Pub Date : 2026-01-01Epub Date: 2026-01-06DOI: 10.1016/j.apsadv.2025.100926
Gyutae Park , Hyunho Yang , Minjin Lee , Kiin Choi , Hyun S. Kum
<div><div>Yttrium oxide (Y₂O₃) coatings serve as essential barrier layers for protecting chamber surfaces from plasma-induced erosion and contamination during dry etching in semiconductor and display fabrication. With increasing device complexity and elevated plasma power conditions, the demand for enhanced coating performance has intensified to support stable processing and high production yields. Accordingly, there is growing interest in coating systems that can sustain harsh plasma etching while maintaining a clean processing environment.</div><div>In this study, Y₂O₃–ZrO₂ composite coatings (hereafter referred to as YZ coatings) were fabricated via atmospheric plasma spraying (APS), and their durability was evaluated through a 10-hour plasma etching process conducted in an 8.6-generation industrial ICP system operated with a CF₄/O₂/Ar gas mixture.</div><div>Key durability metrics— maximum etch depth, mass change, reaction layer degradation, and ion elution—were quantitatively assessed. To evaluate dissolved ion release after plasma etching, Y ion concentrations (measured by ICP-OES) and Zr ion concentrations (measured by ICP-MS) in the ultrasonic cleaning solution were analyzed for high-sensitivity detection.</div><div>The Y₂O₃–ZrO₂ composite coatings (hereafter referred to as YZ coatings) exhibited a 13% shallower maximum etch depth (4306.9 nm) compared to conventional Y₂O₃ (4946.96 nm), along with a reduction in total ionic elution by approximately 19% (from 2.13 mg/kg to 1.73 mg/kg). These improvements are attributed to the dual stabilizing effects of Zr addition, namely mechanical reinforcement of the microstructure and chemical stabilization via preferential Zr–F bonding, which suppresses excessive Y–F formation.</div><div>XPS analysis confirmed that Zr⁴⁺ incorporation modified the surface chemistry by forming stable Zr–F bonds, which suppressed excessive Y–F bond formation and reduced fluorine incorporation.</div><div>This effect can be explained by the smaller ionic radius (0.84 Å vs. 1.02 Å) and higher electronegativity (1.33 vs. 1.22) of Zr⁴⁺ compared to Y³⁺, which enhance its affinity for F⁻ ions and promote selective fluorination, thereby stabilizing the reaction layer.</div><div>The smaller ionic radius of Zr⁴⁺ leads to shorter Zr–F bond lengths, resulting in stronger bonding and enhanced near-surface mechanical integrity. In addition, the higher electronegativity of Zr⁴⁺ favors stronger ionic–covalent interactions with fluorine, reducing the volatility of fluoride species and improving chemical stability at the surface.</div><div>As a result, the YZ composite coating effectively suppresses plasma-induced material degradation and ion release, contributing to improved process stability and reduced chamber contamination under prolonged fluorine-based plasma etching conditions. These findings highlight the industrial significance of Zr-modified Y₂O₃ coatings for advanced semiconductor and display manufacturing environments.</div></di
氧化钇（Y₂O₃）涂层是必不可少的屏障层，用于保护腔室表面在半导体和显示器制造过程中免受等离子体诱导的侵蚀和污染。随着器件复杂性的增加和等离子体功率条件的提高，对增强涂层性能的需求已经增强，以支持稳定的加工和高产量。因此，人们对能够承受苛刻的等离子蚀刻同时保持清洁加工环境的涂层系统越来越感兴趣。在这项研究中，通过大气等离子喷涂（APS）制备了Y₂O₃-ZrO₂复合涂层（以下简称YZ涂层），并通过在8.6代工业ICP系统中使用CF₄/O₂/Ar气体混合物进行10小时的等离子蚀刻工艺来评估其耐久性。关键耐久性指标-最大蚀刻深度，质量变化，反应层降解和离子洗脱-进行了定量评估。为了评估等离子体刻蚀后溶解离子的释放，对超声清洗液中Y离子浓度（ICP-OES）和Zr离子浓度（ICP-MS）进行了高灵敏度检测。与传统的Y₂O₃（4946.96 nm）相比，Y₂O₃-ZrO₂复合涂层（以下简称YZ涂层）的最大蚀刻深度（4306.9 nm）浅了13%，总离子洗涤量减少了大约19%（从2.13 mg/kg降至1.73 mg/kg）。这些改善归因于Zr的双重稳定作用，即机械强化微观结构和通过Zr - f优先键合抑制过量Y-F形成的化学稳定作用。XPS分析证实，Zr⁴⁺通过形成稳定的Zr - f键修饰了表面化学性质，抑制了过量的Y-F键形成，减少了氟的掺入。这种效应可以用Zr⁴⁺比Y³⁺具有更小的离子半径（0.84 Å vs. 1.02 Å）和更高的电负性（1.33 vs. 1.22）来解释，这增强了它对F⁻的亲和力，促进了选择性氟化，从而稳定了反应层。Zr⁴⁺的离子半径越小，Zr - f键的长度越短，从而形成更强的键合，增强了近表面的机械完整性。此外，Zr⁴⁺较高的电负性有利于与氟更强的离子共价相互作用，减少氟化物的挥发性，提高表面的化学稳定性。因此，YZ复合涂层有效地抑制了等离子体诱导的材料降解和离子释放，有助于提高工艺稳定性，减少长时间氟基等离子体蚀刻条件下的腔室污染。这些发现突出了zr修饰的Y₂O₃涂层在先进半导体和显示器制造环境中的工业意义。
{"title":"Etching resistance and particle suppression behavior of Y₂O₃–ZrO₂ composite coatings in fluorine-based plasma","authors":"Gyutae Park , Hyunho Yang , Minjin Lee , Kiin Choi , Hyun S. Kum","doi":"10.1016/j.apsadv.2025.100926","DOIUrl":"10.1016/j.apsadv.2025.100926","url":null,"abstract":"<div><div>Yttrium oxide (Y₂O₃) coatings serve as essential barrier layers for protecting chamber surfaces from plasma-induced erosion and contamination during dry etching in semiconductor and display fabrication. With increasing device complexity and elevated plasma power conditions, the demand for enhanced coating performance has intensified to support stable processing and high production yields. Accordingly, there is growing interest in coating systems that can sustain harsh plasma etching while maintaining a clean processing environment.</div><div>In this study, Y₂O₃–ZrO₂ composite coatings (hereafter referred to as YZ coatings) were fabricated via atmospheric plasma spraying (APS), and their durability was evaluated through a 10-hour plasma etching process conducted in an 8.6-generation industrial ICP system operated with a CF₄/O₂/Ar gas mixture.</div><div>Key durability metrics— maximum etch depth, mass change, reaction layer degradation, and ion elution—were quantitatively assessed. To evaluate dissolved ion release after plasma etching, Y ion concentrations (measured by ICP-OES) and Zr ion concentrations (measured by ICP-MS) in the ultrasonic cleaning solution were analyzed for high-sensitivity detection.</div><div>The Y₂O₃–ZrO₂ composite coatings (hereafter referred to as YZ coatings) exhibited a 13% shallower maximum etch depth (4306.9 nm) compared to conventional Y₂O₃ (4946.96 nm), along with a reduction in total ionic elution by approximately 19% (from 2.13 mg/kg to 1.73 mg/kg). These improvements are attributed to the dual stabilizing effects of Zr addition, namely mechanical reinforcement of the microstructure and chemical stabilization via preferential Zr–F bonding, which suppresses excessive Y–F formation.</div><div>XPS analysis confirmed that Zr⁴⁺ incorporation modified the surface chemistry by forming stable Zr–F bonds, which suppressed excessive Y–F bond formation and reduced fluorine incorporation.</div><div>This effect can be explained by the smaller ionic radius (0.84 Å vs. 1.02 Å) and higher electronegativity (1.33 vs. 1.22) of Zr⁴⁺ compared to Y³⁺, which enhance its affinity for F⁻ ions and promote selective fluorination, thereby stabilizing the reaction layer.</div><div>The smaller ionic radius of Zr⁴⁺ leads to shorter Zr–F bond lengths, resulting in stronger bonding and enhanced near-surface mechanical integrity. In addition, the higher electronegativity of Zr⁴⁺ favors stronger ionic–covalent interactions with fluorine, reducing the volatility of fluoride species and improving chemical stability at the surface.</div><div>As a result, the YZ composite coating effectively suppresses plasma-induced material degradation and ion release, contributing to improved process stability and reduced chamber contamination under prolonged fluorine-based plasma etching conditions. These findings highlight the industrial significance of Zr-modified Y₂O₃ coatings for advanced semiconductor and display manufacturing environments.</div></di","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"31 ","pages":"Article 100926"},"PeriodicalIF":8.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145925641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2025-12-06DOI: 10.1016/j.apsadv.2025.100911
Nils Braun , Dmitry Kalanov , Martin Rudolph , Vladimir Roddatis , Lennart Voß , Sonja Cremer , Hagen Bryja , Lorenz Kienle , Andriy Lotnyk
Chalcogenides are promising materials for various applications due to their tunable properties through materials design. In this work, Cu–Sb–Te thin films are synthesized via Cu diffusion into epitaxial Sb2Te3 thin films using room–temperature DC magnetron sputtering. X–Ray diffraction shows that the diffusion of Cu into the Sb2Te3 is strongly dependent on deposition pressure. A simulation of the sputtering process using a Monte Carlo approach reveals that the Ar working gas pressure impacts the kinetic energy of the sputtered atoms. At lower deposition pressures and therefore higher kinetic energy more Cu diffuses. This results in the formation of disordered layered Cu–Sb–Te structures embedded with Sb2Te3 matrix. Interestingly, a new Cu7(Sb0.4Te0.6)4 phase is obtained by further sputter deposition of Pt and Ti layers on top of the Cu layers at room temperature. The phase represents a layered structure consisting of 3Te layers per building unit. Structure analysis using advanced transmission electron microscopy indicates the formation of Te and Sb antisite defects and a crystal structure model for this phase is proposed based on the microscopy analysis. An additional thermal in situ XRD heating of the Cu7(Sb0.4Te0.6)4 results in out–diffusion of Sb and the formation of Cu7Te4 structures consisting of 2Te and 3Te layers as well as Sb2O3, showing strong diffusion of oxygen. The Cu7(Sb0.4Te0.6)4 and Cu7Te4 layers retain epitaxial properties of the former Sb2Te3 layers. This approach allows for the synthesis of chalcogenides consisting of disordered Cu–Sb–Te and Sb2Te3 structures as well as the fabrication of epitaxial disordered Cu7(Sb0.4Te0.6)4 thin films.
{"title":"Synthesis and microstructural characterization of layered Cu–Sb–Te–based thin films","authors":"Nils Braun , Dmitry Kalanov , Martin Rudolph , Vladimir Roddatis , Lennart Voß , Sonja Cremer , Hagen Bryja , Lorenz Kienle , Andriy Lotnyk","doi":"10.1016/j.apsadv.2025.100911","DOIUrl":"10.1016/j.apsadv.2025.100911","url":null,"abstract":"<div><div>Chalcogenides are promising materials for various applications due to their tunable properties through materials design. In this work, Cu–Sb–Te thin films are synthesized via Cu diffusion into epitaxial Sb<sub>2</sub>Te<sub>3</sub> thin films using room–temperature DC magnetron sputtering. X–Ray diffraction shows that the diffusion of Cu into the Sb<sub>2</sub>Te<sub>3</sub> is strongly dependent on deposition pressure. A simulation of the sputtering process using a Monte Carlo approach reveals that the Ar working gas pressure impacts the kinetic energy of the sputtered atoms. At lower deposition pressures and therefore higher kinetic energy more Cu diffuses. This results in the formation of disordered layered Cu–Sb–Te structures embedded with Sb<sub>2</sub>Te<sub>3</sub> matrix. Interestingly, a new Cu<sub>7</sub>(Sb<sub>0.4</sub>Te<sub>0.6</sub>)<sub>4</sub> phase is obtained by further sputter deposition of Pt and Ti layers on top of the Cu layers at room temperature. The phase represents a layered structure consisting of 3Te layers per building unit. Structure analysis using advanced transmission electron microscopy indicates the formation of Te and Sb antisite defects and a crystal structure model for this phase is proposed based on the microscopy analysis. An additional thermal in situ XRD heating of the Cu<sub>7</sub>(Sb<sub>0.4</sub>Te<sub>0.6</sub>)<sub>4</sub> results in out–diffusion of Sb and the formation of Cu<sub>7</sub>Te<sub>4</sub> structures consisting of 2Te and 3Te layers as well as Sb<sub>2</sub>O<sub>3</sub>, showing strong diffusion of oxygen. The Cu<sub>7</sub>(Sb<sub>0.4</sub>Te<sub>0.6</sub>)<sub>4</sub> and Cu<sub>7</sub>Te<sub>4</sub> layers retain epitaxial properties of the former Sb<sub>2</sub>Te<sub>3</sub> layers. This approach allows for the synthesis of chalcogenides consisting of disordered Cu–Sb–Te and Sb<sub>2</sub>Te<sub>3</sub> structures as well as the fabrication of epitaxial disordered Cu<sub>7</sub>(Sb<sub>0.4</sub>Te<sub>0.6</sub>)<sub>4</sub> thin films.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"31 ","pages":"Article 100911"},"PeriodicalIF":8.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-09-22DOI: 10.1016/j.apsadv.2025.100855
Cyrille Ghislain Fotsop, Alexandra Lieb, Franziska Scheffler
Humidity control is a major issue in industrial processes, the present work focuses on the synthesis of the core-satellite materials: Zeo-X-Mg, Zeo-X-Zn, Zeo-X-ZnO and Zeo-X-MgO, followed by a comparative study of their water vapor adsorption properties. The adsorption mechanism was elucidated using isothermal modeling with Langmuir, Freundlich, Sips and Guggenheim-Anderson-De Boer (GAB) models. The obtained materials were synthesized by an ex situ ion-exchange assisted hydrothermal method and characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), solid-state magic angle spinning (MAS)-nuclear magnetic resonance (NMR), field emission scanning electron microscopy (FE-SEM)/energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA)-differential scanning calorimetry (DSC), N₂ sorption and Fourier transform infrared spectroscopy (FTIR) techniques. XRD analysis revealed additional phases in the Zeo-X-ZnO and Zeo-X-MgO samples due to the presence of ZnO, Zn(OH)₂, MgO, and Mg(OH)₂ on the Zeo-X-Na sample's surface. SEM/EDX analysis revealed uniform octahedral particles corresponding to the six-membered rings (D6R) of sodalite cages and a homogeneous distribution of Mg and Zn elements. The water vapor adsorption capacities were 26.9, 25.1, 21.5, 18.1, and 14.1 mmol/g for Zeo-X-ZnO, Zeo-X-MgO, Zeo-X-Zn, Zeo-X-Mg, and Zeo-X-Na samples, respectively. Despite their low porosities, Zeo-X-ZnO and Zeo-X-MgO showed higher adsorption capacities comparable to samples exchanged with Mg²⁺, Zn²⁺ and pure zeolite. For Zeo-X-MgO and Zeo-X-ZnO samples, water molecule adsorption occurs preferentially on the surface of the zeolite structure, due to the formation of Zn(OH)₂ and Mg(OH)₂ complexes during to the hydration. The GAB model showed a higher R² value with low values of the error functions, indicating adsorption on infinite monolayers and multilayers at variable pressure. The Freundlich model showed that chemisorption occurred at the adsorbent surface during adsorption. The obtained isosteric heat of adsorption were 53.22, 63.03, 80.96, 65.23, and 73.15 kJ/mol for Zeo-X-Na, Zeo-X-Zn, Zeo-X-ZnO, Zeo-X-Mg, and Zeo-X-MgO, respectively. These results point to an innovative approach to industrial processes involving water vapor.
{"title":"Insights into the synergistic effects of ZnO/MgO and Zn/Mg-modified porous zeolite as core-satellite materials for tuning water vapor sorption properties","authors":"Cyrille Ghislain Fotsop, Alexandra Lieb, Franziska Scheffler","doi":"10.1016/j.apsadv.2025.100855","DOIUrl":"10.1016/j.apsadv.2025.100855","url":null,"abstract":"<div><div>Humidity control is a major issue in industrial processes, the present work focuses on the synthesis of the core-satellite materials: Zeo-X-Mg, Zeo-X-Zn, Zeo-X-ZnO and Zeo-X-MgO, followed by a comparative study of their water vapor adsorption properties. The adsorption mechanism was elucidated using isothermal modeling with Langmuir, Freundlich, Sips and Guggenheim-Anderson-De Boer (GAB) models. The obtained materials were synthesized by an ex situ ion-exchange assisted hydrothermal method and characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), solid-state magic angle spinning (MAS)-nuclear magnetic resonance (NMR), field emission scanning electron microscopy (FE-SEM)/energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA)-differential scanning calorimetry (DSC), N₂ sorption and Fourier transform infrared spectroscopy (FTIR) techniques. XRD analysis revealed additional phases in the Zeo-X-ZnO and Zeo-X-MgO samples due to the presence of ZnO, Zn(OH)₂, MgO, and Mg(OH)₂ on the Zeo-X-Na sample's surface. SEM/EDX analysis revealed uniform octahedral particles corresponding to the six-membered rings (D6R) of sodalite cages and a homogeneous distribution of Mg and Zn elements. The water vapor adsorption capacities were 26.9, 25.1, 21.5, 18.1, and 14.1 mmol/g for Zeo-X-ZnO, Zeo-X-MgO, Zeo-X-Zn, Zeo-X-Mg, and Zeo-X-Na samples, respectively. Despite their low porosities, Zeo-X-ZnO and Zeo-X-MgO showed higher adsorption capacities comparable to samples exchanged with Mg²⁺, Zn²⁺ and pure zeolite. For Zeo-X-MgO and Zeo-X-ZnO samples, water molecule adsorption occurs preferentially on the surface of the zeolite structure, due to the formation of Zn(OH)₂ and Mg(OH)₂ complexes during to the hydration. The GAB model showed a higher R² value with low values of the error functions, indicating adsorption on infinite monolayers and multilayers at variable pressure. The Freundlich model showed that chemisorption occurred at the adsorbent surface during adsorption. The obtained isosteric heat of adsorption were 53.22, 63.03, 80.96, 65.23, and 73.15 kJ/mol for Zeo-X-Na, Zeo-X-Zn, Zeo-X-ZnO, Zeo-X-Mg, and Zeo-X-MgO, respectively. These results point to an innovative approach to industrial processes involving water vapor.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100855"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145109966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study aims to provide experimental evidence of the formation and the growth of a viscous layer during the electropolishing of additively manufactured 316 L stainless steel parts, using a combination of optical characterization techniques. A tertiary current distribution model was subsequently developed to simulate the electropolishing process and predict the evolution of the viscous layer. The results demonstrate that the viscous layer forms and grows within a specific potential window before being disrupted by gas evolution due to solvent oxidation. Schlieren imaging estimates the thickness of the layer to be approximately 1.4 mm after 5 min of polarization at the onset of the polishing plateau—about 1 mm thicker than its natural state without polarization. Particle Image Velocimetry (PIV) confirms the presence of a flow-deprived zone near the surface, roughly 1 mm thick, contrasting with the bulk region where natural convection dominates. A simplified reaction mechanism is proposed, based on experimentally determined electron-transfer kinetics. Metal cations are assumed to be instantly complexed, with the diffusion of the resulting complexes considered equivalent to that of the free complexing agents (phosphates), based on literature values. Using these assumptions, the tertiary current distribution model successfully replicates the growth of the viscous layer. The model's predictions were validated by experimental measurements of metal cation concentrations, supporting the hypothesis that the diffusion of “acceptor” species is the primary driving force behind electropolishing. This work also confirms that phosphate-complexed metal cations diffuse analogously to anions.
{"title":"A multi-physics and multi-scale approach to characterize the viscous layer growth formed on SLM 316 L stainless steel during electropolishing in an acid mixture","authors":"Aurélien Boucher , Magali Barthes , Luc Froehly , Marie-Laure Doche , Christine Régent , Jean-Yves Hihn","doi":"10.1016/j.apsadv.2025.100878","DOIUrl":"10.1016/j.apsadv.2025.100878","url":null,"abstract":"<div><div>This study aims to provide experimental evidence of the formation and the growth of a viscous layer during the electropolishing of additively manufactured 316 L stainless steel parts, using a combination of optical characterization techniques. A tertiary current distribution model was subsequently developed to simulate the electropolishing process and predict the evolution of the viscous layer. The results demonstrate that the viscous layer forms and grows within a specific potential window before being disrupted by gas evolution due to solvent oxidation. Schlieren imaging estimates the thickness of the layer to be approximately 1.4 mm after 5 min of polarization at the onset of the polishing plateau—about 1 mm thicker than its natural state without polarization. Particle Image Velocimetry (PIV) confirms the presence of a flow-deprived zone near the surface, roughly 1 mm thick, contrasting with the bulk region where natural convection dominates. A simplified reaction mechanism is proposed, based on experimentally determined electron-transfer kinetics. Metal cations are assumed to be instantly complexed, with the diffusion of the resulting complexes considered equivalent to that of the free complexing agents (phosphates), based on literature values. Using these assumptions, the tertiary current distribution model successfully replicates the growth of the viscous layer. The model's predictions were validated by experimental measurements of metal cation concentrations, supporting the hypothesis that the diffusion of “acceptor” species is the primary driving force behind electropolishing. This work also confirms that phosphate-complexed metal cations diffuse analogously to anions.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100878"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145363284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-10-24DOI: 10.1016/j.apsadv.2025.100882
Alexandre M.P. Botas , Alexandre F. Carvalho , Kiryl Yasakau , Nuno M. Ferreira , Georgina Miranda , João Tedim , Florinda M. Costa
Laser patterning has emerged as a remarkable method for tuning the surface properties of materials, including metals such as copper and its alloys. The copper wettability can be precisely tailored - from superhydrophilic to superhydrophobic – using laser-based surface engineering techniques, unlocking transformative potential across a wide range of applications. This review provides a comprehensive overview of the application of laser technology in the modification of the wettability properties of copper surfaces. Particular attention is given to the evolution of the water contact angle over time of irradiated surfaces after air exposure, as well as to the mechanisms reported in the literature that explain wettability changes. In addition to laser irradiation, spanning wavelengths from ultraviolet to infrared and pulse widths from the nanoseconds to femtoseconds, several studies incorporate post-processing methods to achieve the desire performance, which are also discussed in this review. Moreover, the review highlights successful application of the laser-treated copper surfaces modified with wettability in areas such as oil-water separation, self-cleaning, anti-icing, sensing, heat transfer and microfluids, among others. Finally, a critical analysis of laser surface treatments and conventional chemical methods is performed.
{"title":"Laser patterning for the modification of copper’s wettability: A systematic review","authors":"Alexandre M.P. Botas , Alexandre F. Carvalho , Kiryl Yasakau , Nuno M. Ferreira , Georgina Miranda , João Tedim , Florinda M. Costa","doi":"10.1016/j.apsadv.2025.100882","DOIUrl":"10.1016/j.apsadv.2025.100882","url":null,"abstract":"<div><div>Laser patterning has emerged as a remarkable method for tuning the surface properties of materials, including metals such as copper and its alloys. The copper wettability can be precisely tailored - from superhydrophilic to superhydrophobic – using laser-based surface engineering techniques, unlocking transformative potential across a wide range of applications. This review provides a comprehensive overview of the application of laser technology in the modification of the wettability properties of copper surfaces. Particular attention is given to the evolution of the water contact angle over time of irradiated surfaces after air exposure, as well as to the mechanisms reported in the literature that explain wettability changes. In addition to laser irradiation, spanning wavelengths from ultraviolet to infrared and pulse widths from the nanoseconds to femtoseconds, several studies incorporate post-processing methods to achieve the desire performance, which are also discussed in this review. Moreover, the review highlights successful application of the laser-treated copper surfaces modified with wettability in areas such as oil-water separation, self-cleaning, anti-icing, sensing, heat transfer and microfluids, among others. Finally, a critical analysis of laser surface treatments and conventional chemical methods is performed.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100882"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145363286","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-09-18DOI: 10.1016/j.apsadv.2025.100851
Talha Zafer , Nabil Khossossi , Poulumi Dey
Photocatalytic water splitting represents a promising approach for sustainable hydrogen production, with two-dimensional Janus materials offering unique advantages through intrinsic electric fields that enhance charge separation. We present a comprehensive first-principles investigation of Janus AlXY (X = Ga, In; Y = S, Se, Te) monolayers using density functional theory and ab initio molecular dynamics simulations. All six systems exhibit excellent structural, thermal, and mechanical stability with HSE06 bandgaps of 2.029–2.969 eV suitable for UV-light absorption. The asymmetric structure generates strong intrinsic electric fields of 5.391–6.437 V perpendicular to the monolayer plane, significantly enhancing photogenerated charge carrier separation. While pristine monolayers show poor hydrogen evolution reaction (HER) activity with Gibbs free energies of 1.937–2.371 eV, strategic introduction of metal vacancies dramatically improves performance, reducing G values to −0.371 to ＋0.607 eV and approaching optimal catalytic conditions. These findings demonstrate the potential of defect-engineered 2D Janus AlXY materials for efficient photocatalytic hydrogen production.
{"title":"Boosting photocatalytic hydrogen evolution via intrinsic electric fields in 2D Janus AlXY2 (X = Ga, In; Y = S, Se, Te) monolayers","authors":"Talha Zafer , Nabil Khossossi , Poulumi Dey","doi":"10.1016/j.apsadv.2025.100851","DOIUrl":"10.1016/j.apsadv.2025.100851","url":null,"abstract":"<div><div>Photocatalytic water splitting represents a promising approach for sustainable hydrogen production, with two-dimensional Janus materials offering unique advantages through intrinsic electric fields that enhance charge separation. We present a comprehensive first-principles investigation of Janus AlXY<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> (X = Ga, In; Y = S, Se, Te) monolayers using density functional theory and ab initio molecular dynamics simulations. All six systems exhibit excellent structural, thermal, and mechanical stability with HSE06 bandgaps of 2.029–2.969 eV suitable for UV-light absorption. The asymmetric structure generates strong intrinsic electric fields of 5.391–6.437 V perpendicular to the monolayer plane, significantly enhancing photogenerated charge carrier separation. While pristine monolayers show poor hydrogen evolution reaction (HER) activity with Gibbs free energies of 1.937–2.371 eV, strategic introduction of metal vacancies dramatically improves performance, reducing <span><math><mi>Δ</mi></math></span>G<span><math><msub><mrow></mrow><mrow><mi>H</mi></mrow></msub></math></span> values to −0.371 to ＋0.607 eV and approaching optimal catalytic conditions. These findings demonstrate the potential of defect-engineered 2D Janus AlXY<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> materials for efficient photocatalytic hydrogen production.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100851"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108006","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-11-10DOI: 10.1016/j.apsadv.2025.100893
Ivana Martinović , Zora Pilić , Željka Petrović
{"title":"Preface on corrosion inhibition: A green and sustainable approach","authors":"Ivana Martinović , Zora Pilić , Željka Petrović","doi":"10.1016/j.apsadv.2025.100893","DOIUrl":"10.1016/j.apsadv.2025.100893","url":null,"abstract":"","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100893"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-10-14DOI: 10.1016/j.apsadv.2025.100871
Jaeik Kwak , Sang-Mun Jung , Kyu-Su Kim , Gogwon Choe , Sujung Son , Hyoung Seop Kim , Yong-Tae Kim
Passivation through cathodic modification has largely remained a theoretical concept due to the reliance on noble metals. In this study, we successfully achieved passivation in AISI 409 L steel, an alloy with reduced Ni and Cr content, by applying a cost-effective Fe–N–C oxygen reduction catalyst coating in a 0.5 M solution. The passive state was maintained over 24-hour immersion tests, and corrosion resistance improved significantly compared to the active state. Electrochemical and analytical evaluations confirmed a significant enhancement in corrosion resistance, as demonstrated by a ∼99.94 % reduction in passive current density from polarization curve analysis and a ∼99.98 % reduction in corrosion rate from ICP measurements. These results highlight the potential of using non-noble metal catalysts to improve surface corrosion resistance in low-cost stainless steels or materials with reduced corrosion resistance due to mechanical property optimization.
由于对贵金属的依赖，通过阴极改性的钝化在很大程度上仍然是一个理论概念。在这项研究中，我们通过在0.5 M H2SO4溶液中应用一种经济有效的Fe-N-C氧还原催化剂涂层，成功地实现了AISI 409 L钢（一种镍和铬含量降低的合金）的钝化。在24小时浸泡试验中，钝化状态保持不变，抗腐蚀性能较钝化状态显著提高。电化学和分析评估证实了耐腐蚀性的显著增强，极化曲线分析显示无源电流密度降低了~ 99.94%，ICP测量显示腐蚀速率降低了~ 99.98%。这些结果突出了使用非贵金属催化剂提高低成本不锈钢或由于机械性能优化而降低耐蚀性的材料的表面耐蚀性的潜力。
{"title":"Fe–N–C surface treatment as method for enhancing spontaneous passivation of low Ni and Cr stainless steel","authors":"Jaeik Kwak , Sang-Mun Jung , Kyu-Su Kim , Gogwon Choe , Sujung Son , Hyoung Seop Kim , Yong-Tae Kim","doi":"10.1016/j.apsadv.2025.100871","DOIUrl":"10.1016/j.apsadv.2025.100871","url":null,"abstract":"<div><div>Passivation through cathodic modification has largely remained a theoretical concept due to the reliance on noble metals. In this study, we successfully achieved passivation in AISI 409 L steel, an alloy with reduced Ni and Cr content, by applying a cost-effective Fe–N–C oxygen reduction catalyst coating in a 0.5 M <span><math><mrow><msub><mi>H</mi><mn>2</mn></msub><mi>S</mi><msub><mi>O</mi><mn>4</mn></msub></mrow></math></span> solution. The passive state was maintained over 24-hour immersion tests, and corrosion resistance improved significantly compared to the active state. Electrochemical and analytical evaluations confirmed a significant enhancement in corrosion resistance, as demonstrated by a ∼99.94 % reduction in passive current density from polarization curve analysis and a ∼99.98 % reduction in corrosion rate from ICP measurements. These results highlight the potential of using non-noble metal catalysts to improve surface corrosion resistance in low-cost stainless steels or materials with reduced corrosion resistance due to mechanical property optimization.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100871"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145333483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-10-06DOI: 10.1016/j.apsadv.2025.100866
Nabeel Ahmad , Erfan Maleki , Paul R. Gradl , Shuai Shao , Nima Shamsaei
This study examined the influence of ten different surface treatments on the surface texture and fatigue performance of laser powder bed fused HAYNES® 282. A range of surface treatments, which included mechanical (i.e., abrasive flow machining, machining, ceramic shot peening, steel shot peening, and wet blasting or vapormatt) and chemical treatments (i.e., dry electropolishing, electrochemical polishing (ECP), and chemical milling), as well as laser polishing (LP) and a hybrid chemical mechanical polishing treatment, was applied. X-ray computed tomography and focus variation microscopy were used to characterize the surface texture, while scanning electron microscopy was employed to analyze near-surface microstructures as well as fracture surfaces. Fully reversed strain-controlled fatigue testing was performed at four different strain amplitudes of 0.005, 0.004, 0.003, and 0.0025 mm/mm. The results revealed a notable improvement in fatigue lives after mechanical treatments, especially at lower strain amplitudes (i.e., ≤0.003 mm/mm), which was ascribed to the combined effects of improved surface finish and presence of compressive residual stresses resulting from severe plastic deformation at the surface. Among chemical and hybrid treatments, only ECP showed slight improvement in fatigue lives, mainly at lower strain amplitudes, which was attributed to the improved surface finish. On the other hand, LP did not improve fatigue lives due to induced tensile residual stresses, which suppressed any positive effects from the improved surface finish.
{"title":"Understanding the influence of different surface treatments on surface texture and fatigue behavior of L-PBF HAYNES® 282","authors":"Nabeel Ahmad , Erfan Maleki , Paul R. Gradl , Shuai Shao , Nima Shamsaei","doi":"10.1016/j.apsadv.2025.100866","DOIUrl":"10.1016/j.apsadv.2025.100866","url":null,"abstract":"<div><div>This study examined the influence of ten different surface treatments on the surface texture and fatigue performance of laser powder bed fused HAYNES® 282. A range of surface treatments, which included mechanical (i.e., abrasive flow machining, machining, ceramic shot peening, steel shot peening, and wet blasting or vapormatt) and chemical treatments (i.e., dry electropolishing, electrochemical polishing (ECP), and chemical milling), as well as laser polishing (LP) and a hybrid chemical mechanical polishing treatment, was applied. X-ray computed tomography and focus variation microscopy were used to characterize the surface texture, while scanning electron microscopy was employed to analyze near-surface microstructures as well as fracture surfaces. Fully reversed strain-controlled fatigue testing was performed at four different strain amplitudes of 0.005, 0.004, 0.003, and 0.0025 mm/mm. The results revealed a notable improvement in fatigue lives after mechanical treatments, especially at lower strain amplitudes (i.e., ≤0.003 mm/mm), which was ascribed to the combined effects of improved surface finish and presence of compressive residual stresses resulting from severe plastic deformation at the surface. Among chemical and hybrid treatments, only ECP showed slight improvement in fatigue lives, mainly at lower strain amplitudes, which was attributed to the improved surface finish. On the other hand, LP did not improve fatigue lives due to induced tensile residual stresses, which suppressed any positive effects from the improved surface finish.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100866"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145268943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-09-24DOI: 10.1016/j.apsadv.2025.100854
Mahboobeh Zargazi , Davoud Khademi , Mohammad Chahkandi , Abbas Amini , Seyed Esmaeil Shakib
Titanium nitride (TiN) is recognized for enhancing semiconductor photocatalytic activity due to its plasmonic properties, similar to those of gold and silver nanoparticles. Changing the stoichiometry of TiN enhances free carrier density, resulting in metallic characteristics and optical properties resembling gold in the visible spectrum. New Ti/TiOxNy thin films were synthesized with the aid of the Arc-PVD technique under some conditions, including low temperatures and various concentrations of N2 gas. Under zero and maximum amounts of N2 gas, nonstoichiometric and highly conductive N-rich phases of TiN were created, respectively. A TiO2 semiconductor interlayer was specifically coated on a Ti substrate which served both as a co-catalyst layer and as a means to reduce residual stress in the TiN film. Our results demonstrate that the defects and resistance to oxidation in the TiN structure, dependent on the N2 input, may significantly influence the orientation of stable crystal facet ( [111]) and the excitation of plasmonic-photonic hybrid modes. The highest photocurrent was recorded at about 8.2 mA cm‒2 at 1.4 V vs. RHE for gold-colored Ti/TiOxNy oriented along [111] facet, which is 4.3 and 54.6 times more than samples adjusted along [110] and [001] facets, respectively. The employed PVD method at low temperatures as a strong designing technique for tailoring the metal-semiconductor interface simplifies the creation of highly activated photoelectrodes within the water-splitting performance. This applicable technique brings interesting eco-friendly benefits, including energy efficiency, low environmental footprint, and optimized material utilization, in accordance with green chemistry principles.
氮化钛（TiN）由于其等离子体性质（类似于金和银纳米粒子）而被认为可以增强半导体光催化活性。改变TiN的化学计量增加了自由载流子密度，导致在可见光谱中具有类似金的金属特征和光学性质。在低温和不同浓度的N2气体条件下，利用电弧- pvd技术合成了新型Ti/TiOxNy薄膜。在氮气量为零和最大的条件下，TiN的非化学计量相和高导电性富n相分别被生成。在Ti衬底上专门涂覆了一层TiO2半导体中间层，该中间层既可以作为助催化剂层，又可以作为减少TiN薄膜中残余应力的手段。我们的研究结果表明，依赖于N2输入的TiN结构中的缺陷和抗氧化性可能会显著影响稳定晶面的取向（[111]）和等离子体-光子混合模式的激发。在1.4 V相对于RHE下，沿[111]面取向的金色Ti/TiOxNy的最高光电流约为8.2 mA cm-2，分别是沿[110]和[001]面取向的样品的4.3倍和54.6倍。低温下采用PVD方法作为一种强大的设计技术来定制金属-半导体界面，简化了在水分解性能下高活化光电极的创建。这项适用的技术带来了有趣的生态效益，包括能源效率、低环境足迹和优化材料利用，符合绿色化学原理。
{"title":"Ti/TiOxNy thin films as highly efficient photoelectrode via engineered interfacial facet on plasmonic schottky barriers","authors":"Mahboobeh Zargazi , Davoud Khademi , Mohammad Chahkandi , Abbas Amini , Seyed Esmaeil Shakib","doi":"10.1016/j.apsadv.2025.100854","DOIUrl":"10.1016/j.apsadv.2025.100854","url":null,"abstract":"<div><div>Titanium nitride (TiN) is recognized for enhancing semiconductor photocatalytic activity due to its plasmonic properties, similar to those of gold and silver nanoparticles. Changing the stoichiometry of TiN enhances free carrier density, resulting in metallic characteristics and optical properties resembling gold in the visible spectrum. New Ti/TiO<sub>x</sub>N<sub>y</sub> thin films were synthesized with the aid of the Arc-PVD technique under some conditions, including low temperatures and various concentrations of N<sub>2</sub> gas. Under zero and maximum amounts of N<sub>2</sub> gas, nonstoichiometric and highly conductive N-rich phases of TiN were created, respectively. A TiO<sub>2</sub> semiconductor interlayer was specifically coated on a Ti substrate which served both as a co-catalyst layer and as a means to reduce residual stress in the TiN film. Our results demonstrate that the defects and resistance to oxidation in the TiN structure, dependent on the N<sub>2</sub> input, may significantly influence the orientation of stable crystal facet ( [111]) and the excitation of plasmonic-photonic hybrid modes. The highest photocurrent was recorded at about 8.2 mA cm<sup>‒2</sup> at 1.4 V vs. RHE for gold-colored Ti/TiO<sub>x</sub>N<sub>y</sub> oriented along [111] facet, which is 4.3 and 54.6 times more than samples adjusted along [110] and [001] facets, respectively. The employed PVD method at low temperatures as a strong designing technique for tailoring the metal-semiconductor interface simplifies the creation of highly activated photoelectrodes within the water-splitting performance. This applicable technique brings interesting eco-friendly benefits, including energy efficiency, low environmental footprint, and optimized material utilization, in accordance with green chemistry principles.</div></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":"30 ","pages":"Article 100854"},"PeriodicalIF":8.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145159540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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