First nucleation steps during deposition of SiO2 thin films by plasma enhanced chemical vapour deposition

The initial nucleation stages during deposition of SiO₂ by remote plasma enhanced chemical vapour deposition (PECVD) have been monitored by XPS inelastic peak shape analysis. Experiments have been carried out on two substrates, a flat ZrO₂ thin film and a silicon wafer with a native silicon oxide layer on its surface. For the two substrates it is found that PECVD SiO₂ grows in the form of islands. When the SiO₂ particles reach heights close to 10 nm they coalesce and cover completely the substrate surface. The particle formation mechanism has been confirmed by TEM observation of the particles grown on silicon substrates. The kinetic Monte Carlo simulation of the nucleation and growth of the SiO₂ particles has shown that formation of islands is favoured under PECVD conditions because the plasma species may reach the substrate surface according to off-perpendicular directions. The average energy of these species is the main parameter used to describe their angular distribution function, while the reactivity of the surface is another key parameter used in the simulations.     

Substrate effects on the microstructure of hydrogenated amorphous carbon films

In this work, plasma enhanced chemical vapour deposition was used to prepare hydrogenated amorphous carbon films (a-C:H) on different substrates over a wide range of thickness. In order to observe clear substrate effect the films were produced under identical growth conditions. Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopies were employed to probe the chemical bonding of the films. For the films deposited on silicon substrates, the Raman I_D/I_G ratio and G-peak positions were constant for most thickness. For metallic and polymeric substrates, these parameters increased with film thickness, suggesting a change from a sp³-bonded hydrogenated structure to a more sp² network, NEXAFS results also indicate a higher sp² content of a-C:H films grown on metals than silicon. The metals, which are poor carbide precursors, gave carbon films with low adhesion, easily delaminated from the substrate. The delamination can be decreased/eliminated by deposition of a thin (∼10 nm) silicon layer on stainless steel substrates prior to a-C:H coatings. Additionally we noted the electrical resistivity decreased with thickness and higher dielectric breakdown strength for a-C:H on silicon substrate.     

Wettability and reactivity of molten silicon with various substrates

Contact angles of molten silicon on various substrates have been determined using the sessile drop method and reactivity has been investigated by examining cross sections between silicon and substrates with an electron-probe microanalyzer (EPMA). The contact angles between molten silicon and oxide substrates, such as SiO₂(s), Al₂O₃(s) and MgO(s), are in the range 85° to 88°. The reaction zone is composed of forsterite (2MgO·SiO₂) and clinoenstatite (2MgO·2SiO₂) on the MgO(s)-side of the interface between the Si and MgO. The contact angle between molten silicon and Si₃N₄ is about 90°. Molten silicon spreads over the SiC plate and the contact angle is estimated to be 8°. Large contact-angle values (around 145°) have been observed on BN substrates. At the interface between Si(l) and the BN substrate, a discontinuous Si₃N₄ layer is believed to form and might retard the dissolution of BN into molten silicon. The BN substrate is regarded as being the most suitable substrate for supporting a molten silicon drop during surface tension measurements, due to the large contact angle and low contamination. PACS 68.08.Bc; 06.30.Bp; 73.40.Ns; 61.72.Tt     

IR spectra of carbon-vacancy clusters in the topochemical transformation of silicon into silicon carbide

Using infrared (IR) spectroscopy and spectral ellipsometry, we experimentally confirmed the previously predicted mechanochemical effect of the stoichiometric composition disorder leading to the formation of carbon-vacancy structures in silicon carbide (SiC) films grown on silicon substrates by the atom substitution method. It was found that a band at 960 cm^–1 in the IR spectra of SiC films on silicon, corresponding to “carbon-vacancy clusters” is always present in SiC films grown under pure carbon monoxide (CO) or in a mixture of CO with silane (SiH₄) on Si substrates of different orientation and doping level and type. There is no absorption band in the region of 960 cm–1 in the IR spectra of SiC films synthesized at the optimum ratio of the CO and trichlorosilane (SiHCl₃) gas pressures. The previously predicted mechanism of the chemical reaction of substitution of Si atoms for carbon by the interaction of gases CO and SiHCl₃ on the surface of the silicon substrate, which leads to the formation of epitaxial layers of single-crystal SiC, is experimentally confirmed.     

Thermoelectric properties of manganese silicide films

Manganese silicide films (MnSi and MnSi_1.73) were grown on silicon and glass substrates. The films were characterized by X-ray diffraction, Auger electron spectroscopy, and thermoelectric measurements. The films were n-type when they were deposited on n-type (100) silicon substrates with resistivity of 3–5 ohm-cm. P-type films were obtained when the films were deposited on glass or n-type (100) silicon substrates with resistivity of greater than 6000 ohm-cm. An analysis of the resistivity data in the intrinsic regime suggests that MnSi_1.7 has an energy gap of 0.984 eV. PACS 73.50.Lw; 72.20.-i; 72.80.Ga; 73.61.-r; 73.61.Le     

Heteroepitaxial GaN films on silicon substrates with porous buffer layers

New complex buffer layers based on a porous material have been developed for epitaxial growth of GaN films on Si substrates. The characteristics of gallium nitride heteroepitaxial layers grown on silicon substrates with new buffer layers by metal-organic vapor phase epitaxy are investigated. It is shown that the porous buffer layers improve the electric homogeneity and increase the photoluminescence intensity of epitaxial GaN films on Si substrates to the values comparable with those for reference GaN films on Al₂O₃ substrates. It is found that a fianite layer in a complex buffer is a barrier for silicon diffusion from the substrate into a GaN film.     

Surface morphology and reaction at Cu/Si interface—Effect of native silicon suboxide

Copper thin films are deposited by thermal evaporation on unetched and etched monocrystalline silicon. The study by alpha particles backscattering (RBS) raises a strong diffusion of copper in silicon substrates with and without native suboxide layer. On the other hand, the X-rays diffraction shows the formation and the growth of Cu₃Si and Cu₄Si silicides. Whereas the scanning microscopy underlines large crystallites growth surrounded by black zones of silicon coming from the uncovered substrate, independently to the surface state of the substrate, after annealing at high temperature. The presence of native silicon suboxide at Cu/Si interface, influences in a drastic way the minimal temperature to which the interfacial reaction occurs. The oxygen impurities detected by microanalysis, after heat treatment under vacuum, are closely related to the growth of silicides crystallites.     

Wetting and superhydrophobic properties of PECVD grown hydrocarbon and fluorinated-hydrocarbon coatings

Wetting characteristics of micro-nanorough substrates of aluminum and smooth silicon substrates have been studied and compared by depositing hydrocarbon and fluorinated-hydrocarbon coatings via plasma enhanced chemical vapor deposition (PECVD) technique using a mixture of Ar, CH₄ and C₂F₆ gases. The water contact angles on the hydrocarbon and fluorinated-hydrocarbon coatings deposited on silicon substrates were found to be 72° and 105°, respectively. However, the micro-nanorough aluminum substrates demonstrated superhydrophobic properties upon coatings with fluorinated-hydrocarbon providing a water contact angle of ∼165° and contact angle hysteresis below 2° with water drops rolling off from those surfaces while the same substrates showed contact angle of 135° with water drops sticking on those surfaces. The superhydrophobic properties is due to the high fluorine content in the fluorinated-hydrocarbon coatings of ∼36 at.%, as investigated by X-ray photoelectron spectroscopy (XPS), by lowering the surface energy of the micro-nanorough aluminum substrates.     

Electrons diffusion study on the nitrogen-doped nanocrystalline diamond film grown by MPECVD method

Nitrogen-doped nanocrystalline diamond (NNCD) films were deposited onto p-type silicon substrates with three different layer structures: (i) directly onto the silicon substrate (NNCD/Si), (ii) silicon with undoped nanocrystalline diamond layer which was deposited in the same way as the above mentioned NNCD by the recipe Ar/CH₄/H₂ with a ratio of 98%/1%/1% (NNCD/NCD/Si), and (iii) silicon wafer with 100 nm thickness SiO₂ layer (NNCD/SiO₂/Si). Atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy were employed to characterize the morphology and microstructure of the as-grown nitrogen-doped diamond films. Silver colloid/silver contacts were made at to measure the current-voltage (I-V) characteristics for the three different structures. Electrons from a CVD reactor hydrogen plasma diffuse toward the p-type silicon substrate during a deposition process under the high temperature (∼800 °C). The study concluded that the SiO₂ layer could effectively prevents the diffusion of electrons.     

Synthesis and characterisation of Gd-doped BaTiO3 thin films prepared by laser ablation for optoelectronic applications

The results of gadolinium (Gd)-doped barium titanate (BaTiO₃) thin films prepared by laser ablation on glass and silicon substrates are reported. Rutherford backscattering (RBS) analyses carried out on glass samples indicated the substitution of barium (Ba) by gadolinium (Gd) after annealing, leading to a film with composition Ba_0.76TiGd_0.01O_2.5. There is a reduction in the thickness from 2.21 to 2.02 microns for as-deposited and annealed films. The films on silicon showed a higher degree of crystallinity compared to that of glass substrates due to increased annealing temperature. The average grain size calculated using the X-ray diffraction (XRD) pattern from silicon substrates was 30 nm. The film has a tetragonal structure with a “c/a” ratio of 1.03 signifying that the incorporation of Gd in BaTiO₃ led to the elongation of the c-axis. The percentage transmittance reduced from 80 to 50% due to annealing and this is probably due to structural changes in the film. Swanepoel envelope method employed on the interference fringes of the transmittance pattern led to the determination of the variation of the refractive index with wavelength. Sellmier single oscillator model was applied to determine the optical constants of the films on glass substrates. Bandgap analyses carried out showed the reduction in bandgap with annealing and also the possibility that Gd incorporation has modified the film chemistry leading to the existence of direct (4.35 eV) and indirect (3.88 eV) allowed transitions in the annealed films. Dielectric property measurement carried out under ambient conditions gave a relaxation time τ of 1.6×10⁻⁴ s and conduction by small polaron with the onset of polaron conduction set at about 7 kHz. It is conjectured that these properties, especially the high refractive index and the high bandgaps, can make Gd-doped BaTiO₃ a good candidate for optoelectronic applications.     

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles for strained‐silicon surface enhanced Raman spectroscopy

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles deposited onto strained‐silicon layers grown on graded Si_1−xGe_x virtual substrates are utilized for selective amplification of the Si–Si vibration mode of strained silicon via surface‐enhanced Raman scattering spectroscopy. This solution‐based technique allows rapid, highly sensitive and accurate characterization of strained silicon whose Raman signal would usually be overshadowed by the underlying bulk SiGe Raman spectra. The analysis was performed on strained silicon samples of thickness 9, 17.5 and 42 nm using a 488 nm Ar⁺ micro‐Raman excitation source. The quantitative determination of strained‐silicon enhancement factors was also made. Copyright © 2011 John Wiley & Sons, Ltd.     

Gadolinium scandate as an alternative gate dielectric in field effect transistors on conventional and strained silicon

Long channel n-type metal oxide semiconductor field effect transistors on thin conventional and strained silicon on insulator substrates have been prepared by integrating gadolinium scandate as high-κ gate dielectric in a gate last process. The GdScO₃ films were deposited by electron beam evaporation and subsequently annealed in oxygen atmosphere. Electrical characterization of readily processed devices reveals well behaved output and transfer characteristics with high I _on/I _off ratios of 10⁶–10⁸, and steep inverse subthreshold slopes down to 66 mV/dec. Carrier mobilities of 155 cm²/Vs for the conventional and 366 cm²/Vs for the strained silicon substrates were determined.     

Structure and dielectric properties of ultra-thin ZrO<Subscript>2</Subscript> films for high-<Emphasis Type="Italic">k</Emphasis> gate dielectric application prepared by pulsed laser deposition

ZrO₂ thin films have been prepared on Pt-coated silicon substrates and directly on n-Si(100) substrates by the pulsed laser deposition (PLD) technique using a ZrO₂ ceramic target under different deposition conditions. X-ray diffraction showed that the films prepared at 400 °C in 20 Pa oxygen ambient remained amorphous. Differential thermal analysis was carried out to study the crystallization behavior of ZrO₂. The dielectric constant of ZrO₂ was determined to be around 24 by measuring a Pt/ZrO₂/Pt capacitor structure. Sputtering depth profile X-ray photoelectron spectroscopy was used to investigate the interfacial characteristics of ZrO₂/n-Si stacks. A Zr silicate interfacial layer was formed between the ZrO₂ layer and the silicon substrate. The equivalent oxide thickness (EOT) and leakage current densities of the films with 6.6 nm physical thickness post-annealed in O₂ and N₂ ambient were investigated. An EOT of 1.65 nm with a leakage current of 36.2 mA/cm² at 1 V gate voltage for the film post-annealed in N₂ has been obtained. ZrO₂ thin films prepared by PLD have acceptable structure and dielectric properties required by a candidate material of high-k gate dielectrics. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

Flame synthesis of tungsten oxide nanostructures on diverse substrates

One-dimensional (1D) tungsten oxide nanostructures show great potential for applications in the areas of batteries, photoelectrochemical water-splitting, electrochromic devices, catalysts and gas sensors. 1D tungsten oxide nanostructures are currently synthesized by physical or chemical vapor deposition, which are limited by low temperatures, the need for vacuum conditions, frequently expensive catalysts, and difficulty in scaling up for mass-production. These limitations, however, can be overcome by flame synthesis. Here, using a co-flow multi-element diffusion burner, we demonstrate the atmospheric, catalyst-free, rapid, mild and scalable flame synthesis of diverse, quasi-aligned, large density, and crystalline tungsten oxide nanostructures on a variety of substrates. Specifically, under fuel-rich conditions, monoclinic 1D W₁₈O₄₉ nanowires and nanotubes were grown on tungsten, iron, steel and fluorinated tin oxide (FTO) substrates, with controlled diameters ranging from 10 to 400 nm and axial growth rates ranging from 2 to 60 μm/h. Monoclinic 1D WO₃ nanowires and nanotubes were grown, instead, on silicon and silicon dioxide substrates. Under fuel-lean conditions, diverse WO₃ nanostructures, including monoclinic 1D nanowires, cubic 2D nanobelts and monoclinic 3D nanocones were grown on tungsten and FTO substrates. The success of this versatile flame synthesis method is attributed to the large tunability of several synthesis parameters, including the flame stoichiometry, the tungsten source and growth substrate temperatures, the tungsten oxide vapor concentration, and the material of the growth substrate. This flame synthesis method can be extended to synthesize other 1D transition metal oxides as well, enabling many large-scale electronic and energy conversion applications.     

Silicon based polytetrafluoroethylene electrets: Preparation and corona charging characteristics

In this paper, silicon based planar technology and high performance fluorocarbon polymer polytetrafluoroethylene (PTFE) are combined to achieve PTFE thin film electrets on wafer. The PTFE film is fabricated onto SiO₂ substrates and Pt substrates using spin coating and annealing processes, and its electret effect is demonstrated using negative corona charging method. PTFE electrets with different surface morphology exhibit different charge storage capability. Maximally, surface potential of ?396 V is achieved on Pt substrates and ?361 V is achieved on SiO₂ substrates. The average retain rate of surface potential over 240 h is 90.6% for Pt substrates and 76.3% for SiO₂ substrates. The proposed method presents the primary step toward integrated electrostatic devices.     

Oriented Growth of Nanocrystalline Gamma Ferric Oxide in Electrophoretically Deposited Films

Films of nanocrystalline γ-Fe₂O₃ were deposited on silicon substrates by using the technique of electrophoretic deposition. The precursor powder was nanocrystalline γ-Fe₂O₃, which was synthesized, using DC arc plasma in the oxygen ambient by vapour–vapour interaction in gas phase condensation; at a stabilized arc current of 40 A. This powder was characterized by X-ray diffraction, Transmission Electron Microscopy, Vibrating Sample Magnetometer and Mössbauer Spectroscopy. An increase in directional coercivity was observed in case of films deposited on silicon substrates, which is dramatically significant. Preferred orientation of almost similar sized nanocrystalline magnetic domains in deposited films is evident from the results of X-ray diffraction and Transmission Electron Microscopy results. The preferred alignment of the nanocrystallites seems to be responsible for the significant changes observed in magnetic properties of films.     

Ozone cleaning of the Si-SiO2 system

The cleaning of monocrystalline silicon substrates and thin thermally grown SiO₂ layers on silicon by electrochemically produced ozone has been investigated. In both cases organics are removed very effectively. In comparison with other dry cleaning methods no radiation damage occurs.     

Density functional study of initial HfCl4 adsorption and decomposition reactions on silicon surfaces with SiON interfacial layer

The initial adsorption and decomposition of HfCl₄ on silicon surfaces with different types of SiON interfacial layers are investigated using density functional theory. We find that the reactions of HfCl₄ on both the hydroxylated and nitrided silicon surfaces proceed through similar reaction pathways. By comparison of the reaction energies of HfCl₄ with the hydroxyl and amino surface sites, we find that it is both kinetically and thermodynamically favorable for the reactions of HfCl₄ on hydroxyl site of silicon substrates. Comparing with the adjacent bridging oxygen, we also find that the neighboring hydroxyl can facilitate the adsorption of HfCl₄ on the amido surface site. Also, it is more kinetically and thermodynamically favorable for the reaction of HfCl₄ with bridging NH site than that with NH₂ site.     

Super-hydrophilic properties of TiO2-DLC nanocomposite films fabricated by the simple electrochemical process

Anatase TiO₂ nanoparticles incorporated DLC films were successfully deposited on single crystalline silicon substrates by the electrolysis of TiO₂-methanol solution under ambient atmospheric pressure and low temperature. Anatase TiO₂ nanoparticles were embedded into amorphous carbon matrix, forming the typical nanocrystalline/amorphous nanocomposite films, confirmed by transmission electron microscopy (TEM). TiO₂ incorporation effectively increased the sp³-hybridized carbon concentration in the composite film, and further regulated the microstructure and surface morphology. Furthermore, the static contact testing completely displayed, TiO₂ incorporation got the composite films super-hydrophilic, which fundamentally improved the wetting ability of DLC film.     

Specific features and mechanisms of photoluminescence of nanostructured silicon carbide films grown on silicon in vacuum

The light-emitting properties of cubic silicon carbide films grown by vacuum vapor phase epitaxy on Si(100) and Si(111) substrates under conditions of decreased growth temperatures (T _gr ∼ 900–700°C) have been discussed. Structural investigations have revealed a nanocrystalline structure and, simultaneously, a homogeneity of the phase composition of the grown 3C-SiC films. Photoluminescence spectra of these structures under excitation of the electronic subsystem by a helium-cadmium laser (λ_excit = 325 nm) are characterized by a rather intense luminescence band with the maximum shifted toward the ultraviolet (∼3 eV) region of the spectral range. It has been found that the integral curve of photoluminescence at low temperatures of measurements is split into a set of Lorentzian components. The correlation between these components and the specific features of the crystal structure of the grown silicon carbide layers has been analyzed.