Microstructure evolution of radio-frequency magnetron sputtered oxide thin films in the Cr–Zr–O system

Spitz, Stefanie; Stueber, Michael; Leiste, H.; Ulrich, S.; Seifert, H. J.

doi:10.1016/j.tsf.2013.09.038

Cited by 11 publications

(18 citation statements)

References 74 publications

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“…Still, Spitz et al [7] found that the host structure of hexagonal (corundum-type) (Cr,Zr) 2 O 3 in their Cr-Zr-O thin films accommodates up to 12 at.% of zirconium. These films were deposited by using radiofrequency (rf) magnetron sputtering on heated substrates (T sub = 500°C).…”

Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

“…Chromium oxide thin films are steadily in focus of interest because of their specific optical [1][2][3][4], magnetic [5,6] and mechanical properties [7], which can further be tailored and improved if Cr 2 O 3 is doped by selected metallic elements or prepared in a nanostructured form. In its stoichiometric form, Cr 2 O 3 crystallizes in the corundum-type structure, in which the chromium and oxygen atoms occupy the Wyckoff positions 12c and 18e, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Thermally induced formation of metastable nanocomposites in amorphous Cr-Zr-O thin films deposited using reactive ion beam sputtering

et al. 2016

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Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thermally induced formation of metastable nanocomposites in amorphous Cr-Zr-O thin films deposited using reactive ion beam sputtering

et al. 2016

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“…Stabilization can be done either by template growth (e.g., another material, such as Al2O3, is grown on α-Cr2O3 and adopts that crystal structure) [46][47][48] or by alloying. When alloying other materials with Cr2O3 it promotes a solid solution in the corundum structure [33,[49][50][51].…”

Section: α-Cr2o3mentioning

confidence: 99%

“…The studies of materials formed under non-equilibrium conditions such as PVD can, if care is taken, also benefit strongly from first-principles calculations as exemplified by the reviews of Abrikosov et al [64] and Music et al [65]. The pseudobinary and pseudoternary oxide coatings studied in this thesis, namely Cr-Zr-O (Paper I) and Al-Cr-Si-O (Paper II) systems, were however not chosen based on calculations, but on earlier experimental work [49] and [9,66] respectively.…”

Section: Pseudo-binary and -Ternary Oxidesmentioning

confidence: 99%

“…The hardness and crystallographic stability could potentially be introduced by the naturally hard and stable α-Cr2O3 [52]. The Cr-Zr-O was first deposited over the whole compositional range with reactive RF-magnetron sputtering by Spitz et al [49]. They showed solid solution in the corundum structure at the Cr-rich end of this pseude binary system.…”

Section: Pseudo-binary and -Ternary Oxidesmentioning

confidence: 99%

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Thin Film and Plasma Characterization of PVD Oxides

Landälv¹

2017

Linköping Studies in Science and Technology. Dissertations

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The state-of-the-art tools for machining metals are primarily based on a metal-ceramic composite (WC-Co) coated with different combinations of carbide, nitride and oxide coatings. Combinations of these coating materials are optimized to withstand specific wear conditions. Oxide coatings are especially desired because of their possible high hot hardness, chemical inertness with respect to the workpiece, and their low friction.This thesis deals with process and coating characterization of new oxide coatings deposited by physical vapor deposition (PVD) techniques, focusing on the Cr-Zr-O and Al-Cr-Si-O systems.The thermal stability of α-Cr0.28Zr0.10O0.61 deposited by reactive radio frequency (RF)-magnetron sputtering at 500 °C was investigated after annealing up to 870 °C. The annealed samples showed transformation of α-(Cr,Zr)2O3 and amorphous ZrOx-rich areas into tetragonal ZrO2 and bcc Cr. The instability of the α-(Cr,Zr)2O3 is surprising and possibly related to the annealing being done under vacuum, facilitating the loss of oxygen. The stabilization of the room temperature metastable tetragonal ZrO2 phase, due to surface energy effects, may prove to be useful for metal cutting applications. The observed phase segregation of α-(Cr,Zr)2O3 and formation of tetragonal ZrO2 with corresponding increase in hardness for this pseudo-binary oxide system also opens up design routes for pseudo-binary oxides with tunable microstructural and mechanical properties.The inherent difficulties of depositing insulating oxide films with PVD, demanding a closed circuit, makes the investigation of process stability an important part of this research. In this context, we investigated the influence of adding small amount of Si in Al-Cr cathode on plasma characteristics, process parameters, and coating properties. Si was chosen here due to a previous study showing improved erosion behavior of Al-Cr-Si over pure Al-Cr cathode without Si incorporation in the coating.This work shows small improvements in cathode erosion and process stability (lower pressure and cathode voltage) when introducing 5 at % Si in the Al70Cr30-cathode. This also led to fewer droplets at low cathode current and intermediate O2 flow. A larger positive effect on cathode erosion was observed with respect to cleaning the cathode from oxide contamination by increasing cathode current with 50%. However, higher cathode current also resulted in increased amount of droplets in the coating which is undesirable. Through plasma analysis the presence of volatile SiO species could be confirmed but the loss of Si through volatile SiO species was negligible, since the coating composition matched the cathode composition. The positive effect of added Si on the process stability at the cathode surface should be weighed against Si incorporation in the coating. This incorporation may or may not be beneficial for the final application since literature states that Si promotes the metastable γ-phase over the thermodynamically stable α-phase of pure Al2O3, contrary to the effect o...

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Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

Gonzalez Caranton,

Schmal,

Checca Huaman

et al. 2023

Macro Reaction Engineering

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This work uses sol–gel and sonochemical methods to prepare bimetallic PdCu catalysts supported on modified ZrO2 with Ti and Al. The catalysts are tested for vinyl acetate synthesis from ethylene, acetic acid, and oxygen, varying the reaction temperature for two catalysts prepared, which show higher activity. Catalysts characterization results show bimetallic species and distort alloys with a dispersed distribution of active metal onto the support. The in situ reaction by DRIFT‐MS identifies the surface formation of main intermediates like palladium acetate monomers and mono and bidentate intermediates, associated to vinyl acetate formation, like vinyl hydrogenated species over PdCu. Finally, this behavior will be attributed to the bimetallic distortions of PdCu samples, provided by interaction effects between PdCu and supports, indicating a more exposition of PdCu species suitable for the reaction, according to high‐resolution transmission microscopy electron microscopy results for PdCu/ZrTi sample. Thus, this sample exhibits a minimal formation of sub‐products and catalytic stability for 18 hh. These results evidence the participation of hydroxyls and oxygen vacancies of the catalyst in the catalytic reaction measured in situ, monitoring the products formed at the reactor outlet. Finally, it is proposed a reaction pathway as a function of reaction conditions.

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Microstructure evolution of radio-frequency magnetron sputtered oxide thin films in the Cr–Zr–O system

Cited by 11 publications

References 74 publications

Thermally induced formation of metastable nanocomposites in amorphous Cr-Zr-O thin films deposited using reactive ion beam sputtering

Thermally induced formation of metastable nanocomposites in amorphous Cr-Zr-O thin films deposited using reactive ion beam sputtering

Thin Film and Plasma Characterization of PVD Oxides

Synthesis of Vinyl Acetate Monomer Over PdCu Alloys: The Role of Surface Oxygenation in the Reaction Path

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