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.     

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.     

Band offset of the In2S3/indium tin oxide interface measured by X-ray photoelectron spectroscopy

In₂S₃ thin films have been grown on Indium Tin Oxide (ITO) by Chemical Spray Pyrolysis. The structural and physical-chemical properties of the films have been investigated by means of X-ray Diffraction and X-ray Photoelectron spectroscopy (XPS). The valence band discontinuity at the In₂S₃/ITO interface has been determined by XPS resulting in a value of 1.9 ± 0.2 eV. Consequently, the conduction band offset has been estimated to be 1.0 ± 0.4 eV.     

Chemical states of carbon in amorphous boron carbide thin films deposited by radio frequency magnetron sputtering

Boron carbide thin films were deposited by radio frequency (RF) magnetron sputtering and characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and high resolution transmission electron microscopy. The results reveal that the structure of thin films deposited at substrate temperatures lower than 350 °C is amorphous. We found that there are four chemical states for carbon in amorphous boron carbide thin films deposited by RF magnetron sputtering. One is the segregated carbon in form of the graphitic inclusions in the thin film identified by Raman spectroscopy and Raman mapping using two strong peaks at ~ 1360 cm^− 1 and ~ 1590 cm^− 1, but the XPS results show that the graphitic inclusions do not connect to the substrate directly. On the surface the carbon forms C=O bonds characterized by the peak of C1s core level at 285.0 eV besides B-C bonds in the boron carbide with the peak of C1s being at 282.8 eV. The detailed analysis of B-C bonds in the boron carbide shows that there are two states for carbon atoms in B-C bonds: in the C-B-C models with C1s peak at 282.3 eV and in the icosahedra with C1s peak at 283.3 eV.     

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.     

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。     

Surface studies of crystalline and amorphous Zn-In-Sn-O transparent conducting oxides

X-ray and ultraviolet photoelectron spectroscopy (UPS) studies were made of in situ RF magnetron-sputtered crystalline (c) and amorphous (a) Zn-In-Sn-O (ZITO) thin films, ex situ pulsed laser deposited c- and a-ZITO thin films, and bulk ZITO ceramics. Cosubstitution of Zn and Sn for In results in an increase of the In core level binding energy at a given Fermi level compared to that measured in undoped and Sn-doped In₂O₃ (ITO). In plots of work function vs. Fermi level, in situ c-ZITO and a-ZITO films have low ionization potentials (7.0-7.7 eV) that are similar to undoped In₂O₃. In contrast, dry-air-annealed in situ films, ex situ films, and bulk ceramics have higher ionization potentials (7.7-8.1 eV) that are more similar to ITO and match well with previous work on air-exposed surfaces. Kelvin Probe measurements were made of select a-ZITO films exposed to air and ultraviolet/ozone-treated so as to measure work functions under conditions commonly employed for device fabrication. Results (4.8-5.3 eV) were in good agreement with the UPS work functions of oxygen-exposed materials and with literature values. Lastly, a parallelogram plot of work function vs. Fermi level shows that a wider range of work functions is achievable in ZITO materials as compared to other transparent conducting oxides (Sb-doped SnO₂, Al-doped ZnO, Sn-doped In₂O₃), making ZITO more versatile for applications.     

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.     

Application of Rachinger''s method to separate overlapped doublets in the X-ray photoelectron spectrum

Rachinger's method of separating ₁ and ₂ doublets in X-ray emission spectra is applied for the first time to separate the superimposed doublets due to spin-orbit coupling. This method has been applied to separate closely lying doublets such as (Ag 4p_3/2and Ag 4p_1/2, (Ni 3p_3/2and Ni 3p_1/2) and (Cu 3p_3/2and Cu 3p_1/2). The intensities ratios of the separated peaks are measured and compared with the ratios obtained from a first-order calculation. An excellent agreement between the measured and calculated ratios are obtained. Residual background intensities compared with the estimated values are found to agree within certain uncertainties.     

Formation of a highly oriented FeO thin film by phase transition of Fe3O4 and Fe nanocrystallines

A highly oriented FeO thin film was formed from a Fe₃O₄ thin film containing Fe nanocrystallines by post-annealing at 600°C. Fe₃O₄ thin films were grown on Si(100) substrates by ion beam sputter deposition under oxygen ambient. The stoichiometry of the iron oxide thin film could be precisely controlled by in situ X-ray photoelectron spectroscopy (XPS). X-ray diffraction (XRD) pattern of the Fe₃O₄ thin film grown at substrate temperature of 300°C showed a mixed phase of Fe₃O₄ and Fe nanocrystallines with a preferred orientation (110). However, the mixed phase was converted to a highly oriented FeO(200) phase by post-annealing at 600°C. This could be inverted as a result of Ostwald ripening of the Fe₃O₄ and Fe nanocrystallines.     

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.     

Oxidation study of polycrystalline InN film using in situ X-ray scattering and X-ray photoemission spectroscopy

Oxidation process of polycrystalline InN films were investigated using in situ X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS). The films were grown by dc sputter on sapphire (0001) substrates and were oxidized in air at elevated temperatures. The XRD data showed that the structure of the films changed to the bixbyite In₂O₃ (a = 10.11 Å) above 450 °C. Chemical configurations of the sample surfaces were investigated using high-resolution XPS. For the non-intentionally oxidized InN film, XPS analysis on the In 3d peak and the N 1s main peak at 396.4 eV suggests that indium and nitrogen are bound dominantly in the form of InN. An additional peak observed at 397.4 eV in the N 1s photoelectrons and the O 1s peaks indicate that the InN film surface is partly oxidized to have InO_xN_y configuration. After oxidation of the InN film at elevated temperature, the O 1s spectrum is dominated by In₂O₃ peak, which indicates that the structure is stable chemically with In₂O₃ configuration at least within the XPS probing depth of a few nm.     

Nitric-phosphoric acid etching effects on the surface chemical composition of CdTe thin film

Nitric-phosphoric (NP) acid etching has been regarded as one of the most effective methods for the formation of low resistance back contact with the metal electrode in CdTe based photovoltaic cells. We studied CdTe back surfaces and the changes with time of exposure to NP acid with x-ray photoelectron spectroscopy (XPS), and atomic force microscopy. Strong etching dependence on the back surface chemical composition, and surface roughness, was observed. In order to study the effect of the NP acid etching on surface degradation, the sample was left in open ambient condition for three weeks and XPS measurement in combination with ion sputtering was performed on unetched and highly etched parts. The difference in depth profiles of the NP acid etched and unetched CdTe surface has been discussed.     

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.     

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.     

X-ray photoelectron spectroscopy study of Langmuir–Blodgett films of N-octadecyl-8-hydroxy-2-quinoline carboxamide deposited from subphases containing metal ions

The Langmuir–Blodgett films of N-octadecyl-8-hydroxy-2-quinoline carboxamide (HOQ) deposited from subphase containing metal ions were investigated by X-ray photoelectron spectroscopy (XPS). The amphiphilic HOQ with its complexing head group in contact with the aqueous phase can form metal complexes with the metal ions present in the aqueous phase. The formation of HOQ–metal complexes leads to the appearance of new XPS peaks assigned to the metal ions. The information on stoichiometry provided by XPS indicates that a metal ion is coordinated by one HOQ molecule for transition metal ions of the fourth period, but by two HOQ molecules for the metal ions after the fourth period.     

Effects of organic and inorganic treatment agents on the formation of conversion layer on hot-dip galvanized steel: An X-ray photoelectron spectroscopy study

The formation of a Cr-free conversion layer on hot-dip galvanized (HDG) steel involves various interfacial processes which radically influence the composition of the coating and thus its performance. Here, we investigate the role of the main constituents contained in the treatment bath, the polymeric compounds and manganese phosphate species, by using derivative versions from the standard solution. A detailed X-ray photoelectron spectroscopy (XPS) analysis allowed distinction between oxygen originating from polymeric compounds and oxygen of inorganic nature in oxides/hydroxides or phosphate species. Our results revealed that manganese phosphate present in the treatment bath promotes the polymer adsorption on HDG substrate. Angle-resolved XPS and depth profile showed the presence of TiO₂ layer on the outer part of the conversion layer, when polymeric compounds are not detected.     

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.