Interface effects and the Auger parameter in titanium oxide thin films deposited on metals and in sandwich structures

Very thin films of TiO₂ and Ti₂O₃ were deposited by evaporation on Ag, on silver oxidized by an oxygen plasma and on Pt. Depending on the coverage, there were changes in the values of the binding energy (BE) and the Auger parameter (α′) of O and Ti. These shifts occur in the opposite direction with respect to that previously found for TiO₂ supported on insulators. Among others, reasons for these shifts are the different relaxation energy of photoholes and the occurrence of charge transfer processes at the metal oxide/metal interface. UV-visible absorption spectra of thin films of TiO₂Ag composites have shown a narrowing in the gap energy (E_g) of the oxide in respect to bulk titania. This observation shows the existence of a correlation between E_g and α′ when TiO₂ is supported on a metal surface. The Auger parameter of O and Ti is also sensitive to the intercalation of TiO₂ within a “sandwich” structure of SiO₂ and Ag, and the values found for the spectroscopic parameters are intermediate between those of TiO₂ supported on Ag and SiO₂. This result opens up the possibility of modulating the electronic properties of thin layers of TiO₂ by interaction with other materials.     

Analysis profiles of oxide films on chrome steel by auger emission and x-ray photoelectron spectroscopies

Samples of steel from two different sources were examined. The materials had nominally the same bulk composition but different samples from each batch had been hardened under two slightly different conditions.The surface oxide films were analysed by both Auger emission spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) after a number of ion bombardments, and the variation in composition with depth was established. In general the outermost oxide layers were chromium deficient and XPS results suggested the presence of Fe₂O₃ at the surface, together with atmospheric contamination. After ion bombardment the proportion of chromium oxide increased and both iron metal and oxide (Fe₃O₄) were present. The amount of chromium oxide reached a maximum at the steel oxide interface and on further bombardment was replaced by chromium metal. AES and XPS results were in agreement qualitatively and also quantitatively after measurement with a curve analyser of the areas under the peaks of certain elements.The present investigation has shown that AES and XPS can give very similar analyses provided some simple corrections are applied. However, the use of the higher resolution of XPS can provide additional information which cannot be obtained by AES. Thus, using expanded XPS scans, together with suitable curve analysis techniques, it is relatively simple to separate signals from oxide and from free metal regions of the sample, and to study in detail the changes in composition of the oxide from the oxide-air to the oxide-metal interfaces.The study of the four steel samples in this manner has shown that there is a thin region rich in chromium oxide adjacent to the metal. The high level of chromium falls off fairly rapidly nearer the surface and appears to stabilize at a very low level. This is particularly obvious in the thicker oxides (PH), where there is a thick surface layer which is principally iron oxide. It would appear that under the conditions of the heat treatment given to the present samples the thickening of the oxide is due almost entirely to iron oxide. Other work has shown that the low temperature air-formed oxide on these steels is chromium rich and it is suggested that the thickening is due to diffusion of iron through the original film with little movement of the chromium.In view of the high chromium deficiency in the outer layers of the oxides examined it is apparent that the supposedly protective chromium oxide film on chrome steel is situated at the oxide-metal interface and not on the outer surface.The present investigation has shown the existence of two unreported iron satellites. One would appear to be associated with the mixed valence oxide Fe₃O₄ and another with the purely trivalent oxide Fe₂O₃. The satellites could be associated with a strong plasma loss mechanism, or be due to shake-up phenomena as in the case of copper and nickel oxides¹⁴As might be expected from the normal oxidation behaviour of iron, the present oxide films appear to consist of a thin layer of Fe₂O₃ overlying the main Fe₃O₄ oxide. The removal of this outermost Fe₂O₃ layer is rapid and is accompanied by the changes in the satellites mentioned above, together with changes in the position of the Fe 2p_{$\text{3}\text{2}$} oxide peak.In conclusion, it is clear that a detailed XPS examination can not only provide information on overall compositional changes, as can be obtained by AES, but can also provide a comprehensive picture of changes in oxide composition, including those due to oxides of one metal in different valency states.     

A Comparative Study of the Growth of Cr on (110)TiO2 Rutile, (0001) α-Al2O3 and (100)SrTiO3 Surfaces

Thin Cr films were deposited on single crystal -Al₂O₃, SrTiO₃ and TiO₂ (rutile) substrates under ultrahigh vacuum conditions using molecular beam epitaxy (MBE). The growth behavior and thermal stability of the films were investigated with scanning tunneling microscopy (STM), X-ray phototelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and transmission electron microscopy (TEM). Cr grew as 3D clusters on all substrates. For all three Cr/oxide systems a strong temperature dependent interfacial reaction was observed. The results suggested that these reactions depended greatly on thermodynamics and on transport properties in the oxide substrates.     

The interaction of CO and O2 with the (111) surface of Pt3Ti

The electronic properties of clean and partly oxidized Pt₃Ti(111) surfaces have been studied utilizing carbon monoxide both as a probe and as a reducing agent. Vibrational frequencies and desorption profiles of chemisorbed CO as well as ion scattering and angular resolved X-ray photoelectron spectroscopy (XPS) suggest that the first atomic layer of annealed Pt₃Ti(111) is quasi-pure platinum. Scarcely any (θ ≈ 0.01) dissociation of CO was observed. Minor shifts of vibrational frequencies and desorption temperatures compared to Pt(111) and a p(2 × 2) “reconstruction” of the clean surface reveal some influence of the bulk. Auger spectroscopy, XPS, and ion scattering all show an increased titanium signal as a result of oxidation. Surface bound atomic oxygen gives a vibrational band around 650 cm⁻¹ which coincides with infrared absorption spectra of TiO₂. Flashing with CO shifts the band to 500 cm⁻¹. Correlated with this shift we observe (i) CO₂ desorption at a temperature well above that observed for Pt(111)/O, (ii) an altered Ti XPS signal, and (iii) a reduced oxygen concentration. Subsequently adsorbed CO molecules vibrate at the same frequencies as on the bare surface, give the same c(4 × 2) LEED pattern, and desorb at the same temperatures but with reduced intensity, in all proving that the surface oxide only acts as a site-blocker with respect to the metal surface. Our current understanding of these observations is that oxygen creates “islands of TiO₂”, segregated to the surface but with no electronic influence on remaining areas of the platinum enriched metal surface. The hexacoordinated Ti⁴⁺ ions on the surface of these islands are reduced by CO to pentacoordinated Ti³⁺ species. The vibrational shift, 650 to 500 cm⁻¹, can be understood by the dipole active bands of a triatomic O−Ti⁴⁺ −O vibrator compared to a diatomic Ti³⁺−O vibrator.     

A qualitative and quantitative study of the oxides of aluminum and silicon using AES and XPS

Experimental AES and XPS results from powdered α-Al₂O₃, SiO₂, Al₂Si₂O₇·2H₂O and an aluminosilicate glass are presented. The AES kinetic energy and the XPS binding energy values of core-level states and the peak shapes of X-ray induced O KLL Auger transitions are presented as qualitative reference data for the purpose of aiding in the identification of unknown aluminum oxide/silicon oxide samples. The AES peak-to-peak heights and the XPS peak areas of core-level states are presented as quantitative data and are used in the calculation of empirical relative sensitivity factor values. In addition, the sensitivity factor values are given parameters according to a single variable, f₈, defined as the ratio of the volume density of the oxygen atoms to the sum of the volume densities of the aluminum and silicon atoms.     

Characterization of ceramic PVD thin films on AZ31 magnesium alloys

Ceramic thin films have been widely used to protect the metal substrate as coatings in the past years. In order to improve the poor corrosion resistance of AZ31 magnesium alloy, the study in this paper used the electron beam evaporation method to prepare ceramic PVD films on its surface with TiO₂ and Al₂O₃ as donors, respectively. Atomic force microscopy (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES) and X-ray diffraction (XRD) were used to investigate the surface morphology, composition and microstructure of the thin films. Both films deposited on AZ31 took on compact top surface morphologies and grew as amorphous structures on substrate. AES test not only showed that films compositions deviated the standard stoichiometric ratios, but also found that element Mg diffused into films and existed as magnesium oxide in the TiO_x film as well as the AlO_x film. In the electrochemical corrosion test, the AlO_x coating on AZ31 exhibited the largest electrochemical impedance in a 3.5% NaCl solution. But it did not show better corrosion resistance than others for the poorer adhesion. Even if its thickness was small, the TiO_x coating on AZ31 exhibited the best corrosion resistance in this study. According to the observation and analysis, the damage of these films on AZ31 in aggressive solutions was mainly due to the existence of pores, microcracks, vacancies and poor adhesion between coating and substrate.     

A synchrotron XPS study of the vanadia–titania system as a model for monolayer oxide catalysts

The deposition of vanadium metal onto stoichiometric TiO₂(110) has been studied with photoelectron spectroscopy from low to high coverages of vanadium. A synchrotron source was employed in XPS experiments for the study of submonolayer coverages of vanadium in order to determine the oxidation state of the vanadia species formed at submonolayer coverages. The exposure of the titania surface to vanadium metal results in charge-transfer from vanadium to titania at the interface. At low doses of the metal vigorous interaction between the metal and titania surface yields reduction of the Ti⁴⁺ species to Ti³⁺ at the interface, as evidenced by both changes in the lineshape of the Ti 2p XPS spectra and Ti LIII-edge spectra. Concurrent with this surface reduction vanadium metal is oxidized. At higher vanadium doses the vanadium 2p binding energy indicates the formation of metallic vanadium. When metallic vanadium deposition is followed by exposure of the surface to oxygen, only one vanadium species remains on the surface, the binding energy of which corresponds to that of the oxide present initially at low doses of vanadium metal. By comparison of the V 2p binding energies to those of bulk oxides, it appears that the oxidation state of the vanadium in the oxide species is +3, suggesting the formation of V₂O₃ on the surface. Vanadium LIII-edge data also suggest that V₂O₅ is not formed by the oxidation of predosed vanadium metal.     

Electron spectroscopic studies of clean and oxidized iron

X-ray photoelectron spectroscopy (XPS) and soft X-ray appearance potential spectroscopy (APS) together with Auger electron spectroscopy (AES) were used to study the electronic properties of clean and oxidized (Fe₃O₄) iron surfaces. The features arising from excitations of electrons from Fe 2p core levels are discussed consistently within the common one-electron picture (i.e. neglecting final state effects). For pure Fe the shape of the APS L₃ peak is evaluated taking into consideration the theoretical density of states above the Fermi level and is found to agree well with that observed. As a consequence it is shown that in this case the appearance potential is about 1 eV larger than the threshold energy for the excitation of a core electron to the Fermi level. Thus for $\text{2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ electrons this quantity results to be 704.8 eV from both XPS and APS techniques. Successive oxidation at 500°C leads to an increase of the appearance potentials of the Fe 2p levels by only 0.5 eV, whereas the positions of the corresponding XPS peaks are shifted by as much as 3.5 eV. However this apparent disagreement can be eliminated by taking into account the above mentioned effect concerning the appearance potentials from pure Fe and the fact that the threshold energies (which determine the appearance potentials) of the XPS signals are shifted only by 1.7 eV. This example demonstrates that considerable care has to be taken in discussing “binding energies” or “chemical shifts” as derived from different electron spectroscopic techniques. The observed splitting of the MVV Auger transition of Fe at 47 eV upon oxidation is interpreted in terms of the qualitative features of the valence band structure of Fe₃O₄ and ascribed to the participation of a cross-transition between O 2p and Fe 3p states.     

Electronic structure of Ti metal and TiO2 powder studied by hard and soft (Cu Kα1 and Al Kα1) X-ray photoelectron and Auger spectroscopy

High-energy X-ray photoelectron spectroscopy (XPS) is of particular importance for minimizing the effects of surface contamination by increasing photoelectron escape depths. In this study high-resolution high-energy Cu Kα₁ and soft Al Kα₁ XPS and Auger electron spectroscopy were used to compare the electronic structure of Ti in TiO₂ powder and Ti metal. The Ti 1s in TiO₂ XPS line is narrower and more symmetric than in Ti metal. A comparison of the relative intensities of the L₂₃M₂₃M₄₅ and L₂₃M₂₃M₂₃ Auger transitions in Ti metal and TiO₂ is consistent with the expected transfer of Ti 3d electrons away from the Ti site in the oxide. The satellites accompanying the Ti 1s XPS line excited by Cu Kα₁ X-rays occur at the same energies as the satellites accompanying the Ti 2s and 2p XPS lines excited by Al Kα₁ X-rays indicating that they do not depend on the core-level, the experimental resolution or inelastic scattering processes.     

The desorption and decomposition of trinitrotoluene adsorbed on metal oxide powders

The desorption and decomposition of TNT on Al₂O₃, TiO₂, α-ZrO₂, α-Fe₂O₃, SiO₂ and MgO were studied in UHV by temperature programmed desorption (TPD) and Auger electron spectroscopy (AES). The metal oxide powders ranged in surface character from acidic (alumina) to basic (magnesia). TNT dosed at 110 K on each oxide gave a molecular TNT TPD peak between 285 and 300 K (multilayer desorption). Chemisorbed TNT decomposed completely on Al₂O₃, TiO₂, α-Fe₂O₃, and MgO. The decomposition products consisted mainly of CO, CO₂, HCN, NO and H₂O identified by TPD, and surface carbon and nitrogen residues identified by AES. No TNT decomposition was observed on SiO₂ (neutral). Chemisorbed TNT desorbed from SiO₂ in a single peak at about 350 K. Silica samples that were hydrated by exposure to an ambient atmosphere at 298 K adsorbed about 4 times more TNT at 298 K than did samples that were dehydrated in UHV. TPD results indicate than the enhancement in TNT adsorption was directly proportional to the concentration of molecularly adsorbed water on the silica surface.     

The co-adsorption of copper and oxygen on a tungsten {100} surface

The co-adsorption of Cu on O₂ and a W{100}surface is studied by Auger electron spectroscopy (AES), thermal desorption (TD), low energy electron diffraction (LEED) and by work function change (δø) measurements. It is shown that the presence of Cu on the surface initially decreases s_O, the sticking coefficient of O₂. For longer oxygen exposures and for higher adsorption temperatures, θ_O reaches values larger than those on the clean surface for the same O₂ exposure. Except at the highest θ_O values and temperatures, the sticcking coefficient for copper, s_Cu, is unity and is independent of the oxygen coverage θ_O in the range studied (0 ? θ_O ? 2). Co-adsorption at room temperatures does not produce any long range order while co-adsorption at elevated temperature leads to the ordered structures (1 × 1), p(2 × 1), p(2 × 2) and c(2 × 2). The saturation coverage of the two dimensional co-adsorbate at 800 K is given by the relation $\text{θ}{}_{\mathrm{Cu}}\text{+}\text{8}\text{5}\text{θ}{}_{\mathrm{O}}\text{= 2}$. The work function is a complicated function of θ_O and θ_Cu and is determined predominantly by the temperature at which oxygen is adsorbed. At high temperatures the sequence of adsorption has no influence, in contrast to the room temperature behavior.     

Defect structure of the Spinel,Ni2.44Ti0.77O4

Cation-excess spinels with composition Ni_2(1+x)Ti_(1?x)O₄ (0.16 ≤ x ≤ 1) form a limited solid solution between the rocksalt (NiO) and the hypothetical spinel (Ni₂TiO₄) structure types at temperatures above 1375°C. A quenched product of this series, Ni_2.44Ti_0.77O₄ ($\text{Fd3m;}\text{Z}\text{= 8; ρ}{}_{\mathrm{<mtext>calc</mtext>}}\text{= 5.6}\text{g}\text{/}\text{cm}{}^3\text{; a = 8.339}\text{A}\text{?}$), has been refined with X-ray intensity data in three models. Results indicate partial occupancy of the tetrahedral site (8a) and a second octahedral site (16c). Substitution of one tetrahedral metal atom for two octahedral atoms in random units of the NiO structure accounts for the additional metal atoms over the M₃O₄ stoichiometry. The best agreement with the model is obtained when all Ti₄₊ partially occupies the tetrahedral site.     

Bounded diffusion in solid solution electrode powder compacts. Part II. The simultaneous measurement of the chemical diffusion coefficient and the thermodynamic factor in LixTiS2 and LixCoO2

Two electrochemical methods - involving the application of a long-time galvanostatic current pulse and a small potentiostatic voltage step to a M/M_xSSE cell - are presented. From the overvoltage, respectively current response the chemical diffusion coefficient ($\text{D}{}_{\mathrm{M}}{}^{\mathrm{+}}$) and the thermodynamic factor (? ln a/? ln c) are obtained. The methods have been applied to the cells: Li/1M·LiClO₄ in propylenecarbonate/Li_xTi_1.03S₂ 0.05 < x < 0.95, T = 20°C; and Li_xCoO₂ 0.10 < × < 1, T = 20°C. From the application of the current pulse/voltage decay method it followed: $\text{D}{}_{\mathrm{<mtext>Li</mtext>}}{}^{\mathrm{+}}\text{(}\text{Li}{}_{\mathrm{x}}\text{Ti}{}_{1.03}\text{S}{}_2\text{) = 1?4 × 10}{}^{\mathrm{?8}}\text{cm}{}^2\text{s}{}^{\mathrm{?1}}$, with a slight tendency to increase with decreasing x; $\text{D}{}_{\mathrm{<mtext>Li</mtext>}}\text{C}\text{(}\text{Li}{}_{\mathrm{x}}\text{CoO}{}_2\text{) = 2?40 × 10}{}^{\mathrm{?9}}\text{cm}{}^2\text{s}{}^{\mathrm{?1}}$, decreasing with decreasing x. These values are among the highest found for solid state Li⁺-ion diffusion, and will be closely evaluated and compared with data reported by other workers. The x-dependence of the thermodynamic factor, determined from kinetic data, for Li_xTi_1.03S₂ (x = 0.05-0.95) and Li_xCoO₂ (x = 0.60-1.00) is in accordance with a simple thermodynamic model. Unlike for Li_xTi_1.03S₂, the thermodynamic factor for Li_xCoO₂, determined from the EMF-x relation, cannot be accounted for by this model. Furthermore, a fast, but crude method to determine the average chemical diffusion coefficient in Li_xTi_1.03S₂ and Li_xCoO₂ is discussed.     

X-ray photoelectron spectroscopy of TiO2 and other titanate electrodes and various standard Titanium oxide materials: Surface compositional changes of the TiO2 electrode during photoelectrolysis

Surface compositional changes were observed for TiO₂ single crystal electrodes used for photoelectrolysis of water. Surface stoichiometries of several types of TiO₂, SrTiO₃ and BaTiO₃ electrodes were characterized by XPS and compared with a variety of titanium, titanium oxide and titanium hydride standard materials. Reduction of the electrode surface in a hydrogen atmosphere results in an oxygen deficient surface composition. Photoelectrolysis at current densities of $\text{10–15}\text{mA}\text{cm}{}^2$ for periods up to 8 h appears to return the electrode surface to a nearly stoichiometric oxygen-to-metal ratio. Reduction of the titanium oxide surfaces was also observed by exposure to an argon ion beam. Analysis of the electrode surface by a combination of XPS and ion-sputter profiling was still possible by simultaneous analysis of standard materials.     

Site-selective adsorption of xenon on a stepped Ru(0001) surface

The adsorption of xenon has been studied with UV photoemission (UPS), flash desorption (TDS) and work function measurements on differently conditioned Ru(0001) surfaces at 100 K and at pressures up to 3 × 10^?5 Torr. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) served to ascertain the surface perfectness. On a perfect Ru(0001) surface only one Xe adsorption state is observed, which is characterized by$\text{Xe}\text{5}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$,$\text{1}\text{2}$ electron binding energies of 5.40 and 6.65 eV, an adsorption energy of E_ad≈ 5 kcal/mole and dipole moment of μ'_T ≈ 0.25 D. On a stepped-kinked Ru(0001) surface, the terrace-width, the step-height and step-orientation of which are well characterized with LEED, however, two coexisting xenon adsorption states are distinguishable by an unprecedented separation in$\text{Xe}\text{5}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$,$\text{1}\text{2}$ electron binding energies of 800 meV, by their different UPS intensities and line shapes, by their difference in adsorption energy ofΔE_ad ≈ 3 kcal/mole and finally by their strongly deviating dipole moments of μ_S = 1.0 D and μ_T = 0.34 D. The two xenon states (which are also observed on a slightly sputtered surface) are identified as corresponding to xenon atoms being adsorbed at step and terrace sites, respectively. Their relative concentrations as deduced from the UPS intensities quantitatively correlate with the abundance of step and terrace sites of the ideal TLK surface structure model as derived from LEED. Furthermore, ledge-sites and kink-sites are distinguishable via E_ad. The E_ad heterogeneity on the stepped-kinked Ru(0001) surface is interpreted in terms of different coordination and/or different charge-transfer-bonding at the various surface sites. The enormous increase in Xe 5p electron binding energy of 0.8 eV for Xe atoms at step sites is interpreted as a pure surface dipole potential shift. —The observed effects suggest selective xenon adsorption as a tool for local surface structure determination.     

Characterisation of thin films of bismuth oxide by X-ray photoelectron spectroscopy

The XPS (or ESCA) technique has been used for the characterisation of vacuum-deposited thin films of bismuth oxide. The spectra of Bi metal and Bi₂O₃ powder are used for comparison. The characterisation is carried out by consideration of the positions of the Bi 4f_{$\text{7}\text{2}$} and 4f_{$\text{5}\text{2}$} peaks and by using peak-fitting routines. A lower suboxide of bismuth, and metallic bismuth are observed in bismuth oxide films as evaporated. Oxidation of these films by heating in air results in bismuth(III) oxide. A linear relation is found between the binding energies and oxidation state. The corresponding O 1s spectra for the two types of film are also discussed.     

XPS characterization of sensitized n-TiO2 thin films for dye-sensitized solar cell applications

TiO₂ thin films, employed in dye-sensitized solar cells, were prepared by the sol-gel method or directly by Degussa P25 oxide and their surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The effect of adsorption of the cis-[Ru(dcbH₂)₂(NCS)₂] dye, N3, on the surface of films was investigated. From XPS spectra taken before and after argon-ion sputtering procedure, the surface composition of inner and outer layers of sensitized films was obtained and a preferential etching of Ru peak in relation to the Ti and N ones was identified. The photoelectrochemical parameters were also evaluated and rationalized in terms of the morphological characteristics of the films.     

Deposition of graded TiO2 films featured both hydrophobic and photo-induced hydrophilic properties

Graded TiO₂ films were deposited on unheated glass substrates by using a twin dc magnetron sputtering system. The graded TiO₂ films showed a highly polycrystalline structure of anatase with a little rutile phases revealed by X-ray diffraction spectra. The surface energy of the fresh and UV irradiated films were evaluated by water contact angle measurement. The results indicated that the water contact angle of the fresh graded TiO₂ films was found within 100-112°. The films then became a highly hydrophilic surface with the water contact angle of almost zero under 60 min UV irradiation. The XPS spectrum of Ti 2p revealed that the graded TiO₂ films became a stoichiometric titanium oxide layer near the surface, proving that titanium was fully oxidized. It was found that the surface OH group density depended on the substrates employed for given sputtering conditions. In addition, AFM images revealed a considerably rough surface of the graded films with RMS roughness of 12.6-14.5 nm. One can conclude that the unique properties of highly hydrophobicity and photo-induced hydrophilicity can be attributed to fully oxidized chemical composition and higher roughness on the film surface.     

Effect of N2 ion flux on the photocatalysis of nitrogen-doped titanium oxide films by electron-beam evaporation

Nitrogen-doped titanium oxide (TiO_xN_y) films were prepared with ion-assisted electron-beam evaporation. The nitrogen (N) incorporated in the film is influenced by the N₂ flux modulated by the N₂ flow rate through an ion gun. The TiO_xN_y films have the absorption edge of TiO₂ red-shifted to 500 nm and exhibit visible light-induced photocatalytic properties in the surface hydrophilicity and the degradation of methylene blue. The structures and states of nitrogen in the films are investigated by X-ray diffraction patterns (XRD), and X-ray photoelectron spectroscopy (XPS) and related to their visible light-induced photocatalytic properties. The results indicate that the substitutional N in anatase TiO₂ can induce visible light photocatalysis. The substitutional N is readily doped by the energetic nitrogen ions from the ion gun. The best photocatalytic activity is obtained at the largest N loading about 5.6 at.%, corresponding to the most substitutional N in anatase TiO₂. The film exhibits the degradation of methylene blue with a rate-constant (k) about 0.065 h⁻¹ and retaining 7° water contact angle on the surface under visible light illumination.     

Structural characterization of titanium oxide layers prepared by plasma based ion implantation with oxygen on Ti6Al4V alloy

Ti6Al4V alloy was implanted with oxygen by using plasma based ion implantation (PBII) at pulsed voltage ranging from −10 to −50 kV with a frequency of 100 Hz. In order to maintain a lower implantation temperature, an oil cooling working table was employed. The structure of the modified layers was characterized by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results show that the thickness of the titanium oxide layer increases significantly with the increase of implanted voltage. The structure of the modified layer changes along depth. It is found that the surface layer consists of TiO₂, and the subsurface layer is a mixing structure of TiO_2, Ti₂O₃ and TiO. There is crystalline rutile phase existing in the modified layer of sample implanted at high implanted voltage. In addition, in the outmost modified surface, aluminum present as oxidized state, and vanadium could not be detected.