Spatial distribution of high-density microwave plasma for fast deposition of microcrystalline silicon film

The high-density microwave plasma utilizing a spokewise antenna was successfully applied to fast deposition of highly crystallized and photoconductive microcrystalline silicon (μc-Si:H) film at low temperatures. Among various deposition parameters, spatial distribution of ion energy (IDF) mainly determines film crystallinity. The best crystallinity was obtained at the axial distance, Z from the quartz glass plate, where the spread of mean ion energy is minimum. By optimizing the axial distance, Z and total pressure, highly crystallized and photoconductive μc-Si:H film could be fabricated with a high deposition rate of 47 Å/s at 50 mTorr in SiH₄ and Ar plasma.     

Deposition of microcrystalline silicon by electron beam excited plasma

Hydrogenated microcrystalline silicon (μc-Si:H) films were deposited by electron beam excited plasma (EBEP) CVD. As the SiH₄ flow rate increases, deposition rate steeply increases, however, crystalline fraction and grain size decrease. A high deposition rate of 69 nm/min is achieved using SiH₄ without H₂ dilution. It is shown that H atom plays key roll for μc-Si:H formation. Results show that deposition mechanism of μc-Si:H by EBEP is mainly controlled by the reaction in the plasma rather than the reaction on the film surface.     

Microcrystalline-silicon thin films prepared by chemical transport deposition

We have investigated on the production of microcrystalline-silicon (μc-Si) films from solid Si sources by the chemical transport deposition, and could obtain photo-sensitive μc-Si films. The crystallinity and photo-sensitivity of μc-Si films are improved by increasing hydrogen pressure and the highest photo-sensitivity of 50 times is obtained at 200 Pa. The high density of atomic hydrogen probably causes the defect passivation in the high-pressure conditions. The distance between the Si target and the substrate is also important to improve the film properties, and a shorter distance is effective for higher deposition rate, crystallinity and photo-sensitivity.     

Solar cell of 6.3% efficiency employing high deposition rate (8 nm/s) microcrystalline silicon photovoltaic layer

Microcrystalline silicon (μc-Si) films deposited at high growth rates up to 8.1 nm/s prepared by very-high-frequency-plasma-enhanced chemical vapor deposition (VHF-PECVD) at 18–24 Torr have been investigated. The relation between the deposition rates and input power revealed the depletion of silane. Under high-pressure deposition (HPD) conditions, the structural properties were improved. Furthermore, applying μc-Si to n–i–p solar cells, short-circuit current density (J_SC) was increased in accordance with the improvement of microstructure of i-layer. As a result, a conversion efficiency of 6.30% has been achieved employing the i-layer deposited at 8.1 nm/s under the HPD conditions.     

Promotion of microcrystallization by argon in moderately hydrogen diluted silane plasma

Using argon as a diluent of SiH₄, undoped hydrogenated microcrystalline silicon (μc-Si:H) films, having σ_D10⁻⁵ S cm⁻¹, were prepared at a very high deposition rate of 36 Å/min. Micrograins were identified with several well-defined crystallographic orientations. The effect of variation of Ar-dilution on the electrical and structural properties of Si:H films were studied systematically. Addition of H₂ to the Ar-diluted SiH₄ plasma improved the network structure by eliminating defects, introducing structural reorientation and grain growth, although, reducing the deposition rate. Accordingly, highly conducting (σ_D10⁻³S cm⁻¹) undoped μc-Si:H film was achieved utilizing energy released by de-excitation of metastable state of Ar (denoted as Ar*), in association with network modulation by atomic hydrogen in the plasma.     

Fast deposition of microcrystalline silicon films with preferred (2 2 0) crystallographic texture using the high-density microwave plasma

A novel high-density and low-temperature microwave discharge utilizing a spoke antenna has been applied for the fast deposition of microcrystalline silicon (μc-Si:H) films with preferred (2 2 0) orientation. Systematic deposition studies were performed from pure and H₂-diluted SiH₄ systems with microwave power, total pressure, H₂ dilution ratio and substrate temperature as variables, combined with plasma diagnostics using optical emission spectroscopy and Langmuir probe techniques. The effects of deposition parameters on the film crystallinity, crystal orientation and defect density are demonstrated.     

Silicon lifetime enhancement by SiNx:H anti-reflective coating deposed by PECVD using SiH4 and N2 reactive gas

Hydrogenated films of silicon nitride SiN_x:H are largely used as antireflective coating as well as passivation layer for industrial crystalline and multicrystalline silicon solar cells. In this work, we present a low cost plasma enhanced chemical vapor deposition (PECVD) of this thin layer by using SiH₄ and N₂ as a reactive gases. A study was carried out on the variation effect of the ratio silane (SiH₄) to nitrogen (N₂) and time deposition on chemical composition, morphologies, reflectivity and carrier lifetime. The thickness was varied, in order to obtain a homogeneous antireflective layer. The Fourier transmission infrared spectroscopy (FTIR) shows the existence of Si–N and Si–H bonds. The morphologies of the sample were studied by Atomic Force Microscopy (AFM). The resulting surface of the SiN_x:H shows low-reflectivity less than 5% in wavelength range 400–1200 nm. As a result, an improvement in minority carrier lifetime has been achieved to about 15 μs.     

Growth mechanism of thin films of yttria-stabilized zirconia by chemical vapor infiltration using NiO–ceria substrate as oxygen source

The deposition of yttria-stabilized zirconia films on a NiO–ceria substrate by chemical vapor infiltration (CVI) using ZrCl₄ and YCl₃ as metal sources and NiO–ceria as oxygen source was studied. The resultant films were cubic YSZ with a Y₂O₃ content of 3.7–4.2 mol%, and were transparent and strong. A NiO content of NiO–ceria above 60 mol% increases the growth rate of the YSZ film from about 5 to 25 μm over 2 h, indicating that chemical vapor deposition (CVD) occurred in addition to electrochemical vapor deposition (EVD), whereas NiO contents below 60 mol% does not affect the growth rate, indicating that only electrochemical vapor deposition occurred. The growth mechanism of the YSZ film is determined and a YSZ thin film is successfully fabricated on NiO–ceria to improve mechanical strength.     

Material properties of microcrystalline silicon for solar cell application

The paper reviews the material requirements of microcrystalline silicon (μc-Si) in terms of the device operation and configuration for thin film solar cells and thin film transistors (TFTs). We investigated the material properties of μc-Si films deposited by using 13.56 MHz plasma-enhanced chemical vapor deposition (PECVD) from a conventional H₂ dilution in SiH₄. Two types of intrinsic μc-Si films deposited at the high pressure narrow electrode gap and the low pressure wide electrode gap were studied for the solar cell absorption layers. The material properties were characterized using dark conductivity, Raman spectroscopy, and transmission electron microscope (TEM) measurements. The μc-Si quality and solar cell performance were mainly determined by microstructure characteristics. Solar cells adopting the optimized μc-Si film demonstrated high stability with no significant changes in solar cell performance after air exposure for six months and subsequent illumination for over 300 h. The results can be explained that low ion bombardment and high atomic hydrogen density under the PECVD condition of the high pressure narrow electrode gap produce high-quality μc-Si films for solar cell application.     

Control of the properties of wide bandgap a-SiC : H films prepared by RF PECVD method by varying methane flow rate

The influence of increase in flow rate of CH₄ in a source gas mixture of SiH₄+CH₄+H₂ for the preparation of high-quality wide band gap a-SiC : H film by the RF PECVD method has been studied. We have been able to increase the optical gap of the film by increasing CH₄ flow rate under appropriate deposition conditions. These films are structurally better which also shows good opto-electronic properties. This has been achieved mainly by using CH_n (where n=3, 2 or 1) precursors in the plasma as the etchant for weak bonds on the growing surface of a-SiC : H films.     

Microcrystallisation in Si:H: the effect of gas pressure in Ar-diluted SiH4 plasma

Using noble gas argon as a diluent of SiH₄ in RF glow discharge, undoped μc-Si:H thin films have been developed at a low power density of 30 mW/cm². It has been found that the gas pressure is a critical factor for the growth of μc-Si:H films. Undoped μc-Si:H films having σ_D10⁻⁶ S/cm and ΔE<0.57 eV have been obtained at and above a critical pressure of 0.8 Torr. When the RF power density is increased to 90 mW/cm², a more crystalline as well as highly conducting (σ_D10⁻⁴ S/cm) μc-Si:H film has been achieved at a deposition rate of 30 Å/min, which is much higher than that attained from H₂-diluted SiH₄ plasma, by conventional approach. The crystallinity of the films has been identified by the sharp Raman peak at 520 cm⁻¹ and a large number of micrograins in the TEM micrographs. The metastable state of Ar, denoted as Ar^*, plays the crucial role in inducing microcrystallisation by transferring its de-excitation energy at the surface of the growing film. A mechanism has been proposed to explain the dependence of the formation of μc-Si:H film on the working gas pressure in the plasma.     

Structural studies on the microcrystallization of Si:H network developed by hot-wire CVD

Effect of H₂-dilution to the SiH₄ plasma, R(H₂), on the microcrystallization of Si:H network at a low substrate temperature (180 °C) has been studied by using hot-wire CVD. Structural characterization of the films has been performed by micro-Raman, ellipsometry, infrared absorption and X-ray diffraction studies. A dramatic structural transformation from amorphous to microcrystalline phase has been identified at an H₂-dilution beyond 92.0%, induced by high atomic H density in the plasma. A virtual saturation in overall crystallinity has been attained for H₂-dilution in the range 92.75⩽R(H₂) (%)⩽93.75, contributing crystalline volume fraction changing between 60% and 64%, the average crystalline grain size varying between 150 and 200 Å and bonded hydrogen content maintaining between 3.3 and 2.6 at%. A crystalline volume fraction of 86.6% was obtained along with a low bonded H-content of 1.76 at% at R(H₂)=98.0%. However, at such extremely high H₂-dilution, overall crystallization is hindered due to enormous polyhydrogenation and formation of lesser dense network full of voids. Hence, microcrystallization in Si-network can be easily obtained in HWCVD, at a relatively low hydrogen dilution and low substrate temperature, without compromising much with the deposition rate arising out of those two stringent factors affecting in the conventional technique; and thereby, enhancing the technological acceptability of the deposition process presently dealt with.     

Deposition of ZrO2 film by liquid phase deposition

In this study, undoped ZrO₂ thin films were deposited on single-crystal silicon substrates using liquid phase deposition. The undoped films were formed by hydrolysis of zirconium sulfate (Zr(SO₄)₂·4H₂O) in the presence of H₂O. A continuous oxide film was obtained by controlling adequate (NH₄)₂S₂O₈ concentration. The deposited films were characterized by SEM, FT-IR, XRD and DTA. Typically, the films showed excellent adhesion to the substrate with uniform particle diameter about 150 nm. The thicknesses of ZrO₂ film were about 200 nm after 10 h deposition at 30 °C. These films shows single tetragonal phase after heat treated at 600 °C. High annealing temperature (e.g. 750 °C) may result in the phase transformation of (t)-ZrO₂ into (m)-ZrO₂.     

Large grain Cu(In,Ga)Se2 thin film growth using a Se-radical beam source

Cu(In,Ga)Se₂ (CIGS) thin films were grown by the three-stage process using a rf-plasma cracked Se-radical beam source. CuGaSe₂ (CGS) films grown at a maximum substrate temperature of 550 °C and CuInSe₂ (CIS) and CIGS films grown at the lower temperature of 400 °C exhibited highly dense surfaces and large grain size compared with films grown using a conventional Se-evaporative source. This result is attributed to the modification of the growth kinetics due to the presence of active Se-radical species and enhanced surface migration during growth. The effect on CIGS film properties and solar cell performance has been investigated. Enhancements in the cell efficiencies of 400 °C-grown CIS and CIGS solar cells have been demonstrated using a Se-radical source.     

Thin film silicon solar cells by AIC on foreign substrates

This paper presents the fabrication of thin film crystalline silicon solar cells on foreign substrates like alumina, glass–ceramic (GC) and metallic foils (ferritic steel—FS) using seed layer approach, which employs aluminium induced crystallisation (AIC) of amorphous silicon. Effect of hydrogen content in a-Si:H precursor films on the AIC process has been studied and the results showed that defects in the AIC grown films increased with increase of hydrogen content. At the optimal thermal annealing conditions, the AIC grown poly-Si films showed an average grain size of 7.6, 26, and 8.1 μm for the films synthesised on alumina, GC, and FS, respectively. The grains were (1 0 0) oriented with a sharp Raman peak around 520 cm^?1. Similarly, n-type seed layers were also fabricated by over-doping of as-grown AIC layers using a highly phosphorus doped glass solution. The resistivity of as-grown films reduced from 8.4×10^?2 Ω cm (p-type) to 4.1×10^?4 Ω cm (n-type) after phosphorus diffusion. These seed layers of n-type/p-type were thickened to form an absorber layer by vapour phase epitaxy or solid phase epitaxy. The passivation step was applied before the heterojunction formation, while it was after in the case of homojunction. Open circuit voltage of the junctions showed a strong dependence on the hydrogenation temperature and microwave (μW) power of electron cyclotron resonance (ECR) plasma of hydrogen. Effective passivation was achieved at a μW power of 650 W and hydrogenation temperature of 400 °C. Higher values of solar conversion efficiencies of 5% and 2.9% were achieved for the n-type and p-type heterojunction cells, respectively fabricated on alumina substrates. The analysis of the results and limiting factors are discussed in detail.     

A thin film silicon anode for Li-ion batteries having a very large specific capacity and long cycle life

A thin film of Si was vacuum-deposited onto a 30 μm thick Ni foil from a source of n-type of Si, the film thickness examined being 200–1500 Å. Li insertion/extraction evaluation was performed mainly with cyclic voltammetry (CV) and constant current charge/discharge cycling in propylene carbonate (PC) containing 1 M LiClO₄ at ambient temperature. The cycleability and the Li accommodation capacity were found to depend on the film thickness. Thinner films gave larger accommodation capacity. A 500 Å thick Si film gave a charge capacity over 3500 mAh g⁻¹ being maintained during 200 cycles under 2 C charge/discharge rate, while a 1500 Å film revealed around 2200 mAh g⁻¹ during 200 cycles under 1 C rate. The initial charge loss could not be ignored but it could be reduced by controlling the deposition conditions.     

Physical properties of the CNT:TiO2 thin films prepared by sol–gel dip coating

Uniform and highly adherent thin films of CNT:TiO₂ were synthesized by sol–gel dip coating method. Both TiO₂ and CNT:TiO₂ films showed very identical structural characteristics and no significant changes in the lattice values were observed. The crystalline size decreased from 20 nm for TiO₂ film to 17 nm for the 4%CNT:TiO₂ film. The film surface was very smooth and compact, as indicated by the roughness data obtained from AFM measurements; the root mean square (rms) average of the roughness was as low as 3 nm. The HRTEM showed that the CNTs are embedded in the matrix of TiO₂ indicating the formation of a composite. In Raman spectra the characteristic vibrations of the TiO₂ are identified, the increase in the FWHM of main anatase peak (144 cm^?1) in the case of the 4%CNT:TiO₂ film is interpreted as due to the incorporation of CNTs in the film. At the wavelength of 600 nm the refractive index of pure TiO₂ was 2.07 and the 4%CNT:TiO₂ showed a value of 2.29. The photoresponse curves showed typical features of charge trapping centers in the band gap of the films.     

Silicon-organic pigment material hybrids for photovoltaic application

Hybrid materials of silicon and organic dyes have been investigated for possible application as photovoltaic material in thin film solar cells. High conversion efficiency is expected from the combination of the advantages of organic dyes for light absorption and those of silicon for charge carrier separation and transport. Low temperature remote hot wire chemical vapor deposition (HWCVD) was developed for microcrystalline silicon (μc-Si) deposition using SiH₄/H₂ mixtures. As model dyes zinc phthalocyanines have been evaporated from Knudsen type sources. Layers of dye on μc-Si and μc-Si on dye films, and composites of simultaneously and sequentially deposited Si and dye have been prepared and characterized. Raman, absorption, and photoemission spectroscopy prove the stability of the organic molecules against the rough HWCVD-Si process. Transient microwave conductivity (TRMC) indicates good electronic quality of the μc-Si matrix. Energy transfer from dye to Si is indicated indirectly by luminescence and directly by photoconductivity measurements. F_xZnPc pigments with x=0,4,8,16 have been synthesized, purified and adsorbed onto H-terminated Si(1 1 1) for electronic state line up determination by photoelectron spectroscopy. For x=4 and 8 the dye frontier orbitals line up symmetrically versus the Si energy gap offering similar energetic driving forces for electron and hole injection, which is considered optimum for bulk sensitization and indicates a direction to improve the optoelectronic coupling of the organic dyes to silicon.     

Polycrystalline silicon film deposited by ICP-CVD

We studied the deposition of polycrystalline silicon (poly-Si) using SiH₄/SiH₂Cl₂/H₂ mixtures by inductively coupled plasma chemical vapor deposition. The deposition rate and crystalline quality were improved by increasing RF power. The poly-Si film deposited with the [SiH₂Cl₂]/[SiH₄] ratio of 2 and the RF power of 1500 W exhibited the deposition rate of 4.2 Å/s, the polycrystalline volume fraction of 88%, the Raman FWHM of 7 cm⁻¹, and the TEM grain size of 1200 Å. The solar cell made of this material exhibited a conversion efficiency of 3.14%.     

Total SiH4/H2 pressure effect on microcrystalline silicon thin films growth and structure

The effect of the total SiH₄/H₂ gas pressure (1–10 Torr) on the growth rate, the film crystallinity and the nature of hydrogen bonding of microcrystalline silicon thin films deposited by 13.56 MHz plasma-enhanced chemical vapour deposition (PECVD) was investigated under well-controlled discharge conditions. The deposition rate presents an optimum for 2.5 Torr, which does not follow the trend of silane consumption that increases with pressure and is attributed to an increase in plasma density. The film crystallinity increases with pressure from 1–2.5 Torr and then remains almost the same, whereas the films deposited at 1 Torr are highly stressed. On the other hand, hydrogen bonding is also drastically affected.