X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy，XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis，ESCA）．XPS属表面分析法，它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息，在各种固体材料的基础研究和实际应用中起着重要的作用．文章简要介绍了XPS仪器的工作原理和分析方法，并给出了XPS在科学研究工作中的应用实例．     

X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy, XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis,ESCA）.XPS属表面分析法,它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息,在各种固体材料的基础研究和实际应用中起着重要的作用.文章简要介绍了XPS仪器的工作原理和分析方法,并给出了XPS在科学研究工作中的应用实例.     

Surface depth analysis for fluorinated block copolymer films by X-ray photoelectron spectroscopy using C60 cluster ion beam

X-ray photoelectron spectroscopy (XPS) using fullerene (C₆₀) cluster ion bombardment was applied to films of a fluorinated block copolymer. Spectra so obtained were essentially different from those using Ar ion beam. Structure in the surface region with the depth down to 60 nm drawn on the basis of XPS with C₆₀ beam was essentially the same as the one drawn by the result using dynamic secondary ion mass spectrometry, which is a well-established method for the depth analysis of polymers. This implies that XPS using C₆₀ beam enables one to gain access to the depth analysis of structure in polymer films with the depth range over the analytical depth of conventional XPS, that is, three times inelastic mean-free path of photoelectrons.     

Photoelectron spectroscopy of the valence electronic structure of polymers

Photoelectron spectroscopy has been highly developed as an investigative tool of the bulk and surface chemical and electronic structure of condensed matter during the past 2 decades. The use of soft X-ray sources led to the development of electroq spectroscopy for chemical applications (ESCA),^1,2 which is also known to the physicst as X-ray photoelectron spectroscopy (XPS). These developments were followed by the use of ultraviolet sources for the study of gases³ and the bulk and surface electronic structure of solids.^4,5 Recently, the use of the continuous spectral distribution of synchrotron radiation has had a major impact upon the study of solid surfaces^6,7 and has made the largely historical terminology of XPS (or ESCA) and ultraviolet photoelectron spectroscopy (UPS) somewhat less meaningful. Angle-resolved UPS and XPS (ARUPS and ARXPS) can provide additional information about electronic band structure, surface states, and adsorbates, but are typically applied to the study of the surfaces of ideal single crystals, where crystallographic high-symmetry directions as well as the polarization of the light source can be used to high advantage.⁷ Since polymers are almost never single crystals, the angle-resolved issue will not be addressed here.     

Theory of core-level spectroscopy in f and d electron systems

A review is presented of many body effects in core-level spectroscopy (CLS) of f and d electron systems from a theoretical point of view. Historical developments and the most recent topics in this field are described. The impurity Anderson model (IAM) has been successfully applied to the analysis of X-ray photoemission spectra (XPS) and X-ray absorption spectra (XAS) in f and d electron systems, where the f and d electron states are treated as being on a single atomic site and they are hybridized with valence or conduction electron states. The effect of a core-hole potential in the final state of CLS plays an important role. Typical examples of calculated results for XPS in rare-earth compounds and transition metal compounds are given. Recent developments in the study of resonant X-ray emission spectra (RXES) are also introduced. A theoretical approach beyond the IAM is discussed mainly for the analysis of RXES of transition metal compounds.     

Soft X-ray photoelectron spectroscopy of compound semiconductor surfaces and interfaces

Photoelectron spectroscopy is one of the leading techniques in the study of solid surfaces. In particular, X-ray photoelectron spectroscopy (XPS) — also known as ESCA (electron spectroscopy for chemical analysis) — is extensively used in materials science. This paper discusses the advantages of coupling the soft X-ray continuum of synchrotron radiation with this technique (SXPS). The primary advantage of high surface sensitivity is illustrated with case studies of clean semiconductor surfaces and of the initial stages of formation of metal/semiconductor and semiconductor/semiconductor interfaces. The prospects for soft X-ray photoelectron microscopy are briefly discussed.     

X-ray photoelectron spectroscopy analysis of electronic states in the oxide layer on an ultradisperse copper surface

X-ray photoelectron spectroscopy (XPS) is used to study the electronic states of copper oxide covering a thin (2.0 ± 0.5 nm) layer of ultradisperse copper. A reduction in the thickness of the CuO layer is found to cause extremal behavior in the XPS spectrum parameters as opposed to their monontonic variations for CuO nanoparticles. This behavior is explained by the competition of two factors which affect the system under study: the dimensions of the substrate material and the electrostatic field in it.     

Electronic structure of Alq3 and Liq using soft X-ray spectroscopy and density functional theory calculation

The electronic structure of aluminum tris-8-hydroxyquinoline (Alq₃) and 8-hydroquinolatolithium (Liq) was investigated using a combination of X-ray emission spectroscopy (XES), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and spectral simulation with density functional theory. The chemical bonding states of Alq₃ and Liq were analyzed using XPS core-level spectra. The band gaps of Alq₃ and Liq were measured by combining the XAS and XES results. Additionally, resonant and non-resonant XES were used to measure the density of states for O sites in the molecules.     

Surface sensitivity of Auger-electron spectroscopy and X-ray photoelectron spectroscopy

A convenient measure of surface sensitivity in Auger-electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) is the mean escape depth (MED). If the effects of elastic-electron scattering are neglected, the MED is equal to the electron inelastic mean free path (IMFP) multiplied by the cosine of the emission angle with respect to the surface normal, and depends on the material and electron energy of interest. An overview is given here of recent calculations of IMFPs for 50–2000 eV electrons in a range of materials. This work has led to the development of a predictive formula based on the Bethe equation for inelastic electron scattering in matter from which IMFPs can be determined. Estimates show, however, that elastic-electron scattering can significantly modify the MED. Thus, for AES, the MED will be reduced by up to about 35%. For XPS, however, the MED can be changed by up to ±30% for common measurement conditions although it can be much larger (by up to a factor of 2) for near-grazing emission angles. Ratios of MED values, calculated with elastic scattering considered and neglected for XPS from the 3s, 3p, and 3d subshells of silver with Mg Kα X-rays are approximately constant (to about 10%) over a range of emission angles that varies from 40° to 60° depending on the subshell and the angle of X-ray incidence. Recommendations are given on how to determine the optimum range of emission angles for satisfactory analysis of angle-resolved XPS (ARXPS) data. Definitions are included of three terms often used for describing surface sensitivity (IMFP, MED, and effective attenuation length (EAL)), and examples are given of the varying magnitudes of these quantities for different analytical conditions.     

Monolayer vs. multilayer self-assembled alkylphosphonate films: X-ray photoelectron spectroscopy studies

Combining functional organic self-assembled monolayers (SAMs) with conventional semiconductor materials is a key step in the development of integrated electronics-based devices. T-BAG (Tethering by Aggregation and Growth) has been shown to be a simple and reliable method to grow SAMs of alkylphosphonates on oxide surfaces. However, distinguishing SAMs from ultra-thin multilayers is a challenge for most conventional surface characterization techniques.Self-assembled films of octadecylphosphonic acid (ODPA) were deposited on oxide-covered silicon coupons, converted to the corresponding phosphonates, and characterized by high resolution angularly resolved X-ray photoelectron spectroscopy (XPS). It was our goal to distinguish among different bonding configurations for phosphorous in the phosphonate head groups, namely, mono-dentate, bi-dentate or tri-dentate interactions with the oxide surface, as well as to assess quantitatively the near-surface layer composition.We also present an innovative method that allows us to distinguish between monolayer and multilayer films of ODPA on silicon oxide surfaces. This method is based on differential surface charging effects in XPS. It was found that variation in the ODPA film thickness causes differential responses of various spectral characteristics to an electrical bias applied to the sample during XPS measurements. Both positive and negative applied biases were found to affect the carbon core-level (C1s) line-shape and intensity in the case of the multilayer ODPA film, whereas line-shapes and intensities of all XPS lines measured for the monolayer film were unaffected by the application of a dc bias in the ±30 V range.     

Complex impedance spectroscopy of Mn-doped zinc oxide nanorod films

The frequency-dependent properties of Mn-doped (3-5 at.%) aligned zinc oxide (Mn-ZnO) nanorods, synthesized by hybrid wet chemical route onto glass substrates, were investigated by bias-dependent impedance spectroscopy. No peak of Mn cluster/secondary phases was detected in the X-ray diffraction traces of the samples. XPS studies show the presence of oxygen vacancies in Mn-ZnO nanorods and Mn in Mn²⁺ and Mn⁴⁺ charge states. Although X-ray diffraction/X-ray photoelectron spectroscopy does not give any indication of the presence of metal clusters in the samples, bias-dependent impedance spectroscopy demonstrates significant sensitivity to the formation of Mn clusters in Mn-ZnO nanorods.     

An extension of the mean free path approach to X-ray absorption spectroscopy

In the partial electron yield (PEY) acquisition mode commonly used in X-ray absorption spectroscopy (XAS) both elastically and inelastically scattered electrons are acquired, the latter contribution dominating the detector signal. Hence, the majority of the inelastic scattering events will not result in signal attenuation as happens in the case of X-ray photoelectron spectroscopy (XPS). To determine the respective changes in the effective mean free paths (MFP) we have performed XPS and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements for a series of self-assembled monolayers of alkanethiols on gold substrates. The length of the alkyl chain and, therefore, the film thickness was varied. In agreement with expectations, the obtained MFPs for the Au 4f photoelectrons and C_KLL Auger electrons in the PEY acquisition mode (with the respective inelastic contributions) exceed the corresponding values for the Au 4f and C_KLL electrons of the same kinetic energies in the constant final state acquisition mode. Furthermore, the effective PEY-MFP for the C_KLL Auger electrons increased with decreasing retarding voltage of the PEY detector, which correlates with the enhanced contribution of the inelastically scattered electrons in the acquired signal. The results obtained are of importance for the analysis of XAS spectra of thin organic films and polymers.     

Core level spectroscopy and RHEED analysis of KGd(WO4)2 surface

Structural and electronic characterisation of mechanically polished (010) KGd(WO₄)₂ (KGW) has been produced by reflection high-energy electron diffraction (RHEED) and X-ray photoelectron spectroscopy (XPS). With XPS analysis the original element binding energies, chemical composition and valence band structure of KGW have been determined.     

Photoelectron spectroscopy of nanocrystalline anatase TiO2 films

Nanocrystalline TiO₂ (anatase) films were prepared using either colloidal suspensions or a sol-gel route. The electronic structure of these films was analyzed using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). Apart from pristine films, films containing defects introduced by annealing under ultra-high vacuum conditions or by ion bombardment were investigated. Generally, annealing in the temperature range up to 720 K results in no significant changes in the XPS and UPS spectra as compared to the pristine state, indicating that the amount of defect formation is too low to be observable by these techniques. On the other hand, ion irradiation causes the appearance of distinct defect states; these could be identified in agreement with previous data from photoemission studies on rutile and anatase single crystals. From UPS, a valence-band width of ∼4.6 eV was determined for the nanocrystalline anatase films.     

Application of XPS spectral subtraction and multivariate analysis for the characterization of Ar ion beam modified polyimide surfaces

This paper presents results of a detailed X-ray photoelectron spectroscopy (XPS) characterization of complex changes at a polyimide surface resulting from Ar⁺ ion beam modification. The changes in chemical composition in the surface layer lead to formation of a layer that can act as an alignment layer for liquid crystals. The goal of this paper is to report on the result of a combination of spectral subtraction and multivariate analysis for analysis of XPS spectra. Principal component analysis (PCA), applied to curve-fitting results of difference spectra and multivariate curve resolution (MCR), applied to raw spectra, provided consistent results, and allowed for extraction of chemical anisotropy, defining factor in the ion beam (IB) alignment mechanism. This study demonstrated that more detailed chemical information about complex systems can be obtained through application of multivariate analysis to XPS spectra and curve-fits. Further, this approach can be effectively used in the characterization of various complex materials to link chemical structure to their properties.     

X-ray photoelectron spectroscopy of Se films grown by hot wall epitaxy

The X-ray photoelectron spectroscopy (XPS) performed on Se films obtained by vacuum deposition and hot wall epitaxy (HWE) indicated shifts in the binding energies of the core-levels. The observed shift of 3.5 eV in the XPS spectrum of 3d level towards the higher binding energy in vacuum deposited film was associated with the Se₈ molecular state. On the other hand, the 3d-level XPS spectrum of Se films grown by HWE indicated an assymmetrical doublet. From the peak positions it was ascertained that the film was retained its bulk characteristic and a partial shift of 2.6 eV was interpretated for the presence of Se₆ molecules.     

X-ray photoelectron spectroscopy study of NiSi formation on shallow junctions

The influence of boron (B)/arsenic (As) on X-ray photoelectron spectroscopy (XPS) study of NiSi formation on shallow junctions is investigated in this paper. The Ni-silicide film was formed after 30 s soak anneal at 450 °C on ultra shallow p+/n or n+/p junctions. The atomic ratio of Ni/Si profile in depth was probed by XPS and the results show that a uniform NiSi layer forms on B-doped p+/n junction while a non-uniform, Ni-rich silicide layer forms on As-doped n+/p junction. It does not agree with the results of other independent phase identification methods such as X-ray diffraction, Rutherford backscattering spectroscopy, and Raman scattering spectroscopy, which all demonstrate the formation of NiSi on both n+/p and p+/n junctions. Comparing the raw binding energy spectra of Ni and Si for each silicide film, the similar spectra for Ni signals are revealed. But the Si signals with an obviously smaller intensity is found to be responsible for the apparent Ni rich silicide formation on As-doped n+/p junction. It indicates that As atoms in the silicide film can affect the sputtering yield of Ni and Si, while no noticeable effect is observed for B atoms. More As atoms than B atoms segregation into the silicide layer is indeed verified by secondary ion mass spectroscopy. And micro-Raman scattering spectroscopy further confirms that the degree of crystallinity for NiSi on n+/p junction is inferior to that on p+/n junction.     

Energy band alignment at ferroelectric/electrode interface determined by photoelectron spectroscopy

The most important interface-related quantities determined by band alignment are the barrier heights for charge transport, given by the Fermi level position at the interface. Taking Pb(Zr,Ti)O3(PZT) as a typical ferroelectric material and applying X-ray photoelectron spectroscopy(XPS), we briefly review the interface formation and barrier heights at the interfaces between PZT and electrodes made of various metals or conductive oxides. Polarization dependence of the Schottky barrier height at a ferroelectric/electrode interface is also directly observed using XPS.     

X-ray photoelectron spectroscopy and low energy ion scattering studies on 1-buthyl-3-methyl-imidazolium bis(trifluoromethane) sulfonimide

In this communication we report the study of a ionic liquid (IL) performed by X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). The data show how within the layer investigated by XPS (about 6 nm), the composition results the same as the bulk IL, while the LEIS spectra show how the outermost layer is mainly constituted by fluorine atoms.