Thin films of iron oxide by low pressure MOCVD using a novel precursor: tris(t-butyl-3-oxo-butanoato)iron(III)

Deposition of thin films of iron oxide on glass has been carried out using a novel precursor, tris(t-butyl-3-oxo-butanoato)iron(III), in a low-pressure metalorganic chemical vapor deposition (MOCVD) system. The new precursor was characterized for its thermal properties by thermogravimetry and differential thermal analysis. The films were characterized by X-ray diffraction (XRD), transmission electron microscopy, scanning electron microscopy, and by optical measurements. XRD studies reveal that films grown at substrate temperatures below ∼550 °C and at low oxygen flow rates comprise only the phase Fe₃O₄ (magnetite). At higher temperatures and at higher oxygen flow rates, an increasing proportion of α-Fe₂O₃ is formed along with Fe₃O₄. Films of magnetite grown under different reactive ambients—oxygen and nitrous oxide—have very different morphologies, as revealed by scanning electron microscopic studies.     

X-ray diffraction studies of Bi2O3 films prepared by reactive and activated reactive evaporation

Bi₂O₃ films were prepared by reactive evaporation and by activated reactive evaporation. The various phases obtained were studied using X-ray diffraction. Reactive evaporation always produced β-Bi₂O₃ films. For a given substrate temperature, low rates of deposition (less than 20 Å s^-1) always produced β-Bi₂O₃ films, whereas high rates of deposition (greater than 35 Å s^-1) produced α-Bi₂O₃ films when the oxygen partial pressure inside the chamber was kept constant. Films prepared by both reactive evaporation and activated reactive evaporation at substrate temperatures below 400 K were amorphous in nature and at higher substrate temperatures polycrystalline films were produced. The results obtained on annealing these films in high vacuum and in air are also reported.     

Composition of alumina films grown on Si at low temperature with catalytic CVD

The X-ray photoelectron spectroscopy (XPS) measurements have been used to reveal the compositions of alumina (Al₂O₃) films formed on Si wafers using tri-methyl aluminium (TMA) and molecular oxygen (O₂) with catalytic chemical vapour deposition (Cat-CVD). The atomic ratio (O/Al) for Al₂O₃ samples formed at substrate temperature of 200-400 °C has been obtained to be 1.4 which is close to stoichiometry. The increase of growth rate at substrate temperatures below 200 °C and above 400 °C can be attributed to formation of aluminum oxides with non-stoichiometry and metallic aluminum incorporated in the films resulting from deficient oxygen. Angle resolved XPS measurements have revealed that the alumina/Si interface with no SiO₂ film has been obtained at substrate temperatures below 200 °C.     

The adhesion between physically vapour-deposited or chemically vapour-deposited alumina and TiC-coated cemented carbides as characterized by Auger electron spectroscopy and scratch testing

The adhesion of alumina films (obtained by either physical vapour deposition (PVD) or chemical vapour deposition (CVD) on TiC-, TiN- or Ti(C,N)-precoated cemented carbides is discussed on the basis of scratch test measurements. When alumina is deposited at low temperatures (e.g. by PVD such as ion sputtering), the adhesion remains poor (L_c ≈ 3–4 N) and failure is of the pure adhesive type, owing to insufficient chemical interdiffusion. However, when alumina is deposited at high temperatures (e.g. by CVD), the adhesive bond is of much higher strength (L_c ≈ 40–60 N), is of the mixed adhesive-cohesive type and has been related to significant chemical interdiffusion between the coating and the substrate. Surface oxidation of the substrate, e.g. TiC, prior to alumina deposition, results in a thin layer of oxides (mainly TiO₂ and Ti₃O₅) which is responsible for a significant lowering of adhesion of the alumina films (L_c ≈ 10 N). High temperature post-deposition annealing is thought to have a marked effect on adhesion for the Al₂O₃ (PVD) films but only a weak influence on that of Al₂O₃ (CVD) films. The film-substrate adherence has been correlated to the interface composition as analysed by Auger electron spectroscopy depth profiling.     

A hexane solution deposition of SnS2 films from tetrabutyltin via a solvothermal route at moderate temperature

SnS₂ films have been deposited on glass and alumina plate substrates by the reactions between an organotin precursor [tetrabuyltin, (CH₂CH₂CH₂CH₃)₄Sn] and carbon disulfide in n-hexane at the temperature range 180-200 °C for 10-40 h. The reaction system was oxygen free and applied at a moderate temperature. The films so prepared were characterized by techniques of X-ray diffraction, Scanning electron microscopy, Raman and Mössbauer spectroscopies. The films deposited on glass as well as on alumina plate have an average thickness of 30 μm, but have different rose-like morphologies, which are influenced by both the anisotropic growths of crystals and the different substrate structures. Photoluminescence measurements show that the films have an emission peak at approximately 590 nm.     

Electrical properties of alumina films grown on Si at low temperature using catalytic CVD

The electrical properties of alumina films formed at substrate temperatures as low as 27 °C using tri-methyl aluminum (TMA) and molecular oxygen (O₂) by catalytic chemical vapor deposition (Cat-CVD) have been investigated by capacitance-voltage (C-V), current-voltage (I-V) measurements and X-ray photoelectron spectroscopy (XPS). Substrate temperature dependence of dielectric constant and leakage current of the films has been explained on the basis of deficiency in oxygen. Interface trapping density of the order of 10⁹ ev^− 1cm^− 2 has been obtained. Angle resolved XPS measurements have revealed that the direct bonding of alumina and Si was realized with very small interface trapping density.     

Growth and physicochemical characterization of CuAlTe2 films obtained by reaction, induced by annealing, between Cu/Al/Te/Al/Cu... Al/Cu/Al/Te layers sequentially deposited

CuAlTe₂ thin films have been synthesized by annealing under an argon flow a multilayer structure of thin Cu, Al and Te layers sequentially deposited by evaporation under vacuum. The films have been characterized by X-ray diffraction, microprobe analysis, photoelectron spectroscopy and Raman scattering. At the end of the process, the XRD spectra demonstrate that textured CuAlTe₂ films have been obtained with preferential orientation of the crystallites along the (112) direction. The Raman patterns are in good accordance with the reference. The XPS spectra show that the binding energies of the elements are in good agreement with bonds of CuAlTe₂. Even after a decrease of the oxygen contamination by improvement of the depositing process the oxygen present in the films is found to be about 12 at %. This revised version was published online in September 2006 with corrections to the Cover Date.     

Evaporation characteristics of TeO2 in the formation of tellurium oxide thin films

Thin films of tellurium oxide have been formed by evaporating TeO₂ with different boat materials (molybdenum and tantalum) in a high vacuum and at different oxygen partial pressures. The optical and structural properties of the films have been studied. From the variations in the properties with respect to the formation conditions the evaporation characteristics of TeO₂ have been discussed.     

Effect of processing conditions on superconductive properties of laser-deposited YBCO thin films

Thin superconductive films of YBa₂Cu₃O_7−x have been deposited on (100) single crystal SrTiO₃ substrates by using technique of ArF pulse excimer laser evaporation of bulk YBCO target in a vacuum, followed by slow cooling in an oxygen atmosphere. Thin-film properties are strongly influenced by the processing conditions. The effect of pulse repetition rate, beam power, beam size on the target surface and oxygen pressure on the surface morphology and superconductive properties of deposited films has been investigated. Film characterization has been performed by using X-ray diffractometry, scanning electron microscopy and four-point probe electrical instruments.     

Behaviors of carrier concentrations and mobilities in indium-tin oxide thin films by DC magnetron sputtering at various oxygen flow rates

The behaviors of the carrier concentrations and mobilities of indium-tin oxide (ITO) thin films, prepared by DC magnetron sputtering at the various oxygen flow rates, were investigated by means of the Hall technique. The relationship between the carrier concentrations and mobilities along the oxygen flow rates had two distinct features: (i) in the optimum oxygen region to 1.25 O₂/Ar vol%, the carrier mobilities increased as the carrier concentrations decreased with the oxygen flow rates and (ii) in the excess oxygen region roughly above 1.25 O₂/Ar vol%, both the carrier concentrations and mobilities decreased with the increases in the oxygen flow rates.The continuous decreases in the carrier concentrations with the oxygen flow rates were due to filling the oxygen vacancies and deactivating the Sn donor by the overflowing oxygens. The behaviors of the carrier mobilities were affected by two different scattering mechanisms of (i) the ionized impurity scattering in the optimum oxygen region and (ii) the neutral defect scattering and the negatively charged oxygen scattering in the excess oxygen region.     

Effect of high temperature post-annealing of La0.7Sr0.3MnO3 films deposited by radio frequency magnetron sputtering on SiO2/Si substrates heated at low temperature

La_0.7Sr_0.3MnO₃ thin films were deposited on SiO₂/Si substrates by RF magnetron sputtering under different oxygen gas flow rates with a sputtering power of 100 W. During deposition, the substrate was heated at 623 K. To investigate post-annealing effects, the as-deposited La_0.7Sr_0.3MnO₃ thin films were thermal-treated at 973 K for 1 h. The effects of oxygen gas flow rate and post-annealing treatment on the physical properties of the films were systematically studied. X-ray diffraction results show that the growth orientation and crystallinity of the films were greatly affected by the oxygen gas flow rate and substrate heating during deposition. The sheet resistance of the films gradually decreased with increasing oxygen gas flow rate, while the post-annealed films showed the opposite behavior. The temperature coefficient of resistance at 300 K of La_0.7Sr_0.3MnO₃ thin films deposited at an oxygen gas flow rate of 40 sccm decreased from − 2.40%/K to − 1.73%/K after post annealing. The crystalline state of the La_0.7Sr_0.3MnO₃ thin films also affected its electrical properties.     

Preparation of anatase TiO2 thin films by vacuum arc plasma evaporation

Anatase titanium dioxide (TiO₂) thin films with high photocatalytic activity have been prepared with deposition rates as high as 16 nm/min by a newly developed vacuum arc plasma evaporation (VAPE) method using sintered TiO₂ pellets as the source material. Highly transparent TiO₂ thin films prepared at substrate temperatures from room temperature to 400 °C exhibited photocatalytic activity, regardless whether oxygen (O₂) gas was introduced during the VAPE deposition. The highest photocatalytic activity and photo-induced hydrophilicity were obtained in anatase TiO₂ thin films prepared at 300 °C, which correlated to the best crystallinity of the films, as evidenced from X-ray diffraction. In addition, a transparent and conductive anatase TiO₂ thin film with a resistivity of 2.6 × 10^− 1 Ω cm was prepared at a substrate temperature of 400 °C without the introduction of O₂ gas.     

TI-Based Superconducting Films Prepared by Spray Pyrolysis and Vacuum Evaporation

TI-based films were prepared by the 2-step procedure. First, Ba-Ca-Cu-O precursors were deposited either from an aerosol or by thermal evaporation on MgO substrates. Thallination of precursors was then performed at 850 °C in flowing oxygen with annealing time up to 30 min. Films were characterized by T_c and X-ray measurements, and their depth profiles (RBS), surface morphology (SEM) and oxygen Raman modes were also investigated. The aerosol deposited films gave T_c = 94–103.5 K. Films grown by thermal evaporation revealed unusual T_c and structural changes during their 20-months storage in laboratory surroundings. Their T_c has increased from 94 to 106 K.     

Deposition of photocatalytic TiO2 layers by pulse magnetron sputtering and by plasma-activated evaporation

Crystalline TiO₂ thin films, especially layers with predominantly anatase phase, exhibit photocatalytic activities resulting in photoinduced hydrophilic, self-cleaning and antifogging properties. In this paper, a comparison of the photocatalytic properties of layers deposited with two different PVD techniques is given.On one hand, a reactive pulse magnetron sputtering (PMS) system has been used to obtain TiO₂ films at dynamic deposition rates from 8 to 50 nm m/min. On the other hand, TiO₂ layers were deposited by reactive electron beam evaporation at very high deposition rates between 500 and 1000 nm m/min. An additional spotless arc discharge (Spotless arc Activated Deposition—SAD process) was used for plasma activation to improve layer properties. Photoinduced hydrophilicity was investigated by measuring the decrease of the water contact angle during UV-A irradiation.     

Characterization of nanocrystalline indium tin oxide thin films prepared by ion beam sputter deposition method

Indium tin oxide (ITO) thin films were deposited on glass substrates by ion beam sputter deposition method in three different deposition conditions [(i) oxygen (O₂) flow rate varied from 0.05 to 0.20 sccm at a fixed argon (1.65 sccm) flow rate, (ii) Ar flow rate changed from 1.00 to 1.65 sccm at a fixed O₂ (0.05 sccm) flow rate, and (iii) the variable parameter was the deposition time at fixed Ar (1.65 sccm) and O₂ (0.05 sccm) flow rates]. (i) The X-ray diffraction (XRD) patterns show that the ITO films have a preferred orientation along (400) plane; the orientation of ITO film changes from (400) to (222) direction as the O₂ flow rate is increased from 0.05 to 0.20 sccm. The optical transmittance in the visible region increases with increasing O₂ flow rate. The sheet resistance (R_s) of ITO films also increases with increasing O₂ flow rate; it is attributed to the decrease of oxygen vacancies in the ITO film. (ii) The XRD patterns show that the ITO film has a strong preferred orientation along (222) direction. The optical transmittance in the visible spectral region increases with an increase in Ar flow rate. The R_s of ITO films increases with increasing Ar flow rate; it is attributed to the decrease of grain size in the films. (iii) A change in the preferred orientations of ITO films from (400) to (222) was observed with increasing film thickness from 314 to 661 nm. The optical transmittance in the visible spectral region increases after annealing at 200 °C. The R_s of ITO film decreases with the increase of film thickness.     

Preparation of alumina films by the sol-gel method

This review describes our study on preparation of alumina films by a sol-gel process and their several applications that have been investigated since 1986. Alumina films were prepared from alkoxide or inorganic salt. Both as-prepared alumina films were transparent in ultraviolet, visible and near infrared regions. The alumina from inorganic salt (inorganic alumina) was structureless even after annealed at 300–700°C in air, while the alumina from alkoxide (alkoxide alumina) was in pseudo-boehmite at an annealing temperature lower than 400°C and was in - or -type at 400–700°C. Both alumina films became opaque after annealed at temperatures above 1000°C. The inorganic alumina film annealed at 800°C showed a gas permeability that was influenced by physico-chemical properties of penetrant and alumina. Composite films of alumina and poly(vinyl alcohol) (PVA) were hydrophilic but insoluble in water, and removal of PVA from the composite films by annealing at 600°C led to formation of transparent alumina films. Such properties enabled us to use a counter diffusion method for fabricating -Fe₂O₃-doped alumina films. Alumina films doped with organic dyes such as laser dyes, hole-burning dyes and non-linear optical dyes, which were fabricated by gelation of dye-added alumina sol, exhibited laser emission, hole-spectra and second- or third-harmonic generation properties, respectively. Hydrogenation of alkene was catalyzed by Ni nanoparticles doped alumina films that were prepared by gelation of Ni²⁺ solution-added alumina sol and annealing the Ni²⁺-doped alumina gel in hydrogen gas. Nonlinear optical properties were observed for alumina films doped with CdS, Au and Ag nanoparticles, which were fabricated by gelation of Cd²⁺, HAuCl₄ and AgNO₃ solution-added alumina sols and annealing the Cd²⁺-doped alumina gel in H₂S gas and the Ag⁺- and Au³⁺-doped alumina gels in H₂ gas. Rare earth metal ion-doped alumina films, which were prepared by gelation of rare earth metal ion solution-added alumina sol and annealed the ion-doped alumina gel, exhibited not only normal luminescence but also up-conversion emission, energy transfer type luminescence and long lasting luminescence.     

Preparation of Cr(N,O) thin films by RF reactive unbalanced magnetron sputtering

Chromium oxynitride thin films were deposited by radio-frequency (RF) reactive unbalanced magnetron sputtering at various O₂ flow rates onto Si(100) and glassy carbon substrates. The compositions of the thin films were analyzed by Rutherford backscattering spectroscopy. The thin films were found to contain up to 44 at.% oxygen. In Fourier-transform infrared spectra, a peak attributed to the Cr-N bond of CrN was observed, but no peak attributable to the Cr-O bond of Cr₂O₃ was found. The textures of the thin films were observed by transmission electron microscopy, which revealed that samples had a columnar structure. The hardness of the thin films was measured by nanoindentation. The hardness increased from 20 GPa to a maximum value of 31 GPa with increasing oxygen content.     

Structural, electrical and optical properties of thermochromic VO2 thin films obtained by reactive electron beam evaporation

We present the structural and physical characterization of vanadium dioxide (VO₂) thin films prepared by reactive electron beam evaporation from a vanadium target under oxygen atmosphere. We correlate the experimental parameters (substrate temperature, oxygen flow) with the films structural properties under a radiofrequency incident power fixed to 50 W. Most of the obtained layers exhibit monocrystalline structures matching that of the monoclinic VO₂ phase. The temperature dependence of the electrical resistivity and optical transmission for the obtained films show that they present thermoelectric and thermochromic properties, with a phase transition temperature around 68 °C. The results show that for specific experimental conditions the VO₂ layers exhibit sharp changes in electrical and optical properties across the phase transition.     

Effects of precursor evaporation temperature on the properties of the yttrium oxide thin films deposited by microwave electron cyclotron resonance plasma assisted metal organic chemical vapor deposition

Yttrium oxide thin films are deposited using indigenously developed metal organic precursor (2,2,6,6-tetra methyl-3,5-hepitane dionate) yttrium, commonly known as Y(thd)₃ (synthesized by ultrasound method). Microwave electron cyclotron resonance plasma assisted metal organic chemical vapor deposition process was used for these depositions. Depositions were carried out at a substrate temperature of 350 °C with argon to oxygen gas flow rates fixed to 1 sccm and 10 sccm respectively throughout the experiments. The precursor evaporation temperature (precursor temperature) was varied over a range of 170-275 °C keeping all other parameters constant. The deposited coatings are characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and refractive index of the coatings are measured by the spectroscopic ellipsometry. Hardness and elastic modulus of the films are measured by load depth sensing nanoindentation technique.C-Y₂O₃ phase is deposited at lower precursor temperature (170 °C). At higher temperature (220 °C) cubic yttrium oxide is deposited with yttrium hydroxide carbonate as a minor phase. When the temperature of the precursor increased (275 °C) further, hexagonal Y₂O₃ with some multiphase structure including body centered cubic yttria and yttrium silicate is observed in the deposited film. The properties of the films drastically change with these structural transitions. These changes in the film properties are correlated here with the precursor evaporation characteristics obtained at low pressures.     

Growth, structure and properties of sputtered niobium oxide thin films

Niobium oxide (NbO_x) films were deposited by pulsed dc magnetron sputtering at different total gas pressures and oxygen flow rates. Various film properties were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, variable angle spectroscopic ellipsometry and four point probe. It was found that oxygen flow rates required for preparing NbO, NbO₂ and Nb₂O₅ at a constant total pressure of 0.93 Pa were approximately 2, 4 and > 6 sccm, respectively. The results showed that the film properties, specifically composition can be significantly changed by the total gas pressure and the oxygen flow rate.