Application of Cr Kα X‐ray photoelectron spectroscopy system to overlayer thickness determination

A laboratory hard X‐ray photoelectron spectroscopy (HXPS) system at 5.4‐keV excitation energy was used to measure the angle dependence of a silicon oxide overlayer on a Si(0 0 1) substrate with overlayer thickness ranging from 4 to 25 nm. The thickness values of the SiO₂ overlayers were determined by utilizing a focused monochromatized Cr Kα source and a high‐energy hemispherical analyzer with an angle‐resolved wide acceptance angle objective lens. The modulation of the photoemission intensity due to photoelectron diffraction, which deteriorates high‐precision thickness determination, was suppressed significantly by continuous sample rotation around the sample's normal during the measurements. The resultant thickness values very well agree with those determined by ellipsometry in the same sample set. To demonstrate merits of the large information depth measurements, profiling of a wedged SiO₂ layer buried in a gate stack model structure with Ir (8 nm) and HfO₂ (2 nm) overlayers was performed. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation of Ti/CuO interface by X-ray photoelectron spectroscopy and atomic force microscopy

The Ti/CuO interface has been studied by the techniques of X-ray photoelectron spectroscopy and atomic force microscopy. Thin films of titanium were deposited on a CuO substrate at room temperature by the e-beam technique. The photoelectron spectra of titanium and copper were found to exhibit significant chemical interaction at the interface. The titanium overlayer was observed to get oxidized to TiO₂, while the CuO was observed to get reduced to elemental copper. This chemical interaction was observed to occur until a thickness of 7 nm of the titanium overlayer. For thicknesses greater than this value, the presence of unreacted titanium in the sample was detected. Barrier characteristics at the Ti/CuO interface were also carried out for substrate temperatures of 300°C, 400°C, 500°C, and 600°C as a function of the titanium overlayer thickness. A linear trend in the barrier thickness of the overlayer was observed between 400°C and 600°C substrate temperatures. The atomic force microscopy micrographs of the unannealed samples depicted layer-by-layer growth of elemental titanium on copper. At the Ti/CuO interface in such samples, the micrographs exhibited island formation of TiO₂ corresponding to the Volmer-Weber growth model. This formation has been interpreted as the relaxation in the strain energy. The percentage coverage of the underlying substrate by the TiO₂ islands showed a linear trend for the thicknesses of the titanium overlayer investigated. The average size of these islands also showed a linear trend as a function of the thickness of the overlayer.     

Microgel-based etalon coated quartz crystal microbalances for detecting solution pH: The effect of Au overlayer thickness

Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgels were “painted” on the Au electrode of a quartz crystal microbalance (QCM). Another Au layer (overlayer) was subsequently deposited on the microgel layer. This structure is known as a microgel-based etalon. These devices have been shown to exhibit optical properties (i.e., color) that depend on solution pH and temperature, among other things. Previously, we measured QCM frequency shifts that are a result of solution pH changes; the frequency shifts are a direct result of the pH dependent solvation state of the microgels that make up the etalon. In fact, the shifts observed for the etalons were much greater in magnitude than just a microgel layer immobilized on the QCM crystal without the Au overlayer. We reasoned that the Au overlayer lead to an enhancement of the observed frequency change due to its mass. In this submission we investigate how the Au overlayer thickness (mass) affects the observed sensitivity to solution pH. We found that the change in QCM resonant frequency depended dramatically on the mass of the Au overlayer.     

A practical approach for determination of mass spectral baselines

Precise determination of the baseline levels of mass spectra is critical for identification and quantification of analytes. Herein, we present a practical approach for determination of the baselines of mass spectra acquired under differential conditions. The baseline determined by this approach was the sum of baseline drift and noise level. The baseline drift was determined by averaging a number of lowest ion intensities. The noise level was determined based on the fact that an accelerated intensity change exists from noise to signal. This change was best revealed by the established accumulative layer thickness curve that was derived from the thicknesses of individual deducted layers. Deductions were performed sequentially layer by layer, each of which has a thickness of averaged lowest ion intensities from existing spectral data. The layer where the accelerated intensity change occurred was defined as a transition layer, which was determined from the polynomial regression in the sixth order of the accumulative layer thickness curve followed by resolving the roots of its fourth derivative. We validated the presence of this transition layer through determination of its convergence from various accumulative layer thickness curves generated by varying either the ending or the fineness of the sequential layer deductions. This simple, practical, program-based baseline determination approach should greatly increase the accuracy and consistency of identification and quantification by mass spectrometry, and facilitate the automation of data processing, thereby increasing the power of any high throughput methodology in general and of shotgun lipidomics in particular.     

Multi-technique Characterization of Self-assembled Carboxylic Acid Terminated Alkanethiol Monolayers on Nanoparticle and Flat Gold Surfaces

Gold nanoparticles (AuNPs) with 14, 25 and 40nm diameters were functionalized with different chain length (C6, C8, C11 and C16) carboxylic acid terminated alkanethiol self-assembled monolayers (COOH-SAMs). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to examine the changes in surface chemistry as both AuNP diameter and SAM chain length were varied. COOH-SAMs on flat gold surfaces were also examined and compared to the COOH-SAM on AuNP results. For a given surface, as the COOH-SAM chain length increased the XPS C/Au atomic ratio increased due to an increased number of carbon atoms per molecule in the overlayer and an increased attenuation of the Au substrate signal. For the C16 COOH-SAMs, as the size of AuNPs decreased the XPS C/Au atomic ratio and the apparent SAM thickness increased due to the increased curvature of the smaller AuNPs. The C16 COOH-SAMs on the flat Au had the lowest XPS C/Au atomic ratio and apparent SAM thickness of any C16 COOH-SAM covered Au surface. The effective take-off angles of the COOH-SAMs were also calculated by comparing the apparent thickness of COOH-SAMs with literature values. The effective take-off angle for C16 COOH-SAM on 14nm, 25nm and 40nm diameter AuNPs and flat Au were found to be 57°, 53°, 51° and 39°, respectively, for data acquired in a mode that collects a wide range of photoelectron take-off angles. The effective take-off angle for C16 COOH-SAM on 14nm AuNP and flat Au decreased to 52° and 0°, respectively, for data acquired in a mode that collects a narrow range of photoelectron take-off angles. The ToF-SIMS results showed similar changes in surface chemistry with COOH-SAM chain length and AuNP size. For example, the ratio of the sum of the C(1-4)H(x)O(y) positive ion intensities to the sum of the Au-containing positive ions intensities increased with decreasing AuNP size and increasing COOH-SAM chain length. Fourier transform IR spectroscopy in the attenuated total reflectance mode (FTIR-ATR) was used to characterize the crystallinity of the COOH-SAMs. The CH(2) stretching frequencies decreased with increasing COOH-SAM chain length on flat Au. The C16 COOH-SAM on the 14nm AuNPs exhibited a crystalline-like CH(2) stretching frequency. The size, size distribution, shapes and solution stability of AuNPs were investigated with transmission electron microscopy (TEM) and UV/VIS spectroscopy. As the average diameter of the AuNPs decreased the size distribution became narrower and the shape became more spherical.     

Oxide‐Modified Nickel Photocatalysts for the Production of Hydrocarbons in Visible Light

Metallic nickel nanostructures that were partially decorated by discrete nickel oxide layers were fabricated by in situ reduction of calcinated Ni‐containing layered double hydroxide nanosheets, the structure of which was confirmed by extended X‐ray absorption fine structure spectroscopy, X‐ray photoelectron spectroscopy, and transmission electron microscopy. The existence of the abundant interfaces between the surface Ni oxide overlayer and metallic Ni altered the geometric/electronic structure of the Ni nanoparticles, making them apt for CO activation under light irradiation. Most importantly, the unique structure favors the C?C coupling reaction on its surface, which confers the catalyst unexpected reaction power towards higher hydrocarbons at moderate reaction conditions. This study leads to a green and sustainable approach for the photocatalytic production of highly valuable chemical fuels.     

Analytical applications of elastic electron backscattering from surfaces

Measurements of probability of elastic electron backscattering from surfaces can provide information on physical properties of the surface region with thickness comparable to the inelastic mean free path (IMFP) of electrons. The analytical technique, based on such measurements, is known as elastic peak electron spectroscopy (EPES). The most frequent application of EPES is the determination of the IMFP in solids. However, this technique can also be used to measure overlayer thickness, or to determine surface composition.

Quantitative applications of EPES, addressed here, require a reliable theoretical model describing the elastic backscattering probability from surfaces with a given structure and composition. Unfortunately, there is no simple analytical model which describes the elastic backscattering probability with an acceptable accuracy. Values of the elastic backscattering probability are usually estimated from Monte Carlo (MC) simulations of elastic backscattering events, since the theoretical model implemented in the MC scheme seems closest to reality, as compared with models leading to different analytical expressions. It is shown that the reliability of the theory is associated with accuracy of the parameters needed in the calculations. The most important parameters are the differential elastic scattering cross-sections which are presently known, especially in some angular regions, with limited accuracy. The IMFP values, determined in different laboratories via EPES, exhibit a considerable scatter, which may be due to the fact that different experimental geometries are used in measurements. Other sources of errors are briefly discussed.     

Effects of elastic scattering and analyzer‐acceptance angle on the analysis of angle‐resolved X‐ray photoelectron spectroscopy data

We have made calculations of N 1s, O 1s, Si(oxide) 2p, Hf 4f, and Si(substrate) 2p photoelectron intensities at selected emission angles for films of SiO_1.6N_0.4 and HfO_1.9N_0.1 of various thicknesses on silicon. These calculations were made with the National Institute of Standards and Technology (NIST) Database for Simulation of Electron Spectra for Surface Analysis (SESSA) to investigate effects of elastic scattering and analyzer‐acceptance angle that could be relevant in the analysis of angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) experiments. The simulations were made for an XPS configuration with a fixed angle between the X‐ray source (i.e. for the sample‐tilting mode of ARXPS) and with Al and Cu Kα X‐ray sources. The no‐loss intensities changed appreciably as elastic scattering was switched ‘on’ and ‘off’, but changing the analyzer‐acceptance angle had a smaller effect. Ratios of intensities for each line from the overlayer film for the least realistic model condition (elastic scattering switched ‘off’, small analyzer‐acceptance angle) to those from the most realistic model condition (elastic scattering switched ‘on’, finite analyzer‐acceptance angle) changed relatively slowly with emission angle, but the corresponding intensity ratio for the Si(substrate) 2p line changed appreciably with emission angle. The latter changes, in particular, indicate that neglect of elastic‐scattering effects can lead to erroneous results in the analysis of measured ARXPS data. The elastic‐scattering effects were larger in HfO_1.9N_0.1 than in SiO_1.6N_0.4 (due to the larger average atomic number in the former compound) and were larger with the Al Kα X‐ray source than with the Cu Kα source because of the larger cross sections for elastic scattering at the lower photoelectron energies. Copyright © 2010 John Wiley & Sons, Ltd.     

Analysis of thin films and molecular orientation using cluster SIMS

A study of phenylalanine films of different thicknesses from submonolayer to 55 nm on Si wafers has been made using Bi_n⁺ and C₆₀⁺ cluster primary ions in static SIMS. This shows that the effect of film thickness on ion yield is very similar for all primary ions, with an enhanced molecular yield at approximately 1 monolayer attributed to substrate backscattering. The static SIMS ion yields of phenylalanine at different thicknesses are, in principle, the equivalent of a static SIMS depth profile, without the complication of ion beam damage and roughness resulting from sputtering to the relevant thickness. Analyzing thin films of phenylalanine of different thicknesses allows an interpretation of molecular bonding to, and orientation on, the silicon substrate that is confirmed by XPS. The large crater size for cluster ions has interesting effects on the secondary ion intensities of both the overlayer and the substrate for monolayer and submonolayer quantities. This study expands the capability of SIMS for identification of the chemical structure of molecules at surfaces. © Crown copyright 2010.     

Determination of the oxide layer thickness in core-shell zerovalent iron nanoparticles

Zerovalent iron (nZVI) nanoparticles have long been used in the electronic and chemical industries due to their magnetic and catalytic properties. Increasingly, applications of nZVI have also been reported in environmental engineering because of their ability to degrade a wide variety of toxic pollutants in soil and water. It is generally assumed that nZVI has a core-shell morphology with zerovalent iron as the core and iron oxide/hydroxide in the shell. This study presents a detailed characterization of the nZVI shell thickness using three independent methods. High-resolution transmission electron microscopy analysis provides direct evidence of the core-shell structure and indicates that the shell thickness of fresh nZVI was predominantly in the range of 2-4 nm. The shell thickness was also determined from high-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis through comparison of the relative integrated intensities of metallic and oxidized iron with a geometric correction applied to account for the curved overlayer. The XPS analysis yielded an average shell thickness in the range of 2.3-2.8 nm. Finally, complete oxidation reaction of the nZVI particles by Cu(II) was used as an indication of the zerovalent iron content of the particles, and these observations further correlate the chemical reactivity of the particles and their shell thicknesses. The three methods yielded remarkably similar results, providing a reliable determination of the shell thickness, which fills an essential gap in our knowledge about the nZVI structure. The methods presented in this work can also be applied to the study of the aging process of nZVI and may also prove useful for the measurement and characterization of other metallic nanoparticles.     

Photoelectron emission and XPS studies of real iron surfaces subjected to scratching in air,water, and organic liquids

The influence of temperature and surface overlayer on the photoelectron emission from scratched real iron surfaces was investigated using thermally assisted photoelectron emission (TAPE) and X‐ray photoelectron spectroscopy (XPS) measurements. The scratching was conducted with a diamond cutter in seven atmospheres. The intensity of TAPE as a function of temperature, called glow curve, was measured in the range 25–339 °C using a Geiger counter under ultraviolet irradiation at 210 nm. The temperature was scanned in two cycles (Up1 and Down1, and Up2 and Down2). The XPS measurements were carried out at 25 °C and after TAPE measurements at 200 and 339 °C. The photoelectron emission intensity at 40 °C in the Up1 scan increased in the order of air < water ≈ methanol ≈ cyclohexane < ethanol < benzene < acetone, and then each glow curve exhibited a gradual increase with temperature through a broad peak. It was found that the dependence of the emission intensity in the Up1 scan on the oxygen component ratio, Z_O = O^2?/(OH^? + O^2?) and the percentage of the Fe metal and FeOOH components of the Fe3p spectra for the atmospheres greatly differed. Additionally, the glow curve in the Up1 scan was completely different from that in the other scans. It was proposed that the photoelectron emission in the Up1 scan originates from not only the base metal but also the surface overlayer having trapped electrons and is strongly influenced by the acid–base interaction of the surface hydroxyl groups with the liquids molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

硅晶片上超薄氧化硅层厚度纳米尺寸效应的XPS研究

用X射线光电子能谱(XPS)测定了一系列厚度经过国际比对准确已知的硅晶片上的超薄(1.45nmd7.2nm)氧化硅膜的Si2p电子能谱和价带谱.结果表明:SiO2膜厚d2nm时,Si2p结合能最低,其原因可归结于此时光电离空穴既有来自SiO2中的原子极化对空穴的原子外弛豫,也有来自衬底Si的电荷移动对空穴的屏蔽(有效屏蔽距离大约是(2.5±0.6)nm);当d3nm时Si2p结合能增大,此时只有来自SiO2的原子外弛豫,d较小者的Si2p结合能较高.SiO2的价带电子结构也与其厚度纳米尺寸效应有关:当d2nm时价带中SiO2的O2p非成键电子峰的相对强度较强,O2p—Si3p和O2p—Si3s成键电子峰较弱.     

Sensitivity of transmission surface plasmon resonance (T-SPR) spectroscopy: self-assembled multilayers on evaporated gold island films

The distance dependence of the localized surface plasmon (SP) extinction of discontinuous gold films is a crucial issue in the application of transmission surface plasmon resonance (T-SPR) spectroscopy to chemical and biological sensing. This derives from the usual sensing configuration, whereby an analyte binds to a selective receptor layer on the gold film at a certain distance from the metal surface. In the present work the distance sensitivity of T-SPR spectroscopy of 1.0-5.0 nm (nominal thickness) gold island films evaporated on silanized glass substrates is studied by using coordination-based self-assembled multilayers, offering thickness tuning in the range from approximately 1 to approximately 15 nm. The morphology, composition and optical properties of the Au/multilayer systems were studied at each step of multilayer construction. High-resolution scanning electron microscopy (HRSEM) showed no apparent change in the underlying Au islands, while atomic force microscopy (AFM) indicated flattening of the surface topography during multilayer construction. A regular growth mode of the organic layers was substantiated by X-ray photoelectron spectroscopy (XPS). Transmission UV-visible spectra showed an increase of the extinction and a red shift of the maximum of the SP band upon addition of organic layers, establishing the distance dependence of the Au SP absorbance. The distance sensitivity of T-SPR spectroscopy can be varied by using characteristic substrate parameters, that is, Au nominal thickness and annealing. In particular, effective sensitivity up to a distance of at least 15 nm is demonstrated with 5 nm annealed Au films. It is shown that intensity measurements, particularly in the plasmon intensity change (PIC) presentation, provide an alternative to the usually measured plasmon band position, offering good accuracy and the possibility of measuring at a single wavelength. The present distance sensitivity results provide the basis for further development of T-SPR transducers based on receptor-coated Au island films.     

Effective attenuation lengths for photoelectrons in thin films of silicon oxynitride and hafnium oxynitride on silicon

We have used the National Institute of Standards and Technology Database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to simulate photoelectron intensities for thin films of SiO_1.6N_0.4 and HfO_1.9N_0.1 on silicon with excitation by Al Kα X‐rays. We considered Si 2p_3/2 photoelectrons from SiO_1.6N_0.4 and the substrate and Hf 4f_7/2 photoelectrons from HfO_1.9N_0.1. The simulations were performed for ranges of film thicknesses and photoelectron emission angles and for two common configurations for X‐ray photoelectron spectroscopy (XPS), the sample‐tilting configuration and the Theta Probe configuration. We determined photoelectron effective attenuation lengths (EALs) by two methods, one by analyzing photoelectron intensities as a function of film thickness for each emission angle (Method 1) and the other by analyzing photoelectron intensities as a function of emission angle for each film thickness (Method 2). Our analyses were made with simple expressions that had been derived with the assumption that elastic‐scattering effects were negligible. We found that EALs from both methods were systematically larger for the Theta Probe configuration, by amounts varying between 1% and 5%, than those for the sample‐tilting configuration. These differences were attributed to anisotropy effects in the photoionization cross section that are expected to occur in the former configuration. Generally, similar EALs were found by each method for each film material although larger EALs were found from Method 2 for film thicknesses less than 1.5 nm. SESSA is a useful tool for showing how elastic scattering of photoelectrons modifies EALs for particular materials, film thicknesses, and XPS configurations. Copyright © 2012 John Wiley & Sons, Ltd.     

Investigation of thin surface films by microprobe analysis

The electron microprobe has been applied to study thin films on metallic substrates. The intensities of the characteristic X-rays emitted by thin films of various elements and thicknesses on sublayers of different materials were measured. Two different theoretical approaches (Bishop and Poole, as well as Yakowitz and Newbury) were applied to interpet the X-ray intensities and to determine the film thickness from the intensity measurements. The effect of backscattering from the substrate, resulting in an increase of the intensity of characteristic X-rays of the film, is being described on the basis of a theory given by Hutchins. The corresponding equation for the backscattering factor has been modified to take into account the transmission of the electrons through the film, depending on the mass thickness of the film and the electron energy. The results obtained from theory and experiment are in good agreement for the different experimental parameters applied, except for very thick layers of high atomic numbers measured at low energies where the absorption of electrons in the film plays a dominant role.     

Thickness determination of TiN and TiAl coatings on steel substrates using X‐ray diffraction method and their composition measurements by GD‐OES

This paper presents a nondestructive X‐ray diffraction method for the accurate determination of thicknesses of polycrystalline TiN and amorphous‐like TiAl coatings deposited by DC magnetron sputtering onto thick polycrystalline stainless steel and carbon steel substrates. This method relies on the measurement of intensity loss of a substrate reflection caused by the deposition of the coating. The uncertainty of the thickness measurements by the X‐ray diffraction depends on the mass absorption coefficient of the coating material and the quality of the collected diffraction patterns. For the coatings considered, thicknesses determined by the X‐ray diffraction method show very good agreement with the thickness values measured by scanning electron microscopy and ball crater techniques.     

Thickness and coverage determination of multilayer with an island‐like overlayer by hard X‐ray photoelectron spectroscopy at multiple photon energies

To obtain depth profiles of the elemental composition of materials, we propose the use of hard X‐ray photoelectron spectroscopy (HAXPES) over a range of incident photon energies (PEs). Photoelectron intensities are measured as a function of PE and take‐off angle (TOA) from a multilayer sample (Au/SiO₂/Si). The top layer of the sample (Au) formed an island‐like structure, which we modeled as bumps and dips (surface roughness). The PE dependence, measured at angles close to the surface normal, is consistent with the theoretical results, in contrast to the TOA dependence. The Au coverage and layer thicknesses are calculated by curve fitting using experimental and theoretical results. Copyright © 2014 John Wiley & Sons, Ltd.     

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。     

Effect of molecule-substrate interaction on thin-film structures and molecular orientation of pentacene on silver and gold

Evaporated pentacene thin films with thicknesses from several nm to 150 nm on gold and silver substrates have been studied by ultraviolet photoelectron spectroscopy (UPS), near-edge X-ray absorption fine structure (NEXAFS), scanning tunneling microscopy (STM), and atomic force microscopy (AFM). It was found that pentacene thin-film structures, particularly their molecular orientations, are strongly influenced by the metal substrates. UPS measurements revealed a distinct change in the valence band structures of pentacene on Au compared to those on Ag, which is attributed to the different packing between adjacent molecules. Using NEXAFS, we observed 74+/-5 degrees and 46+/-5 degrees molecular tilt angles on Ag and Au, respectively, for all measured thicknesses. We propose that pentacene molecules stand up on the surface and form the "thin-film phase" structure on Ag. On Au, pentacene films grow in domains with molecules either lying flat or standing up on the substrate. Such a mixture of two crystalline phases leads to an average tilt angle of 46 degrees for the whole film and the change in valence band structures. STM and distance-voltage (z-V) spectroscopy studies confirm the existence of two crystalline phases on Au with different conducting properties. z-V spectra on the low conducting phase clearly indicate its nature as "thin-film phase".