, giving rise to the enhancement of PEC water oxidation performance. Importantly, for the designed abnormal type-II heterostructure between Fe 2 O 3 /TiO 2 , the conduction band position of Fe 2 O 3 is higher than that of TiO 2 , the photogenerated electrons from Fe 2 O 3 will rapidly recombine with the photogenerated holes from TiO 2 , thus leads to an efficient separation of photogenerated electrons from Fe 2 O 3 /holes from TiO 2 at the Fe 2 O 3 /TiO 2 interface, greatly improving the separation efficiency of photogenerated holes within Fe 2 O 3 and enhances the photogenerated electron injection efficiency in TiO 2 . Working as the photoanodes of PEC water oxidation, CdS/α-Fe 2 O 3 /TiO 2 heterostucture electrode exhibits improved photocurrent density of 0.62 mA cm - 2 at 1.23 V vs. reversible hydrogen electrode (RHE) in alkaline electrolyte, with an obviously negatively shifted onset potential of 80 mV. This work provides promising methods to enhance the PEC water oxidation performance of the TiO 2 -based heterostructure photoanodes.

Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO{sub 2} using “water-free” metal-halide/metal alkoxide reactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atanasov, Sarah E.; Kalanyan, Berç; Parsons, Gregory N., E-mail: gnp@ncsu.edu

2016-01-15

Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl{sub 4}) and titanium tetra-isopropoxide [Ti(OCH(CH{sub 3}){sub 2}){sub 4}, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO{sub 2} film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO{sub 2} on SiO{sub 2} before substantial growth takes place on Si–H. On both Si–H and Si–OH, themore » surface reactions proceed during the first few TiCl{sub 4}/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-area growth.« less

Tunable growth of TiO2 nanostructures on Ti substrates

NASA Astrophysics Data System (ADS)

Peng, Xinsheng; Wang, Jingpeng; Thomas, Dan F.; Chen, Aicheng

2005-10-01

A simple and facile method is described to directly synthesize TiO2 nanostructures on titanium substrates by oxidizing Ti foil using small organic molecules as the oxygen source. The effect of reaction temperature and oxygen source on the formation of the TiO2 nanostructures has been studied using scanning electron microscopy, x-ray diffraction, transmission electron microscopy, Raman spectroscopy and water contact angle measurement. Polycrystalline grains are formed when pure oxygen and formic acid are used as the oxygen source; elongated micro-crystals are produced when water vapour is used as the oxygen source; oriented and aligned TiO2 nanorod arrays are synthesized when ethanol, acetaldehyde or acetone are used as the oxygen source. The growth mechanism of the TiO2 nanostructures is discussed. The diffusion of Ti atoms to the oxide/gas interface via the network of the grain boundaries of the thin oxide layer is the determining factor for the formation of well-aligned TiO2 nanorod arrays. The wetting properties of the TiO2 nanostructured surfaces formed are dictated by their structure, varying from a hydrophilic surface to a strongly hydrophobic surface as the surface structure changes from polycrystalline grains to well-aligned nanorod arrays. This tunable growth of TiO2 nanostructures is desirable for promising applications of TiO2 nanostructures in the development of optical devices, sensors, photo-catalysts and self-cleaning coatings.

c-Axis oriented epitaxial Ba 0.25Sr 0.75TiO 3 films display Curie-Weiss behavior

NASA Astrophysics Data System (ADS)

Boikov, Yu. A.; Claeson, T.

2002-02-01

Thin films of ferroelectrics have inferior dielectric properties, including microwave losses, compared to bulk material and generally do not display a proper Curie-Weiss behavior. This study shows that the film properties can be improved considerably, with a Curie-Weiss behavior, by choosing lattice matched electrodes and proper stoichiometry. A 700 nm thick Ba 0.25Sr 0.75TiO 3 layer was inserted, by laser ablation, between two epitaxial metallic oxide (200 nm) SrRuO 3 electrodes. Because of compressive stress in the plane of the substrate, the c-axis of the unit cell in the Ba 0.25Sr 0.75TiO 3 layer was normal to the substrate plane. Grains were of the order of 100-200 nm (with small misorientation angles in a× b plane) as determined by X-rays and AFM. The positions of pronounced maxima in the temperature dependence of the permittivity depended on external bias voltage applied between the SrRuO 3 electrodes to the dielectric film. The measured ε( T) curves agreed well with existing theoretical models at temperatures below and above the ferroelectric phase transition point. At T≈200 K, ε/ ε0 for the Ba 0.25Sr 0.75TiO 3 layer was suppressed up to 85% (from 4400 down to 560) when ±2.5 V bias voltage was applied to the metallic oxide electrodes. Well saturated polarization-vs.-voltage hysteresis loops were measured for the Ba 0.25Sr 0.75TiO 3 layer in the temperature interval 4.2-200 K. Because of depolarization effects, the polarization of the Ba 0.25Sr 0.75TiO 3 layer was suppressed at positive voltage applied between the electrodes, as compared with a negative one.

The effect of molten salt on high temperature behavior of stainless steel and titanium alloy with the presence of water vapor

NASA Astrophysics Data System (ADS)

Baharum, Azila; Othman, Norinsan Kamil; Salleh, Emee Marina

2018-04-01

The high temperature oxidation experiment was conducted to study the behavior of titanium alloy Ti6A14V and stainless steel 316 in Na2SO4-50%NaCl + Ar-20%O2 (molten salt) and Na2SO4-50%NaCl + Ar-20%O2 + 12% H2O (molten salt + water vapor) environment at 900°C for 30 hours using horizontal tube furnace. The sample then was investigated using weight change measurement analysis and X-ray diffraction (XRD) analysis to study the weight gained and the phase oxidation that occurred. The weight gained of the titanium alloy was higher in molten salt environment compared to stainless steel due to the rapid growth in the oxide scale but showed almost no change of weight gained upon addition of water vapor. This is due to the alloy was fully oxidized. Stainless steel showed more protection and better effect in molten salt environment compared to mixed environment showed by slower weight gain and lower oxidation rate. Meanwhile, the phase oxidation test of the samples showed that the titanium alloy consist of multi oxide layer of rutile (TiO2) and Al2O3 on the surface of the exposed sample. While stainless steel show the formation of both protective Cr-rich oxide and non-protective Fe-rich oxide layer. This can be concluded that stainless steel is better compared to Ti alloy due to slow growing of chromia oxide. Therefore it is proven that stainless steel has better self-protection upon high temperature exposure.

Compositionally modulated multilayer diamond-like carbon coatings with AlTiSi multi-doping by reactive high power impulse magnetron sputtering

NASA Astrophysics Data System (ADS)

Dai, Wei; Gao, Xiang; Liu, Jingmao; Kwon, Se-Hun; Wang, Qimin

2017-12-01

Diamond-like carbon (DLC) coatings with AlTiSi multi-doping were prepared by a reactive high power impulse magnetron sputtering with using a gas mixture of Ar and C2H2 as precursor. The composition, microstructure, compressive stress, and mechanical property of the as-deposited DLC coatings were studied systemically by using SEM, XPS, TEM, Raman spectrum, stress-tester, and nanoindentation as a function of the Ar fraction. The results show that the doping concentrations of the Al, Ti and Si atoms increased as the Ar fraction increased. The doped Ti and Si preferred to bond with C while the doped Al mainly existed in oxidation state without bonding with C. As the doping concentrations increased, TiC carbide nanocrystals were formed in the DLC matrix. The microstructure of coatings changed from an amorphous feature dominant AlTiSi-DLC to a carbide nanocomposite AlTiSi-DLC with TiC nanoparticles embedding. In addition, the coatings exhibited the compositionally modulated multilayer consisting of alternate Al-rich layer and Al-poor layer due to the rotation of the substrate holder and the diffusion behavior of the doped Al which tended to separate from C and diffuse towards the DLC matrix surface owing to its weak interactions with C. The periodic Al-rich layer can effectively release the compressive stress of the coatings. On the other hand, the hard TiC nanoparticles were conducive to the hardness of the coatings. Consequently, the DLC coatings with relatively low residual stress and high hardness could be acquired successfully through AlTiSi multi-doping. It is believed that the AlCrSi multi-doping may be a good way for improving the comprehensive properties of the DLC coatings. In addition, we believe that the DLC coatings with Al-rich multilayered structure have a high oxidation resistance, which allows the DLC coatings application in high temperature environment.

XPS and SEM analysis of the surface of gas atomized powder precursor of ODS ferritic steels obtained through the STARS route

NASA Astrophysics Data System (ADS)

Gil, E.; Cortés, J.; Iturriza, I.; Ordás, N.

2018-01-01

An innovative powder metallurgy route to produce ODS FS, named STARS, has succeeded in atomizing steel powders containing the oxide formers (Y and Ti) and, hence, avoids the mechanical alloying (MA) step to dissolve Y in the matrix. A metastable oxide layer forms at the surface of atomized powders and dissociates during HIP consolidation at high temperatures, leading to precipitation of more stable Y-Ti-O nanoparticles.

Cation Ordering within the Perovskite Block of a Six-layer Ruddlesden-Popper Oxide from Layer-by-layer Growth

NASA Astrophysics Data System (ADS)

Yan, Lei; Niu, H. J.; Rosseinsky, M. J.

2011-03-01

The (AO)(A BO3)n Ruddlesden-Popper structure is an archetypal complex oxide consisting of two distinct structural units, an (AO) rock salt layer separating an n-octahedra thick perovskite block. Conventional high-temperature oxide synthesis methods cannot access members with n > 3 , butlowtemperaturelayer - by - layerthinfilmmethodsallowthepreparationofmaterialswiththickerperovskiteblocks , exploitinghighsurfacemobilityandlatticematchingwiththesubstrate . Thispresentationdescribesthegrowthofann = 6 memberCaO / (ABO 3)n (ABO 3 : CaMnO 3 , La 0.67 Ca 0.33 MnO 3 orCa 0.85 Sm 0.15 MnO 3) epitaxialsinglecrystalfilmsonthe (001) SrTiO 3 substrates by pulsed laser deposition with the assistance of a reflection high energy electron diffraction (RHEED).

Characteristics and porcelain bond strength of (Ti,Al)N coating on dental alloys.

PubMed

Chung, Kwok-Hung; Duh, Jeng-Gong; Shin, Daehwan; Cagna, David R; Cronin, Robert J

2002-01-01

The effect of a novel titanium-aluminum nitride film, or (Ti,Al)N film, on the bond strength between a dental porcelain and two nickel-based dental alloy substrates was investigated. A thin layer of (Ti,Al)N film was deposited on flat metal samples using a reactive radio-frequency sputtering method. A uniform thickness of porcelain was applied to the film- coated metal samples. Metal-ceramic specimens were subjected to three-point bending, and failure loads were recorded. Bond strengths between the porcelain and (Ti,Al)N-coated metal alloys ranged from 159.0 +/- 11.7 N to 278.0 +/- 12.3 N. These values were significantly greater (p< 0.05) than bond strengths recorded for control samples that did not incorporate the (Ti,Al)N film. An electron probe microanalyzer with a line profile mode was used to characterize the interface between the (Ti,Al)N film and the porcelain. Results of this investigation suggest that the (Ti,Al)N film (1) increases the flexural bond strength between dental porcelain and nickel-based alloy substrates by permitting elemental diffusion, (2) interferes with the surface oxide formation that characteristically originates from the nickel-based metal alloy substrate, and (3) provides an appropriate oxide layer for porcelain application. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 516-521, 2002

In-operando hard X-ray photoelectron spectroscopy study on the impact of current compliance and switching cycles on oxygen and carbon defects in resistive switching Ti/HfO{sub 2}/TiN cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sowinska, Malgorzata, E-mail: sowinska@ihp-microelectronics.com; Bertaud, Thomas; Walczyk, Damian

2014-05-28

In this study, direct experimental materials science evidence of the important theoretical prediction for resistive random access memory (RRAM) technologies that a critical amount of oxygen vacancies is needed to establish stable resistive switching in metal-oxide-metal samples is presented. In detail, a novel in-operando hard X-ray photoelectron spectroscopy technique is applied to non-destructively investigates the influence of the current compliance and direct current voltage sweep cycles on the Ti/HfO{sub 2} interface chemistry and physics of resistive switching Ti/HfO{sub 2}/TiN cells. These studies indeed confirm that current compliance is a critical parameter to control the amount of oxygen vacancies in themore » conducting filaments in the oxide layer during the RRAM cell operation to achieve stable switching. Furthermore, clear carbon segregation towards the Ti/HfO{sub 2} interface under electrical stress is visible. Since carbon impurities impact the oxygen vacancy defect population under resistive switching, this dynamic carbon segregation to the Ti/HfO{sub 2} interface is suspected to negatively influence RRAM device endurance. Therefore, these results indicate that the RRAM materials engineering needs to include all impurities in the dielectric layer in order to achieve reliable device performance.« less

It Takes Two to Tango-Double-Layer Selective Contacts in Perovskite Solar Cells for Improved Device Performance and Reduced Hysteresis.

PubMed

Kegelmann, Lukas; Wolff, Christian M; Awino, Celline; Lang, Felix; Unger, Eva L; Korte, Lars; Dittrich, Thomas; Neher, Dieter; Rech, Bernd; Albrecht, Steve

2017-05-24

Solar cells made from inorganic-organic perovskites have gradually approached market requirements as their efficiency and stability have improved tremendously in recent years. Planar low-temperature processed perovskite solar cells are advantageous for possible large-scale production but are more prone to exhibiting photocurrent hysteresis, especially in the regular n-i-p structure. Here, a systematic characterization of different electron selective contacts with a variety of chemical and electrical properties in planar n-i-p devices processed below 180 °C is presented. The inorganic metal oxides TiO 2 and SnO 2 , the organic fullerene derivatives C 60 , PCBM, and ICMA, as well as double-layers with a metal oxide/PCBM structure are used as electron transport materials (ETMs). Perovskite layers deposited atop the different ETMs with the herein applied fabrication method show a similar morphology according to scanning electron microscopy. Further, surface photovoltage spectroscopy measurements indicate comparable perovskite absorber qualities on all ETMs, except TiO 2 , which shows a more prominent influence of defect states. Transient photoluminescence studies together with current-voltage scans over a broad range of scan speeds reveal faster charge extraction, less pronounced hysteresis effects, and higher efficiencies for devices with fullerene compared to those with metal oxide ETMs. Beyond this, only double-layer ETM structures substantially diminish hysteresis effects for all performed scan speeds and strongly enhance the power conversion efficiency up to a champion stabilized value of 18.0%. The results indicate reduced recombination losses for a double-layer TiO 2 /PCBM contact design: First, a reduction of shunt paths through the fullerene to the ITO layer. Second, an improved hole blocking by the wide band gap metal oxide. Third, decreased transport losses due to an energetically more favorable contact, as implied by photoelectron spectroscopy measurements. The herein demonstrated improvements of multilayer selective contacts may serve as a general design guideline for perovskite solar cells.

Nano Titanium Monoxide Crystals and Unusual Superconductivity at 11 K.

PubMed

Xu, Jijian; Wang, Dong; Yao, Heliang; Bu, Kejun; Pan, Jie; He, Jianqiao; Xu, Fangfang; Hong, Zhanglian; Chen, Xiaobo; Huang, Fuqiang

2018-03-01

Nano TiO 2 is investigated intensely due to extraordinary photoelectric performances in photocatalysis, new-type solar cells, etc., but only very few synthesis and physical properties have been reported on nanostructured TiO or other low valent titanium-containing oxides. Here, a core-shell nanoparticle made of TiO core covered with a ≈5 nm shell of amorphous TiO 1+ x is newly constructed via a controllable reduction method to synthesize nano TiO core and subsequent soft oxidation to form the shell (TiO 1+ x ). The physical properties measurements of electrical transport and magnetism indicate these TiO@TiO 1+ x nanocrystals are a type-ІІ superconductor of a recorded T c onset = 11 K in the binary Ti-O system. This unusual superconductivity could be attributed to the interfacial effect due to the nearly linear gradient of O/Ti ratio across the outer amorphous layer. This novel synthetic method and enhanced superconductivity could open up possibilities in interface superconductivity of nanostructured composites with well-controlled interfaces. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Well-Defined Nanostructured, Single-Crystalline TiO2 Electron Transport Layer for Efficient Planar Perovskite Solar Cells.

PubMed

Choi, Jongmin; Song, Seulki; Hörantner, Maximilian T; Snaith, Henry J; Park, Taiho

2016-06-28

An electron transporting layer (ETL) plays an important role in extracting electrons from a perovskite layer and blocking recombination between electrons in the fluorine-doped tin oxide (FTO) and holes in the perovskite layers, especially in planar perovskite solar cells. Dense TiO2 ETLs prepared by a solution-processed spin-coating method (S-TiO2) are mainly used in devices due to their ease of fabrication. Herein, we found that fatal morphological defects at the S-TiO2 interface due to a rough FTO surface, including an irregular film thickness, discontinuous areas, and poor physical contact between the S-TiO2 and the FTO layers, were inevitable and lowered the charge transport properties through the planar perovskite solar cells. The effects of the morphological defects were mitigated in this work using a TiO2 ETL produced from sputtering and anodization. This method produced a well-defined nanostructured TiO2 ETL with an excellent transmittance, single-crystalline properties, a uniform film thickness, a large effective area, and defect-free physical contact with a rough substrate that provided outstanding electron extraction and hole blocking in a planar perovskite solar cell. In planar perovskite devices, anodized TiO2 ETL (A-TiO2) increased the power conversion efficiency by 22% (from 12.5 to 15.2%), and the stabilized maximum power output efficiency increased by 44% (from 8.9 to 12.8%) compared with S-TiO2. This work highlights the importance of the ETL geometry for maximizing device performance and provides insights into achieving ideal ETL morphologies that remedy the drawbacks observed in conventional spin-coated ETLs.

Giant dielectric constant dominated by Maxwell-Wagner relaxation in Al{sub 2}O{sub 3}/TiO{sub 2} nanolaminates synthesized by atomic layer deposition.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, W.; Auciello, O.; Premnath, R. N.

2010-01-01

Nanolaminates consisting of Al{sub 2}O{sub 3} and TiO{sub 2} oxide sublayers were synthesized by using atomic layer deposition to produce individual layers with atomic scale thickness control. The sublayer thicknesses were kept constant for each multilayer structure, and were changed from 50 to 0.2 nm for a series of different samples. Giant dielectric constant ({approx}1000) was observed when the sublayer thickness is less than 0.5 nm, which is significantly larger than that of Al{sub 2}O{sub 3} and TiO{sub 2} dielectrics. Detailed investigation revealed that the observed giant dielectric constant is originated from the Maxwell-Wagner type dielectric relaxation.

Nanoscale self-templating for oxide epitaxy with large symmetry mismatch

DOE PAGES

Gao, Xiang; Lee, Shinbuhm; Nichols, John A.; ...

2016-12-02

Direct observations using scanning transmission electron microscopy unveil an intriguing interfacial bi-layer that enables epitaxial growth of a strain-free, monoclinic, bronze-phase VO 2(B) thin film on a perovskite SrTiO 3 (STO) substrate. For this study, we observe an ultrathin (2–3 unit cells) interlayer best described as highly strained VO 2(B) nanodomains combined with an extra (Ti,V)O 2 layer on the TiO 2 terminated STO (001) surface. By forming a fully coherent interface with the STO substrate and a semi-coherent interface with the strain-free epitaxial VO 2(B) film above, the interfacial bi-layer enables the epitaxial connection of the two materials despitemore » their large symmetry and lattice mismatch.« less

Influence of interface layer on optical properties of sub-20 nm-thick TiO2 films

NASA Astrophysics Data System (ADS)

Shi, Yue-Jie; Zhang, Rong-Jun; Li, Da-Hai; Zhan, Yi-Qiang; Lu, Hong-Liang; Jiang, An-Quan; Chen, Xin; Liu, Juan; Zheng, Yu-Xiang; Wang, Song-You; Chen, Liang-Yao

2018-02-01

The sub-20 nm ultrathin titanium dioxide (TiO2) films with tunable thickness were deposited on Si substrates by atomic layer deposition (ALD). The structural and optical properties were acquired by transmission electron microscopy, atomic force microscopy and spectroscopic ellipsometry. Afterwards, a constructive and effective method of analyzing interfaces by applying two different optical models consisting of air/TiO2/Ti x Si y O2/Si and air/effective TiO2 layer/Si, respectively, was proposed to investigate the influence of interface layer (IL) on the analysis of optical constants and the determination of band gap of TiO2 ultrathin films. It was found that two factors including optical constants and changing components of the nonstoichiometric IL could contribute to the extent of the influence. Furthermore, the investigated TiO2 ultrathin films of 600 ALD cycles were selected and then annealed at the temperature range of 400-900 °C by rapid thermal annealing. Thicker IL and phase transition cause the variation of optical properties of TiO2 films after annealing and a shorter electron relaxation time reveals the strengthened electron-electron and electron-phonon interactions in the TiO2 ultrathin films at high temperature. The as-obtained results in this paper will play a role in other studies of high dielectric constants materials grown on Si substrates and in the applications of next generation metal-oxide-semiconductor devices.

ALD TiO x as a top-gate dielectric and passivation layer for InGaZnO115 ISFETs

NASA Astrophysics Data System (ADS)

Pavlidis, S.; Bayraktaroglu, B.; Leedy, K.; Henderson, W.; Vogel, E.; Brand, O.

2017-11-01

The suitability of atomic layer deposited (ALD) titanium oxide (TiO x ) as a top gate dielectric and passivation layer for indium gallium zinc oxide (InGaZnO115) ion sensitive field effect transistors (ISFETs) is investigated. TiO x is an attractive barrier material, but reports of its use for InGaZnO thin film transistor (TFT) passivation have been conflicting thus far. In this work, it is found that the passivated TFT’s behavior depends on the TiO x deposition temperature, affecting critical device characteristics such as threshold voltage, field-effect mobility and sub-threshold swing. An O2 annealing step is required to recover TFT performance post passivation. It is also observed that the positive bias stress response of the passivated TFTs improves compared the original bare device. Secondary ion mass spectroscopy excludes the effects of hydrogen doping and inter-diffusion as sources of the temperature-dependent performance change, therefore indicating that oxygen gettering induced by TiO x passivation is the likely source of oxygen vacancies and, consequently, carriers in the InGaZnO film. It is also shown that potentiometric sensing using ALD TiO x exhibits a near Nernstian response to pH change, as well as minimizes V TH drift in TiO x passivated InGaZnO TFTs immersed in an acidic liquid. These results add to the understanding of InGaZnO passivation effects and underscore the potential for low-temperature fabricated InGaZnO ISFETs to be used as high-performance mobile chemical sensors.

Rational Design of Solution-Processed Ti-Fe-O Ternary Oxides for Efficient Planar CH3NH3PbI3 Perovskite Solar Cells with Suppressed Hysteresis.

PubMed

Li, Xin; Hao, Feng; Zhao, Xingyue; Yin, Xuewen; Yao, Zhibo; Guo, Ying; Shen, Heping; Lin, Hong

2017-10-11

Electron-extraction layer (EEL) plays a critical role in determining the charge extraction and the power conversion efficiencies of the organometal-halide perovskite solar cells (PSCs). In this work, Ti-Fe-O ternary oxides were first developed to work as an efficient EEL in planar PSC. Compared with the widely used TiO x and the pure FeO x , the ternary composites show superior properties in multiple aspects including the excellent stability of the precursor solution, good coverage on the substrates, outstanding electrical properties, and suitable energy levels. By varying the Fe content from 0 to 100% in the Ti-Fe-O composites, the conductivity of the resultant compact layer was markedly improved, confirmed by consistent results from the conductive atomic force microscopy and the linear sweep voltammetry measurements. Meanwhile, the compositional engineering tunes the energy level alignment of the Ti-Fe-O EEL/CH 3 NH 3 PbI 3 interface to a region that is favorable for obtaining excellent charge-extraction property. The combinational advantages of the Ti-Fe-O composites significantly improved the photovoltaic performance of the as-prepared solar cells. An increase of over 20% in the short-circuit current (J SC ) density has been achieved due to a modified EEL conductivity and energy alignment with the perovskite layer. The reduction in the surface recombination and enhancement of the charge collection efficiency also result in about 15% increase in the fill factor. Notably, the device also showed remarkably alleviated hysteresis behavior, revealing a prominently inhibited surface recombination.

Investigation of Corrosion Behavior of Ti/TiN Multilayers on Al7075 Deposited by High-Vacuum Magnetron Sputtering in 3.5% NaCl Solution

NASA Astrophysics Data System (ADS)

Molavi, Esfandiar; Shanaghi, Ali; Chu, Paul K.

2018-05-01

Although Al 7075 has many favorable mechanical properties such as the large strength-to-weight ratio, the relatively poor corrosion resistance has restricted industrial applications. In this work, Ti/TiN as hard multilayered and nanostructured coatings are deposited on the relatively soft Al 7075 structure by high-vacuum radio-frequency magnetron sputtering and the phase, structure, and morphology are investigated in details. The corrosion behavior is evaluated by electrochemical impedance spectroscopy in 3.5% NaCl at a pH of 7.5 for 1, 6, 12, 24, 36, 48, 60, and 72 h. At time points of 1, 6, 12, and 24 h, primary oxide layers and double layers are formed, but the corrosive medium penetrates the primary titanium nitride columnar structure. At longer time points of 24, 36, 48, 60, and 72 h, formation of stronger oxide and double layers leads to better corrosion resistance which is 14.8 times better than that observed from the uncoated substrate after immersion for 36 h. According to R ct, the corrosion resistances of the short and long immersion groups are 808.5-1984 and 808.5-1248 kΩ cm2, respectively, thereby confirming the effectiveness of the Ti/TiN coating against corrosion in comparison with the corrosion resistance of 84.3 kΩ cm2 observed from the uncoated Al 7075. The smallest corrosion resistance of 808.5 kΩ cm2 observed at the time point of 24 h is 9.6 times that of the uncoated substrate.

Enhanced performance of P3HT/(PCBM:ZnO:TiO{sub 2}) blend based hybrid organic solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikram, M., E-mail: mianraj.1981@gmail.com; Murray, R.; Imran, M.

Highlights: • We fabricated hybrid bulk heterojunction organic solar cells. • TiO{sub 2} and ZnO nanoparticles replace PCBM with fixed amount of P3HT in active layer • PCE was significantly improved by the introduction of TiO{sub 2} and ZnO. • A possible route toward low-cost OPV. • To the best of my knowledge, this work is the first time going to report. - Abstract: Quaternary blend hybrid organic solar cells enjoy both an increased light absorption range and an easy method to fabricate because of the simple structure. In this study effects of mixing inorganic metal oxides (ZnO and TiO{submore » 2}) nanoparticles to the active layer of organic photovoltaics devices were investigated. The active layer primarily consists of various ratios of electron donor poly (3-hexylthiophene) (P3HT) and an electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) together with nanostructured ZnO and TiO{sub 2} dispersed in chlorobenzene (CB) and 1,2-dichlorobenzene (DCB). The ratio of PCBM to nanoparticles was varied keeping the ratio of P3HT to acceptor material constant. Mixing of nanoparticle plays a significant role in the resulting power conversion efficiency (PCE) of the devices. An increased PCE for ZnO/TiO{sub 2} doped devices can be attributed to increased absorption in the visible region and enhanced charge collection due to the percolation networks formed by metal oxides nanoparticles.« less

Layer-by-Layer Molecular Assemblies for Dye-Sensitized Photoelectrosynthesis Cells Prepared by Atomic Layer Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Degao; Sheridan, Matthew V.; Shan, Bing

2017-08-30

In a Dye Sensitized Photoelectrosynthesis Cell (DSPEC) the relative orientation of catalyst and chromophore play important roles. Here we introduce a new, robust, Atomic Layer Deposition (ALD) procedure for the preparation of assemblies on wide bandgap semiconductors. In the procedure, phosphonated metal complex precursors react with metal ion bridging to an external chromophore or catalyst to give assemblies bridged by Al(III), Sn(IV), Ti(IV), or Zr(IV) metal oxide units as bridges. The procedure has been extended to chromophore-catalyst assemblies for water oxidation catalysis. A SnO2 bridged assembly on SnO2/TiO2 core/shell electrodes undergoes water splitting with an incident photon conversion efficiency (IPCE)more » of 17.1% at 440 nm. Reduction of water at a Ni(II)-based catalyst on NiO films has been shown to give H2. Compared to conventional solution-based procedures, the ALD approach offers significant advantages in scope and flexibility for the preparation of stable surface structures.« less

UiO-66-NH2 Metal-Organic Framework (MOF) Nucleation on TiO2, ZnO, and Al2O3 Atomic Layer Deposition-Treated Polymer Fibers: Role of Metal Oxide on MOF Growth and Catalytic Hydrolysis of Chemical Warfare Agent Simulants.

PubMed

Lee, Dennis T; Zhao, Junjie; Oldham, Christopher J; Peterson, Gregory W; Parsons, Gregory N

2017-12-27

Metal-organic frameworks (MOFs) chemically bound to polymeric microfibrous textiles show promising performance for many future applications. In particular, Zr-based UiO-66-family MOF-textiles have been shown to catalytically degrade highly toxic chemical warfare agents (CWAs), where favorable MOF/polymer bonding and adhesion are attained by placing a nanoscale metal-oxide layer on the polymer fiber preceding MOF growth. To date, however, the nucleation mechanism of Zr-based MOFs on different metal oxides and how product performance is affected are not well understood. Herein, we provide new insight into how different inorganic nucleation films (i.e., Al 2 O 3 , ZnO, or TiO 2 ) conformally coated on polypropylene (PP) nonwoven textiles via atomic layer deposition (ALD) influence the quality, overall surface area, and the fractional yield of UiO-66-NH 2 MOF crystals solvothermally grown on fiber substrates. Of the materials explored, we find that TiO 2 ALD layers lead to the most effective overall MOF/fiber adhesion, uniformity, and a rapid catalytic degradation rate for a CWA simulant, dimethyl p-nitrophenyl phosphate (DMNP) with t 1/2 = 15 min, 580-fold faster than the catalytic performance of untreated PP textiles. Interestingly, compared to ALD TiO 2 and Al 2 O 3 , ALD ZnO induces a larger MOF yield in solution and mass loading on PP fibrous mats. However, this larger MOF yield is ascribed to chemical instability of the ZnO layer under MOF formation condition, leading to Zn 2+ ions that promote further homogeneous MOF growth. Insights presented here improve understanding of compatibility between active MOF materials and substrate surfaces, which we believe will help advanced MOF composite materials for a variety of useful functions.

Zinc Oxide/TiO2 Bilayer Heterojunction as a Working Electrode in Quasi Solid Dye Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Aprilia, A.; Safriani, L.; Arsyad, Wa Ode S.; Syakir, N.; Susilawati, T.; Mulyana, C.; Fitrilawati; Hidayat, R.

2017-07-01

Bilayer heterojunction of aluminium doped zinc oxide (AZO) and titanium dioxide (TiO2) mesoporous has been successfully deposited on fluorine tin oxide (FTO) substrate as working electrode in dye sensitized solar cell. This layer was used as working electrode in quasi solid dye sensitized solar cell. The solar cell structure is FTO/ZnO/TiO2/PGE/Pt/FTO using polymer gel electrolyte (PGE). In polymer gel electrolyte system, hybrid copolymer based on poly-TMSPMA (3-methoxysilyl propyl methacrylate) was used as a matrix to trap ionic liquid. An addition of aluminum as atom dopant also studied to observe the physical properties changes of photoanode related to solar cell performance. AlCl3 was used as dopant material with the concentrations at 0.5 weight % and 1.0 weight% of zinc acetate dehydrate as raw material. Based on our previous result, the existence of Al dopant would decrease the surface roughness of ZnO layer, reduce the grain size of ZnO particles, transmittance at visible light increase and also change the charge carrier density. Nevertheless, the highest efficiency was achieved for undoped ZnO/TiO2 photoanode (η=0.67%). Based on current-voltage measurement data analysis (using diode model equation) the ideality factor (n) of device using undoped ZnO was smaller (n=2.96) than AZO 0.5 wt% and 1.0 wt% (n=∼4), indicate better quality of undoped ZnO/TiO2 interfaces rather than AZO/TiO2.

A novel anti-frictional multiphase layer produced by plasma nitriding of PVD titanium coated ZL205A aluminum alloy

NASA Astrophysics Data System (ADS)

Lu, C.; Yao, J. W.; Wang, Y. X.; Zhu, Y. D.; Guo, J. H.; Wang, Y.; Fu, H. Y.; Chen, Z. B.; Yan, M. F.

2018-02-01

The heat treatment (consisting of solid solution and aging), is integrated with the nitriding process of titanium coated ZL205A aluminum alloy to improve the surface and matrix mechanical properties simultaneously. Two-step duplex treatment is adopted to prepare the gradient multiphase layer on a magnesium-free ZL205A aluminum-copper based alloy. Firstly, pure titanium film is deposited on the aluminum alloy substrate using magnetron sputtering. Secondly, the Ti-coated specimen is nitrided at the solid solution temperature of the substrate alloying elements in a gas mixture of N2 and H2 and aged at 175 °C. The microstructure evolution, microhardness as well as the wear resistance of obtained multiphase layers are investigated by means of scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), microhardness tester and pin-on-disc tribometer. The multiphase layer, dominated by TiN0.3 or Al3Ti, is prepared with significantly increased layer depth after duplex treatment. The surface hardness of multiphase layer is remarkably improved from 23.7HV to 457HV. The core matrix hardness is also increased to 65HV after aging. The wear rate of the multiphase layer decreases about 55.22% and 49.28% in comparison with the aged and Ti coated specimens, respectively. The predominant wear mechanism for the multiphase layer is abrasive and oxidation, but severe adhesive wear for the aged and Ti coated specimens.

Tea Polyphenol-Reduced Graphene Oxide Deposition on Titanium Surface Enhances Osteoblast Bioactivity.

PubMed

Liu, Mengting; Hao, Liying; Huang, Qian; Zhao, Dan; Li, Qianshun; Cai, Xiaoxiao

2018-05-01

Graphene, a novel carbon-based material, has been widely used as osteogenic agent for the potential effect on the promotion of osteoblast proliferation. Tea polyphenol-reduced graphene oxide (TPG) is a simple and environmental-friendly raw material to obtain graphene. In this study, TPG was deposited on the Ti substrate to promote the bone regeneration. We prepared a honeycomb-like structure by acid and alkali pretreatment and immobilized the TPG layer (Ti-TPG) on the surface via electrochemical deposition. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) were used to identify the immobilization of TPG on the titanium (Ti) successfully. Furthermore, the biological response of the Ti-TPG surface to rat osteoblast was evaluated. We also studied the cell adhesion, proliferation and expression of ossification genes on the sample. The results revealed that Ti-TPG had an advantage over Ti alloys in modulating cellular activity and Ti-TPG may be a promising coating for biological materials.

Reduced thermal conductivity by nanoscale intergrowths in perovskite like layered structure La{sub 2}Ti{sub 2}O{sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khaliq, Jibran; Chen, Kan; Li, Chunchun

2015-02-21

The effect of substitution and oxidation-reduction on the thermal conductivity of perovskite-like layered structure (PLS) ceramics was investigated in relation to mass contrast and non-stoichiometry. Sr (acceptor) was substituted on the A site, while Ta (donor) was substituted on the B site of La{sub 2}Ti{sub 2}O{sub 7}. Substitution in PLS materials creates atomic scale disorders to accommodate the non-stoichiometry. High resolution transmission electron microscopy and X ray diffraction revealed that acceptor substitution in La{sub 2}Ti{sub 2}O{sub 7} produced nanoscale intergrowths of n = 5 layered phase, while donor substitution produced nanoscale intergrowths of n = 3 layered phase. As a result of these nanoscalemore » intergrowths, the thermal conductivity value reduced by as much as ∼20%. Pure La{sub 2}Ti{sub 2}O{sub 7} has a thermal conductivity value of ∼1.3 W/m K which dropped to a value of ∼1.12 W/m K for Sr doped La{sub 2}Ti{sub 2}O{sub 7} and ∼0.93 W/m K for Ta doped La{sub 2}Ti{sub 2}O{sub 7} at 573 K.« less

Ab Initio Study of the Atomic Level Structure of the Rutile TiO2(110)-Titanium Nitride (TiN) Interface.

PubMed

Gutiérrez Moreno, José Julio; Nolan, Michael

2017-11-01

Titanium nitride (TiN) is widely used in industry as a protective coating due to its hardness and resistance to corrosion and can spontaneously form a thin oxide layer when it is exposed to air, which could modify the properties of the coating. With limited understanding of the TiO 2 -TiN interfacial system at present, this work aims to describe the structural and electronic properties of oxidized TiN based on a density functional theory (DFT) study of the rutile TiO 2 (110)-TiN(100) interface model system, also including Hubbard +U correction on Ti 3d states. The small lattice mismatch gives a good stability to the TiO 2 -TiN interface after depositing the oxide onto TiN through the formation of interfacial Ti-O bonds. Our DFT+U study shows the presence of Ti 3+ cations in the TiO 2 region, which are preferentially located next to the interface region as well as the rotation of the rutile TiO 2 octahedra in the interface structure. The DFT+U TiO 2 electronic density of states (EDOS) shows localized Ti 3+ defect states forming in the midgap between the top edge of the valence and the bottom of the conduction band. We increase the complexity of our models by the introduction of nonstoichiometric compositions. Although the vacancy formation energies for Ti in TiN (E vac (Ti) ≥ 4.03 eV) or O in the oxide (E vac (O) ≥ 3.40 eV) are quite high relative to perfect TiO 2 -TiN, defects are known to form during the oxide growth and can therefore be present after TiO 2 formation. Our results show that a structure with exchanged O and N can lie 0.82 eV higher in energy than the perfect system, suggesting the stability of structures with interdiffused O and N anions at ambient conditions. The presence of N in TiO 2 introduces N 2p states localized between the top edge of the O 2p valence states and the midgap Ti 3+ 3d states, thus reducing the band gap in the TiO 2 region for the exchanged O/N interface EDOS. The outcomes of these simulations give us a most comprehensive insight on the atomic level structure and the electronic properties of oxidized TiN surfaces.

Enhanced fatigue performance of porous coated Ti6Al4V biomedical alloy

NASA Astrophysics Data System (ADS)

Apachitei, I.; Leoni, A.; Riemslag, A. C.; Fratila-Apachitei, L. E.; Duszczyk, J.

2011-05-01

Biofunctional coatings are necessary to improve integration of titanium implants in the host tissue but they may be detrimental for the implant fatigue properties. This study presents an attempt towards enhancement of the in vitro fatigue strength of plasma electrolytic oxidation coated Ti6Al4V alloy by applying shot peening process prior to coating. The electrolytic oxidation was performed in calcium acetate and calcium glycerophosphate electrolytes that allowed formation of porous oxide coatings with high surface free energy and apatite like ability. A deformed surface layer coupled with induced residual compressive stresses seem to affect oxide growth rate and fatigue behavior of the titanium alloy.

Superlattice assembly of graphene oxide (GO) and titania nanosheets: fabrication, in situ photocatalytic reduction of GO and highly improved carrier transport

NASA Astrophysics Data System (ADS)

Cai, Xingke; Ma, Renzhi; Ozawa, Tadashi C.; Sakai, Nobuyuki; Funatsu, Asami; Sasaki, Takayoshi

2014-11-01

Two different kinds of two-dimensional (2D) materials, graphene oxide (GO) and titanium oxide nanosheets (Ti0.87O20.52-), were self-assembled layer-by-layer using a polycation as a linker into a superlattice film. Successful construction of an alternate molecular assembly was confirmed by atomic force microscopy and UV-visible absorption spectroscopy as well as X-ray diffraction analysis. Exposure of the resulting film to UV light effectively promoted photocatalytic reduction of GO as well as decomposition of the polycation, which are due to their intimate molecular-level contact. The reduction completed within 3 hours, bringing about a decrease of the sheet resistance by ~106. This process provides a clean and mild route to reduced graphene oxide (rGO), showing advantages over other chemical and thermal reduction processes. A field-effect-transistor device was fabricated using the resulting superlattice assembly of rGO/Ti0.87O20.52- as a channel material. The rGO in the film was found to work as a unipolar n-type conductor, which is in contrast to ambipolar or unipolar p-type behavior mostly reported for rGO films. This unique property may be associated with the electron doping effect from Ti0.87O20.52- nanosheets. A significant improvement in the conductance and electron carrier mobility by more than one order of magnitude was revealed, which may be accounted for by the heteroassembly with Ti0.87O20.52- nanosheets with a high dielectric constant as well as the better 2D structure of rGO produced via the soft photocatalytic reduction.Two different kinds of two-dimensional (2D) materials, graphene oxide (GO) and titanium oxide nanosheets (Ti0.87O20.52-), were self-assembled layer-by-layer using a polycation as a linker into a superlattice film. Successful construction of an alternate molecular assembly was confirmed by atomic force microscopy and UV-visible absorption spectroscopy as well as X-ray diffraction analysis. Exposure of the resulting film to UV light effectively promoted photocatalytic reduction of GO as well as decomposition of the polycation, which are due to their intimate molecular-level contact. The reduction completed within 3 hours, bringing about a decrease of the sheet resistance by ~106. This process provides a clean and mild route to reduced graphene oxide (rGO), showing advantages over other chemical and thermal reduction processes. A field-effect-transistor device was fabricated using the resulting superlattice assembly of rGO/Ti0.87O20.52- as a channel material. The rGO in the film was found to work as a unipolar n-type conductor, which is in contrast to ambipolar or unipolar p-type behavior mostly reported for rGO films. This unique property may be associated with the electron doping effect from Ti0.87O20.52- nanosheets. A significant improvement in the conductance and electron carrier mobility by more than one order of magnitude was revealed, which may be accounted for by the heteroassembly with Ti0.87O20.52- nanosheets with a high dielectric constant as well as the better 2D structure of rGO produced via the soft photocatalytic reduction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04830j

Engineering correlation effects via artificially designed oxide superlattices.

PubMed

Chen, Hanghui; Millis, Andrew J; Marianetti, Chris A

2013-09-13

Ab initio calculations are used to predict that a superlattice composed of layers of LaTiO3 and LaNiO3 alternating along the [001] direction is a S=1 Mott insulator with large magnetic moments on the Ni sites, negligible moments on the Ti sites and a charge transfer gap set by the energy difference between Ni d and Ti d states, distinct from conventional Mott insulators. Correlation effects are enhanced on the Ni sites via filling the oxygen p states and reducing the Ni-O-Ni bond angle. Small hole (electron) doping of the superlattice leads to a two-dimensional single-band situation with holes (electrons) residing on the Ni d(x2-y2) (Ti d(xy)) orbital and coupled to antiferromagnetically correlated spins in the NiO2 layer.

Engineering Correlation Effects via Artificially Designed Oxide Superlattices

NASA Astrophysics Data System (ADS)

Chen, Hanghui; Millis, Andrew J.; Marianetti, Chris A.

2013-09-01

Ab initio calculations are used to predict that a superlattice composed of layers of LaTiO3 and LaNiO3 alternating along the [001] direction is a S=1 Mott insulator with large magnetic moments on the Ni sites, negligible moments on the Ti sites and a charge transfer gap set by the energy difference between Ni d and Ti d states, distinct from conventional Mott insulators. Correlation effects are enhanced on the Ni sites via filling the oxygen p states and reducing the Ni-O-Ni bond angle. Small hole (electron) doping of the superlattice leads to a two-dimensional single-band situation with holes (electrons) residing on the Ni dx2-y2 (Ti dxy) orbital and coupled to antiferromagnetically correlated spins in the NiO2 layer.

Production and Precipitation Hardening of Beta-Type Ti-35Nb-10Cu Alloy Foam for Implant Applications

NASA Astrophysics Data System (ADS)

Mutlu, Ilven; Yeniyol, Sinem; Oktay, Enver

2016-04-01

In this study, beta-type Ti-35Nb-10Cu alloy foams were produced by powder metallurgy method for dental implant applications. 35% Nb was added to stabilize the beta-Ti phase with low Young's modulus. Cu addition enhanced sinterability and gave precipitation hardening capacity to the alloy. Sintered specimens were precipitation hardened in order to enhance the mechanical properties. Electrochemical corrosion behavior of the specimens was examined by electrochemical impedance spectroscopy in artificial saliva. Electrochemical impedance spectroscopy results indicated that the oxide film on the surface of foam is a bi-layer structure consisting of outer porous layer and inner barrier layer. Impedance values of barrier layer were higher than porous layer. Corrosion resistance of specimens decreased at high fluoride concentrations and at low pH of artificial saliva. Corrosion resistance of alloys was slightly decreased with aging. Mechanical properties, microstructure, and surface roughness of the specimens were also examined.

Bioactivity of self-organized TiO2 nanotubes used as surface treatment on Ti biomaterials

NASA Astrophysics Data System (ADS)

Souza, M. R.; Reyes, K. M.; Oliveira, N. T. C.; Kuromoto, N. K.; Marino, C. E. B.

2016-03-01

Titanium and its alloys are widely used as implants due to their excellent mechanical properties, corrosion resistance and biocompatibility. TiO2 nanotubes have been studied as surface treatment to increase the specific area and to improve osseointegration. However, the thermodynamic stability and bioactivity of these nanostructures must be evaluated. The objective of this research was to obtain nanotubes oxides on Ti6Al4V alloy and to analyze the electrochemical stability in physiological solution at 37 °C and the bioactive response of the biomaterial. The nanotubes were obtained by potentiostatic anodization. The morphology of the oxides was evaluated by scanning electron microscopy. The chemical characterization was analyzed by energy dispersive spectroscopy and x-ray photoelectron spectroscopy techniques. The electrochemical stability was analyzed by open circuit potential (OCP) and the bioactivity by biomimetic test in a simulated body fluid (SBF) solution. The OCP of the nanotubes oxides was shown to be more noble and stable than the compacted oxides. The biomaterial covered with theses oxides showed sealing by Ca and P after 30 d immersion in artificial blood. And after 15 d of immersion in SBF, the hydroxyapatite could be seen on the non-sealed nanotubes. TiO2 nanotube layers could improve the superficial chemical stability and also the osseointegration process.

Micro arc oxidized HAp-TiO 2 nanostructured hybrid layers-part I: Effect of voltage and growth time

NASA Astrophysics Data System (ADS)

Abbasi, S.; Bayati, M. R.; Golestani-Fard, F.; Rezaei, H. R.; Zargar, H. R.; Samanipour, F.; Shoaei-Rad, V.

2011-05-01

Micro arc oxidation was employed to grow hydroxyapatite-TiO 2 nanostructured porous composite layers. The layers were synthesized on the titanium substrates in the electrolytes consisting of calcium acetate and sodium β-glycerophosphate salts under different applied voltages for various times. SEM and AFM investigations revealed a porous structure and rough surface where the pores size and the surface roughness were respectively determined as 70-650 nm and 9.8-12.7 nm depending on the voltage and time. Chemical composition and phase structure of the layers were evaluated using EDX, XPS, and XRD methods. The layers consisted of the hydroxyapatite, anatase, α-TCP, and calcium titanatephases with a varying fraction depending on the growth conditions. The hydroxyapatite crystalline size was also determined as ˜42 nm. The sample fabricated under the voltage of 350 V for 3 min exhibited the most appropriate Ca/P ratio (˜1.60) as well as the highest amount of the hydroxyapatite phase. This sample had a fine surface morphology and a high pores density.

The genesis of the newly discovered giant Wuben magmatic Fe-Ti oxide deposit in the Emeishan Large Igneous Province: a product of the late-stage redistribution and sorting of crystal slurries

NASA Astrophysics Data System (ADS)

Bai, Zhong-Jie; Zhong, Hong; Zhu, Wei-Guang; Hu, Wen-Jun; Chen, Cai-Jie

2018-04-01

A giant Fe-Ti oxide deposit hosted by the Wuben mafic intrusion has recently been discovered in the Pan-Xi area of the Emeishan Large Igneous Province (ELIP). The evolved compositions of the gangue minerals within the Fe-Ti oxide ores indicate that they formed during later stages of magma differentiation than those within the neighboring Panzhihua intrusion or other ore-bearing intrusions in this area. The rocks from the Wuben intrusion and MZb of the Panzhihua intrusion contain compositionally similar silicate minerals and have similar titanomagnetite/ilmenite ratios, suggesting that the former is related to and probably connected to the latter by subsurface magmatic conduits. This indicates that unconsolidated minerals that formed in the MZb flowed as crystal slurries into the Wuben magma chamber during the later stages of evolution of the parental magma. The later secondary enrichment of Fe-Ti oxides by mechanical redistribution and the sorting of crystals as a result of density and size differences generated the Wuben massive Fe-Ti oxide bodies. The ilmenite was commonly saturated in the magma at late stage of differentiation in the ELIP, thereby the associated deposit contains much higher contents of ilmenite. This indicates that future exploration for Fe-Ti oxide mineralization in the ELIP should not merely focus on the lower parts of large layered intrusions but should also include nearby relatively small intrusions or even the upper parts of large intrusions, especially as ilmenite-enriched Fe-Ti oxide deposits may have greater economic value than ilmenite-poor deposits.

Biaxially textured composite substrates

DOEpatents

Groves, James R.; Foltyn, Stephen R.; Arendt, Paul N.

2005-04-26

An article including a substrate, a layer of a metal phosphate material such as an aluminum phosphate material upon the surface of the substrate, and a layer of an oriented cubic oxide material having a rock-salt-like structure upon the metal phosphate material layer is provided together with additional layers such as a HTS top-layer of YBCO directly upon a layer of a buffer material such as a SrTi.sub.x Ru.sub.1-x O.sub.3 layer.

Nanometer-resolved chemical analyses of femtosecond laser-induced periodic surface structures on titanium

NASA Astrophysics Data System (ADS)

Kirner, Sabrina V.; Wirth, Thomas; Sturm, Heinz; Krüger, Jörg; Bonse, Jörn

2017-09-01

The chemical characteristics of two different types of laser-induced periodic surface structures (LIPSS), so-called high and low spatial frequency LIPSS (HSFL and LSFL), formed upon irradiation of titanium surfaces by multiple femtosecond laser pulses in air (30 fs, 790 nm, 1 kHz), are analyzed by various optical and electron beam based surface analytical techniques, including micro-Raman spectroscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The latter method was employed in a high-resolution mode being capable of spatially resolving even the smallest HSFL structures featuring spatial periods below 100 nm. In combination with an ion sputtering technique, depths-resolved chemical information of superficial oxidation processes was obtained, revealing characteristic differences between the two different types of LIPSS. Our results indicate that a few tens of nanometer shallow HSFL are formed on top of a ˜150 nm thick graded superficial oxide layer without sharp interfaces, consisting of amorphous TiO2 and partially crystallized Ti2O3. The larger LSFL structures with periods close to the irradiation wavelength originate from the laser-interaction with metallic titanium. They are covered by a ˜200 nm thick amorphous oxide layer, which consists mainly of TiO2 (at the surface) and other titanium oxide species of lower oxidation states underneath.

S-TiO2/S-reduced graphene oxide for enhanced photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Elbakkay, Mohamed H.; El Rouby, Waleed M. A.; El-Dek, S. I.; Farghali, Ahmed A.

2018-05-01

Sulfur-doped titanium oxide on the surface of sulfur-doped reduced graphene oxide nanocomposites (S-TiO2/S-RGO) were successfully synthesized for the first time through a simple low cost solvothermal reaction process. The sulfur doping was detected in both TiO2 matrix and carbon framework structure of reduced graphene oxide using X-ray photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX). Cross-sectional AFM analysis of S-RGO nanosheets reveals a thickness of 0.51 nm which is much thinner than those previously reported of heteroatom doped-RGO, confirming the single-layer feature. When the as-prepared (S-TiO2/S-RGO) nanocomposites are utilized as photoanodes for photoelectrochemical (PEC) water splitting, they exhibited an enhanced photoelectrochemical performance and long-term stability. The photocurrent density of S-TiO2/S-RGO(0.2) photoanode revealed 3.36 mA/cm2 at 1 V vs Ag/AgCl which is considered 3 times compared to bare synthesized TiO2. This improvement in the photocurrent density was attributed to the increased separation rate of photogenerated electrons and holes and efficient visible light harvesting as a result of the successful combination of the S-TiO2 and the S-RGO in the same nanocomposite photoanode. This promising result presents a new approach for the synthesis of high-efficient future metal-free photoelectrocatalysts.

Improvement of the photovoltaic parameters of perovskite solar cells using a reduced-graphene-oxide-modified titania layer and soluble copper phthalocyanine as a hole transporter.

PubMed

Nouri, Esmaiel; Mohammadi, Mohammad Reza; Xu, Zong-Xiang; Dracopoulos, Vassilios; Lianos, Panagiotis

2018-01-24

Functional perovskite solar cells can be made by using a simple, inexpensive and stable soluble tetra-n-butyl-substituted copper phthalocyanine (CuBuPc) as a hole transporter. In the present study, TiO 2 /reduced graphene oxide (T/RGO) hybrids were synthesized via an in situ solvothermal process and used as electron acceptor/transport mediators in mesoscopic perovskite solar cells based on soluble CuBuPc as a hole transporter and on graphene oxide (GO) as a buffer layer. The impact of the RGO content on the optoelectronic properties of T/RGO hybrids and on the solar cell performance was studied, suggesting improved electron transport characteristics and photovoltaic parameters. An enhanced electron lifetime and recombination resistance led to an increase in the short circuit current density, open circuit voltage and fill factor. The device based on a T/RGO mesoporous layer with an optimal RGO content of 0.2 wt% showed 22% higher photoconversion efficiency and higher stability compared with pristine TiO 2 -based devices.

Effect of alloy chemistry and exposure conditions on the oxidation of titanium

NASA Technical Reports Server (NTRS)

Unnam, J.; Shenoy, R. N.; Clark, R. K.

1984-01-01

Multiwall is a new thermal protection system concept for advanced space transportation vehicles. The system consists of discrete panels made up of multiple layers of foil gage metal. Titanium is the proposed candidate metal for multiwall panels in the reentry temperature range up to 675 C. Oxidation and embrittlement are the principal concerns related to the use of Ti in heat shield applications. The results of a broad study on the oxidation kinetics of several titanium alloys subjected to different exposure conditions are described. The alloys include commercially pure titanium, Ti-6Al-4V, and Ti-6Al-2Sn-4Zr-2Mo. Oxidation studies were performed on these alloys exposed at 704 C in 5-760 torr air pressure and 0 to 50% relative humidity. The resulting weight gains were correlated with oxide thickness and substrate contamination. The contamination depth and weight gains due to solid solutioning were obtained from microhardness depth profiles and hardness versus weight percent oxygen calibration data.

Recent progress in oxide thermoelectric materials: p-type Ca3Co4O9 and n-type SrTiO3(-).

PubMed

Ohta, Hiromichi; Sugiura, Kenji; Koumoto, Kunihito

2008-10-06

Thermoelectric energy conversion technology to convert waste heat into electricity has received much attention. In addition, metal oxides have recently been considered as thermoelectric power generation materials that can operate at high temperatures on the basis of their potential advantages over heavy metallic alloys in chemical and thermal robustness. We have fabricated high-quality epitaxial films composed of oxide thermoelectric materials that are suitable for clarifying the intrinsic "real" properties. This review focuses on the thermoelectric properties of two representative oxide epitaxial films, p-type Ca 3Co 4O 9 and n-type SrTiO 3, which exhibit the best thermoelectric figures of merit, ZT (= S (2)sigma Tkappa (-1), S = Seebeck coefficient, sigma = electrical conductivity, kappa = thermal conductivity, and T = absolute temperature) among oxide thermoelectric materials reported to date. In addition, we introduce the recently discovered giant S of two-dimensional electrons confined within a unit cell layer thickness ( approximately 0.4 nm) of SrTiO 3.

Monitoring N3 dye adsorption and desorption on TiO2 surfaces: a combined QCM-D and XPS study.

PubMed

Wayment-Steele, Hannah K; Johnson, Lewis E; Tian, Fangyuan; Dixon, Matthew C; Benz, Lauren; Johal, Malkiat S

2014-06-25

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

Novel Montmorillonite/TiO₂/MnAl-Mixed Oxide Composites Prepared from Inverse Microemulsions as Combustion Catalysts.

PubMed

Napruszewska, Bogna D; Michalik-Zym, Alicja; Rogowska, Melania; Bielańska, Elżbieta; Rojek, Wojciech; Gaweł, Adam; Wójcik-Bania, Monika; Bahranowski, Krzysztof; Serwicka, Ewa M

2017-11-19

A novel design of combustion catalysts is proposed, in which clay/TiO₂/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts' thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N₂ adsorption/desorption at -196 °C, and H₂ TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO₂ component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH₃ (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO₂/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO₂/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials' composition and their structural, textural, and redox properties.

Atomic layer deposition TiO 2-Al 2O 3 stack: An improved gate dielectric on Ga-polar GaN metal oxide semiconductor capacitors

DOE PAGES

Wei, Daming; Edgar, James H.; Briggs, Dayrl P.; ...

2014-10-15

This research focuses on the benefits and properties of TiO 2-Al 2O 3 nano-stack thin films deposited on Ga 2O 3/GaN by plasma-assisted atomic layer deposition (PA-ALD) for gate dielectric development. This combination of materials achieved a high dielectric constant, a low leakage current, and a low interface trap density. Correlations were sought between the films’ structure, composition, and electrical properties. The gate dielectrics were approximately 15 nm thick and contained 5.1 nm TiO 2, 7.1 nm Al 2O 3 and 2 nm Ga 2O 3 as determined by spectroscopic ellipsometry. The interface carbon concentration, as measured by x-ray photoelectronmore » spectroscopy (XPS) depth profile, was negligible for GaN pretreated by thermal oxidation in O 2 for 30 minutes at 850°C. The RMS roughness slightly increased after thermal oxidation and remained the same after ALD of the nano-stack, as determined by atomic force microscopy. The dielectric constant of TiO 2-Al 2O 3 on Ga2O3/GaN was increased to 12.5 compared to that of pure Al 2O 3 (8~9) on GaN. In addition, the nano-stack's capacitance-voltage (C-V) hysteresis was small, with a total trap density of 8.74 × 10 11 cm -2. The gate leakage current density (J=2.81× 10 -8 A/cm 2) was low at +1 V gate bias. These results demonstrate the promising potential of plasma ALD deposited TiO 2/Al 2O 3 for serving as the gate oxide on Ga 2O 3/GaN based MOS devices.« less

Atomic layer deposition TiO 2-Al 2O 3 stack: An improved gate dielectric on Ga-polar GaN metal oxide semiconductor capacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Daming; Edgar, James H.; Briggs, Dayrl P.

This research focuses on the benefits and properties of TiO 2-Al 2O 3 nano-stack thin films deposited on Ga 2O 3/GaN by plasma-assisted atomic layer deposition (PA-ALD) for gate dielectric development. This combination of materials achieved a high dielectric constant, a low leakage current, and a low interface trap density. Correlations were sought between the films’ structure, composition, and electrical properties. The gate dielectrics were approximately 15 nm thick and contained 5.1 nm TiO 2, 7.1 nm Al 2O 3 and 2 nm Ga 2O 3 as determined by spectroscopic ellipsometry. The interface carbon concentration, as measured by x-ray photoelectronmore » spectroscopy (XPS) depth profile, was negligible for GaN pretreated by thermal oxidation in O 2 for 30 minutes at 850°C. The RMS roughness slightly increased after thermal oxidation and remained the same after ALD of the nano-stack, as determined by atomic force microscopy. The dielectric constant of TiO 2-Al 2O 3 on Ga2O3/GaN was increased to 12.5 compared to that of pure Al 2O 3 (8~9) on GaN. In addition, the nano-stack's capacitance-voltage (C-V) hysteresis was small, with a total trap density of 8.74 × 10 11 cm -2. The gate leakage current density (J=2.81× 10 -8 A/cm 2) was low at +1 V gate bias. These results demonstrate the promising potential of plasma ALD deposited TiO 2/Al 2O 3 for serving as the gate oxide on Ga 2O 3/GaN based MOS devices.« less

Iron(III)-oxo centers on TiO{sub 2} for visible light photocatalysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Libera, J. A.; Elam, J. W.; Sather, N. F.

Isolated iron(III)-oxo clusters were synthesized onto TiO{sub 2} using atomic layer deposition. The Fe{sub x}O{sub y}/TiO{sub 2} nanocomposites have unique properties that enable not only absorption of visible light, but efficient photocatalysis as demonstrated by methylene blue degradation. The localization of photogenerated electrons in core TiO{sub 2} nanocrystallites upon visible light excitation demonstrates coupling of conduction bands of mixed oxides. The redox properties of photogenerated charges in nanocomposites were studied using in situ electron paramagnetic resonance spectroscopy.

Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

DOE PAGES

Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke; ...

2016-04-27

Here, we report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Moreover, transport measurements of exfoliated graphene, after SrO deposition, show a strong dependence between the Dirac point and Sr oxidation. As a result, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

Molecular beam epitaxy growth of SrO buffer layers on graphite and graphene for the integration of complex oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, Adam S.; Wen, Hua; Ohta, Taisuke

Here, we report the successful growth of high-quality SrO films on highly-ordered pyrolytic graphite (HOPG) and single-layer graphene by molecular beam epitaxy. The SrO layers have (001) orientation as confirmed by X-ray diffraction (XRD) while atomic force microscopy measurements show continuous pinhole-free films having rms surface roughness of <1.5 Å. Moreover, transport measurements of exfoliated graphene, after SrO deposition, show a strong dependence between the Dirac point and Sr oxidation. As a result, the SrO is leveraged as a buffer layer for more complex oxide integration via the demonstration of (001) oriented SrTiO3 grown atop a SrO/HOPG stack.

Observation of nanometer-sized electro-active defects in insulating layers by fluorescence microscopy and electrochemistry.

PubMed

Renault, Christophe; Marchuk, Kyle; Ahn, Hyun S; Titus, Eric J; Kim, Jiyeon; Willets, Katherine A; Bard, Allen J

2015-06-02

We report a method to study electro-active defects in passivated electrodes. This method couples fluorescence microscopy and electrochemistry to localize and size electro-active defects. The method was validated by comparison with a scanning probe technique, scanning electrochemical microscopy. We used our method for studying electro-active defects in thin TiO2 layers electrodeposited on 25 μm diameter Pt ultramicroelectrodes (UMEs). The permeability of the TiO2 layer was estimated by measuring the oxidation of ferrocenemethanol at the UME. Blocking of current ranging from 91.4 to 99.8% was achieved. Electro-active defects with an average radius ranging between 9 and 90 nm were observed in these TiO2 blocking layers. The distribution of electro-active defects over the TiO2 layer is highly inhomogeneous and the number of electro-active defect increases for lower degree of current blocking. The interest of the proposed technique is the possibility to quickly (less than 15 min) image samples as large as several hundreds of μm(2) while being able to detect electro-active defects of only a few tens of nm in radius.

Oxidation and alpha-case formation in Ti–6Al–2Sn–4Zr–2Mo alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaddam, Raghuveer, E-mail: raghuveer.gaddam@ltu.se; Sefer, Birhan; Pederson, Robert

2015-01-15

Isothermal heat treatments in ambient air were performed on wrought Ti–6Al–2Sn–4Zr–2Mo (Ti-6242) material at 500, 593 and 700°C for times up to 500 h. In the presence of oxygen at elevated temperatures simultaneous reactions occurred in Ti-6242 alloy, which resulted in the formation of an oxide scale and a layer with higher oxygen concentration (termed as alpha-case). Total weight gain analysis showed that there was a transition in the oxidation kinetics. At 500°C, the oxidation kinetics obeyed a cubic relationship up to 200 h and thereafter changed to parabolic at prolonged exposure times. At 593°C, it followed a parabolic relationship.more » After heat treatment at 700°C, the oxidation obeyed a parabolic relationship up to 200 h and thereafter changed to linear at prolonged exposure times. The observed transition is believed to be due to the differences observed in the oxide scale. The activation energy for parabolic oxidation was estimated to be 157 kJ/mol. In addition, alpha-case layer was evaluated using optical microscope, electron probe micro-analyser and microhardness tester. The thickness of the alpha-case layer was found to be a function of temperature and time, increasing proportionally, and following a parabolic relationship. The activation energy for the formation of alpha-case layer was estimated to be 153 kJ/mol. - Highlights: • Transition in oxidation kinetics was observed in Ti–6Al–2Sn–4Zr–2Mo alloy in the temperature range 500–700°C. • The activation energy for parabolic oxidation and for alpha-case formation is about 157 kJ/mol and 153 kJ/mol. • Thickness of alpha-case layer estimated by optical microscopy and electron probe microanalysis is comparable.« less

Titanium magnetic polarization at the Fe/BaTiO3 interfaces: An effect of ferroelectric polarization discontinuity

NASA Astrophysics Data System (ADS)

Paul, Amitesh; Zheng, Jian-Guo; Aoki, Toshihiro

2017-10-01

The exotic magnetic phenomena and the associated functionalities have attracted extensive scientific interest in fundamental physics and cater to the purpose of the novel material search. In this article, with a combination of the electron energy-loss spectroscopy and the X-ray absorption spectroscopy, we have investigated the interfacial Fe atoms and the induced ferromagnetic moment of Ti atoms in Fe/BaTiO3 (BTO) heterostructures. The samples were grown with two different BTO thicknesses, thus resulting in two different states of distorted oxygen environments or different electrostatic potentials. We demonstrate that in these systems, the electronic and magnetic proximity effects remain coupled as the ferroelectric polar discontinuity is held responsible for an induced transfer of the interface electrons. These electrons migrate from the Fe2+ layers to the Ti(4+)-δ layers with the hybridization via O-2p oxide orbitals into Ti orbitals to screen the ferroelectric polarization. These findings, in charge neutral BaO-TiO2 and FeO layers or nonpolar/nopolar interface, essentially underline the central role of the covalent bonding in defining the spin-electronic properties.

C@SiNW/TiO2 Core-Shell Nanoarrays with Sandwiched Carbon Passivation Layer as High Efficiency Photoelectrode for Water Splitting

PubMed Central

Devarapalli, Rami Reddy; Debgupta, Joyashish; Pillai, Vijayamohanan K.; Shelke, Manjusha V.

2014-01-01

One-dimensional heterostructure nanoarrays are efficiently promising as high performance electrodes for photo electrochemical (PEC) water splitting applications, wherein it is highly desirable for the electrode to have a broad light absorption, efficient charge separation and redox properties as well as defect free surface with high area suitable for fast interfacial charge transfer. We present highly active and unique photoelectrode for solar H2 production, consisting of silicon nanowires (SiNWs)/TiO2 core-shell structures. SiNWs are passivated to reduce defect sites and protected against oxidation in air or water by forming very thin carbon layer sandwiched between SiNW and TiO2 surfaces. This carbon layer decreases recombination rates and also enhances the interfacial charge transfer between the silicon and TiO2. A systematic investigation of the role of SiNW length and TiO2 thickness on photocurrent reveals enhanced photocurrent density up to 5.97 mA/cm2 at 1.0 V vs.NHE by using C@SiNW/TiO2 nanoarrays with photo electrochemical efficiency of 1.17%. PMID:24810865

Dual role of TiO2 buffer layer in Pt catalyzed BiFeO3 photocathodes: Efficiency enhancement and surface protection

NASA Astrophysics Data System (ADS)

Shen, Huanyu; Zhou, Xiaoxue; Dong, Wen; Su, Xiaodong; Fang, Liang; Wu, Xi; Shen, Mingrong

2017-09-01

Polycrystalline ferroelectric BiFeO3 (BFO) films deposited on transparent indium tin oxide (ITO) electrodes have shown to be an interesting photocathode for photoelectrochemical (PEC) water splitting; however, its PEC performance and stability are far from perfection. Herein, we reported an amorphous TiO2 buffer layer, inserted between BFO and Pt catalyst, improves significantly both its PEC activity and stability. A photocathodic current density of -460 μA/cm2 at 0 V vs. reversible hydrogen electrode (RHE) and an onset potential of 1.25 V vs. RHE were obtained in ITO/BFO/TiO2/Pt photocathode under 100 mW/cm2 Xe-lamp illumination. TiO2 functions as a buffer layer to remove the upward barrier between BFO and Pt, and makes the photogenerated carriers separate efficiently. The photocathode also shows high stability in acid solution after a 10-h PEC continuous testing.

Rutile IrO2/TiO2 superlattices: A hyperconnected analog to the Ruddelsden-Popper structure

NASA Astrophysics Data System (ADS)

Kawasaki, Jason K.; Baek, David; Paik, Hanjong; Nair, Hari P.; Kourkoutis, Lena F.; Schlom, Darrell G.; Shen, Kyle M.

2018-05-01

Dimensionality and connectivity among octahedra play important roles in determining the properties, electronic structure, and phase transitions of transition-metal oxides. Here we demonstrate the epitaxial growth of (110)-oriented alternating layers of IrO2 and TiO2, both of which have the rutile structure. These (IrO2)n/(TiO2)2 superlattices consist of IrO6 and TiO6 octahedra tiled in a hyperconnected, edge- and corner-sharing network. Despite the large lattice mismatch between constituent layers (Δ d∥=-2.1 % and Δ c =+6.6 % ), our reactive molecular-beam epitaxy-grown superlattices show high structural quality as determined by x-ray diffraction and sharp interfaces as observed by transmission electron microscopy. The large strain at the interface is accommodated by an ordered interfacial reconstruction. The superlattices show persistent metallicity down to n =3 atomic layers, and angle-resolved photoemission spectroscopy measurements reveal quantized sub-bands with signatures of IrO2-IrO2 interlayer coupling.

A study of the physical, chemical and biological properties of TiO2 coatings produced by micro-arc oxidation in a Ca-P-based electrolyte.

PubMed

dos Santos, Amanda; Araujo, Joyce R; Landi, Sandra M; Kuznetsov, Alexei; Granjeiro, José M; de Sena, Lidia Ágata; Achete, Carlos Alberto

2014-07-01

In this work, a porous and homogeneous titanium dioxide layer was grown on commercially pure titanium substrate using a micro-arc oxidation (MAO) process and Ca-P-based electrolyte. The structure and morphology of the TiO2 coatings were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, and profilometry. The chemical properties were studied using electron dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy. The wettability of the coating was evaluated using contact angle measurements. During the MAO process, Ca and P ions were incorporated into the oxide layer. The TiO2 coating was composed of a mixture of crystalline and amorphous structures. The crystalline part of the sample consisted of a major anatase phase and a minor rutile phase. A cross-sectional image of the coating-substrate interface reveals the presence of voids elongated along the interface. An osteoblast culture was performed to verify the cytocompatibility of the anodized surface. The results of the cytotoxicity tests show satisfactory cell viability of the titanium dioxide films produced in this study.

Non-Fermi liquids in oxide heterostructures

NASA Astrophysics Data System (ADS)

Stemmer, Susanne; Allen, S. James

2018-06-01

Understanding the anomalous transport properties of strongly correlated materials is one of the most formidable challenges in condensed matter physics. For example, one encounters metal-insulator transitions, deviations from Landau Fermi liquid behavior, longitudinal and Hall scattering rate separation, a pseudogap phase, and bad metal behavior. These properties have been studied extensively in bulk materials, such as the unconventional superconductors and heavy fermion systems. Oxide heterostructures have recently emerged as new platforms to probe, control, and understand strong correlation phenomena. This article focuses on unconventional transport phenomena in oxide thin film systems. We use specific systems as examples, namely charge carriers in SrTiO3 layers and interfaces with SrTiO3, and strained rare earth nickelate thin films. While doped SrTiO3 layers appear to be a well behaved, though complex, electron gas or Fermi liquid, the rare earth nickelates are a highly correlated electron system that may be classified as a non-Fermi liquid. We discuss insights into the underlying physics that can be gained from studying the emergence of non-Fermi liquid behavior as a function of the heterostructure parameters. We also discuss the role of lattice symmetry and disorder in phenomena such as metal-insulator transitions in strongly correlated heterostructures.

Processing Ti-25Ta-5Zr Bioalloy via Anodic Oxidation Procedure at High Voltage

NASA Astrophysics Data System (ADS)

Ionita, Daniela; Grecu, Mihaela; Dilea, Mirela; Cojocaru, Vasile Danut; Demetrescu, Ioana

2011-12-01

The current paper reports the processing of Ti-25Ta-5Zr bioalloy via anodic oxidation in NH4BF4 solution under constant potentiostatic conditions at high voltage to obtain more suitable properties for biomedical application. The maximum efficiency of the procedure is reached at highest applied voltage, when the corrosion rate in Hank's solution is decreased approxomately six times. The topography of the anodic layer has been studied using atomic force microscopy (AFM), and the results indicated that the anodic oxidation process increases the surface roughness. The AFM images indicated a different porosity for the anodized surfaces as well. After anodizing, the hydrophilic character of Ti-25Ta-5Zr samples has increased. A good correlation between corrosion rate obtained from potentiodynamic curves and corrosion rate from ions release analysis was obtained.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Sangkyu; Park, Hun; Paik, Ungyu

We have discovered a methodology to realize the fabrication of flexible metal oxide film using two-dimensional (2D) nanosheets. Atomic scale titanium oxide (TiO{sub x}) nanosheets were exfoliated from bulk TiO{sub x} powder that had a layered structure via the modified Sasaki’s method. The vacuum-assisted filtration generates films with laterally aligned TiO{sub x} nanosheets. The 2D sheet-like structure and hydrophilic nature of TiO{sub x} nanosheets enables the film consisting of TiO{sub x} nanosheets to be bendable. Also, we demonstrate the fabrication of electrochemical capacitors using this film. The mechanically flexible metal oxide film is expected to open up the possibility ofmore » fabricating flexible energy storage devices from 2D metal oxide nanosheets. - Graphical abstract: The modified Sasaki’s method, combined process of hydrothermal reaction and bulky ion exchange, enables to obtain TiO{sub x} monolayer nanosheets. The vacuum-assisted filtration generates bendable films with laterally aligned TiO{sub x} nanosheets. Also, we demonstrate the fabrication of electrochemical capacitors using this film. - Highlights: • TiO{sub x} single sheets, a novel 2-dimensional material, were exfoliated from bulk powders via the modified Sasaki’s method. • In our method, the acid treatment of TiO{sub x} bulk powders was simply modified by applying the hydrothermal reaction. • Then, the delamination procedures of large cation exchange were conducted following the method proposed by Sasaki et al. • Reassembly of TiO{sub x} sheets into flexible free-standing films was simply achieved via vacuum assisted filtration method. • TiO{sub x} films were used as a flexible supercapaictor electrode material.« less

Built-in potential shift and Schottky-barrier narrowing in organic solar cells with UV-sensitive electron transport layers.

PubMed

Li, Cheng; Credgington, Dan; Ko, Doo-Hyun; Rong, Zhuxia; Wang, Jianpu; Greenham, Neil C

2014-06-28

The performance of organic solar cells incorporating solution-processed titanium suboxide (TiOx) as electron-collecting layers can be improved by UV illumination. We study the mechanism of this improvement using electrical measurements and electroabsorption spectroscopy. We propose a model in which UV illumination modifies the effective work function of the oxide layer through a significant increase in its free electron density. This leads to a dramatic improvement in device power conversion efficiency through several mechanisms - increasing the built-in potential by 0.3 V, increasing the conductivity of the TiOx layer and narrowing the interfacial Schottky barrier between the suboxide and the underlying transparent electrode. This work highlights the importance of considering Fermi-level equilibration when designing multi-layer transparent electrodes.

Amorphous TiO2 Shells: A Vital Elastic Buffering Layer on Silicon Nanoparticles for High-Performance and Safe Lithium Storage.

PubMed

Yang, Jianping; Wang, Yunxiao; Li, Wei; Wang, Lianjun; Fan, Yuchi; Jiang, Wan; Luo, Wei; Wang, Yang; Kong, Biao; Selomulya, Cordelia; Liu, Hua Kun; Dou, Shi Xue; Zhao, Dongyuan

2017-12-01

Smart surface coatings of silicon (Si) nanoparticles are shown to be good examples for dramatically improving the cyclability of lithium-ion batteries. Most coating materials, however, face significant challenges, including a low initial Coulombic efficiency, tedious processing, and safety assessment. In this study, a facile sol-gel strategy is demonstrated to synthesize commercial Si nanoparticles encapsulated by amorphous titanium oxide (TiO 2 ), with core-shell structures, which show greatly superior electrochemical performance and high-safety lithium storage. The amorphous TiO 2 shell (≈3 nm) shows elastic behavior during lithium discharging and charging processes, maintaining high structural integrity. Interestingly, it is found that the amorphous TiO 2 shells offer superior buffering properties compared to crystalline TiO 2 layers for unprecedented cycling stability. Moreover, accelerating rate calorimetry testing reveals that the TiO 2 -encapsulated Si nanoparticles are safer than conventional carbon-coated Si-based anodes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D nanostructured N-doped TiO2 photocatalysts with enhanced visible absorption.

PubMed

Cho, Sumin; Ahn, Changui; Park, Junyong; Jeon, Seokwoo

2018-05-24

Considering the environmental issues, it is essential to develop highly efficient and recyclable photocatalysts in purification systems. Conventional TiO2 nanoparticles have strong intrinsic oxidizing power and high surface area, but are difficult to collect after use and rarely absorb visible light, resulting in low photocatalytic efficiency under sunlight. Here we develop a new type of highly efficient and recyclable photocatalyst made of a three-dimensional (3D) nanostructured N-doped TiO2 monolith with enhanced visible light absorption. To prepare the sample, an ultrathin TiN layer (∼10 nm) was conformally coated using atomic layer deposition (ALD) on 3D nanostructured TiO2. Subsequent thermal annealing at low temperature (550 °C) converted TiN to anatase phase N-doped TiO2. The resulting 3D N-doped TiO2 showed ∼33% enhanced photocatalytic performance compared to pure 3D TiO2 of equivalent thickness under sunlight due to the reduced bandgap, from 3.2 eV to 2.75 eV through N-doping. The 3D N-doped TiO2 monolith could be easily collected and reused at least 5 times without any degradation in photocatalytic performance.

Engineering charge ordering into multiferroicity

NASA Astrophysics Data System (ADS)

He, Xu; Jin, Kui-juan

2016-04-01

Multiferroic materials have attracted great interest but are rare in nature. In many transition-metal oxides, charge ordering and magnetic ordering coexist, so that a method of engineering charge-ordered materials into ferroelectric materials would lead to a large class of multiferroic materials. We propose a strategy for designing new ferroelectric or even multiferroic materials by inserting a spacing layer into each two layers of charge-ordered materials and artificially making a superlattice. One example of the model demonstrated here is the perovskite (LaFeO3)2/LaTiO3 (111) superlattice, in which the LaTiO3 layer acts as the donor and the spacing layer, and the LaFeO3 layer is half doped and performs charge ordering. The collaboration of the charge ordering and the spacing layer breaks the space inversion symmetry, resulting in a large ferroelectric polarization. As the charge ordering also leads to a ferrimagnetic structure, (LaFeO3)2/LaTiO3 is multiferroic. It is expected that this work can encourage the designing and experimental implementation of a large class of multiferroic structures with novel properties.

Photocatalytic activity of low temperature oxidized Ti-6Al-4V.

PubMed

Unosson, Erik; Persson, Cecilia; Welch, Ken; Engqvist, Håkan

2012-05-01

Numerous advanced surface modification techniques exist to improve bone integration and antibacterial properties of titanium based implants and prostheses. A simple and straightforward method of obtaining uniform and controlled TiO(2) coatings of devices with complex shapes is H(2)O(2)-oxidation and hot water aging. Based on the photoactivated bactericidal properties of TiO(2), this study was aimed at optimizing the treatment to achieve high photocatalytic activity. Ti-6Al-4V samples were H(2)O(2)-oxidized and hot water aged for up to 24 and 72 h, respectively. Degradation measurements of rhodamine B during UV-A illumination of samples showed a near linear relationship between photocatalytic activity and total treatment time, and a nanoporous coating was observed by scanning electron microscopy. Grazing incidence X-ray diffraction showed a gradual decrease in crystallinity of the surface layer, suggesting that the increase in surface area rather than anatase formation was responsible for the increase in photocatalytic activity.

Improved interfacial and electrical properties of GaAs metal-oxide-semiconductor capacitors with HfTiON as gate dielectric and TaON as passivation interlayer

NASA Astrophysics Data System (ADS)

Wang, L. S.; Xu, J. P.; Zhu, S. Y.; Huang, Y.; Lai, P. T.

2013-08-01

The interfacial and electrical properties of sputtered HfTiON on sulfur-passivated GaAs with or without TaON as interfacial passivation layer (IPL) are investigated. Experimental results show that the GaAs metal-oxide-semiconductor capacitor with HfTiON/TaON stacked gate dielectric annealed at 600 °C exhibits low interface-state density (1.0 × 1012 cm-2 eV-1), small gate leakage current (7.3 × 10-5 A cm-2 at Vg = Vfb + 1 V), small capacitance equivalent thickness (1.65 nm), and large equivalent dielectric constant (26.2). The involved mechanisms lie in the fact that the TaON IPL can effectively block the diffusions of Hf, Ti, and O towards GaAs surface and suppress the formation of interfacial As-As bonds, Ga-/As-oxides, thus unpinning the Femi level at the TaON/GaAs interface and improving the interface quality and electrical properties of the device.

Transmission electron microscopy study of erbium silicide formation from Ti/Er stack for Schottky contact applications.

PubMed

Ratajczak, J; Łaszcz, A; Czerwinski, A; Katcki, J; Phillipp, F; Van Aken, P A; Reckinger, N; Dubois, E

2010-03-01

In this paper, we present results of transmission electron microscopy studies on erbium silicide structures fabricated under various thermal conditions. A titanium cap has been used as a protective layer against oxidation during rapid thermal annealing of an erbium layer in a temperature range of 300-700 degrees C. Both layers (200 nm Ti and 25 nm Er) were deposited by electron-beam sputtering. The investigations have shown that the transformation of the 25-nm-thick erbium into erbium silicide is completed after annealing at 500 degrees C. At higher temperatures, the formation of a titanium silicide layer above erbium silicide is observed. The lowest Schottky barrier has been measured in the sample annealed at 700 degrees C.

Microstructure, nickel suppression and mechanical characteristics of electropolished and photoelectrocatalytically oxidized biomedical nickel titanium shape memory alloy.

PubMed

Chu, C L; Guo, C; Sheng, X B; Dong, Y S; Lin, P H; Yeung, K W K; Chu, Paul K

2009-07-01

A new surface modification protocol encompassing an electropolishing pretreatment (EP) and subsequent photoelectrocatalytic oxidation (PEO) has been developed to improve the surface properties of biomedical nickel titanium (NiTi) shape memory alloy (SMA). Electropolishing is a good way to improve the resistance to localized breakdown of NiTi SMA whereas PEO offers the synergistic effects of advanced oxidation and electrochemical oxidation. Our results indicate that PEO leads to the formation of a sturdy titania film on the EP NiTi substrate. There is an Ni-free zone near the top surface and a graded interface between the titania layer and NiTi substrate, which bodes well for both biocompatibility and mechanical stability. In addition, Ni ion release from the NiTi substrate is suppressed, as confirmed by the 10-week immersion test. The modulus and hardness of the modified NiTi surface increase with larger indentation depths, finally reaching plateau values of about 69 and 3.1GPa, respectively, which are slightly higher than those of the NiTi substrate but much lower than those of a dense amorphous titania film. In comparison, after undergoing only EP, the mechanical properties of NiTi exhibit an inverse change with depth. The deformation mechanism is proposed and discussed. Our results indicate that surface modification by dual EP and PEO can notably suppress Ni ion release and improve the biocompatibility of NiTi SMA while the surface mechanical properties are not compromised, making the treated materials suitable for hard tissue replacements.

Development of Plasma-Sprayed Molybdenum Carbide-Based Anode Layers with Various Metal Oxides for SOFC

NASA Astrophysics Data System (ADS)

Faisal, N. H.; Ahmed, R.; Katikaneni, S. P.; Souentie, S.; Goosen, M. F. A.

2015-12-01

Air plasma-sprayed (APS) coatings provide an ability to deposit a range of novel fuel cell materials at competitive costs. This work develops three separate types of composite anodes (Mo-Mo2C/Al2O3, Mo-Mo2C/ZrO2, Mo-Mo2C/TiO2) using a combination of APS process parameters on Hastelloy®X for application in intermediate temperature proton-conducting solid oxide fuel cells. Commercially available carbide of molybdenum powder catalyst (Mo-Mo2C) and three metal oxides (Al2O3, ZrO2, TiO2) was used to prepare three separate composite feedstock powders to fabricate three different anodes. Each of the modified composition anode feedstock powders included a stoichiometric weight ratio of 0.8:0.2. The coatings were characterized by scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction, nanoindentation, and conductivity. We report herein that three optimized anode layers of thicknesses between 200 and 300 µm and porosity as high as 20% for Mo-Mo2C/Al2O3 (250-µm thick) and Mo-Mo2C/TiO2 (300 µm thick) and 17% for Mo-Mo2C/ZrO2 (220-µm thick), controllable by a selection of the APS process parameters with no addition of sacrificial pore-forming material. The nanohardness results indicate the upper layers of the coatings have higher values than the subsurface layers in coatings with some effect of the deposition on the substrate. Mo-Mo2C/ZrO2 shows high electrical conductivity.

Surface Chemistry and Interface Evolution during the Atomic Layer Deposition of High-k Metal Oxides on InAs(100) and GaAs(100) Surfaces

NASA Astrophysics Data System (ADS)

Henegar, Alex J.

Device scaling has been key for creating faster and more powerful electronic devices. Integral circuit components like the metal-oxide semiconductor field-effect transistor (MOSFET) now rely on material deposition techniques, like atomic layer deposition (ALD), that possess atomic-scale thickness precision. At the heart of the archetypal MOSFET is a SiO2/Si interface which can be formed to near perfection. However when the thickness of the SiO 2 layer is shrunk down to a few nanometers several complications arise like unacceptably high leakage current and power consumption. Replacing Si with III-V semiconductors and SiO2 with high-k dielectric materials is appealing but comes with its own set of challenges. While SiO2 is practically defect-free, the native oxides of III-Vs are poor dielectrics. In this dissertation, the surface chemistry and interface evolution during the ALD of high-k metal oxides on Si(100), GaAs(100) and InAs(100) was studied. In particular, the surface chemistry and crystallization of TiO2 films grown on Si(100) was investigated using transmission Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Large, stable, and highly reactive anatase TiO2 grains were found to form during a post-deposition heat treatment after the ALD at 100 °C. The remainder of this work was focused on the evolution of the interfacial oxides during the deposition of TiO2 and Al2O3 on InAs(100) and GaAs(100) and during the deposition of Ta2O 5 on InAs(100). In summary the ALD precursor type, deposited film, and substrate had an influence in the evolution of the native oxides. Alkyl amine precursors fared better at removing the native oxides but the deposited films (TiO2 and Ta2O5) were susceptible to significant native oxide diffusion. The alkyl precursor used for the growth of Al 2O3 was relatively ineffective at removing the oxides but was a good diffusion barrier. In all cases the native oxides were more stable on GaAs compared to InAs. This project utilized a new methodology for the detection of arsenic oxide diffusion using transmission FTIR, and expanded the knowledge of the complexities of the high-k/III-V interface.

Spin State Control using Oxide Interfaces in LaCoO3-based Heterostructures

NASA Astrophysics Data System (ADS)

Lee, Sangjae; Disa, Ankit; Walker, Frederick; Ahn, Charles

The flexibility of the spin degree of freedom of the Co 3d orbitals in LaCoO3 suggests that they can be changed through careful design of oxide heterostructures. Interfacial coupling and dimensional confinement can be used to control the magnetic exchange, crystal fields, and Hund's coupling, through orbital and charge reconstructions. These parameters control the balance between multiple spin configurations, thereby modifying the magnetic ordering of LaCoO3. We study (LaCoO3)m /(LaTiO3)2 heterostructures grown by molecular beam epitaxy, which allow interfacial charge transfer from Ti to Co, in addition to structural and dimensional constraints. The electronic polarization at the interface and consequent structural distortions suppress the ferromagnetism in the LaCoO3 layers. This effect extends well beyond the interface, with ferromagnetic order absent up to LaCoO3 layer thickness of m =10. We compare the properties of the LaCoO3/LaTiO3heterostructureswithLaCoO3/SrTiO3, to untangle how charge transfer and structural modifications control the spin and magnetic configuration in cobaltates.

Enhanced photovoltaic properties in dye sensitized solar cells by surface treatment of SnO2 photoanodes

PubMed Central

Basu, Kaustubh; Benetti, Daniele; Zhao, Haiguang; Jin, Lei; Vetrone, Fiorenzo; Vomiero, Alberto; Rosei, Federico

2016-01-01

We report the fabrication and testing of dye sensitized solar cells (DSSC) based on tin oxide (SnO2) particles of average size ~20 nm. Fluorine-doped tin oxide (FTO) conducting glass substrates were treated with TiOx or TiCl4 precursor solutions to create a blocking layer before tape casting the SnO2 mesoporous anode. In addition, SnO2 photoelectrodes were treated with the same precursor solutions to deposit a TiO2 passivating layer covering the SnO2 particles. We found that the modification enhances the short circuit current, open-circuit voltage and fill factor, leading to nearly 2-fold increase in power conversion efficiency, from 1.48% without any treatment, to 2.85% achieved with TiCl4 treatment. The superior photovoltaic performance of the DSSCs assembled with modified photoanode is attributed to enhanced electron lifetime and suppression of electron recombination to the electrolyte, as confirmed by electrochemical impedance spectroscopy (EIS) carried out under dark condition. These results indicate that modification of the FTO and SnO2 anode by titania can play a major role in maximizing the photo conversion efficiency. PMID:26988622

Ni-BaTiO3-Based Base-Metal Electrode (BME) Ceramic Capacitors for Space Applications

NASA Technical Reports Server (NTRS)

Liu, Donhang; Fetter, Lula; Meinhold, Bruce

2015-01-01

A multi-layer ceramic capacitor (MLCC) is a high-temperature (1350C typical) co-fired ceramic monolithic that is composed of many layers of alternately stacked oxide-based dielectric and internal metal electrodes. To make the dielectric layers insulating and the metal electrode layers conducting, only highly oxidation-resistant precious metals, such as platinum, palladium, and silver, can be used for the co-firing of insulating MLCCs in a regular air atmosphere. MLCCs made with precious metals as internal electrodes and terminations are called precious-metal electrode (PME) capacitors. Currently, all military and space-level applications only address the use of PME capacitors.

Electrochemical studies on nanometal oxide-activated carbon composite electrodes for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Ho, Mui Yen; Khiew, Poi Sim; Isa, Dino; Chiu, Wee Siong

2014-11-01

In present study, the electrochemical performance of eco-friendly and cost-effective titanium oxide (TiO2)-based and zinc oxide-based nanocomposite electrodes were studied in neutral aqueous Na2SO3 electrolyte, respectively. The electrochemical properties of these composite electrodes were studied using cyclic voltammetry (CV), galvanostatic charge-discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that these two nanocomposite electrodes achieve the highest specific capacitance at fairly low oxide loading onto activated carbon (AC) electrodes, respectively. Considerable enhancement of the electrochemical properties of TiO2/AC and ZnO/AC nanocomposite electrodes is achieved via synergistic effects contributed from the nanostructured metal oxides and the high surface area mesoporous AC. Cations and anions from metal oxides and aqueous electrolyte such as Ti4+, Zn2+, Na+ and SO32- can occupy some pores within the high-surface-area AC electrodes, forming the electric double layer at the electrode-electrolyte interface. Additionally, both TiO2 and ZnO nanoparticles can provide favourable surface adsorption sites for SO32- anions which subsequently facilitate the faradaic processes for pseudocapacitive effect. These two systems provide the low cost material electrodes and the low environmental impact electrolyte which offer the increased charge storage without compromising charge storage kinetics.

Corrosion characteristics of Ni-base superalloys in high temperature steam with and without hydrogen

NASA Astrophysics Data System (ADS)

Kim, Donghoon; Kim, Daejong; Lee, Ho Jung; Jang, Changheui; Yoon, Duk Joo

2013-10-01

The hot steam corrosion behavior of Alloy 617 and Haynes 230 were evaluated in corrosion tests performed at 900 °C in steam and steam + 20 vol.% H2 environments. Corrosion rates of Alloy 617 was faster than that of Haynes 230 at 900 °C in steam and steam + 20 vol.% H2 environments. When hydrogen was added to steam, the corrosion rate was accelerated because added hydrogen increased the concentration of Cr interstitial defects in the oxide layer. Isolated nodular MnTiO3 oxides were formed on the MnCr2O4/Cr2O3 oxide layer and sub-layer Cr2O3 was formed in steam and steam + 20 vol.% H2 for Alloy 617. On the other hand, a MnCr2O4 layer was formed on top of the Cr2O3 oxide layer for Haynes 230. The extensive sub-layer Cr2O3 formation resulted from the oxygen or hydroxide inward diffusion in such environments. When hydrogen was added, the initial surface oxide morphology was changed from a convex shape to platelets because of the accelerated diffusion of cations under the oxide layer.

Tuning the dead-layer behavior of La{sub 0.67}Sr{sub 0.33}MnO{sub 3}/SrTiO{sub 3} via interfacial engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, R.; Xu, H. C.; Xia, M.

The dead-layer behavior, deterioration of the bulk properties in near-interface layers, restricts the applications of many oxide heterostructures. We present the systematic study of the dead-layer in La{sub 0.67}Sr{sub 0.33}MnO{sub 3}/SrTiO{sub 3} grown by ozone-assisted molecular beam epitaxy. Dead-layer behavior is systematically tuned by varying the interfacial doping, while unchanged with varied doping at any other atomic layers. In situ photoemission and low energy electron diffraction measurements suggest intrinsic oxygen vacancies at the surface of ultra-thin La{sub 0.67}Sr{sub 0.33}MnO{sub 3}, which are more concentrated in thinner films. Our results show correlation between interfacial doping, oxygen vacancies, and the dead-layer, whichmore » can be explained by a simplified electrostatic model.« less

Few layer graphene wrapped mixed phase TiO2 nanofiber as a potential electrode material for high performance supercapacitor applications

NASA Astrophysics Data System (ADS)

Thirugnanam, Lavanya; Sundara, Ramaprabhu

2018-06-01

A combination of favorable composition and optimized anatase/rutile mixed-phase TiO2 (MPTNF)/Hydrogen exfoliated graphene (HEG) composite nanofibers (MPTNF/HEG) and anatase/rutile mixed-phase TiO2/reduced graphene oxide (rGO) composite nanofibers (MPTNF/rGO) have been reported to enhance the electrochemical properties for supercapacitor applications. These composite nanofibers have been synthesized by an efficient route of electrospinning together with the help of easy chemical methods. Both the composites exhibit good charge storage capability with enhanced pseudocapacitance and electric double-layer capacitance (EDLC) as confirmed by cyclic voltammetry studies. MPTNF/HEG composite showed maximum specific capacitance of 210.5 F/g at the current density of 1 A/g, which was mainly due to its availability of the more active sites for ions adsorption on a few layers of graphene wrapped TiO2 nanofiber surface. The synergistic effect of anatase/rutile mixed phase with one dimensional nanostructure and the electronic interaction between TiO2 and few layer graphene provided the subsequent improvement of ion adsorption capacity. Also exhibit excellent electrochemical performance to improve the capacitive properties of TiO2 electrode materials which is required for the development of flexible electrodes in energy storage devices and open up new opportunities for high performance supercapacitors.

Low Power Consumption Gas Sensor Created from Silicon Nanowires/TiO2 Core-Shell Heterojunctions.

PubMed

Liu, Dong; Lin, Leimiao; Chen, Qiaofen; Zhou, Hongzhi; Wu, Jianmin

2017-10-27

Silicon nanowires/TiO 2 (SiNWs/TiO 2 ) array with core-shell nanostructure was created by sol-gel and drop-casting methods. The hybrid material displayed excellent sensing performance for CH 4 detection at room temperature. The chemiresistor sensor has a linear response toward CH 4 gas in the 30-120 ppm range with a detection limit of 20 ppm, which is well below most CH 4 sensors reported before. The enhanced gas sensing performance at room temperature was attributed to the creation of heterojunctions that form a depletion layer at the interface of SiNWs and TiO 2 layer. Adsorption of oxygen and corresponding gas analyte on TiO 2 layer could induce the change of depletion layer thickness and consequently the width of the SiNWs conductive channel, leading to a sensitive conductive response toward gas analyte. Compared to conventional metal oxide gas sensors, the room temperature gas sensors constructed from SiNWs/TiO 2 do not need an additional heating device and work at power at the μW level. The low power consumption feature is of great importance for sensing devices, if they are widely deployed and connected to the Internet of Things. The innovation of room temperature sensing materials may push forward the integration of gas sensing element with wireless device.

Enhancement of spin-lattice coupling in nanoengineered oxide films and heterostructures by laser MBE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xi, Xiaoxing

The objective of the proposed research is to investigate nanoengineered oxide films and multilayer structures that are predicted to show desirable properties. The main focus of the project is an atomic layer-by-layer laser MBE (ALL-Laser MBE ) technique that is superior to the conventional laser MBE in broadening the conditions for the synthesis of high quality nanoscale oxides and new designer materials. In ALL-Laser MBE, separate oxide targets are used instead of one compound target in the conventional laser MBE. The targets are switched back and forth in front of a UV laser beam as they are alternately ablated. Themore » oxide film is thus constructed one atomic layer at a time. The growth of each atomic layer is monitored and controlled by the reflection high energy electron diffraction (RHEED). The intensity of the diffraction spots increases or decreases depending on the chemistry of each atomic layer as well as the surface roughness. This allows us to determine whether the chemical ratio of the different elements in the films meets the desired value and whether each atomic layer is complete. ALL-Laser MBE is versatile: it works for non-polar film on non-polar substrate, polar film on polar substrate, and polar film on non-polar substrate. (In a polar material, each atomic layer is charged whereas in a non-polar material the atomic layers are charge neutral.) It allows one to push the thermodynamic boundary further in stabilizing new phases than reactive MBE and PLD, two of the most successful techniques for oxide thin films. For example, La 5Ni 4O 13, the Ruddlesden-Popper phase with n = 4, has never been reported in the literature because it needs atomic layer-by-layer growth at high oxygen pressures, not possible with other growth techniques. ALL-Laser MBE makes it possible. We have studied the interfacial 2-dimensional electron gas in the LaAlO 3/SrTiO 3 system, whose mechanism has been a subject of controversy. According to the most prevailing electronic reconstruction mechanism, a positive diverging electric potential is built up in the polar LaAlO 3 film when it is grown on a TiO 2-terminated SrTiO 3 substrate, which is non-polar. This leads to the transfer of half of an electron from the LaAlO 3 film surface to SrTiO 3 when the LaAlO 3 layer is thicker than 4 unit cells, creating a 2D electron gas at the interface with a sheet carrier density of 3.3×10 14/cm 2 for sufficiently thick LaAlO 3. A serious inconsistency with this mechanism is that the carrier densities reported experimentally are invariably lower than the expected value. The most likely reason is that the SrTiO 3 substrate is oxygen difficient due to the low oxygen pressures (< 10 mTorr) during growth, and post-growth annealing in oxygen is often used to remove the oxygen vacancies. People cannot grow the LaAlO 3 film in higher oxygen pressures - it results in insulating samples or 3D island growth. Because we grow the LaAlO 3 film one atomic layer at a time, we were able to grow conducting LaAlO 3/SrTiO 3 interfaces at a high oxygen pressure with ALL-Laser MBE, as high as 37 mTorr. The high oxygen pressure helps to prevent the possible oxygen reduction in SrTiO 3, ensure that the LaAlO 3 films are sufficiently oxygenated. Measurements of x-ray linear dichroism (XLD) and x-ray magnetic circular dichroism (XMCD) both show that the spectra of our films are similar to those of well oxygenated samples. In the LaAlO 3/SrTiO 3 interfaces grown by ALL-Laser MBE at 37 mTorr oxygen pressure, a quantitative agreement between our experimental result and the theoretical prediction was observed, which provides a strong support to the electronic reconstruction mechanism. The key differences between our result and the previous reports are the high oxygen pressure during the film growth and the high film crystallinity. The high oxygen pressure suppresses the likelihood of oxygen vacancies in SrTiO 3. Well oxygenated samples produced during film growth can avoid possible defects when sufficient oxygen is provided only after the growth by annealing. Using ALL-Laser MBE, we also synthesized high-quality singlec-rystalline CaMnO 3 films. The systematic increase of the oxygen vacancy content in CaMnO 3 as a function of applied in-plane strain is observed and confirmed experimentally using high-resolution soft x-ray XAS and hard x-ray photoemission spectroscopy (HAXPES). The relevant defect states in the densities of states are identified and the vacancy content in the films quantified using the combination of first-principles theory and core-hole multiplet calculations with holistic fitting. The strain-induced oxygen-vacancy formation and ordering are a promising avenue for designing and controlling new functionalities in complex transition-metal oxides.« less

All-oxide-based synthetic antiferromagnets exhibiting layer-resolved magnetization reversal

NASA Astrophysics Data System (ADS)

Chen, Binbin; Xu, Haoran; Ma, Chao; Mattauch, Stefan; Lan, Da; Jin, Feng; Guo, Zhuang; Wan, Siyuan; Chen, Pingfan; Gao, Guanyin; Chen, Feng; Su, Yixi; Wu, Wenbin

2017-07-01

Synthesizing antiferromagnets with correlated oxides has been challenging, owing partly to the markedly degraded ferromagnetism of the magnetic layer at nanoscale thicknesses. Here we report on the engineering of an antiferromagnetic interlayer exchange coupling (AF-IEC) between ultrathin but ferromagnetic La2/3Ca1/3MnO3 layers across an insulating CaRu1/2Ti1/2O3 spacer. The layer-resolved magnetic switching leads to sharp steplike hysteresis loops with magnetization plateaus depending on the repetition number of the stacking bilayers. The magnetization configurations can be switched at moderate fields of hundreds of oersted. Moreover, the AF-IEC can also be realized with an alternative magnetic layer of La2/3Sr1/3MnO3 that possesses a Curie temperature near room temperature. The findings will add functionalities to devices with correlated-oxide interfaces.

An Atomic-Scale X-ray View of Functional Oxide Films

NASA Astrophysics Data System (ADS)

Tung, I.-Cheng

Complex oxides are a class of materials that exhibit a wide variety of physical functionalities, such as ferroelectricity, colossal magnetoresistance, mulitferroicity and superconductivity, with outstanding potential for meeting many of our technological demands. The primary objective of this dissertation is to understand the structural and electronic behavior of complex oxide ultrathin films subjected to confinement, lattice misfit and broken symmetry at the interface. In complex oxide ultrathin films, heteroepitaxial synthesis has evolved into a reliable strategy to engineer orbital-lattice interactions in correlated materials and led to new and entirely unexpected phenomena at their interfaces. I experimentally demonstrated that the bulk crystal symmetry directs the atomic and orbital responses adopted by coherently strained ultrathin films of RNiO3 (R = La, Nd) with detailed X-ray scattering, polarization-dependent X-ray absorption spectroscopy (XAS) and supported by a mathematical point group symmetry analysis, found that strain-stabilized phases maintain a ``memory'' of their bulk state. This topic, however, touched only upon the properties of such films. A fundamental challenge in this research area occurs before this and centers around the understanding of how to create high-quality films with arbitrary configurations. A longstanding challenge in the oxide thin film community has been the growth of An+1BnO3 n+1 Ruddlesden-Popper (RP) compounds. To understand this problem, we have utilized a newly constructed oxide MBE with in situ synchrotron X-ray scattering capability to study the initial growth of such layered oxides and track the dynamic evolution. X-ray results are supported by theoretical calculations that demonstrated the layered oxide films dynamically rearrange during growth, leading to structures that are highly unexpected, and suggest a general approach that may be essential for the construction of metastable RP phases with performing the first atomically controlled synthesis of single-crystalline La3Ni2O7. By building upon this knowledge, I have completed the first to date study of in situ surface X-ray scattering during homoepitaxial MBE growth of SrTiO3, which demonstrates codeposition is consistent with a 2D island growth mode with SrTiO3 islands, but shuttered deposition proceeds by the growth of SrO islands which then restructure into atomically flat SrTiO3 layer during the deposition of the TiO2. From this point, we have conducted a detailed microscopic study of epitaxial LaNiO3 ultrathin films grown on SrTiO3 (001) by using reactive MBE with in situ surface X-ray diffraction and ex situ soft XAS to explore the influence of polar mismatch on the resulting structural and electronic properties. Overall, this thesis highlights the power of artificial confinement to harness control over competing phases in complex oxides with atomic-scale precision.

Growth mechanism of atomic-layer-deposited TiAlC metal gate based on TiCl4 and TMA precursors

NASA Astrophysics Data System (ADS)

Jinjuan, Xiang; Yuqiang, Ding; Liyong, Du; Junfeng, Li; Wenwu, Wang; Chao, Zhao

2016-03-01

TiAlC metal gate for the metal-oxide-semiconductor field-effect-transistor (MOSFET) is grown by the atomic layer deposition method using TiCl4 and Al(CH3)3(TMA) as precursors. It is found that the major product of the TiCl4 and TMA reaction is TiAlC, and the components of C and Al are found to increase with higher growth temperature. The reaction mechanism is investigated by using x-ray photoemission spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscope (SEM). The reaction mechanism is as follows. Ti is generated through the reduction of TiCl4 by TMA. The reductive behavior of TMA involves the formation of ethane. The Ti from the reduction of TiCl4 by TMA reacts with ethane easily forming heterogenetic TiCH2, TiCH=CH2 and TiC fragments. In addition, TMA thermally decomposes, driving Al into the TiC film and leading to TiAlC formation. With the growth temperature increasing, TMA decomposes more severely, resulting in more C and Al in the TiAlC film. Thus, the film composition can be controlled by the growth temperature to a certain extent. Project supported by the Key Technology Study for 16/14 nm Program of the Ministry of Science and Technology of China (Grant No. 2013ZX02303).

Atomic Layer Deposition of Metal Oxides on sp2-Graphitic Carbon Substrates

DTIC Science & Technology

2014-03-31

supercapacitors . The research explored the ALD nucleation procedure based on NO2 and TMA. Al2O3 ALD films resulting from the nucleation procedure were...TiO2 and ZnO were used for electrodes for Li ion batteries and pseudocapacitance supercapacitors . 15. SUBJECT TERMS F-16 Aircraft, High Power...sp2 Graphitic Carbon Substrates 11 4.4.1 TiO2 ALD as Anode Material for Li Ion Batteries 11 4.4.2 TiO2 ALD for Pseudocapacitance Supercapacitors

Chromatic Titanium Photoanode for Dye-Sensitized Solar Cells under Rear Illumination.

PubMed

Huang, Chih-Hsiang; Chen, Yu-Wen; Chen, Chih-Ming

2018-01-24

Titanium (Ti) has high potential in many practical applications such as biomedicine, architecture, aviation, and energy. In this study, we demonstrate an innovative application of dye-sensitized solar cells (DSSCs) based on Ti photoanodes that can be integrated into the roof engineering of large-scale architectures. A chromatic Ti foil produced by anodizing oxidation (coloring) technology is an attractive roof material for large-scale architecture, showing a colorful appearance due to the formation of a reflective TiO 2 thin layer on both surfaces of Ti. The DSSC is fabricated on the backside of the chromatic Ti foil using the Ti foil as the working electrode, and this roof-DSSC hybrid configuration can be designed as an energy harvesting device for indoor artificial lighting. Our results show that the facet-textured TiO 2 layer on the chromatic Ti foil not only improves the optical reflectance for better light utilization but also effectively suppresses the charge recombination for better electron collection. The power conversion efficiency of the roof-DSSC hybrid system is improved by 30-40% with a main contribution from an improvement of short-circuit current density under standard 1 sun and dim-light (600-1000 lx) illumination.

Adsorption effect on the formation of conductive path in defective TiO2: ab initio calculations

NASA Astrophysics Data System (ADS)

Li, Lei; Li, Wenshi; Qin, Han; Yang, Jianfeng; Mao, Ling-Feng

2017-10-01

Although the metal/TiO2/metal junctions providing resistive switching properties have attracted lots of attention in recent decades, revealing the atomic-nature of conductive path in TiO2 active layer remains a critical challenge. Here the effects of metal adsorption on defective TiO2(1 1 0) surface are theoretically investigated via ab initio calculations. The dependence of the conductive path on the adsorption of Ti/Zr/Cu/Pt/O atoms above a lattice Ti-ion in (1 1 0) plane and at 〈1 1 0〉 direction of the defective TiO2(0 0 1) surface are compared. It is found that Ti adsorptions in both sites give larger contributions to the presence of conductive path with more stability and larger transport coefficients at Fermi level, whereas the O adsorptions at both sites fail to produce conductive path. Moreover, the adsorptions of Zr/Cu/Pt atoms reduce the existence possibility of conductive path, especially absorbed above the lattice Ti-ion at 〈1 1 0〉 direction. Thus, it is helpful to clarify the interaction of the metal electrode and oxide layer in resistive random access memory.

Effect of geometric nanostructures on the absorption edges of 1-D and 2-D TiO₂ fabricated by atomic layer deposition.

PubMed

Chang, Yung-Huang; Liu, Chien-Min; Cheng, Hsyi-En; Chen, Chih

2013-05-01

2-Dimensional (2-D) TiO2 thin films and 1-dimensional (1-D) TiO2 nanotube arrays were fabricated on Si and quartz substrates using atomic layer deposition (ALD) with an anodic aluminum oxide (AAO) template at 400 °C. The film thickness and the tube wall thickness can be precisely controlled using the ALD approach. The intensities of the absorption spectra were enhanced by an increase in the thickness of the TiO2 thin film and tube walls. A blue-shift was observed for a decrease in the 1-D and 2-D TiO2 nanostructure thicknesses, indicating a change in the energy band gap with the change in the size of the TiO2 nanostructures. Indirect and direct interband transitions were used to investigate the change in the energy band gap. The results indicate that both quantum confinement and interband transitions should be considered when the sizes of 1-D and 2-D TiO2 nanostructures are less than 10 nm.

Suppressing the Photocatalytic Activity of TiO2 Nanoparticles by Extremely Thin Al2O3 Films Grown by Gas-Phase Deposition at Ambient Conditions

PubMed Central

Guo, Jing; Valdesueiro, David; Yuan, Shaojun; Liang, Bin; van Ommen, J. Ruud

2018-01-01

This work investigated the suppression of photocatalytic activity of titanium dioxide (TiO2) pigment powders by extremely thin aluminum oxide (Al2O3) films deposited via an atomic-layer-deposition-type process using trimethylaluminum (TMA) and H2O as precursors. The deposition was performed on multiple grams of TiO2 powder at room temperature and atmospheric pressure in a fluidized bed reactor, resulting in the growth of uniform and conformal Al2O3 films with thickness control at sub-nanometer level. The as-deposited Al2O3 films exhibited excellent photocatalytic suppression ability. Accordingly, an Al2O3 layer with a thickness of 1 nm could efficiently suppress the photocatalytic activities of rutile, anatase, and P25 TiO2 nanoparticles without affecting their bulk optical properties. In addition, the influence of high-temperature annealing on the properties of the Al2O3 layers was investigated, revealing the possibility of achieving porous Al2O3 layers. Our approach demonstrated a fast, efficient, and simple route to coating Al2O3 films on TiO2 pigment powders at the multigram scale, and showed great potential for large-scale production development. PMID:29364840

Study of nickel silicide formation by physical vapor deposition techniques

NASA Astrophysics Data System (ADS)

Pancharatnam, Shanti

Metal silicides are used as contacts to the highly n-doped emitter in photovoltaic devices. Thin films of nickel silicide (NiSi) are of particular interest for Si-based solar cells, as they form at lower temperature and consume less silicon. However, interfacial oxide limits the reduction in sheet resistance. Hence, different diffusion barriers were investigated with regard to optimizing the conductivity and thermal stability. The formation of NiSi, and if it can be doped to have good contact with the n-side of a p-n junction were studied. Reduction of the interfacial oxide by the interfacial Ti layer to allow the formation of NiSi was observed. Silicon was treated in dilute hydrofluoric acid for removing the surface oxide layer. Ni and a Ti diffusion barrier were deposited on Si by physical vapor deposition (PVD) methods - electron beam evaporation and sputtering. The annealing temperature and time were varied to observe the stability of the deposited film. The films were then etched to observe the retention of the silicide. Characterization was done using scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and Rutherford back scattering (RBS). Sheet resistance was measured using the four-point probe technique. Annealing temperatures from 300°C showed films began to agglomerate indicating some diffusion between Ni and Si in the Ti layer, also supported by the compositional analysis in the Auger spectra. Films obtained by evaporation and sputtering were of high quality in terms of coverage over substrate area and uniformity. Thicknesses of Ni and Ti were optimized to 20 nm and 10 nm respectively. Resistivity was low at these thicknesses, and reduced by about half post annealing at 300°C for 8 hours. Thus a low resistivity contact was obtained at optimized thicknesses of the metal layers. It was also shown that some silicide formation occurs at temperatures starting from 300°C and can thus be used to make good silicide contacts.

Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2.

PubMed

Li, Wei; He, Da; Hu, Guoxiang; Li, Xiang; Banerjee, Gourab; Li, Jingyi; Lee, Shin Hee; Dong, Qi; Gao, Tianyue; Brudvig, Gary W; Waegele, Matthias M; Jiang, De-En; Wang, Dunwei

2018-05-23

The inertness of the C-H bond in CH 4 poses significant challenges to selective CH 4 oxidation, which often proceeds all the way to CO 2 once activated. Selective oxidation of CH 4 to high-value industrial chemicals such as CO or CH 3 OH remains a challenge. Presently, the main methods to activate CH 4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH 4 oxidation exhibit limited control over the product selectivity, with CO 2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH 4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO 2 grown by atomic layer deposition (ALD), which features high concentrations of Ti 3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO 2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO 2 . Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO 2 reduction mechanisms. Our results not only present a new route to selective CH 4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.

Enhanced photoelectrochemical properties of TiO2 nanorod arrays decorated with CdS nanoparticles

PubMed Central

Xie, Zheng; Liu, Xiangxuan; Wang, Weipeng; Liu, Can; Li, Zhengcao; Zhang, Zhengjun

2014-01-01

TiO2 nanorod arrays (TiO2 NRAs) sensitized with CdS nanoparticles were fabricated via successive ion layer adsorption and reaction (SILAR), and TiO2 NRAs were obtained by oxidizing Ti NRAs obtained through oblique angle deposition. The TiO2 NRAs decorated with CdS nanoparticles exhibited excellent photoelectrochemical and photocatalytic properties under visible light, and the one decorated with 20 SILAR cycles CdS nanoparticles shows the best performance. This can be attributed to the enhanced separation of electrons and holes by forming heterojunctions of CdS nanoparticles and TiO2 NRAs. This provides a promising way to fabricate the material for solar energy conversion and wastewater degradation. PMID:27877718

Ultrathin and Atomically Flat Transition-Metal Oxide: Promising Building Blocks for Metal-Insulator Electronics.

PubMed

Cui, Qingsong; Sakhdari, Maryam; Chamlagain, Bhim; Chuang, Hsun-Jen; Liu, Yi; Cheng, Mark Ming-Cheng; Zhou, Zhixian; Chen, Pai-Yen

2016-12-21

We present a new and viable template-assisted thermal synthesis method for preparing amorphous ultrathin transition-metal oxides (TMOs) such as TiO 2 and Ta 2 O 5 , which are converted from crystalline two-dimensional (2D) transition-metal dichalcogenides (TMDs) down to a few atomic layers. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning transmission electron microscopy (STEM) were used to characterize the chemical composition and bonding, surface morphology, and atomic structure of these ultrathin amorphous materials to validate the effectiveness of our synthesis approach. Furthermore, we have fabricated metal-insulator-metal (MIM) diodes using the TiO 2 and Ta 2 O 5 as ultrathin insulating layers with low potential barrier heights. Our MIM diodes show a clear transition from direct tunneling to Fowler-Nordheim tunneling, which was not observed in previously reported MIM diodes with TiO 2 or Ta 2 O 5 as the insulating layer. We attribute the improved performance of our MIM diodes to the excellent flatness and low pinhole/defect densities in our TMO insulting layers converted from 2D TMDs, which enable the low-threshold and controllable electron tunneling transport. We envision that it is possible to use the ultrathin TMOs converted from 2D TMDs as the insulating layer of a wide variety of metal-insulator and field-effect electronic devices for various applications ranging from microwave mixing, parametric conversion, infrared photodetection, emissive energy harvesting, to ultrafast electronic switching.

Fabrication of Al2O3 coated 2D TiO2 nanoparticle photonic crystal layers by reverse nano-imprint lithography and plasma enhanced atomic layer deposition.

PubMed

Kim, Ki-Kang; Ko, Ki-Young; Ahn, Jinho

2013-10-01

This paper reports simple process to enhance the extraction efficiency of photoluminescence (PL) from Eu-doped yttrium oxide (Y2O3:Eu3+) thin-film phosphor (TFP). Two-dimensional (2D) photonic crystal layer (PCL) was fabricated on Y2O3:Eu3+ phosphor films by reverse nano-imprint method using TiO2 nanoparticle solution as a nano-imprint resin and a 2D hole-patterned PDMS stamp. Atomic scale controlled Al2O3 deposition was performed onto this 2D nanoparticle PCL for the optimization of the photonic crystal pattern size and stabilization of TiO2 nanoparticle column structure. As a result, the light extraction efficiency of the Y2O3:Eu3+ phosphor film was improved by 2.0 times compared to the conventional Y2O3:Eu3+ phosphor film.

Growth, characterization and post-processing of inorganic and hybrid organic-inorganic thin films deposited using atomic and molecular layer deposition techniques

NASA Astrophysics Data System (ADS)

Abdulagatov, Aziz Ilmutdinovich

Atomic layer deposition (ALD) and molecular layer deposition (MLD) are advanced thin film coating techniques developed for deposition of inorganic and hybrid organic-inorganic films respectively. Decreasing device dimensions and increasing aspect ratios in semiconductor processing has motivated developments in ALD. The beginning of this thesis will cover study of new ALD chemistry for high dielectric constant Y 2O3. In addition, the feasibility of conducting low temperature ALD of TiN and TiAlN is explored using highly reactive hydrazine as a new nitrogen source. Developments of these ALD processes are important for the electronics industry. As the search for new materials with more advanced properties continues, attention has shifted toward exploring the synthesis of hierarchically nanostructured thin films. Such complex architectures can provide novel functions important to the development of state of the art devices for the electronics industry, catalysis, energy conversion and memory storage as a few examples. Therefore, the main focus of this thesis is on the growth, characterization, and post-processing of ALD and MLD films for fabrication of novel composite (nanostructured) thin films. Novel composite materials are created by annealing amorphous ALD oxide alloys in air and by heat treatment of hybrid organic-inorganic MLD films in inert atmosphere (pyrolysis). The synthesis of porous TiO2 or Al2O3 supported V2O5 for enhanced surface area catalysis was achieved by the annealing of inorganic TiVxOy and AlV xOy ALD films in air. The interplay between phase separation, surface energy difference, crystallization, and melting temperature of individual oxides were studied for their control of film morphology. In other work, a class of novel metal oxide-graphitic carbon composite thin films was produced by pyrolysis of MLD hybrid organic-inorganic films. For example, annealing in argon of titania based hybrid films enabled fabrication of thin films of intimately mixed TiO2 and nanographitized carbon. The graphitized carbon in the film was formed as a result of the removal of hydrogen by pyrolysis of the organic constituency of the MLD film. The presence of graphitic carbon allowed a 14 orders of magnitude increase in the electrical conductivity of the composite material compared fully oxidized rutile TiO 2.

Perpendicularly magnetized (001)-textured D0{sub 22} MnGa films grown on an (Mg{sub 0.2}Ti{sub 0.8})O buffer with thermally oxidized Si substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hwachol; Sukegawa, Hiroaki, E-mail: sukegawa.hiroaki@nims.go.jp; Liu, Jun

2015-10-28

We report the growth of (001)-textured polycrystalline D0{sub 22} MnGa films with perpendicular magnetic anisotropy (PMA) on thermally oxidized Si substrates using an (Mg{sub 0.2}Ti{sub 0.8})O (MTO) buffer layer. The ordered D0{sub 22} MnGa film grown at the optimum substrate temperature of 530 °C on the MTO buffer layer shows PMA with magnetization of 80 kA/m, PMA energy density of 0.28 MJ/m{sup 3}, and coercivity of 2.3 T. The scanning transmission electron microscope analysis confirms the formation of a highly (001)-textured structure and the elementally sharp interfaces between the MTO layer and the MnGa layer. The achieved D0{sub 22} MnGa PMA films on anmore » amorphous substrate will provide the possible pathway of integration of a Mn-based PMA film into Si-based substrates.« less

The effect of a Ta oxygen scavenger layer on HfO 2-based resistive switching behavior: Thermodynamic stability, electronic structure, and low-bias transport

DOE PAGES

Zhong, Xiaoliang; Rungger, Ivan; Zapol, Peter; ...

2016-02-15

Reversible resistive switching between high-resistance and low-resistance states in metal-oxide-metal heterostructures makes them very interesting for applications in random access memories. While recent experimental work has shown that inserting a metallic "oxygen scavenger layer'' between the positive electrode and oxide improves device performance, the fundamental understanding of how the scavenger layer modifies the heterostructure properties is lacking. We use density functional theory to calculate thermodynamic properties and conductance of TiN/HfO 2/TiN heterostructures with and without a Ta scavenger layer. First, we show that Ta insertion lowers the formation energy of low-resistance states. Second, while the Ta scavenger layer reduces themore » Schottky barrier height in the high-resistance state by modifying the interface charge at the oxide-electrode interface, the heterostructure maintains a high resistance ratio between high-and low-resistance states. Lastly, we show that the low-bias conductance of device on-states becomes much less sensitive to the spatial distribution of oxygen removed from the HfO 2 in the presence of the Ta layer. By providing a fundamental understanding of the observed improvements with scavenger layers, we open a path to engineer interfaces with oxygen scavenger layers to control and enhance device performance. In turn, this may enable the realization of a non-volatile low-power memory technology with concomitant reduction in energy consumption by consumer electronics and offering significant benefits to society.« less

A critical study of the role of the surface oxide layer in titanium bonding

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1982-01-01

The molecular understanding of the role which the surface oxide layer of the adherend plays in titanium bonding is studied. The effects of Ti6-4 adherends pretreatment, bonding conditions, and thermal aging of the lap shear specimens were studied. The use of the SEM/EDAX and ESCA techniques to study surface morphology and surface composition was emphasized. In addition, contact angles and both infrared and visible reflection spectroscopy were used in ancillary studies.

Core-shell titanium dioxide-titanium nitride nanotube arrays with near-infrared plasmon resonances

NASA Astrophysics Data System (ADS)

Farsinezhad, Samira; Shanavas, Thariq; Mahdi, Najia; Askar, Abdelrahman M.; Kar, Piyush; Sharma, Himani; Shankar, Karthik

2018-04-01

Titanium nitride (TiN) is a ceramic with high electrical conductivity which in nanoparticle form, exhibits localized surface plasmon resonances (LSPRs) in the visible region of the solar spectrum. The ceramic nature of TiN coupled with its dielectric loss factor being comparable to that of gold, render it attractive for CMOS polarizers, refractory plasmonics, surface-enhanced Raman scattering and a whole host of sensing applications. We report core-shell TiO2-TiN nanotube arrays exhibiting LSPR peaks in the range 775-830 nm achieved by a simple, solution-based, low cost, large area-compatible fabrication route that does not involve laser-writing or lithography. Self-organized, highly ordered TiO2 nanotube arrays were grown by electrochemical anodization of Ti thin films on fluorine-doped tin oxide-coated glass substrates and then conformally coated with a thin layer of TiN using atomic layer deposition. The effects of varying the TiN layer thickness and thermal annealing on the LSPR profiles were also investigated. Modeling the TiO2-TiN core-shell nanotube structure using two different approaches, one employing effective medium approximations coupled with Fresnel coefficients, resulted in calculated optical spectra that closely matched the experimentally measured spectra. Modeling provided the insight that the observed near-infrared resonance was not collective in nature, and was mainly attributable to the longitudinal resonance of annular nanotube-like TiN particles redshifted due to the presence of the higher permittivity TiO2 matrix. The resulting TiO2-TiN core-shell nanotube structures also function as visible light responsive photocatalysts, as evidenced by their photoelectrochemical water-splitting performance under light emitting diode illumination using 400, 430 and 500 nm photons.

Avoiding polar catastrophe in the growth of polarly orientated nickel perovskite thin films by reactive oxide molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Yang, H. F.; Liu, Z. T.; Fan, C. C.; Yao, Q.; Xiang, P.; Zhang, K. L.; Li, M. Y.; Liu, J. S.; Shen, D. W.

2016-08-01

By means of the state-of-the-art reactive oxide molecular beam epitaxy, we synthesized (001)- and (111)-orientated polar LaNiO3 thin films. In order to avoid the interfacial reconstructions induced by polar catastrophe, screening metallic Nb-doped SrTiO3 and iso-polarity LaAlO3 substrates were chosen to achieve high-quality (001)-orientated films in a layer-by-layer growth mode. For largely polar (111)-orientated films, we showed that iso-polarity LaAlO3 (111) substrate was more suitable than Nb-doped SrTiO3. In situ reflection high-energy electron diffraction, ex situ high-resolution X-ray diffraction, and atomic force microscopy were used to characterize these films. Our results show that special attentions need to be paid to grow high-quality oxide films with polar orientations, which can prompt the explorations of all-oxide electronics and artificial interfacial engineering to pursue intriguing emergent physics like proposed interfacial superconductivity and topological phases in LaNiO3 based superlattices.

Tuning the Two-Dimensional Electron Liquid at Oxide Interfaces by Buffer-Layer-Engineered Redox Reactions.

PubMed

Chen, Yunzhong; Green, Robert J; Sutarto, Ronny; He, Feizhou; Linderoth, Søren; Sawatzky, George A; Pryds, Nini

2017-11-08

Polar discontinuities and redox reactions provide alternative paths to create two-dimensional electron liquids (2DELs) at oxide interfaces. Herein, we report high mobility 2DELs at interfaces involving SrTiO 3 (STO) achieved using polar La 7/8 Sr 1/8 MnO 3 (LSMO) buffer layers to manipulate both polarities and redox reactions from disordered overlayers grown at room temperature. Using resonant X-ray reflectometry experiments, we quantify redox reactions from oxide overlayers on STO as well as polarity induced electronic reconstruction at epitaxial LSMO/STO interfaces. The analysis reveals how these effects can be combined in a STO/LSMO/disordered film trilayer system to yield high mobility modulation doped 2DELs, where the buffer layer undergoes a partial transformation from perovskite to brownmillerite structure. This uncovered interplay between polar discontinuities and redox reactions via buffer layers provides a new approach for the design of functional oxide interfaces.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poletika, T. M., E-mail: poletm@ispms.tsc.ru; Girsova, S. L., E-mail: girs@ispms.tsc.ru; Meisner, L. L., E-mail: lm@ispms.tsc.ru

The effect of the Ta-ion beam implantation on the micro- and nanostructures of the surface layers of NiTi alloy was investigated using transmission electron microscopy and Auger spectroscopy. It is found that the elements are distributed non-uniformly with depth, so that the sublayers differ significantly in structure. The modified surface layer was found to consist of two sublayers, i.e. the upper oxide layer and the lower-lying amorphous layer that contains a maximum of Ta atoms.

Microstructural characterization and mechanical property of active soldering anodized 6061 Al alloy using Sn-3.5Ag-xTi active solders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wei-Lin, E-mail: wangwl77@gmail.com; Tsai, Yi-Chia, E-mail: tij@itri.org.tw

2012-06-15

Active solders Sn-3.5Ag-xTi varied from x = 0 to 6 wt.% Ti addition were prepared by vacuum arc re-melting and the resultant phase formation and variation of microstructure with titanium concentration were analyzed using X-ray diffraction, optical microscopy and scanning electron microscopy. The Sn-3.5Ag-xTi active solders are used as metallic filler to join with anodized 6061 Al alloy for potential applications of providing a higher heat conduction path. Their joints and mechanical properties were characterized and evaluated in terms of titanium content. The mechanical property of joints was measured by shear testing. The joint strength was very dependent on themore » titanium content. Solder with a 0.5 wt.% Ti addition can successfully wet and bond to the anodized aluminum oxide layers of Al alloy and posses a shear strength of 16.28 {+-} 0.64 MPa. The maximum bonding strength reached 22.24 {+-} 0.70 MPa at a 3 wt.% Ti addition. Interfacial reaction phase and chemical composition were identified by a transmission electron microscope with energy dispersive spectrometer. Results showed that the Ti element reacts with anodized aluminum oxide to form Al{sub 3}Ti-rich and Al{sub 3}Ti phases at the joint interfaces. - Highlights: Black-Right-Pointing-Pointer Active solder joining of anodized Al alloy needs 0.5 wt.% Ti addition for Sn-3.5Ag. Black-Right-Pointing-Pointer The maximum bonding strength occurs at 3 wt.% Ti addition. Black-Right-Pointing-Pointer The Ti reacts with anodized Al oxide to form Al{sub 3}Ti-rich and Al{sub 3}Ti at joint interface.« less

Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

NASA Astrophysics Data System (ADS)

Henegar, A. J., , Dr.; Gougousi, T., , Prof.

2016-12-01

In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al2O3 and TiO2, using H2O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al2O3 ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO2 and the native oxides continues well after the surface has been covered with 2 nm of TiO2. This difference is traced to the superior properties of Al2O3 as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to lower native oxide stability as well as an initial diffusion path formation by the indium oxides.

Surface structure of MgO underlayer with Ti diffusion for (002) oriented L10 FePt-based heat assisted magnetic recording media

NASA Astrophysics Data System (ADS)

Hinata, Sintaro; Jo, Shin; Saito, Shin

2018-05-01

Surface morphology of the MgO layer and magnetic properties of FePt-C layer deposited on the MgO were investigated for the FePt-based heat assisted magnetic recording media. Stacking structure of the underlayer for the FePt-C layer was MgO (0-5 nm)/Cr80Mn20 (0-30 nm)/Cr50Ti50 (0-50 nm)/glass sub.. Surface observation result for the MgO film by using an atomic force microscope revealed the existence of nodules with a height of about 2 nm and a network-like convex structure with a height difference of about sub nm (boundary wall, BW) on the MgO crystal grain boundary. Density of the nodules largely depends on the surface roughness of the CrTi layer, RaCrTi and it is suppressed from 10 to 2/0.5 μm2 by reducing RaCrTi from 420 to 260 pm. Height of the BW depends on thickness of the MgO layer, tMgO and it can be suppressed by reducing tMgO to less than 4 nm. From the cross-sectional energy dispersive x-ray mapping, it is clarified that the BW is formed by atomic diffusion of Ti atoms from CrTi layer due to the substrate heating process, and a compound consists of Mg, Ti and O atoms. This BW can be used as a template to magnetically isolate the FePt column in the FePt-based granular film, such as FePt-SiO2, if the size of the BW is reduced to less than 10 nm. M-H loop of the FePt-C granular film deposited on the underlayer showed that the nodule and BW induce oxidation of the FePt grains, and reduction of intergranular exchange coupling.

New generation photoelectric converter structure optimization using nano-structured materials

NASA Astrophysics Data System (ADS)

Dronov, A.; Gavrilin, I.; Zheleznyakova, A.

2014-12-01

In present work the influence of anodizing process parameters on PAOT geometric parameters for optimizing and increasing ETA-cell efficiency was studied. During the calculations optimal geometrical parameters were obtained. Parameters such as anodizing current density, electrolyte composition and temperature, as well as the anodic oxidation process time were selected for this investigation. Using the optimized TiO2 photoelectrode layer with 3,6 μm porous layer thickness and pore diameter more than 80 nm the ETA-cell efficiency has been increased by 3 times comparing to not nanostructured TiO2 photoelectrode.

CoFe2O4-TiO2 and CoFe2O4-ZnO thin film nanostructures elaborated from colloidal chemistry and atomic layer deposition.

PubMed

Clavel, Guylhaine; Marichy, Catherine; Willinger, Marc-Georg; Ravaine, Serge; Zitoun, David; Pinna, Nicola

2010-12-07

CoFe(2)O(4)-TiO(2) and CoFe(2)O(4)-ZnO nanoparticles/film composites were prepared from directed assembly of colloidal CoFe(2)O(4) in a Langmuir-Blodgett monolayer and atomic layer deposition (ALD) of an oxide (TiO(2) or ZnO). The combination of these two methods permits the use of well-defined nanoparticles from colloidal chemistry, their assembly on a large scale, and the control over the interface between a ferrimagnetic material (CoFe(2)O(4)) and a semiconductor (TiO(2) or ZnO). Using this approach, architectures can be assembled with a precise control from the Angstrom scale (ALD) to the micrometer scale (Langmuir-Blodgett film). The resulting heterostructures present well-calibrated thicknesses. Electron microscopy and magnetic measurement studies give evidence that the size of the nanoparticles and their intrinsic magnetic properties are not altered by the various steps involved in the synthesis process. Therefore, the approach is suitable to obtain a layered composite with a quasi-monodisperse layer of ferrimagnetic nanoparticles embedded in an ultrathin film of semiconducting material.

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Effect of surface treatment and sterilization processes on the corrosion behavior of NiTi shape memory alloy.

PubMed

Thierry, B; Tabrizian, M; Trepanier, C; Savadogo, O; Yahia, L

2000-09-15

Nickel-titanium (NiTi) alloy derives its biocompatibility and good corrosion resistance from a homogeneous oxide layer mainly composed of TiO(2), with a very low concentration of nickel. In this article, we described the corrosion behavior of NiTi alloys after mechanical polishing, electropolishing, and sterilization processes using cyclic polarization and atomic absorption. As a preparative surface treatment, electropolishing decreased the amount of nickel on the surface and remarkably improved the corrosion behavior of the alloy by increasing the mean breakdown potential value and the reproducibility of the results (0.99 +/- 0.05 V/SCE vs. 0.53 +/- 0. 42). Ethylene oxide and Sterrad(R) sterilization techniques did not modify the corrosion resistance of electropolished NiTi, whereas a steam autoclave and, to a lesser extent, peracetic acid sterilization produced scattered breakdown potential. In comparing the corrosion resistance of common biomaterials, NiTi ranked between 316L stainless steel and Ti6A14V even after sterilization. Electropolished NiTi and 316L stainless-steel alloys released similar amounts of nickel after a few days of immersion in Hank's solution. Measurements by atomic absorption have shown that the amount of released nickel from passive dissolution was below the expected toxic level in the human body. Auger electron spectroscopy analyses indicated surface contamination by Ca and P on NiTi during immersion, but no significant modification in oxide thickness was observed.

Improved Osteoblast and Chondrocyte Adhesion and Viability by Surface-Modified Ti6Al4V Alloy with Anodized TiO2 Nanotubes Using a Super-Oxidative Solution

PubMed Central

Beltrán-Partida, Ernesto; Moreno-Ulloa, Aldo; Valdez-Salas, Benjamín; Velasquillo, Cristina; Carrillo, Monica; Escamilla, Alan; Valdez, Ernesto; Villarreal, Francisco

2015-01-01

Titanium (Ti) and its alloys are amongst the most commonly-used biomaterials in orthopedic and dental applications. The Ti-aluminum-vanadium alloy (Ti6Al4V) is widely used as a biomaterial for these applications by virtue of its favorable properties, such as high tensile strength, good biocompatibility and excellent corrosion resistance. TiO2 nanotube (NTs) layers formed by anodization on Ti6Al4V alloy have been shown to improve osteoblast adhesion and function when compared to non-anodized material. In his study, NTs were grown on a Ti6Al4V alloy by anodic oxidation for 5 min using a super-oxidative aqueous solution, and their in vitro biocompatibility was investigated in pig periosteal osteoblasts and cartilage chondrocytes. Scanning electron microscopy (SEM), energy dispersion X-ray analysis (EDX) and atomic force microscopy (AFM) were used to characterize the materials. Cell morphology was analyzed by SEM and AFM. Cell viability was examined by fluorescence microscopy. Cell adhesion was evaluated by nuclei staining and cell number quantification by fluorescence microscopy. The average diameter of the NTs was 80 nm. The results demonstrate improved cell adhesion and viability at Day 1 and Day 3 of cell growth on the nanostructured material as compared to the non-anodized alloy. In conclusion, this study evidences the suitability of NTs grown on Ti6Al4V alloy using a super-oxidative water and a short anodization process to enhance the adhesion and viability of osteoblasts and chondrocytes. The results warrant further investigation for its use as medical implant materials. PMID:28787976

Improved Osteoblast and Chondrocyte Adhesion and Viability by Surface-Modified Ti6Al4V Alloy with Anodized TiO₂ Nanotubes Using a Super-Oxidative Solution.

PubMed

Beltrán-Partida, Ernesto; Moreno-Ulloa, Aldo; Valdez-Salas, Benjamín; Velasquillo, Cristina; Carrillo, Monica; Escamilla, Alan; Valdez, Ernesto; Villarreal, Francisco

2015-03-02

Titanium (Ti) and its alloys are amongst the most commonly-used biomaterials in orthopedic and dental applications. The Ti-aluminum-vanadium alloy (Ti6Al4V) is widely used as a biomaterial for these applications by virtue of its favorable properties, such as high tensile strength, good biocompatibility and excellent corrosion resistance. TiO₂ nanotube (NTs) layers formed by anodization on Ti6Al4V alloy have been shown to improve osteoblast adhesion and function when compared to non-anodized material. In his study, NTs were grown on a Ti6Al4V alloy by anodic oxidation for 5 min using a super-oxidative aqueous solution, and their in vitro biocompatibility was investigated in pig periosteal osteoblasts and cartilage chondrocytes. Scanning electron microscopy (SEM), energy dispersion X-ray analysis (EDX) and atomic force microscopy (AFM) were used to characterize the materials. Cell morphology was analyzed by SEM and AFM. Cell viability was examined by fluorescence microscopy. Cell adhesion was evaluated by nuclei staining and cell number quantification by fluorescence microscopy. The average diameter of the NTs was 80 nm. The results demonstrate improved cell adhesion and viability at Day 1 and Day 3 of cell growth on the nanostructured material as compared to the non-anodized alloy. In conclusion, this study evidences the suitability of NTs grown on Ti6Al4V alloy using a super-oxidative water and a short anodization process to enhance the adhesion and viability of osteoblasts and chondrocytes. The results warrant further investigation for its use as medical implant materials.

Microstructure of rapidly solidified Nb-based pre-alloyed powders for additive manufacturing

NASA Astrophysics Data System (ADS)

Guo, Yueling; Jia, Lina; Kong, Bin; Zhang, Shengnan; Zhang, Fengxiang; Zhang, Hu

2017-07-01

For powder-based additive manufacturing, sphere-shaped Nb-37Ti-13Cr-2Al-1Si pre-alloyed powders were prepared by plasma rotating electrode processing (PREP). The microstructure, surface oxidation and microhardness of the pre-alloyed powders were systematically investigated. Results showed that the main phases were Nb solid solution (Nbss) and Cr2Nb. The Cr2Nb phases were further determined using transmission electron microscopy (TEM). Fine dendrite structures were observed in the as-fabricated pre-alloyed powders, which transformed to large grains after heat treatment (HT) at 1450 °C for 3 h. With the increase of powder size, the secondary dendrite arm spacing (SDAS) increased and the microhardness (HV) decreased. A clean powder surface free of oxide particles was obtained by PREP and an oxide layer with 9.39 nm in thickness was generated on the powder surface. Compared with Cr- and Nb-oxides, more Ti-oxides were formed on outmost powder surface with a higher content of Ti (up to 47.86 at.%). The differences upon the microstructure and microhardness of the pre-alloyed powders with different sizes were discussed.

Preparation and characterization of porous bioceramic layers on pure titanium surfaces obtained by micro-arc oxidation process

NASA Astrophysics Data System (ADS)

Chien, Chi-Sheng; Hung, Yu-Chien; Hong, Ting-Fu; Wu, Chung-Chun; Kuo, Tsung-Yuan; Lee, Tzer-Min; Liao, Tze-Yuan; Lin, Huan-Chang; Chuang, Cheng-Hsin

2017-03-01

Fluorapatite (FA) has better chemical and thermal stability than hydroxyapatite (HA), and has thus attracted significant interest for biomaterial applications in recent years. In this study, porous bioceramic layers were prepared on pure titanium surfaces using a micro-arc oxidation (MAO) technique with an applied voltage of 450 V and an oxidation time of 5 min. The MAO process was performed using three different electrolyte solutions containing calcium fluoride (CaF2), calcium acetate monohydrate (Ca(CH3COO)2·H2O), and sodium phosphate monobasic dihydrate (NaH2PO4·2H2O) mixed in ratios of 0:2:1, 1:1:1, and 2:0:1, respectively. The surface morphology, composition, micro-hardness, porosity, and biological properties of the various MAO coatings were examined and compared. The results showed that as the CaF2/Ca(CH3COO)2·H2O ratio increased, the elemental composition of the MAO coating transformed from HA, A-TiO2 (Anatase) and R-TiO2 (Rutile); to A-TiO2, R-TiO2, and a small amount of HA; and finally A-TiO2, R-TiO2, CaF2, TiP2O5, and FA. The change in elemental composition was accompanied by a higher micro-hardness and a lower porosity. The coatings exhibited a similar in vitro bioactivity performance during immersion in simulated body fluid for 7-28 days. Furthermore, for in initial in vitro biocompatibility tests performed for 24 h using Dulbecco's Modified Eagle Medium (DMEM) supplement containing 10%Fetal bovine serum, the attachment and spreading of osteoblast-like osteosarcoma MG63 cells were found to increase slightly with an increasing CaF2/Ca(CH3COO)2·H2O ratio. In general, the results presented in this study show that all three MAO coatings possess a certain degree of in vitro bioactivity and biocompatibility.

TiO2-photocatalyzed As(III) oxidation in a fixed-bed, flow-through reactor.

PubMed

Ferguson, Megan A; Hering, Janet G

2006-07-01

Compliance with the U.S. drinking water standard for arsenic (As) of 10 microg L(-1) is required in January 2006. This will necessitate implementation of treatment technologies for As removal by thousands of water suppliers. Although a variety of such technologies is available, most require preoxidation of As(III) to As(V) for efficient performance. Previous batch studies with illuminated TiO2 slurries have demonstrated that TiO2-photocatalyzed AS(III) oxidation occurs rapidly. This study examined reaction efficiency in a flow-through, fixed-bed reactor that provides a better model for treatment in practice. Glass beads were coated with mixed P25/sol gel TiO2 and employed in an upflow reactor irradiated from above. The reactor residence time, influent As(III) concentration, number of TiO2 coatings on the beads, solution matrix, and light source were varied to characterize this reaction and determine its feasibility for water treatment. Repeated usage of the same beads in multiple experiments or extended use was found to affect effluent As(V) concentrations but not the steady-state effluent As(III) concentration, which suggests that As(III) oxidation at the TiO2 surface undergoes dynamic sorption equilibration. Catalyst poisoning was not observed either from As(V) or from competitively adsorbing anions, although the higher steady-state effluent As(III) concentrations in synthetic groundwater compared to 5 mM NaNO3 indicated that competitive sorbates in the matrix partially hinder the reaction. A reactive transport model with rate constants proportional to incident light at each bead layer fit the experimental data well despite simplifying assumptions. TiO2-photocatalyzed oxidation of As(III) was also effective under natural sunlight. Limitations to the efficiency of As(III) oxidation in the fixed-bed reactor were attributable to constraints of the reactor geometry, which could be overcome by improved design. The fixed-bed TiO2 reactor offers an environmentally benign method for As(III) oxidation.

The Effect of Film Thickness on the Gas Sensing Properties of Ultra-Thin TiO₂ Films Deposited by Atomic Layer Deposition.

PubMed

Wilson, Rachel L; Simion, Cristian Eugen; Blackman, Christopher S; Carmalt, Claire J; Stanoiu, Adelina; Di Maggio, Francesco; Covington, James A

2018-03-01

Analyte sensitivity for gas sensors based on semiconducting metal oxides should be highly dependent on the film thickness, particularly when that thickness is on the order of the Debye length. This thickness dependence has previously been demonstrated for SnO₂ and inferred for TiO₂. In this paper, TiO₂ thin films have been prepared by Atomic Layer Deposition (ALD) using titanium isopropoxide and water as precursors. The deposition process was performed on standard alumina gas sensor platforms and microscope slides (for analysis purposes), at a temperature of 200 °C. The TiO₂ films were exposed to different concentrations of CO, CH₄, NO₂, NH₃ and SO₂ to evaluate their gas sensitivities. These experiments showed that the TiO₂ film thickness played a dominant role within the conduction mechanism and the pattern of response for the electrical resistance towards CH₄ and NH₃ exposure indicated typical n -type semiconducting behavior. The effect of relative humidity on the gas sensitivity has also been demonstrated.

Topotactical growth of thick perovskite oxynitride layers by nitridation of single crystalline oxides

NASA Astrophysics Data System (ADS)

Ebbinghaus, Stefan G.; Aguiar, Rosiana; Weidenkaff, Anke; Gsell, Stefan; Reller, Armin

2008-06-01

Thick films of the perovskite-related oxynitrides LaTiO 2N, NdTiO 2N, SrNbO 2N and SrTaO 2N were synthesised by nitridation of single crystals of the corresponding oxides with general composition ABO 3.5. The oxide crystals were obtained by optical floating zone growth. They correspond to n = 4 member of the A nB nO 3 n+2 family of layered perovskites and were reacted at temperatures between 900 °C and 1050 °C to form the oxynitrides. Electron probe microanalysis proved the presence of nitrogen in a surface layer of a few micrometer thickness. Cross-section SEM revealed additional thin stripes of oxynitride within the bulk of the crystals, indicating that nitrogen is incorporated preferably parallel to the perovskite-type layers, which in turn are connected in a zipper-type mechanism. The formation of the desired perovskite-type oxynitrides was confirmed by X-ray diffraction. Pole figure measurements proved an epitaxial orientation ABO 2N (110)[001] ‖ ABO 3.5 (001)[100]. The mosaicity of the oxynitrides both in polar and azimuthal direction was very small (<2°) indicating a nearly single crystalline quality of the surface layer. The nitridation of the crystals results in a dramatic change in colour. Optical spectroscopy revealed shifts of the absorption edge by more than 200 nm to longer wavelengths with respect to the parent oxides, corresponding to a reduction of the band gap energies by 1.4-1.8 eV.

Molybdeno-Aluminizing of Powder Metallurgy and Wrought Ti and Ti-6Al-4V alloys by Pack Cementation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsipas, Sophia A., E-mail: stsipas@ing.uc3m.es; Go

Wear and high temperature oxidation resistance of some titanium-based alloys needs to be enhanced, and this can be effectively accomplished by surface treatment. Molybdenizing is a surface treatment where molybdenum is introduced into the surface of titanium alloys causing the formation of wear-resistant surface layers containing molybdenum, while aluminizing of titanium-based alloys has been reported to improve their high temperature oxidation properties. Whereas pack cementation and other surface modification methods have been used for molybdenizing or aluminizing of wrought and/or cast pure titanium and titanium alloys, such surface treatments have not been reported on titanium alloys produced by powder metallurgymore » (PM). Also a critical understanding of the process parameters for simultaneous one step molybdeno-aluminizing of titanium alloys by pack cementation and the predominant mechanism for this process have not been reported. The current research work describes the surface modification of titanium and Ti-6Al-4V prepared by PM by molybdeno-aluminizing and analyzes thermodynamic aspects of the deposition process. Similar coatings are also deposited to wrought Ti-6Al-4V and compared. Characterization of the coatings was carried out using scanning electron microscopy and x-ray diffraction. For both titanium and Ti-6Al-4V, the use of a powder pack containing ammonium chloride as activator leads to the deposition of molybdenum and aluminium into the surface but also introduces nitrogen causing the formation of a thin titanium nitride layer. In addition, various titanium aluminides and mixed titanium aluminium nitrides are formed. The appropriate conditions for molybdeno-aluminizing as well as the phases expected to be formed were successfully determined by thermodynamic equilibrium calculations. - Highlights: •Simultaneous co-deposition of Mo-Al onto powder metallurgy and wrought Ti alloy •Thermodynamic calculations were used to optimize deposition conditions •External TiN and internal a Mo-rich layer on all alloy substrates •Titanium aluminides and Ti-Al mixed nitrides are formed on Ti-6Al-4V •The presence of Al and V alloying elements modifies the diffusion of Mo.« less

Titanium Dioxide Volatility in High Temperature Water Vapor

NASA Technical Reports Server (NTRS)

Nguyen, QynhGiao N.

2008-01-01

Titanium (Ti) containing materials are of high interest to the aerospace industry due to its high temperature capability, strength, and light weight. As with most metals an exterior oxide layer naturally exists in environments that contain oxygen (i.e. air). At high temperatures, water vapor plays a key role in the volatility of materials including oxide surfaces. This study will evaluate cold pressed titanium dioxide (TiO2) powder pellets at a temperature range of 1400 C - 1200 C in water containing environments to determine the volatile hydroxyl species using the transpiration method. The water content ranged from 0-76 mole% and the oxygen content range was 0-100 mole % during the 20-250 hour exposure times. Preliminary results indicate that oxygen is not a key contributor at these temperatures and the following reaction is the primary volatile equation for all three temperatures: TiO2 (s) + H2O (g) = TiO(OH)2 (g).

Solute redistribution and phase stability at FeCr/TiO 2–x interfaces under ion irradiation

DOE PAGES

Xu, Y.; Aguiar, J. A.; Yadav, S. K.; ...

2015-02-26

Cr diffusion in trilayer thin films of 100 nm Fe–18Cr/125 nm TiO 2–x/100 nm Fe–18Cr deposited on MgO substrates at 500 °C was studied by either annealing at 500 °C or Ni 3+ ion irradiation at 500 °C. Microchemistry and microstructure evolution at the metal/oxide interfaces were investigated using (high-resolution) transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy. Diffusion of Cr into the O-deficient TiO 2 layer, with negligible segregation to the FeCr/TiO 2–x interface itself, was observed under both annealing and irradiation. Cr diffusion into TiO 2–x was enhanced in ion-irradiated samples as compared to annealed.more » Irradiation-induced voids and amorphization of TiO 2–x was also observed. The experimental results are rationalized using first-principles calculations that suggest an energetic preference for substituting Ti with Cr in sub-stoichiometric TiO 2. Furthermore, the implications of these results on the irradiation stability of oxide-dispersed ferritic alloys are discussed.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cats, K. H.; Andrews, J. C.; Stephan, O.

In this study, the Fischer-Tropsch synthesis (FTS) reaction is one of the most promising processes to convert alternative energy sources, such as natural gas, coal or biomass, into liquid fuels and other high-value products. Despite its commercial implementation, we still lack fundamental insights into the various deactivation processes taking place during FTS. In this work, a combination of three methods for studying single catalyst particles at different length scales has been developed and applied to study the deactivation of Co/TiO 2 Fischer-Tropsch synthesis (FTS) catalysts. By combining transmission X-ray microscopy (TXM), scanning transmission X-ray microscopy (STXM) and scanning transmission electronmore » microscopy-electron energy loss spectroscopy (STEM-EELS) we visualized changes in the structure, aggregate size and distribution of supported Co nanoparticles that occur during FTS. At the microscale, Co nanoparticle aggregates are transported over several μm leading to a more homogeneous Co distribution, while at the nanoscale Co forms a thin layer of ~1-2 nm around the TiO 2 support. The formation of the Co layer is the opposite case to the “classical” strong metal-support interaction (SMSI) in which TiO 2 surrounds the Co, and is possibly related to the surface oxidation of Co metal nanoparticles in combination with coke formation. In other words, the observed migration and formation of a thin CoO x layer are similar to a previously discussed reaction-induced spreading of metal oxides across a TiO 2 surface.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bronson, Arturo; Kumar, Vinod

The effects of plasma on carbides were computationally investigated for the ultimate development of adherent, dense scales such as Al 2O 3-TiO 2 systems toward oxidation resistance at 1873 K. An alumina scale forms on the carbide because of the significant stability of Al 2O 3 as the outer scale adjacent to the gas phase compared to rutile, though TiO and Ti 2O 3 may form as components of an inner layer of a complicated scale. A sequence of surface reactions starting with the adsorption of oxygen on the surface was applied to experimental data from Donnelly’s research group whomore » reported the adsorption of O 2 in a plasma atmosphere as a function of power. In addition to the adsorbed oxygen (Oad) as the rate determining step, it controlled the cascading reaction sequence of the adsorbed species of AlO, AlO 2 and AlO 3, as indicated in the present study. The rate of oxygen adsorption also depends on the ratio of the final to initial adsorbed oxygen as a function the oxygen potential. In a secondary research thrust, Ti 3AlC was synthesized and subsequently oxidized. A 39Ti-14Al-47TiC (in wt%) mixture was equilibrated by using a pseudo-isopiestic technique to form ultimately an aggregate of Ti3AlC, Ti 2AlC and TiC phases. The aggregate was primarily composed of Ti 3AlC with minor amounts of Ti 2AlC and TiC, as determined by an X-ray diffraction analysis. The Ti 3AlC/Ti 2AlC/TiC aggregate was subsequently oxidized at 1873 K to form a scale composed of an outer layer of Al 2O 3-TiO 2-Al 2TiO 5 with an inner layer consisting of TiO-Al 2O 3- Al 4CO 3. The measured scale thickness grew according to Wagner’s parabolic growth rate, which estimates an effective diffusion coefficient of 6 (10)-8 cm 2/s. The scale appears to grow with Ti ions migrating outward from the Ti 3AlC/Ti 2AlC/TiC core and oxygen ions diffusing inwardly toward the core. The transient temperature distribution of a cylindrical, carbide packed bed (i.e., B4C) was simulated with COMSOL software to determine the response of the bed to a sudden temperature spike exposed to the outer wall of the bed. The temperature distribution of B4C was similarly heated and compared with Hf and Zr metal. The thermal conductivity of Hf and Zr is higher than the B4C packed bed and hence they respond quicker than B4C. The packed bed still takes approximately 1200 s to plateau the temperature distribution between the cylinder surfaces to the centerline of the carbide packed bed of 5 cm diameter. Though the modeling of the distributions in the carbide packed bed gives an understanding of the transient heat response behavior driven by radiation, the effect of the plasma on the surface temperature of individual carbide particles needs further investigation to understand the plasma contribution to densification of a carbide packed bed.« less

Visible photoelectrochemical water splitting into H 2 and O 2 in a dye-sensitized photoelectrosynthesis cell

DOE PAGES

Alibabaei, Leila; Sherman, Benjamin D.; Norris, Michael R.; ...

2015-04-27

A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO 2/TiO 2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO 3H 2) 2bpy) 2Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH 2)] 4+ ([RuaII-RubII-OH 2] 4+, combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO 2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al 2O 3 or TiO 2 overlayers. Illumination of the resulting fluorine-dopedmore » tin oxide (FTO)|SnO 2/TiO 2|-[Ru a II-Ru b II-OH 2] 4+(Al 2O 3 or TiO 2) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H 2 and O 2. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO 2/TiO 2 core/shell compared with nanoITO/TiO 2 with the same assembly results in photocurrent enhancements of ~5. In conclusion, systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm 2 with 445-nm, ~90-mW/cm 2 illumination in a phosphate buffer at pH 7.« less

Au-free ohmic Ti/Al/TiN contacts to UID n-GaN fabricated by sputter deposition

NASA Astrophysics Data System (ADS)

Garbe, V.; Weise, J.; Motylenko, M.; Münchgesang, W.; Schmid, A.; Rafaja, D.; Abendroth, B.; Meyer, D. C.

2017-02-01

The fabrication and characterization of an Au-free Ti/Al/TiN (20/100/100 nm) contact stack to unintentionally doped n-GaN with TiN serving as the diffusion barrier is presented. Sputter deposition and lift-off in combination with post deposition annealing at 850 °C are used for contact formation. After annealing, contact shows ohmic behavior to n-GaN and a specific contact resistivity of 1.60 × 10-3 Ω cm2. To understand the contact formation on the microscopic scale, the contact was characterized by current-voltage measurements, linear transmission line method, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show the formation of Ti-N bonds at the GaN/Ti interface in the as-deposited stack. Annealing leads to diffusion of Ti, Al, Ga, and N, and the remaining metallic Ti is fully consumed by the formation of the intermetallic tetragonal Al3Ti phase. Native oxide from the GaN surface is trapped during annealing and accumulated in the Al interlayer. The TiN capping layer, however, was chemically stable during annealing. It prevented oxidation of the Ti/Al contact bilayer successfully and thus proved to be a well suitable diffusion barrier with ideal compatibility to the Ti/Al contact metallization.

Enhanced photochemical catalysis of TiO2 inverse opals by modification with ZnO or Fe2O3 using ALD and the hydrothermal method

NASA Astrophysics Data System (ADS)

Liu, Jiatong; Sun, Cuifeng; Fu, Ming; Long, Jie; He, Dawei; Wang, Yongsheng

2018-02-01

The development of porous materials exhibiting photon regulation abilities for improved photoelectrochemical catalysis performance is always one of the important goals of solar energy harvesting. In this study, methods to improve the photocatalytic activity of TiO2 inverse opals were discussed. TiO2 inverse opals were prepared by atomic layer deposition (ALD) using colloidal crystal templates. In addition, TiO2 inverse opal heterostructures were fabricated using colloidal heterocrystals by repeated vertical deposition using different colloidal spheres. The hydrothermal method and ALD were used to prepare ZnO- or Fe2O3-modified TiO2 inverse opals on the internal surfaces of the TiO2 porous structures. Although the photonic reflection band was not significantly varied by oxide modification, the presence of Fe2O3 in the TiO2 inverse opals enhanced their visible absorption. The conformally modified oxides on the TiO2 inverse opals could also form energy barriers and avoid the recombination of electrons and holes. The fabrication of the TiO2 photonic crystal heterostructures and modification with ZnO or Fe2O3 can enhance the photocatalytic activity of TiO2 inverse opals.

Petrography and trace element signatures in silicates and Fe-Ti-oxides from the Lanjiahuoshan deposit, Panzhihua layered intrusion, Southwest China

NASA Astrophysics Data System (ADS)

Gao, Wenyuan; Ciobanu, Cristiana L.; Cook, Nigel J.; Huang, Fei; Meng, Lin; Gao, Shang

2017-12-01

Permian mafic-ultramafic layered intrusions in the central part of the Emeishan Large Igneous Province (ELIP), Southwestern China, host Fe-Ti-V-oxide ores that have features which distinguish them from other large layered intrusion-hosted deposits. The origin of these ores is highly debated. Careful petrographic examination, whole rock analysis, electron probe microanalysis, and measurement and mapping of trace element concentrations by laser ablation inductively coupled plasma mass spectrometry in all major and minor minerals (clinopyroxene, plagioclase, olivine, amphibole, titanomagnetite, ilmenite, pleonaste and pyrrhotite) has been undertaken on samples from the Lanjiahuoshan deposit, representing the Middle, Lower and Marginal Zone of the Panzhihua intrusion. Features are documented that impact on interpretation of intrusion petrology and with implications for genesis of the Fe-Ti-V-oxide ores. Firstly, there is evidence, as symplectites between clinopyroxene and plagioclase, for introduction of complex secondary melts. Secondly, reaction between a late hydrothermal fluid and clinopyroxene is recognized, which has led to formation of hydrated minerals (pargasite, phlogopite), as well as a potassium metasomatic event, postdating intrusion solidification, which led to formation of K-feldspar. Lastly, partitioning of trace elements between titanomagnetite and silicates needs to consider scavenging of metals by ilmenite (Mn, Sc, Zr, Nb, Sn, Hf and Ta) and sulfides, as well as the marked partitioning of Co, Ni, Zn, Ga, As and Sb into spinels exsolved from titanomagnetite. The role of these less abundant phases may have been understated in previous studies, highlighting the importance of petrographic examination of complex silicate-oxide-sulfide assemblages, as well as the need for a holistic approach to trace element analysis, acknowledging all minerals within the assemblage.

Influence of microstructure and chemical composition of sputter deposited TiO2 thin films on in vitro bioactivity.

PubMed

Lilja, Mirjam; Genvad, Axel; Astrand, Maria; Strømme, Maria; Enqvist, Håkan

2011-12-01

Functionalisation of biomedical implants via surface modifications for tailored tissue response is a growing field of research. Crystalline TiO(2) has been proven to be a bone bioactive, non-resorbable material. In contact with body fluids a hydroxyapaptite (HA) layer forms on its surface facilitating the bone contact. Thus, the path of improving biomedical implants via deposition of crystalline TiO(2) on the surface is interesting to follow. In this study we have evaluated the influence of microstructure and chemical composition of sputter deposited titanium oxide thin films on the in vitro bioactivity. We find that both substrate bias, topography and the flow ratio of the gases used during sputtering affect the HA layer formed on the films after immersion in simulated body fluid at 37°C. A random distribution of anatase and rutile crystals, formed at negative substrate bias and low Ar to O(2) gas flow ratios, are shown to favor the growth of flat HA crystal structures whereas higher flow ratios and positive substrate bias induced growth of more spherical HA structures. These findings should provide valuable information when optimizing the bioactivity of titanium oxide coatings as well as for tailoring process parameters for sputtered-based production of bioactive titanium oxide implant surfaces.

Enhanced photocatalytic activity of hydrogenated and vanadium doped TiO2 nanotube arrays grown by anodization of sputtered Ti layers

NASA Astrophysics Data System (ADS)

Motola, Martin; Satrapinskyy, Leonid; Čaplovicová, Mária; Roch, Tomáš; Gregor, Maroš; Grančič, Branislav; Greguš, Ján; Čaplovič, Ľubomír; Plesch, Gustav

2018-03-01

TiO2 nanotube (TiNT) arrays were grown on silicon substrate via electrochemical anodization of titanium films sputtered by magnetron. To improve the photocatalytic activity of arrays annealed in air (o-TiNT), doping of o-TiNT with vanadium was performed (o-V/TiNT). These non-doped and doped TiNT arrays were also hydrogenated in H2/Ar atmosphere to r-TiNT and r-V/TiNT samples, respectively. Investigation of composition and morphology by X-ray diffraction (XRD), electron microscopy (SEM and TEM) and X-ray photoelectron spectroscopy (XPS) showed the presence of well-ordered arrays of anatase nanotubes with average diameter and length of 100 nm and 1.3 μm, respectively. In both oxidized and reduced V-doped samples, vanadium is partly dissolved in the structure of anatase and partly deposited in form of oxide on the nanotube surface. Vanadium-doped and reduced samples exhibited higher rates in the photodegradation of organic dyes (compared to non-modified o-TiNT sample) and this is caused by limitation of electron-hole recombination rates and by shift of the energy gap into visible region. The photocatalytic activity was measured under UV, sunlight and visible irradiation, and the corresponding efficiency increased in the order (o-TiNT) < (r-TiNT) < (o-V/TiNT) < (r-V/TiNT). Under visible light, only r-TiNT and r-V/TiNT showed significant photocatalytic activity.

Electronic structure of layered ferroelectric high-k titanate La2Ti2O7

NASA Astrophysics Data System (ADS)

Atuchin, V. V.; Gavrilova, T. A.; Grivel, J.-C.; Kesler, V. G.

2009-02-01

The electronic structure of binary titanate La2Ti2O7 has been studied by x-ray photoelectron spectroscopy. Spectral features of valence band and all constituent element core levels have been considered. The Auger parameters of titanium and oxygen in La2Ti2O7 are determined as αTi = 872.4 and αO = 1042.3 eV. Chemical bonding effects have been discussed with binding energy (BE) differences ΔTi = (BE O 1s - BE Ti 2p3/2) = 71.6 eV and ΔLa = (BE La 3d5/2 - BE O 1s) = 304.7 eV as key parameters in comparison with those in several titanium- and lanthanum-bearing oxides.

Electronic structure of layered titanate Nd 2Ti 2O 7

NASA Astrophysics Data System (ADS)

Atuchin, V. V.; Gavrilova, T. A.; Grivel, J.-C.; Kesler, V. G.

2008-10-01

The electronic structure of the binary titanate Nd 2Ti 2O 7 has been studied by X-ray photoelectron spectroscopy (XPS). Spectral features of the valence band and all constituent element core levels have been considered. The Auger parameters of titanium and oxygen in Nd 2Ti 2O 7 are determined as αTi = 873.5 and αO = 1042.2 eV. Chemical bonding effects have been discussed with the binding energies differences ΔTi = (BE O 1s - BE Ti 2p 3/2) = 71.5 eV and ΔNd = (BE Nd 3d 5/2 - BE O 1s) = 452.5 eV as key parameters in comparison with those in other titanium- and neodymium-bearing oxides.

Comparative study of ITO and TiN fabricated by low-temperature RF biased sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simon, Daniel K., E-mail: daniel.simon@namlab.com; Schenk, Tony; Dirnstorfer, Ingo

2016-03-15

Radio frequency (RF) biasing induced by a second plasma source at the substrate is applied to low-temperature sputtering processes for indium tin oxide (ITO) and titanium nitride (TiN) thin films. Investigations on crystal structure and surface morphology show that RF-biased substrate plasma processes result in a changed growth regime with different grain sizes and orientations than those produced by processes without a substrate bias. The influence of the RF bias is shown comparatively for reactive RF-sputtered ITO and reactive direct-current-sputtered TiN. The ITO layers exhibit an improved electrical resistivity of 0.5 mΩ cm and an optical absorption coefficient of 0.5 × 10{sup 4 }cm{supmore » −1} without substrate heating. Room-temperature sputtered TiN layers are deposited that possess a resistivity (0.1 mΩ cm) of 3 orders of magnitude lower than, and a density (5.4 g/cm{sup 3}) up to 45% greater than, those obtained from layers grown using the standard process without a substrate plasma.« less

Performance enhancement of perovskite solar cells with Mg-doped TiO{sub 2} compact film as the hole-blocking layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jing; Qin, Minchao; Tao, Hong

2015-03-23

In this letter, we report perovskite solar cells with thin dense Mg-doped TiO{sub 2} as hole-blocking layers (HBLs), which outperform cells using TiO{sub 2} HBLs in several ways: higher open-circuit voltage (V{sub oc}) (1.08 V), power conversion efficiency (12.28%), short-circuit current, and fill factor. These properties improvements are attributed to the better properties of Mg-modulated TiO{sub 2} as compared to TiO{sub 2} such as better optical transmission properties, upshifted conduction band minimum (CBM) and downshifted valence band maximum (VBM), better hole-blocking effect, and higher electron life time. The higher-lying CBM due to the modulation with wider band gap MgO and themore » formation of magnesium oxide and magnesium hydroxides together resulted in an increment of V{sub oc}. In addition, the Mg-modulated TiO{sub 2} with lower VBM played a better role in the hole-blocking. The HBL with modulated band position provided better electron transport and hole blocking effects within the device.« less

The impact of ultra-thin titania interlayers on open circuit voltage and carrier lifetime in thin film solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moerman, David; Colbert, Adam E.; Ginger, David S., E-mail: ginger@chem.washington.edu

We study the effects of modifying indium tin oxide electrodes with ultrathin titania (TiO{sub 2}) layers grown via plasma-enhanced atomic layer deposition (PE-ALD). We find an optimal thickness of PE-ALD-grown titania by tracking performance, which initially increases, peaks, and eventually decreases with increasing TiO{sub 2} thickness. We use scanning Kelvin probe microscopy (SKPM) to measure both the local work function and its distribution as a function of TiO{sub 2} thickness. We find that the variance in contact potential difference across the surface of the film is related to either the amorphous or anatase TiO{sub 2} form. Finally, we use localmore » SKPM recombination rate experiments, supported by bulk transient photovoltage and charge extraction measurements. We show that the optimum TiO{sub 2} thickness is the one for which the carrier lifetime is the longest and the charge carrier density is the highest, when the TiO{sub 2} is amorphous, in agreement with the device measurements.« less

Biocorrosion studies of TiO2 nanoparticle-coated Ti-6Al-4V implant in simulated biofluids

NASA Astrophysics Data System (ADS)

Zaveri, Nikita; McEwen, Gerald D.; Karpagavalli, Ramji; Zhou, Anhong

2010-06-01

The corrosion behaviors of the TiO2 nanoparticles coated bioimplant Ti-6Al-4V exposed to three different simulated biofluids (SBF), namely, (1) NaCl solution, (2) Hank's solution, and (3) Cigada solution, were studied by using micro-Raman spectroscopy, electrochemical techniques, and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS). The different electrochemical impedance spectroscopy models were applied to fit the data obtained from the implants before and after the coating of TiO2 nanoparticles (50-100 nm). It was found that the TiO2 nanoparticle coatings increased the thickness of the pre-existing oxide layer on the Ti-6Al-4V surface, serving to improve the bioimplant corrosion resistance.

Role of the conducting layer substrate on TiO2 nucleation when using microwave activated chemical bath deposition

NASA Astrophysics Data System (ADS)

Zumeta, I.; Espinosa, R.; Ayllón, J. A.; Vigil, E.

2002-12-01

Nanostructured TiO2 is used in novel dye sensitized solar cells. Because of their interaction with light, thin TiO2 films are also used as coatings for self-cleaning glasses and tiles. Microwave activated chemical bath deposition represents a simple and cost-effective way to obtain nanostructured TiO2 films. It is important to study, in this technique, the role of the conducting layer used as the substrate. The influence of microwave-substrate interactions on TiO2 deposition is analysed using different substrate positions, employing substrates with different conductivities, and also using different microwave radiation powers for film deposition. We prove that a common domestic microwave oven with a large cavity and inhomogeneous radiation field can be used with equally satisfactory results. The transmittance spectra of the obtained films were studied and used to analyse film thickness and to obtain gap energy values. The results, regarding different indium-tin oxide resistivities and different substrate positions in the oven cavity, show that the interaction of the microwave field with the conducting layer is determinant in layer deposition. It has also been found that film thickness increases with the power of the applied radiation while the gap energies of the TiO2 films decrease approaching the 3.2 eV value reported for bulk anatase. This indicates that these films are not crystalline and it agrees with x-ray spectra that do not reveal any peak.

Effects of Oxide Film on the Corrosion Resistance of Titanium Grade 7 in Fluoride-Containing NaCl Brines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lian, T; Whalen, M T; Wong, L

2004-11-30

The effects of oxide film on the corrosion behavior of Titanium Grade 7 (0.12-0.25% Pd) in fluoride-containing NaCl brines have been investigated. With the presence of a 0.6 {micro}m thick oxide layer, the annealed Ti grade 7 exhibited a significant improvement on the anodic polarization behavior. However, the oxide film did not demonstrate sustainable corrosion resistance in fluoride-containing solutions.

Structures, Properties and Defects of SrTiO3/GaAs Hetero-interfaces

NASA Astrophysics Data System (ADS)

Hong, Liang; Bhatnagar, Kunal; Droopad, Ravi; Öğüt, Serdar; Klie, Robert

SrTiO3 thin film can be epitaxially grown on GaAs substrate and used as a platform for growing other oxides to create functional metal-oxide-semiconductor devices, where a high-quality SrTiO3/GaAs interface is essential. We studied the structural and electronic properties of SrTiO3/GaAs hetero-interfaces at atomic level using scanning transmission electron microscopy and first-principles calculations. Our results suggest the preferred termination of GaAs (001) is significantly dependent on the oxygen concentration in the first oxide layer. The favorable interface structure is characterized as oxygen-deficient SrO in contact with arsenic and is observed in both experiment and simulation. The electronic properties are calculated and found to be tunable by interfacial defects such as oxygen, gallium and arsenic vacancies. This work was supported by the National Science Foundation (Grant No. DMR-1408427). This work made use of instruments in the Electron Microscopy Service and the High Performance Computing Clusters at University of Illinois at Chicago.

Development of active and sensitive material systems based on composites

NASA Astrophysics Data System (ADS)

Asanuma, Hiroshi

2002-07-01

This paper describes new concepts proposed by the author to realize active and sensitive structural material systems. Two examples of multifunctional composites were fabricated and evaluated in this study as follows: (1) An active laminate of aluminum plate (works as muscle), epoxy film (as insulator), unidirectional CFRP prepreg (as bone and blood vessel) and copper foil electrode (to apply voltage on CFRP) was made with an embedded optical fiber multiply fractured in the CFRP layer (works as nerve), of which curvature change could be effectively monitored with the fractured optical fiber. (2) A stainless steel fiber/aluminum active composite with embedded Ti oxide/Ti composite fiber was fabricated. The Ti oxide/Ti fiber could work as a sensor for temperature by removing a part of the oxide before embedment to make a metallic contact between the embedded titanium fiber and aluminum matrix to be able to generate thermal electromotive force, and also could work as a sensor for strain and as a heater for actuation. In the both cases, the outputs from their embedded sensors can be used to control their actuations.

Thermal coatings for titanium-aluminum alloys

NASA Technical Reports Server (NTRS)

Cunnington, George R.; Clark, Ronald K.; Robinson, John C.

1993-01-01

Titanium aluminides and titanium alloys are candidate materials for use in hot structure and heat-shield components of hypersonic vehicles because of their good strength-to-weight characteristics at elevated temperature. However, in order to utilize their maximum temperature capability, they must be coated to resist oxidation and to have a high total remittance. Also, surface catalysis for recombination of dissociated species in the aerodynamic boundary layer must be minimized. Very thin chemical vapor deposition (CVD) coatings are attractive candidates for this application because of durability and very light weight. To demonstrate this concept, coatings of boron-silicon and aluminum-boron-silicon compositions were applied to the titanium-aluminides alpha2 (Ti-14Al-21Nb), super-alpha2 (Ti-14Al-23-Nb-2V), and gamma (Ti-33Al-6Nb-1Ta) and to the titanium alloy beta-21S (Ti-15Mo-3Al-3Nb-0.2Si). Coated specimens of each alloy were subjected to a set of simulated hypersonic vehicle environmental tests to determine their properties of oxidation resistance, surface catalysis, radiative emittance, and thermal shock resistance. Surface catalysis results should be viewed as relative performance only of the several coating-alloy combinations tested under the specific environmental conditions of the LaRC Hypersonic Materials Environmental Test System (HYMETS) arc-plasma-heated hypersonic wind tunnel. Tests were also conducted to evaluate the hydrogen transport properties of the coatings and any effects of the coating processing itself on fatigue life of the base alloys. Results are presented for three types of coatings, which are as follows: (1) a single layer boron silicon coating, (2) a single layer aluminum-boron-silicon coating, and (3) a multilayer coating consisting of an aluminum-boron-silicon sublayer with a boron-silicon outer layer.

Synchrotron radiation x-ray photoelectron spectroscopy study on the interface chemistry of high-k PrxAl2-xO3 (x=0-2) dielectrics on TiN for dynamic random access memory applications

NASA Astrophysics Data System (ADS)

Schroeder, T.; Lupina, G.; Sohal, R.; Lippert, G.; Wenger, Ch.; Seifarth, O.; Tallarida, M.; Schmeisser, D.

2007-07-01

Engineered dielectrics combined with compatible metal electrodes are important materials science approaches to scale three-dimensional trench dynamic random access memory (DRAM) cells. Highly insulating dielectrics with high dielectric constants were engineered in this study on TiN metal electrodes by partly substituting Al in the wide band gap insulator Al2O3 by Pr cations. High quality PrAlO3 metal-insulator-metal capacitors were processed with a dielectric constant of 19, three times higher than in the case of Al2O3 reference cells. As a parasitic low dielectric constant interface layer between PrAlO3 and TiN limits the total performance gain, a systematic nondestructive synchrotron x-ray photoelectron spectroscopy study on the interface chemistry of PrxAl2-xO3 (x =0-2) dielectrics on TiN layers was applied to unveil its chemical origin. The interface layer results from the decreasing chemical reactivity of PrxAl2-xO3 dielectrics with increasing Pr content x to reduce native Ti oxide compounds present on unprotected TiN films. Accordingly, PrAlO3 based DRAM capacitors require strict control of the surface chemistry of the TiN electrode, a parameter furthermore of importance to engineer the band offsets of PrxAl2-xO3/TiN heterojunctions.

Effect of Atomic Layer Depositions (ALD)-Deposited Titanium Oxide (TiO2) Thickness on the Performance of Zr40Cu35Al15Ni10 (ZCAN)/TiO2/Indium (In)-Based Resistive Random Access Memory (RRAM) Structures

DTIC Science & Technology

2015-08-01

metal structures, memristors, resistive random access memory, RRAM, titanium dioxide, Zr40Cu35Al15Ni10, ZCAN, resistive memory, tunnel junction 16...TiO2 thickness ........................6 1 1. Introduction Resistive-switching memory elements based on metal-insulator-metal (MIM) diodes ...have attracted great interest due to their potential as components for simple, inexpensive, and high-density non-volatile storage devices. MIM diodes

Single-step preparation of TiO2/MWCNT Nanohybrid materials by laser pyrolysis and application to efficient photovoltaic energy conversion.

PubMed

Wang, Jin; Lin, Yaochen; Pinault, Mathieu; Filoramo, Arianna; Fabert, Marc; Ratier, Bernard; Bouclé, Johann; Herlin-Boime, Nathalie

2015-01-14

This paper presents the continuous-flowand single-step synthesis of a TiO2/MWCNT (multiwall carbon nanotubes) nanohybrid material. The synthesis method allows achieving high coverage and intimate interface between the TiO2particles and MWCNTs, together with a highly homogeneous distribution of nanotubes within the oxide. Such materials used as active layer in theporous photoelectrode of solid-state dye-sensitized solar cells leads to a substantial performance improvement (20%) as compared to reference devices.

Dilute electrodeposition of TiO2 and ZnO thin film memristors on Cu substrate

NASA Astrophysics Data System (ADS)

Fauzi, F. B.; Ani, M. H.; Herman, S. H.; Mohamed, M. A.

2018-03-01

Memristor has become one of the alternatives to replace the current memory technologies. Fabrication of titanium dioxide, TiO2 memristor has been extensively studied by using various deposition methods. However, recently more researches have been done to explore the compatibility of other transition metal oxide, TMO such as zinc oxide, ZnO to be used as the active layer of the memristor. This paper highlights the simple and easy-control electrodeposition to deposit titanium, Ti and zinc, Zn thin film at room temperature and subsequent thermal oxidation at 600 °C. Gold, Au was then sputtered as top electrode to create metal-insulator-metal, MIM sandwich of Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristors. The structural, morphological and memristive properties were characterized using Field Emission Scanning Electron Microscopy, FESEM, X-Ray Diffraction, XRD and current-voltage, I-V measurement. Both Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristivity were identified by the pinched hysteresis loop with resistive ratio of 1.2 and 1.08 respectively. Empirical study on diffusivity of Ti4+, Zn2+ and O2‑ ions in both metal oxides show that the metal vacancies were formed, thus giving rise to its memristivity. The electrodeposited Au/TiO2-Cu2O-CuO/Cu and Au/ZnO-Cu2O-CuO/Cu memristors demonstrate comparable performances to previous studies using other methods.

Formation of 100-nm periodic structures on a titanium surface by exploiting the oxidation and third harmonic generation induced by femtosecond laser pulses.

PubMed

Li, Xian-Feng; Zhang, Cheng-Yun; Li, Hui; Dai, Qiao-Feng; Lan, Sheng; Tie, Shao-Long

2014-11-17

Periodic surface structures with periods as small as about one-tenth of the irradiating femtosecond (fs) laser light wavelength were created on the surface of a titanium (Ti) foil by exploiting laser-induced oxidation and third harmonic generation (THG). They were achieved by using 100-fs laser pulses with a repetition rate of 1 kHz and a wavelength ranging from 1.4 to 2.2 μm. It was revealed that an extremely thin TixOy layer was formed on the surface of the Ti foil after irradiating fs laser light with a fluence smaller than the ablation threshold of Ti, leading to a significant enhancement in THG which may exceed the ablation threshold of TixOy. As compared with Ti, the maximum efficacy factor for TixOy appears at a larger normalized wavevector in the direction perpendicular to the polarization of the fs laser light. As a result, the THG-dominated laser ablation of TixOy induces 100-nm periodic structures parallel to the polarization of the fs laser light. The depth of the periodic structures was found to be ~10 nm by atomic force microscopy and the formation of the thin TixOy layer was verified by energy dispersive X-ray spectroscopy.

Monitoring Tensile Fatigue of Superelastic NiTi Wire in Liquids by Electrochemical Potential

NASA Astrophysics Data System (ADS)

Racek, Jan; Stora, Marc; Šittner, Petr; Heller, Luděk; Kopeček, Jaromir; Petrenec, Martin

2015-06-01

Fatigue of superelastic NiTi wires was investigated by cyclic tension in simulated biofluid. The state of the surface of the fatigued NiTi wire was monitored by following the evolution of the electrochemical open circuit potential (OCP) together with macroscopic stresses and strains. The ceramic TiO2 oxide layer on the NiTi wire surface cannot withstand the large transformation strain and fractures in the first cycle. Based on the analysis of the results of in situ OCP experiments and SEM observation of cracks, it is claimed that the cycled wire surface develops mechanochemical reactions at the NiTi/liquid interface leading to cumulative generation of hydrogen, uptake of the hydrogen by the NiTi matrix, local loss of the matrix strength, crack transfer into the NiTi matrix, accelerated crack growth, and ultimately to the brittle fracture of the wire. Fatigue degradation is thus claimed to originate from the mechanochemical processes occurring at the excessively deforming surface not from the accumulation of defects due to energy dissipative bulk deformation processes. Ironically, combination of the two exciting properties of NiTi—superelasticity due to martensitic transformation and biocompatibility due to the protective TiO2 surface oxide layer—leads to excessive fatigue damage during cyclic mechanical loading in biofluids.

Enhanced photovoltaic performance of novel TiO2 photoelectrode on TCO substrates for dye-sensitized solar cells.

PubMed

Nam, Jung Eun; Kwon, Soon Jin; Jo, Hyo Jeong; Yi, Kwang Bok; Kim, Dae-Hwan; Kang, Jin-Kyu

2014-12-01

In this study, we report synthesis and growth of rutile-anatase TiO2 thin film on fluorine-doped tin oxide (FTO) glass by a two-step hydrothermal method. The effects of additional treatments (i.e., TiCl4 post-treatment and seed layer formation were also studied. Photocurrent-voltage (I-V) measurement of rutile-anatase TiO2 thin film was performed under 1.5 G light illumination. Photovoltaic performance was investigated by incident photon-to-electron conversion efficiency (IPCE), electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent/photovoltage spectroscopy (IMVS/IMPS) and open-circuit photovoltage decay (OCVD).

An investigation of adhesive/adherend and fiber/matrix interactions. Part B: SEM/ESCA analysis of fracture surfaces

NASA Technical Reports Server (NTRS)

Beck, B.; Widyani, E.; Wightman, J. P.

1983-01-01

Adhesion was studied with emphasis on the characterization of surface oxide layers, the analysis of fracture surfaces, and the interaction of matrices and fibers. A number of surface features of the fractured lap shear samples were noted in the SEM photomicrographs including the beta phase alloy of the Ti 6-4 adherend, the imprint of the adherend on the adhesive failure surface, increased void density for high temperature samples, and the alumina filler particles. Interfacial failure of some of the fractured lap shear samples is invariably characterized by the appearance of an ESCA oxygen photopeak at 530.3 eV assigned to the surface oxide layer of Ti 6-4 adherend. The effect of grit blasting on carbon fiber composites is evident in the SEM analysis. A high surface fluorine concentration on the composite surface is reduced some ten fold by grit blasting.

Tensile properties of V-5Cr-5Ti alloy after exposure in air environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Natesan, K.; Soppet, W.K.

1997-04-01

Oxidation studies were conducted on V-5Cr-5Ti alloy specimens in an air environment to evaluate the oxygen uptake behavior of the alloy as a function of temperature and exposure time. The oxidation rates, calculated from parabolic kinetic measurements of thermogravimetric testing and confirmed by microscopic analysis of cross sections of exposed specimens, were 5, 17, and 27 {mu}m per year after exposure at 300, 400, and 500{degrees}C, respectively. Uniaxial tensile tests were conducted at room temperature and at 500{degrees}C on preoxidized specimens of the alloy to examine the effects of oxidation and oxygen migration on tensile strength and ductility. Correlations weremore » developed between tensile strength and ductility of the oxidized alloy and microstructural characteristics such as oxide thickness, depth of hardened layer, depth of intergranular fracture zone, and transverse crack length.« less

Strong metal support interaction of Pt on TiO2 grown by atomic layer deposition and physical vapor deposition for fuel cell applications

NASA Astrophysics Data System (ADS)

Hansen, Robin Paul

Several roadblocks prevent the large-scale commercialization of hydrogen fuel cells, including the stability of the Pt catalysts and their substrates, as well as the high cost of Pt. This is particularly true for the cathode, which requires a higher Pt loading because of the slow kinetics of the oxygen reduction reaction (ORR). The problem with the stability of the substrate can be solved by replacing the traditional carbon support with a conductive metal oxide such as reduced TiO2, which will not easily corrode and should result in longer lasting fuel cells. In this study, Pt was deposited either by atomic layer deposition (ALD) or physical vapor deposition (PVD). The typical size of the Pt islands that were grown using these deposition techniques was 3-8 nm. One factor that can inhibit the catalytic activity of a metal catalyst on a metal oxide is the strong metal support interaction (SMSI). This is where a metal on a reducible metal oxide can be encapsulated by a layer of the metal oxide support material at elevated temperatures. The processing of materials through atomic layer deposition can exceed this temperature. The TiO2 substrates used in this study were either grown by ALD, which results in a polycrystalline anatase film, or were single-crystal rutile TiO2(110) samples prepared in ultra-high vacuum (UHV). The Pt/TiO2 samples were tested electrochemically using cyclic voltammetry (CV) to determine the level of catalytic activity. To determine the effect of the SMSI interaction on the catalytic activity of the PVD grown samples, CV was performed on samples that were annealed in high vacuum after Pt deposition. Additional characterization was performed with scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry (RBS), and four point probe analysis. Platinum that was deposited by PVD was used as a standard since it is not affected by the SMSI at the low temperature of the substrate during deposition. These samples were analyzed after deposition and then annealed to higher temperatures to induce the SMSI effect. The AR-XPS results for the single crystal TiO2 substrate show that there is an increase in the Ti emission at glancing exit angle after an anneal at 150 °C, which indicates the onset of the SMSI. For the ALD TiO2 substrate, the onset of SMSI was at 380 °C. This work is believed to be the first time in which the SMSI was observed in this fashion. The CV data for the samples with PVD Pt the single crystal TiO2 substrate showed a large reduction of the hydrogen adsortion at 380 °C. For the ORR, there was a reduction in the ORR signal at 380 °C. By 750 °C, the ORR was almost completely suppressed. For the PVD Pt grown on the ALD TiO2 substrates, there was a large increase in the resistivity of the samples after exposure to the acidic electrolyte used during the CV measurements. This resulted in no CV signal for those samples. Another aspect that was significantly different for the two different substrates was the Pt growth morphology. Both the AR-XPS and SEM measurements indicate that the Pt on the single crystal TiO2 substrates grows as distinct islands. For the ALD TiO2 substrates, the Pt islands had a lower profile than the islands grown on the single crystal substrates. This morphology difference is believed to be due to the large defect density of the ALD generated TiO2 or possibly from the different chemical properties of the anatase surface. These results indicate that the ALD generated substrates are more resistant to the effects of the SMSI, but that the ALD substrates are more sensitive to surface contamination.

Dense and high-stability Ti2AlN MAX phase coatings prepared by the combined cathodic arc/sputter technique

NASA Astrophysics Data System (ADS)

Wang, Zhenyu; Liu, Jingzhou; Wang, Li; Li, Xiaowei; Ke, Peiling; Wang, Aiying

2017-02-01

Ti2AlN belongs to a family of ternary nano-laminate alloys known as the MAX phases, which exhibit a unique combination of metallic and ceramic properties. In the present work, the dense and high-stability Ti2AlN coating has been successfully prepared through the combined cathodic arc/sputter deposition, followed by heat post-treatment. It was found that the as-deposited Ti-Al-N coating behaved a multilayer structure, where (Ti, N)-rich layer and Al-rich layer grew alternately, with a mixed phase constitution of TiN and TiAlx. After annealing at 800 °C under vacuum condition for 1.5 h, although the multilayer structure still was found, part of multilayer interfaces became indistinct and disappeared. In particular, the thickness of the Al-rich layer decreased in contrast to that of as-deposited coating due to the inner diffusion of the Al element. Moreover, the Ti2AlN MAX phase emerged as the major phase in the annealed coatings and its formation mechanism was also discussed in this study. The vacuum thermal analysis indicated that the formed Ti2AlN MAX phase exhibited a high-stability, which was mainly benefited from the large thickness and the dense structure. This advanced technique based on the combined cathodic arc/sputter method could be extended to deposit other MAX phase coatings with tailored high performance like good thermal stability, high corrosion and oxidation resistance etc. for the next protective coating materials.

Incorporation of Ca and P on anodized titanium surface: Effect of high current density.

PubMed

Laurindo, Carlos A H; Torres, Ricardo D; Mali, Sachin A; Gilbert, Jeremy L; Soares, Paulo

2014-04-01

This study systematically evaluated the surface and corrosion characteristics of commercially pure titanium (grade 2) modified by plasma electrolytic oxidation (PEO) with high current density. The anodization process was carried out galvanostatically (constant current density) using a solution containing calcium glycerophosphate (0.02mol/L) and calcium acetate (0.15mol/L). The current densities applied were 400, 700, 1000 and 1200mA/cm(2) for a period of 15s. Composition, crystalline structure, morphology, roughness, wettability and "in-vitro" bioactivity test in SBF of the anodized layer were evaluated by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, profilometry and contact angle measurements. Corrosion properties were evaluated by open circuit potential, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The results show that the TiO2 oxide layers present an increase of thickness, porosity, roughness, wettability, Ca/P ratio, and bioactivity, with the applied current density up to 1000mA/cm(2). Corrosion resistance also increases with applied current density. It is observed that for 1200mA/cm(2), there is a degradation of the oxide layer. In general, the results suggest that the anodized TiO2 layer with better properties is formed with an applied current of 1000mA/cm(2). Copyright © 2014 Elsevier B.V. All rights reserved.

Gas Transport Properties of Polybenzimidazole and Poly(Phenylene Oxide) Mixed Matrix Membranes Incorporated with PDA-Functionalised Titanate Nanotubes

NASA Astrophysics Data System (ADS)

Giel, V.; Perchacz, M.; Kredatusová, J.; Pientka, Z.

2017-01-01

Functionalised titanate nanotubes (TiNTs) were incorporated to poly(5,5-bisbenzimidazole-2,2-diyl-1,3-phenylene) (PBI) or poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) for improving the interfacial compatibility between the polymer matrix and inorganic material and for altering the gas separation performance of the neat polymer membranes. Functionalisation consisted in oxidative polymerisation of dopamine-hydrochloride on the surface of non-functionalised TiNTs. Transmission electron microscopy (TEM) confirmed that a thin polydopamine (PDA) layer was created on the surface of TiNTs. 1.5, 3, 6, and 9 wt.% of PDA-functionalised TiNTs (PDA-TiNTs) were dispersed to each type of polymer matrix to create so-called mixed matrix membranes (MMMs). Infrared spectroscopy confirmed that -OH and -NH groups exist on the surface of PDA-TiNTs and that the nanotubes interact via H-bonding with PBI but not with PPO. The distribution of PDA-TiNTs in the MMMs was to some extent uniform as scanning electron microscope (SEM) studies showed. Beyond, PDA-TiNTs exhibit positive effect on gas transport properties, resulting in increased selectivities of MMMs. The addition of nanotubes caused a decrease in permeabilities but an increase in selectivities. It is shown that 9 wt.% of PDA-TiNTs in PBI gave a rise to CO2/N2 and CO2/CH4 selectivities of 112 and 63 %, respectively. In case of PPO-PDA-TiNT MMMs, CO2/N2 and CO2/CH4 selectivity increased about 25 and 17 %, respectively. Sorption measurement showed that the presence of PDA-TiNTs in PBI caused an increase in CO2 sorption, whereas the influence on other gases is less noticeable.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poletika, T. M., E-mail: poletm@ispms.tsc.ru; Girsova, S. L., E-mail: llm@ispms.tsc.ru; Meisner, L. L., E-mail: girs@ispms.tsc.ru

The structure of the surface and near-surface layers of single crystals of NiTi, differently oriented relative to the direction of ion beam treatment was investigated. The role of the crystallographic orientation in formation of structure of surface layers after ion-plasma alloying was revealed. It was found that the orientation effects of selective sputtering and channeling determine the thickness of the oxide and amorphous layers, the depth of penetration of ions and impurities, the distribution of Ni with depth.

The Dye Sensitized Photoelectrosynthesis Cell (DSPEC) for Solar Water Splitting and CO2 Reduction

NASA Astrophysics Data System (ADS)

Meyer, Thomas; Alibabaei, Leila; Sherman, Benjamin; Sheridan, Matthew; Ashford, Dennis; Lapides, Alex; Brennaman, Kyle; Nayak, Animesh; Roy, Subhangi; Wee, Kyung-Ryang; Gish, Melissa; Meyer, Jerry; Papanikolas, John

The dye-sensitized photoelectrosynthesis cell (DSPEC) integrates molecular level light absorption and catalysis with the bandgap properties of stable oxide materials such as TiO2 and NiO. Excitation of surface-bound chromophores leads to excited state formation and rapid electron or hole injection into the conduction or valence bands of n or p-type oxides. Addition of thin layers of TiO2 or NiO on the surfaces of mesoscopic, nanoparticle films of semiconductor or transparent conducting oxides to give core/shell structures provides a basis for accumulating multiple redox equivalents at catalysts for water oxidation or CO2 reduction. UNC EFRC Center for Solar Fuels, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001011.

MAO-derived hydroxyapatite/TiO2 nanostructured multi-layer coatings on titanium substrate

NASA Astrophysics Data System (ADS)

Abbasi, S.; Golestani-Fard, F.; Rezaie, H. R.; Mirhosseini, S. M. M.

2012-11-01

In this study, titanium substrates which previously oxidized through Micro arc oxidation method, was coated by Hydroxyapatite (HAp) coating once more by means of the same method. Morphology, topography and chemical properties as well as phase composition and thickness of layers were studied to reveal the effect of the electrolyte concentration on coating features. According to results, the obtained coatings are consisted of HAp and titania as the major phases along with minor amounts of calcium titanate and α-tri calcium phosphate. Ca and P are present on surface of obtained layers as well as predictable Ti and O based on the XPS results. Thickness profile of coatings figured out that by increasing the electrolyte concentration, especially by addition of more Calcium Acetate (CA) to electrolyte, the thickness of HAp layer would rise, consequently. However, the influence of coating time on thickness of obtained coatings would be more considerable than electrolyte concentration. High specific area coatings with nest morphology were obtained in Electrolyte containing 5 g/L β-Glycero Phosphate (β-GP) and 5 g/L CA. Increasing coating duration time in this kind of coatings would cause deduction of the nesting in their structure.

Structural properties and sensing performance of high-k Nd2TiO5 thin layer-based electrolyte-insulator-semiconductor for pH detection and urea biosensing.

PubMed

Pan, Tung-Ming; Lin, Jian-Chi; Wu, Min-Hsien; Lai, Chao-Sung

2009-05-15

For high sensitive pH sensing, an electrolyte-insulator-semiconductor (EIS) device with Nd(2)TiO(5) thin layers fabricated on Si substrates by means of reactive sputtering and the subsequent post-deposition annealing (PDA) treatment was proposed. In this work, the effect of thermal annealing (600, 700, 800, and 900 degrees C) on the structural characteristics of Nd(2)TiO(5) thin layer was investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and atomic force microscopy. The observed structural properties were then correlated with the resulting pH sensing performances. For enzymatic field-effect-transistors-based urea biosensing, a hybrid configuration of the proposed Nd(2)TiO(5) thin layer with urease-immobilized alginate film attached was established. Within the experimental conditions investigated, the EIS device with the Nd(2)TiO(5) thin layer annealed at 800 degrees C exhibited a higher pH detection sensitivity of 57.2 mV/pH, a lower hysteresis voltage of 2.33 mV, and a lower drift rate of 1.80 mV/h compared to those at other annealing temperatures. These results are attributed to the formation of a thinner low-k interfacial layer at the oxide/Si interface and the higher surface roughness occurred at this annealing temperature. Furthermore, the presented urea biosensor was also proved to be able to detect urea with good linearity (R(2)=0.99) and reasonable sensitivity of 9.52 mV/mM in the urea concentration range of 3-40 mM. As a whole, the present work has provided some fundamental data for the use of Nd(2)TiO(5) thin layer for EIS-based pH detection and the extended application for biosensing.

Investigation of Coatings for Langmuir Probes in an Oxygen-Rich Space Environment

NASA Astrophysics Data System (ADS)

Samaniego, J. I.; Wang, X.; Andersson, L.; Malaspina, D.; Ergun, R.; Horanyi, M.

2017-12-01

The surface properties of the Langmuir probes, such as the one on the MAVEN mission, will change after exposure to upper planetary atmospheres where high concentrations of atomic oxygen and other oxidizing compounds are present. TiN (Titanium Nitride) or DAG (a resin based graphite dispersion) are the most common coatings for current Langmuir probes, yet both of these coatings pose issues when exposed to oxygen-rich space environment. TiN showed reduced surface conductivity while the DAG layers erode with exposure to oxygen. It is known that Iridium (Ir) and Rhenium (Rh) are difficult to oxidize and maintain high conductivity even in their oxidized forms, suggesting them to be good candidates for probe coatings. Oxidation of most metals creates a resistive layer on the surface of the probe that will affect the amount of current being collected at a given voltage during the probe sweep and therefore affect the accuracy of plasma parameters determined by the Langmuir probe (e.g. density, temperature). We present the results of the oxidation effect on the current-voltage curves (I-V curves) and therefore the resulting measured plasma parameters of Ir and Rh wire probes compared with other control metals and coatings (Cu, Ni, TiN) in controlled plasma environments. The oxidation process is performed in an oxygen plasma chamber in which both O+ and O2+ are created and accelerated toward the probes with energies < 10 eV. An argon plasma chamber is used to compare the probe's I-V curves before and after the oxidation process. Our preliminary results indicate that iridium shows the least effect of oxidation on the probe measurements. The second objective of this study is to identify methods that can be used in orbit to clean the surface of Langmuir probes to minimize the effect of exposure to oxidizing compounds.

Film growth and structure design in the barium oxide-strontium oxide-titanium dioxide system

NASA Astrophysics Data System (ADS)

Fisher, Patrick J.

This thesis describes the growth and characterization of thin films in the SrO-BaO-TiO2 system. The films are grown by molecular beam cpitaxy (MBE) and pulsed laser deposition (PLD) on ceramic substrates, and characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), reflection-high energy electron diffraction (RHEED), and transmission electron microscopy (TEM). Films are grown with varied global and initial local stoichiometries, with the goal of determining the stability of specific cation organizations. Simple oxides, TiO2 (anatase) and SrO (rock salt) were grown on oxide substrates using MBE. Growth conditions, including substrate material, substrate temperature, O3 flux, and metal flux, are varied in each case. It is observed that the growth morphology of anatase is highly dependent on the ozone flux, with fluxes of 1.00 sccm and greater resulting in flat anatase surfaces. Increased roughness at higher substrate was determined to be a result of rutile inclusions. Growth oscillations are observed in the RHEED intensity for both TiO2 and SrO in overlapping regions of growth space, indicating 2D growth modes. Varied shuttering sequences were used during MBE growth of perovskites: globally non-stoichiometric films, as well as locally non-stoichiometric but globally stoichiometric perovskite. Films were grown within a (SrO) m(TiO2)n framework, where growth cycles involved m monolayers of SrO followed by n monolayers of TiO2. XRD results indicate that Ruddlesden-Popper defects, that is, rock salt double layers, enable incorporation of all levels of Sr excess, whereas excess Ti is observed to incorporate into the perovskite structure only at extreme excesses. A series of films with m equal to n were grown; that is, multiple monolayers of SrO deposited followed by multiple monolayers of TiO2. These initially locally non-stoichiometric arrangements interreact to form highly crystalline perovskite, even with layer thicknesses of up to 33 monolayers. The Ba0.6Sr0.4TiO3 films were characterized for their microwave dielectric properties, and were found to have high dielectric constants (epsilonr ˜1300 in each case, implying high tunabilities) but high tan delta values as well. The mechanisms by which the perovskite structure incorporates cation excesses is discussed, and it is argued that two probable mechanisms, one involving plane-sharing of Ti and Sr cations and the other involving rock salt multilayers, also enable the observed transport necessary for multilayer reaction. Working under the argument that these mechanisms involve low-energy architectures, a novel homologous series of phases based on rock salt multilayers is grown using monotayer control: the SrmTiO2+ m series, with each TiO2 monolayer followed by m SrO monolayers (m = 1-5). The phases in this series were characterized structurally, and an in-plane contraction was observed between the m = 2 and m = 3 phases, which is argued to be a relaxation of the SrO monolayers. Considering Ti-excess organizations, the BaTi2O5 structure is grown and observed to nucleate over a narrow window of growth conditions and substrates. LaAlO 3(100) promotes the nucleation of anatasc and ejection of perovskite; SrTiO3(100) promotes the nucleation of perovskite and ejection of TiO2; importantly, MgO(100) promotes the nucleation (010)-oriented BaTi2O5 growing with multiple domains. A BaTi2 O5 buffer layer was then used to promote the inclusion of Sr into (Ba,SOTi205 epilayers. Sr incorporation into a perovskite-related structure was observed to occur over the full range of (Ba,Sr)Ti2O 5 compositions.

Investigation of energy band alignments and interfacial properties of rutile NMO2/TiO2 (NM = Ru, Rh, Os, and Ir) by first-principles calculations.

PubMed

Yang, Chen; Zhao, Zong-Yan

2017-11-08

In the field of photocatalysis, constructing hetero-structures is an efficient strategy to improve quantum efficiency. However, a lattice mismatch often induces unfavorable interfacial states that can act as recombination centers for photo-generated electron-hole pairs. If the hetero-structure's components have the same crystal structure, this disadvantage can be easily avoided. Conversely, in the process of loading a noble metal co-catalyst onto the TiO 2 surface, a transition layer of noble metal oxides is often formed between the TiO 2 layer and the noble metal layer. In this article, interfacial properties of hetero-structures composed of a noble metal dioxide and TiO 2 with a rutile crystal structure have been systematically investigated using first-principles calculations. In particular, the Schottky barrier height, band bending, and energy band alignments are studied to provide evidence for practical applications. In all cases, no interfacial states exist in the forbidden band of TiO 2 , and the interfacial formation energy is very small. A strong internal electric field generated by interfacial electron transfer leads to an efficient separation of photo-generated carriers and band bending. Because of the differences in the atomic properties of the components, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures demonstrate band dividing, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures have a pseudo-gap near the Fermi energy level. Furthermore, NMO 2 /TiO 2 hetero-structures show upward band bending. Conversely, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures present a relatively strong infrared light absorption, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures show an obvious absorption edge in the visible light region. Overall, considering all aspects of their properties, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures are more suitable than others for improving the photocatalytic performance of TiO 2 . These findings will provide useful information for understanding the role and effects of a noble metal dioxide as a transition layer between a noble metal co-catalyst and a TiO 2 photocatalyst.

Size-Selective Synthesis and Stabilization of Small Silver Nanoparticles on TiO 2 Partially Masked by SiO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bo, Zhenyu; Eaton, Todd R.; Gallagher, James R.

Controlling metal nanoparticle size is one of the principle challenges in developing new supported catalysts. Typical methods where a metal salt is deposited and reduced can result in a polydisperse mixture of metal nanoparticles, especially at higher loading. Polydispersity can exacerbate the already significant challenge of controlling sintering at high temperatures, which decreases catalytic surface area. Here, we demonstrate the size-selective photoreduction of Ag nanoparticles on TiO2 whose surface has been partially masked with a thin SiO2 layer. To synthesize this layered oxide material, TiO2 particles are grafted with tert-butylcalix[4]arene molecular templates (~2 nm in diameter) at surface densities ofmore » 0.05–0.17 templates.nm–2, overcoated with ~2 nm of SiO2 through repeated condensation cycles of limiting amounts of tetraethoxysilane (TEOS), and the templates are removed oxidatively. Ag photodeposition results in uniform nanoparticle diameters ≤ 3.5 nm (by transmission electron microscopy (TEM)) on the partially masked TiO2, whereas Ag nanoparticles deposited on the unmodified TiO2 are larger and more polydisperse (4.7 ± 2.7 nm by TEM). Furthermore, Ag nanoparticles on the partially masked TiO2 do not sinter after heating at 450 °C for 3 h, while nanoparticles on the control surfaces sinter and grow by at least 30%, as is typical. Overall, this new synthesis approach controls metal nanoparticle dispersion and enhances thermal stability, and this facile synthesis procedure is generalizable to other TiO2-supported nanoparticles and sizes and may find use in the synthesis of new catalytic materials.« less

Avoiding polar catastrophe in the growth of polarly orientated nickel perovskite thin films by reactive oxide molecular beam epitaxy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, H. F.; Liu, Z. T.; Fan, C. C.

2016-08-15

By means of the state-of-the-art reactive oxide molecular beam epitaxy, we synthesized (001)- and (111)-orientated polar LaNiO{sub 3} thin films. In order to avoid the interfacial reconstructions induced by polar catastrophe, screening metallic Nb-doped SrTiO{sub 3} and iso-polarity LaAlO{sub 3} substrates were chosen to achieve high-quality (001)-orientated films in a layer-by-layer growth mode. For largely polar (111)-orientated films, we showed that iso-polarity LaAlO{sub 3} (111) substrate was more suitable than Nb-doped SrTiO{sub 3}. In situ reflection high-energy electron diffraction, ex situ high-resolution X-ray diffraction, and atomic force microscopy were used to characterize these films. Our results show that special attentionsmore » need to be paid to grow high-quality oxide films with polar orientations, which can prompt the explorations of all-oxide electronics and artificial interfacial engineering to pursue intriguing emergent physics like proposed interfacial superconductivity and topological phases in LaNiO{sub 3} based superlattices.« less

Phenol Contaminated Water Treatment on Several Modified Dimensionally Stable Anodes.

PubMed

Jayathilaka, Pavithra Bhakthi; Hapuhinna, Kushani Umanga Kumari; Bandara, Athula; Nanayakkara, Nadeeshani; Subasinghe, Nalaka Deepal

2017-08-01

  Phenolic compounds are some of the most common hazardous organics in wastewater. Removal of these pollutants is important. Physiochemical method such as electrochemical oxidation on dimensionally stable anodes is more convenient in removing such organic pollutants. Therefore, this study focuses on development of three different anodes for phenol contaminated water treatment. The performances of steel/IrO2, steel/IrO2-Sb2O3, and Ti/IrO2-Sb2O3 anodes were tested and compared. Nearly 50, 76, and 84% of chemical oxygen demand removal efficiencies were observed for steel/IrO2, steel/IrO2-Sb2O3, and Ti/IrO2-Sb2O3 anodes, respectively. The formation of intermediates was monitored for three anodes and the Ti/IrO2-Sb2O3 anode showed the most promising results. Findings suggest that the developed anode materials can enhance phenol oxidation efficiency and that mixed metal oxide layer has major influence on the anode. Among the selected metal oxide mixtures IrO2-Sb2O3 was the most suitable under given experimental conditions.

Amorphous alumina thin films deposited on titanium: Interfacial chemistry and thermal oxidation barrier properties

DOE PAGES

Baggetto, Loic; Charvillat, Cedric; Thebault, Yannick; ...

2015-12-02

Ti/Al 2O 3 bilayer stacks are used as model systems to investigate the role of atomic layer deposition (ALD) and chemical vapor deposition (CVD) to prepare 30-180 nm thick amorphous alumina films as protective barriers for the medium temperature oxidation (500-600⁰C) of titanium, which is employed in aeronautic applications. X-ray diffraction (XRD), transmission electron microscopy (TEM) with selected area electron diffraction (SAED), and X-ray photoelectron spectroscopy (XPS) results show that the films produced from the direct liquid injection (DLI) CVD of aluminum tri-isopropoxide (ATI) are poor oxygen barriers. The films processed using the ALD of trimethylaluminum (TMA) show good barriermore » properties but an extensive intermixing with Ti which subsequently oxidizes. In contrast, the films prepared from dimethyl aluminum isopropoxide (DMAI) by CVD are excellent oxygen barriers and show little intermixing with Ti. Overall, these measurements correlate the effect of the alumina coating thickness, morphology, and stoichiometry resulting from the preparation method to the oxidation barrier properties, and show that compact and stoichiometric amorphous alumina films offer superior barrier properties.« less

Efficient phosphate sequestration for water purification by unique sandwich-like MXene/magnetic iron oxide nanocomposites

NASA Astrophysics Data System (ADS)

Zhang, Qingrui; Teng, Jie; Zou, Guodong; Peng, Qiuming; Du, Qing; Jiao, Tifeng; Xiang, Jianyong

2016-03-01

Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene.Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09303a

Pulsed photoinitiated fabrication of inkjet printed titanium dioxide/reduced graphene oxide nanocomposite thin films.

PubMed

Bourgeois, Briley; Luo, Sijun; Riggs, Brian; Ji, Yaping; Adireddy, Shiva; Schroder, Kurt; Farnsworth, Stan; Chrisey, Douglas; Escarra, Matthew

2018-08-03

This work reports a new technique for scalable and low-temperature processing of nanostructured TiO 2 thin films, allowing for practical manufacturing of TiO 2 -based devices such as perovskite solar cells at low-temperature or on flexible substrates. Dual layers of dense and mesoporous TiO 2 /graphitic oxide nanocomposite films are synthesized simultaneously using inkjet printing and pulsed photonic irradiation. Investigation of process parameters including precursor concentration (10-20 wt%) and exposure fluence (4.5-8.5 J cm -2 ) reveals control over crystalline quality, graphitic oxide phase, film thickness, dendrite density, and optical properties. Raman spectroscopy shows the E g peak, characteristic of anatase phase titania, increases in intensity with higher photonic irradiation fluence, suggesting increased crystallinity through higher fluence processing. Film thickness and dendrite density is shown to increase with precursor concentration in the printed ink. The dense base layer thickness was controlled between 20 and 80 nm. The refractive index of the films is determined by ellipsometry to be 1.92 ± 0.08 at 650 nm. Films exhibit an energy weighted optical transparency of 91.1%, in comparison to 91.3% of a thermally processed film, when in situ carbon materials were removed. Transmission and diffuse reflectance are used to determine optical band gaps of the films ranging from 2.98 to 3.38 eV in accordance with the photonic irradiation fluence and suggests tunability of TiO 2 phase composition. The sheet resistance of the synthesized films is measured to be 14.54 ± 1.11 Ω/□ and 28.90 ± 2.24 Ω/□ for films as-processed and after carbon removal, respectively, which is comparable to high temperature processed TiO 2 thin films. The studied electrical and optical properties of the light processed films show comparable results to traditionally processed TiO 2 while offering the distinct advantages of scalable manufacturing, low-temperature processing, simultaneous bilayer fabrication, and in situ formation of removable carbon nanocomposites.

Impact of semiconducting electrodes on the electroresistance of ferroelectric tunnel junctions

NASA Astrophysics Data System (ADS)

Asa, M.; Bertacco, R.

2018-02-01

Ferroelectric tunnel junctions are promising candidates for the realization of energy-efficient digital memories and analog memcomputing devices. In this work, we investigate the impact of a semiconducting layer in series to the junction on the sign of electroresistance. To this scope, we compare tunnel junctions fabricated out of Pt/BaTiO3/La1/3Sr2/3MnO3 (LSMO) and Pt/BaTiO3/Nb:SrTiO3 (Nb:STO) heterostructures, displaying an opposite sign of the electroresistance. By capacitance-voltage profiling, we observe a behavior typical of Metal-Oxide-Semiconductor tunnel devices in both cases but compatible with the opposite sign of charge carriers in the semiconducting layer. While Nb:STO displays the expected n-type semiconducting character, metallic LSMO develops an interfacial p-type semiconducting layer. The different types of carriers at the semiconducting interfaces and the modulation of the depleted region by the ferroelectric charge have a deep impact on electroresistance, possibly accounting for the different sign observed in the two systems.

Multifunctional MgO Layer in Perovskite Solar Cells.

PubMed

Guo, Xudong; Dong, Haopeng; Li, Wenzhe; Li, Nan; Wang, Liduo

2015-06-08

A multifunctional magnesium oxide (MgO) layer was successfully introduced into perovskite solar cells (PSCs) to enhance their performance. MgO was coated onto the surface of mesoporous TiO(2) by the decomposition of magnesium acetate and, therefore, could block contact between the perovskite and TiO(2). X-ray photoelectron spectroscopy and infrared spectroscopy showed that the amount of H(2)O/hydroxyl absorbed on the TiO(2) decreased after MgO modification. The UV/Vis absorption spectra of the perovskite with MgO modification revealed an enhanced photoelectric performance compared with that of unmodified perovskite after UV illumination. In addition to the photocurrent, the photovoltage and fill factor also showed an enhancement after modification, which resulted in an increase in the overall efficiency of the cell from 9.6 to 13.9 %. Electrochemical impedance spectroscopy (EIS) confirmed that MgO acts as an insulating layer to reduce charge recombination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Electrochemical, Microtopographical and Ambient Pressure X-Ray Photoelectron Spectroscopic Investigation of Si/TiO 2/Ni/Electrolyte Interfaces

DOE PAGES

Lichterman, Michael F.; Richter, Matthias H.; Hu, Shu; ...

2015-12-05

The electrical and spectroscopic properties of the TiO 2/Ni protection layer system, which enables stabilization of otherwise corroding photoanodes, have been investigated in contact with electrolyte solutions by scanning-probe microscopy, electrochemistry and in-situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Specifically, the energy-band relations of the p +-Si/ALD-TiO 2/Ni interface have been determined for a selected range of Ni thicknesses. AP-XPS measurements using tender X-rays were performed in a three-electrode electrochemical arrangement under potentiostatic control to obtain information from the semiconductor near-surface region, the electrochemical double layer (ECDL) and the electrolyte beyond the ECDL. The degree of conductivity depended on themore » chemical state of the Ni on the TiO 2 surface. At low loadings of Ni, the Ni was present primarily as an oxide layer and the samples were not conductive, although the TiO 2 XPS core levels nonetheless displayed behavior indicative of a metal-electrolyte junction. In contrast, as the Ni thickness increased, the Ni phase was primarily metallic and the electrochemical behavior became highly conductive, with the AP-XPS data indicative of a metal-electrolyte junction. Electrochemical and microtopographical methods have been employed to better define the nature of the TiO 2/Ni electrodes and to contextualize the AP-XPS results.« less

Resistance switching behavior of atomic layer deposited SrTiO3 film through possible formation of Sr2Ti6O13 or Sr1Ti11O20 phases

PubMed Central

Lee, Woongkyu; Yoo, Sijung; Yoon, Kyung Jean; Yeu, In Won; Chang, Hye Jung; Choi, Jung-Hae; Hoffmann-Eifert, Susanne; Waser, Rainer; Hwang, Cheol Seong

2016-01-01

Identification of microstructural evolution of nanoscale conducting phase, such as conducting filament (CF), in many resistance switching (RS) devices is a crucial factor to unambiguously understand the electrical behaviours of the RS-based electronic devices. Among the diverse RS material systems, oxide-based redox system comprises the major category of these intriguing electronic devices, where the local, along both lateral and vertical directions of thin films, changes in oxygen chemistry has been suggested to be the main RS mechanism. However, there are systems which involve distinctive crystallographic phases as CF; the Magnéli phase in TiO2 is one of the very well-known examples. The current research reports the possible presence of distinctive local conducting phase in atomic layer deposited SrTiO3 RS thin film. The conducting phase was identified through extensive transmission electron microscopy studies, which indicated that oxygen-deficient Sr2Ti6O13 or Sr1Ti11O20 phase was presumably present mainly along the grain boundaries of SrTiO3 after the unipolar set switching in Pt/TiN/SrTiO3/Pt structure. A detailed electrical characterization revealed that the samples showed typical bipolar and complementary RS after the memory cell was unipolar reset. PMID:26830978

Dissimilar welding of nickel-based Alloy 690 to SUS 304L with Ti addition

NASA Astrophysics Data System (ADS)

Lee, H. T.; Jeng, S. L.; Yen, C. H.; Kuo, T. Y.

2004-10-01

This study investigates the effects of Ti addition on the weldability, microstructure and mechanical properties of a dissimilar weldment of Alloy 690 and SUS 304L. Shielding metal arc welding (SMAW) is employed to butt-weld two plates with three welding layers, where each layer is deposited in a single pass. To investigate the effects of Ti addition, the flux coatings of the electrodes used in the welding process are modified by varying additions of either a Ti-Fe compound or a Ti powder. The results indicate that the microstructure of the fusion zone (FZ) is primarily dendritic. With increasing Ti content, it is noted that the microstructure changes from a columnar dendritic to an equiaxed dendritic, in which the primary dendrite arm spacing (PDAS) becomes shorter. Furthermore, it is observed that the amount of Al-Ti oxide phase increases in the inter-dendritic region, while the amount of Nb-rich phase decreases. Moreover, the average hardness of the FZ increases slightly. The results indicate that Ti addition prompts a significant increase in the elongation of the weldment (i.e. 36.5%, Ti: 0.41 wt%), although the tensile strength remains relatively unchanged. However, at an increased Ti content of 0.91 wt%, an obvious reduction in the tensile strength is noted, which can be attributed to a general reduction in the weldability of the joint.

Study of non-stoichiometric BaSrTiFeO3 oxide dedicated to semiconductor gas sensors

NASA Astrophysics Data System (ADS)

Fasquelle, D.; Verbrugghe, N.; Deputier, S.

2016-11-01

Developing instrumentation systems compatible with the European RoHS directive (restriction of hazardous substances) to monitor our environment is of great interest for our society. Our research therefore aims at developing innovating integrated systems of detection dedicated to the characterization of various environmental exposures. These systems, which integrate new gas sensors containing lead-free oxides, are dedicated to the detection of flammable and toxic gases. We have firstly chosen to study semiconductor gas sensors implemented with lead-free oxides in view to develop RoHS devices. Therefore thick films deposited by spin-coating and screen-printing have been chosen for their robustness, ease to realize and ease to finally obtain cost-effective sensors. As crystalline defects and ionic vacancies are of great interest for gas detection, we have decided to study a non-stoichiometric composition of the BaSrTiFeO3 sensible oxide. Nonstoichiometric BaSrTiFeO3 lead-free oxide thick films were deposited by screen-printing on polycrystalline AFO3 substrates covered by a layer of Ag-Pd acting as bottom electrode. The physical characterizations have revealed a crystalline structure mainly composed of BaTiO3 pseudo-cubic phase and Ba4Ti12O27 monoclinic phase for the powder, and a porous microstructure for the thick films. When compared to a BSTF thick film with a stoichiometric composition, a notable increase in the BSTF dielectric constant value was observed when taking into account of a similar microstructure and grain size. The loss tangent mean value varies more softly for the non-stoichiometric BaSrTiFeO3 films than for the perovskite BSTF film as tanδ decreases from 0.45 to 0.04 when the frequency increases from 100 Hz to 1 MHz.

Numerical and experimental investigation of GaN-based flip-chip light-emitting diodes with highly reflective Ag/TiW and ITO/DBR Ohmic contacts.

PubMed

Zhou, Shengjun; Liu, Xingtong; Gao, Yilin; Liu, Yingce; Liu, Mengling; Liu, Zongyuan; Gui, Chengqun; Liu, Sheng

2017-10-30

We demonstrate two types of GaN-based flip-chip light-emitting diodes (FCLEDs) with highly reflective Ag/TiW and indium-tin oxide (ITO)/distributed Bragg reflector (DBR) p-type Ohmic contacts. We show that a direct Ohmic contact to p-GaN layer using pure Ag is obtained when annealed at 600°C in N 2 ambient. A TiW diffusion barrier layer covered onto Ag is used to suppress the agglomeration of Ag and thus maintain high reflectance of Ag during high temperature annealing process. We develop a strip-shaped SiO 2 current blocking layer beneath the ITO/DBR to alleviate current crowding occurring in FCLED with ITO/DBR. Owing to negligibly small spreading resistance of Ag, however, our combined numerical and experimental results show that the FCLED with Ag/TiW has a more favorable current spreading uniformity in comparison to the FCLED with ITO/DBR. As a result, the light output power of FCLED with Ag/TiW is 7.5% higher than that of FCLED with ITO/DBR at 350 mA. The maximum output power of the FCLED with Ag/TiW obtained at 305.6 A/cm 2 is 29.3% larger than that of the FCLED with ITO/DBR obtained at 278.9 A/cm 2 . The improvement appears to be due to the enhanced current spreading and higher optical reflectance provided by the Ag/TiW.

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Influence of Nitinol wire surface treatment on oxide thickness and composition and its subsequent effect on corrosion resistance and nickel ion release.

PubMed

Clarke, B; Carroll, W; Rochev, Y; Hynes, M; Bradley, D; Plumley, D

2006-10-01

Medical implants and devices are now used successfully in surgical procedures on a daily basis. Alloys of nickel and titanium, and in particular Nitinol are of special interest in the medical device industry, because of their shape memory and superelastic properties. The corrosion behavior of nitinol in the body is also of critical importance because of the known toxicological effects of nickel. The stability of a NiTi alloy in the physiological environment is dependant primarily on the properties of the mostly TiO(2) oxide layer that is present on the surface. For the present study, a range of nitinol wires have been prepared using different drawing processes and a range of surface preparation procedures. It is clear from the results obtained that the wire samples with very thick oxides also contain a high nickel content in the oxide layer. The untreated samples with the thicker oxides show the lowest pitting potential values and greater nickel release in both long and short-term experiments. It was also found that after long-term immersion tests breakdown potentials increased for samples that exhibited lower values initially. From these results it would appear that surface treatment is essential for the optimum bioperformance of nitinol. (c) 2006 Wiley Periodicals, Inc

Active phase distribution changes within a catalyst particle during Fischer–Tropsch synthesis as revealed by multi-scale microscopy

DOE PAGES

Cats, K. H.; Andrews, J. C.; Stephan, O.; ...

2016-02-16

In this study, the Fischer-Tropsch synthesis (FTS) reaction is one of the most promising processes to convert alternative energy sources, such as natural gas, coal or biomass, into liquid fuels and other high-value products. Despite its commercial implementation, we still lack fundamental insights into the various deactivation processes taking place during FTS. In this work, a combination of three methods for studying single catalyst particles at different length scales has been developed and applied to study the deactivation of Co/TiO 2 Fischer-Tropsch synthesis (FTS) catalysts. By combining transmission X-ray microscopy (TXM), scanning transmission X-ray microscopy (STXM) and scanning transmission electronmore » microscopy-electron energy loss spectroscopy (STEM-EELS) we visualized changes in the structure, aggregate size and distribution of supported Co nanoparticles that occur during FTS. At the microscale, Co nanoparticle aggregates are transported over several μm leading to a more homogeneous Co distribution, while at the nanoscale Co forms a thin layer of ~1-2 nm around the TiO 2 support. The formation of the Co layer is the opposite case to the “classical” strong metal-support interaction (SMSI) in which TiO 2 surrounds the Co, and is possibly related to the surface oxidation of Co metal nanoparticles in combination with coke formation. In other words, the observed migration and formation of a thin CoO x layer are similar to a previously discussed reaction-induced spreading of metal oxides across a TiO 2 surface.« less

Direct k-space mapping of the electronic structure in an oxide-oxide interface.

PubMed

Berner, G; Sing, M; Fujiwara, H; Yasui, A; Saitoh, Y; Yamasaki, A; Nishitani, Y; Sekiyama, A; Pavlenko, N; Kopp, T; Richter, C; Mannhart, J; Suga, S; Claessen, R

2013-06-14

The interface between LaAlO(3) and SrTiO(3) hosts a two-dimensional electron system of itinerant carriers, although both oxides are band insulators. Interface ferromagnetism coexisting with superconductivity has been found and attributed to local moments. Experimentally, it has been established that Ti 3d electrons are confined to the interface. Using soft x-ray angle-resolved resonant photoelectron spectroscopy we have directly mapped the interface states in k space. Our data demonstrate a charge dichotomy. A mobile fraction contributes to Fermi surface sheets, whereas a localized portion at higher binding energies is tentatively attributed to electrons trapped by O vacancies in the SrTiO(3). While photovoltage effects in the polar LaAlO(3) layers cannot be excluded, the apparent absence of surface-related Fermi surface sheets could also be fully reconciled in a recently proposed electronic reconstruction picture where the built-in potential in the LaAlO(3) is compensated by surface O vacancies serving also as a charge reservoir.

Composite WO 3/TiO 2 nanostructures for high electrochromic activity

DOE PAGES

Reyes-Gil, Karla R.; Stephens, Zachary D.; Stavila, Vitalie; ...

2015-01-06

A composite material consisting of TiO 2 nanotubes (NT) with WO 3 electrodeposited on its surface has been fabricated, detached from its Ti substrate, and attached to a fluorine-doped tin oxide (FTO) film on glass for application to electrochromic (EC) reactions. Several adhesion layers were tested, finding that a paste of TiO 2 made from commercially available TiO 2 nanoparticles creates an interface for the TiO 2 NT film to attach to the FTO glass, which is conductive and does not cause solution-phase ions in an electrolyte to bind irreversibly with the material. The effect of NT length and WOmore » 3 concentration on the EC performance were studied. As a result, the composite WO 3/TiO 2 nanostructures showed higher ion storage capacity, better stability, enhanced EC contrast, and longer memory time compared with the pure WO 3 and TiO 2 materials« less

Anode Design Based on Microscale Porous Scaffolds for Advanced Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Park, Hyeji; Choi, Hyelim; Nam, Kyungju; Lee, Sukyung; Um, Ji Hyun; Kim, Kyungbae; Kim, Jae-Hun; Yoon, Won-Sub; Choe, Heeman

2017-06-01

Considering the increasing demands for advanced power sources, present-day lithium-ion batteries (LIBs) must provide a higher energy and power density and better cycling stability than conventional LIBs. This study suggests a promising electrode design solution to this problem using Cu, Co, and Ti scaffolds with a microscale porous structure synthesized via freeze-casting. Co3O4 and TiO2 layers are uniformly formed on the Co and Ti scaffolds, respectively, through a simple thermal heat-treatment process, and a SnO2 layer is formed on the Cu scaffold through electroless plating and thermal oxidation. This paper characterizes and evaluates the physical and electrochemical properties of the proposed electrodes using scanning electron microscopy, four-point probe and coin-cell tests to confirm the feasibility of their potential use in LIBs.

Structural and Optical Properties of La1−xSrxTiO3+δ

PubMed Central

Gao, Lihong; Ma, Zhuang; Wang, Song; Wang, Fuchi; Yang, Cai

2014-01-01

La1−xSrxTiO3+δ has attracted much attention as an important perovskite oxide. However, there are rare reports on its optical properties, especially reflectivity. In this paper, its structural and optical properties were studied. The X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and spectrophotometer were used to characterize the sample. The results show that with increasing Sr concentration, the number of TiO6 octahedral layers in each “slab” increases and the crystal structure changes from layered to cubic structure. A proper Sr doping (x = 0.1) can increase the reflectivity, reaching 95% in the near infrared range, which is comparable with metal Al measured in the same condition. This indicates its potential applications as optical protective coatings or anti-radiation materials at high temperatures. PMID:28788115

XPS investigations of tribolayers formed on TiN and (Ti,Re)N coatings

NASA Astrophysics Data System (ADS)

Oktay, Serkan; Kahraman, Zafer; Urgen, Mustafa; Kazmanli, Kursat

2015-02-01

TiN and (Ti,Re)N coatings were deposited on high-speed-steel substrates by a hybrid coating system composed of cathodic arc PVD and magnetron sputtering techniques. In order to keep rhenium content low (8 ± 1.9 at.%) in the coating, magnetron sputtering technique was utilized to evaporate rhenium. The (Ti,Re)N coating consisted of TiN and ReNx (x > 1.33) phases. The hardness of TiN and (Ti,Re)N were 31 GPa and 29 GPa (± 2 GPa), respectively. Tribological behaviors of the samples were tested against Al2O3 balls at 21 °C (RT) and 150 °C (HT) by reciprocating wear technique. The tribolayers were analyzed by XPS technique. Friction coefficients of TiN were 0.56, 0.35 for 21 °C and 150 °C tests, respectively. Rhenium addition to TiN drastically dropped the friction coefficients to 0.22 and 0.17 for RT and HT samples. Rhenium addition also improved the wear resistance of the coating at both test temperatures. For TiN, main oxide component of the tribolayers was Ti2O3 for RT tests and TiO2 for HT tests. The oxide layer formed on (Ti,Re)N were the mixture of TiO2, Tisbnd Osbnd N, ReO2 and Re2O7 for both test temperatures. Re2O7 provided very low friction coefficient to (Ti,Re)N. The findings are consistent with the crystal chemistry approach.

Deposition of conductive TiN shells on SiO2 nanoparticles with a fluidized bed ALD reactor

NASA Astrophysics Data System (ADS)

Didden, Arjen; Hillebrand, Philipp; Wollgarten, Markus; Dam, Bernard; van de Krol, Roel

2016-02-01

Conductive TiN shells have been deposited on SiO2 nanoparticles (10-20 nm primary particle size) with fluidized bed atomic layer deposition using TDMAT and NH3 as precursors. Analysis of the powders confirms that shell growth saturates at approximately 0.4 nm/cycle at TDMAT doses of >1.2 mmol/g of powder. TEM and XPS analysis showed that all particles were coated with homogeneous shells containing titanium. Due to the large specific surface area of the nanoparticles, the TiN shells rapidly oxidize upon exposure to air. Electrical measurements show that the partially oxidized shells are conducting, with apparent resistivity of approximately 11 kΩ cm. The resistivity of the powders is strongly influenced by the NH3 dose, with a smaller dose giving an order-of-magnitude higher resistivity.

Evaluating tetracycline degradation pathway and intermediate toxicity during the electrochemical oxidation over a Ti/Ti4O7 anode.

PubMed

Wang, Jianbing; Zhi, Dan; Zhou, Hao; He, Xuwen; Zhang, Dayi

2018-06-15

Tetracycline (TC) is one of the most widely used antibiotics with significant impacts on human health and thus it needs appropriate approaches for its removal. In the present study, we evaluated the performance and complete pathway of the TC electrochemical oxidation on a Ti/Ti 4 O 7 anode prepared by plasma spraying. Morphological data and composition analysis indicated a compact coating layer on the anode, which had the characteristic peaks of Ti 4 O 7 as active constituent. The TC electrochemical oxidation on the Ti/Ti 4 O 7 anode followed a pseudo-first-order kinetics, and the TC removal efficiency reached 95.8% in 40 min. The influential factors on TC decay kinetics included current density, anode-cathode distance and initial TC concentration. This anode also had high durability and the TC removal efficiency was maintained over 95% after five times reuse. For the first time, we unraveled the complete pathway of the TC electrochemical oxidation using high-performance liquid chromatograph (HPLC) and gas chromatograph (GC) coupled with mass spectrometer (MS). ·OH radicals produced from electrochemical oxidation attack the double bond, phenolic group and amine group of TC, forming a primary intermediate (m/z = 461), secondary intermediates (m/z = 432, 477 and 509) and tertiary intermediates (m/z = 480, 448 and 525). The latter were further oxidized to the key downstream intermediate (m/z = 496), followed by further downstream intermediates (m/z = 451, 412, 396, 367, 351, 298 and 253) and eventually short-chain carboxylic acids. We also evaluated the toxicity change during the electrochemical oxidation process with bioluminescent bacteria. The bioluminescence inhibition ratio peaked at 10 min (55.41%), likely owing to the high toxicity of intermediates with m/z = 461, 432 and 477 as obtained from quantitative structure activity relationship (QSAR) analysis. The bioluminescence inhibition ratio eventually decreased to 16.78% in 40 min due to further transformation of TC and intermediates. By comprehensively analyzing the influential factors and complete degradation pathway of TC electrochemical oxidation on the Ti/Ti 4 O 7 anode, our research provides deeper insights into the risk assessment of intermediates and their toxicity, assigning new perspectives for practical electrochemical oxidation to effectively eliminate the amount and toxicity of TC and other antibiotics in wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Novel stable hard transparent conductors in TiO2-TiC system: Design materials from scratch

PubMed Central

Meng, Xiangying; Liu, Dongyan; Dai, Xuefeng; Pan, Haijun; Wen, Xiaohong; Zuo, Liang; Qin, Gaowu

2014-01-01

Two new ternary compounds in the TiO2-TiC system, Ti5C2O6 and Ti3C2O2, are reported for the first time based on ab initio evolutionary algorithm. Ti5C2O6 has a tube-structure in which sp1 hybridized carbon chains run through the lattice along the b-axis; while in the Ti3C2O2 lattice, double TiO6 polyhedral are separated by the non-coplanar sp2 hybridized hexagon graphite layers along the c-axis, forming a sandwich-like structure. At ambient conditions, the two compounds are found to be mechanically and dynamically stable and intrinsic transparent conductors with high hardness (about twice harder than the conventional transparent conducting oxides). These mechanical, electronic, and optical properties make Ti5C2O6 and Ti3C2O2 ternary compounds be promising robust, hard, transparent, and conductive materials. PMID:25511583

The Effect of Film Thickness on the Gas Sensing Properties of Ultra-Thin TiO2 Films Deposited by Atomic Layer Deposition

PubMed Central

Wilson, Rachel L.; Blackman, Christopher S.; Carmalt, Claire J.; Stanoiu, Adelina; Di Maggio, Francesco

2018-01-01

Analyte sensitivity for gas sensors based on semiconducting metal oxides should be highly dependent on the film thickness, particularly when that thickness is on the order of the Debye length. This thickness dependence has previously been demonstrated for SnO2 and inferred for TiO2. In this paper, TiO2 thin films have been prepared by Atomic Layer Deposition (ALD) using titanium isopropoxide and water as precursors. The deposition process was performed on standard alumina gas sensor platforms and microscope slides (for analysis purposes), at a temperature of 200 °C. The TiO2 films were exposed to different concentrations of CO, CH4, NO2, NH3 and SO2 to evaluate their gas sensitivities. These experiments showed that the TiO2 film thickness played a dominant role within the conduction mechanism and the pattern of response for the electrical resistance towards CH4 and NH3 exposure indicated typical n-type semiconducting behavior. The effect of relative humidity on the gas sensitivity has also been demonstrated. PMID:29494504

Investigation of anodic TiO2 nanotube composition with high spatial resolution AES and ToF SIMS

NASA Astrophysics Data System (ADS)

Dronov, Alexey; Gavrilin, Ilya; Kirilenko, Elena; Dronova, Daria; Gavrilov, Sergey

2018-03-01

High resolution Scanning Auger Electron Spectroscopy (AES) and Time-of-Flight Secondary Ion Mass-Spectrometry (ToF SIMS) were used to investigate structure and elemental composition variation of both across an array of TiO2 nanotubes (NTs) and single tube of an array. The TiO2 NT array was grown by anodic oxidation of Ti foil in fluorine-containing ethylene glycol electrolyte. It was found that the studied anodic TiO2 nanotubes have a layered structure with rather sharp interfaces. The differences in AES depth profiling results of a single tube with the focused primary electron beam (point analysis) and over an area of 75 μm in diameter of a nanotube array with the defocused primary electron beam are discussed. Depth profiling by ToF SIMS was carried out over approximately the same size of a nanotube array to determine possible ionic fragments in the structure. The analysis results show that the combination of both mentioned methods is useful for a detailed analysis of nanostructures with complex morphology and multi-layered nature.

Low thermal budget, photonic-cured compact TiO 2 layers for high-efficiency perovskite solar cells

DOE PAGES

Das, Sanjib; Gu, Gong; Joshi, Pooran C.; ...

2016-05-25

Rapid advances in organometallic trihalide perovskite solar cells (PSCs) have positioned them to be one of the leading next generation photovoltaic technologies. However, most of the high-performance PSCs, particularly those using compact TiO 2 as an electron transport layer, require a high-temperature sintering step, which is not compatible with flexible polymer-based substrates. Considering the materials of interest for PSCs and corresponding device configurations, it is technologically imperative to fabricate high-efficiency cells at low thermal budget so that they can be realized on low-temperature plastic substrates. In this paper, we report on a new photonic curing technique that produces crystalline anatase-phasemore » TiO 2 films on indium tin oxide-coated glass and flexible polyethylene terephthalate (PET) substrates. Finally, the planar PSCs, using photonic-cured TiO 2 films, exhibit PCEs as high as 15.0% and 11.2% on glass and flexible PET substrates, respectively, comparable to the device performance of PSCs incorporating furnace annealed TiO 2 films.« less

Isolation and characterization of nanosheets containing few layers of the Aurivillius family of oxides and metal-organic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sreedhara, M.B.; Prasad, B.E.; Moirangthem, Monali

2015-04-15

Nanosheets containing few-layers of ferroelectric Aurivillius family of oxides, Bi{sub 2}A{sub n−1}B{sub n}O{sub 3n+3} (where A=Bi{sup 3+}, Ba{sup 2+} etc. and B=Ti{sup 4+}, Fe{sup 3+} etc.) with n=3, 4, 5, 6 and 7 have been prepared by reaction with n-butyllithium, followed by exfoliation in water. The few-layer samples have been characterized by Tyndall cones, atomic force microscopy, optical spectroscopy and other techniques. The few-layer species have a thickness corresponding to a fraction of the c-parameter along which axis the perovskite layers are stacked. Magnetization measurements have been carried out on the few-layer samples containing iron. Few-layer species of a fewmore » layered metal-organic compounds have been obtained by ultrasonication and characterized by Tyndall cones, atomic force microscopy, optical spectroscopy and magnetic measurements. Significant changes in the optical spectra and magnetic properties are found in the few-layer species compared to the bulk samples. Few-layer species of the Aurivillius family of oxides may find uses as thin layer dielectrics in photovoltaics and other applications. - Graphical abstract: Exfoliation of the layered Aurivillius oxides into few-layer nanosheets by chemical Li intercalation using n-BuLi followed by reaction in water. Exfoliation of the layered metal-organic compounds into few-layer nanosheets by ultrasonication. - Highlights: • Few-layer nanosheets of Aurivillius family of oxides with perovskite layers have been generated by lithium intercalation. • Few-layer nanosheets of few layered metal-organic compounds have been generated by ultrasonication. • Few-layer nanosheets of the Aurivillius oxides have been characterized by AFM, TEM and optical spectroscopy. • Aurivillius oxides containing Fe show layer dependent magnetic properties. • Exfoliated few-layer metal-organic compounds show changes in spectroscopic and magnetic properties compared with bulk materials.« less

Evolution of resistive switching mechanism through H2O2 sensing by using TaOx-based material in W/Al2O3/TaOx/TiN structure

NASA Astrophysics Data System (ADS)

Chakrabarti, Somsubhra; Panja, Rajeswar; Roy, Sourav; Roy, Anisha; Samanta, Subhranu; Dutta, Mrinmoy; Ginnaram, Sreekanth; Maikap, Siddheswar; Cheng, Hsin-Ming; Tsai, Ling-Na; Chang, Ya-Ling; Mahapatra, Rajat; Jana, Debanjan; Qiu, Jian-Tai; Yang, Jer-Ren

2018-03-01

Understanding of resistive switching mechanism through H2O2 sensing and improvement of switching characteristics by using TaOx-based material in W/Al2O3/TaOx/TiN structure have been reported for the first time. Existence of amorphous Al2O3/TaOx layer in the RRAM devices has been confirmed by transmission electron microscopy. By analyzing the oxidation states of Ta2+/Ta5+ for TaOx switching material and W0/W6+ for WOx layer at the W/TaOx interface through X-ray photoelectron spectroscopy and H2O2 sensing, the reduction-oxidation mechanism under Set/Reset occurs only in the TaOx layer for the W/Al2O3/TaOx/TiN structures. This leads to higher Schottky barrier height at the W/Al2O3 interface (0.54 eV vs. 0.46 eV), higher resistance ratio, and long program/erase endurance of >108 cycles with 100 ns pulse width at a low operation current of 30 μA. Stable retention of more than 104 s at 85 °C is also obtained. Using conduction mechanism and reduction-oxidation reaction, current-voltage characteristic has been simulated. Both TaOx and WOx membranes have high pH sensitivity values of 47.65 mV/pH and 49.25 mV/pH, respectively. Those membranes can also sense H2O2 with a low concentration of 1 nM in an electrolyte-insulator-semiconductor structure because of catalytic activity, while the Al2O3 membrane does not show sensing. The TaOx material in W/Al2O3/TaOx/TiN structure does not show only a path towards high dense, small size memory application with understanding of switching mechanism but also can be used for H2O2 sensors.

Interfacial Metal-Oxide Interactions in Resistive Switching Memories.

PubMed

Cho, Deok-Yong; Luebben, Michael; Wiefels, Stefan; Lee, Kug-Seung; Valov, Ilia

2017-06-07

Metal oxides are commonly used as electrolytes for redox-based resistive switching memories. In most cases, non-noble metals are directly deposited as ohmic electrodes. We demonstrate that irrespective of bulk thermodynamics predictions an intermediate oxide film a few nanometers in thickness is always formed at the metal/insulator interface, and this layer significantly contributes to the development of reliable switching characteristics. We have tested metal electrodes and metal oxides mostly used for memristive devices, that is, Ta, Hf, and Ti and Ta 2 O 5 , HfO 2 , and SiO 2 . Intermediate oxide layers are always formed at the interfaces, whereas only the rate of the electrode oxidation depends on the oxygen affinity of the metal and the chemical stability of the oxide matrix. Device failure is associated with complete transition of short-range order to a more disordered main matrix structure.

Hydroxyapatite-coated Ti-6Al-4V part 2: the effects of post-deposition heat treatment at low temperatures.

PubMed

Lynn, A K; DuQuesnay, D L

2002-05-01

The present investigation explores the effects of a 90-h post-deposition annealing treatment at 400 degrees C in air on the crystallographic and chemical properties of a plasma-sprayed hydroxyapatite (HA) coating, the thickness and composition of the interfacial oxide layer, and the fatigue behaviour of the underlying Ti-6Al-4V substrate. X-ray diffraction analysis revealed that significant recovery of the crystalline HA structure occurred as a result of the treatment, however, as compared with results obtained through treatment at higher temperatures, recovery obtained through use of the present treatment was incomplete. X-ray photoelectron spectroscopy analysis showed no changes in the constituents of the oxide layer, with the oxide species TiO2, Al2O3, V2O5, V2O3, and VO2 present on both the as-sprayed and the heat-treated substrates. A change in film thickness was observed, however, as evidenced by a change in colour from opaque bronze to dark purple. The fatigue resistance of the substrate was found to be significantly reduced by the heat treatment, with the lives of heat-treated coupons with coatings of all thicknesses closely resembling those of as-sprayed coupons with thick HA coatings and uncoated stress-relieved coupons presented in Part I of this study. Stress relief was identified as the most likely cause of these reductions.

Ionic Segregation on Grain Boundaries in Thermally Grown Alumina Scales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pint, Bruce A; Unocic, Kinga A

2012-01-01

This study first examined segregation behaviour in the alumina scale formed after 100 h at 1100 C on bare and MCrAlYHfSi-coated single-crystal superalloys with {approx}10 ppma La and Y. For the bare superalloy, Hf and Ti were detected on the grain boundaries of the inner columnar alumina layer. Increasing the oxidation temperature to 1200 C for 2 h did not change the segregation behavior. With the bond coating, both Y and Hf were segregated to the grain boundaries as expected. However, there was evidence of Ti-rich oxide particles near the gas interface suggesting that Ti diffused from the superalloy throughmore » the coating. To further understand these segregation observations with multiple dopants, other alumina-forming systems were examined. Alumina scale grain boundary co-segregation of Ti with Y is common for FeCrAl alloys. Co-segregation of Hf and Ti was observed in the scale formed on co-doped NiAl. No La segregation was detected in the scale formed on NiCrAl with only a 19 ppma La addition, however, the scale was adherent.« less

Development of Biomimetic NiTi Alloy: Influence of Thermo-Chemical Treatment on the Physical, Mechanical and Biological Behavior

PubMed Central

Rupérez, Elisa; Manero, José María; Bravo-González, Luis-Alberto; Espinar, Eduardo; Gil, F.J.

2016-01-01

A bioactive layer, free of nickel, has been performed for its greater acceptability and reliability in clinical applications for NiTi shape memory alloys. In the first step, a safe barrier against Ni release has been produced on the surface by means of a thicker rutile/anastase protective layer free of nickel. In the second step, a sodium alkaline titanate hydrogel, which has the ability to induce apatite formation, has been performed from oxidized surface. An improvement of host tissue–implant integration has been achieved in terms of Ni ions release and the bioactivity of the treated NiTi alloys has been corroborated with both in vitro and in vivo studies. The transformation temperatures (As, Af, Ms, and Mf), as well as the critical stresses (σβ⇔M), have been slightly changed due to this surface modification. Consequently, this fact must be taken into account in order to design new surface modification on NiTi implants. PMID:28773526

Parasitic resistive switching uncovered from complementary resistive switching in single active-layer oxide memory device

NASA Astrophysics Data System (ADS)

Zhu, Lisha; Hu, Wei; Gao, Chao; Guo, Yongcai

2017-12-01

This paper reports the reversible transition processes between the bipolar and complementary resistive switching (CRS) characteristics on the binary metal-oxide resistive memory devices of Pt/HfO x /TiN and Pt/TaO x /TiN by applying the appropriate bias voltages. More interestingly, by controlling the amplitude of the negative bias, the parasitic resistive switching effect exhibiting repeatable switching behavior is uncovered from the CRS behavior. The electrical observation of the parasitic resistive switching effect can be explained by the controlled size of the conductive filament. This work confirms the transformation and interrelationship among the bipolar, parasitic, and CRS effects, and thus provides new insight into the understanding of the physical mechanism of the binary metal-oxide resistive switching memory devices.

Laser method for forming low-resistance ohmic contacts on semiconducting oxides

DOEpatents

Narayan, Jagdish

1981-01-01

This invention is a new method for the formation of high-quality ohmic contacts on wide-band-gap semiconducting oxides. As exemplified by the formation of an ohmic contact on n-type BaTiO.sub.3 containing a p-n junction, the invention entails depositing a film of a metallic electroding material on the BaTiO.sub.3 surface and irradiating the film with a Q-switched laser pulse effecting complete melting of the film and localized melting of the surface layer of oxide immediately underlying the film. The resulting solidified metallic contact is ohmic, has unusually low contact resistance, and is thermally stable, even at elevated temperatures. The contact does not require cleaning before attachment of any suitable electrical lead. This method is safe, rapid, reproducible, and relatively inexpensive.

Method for forming low-resistance ohmic contacts on semiconducting oxides

DOEpatents

Narayan, J.

1979-10-01

The invention provides a new method for the formation of high-quality ohmic contacts on wide-band-gap semiconducting oxides. As exemplified by the formation of an ohmic contact on n-type BaTiO/sub 3/ containing a p-n junction, the invention entails depositing a film of a metallic electroding material on the BaTiO/sub 3/ surface and irradiating the film with a Q-switched laser pulse effecting complete melting of the film and localized melting of the surface layer of oxide immediately underlying the film. The resulting solidified metallic contact is ohmic, has unusually low contact resistance, and is thermally stable, even at elevated temmperatures. The contact does not require cleaning before attachment of any suitable electrical lead. This method is safe, rapid, reproducible, and relatively inexpensive.

Formation, Phase, and Elemental Composition of Micro- and Nano-Dimensional Particles of the Fe-Ti System

NASA Astrophysics Data System (ADS)

Dresvyannikov, A. F.; Kolpakov, M. E.

2018-05-01

X-ray fluorescence, X-ray phase analysis, and transmission Mössbauer and NGR spectrometry are used to study the formation, phase, and elemental composition of Fe-Ti particles. The interaction between Fe(III) ions and dispersed titanium in an aqueous solution containing chloride ions and HF is studied. It is shown that the resulting Fe-Ti samples are a set of core-shell microparticles with titanium cores coated with micro- and nanosized α-Fe nucleation centers with the thinness outer layer of iron(III) oxide characterized by a developed surface.

Strain Effects in Epitaxial VO2 Thin Films on Columnar Buffer-Layer TiO2/Al2O3 Virtual Substrates.

PubMed

Breckenfeld, Eric; Kim, Heungsoo; Burgess, Katherine; Charipar, Nicholas; Cheng, Shu-Fan; Stroud, Rhonda; Piqué, Alberto

2017-01-18

Epitaxial VO 2 /TiO 2 thin film heterostructures were grown on (100) (m-cut) Al 2 O 3 substrates via pulsed laser deposition. We have demonstrated the ability to reduce the semiconductor-metal transition (SMT) temperature of VO 2 to ∼44 °C while retaining a 4 order of magnitude SMT using the TiO 2 buffer layer. A combination of electrical transport and X-ray diffraction reciprocal space mapping studies help examine the specific strain states of VO 2 /TiO 2 /Al 2 O 3 heterostructures as a function of TiO 2 film growth temperatures. Atomic force microscopy and transmission electron microscopy analyses show that the columnar microstructure present in TiO 2 buffer films is responsible for the partially strained VO 2 film behavior and subsequently favorable transport characteristics with a lower SMT temperature. Such findings are of crucial importance for both the technological implementation of the VO 2 system, where reduction of its SMT temperature is widely sought, as well as the broader complex oxide community, where greater understanding of the evolution of microstructure, strain, and functional properties is a high priority.

Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural with ALD overcoating (II) – Comparison between TiO2 and Al2O3 overcoatings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hongbo; Canlas, Christian; Kropf, A. Jeremy

2015-01-01

TiO2 atomic layer deposition (ALD) overcoatings were applied to copper chromite catalysts to increase the stability for 2-furfuraldehyde (“furfural”) hydrogenation. After overcoating, about 75% activity was preserved compared to neat copper chromite: much higher activity than an alumina ALD overcoated catalyst with a similar number of ALD cycles. The effects of ALD TiO2 on the active Cu nanoparticles were studied extensively using both in-situ TPR/isothermal-oxidation and in-situ furfural hydrogenation via Cu XAFS. The redox properties of Cu were modified only slightly by the TiO2 ALD overcoat. However, a subtle electronic interaction was observed between the TiO2 ALD layers and themore » Cu nanoparticles. With calcination at 500 °C the interaction between the TiO2 overcoat and the underlying catalyst is strong enough to inhibit migration and site blocking by chromite, but is sufficiently weaker than the interaction between the Al2O3 overcoat and copper chromite that it does not strongly inhibit the catalytic activity of the copper nanoparticles.« less