Aerosol assisted chemical vapor deposition using nanoparticle precursors: a route to nanocomposite thin films

Gold nanoparticle and gold/semiconductor nanocomposite thin films have been deposited using aerosol assisted chemical vapor deposition (CVD). A preformed gold colloid in toluene was used as a precursor to deposit gold films onto silica glass. These nanoparticle films showed the characteristic plasmon absorption of Au nanoparticles at 537 nm, and scanning electron microscopic (SEM) imaging confirmed the presence of individual gold particles. Nanocomposite films were deposited from the colloid concurrently with conventional CVD precursors. A film of gold particles in a host tungsten oxide matrix resulted from co-deposition with [W(OPh)(6)], while gold particles in a host titania matrix resulted from co-deposition with [Ti(O(i)Pr)(4)]. The density of Au nanoparticles within the film could be varied by changing the Au colloid concentration in the original precursor solution. Titania/gold composite films were intensely colored and showed dichromism: blue in transmitted light and red in reflected light. They showed metal-like reflection spectra and plasmon absorption. X-ray photoelectron spectroscopy and energy-dispersive X-ray analysis confirmed the presence of metallic gold, and SEM imaging showed individual Au nanoparticles embedded in the films. X-ray diffraction detected crystalline gold in the composite films. This CVD technique can be readily extended to produce other nanocomposite films by varying the colloids and precursors used, and it offers a rapid, convenient route to nanoparticle and nanocomposite thin films.     

Thermal analysis and vapour pressure of a new series of tungsten(VI) oxo-alkoxide-β-ketoesterate complex precursors for the chemical vapour deposition of tungsten oxide

A new series of tungsten complexes, tungsten(VI) oxo-alkoxide-β-ketoesterate complexes have been synthesized and characterized by infrared and NMR spectroscopy. Thermogravimetric analysis has been carried out on the complexes as a function of temperature, and isothermally as a function of time. Based on the thermal analysis data, these complexes are evaluated for their suitability as precursors for the chemical vapour deposition of tungsten oxide thin films. The vapour pressure of these precursors is estimated using the Langmuir equation.     

Atmospheric pressure chemical vapour deposition of fluorine‐doped tin(IV) oxide from fluoroalkyltin precursors

Perfluoroalkytin compounds R_(4−n)Sn(R_f)_n (R = Me, Et, Bu, R_f = C₄F₉, n = 1; R = Bu, R_f = C₄F₉, n = 2, 3; R = Bu, R_f = C₆F₁₃, n = 1) have been synthesized, characterized by ¹H, ¹³C, ¹⁹F and ¹¹⁹Sn NMR, and evaluated as precursors for the atmospheric pressure chemical vapour deposition of fluorine‐doped SnO₂ thin films. All precursors were sufficiently volatile in the range 84–136 °C and glass substrate temperatures of ca 550 °C to yield high‐quality films with ca 0.79–2.02% fluorine incorporation, save for Bu₃SnC₆F₁₃, which incorporated <0.05% fluorine. Films were characterized by X‐ray diffraction, scanning electron microscopy, thickness, haze, emissivity, and sheet resistance. The fastest growth rates and highest quality films were obtained from Et₃SnC₄F₉. An electron diffraction study of Me₃SnC₄F₉ revealed four conformations, of which only the two of lowest abundance showed close F Sn contacts that could plausibly be associated with halogen transfer to tin, and in each case it was fluorine attached to either the γ‐ or δ‐carbon atoms of the R_f chain. Copyright © 2005 John Wiley & Sons, Ltd.     

Aerosol assisted chemical vapor deposition of In2O3 films from Me3In and donor functionalized alcohols

The reaction of Me3In and ROH (R = CH2CH2NMe2, CH(CH3)CH2NMe2, C(CH3)2CH2OMe, CH2CH2OMe) in toluene under aerosol assisted chemical vapor deposition (AACVD) conditions leads to the production of indium oxide thin films on glass. The indium oxide films were deposited at 550 degrees C and analyzed by scanning electron microscopy (SEM), X-ray powder diffraction, wavelength dispersive analysis of X-rays (WDX), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. This CVD technique offers a rapid, convenient route to In2O3, which presumably involves the in situ formation of dimethylindium alkoxides, of the type [Me2InOR]2. In order to identify compounds present in the aerosol mist, the solution-phase reaction between Me3In and ROH (R = CH2CH2NMe2, C(CH3)2CH2OMe, CH(CH3)CH2NMe2, CH(CH2NMe2)2) at room temperature in toluene was carried out. Dimeric indium alkoxides, of the type [Me2In(OR)]2, were isolated, and their structures were determined by X-ray crystallography.     

Novel monomeric barium complexes as volatile precursors for chemical vapour deposition

A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD). A novel pathway providing an unprecedented sequence of barium carbamates is reported. New dianionic bis β-ketoesterates and their barium, strontium and calcium derivatives were synthesised. High resolution mass spectrometry showed some barium derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Calcium and strontium complexes were found to have nuclearities that varied according to their ionic radii relative to the chain length of the encapsulating ligand.     

Quantum chemical modeling of electrochromism of tungsten oxide films

A cluster model is proposed to describe the excitations in solid tungsten oxide. The density-functional theory approach is used to calculate the ground-state electronic structure of the model cluster and its optimum geometry; subsequently, time-dependent density-functional theory calculations are performed to obtain the oscillator strengths and energies of the excited states. The results are reported both for the electrically neutral cluster and for the cluster with an extra electron (mimicking the effect of electron injection from the cathode). They correctly locate the electrochemically active transition. The corresponding wave functions are delocalized, suggesting that electron localization at one tungsten center is rather unlikely, thereby shedding doubt as to the validity of the polaron model. Local lattice distortions presumably created at the stage of sample preparation are found to affect the excitation energies to a considerable extent, which explains the experimentally observable large width of optical absorption responsible for electrochromism.     

Textured fluorine-doped tin dioxide films formed by chemical vapour deposition

The use of an aerosol delivery system enabled fluorine-doped tin dioxide films to be formed from monobutyltin trichloride methanolic solutions at 350-550 °C with enhanced functional properties compared with commercial standards. It was noted that small aerosol droplets (0.3 μm) gave films with better figures of merit than larger aerosol droplets (45 μm) or use of a similar precursor set using atmospheric pressure chemical vapour deposition (CVD) conditions. Control over the surface texturing and physical properties of the thin films were investigated by variation in the deposition temperature and dopant concentration. Optimum deposition conditions for low-emissivity coatings were found to be at a substrate temperature of about 450 °C with a dopant concentration of 1.6 atm% (30 mol% F:Sn in solution), which resulted in films with a low visible light haze value (1.74%), a high charge-carrier mobility (25 cm(2) V s(-1)) and a high charge-carrier density (5.7×10(20) cm(-3)) resulting in a high transmittance across the visible (≈80%), a high reflectance in the IR (80% at 2500 nm) and plasma-edge onset at 1400 nm. Optimum deposition conditions for coatings with applications as top electrodes in thin film photovoltaics were found to be a substrate temperature of about 500 °C with a dopant concentration of 2.2 atm% (30 mol% F:Sn in solution), which resulted in films with a low sheet resistance (3 Ω sq(-1)), high charge-carrier density (6.4×10(20) cm(-3)), a plasma edge onset of 1440 nm and the films also showed pyramidal surface texturing on the micrometer scale which corresponded to a high visible light haze value (8%) for light scattering and trapping within thin film photovoltaic devices.     

Specific features of chemical deposition of polytetrafluoroethylene films from hexafluoropropylene oxide

Influence of the main process parameters on the hot wire chemical vapor deposition (HW-CVD) of polytetraethylene (PTFE) films in the hexafluoropropylene (HFPO)-argon system at low pressure as well as the gas flow structure in the reactor and its effect on the precursor conversion was evaluated. It was found out that that the conversion reaches ～90% at the hot wire temperature above 800°C, increases ～5.5 times with the increase in pressure from 7.5 to 35 Pa and decreases twice with the increase of precursor flow from 8 to 33 ml min^?1. It was shown that the process parameters affect significantly the gas residence time and average temperature, and also the intensity of gas flow recirculation in the reactor.     

Titanium arsenide films from the atmospheric pressure chemical vapour deposition of tetrakisdimethylamidotitanium and tert-butylarsine

Thin films of titanium arsenide have been deposited from the atmospheric pressure chemical vapour deposition (APCVD) of [Ti(NMe(2))(4)] and (t)BuAsH(2) at substrate temperatures between 350-550 °C. Highly reflective, silver coloured films were obtained which showed borderline metallic-semiconductor resistivities. The titanium arsenide films were analyzed by scanning electron microscopy (SEM), Raman spectroscopy, wavelength dispersive analysis of X-rays (WDX), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The films showed variable titanium to arsenic ratios but at substrate temperatures of 500 and 550 °C films with a 1 : 1 ratio of Ti : As, consistent with the composition TiAs, were deposited. Powder XRD showed that all of the films were crystalline and consistent with the formation of TiAs. Both nitrogen and carbon contamination of the films were negligible.     

Synthesis and characterisation of tungsten(VI) oxo-salicylate complexes for use in the chemical vapour deposition of self-cleaning films

Tungsten(VI) oxo-salicylate complexes were prepared in moderate yield (47 to 63%) by the reactions of WOCl4 and two equivalents of either 3-methylsalicylic acid (MesaliH2) or 3,5-di-isopropylsalicylic acid (di-i-PrsaliH2). Performing the reaction in refluxing toluene afforded the two analogous ditungsten complexes 1, [{WO(Mesali)(MesaliH)}2(mu-O)], and 2, [{WO(di-i-Prsali)(di-i-PrsaliH)}2(mu-O)], however in refluxing hexane the mononuclear tungsten complex , [WO(di-i-Prsali)(di-i-PrsaliH)Cl], was isolated. The single crystal X-ray study of revealed a pseudo-octahedral geometry around the tungsten centres. Aerosol assisted chemical vapour deposition of or afforded brown tungsten trioxide thin films. These films were converted to yellow fully oxidised WO3 on annealing in air at 550 degrees C for 30 minutes. The yellow WO3 films demonstrate preferred orientation on the substrate and show interesting functional properties-photo induced hydrophilicity and photocatalytic activity.     

Perhydridosilicone films produced by IR laser‐induced chemical vapour deposition from disiloxane

Solid perhydridosilicone films have been produced by transversely excited atmospheric (TEA) and continuous‐wave CO₂ laser‐induced gas‐phase decompositions of H₃SiOSiH₃ controlled by elimination and polymerization of transient silanone H₂SiO and affording silane and hydrogen as side products. The decomposition mechanism is supported by evidence of scavenged intermediates and minor volatile products. The films are characterized by FT infrared and x‐ray photoelectron spectroscopy and by scanning electron microscopy and shown to undergo facile oxidation of the topmost layers in air and chemical changes upon argon ion sputtering. Copyright © 2000 John Wiley & Sons, Ltd.     

The use of cationic surfactants to control the structure of zinc oxide films prepared by chemical vapour deposition

This paper describes a powerful and versatile new method for controlling the structure of zinc oxide thin films prepared by aerosol assisted chemical vapour deposition, based on the use of a common surfactant. The technique combines the benefits of solution and vapour based methods and leads to high quality morphologically-defined and orientated thin films.     

A secondary ion mass spectrometric study of thallium oxide thin films grown via metal organic chemical vapour deposition

Within a comprehensive programme including synthesis via metal organic chemical vapour deposition (MOCVD) and characterization of inorganic compounds and materials of possible interest in technologies based on thin films, results concerning the deposition of metal oxides by means of volatile organometal precursors are reported. In particular, thallium oxide films obtained by the MOCVD technique and commercial powders of Tl₂O₃ and Tl₂O adsorbed on several metal substrates (stainless steel, Si, Cu, Mo, Pt) were studied by secondary ion mass Spectrometry (SIMS) under ion beam bombardment at different ion energies. The positive- and negative-ion mass spectra exhibit typical isotopic patterns of several ionic species produced by interesting interfacial reactions, and the analysis of their relative abundances provides a measure of oxide reactivity towards different substrates. SIMS measurements of metal substrates were also performed. The ability and limits of SIMS in the reactivity study of thallium oxide powders and films and, in addition, in the identification of reaction products evidencing impurity species that, in turn, can be ascribed to the substrates or to the precursors used for the oxide synthesis is pointed out.     

AFM investigation of silicon substrates for chemical vapour deposition of diamond films

AFM has been used to study surface modifications on silicon (100) substrates for CVD diamond deposition during bias pretreatment in a hot-filament reactor under various conditions. Both topographical images, force-distance measurements and chemical etching with HF have been implemented to obtain information on the processes involved. The results show, that the observed roughening, which strongly depends on the gas phase composition, is caused by chemical etching of the surface dominated by removal of elemental silicon via formation of silicon hydride.     

Plasma deposition of silicon nitride-like thin films from organosilicon precursors

Plasmas containing hexamethyldisilazane or hexamethylcyclotrisilazane and nitrogen or ammonia were used to deposit silicon nitride-like films at low substrate temperature (T<60°C). Optical properties (refractive index and absorption coefficient), chemical composition of the deposit and film growth rate were examined with respect to the deposition parameters (rf power, pressure and feed composition). As deposited films from ammonia containing mixtures were silicon nitride-like, contained carbon, and were nearly oxygen free. Furthermore, only Si−N, Si−H, and N−H bonds were identified in as-deposited films. The reactive Si−H bonds progressively transformed into Si−O bonds as the films were exposed to air. Films deposited from highly ammonia-diluted mixtures, high RF power and low pressure showed the highest stability with refractive indices as high as 1.8.     

Fabrication of CdS films with superhydrophobicity by the microwave assisted chemical bath deposition

A simple method of microwave assisted chemical bath deposition (MA-CBD) was adopted to fabricate cadmium sulfide (CdS) thin films. The superhydrophobic surface with a water contact angle (CA) of 151 degrees was obtained. Via a scanning electron microscopy (SEM) observation, the film was proved having a porous micro/nano-binary structure which can change the property of the surface and highly enhance the hydrophobicity of the film. A possible mechanism was suggested to describe the growth of the porous structure, in which the microwave heating takes an important role in the formation of two distinct characteristic dimensions of CdS precipitates, the growth of CdS sheets in micro-scale and sphere particles in nano-scale. The superhydrophobic films may provide novel platforms for photovoltaic, sensor, microfluidic and other device applications.     

Single source heterobimetallic precursors for the deposition of Cu-Ti mixed metal oxide thin films

Heterobimetallic molecular precursors [Ti(4)(dmae)(6)(mu-OH)(mu-O)(6)Cu(6)(benzoate)(9)] (1) and [Ti(4)(dmae)(6)(mu-OH)(mu-O)(6)Cu(6)(2-methylbenzoate)(9)] (2) were prepared by the interaction of Ti(dmae)(4) [dmae=N,N-dimethylaminoethanolate] with Cu(benzoate)(2).2H(2)O for (2) and Cu(2-methylbenzoate)(2).2H(2)O for (2), respectively, in dry toluene, for selective deposition of Cu/Ti oxide thin films for possible technological applications. Both the complexes were characterized by melting point, elemental analysis, FT-IR, thermal analysis and single crystal X-ray analysis. Complex (1) crystallizes in the triclinic space group P-1 and complex (2) in the rhombohedral space group R-3. The TGA analysis proves that complexes (1) and (2) undergo facile thermal decomposition at 550 degrees C to form copper titanium mixed metal oxides. The SEM/EDX and XRD analyses suggest the formation of carbonaceous impurity free good quality thin films of crystalline mixtures of beta-Cu(3)TiO(4) and TiO(2) for both (1) and (2), with average grain sizes of 0.29 and 0.74 microm, respectively. Formation of two different homogeneously dispersed oxide phases is also supported by electrical impedance measurements.     

Hot filament chemical vapour deposition of diamond ultramicroelectrodes

The hot filament chemical vapour deposition of boron-doped diamond was optimised for the fabrication of diamond ultramicroelectrodes. Applications of ultramicroelectrodes require thin, conformal and non-porous diamond coatings, which display electrochemical properties similar to those associated with good quality doped diamond electrodes. The growth conditions to attain these goals are elucidated. The influence of the use of nanodiamond ultrasonic seeding prior to growth, in order to promote nucleation, and varying the negative electrical bias and methane concentration during growth, to control the growth chemistry, are explored. Although Raman spectroscopy shows a deterioration of diamond phase quality with increased negative bias voltage during growth, cyclic voltammetry indicates an improved electrochemical performance due to decreased porosity at reduced grain size under moderate bias voltage. At even higher bias voltage, the electrochemical properties deteriorate due to aggregation of sp(2) hybridised carbon at grain boundaries. By combining efficient nucleation methods and appropriate methane concentrations and electrical bias during growth, small grain polycrystalline diamond coatings can be obtained, which show optimal electrochemical properties most suitable for ultramicroelectrode applications.