Characterization of Hafnium-Zirconium-Oxide-Nitride films grown by ion beam assisted deposition

Hafnium-Zirconium-Oxide-Nitride (Hf_1−xZr_xO_1−yN_y) films are prepared by ion beam assisted deposition on p-Si and quartz substrates with a composite target of sintered high-purity HfO₂ and ZrO₂. The thermal stability and microstructure characteristics for Hf_1−xZr_xO_1−yN_y films have been investigated. EDS results confirmed that nitrogen was successfully incorporated into the Hf_1−xZr_xO₂ films. XRD and Raman analyses showed that the Hf_1−xZr_xO_1−yN_y films remain amorphous after 1100 °C under vacuum ambient, and monoclinic HfO₂ and ZrO₂ crystals separate from Hf_1−xZr_xO_1−yN_y films with a increase of the annealing temperature up to 1300 °C. Meanwhile, the Hf_1−xZr_xO_1−yN_y films can also effectively suppress oxygen diffusion during high temperature annealing. AFM measurements demonstrated that surface roughness of the Hf_1−xZr_xO_1−yN_y films increase slightly. Then the optical properties of the samples were observed in the ultraviolet-visible range at room temperature. The variation in E_g from 5.64 to 6.09 eV as a function of annealing temperature has also been discussed briefly.     

Heterogeneous nucleation and growth of polycrystalline silicon

The heterogeneous nucleation theory of silicon on SiO₂ and Si₃N₄ substrates has been developed using classical theory. It is shown that the experimental observations can be explained on the basis of the bond energies of O-H, N-H and Si-H. A reaction model is proposed for the growth of silicon on silicon from silane, using hydrogen as a carrier gas in the temperature region 600–900°C. The growth rate of silicon is shown to be equal toP _{SiH 4} P _{H 2} when the partial pressure of hydrogen is high, and is independent of the total pressure and the partial pressure of hydrogen in the lower region.     

Improved transport properties of microcrystalline silicon films grown by HWCVD with a variable hydrogen dilution process

The structure and the transport properties of microcrystalline silicon films prepared by hot-wire/catalytic chemical vapor deposition (HWCVD/Cat-CVD), using different dilution ratios of silane in hydrogen, were investigated. Spectroscopic ellipsometry analysis revealed an increase in the thickness of amorphous incubation layer formed before nucleation and a reduction of the void volume fraction when hydrogen dilution decreases. Thus, a specific microcrystalline silicon film growth process was proposed, based on a variable dilution of silane in hydrogen. For films prepared in such conditions, the formation of the incubation layer was inhibited, which led to a drastic improvement in carrier transport along the growth direction as proved by the diffusion-induced time-resolved microwave conductivity data.     

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.     

Microcrystalline silicon carbide thin films grown by HWCVD at different filament temperatures and their application in n-i-p microcrystalline silicon solar cells

To optimize the performance of microcrystalline silicon carbide (µc-SiC:H) window layers in n-i-p type microcrystalline silicon (µc-Si:H) solar cells, the influence of the rhenium filament temperature in the hot wire chemical vapor deposition process on the properties of µc-SiC:H films and corresponding solar cells were studied. The filament temperature T_F has a strong effect on the structure and optical properties of µc-SiC:H films. Using these µc-SiC:H films prepared in the range of T_F = 1800-2000 °C as window layers in n-side illuminated µc-Si:H solar cells, cell efficiencies of above 8.0% were achieved with 1 µm thick µc-Si:H absorber layer and Ag back reflector.     

SiC-SiO2 nanocomposite films prepared by laser CVD using tetraethyl orthosilicate and acetylene as precursors

SiC-SiO₂ nanocomposite films were prepared by laser chemical vapor deposition (LCVD) using a CO₂ laser with tetraethyl orthosilicate (TEOS) and acetylene (C₂H₂) as precursors. The effects of laser power on the crystal phase and microstructure of the SiC-SiO₂ nanocomposite films were investigated. Films produced with laser power below 150 W (below 1523 K) had an amorphous structure, while those produced above 200 W (above 1673 K) were a mixture of crystalline SiC and amorphous phase. At 245 W (1774 K) the film contained 3C-SiC nanocrystals 100 to 200 nm in diameter dispersed in an amorphous matrix having high-density stacking faults formed on the (1?1?1?) and (111?) planes.     

Micro-structures of BF2- and As-implanted polycrystalline silicon thin films of various thicknesses and heat treatments

Characterization of annealed BF₂⁺- and As⁺-doped polycrystalline silicon (polysilicon) films is presented. Effects of heat treatment, doping concentration, and thickness of film on the grain size and mobility of polysilicon films are investigated and discussed. By using transmission electron microscopy (TEM), it is found that the grain size, effective carrier concentration, and carrier mobility of a polysilicon thin film increases with increasing film thickness. Our results show that a high concentration of As dopant could enhance the recrystallization of the polysilicon films. Heavily As⁺-doped samples were seen to have a relatively larger grain size compared to the lightly doped film. The maximum grain size of about 278 nm can be realized in a polysilicon film with 150 nm in thickness. In contrast, the B dopant has a negligible effect on the recrystallization of polysilicon films. With increasing film thickness and thermal annealing temperature, a high performance polysilicon film with high mobility and grain size can be obtained.     

An atomic force microscopy and optical microscopy study of various shaped void formation and reduction in 3C-SiC films grown on Si using chemical vapor deposition

The formation of various uncommon shaped voids along with regular triangular and square voids in the epitaxial 3C-SiC films on Si has been investigated by optical microscopy and atomic force microscopy. Heteroepitaxial growth of 3C-SiC films on Si (001) and (111) substrates has been performed using hexamethyldisilane in a resistance-heated chemical vapor deposition reactor. The influence of the orientation of the Si substrate in determining the shape of the voids has clearly been observed. In addition, the growth period and the growth-temperature have been considered as the major parameters to control the size, density and shape of the voids. Generally, voids are faceted along {111} planes, but depending upon growth conditions, other facets with higher surface energy have also been observed. Finally the size and density of the voids are remarkably reduced, by suitable growth technique.     

Properties of hetero-structured SiCX films deposited by hot-wire CVD using SiH3CH3 as carbon source

The hetero-structured SiC_X films have been deposited by hot-wire CVD using SiH₃CH₃ as the carbon source gas. Although the carbon source gas ratio and filament temperature in the deposition using SiH₃CH₃ were smaller than those using C₂H₆, the carbon content in the sample deposited using SiH₃CH₃ was similar to that deposited using C₂H₆. The optical energy gap in the sample deposited using SiH₃CH₃ was larger than that deposited using C₂H₆. The sample deposited using SiH₃CH₃ under optimized condition showed a wide optical energy gap of 1.99 eV and a large dark conductivity of 15.1 S/cm. The p-type sample deposited using SiH₃CH₃ under the optimized condition has been used as a window layer material in p-i-n a-Si:H based solar cells.     

Improvement of μc-Si:H n-i-p cell efficiency with an i-layer made by hot-wire CVD by reverse H2-profiling

The technique of maintaining a proper crystalline ratio in microcrystalline silicon (μc-Si:H) layers along the thickness direction by decreasing the H₂ dilution ratio during deposition (H₂ profiling) was introduced by several laboratories while optimizing either n-i-p or p-i-n μc-Si:H cells made by PECVD. With this technique a great increase in the energy conversion efficiency was obtained. Compared to the PECVD technique, the unique characteristics of HWCVD, such as the catalytic reactions, the absence of ion bombardment, the substrate heating by the filaments and filament aging effects, necessitate a different strategy for device optimization. We report in this paper the result of our method of using a reverse H₂ profiling technique, i.e. increasing the H₂ dilution ratio instead of decreasing it, to improve the performance of μc-Si:H n-i-p cells with an i-layer made by HWCVD. The principle behind this technique is thought to be a compensation effect for the influence of progressing silicidation of the filaments during the growth of μc-Si:H, if the filament current is held constant during growth. The dependence of the material crystallinity on thickness with and without H₂ profiling is discussed and solar cell J-V parameters are presented. Thus far, the best efficiency of μc-Si:H n-i-p cells made on a stainless steel substrate with an Ag/ZnO textured back reflector made in house has been improved to 8.5%, which is the highest known efficiency obtained for n-i-p cells with a hot-wire μc-Si:H i-layer.     

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 characterization of group-III impurity-doped semiconducting BaSi2 films grown by molecular beam epitaxy

Ga- or In-doped BaSi₂ films were grown on Si(111) by molecular beam epitaxy (MBE). The Ga-doped BaSi₂ showed n-type conductivity. The electron concentration and resistivity of the Ga-doped BaSi₂ depended on the Ga temperature; however, the electron concentration and resistivity could not be controlled properly. In contrast, the In-doped BaSi₂ showed p-type conductivity and its hole concentration was controlled in the range between 10¹⁶ and 10¹⁷ cm^− 3 at RT.     

Oxide and interface charges in thin SiO2 films thermally grown on RF plasma hydrogenated silicon

A study of the defect centres, related to oxide charge and interface traps, induced in thin SiO₂ layer by technological procedures has been made. Thermal oxidation of Si was performed in dry O₂ at a temperature of 850°C. The Si cleaning procedures included dry hydrogen plasma treatment at different substrate temperatures and standard RCA wet cleaning. Characterization of defects was performed by analyzing the frequency dispersion of the capacitance-voltage characteristics. The origin of the defects was assessed by analysis of the IR spectra through computer simulation of the oxide structure and AFM images.     

Epitaxial and polycrystalline CuInS2 thin films: A comparison of opto-electronic properties

Epitaxial and polycrystalline thin CuInS₂ (CIS) layers were grown by means of molecular beam epitaxy (MBE) on single crystalline silicon substrates of 4 inch diameter. Photoluminescence (PL) studies were performed to investigate the opto-electronic properties of these layers. For the epitaxial CIS, low-energy-hydrogen implantation leads to the passivation of deep defects and several donor-acceptor (DA) pair recombinations (from 1.034 eV to 1.439 eV) and two free-to-bound (FB) transitions (at 1.436 eV and 1.485 eV) become observable at low temperatures (5 to 100 K). Excitonic luminescence is completely absent for all investigated epitaxial CIS layers. This contrasts sharply with the PL of the polycrystalline films which is dominated by excitonic luminescence (1.527 eV). Also a donor-to-valence band transition at 1.465 eV (BF-1) and one donor-acceptor recombination at 1.435 eV (DA-1) were observed, while luminescence from deep levels is not present at all. Based on these data, a refined defect model for CuInS₂ with two donor and two acceptor states is presented. Under comparable growth conditions, the electronic quality of polycrystalline CIS is superior to epitaxially grown material.     

Chemical vapor deposition of NiSi using Ni(PF3)4 and Si3H8

NiSi_x films were deposited using chemical vapor deposition (CVD) with a Ni(PF₃)₄ and Si₃H₈/H₂ gas system. The step coverage quality of deposited NiSi_x was investigated using a horizontal type of hot-wall low pressure CVD reactor, which maintained a constant temperature throughout the deposition area. The step coverage quality improved as a function of the position of the gas flow direction, where PF₃ gas from decomposition of Ni(PF₃)₄ increased. By injecting PF₃ gas into the Ni(PF₃)₄ and Si₃H₈/H₂ gas system, the step coverage quality markedly improved. This improvement in step coverage quality naturally occurred when PF₃ gas was present, indicating a strong relationship. The Si/Ni deposit ratio at 250 °C is larger than at 180 °C. It caused a decreasing relative deposition rate of Ni to Si. PF₃ molecules appear to be adsorbed on the surface of the deposited film and interfere with faster deposition of active Ni deposition species.     

Interaction of reducing gases with tin oxide films prepared by reactive evaporation techniques

SnO_2−x films were prepared by reactive thermal and e-beam evaporation of Sn on alumina substrates and by post deposition thermal treatment. X-ray diffraction measurements found that films are tin dioxide (SnO₂) phase with small amounts of SnO phase. The surface conductivity of films was measured in air and in presence of H₂S, H₂ and C₂H₅OH vapors at four sensor operating temperatures of 433-493 K. The resistance of SnO_2−x films decreases on exposure to H₂S but shows no change with hydrogen and ethanol. H₂S response decreases with rise in sensor temperature while both response and recovery times improve. H₂S signal enhances with increase in resistivity of SnO_2−x coatings. Our experiments conclude that increase in film conductance is due to chemical reaction between H₂S and SnO_2−x surface and there is little or no role of interaction of gas molecules with surface adsorbed charged oxygen species.     

Optical and structural properties of CuSbS2 thin films grown by thermal evaporation method

Structural, optical and electrical properties of CuSbS₂ thin films grown by thermal evaporation have been studied relating the effects of substrate heating conditions of these properties. The CuSbS₂ thin films were carried out at substrate temperatures in the temperature range 100-200 °C. The structure and composition were characterized by XRD, SEM and EDX. X-ray diffraction revealed that the films are (111) oriented upon substrate temperature 170 °C and amorphous for the substrate temperatures below 170 °C. No secondary phases are observed for all the films. The optical absorption coefficients and band gaps of the films were estimated by optical transmission and reflection measurements at room temperature. Strong absorption coefficients in the range 10⁵-10⁶ cm^− 1 at 500 nm were found. The direct gaps Eg lie between 0.91-1.89 eV range. It is observed that there is a decrease in optical band gap Eg with increasing the substrate temperature. Resistivity of 0.03-0.96 Ω cm, in dependence on substrate temperature was characterized. The all unheated films exhibit p-type conductivity. The characteristics reported here also offer perspective for CuSbS₂ as an absorber material in solar cells applications.     

Growth and dielectric properties of solvothermal BaTiO3 polycrystalline thin films

Polycrystalline BaTiO₃ thin films were grown solvothermally on Ti-covered substrates in ethanol, distilled water and 1,4-butanediol at 80 °C, 150 °C and 200 °C. Films grown in organic media are finer grained and required more stringent crystallization conditions due to lower solubility of constituent ions. Solvothermal films exhibit less severe proton incorporation. Solvothermal films grown close to the boundary crystallization conditions tend to have higher frequency dispersion and loss tangents. Dielectric properties of BaTiO₃ films grown in ethanol are comparable to that of hydrothermal films. Butanediol-derived films have lower dielectric constants than the aqueous equivalent.     

Fabrication of highly conductive Ta-doped SnO2 polycrystalline films on glass using seed-layer technique by pulse laser deposition

We discuss the fabrication of highly conductive Ta-doped SnO₂ (Sn_1 − xTa_xO₂; TTO) thin films on glass by pulse laser deposition. On the basis of the comparison of X-ray diffraction patterns and resistivity (ρ) values between epitaxial films and polycrystalline films deposited on bare glass, we proposed the use of seed-layers for improving the conductivity of the TTO polycrystalline films. We investigated the use of rutile TiO₂ and NbO₂ as seed-layers; these are isostructural materials of SnO_2, which are expected to promote epitaxial-like growth of the TTO films. The films prepared on the 10-nm-thick seed-layers exhibited preferential growth of the TTO (110) plane. The TTO film with x = 0.05 on rutile TiO₂ exhibited ρ  = 3.5 × 10^− 4 Ω cm, which is similar to those of the epitaxial films grown on Al₂O₃ (0001).