Sputtering Gas Research Articles

Magnetron Sputtering Formation of Germanium Nanoparticles for Electrochemical Lithium Intercalation.

In the drive towards increased lithium based battery capacity, germanium is an attractive material due to its very high lithium storage capacity, second only to silicon. The persistent down-side is the considerable embrittlement accompanying its remarkable volume expansion of close to 300 %. A proven method to accommodate for this lattice expansion is the reduction of the size towards the nanoscale at which the fracturing is prevented by "breathing". In this work we employed a novel magnetron sputtering gas aggregation nanoparticle generator to create unprecedented layers of well-defined germanium nanoparticles with sizes below 20 nm. The electrochemical lithium intercalation was monitored by a suite of techniques under which Raman spectroscopy, which provided clear evidence of the presence of lithium inside the germanium nanoparticles. Moreover, the degree of lattice order was measured and correlated to the initial phases of the lithium-germanium alloy. This was corroborated by electron diffraction and optical absorption spectroscopy, of which the latter provided a strong dielectric change upon lithium intercalation. This study of low lithium concentrations inside layers of well-defined and very small germanium nanoparticles, forms a new avenue towards significantly increasing the lithium battery capacity.

Synthesis and Characterization of Boron Nitride Thin Films Deposited by High-Power Impulse Reactive Magnetron Sputtering

In the present research, hexagonal boron nitride (h-BN) films were deposited by reactive high-power impulse magnetron sputtering (HiPIMS) of the pure boron target. Nitrogen was used as both a sputtering gas and a reactive gas. It was shown that, using only nitrogen gas, hexagonal-boron-phase thin films were synthesized successfully. The deposition temperature, time, and nitrogen gas flow effects were studied. It was found that an increase in deposition temperature resulted in hydrogen desorption, less intensive hydrogen-bond-related luminescence features in the Raman spectra of the films, and increased h-BN crystallite size. Increases in deposition time affect crystallites, which form larger conglomerates, with size decreases. The conglomerates’ size and surface roughness increase with increases in both time and temperature. An increase in the nitrogen flow was beneficial for a significant reduction in the carbon amount in the h-BN films and the appearance of the h-BN-related features in the lateral force microscopy images.

Key Sputtering Parameters for Precursor In2O3 Films to Achieve High Carrier Mobility.

Owing to their extremely high carrier mobility (μ) of >100 cm2/(V s) and suitable low carrier concentrations, transparent conducting films of solid-phase crystallized H-doped In2O3 (spc-IO:H) exhibit high conductivity with high optical transparency over a broad frequency range. These properties can be attributed to solid-phase crystallization of the amorphous precursor film. Therefore, the development of high-quality spc-IO:H films requires the deposition conditions of the precursor films to be optimized. This study systematically investigates the effects of three key sputtering parameters, namely, water vapor partial pressure (PH2O), radio frequency magnetron sputtering power (PRF), and flow ratio of O2 to total sputter gas (fO2) on the crystallographic texture evolution of spc-IO:H films during solid-phase crystallization. In addition, the carrier transport in the resulting films is examined. PH2O, PRF, and fO2 are found to be indispensable for producing high-mobility (>100 cm2/(V s)) spc-IO:H films. Furthermore, it is found that introducing a small amount of PH2O during deposition, a lower PRF, and a suitable fO2 facilitates the formation of precursor films having a lower crystallite density. Moreover, after annealing at a temperature of 200 °C, the IO:H precursor films with a lower crystallite density are found to have larger crystal grains. However, the μ values of the postannealed IO:H films are mainly correlated with the stoichiometric deviation.

INFLUENCE OF GAS ENVIRONMENT OF SPRAYING ON THE PROPERTIES OF GAS-THERMAL METALLIZED COATINGS

This article is devoted to the study of the influence of the technological parameters of spraying, in particular the gaseous medium, on the physical and mechanical properties and corrosion resistance of gas-thermal metallization coatings. To protect the housings of submersible electric motors (PAD) in oil and gas wells, the method of electric arc metallization (EDM) has become widespread, due to the high level of physical and mechanical properties of the resulting gas-thermal metallization coating, high productivity and cost-effectiveness of the process, as well as the mobility of equipment. Despite the effectiveness of this method of protection, it does not exclude the occurrence of corrosion processes in the metal of the PAD body. In this regard, research aimed at increasing the operational life of the metallization coating is relevant and promising.The article considers the theoretical aspects of the influence of the technological parameters of the spraying process on the properties of the metallization coating. The effect of the sputtering gas medium on the physical and mechanical properties and corrosion resistance of metallization coatings has been experimentally investigated. Comparative tests and studies of gas-thermal metallization chromium-nickel coatings applied by the EDM method in an air environment and in an argon environment have been carried out. The main trends and features of the formation of metallization chromium-nickel coatings applied by the EDM method and the effect of the application mode, in particular the technological gas spraying medium on the microstructure studied on metallographic grinds using a scanning electron microscope with an attachment for energy dispersion analysis; microhardness determined by the Vickers method are determined; The wear resistance is determined by abrasive wear during friction against non-rigidly fixed abrasive particles and the corrosion resistance of the resulting coatings, determined by autoclave tests during exposure in a simulated environment containing corrosive components.The study of the influence of certain technological parameters of spraying of gas-thermal metallization coatings, including the gas medium, on the properties of the coatings obtained is a fairly promising task aimed at increasing the operational life of the metallization coating, which in the future will reduce the cases of premature failure of oilfield equipment.

Enhancement of W Nanoparticles Synthesis by Injecting H2 in a Magnetron Sputtering Gas Aggregation Cluster Source Operated in Ar

Synthesis of W nanoparticles by magnetron sputtering combined with gas aggregation operated in Ar suffers from a continuous decrease of the synthesis rate, ceasing in a finite time interval, in the range of minutes to tens of minutes. Experimentally, we noticed that adding small amounts of H2 to Ar (5–20%) increases the synthesis rate, which remains constant over time, at a value dependent on the amount of injected hydrogen. Mass spectrometry investigations revealed, in the hydrogen presence, a dominance of the ArH+ ions over the Ar+ ones, associated also with an increased number of W+ and WH+ species in plasma, sustaining a substantial increase in the nucleation rate.

Structural and electrochromic property control of WO3 films through fine-tuning of film-forming parameters

Abstract Tungsten trioxide (WO3) films, extensively investigated for their remarkable electrochromic properties, have proven to be highly versatile in numerous applications. However, the challenge of achieving large-scale WO3 films with substantial dimensions and volumes remains a critical obstacle for industrial-scale production. Among the available techniques, magnetron sputtering stands out as the most efficient and straightforward method for the industrial preparation of WO3 films. In this comprehensive study, we meticulously explored the impact of various process parameters in magnetron sputtering on the film formation properties. By employing a controlled variable approach, we systematically investigated the influence of gas flow (Ar), sputtering pressure, power, and time. Our meticulous observations revealed that each parameter exerted distinct effects on the intricate film formation process. Careful analysis of the final dataset unequivocally demonstrated that when the sputtering conditions were meticulously optimized, the resulting films exhibited an extraordinary maximum transmittance change of 85% at a specific wavelength of 0.6 μm. Furthermore, these films showcased rapid coloring and bleaching response times, clocking in at an impressive 15 and 20 s, respectively, without any significant degradation even after undergoing 5,000 cycles. These groundbreaking findings provide invaluable insights into the intricate film formation process associated with magnetron-sputtered WO3.

N-Alkanes formed by methyl-methylene addition as a source of meteoritic aliphatics

Aliphatics prevail in asteroids, comets, meteorites and other bodies in our solar system. They are also found in the interstellar and circumstellar media both in gas-phase and in dust grains. Among aliphatics, linear alkanes (n-CnH2n+2) are known to survive in carbonaceous chondrites in hundreds to thousands of parts per billion, encompassing sequences from CH4 to n-C31H64. Despite being systematically detected, the mechanism responsible for their formation in meteorites has yet to be identified. Based on advanced laboratory astrochemistry simulations, we propose a gas-phase synthesis mechanism for n-alkanes starting from carbon and hydrogen under conditions of temperature and pressure that mimic those found in carbon-rich circumstellar envelopes. We characterize the analogs generated in a customized sputter gas aggregation source using a combination of atomically precise scanning tunneling microscopy, non-contact atomic force microscopy and ex-situ gas chromatography-mass spectrometry. Within the formed carbon nanostructures, we identify the presence of n-alkanes with sizes ranging from n-C8H18 to n-C32H66. Ab-initio calculations of formation free energies, kinetic barriers, and kinetic chemical network modelling lead us to propose a gas-phase growth mechanism for the formation of large n-alkanes based on methyl-methylene addition (MMA). In this process, methylene serves as both a reagent and a catalyst for carbon chain growth. Our study provides evidence of an aliphatic gas-phase synthesis mechanism around evolved stars and provides a potential explanation for its presence in interstellar dust and meteorites.

Copper tantalum nitride (CuTaN2) thin films prepared by reactive radio-frequency magnetron sputtering

RF reactive sputtering was used to deposit copper tantalum nitride (CuTaN2) films from a Cu/Ta target in an environment containing a mixture of argon and nitrogen at two different substrate temperatures: room temperature and 200 °C. The films were studied by SEM, EDS, XRD, Raman spectroscopy, spectrophotometry, and resistivity measurements. The deposition conditions significantly impacted the morphology of the films, which varied from smooth, void-free films at high nitrogen concentrations and at room temperature substrates to cauliflower-like grains with voids at low nitrogen contents and elevated substrate temperatures. Despite the target’s 1:1 Cu: Ta ratio, the stoichiometric analysis showed a lower Ta content in the deposited film. The films produced on silicon substrates were polycrystalline, whereas those deposited on glass substrates were amorphous. The band gap (0.9 eV to 1.55 eV) and film resistivity (20 kΩ-cm to 76 kΩ-cm) are strongly affected by the nitrogen fraction in the sputtering gas. Increasing the nitrogen percentage in semiconductor films results in smoother films with larger bandgaps (approximately 1.5 eV), higher resistivity, and compositions closest to those of stoichiometric CuTaN2.

One-step formation of ZrON thin film on surface of carbon fine particles for membrane electrode assembly

Zirconium nitride and oxynitride films were deposited on alumina or carbon particles by reactive sputtering using a magnetron sputtering apparatus with a Zr hollow cylindrical target and a vibrating equipment with heating capability. The vibrating equipment developed in this study was effective if the particles are spherical and highly monodisperse. Uniform film deposition was achieved over the entire surface of highly monodisperse spherical alumina particles using the vibrating equipment during deposition. Pure ZrN crystalline layers was deposited under Ar and N2 gas flows with heating on XC-72 carbon powder particles removed adsorbed oxygen. Energy dispersive x-ray spectroscopy mapping analysis for deposited XC-72 carbon particles showed ubiquitous film deposition on agglomerated particles regardless of vibration during sputtering. Uniform film deposition with vibrating equipment was achieved on the entire surface of CGB-10 particles with more spherical and monodisperse than XC-72 but precipitated crystalline phase depended on unintentional oxygen chemisorbed on the particles. Addition and increase in flow rate of oxygen to the sputtering gas resulted in the formation of desired crystalline phase, Zr2ON2, Zr7O8N4, and monoclinic ZrO2, precipitated in the film using CGB-10 particles with chemisorbed oxygen removed. Current density for oxygen reduction reaction measured for MEA made from CGB-10 particles with ZrON-based crystals deposited was larger than that for thin film deposited on a carbon plate substrate.

Zirconium Oxynitride Thin Films for Photoelectrochemical Water Splitting.

Transition metal oxynitrides are a promising class of functional materials for photoelectrochemical (PEC) applications. Although these compounds are most commonly synthesized via ammonolysis of oxide precursors, such synthetic routes often lead to poorly controlled oxygen-to-nitrogen anion ratios, and the harsh nitridation conditions are incompatible with many substrates, including transparent conductive oxides. Here, we report direct reactive sputter deposition of a family of zirconium oxynitride thin films and the comprehensive characterization of their tunable structural, optical, and functional PEC properties. Systematic increases of the oxygen content in the reactive sputter gas mixture enable access to different crystalline structures within the zirconium oxynitride family. Increasing oxygen contents lead to a transition from metallic to semiconducting to insulating phases. In particular, crystalline Zr2ON2-like films have band gaps in the UV-visible range and are n-type semiconductors. These properties, together with a valence band maximum position located favorably relative to the water oxidation potential, make them viable photoanode candidates. Using chopped linear sweep voltammetry, we indeed confirm that our Zr2ON2 films are PEC-active for the oxygen evolution reaction in alkaline electrolytes. We further show that high-vacuum annealing boosts their PEC performance characteristics. Although the observed photocurrents are low compared to state-of-the-art photoanodes, these dense and planar thin films can offer a valuable platform for studying oxynitride photoelectrodes, as well as for future nanostructuring, band gap engineering, and defect engineering efforts.

Enhanced Durability and Antireflective Performance of Ag-Based Transparent Conductors Achieved via Controlled N-Doping.

Ag-based transparent conductors (TCs) are often proposed as an alternative to ITO coatings. However, while their performance has been widely demonstrated, their environmental durability is frequently overlooked or addressed with the use of highly specific encapsulating layers. In this work, the durability and antireflective performance of Ag-based TCs are simultaneously enhanced. To do so, a transfer matrix modeling approach is used to determine the general requirements for high performance antireflective properties as a function of Ag thickness and dielectric refractive indices, offering more widely applicable insight into stack optimization. Coating durability is investigated as a function of the Ag microstructure, which is modified by altering the N2 concentration used for doping of the Ag layer and the selection of the seed layer. Increasing N2 concentration during Ag deposition was found to decrease grain size and durability of Ag coatings deposited on Si3N4 whereas all coatings on ZnO(Al) showed higher stability. Significantly higher durability is found when specifically combining intermediate N2 concentrations in the sputtering gas mixture (Ag(N):5%, compared to 0% and 50%) and a ZnO(Al) seed layer, and a mechanism accounting for this increased durability is proposed. The addition of NiCrNx protective coatings increases the system durability without altering these trends. These findings are combined to fabricate a highly performant Ag-based TC (TV = 89.2%, RVFS = 0.23%, 21.4 Ω), which shows minimal property changes following corrosion testing by immersion in a heated and highly concentrated aqueous NaCl solution (200 g/L, 50 °C).

Effects of hydrogen doping on the phase structure and optoelectronic properties of p-type transparent SnO

Hydrogen (H) is a ubiquitous impurity, which can significantly affect the phase structure and the optoelectronic properties of oxide semiconductors. To date, a well-established understanding of the effects of H doping on the properties of p-type transparent SnO is still lacking. Here, we present a comparative study to reveal the role of H in SnO films by magnetron sputtering. We find that in as-grown undoped SnO films, in addition to the tetragonal SnO phase, secondary phases of SnO2 or Sn3O4 are present under certain growth temperatures. In contrast, a small fraction of metallic Sn phase is included in the as-grown H-doped SnO (SnO:H) films, attributed to the partial reduction of SnO by the H2 in the sputtering gas. Effects of post thermal annealing (PTA) on the properties of SnO films are also explored. Results strongly indicate that H doping or PTA facilitates the formation of Sn phase and Sn vacancies related defects, giving rise to the p-type conductivity observed in the undoped or H-doped SnO films. The present study provides a comprehensive understanding of the evolution of phase structures as well as defect properties of SnO films, which is crucial for their future studies and optoelectronic applications.

Influence of Ar:O2 Mixing Ratio on Characteristics of Tio2 Nanostructured Thin Films Deposited by DC Reactive Magnetron Sputtering Method

Abstract: In this paper, titanium dioxide nanostructured thin films TiO2 were deposited on unheated glass substrates by applying the DC reactive magnetron sputtering method. Three TiO2 films were deposited using argon sputtering gas with different oxygen ratios: 10%, 25%, and 50%. The resulting films had thicknesses of 200, 184, and 140 nm, respectively. The structural, morphological, optical, and electrical properties of deposited thin films were studied. X-ray diffraction (XRD) data showed that the samples exhibited an amorphous phase. It was found from atomic force microscopy (AFM) that the deposited thin films had a nanostructure, and the heights of their nanograins were 16, 24, and 30 nm, respectively. It was observed from the root-mean-square height RMS values that the films had low roughness. The UV-Vis-NIR spectroscopy showed that the films become more transparent with the increase in oxygen content. The direct band gap ranged between 3.68 and 3.88 eV, while the indirect band gap ranged from 3.3 to 3.66 eV. The highest intensity photoluminescence emission was obtained for the film deposited at 50% O2. In addition, the impedance spectroscopy showed that the films’ resistance did not change with changing oxygen content. Keywords: Magnetron sputtering, Titanium dioxide, X-ray diffraction, Absorption spectra, Atomic Force Microscopy, Photoluminescence, Impedance.

Highly active ultralow loading Pt electrodes for hydrogen evolution reaction developed by magnetron sputtering

Developing cost-effective components for PEM electrolyzers is key to transforming renewable energy into H2. Platinum is a scarce and expensive material but also, is the most active known catalyst for hydrogen evolution reaction in PEM electrolysis; thus it is of utmost importance to focus on developing electrocatalysts that utilize the minimum amount of platinum without losses in cell performance to make PEM electrolysis affordable. In addition, and with the aim of scaling up electrode production, it is imperative to develop a robust automated industrial manufacturing process to avoid the waste of catalyst during electrode preparation. In this work, magnetron sputtering gas aggregation method is studied for developing three low loading Pt electrodes (0.105, 0.062, and 0.052 mg cm−2), achieving remarkable overpotentials as low as 8 mV at 10 mA cm−2 for HER, showing similar activity than commercial Pt electrodes with more than 4 times less Pt (compared to 0.3 mgcm−2 Pt commercial GDL).

Influence of oxygen content on the properties of In2(OxS1−x)3 used as buffer material in Cu(In,Ga)Se2 solar cells

We investigate magnetron-sputtered In2(OxS1−x)3 compounds acting as an alternative buffer system to the solution-grown CdS or Zn(O,S) buffer layers in Cu(In,Ga)Se2 (CIGS) thin-film solar cells. The influence of the oxygen content on the solar cell performance, microstructure of the mixed systems, bandgap, and band offsets to CIGS is investigated experimentally and also characterized by calculations based on density functional theory. Samples in a series with different chemical compositions ranging from In2S3 to In2O3 are either directly deposited from ceramic targets or from a pure In2S3 target by reactive sputtering by adding O2 in the Ar sputtering gas. The binary compounds In2S3 and In2O3 sputtered at 220 °C substrate temperature from ceramic targets exhibit a crystalline structure, whereas the ternary In2(O,S)3 compounds are either nanocrystalline in the case of In2(O0.25S0.75)3 or amorphous for In2(O0.5S0.5)3 and In2(O0.75S0.25)3. For [O]/([O] + [S]) ratios above 0.25, the cell efficiencies decrease drastically, mainly due to lower open-circuit voltages (VOC). This behavior can be explained by an increase of the negative conduction band offset between the CIGS absorber and the oxygen-rich In2(OxS1−x)3 or In2O3 buffer, resulting in pronounced VOC losses. Adding oxygen to In2S3 with optical bandgap energies of around 2 eV results in a bowing of the values to below 2 eV and finally reaching values of around 2.7 eV for In2O3 if an indirect band transition is assumed. In summary, our results reveal that pronounced oxygen incorporation in In2S3 is not beneficial in terms of CIGS device efficiency because oxygen is electronically inactive and poorly miscible.

Study on Crystallinity and Magnetic Properties of NiCuZn Ferrite Films Deposited by RF Sputtering

Nickel-zinc ferrite proves to be the top-performing material in terms of soft magnetic features for high-frequency applications. The purpose of this study is to explore the impact of various factors such as sputtering pressure, substrate temperature, sputtering power, and sputtering gas, on the magnetic and structural properties of NiCuZn ferrite thin films. In this research, radio-frequency magnetron sputtering of NiCuZn ferrite thin films on silicon substrates was used to investigate the matter. The study demonstrates that reducing sputtering pressure enhances the crystallization of NiCuZn ferrite films and improves their magnetic properties. The saturation magnetization and crystallinity of the thin films initially increased, then decreased as substrate temperature and sputtering power increased. Furthermore, the sputtered films exhibited higher crystallinity and saturation magnetization in a pure Ar atmosphere compared to an oxygen-containing environment. In this study, we optimized the sputtering parameters to achieve a maximum saturation magnetization strength of 253 emu/cc.

A multi-reflection time-of-flight setup for the study of atomic clusters produced by magnetron sputtering

The Greifswald multi-reflection time-of-flight setup has been extended with a magnetron sputtering gas aggregation source for the production of atomic cluster ions with sizes ranging from a single to thousands of atoms. This source, combined with a newly added quadrupole mass filter and a linear Paul trap, opens up the possibility of many new atomic-cluster studies not feasible with the setup before. The new components and their interfacing with the previous setup are described, and benchmarking as well as the first experimental results are presented. The capability of the system to handle singly charged ions with masses of several ten thousand atomic mass units is demonstrated.

Structural, Optical, and Electrical Characteristics of Cu3N with Respect to Substrate Temperature and N2 Concentration in Mixed Sputtering Gas

Structural, Optical, and Electrical Characteristics of Cu3N with Respect to Substrate Temperature and N2 Concentration in Mixed Sputtering Gas

Advances in Nanomaterials: Types, Synthesis, and Manufacturing Methods

By virtue of their unique properties at the nanoscale, nanomaterials have revolutionized the field of material science. The current work provides a thorough analysis of nanomaterials, classifying them into three main categories: nanoparticles, nanosolids, and nanoassembled systems. Further analysis of the classes is conducted based on their morphologies, chemical composition, and structural variety, which include carbon-based nanomaterials such as fullerene, carbon nanotubes (CNTs), and graphene. Moreover, the synthesis and manufacturing techniques of nanomaterials are analyzed, with a particular focus on physical and chemical approaches. The methods highlighted for their ability to produce nanomaterials with a broad variety of applications include gas evaporation, vacuum condensation, sputtering, yeast-cell-based synthesis, and sol-gel processing. The major aim of this work is to provide a comprehensive guide on the classification, properties, and production techniques of nanomaterials, thereby enhancing comprehension of their importance in many scientific and practical domains.

Investigation of Antibacterial Efficacy of CuCrO2 Delafossite Thin Films Against E. coli

Terminals used in hospitals, information systems displaying patient information, and smartphones use touch panels that incorporate n and p transparent conducting oxide (TCO) layers [1]. There are a lot of pre-existing research present on n-type TCO while at the same time similar research interest related to p-type TCOs has been lacking. This is due to the inherently high electrical resistivity or low optical transparency of p-type TCOs. Recently, there has been a spike in research related to p-type delafossite thin films, owing to their excellent electrical and optical properties as compared to the other p-type counterparts. Cu-based p-type delafossite materials exhibit low resistivity and at the same time good optical transparency in the visible region. Among the Cu-based delafossites, copper chromium oxide (CuCrO2) exhibits the lowest electrical resistivity reported yet. Use of CuCrO2 as the p-type TCO along with a suitable n-type TCO might demonstrates significant potential to be used for optoelectronic applications.In this work, CuCrO2 thin films have been deposited on quartz substrates using dual target RF magnetron sputtering technique. This involved dual sputtering of 3- inch Cu2O and Cr2O3 targets. The substrate temperature was maintained at 400 °C during the deposition with Ar used as the sputtering gas. This was followed by post deposition annealing. Previous research carried out by our group has indicated that single-phase CuCrO2 was obtained at an annealing temperature of 650 °C in N2 ambiance for 4 hours [2, 3]. Successful synthesis of single-phase CuCrO2 has been confirmed using XPS and XRD study. The resistivity of CuCrO2 was obtained as 0.652 Ω-cm, which is the lowest reported so far. The optical study denoted an average optical transmission of > 60% in the visible wavelength spectrum and a high optical bandgap of 3.2 eV. The antibacterial efficacy of different thickness of CuCrO2 thin films was tested against E. coli bacterial strain and compared against the efficacy of plain quartz in this research work. Results showed that with an increase in the thickness of CuCrO2 thin films, the efficacy against E. coli increases. The highest antibacterial efficacy of 78.07 % was shown by 2000 A° CuCrO2 thin film.[1] Chiu T-W, Yang Y-C, Yeh A-C, Wang Y-P, Feng Y-W. Antibacterial property of CuCrO2 thin films prepared by RF magnetron sputtering deposition. Vacuum. 2013;87:174-177.[2] Sundaresh S, Bharath AH, Sundaram KB. Effect of Annealing Temperature on Radio Frequency Sputtered p-Type Delafossite Copper Chromium Oxide (CuCrO2) Thin Films and Investigation of Diode Characteristics Forming Transparent pn-Heterojunction. Coatings2023.[3] Sundaresh S, Bharath AH, Sundaram KB. Effect of Cu2O Sputtering Power Variation on the Characteristics of Radio Frequency Sputtered p-Type Delafossite CuCrO2 Thin Films. Coatings2023.