Advanced Strategies in Thin Film Engineering by Magnetron Sputtering

A special issue of Coatings (ISSN 2079-6412).

Deadline for manuscript submissions: closed (31 October 2019) | Viewed by 44739

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Guest Editor
Spanish Council of Research (CSIC), Institute of Materials Science of Seville (CSIC/US), Américo Vespucio 49, 41092 Seville, Spain
Interests: thin film growth; atomistic processes; porous thin films; oblique angle deposition; magnetron sputtering; physical vapor deposition
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FEMTO-ST Institute,University of Bourgogne Franche-Comté,15B avenue des montboucons,25030 Besancon Cedex, France
Interests: physics of metallic and ceramic thin films; reactive sputtering; glancing angle deposition; electronic transport properties

Special Issue Information

Dear Colleagues,

Recent years have witnessed the flourishing of numerous novel strategies based on the magnetron sputtering technique aimed at the advanced engineering of thin films, such as HiPIMS, combined vacuum processes, the implementation of complex precursor gases or the inclusion of particle guns in the reactor, among others. At the forefront of these approaches, investigations focused on nanostructured coatings appear today as one of the priorities in many scientific and technological communities: The science behind them appears in most of the cases as a "terra incognita", fascinating both the fundamentalist, who imagines new concepts, and the experimenter, who is able to create and study new films with as of yet unprecedented performances. These scientific and technological challenges, along with the existence of numerous scientific issues that have yet to be clarified in classical magnetron sputtering depositions (e.g., process control and stability, nanostructuration mechanisms, connection between film morphology and properties or upscaling procedures from the laboratory to industrial scales) have motivated us to edit a specialized volume containing the state-of-the art that put together these innovative fundamental and applied research topics. These include, but are not limited to:

  • Nanostructure-related properties;
  • Atomistic processes during film growth;
  • Process control, process stability, and in situ diagnostics;
  • Fundamentals and applications of HiPIMS;
  • Thin film nanostructuration phenomena;
  • Tribological, anticorrosion, and mechanical properties;
  • Combined procedures based on the magnetron sputtering technique;
  • Industrial applications;
  • Devices.

Prof. Dr. Alberto Palmero
Prof. Dr. Nicolas Martin
Guest Editors

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Keywords

  • Magnetron sputtering
  • Nanostructures
  • Growth mechanism
  • Functional properties
  • HiPIMS

Published Papers (12 papers)

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Editorial

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5 pages, 183 KiB  
Editorial
Advanced Strategies in Thin Films Engineering by Magnetron Sputtering
by Alberto Palmero and Nicolas Martin
Coatings 2020, 10(4), 419; https://doi.org/10.3390/coatings10040419 - 23 Apr 2020
Cited by 4 | Viewed by 2692
Abstract
This Special Issue contains a series of reviews and papers representing some recent results and some exciting perspectives focused on advanced strategies in thin films growth, thin films engineering by magnetron sputtering and related techniques. Innovative fundamental and applied research studies are then [...] Read more.
This Special Issue contains a series of reviews and papers representing some recent results and some exciting perspectives focused on advanced strategies in thin films growth, thin films engineering by magnetron sputtering and related techniques. Innovative fundamental and applied research studies are then reported, emphasizing correlations between structuration process parameters, new ideas and approaches for thin films engineering and resulting properties of as-deposited coatings. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)

Research

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17 pages, 5817 KiB  
Article
Structural Properties and Oxidation Resistance of ZrN/SiNx, CrN/SiNx and AlN/SiNx Multilayered Films Deposited by Magnetron Sputtering Technique
by Ihar Saladukhin, Gregory Abadias, Vladimir Uglov, Sergey Zlotski, Arno Janse van Vuuren and Jacques Herman O’Connell
Coatings 2020, 10(2), 149; https://doi.org/10.3390/coatings10020149 - 07 Feb 2020
Cited by 4 | Viewed by 3207
Abstract
In the present work, the structure, stress state and phase composition of MeN/SiNx (Me = Zr, Cr, Al) multilayered films with the thickness of elementary layers in nanoscale range, as well as their stability to high temperature oxidation, were studied. Monolithic (reference) [...] Read more.
In the present work, the structure, stress state and phase composition of MeN/SiNx (Me = Zr, Cr, Al) multilayered films with the thickness of elementary layers in nanoscale range, as well as their stability to high temperature oxidation, were studied. Monolithic (reference) and multilayered films were deposited on Si substrates at the temperatures of 300 °C (ZrN/SiNx and AlN/SiNx systems) or 450 °C (CrN/SiNx) by reactive magnetron sputtering. The thickness ratios of MeN to SiNx were 5 nm/2 nm, 5 nm/5 nm, 5 nm/10 nm and 2 nm/5 nm. Transmission electron microscopy (TEM), X-ray Reflectivity (XRR) and X-ray Diffraction (XRD) testified to the uniform alternation of MeN and SiNx layers with sharp interlayer boundaries. It was observed that MeN sublayers have a nanocrystalline structure with (001) preferred orientation at 5 nm, but are X-ray amorphous at 2 nm, while SiNx sublayers are always X-ray amorphous. The stability of the coatings to oxidation was investigated by in situ XRD analysis (at the temperature range of 400–950 °C) along with the methods of wavelength-dispersive X-ray spectroscopy (WDS) and scanning electron microscopy (SEM) after air annealing procedure. Reference ZrN and CrN films started to oxidize at the temperatures of 550 and 700 °C, respectively, while the AlN reference film was thermally stable up to 950 °C. Compared to reference monolithic films, MeN/SiNx multilayers have an improved oxidation resistance (onset of oxidation is shifted by more than 200 °C), and the performance is enhanced with increasing fraction of SiNx layer thickness. Overall, CrN/SiNx and AlN/SiNx multilayered films are characterized by noticeably higher resistance to oxidation as compared to ZrN/SiNx multilayers, the best performance being obtained for CrN/SiNx and AlN/SiNx with 5 nm/5 nm and 5 nm/10 nm periods, which remain stable at least up to 950 °C. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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10 pages, 7672 KiB  
Article
Electrical Characterization of RF Reactive Sputtered p–Mg-InxGa1−xN/n–Si Hetero-Junction Diodes without Using Buffer Layer
by Thi Tran Anh Tuan, Dong-Hau Kuo, Phuong Thao Cao, Van Sau Nguyen, Quoc-Phong Pham, Vinh Khanh Nghi and Nguyen Phuong Lan Tran
Coatings 2019, 9(11), 699; https://doi.org/10.3390/coatings9110699 - 25 Oct 2019
Cited by 5 | Viewed by 2625
Abstract
The modeling of p–InxGa1−xN/n–Si hetero junction diodes without using the buffer layer were investigated with the “top-top” electrode. The p–Mg-GaN and p–Mg-In0.05Ga0.95N were deposited directly on the n–Si [...] Read more.
The modeling of p–InxGa1−xN/n–Si hetero junction diodes without using the buffer layer were investigated with the “top-top” electrode. The p–Mg-GaN and p–Mg-In0.05Ga0.95N were deposited directly on the n–Si (100) wafer by the RF reactive sputtering at 400 °C with single cermet targets. Al and Pt with the square size of 1 mm2 were used for electrodes of p–InxGa1−xN/n–Si diodes. Both devices had been designed to prove the p-type performance of 10% Mg-doped in GaN and InGaN films. By Hall measurement at the room temperature (RT), the holes concentration and mobility were determined to be Np = 3.45 × 1016 cm−3 and µ = 145 cm2/V·s for p–GaN film, Np = 2.53 × 1017 cm−3, and µ = 45 cm2/V·s for p–InGaN film. By the I–V measurement at RT, the leakage currents at −5 V and turn-on voltages were found to be 9.31 × 10−7 A and 2.4 V for p–GaN/n–Si and 3.38 × 10−6 A and 1.5 V for p–InGaN/n–Si diode. The current densities at the forward bias of 20 V were 0.421 and 0.814 A·cm−2 for p–GaN/n–Si and p–InGaN/n–Si devices. The electrical properties were measured at the temperature range of 25 to 150 °C. By calculating based on the TE mode, Cheungs’ and Norde methods, and other parameters of diodes were also determined and compared. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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10 pages, 1969 KiB  
Article
Electrical and Structural Properties of All-Sputtered Al/SiO2/p-GaN MOS Schottky Diode
by Tran Anh Tuan Thi, Dong-Hau Kuo, Phuong Thao Cao, Pham Quoc-Phong, Vinh Khanh Nghi and Nguyen Phuong Lan Tran
Coatings 2019, 9(10), 685; https://doi.org/10.3390/coatings9100685 - 21 Oct 2019
Cited by 8 | Viewed by 4401
Abstract
The all-sputtered Al/SiO2/p-GaN metal-oxide-semiconductor (MOS) Schottky diode was fabricated by the cost-effective radio-frequency sputtering technique with a cermet target at 400 °C. Using scanning electron microscope (SEM), the thicknesses of the electrodes, insulator SiO2 layer, and p-GaN [...] Read more.
The all-sputtered Al/SiO2/p-GaN metal-oxide-semiconductor (MOS) Schottky diode was fabricated by the cost-effective radio-frequency sputtering technique with a cermet target at 400 °C. Using scanning electron microscope (SEM), the thicknesses of the electrodes, insulator SiO2 layer, and p-GaN were found to be ~250 nm, 70 nm, and 1 µm, respectively. By Hall measurement of a p-Mg-GaN film on an SiO2/Si (100) substrate at room temperature, the hole’s concentration (Np) and carrier mobility (μ) were found to be Np = 4.32 × 1016 cm−3 and μ = 7.52 cm2·V−1·s−1, respectively. The atomic force microscope (AFM) results showed that the surface topography of the p-GaN film had smoother, smaller grains with a root-mean-square (rms) roughness of 3.27 nm. By I–V measurements at room temperature (RT), the electrical properties of the diode had a leakage current of ~4.49 × 10−8 A at −1 V, a breakdown voltage of −6 V, a turn-on voltage of ~2.1 V, and a Schottky barrier height (SBH) of 0.67 eV. By C–V measurement at RT, with a frequency range of 100–1000 KHz, the concentration of the diode’s hole increased from 3.92 × 1016 cm−3 at 100 kHz to 5.36 × 1016 cm−3 at 1 MHz, while the Fermi level decreased slightly from 0.109 to 0.099 eV. The SBH of the diode at RT in the C–V test was higher than in the I–V test because of the induced charges by dielectric layer. In addition, the ideality factor (n) and series resistance (Rs) determined by Cheung’s and Norde’s methods, other parameters for MOS diodes were also calculated by C–V measurement at different frequencies. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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10 pages, 4655 KiB  
Article
The Effect of RF Sputtering Conditions on the Physical Characteristics of Deposited GeGaN Thin Film
by Cao Phuong Thao, Dong-Hau Kuo, Thi Tran Anh Tuan, Kim Anh Tuan, Nguyen Hoang Vu, Thach Thi Via Sa Na, Khau Van Nhut and Nguyen Van Sau
Coatings 2019, 9(10), 645; https://doi.org/10.3390/coatings9100645 - 06 Oct 2019
Cited by 4 | Viewed by 3343
Abstract
Ge0.07GaN films were successfully made on Si (100), SiO2/Si (100) substrates by a radio frequency reactive sputtering technique at various deposition conditions listed as a range of 100–400 °C and 90–150 W with a single ceramic target containing 7 [...] Read more.
Ge0.07GaN films were successfully made on Si (100), SiO2/Si (100) substrates by a radio frequency reactive sputtering technique at various deposition conditions listed as a range of 100–400 °C and 90–150 W with a single ceramic target containing 7 at % dopant Ge. The results showed that different RF sputtering power and heating temperature conditions affected the structural, electrical and optical properties of the sputtered Ge0.07GaN films. The as-deposited Ge0.07GaN films had an structural polycrystalline. The GeGaN films had a distorted structure under different growth conditions. The deposited-150 W Ge0.07GaN film exhibited the lowest photoenergy of 2.96 eV, the highest electron concentration of 5.50 × 1019 cm−3, a carrier conductivity of 35.2 S∙cm−1 and mobility of 4 cm2·V−1∙s−1. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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13 pages, 4394 KiB  
Article
Phase Selectivity in Cr and N Co-Doped TiO2 Films by Modulated Sputter Growth and Post-Deposition Flash-Lamp-Annealing
by Raúl Gago, Slawomir Prucnal, René Hübner, Frans Munnik, David Esteban-Mendoza, Ignacio Jiménez and Javier Palomares
Coatings 2019, 9(7), 448; https://doi.org/10.3390/coatings9070448 - 17 Jul 2019
Cited by 3 | Viewed by 3161
Abstract
In this paper, we report on the phase selectivity in Cr and N co-doped TiO2 (TiO2:Cr,N) sputtered films by means of interface engineering. In particular, monolithic TiO2:Cr,N films produced by continuous growth conditions result in the formation of [...] Read more.
In this paper, we report on the phase selectivity in Cr and N co-doped TiO2 (TiO2:Cr,N) sputtered films by means of interface engineering. In particular, monolithic TiO2:Cr,N films produced by continuous growth conditions result in the formation of a mixed-phase oxide with dominant rutile character. On the contrary, modulated growth by starting with a single-phase anatase TiO2:N buffer layer, can be used to imprint the anatase structure to a subsequent TiO2:Cr,N layer. The robustness of the process with respect to the growth conditions has also been investigated, especially regarding the maximum Cr content (<5 at.%) for single-phase anatase formation. Furthermore, post-deposition flash-lamp-annealing (FLA) in modulated coatings was used to improve the as-grown anatase TiO2:Cr,N phase, as well as to induce dopant activation (N substitutional sites) and diffusion. In this way, Cr can be distributed through the whole film thickness from an initial modulated architecture while preserving the structural phase. Hence, the combination of interface engineering and millisecond-range-FLA opens new opportunities for tailoring the structure of TiO2-based functional materials. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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12 pages, 2734 KiB  
Article
Experimental and Modeling Study of the Fabrication of Mg Nano-Sculpted Films by Magnetron Sputtering Combined with Glancing Angle Deposition
by Hui Liang, Xi Geng, Wenjiang Li, Adriano Panepinto, Damien Thiry, Minfang Chen and Rony Snyders
Coatings 2019, 9(6), 361; https://doi.org/10.3390/coatings9060361 - 01 Jun 2019
Cited by 9 | Viewed by 3872
Abstract
Today, Mg is foreseen as one of the most promising materials for hydrogen storage when prepared as nano-objects. In this context, we have studied the fabrication of Mg nano-sculpted thin films by magnetron sputtering deposition in glancing angle configuration. It is demonstrated that [...] Read more.
Today, Mg is foreseen as one of the most promising materials for hydrogen storage when prepared as nano-objects. In this context, we have studied the fabrication of Mg nano-sculpted thin films by magnetron sputtering deposition in glancing angle configuration. It is demonstrated that the microstructure of the material is controllable by tuning important deposition parameters such as the tilt angle or the deposition pressure which both strongly affect the shadowing effect during deposition. As an example, the angle formed by the column and the substrate and the intercolumnar space varies between ~20° to ~50° and ~45 to ~120 nm, respectively, when increasing the tilt angle from 60° to 90°. These observations are highlighted by modeling the growth of the material using kinetic Monte Carlo methods which highlights the role of surface diffusion during the synthesis of the coating. This work is a first step towards the development of an air-stable material for hydrogen storage. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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9 pages, 3505 KiB  
Article
Nickel Film Deposition with Varying RF Power for the Reduction of Contact Resistance in NiSi
by Sunil Babu Eadi, Hyeong-Sub Song, Hyun-Dong Song, Jungwoo Oh and Hi-Deok Lee
Coatings 2019, 9(6), 349; https://doi.org/10.3390/coatings9060349 - 28 May 2019
Cited by 8 | Viewed by 3979
Abstract
In this study, the effect of radio frequency (RF) power on nickel (Ni) film deposition was studied to investigate the applications of lowering the contact resistance in the NiSi/Si junction. The RF powers of 100, 150, and 200 W were used for the [...] Read more.
In this study, the effect of radio frequency (RF) power on nickel (Ni) film deposition was studied to investigate the applications of lowering the contact resistance in the NiSi/Si junction. The RF powers of 100, 150, and 200 W were used for the deposition of the Ni film on an n/p silicon substrate. RMS roughnesses of 1.354, 1.174 and 1.338 nm were obtained at 100, 150, and 200 W, respectively. A circular transmission line model (CTLM) pattern was used to obtain the contact resistance for three different RF-power-deposited films. The lowest contact resistivity of 5.84 × 10−5 Ω-cm2 was obtained for the NiSi/n-Si substrate for Ni film deposited at 150 W RF power. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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11 pages, 3694 KiB  
Article
Gas Sensing with Nanoplasmonic Thin Films Composed of Nanoparticles (Au, Ag) Dispersed in a CuO Matrix
by Manuela Proença, Marco S. Rodrigues, Joel Borges and Filipe Vaz
Coatings 2019, 9(5), 337; https://doi.org/10.3390/coatings9050337 - 25 May 2019
Cited by 15 | Viewed by 4575
Abstract
Magnetron sputtered nanocomposite thin films composed of monometallic Au and Ag, and bimetallic Au-Ag nanoparticles, dispersed in a CuO matrix, were prepared, characterized, and tested, which aimed to find suitable nano-plasmonic platforms capable of detecting the presence of gas molecules. The Localized Surface [...] Read more.
Magnetron sputtered nanocomposite thin films composed of monometallic Au and Ag, and bimetallic Au-Ag nanoparticles, dispersed in a CuO matrix, were prepared, characterized, and tested, which aimed to find suitable nano-plasmonic platforms capable of detecting the presence of gas molecules. The Localized Surface Plasmon Resonance phenomenon, LSPR, induced by the morphological changes of the nanoparticles (size, shape, and distribution), and promoted by the thermal annealing of the films, was used to tailor the sensitivity to the gas molecules. Results showed that the monometallic films, Au:CuO and Ag:CuO, present LSPR bands at ~719 and ~393 nm, respectively, while the bimetallic Au-Ag:CuO film has two LSPR bands, which suggests the presence of two noble metal phases. Through transmittance-LSPR measurements, the bimetallic films revealed to have the highest sensitivity to the refractive index changes, as well as high signal-to-noise ratios, respond consistently to the presence of a test gas. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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13 pages, 3813 KiB  
Article
The Seebeck Coefficient of Sputter Deposited Metallic Thin Films: The Role of Process Conditions
by Florian G. Cougnon and Diederik Depla
Coatings 2019, 9(5), 299; https://doi.org/10.3390/coatings9050299 - 01 May 2019
Cited by 17 | Viewed by 4047
Abstract
Because of their reduced dimensions and mass, thin film thermocouples are a promising candidate for embedded sensors in composite materials, especially for application in lightweight and smart structures. The sensitivity of the thin film thermocouple depends however on the process conditions during deposition. [...] Read more.
Because of their reduced dimensions and mass, thin film thermocouples are a promising candidate for embedded sensors in composite materials, especially for application in lightweight and smart structures. The sensitivity of the thin film thermocouple depends however on the process conditions during deposition. In this work, the influence of the discharge current and residual gas impurities on the Seebeck coefficient is experimentally investigated for sputter deposited copper and constantan thin films. The influence of the layer thickness on the film Seebeck coefficient is also discussed. Our observations indicate that both a decreasing discharge current or an increasing background pressure results in a growing deviation of the film Seebeck coefficient compared to its bulk value. Variations in discharge current or background pressure are linked as they both induce a variation in the ratio between the impurity flux to metal flux towards the growing film. This latter parameter is considered a quantitative measure for the background residual gas incorporation in the film and is known to act as a grain refiner. The observed results emphasize the importance of the domain size on the Seebeck coefficient of metallic thin films. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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14 pages, 2522 KiB  
Article
Correlative Experimental and Theoretical Investigation of the Angle-Resolved Composition Evolution of Thin Films Sputtered from a Compound Mo2BC Target
by Jan-Ole Achenbach, Stanislav Mráz, Daniel Primetzhofer and Jochen M. Schneider
Coatings 2019, 9(3), 206; https://doi.org/10.3390/coatings9030206 - 22 Mar 2019
Cited by 13 | Viewed by 3927
Abstract
The angle-resolved composition evolution of Mo-B-C thin films deposited from a Mo2BC compound target was investigated experimentally and theoretically. Depositions were carried out by direct current magnetron sputtering (DCMS) in a pressure range from 0.09 to 0.98 Pa in Ar and [...] Read more.
The angle-resolved composition evolution of Mo-B-C thin films deposited from a Mo2BC compound target was investigated experimentally and theoretically. Depositions were carried out by direct current magnetron sputtering (DCMS) in a pressure range from 0.09 to 0.98 Pa in Ar and Kr. The substrates were placed at specific angles α with respect to the target normal from 0 to ±67.5°. A model based on TRIDYN and SIMTRA was used to calculate the influence of the sputtering gas on the angular distribution function of the sputtered species at the target, their transport through the gas phase, and film composition. Experimental pressure- and sputtering gas-dependent thin film chemical composition data are in good agreement with simulated angle-resolved film composition data. In Ar, the pressure-induced film composition variations at a particular α are within the error of the EDX measurements. On the contrary, an order of magnitude increase in Kr pressure results in an increase of the Mo concentration measured at α = 0° from 36 at.% to 43 at.%. It is shown that the mass ratio between sputtering gas and sputtered species defines the scattering angle within the collision cascades in the target, as well as for the collisions in the gas phase, which in turn defines the angle- and pressure-dependent film compositions. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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7 pages, 1616 KiB  
Article
Electrochemical Stability Enhancement in Reactive Magnetron Sputtered VN Films upon Annealing Treatment
by Amine Achour, Mohammad Islam, Iftikhar Ahmad, Khalid Saeed and Shahram Solaymani
Coatings 2019, 9(2), 72; https://doi.org/10.3390/coatings9020072 - 25 Jan 2019
Cited by 11 | Viewed by 3505
Abstract
Vanadium nitride (VN) thin films were produced via direct-current reactive magnetron sputtering technique followed by vacuum annealing. The treatment was carried out at different temperatures for any effect on their electrochemical (EC) stability, up to 10,000 charge–discharge cycles in 0.5 M K2 [...] Read more.
Vanadium nitride (VN) thin films were produced via direct-current reactive magnetron sputtering technique followed by vacuum annealing. The treatment was carried out at different temperatures for any effect on their electrochemical (EC) stability, up to 10,000 charge–discharge cycles in 0.5 M K2SO4 solution. The film surface chemistry was investigated by using X-ray photoelectron spectroscope (XPS) and cyclic voltammetry (CV) techniques. For the as-deposited film, the oxide layer formed on the VN surface was unstable upon K2SO4 immersion treatment, along with ~23% reduction in the EC capacitance. Vacuum annealing under optimized conditions, however, made the oxide layer stable with almost no capacitance loss upon cycling for up to 10,000 cycles. Annealing treatment of the VN films makes them a potential candidate for long-term use in electrochemical capacitors. Full article
(This article belongs to the Special Issue Advanced Strategies in Thin Film Engineering by Magnetron Sputtering)
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