The electronic structure of carbon films deposited in rf argon–hydrogen plasma

The electronic structure of C films deposited by sputtering a graphite target in rf. Ar–H₂ plasma is investigated by photoemission, Auger emission and electron energy loss spectroscopy (EELS) as a function of the H₂ concentration in the feed gas, referred to as [H₂]. Adding hydrogen to the plasma causes the films to change from a graphite-like unhydrogenated structure to a non-graphitic hydrogenated structure. The film mass density, as derived from the π + σ plasmon energy, decreases upon H₂ addition to the gas mixture, goes through a minimum at low [H₂] and increases with increasing [H₂]. It reveals a non-monotonous behavior of the film H content as a function of [H₂], the maximum H incorporation occurring at low [H₂]. This appears to be a characteristic of C deposition via graphite sputtering in Ar–H₂ plasma and it is discussed in connection with previous results on the subject.     

氧化物薄膜研制中的电子能谱技术

随着科学技术的不断发展，人们正在寻求更新的实用材料．金属氧化物，包括金属氧化物薄膜的各种实用材料，在工业界、信息产业界和能源开发等方面的应用前景，早已引起国内外学者的极大关注．例如，由于氧化物具有各种特殊的介电和光学性质，研究和开发基于氧化物薄膜的气敏材料非常热门．如何制备出有实用价值的各种薄膜材料，是科学家们一直关心和深入研究的课题．电子能谱技术在各种材料的基础研究和实际应用中起着重要的作用．本文以有序金属氧化物薄膜研制为例，简要评述了电子能谱技术（包括X射线光电子能谱（XPS），紫外光电子能谱（UPS），俄歇电子能谱（AES）和高分辨电子能量损失谱（HREELS）），以及低能电子衍射（LEED）等技术在氧化物薄膜材料制备和表征中的应用．     

氧化物薄膜研制中的电子能谱技术

随着科学技术的不断发展,人们正在寻求更新的实用材料.金属氧化物,包括金属氧化物薄膜的各种实用材料,在工业界、信息产业界和能源开发等方面的应用前景,早已引起国内外学者的极大关注.例如,由于氧化物具有各种特殊的介电和光学性质,研究和开发基于氧化物薄膜的气敏材料非常热门.如何制备出有实用价值的各种薄膜材料,是科学家们一直关心和深入研究的课题.电子能谱技术在各种材料的基础研究和实际应用中起着重要的作用.本文以有序金属氧化物薄膜研制为例,简要评述了电子能谱技术（包括X射线光电子能谱（XPS）,紫外光电子能谱（UPS）,俄歇电子能谱（AES）和高分辨电子能量损失谱（HREELS））,以及低能电子衍射（LEED）等技术在氧化物薄膜材料制备和表征中的应用.     

Work function changes and surface chemistry of oxygen, hydrogen, and carbon on indium tin oxide

The surface chemistry of indium tin oxide (ITO) has been investigated with Auger electron spectroscopy (AES) and high resolution electron energy loss spectroscopy (HREELS). A vibrating Kelvin probe (KP) with a graphite reference was used to monitor the absolute work function (Φ) of ITO as a function of chemical modification. The ITO was exposed in situ to molecular hydrogen (H₂), hot-filament-activated oxygen (O₂^*), and hot-filament-activated deuterium (D₂^*). The initial Φ of ITO was determined to be 5.2 eV, and surface chemical changes had strong effects on this value, as seen by KP. Exposure of clean ITO to O₂^* increased Φ to 5.6 eV, but the increase was short-lived. The changes in Φ over time were correlated with the uptake of carbon impurities in ultra high vacuum (UHV), as monitored by AES.

The HREELS of ITO revealed significant hydrocarbon impurities. Chemical reduction of ITO produced a metallic surface and dehydrogenated the adsorbed hydrocarbons. Both re-oxidation of metallic ITO and oxidation of clean ITO temporarily removed adventitious carbon from the surface, but oxidized ITO adsorbed an even larger quantity of carbon over time.     

Vanadium oxide thin films deposited on indium tin oxide glass by radio—frequency magnetron sputtering

Highly oriented VO₂(B), VO₂(B) + V₆O₁₃ films were grown on indium tin oxide glass by radio-frequency magnetron sputtering. Single phase V₆O₁₃ films were obtained from VO₂(B) +V₆O₁₃ films by annealing at 480℃ in vacuum. The vanadium oxide films were characterized by x-ray diffraction and x-ray photoelectron spectra (XPS). It was found that the formation of vanadium oxide films was affected by substrate temperature and annealing time, because high substrate temperature and annealing were favourable to further oxidation. Therefore, the formation of high valance vanadium oxide films was realized. The V₆O₁₃ crystalline sizes become smaller with the increase of annealing time. XPS analysis revealed that the energy position for all the samples was almost constant, but the broadening of the V_2p3/2 line of the annealed sample was due to the smaller crystal size of V₆O₁₃.     

Work function measurements on indium tin oxide films

We determined the work function of indium tin oxide (ITO) films on glass substrates using photoemission spectroscopy (PES). The ITO coated glass substrates were chemically cleaned ex-situ, oxygen plasma treated ex-situ, or sputtered in-situ. Our results suggest that the performance of ultraviolet photoemission spectroscopy (UPS) measurements can induce a significant work function reduction on the order of 0.4–0.5 eV, on ex-situ chemically and oxygen-plasma treated ITO samples. This was demonstrated by the use of low intensity X-ray photoemission spectroscopy (XPS) work function measurements before and after the UPS measurements were carried out.     

X-ray and electron beam modification of thiophene overlayers on TiO2(100)1 × 1 and 1 × 3

The effects of electron and X-ray beams on thiophene overlayers on TiO₂(100) 1 × 1 and 1 × 3 surfaces have been investigated using AES, UPS and XPS. Mg K X-rays were found to polymerise a thiophene multilayer condensed at 120 K. The evidence points to a substrate-secondary-electron mediated process. A 3 keV electron beam also modifies a condensed thiophene overlayer, probably by polymerisation.     

X-ray photoelectron and X-ray Auger electron spectroscopy studies of heavy ion irradiated C60 films

The influence of 200 MeV Au ion irradiation on the surface properties of polycrystalline fullerene films has been investigated. The X-ray photoelectron and X-ray Auger electron spectroscopies are employed to study the ion-induced modification of the fullerene, near the surface region. The shift of C 1s core level and decrease in intensity of shake-up satellite were used to investigate the structural changes (like sp² to sp³ conversion) and reduction of π electrons, respectively, under heavy ion irradiation. Further, X-ray Auger electron spectroscopy was employed to investigate hybridization conversion qualitatively as a function of ion fluence.     

Dissociative adsorption of NO on TiO2(1 1 0) argon ion bombarded surfaces

The interaction of NO with TiO₂(1 1 0) Ar⁺-ion-bombarded surfaces has been studied by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, Auger electron spectroscopy. Surfaces with different degrees of defects have been characterized by monitoring the evolution of the electronic structure of the surface, with the aim of studying the influence of the surface defects on the interaction with NO. The interaction was studied for exposures up to 500 L. However, the main effects occur already in the first 10 L. The exposure of the surfaces to NO resulted in the removal of defect sites without adsorption of N.     

Luminescence characterization and electron beam induced chemical changes on the surface of ZnAl2O4:Mn nanocrystalline phosphor

Luminescence characteristics and surface chemical changes of nanocrystalline Mn²⁺ doped ZnAl₂O₄ powder phosphors are presented. Stable green cathodoluminescence (CL) or photoluminescence (PL) with a maximum at ∼512 nm was observed when the powders were irradiated with a beam of high energy electrons or a monochromatic xenon lamp at room temperature. This green emission can be attributed to the ⁴T₁ → ⁶A₁ transitions of the Mn²⁺ ion. Deconvoluted CL spectra resulted in two additional emission peaks at 539 and 573 nm that may be attributed to vibronic sideband and Mn⁴⁺ emission, respectively. The luminescence decay of the Mn²⁺ 512 nm emission under 457 nm excitation is single exponential with a lifetime of 5.20 ± 0.11 ms. Chemical changes on the surface of the ZnAl₂O₄:Mn²⁺ phosphor during prolonged electron beam exposure were monitored using Auger electron spectroscopy. The X-ray photoelectron spectroscopy (XPS) was used to determine the chemical composition of the possible compounds formed on the surface as a result of the prolonged electron beam exposure. The XPS data suggest that the thermodynamically stable Al₂O₃ layer was formed on the surface and is possibly contributing to the CL stability of ZnAl₂O₄:Mn phosphor.     

Surface oxidation behavior of MgNd alloys

The oxidation kinetics of MgNd alloys oxidized in pure O₂ at high temperatures has been investigated. The results revealed two stages of the reaction: A fast initial oxidation was followed by a slow oxide growth with a parabolic kinetics. For MgNd alloys (Nd = 25 wt.%), the oxidation rate increased with the enhancement of the oxidation temperature. A sudden ignition was found for this alloys oxidized at 873 K up to about 80 min. Moreover, the increase of the Nd content would harm the oxidation resistance of the MgNd alloys. By Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, it was found that a triplex structure of oxide film formed. The outer layer was composed of MgO, Nd₂O₃ and Nd(OH)₃, the middle layer mainly consisted of MgO and Nd₂O₃, and the inner layer was the transitional layer made of MgO, Nd₂O₃ and the content of the substrate. The protective oxidation was associated with the formation of the dense Nd₂O₃/MgO layer during isothermal oxidation process. The oxidation mechanisms for the formation of oxide film are discussed.     

Structural and compositional stability of Co oxide grown on (001) bct Co

Room temperature (RT) adsorption of oxygen on the (001) surface of metastable, cubic Co film epitaxially grown on a Fe substrate results in the formation of about 7 monolayers (ML) crystalline CoO film, in the typical rocksalt structure 45° rotated with respect to the square unit mesh of the underlying Co film. We investigated the stability of this oxide layer upon annealing in the RT–620 K temperature range, by means of primary-beam diffraction modulated electron emission (PDMEE), and X-ray photoelectron spectroscopy (XPS). For temperatures up to 570 K, film thickness and local order are preserved, in spite of an increasing number of Co and O atoms bonded in sites of reduced coordination. For larger temperatures, thickness also reduces, but the oxide film is still characterized by a high degree of CoO-like local order.     

Interface effects for metal oxide thin films deposited on another metal oxide I. SnO deposited on SiO2

The growing mode of SnO overlayers deposited on SiO₂ has been studied by ISS and XPS. This study has shown that SnO spreads on the surface of SiO₂. The oxidation state of tin under different experimental conditions of preparation has been characterized by XPS and ELS and a procedure has been found to produce pure SnO. For comparison, SnO has been evaporated on highly oriented pyrolytic graphite (HOPG). In this case, independent of the deposited amount of SnO, XPS and ELS did not show any significant difference in the photoemission and loss features of this material as a function of coverage (i.e. there are no size effects). On the contrary, at low coverages of SnO deposited on SiO₂ XPS showed a shift of 1 eV in the BE of the Sn 3d_5/2 peak another of 1.7 eV in the values of the Auger parameter with respect to the values found for the bulk material. These shifts, very common on deposited metal particles, have been previously reported by us for TiO₂/SiO₂, and are tentatively attributed to t of the interaction of small deposits of SnO with the surface of SiO₂. The characterization by ELS and valence band photoemission of SnO completes the set of results reported in this paper.     

Adsorption of silane and methylsilane on gold surfaces

The adsorption of silane and methylsilane on the (1 1 0) and polycrystalline surfaces of gold is examined using vibrational electron energy loss spectroscopy (VEELS), angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) and X-ray photoelectron spectroscopy (XPS). Adsorption of silane onto the Au(1 1 0) surface at low temperatures is dissociative and yields an SiH₂ and possibly also SiH₃ surface species. Further dissociation occurs at room temperature to yield adsorbed SiH, which is tilted on the surface, with complete dissociation to Si occurring by 110 °C. The similarity in the UP spectra for silane adsorbed on the polycrystalline sample suggests that the same surface species are present over that temperature range. Above 200 °C, spectral changes suggest rearrangement of the Si atoms, which, by 350 °C, have diffused into the bulk. Adsorption of methylsilane onto the (1 1 0) surface at low temperatures initially produces adsorbed CH₃SiH or CH₃SiH₂, with undissociated methylsilane physisorbing at higher exposures. By room temperature, desorption and decomposition leaves (or direct adsorption yields) only adsorbed CH₃Si. After further heating, the hydrogen-carbon bonds of the CH₃ group break to leave an adsorbed SiC species. On the polycrystalline surface, methylsilane adsorption is the same at low temperatures as on (1 1 0). In contrast to the latter, though, the UP spectra indicate that direct exposures at room temperature yield adsorbed Si or SiC initially, with CH₃Si again adsorbing at higher exposures. Upon further heating to 330 °C, little if any methyl-groups remain on the surface and the Si has started to diffuse into the bulk.     

Construction of an electron analyzer with a wide acceptance solid angle

We have developed a new electron energy analyzer with a large solid angle of 0.14π, which is comparable to that of cylindrical mirror analyzer. Typical energy resolution was ΔE/E₀ ∼ 0.016 for the aperture of 1 mm and central radius of 100 mm, and typical angular resolution was less than 0.5°.     

Influence of ion implantation on titanium surfaces for medical applications

The implantation of ions into the near surface layer is a new approach to improve the osseointegration of metallic biomaterials like titanium. Meanwhile it is well known that surface topography and surface physico-chemistry as well as visco-elastic properties influence the cell response after implantation of implants into the human body. To optimize the cell response of titanium, ion implantation techniques have been used to integrate calcium and phosphorus, both elements present in the inorganic bone phase. In this context, the concentration profile of the detected elements and their chemical state have been investigated using X-ray photoelectron spectroscopy and Auger electron spectroscopy depth profiling. Ion implantation leads to strong changes of the chemical composition of the near surface region, which are expected to modify the biofunctionality as observed in previous experiments on the cell response. The co-implantation of calcium and phosphorus samples, which showed best results in the performed tests (biological and physical), leads to a strong modification of the chemical surface composition.     

Surface cleaning procedures for thin films of indium gallium nitride grown on sapphire

Surface preparation procedures for indium gallium nitride (InGaN) thin films were analyzed for their effectiveness for carbon and oxide removal as well as for the resulting surface roughness. Aqua regia (3:1 mixture of concentrated hydrochloric acid and concentrated nitric acid, AR), hydrofluoric acid (HF), hydrochloric acid (HCl), piranha solution (1:1 mixture of sulfuric acid and 30% H₂O₂) and 1:9 ammonium sulfide:tert-butanol were all used along with high temperature anneals to remove surface contamination. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were utilized to study the extent of surface contamination and surface roughness, respectively. The ammonium sulfide treatment provided the best overall removal of oxygen and carbon. Annealing over 700 °C after a treatment showed an even further improvement in surface contamination removal. The piranha treatment resulted in the lowest residual carbon, while the ammonium sulfide treatment leads to the lowest residual oxygen. AFM data showed that all the treatments decreased the surface roughness (with respect to as-grown specimens) with HCl, HF, (NH₄)₂S and RCA procedures giving the best RMS values (∼0.5-0.8 nm).     

Studies of the adsorption of tetraphenylporphyrin molecules on graphite

Combined scanning tunneling microscopy, reflection electron energy loss spectroscopy and X-ray photoelectron studies have been performed in situ under ultra high vacuum condition, on tetraphenylporphyrin molecules (H₂TPP) vacuum sublimated on highly oriented pyrolitic graphite. The experimental studies were performed at room temperature, as a function of the amount of deposited porphyrins.The propensity of H₂TPP to self-assembly on the graphite surface could be detected after a threshold of deposited material. In this case tetraphenylporphyrin molecules arranged according to a quasi-hexagonal lattice separated from their nearest neighbours by a minimum distance of about 1 nm. The formation of an additional incomplete layer, at a slightly higher coverage, was also detected where the quasi-hexagonal symmetry is retained. Finally, subsequent tetraphenylporphyrins depositions gave molecular aggregates randomly distributed on the graphite surface with subsequent loss of order.     

Covalent binding of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7

The adsorption reactions and binding configurations of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7 were studied using high-resolution electron energy loss spectroscopy (HREELS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and DFT calculation. The covalent attachments of these unsaturated hydrocarbons to Si(1 1 1)-7 × 7 through the formation of Si–C linkages are clearly demonstrated by the observation of the Si–C stretching mode at 450–500 cm⁻¹ in their HREELS spectra. For chemisorbed cyclohexene, the involvement of π_C=C in binding is further supported by the absence of C=C stretching modes and the disappearance of the π_C=C photoemission. The chemisorption of both 1,3-cyclohexadiene and 1,4-cyclohexadiene leads to the formation of cyclohexene-like intermediates through di-σ bonding. The existence of one π_C=C bond in their chemisorbed states is confirmed by the observation of the C=C and (sp²)C---H stretching modes and the UPS and XPS results. DFT calculations show that [4 + 2]-like cycloaddition is thermodynamically preferred for 1,3-cyclohexadiene on Si(1 1 1)-7 × 7, but a [2 + 2]-like reaction mechanism is proposed for the covalent attachment of cyclohexene and 1,4-cyclohexadiene.     

Penetration of electronic states from silicon substrate into silicon oxide

The depth profiling of O 1s energy loss in silicon oxide near the SiO₂/Si interface was performed using extremely small probing depth. As a result, the energy loss of O 1s photoelectrons with threshold energy of 3.5 eV was found. This value of 3.5 eV is much smaller than the SiO₂ bandgap of 9.0 eV, but quite close to direct interband transition at Γ point in energy band structure of silicon. This can be explained by considering the penetration of electronic states from silicon substrate into silicon oxide up to 0.6 nm from the interface. In addition, the penetrating depth is larger than the thickness of the compositional transition layer.