Atomic layer deposition of the titanium dioxide thin film from tetraethoxytitanium and water

Using the methods of Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy, X-ray diffraction in the geometry of the grazing beam, and Fourier transform infrared spectroscopy, we studied the chemical composition and structure of thin films of titanium dioxide formed by atomic layer deposition from tetraethoxytitanium and water. It is shown that the films obtained are characterized by a high stoichiometry of composition and by amorphous or polycrystalline structure of the anatase modification, depending on the number of reaction cycles. Using a model of the process of atomic layer deposition that takes into account the size and number of ligands of the reacting molecules, we calculated the amount of titanium dioxide deposited in a single reaction cycle.     

Atomic layer deposition of crystalline molybdenum oxide thin films and phase control by post-deposition annealing

Molybdenum forms a range of oxides with different stoichiometries and crystal structures, which lead to different properties and performance in diverse applications. Herein, crystalline molybdenum oxide thin films with controlled phase composition are deposited by atomic layer deposition. The MoO₂(thd)₂ and O₃ as precursors enable well-controlled growth of uniform and conformal films at 200–275 °C. The as-deposited films are rough and, in most cases, consist of a mixture of α- and β-MoO₃ as well as an unidentified suboxide MoO_x (2.75 ≤ x ≤ 2.89) phase. The phase composition can be tuned by changing deposition conditions. The film stoichiometry is close to MoO₃ and the films are relatively pure, the main impurity being hydrogen (2–7 at-%), with ≤1 at-% of carbon and nitrogen. Post-deposition annealing is studied in situ by high-temperature X-ray diffraction in air, O₂, N₂, and forming gas (10% H₂/90% N₂) atmospheres. Phase-pure films of MoO₂ and α-MoO₃ are obtained by annealing at 450 °C in forming gas and O₂, respectively. The ability to tailor the phase composition of MoO_x films deposited by scalable atomic layer deposition method represents an important step towards various applications of molybdenum oxides.     

Atomic layer deposition of thin films of titanium dioxide from titanium tetramethoxide and water

The atomic layer deposition of titanium oxide in the precursor systems Ti(OCH₃)₄-H₂O and Ti(OC₂H₅)₄-H₂O was compared. The growth rate of titanium oxide formed by the atomic layer deposition in the Ti(OCH₃)₄-H₂O system can be adequately estimated with due to regard for the number and size of ligands of a metal-containing precursor. The study in simulated body fluid solutions showed that polycrystallin TiO₂ coatings with anatase structure are prone to accelerated osseointegration and, consequently, promising for the development of new biomedical products.     

Atomic layer deposition of hafnium oxide from hafnium chloride and water

Hafnium oxide (HfO2) is a leading candidate to replace silicon oxide as the gate dielectric for future generation metal-oxide-semiconductor based nanoelectronic devices. Atomic layer deposition (ALD) has recently gained interest because of its suitability for fabrication of conformal films with thicknesses in the nanometer range. This study uses periodic density functional theory (DFT) to investigate the mechanisms of both half-reactions occurring on the growing surface during the ALD of HfO2 using HfCl4 and water as precursors. We find that the adsorption energy and the preferred site of adsorption of the metal precursor are strong functions of the water coverage. As water coverage increases, the metal precursor preferentially interacts with multiple surface adsorption sites. During the water pulse the removal of Cl can be facilitated by either a ligand exchange reaction or the dissociation of Cl upon increase in coordination of the Hf atom of the precursor. Our predicted potential energy surface indicates that a more likely mechanism is hydration of the adsorbed Hf complex up to a coordination number of 7, followed by the dissociation of a chloride ion that is stabilized by solvation. Born-Oppenheimer molecular dynamics (BOMD) simulations of an adsorbed metal precursor in the presence of a multilayer of water shows that Cl dissociation is facile if sufficient water molecules are present to solvate the Cl(-) anions. Hence, solvation plays a crucial role during the water pulse and provides an alternative explanation for why ALD growth rates for this system decrease at high temperatures.     

Atomic layer deposition of TiO2−xNx thin films for photocatalytic applications

Titanium dioxide (TiO₂) is recognized as the most efficient photocatalytic material, but due to its large band gap energy it can only be excited by UV irradiation. Doping TiO₂ with nitrogen is a promising modification method for the utilization of visible light in photocatalysis. In this work, nitrogen-doped TiO₂ films were grown by atomic layer deposition (ALD) using TiCl₄, NH₃ and water as precursors. All growth experiments were done at 500 °C. The films were characterized by XRD, XPS, SEM and UV–vis spectrometry. The influence of nitrogen doping on the photocatalytic activity of the films in the UV and visible light was evaluated by the degradation of a thin layer of stearic acid and by linear sweep voltammetry. Light-induced superhydrophilicity of the films was also studied. It was found that the films could be excited by visible light, but they also suffered from increased recombination.     

Gallium oxide thin films from the AACVD of [Ga(NMe2)3]2 and donor functionalised alcohols

Thin films of Ga(2)O(3) have been produced from [Ga(NMe(2))(3)](2) and ROH (R = CH(2)CH(2)NMe(2), CH(CH(2)NMe(2))(2), CH(CH(3))CH(2)NMe(2), CH(2)CH(2)OMe and C(CH(3))(2)CH(2)OMe) by aerosol assisted chemical vapour deposition on glass. Transparent, unreflective films were obtained at a deposition temperature of 550 degrees C using toluene as solvent. The gallium oxide films were analyzed by Scanning electron microscopy (SEM), Raman spectroscopy, wavelength dispersive analysis of X-rays (WDX) and X-ray photoelectron spectroscopy (XPS). The gallium oxide films obtained were X-ray amorphous. Gas-sensing experiments indicated that the films showed an n-type response to ethanol at a variety of temperatures.     

Photoresponse of p-type zinc-doped iron(III) oxide thin films

Stable zinc-doped iron(III) oxide thin films that exhibit p-type behavior were synthesized by spray pyrolytic deposition (SPD) on conducting indium-doped tin oxide-coated glass substrate. The highest photocurrent density of 1.1 mA/cm2 was observed at an illumination intensity of 40 mW/cm2 at -0.8 V vs Pt for zinc-doped p-Fe2O3 samples prepared at an optimum substrate temperature of 663 K using an optimum spray time of 70 s. A quantum efficiency of 21.1% at 325 nm was found for SPD samples prepared using a dopant concentration of 0.0088 M zinc nitrate hexahydrate. X-ray diffraction results showed structures of alpha-Fe2O3 and ZnFe2O4. A direct band gap energy of 2.2 eV was found from monochromatic photocurrent density data and agrees closely with the band gap obtained from UV-vis absorption. The X-ray photoelectron spectroscopy results also confirm the presence of zinc dopant (4.0 atomic %) in thin films of zinc-doped p-Fe2O3.     

Gas-phase photofragmentation of tris(methyl vinyl ketone) tungsten(0) and the relationship to laser-assisted CVD of tungsten oxide thin films

The gas-phase laser-induced photofragmentation of tris(methyl vinyl ketone) tungsten(0) is studied, and the photoproducts are identified by time-of-flight mass spectroscopy. The initially populated excited electronic state of the complex is attributed to metal-to-ligand charge transfer by analysis of the electronic and preresonance Raman spectra. The major metal-containing photofragmentation products are W(+) and WO(+); smaller amounts of WC(+) and W(C(2)H(2))(+) are also observed. Intramolecular ligand coupling occurs, and dimeric products and their fragments are identified. Reaction pathways that explain the observed products are proposed. Thin films on silicon substrates are produced by laser-assisted chemical vapor deposition. The films consist of polycrystalline tungsten oxide with less than 10% tungsten carbide and are characterized by X-ray diffraction, SEM, and Auger electron spectroscopy. Relationships between the composition of the gas-phase photofragments and that of the solid films are discussed.     

Aerosol assisted chemical vapour deposition of tungsten oxide films from polyoxotungstate precursors: active photocatalysts

Aerosol assisted chemical vapour deposition of polyoxotungstate precursors [n-Bu4N]2[W6O19] and [n-Bu4N]4H3[PW11O39] produces films of WO(3 - x) and WO3 on glass substrates; the WO3 films show significant photocatalytic decomposition of a test organic pollutant--stearic acid--when irradiated with either 254 or 365 nm radiation.     

Poly(ethylene oxide) thin films produced by electrospray deposition: morphology control and additive effects of alcohols on nanostructure

Nanostructured thin films were prepared by electrospray deposition (ESD) from poly(ethylene oxide) (PEO) aqueous solution. The surface morphologies of the deposited films were observed using scanning electron microscopy (SEM). The SEM images revealed the correlations between the morphologies and the ESD conditions. By changing the applied voltage and solution properties such as viscosity, surface tension, conductivity, and molecular weight, PEO thin films with diverse nanostructures--from nanospheres to nanofibers--were fabricated. It was also revealed that the addition of alcohols to polymer solution, which enables simultaneously changing the viscosity, the surface tension, and the conductivity, enhanced the formation of the fibrous structure. These results indicate that the ESD method is potentially a useful option for producing nanoengineered polymer surface.     

Contact angle of water on polystyrene thin films: effects of CO(2) environment and film thickness

We examine the contact angle of water droplets on polystyrene (PS) thin films of varying thicknesses supported by silicon wafers under both air and pressurized carbon dioxide (CO2) environments. At 23 degrees C, the contact angle is found to increase upon increasing CO2 pressure in the vapor regime and then levels off in the liquid CO2 regime. A macroscopic model based on Young's equation and the geometric-mean method for interfacial tensions, and long-range van der Waals interactions, correctly predicts the trends and the magnitude of the contact angle dependence on pressure, although deviations occur at high CO2 activities. The contact angle was also found to depend on film thickness, h, when h was comparable to or smaller than 50 nm. Specifically, the contact angle decreases with decreasing PS film thickness. This behavior could be accounted for with the use of a model that incorporates the effects of film thickness, CO2 pressure, and the long-range van der Waals potential.     

Atmospheric pressure chemical vapour deposition of WO3 thin films from a volatile fluorinated tungsten oxo‐alkoxide precursor,W(O)(OCH2CF3)4

The monomeric tungsten oxo‐fluoroalkoxide W(O)(CH₂CF₃)₄ ( 1 ) was synthesized from W(O)Cl₄ and CF₃CH₂OH in the presence of ammonia. It was used in atmospheric pressure chemical vapour deposition experiments to deposit non‐stoichiometric WO_2.9 when used as a single‐source precursor or stoichiometric WO₃ when O₂ was used as co‐reagent. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthetic entry into polynuclear bismuth-manganese chemistry: high oxidation state Bi(III)2Mn(IV)6 and Bi(III)Mn(III)10 complexes

The first high nuclearity, mixed-metal Bi(III)/Mn(IV) and Bi(III)/Mn(III) complexes are reported. The former complexes are [Bi(2)Mn(IV)(6)O(9)(O(2)CEt)(9)(HO(2)CEt)(NO(3))(3)] (1) and [Bi(2)Mn(IV)(6)O(9)(O(2)CPh)(9)(HO(2)CPh)(NO(3))(3)] (2) and were obtained from the comproportionation reaction between Mn(O(2)CR)(2) and MnO(4)(-) in a 10:3 ratio in the presence of Bi(NO(3))(3) (3 equiv) in either a H(2)O/EtCO(2)H (1) or MeCN/PhCO(2)H (2) solvent medium. The same reaction that gives 2, but with Bi(O(2)CMe)(3) and MeNO(2) in place of Bi(NO(3))(3) and MeCN, gave the lower oxidation state product [BiMn(III)(10)O(8)(O(2)CPh)(17)(HO(2)CPh)(H(2)O)] (3). Complexes 1 and 2 are near-isostructural and possess an unusual and high symmetry core topology consisting of a Mn(IV)(6) wheel with two central Bi(III) atoms capping the wheel on each side. In contrast, the [BiMn(III)(10)O(8)](17+) core of 3 is low symmetry, comprising a [BiMn(3)(μ(3)-O)(2)](8+) butterfly unit, four [BiMn(3)(μ(4)-O)](10+) tetrahedra, and two [BiMn(2)(μ(3)-O)](7+) triangles all fused together by sharing common Mn and Bi vertices. Variable-temperature, solid-state dc and ac magnetization data on 1-3 in the 1.8-300 K range revealed that 1 and 2 possess an S = 0 ground state spin, whereas 3 possesses an S = 2 ground state. The work offers the possibility of access to molecular analogs of the multifunctional Bi/Mn/O solids that are of such great interest in materials science.     

Unexpected formation of anti-1,2-W2(SBut)2(NMe2)4 in the thiolysis of gauche-1,2-W2Cp2(NMe2)4 and W2COT(NMe2)4 with ButSH

Thiolysis of W₂Cp₂(NMe₂)₄ and W₂COT(NMe₂)₄ with excess Bu^tSH leads to cleavage of the respective carbocyclic rings from the ditungsten center and formation of the compound anti-1,2-W₂(SBu^t)₂(NMe₂)₄ which was characterized via a single-crystal X-ray diffraction study. This product was found to be isostructural with its dimolybdenum analogue. The compound is a prototypical ethane-like dimer having a WW bond distance of 2.3011(3) Å and thiolate ligands in an anti configuration about the WW bond. The thiolysis reactions for both dimethylamide precursors are contrasted with the results of their respective alcoholysis reactions.     

Role of water in the atomic layer deposition of TiO(2) on SiO(2)

Atomic layer deposition (ALD) of TiO(2) on SiO(2) powder using sequential addition of TiCl(4) and H(2)O vapors has been investigated by infrared spectroscopy. In the first cycle, TiCl(4) reacts monofunctionally or bifunctionally with surface silanols forming (Si-O-)(n)Ti-Cl(4)(-)(n) (n = 1, 2) species. Subsequent addition of water vapor leads to the hydrolysis of the (Si-O-)(n)Ti-Cl(4)(-)(n) to form a Ti-O-Ti network, and at the same time, some cleavage of Si-O-Ti bonds occurs, regenerating Si-OH in the process. It is shown that the species formed on the surface in the first TiCl(4) dose are temperature dependent. However, after addition of H(2)O vapor, the amount of TiO(2) deposited in the first complete cycle is independent of reaction temperature. In the second and above cycles, the amount of TiO(2) deposited as a function of ALD cycles strongly correlates with the amount of water on the surface. This, in turn, led to a temperature dependence of the growth rate of the TiO(2) per cycle.     

Orientation control of perovskite thin films on glass substrates by the application of a seed layer prepared from oxide nanosheets

Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa₂Nb₃O₁₀ oxide grains. A seed layer composed of (TBA)Ca₂Nb₃O₁₀ nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO₃ (LNO) and Pb(Zr,Ti)O₃ (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.     

Vanadium(IV) oxide thin films on glass and silicon from the atmospheric pressure chemical vapour deposition reaction of VOCl3 and water

The dual source atmospheric pressure chemical vapour deposition (APCVD) reaction of VOCl₃ and H₂O was used to prepare thin films of vanadium oxides on glass and silicon substrates. The thin films were characterised by X-ray diffraction, Raman spectroscopy X-ray photoelectron spectroscopy and scanning electron microscopy. At reactor temperatures above 600 °C with a gas-phase excess of water over VOCl₃, vanadium(IV) oxide thin films were produced which show a thermochromic transition temperature of 67 °C. The APCVD process is directly compatible with high throughput float-glass production enabling the use of a thin film of VO₂ as an intelligent window coating. With reactor temperatures below 600 °C or with a gas-phase excess of VOCl₃ over water, V₂O₅ thin films were produced. Vanadium(IV) oxide thin films could also be prepared on silicon substrates from the APCVD reaction of VOCl₃ and H₂O, which opens up further technological applications for the APCVD of VO₂ thin films.     

Preliminary studies in the electrodeposition of PbSe/PbTe superlattice thin films via electrochemical atomic layer deposition (ALD)

This paper concerns the electrochemical growth of compound semiconductor thin film superlattice structures using electrochemical atomic layer deposition (ALD). Electrochemical ALD is the electrochemical analogue of atomic layer epitaxy (ALE) and ALD, methods based on nanofilm formation an atomic layer at a time, using surface-limited reactions. Underpotential deposition (UPD) is a type of electrochemical surfaced-limited reaction used in the present studies for the formation of PbSe/PbTe superlattices via electrochemical ALD. PbSe/PbTe thin-film superlattices with modulation wavelengths (periods) of 4.2 and 7.0 nm are reported here. These films were characterized using electron probe microanalysis, X- ray diffraction, atomic force microscopy (AFM), and infrared reflection absorption measurements. The 4.2 nm period superlattice was grown after deposition of 10 PbSe cycles, as a prelayer, resulting in an overall composition of PbSe0.52Te0.48. The 7.0 nm period superlattice was grown after deposition of 100 PbTe cycle prelayer, resulting for an overall composition of PbSe0.44Te0.56. The primary Bragg diffraction peak position, 2theta, for the 4.2 superlattice was consistent with the average (111) angles for PbSe and PbTe. First-order satellite peaks, as well as a second, were observed, indicating a high-quality superlattice film. For the 7.0 nm superlattice, Bragg peaks for both the (200) and (111) planes of the PbSe/PbTe superlattice were observed, with satellite peaks shifted 1 degrees closer to the (111), consistent with the larger period of the superlattice. AFM suggested conformal superlattice growth on the Au on glass substrate. Band gaps for the 4.2 and 7.0 nm period superlattices were measured as 0.48 and 0.38 eV, respectively.     

Fabrication of polycrystalline La2NiMnO6 thin films on Si (1 0 0) substrates by chemical solution deposition

Polycrystalline double perovskite La₂NiMnO₆ thin films are successfully deposited on Si (1 0 0) substrates via chemical solution deposition. The X-ray diffraction and Raman scattering spectroscopy are used to characterize all the films, it is found that all films are single phase and polycrystalline. The field-emission scanning electron microscopy shows that the films are relatively smooth and dense. The magnetic measurements indicate that one sample exhibits a Curie temperature of about 271 K, which is close to that of the bulk material. Moreover, the low-temperature magnetization of the films is lower than that of the films deposited on LaAlO₃ (1 0 0) substrates, which can be attributed to the large mismatch between the films and the Si substrates.     

The APCVD of tungsten oxide thin films from reaction of WCl6 with ethanol and results on their gas-sensing properties

The APCVD reaction of WCl₆ with ethanol was examined to deposit tungsten oxide on gas sensor substrates. Deposited films, which were WO_3−x, displayed a different morphology than those seen previously for CVD tungsten oxide. The gas-sensing properties of the deposited films were examined.