X-ray photoelectron spectroscopy (XPS) is widely used to determine the composition of elements and oxygen-containing functional groups. Accurate determination of core-electron binding energies (CEBEs) is essential for identifying the types and contents of oxygen-functional groups present on the surface of coal. The △SCF method has been carried out on CEBEs for an extensive series of oxygen-containing organic systems encompassing the most common functionalities. The polymers for which experimental values are available for comparison demonstrate the adequacy of the treatment for describing CEBEs for the O1s core level. Therefore, a sound basis is provided for the discussion of CEBEs (O1s) for functionalities for which experimental values are not accurate or available, such as carbonyl, carboxyl, and peroxide. The results are applied to the XPS study of oxidized coal. The change law of peroxide and oxygen-containing functional groups was discussed. The calculation method and results in this paper can provide a guide for readers to use XPS to study the oxidation of coal surfaces.
{"title":"Characterization of peroxide on coal surface: A combined △SCF and XPS study","authors":"Hao Liu, Zenghua Li","doi":"10.1002/sia.7281","DOIUrl":"https://doi.org/10.1002/sia.7281","url":null,"abstract":"X-ray photoelectron spectroscopy (XPS) is widely used to determine the composition of elements and oxygen-containing functional groups. Accurate determination of core-electron binding energies (CEBEs) is essential for identifying the types and contents of oxygen-functional groups present on the surface of coal. The △SCF method has been carried out on CEBEs for an extensive series of oxygen-containing organic systems encompassing the most common functionalities. The polymers for which experimental values are available for comparison demonstrate the adequacy of the treatment for describing CEBEs for the O1s core level. Therefore, a sound basis is provided for the discussion of CEBEs (O1s) for functionalities for which experimental values are not accurate or available, such as carbonyl, carboxyl, and peroxide. The results are applied to the XPS study of oxidized coal. The change law of peroxide and oxygen-containing functional groups was discussed. The calculation method and results in this paper can provide a guide for readers to use XPS to study the oxidation of coal surfaces.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"106 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139079475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pascal Bargiela, Vincent Fernandez, William Ravisy, David Morgan, Mireille Richard-Plouet, Neal Fairley, Jonas Baltrusaitis
It is common practice to describe the coordination of metal atoms in a binding configuration with their nearest neighbors in terms of oxidation state, a measure by which the number of electrons redistributed between atoms forming chemical bonds. In XPS terms, change to an oxidation state is commonly inferred by correlating photoemission signal with binding energy. The assumption, when classifying photoemission signals into distinct spectral shapes, is that a distribution of intensities shifted to lower binding energy is evidence of a reduction in oxidation state. In this Insight note, we raise the prospect that changes in photoemission peak shape may occur without obvious changes, determined by XPS in stoichiometry for a material. It is well known that TiO2 measured by XPS yields reproducible Ti 2p photoemission peaks. However, on exposing TiO2 to ion beams, Ti 2p photoemission evolves to complex distributions in intensity, which are particularly difficult to analyze by traditional fitting of bell-shaped curves to these data. For these reasons, in this Insight note, a thin film of TiO2 deposited on a silicon substrate is chosen for analysis by XPS and linear algebraic techniques. Alterations in spectral shapes created from modified TiO2, which might be interpreted as the change in oxidation state, are assessed in terms of relative proportions of titanium to oxygen. It is found through detailed analysis of spectra that quantification by XPS, using procedures routinely used in practice, is not in accord with the typical interpretations of photoemission shapes. The data processing methods used and results presented in this work are of particular relevance to elucidating fundamental phenomena governing the surface evolution of materials-enabled energy processes where cyclic/non-steady usage changes the nature of bonding, especially in the presence of contaminants.
{"title":"Surface Analysis Insight Note: Observations relating to photoemission peak shapes, oxidation state, and chemistry of titanium oxide films","authors":"Pascal Bargiela, Vincent Fernandez, William Ravisy, David Morgan, Mireille Richard-Plouet, Neal Fairley, Jonas Baltrusaitis","doi":"10.1002/sia.7283","DOIUrl":"https://doi.org/10.1002/sia.7283","url":null,"abstract":"It is common practice to describe the coordination of metal atoms in a binding configuration with their nearest neighbors in terms of oxidation state, a measure by which the number of electrons redistributed between atoms forming chemical bonds. In XPS terms, change to an oxidation state is commonly inferred by correlating photoemission signal with binding energy. The assumption, when classifying photoemission signals into distinct spectral shapes, is that a distribution of intensities shifted to lower binding energy is evidence of a reduction in oxidation state. In this <i>Insight</i> note, we raise the prospect that changes in photoemission peak shape may occur without obvious changes, determined by XPS in stoichiometry for a material. It is well known that TiO<sub>2</sub> measured by XPS yields reproducible Ti 2p photoemission peaks. However, on exposing TiO<sub>2</sub> to ion beams, Ti 2p photoemission evolves to complex distributions in intensity, which are particularly difficult to analyze by traditional fitting of bell-shaped curves to these data. For these reasons, in this <i>Insight</i> note, a thin film of TiO<sub>2</sub> deposited on a silicon substrate is chosen for analysis by XPS and linear algebraic techniques. Alterations in spectral shapes created from modified TiO<sub>2</sub>, which might be interpreted as the change in oxidation state, are assessed in terms of relative proportions of titanium to oxygen. It is found through detailed analysis of spectra that quantification by XPS, using procedures routinely used in practice, is not in accord with the typical interpretations of photoemission shapes. The data processing methods used and results presented in this work are of particular relevance to elucidating fundamental phenomena governing the surface evolution of materials-enabled energy processes where cyclic/non-steady usage changes the nature of bonding, especially in the presence of contaminants.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"18 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139067080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mona H. Gomaa, Ahmed Ibrahim, Kh. El-Sayed, Z. Abdel Hamid
This article clarifies the thin layer deposition of superhydrophobic coating using eco-friendly polymer (polyaniline [PANI]) incorporated with TiO2 and ZnO nanoparticles on indium tin oxide substrate. Using the cyclic voltammetry method, in situ polymerization of PANI incorporated with hybrid (TiO2–ZnO) was accomplished. The morphology and hydrophobicity of electro-deposited films were examined; the impact of deposition cycles was also investigated. The morphological structure was studied using field-emission scanning electron microscopy and high-resolution transmission electron microscopy. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analysis proved the incorporation of nanoparticles into the composite matrix. Additionally, the water contact angle of the PANI composite was found to be 150.4°, and the findings reflected that (TiO2–ZnO) nanoparticles were significantly implicated in enhancing this superhydrophobicity. The surface roughness of the PANI matrix was increased when TiO2 and ZnO are added, as was shown by atomic force microscope investigation.
本文阐明了在铟锡氧化物基底上使用与 TiO2 和 ZnO 纳米粒子结合的环保聚合物（聚苯胺 [PANI]）薄层沉积超疏水涂层的方法。利用循环伏安法，完成了 PANI 与杂化物（TiO2-ZnO）的原位聚合。研究了电沉积薄膜的形态和疏水性，并探讨了沉积周期的影响。使用场发射扫描电子显微镜和高分辨率透射电子显微镜对形态结构进行了研究。X 射线光电子能谱和傅立叶变换红外光谱分析证明了纳米颗粒与复合基质的结合。此外，还发现 PANI 复合材料的水接触角为 150.4°，研究结果表明（TiO2-ZnO）纳米粒子在增强这种超疏水性能方面发挥了重要作用。原子力显微镜研究表明，加入 TiO2 和 ZnO 后，PANI 基体的表面粗糙度增加。
{"title":"Boosting the hydrophobicity of eco-friendly polyaniline coating using TiO2 and ZnO nanoparticles","authors":"Mona H. Gomaa, Ahmed Ibrahim, Kh. El-Sayed, Z. Abdel Hamid","doi":"10.1002/sia.7280","DOIUrl":"https://doi.org/10.1002/sia.7280","url":null,"abstract":"This article clarifies the thin layer deposition of superhydrophobic coating using eco-friendly polymer (polyaniline [PANI]) incorporated with TiO<sub>2</sub> and ZnO nanoparticles on indium tin oxide substrate. Using the cyclic voltammetry method, in situ polymerization of PANI incorporated with hybrid (TiO<sub>2</sub>–ZnO) was accomplished. The morphology and hydrophobicity of electro-deposited films were examined; the impact of deposition cycles was also investigated. The morphological structure was studied using field-emission scanning electron microscopy and high-resolution transmission electron microscopy. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analysis proved the incorporation of nanoparticles into the composite matrix. Additionally, the water contact angle of the PANI composite was found to be 150.4°, and the findings reflected that (TiO<sub>2</sub>–ZnO) nanoparticles were significantly implicated in enhancing this superhydrophobicity. The surface roughness of the PANI matrix was increased when TiO<sub>2</sub> and ZnO are added, as was shown by atomic force microscope investigation.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"26 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139055344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Claudiu Colbea, Milivoj Plodinec, Marc Willinger, Jeroen A. van Bokhoven, Luca Artiglia
In this work, we present a recent advancement in high-temperature instrumentation in the form of a heating stage that enables studies to be performed in the temperature range of 20–1250°C under high-vacuum, millibar, and atmospheric pressure conditions (10−7–1000 mbar). The newly developed laser-based heating solution is described in detail. Its functionality is highlighted in this study in the form of a heating stage compatible with in situ ambient pressure X-ray photoelectron spectroscopy (APXPS). The proof-of-concept experiment presented in this work involves a polycrystalline nickel foil, a material of considerable interest in the scientific field due to its applications in catalysis, batteries, and electrochemistry. Owing to the intrinsic oxophilicity of nickel, the experiment targeted the high-temperature oxidation (600°C) and reduction (1050°C) that serves interest as both, a pretreatment and preparation method, and as a model reaction for the redox behavior of non-noble materials under reactive conditions. Complete and reversible surface state changes from metallic to oxide and back to metallic were achieved through stepwise variations of the gas phase composition and temperature. The heating stage showed high stability at high temperatures under reducing and oxidizing conditions, demonstrating the benefit of this design. The in situ characterization possibilities enabled by this stage will allow a better understanding of the inherent properties of materials that function at high temperatures, leading to their optimization in relevant application fields such as catalysis, materials, and surface science.
在这项工作中，我们介绍了高温仪器领域的最新进展，这种加热台可以在高真空、毫巴和大气压力条件（10-7-1000 毫巴）下，在 20-1250°C 的温度范围内进行研究。本文详细介绍了新开发的激光加热解决方案。在本研究中，它的功能以与原位常压 X 射线光电子能谱（APXPS）兼容的加热阶段的形式得到了强调。由于多晶镍箔在催化、电池和电化学方面的应用，它在科学领域备受关注。由于镍的固有亲氧化性，实验以高温氧化（600°C）和还原（1050°C）为目标，这既是一种预处理和制备方法，也是非贵金属材料在反应条件下氧化还原行为的模型反应。通过逐步改变气相成分和温度，实现了从金属到氧化物再到金属的完全可逆的表面状态变化。在还原和氧化条件下，加热阶段在高温下表现出很高的稳定性，证明了这种设计的优势。通过这一阶段的现场表征，可以更好地了解材料在高温下的固有特性，从而在催化、材料和表面科学等相关应用领域对其进行优化。
{"title":"Development of a compact laser-based heating stage for in situ spectroscopic characterizations","authors":"Claudiu Colbea, Milivoj Plodinec, Marc Willinger, Jeroen A. van Bokhoven, Luca Artiglia","doi":"10.1002/sia.7278","DOIUrl":"https://doi.org/10.1002/sia.7278","url":null,"abstract":"In this work, we present a recent advancement in high-temperature instrumentation in the form of a heating stage that enables studies to be performed in the temperature range of 20–1250°C under high-vacuum, millibar, and atmospheric pressure conditions (10<sup>−7</sup>–1000 mbar). The newly developed laser-based heating solution is described in detail. Its functionality is highlighted in this study in the form of a heating stage compatible with in situ ambient pressure X-ray photoelectron spectroscopy (APXPS). The proof-of-concept experiment presented in this work involves a polycrystalline nickel foil, a material of considerable interest in the scientific field due to its applications in catalysis, batteries, and electrochemistry. Owing to the intrinsic oxophilicity of nickel, the experiment targeted the high-temperature oxidation (600°C) and reduction (1050°C) that serves interest as both, a pretreatment and preparation method, and as a model reaction for the redox behavior of non-noble materials under reactive conditions. Complete and reversible surface state changes from metallic to oxide and back to metallic were achieved through stepwise variations of the gas phase composition and temperature. The heating stage showed high stability at high temperatures under reducing and oxidizing conditions, demonstrating the benefit of this design. The in situ characterization possibilities enabled by this stage will allow a better understanding of the inherent properties of materials that function at high temperatures, leading to their optimization in relevant application fields such as catalysis, materials, and surface science.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"11 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139067077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Claes-Olof A. Olsson, Roland Hauert, Anna Neus Igual-Muñoz, Stefano Mischler, Patrik Schmutz
Passive films on the superaustenitic stainless steel 1.4652 were studied using angular resolved hard X-ray photo-electron spectroscopy (HAXPES), which provides an increased information depth compared to conventional X-ray photo-electron spectroscopy (XPS). Elemental depth profiles in the oxide as well as gradients in the underlying metal were established using a dedicated algorithm. The utility was exemplified for three different conditions of film formation: (i) as polished and as polarized to the high passive end in (ii) 1 M H2SO4 and (iii) 1 M NaOH. The use of a superaustenitic material ascertained that metal signals from the main contributors to film formation: Fe, Cr, Ni, and Mo remained above the detection limit throughout the data set. With the dual-source technique (XPS, HAXPES), it was possible to investigate metal gradients underneath the passive film. For polarizations in an acidic environment, a metallic nickel enrichment of the order of 5 Å was found. For a corresponding polarization in an alkaline environment, the metal region closest to the oxide/metal interface was enriched in iron, followed by concentration gradients down to about 50 Å into the metal.
使用角度分辨硬 X 射线光电子能谱 (HAXPES) 对超奥氏体不锈钢 1.4652 上的被动薄膜进行了研究，与传统的 X 射线光电子能谱 (XPS) 相比，HAXPES 提供了更高的信息深度。使用专用算法建立了氧化物中的元素深度剖面以及底层金属中的梯度。在三种不同的成膜条件下对其实用性进行了示范：(i) 在 (ii) 1 M H2SO4 和 (iii) 1 M NaOH 中抛光和极化至高被动端。超奥氏体材料的使用确定了薄膜形成的主要金属信号：在整个数据集中，铁、铬、镍和钼的金属信号始终高于检测限。利用双源技术（XPS、HAXPES），可以研究被动膜下的金属梯度。对于酸性环境中的极化，发现金属镍富集了 5 Å。在碱性环境中进行相应的极化时，最靠近氧化物/金属界面的金属区域富含铁，其次是向下约 50 Å 的金属浓度梯度。
{"title":"Revealing cation and metal gradients in and underneath passive films of the stainless steel 1.4652 in acidic and alkaline electrolytes with angular resolved dual energy X-ray photo-electron spectroscopy","authors":"Claes-Olof A. Olsson, Roland Hauert, Anna Neus Igual-Muñoz, Stefano Mischler, Patrik Schmutz","doi":"10.1002/sia.7275","DOIUrl":"https://doi.org/10.1002/sia.7275","url":null,"abstract":"Passive films on the superaustenitic stainless steel 1.4652 were studied using angular resolved hard X-ray photo-electron spectroscopy (HAXPES), which provides an increased information depth compared to conventional X-ray photo-electron spectroscopy (XPS). Elemental depth profiles in the oxide as well as gradients in the underlying metal were established using a dedicated algorithm. The utility was exemplified for three different conditions of film formation: (i) as polished and as polarized to the high passive end in (ii) 1 M H<sub>2</sub>SO<sub>4</sub> and (iii) 1 M NaOH. The use of a superaustenitic material ascertained that metal signals from the main contributors to film formation: Fe, Cr, Ni, and Mo remained above the detection limit throughout the data set. With the dual-source technique (XPS, HAXPES), it was possible to investigate metal gradients underneath the passive film. For polarizations in an acidic environment, a metallic nickel enrichment of the order of 5 Å was found. For a corresponding polarization in an alkaline environment, the metal region closest to the oxide/metal interface was enriched in iron, followed by concentration gradients down to about 50 Å into the metal.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"66 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138572652","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sheng He, Yang Li, Li-Guang Wu, Rui-Ping Liu, Dong-Fa Guo, Zi-Ying Li, Xian-Hua Li
Cassiterite is the principal ore mineral for tin, and its oxygen isotope is a promising proxy to trace the origin and evolution of ore-forming fluids, which requires precise and accurate oxygen isotopic analysis. Secondary ion mass spectrometry (SIMS) is a powerful tool for oxygen isotope analysis, especially when samples bear complicated textures, but matrix-matched reference materials are critical for accurate microanalysis. The only available matrix-matched reference material for cassiterite oxygen isotope analysis is Yongde-Cst, and more reference materials are required. Here, we report Piaotang-Cst as a potential working reference material for cassiterite oxygen isotope microanalysis. Our extensive SIMS microanalysis confirmed that Piaotang-Cst is relatively homogeneous, with an average two standard deviations (2SD) of 0.49‰ (n = 626). The δ18OVSMOW value of Piaotang-Cst is 5.33 ± 0.07‰ (2SD, n = 5) as determined by a conventional fluorination isotope ratio mass spectrometer. We also demonstrated that there is no measurable matrix effect caused by the variable contents of trace elements for cassiterite oxygen isotope microanalysis. We proposed that the Piaotang-Cst can be used as a working reference material for monitoring the external reproducibility and accuracy of SIMS analysis.
{"title":"A new working reference material for cassiterite oxygen isotope microanalysis","authors":"Sheng He, Yang Li, Li-Guang Wu, Rui-Ping Liu, Dong-Fa Guo, Zi-Ying Li, Xian-Hua Li","doi":"10.1002/sia.7279","DOIUrl":"https://doi.org/10.1002/sia.7279","url":null,"abstract":"Cassiterite is the principal ore mineral for tin, and its oxygen isotope is a promising proxy to trace the origin and evolution of ore-forming fluids, which requires precise and accurate oxygen isotopic analysis. Secondary ion mass spectrometry (SIMS) is a powerful tool for oxygen isotope analysis, especially when samples bear complicated textures, but matrix-matched reference materials are critical for accurate microanalysis. The only available matrix-matched reference material for cassiterite oxygen isotope analysis is Yongde-Cst, and more reference materials are required. Here, we report Piaotang-Cst as a potential working reference material for cassiterite oxygen isotope microanalysis. Our extensive SIMS microanalysis confirmed that Piaotang-Cst is relatively homogeneous, with an average two standard deviations (2SD) of 0.49‰ (<i>n</i> = 626). The δ<sup>18</sup>O<sub>VSMOW</sub> value of Piaotang-Cst is 5.33 ± 0.07‰ (2SD, <i>n</i> = 5) as determined by a conventional fluorination isotope ratio mass spectrometer. We also demonstrated that there is no measurable matrix effect caused by the variable contents of trace elements for cassiterite oxygen isotope microanalysis. We proposed that the Piaotang-Cst can be used as a working reference material for monitoring the external reproducibility and accuracy of SIMS analysis.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"48 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138569397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Claire Guyot, Jean-Paul Barnes, Olivier Renault, Tony Maindron
With the development in the early 2000s of new cluster ion sputtering sources, a reliable analysis of organic multilayers and interfaces has become possible. Nowadays, time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) depth profiling are routinely used to investigate organic stacks. However, analysis beams can cause bond scission or beam-induced degradations that accumulate in buried layers. We developed a correlative protocol that minimises damages related to analysis beams. It uses a shallow angle bevel crater fabricated inside the ToF-SIMS analysis chamber. With this preparation method, the in-depth information is displayed over the surface of the bevel crater. XPS profiles and high-resolution spectra paired with ToF-SIMS images enable an easy identification of the organic layers and complete understanding of their chemistry. The reduction of beam-induced degradation is achieved by minimising the acquisition times, therefore beam exposure on materials. Finally, an important advantage of this preparation method is that the analysis can be performed on exactly the same spot by multiple techniques. Several ToF-SIMS and XPS acquisitions can be carried out with various parameters (investigation of backscattered Arn+ cluster ion fragments, tandem MS imaging…) as well as analysis with other techniques that possess limitations in spatial resolution and/or inaptitude to probe buried layers such as Raman or AFM.
随着 21 世纪初新型簇离子溅射源的开发，对有机多层膜和界面进行可靠分析成为可能。如今，飞行时间二次离子质谱法（ToF-SIMS）和 X 射线光电子能谱法（XPS）深度剖面分析已成为研究有机叠层的常规方法。然而，分析光束会导致键裂或光束诱导的降解，从而在埋层中累积。我们开发了一种相关协议，可最大限度地减少与分析光束有关的损害。它使用在 ToF-SIMS 分析室内部制作的浅角斜面凹坑。利用这种制备方法，可以在斜面陨石坑表面显示深度信息。XPS 剖面图和高分辨率光谱与 ToF-SIMS 图像相配合，可轻松识别有机层并全面了解其化学性质。通过最大限度地缩短采集时间，从而减少光束对材料的照射，减少了光束引起的降解。最后，这种制备方法的一个重要优势是可以通过多种技术对完全相同的点进行分析。可以使用各种参数进行多次 ToF-SIMS 和 XPS 采集（研究反向散射 Arn+ 簇离子碎片、串联 MS 成像......），也可以使用其他技术进行分析，这些技术在空间分辨率方面存在局限性，并且/或者不适合探测埋藏层，例如拉曼或原子力显微镜。
{"title":"Time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy protocol for the analysis of organic multilayers","authors":"Claire Guyot, Jean-Paul Barnes, Olivier Renault, Tony Maindron","doi":"10.1002/sia.7277","DOIUrl":"https://doi.org/10.1002/sia.7277","url":null,"abstract":"With the development in the early 2000s of new cluster ion sputtering sources, a reliable analysis of organic multilayers and interfaces has become possible. Nowadays, time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) depth profiling are routinely used to investigate organic stacks. However, analysis beams can cause bond scission or beam-induced degradations that accumulate in buried layers. We developed a correlative protocol that minimises damages related to analysis beams. It uses a shallow angle bevel crater fabricated inside the ToF-SIMS analysis chamber. With this preparation method, the in-depth information is displayed over the surface of the bevel crater. XPS profiles and high-resolution spectra paired with ToF-SIMS images enable an easy identification of the organic layers and complete understanding of their chemistry. The reduction of beam-induced degradation is achieved by minimising the acquisition times, therefore beam exposure on materials. Finally, an important advantage of this preparation method is that the analysis can be performed on exactly the same spot by multiple techniques. Several ToF-SIMS and XPS acquisitions can be carried out with various parameters (investigation of backscattered Ar<sub>n</sub><sup>+</sup> cluster ion fragments, tandem MS imaging…) as well as analysis with other techniques that possess limitations in spatial resolution and/or inaptitude to probe buried layers such as Raman or AFM.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"108 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138568695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, the effect of annealing on the structural, surface morphology and chemical structure of titanium suboxide (TiO2-x) thin films has been investigated. TiO2-x films had been grown on Si substrates by DC-magnetron sputtering with different sputter powers (75 and 100 W) at room temperature (RT) and 200°C substrate temperature (ST). The films were subsequently annealed for 1 h at 300, 400 and 500°C in vacuum. The impact of ST, post-annealing and sputter power on crystallinity, surface morphology and chemical state of the films were studied. Grazing incidence X-ray diffraction (GIXRD) data revealed that the films were amorphous or exhibited a very low crystalline structure while deposited at RT and even after annealing. Moreover, the films showed crystallinity while deposited at ST and exhibited an anatase-rutile (A-R) mix phase from anatase (A) annealed at 300°C (75 W at ST). X-ray reflectivity (XRR) data showed that the mass density of the films increased with the annealing temperature. Images obtained using atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) revealed that post-annealing increased the surface roughness of the films. X-ray photoelectron spectroscopy (XPS) analysis indicated the films were sub stoichiometric. It was also indicated that Ti was in the form of Ti4+ and Ti3+ states in all films, and the proportion of Ti4+ slightly increased after post-annealing at 500°C. The findings showed that post-annealing, ST and sputtering power can all affect the growth of TiO2-x films.
{"title":"Effect of substrate temperature and annealing on the growth of TiO2-x thin films deposited by using DC-magnetron sputtering technique","authors":"Swapan Jana, Anil Krishna Debnath, Veerender Putta, Jitendra Bahadur, Jugal Kishor, Anil Kumar Chauhan, Debarati Bhattacharya","doi":"10.1002/sia.7274","DOIUrl":"https://doi.org/10.1002/sia.7274","url":null,"abstract":"In this study, the effect of annealing on the structural, surface morphology and chemical structure of titanium suboxide (TiO<sub>2-x</sub>) thin films has been investigated. TiO<sub>2-x</sub> films had been grown on Si substrates by DC-magnetron sputtering with different sputter powers (75 and 100 W) at room temperature (RT) and 200°C substrate temperature (ST). The films were subsequently annealed for 1 h at 300, 400 and 500°C in vacuum. The impact of ST, post-annealing and sputter power on crystallinity, surface morphology and chemical state of the films were studied. Grazing incidence X-ray diffraction (GIXRD) data revealed that the films were amorphous or exhibited a very low crystalline structure while deposited at RT and even after annealing. Moreover, the films showed crystallinity while deposited at ST and exhibited an anatase-rutile (A-R) mix phase from anatase (A) annealed at 300°C (75 W at ST). X-ray reflectivity (XRR) data showed that the mass density of the films increased with the annealing temperature. Images obtained using atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) revealed that post-annealing increased the surface roughness of the films. X-ray photoelectron spectroscopy (XPS) analysis indicated the films were sub stoichiometric. It was also indicated that Ti was in the form of Ti<sup>4+</sup> and Ti<sup>3+</sup> states in all films, and the proportion of Ti<sup>4+</sup> slightly increased after post-annealing at 500°C. The findings showed that post-annealing, ST and sputtering power can all affect the growth of TiO<sub>2-x</sub> films.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"19 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138569330","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Adventitious carbon contaminations are not only omnipresent and used for charge referencing of XPS spectra but also can alter the apparent presence of the element peaks that span over the large spectral window of binding energies. This Insight note describes the effect of an adventitious contamination layer on Pt and presents, in brief, the approach whereby the component spectra are derived for ion beam cleaned Pt samples that can then utilize linear mathematics to peak fit said spectra thus quantifying the amount of each component including that assigned to the contamination itself of Pt metal.
{"title":"Surface analysis insight note: Illustrating the effect of adventitious contamination on Pt photoemission peak intensities","authors":"Neal Fairley, Pascal Bargiela, Jonas Baltrusaitis","doi":"10.1002/sia.7276","DOIUrl":"https://doi.org/10.1002/sia.7276","url":null,"abstract":"Adventitious carbon contaminations are not only omnipresent and used for charge referencing of XPS spectra but also can alter the apparent presence of the element peaks that span over the large spectral window of binding energies. This <i>Insight</i> note describes the effect of an adventitious contamination layer on Pt and presents, in brief, the approach whereby the component spectra are derived for ion beam cleaned Pt samples that can then utilize linear mathematics to peak fit said spectra thus quantifying the amount of each component including that assigned to the contamination itself of Pt metal.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"4 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138536007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Analysis of the spectrum of inelastically scattered electrons in XPS has been used for decades to determine the structure of materials on the nanoscale. Using the higher photon energies available in HAXPES, the method was recently shown to determine structures rather accurately with a more than 100 nm probing depth. In this paper, these HAXPES applications are briefly reviewed. Only two parameters are required for the analysis, namely, the inelastic mean free path and the cross section for inelastic electron scattering. We also discuss in detail how these parameters are best selected.
{"title":"HAXPES: Inelastic background for characterization of nanostructured materials","authors":"Sven Tougaard","doi":"10.1002/sia.7273","DOIUrl":"https://doi.org/10.1002/sia.7273","url":null,"abstract":"Analysis of the spectrum of inelastically scattered electrons in XPS has been used for decades to determine the structure of materials on the nanoscale. Using the higher photon energies available in HAXPES, the method was recently shown to determine structures rather accurately with a more than 100 nm probing depth. In this paper, these HAXPES applications are briefly reviewed. Only two parameters are required for the analysis, namely, the inelastic mean free path and the cross section for inelastic electron scattering. We also discuss in detail how these parameters are best selected.","PeriodicalId":22062,"journal":{"name":"Surface and Interface Analysis","volume":"56 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138534738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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