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Journal articles on the topic 'Metal supported oxide thin films'

Author: Grafiati

Published: 9 March 2023

Last updated: 10 March 2023

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1

Wayne Goodman, D. "Surface spectroscopic studies of model supported-metal catalysts." Proceedings, annual meeting, Electron Microscopy Society of America 53 (August 13, 1995): 394–95. http://dx.doi.org/10.1017/s0424820100138348.

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A new surface science approach to the study of supported-metal catalysts will be described. Thin oxide films (~100 Å) of SiO2, Al2O3, or MgO supported on a refractory metal substrate (e.g., Mo or W) have been prepared by depositing the oxide metal precursor in a background of oxygen (ca. l×l0-5 Torr) [1]. The thin-film catalysts facilitate investigation by an array of surface techniques, many of which are precluded when applied to the corresponding bulk oxide [1,2]. In particular, the oxide films have been characterized by AES, ELS, HREELS, XPS, UPS, ISS, IRAS, and TD spectroscopies and shown to have essentially identical electronic and vibrational properties of the corresponding bulk oxides. These studies indicate then that these films can serve as convenient models for oxide catalysts or metal supports. Metal thin films (e.g., Cu, Pd, Ni) have subsequently been deposited onto the oxide films and the properties of the metal/oxide system then studied with the above array of surface techniques [3]. By properly defining the metal thin film thickness, metal particles of varying sizes can be synthesized with dispersions from a few nanometers to tens of nanometers.

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2

St. Clair, Todd P., and D. Wayne Goodman. "ChemInform Abstract: Metal Nanoclusters Supported on Metal Oxide Thin Films: Bridging the Materials Gap." ChemInform 31, no. 47 (November 21, 2000): no. http://dx.doi.org/10.1002/chin.200047240.

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3

Zhu, Jiaxin, Jung-Woo Lee, Hyungwoo Lee, Lin Xie, Xiaoqing Pan, Roger A. De Souza, Chang-Beom Eom, and Stephen S. Nonnenmann. "Probing Vacancy Behavior in Complex Oxide Heterostructured Films." ECS Meeting Abstracts MA2018-01, no. 32 (April 13, 2018): 1931. http://dx.doi.org/10.1149/ma2018-01/32/1931.

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Oxygen vacancies (Vo•• ) play a critical role in the transport mechanisms within complex oxides, analogous to electrons and holes within semiconductors. Systems including memristors, all-oxide electronics, and electrochemical cells comprise substrate-supported thin films either in metal-insulator-metal or complex oxide heterostructure configurations. As well-studied defect chemistry dictates mixed electronic/ionic functionality, improving oxide-oxide interfaces necessitates a direct, spatial understanding of vacancy distributions that define electrochemically active regions. Here we show that vacancies deplete over large, micron-level distances within single crystalline perovskite Nb-doped SrTiO3 substrate (Nb:SrTiO3) substrates after typical vacuum film deposition and post-annealing processes. We demonstrate the conversion of the surface potential across a four-layer strontium titanate / yttria-stabilized zirconia (STO/YSZ) heterostructured film to spatially defined (< 100 nm) [Vo•• ] profiles within STO through a unique combination of high temperature (500 °C), in situ scanning probes and classic semiconductor energy band diagram model analysis. Further comparison between room temperature and high temperature potential profiles clearly distinguishes between electronic-dominant and activated, ionic-dominant transport characteristics within the oxide layers. Consequently, we determined that oxygen scavenging by deposited films during pulsed laser deposition significantly reduce the Nb:STO, which is then partially reoxidized in the ambient environment during cooling. The results presented herein i) introduce the means to spatially resolve quantitative vacancy distributions across oxide films, and ii) pose the mechanism by which oxide thin film getters both enhance then deplete vacancies within the underlying substrate.

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4

GOODMAN, D. W. "MODEL CATALYSTS: FROM EXTENDED SINGLE CRYSTALS TO SUPPORTED PARTICLES." Surface Review and Letters 02, no. 01 (February 1995): 9–24. http://dx.doi.org/10.1142/s0218625x95000030.

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Model oxide-supported metal catalysts have been prepared by evaporating a metal (e.g., Cu, Pd) onto an oxide ( SiO 2, Al 2 O 3) thin film (~100 Å) which, in turn, is supported on a refractory metal (Mo, W, Ta) surface. The deposited metal films, upon annealing, form small metallic clusters on the oxide surface whose sizes are dependent upon the initial metal film thickness. The surface structures and particle morphologies have been characterized using scanning probe microscopies, temperature programed desorption, X-ray and ultraviolet photoemission, and high-resolution electron energy-loss spectroscopy/infrared reflection-absorption spectroscopy of adsorbed carbon monoxide. The catalytic properties of these particles have also been investigated with respect to several reactions including CO/O 2 and CO/NO. The chemical and electronic properties of the metal particles with respect to size are compared to the analogous properties of extended single-crystal surfaces.

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5

Freund, Hans-Joachim, and Gianfranco Pacchioni. "Oxide ultra-thin films on metals: new materials for the design of supported metal catalysts." Chemical Society Reviews 37, no. 10 (2008): 2224. http://dx.doi.org/10.1039/b718768h.

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6

GOODMAN, D. W. "CATALYSIS BY METALS: FROM EXTENDED SINGLE CRYSTALS TO SMALL CLUSTERS." Surface Review and Letters 01, no. 04 (December 1994): 449–55. http://dx.doi.org/10.1142/s0218625x94000424.

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Model oxide-supported metal cluster catalysts have been prepared by evaporating the corresponding metal (e.g., Cu, Pd, Ni) onto a oxide thin film (~100 Å), which in turn is supported on a refractory metal (Mo, W, Ta) surface. The deposited metal films, upon annealing, form small metallic clusters on the oxide surface whose size are dependent upon the initial metal film thickness. The surface structures and cluster morphologies have been characterized using scanning probe microscopies, temperature-programed desorption, X-ray, and ultraviolet photoemission; and high-resolution electron energy loss spectroscopy/infrared reflection-absorption spectroscopy of adsorbed carbon monoxide. The catalytic properties of these clusters have also been investigated with respect to several reactions including CO/O 2 and CO/NO. The chemical and electronic properties of the metal clusters with respect to size are compared to the analogous properties of extended single crystal surfaces.

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7

Mustajab, M. A., T. Winata, and P. Arifin. "Lithium doping effect on microstructural and electrical properties of zinc oxide thin film grown by metal-organic chemical vapor deposition." Journal of Physics: Conference Series 2243, no. 1 (June 1, 2022): 012054. http://dx.doi.org/10.1088/1742-6596/2243/1/012054.

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Abstract In this study, the undoped and Li-doped ZnO thin films were grown on Si(100) substrate using metal-organic chemical vapor deposition (MOCVD). Zinc acetylacetonate hydrate and lithium acetylacetonate solution were used as ZnO thin film precursor and Li dopant source. The effect of lithium doping on microstructural was characterized using a scanning electron microscope (SEM) and X-ray diffractometer (XRD). XRD diffractogram analysis shows that undoped and Li-doped ZnO thin films have polycrystalline hexagonal wurtzite structures with preferred peak crystal orientation (103). Li doping slightly changes the lattice parameters and cell volume of ZnO thin films through the increase of crystallite size and slightly affects the surface morphology of ZnO thin films. Current-voltage (I-V) measurement and four-point probe method were used to measure the electrical properties of lithium doped ZnO thin films. The electrical conductivity of ZnO thin films increases as Li doping is given compared to undoped films. These results are also supported by the I-V curve of Li-doped ZnO thin films by having a higher slope, indicating improvement in electrical properties.

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8

Baltrus, John P., Gordon R. Holcomb, Joseph H. Tylczak, and Paul R. Ohodnicki. "Factors Influencing the Stability of Au-Incorporated Metal-Oxide Supported Thin Films for Optical Gas Sensing." Journal of The Electrochemical Society 164, no. 4 (2017): B159—B167. http://dx.doi.org/10.1149/2.1451704jes.

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9

D'Souza, Francis, Ashwin Ganesan, Adaeze Osonkie, Precious Chukwunenye, Ishika Rashed, Fatima Anwar, Mojgan Gharee, Kabirat Balogun, Thomas R. Cundari, and Jeffry Kelber. "Electro-Catalytic Reduction of Nitrogen to Ammonia By Vanadium Oxide and Vanadium Oxynitride Thin Films: The Roles of Metal Oxophilicity, and Lattice Oxygen and Nitrogen Towards NRR." ECS Meeting Abstracts MA2022-01, no. 45 (July 7, 2022): 1893. http://dx.doi.org/10.1149/ma2022-01451893mtgabs.

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Electro-catalytic reduction of N2 to NH3 using Earth-abundant oxide and oxynitrides is an energy- and environmentally-friendly alternative to the Haber-Bosch process. The present contribution summarizes our recent progress on vanadium oxide (VO) and vanadium oxynitride (VON) thin films1,2 as electrochemical nitrogen reduction reaction (NRR) catalysts at neutral pH conditions. In the case of VO films, the N-free VIII/IV-oxide, created by O2 plasma oxidation of polycrystalline vanadium, exhibited N2 reduction at an onset potential of -0.16 V vs. Ag/AgCl. DFT calculations indicated that N2 scission from O-supported V-centers is energetically favorable by ~18 kcal/mole as compared to N-supported sites. Interestingly, in the case of VON catalysts, both electrochemistry and photoemission data revealed the involvement of both lattice N and dissolved N2 in the NRR process. Our results also show that NH3 production from VON lattice N occurs in the presence or absence of N2 and involves the formation of V≡N: intermediates or similar unsaturated VN surface states. This is in contrast to VO where N2 reduction occurred in the presence or absence of lattice N, and without N incorporation into a vanadium oxide lattice. Thus, both lattice N and N2 reduction mechanisms involve oxide-supported V surface sites ([V]O) in preference to N-supported sites ([V]N). DFT calculations revealed the formation of V≡N:, V-N=N-H, plus other plausible reaction intermediates that are energetically favored at [V]O rather than at [V]N surface sites. Acknowledgment: This work was supported by the National Science Foundation through grants DMR-2112864 (to JAK, TRC, and FD) and partial support by CHE-1953547 (to TRC). Additional NSF support for the UNT CASCaM HPC cluster via Grant CHE-1531468 is also gratefully acknowledged. Ganesan, A. Osonkie, P. Chukwunenye, T. Cundari, F. D'Souza, J. Kelber. Electrochemical Reduction of N2 to ammonia by vanadium oxide thin films at neutral pH, J. Electrochem. Soc., 2021, 168, 026504. Osonkie, A. Ganesan, P. Chukwunenye, F. Anwar, K. Balogun, M. Gharee, I. Rashed, T. R. Cundari, F. D’Souza, and J. A. Kelber, Electro-catalytic reduction of nitrogen to ammonia: The roles of lattice O and N in reduction at vanadium oxynitride surfaces, ACS Adv. Mater & Interface, 2021, in revision.

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Rodrigues, Marco S., Joel Borges, Cláudia Lopes, Rui M. S. Pereira, Mikhail I. Vasilevskiy, and Filipe Vaz. "Gas Sensors Based on Localized Surface Plasmon Resonances: Synthesis of Oxide Films with Embedded Metal Nanoparticles, Theory and Simulation, and Sensitivity Enhancement Strategies." Applied Sciences 11, no. 12 (June 10, 2021): 5388. http://dx.doi.org/10.3390/app11125388.

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This work presents a comprehensive review on gas sensors based on localized surface plasmon resonance (LSPR) phenomenon, including the theory of LSPR, the synthesis of nanoparticle-embedded oxide thin films, and strategies to enhance the sensitivity of these optical sensors, supported by simulations of the electromagnetic properties. The LSPR phenomenon is known to be responsible for the unique colour effects observed in the ancient Roman Lycurgus Cup and at the windows of the medieval cathedrals. In both cases, the optical effects result from the interaction of the visible light (scattering and absorption) with the conduction band electrons of noble metal nanoparticles (gold, silver, and gold–silver alloys). These nanoparticles are dispersed in a dielectric matrix with a relatively high refractive index in order to push the resonance to the visible spectral range. At the same time, they have to be located at the surface to make LSPR sensitive to changes in the local dielectric environment, the property that is very attractive for sensing applications. Hence, an overview of gas sensors is presented, including electronic-nose systems, followed by a description of the surface plasmons that arise in noble metal thin films and nanoparticles. Afterwards, metal oxides are explored as robust and sensitive materials to host nanoparticles, followed by preparation methods of nanocomposite plasmonic thin films with sustainable techniques. Finally, several optical properties simulation methods are described, and the optical LSPR sensitivity of gold nanoparticles with different shapes, sensing volumes, and surroundings is calculated using the discrete dipole approximation method.

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11

Jirátová, Květa, Roman Perekrestov, Michaela Dvořáková, Jana Balabánová, Martin Koštejn, Martin Veselý, Martin Čada, et al. "Modification of Cobalt Oxide Electrochemically Deposited on Stainless Steel Meshes with Co-Mn Thin Films Prepared by Magnetron Sputtering: Effect of Preparation Method and Application to Ethanol Oxidation." Catalysts 11, no. 12 (November 29, 2021): 1453. http://dx.doi.org/10.3390/catal11121453.

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Magnetron sputtering is an advantageous method for preparing catalysts supported on stainless steel meshes. Such catalysts are particularly suitable for processes carried out at high space velocities. One of these is the catalytic total oxidation of volatile organic compounds (VOC), economically feasible and environmentally friendly method of VOC abatement. The reactive radio frequency (RF) magnetron sputtering of Mn and Co + Mn mixtures in an oxidation Ar + O2 atmosphere was applied to form additional thin oxide coatings on cobalt oxide layers prepared by electrochemical deposition and heating on stainless steel meshes. Time of the RF magnetron sputtering was changed to obtain MnOx and CoMnOx coatings of various thickness (0.1–0.3 µm). The properties of the supported CoOx-MnOx and CoOx-CoMnOx catalysts were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), temperature programmed reduction (H2-TPR), Fourier-transform infrared (FTIR) and Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The catalytic activity was investigated in the deep oxidation of ethanol, which was employed as a model VOC. According to the specific activities (amount of ethanol converted per unit mass of metal oxides per hour), the performance of CoOx-MnOx catalysts was higher than that of CoOx-CoMnOx ones. The catalysts with the smallest layer thickness (0.1 µm) showed the highest catalytic activity. Compared to the commercial pelletized Co-Mn-Al mixed oxide catalyst, the sputtered catalysts exhibited considerably higher (23–87 times) catalytic activity despite the more than 360–570 times lower content of the Co and Mn active components in the catalytic bed.

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12

Förster, Stefan, Eva Zollner, Klaus Meinel, Renè Hammer, Martin Trautmann, and Wolf Widdra. "2D quasicrystals from perovskites." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C80. http://dx.doi.org/10.1107/s2053273314099197.

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Perovskite oxides represent a versatile class of materials with a simple cubic or pseudo-cubic crystal structure. The family of perovskite oxides contains insulators, metals, semiconductors, and superconductors with nearly identical lattice parameters. This structural equivalence additionally allows to combine perovskites with different properties in multilayer systems to produce functional materials with unique properties. We report here on the formation of a quasicrystal (QC) thin film on a threefold Pt(111) surface. This QC film is derived from the classical perovskite oxide BaTiO3 which is the most intensely studied ferroelectric perovskite oxide. An easily accessible ferroelectric to paraelectric phase transition at 400 K makes the material so interesting for basic and applied research. Due to matching lattice conditions BaTiO3 can be grown epitaxially on selected metal substrates. Periodic thin films of either BaTiO3(100) or BaTiO3(111) have been grown depending on substrate orientation and preparation conditions on Pt(001) and on Pt(111) [1, 2]. As we demonstrate here, astonishingly also a two-dimensional dodecagonal quasicrystalline structure can be formed by annealing an initially 1.4 nm thick BaTiO3 film on Pt(111) [3]. It develops at a temperature of 1250 K from a wetting layer spreading between a few thicker BaTiO3(111) islands. Surface sensitive electron diffraction (LEED) shows a bright and sharp pattern with dodecagonal symmetry. High-resolution scanning tunneling microscopy (STM) images reveal an arrangement of quadratic, triangular, and rhombic elements which compares well to a Gähler tiling. The development of higher-order self-similar structures is widely suppressed by a linear phason strain. This is supported by the fine structure of the diffraction data.

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13

Lee, Sunghwan, Donghun Lee, Fei Qin, Yuxuan Zhang, Molly Rothschild, Han Wook Song, and Kwangsoo No. "(Invited) Oxide Electronics and Recent Progress in Bipolar Applications." ECS Meeting Abstracts MA2022-01, no. 19 (July 7, 2022): 1071. http://dx.doi.org/10.1149/ma2022-01191071mtgabs.

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The discovery of oxide electronics is of increasing importance today as one of the most promising new technologies and manufacturing processes for a variety of electronic and optoelectronic applications such as next-generation displays, batteries, solar cells, memory devices, and photodetectors[1]. The high potential use seen in oxide electronics is due primarily to their high carrier mobilities and their ability to be fabricated at low temperatures[2]. However, since the majority of oxide semiconductors are n-type oxides, current applications are limited to unipolar devices, eventually developing oxide-based bipolar devices such as p-n diodes and complementary metal-oxide semiconductors. We have contributed to a wide range of oxide semiconductors and their electronics and optoelectronic device applications. Particularly, we have demonstrated n-type oxide-based thin film transistors (TFT), integrating In2O3-based n-type oxide semiconductors from binary cation materials to ternary cation species including InZnO, InGaZnO (IGZO), and InAlZnO. We have suggested channel/metallization contact strategies to achieve stable and high TFT performance[3, 4], identified vacancy-based native defect doping mechanisms[5], suggested interfacial buffer layers to promote charge injection capability[6], and established the role of third cation species on the carrier generation and carrier transport[7]. More recently, we have reported facile manufacturing of p-type SnOx through reactive magnetron sputtering from a Sn metal target[8]. The fabricated p-SnOx was found to be devoid of metallic phase of Sn from x-ray photoelectron spectroscopy and demonstrated stable performance in a fully oxide-based p-n heterojunction together with n-InGaZnO. The oxide-based p-n junctions exhibited a high rectification ratio greater than 103 at ±3 V, a low saturation current of ~2x10-10, and a small turn-on voltage of -0.5 V. In this presentation, we review recent achievements and still remaining issues in transition metal oxide semiconductors and their device applications, in particular, bipolar applications including p-n heterostructures and complementary metal-oxide-semiconductor devices as well as single polarity devices such as TFTs and memristors. In addition, the fundamental mechanisms of carrier transport behaviors and doping mechanisms that govern the performance of these oxide-based devices will also be discussed. ACKNOWLEDGMENT This work was supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 20011028) by KRISS. K.N. was supported by Basic Science Research Program (NRF-2021R11A1A01051246) through the NRF Korea funded by the Ministry of Education. REFERENCES [1] K. Nomura et al., Nature, vol. 432, no. 7016, pp. 488-492, Nov 25 2004. [2] D. C. Paine et al., Thin Solid Films, vol. 516, no. 17, pp. 5894-5898, Jul 1 2008. [3] S. Lee et al., Journal of Applied Physics, vol. 109, no. 6, p. 063702, Mar 15 2011, Art. no. 063702. [4] S. Lee et al., Applied Physics Letters, vol. 104, no. 25, p. 252103, 2014. [5] S. Lee et al., Applied Physics Letters, vol. 102, no. 5, p. 052101, Feb 4 2013, Art. no. 052101. [6] M. Liu et al., ACS Applied Electronic Materials, vol. 3, no. 6, pp. 2703-2711, 2021/06/22 2021. [7] A. Reed et al., Journal of Materials Chemistry C, 10.1039/D0TC02655G vol. 8, no. 39, pp. 13798-13810, 2020. [8] D. H. Lee et al., ACS Applied Materials & Interfaces, vol. 13, no. 46, pp. 55676-55686, 2021/11/24 2021.

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Hamid, Sharifah Bee Abd, Mariom Zamila Shilpy, and Md Eaqub Ali. "Green Catalytic Approach for the Synthesis of Platform Chemicals from Palm Tree Lignin." Advanced Materials Research 925 (April 2014): 62–66. http://dx.doi.org/10.4028/www.scientific.net/amr.925.62.

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Lignin is the second most abundant naturally occurring macromolecule found in plant cell-wall, vascular components and woody stems. It is the largest renewable source of aromatic biopolymer. However, lignin is recalcitrant to be broken down by most chemicals. This is because of its complicated heterogeneous molecular structure. However, lignin depolymerization has huge potentials for the synthesis of a number of useful chemicals, perfumes and pharmaceuticals and toiletries. The oxidation products of lignin are important precursors for pulp/paper and food industries, synthetic thin films. Vanillin, veratryl aldehyde and para-benzoquinone are the oxidation products of lignin. These chemicals are the precursors of optically active alcohol, ketone, violuric acid and benzaldehyde. However, the oxidation of biolignin has been remaining a challenging task. Green catalytic approaches might be an interesting solution for the selective depolymerization of lignin into various platform chemicals. Metal oxide/silica supported nanoporous gold has received strong attention as green catalyst for the transformation of various natural polymers. Mesoporous metal oxide/silica provide enlarged surfaces for the breakdown of C-C, C-H and C-OH bonds. This paper has reviewed various green catalytic approaches for the control depolymerization of biolignin into platform chemicals.

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Jamoussi, Bassem, Radhouane Chakroun, Abdelmajid Timoumi, and Khaled Essalah. "Synthesis and Characterization of New Imidazole Phthalocyanine for Photodegradation of Micro-Organic Pollutants from Sea Water." Catalysts 10, no. 8 (August 8, 2020): 906. http://dx.doi.org/10.3390/catal10080906.

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In this study, a series of new metal phthalocyanines with imidazole function MPc(Imz) (M: Cd, Hg, Zn and Pd) were synthesized to improve the photocatalyst performances. All physical properties such as total energy, HOMO, LUMO energies of MPc(Imz), as well as their vibrational frequencies have been determined by DFT method using B3LYP theory level at 6-311G (d, p) and sdd basis set. The gap of energy level between work function (WF) of ITO and LUMO of PdPc(Imdz) was 1.53 eV and represents the highest barrier beneficial to electron injection compared to WF of ZnPc(Imz), HgPc(Imz), and CdPc(Imz). Furthermore, the PdPc(Imdz) thin films on indium tin oxide (ITO) glass were prepared by spin coating and vacuum evaporation technique, and were characterized by X-ray diffraction (XRD), surface electron morphology (SEM), atomic force microscopy (AFM), and UV–Vis spectroscopy. The photocatalytic activity of the ITO/glass supported thin films and degradation rates of chlorinated phenols in synthetic seawater, under visible light irradiation were optimized to achieve conversions of 80–90%. Experiments on synthetic seawater samples showed that the chloride-specific increase in photodegradation could be attributed to photochemically generated chloride radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet PdPc(Imz) (3PdPc(Imz)*), reactive oxygen species]. The major 2,3,4,5-Tetrachlorophenol degradation intermediates identified by gas chromatography-mass spectrometry (GC/MS) were 2,3,5-Trichlorophenol, 3,5-dichlorophenol, dichlorodihydroxy-benzene and 3,4,5-trichlorocatechol.

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16

Rutkowska, Iwona A., Marzena Krech, Yuki Sato, Kamila Brzozowska, and Pawel J. Kulesza. "(Invited) Prussian-Blue Type Cobalt Hexacyanoferrate Overlayers As Cocatalytic Components for Oxygen Evolution during Water Electrolysis in Acid Medium." ECS Meeting Abstracts MA2022-02, no. 59 (October 9, 2022): 2212. http://dx.doi.org/10.1149/ma2022-02592212mtgabs.

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Electrochemical water splitting (oxidation) leading to the oxygen evolution at anode and hydrogen generation at cathode is a topic of growing scientific and technological interest. The reaction provides not only means for producing oxygen but, more importantly, for generation of highly pure hydrogen, a carrier for storing renewable energy and further utilization in low-temperature fuel cells. Among important issues are choice of the catalytic material, its morphology and operating conditions including temperature, electrolyte, pH etc. In some cases of electrolysis cells, at cathode, the hydrogen evolution could be accompanied by CO2-reduction (to simple organic molecules), regardless of water oxidation, at anode. The suitability of polynuclear mixed-valence inorganic materials (e.g. polyoxometallates, infinite metal oxides, cyanometallates) for the preparation of thin electrocatalytic films on electrode surfaces has been recognized in recent years. Among such systems, Prussian Blue (iron hexacyanoferrate) and the metal-substituted (e.g. with Co, Ni, or Ru) analogues known as transition metal cyanometallates have received considerable attention owing to their physicochemical stability, well-defined redox transitions, counter-ion-sorption selectivity and catalytic electroactivity. In the present work, we explore Prussian-Blue-like cobalt(II,III) hexacyanoferrate(II,III) cocatalytic overlayers together with ruthenium oxide (conventional electrocatalysis) and tungsten oxide n-type semiconductors (photoelectrochemistry). While cobalt hexacyanoferrate has already been demonstrated to exhibit some activity toward oxidation of water under photoelectrochemical conditions, its intrinsic electrocatalytic activity is unclear, and it will be addressed during presentation. The mixed, or multi-layered, cyanometallates of cobalt, ruthenium and were fabricated through electrodeposition in the appropriate mixtures for modification. Special attention was paid to their morphological, structural properties and the presence of counter-cations (e.g., potassium or sodium, in addition to protons). Electrochemical measurements were performed using cyclic voltammetry, chronoamperometry and chronocoulometry. The systems’ structural modifications as well as their effect on the electroactivity of the catalytic systems towards the oxygen evolution reaction in acid media were addressed. It is noteworthy that some of the hybrid cobalt-ruthenium hexacyanoferrate compositions showed remarkable catalytic ability towards the oxygen evolution reaction in acid electrolyte. In other words, the cyanide-linked ruthenium-oxo species was used to promote oxygen evolution while cobalt hexacyanoferrates acted as stabilizing agents. The enhanced catalytic activities of the as-synthesized electrodes should also be attributed to such features as high population of hydroxyl groups and high Broensted acidity (due to presence of Ru or W oxo sites) and related fast electron transfers coupled to unimpeded proton displacements. The possibility of metal-metal interactions between nanosized metals (Co and Ru or Co and W) cannot be excluded. Acknowledgements: This work was supported by the National Science Center (Poland) under Opus Project (2018/29/B/ST5/02627).

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Azam, Mohd Asyadi, Akihiko Fujiwara, and Tatsuya Shimoda. "Direct Growth of Vertically-Aligned Single-Walled Carbon Nanotubes on Conducting Substrates using Ethanol for Electrochemical Capacitor." Journal of New Materials for Electrochemical Systems 14, no. 3 (May 5, 2011): 173–78. http://dx.doi.org/10.14447/jnmes.v14i3.106.

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A massive growth of vertically-aligned single-walled carbon nanotubes (VA-SWCNTs) from aluminum oxide (Al-O)-supported Co catalyst and high purity ethanol was performed using alcohol catalytic chemical vapor deposition (ACCVD) technique. SWCNTs with 50-μm thickness were grown on the substrates via this technique. The Al metal layer of 20 nm thickness was thermally-oxidized for the production of Al-O, and 0.5 nm cobalt (Co) thin films was used as catalyst for the CVD process. The CNT growth was optimized using SiO2/Si substrates, and similar experimental condition was applied to the conducting substrates. The as-grown CNTs were characterized using Raman spectroscopy and electron microscopies for growth confirmation and for quality level investigation. Development of the catalyst nanoparticles and Al-O support layer was observed using atomic force microscopy (AFM) and transmission electron microscopy (TEM). The electrodes were fabricated using directly-grown VA-SWCNTs on SUS 310S, and were successfully used as an electrochemical capacitor. Electrochemical analysis using KOH aqueous electrolyte was performed by cyclic voltammetric (CV) and galvanostatic chargedischarge measurements; a maximum 52 Fg-1 specific gravimetric capacitance was obtained from the VA-SWCNT electrodes.

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18

Stühmeier, Björn M., Robin J. Schuster, Louis Hartmann, Sören Selve, Hany A. El-Sayed, and Hubert A. Gasteiger. "Modification of the Electrochemical Surface Oxide Formation and the Hydrogen Oxidation Activity of Ruthenium by Strong Metal Support Interactions." Journal of The Electrochemical Society 169, no. 3 (March 1, 2022): 034519. http://dx.doi.org/10.1149/1945-7111/ac58c9.

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A major hurdle for the wide spread commercialization of proton exchange membrane based fuel cells (PEMFCs) and water electrolyzers are the durability and high cost of noble metal catalysts. Here, alternative support materials might offer advantages, as they can alter the properties of a catalyst by means of a strong metal support interaction (SMSI) that has been shown to prevent platinum oxidation and suppress the oxygen reduction reaction on titanium oxide supported platinum nanoparticles deposited on a carbon support (Pt/TiOx/C). Herein, we report a novel Ru/TiOx/C catalyst that according to tomographic transmission electron microscopy analysis consists of partially encapsulated Ru particles in a Ru/TiOx-composite matrix supported on a carbon support. It is shown by cyclic voltammetry and X-ray photoelectron spectroscopy that ruthenium oxidation is mitigated by an SMSI between Ru and TiOx after reductive heat-treatment (Ru/TiOx/C400°C,H2 ). As a result, the catalyst is capable of oxidizing hydrogen up to the onset of oxygen evolution reaction, in stark contrast to a Ru/C reference catalyst. PEMFC-based hydrogen pump measurements confirmed the stabilization of the hydrogen oxidation reaction (HOR) activity on Ru/TiOx/C400°C,H2 and showed a ≈3-fold higher HOR activity compared to Ru/C, albeit roughly two orders of magnitude less active than Pt/C.

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Quino, Candell Grace Paredes, Juan Paolo Bermundo, Mutsunori Uenuma, and Yukiharu Uraoka. "Performance Enhancement of Solution-Processed Si_xSn_yO TFTs using Solution Combustion Synthesis." ECS Meeting Abstracts MA2022-02, no. 35 (October 9, 2022): 1280. http://dx.doi.org/10.1149/ma2022-02351280mtgabs.

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Amorphous oxide semiconductors thin-film transistors (AOs TFTs) have gained interest over the years because of their advantages over a-Si and poly-Si transistors.In particular, tin oxide is used as a semiconductor material because of its abundance, low toxicity, and high intrinsic mobility. Performance-wise, tin oxide TFTs need improvement because the reported average mobility remains < 10 cm2/Vs.1 Previous research used silicon doping to reduce tin oxide’s oxygen vacancies and improve its performance as a semiconductor channel.Currently, SixSnyO TFTs are fabricated using vacuum process, but solution processing is important to realize large-scale and high-throughput electronics. Sol-gel method is one of the conventional routes to produce solution-processed metal oxides. However, it requires high temperature (≤500°C) to facilitate film densification which is not compatible with flexible substrates having low degradation temperatures. Among the approaches for low-temperature TFT fabrication, solution combustion synthesis (SCS) has garnered significant attention because of its simplicity and versatility.2 SCS uses the energy released by combustion to help the formation of more M-O-M networks in the film. Thus, there is no need to use high temperature to condense and densify the film. This study attempts to produce SixSnyO TFTs through solution processing for the first time. We investigated the effect of solution combustion synthesis to the quality of SixSnyO films. Next, we optimized the aging time and oxidizer to fuel ratio (ammonium nitrate to urea) to determine the films with better quality. For aging time optimization, SixSnyO precursors were stirred at RT for 24-h, 48-h, and 72-h. Lastly, we compared the TFT performance in terms transfer characteristics of SixSnyO TFTs fabricated by sol-gel and SCS annealed at the same temperature. Secondary ion mass spectrometry (SIMS) analysis was used to compare the carbon impurities present in both SixSnyO films. The sol-gel film contained higher amounts of carbon impurities, about an order of magnitude higher as shown in Figure 1. This proves that SCS provides extra energy to help degrade the carbon-containing compounds in the film. Carbon atoms are considered impurities that can introduce defects in the SixSnyO film. These defects are detrimental to the performance characteristics of the fabricated TFT device. In addition, the thickness of the films was determined using X-ray reflectivity. The SCS film is 15.70 nm-thick while the sol-gel film is 18.88-nm thick. Furthermore, optimization of the SixSnyO films via SCS revealed that oxidizer to fuel ratio affects the roughness and amount of M-O bonds formed in the film. The 3:1 ratio failed to produce a film while other ratios were successful in producing films. Although the film with 1:1 ratio has root mean square roughness (Rq) value of 0.380 nm, it contains depressions and voids. On the other hand, the film using a 1:3 ratio showed a uniform and even surface with Rq value of 0.377 nm. In addition, characterization of the two films through X-ray photoelectron spectroscopy (XPS) showed higher percentage of M-O bonds in the O1s spectrum (530.5 eV) for the film with 1:3 ratio. The values are 45.9% and 59.3% for 1:1 and 1:3 ratios, respectively. The amount of oxygen vacancy and H- containing compounds also decreased in the 1:3 film. SixSnyO TFTs were fabricated from both SCS and sol-gel methods. Both TFTs showed high off-current and highly negative Vth, as shown in Figure 1. Therefore, both TFTs still contain several defects which suggests that 3% Si doping may be insufficient and must be increased to produce a significant effect. The sol-gel fabricated TFT also showed lower drain current. Therefore, the low annealing temperature at 300 ˚C is insufficient to densify the film and reduce impurities. On the other hand, SCS-assisted fabrication showed higher mobility at 3.14 cm2/Vs – confirming that SCS provided additional energy to degrade impurities and improve the M-O network in the SixSnyO channel. In conclusion, we were able to produce SixSnyO TFTs with improved mobility using solution combustion synthesis. However, the high V th and high off-current issues need to be addressed by increasing silicon dopant addition and exploring other fuel options. But overall, we can confirm that SCS is beneficial in improving the quality of SixSnyO films annealed at 300 ˚C. In the future, this low temperature fabrication is important to realize flexible SixSnyO TFT devices. Acknowledgements This research was supported by NAIST foundation grant. References Chang, H., et al. ACS Applied Electronic Materials, 3(11), 4943–4949. Carlos, E., et al. Chemistry - A European Journal, 26(42), 9099–9125. Figure 1

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Zrinski, Ivana, Andrei Ionut Mardare, Achim Walter Hassel, Alexey Minenkov, and Claudia Cancellieri. "Evolution of Nb-Ta Anodic Memristors Identified By Combinatorial Screening." ECS Meeting Abstracts MA2022-01, no. 18 (July 7, 2022): 1028. http://dx.doi.org/10.1149/ma2022-01181028mtgabs.

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The conventional memory technology, based on von Neumann architecture, has challenged technical and scaling limitations. The architectures with separated memory and computing units have resulted in the low efficiency of computing systems. Hence, huge scientific attention has been recently drawn into the development of novel systems using the in-memory computing concept. Memristors are foreseen as a type of non-volatile memories that can fulfill such requirements but also as electronic components that can solve sneak path currents problems while consuming low power. The information storage mechanism is based on the resistance change of memristors which is driven by an applied external electric field. With this regard, the memory medium plays a crucial role, being an oxide layer sandwiched between the metallic bottom and top electrode. Valve metals and their oxides have shown promising switching properties when used as elements of metal-insulator-metal memristive (MIM) structures. The switching mechanism still depends on the nano-dimensional conductive filaments formation inside the oxide. Even though devices based on Hf, Nb, Ti, and Ta demonstrated a long lifetime, high data retention or resistive state ratio, devices are suffering from low lifetimes in the order of several thousand switching cycles, mainly due to the unpredictable size and position of conductive filaments being affected by the movement of cations or O species. Therefore, the development of materials for defect-engineered memristive applications is crucial. This was the main motivation for this study supported by the fact that memristors based on pure valve metals exhibited promising switching behavior. In this work, devices based on Ta, Nb, and their alloys were investigated. Since the goal was to improve the properties of devices based on pure metals, Nb and Ta were mixed and their alloys were used as bottom electrode for anodic memristors. It can be inferred that by mixing Ta and Nb, multifunctional devices can be produced. High number of Nb-Ta alloys were co-deposited by sputtering onto previously oxidized Si wafers. Afterwards, the samples were anodized for growing an insulating active layer for memristive devices. Onto the so-formed mixed oxides, Pt was deposited as top electrode. The compositional gradient was mapped by a scanning energy-dispersive X-ray spectroscopy (SEDX) system. The total compositional spread of the Nb-Ta library was ranging from Nb - 13 at.%Ta to Nb – 80 at% Ta over three Si wafers. Memristive devices based on Nb or Ta were also fabricated in identical conditions and used as reference samples. By using a combinatorial approach, the investigation of various electrical parameters could be established for more than 300 memristive devices produced per Si wafer. Electrical characterization was performed by a self-developed Gantry robot controlled via Labview software specifically designed for basic tests required for memristive characterization (I-U sweeps, endurance, retention tests). Electrical properties were screened with a compositional resolution of 1 at.%. The results have shown that memristive devices based on Ta reached a long lifetime and high resistive state ratio, whereas devices based on Nb indicated multi-level switching as well as non-volatile and threshold switching characteristics. The formation of Ta-oxyphosphate, responsible for conductive filaments pining, was confirmed by hard X-ray photoelectron spectroscopy. Similarly, multi-level switching characteristics were explained by the incorporation of electrolyte species in Nb2O5. However, Nb devices did not show reversible switching from unipolar to bipolar mode and vice versa. The improvement regarding reversible switching between unipolar and bipolar mode has been observed for memristive devices based on alloys containing Nb -35 at. % Ta. These memristors have also demonstrated longer endurance and data retention as compared to devices based on pure Nb and Ta. The switching mechanism was investigated by conductive filaments imaging using transmission electron microscopy. Conclusively, anodic memristors based on Nb and Ta exhibited non-volatile and threshold characteristics which can spread the range of memristive applications. Reversible switching behavior and multi-level switching possibilities are relevant for the development of memristive synapses and neuromorphic systems. The anodic growth of an insulating layer for devices based on Nb, Ta, and Nb/Ta alloys has simplified, speed up and decreased the cost of fabrication processes. The performance of anodic memristors based on metallic thin films containing Nb -35 at. % Ta indicated a substantial improvement. The switching mechanisms could be suggested based on the nanostructures found in oxide revealing the position and size of conductive filaments. I. Zrinski et al., Appl. Surf. Sci., 548, 149093 (2021) https://doi.org/10.1016/j.apsusc.2021.149093. I. Zrinski, et al., Appl. Mater. Today, accepted, (2021). I. Zrinski, et. al, J. Phys. Chem. Lett., 12, 8917 (2021) https://doi.org/10.1021/acs.jpclett.1c02346 Figure 1

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Kuo, Y., and C. C. Lin. "Electroluminescence from Metal Oxide Thin Films." ECS Solid State Letters 2, no. 8 (May 15, 2013): Q59—Q61. http://dx.doi.org/10.1149/2.002308ssl.

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22

Moshe, Hagay, Maarten Vanbel, Ventsislav Kolev Valev, Thierry Verbiest, David Dressler, and Yitzhak Mastai. "Chiral Thin Films of Metal Oxide." Chemistry - A European Journal 19, no. 31 (June 21, 2013): 10295–301. http://dx.doi.org/10.1002/chem.201300760.

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23

Carretero-Genevrier, Adrian, Glenna L. Drisko, David Grosso, Cédric Boissiere, and Clement Sanchez. "Mesoscopically structured nanocrystalline metal oxide thin films." Nanoscale 6, no. 23 (2014): 14025–43. http://dx.doi.org/10.1039/c4nr02909g.

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24

Stahl, B., M. Ghafari, R. Gomez-Escoto, and H. Hahn. "Magnetoresistance of granular metal-oxide thin films." IEEE Transactions on Magnetics 35, no. 5 (1999): 2880–82. http://dx.doi.org/10.1109/20.801012.

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25

Fazinić, S., I. Bogdanović, E. Cereda, M. Jakšić, and V. Valković. "Stoichiometric determination of thin metal oxide films." Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 75, no. 1-4 (April 1993): 371–74. http://dx.doi.org/10.1016/0168-583x(93)95678-x.

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26

Humphrey, Jonathan L., and Darius Kuciauskas. "Optical susceptibilities of supported indium tin oxide thin films." Journal of Applied Physics 100, no. 11 (2006): 113123. http://dx.doi.org/10.1063/1.2392995.

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27

Andersson, S., P. A. Brühwiler, A. Sandell, M. Frank, J. Libuda, A. Giertz, B. Brena, et al. "Metal–oxide interaction for metal clusters on a metal-supported thin alumina film." Surface Science 442, no. 1 (November 1999): L964—L970. http://dx.doi.org/10.1016/s0039-6028(99)00915-2.

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George, Sheby Mary, Bo Keun Park, Chang Gyoun Kim, and Taek-Mo Chung. "Heteroleptic Group 2 Metal Precursors for Metal Oxide Thin Films." European Journal of Inorganic Chemistry 2014, no. 11 (February 28, 2014): 2002–10. http://dx.doi.org/10.1002/ejic.201301296.

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Wakamatsu, Takashi, Ryushi Fujimura, and Kotaro Kajikawa. "Emission waveguiding in organic thin films supported by metal." Applied Optics 56, no. 3 (January 13, 2017): 482. http://dx.doi.org/10.1364/ao.56.000482.

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30

Yakubovsky, Dmitry I., Yury V. Stebunov, Roman V. Kirtaev, Kirill V. Voronin, Artem A. Voronov, Aleksey V. Arsenin, and Valentyn S. Volkov. "Graphene-Supported Thin Metal Films for Nanophotonics and Optoelectronics." Nanomaterials 8, no. 12 (December 15, 2018): 1058. http://dx.doi.org/10.3390/nano8121058.

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Graphene-metal hybrid nanostructures have attracted considerable attention due to their potential applications in nanophotonics and optoelectronics. The output characteristics of devices based on such nanostructures largely depend on the properties of the metals. Here, we study the optical, electrical and structural properties of continuous thin gold and copper films grown by electron beam evaporation on monolayer graphene transferred onto silicon dioxide substrates. We find that the presence of graphene has a significant effect on optical losses and electrical resistance, both for thin gold and copper films. Furthermore, the growth kinetics of gold and copper films vary greatly; in particular, we found here a significant dependence of the properties of thin copper films on the deposition rate, unlike gold films. Our work provides new data on the optical properties of gold and copper, which should be considered in modeling and designing devices with graphene-metal nanolayers.

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Mende, Mathias, Florian Carstens, Henrik Ehlers, and Detlev Ristau. "Preferential sputtering of metal oxide mixture thin films." Journal of Vacuum Science & Technology A 39, no. 2 (March 2021): 023406. http://dx.doi.org/10.1116/6.0000799.

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32

Pellegrino, L., I. Pallecchi, E. Bellingeri, G. Canu, A. S. Siri, D. Marré, Y. Yanagisawa, et al. "AFM Nanopatterning of Transition Metal Oxide Thin Films." Journal of Nanoscience and Nanotechnology 10, no. 7 (July 1, 2010): 4471–76. http://dx.doi.org/10.1166/jnn.2010.2363.

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33

Vayssieres, L. "Aqueous purpose-built nanostructured metal oxide thin films." International Journal of Materials and Product Technology 18, no. 4/5/6 (2003): 330. http://dx.doi.org/10.1504/ijmpt.2003.002494.

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34

Malik, Alexander, Ana Sêco, Elvira Fortunato, and Rodrigo Martins. "Microcrystalline thin metal oxide films for optoelectronic applications." Journal of Non-Crystalline Solids 227-230 (May 1998): 1092–95. http://dx.doi.org/10.1016/s0022-3093(98)00248-8.

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35

Steele, John J., Michael T. Taschuk, and Michael J. Brett. "Nanostructured Metal Oxide Thin Films for Humidity Sensors." IEEE Sensors Journal 8, no. 8 (August 2008): 1422–29. http://dx.doi.org/10.1109/jsen.2008.920715.

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36

Lange, S., I. Sildos, V. Kiisk, J. Aarik, and M. Kirm. "Photoluminescence of RE-doped thin metal oxide films." physica status solidi (c) 2, no. 1 (January 2005): 326–29. http://dx.doi.org/10.1002/pssc.200460176.

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37

Conley, J. F., Y. Ono, D. J. Tweet, and R. Solanki. "Pulsed deposition of metal–oxide thin films using dual metal precursors." Applied Physics Letters 84, no. 3 (January 19, 2004): 398–400. http://dx.doi.org/10.1063/1.1643545.

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38

Mondal, Kunal, Jitendra Kumar, and Ashutosh Sharma. "Self-organized macroporous thin carbon films for supported metal catalysis." Colloids and Surfaces A: Physicochemical and Engineering Aspects 427 (June 2013): 83–94. http://dx.doi.org/10.1016/j.colsurfa.2013.03.024.

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39

SUZUKI, Naoki, Hidekazu TANAKA, Yoshihiko YANAGISAWA, Satoru YAMANAKA, Luca PELLEGRINO, Bong Kuk LEE, Hea Yeon LEE, and Tomoji KAWAI. "Nano Fabrication of Functional Transition Metal Oxide Thin Films." Journal of the Vacuum Society of Japan 51, no. 1 (2008): 37–43. http://dx.doi.org/10.3131/jvsj2.51.37.

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40

LEE, Sang A., Jegon LEE, and Woo Seok CHOI. "Electrochemical Catalytic Activity in Transition-Metal-Oxide Thin Films." Physics and High Technology 26, no. 5 (May 31, 2017): 21–26. http://dx.doi.org/10.3938/phit.26.021.

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41

Gallagher, Dennis, Francis Scanlan, Raymond Houriet, Hans Jörg Mathieu, and Terry A. Ring. "Indium-tin oxide thin films by metal-organic decomposition." Journal of Materials Research 8, no. 12 (December 1993): 3135–44. http://dx.doi.org/10.1557/jmr.1993.3135.

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In2O3–SnO2 films were produced by thermal decomposition of a deposit which was dip coated on borosilicate glass substrates from an acetylacetone solution of indium and tin acetoacetonate. Thermal analysis showed complete pyrolysis of the organics by 400 °C. The thermal decomposition reaction generated acetylacetone gas and was found to be first order with an activation energy of 13.6 Kcal/mole. Differences in thermal decomposition between the film and bulk materials were noted. As measured by differential scanning calorimetry using a 40 °C/min temperature ramp, the glass transition temperature of the deposited oxide film was found to be ∼462 °C, and the film crystallization temperature was found to be ∼518 °C. For film fabrication, thermal decomposition of the films was performed at 500 °C in air for 1 h followed by reduction for various times at 500 °C in a reducing atmosphere. Crystalline films resulted for these conditions. A resistivity of ∼1.01 × 10−3 Ω · cm, at 8 wt. % tin oxide with a transparency of ∼95% at 400 nm, has been achieved for a 273 nm thick film.

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42

Bouclé, Johann, Punniamoorthy Ravirajan, and Jenny Nelson. "Hybrid polymer–metal oxide thin films for photovoltaic applications." Journal of Materials Chemistry 17, no. 30 (2007): 3141. http://dx.doi.org/10.1039/b706547g.

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43

Merkulov, Vladimir I., Jon R. Fox, Hong-Cheng Li, Weidong Si, A. A. Sirenko, and X. X. Xi. "Metal–oxide bilayer Raman scattering in SrTiO3 thin films." Applied Physics Letters 72, no. 25 (June 22, 1998): 3291–93. http://dx.doi.org/10.1063/1.121627.

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44

Tung, Mai Thanh, Hoang Thi Bich Thuy, and Le Thi Thu Hang. "Metal Doped Manganese Oxide Thin Films for Supercapacitor Application." Journal of Nanoscience and Nanotechnology 15, no. 9 (September 1, 2015): 6949–56. http://dx.doi.org/10.1166/jnn.2015.10525.

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Kiriakidis, G., K. Moschovis, I. Kortidis, and V. Binas. "Ultra-low gas sensing utilizing metal oxide thin films." Vacuum 86, no. 5 (January 2012): 495–506. http://dx.doi.org/10.1016/j.vacuum.2011.10.013.

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46

Hong, Nguyen Hoa. "Ferromagnetism in transition-metal-doped semiconducting oxide thin films." Journal of Magnetism and Magnetic Materials 303, no. 2 (August 2006): 338–43. http://dx.doi.org/10.1016/j.jmmm.2006.01.067.

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47

Croitoru, N., A. Seidman, and K. Yassin. "Secondary electron emission of metal oxide sputtered thin films." Thin Solid Films 191, no. 2 (October 1990): 361–67. http://dx.doi.org/10.1016/0040-6090(90)90386-r.

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48

Jäger, S. "Dye-metal oxide composite thin films for decorative applications." Thin Solid Films 286, no. 1-2 (September 1996): 154–58. http://dx.doi.org/10.1016/s0040-6090(96)08546-x.

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49

McMillan, C. S., J. P. H. Sukamto, and W. H. Smyrl. "Surface-controlled photoelectrochemical microscopy of thin metal oxide films." Faraday Discussions 94 (1992): 63. http://dx.doi.org/10.1039/fd9929400063.

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50

György, E., E. Axente, I. N. Mihailescu, C. Ducu, and H. Du. "Doped thin metal oxide films for catalytic gas sensors." Applied Surface Science 252, no. 13 (April 2006): 4578–81. http://dx.doi.org/10.1016/j.apsusc.2005.07.138.

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