Fabrication of nano-crystalline silicon thin film at low temperature by using a neutral beam deposition method

Low temperature (<80 °C) neutral beam deposition (LTNBD) was investigated as a new approach to the fabrication and development of nano-crystalline silicon (nc-Si), which has better properties than that of amorphous silicon (α-Si). The difference between LTNBD and conventional PECVD is that the film formation energy of the nc-Si in LTNBD is supplied by controlled neutral beam energies at a low temperature rather than by heating. Especially, in this study, the characteristics of the nc-Si thin film were investigated by adding 10% of an inert gas such as Ne, Ar or Xe to SiH₄/H₂. Increasing the beam energy resulted in an increase in the deposition rate, but the crystallinity was decreased, due to the increased damage to the substrate. However, the addition of a higher mass inert gas to the gas mixture at a fixed beam energy resulted not only in a higher deposition rate but also in a higher crystallization volume fraction. The high resolution transmission electron microscopy image showed that the grown film is composed of about 10 nm-size grains.     

A new approach to thin film crystal silicon on glass: Biaxially-textured silicon on foreign template layers

We propose a new approach to growing photovoltaic-quality crystal silicon films on glass. Other approaches to film Si focus on increasing grain size in order to reduce the deleterious effects of grain boundaries. Instead, we propose aligning the silicon grains biaxially (both in and out of plane) so that (1) grain boundaries are ‘low-angle’ and have less effect on the electronic properties of the material and (2) subsequent epitaxial thickening is simplified. They key to our approach is the use of a foreign template layer that can be grown with biaxial texture directly on glass by a technique such as ion-beam-assisted deposition or inclined substrate deposition. After deposition of the template layer, silicon is then grown aligned to the template and subsequently thickened. Here, we outline this new approach to silicon on glass, describe initial experimental results and discuss challenges that must be overcome.     

High-pressure water vapor treatment for poly-crystalline germanium thin films

We have investigated the high-pressure water (H₂O) vapor treatment for poly-crystalline Ge (poly-Ge) thin films, which were prepared by solid phase crystallization. The optical-absorption coefficients of poly-Ge were reduced by the treatment, suggesting that the grain-boundary defects were successfully passivated. But the poly-Ge films were sometimes damaged by the treatment in higher pressure and temperature. Compromised conditions should be pursued between the effective passivation and avoiding the damage. The rapid cooling after the treatment promotes defect passivation but causes structural distortion. The results show that the high-pressure H₂O vapor treatment is an effective method for the defect passivation of poly-Ge films.     

Selective crystallization of amorphous silicon thin film by a CW green laser

A simple and effective method for selective CW laser crystallization of a-Si (CLC) without pre-patterning of a-Si has been reported. By using a metallic shadow mask instead of a photolithographic process, we can reduce the process steps and time compared with a conventional CLC process. It shows very high performance – mobility of 173 cm²/s, I_off of ∼10⁻¹³ A @ V_d = −5 V, I_on/I_off of >10⁸ – as a p-channel poly-Si TFT even without any pre-/post-treatment to improve TFT characteristics such as plasma hydrogenation.     

The effect of dopants on the microstructure of polycrystalline silicon thin film grown by MILC method

The effect of dopants on the crystal growth and the microstructure of poly-crystalline silicon (poly-Si) thin film grown by metal induced lateral crystallization (MILC) method was intensively investigated. PH₃ and B₂H₆ were used as source gases in ion mass doping (IMD) process to make n-type and p-type semiconductor respectively. It was revealed that the microstructure of MILC region varies significantly as the doping type of the samples varied from intrinsic to n-type and p-type, which was investigated by field emission (FE)-SEM. The microstructure of MILC region of the intrinsic was bi-directional needle network structure whose crystal structure has a (1 1 0) preferred orientation. For p-type doped sample, the microstructure of MILC region was revealed to become unidirectional parallel growth structure more and more as MILC growth proceed, which was led by unidirectional division of needlelike grain at the front of MILC region. And for n-type doped sample, the microstructure was random-directional needlelike growth structure. These phenomena can be explained by an original model of Ni ion and Ni vacancy hopping in the NiSi₂ phase and its interface at the front of MILC region.     

Effect of oxygen content on barrier properties of silicon oxide thin film deposited by dual ion-beam sputtering

A silicon oxide thin film barrier was prepared with various oxygen contents and its chemical composition, surface morphology and optical and barrier properties were related to the deposition conditions used. Our study showed that under Ar and O₂ assisted process conditions, a stoichiometric silicon oxide thin film formed at a critical oxygen content during deposition of 40-50%. The thin films deposited at the critical condition showed the lowest surface roughness giving similar or higher optical transmittance than that of the bare polycarbonate (PC) substrate. The boiling and tensile strength test performed on the thin film deposited with assisted ions before the deposition process showed improvement in the adhesion between the oxide layer and the polymer substrate. In addition, interface modification to improve for improving the barrier layer properties of the silicon oxide thin film was achieved through the introduction of dual ion beam sputtering without pre-treatment.     

Effect of ex-situ hydrogen passivation on the structural properties of e-beam evaporated amorphous silicon thin film for solar cell applications

Thin-film photovoltaics greatly reduce the semiconductor material content in the finished product, using 150–200 times less material as compared with conventional Si wafer based cells. Electron beam evaporation (e-beam), a non-ultra-high vacuum technique has the potential for being inexpensive, and simpler process for a-Si deposition. It offers specific advantages such as high Si deposition rate (up to 1 μm/min), excellent Si source material usage, avoidance of toxic gases, and simple sample preparation conditions. In this work, we report the growth of a-Si films using e-beam at a growth rate exceeding 30 Å/s (1–5 Å/s for conventional PECVD process). We report the effect of hydrogen passivation on amorphous silicon network and on silicon-bonded hydrogen configuration under ex-situ hydrogenation in hydrogen plasma. The hydrogen concentration and silicon-hydrogen bonding configuration was evaluated using nuclear reaction analysis (NRA) and Fourier transform infrared spectroscopy (FTIR). Hydrogen plasma treatment shows an increase in the monohydride bond concentration with substrate temperature, and is corroborated by our FTIR investigation, in addition to reducing clustered monohydride bonds or polyhydride bonds in a-Si:H film. Raman analysis indicates reduction in silicon bond angle as well as the bond distance, both leading to significant structural improvement in short-range and medium range order in the amorphous phase. Thus, ex-situ hydrogenation clearly demonstrates the possibility of comparable hydrogen passivation in e‐beam evaporated a-Si films with high growth rate. One can easily extrapolate this result to microcrystalline film growth, assuming the structural improvement of the silicon network preceding the microcrystalline nucleation, where ex-situ passivation is most effective. Thus ex-situ hydrogenation opens up new possibilities in minutely tailoring the a:Si film properties especially for solar cell applications.     

Advances in hot wire chemical vapor deposition technology for the synthesis of novel silicon thin films materials

We report in this paper on fabrication of an advanced hot wire chemical vapor deposition technique. We introduced for the first time ‘box-type’ ceramics filament holder in hot-wire CVD technology. The surface topography and atomic-scale structure of the films synthesized by the new ceramics hot-wire CVD technique have been compared with that of films prepared with that of standard hot-wire CVD.     

Raman scattering in low wavenumber region as a new probe to structural properties of microcrystalline silicon

The structural properties of microcrystalline silicon (μc-Si) are studied by Raman scattering. It is found that the intensity of each Raman band closely correlates with the absorption coefficient in the interband region and that the Raman band at ca. 150 cm^?1 is a sensitive probe to randomness of Si-Si bonding structure in μc-Si.     

Structure and properties of amorphous thin film for optical data storage

In this paper the magnetic and magneto-optical properties of amorphous rare earth-transition metal (RE-TM) alloys as well as the magnetic coupling in the multi-layer thin films for high density optical data storage are presented. Using magnetic effect in scanning tunneling microscopy the clusters structure of amorphous RE-TM thin films has been observed and the perpendicular magnetic anisotropy in amorphous RE-TM thin films has been interpreted. Experimental results of quick phase transformation under short pulse laser irradiation of amorphous semiconductor and metallic alloy thin films for phase change optical recording are reported. A step-by-step phase transformation process through metastable states has been observed. The waveform of crystallization propagation in micro-size spot during laser recording in amorphous semiconductor thin films is characterized and quick recording and erasing mechanism for optical data storage with high performance are discussed. The nonlinear optical effects in amorphous alloy thin films have been studied. By photo-thermal effect or third order optical nonlinearity, the optical self-focusing is observed in amorphous mask thin films. The application of amorphous thin films with super-resolution near field structure for high-density optical data storage is performed.     

Structure of the ESR spectra of thin film silicon after electron bombardment

Defect creation by MeV electron bombardment of a-Si:H and μc-Si:H thin films is used to explore hidden features of the electron spin resonance spectra. Different dynamics of creation and annealing for different paramagnetic states is expected and found. In a-Si:H the g-value of the db resonance does not change after irradiation, but a pair of satellites is observed on its wings. In the spectra of μc-Si:H three additional lines can be extracted after irradiation, overlapping with the central resonance. Careful analysis of the spectra shows also modification of the dangling bond resonance in μc-Si:H that is compatible with variations of two components of the spectra and supports the model of two dominant defect states in μc-Si:H.     

A novel structured plastic substrate for light confinement in thin film silicon solar cells by a geometric optical effect

We present a novel method to achieve light trapping in thin film silicon solar cells. Unlike the commonly used surface textures, such as Asahi U-type TCO, that rely on light scattering phenomena, we employ embossed periodically arranged micro-pyramidal structures with feature sizes much larger than the wavelength of visible light. Angular resolved transmission of light through these substrates indeed showed diffraction patterns, unlike in the case of Asahi U-type substrates, which show angular resolved scattering. Single junction amorphous silicon (a-Si) solar cells made at 125 °C on the embossed structured polycarbonate (PC) substrates showed an increase in current density by 24% compared to a similar solar cell on a flat substrate. The band gap and thickness of the i-layer made by VHF PECVD are 1.9 eV and 270 nm respectively. A double p-layer (nc-Si:H/a-Si:H) was used to make proper contact with ZnO:Al TCO.Numerical modeling, called DokterDEP was performed to fit the dark and light current–voltage parameters and understand the characteristics of the cell. The output parameters from the modeling suggest that the cells have excellent built-in potential (V_bi). However, a rather high recombination voltage, V_μ, affects the FF and short circuit current density (J_sc) for the cells on Asahi as well as for the cells on PC. A rather high parallel resistance ? 1 MΩ cm² (obtained from the modeling) infers that there is no significant shunt leakage, which is often observed for solar cells made at low temperatures on rough substrates. An efficiency of more than 6% for a cell on PC shows enormous potential of this type of light trapping structures.     

Properties of thin film silicon,prepared at high growth rate in a wide range of thicknesses

Preparation of thin film silicon at high growth rate is an important target for its application in solar cells. The properties of hydrogenated microcrystalline silicon, prepared with the help of PECVD multi-hole cathode in a high pressure and depletion regime in a wide range of thicknesses are described in detail. We illustrate the surprising result that we can prepare high growth rate microcrystalline silicon from 0.4 up to 30 μm thickness without great peel-off problems. The room temperature dark DC conductivity, as well as the crystallinity, increased up to 5 μm film thickness and then started to decrease again. These results are explained by the initial temperature profiling and a thickness-induced increase of the lateral inhomogeneity.     

Deposition of amorphous fluorosilane thin film on silicon surface: Atomic simulation

We utilized the Tersoff–Brenner potential form potential to investigate SiF₃ continuously bombarding silicon surface with energies of 10, 50 and 100 eV at normal incidence and room temperature by molecular dynamics method. The saturation of deposition yield of F and Si atoms on the surface is observed. A F-containing amorphous layer is formed whose thickness increases with incident energy. In the ejected gas-phase species, F, SiF and SiF₂ species increases with increasing incident energy, while the amount of SiF₃ species decreases.     

Preparation and properties of microcrystalline silicon films using photochemical vapor deposition

microcrystalline silicon films have been prepared through mercury photosensitized decomposition of monosilane at low gas pressures. The dark and light conductivities of the silicon films tend to increase at reactant pressures lower than 65 Pa and become 10^?2Ω^?1· cm^?1 at 26 Pa. From the Raman scattering and x-ray diffraction, silicon films were found to consist of a mixed phase structure including both microcrystalline and amorphous regions.     

Photocatalytic properties of TiO2/ZnO thin film

ABSTRACT

TiO₂, ZnO and ZnO/TiO₂ thin films have been prepared by radio frequency magnetron sputtering method under different temperatures. Their photo catalytic activities have been investigated. The structural of the thin films were characterized by X-ray diffraction and Raman spectroscopy. The photo catalytic activities of TiO₂ and ZnO/TiO₂ samples were evaluated by the photo decomposition of methylene blue. We note that the structural proprieties of the thin films showed a perfect crystallization along the (002) for ZnO, Rutile (110) for TiO₂ and Anatase (101) for TiO₂. The experimental results show that the bilayer ZnO/TiO₂ were the most efficient photo catalysts compared to the layer of TiO₂. This increased catalytic effect can attributed to the interface between the ZnO layer and the TiO₂ one, which modify significantly the chemical potential of the bilayer.     

Determination factor of <110> direction growth in microcrystalline silicon thin film deposition

We have proposed the mechanism of the <110> directional growth of microcrystalline silicon (μc-Si) thin films deposited by PECVD (plasma enhanced chemical vapor deposition) from SiH₄ and H₂ gas mixture, where dimeric radicals act a key role to form bridge nuclei for the ledge formation on the (110) facet. In order to look further into details of the mechanism, we investigated other important factors that influence the growth of μc-Si in <110> direction in terms of their impact on crystallinity with varying deposition temperature. The enhancement of surface diffusion length of radicals is inferred from the enlargement of the crystalline grain size accompanied with the increase of the deposition temperature. The growth in <110> direction is also promoted as the deposition temperature increases. Therefore, it is suggested that the surface diffusion length of radicals is another key factor that governs the crystalline growth in <110> direction. The growth mechanism of μc-Si thin films in <110> direction is discussed in terms of the relation between the surface diffusion length of monomeric radicals depending on the substrate surface temperature and the average space of bridges depending on the density of dimeric radicals on the growing surface.     

Effect of plasma carrier gas on the moisture barrier properties of plasma-enhanced chemical vapor deposited (PECVD) polyorganosiloxane thin film

Abstract

A polyorganosiloxane thin film was deposited on an optically transparent poly(ethylene 2,6-naphthalate) (PEN) film using plasma-enhanced chemical vapor deposition (PECVD) at room temperature to improve the moisture barrier property of the PEN film. In the PECVD process, hexamethyldisiloxane (HMDSO) was used as the monomer. Argon or oxygen and their mixture gases were used as the plasma carrier gas. Poly(HMDSO) thin film was successfully deposited through plasma-induced radical polymerization reaction on the surface of PEN film. It was observed that the mixture ratio of argon-oxygen carrier gas significantly affected the surface and the moisture barrier properties of the resulting poly(HMDSO) film. Chemical structures of the poly(HMDSO) were confirmed using FT-IR analysis. Surface properties of the poly(HMDSO) thin film were investigated by water contact angle measurement and atomic force microscopy (AFM). Water vapor transmission rate (WVTR) value was obtained by an electrical calcium test (Ca test) at 85?°C and 85% relative humidity condition. It was confirmed that the poly(HMDSO) thin film exhibited excellent water vapor barrier capability. WVTR value of the PEN film coated with poly(HMDSO) deposited with a mixture of argon and oxygen (Ar: O₂ = 2: 8) was 5.09?g/m²-day, which is much lower than 18.4?g/m²-day of a bare PEN film.     

Study of ZnSe and CdSe thin film epitaxy on germanium and silicon substrates

The parameters of vaporization, mass-transfer, condensation, and epitaxial growth by hot wall technique (HWT) of ZnSe and CdSe thin films on monocrystalline Ge and Si substrates are studied (Bubnov et al.). It is shown, that the layers structure is improved as the mass transfer mechanism approaches to gasodinamical vapor flow. The influence of condensation temperature of the layers on their crystallographic structure is shown. The increase of the temperature gradient from the source towards the substrate as well as the substrate temperature conditions for growing layers of hexagonal modification. The decrease of the temperature gradient leads to cubic modification. The electron diffraction study revealed the stepwise character of the zinc selenide and cadmium selenide film growth. The knowledge of the parameters of ZnSe and CdSe thin films on monocrystalline Ge and Si by hot wall technique at relatively low substrate temperatures allows to obtain layers, suitable for formation of solid state devices for registration and reflection of optical information.     

Advances in applications of nanostructured silicon as a new multifunctional material

Abstract

The presented method of surface modification of single-crystal silicon by chemical etching makes it possible to obtain homogeneous nanostructured silicon layers with a thickness from 3 to 60?nm for application in micro- and nano-electronics as new multifunctional material. These results could be applied to the creation of sensitive photodetectors for visible and ultraviolet ranges. The method of scanning tunneling spectroscopy shows, that the changes in the thickness of nanostructured silicon layers affect the type of conductivity, and it opens new prospective for a practical application of nanostructured silicon in nano-electronics. The obtained current-voltage characteristics of nanostructured silicon layers showed different degrees of filling of the valence band, the conduction band and the appearance on the curve of the tunneling conductance of new peaks in the gas environment. The latter gives the possibility to use the method of scanning tunneling spectroscopy for a generation of gas and biosensors. The immune biosensor is proposed in the lab on a chip form based on the nanostructured silicon for the simultaneous analysis of numerous samples. The developed biosensor based on nanostructured silicon is very promising for use in so-called systems of lab-on-chip because it can be used for rapid analysis of various immune responses and is fully compatible with silicon planar technology used in the manufacturing of the semiconductor devices.