Formation and structural characterization of nanocrystalline Si/SiC multilayers grown by hot filament assisted chemical vapor deposition using CH3SiH3 gas jets

We report on the formation and the structural characterization of nanocrystalline Si/SiC (nc-Si/SiC) multilayers on Si(100) by hot filament assisted chemical vapor deposition using CH₃SiH₃ gas pulse jets. Si rich amorphous SiC (a-Si_1 − xC_x, x ~ 0.33) was initially grown at the substrate temperature (T_s) of 600 °C with heating a hot filament at ~ 2000 °C. The following crystalline SiC layers were grown at T_s = 850 °C without utilizing a hot filament. When the a-Si_1 − xC_x layer was ultrathin (< 2 nm) on Si(100), this a-Si_1 − xC_x layer was transformed to a single epitaxial SiC layer during the subsequent SiC growth process. The Si{111} faceted pits were formed at the SiC/Si(100) interface due to Si diffusion processes from the substrate. When the thickness of the initial a-Si_1 − xC_x layer was increased to ~ 5 nm, a double layer structure was formed in which this amorphous layer was changed to nc-Si and nc-SiC was grown on the top resulting in the considerable reduction of the {111} faceted pits. It was found that nc-SiC was formed by consuming the Si atoms uniformly diffused from the a-Si_1 − xC_x layer below and that Si nanocrystals were generated in the a-Si_1 − xC_x layers due to the annealing effect during further multilayer growths.     

Formation of size-controlled silicon nanocrystals in plasma enhanced chemical vapor deposition grown SiOxNy/SiO2 superlattices

Size controlled silicon nanocrystals (SiNC) in silicon oxynitride matrix were prepared using plasma enhanced chemical vapor deposition. The as-deposited superlattices (SLs) and the corresponding bulk films were treated by thermal annealing. Hydrogen effusion was performed during the heating up by choosing a sufficiently low heating ramp. The phase separation of the layers into SiNCs and surrounding oxynitride matrix was studied at temperatures of up to 1150 °C. The influence of the annealing temperature on SiO_xN_y/SiO₂ - SLs with varying SiO_xN_y layer thickness was investigated by several analytical techniques including variable angle spectroscopic ellipsometry, photoluminescence (PL) spectroscopy, x-ray photoelectron spectroscopy, Fourier transform infrared spectrometry (FTIR) and transmission electron microscopy (TEM). Before annealing FTIR investigations show in addition to the expected Si-O bonds also the formation of nitrogen and hydrogen related bonds. The shift of the Si-O-Si stretching vibration to higher wave numbers after annealing indicates phase separation. The disappearance of the hydrogen related bonds indicates the hydrogen effusion. The PL signal is rising significantly with increasing annealing temperature and the PL peak position is strongly related to the thickness of the SiO_xN_y sublayers due to quantum confinement effects. TEM investigations confirm the size-controlled growth of SiNCs within the oxynitride matrix. The role of incorporated nitrogen and hydrogen is discussed.     

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.     

Raman study of stress effect on Ge nanocrystals embedded in Al2O3

Ge nanocrystals (NCs) embedded in Al₂O₃ were grown by RF-sputtering. X-ray diffraction, high resolution transmission electron microscopy, and Raman spectroscopy techniques were used to characterize the stresses on the NCs. While small NCs (< 10 nm) have been observed to be spherical and fully relaxed in the matrix, the larger ones (> 17 nm) demonstrated a compressive stress effect. This could be linked to the crystal structure of the adjacent Al₂O₃ matrix.     

Orientation dependent growth of SiC nanocrystals at the SiO2/Si interface

Cubic SiC nanocrystals are formed epitaxially and void-free on single crystal Si substrate by reactive annealing in CO. In this study characterization of the nucleation, growth and morphology is presented on differently oriented single crystal Si substrates. It is found that SiC nanocrystals of various shape can be grown in different densities on the (100), (110) and (111) Si surfaces with an average size of 30-60 nm. Effect of annealing time, CO concentration, substrate orientation and crystal size on crystallite growth is discussed. Parameters to obtain increased SiC nucleation density are determined.     

Temperature dependent biaxial texture evolution in Ge films under oblique angle vapor deposition

The morphology and texture of Ge films grown under oblique angle vapor deposition on native oxide covered Si(001) substrates at temperatures ranging from 230 °C to 400 °C were studied using scanning electron microscopy, X-ray diffraction and X-ray pole figure techniques. A transition from polycrystalline to {001}<110> biaxial texture was observed within this temperature range. The Ge films grown at substrate temperatures < 375 °C were polycrystalline. At substrate temperatures of 375 °C and 400 °C, a mixture of polycrystalline and biaxial texture was observed. The 230 °C sample consisted of isolated nanorods, while all other films were continuous. The observed biaxial texture is proposed to be a result of the loss of the interface oxide layer, resulting in epitaxial deposition of Ge on the Si and a texture following that of the Si(001) substrates used. The rate of oxide loss was found to increase under oblique angle vapor deposition.     

TiO2 thin films using organic liquid materials prepared by Hot-Wire CVD method

TiO₂ thin films prepared by Hot-Wire CVD method have been studied as a protecting material of transparent conducting oxide (TCO) against atomic hydrogen exposures for the fabrications of Si thin film solar cells. It was found that electrical conductivity of the films at room temperature reached a value of 0.4 S/cm. This value is 2-3 orders of magnitude higher than that of TiO₂ films prepared by RF magnetron sputtering and electron-beam evaporation methods in our previous works. The conductivity improvement seems to be partly due to the enlargement of TiO₂ crystallites.     

Silicon nanostructures fabricated by Au and SiH4 co-deposition technique using hot-wire chemical vapor deposition

In this study, the fabrication of Si nanostructures by Au and SiH₄ co-deposition technique using hot-wire chemical vapor deposition was demonstrated. A high deposition rate of 2.7 nm/s and a high density of silicon nanostructures with a diameter of about 140 nm were obtained at T_s of 250 °C. An increase in T_s led to a significant reduction in the size of the nanostructures. However, coalescence on the nanostructures was observed at T_s of 400 °C. The Si nanostructures exhibited a highly crystalline structure, which was induced by Au crystallites. The crystallite size and crystallinity of the Si nanostructures amplified with the increase in T_s. The presence of nanostructures enhanced the surface roughness of the samples and clearly reduced the reflection, especially in the visible region.     

Synthesis and structural characterization of mesoporous V2O5 thin films for electrochromic applications

Mesoporous vanadium pentoxide (V₂O₅) films have been synthesized by hydrolysis of vanadium tri-isopropoxide (VO(OC₃H₇)₃) in the presence of polyethylene glycol (PEG) as a structure-directing agent. The structure, the stoichiometry and the morphology of the films have been studied as a function of the thermal annealing by X-ray diffraction (XRD), micro-Raman spectroscopy, optical microscopy, scanning electron microscopy and atomic force microscopy. XRD patterns and Raman spectra show the presence of two previously unreported crystalline phases. The PEG:V₂O₅ molar ratio affects the temperature of phase formation, the amount and even the order in which the phases appear. The morphological characterization underlines the role of the surfactant to promote porous networks, formed by micrometric clusters of controlled shapes and patterns embedded in a homogeneous host matrix.     

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.     

Chemical vapor deposition of aluminum from methylpyrrolidine alane complex

Chemical vapor deposition of aluminum from a recently developed precursor, methylpyrrolidine alane complex, has been studied. Aluminum films deposited on conducting surfaces (titanium nitride, copper, gold), but not on insulating surfaces (silicon, silicon dioxide, glass) at low substrate temperatures, showing deposition selectivity, while the deposition selectivity was lost at high substrate temperatures (> 210 °C). Al deposition rates on TiN and Cu were very close, but much higher than on Au. Deposition rates on all conducting substrates increased with the temperature and reached maximum at 180 °C. Al films deposited on as-sputtered TiN or Cu have no preferred orientations. Al–Au alloys and intermetallics were observed in the films deposited on Au. Surface morphology observation revealed that the film growth on TiN or Cu is different from that on Au. The surface roughness of Al films increased with the deposition time or the film thickness.     

Preparation of Magnéli phases of Ti27O52 and Ti6O11 films by laser chemical vapor deposition

Magnéli phases of Ti₂₇O₅₂ and Ti₆O₁₁ films were prepared by laser chemical vapor deposition using Ti(dpm)₂(O-i-Pr)₂ as a precursor. Ti₆O₁₁ film was obtained at a laser power (P_L) of 200 W and a deposition temperature (T_dep) of 1270 K. Ti₂₇O₅₂ film was obtained at P_L = 150 to 200 W and T_dep = 1120 to 1250 K. Ti₆O₁₁ and Ti₂₇O₅₂ films had a faceted texture about 2 μm in grain size and a columnar cross section. The deposition rate of Ti₂₇O₅₂ and Ti₆O₁₁ films were 90 and 70 μm h^− 1, respectively.     

Formation and composition of titanium oxinitride nanocrystals synthesized via nitridizing titanium oxide for nonvolatile memory applications

Formation and composition analyses of titanium oxinitride nanocrystals (NCs) fabricated via treating a magnetron co-sputtered thin film of titanium and silicon dioxide with a rapid thermal annealing in nitrogen ambient were demonstrated for nonvolatile memory applications. Phase separation characteristics with different annealing conditions were examined by transmission electron microscopy and chemical bonding characteristics were confirmed by X-ray photon emission spectra. It was observed that a blanket layer composed mainly of titanium oxide was still present as annealing temperature was increased to 700 °C, associated with the thermodynamically stable phase of titanium oxide. Furthermore, a higher thermal treatment of 900 °C induced formation of a well-separated NC structure and caused simultaneously partial nitridation of the titanium oxide, thereby forming titanium oxinitride NCs. A significant capacitance-voltage hysteresis in threshold voltage shift at 1 V was easily achieved under a small sweeping voltage range of + 2 V/−2 V, and a memory window retention of 2.2 V was obtained after 10⁷ s by extrapolation under a 1 s initial-program/erase condition of + 5 V/−5 V, respectively.     

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.     

Photochemical synthesis and characterization of Bi2S3 nanofibers

Bismuth sulfide (Bi₂S₃) nanofibers have been successfully prepared by a photochemical method from an aqueous solution of bismuth nitrate (Bi(NO₃)₃) and thioacetamide (TAA) in the presence of complexing agents of nitrilotriacetic acid (NTA) at room temperature. It was found that the irradiation time, the pH of the solution, and the species of complexing agents play important roles in the morphology control of the bismuth sulfate (Bi₂S₃) nanomaterials. The nanofibers were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectra (XPS), and UV-Visible absorption spectra (UV-Vis). Probable mechanisms for the photochemical formation of Bi₂S₃ nanofibers in aqueous solutions are proposed. The photochemical method is a convenient approach for controlling the shape for other metal sulfide semiconductor nanocrystals.     

Synthesis of (Na2O,PbO)-Nb2O5, (Na2O,BaO)-Nb2O5, and (K2O,SrO)-Nb2O5 thin films using sol-gel method

Homogeneous pore-free Ba₂NaNb₅O₁₅, KSr₂Nb₅O₁₅, and 2·Na₂O-PbO-6·Nb₂O₅ thin films were fabricated on sapphire substrates using the sol-gel technique. By controlling the gelation and coating process, thickness of thin films fabricated was controllable from ~ 40 nm to ~ 10 μm. Synthesized thin films possessed highly preferred orientated microstructure. Another advantage of this method is the subsequent heat treatment temperature dramatically decreased compared with other methods. This increases stoichiometry control and makes the large scale fabrication more feasible and efficient.     

Characteristics of atomic layer deposition grown HfO2 films after exposure to plasma treatments

Ultra thin HfO₂ films were grown by the atomic layer deposition (ALD) technique using tetrakismethylethylaminohafnium (Hf[N(CH)₃(C₂H₅)]₄) and ozone (O₃) as the precursors and subsequently exposed to various plasma conditions, i.e., CCP (capacitively coupled plasma) and MMT (modified magnetron typed plasma) in N₂ or N₂/O₂ ambient. The conventional CCP treatment was not effective in removing the carbon impurities, which were incorporated during the ALD process, from the HfO₂ films. However, according to the X-ray photoelectron spectroscopy measurements, the MMT treated films exhibited a significant reduction in their carbon contents and the efficient incorporation of nitrogen atoms. Although the incorporated nitrogen was easily released during the post-thermal annealing of the MMT treated samples, it was more effective than the CCP treatment in removing the film impurities. Consequently, the MMT treated samples exhibited excellent electrical properties as compared to the as-deposited HfO₂ films, including negligible hysteresis (flatband voltage shift), a low leakage current, and the reduced equivalent oxide thickness of the gate stack. In conclusion, MMT post treatment is more effective than conventional CCP treatment in improving the electrical properties of high-k films by reducing the carbon contamination and densifying the as-deposited defective films.     

Non-catalytic growth of graphene-like thin film near pattern edges fabricated on SiO2 substrates

Graphene-like thin films were grown on patterned SiO₂ substrates by simple thermal chemical vapor deposition using ethanol. The film growth occurred preferentially in the vicinity of pattern edges. Catalytic metal is not necessary for the substrate or the pattern. The films consist of graphitic nanocrystals of several nanometer scale. In the electric properties, the field effect is observed at room temperature.     

Multi-orientation patterned deposition of BaTiO3 thin films using an Au buffer layer

The control of crystallographic orientation for ferroelectric oxide thin films grown on single crystal substrates has been investigated. We find that perovskite BaTiO₃ has unusual orientation distributions when deposited on (100)- and (110)-oriented SrTiO₃ single crystal substrates that have predeposited patterned Au regions. BTO areas deposited on gold islands were found to have a (111) orientation, whereas those deposited directly on STO had the same orientation as the substrate. Based on this method, we can select, locate, and pattern an oxide film to have different orientation distributions, and thereby engineer films with the complete property anisotropy in-plane.     

Cr2O3 thin films grown at room temperature by low pressure laser chemical vapour deposition

Chromia (Cr₂O₃) has been extensively explored for the purpose of developing widespread industrial applications, owing to the convergence of a variety of mechanical, physical and chemical properties in one single oxide material. Various methods have been used for large area synthesis of Cr₂O₃ films. However, for selective area growth and growth on thermally sensitive materials, laser-assisted chemical vapour deposition (LCVD) can be applied advantageously.Here we report on the growth of single layers of pure Cr₂O₃ onto sapphire substrates at room temperature by low pressure photolytic LCVD, using UV laser radiation and Cr(CO)₆ as chromium precursor. The feasibility of the LCVD technique to access selective area deposition of chromia thin films is demonstrated. Best results were obtained for a laser fluence of 120 mJ cm⁻² and a partial pressure ratio of O₂ to Cr(CO)₆ of 1.0. Samples grown with these experimental parameters are polycrystalline and their microstructure is characterised by a high density of particles whose size follows a lognormal distribution. Deposition rates of 0.1 nm s⁻¹ and mean particle sizes of 1.85 μm were measured for these films.