Auger and X-ray photoelectron spectroscopic and electrochemical characterization of titanium thin film electrodes

Auger (AES) and X-ray photoelectron spectroscopic (XPS) characterizations of electrochemically oxidized titanium are described. Surface oxides on thin (200–250 Å) vacuum deposited titanium films were formed under conditions of linear potential scan in 1 N KClO₄, 1 N HClO₄ and 1 N H₂SO₄. Current/voltage, capacitance/voltage and surface conductance/voltage relationships confirmed the irreversible formation of the surface oxide at thickness of 20–30 Å/V, for low applied potentials. Post moretem analysis of the thin films by AES and XPS indicated a mixture of metal and metal oxides (TiO₂, Ti₂O₃, TiO) on each surface, with the higher oxide states predominating on the electrochemically oxidized films. Observation of the L_IIIM_2,3M_4,5, N(E) signal shape in the Auger spectra of the potentially oxidized oxidized films showed a suboxide TiO-like surface rather than an TiO₂ surface state. Deconvolution of the $\text{Ti}\text{(2}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext><mtext>,\; </mtext><mtext>3</mtext><mtext>2</mtext>}}\text{)}\text{XPS}$ spectra confirmed the coexistence of multiple oxidation states of Ti during electrochemical or atmospheric oxidation of the films. Ion sputtering of each surface was used to characterize the subsurface metal/metal oxide composition and to correlate the oxygen to metal atomic ratio with electrochemical pretreatment.     

Structure and phase composition of thin a-C:H films modified by Ag and Ti

The structure and phase composition of thin a-C:H and a-C:H〈M〉 films (M = Ag, Ti, or Ag + Ti) have been studied by Raman and X-ray photoelectron spectroscopy. The a-C:H〈M〉 films were prepared by ion-plasma magnetron sputtering of a combined target of graphite and metal in an Ar–CH₄ gas mixture. The Raman spectra of these films indicate that their structure is amorphous. The a-C:H〈Ag + Ti〉 films have a more graphitized structure in comparison with pure a-C:H films and films containing only one metal. It is established that carbon in the a-C:H〈Ag + Ti〉 films is in the sp ², sp ³, and C=O states, which are characteristic of the a-C:H, a-C:H〈Ag〉, and a-C:H〈Ti〉 films. In addition, there are also ether (–C–O–C–) or epoxy (?C?O–) carbon groups in the a-C:H〈Ag + Ti〉 films. It has been revealed that silver atoms in the a-C:H〈Ag〉 and a-C:H〈Ag + Ti〉 films form no chemical bonds with carbon, oxygen, and titanium. Titanium in the a-C:H〈Ti〉 and a-C:H〈Ag + Ti〉 films exists in the form of titanium IV oxide (TiO₂).     

Oxidation kinetics of thin titanium films grown on tungsten

Growth of thin Ti films on (100)W and the kinetics of their oxidation are studied using thermal-desorption spectroscopy and Auger electron spectroscopy. Titanium films grow nearly layer by layer on the (100)W face at room temperature. The activation energy for desorption of Ti atoms decreases from 5.2 eV for coverage θ=0.1 to 4.9 eV in a multilayer film. Oxidation of a thin (θ=6) titanium film starts with dissolution of oxygen atoms in its bulk to the limiting concentration for a given temperature, after which the film oxidizes to TiO, with the TiO₂ oxide starting to grow when exposure of the film to oxygen is prolonged. The thermal desorption of oxides follows zero-order kinetics and is characterized by desorption activation energies of 5.1 (TiO) and 5.9 eV (TiO₂).     

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb_1−XLa_XTiO₃ thin films, (X=0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300°C range in an O₂ atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO₃. The films deposited on Pt/Ti/SiO₂/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration.     

Structural, electrical and optical properties of TiO2 doped WO3 thin films

TiO₂ doped WO₃ thin films were deposited onto glass substrates and fluorine doped tin oxide (FTO) coated conducting glass substrates, maintained at 500 °C by pyrolytic decomposition of adequate precursor solution. Equimolar ammonium tungstate ((NH₄)₂WO₄) and titanyl acetyl acetonate (TiAcAc) solutions were mixed together at pH 9 in volume proportions and used as a precursor solution for the deposition of TiO₂ doped WO₃ thin films. Doping concentrations were varied between 4 and 38%. The effect of TiO₂ doping concentration on structural, electrical and optical properties of TiO₂ doped WO₃ thin films were studied. Values of room temperature electrical resistivity, thermoelectric power and band gap energy (E_g) were estimated. The films with 38% TiO₂ doping in WO₃ exhibited lowest resistivity, n-type electrical conductivity and improved electrochromic performance among all the samples. The values of thermoelectric power (TEP) were in the range of 23-56 μV/K and the direct band gap energy varied between 2.72 and 2.86 eV.     

Raman investigations of TiO2 nanotube substrates covered with thin Ag or Cu deposits

A tubular array of TiO₂ nanotubes on Ti matrix was used as a support for Ag or Cu sputter‐deposited layers intended for surface‐enhanced Raman scattering (SERS) investigations. The composite samples of Ag/TiO₂–nanotube/Ti and Cu/TiO₂–nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) [and scanning Auger microscopy (SAM)] to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured after it had been adsorbed on the TiO₂–nanotube/Ti substrates covered with thin Ag or Cu deposit as well as on the bulk electrochemically roughened Ag or Cu reference substrates. It was found that the SERS spectra measured for pyridine adsorbed on the bulk silver substrate were significantly different than the spectra measured on the TiO₂–nanotube/Ti substrates covered the Ag layer. The spectra measured for pyridine adsorbed on the Ag/TiO₂–nanotube/Ti suggest that on the surface of such a composite substrate there are many Lewis acidic sites. Spectra typical for pyridine adsorbed on acidic sites were observed even after deposition of a relatively thick silver layer (e.g. an Ag layer with an average thickness of 80 nm) on the TiO₂–nanotube/Ti support. Our findings suggest that TiO₂–nanotube/Ti support is a promising substrate for the preparation of metallic nano‐clusters on a support containing acidic active sites. Copyright © 2009 John Wiley & Sons, Ltd.     

Selective MOCVD of titanium oxide and zirconium oxide thin films using single molecular precursors on Si(1 0 0) substrates

Titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films have been deposited on modified Si(1 0 0) substrates selectively by metal-organic chemical vapor deposition (MOCVD) method using new single molecular precursor of [M(OⁱPr)₂(tbaoac)₂] (M=Ti, Zr; tbaoac=tertiarybutyl-acetoacetate). For changing the characteristic of the Si(1 0 0) surface, micro-contact printing (μCP) method was adapted to make self-assembled monolayers (SAMs) using an octadecyltrichlorosilane (OTS) organic molecule which has -CH₃ terminal group. The single molecular precursors were prepared using metal (Ti, Zr) isopropoxide and tert-butylacetoacetate (tbaoacH) by modifying standard synthetic procedures. Selective depositions of TiO₂ and ZrO₂ were achieved in a home-built horizontal MOCVD reactor in the temperature range of 300-500 °C and deposition pressure of 1×10⁻³-3×10⁻² Torr. N₂ gas (5 sccm) was used as a carrier gas during film depositions. TiO₂ and ZrO₂ thin films were able to deposit on the hydrophilic area selectively. The difference in surface characteristics (hydrophobic/hydrophilic) between the OTS SAMs area and the SiO₂ or Si-OH layer on the Si(1 0 0) substrate led to the site-selectivity of oxide thin film growth.     

Optical properties of TiO2-MnO2 thin films prepared by electron-beam evaporation

The optical constants and thickness of TiO₂-MnO₂ films (with MnO₂ concentration of 0, 1, and 5%) prepared by electron-beam evaporation are determined. A considerable dependence of the optical properties of thin TiO₂ films on the manganese concentration is observed. It is found that thin films are indirect gap semiconductors with gap width E _g = 3.43 eV (TiO₂), 2.89 eV (TiO₂-MnO₂ (1%)), and 2.73 eV (TiO₂-MnO₂ (5%)).     

Structural, magnetic and electronic structure studies of Mn doped TiO2 thin films

We report structural, magnetic and electronic structure study of Mn doped TiO₂ thin films grown using pulsed laser deposition method. The films were characterized using X-ray diffraction (XRD), dc magnetization, X-ray magnetic circular dichroism (XMCD) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements. XRD results indicate that films exhibit single phase nature with rutile structure and exclude the secondary phase related to Mn metal cluster or any oxide phase of Mn. Magnetization studies reveal that both the films (3% and 5% Mn doped TiO₂) exhibit room temperature ferromagnetism and saturation magnetization increases with increase in concentration of Mn doping. The spectral features of XMCD at Mn L_3,2 edge show that Mn²⁺ ions contribute to the ferromagnetism. NEXAFS spectra measured at O K edge show a strong hybridization between Mn, Ti 3d and O 2p orbitals. NEXAFS spectra measured at Mn and Ti L_3,2 edge show that Mn exist in +2 valence state, whereas, Ti is in +4 state in Mn doped TiO₂ films.     

Synthesis and characterization of Zn(O,OH)S and AgInS2 layers to be used in thin film solar cells

In this paper AgInS₂ and Zn(O,OH)S thin films were synthesized and characterized. AgInS₂ layers were grown by co-evaporation from metal precursors in a two-step process, and, Zn(O,OH)S thin films were deposited from chemical bath containing thiourea, zinc acetate, sodium citrate and ammonia. X-ray diffraction measurements indicated that AgInS₂ thin films grown with chalcopyrite structure, and the as-grown Zn(O,OH)S thin films were polycrystalline. It was also found that the AgInS₂ films presented p-type conductivity, a high absorption coefficient (greater than 10⁴ cm⁻¹) and energy band-gap E_g of about 1.95 eV, Zn(O,OH),S thin films presented E_g of about 3.89 eV. Morphological analysis showed that under this synthesis conditions Zn(O,OH),S thin films coated uniformly the absorber layer. Additionally, the Zn(O,OH)S kinetic growth on AgInS₂ layer was studied also. Finally, the results suggest that these layers possibly could be used in one-junction solar cells and/or as top cell in a tandem solar cell.     

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.     

Effect of Er doping on optical band gap energy of TiO2 thin films prepared by spin coating

In order to evaluate the effect of Er doping in the range of 0–1.0 mol% on optical indirect band gap energy (E_g) of the film, the Er-doped TiO₂ (Er-TiO₂) thin films were spin-coated onto fluorine-doped SnO₂ coated (FTO) glasses. Glancing angle X-ray diffraction (GAXRD) results indicated that the films whose thickness was 550 nm consisted of pure anatase and FTO substrate. The anatase (101) TiO₂ peaks became broader and weaker with the rise in Er content. The apparent crystallite size decreased from 12 nm to 10 nm with increasing the amount of Er from 0 mol% to 1.0 mol%. UV–vis spectrophotometry showed that the values of E_g decreased from 3.25 eV to 2.81 eV with the increase of Er doping from 0 to 0.7 mol%, but changed to 2.89 eV when Er content was 1.0 mol%. The reduction in E_g might be attributed to electron and/or hole trapping at the donor and acceptor levels in the TiO₂ band structure.     

Preparation and optical properties of ZnGa2O4:Cr thin films derived by sol-gel process

ZnGa₂O₄:Cr³⁺ thin films with bright red emission were synthesized using a sol-gel process, characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Auger electron spectroscopy (AES) and UV-vis and fluorescence spectrophotometry measurements. Effects of calcining temperature, film thickness, calcining duration and substrates on the crystal structure and photoluminescent property have been investigated. It is found that the crystallinity, Ga/Zn ratio and band gap energy (E_g) are significant factors influencing optical characteristics, while the nature of substrates affect the surface morphologies of ZnGa₂O₄:Cr³⁺ thin films.     

Magnetoelectric properties of Mn-substituted BiFeO3 thin films with a TiO2 barrier

Multiferroic thin films with the general formula TiO₂/BiFe_1−xMn_xO₃ (x=0.00, 0.05, 0.10 and 0.15) (TiO₂/BFMO) were synthesized on Au/Ti/SiO₂/Si substrates using a chemical solution deposition (CSD) method assisted with magnetron sputtering. X-ray diffraction analysis shows the thin films contained perovskite structures with random orientations. Compared with BFMO films, the leakage current density of the TiO₂/BFMO thin films was found to be lower by nearly two orders of magnitude, and the remnant polarizations were increased by nearly ten times. The enhanced ferroelectric properties may be attributed to the lower leakage current caused by the introduction of the TiO₂ layer. The J-E characteristics indicated that the main conduction mechanism for the TiO₂/BFMO thin film was trap-free Ohmic conduction over a wide range of electric fields (0-500 kV/cm). In addition, ferromagnetism was observed in the Mn doped BFO thin films at room temperature. The origin of ferromagnetism is related to the competition between distortion of structure and decrease of grain size and decreasing net magnetic moment in films due to Mn doping.     

Improvement of dielectric tunability and loss tangent of (Ba,Sr)TiO3 thin films with K doping

Ba_0.6Sr_0.4TiO₃ thin films doped with K were deposited on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method. The structure, surface morphology, and dielectric and tunable properties of Ba_0.6Sr_0.4TiO₃ thin films have been studied in detail. The K content in Ba_0.6Sr_0.4TiO₃ thin films has a strong influence on the material's properties including surface morphology, dielectric and tunable properties. It is found that the Curie temperature of K-doped Ba_0.6Sr_0.4TiO₃ films shifts to higher values compared with that of undoped Ba_0.6Sr_0.4TiO₃ thin films, which leads to a dielectric enhancement of K-doped Ba_0.6Sr_0.4TiO₃ films at room temperature. At the optimized content of 0.02 mol, the dielectric loss tangent is reduced significantly from 0.057 to 0.020. Meanwhile, the tunability is enhanced obviously from 26% to 48% at the measured frequency of 1 MHz and the maximum value of the figure of merit is 23.8. This suggests that such films have potential applications for tunable devices.     

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.     

Influence of porous morphology on optical dispersion properties of template free mesoporous titanium dioxide (TiO2) films

This paper focuses the influence of porous morphology on the microstructure and optical properties of TiO₂ films prepared by different sol concentration and calcination temperatures. Mesoporous TiO₂ thin films were prepared on the glass substrates by sol-gel dip coating technique using titanium (IV) isopropoxide. Porous morphology of the films can be regulated by chemical kinetics and is studied by scanning electron microscopy. The optical dispersion parameters such as refractive index (n), oscillator energy (E_d), and particle co-ordination number (N_c) of the mesoporous TiO₂ films were studied using Swanepoel and Wemple-DiDomenico single oscillator models. The higher precursor concentration (0.06 M), films exhibit high porosity and refractive index, which are modified under calcination treatment. Calcinated films of low metal precursor concentration (0.03 M) possess higher particle co-ordination number (N_c = 5.05) than that of 0.06 M films (N_c = 4.90) due to calcination at 400 °C. The lattice dielectric constant (E_∞) of mesoporous TiO₂ films was determined by using Spintzer model. Urbach energy of the mesoporous films has been estimated for both concentration and the analysis revealed the strong dependence of Urbach energy on porous morphology. The influence of porous morphology on the optical dispersion properties also has been explained briefly in this paper.     

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO₂ sol-gels with various Ag/TiO₂ molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO₂ thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO₂ nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO₂ sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO₂ sol-gel, four types of the TiO₂ thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO₂), TA (bottom layer was pure TiO₂, surface layer was Ag modified), TT (pure TiO₂ thin film) and AA (TiO₂ thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I_ph). LSV confirmed the existence of Ag⁰ state in the TiO₂ thin film. SEM and XRD experiments indicated that the sizes of the TiO₂ nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO₂ thin film.     

The electrical properties and phase transformation of PLZST 2/85/13/2 antiferroelectric thin films on different bottom electrode

Pb_0.97La_0.02(Zr_0.85Sn_0.13Ti_0.02)O₃ (PLZST 2/85/13/2) antiferroelectric thin films were deposited on Pt(111)/Ti/SiO₂/Si and LaNiO₃(LNO)/SiO₂/Si substrates through a modified sol-gel process. The phase structure and microstructure of PLZST 2/85/13/2 antiferroelectric thin films were analysed by x-ray diffraction (XRD), scanning electron microcopy (SEM) and field-emission SEM (FE-SEM). The antiferroelectric nature of the PLZST 2/85/13/2 thin films on two electrodes was demonstrated by the C-V (capacitance-voltage) and P-E (polarization-electric field) measurement. The maximum polarizations for PLZST 2/85/13/2 films on Pt and LNO electrodes were 42 and 18 μC/cm², respectively. The temperature dependence of the dielectric property of the PLZST 2/85/13/2 films was measured under different dc electric fields. Also, the phase transformation of the PLZST 2/85/13/2 films was studied in detail as a function of temperature and dc electric field.     

Dielectric and piezoelectric properties of the Ba0.92Ca0.08Ti0.95Zr0.05O3 thin films grown on different substrate

Lead free Ba_0.92Ca_0.08Ti_0.95Zr_0.05O₃ (BCZT) thin films were deposited on Pt/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt/Ti/SiO₂/Si substrates by a sol–gel processing technique, respectively. The effects of substrate on structure, dielectric and piezoelectric properties were investigated in detail. The BCZT thin films deposited on LNO/Pt/Ti/SiO₂/Si substrates exhibit (100) orientation, larger grain size and higher dielectric tunability (64%). The BCZT thin films deposited on Pt/Ti/SiO₂/Si exhibit (110) orientation, higher Curie temperature (75 °C), better piezoelectric property (d₃₃ of 50 pm/V) and lower dielectric loss (0.02). The differences in dielectric and piezoelectric properties in the two kinds of oriented BCZT films should be attributed to the difference of structure, in-plane stress and polarization rotation in orientation engineered BCZT films.