Dynamics of low temperature PECVD growth of microcrystalline silicon thin films: Impact of substrate surface treatments

Microcrystalline silicon (μc-Si) films have been deposited on polyimide, Corning glass and c-Si(0 0 1) by rf plasma-enhanced chemical vapour deposition (PECVD) using both SiF₄–H₂ and SiH₄–H₂ plasmas. The effect of substrate pre-treatment using SiF₄–He and H₂ plasmas on the nucleation of crystallites is investigated. Real-time laser reflectance interferometry monitoring (LRI) revealed the existence of a ‘crystalline seeding time’ that strongly impacts on the crystallite nucleation, on the structural quality of the substrate/μc-Si interface and on film microstructure. It is found that SiF₄–He pre-treatment of substrates is effective in suppressing porous and amorphous interface layer at the early nucleation stage of crystallites, resulting in direct deposition of μc-Si films also on polyimide at the temperature of 120 °C.     

Substrate holder biasing for improvement of microcrystalline silicon deposition process

Application of a dual frequency plasma source for the deposition of microcrystalline silicon thin films from highly diluted SiH₄/H₂ was investigated in this paper. A positively or negatively biased low frequency voltage was applied on the substrate holder while the conventional frequency of 13.56 MHz was used for the powered electrode. The results show a significant increase of the deposition rate and an improvement of the film crystallinity in the case of the positive biasing. Plasma diagnostics and modeling were used to understand the beneficial effect of positive biasing on the deposition process. The results revealed that the observed changes are not only due to the variation of ion flux and ion bombardment but also depend on the changes in the production and distribution of neutral species in the discharge space.     

PECVD growth of crystalline silicon from its tetrafluoride

The process of plasma chemical deposition of silicon from inductively coupled plasma of the mixture of high‐purity SiF₄ and H₂ sustained by RF discharge at 13.56 MHz in amount sufficient for subsequent growth of crystal by Czochralski method was investigated. The structure and impurity content of the produced layers as well as of the grown crystal have been studied (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of microcrystalline silicon solar cells on microcrystalline silicon carbide window layers grown with HWCVD at low temperature

N-type microcrystalline silicon carbide layers prepared by hot-wire chemical vapor deposition were used as window layers for microcrystalline silicon n–i–p solar cells. The microcrystalline silicon intrinsic and p-layers of the solar cells were prepared with plasma-enhanced chemical vapor deposition at a very high frequency. Amorphous silicon incubation layers were observed at the initial stages of the growth of the microcrystalline silicon intrinsic layer under conditions close to the transition from microcrystalline to amorphous silicon growth. ‘Seed layers’ were developed to improve the nucleation and growth of microcrystalline silicon on the microcrystalline silicon carbide layers. Raman scattering measurement demonstrates that an incorporation of a ‘seed layer’ can drastically increase the crystalline volume fraction of the total absorber layer. Accordingly, the solar cell performance is improved. The correlation between the cell performance and the structural property of the absorber layer is discussed. By optimizing the deposition process, a high short-circuit current density of 26.7 mA/cm² was achieved with an absorber layer thickness of 1 μm, which led to a cell efficiency of 9.2%.     

Transport properties of microcrystalline silicon,prepared at high growth rate

Amorphous/microcrystalline transition was studied in the high growth-rate depositions of hydrogenated silicon films at a high pressure (700 Pa) in a depletion regime using a series of samples with the ratio of hydrogen to silane flows from 10 to 32. Results show the characteristic features of the amorphous/microcrystalline transition: abrupt change of dark conductivity and crystallinity accompanied by peaks of roughness and diffusion length, observed previously at standard growth rates.     

Characterization of microcrystalline silicon by Hall and photo-Hall measurements

Transport properties of microcrystalline silicon are studied by Hall and photo-Hall measurements. The temperature dependence of the mobility shows that there exist potential barriers for majority carrirs to jump over. Illumination increases the majority carrier mobility while the minority carrier mobility turns out to be very small (<0.1 cm²/Vs) compared with the majority carrier mobility (5–30 cm²/Vs).     

Argon-plasma-induced growth of crystalline grains in microcrystalline silicon: Formation mechanism of grains

A thick (∼300 nm) microcrystalline silicon (μc-Si:H) film with a low crystalline volume fraction (∼24%) and a columnar grain size of about 100 nm was exposed to an argon plasma at a substrate temperature of 220 °C after deposition. It is shown that argon plasma treatment significantly enhances film-crystallinity throughout the μc-Si:H layer: over a factor of 2 in crystalline fraction and by a factor of 3 in columnar grain size after a 90-min argon treatment. Based on these experimental results, it is proposed that crystallization of μc-Si:H is likely mediated by the energy transferred from energetic argon atoms.     

Carrier dynamics in microcrystalline silicon studied by time-resolved terahertz spectroscopy

We present results of optical pump – terahertz probe experiments applied to a set of thin film silicon samples on sapphire substrates. Structure of the films varied from amorphous to fully microcrystalline. Picosecond time scale evolution of electrical transport properties of photoexcited samples is investigated and discussed. Three different mechanisms are found to contribute to the dynamical conductivity at terahertz frequencies.     

Photocarrier diffusion lengths of high-growth-rate microcrystalline silicon

We report on photocarrier transport of high-growth-rate microcrystalline Si (μc-Si) in conjunction with the lateral size, σ_L, of crystallites’ conglomerate (grain) determined from the atomic force microscope (AFM) topographic images on the basis of fractal concepts. μc-Si films were prepared using very-high-frequency plasma-enhanced chemical vapor deposition at a high deposition rate of 6.8 ± 0.5 nm/s. μc-Si thicknesses, d, were varied from 0.53 μm to 5.6 μm. With an increase in d, σ_L increased from 70 nm to 590 nm. At the same time, the ambipolar diffusion lengths, L_amb, of photocarriers, observed using the steady-state photocarrier grating (SSPG) technique, increased from 50 nm to 420 nm. Log–log plots of L_amb versus d and σ_L versus d were both expressed as a power law with an exponent of 0.9, yielding a simple linear relation between L_amb and σ_L. Moreover, their ratio, L_amb/σ_L, was below unity, implying the intra-grain carrier diffusion. From these results, the role of the grain (column) boundaries for photocarrier diffusion in μc-Si is discussed.     

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.     

Amorphous and nanocrystalline silicon made by varying deposition pressure in PECVD process

Silicon thin films are deposited using plasma enhanced chemical vapor deposition (PECVD) of silane, argon, hydrogen mixture at various pressures in the range of 2–8 Torr. Raman scattering shows these to be amorphous in the pressure range 6–8 Torr, and nanocrystalline in the range 2–4 Torr. The volume fraction of nanocrystals is estimated by fitting the Raman data to three peaks and is found to be ～75% for the films deposited at low pressure, density of states of these films was measured. It is observed that the electrical conduction in these films depends on the crystalline volume fraction (ρ), estimated from the laser Raman Spectroscopy. Temperature dependence electrical conductivity shows that at lower temperatures thermionic emission dominates for the films with lower ρ, whereas, hopping is the main conduction mechanism for the films having high ρ. The density of states is estimated from the space charge limited currents (SCLC) observed at high fields. Photoconductivity at room temperature is also measured. The amorphous films are found to be more photosensitive than the nanocrystalline one. In the context of these findings, changes in the properties of silicon from amorphous to nanocrystalline are described.     

Scaling properties of growing surfaces of microcrystalline silicon

Growth-induced roughening of microcrystalline Si (μc-Si) surfaces has been studied from the viewpoint of self-similar and fractal structures in conjunction with crystallographic preferential orientations of μc-Si films. Typically, μc-Si films are prepared by plasma enhanced chemical vapor deposition (PECVD) with various preparation conditions including excitation frequency. Irrespective of preparation conditions, self-similarity of the μc-Si surface roughness derived by an atomic force microscope is well characterized in terms of its scaling exponents. Furthermore, the scaling exponents revealed that growth-induced roughness shows different behaviors in accordance with the crystallographic preferential orientations of the μc-Si films. Experimental results of scaling exponents are discussed regarding the origins of surface roughening in comparison to analytical results and numerical simulation results.     

Influence of boron doping on roughness microcrystalline silicon

We have studied roughness of boron-doped microcrystalline Si (μc-Si) surfaces with an emphasis on the influence of heavy doping. μc-Si films were prepared using plasma-enhanced chemical vapor deposition (PECVD) with different boron concentrations in gas phase from 0% to 2%. Growth-induced roughening of μc-Si surfaces was monitored ex situ using an atomic force microscope (AFM). With an increase in the deposition time, the surface width (rms roughness), w, of undoped μc-Si surface exhibited usual behaviors; first, (a) w increased, (b) slightly dropped, (c) rose again, and then (d) gradually increased. In the case of B-doped μc-Si, w differently behaved; (a) w increased very soon, (b) slightly dropped, (a′) rose again, (b′) slightly dropped again, (c) rose, and finally (d) gradually increased. The quick increase in w indicates that boron doping promotes the nucleation, and the repeated nucleation is responsible for the behavior (a′)–(b′). Additionally, the nucleation density, that was derived using the lateral correlation length of surface heights, monotonically increased with an increase in the boron concentration. The effects of boron doping are discussed with the catalytic effects and the formation of the surface-covering layer.     

Metastable dark and photoconductive properties of microcrystalline silicon

Metastable changes in the dark conductivity of microcrystalline silicon upon heat treatment at different temperatures obey the Meyer–Neldel rule. Dark conductivity variations are accompanied by changes in the photoconductivity or the majority-carrier mobility-lifetime product. The minority-carrier mobility-lifetime product is not affected. The observations can be related to Fermi-level induced changes of the excess carrier lifetimes.     

Structure and properties of hydrogenated amorphous silicon carbide thin films deposited by PECVD

a-Si_1?xC_x:H films are deposited by RF plasma enhanced chemical vapor deposition (PECVD) at different RF powers with hydrogen-diluted silane and methane mixture as reactive gases. The structure and properties of the thin films are measured by infrared spectroscope (IR), Raman scattering spectroscope and ultra violet–visible transmission spectroscope (UV–vis), respectively. Results show that the optical band gap of the a-Si_1?xC_x:H thin films increases with increasing Si–C bond fraction. It can be easily controlled through controlling Si–C bond formed by modulating deposition power. At low deposition power, the bond configuration of the a-Si_1?xC_x:H thin film is more disordered owing to the distinct different bond lengths and bond strengths between Si and C atoms. At a too high deposition power, it becomes still high disordered due to dangling bonds appearing in the a-Si_1?xC_x:H thin film. The low disordered bond configuration appears in the thin film deposited with moderate deposition power density of about 2.5 W/cm².     

The application of very high frequency inductively coupled plasma to high-rate growth of microcrystalline silicon films

High-rate growth of microcrystalline silicon films (μc-Si:H) from inductively coupled plasma (ICP) of H₂ diluted SiH₄ generated with a very high frequency (VHF: 60 MHz) power source has been studied from the viewpoint of efficient gas dissociation. From the VHF power and gas pressure dependences of the film growth rate and optical emission intensities, we have found that the Si and SiH emission intensities and the intensity ratio of H_α to SiH are good indicators for the film growth rate and crystallinity, respectively. The generation rate of film precursors is reflected by the Si and SiH emission intensities while the flux ratio of atomic hydrogen to film precursors, which plays an important role on the structural relaxation for the crystalline network formation, is characterized by the intensity ratio of H_α to SiH. An increase in SiH emission while keeping the intensity ratio of H_α to SiH at a certain level enables us to enhance the film growth rate without significant deterioration in the crystallinity. In this study, a growth rate as high as 10 nm/s was obtained for highly crystallized films.