Evaluating industrial grade functionalized multiwalled carbon nanotubes by X-ray photoelectron spectroscopy

Utilization of carbon nanotubes in various applications is a function of their dispersion in respective matrix which effectively depends on the functionalization employed. Functional group distribution on Carbon Nanotube surface is usually a complex mixture of groups depending on the oxidizing agent employed. In this regard, nine varieties of Industrial grade multiwalled carbon nanotubes belonging to 10–30, 20–40 and 50–80?nm outer diameter ranges but differing in functionality (carboxyl and hydroxyl) were analyzed. X-ray photoelectron spectroscopy was employed to quantify the different functionalities on pristine, hydroxyl and carboxyl functionalized multiwalled carbon nanotubes and high-resolution transmission electron microscopy was used to image the internal structure including the side wall damage in functionalized varieties. X-ray photoelectron spectroscopy measurements on nine batches have suggested the presence of carbonyl, carboxyl and hydroxyl functional groups on all multiwalled carbon nanotubes in different proportions. This implies that it is not possible to have exclusive hydroxyl or carboxyl functionalization on a CNT surface Additionally, comparison is drawn between already existing deconvolution procedures from literature.     

Thickness measurement of SiO2 films thinner than 1 nm by X-ray photoelectron spectroscopy

The thickness measurement of ultra-thin SiO₂ films thinner than 1 nm was studied by X-ray photoelectron spectroscopy (XPS). Amorphous SiO₂ thin films were grown on amorphous Si films to avoid the thickness difference due to the crystalline structure of a substrate. SiO₂ thin films were grown by ion beam sputter deposition under oxygen gas flow and the thickness was measured by in situ XPS. The attenuation length was determined experimentally by a SiO₂ film with a known thickness. The straight line fit between the measured thickness using XPS and the nominal thickness showed a good linear relation with a gradient of 0.969 and a small offset of 0.126 nm. The gradient measured at the range of 3.4–0.28 nm was very close to that measured at sub-nanometer range of 1.13–0.28 nm. This result means that the reliable measurement of SiO₂ film thickness below 1 nm is possible by XPS.     

Ar离子轰击高定向石墨表面结构变化的X射线光电子能谱分析

用X射线光电子能谱（XPS）研究了3．0keV Ar离子轰击高定向裂解石墨（HOPG）引起的表面结构的变化。通过对C1sC KLL及C2s谱峰形状的定性和定量分析，表明Ar离子轰击将破坏共价π键并导致表面局域sp^2杂化C键向sp^3杂化C键转化。sp^3／sp^2之比依赖于离子轰击时间。     

Band bending at free Pb(Zr,Ti)O3 surfaces analyzed by X-ray photoelectron spectroscopy

This paper analyses in detail the core levels evolution of Pb(Zr,Ti)O₃, i.e. Pb 4f, Zr 3d, Ti 2p, O 1s in various conditions: absolutely freshly prepared sample, sample stored under air, and the effects of in vacuum annealing. The aim of the study is to quantify separately the chemical reactivity at the surface and the band bending effects due to the ferroelectric polarization. It is found that freshly prepared samples present mostly inwards (↓) polarization. This phenomenon is mostly revealed by the Ti 2p and O 1s spectra, manifested as a distinct component with 1.8 eV lower binding energy in the O 1s binding energy and by 1.1 eV in the Ti 2p binding energy. Sample aging under air suppresses the inwards polarization, and most signal comes from surfaces not presenting ferroelectric permanent polarization perpendicular to the sample surface. This process conducts also to the formation of Pb(CO₃)₂ on the surface. Annealing to temperatures up to 400 °C stabilizes a surface composed by a main part of surface without polarization perpendicular to the surface, and with some areas presenting outwards (↑) polarization. These areas have, most probably, different terminations, the polarized area being (Ti,Zr)O₂ terminated.     

用X射线光电子谱研究Pt和CeO2间的相互作用

用X射线光电子谱研究了CeO2和Pt间的相互作用,探讨了通过相互作用能提高CeO2的氧化还原反应活性的机理,并与通常的金属和载体强相互作用的机理进行了比较.对高结合能端O1s峰和表面O-离子的产生过程进行了讨论.     

Atomic force microscopy and X-ray photoelectron spectroscopy evaluation of adhesion and nanostructure of thin Cr films

Chromium (Cr) thin films were deposited on float glass using electron beam (e-beam) physical vapor deposition and radio frequency (RF) magnetron sputtering techniques. Surface morphology of these Cr films was studied using atomic force microscopy (AFM). The e-beam deposited Cr films consisted of isolated surface mounds while in RF sputtered samples, these mounds combined to form larger islands. Lower surface adhesive properties were observed for e-beam deposited films, as determined from AFM force-distance curves, presumably due to the nanostructural differences. Similar amounts of adsorbed atmospheric carbonaceous contaminants and water vapor were detected on samples deposited using both methods with e-beam deposited samples having additional carbide species, as determined by X-ray photoelectron spectroscopy data. The dominant crystallographic plane in both e-beam deposited and RF sputtered Cr thin films was (110) of body-centered cubic Cr metal structure as determined from X-ray diffraction data. Weak (211) reflection was also observed in RF sputtered samples and was attributed to a different thin Cr film condensation and growth mechanism which resulted in nanostructural differences between films deposited using two different methods.     

X-ray photoelectron spectroscopy on implanted argon as a tool to follow local structural changes in thin films

Argon ions were implanted in metallic, semiconducting or insulating substrates, and investigated with X-ray photoelectron spectroscopy. Analysis of the Ar2p core level of argon showed clear differences in binding energy position and width as function of the matrix material, implantation energy, and post-annealing treatment. Although argon is not expected to form chemical bonds with the host matrix, the electronic shells within the gas atom can react to their environment according to different effects. It is shown that the precise determination and correct interpretation of the binding energy levels of the embedded gas atoms provides information about the local environment of the matrix such as amorphization of the crystalline structure, defect healing or gas bubble formation.     

High-resolution X-ray photoelectron spectroscopy study of InTe thin film in structural phase transition from amorphous to crystalline phase

We investigated the chemical states of InTe thin film in the structural phase transition from the amorphous to the crystalline phase, using high-resolution X-ray photoelectron spectroscopy with synchrotron radiation. We confirmed the structural phase transition by transmission electron microscopy. Clean amorphous InTe (a-InTe) free of oxygen impurity was obtained after Ne⁺ ion sputtering at the ion beam energy of 1 kV for 1 h. Additionally, we obtained crystalline InTe (c-InTe) from clean a-InTe by annealing at 250 °C in an ultra-high vacuum. During the transition to the crystalline phase, the binding energy of the Te 4d core-level was unchanged, but the peak width was somewhat wider than in the amorphous phase. In the case of the In 4d core-level, the chemical shift was 0.1 eV at the higher binding energy between the amorphous and crystalline phases. The valence band maximum was shifted at the higher binding energy of 0.34 eV. We assumed that the Te atom was almost fixed and that the In atoms moved in the tight binding energy state to the center of the 4-Te atoms.     

原子力显微镜与X射线光电子能谱对ITO表面改性的研究

采用氧气等离子体(OP)处理对氧化铟锡(ITO)薄膜进行表面改性,通过原子力显微镜(AFM)、X射线光电子能谱(XPS)和四探针等测试手段对薄膜样品进行表征,研究了OP处理对ITO表面性质的影响.实验结果表明OP处理有效去除了ITO表面的污染物,优化了ITO表面的化学组分,降低了ITO表面的粗糙度和方块电阻,改善了ITO的表面形态.与此同时,通过XPS监测研究了OP处理后ITO表面化学组分随老化时间的变化,结果显示经过优化的化学组分随老化时间增加而逐渐退化.另外,以OP处理后经过不同老化时间的ITO样品作为空穴注入电极,制备了有机电致发光器件(OELD),通过测试器件的电压-电流-亮度特性,进一步研究了ITO表面性质对于OELD光电性能的影响.     

Thermal activation energy of silver in ion-exchanged soda–lime glass investigated by X-ray photoelectron spectroscopy

The thermal effect on silver in ion-exchanged glasses was investigated in situ by X-ray photoelectron spectroscopy (XPS) in an ultra-high vacuum environment. Each XPS signal of Ag 3d_3/2 and 3d_5/2 consists of two components, the metallic state (Ag⁰) and the oxidized state (Ag⁺), resolved after curve fitting. The toward-surface diffusion of silver was observed by monitoring the changes in concentration on the surface during sample annealing between 20 and 450°C. Judging from the variations in line shape and binding energy and from the enhancement of surface silver under annealing, both metallic and oxidized silver are accumulated on the surface. By applying the diffusion theory in a semi-infinite system to the experimental data, the thermal activation energy of the oxidized silver in ion-exchanged glass, 0.16 eV, was estimated. The activation energy of metallic Ag precipitated during heating, 0.23 eV, was estimated as well.     

Effect of organic additives on the corrosion resistance properties of electroless nickel deposits

The effects of two organic additives, 3-S isothiuronium propyl sulfonate (UPS) and thiourea (TU) on the properties of electroless nickel (EN) deposit were investigated. The properties of EN deposits were examined by electrochemical impedance spectroscopy (EIS) and nitric acid corrosion test in combination with scanning electron microscope, X-ray fluorescence spectrometer, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy analysis. The results show that TU and UPS had different influences on the morphology of EN deposits. The two additives decreased phosphorus content and increased sulfur content in the EN deposit. XRD studies indicated that addition TU or UPS could enhance the crystallization of EN deposits. EIS studies demonstrated that the EN coating with TU or UPS has a lower corrosion resistance. However, the nitric acid test indicated that the corrosion resistance of EN deposit could be improved by adding UPS to EN bath. A cause for understanding the increase of the nitric acid corrosion resistance with UPS was indicated based on the above experiments.     

Investigation of interdiffusion in Sb/As2S3 nano-layered structures by high-resolution X-ray photoelectron spectroscopy

The photo-stimulated interdiffusion within chalcogenide based nano-layered structures (NLS) produces large changes in properties, which have potential application in optical pattern recording. The mechanism of these changes is investigated for two NLS consisting of 100 alternate layers of antimony and As₂S₃, but of different relative thicknesses, by high-resolution X-ray photoelectron spectroscopy. The results suggest the formation of Sb-S bonds at the expense of As-S bonds, with a consequent increase in the refractive index but minimal change in thickness. The role of oxygen in photoinduced transformations, especially in the top layers, is characterized and discussed.     

Ultraviolet-induced surface modification of polyurethane films in the presence of oxygen or acrylic acid vapours

An efficient surface functionalization of polyurethane (PU) films has been obtained by ultraviolet (UV)-assisted modification in the presence of oxygen or acrylic acid (AA) vapours. Film analyses were carried out by water contact angle measurements, X-ray photoelectron spectroscopy (XPS) and Near-edge X-ray absorption fine structure (NEXAFS). Film hydrophilicity increased with photolysis time in the presence of oxygen or AA vapours. Incorporation of COO and CO functional groups at the polymer surface after the UV-assisted treatments was observed. In addition, High resolution XPS and NEXAFS results showed that a thin film of poly (acrylic acid) (PAA) is formed over the PU films during the UV irradiation with AA vapours. The obtained results are compared with previous published oxygen and AA low-power plasma treatments. Similarity between both treatment methodologies is shown. UV surface functionalization and polymerization of PAA can be used instead of a traditional plasma treatment with the advantage of set-up simplicity and lower costs.     

Electronic structural analysis of transparent In2O3-ZnO films by hard X-ray photoelectron spectroscopy

The electronic structural analysis of the conductive transparent films was carried out using bulk sensitive hard X-ray photoelectron spectroscopy (HAXPES). The In₂O₃-ZnO film has amorphous structure before and after annealed, and the conduction band spectrum around Fermi level showed the similar spectra with that of as-deposited amorphous In₂O₃ film. In these amorphous films, the conduction band minimum locates at the deeper level than the crystalline In₂O₃ film. The electronic state which comes from randomness of amorphous structure possibly exists around this level or below. These electrons are expected to act as scattering center. We concluded that the electron mobility depends on the density of this electronic state.     

X-ray photoelectron spectroscopy analyses of titanium oxynitride films prepared by magnetron sputtering using air/Ar mixtures

X-ray photoelectron spectroscopy (XPS) has been employed to investigate titanium oxynitride (TiN_xO_y) films prepared by d.c. magnetron sputtering using air/Ar mixtures, which allows one to perform the deposition at a high base pressure (1.3 × 10^− 2 Pa) and can reduce substantially the processing time. XPS analyses revealed that all the prepared TiN_xO_y films comprised Ti-N, Ti-N-O, and Ti-O chemical states. When the air/Ar ratio was below 0.3, nitrogen-rich TiN_xO_y films were obtained. As the air/Ar ratio was above 0.4, oxygen-rich TiN_xO_y films were formed. XPS depth profile analyses were also performed in selected specimens. It has been found that at relatively low air/Ar ratios, such as 0.5, the oxygen content of the films increased toward the film/substrate interface and when the air/Ar ratio was higher, TiN_xO_y films with large oxygen content with uniform concentrations were then formed.     

Further insights into the photodegradation of poly(3-hexylthiophene) by means of X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy (XPS) was used to monitor the chemical changes resulting from irradiation (> 295 nm) in air of poly(3-hexylthiophene) (P3HT), polymer which is a good candidate for photovoltaic applications. The formation of carbonyl moieties and the stepwise oxidation of sulphur atoms were characterised. The oxidation and the cleavage of the hexyl side-chain was monitored. It is also shown that sulfur was first converted into sulfoxides, then into sulfones and finally into sulfinate esters. The formation of these ultimate degradation products provoked a disruption of π-conjugation in P3HT, leading to diminished visible absorbance. Based on these results, a mechanism of P3HT photooxidation is proposed. Comparison of XPS data with previously reported infrared and UV-visible spectral analysis showed that the information provided by these techniques is completely consistent.     

Specific features of the electronic structure and optical properties of KPb2Br5: DFT calculations and X-ray spectroscopy measurements

Density functional theory (DFT) calculations are made in order to explore the total and partial densities of states of potassium dilead pentabromide, KPb₂Br₅, by using the augmented plane wave + local orbitals (APW + lo) method as incorporated in the WIEN2k package. The present calculations reveal that the principle contributors to the valence band of KPb₂Br₅ are the Pb 6s and Br 4p states contributing predominantly at the bottom and at the top of the band, respectively, while the bottom of the conduction band is formed mainly from contributions of the unoccupied Pb 6p states. The curves of total density of states derived by the present DFT calculations of KPb₂Br₅ are found to be in agreement with the experimental X-ray photoelectron valence-band spectrum of the compound studied. Comparison on a common energy scale of the X-ray emission bands representing the energy distribution of the valence Br p and K s states and the X-ray photoelectron valence-band spectrum of the KPb₂Br₅ single crystal indicate that the Br 4p and K 4s states contribute mainly at the top and in the upper portion of the valence band, respectively, being in agreement with data of the present DFT band-structure calculations of this compound. Principal optical characteristics of KPb₂Br₅, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity are also studied by the DFT calculations.     

Effects of surface treatment of field emitter arrays on electrical characteristics of active matrix cathode

The effects of a wet chemical surface treatment of molybdenum-tip (Mo-tip) emitters on the electrical characteristics of an active matrix cathode composed of hydrogenated amorphous silicon thin film transistors and Mo-tip emitters are described. X-Ray photoelectron spectroscopy measurements showed that the surface treatment removed MoO₃ from the surface of the e-beam evaporated Mo film. In addition, the surface roughness of the Mo film was increased as the result of the surface treatment. The surface-treated active matrix cathode showed stable emission characteristics and immunity from emitter failures during its operation. The response time of the active matrix cathode was decreased by the surface treatment of the Mo-tip emitters. A change in surface composition and surface roughness appear to be responsible for the enhancement of the active matrix cathode.     

XPS and X-ray diffraction studies of aluminum-doped zinc oxide transparent conducting films

Aluminum-doped zinc oxide transparent conducting films are prepared by spray pyrolysis at different dopant concentrations. These films are subsequently characterized by X-ray diffractometric and X-ray photoelectron spectroscopic (XPS) techniques. The results are compared with those obtained from pure zinc oxide films prepared under identical conditions. X-ray diffraction measurements show an increase in lattice parameters (c and a) for aluminum-doped films while their ratio remains the same. This study also indicates that within the XPS detection limit the films are chemically identical to pure zinc oxide. However, a difference in the core-electron line shape of the Zn 2p_3/2 photoelectron peaks is predicted. An asymmetry in Zn 2p_3/2 photoelectron peaks has been observed for aluminium-doped films. The asymmetry parameters evaluated from core-electron line-shape analysis yield a value of the order of 0.04±0.01. The value is found to lie between those obtained for pure zinc oxide and has been attributed to the presence of excess zinc in the films.