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About this book

This book highlights the latest advances in chemical and physical methods for thin-film deposition and surface engineering, including ion- and plasma-assisted processes, focusing on explaining the synthesis/processing–structure–properties relationship for a variety of thin-film systems. It covers topics such as advances in thin-film synthesis; new thin-film materials: diamond-like films, granular alloys, high-entropy alloys, oxynitrides, and intermetallic compounds; ultra-hard, wear- and oxidation-resistant and multifunctional coatings; superconducting, magnetic, semiconducting, and dielectric films; electrochemical and electroless depositions; thin-film characterization and instrumentation; and industrial applications.

Table of Contents

Frontmatter

Thin Film Deposition by Plasma Beam of a Vacuum Arc with Refractory Anodes

Abstract
Thin film deposition using hot anode vacuum arcs developed in the last decade is described. Two configurations were used: (i) with an open gap—the hot refractory anode vacuum arc (HRAVA) and (ii) with a closed gap—the vacuum arc with black body assembly (VABBA). In both configurations, the anode was heated by the arc with current I = 145–340 A, and a relatively dense plasma plume of cathode material (Cu, Ti, Cr, Al, Sn, Mo, Nb), was formed by re-evaporation of cathode material from the hot (2000–2500 K) anode, which was fabricated from graphite, Mo, Ta, or W. A steady state mode was reached when the anode was sufficiently hot and a plasma plume expanded, either radially (HRAVA) or directly from the front hot anode surface. As an example, the deposition rate measured in 300 A HRAVAs at distances of 80 mm from the arc axis, to be 3.6; 1.4 and 1.8 μm/min for Cu, Cr and Ti cathodes respectively. Interconnector trenches (100 nm wide ×300 nm deep) on microelectronic wafers were filled using a Cu HRAVA at a rate of 0.5 µm/min.
I. I. Beilis, R. L. Boxman

Multilayer Design of CrN/MoN Superhard Protective Coatings and Their Characterisation

Abstract
Multilayer CrN/MoN transition metal nitride coatings were studied in this research. Films were deposited by vacuum arc deposition (Arc-PVD) from Cr and Mo cathodes in nitrogen atmosphere pN = 0.4 Pa. Three series of samples with different values of negative bias voltage (−20, −150, and −300 V) applied to the surface were fabricated. Each series has samples with 11, 22, 44, 88, 180 and 354 layers while total thickness was maintained with the same value. Samples were studied by scanning electron microscopy (SEM) on cross-sections and coatings surface, energy-dispersive X-ray spectroscopy (EDS), electron backscatter diffraction (EBSD), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), micro-indentation. Two main cubic phases of γ-Mo2N and cubic CrN were detected. It was observed that the crystal growth orientation changes while the negative bias voltage of the substrate decreases. The maximum values of hardness (38–42 GPa) among the studied samples were obtained for coatings with a minimal individual layer thickness of 20 nm deposited at Ub = −20 V.
B. O. Postolnyi, O. V. Bondar, K. Zaleski, E. Coy, S. Jurga, L. Rebouta, J. P. Araujo

Structure and Properties of Combined Multilayer Coatings Based on Alternative Triple Nitride and Binary Metallic Layers

Abstract
Combined multilayered coatings based on alternative triple nitride and binary metallic layers were deposited using vacuum-arc evaporation of a cathode. (TiMo)N/TiMo, (CrMo)N/CrMo, (CrZr)N/CrZr, (TiCr)N/TiCr and (MoZr)N/MoZr multilayer coatings were fabricated under the same deposition conditions, while bias potential was −200 V. Total thickness of the coatings was around 54 μm, while bilayer thickness was around 900 nm and we had 60 bilayers in each coating. Thicknesses of triple nitride and binary metallic layers were 750 and 150 nm respectively. Various methods of analysis were used for coatings characterization, including, but not limited to, XRD, SEM, EDS, TEM, HR-TEM, SIMS, as well as indentation tests. Forming of two-phase state with (111) and (200) preferable orientation was found in the coatings. Vickers hardness HV0.1, HV0.5 and HV1 of the coatings varied from 2347 to 2912, 2077 to 2584 and from 1369 to 2327 respectively, which makes them perspective for application as hard protective coatings.
O. V. Bondar, Alexander D. Pogrebnjak, Y. Takeda, B. Postolnyi, P. Zukowski, R. Sakenova, V. Beresnev, V. Stolbovoy

DSC Investigations of the Effect of Annealing Temperature on the Phase Transformation Behaviour in (Zr–Ti–Nb)N Coatings Deposited by CA-PVD

Abstract
Changes in thermal transformation properties due to annealing and consequent cooling within the temperature ranged from 30 to 1400 °C were studied for (Zr–Ti–Nb)N coatings by differential scanning calorimetry (DSC) measurements in an argon atmosphere. Temperature and phase transformations in investigated coatings occurred in two stages: at intermediate temperature region (>670 °C) and high-temperature region (>1100 °C). There were also noticeable changes in values of heat capacity depending on nitrogen pressure applied during a deposition process.
O. V. Maksakova, M. K. Kylyshkanov, S. Simoẽs

Microstructure and Mechanical Properties of Multilayered α-AlN/α-BCN Coatings Depending on Flux Density During Target B4C Sputtering

Abstract
Multilayered AlN/BCN coatings with nanoscale layers were fabricated by magnetron sputtering of Al and B4C targets on Si substrate. Deposited amorphous AlN/BCN coatings have demonstrated increased nano- and Knoop hardnesses, Young’s modulus in compare with AlN and BCN coatings, which explained by strain modulation in amorphous layers of AlN and BCN. The application of flux density IB4C (100 mA) has led to significant increasing of hardness from 18 to 27 GPa due to the formation of α-BCN phase according to Fourier spectra. Nanolayered coatings have been thermally stable up to 600 °C due to the slow diffusion processes in amorphous sublayer, which indicates higher oxidation resistance then nanocrystalline.
V. I. Ivashchenko, V. M. Rogoz, T. N. Koltunowicz, A. I. Kupchishin

Mass Transfer Model of Sputtering from Rod-Like Targets for Synthesis of Multielement Nanocoatings

Abstract
This work develops the mathematical model that allows calculating element concentration depending on substrate location at low working gas pressures for coatings deposited by new magnetron sputtering device on the basis of hollow cathode and rod-like target. In this work, a target composed of two semicylindrical constituents is considered. As the rod-like target can be made of multiple materials in any geometry, the model can be adjusted for any particular case. The calculations explain the general trend of experimental data behavior.
Yu. O. Kosminska, V. I. Perekrestov

Self-organized Growth by Sputtering and Other PVD Techniques

Abstract
This paper presents a brief review on known self-organized growth by deposition and reports on a new approach of self-organized growth of micro- and nanostructures that can be realized by modified magnetron sputtering. Since self-organization phenomena are multidisciplinary, general ideas on self-organization and related concepts are considered first. Then, known methods of porous structure fabrication in contrast to solid layers and established self-organized growth types are discussed with an emphasis on using PVD techniques. Finally, new steps in plasma-assisted self-organized growth under quasi-equilibrium conditions are presented.
Yu. O. Kosminska, V. I. Perekrestov

On the Possibility of Training Demonstration of the Giant Magnetoresistance Effect in Higher School

Abstract
The method and technique of training demonstration of the giant magnetoresistance effect on the example of film samples (single layer Co film and three-layer film Co/Cu/Co) in CIP-geometry with the help of simple experimental equipment are presented.
V. B. Loboda, M. Ya. Dovzhyk, V. O. Kravchenko, S. M. Khursenko, Yu. O. Shkurdoda

Multifractal Analysis of the Surfaces of Protective (TiAlSiY)N, Me1−xN/CrN and Me1−xN/ZrN Coatings

Abstract
In the present paper, a technique for the preparation of protective (TiAlSiY)N, MexN/CrN and Mex/ZrN coatings is shown. The algorithm of multifractal fluctuation analysis is described, and the results of the numerical investigation of microroughness of surfaces of investigated samples are presented. As follows from the calculated numerical parameters, the surface of (TiAlSiY)N/CrN coating is the smoothest and the surface of (TiAlSiY)N is the most non-uniform.
Ya. Kravchenko, B. Natalich, M. Opielak, V. Borysiuk

Multilayer Nickel–Copper Metal Hydroxide Coating as Cathode Material for Hydrogen Evolution Reaction

Abstract
The comparison of the electrochemical behavior of electrodes with Ni–Cu alloy coating and multilayer coating consisting of alternating layers of alloy and metal hydroxide layers in alkaline water electrolysis is presented. The coatings were electrodeposited in polyligand pyrophosphate-ammonia electrolyte. It is shown that the electrode with multilayer coating is more corrosion resistant, has higher activity in the hydrogen evolution reaction due to both more developed surface and higher intrinsic catalytic activity. The value of the exchange current of hydrogen evolution reaction on the multilayer coating is comparable to the value of the exchange current on the Ni–Cu–Mo ternary alloy and nickel-containing electrodes with the highly developed 3D nanostructured surface.
A. Maizelis, B. Bairachniy

Effect of Nano-Structured Factors on the Properties of the Coatings Produced by Detonation Spraying Method

Abstract
Surface treatment by detonation spraying of composite coatings significantly increases the service life of structures. The demanded direction of application of this method is spraying of powders of various systems. The purpose of this paper is to study the structure (phase composition, microhardness, grain and subgrain structure, dislocation density, dispersed micro- and nano-particles, their composition, and distribution), and the properties of metal-ceramic coatings: Al2O3–Ti; Al2O3–Al; ZrSiO4 sprayed on various substrates materials (aluminum, titanium). The investigations of structural-phase state of coatings were carried out at all the structural levels using comprehensive methodological approach including optical metallography, analytical scanning electron microscopy, X-ray structural phase analysis, as well as transmission micro diffraction electron microscopy. As a result of the carried out work the experimental data on the full complex of structural and phase parameters of coatings, sprayed at different modes of cumulative-detonation spraying, were obtained. The obtained results showed the prospects of using multi-chamber detonation spraying, which ensures the necessary complex of mechanical properties of coatings by forming the most favorable structure. The surface treatment of metals by the detonation spraying of coatings makes it possible to obtain composite surface layers with high operational properties. The matrix of such coatings is characterized by a significant dispersion of the substructure, the formation of strengthening phases of nanoscale dimensions and a uniform distribution of dislocation density.
L. Markashova, Yu. Tyurin, O. Berdnikova, O. Kolisnichenko, I. Polovetskyi, Ye. Titkov

Nanostructures in Welded Joints and Their Interconnection with Operation Properties

Abstract
The role of structural factors in ensuring optimal properties of materials and their operational reliability has been shown. Studying the phase composition and nanostructures in the welded joints (heat-affected zone, weld metal) of high-strength structural steel produced by advanced high-speed technologies hybrid laser-arc welding. Structural parameters (dimension of grains and subgrains, dislocation density, nanoparticles) and phase changes in the welded joints were studied by using of analytical scanning electron microscopy, optical metallography, and for fine study the transmission electron microscopy was used as well. The most influential structural factors are the dispersing of martensite structure and bainite substructure, equable distribution of particles of structural phases and the absence of extended dislocation clusters—zones of crack incipience and propagation. Such substructure of welding joints of high-strength structural steel produced by laser-arc welding provides the high complex of strength properties and crack resistance.
Liudmyla Markashova, Olena Berdnikova, Tetiana Alekseienko, Artemii Bernatskyi, Volodymyr Sydorets

Development of a Controlled In Situ Thin-Film Technology for Porous Anodic Alumina-Based Nanostructures

Abstract
This work is aimed at development of the technology of thin-film porous anodic alumina/aluminum (PAA/Al) structures for optical sensors based on metal-clad waveguides and Al nanomesh films for transparent conductive layers. The method of optical control directly in the process of the structures formation which consists in monitoring of the angular dependence of monochromatic light reflection was used both for the formation of the PAA/Al structures by anodic oxidation, for the widening of pores by wet etching, as well to control the etching of the PAA and monitoring the remaining Al nanomesh.
T. Lebyedyeva, I. Frolov, M. Skoryk, P. Shpylovyy

The Structure and Tribological Properties of Ni/MoS2 Composite Layers Formed on Aluminum and Its Alloys

Abstract
This work investigates the influence of process parameters on microstructure, adhesion of layers to the substrate and wear resistance of Ni/MoS2 micro- and nanocrystalline composite layers. Pure nickel coatings were also fabricated and tested for comparison. The layers were deposited by electrochemical reduction on pure A2 aluminum and on PA6 alloy. The layers were produced at a current density of 3 A/dm2 and a mixing speed of 400 rpm. The bath composition was also modified by the addition of saccharin and the disperse phase of molybdenum disulfide in the bath (2.5 and 5 g/l). Materials prepared in this way underwent structural investigations (using scanning electron microscopy and optical microscopy), a scratch test and tribological tests (using a ball-on-disc method). The results of the tests allowed to determine the dependence of the structure and properties of the produced coatings on the production parameters. The composition of the electrolyte affects the size of crystallites as well as the morphology and topography of the surface. The scratch test confirmed the good adhesion of the nickel and composite layers to the substrate. The best lubricating properties were shown by nanocrystalline coatings. The too high content of molybdenum disulfide in the bath caused an undesirable increase in the coefficient of friction.
B. Kucharska, J. Mizera, M. Szumiata, A. Zagórski, J. R. Sobiecki

The Effect of Organic Additives on the Microstructure, Microhardness and Friction Coefficient of Ni/WS2 Composite Coatings

Abstract
Composite electroplating enables the production of a wide range of coatings with improved tribological properties. One of the most perspective composite coatings due to its lubricating properties are the Ni/WS2 coatings. The aim of this study was to investigate the effect of organic additives to Watts bath on the microstructure and mechanical properties of Ni/WS2 composite coatings produced by the electrochemical method. The study included the composite coatings deposited in a Watts bath modified by saccharine, polyethylene glycol (PEG), sodium dodecyl sulfate (SDS) and 2-butyne-1,4-diol with disperse phase of WS2 in the form of triturated powder. The particular component was used to obtain a good-quality coating and to enable the proper wettability of tungsten disulfide. The coatings were deposited with direct current. The proper stability of the suspension was ensured by application of the mechanical stirring (400 rpm). The use of the properly selected organic additive in the electrodeposition process results in a significant improvement of the coatings homogeneity, smoothness and the higher microhardness in comparison with composite coatings deposited without additives. The coatings are characterized by increased adhesion to the substrate (low acoustic emission) as well as the lower value of the friction coefficient.
B. Kucharska, M. Ptaszek, J. R. Sobiecki, A. Zagórski, Ja. Mizera

Effect of Temperature on the Growth of Pores in Binary Bi/Sn Films

Abstract
The work is devoted to the study of through pores that arise in binary Bi/Sn films when they are annealed near the melting point. It is shown, that the study of the temperature dependence of the average pores size can be used to measure the activation energy of diffusion processes that ensure the de-wetting of the samples under study. Concentration dependence of the activation energy of diffusion in bilayer Bi/Sn films is obtained. It is shown, that the diffusion activation energy has a minimum in the homogeneous region and is practically constant at a component concentration corresponding to the two-phase section of the phase diagram.
S. I. Petrushenko, S. V. Dukarov, Z. V. Bloshenko, I. G. Churilov, V. N. Sukhov

Method for Identification of Optical Resonances of Metal Films

Abstract
In this paper, the properties of thin (10–100 nm, R > 7 Ω) copper films deposited on glass substrates at T = 300 K are considered. The thin films were produced by thermal evaporation in a vacuum with residual gas pressure (10−2–10−3 Pa). The substrates had luminescence under exciting by Raman light (Raman scattering) of 30 mW power, with a wavelength of 785 nm. The resonances were identified by comparing the absorption and Raman spectra at excitation wavelengths of 633 and 785 nm. Among films with a close absorption level, films with the largest amplitude of the Raman signal had a structure with the maximum value of optical resonances. Under the influence of exciting light of 30 mW, the Raman spectrum and the color of these films changed. Copper films deposited on glass substrates at a temperature of 300 °C with an electrical resistivity R < 0.5 Ω/square did not have pronounced Raman peaks, their Raman spectrum and color did not change under 300 mW excitation light with a wavelength λ of 785 nm.
M. Yu. Barabash, G. G. Vlaykov, A. A. Kolesnichenko, L. V. Ryabov

Complex Method of the Composite Nanocoatings Formation

Abstract
The Complex method of chemical treatment and diffusive chrome-plating is offered for the strengthening details of machines, diffusive layers restored method the given are investigated.
A. E. Stetsko, Ya. T. Stetsko

The Role of a Thin Aluminum Film in the Reconstruction of Silicon’s Near-Surface Layers

Abstract
The effect of a thin film of aluminum on morphology and change in the characteristics of p-type silicon crystals was investigated in the work. It is established that a sprayed metallic film receives the nanosized complexes from the inner part of the crystal to the surface. These defects are effective centers of dislocation-related electroluminescence of structures based on p-Si. Additional elastic deformation (for several hours) of silicon leads to an increase in their concentration. This can be used to increase the efficiency of the luminescence of silicon monocrystals in the infrared region.
R. Lys, B. Pavlyk, D. Slobodzyan, J. Cebulski, M. Kushlyk
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