Low temperature chemical vapor deposition of nanocrystalline V2O5 thin films

Spatially uniform, carbon-free thin films of V₂O₅ were deposited on silicon by chemical vapor deposition using vanadium oxide triisopropoxide and water as gaseous precursors, in the temperature range of 100-300 °C. Films with substantial crystallinity were obtained for deposition temperatures as low as 180 °C. The “neat” chemistry that nominally leaves no fragments of ligand or water in the solid promotes film purity and reduces the deposition temperature needed for crystallization. Such deposition temperatures also open up additional possibilities for using crystalline vanadia on fragile substrates such as polymers for electronics and optical applications.     

Preparation of nanocrystalline SnO2 thin film coated Al2O3 ultrafine particles by fluidized chemical vapor deposition

Fluidized chemical vapor deposition (FCVD) technology was developed for coating SnO₂ thin film on Al₂O₃ ultrafine particles. TEM and HREM analysis found that SnO₂ films with different structures were deposited by controlling the coating temperature, reactant concentration, etc. Nanocrystalline SnO₂ film was coated at 573.15 K by gas phase reaction of SnCl₄ with H₂O. EPMA and EDS studies indicated that the distribution of SnO₂ inner and outer of the agglomerates was uniform. Nucleation and film deposition were coexisted mechanism during the FCVD coating process. The fraction of SnO₂ in the composite particles increased with increasing coating temperature, SnCl₄ concentration, and coating time. The mass fraction of SnO₂ in the composite particles increased strongly with the ratio of P_H2O and P_SnCl4 at low mole ratio of H₂O with SnCl₄, but increased little under the conditions of excess H₂O with respect to SnCl₄.     

BiFeO3 thin films prepared using metalorganic chemical vapor deposition

BiFeO₃ thin films were grown on (001) SrTiO₃ and (001) ZrO₂(Y₂O₃) substrates by single source metalorganic chemical vapor deposition in the temperature range T = 500 ÷ 800 °C using Fe(thd)₃ and Bi(C₆H₅)₃ as volatile precursors. X-ray diffraction analysis shows cube-on-cube epitaxial growth of BiFeO₃ on (001) SrTiO₃. The strongly reduced bismuth transfer into the film due to the high thermal stability of Bi(C₆H₅)₃ was counterbalanced by the increase of the total pressure as well as of the residence time of the precursor flow in the reactor; the Bi/Fe ratio in the film thus becomes close to that in the precursor mixture. Optical second harmonic generation measurements have evidenced the ferroelectric ordering in BiFeO₃ films and the apparent decrease of the Curie temperature of the strained films as compared to BiFeO₃ single crystal.     

Evolution of texture of CeO2 thin film buffer layers prepared by ion-assisted deposition

Evolution of texture in CeO₂ thin films was studied using biased magnetron sputtering and ion beam assisted magnetron sputtering. Films deposited onto polycrystalline Hastelloy metal substrates by biased magnetron sputtering develop preferential (002) growth as the energy of the ions is increased from zero to above 100 eV. For ion beam assisted magnetron sputtering (magnetron IBAD), with the ion beam directed at 55° to the substrate normal, the evolution of biaxial alignment is controlled by the ion beam energy and the ion/atom arrival rate ratio. Ion beam energies >200 eV and ion/atom ratios >0.3 lead to perfect biaxial alignment with one pole aligned along the ion beam direction. Epitaxial growth of CeO₂ films was observed for MgO(001) substrates at 750°C without any ion assistance, and on yttria-stabilised zirconia (001) buffer layers at room temperature and a bias of −80 V.     

Single-source chemical vapor deposition of clean oriented Al2O3 thin films

Clean oriented Al₂O₃ thin film with a dominant Al₂O₃ <1 1 3> plane was deposited on Si <1 0 0> substrate at 550 °C, by single-source chemical vapor deposition (CVD) using aluminium(III) diisopropylcarbamate, Al₂(O₂CNⁱPr₂)₆. This process represents a substantial reduction in typical CVD film growth temperatures which are typically > 1000 °C. Through the studies of thermal stability of this precursor, we propose a specific β-elimination decomposition pathway to account for the low temperature of the precursor decomposition at the substrate, and for the lack of carbon impurity byproducts in the resulting alumina films that are characterized using X-ray photoelectron spectroscopy and depth profiling.     

Synthesis of binary and triple carbon nanotubes over Ni/Cu/Al2O3 catalyst by chemical vapor deposition

Novel binary and triple carbon nanotubes (CNTs) with one common catalytic particle encapsulated have been synthesized using Ni/Cu/Al₂O₃ catalyst, which was produced by a sol-gel method. But when using Ni/Al₂O₃ as catalyst, a mass of common CNTs, that is, one CNT with one catalytic particle encapsulated, was obtained. The results showed that copper-element doping to the Ni/Al₂O₃ catalyst played a key role in the synthesis of CNTs, signifying a novel approach to modify the Ni/Al₂O₃ catalyst. Based on the transmission electron microscopy observations, a simple growth mechanism was developed to describe the growth of the binary or triple CNTs, which could be well explained by a diffusion segregation process.     

The preparation and properties of Y2O3/AlN anti-reflection films on chemical vapor deposition diamond

Yttrium oxide (Y₂O₃) films have successfully been applied as anti-reflection (AR) and anti-oxidation films for diamond. For significant adhesion improvement between Y₂O₃ coating and diamond, aluminum nitride (AlN) as an interlayer is introduced. Y₂O₃ and AlN films were prepared by RF magnetron sputtering of Y₂O₃ ceramic target in Ar atmosphere and pure Al metal target in Ar + N₂ atmosphere, respectively. The Y₂O₃ and AlN films were studied by X-ray diffraction, X-ray photoelectron spectroscopy, Atomic force microscopy and Spectroscopic ellipsometry. Adherent Y₂O₃/AlN films on high optical quality chemical vapor deposition diamond with optimum thicknesses for infrared transmission enhancement in 8-10 μm were obtained by a Fourier transform infrared spectrometer. More than 28% increase in maximum transmission was observed for Y₂O₃/AlN//Diamond//AlN/Y₂O₃. Comparing between the designed and experimental AR effects for Y₂O₃/AlN film in 8-10 μm wavebands, experimental average AR effects are smaller for the absorption and scattering loss. AR effects for the Y₂O₃/AlN films on CVD diamond are proved to be excellent.     

Low-temperature growth and orientational control in RuO2 thin films by metal-organic chemical vapor deposition

For growth temperatures in the range of 275°C to 425°C, highly conductive RuO₂ thin films with either (110)- or (101)-textured orientations have been grown by metal-organic chemical vapor deposition (MOCVD) on both SiO₂/Si(001) and Pt/Ti/SiO₂/Si(001) substrates. Both the growth temperature and growth rate were used to control the type and degree of orientational texture of the RuO₂ films. In the upper part of this growth temperature range ( 350°C) and at a low growth rate (< 3.0 nm/min.), the RuO₂ films favored a (110)-textured orientation. In contrast, at the lower part of this growth temperature range ( 300°C) and at a high growth rate (> 3.0 nm/min.), the RuO₂ films favored a (101)-textured orientation. In contrast, higher growth temperatures (> 425°C) always produced randomly-oriented polycrystalline films. For either of these low-temperature growth processes, the films produced were crack-free, well-adhered to the substrates, and had smooth, specular surfaces. Atomic force microscopy showed that the films had a dense microstructure with an average grain size of 50–80 nm and a rms. surface roughness of 3–10 nm. Four-probe electrical transport measurements showed that the films were highly conductive with resistivities of 34–40 μΩ-cm (at 25°C).     

Al2O3 formation on Si by catalytic chemical vapor deposition

Catalytic chemical vapor deposition (Cat-CVD) has been developed to deposit alumina (Al₂O₃) thin films on silicon (Si) crystals using N₂ bubbled tri-methyl aluminum [Al(CH₃)₃, TMA] and molecular oxygen (O₂) as source species and tungsten wires as a catalyzer. The catalyzer dissociated TMA at approximately 600 °C. The maximum deposition rate was 18 nm min⁻¹ at a catalyzer temperature of 1000 °C and substrate temperature of 800 °C. Metal oxide semiconductor (MOS) diodes were fabricated using gates composed of 32.5-nm-thick alumina film deposited at a substrate temperature of 400 °C. The capacitance measurements resulted in a relative dielectric constant of 7.4, fixed charge density of 1.74×10¹² cm⁻², small hysteresis voltage of 0.12 V, and very few interface trapping charges. The leakage current was 5.01×10⁻⁷ A cm⁻² at a gate bias of 1 V.     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

Investigation of nozzle shape effect on Sm0.1Ce0.9O1.95 thin film prepared by electrostatic spray deposition

Dense samarium doped ceria (SDC) thin films are deposited using electrostatic spray deposition (ESD) technique. The influences of nozzle shape on the distribution of liquid jet at the nozzle tip and the morphology of the deposited SDC films are elucidated. Geometries of three nozzles employed are flat, sawtooth and wedge tips. From the observation of jet formation, the nozzle in flat shape gives the highest distribution of emitted droplets. The deposited films are characterized using a combination of XRD, SEM and AFM techniques. XRD results reveal that the single-phase fluorite structure forms at a relatively low deposition temperature of 400 °C. The flat spray tip provides the most uniform and smooth thin films, and also presents the lowest agglomeration of particles on thin-film surface.     

Texture and microstructure of Cr2O3 and (Cr,Al)2O3 thin films deposited by reactive inductively coupled plasma magnetron sputtering

Cr₂O₃ and (Cr,Al)₂O₃ films were grown using reactive dc and inductively coupled plasma magnetron sputtering at substrate temperatures of 300-450 °C. For pure chromia, α-Cr₂O₃ films with fiber texture were grown; the out-of-plane texture could be controlled from < 0001> to < 101?4>. The former texture was obtained as a consequence of competitive growth with no applied bias or inductively coupled plasma, while the latter was obtained at moderate bias (− 50 V), probably due to recrystallization driven by ion-bombardment-induced strain. By reactive codeposition of Cr and Al, a corundum-structured metastable solid solution α-(Cr,Al)₂O₃ with Cr/Al ratios of 2-10 was grown with a dense, fine-grained morphology. Hardness and reduced elastic modulus values were in the ranges 24-27 GPa and 190-230 GPa, respectively.     

Chemical vapor deposition growth of Fe3O4 thin films and Fe/Fe3O4 bi-layers for their integration in magnetic tunnel junctions

A possible route for the synthesis of Fe₃O₄, Fe, and Fe/Fe₃O₄ bi-layers with chemical vapor deposition by employing the same Fe₃(CO)₁₂ carbonyl precursor is presented. The comprehensive structural, chemical, and morphological investigation of the as-deposited thin single films and bi-layers is performed by X-ray diffraction, X-ray reflectivity, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry depth profiling. We present the possibility of performing the deposition of pure metallic Fe and Fe₃O₄/γ-Fe₂O₃ by adjusting the deposition pressure from 10^- 3/^- 4 Pa to 1 Pa, respectively. The integration of Fe₃O₄ thin films in a magnetic tunnel junction stack fully synthesized by in situ atomic layer and chemical vapor deposition processes is also presented, showing good stack stability and marginal interdiffusion.     

Preparation of CuInSe2 thin films through metal organic chemical vapor deposition method by using di-μ-methylselenobis(dimethylindium) and bis(ethylisobutyrylacetato) copper(II) precursors

Highly polycrystalline copper indium diselenide (CuInSe₂) thin films on molybdenum substrate were successfully grown at 330 °C through two-stage metal organic chemical vapor deposition (MOCVD) method by using two precursors at relatively mild conditions. First, phase pure InSe thin film was prepared on molybdenum substrate by using a single-source precursor, di-μ-methylselenobis(dimethylindium). Second, on this InSe/Mo film, bis(ethylisobutyrylacetato) copper(II) designated as Cu(eiac)₂ was treated by MOCVD to produce CuInSe₂ films. The thickness and stoichiometry of the product films were found to be easily controlled in this method by adjusting the process conditions. Also, there were no appreciable amounts of carbon and oxygen impurities in the prepared copper indium diselenide films.     

Characteristics of carbon coatings on optical fibers prepared by radio-frequency plasma enhanced chemical vapor deposition with different H2/C2H2 ratios

Characteristics of carbon coatings on optical fibers prepared by radio-frequency plasma enhanced chemical vapor deposition with different H₂/C₂H₂ ratios are investigated. Five kinds of carbon coatings are prepared with H₂/C₂H₂ ratios of 2, 4, 6, 8, and 10. Experimental results show that the deposition rate and surface roughness of carbon coatings decrease as the H₂/C₂H₂ ratio increases. When the H₂/C₂H₂ ratio changes from 2 to 8, the increase of H₂/C₂H₂ ratios detrimentally yields sp³ carbon atoms and sp³-CH₃ bonds in the carbon coatings. However, when the H₂/C₂H₂ ratio exceeds 8, the hydrogen retards the growth of the graphite structure. Moreover, the redundant hydrogen radicals favor bonding with the dangling bonds in the coating surface. Therefore, when the H₂/C₂H₂ ratio increases from 8 to 10, the amounts of sp³ carbon atoms and sp³-CH₃ bonds in the carbon coatings increase. At an H₂/C₂H₂ ratio of 8, the carbon coating exhibits excellent water-repellency and thermal-loading resistance, and so this ratio is the best for producing a hermetically sealed optical fiber coating.     

Highly (100)-oriented CeO2 films prepared on amorphous substrates by laser chemical vapor deposition

CeO₂ films were prepared on amorphous silica substrates by laser chemical vapor deposition using cerium dipivaloylmethanate precursor and a semiconductor InGaAlAs (808 nm in wavelength) laser system. The laser spot size was about 20 mm, which was sufficient to cover the whole substrate. Highly (100)-oriented CeO₂ films were obtained at extraordinary high deposition rates ranging from 60 to 132 μm/h. Films exhibited a columnar feather-like structure with a large number of nano-sized voids, and a surface morphology consisting of either nearly flat or pyramidal top-ending columns depending on the laser power. Nearly flat top-ending columns could be fairly (100)-oriented at the top and (111)-oriented laterally.     

Characterization of metal-supported Al2O3 thin films by scanning electrochemical microscopy

In this paper, physiochemical properties of amorphous alumina thin films, grown by the metal organic chemical vapour deposition process on the surface of platinum (Pt/Al₂O₃) and stainless steel (SS/Al₂O₃), were investigated in aqueous media. The study was performed by the use of scanning electrochemical microscopy (SECM), which allowed obtaining information on uniformity, topography and chemical stability/reactivity of the alumina coatings with high spatial resolution. In particular, the effects due to local acid, base and fluoride ions attack on alumina layers of thickness of about 250 nm (in the Pt/Al₂O₃ sample) and 1000 nm (in the SS/Al₂O₃ sample) were investigated. In the acid and base attack, high concentrations of H₂SO₄ and KOH were electrogenerated locally by the use of a 25 μm diameter platinum microelectrode. The latter was also used as SECM tip to monitor the chemical effect on the alumina layers. It was found that, regardless of the thickness of the film, alumina provided good resistance against local attack of concentrated H₂SO₄; instead, the film dissolved when subjected to KOH attack. The dissolution rate depended on several experimental parameters, such as SECM-tip to substrate distance, electrolysis time and alumina film thickness. The alumina layer proved also relatively poor resistance to etching in 0.1 M NaF solutions.     

Metalorganic chemical vapor deposition of Er2O3 thin films: Correlation between growth process and film properties

Er₂O₃ thin films have been grown by metalorganic chemical vapor deposition (MOCVD) at 600 °C on different substrates, including glass, Si (100) and sapphire (0001) using tris(isopropylcyclopentadienyl)erbium and O₂. The effects of growth parameters such as the substrate, the O₂ plasma activation and the temperature of organometallic precursor injection, on the nucleation/growth kinetics and, consequently, on film properties have been investigated. Specifically, very smooth (111)-oriented Er₂O₃ thin films (the root mean square roughness is 0.3 nm) are achieved on Si (100), α-Al₂O₃ (0001) and amorphous glass by MOCVD. Growth under O₂ remote plasma activation results in an increase in growth rate and in (100)-oriented Er₂O₃ films with high refractive index and transparency in the visible photon energy range.     

Epitaxial and polycrystalline BaFe12O19 thin films grown by chemical vapour deposition

Epitaxial and polycrystalline barium hexaferrite BaFe₁₂O₁₉ thin films were prepared by metalorganic chemical vapour deposition (MOCVD). Films were grown by a liquid MOCVD technique which aim is to control precisely the precursor vapour pressures. Two kinds of substrates were used: sapphire (001) and silicon thermally oxidized. On Si/SiO₂ films are polycrystalline and the magnetization is isotropic. On Al₂O₃ (001), structural studies reveal the films to be predominantly single phase, well crystallized without annealing procedure and with the c-axis perpendicular to the film plane; epitaxial relationships between the film and the substrate were determined. The magnetic parameters, deduced from vibrating sample magnetometer measurements, show a high dependence of the magnetization with the orientation of the field with respect to the surface of the film.     

Effect of Deposition Temperature on Dynamics and Mechanism of Deposition for Si-B-C Ceramic from BCl3/SiCH3Cl3/H2 Precursor

The deposition rate, phase, chemical composition and microstructure of deposits were determined from 950 to 1100℃. With increasing temperature, the deposition rate increases, and the morphology changes from smooth to coarse, meanwhile, the concentration of silicon increases while that of boron decreases. The deposition process is controlled by chemical reactions, and the activation energy is 271 kJ/mol. At relatively lower temperature (below 1000℃), the deposition process is dominated by formation of B4C. While at higher temperature (above 1000℃), it is governed by formation of SiC. B4C and SiC disperse uniformly in the Si-B-C co-deposition system and form a dense network structure.