新型碳材料表面元素及化学态高分辨XPS定量研究*

X射线光电子能谱(XPS)在科学研究中被广泛应用于碳材料表面官能团识别和结构缺陷判定,对表面组成结构识别和性能调控具有重要指导意义。XPS数据分析主观性强、sp²杂化态对应C1s谱峰峰形不对称以及各化学态对应峰位差异相对较小等因素是导致碳材料XPS数据分析难度高的主要原因。本文通过对XPS分析碳材料现状总结了当前新型碳材料XPS数据分析方法的不足(主要包括■化学态对应C1s谱峰峰形不对称峰形、各化学态半峰宽拟合的随意化以及数据的主观化);并结合实际材料通过■化学态谱峰峰形参考化、半峰宽相对限定化以及多数据分析客观化对新型碳材料XPS数据方法进行进一步规范,为XPS应用于新型碳材料表面元素及化学态定量高分辨研究提供理论依据和技术保障。     

X射线光电子能谱仪的开放使用与管理

X射线光电子能谱仪(XPS)是材料表面元素定性和半定量分析的重要手段之一,是表面分析科研工作的必备仪器.为提高测试效率,实施了大型仪器设备开放共享优化,总结了在推动XPS开放过程中管理的经验和体会.     

成像X射线光电子能谱定量分析研究

探索了直接用实验测得的XPS图像强度来做元素或化学态相对定量分析的可能性。以AgCl和Na2S2O3样品为例，实验结果表明：XPS图像强度与成像时间有良好的线性关系，根据图像强度对两种元素或化学态进行相对定量是可能的。     

X光电子能谱分析中光电子峰和俄歇峰的干扰及消除

X光电子能谱(XPS)在分析多元素材料时,光电子峰可能受到其它元素俄歇谱的干扰.在AlKα激发CrZnSi合金样品时,光电子峰Cr2p和俄歇峰ZnLMM相互干扰,而换用双阳极中的MgKα源激发,虽可消除此相互干扰,但样品表面的Cls和Nls又会受到ZnLMM干扰.类似地,AlKα激发的GaN样品中Nls受俄歇峰GaLMM的严重干扰,而换用MgKα源激发时,Cls峰又受到的GaLMM的干扰.交替使用Mg/Al双阳极激发源,可改变XPS分析中的俄歇谱及其背景对光电子峰的干扰位置,并用未受干扰的峰互相校正2组谱图能量位置,以对样品谱峰作出正确的分析.     

X射线光电子能谱在新型催化材料表征中的应用

X射线光电子能谱(XPS)在分析、表征材料尤其是表面组分分析方面有着极大的优势。综述了近5年来XPS在表征及测定新型光催化材料、新型分子筛催化材料、新型电催化材料、新型金属催化材料、新型金属氧化物催化材料以及其他新型催化材料的表面元素组成、原子价态及元素比率等方面的应用,概述了XPS分析测试过程中对环境的真空度要求,以及氧化对样品检测结果的干扰和影响,并就其应用前景提出了展望。     

XPS和TOF—SIMS在硬盘驱动器（HDD）磁头表面微污染分析中的应用

XPS和TOF－SIMS表面分析仪器联用分析磁头臂焊接位表面有机微污染物成分,找出污染物的来源;XPS能够提供污染物中元素组成及价态信息,而TOF－SIMS能够提供其分子信息。试验证明两者联用是分析表面有机微污染物强有力的手段。     

CL-20电子束的X射线光电子能谱-气体质谱原位同步分析技术研究

X射线光电子能谱仪是材料表面元素定性和半定量分析,尤其是元素化学态分析的重要手段之一. X射线光电子能谱仪的分析腔连接质谱仪进行分析,可有效获得样品表面元素变化及气体产物,实现原位同步分析. 基于炸药CL-20在光作用下存在着明显的分解现象,采用X射线光电子能谱-气体质谱同步分析方法(XPS-MS)获得CL-20在电子束作用下的表面元素及气体产物的变化. 试验结果表明,随着辐照时间增加,N、O元素峰峰强迅速下降,同时质谱仪可以有效获得气态产物峰,证实XPS-MS同步分析技术能够有效地实现对固态光降解反应的原位同步追踪.     

原位XPS技术研究碳化铀的表面氧化

采用X射线光电子能谱(XPS)原位分析研究了298 K时烧结UC的清洁表面在O₂气氛中的初始氧化过程. UC试样清洁表面通过氩离子束长时间溅射获取. 初始反应各阶段U4f, O1s和C1s芯能级谱的变化显示样品表面的氧化产物为UO₂和自由碳. 当O₂饱和吸附后, UC表面氧化膜的增长呈抛物线型, 氧透过氧化膜的扩散为UC进一步氧化的速率控制步骤. 定量分析表明, 反应过程中U, C原子均未出现明显的表面偏析.     

用XPS法精确测量硅片上超薄氧化硅的厚度

简单介绍了硅片表面超薄(0.3～8nm)氧化硅厚度的XPS测量方法。方法根据XPS测得的元素硅和氧化硅的Si2p谱线强度,使用较简单的厚度分析公式计算。本文还介绍了厚度分析公式中两个关键参数(光电子衰减长度LSiO2和氧化硅纯硅体材料的Si2p电子强度比R0)的理论计算和实验测量方法。此外,文中还介绍了用XPS测量厚度的实验步骤,包括样品方位角和光电子发射角的选择以及XPS数据处理方法。使用上述XPS测量方法,目前对于超薄SiO2的厚度测量不确定度已可达到1%。     

X射线光电子能谱仪的数据采集及预处理技巧研究

X射线光电子能谱(XPS)广泛应用于材料表面分析表征,因XPS分析方法的主观性相对较强,谱图测试及分析水平会对数据分析质量产生很大影响。为获得更好的数据质量,文章根据国际标准和实际测试经验总结出一种通用于不同类型材料表面分析表征的XPS数据采集和预处理分析思路,以方便测试人员能够更加系统的进行数据采集和分析,为材料研发人员提供更加全面的元素组成信息和谱图解析注意事项,从而更有效地助力材料表面分析研究,该方法对科研工作者分析准确度的提高具有重要的理论意义和实际应用价值。     

Non-destructive depth profile analysis using synchrotron radiation excited XPS

We have used synchrotron radiation as excitation source in an X-ray photoelectron spectroscopy (XPS) experiment to analyse surface-near element depth profiles non-dectructively. By tuning the photon energy one can vary the kinetic energy of the photoelectrons and in turn the information depth of the measurement. To quantify the sample geometry (e.g. layer thicknesses) model calculations similar as for angle-resolved XPS (ARXPS) measurements are necessary. We have successfully applied this technique to several samples. We will show how to calculate the relative intensities of the peaks, using photoionization cross sections and an experimentally determined analyzer transmission function and the procedure to quantify the geometry for a model sample: natively oxidized Ta covered by carbon contamination. At Sn-doped indium oxide samples we found a sub-monolayer of segregated Sn at the surface which was expected from previous investigations.     

Quantitative analysis of trace levels of surface contamination by X‐ray photoelectron spectroscopy. Part II: Systematic uncertainties and absolute quantification

We discuss analyses of trace levels of surface contamination using X‐ray photoelectron spectroscopy (XPS). The problem of quantifying common sources of statistical and systematic uncertainties for these measurements is formulated in terms of the needs of extreme ultraviolet lithography, but the results and conclusions are applicable to a broad range of XPS applications. We quantify the systematic uncertainties introduced by particular cases of overlapping peaks on different substrate structures by simulating measured spectra with the National Institute of Standards and Technology Database for the Simulation of Electron Spectra for Surface Analysis (SESSA). One example demonstrates that the relative atomic concentrations of trace elements such as S, P, and halogens on a Ru surface could be dramatically overestimated if the fitting of the overlapping Ru 3d and C 1s peaks excludes the contribution from carbon. We also show how spectra generated by SESSA can be compared with measured spectra to determine absolute amounts of surface impurities on layered samples of the type used for extreme ultraviolet lithography. We provide estimates of the total uncertainty for such measurements by considering the systematic limitations of SESSA and the statistical uncertainties of the measurements. The same procedure can be employed for other multilayered materials. Finally, we describe two approaches for converting XPS detection limits for an elemental impurity in an elemental matrix to the corresponding detection limits for the impurity as a thin film on the surface of the matrix material.     

Composition of lignocellulosic surfaces: comments on the interpretation of XPS spectra

The surface compositions of lignocellulosic materials are critical to their end use performance. X-ray photoelectron spectroscopy (XPS) measures the elemental composition sampling of a very thin surface layer, and has long been used to assess the surface composition of dry lignocellulosic materials. The method is based on the quantification of carbon and oxygen XPS peak sizes and shapes, but care is necessary to minimize the effects of surface contamination and degradation. We review the XPS method, and present a simplified approach to estimate the surface lignin content of extractive-free samples. The approach corrects for surface contamination and degradation by measuring the XPS signal of a cellulose standard under the same conditions as the lignin-containing samples. The method is illustrated using XPS results for a series of extracted softwood kraft pulps.     

An X-ray Photoelectron Spectroscopic Study of the Poly-N-vinylpyrrolidone Desorption from the Surface of a Granulated Carbon Sorbent

The surface of a carbon sorbent modified with poly-N-vinylpyrrolidone was studied by X-ray photoelectron spectroscopy (XPS). The modification involves polymerization of N-vinylpyrrolidone on the carbon sorbent surface to form poly-N-vinylpyrrolidone. The elemental composition of the carbon sorbent surface before and after modification was determined by XPS. The electronic state of atoms of the identified elements on the surface was evaluated. The contact of the modified carbon sorbent with normal saline simulating the biological medium leads to partial removal (desorption) of the polymer from the granulated sample.

     

废轮胎回转窑中试热解炭表面组分XPS分析

以X射线光电子能谱（XPS）对废轮胎回转窑中试热解炭表面组分进行实验分析,研究热解炭本体与表面的异同,热解温度、热解炭粒径的影响。与商用炭黒比较,废轮胎热解炭本体中含有更多的Zn、Si、S、Mg等杂质元素,各组分与热解温度没有大的相关性;热解炭表面在热解过程中形成了一吸附沉积层,表面层中杂元素的质量分数极低;低于500℃时,热解不完全,吸附沉积物较少。热解炭按粒径存在一定分布,粒度<0.074 mm的粉末状热解炭来自表面磨损脱落的粉末,各种杂元素的质量分数很低;Zn元素的相对质量分数随热解炭粒径的减小而减少。对热解炭进行深度剖析发现,吸附层是极薄的,表面层对本体的影响是极小的;定量分析结果表明,以C质量分数为100,则O为4～6,S、N约为1,Zn小于0.6,而商用炭黑中S约为0.3,不含N、Zn。     

Raman Scattering Study on the Influence of E-Beam Bombardment on Si Electron Lens

Microcolumns have a stacked structure composed of an electron emitter, electron lens (source lens), einzel lens, and a deflector manufactured using a micro electro-mechanical system process. The electrons emitted from the tungsten field emitter mostly pass through the aperture holes. However, other electrons fail to pass through because of collisions around the aperture hole. We used Raman scattering measurements and X-ray photoelectron spectroscopy analyses to investigate the influence of electron beam bombardment on a Si electron lens irradiated by acceleration voltages of 0, 20, and 30 keV. We confirmed that the crystallinity was degraded, and carbon-related contamination was detected at the surface and edge of the aperture hole of the Si electron lens after electron bombardment for 24 h. Carbon-related contamination on the surface of the Si electron lens was verified by analyzing the Raman spectra of the carbon-deposited Si substrate using DC sputtering and a carbon rod sample. We report the crystallinity and the origin of the carbon-related contamination of electron Si lenses after electron beam bombardment by non-destructive Raman scattering and XPS analysis methods.     

Development of sample preparation technique to characterize chemical structure of humin by synchrotron-radiation–based X-ray photoelectron spectroscopy

Carbon-binding state of humin (HM, a non-conductive insoluble organo-mineral humic substance) was successfully characterized for the first time by synchrotron-radiation–based X-ray photoelectron spectroscopy (XPS). Four sample preparation techniques—HM on double-sided carbon tape, indium sheet, copper mesh, and in pellet formed from the mixture of HM and copper powder (Cu) at different mixing ratios (1:1, 1:2, and 1:6 v/v)—were compared. The results show that HM samples prepared using the first three methods had significant charge buildup, which made the interpretation of the XPS spectra impossible because of the shifts in the binding energy of C 1s XPS spectra. Pellets of HM:Cu mixture enhanced the electrical conductivity and reduced charge buildup on the sample surface. Pellets prepared with HM:Cu ratio of 1:1 (v/v) provided the minimum charge buildup and high sensitivity with difference in C 1s spectra regardless of the observing position. The C 1s spectra, estimated by the subtraction of the carbon contamination in Cu, showed the resolution of CC (284.0 eV), C C/C H (285.1 eV), C O (286.3 eV), CO (287.3 eV), and OC O (288.3 eV) and three additional peaks of CF (289.3 eV), CF₂ (290.2 eV), and CF₃ (291.4 eV). Soft X-ray absorption spectroscopic (XAS) analysis further proved the existence of fluoride (F 1s) in HM structure. The detection of fluorinated carbon in HM showed a great advancement of XPS compared with other conventional analyses. X-ray with the incident angle of 0° provided the smallest (nearly negligible) energy shift in the C 1s spectra of HM and did not damage the surface of the sample.     

The influence of contamination on compositional imaging of self-assembled monolayers by scanning force microscopy

We prepared patterned self-assembled monolayers (SAMs) consisting of hexadecanethiol (16AT) and ferrocenyldodecanethiol (12FAT). The samples were characterized by scanning force microscopy (SFM), X-ray photoelectron spectroscopy (XPS), electrochemistry and contact angle measurements. Lateral force mode (LFM) of SFM shows image contrast even between surface regions of quite similar hydrophobicity. The 12FAT regions undergo irreversible chemical changes and become electrochemically inactive upon long exposure to the laboratory atmosphere. These chemical changes can be monitored by LFM, XPS, contact angle and electrochemistry. The LFM images of the exposed and contaminated samples show a reversed frictional contrast relative to the LFM images of the fresh samples and to the LFM images of the exposed but ethanol-rinsed sample. XPS and SFM data show that the 12FAT regions show more contamination than the 16AT regions. Based on these observations, the mechanism of the LFM image contrast is discussed and other driving forces, arising not only from differences in hydrophobicity but also from basic material properties such as elasticity, packing and contamination, are suggested.     

Effect of CO on surface oxidation of uranium metal

The surface reactions of uranium metal with carbon monoxide at 25 and 200 °C have been studied by X-ray photoelectron spectroscopy (XPS); respectively. Adsorption of carbon monoxide on the surface layer of uranium metal leads to partial reduction of surface oxide and results in U4f photoelectron peak shifting to the lower binding energy. The content of oxygen in the surface oxide is decreased and O1s/O4f ratio decreases with increasing the exposure of carbon monoxide. The investigation indicates the surface layer of uranium metal has resistance to further oxidation in the atmosphere of carbon monoxide.