A narrow process window for the preparation of polytypes of microcrystalline silicon carbide thin films by hot-wire CVD method

Effects of deposition conditions on the structure of microcrystalline silicon carbide (μc-SiC) films prepared by hot-wire chemical vapor deposition (hot-wire CVD) method have been investigated. It is found from X-ray diffraction patterns of the film that a diffraction peak from crystallites from hexagonal polytypes of SiC is observed in addition to those of 3 C-SiC crystallites. This result is obtained in the film under a narrow deposition conditions of SiH₃CH₃ gas pressure of 8 Pa, the H₂ gas pressure of 80–300 Pa and the total gas pressure of 40–300 Pa under fixed substrate and filament temperatures employed in this study. Furthermore, the grain size of hexagonal crystallites (about 20 nm) on c-Si substrates becomes larger than that of 3 C-SiC crystallites (about 10 nm) for the films deposited under the total gas pressure of 36–88 Pa. The fact that microcrystalline hexagonal SiC can be deposited under limited deposition conditions could be interpreted in the context of a result for c-SiC polytypes prepared by thermal CVD method.     

Toward the fast deposition of highly crystallized microcrystalline silicon films with low defect density for Si thin-film solar cells

In this study, employing a high-density, low-temperature SiH₄–H₂ mixture microwave plasma, we investigate the influence of source gas supply configuration on deposition rate and structural properties of microcrystalline silicon (μc-Si) films, and demonstrate the plasma parameters for fast deposition of highly crystallized μc-Si films with low defect density. A fast deposition rate of 65 Å/s has been achieved for a SiH₄ concentration of 67% diluted in H₂ with a high Raman crystallinity of X_c > 65% and a low defect density of (1–2) × 10¹⁶ cm⁻³ by adjusting source gas supply configuration and plasma conditions. A sufficient supply of deposition precursors, such as SiH₃, as well as atomic hydrogen H on film growing surface is effective for the high-rate synthesis of highly crystallized μc-Si films, for the reduction in defect density, and for the improvement in film homogeneity and compactability. A preliminary result of p–i–n structure μc-Si thin-film solar cells using the resulting μc-Si films as an intrinsic absorption layer is presented.     

Deposition of microcrystalline silicon films at ultrafast rate by using a new microwave induced plasma source

Synthesis of microcrystalline silicon (μc-Si) film at an ultrafast deposition rate over 100 nm/s is achieved from SiH₄ + He by using a high density microwave plasma source even without employing H₂ dilution and substrate heating techniques. Systematic deposition studies show that high SiH₄ flow rate and working pressure increase film deposition rate while high He flow rate decreases the rate. On the other hand, crystallinity of deposited Si film decreases with increasing SiH₄ or He flow rate and working pressure. Enhancements of gas phase and surface reactions during film deposition process are responsible for the achievement of high deposition rate and high film crystallinity.     

Large grain μc-Si:H films deposited at low temperature: Growth process and electronic properties

We have studied structural and electronic properties of μc-Si:H films deposited from SiH₄ + H₂ and SiH₄ + H₂ + Ar gas mixtures. The use of Ar containing gas mixtures for depositions allows us to increase deposition rate by a factor of two and to obtain films with an important fraction of large grains in comparison with SiH₄ + H₂ gas mixtures. Electronic properties of fully crystallized films become more intrinsic with the increase of large grain fraction. Deposition of highly p- and n-doped μc-Si:H layers from the dopant/SiH₄ + H₂ gas mixture at a temperature of 175 °C is possible without any remarkable changes in crystallinity in comparison with undoped films deposited with the same discharge conditions.     

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.     

Effect of thermal annealing and hydrogen-plasma treatment in boron-doped microcrystalline silicon

We have investigated the effects of temperature (during film growth and post-deposition thermal annealing) and H₂-plasma treatment on the electronic and structural properties of p-type microcrystalline silicon films (p-μc-Si:H) for solar cell applications. The highest dark conductivity is obtained in the thermally annealed p-μc-Si:H prepared at low substrate temperature of 50 °C. This dark conductivity is decreased by two orders of magnitude when the film is exposed to H₂-plasma, being completely restored after thermal annealing. Namely, reversible dual-conductivity cycle is observed between thermally annealed state and H₂-plasma-treated state in p-μc-Si:H. The dual-conductivity cycle is accompanied with the reversible change in the infrared-absorption spectrum at around 1845 cm^? 1 assigned as SiHB complex in p-μc-Si:H network structure. Taking into account of the reversible structural change by H₂-plasma-exposure and thermal-annealing cycles, necessary process-procedure condition has been proposed for obtaining high photovoltaic performance in thin-film-Si solar cells with high quality p-μc-Si:H.     

Undoped and arsenic-doped low temperature (∼165 °C) microcrystalline silicon for electronic devices process

Microcrystalline silicon films are deposited at 165 °C by plasma enhanced chemical vapor deposition (PECVD) from silane, highly diluted in hydrogen–argon mixtures. Ar addition during the deposition allows to increase the crystallinity from 24% to 58% for 20 nm thick films. The final crystallinity for 350 nm thick films reaches 72% with an increase in the grain size. A further increase, still 80%, is provided by substrate pre-treatment using hydrogen plasma before the deposition process. Arsenic doped μc-Si films, deposited on previous optimized (5 W power and 1.33 mbar pressure) undoped films without stopping the plasma between the deposition of both layers, show high electrical conductivity up to 20 S cm⁻¹.     

Effect of hot-wire passivation on the properties of hydrogenated microcrystalline silicon films to reduce post-deposition oxidation

Hydrogenated microcrystalline silicon (μc-Si:H) films have a large number of grain boundaries that oxidize after deposition, leading to deterioration of device performance. In this study, post-treatment of μc-Si:H thin films was carried out with methane-related radicals generated by a hot wire. The effect of the hot-wire passivation on the properties of the μc-Si:H thin films was investigated using Fourier-transform infrared (FT-IR) transmission spectroscopy. Through post-treatment, hydrogen on the silicon-crystallite surface was substituted with hydrocarbon. Further, an increase in filament temperature (T_ft) was found to enhance passivation. For films treated at T_ft above 1700 °C, post-oxidation and nitridation hardly occurred, whereas films treated at T_ft below 1400 °C were oxidized and nitrided even after post-treatment.     

Microstructures of high-growth-rate (up to 8.3 nm/s) microcrystalline silicon photovoltaic layers and their influence on the photovoltaic performance of thin-film solar cells

Microstructures of microcrystalline silicon (μc-Si) deposited at a high-growth-rate have been investigated in order to apply to the photovoltaic i-layer. μc-Si films were prepared by very-high-frequency (100 MHz) plasma-enhanced chemical vapor deposition at 180 °C. High growth rates of 3.3–8.3 nm/s have been achieved utilizing high deposition pressures up to 24 Torr and large input powers. Applying μc-Si to n–i–p junction solar cells, as the optimum result in this experimental series, a conversion efficiency of 6.30% (J_SC: 22.1 mA/cm², V_OC: 0.470 V, and FF: 60.7%) has been achieved employing the i-layer deposited at 8.1 nm/s. Raman scattering and X-ray diffraction measurements revealed the crystalline volume fraction of around 50% with the (2 2 0) crystallographic preferential orientation, respectively. The cross-sectional transmission electron microscope image shows densely columnar structure grown directly on the underlying n-layer. These structural features are basically in good agreement those of low-growth-rate μc-Si used for a high efficiency solar cell as previously reported, implying advantages of the use of high pressures with regard to providing the photovoltaic i-layers. Finally, the implication is discussed from the photovoltaic performance as a function of the crystalline volume fraction of i-layer, and current problems in improving the photovoltaic performance are extracted.     

Carbon-K NEXAFS measurements of a-CNx films formed from decomposition of BrCN in electron cyclotron resonance plasmas of He,Ne, and Ar

Amorphous carbon nitride (a-CN_x) films were formed from the decomposition of BrCN in the electron cyclotron resonance plasmas of He, Ne, and Ar. The local structures of these films were investigated by the carbon-K near edge X-ray absorption fine structure. It was found that the density of C=C bond in the film prepared with Ar plasma was 7–9 times larger than that with He or Ne plasmas. The [N]/([C] + [N]) ratios of films were estimated from the X-ray photoelectron spectra as 0.34 ± 0.05, 0.35 ± 0.04, and 0.28 ± 0.05 for the He, Ne, and Ar plasmas, respectively. It was found that C atoms in the sp²-hybridized state were incorporated into the two-dimensional and/or one-dimensional conjugated structures composed of ? C=N? in the cases of the He and Ne plasmas and of ? C=C? in the case of the Ar plasma. The compositions and the local structures of films can be explained in terms of a model based on the cyclazine-like network structures.     

Fractional composition of large crystallite grains: A unique microstructural parameter to explain conduction behavior in single phase undoped microcrystalline silicon

We have studied the dark conductivity of a broad microstructural range of plasma deposited single phase undoped microcrystalline silicon (μc-Si:H) films in a wide temperature range (15–450 K) to identify the possible transport mechanisms and the interrelationship between film microstructure and electrical transport behavior. Different conduction behaviors seen in films with different microstructures are explained in the context of underlying transport mechanisms and microstructural features, for above and below room temperature measurements. Our microstructural studies have shown that different ranges of the percentage volume fraction of the constituent large crystallite grains (F_cl) of the μc-Si:H films correspond to characteristically different and specific microstructures, irrespective of deposition conditions and thicknesses. Our electrical transport studies demonstrate that each type of μc-Si:H material having a different range of F_cl shows different electrical transport behaviors.     

Deposition of phosphorus doped a-Si:H and μc-Si:H using a novel linear RF source

A roll-to-roll PECVD system for thin film silicon solar cells on steel foil has been developed by ECN in collaboration with Roth and Rau AG. It combines MW–PECVD for fast deposition of intrinsic Si and novel linear RF sources, which apply very mild deposition conditions, for the growth of doped Si layers. The RF and MW sources can be easily scaled up to deposition widths of up to 150 cm. Here, we report on n-type doping, achieved by RF–PECVD from a H₂/SiH₄/PH₃ mixture in the reaction chamber. The best n-type a-Si:H layers showed E_act = 0.27 eV and σ_d = 2.7 × 10^?3 S/cm. Also thin layers down to 20 nm were of device quality and were deposited at a rate of 0.4 Å/s. Furthermore, n-type μc-Si:H layers with thicknesses of 150 nm, with E_act = 0.034 eV and σ_d = 2 S/cm were grown. Good quality n-type μc-Si:H layers can be made for layer thicknesses down to 50 nm at a rate of 0.15 Å/s. To conclude, the novel RF source is well-suited for the growth of n-doped a-Si:H and μc-Si:H layers for roll-to-roll solar cell production.     

The comparisons of growth mechanisms for Si thin films with different deposition rates in CVD process by the description of the roughness evolution

The roughness evolutions of micro-crystalline silicon thin films (μc-Si:H) with different growth rates prepared by chemical vapor depositions have been investigated by atomic force microscopy. The growth exponent β was measured as 0.8 ± 0.03, 1.1 ± 0.07 and 0.75 ± 0.02 for three sets of samples prepared by PECVD with and without hydrogen dilution ratio modulation and by HWCVD, respectively, and does not correlated with the deposition rate in a set. However, the root-mean-square roughness and lateral correlation length decrease with increasing the deposition rate for both PECVD and HWCVD process. We suggested that the nonstationary growth with large β is correlated with the shadowing effect. The influence of the deposition rate on the surface roughness could be related to the diminishing of the shadowing effect by surface species diffusion with higher mobility on an H-covered surface. The initial surface and nucleation condition play an important role in the surface roughness evolution.     

Study of anomalous behavior of steady state photoconductivity in highly crystallized undoped microcrystalline Si films

The photoconductivity (σ_ph) of highly crystallized dense undoped hydrogenated microcrystalline silicon (μc-Si:H) films was measured as a function of light illumination over a wide temperature range (∼15–325 K). A thermal quenching behavior in σ_ph was observed at ∼240 K. The photoconductivity exponent (γ) was found to be sublinear with γ as low as 0.13. A density of states (DOS) profile having a steep conduction band tail, and valence band tail with two distinct distributions was found to be necessary to understand the electronic transport behavior in the inherently heterogeneous μc-Si:H films.     

Nanocrystalline silicon TFT process using silane diluted in argon–hydrogen mixtures

We have investigated the effect of Ar dilution on the deposition process of intrinsic nc-Si:H (hydrogenated nanocrystalline silicon) thin films used as active layers of top-gate TFTs, in order to improve the TFTs performances. The nc-Si:H films were deposited by plasma enhanced chemical vapor deposition (PECVD) at low temperature (165 °C) and the related TFTs were fabricated with a maximum process temperature of 200 °C. During the nc-Si:H films deposition, the SiH₄ fraction and the total flow of the diluting gases Ar + H₂ mixture was kept constant, H₂ being substituted by Ar. We have pointed out the active role played by the metastable states of excited Ar atoms in both the dissociation of SiH₄ and H₂ by quenching reactions in the plasma. The role of the atomic hydrogen during the film deposition seems to be promoted by the addition of argon into the discharge, leading to an increase of the deposition rate by a factor of about three and an enhancement of the crystalline quality of the nc-Si:H films. This effect is maximized when the Ar fraction in the Ar + H₂ gases mixture reaches 50%. The evolution with Ar addition of the carriers mobility of the related TFTs is closely connected to the evolution of the crystalline fraction of the intrinsic nc-Si:H film. Mobilities values as high as 8 cm² V^?1 s^?1 are obtained at the Ar fraction of 50%. For higher Ar fractions, the fall of the mobility comes with a degradation of the I_D–V_G transfer characteristics of the processed TFTs due to a degradation of the nc-Si:H films quality. OES measurements show that the evolution of the H_α intensity is closely connected to the evolution of the deposition rate, intrinsic films crystalline fraction and TFTs mobility, providing an interesting tool to monitor the TFTs performances.     

Impurities in thin-film silicon: Influence on material properties and solar cell performance

The influence of oxygen and nitrogen impurities on the material properties of a-Si:H and μc-Si:H films and on the corresponding solar cell performances was studied. For intentional contamination of the i-layer the impurities were inserted by two contamination sources: (i) directly into the plasma through a leak at the chamber wall or (ii) into the gas supply line. The critical oxygen and nitrogen concentrations for silicon solar cells were determined as the lowest concentration of these impurities in the i-layer causing a deterioration of the cell performance. Similar critical concentrations for a-Si:H and μc-Si:H cells in the range of 4–6 × 10¹⁸ cm^? 3 for nitrogen and 1–5 × 10¹⁹ cm^? 3 for oxygen by applying a chamber leak are observed. Similar increase of conductivity with increasing impurity concentration in the a-Si:H and μc-Si:H films is found. A more detailed study shows that the critical oxygen concentration depends on the contamination source and the deposition parameters. For a-Si:H cells, the application of the gas pipe leak leads to an increased critical oxygen concentration to 2 × 10²⁰ cm^? 3. Such an effect was not observed for nitrogen. For μc-Si:H, a new deposition regime with reduced discharge power was found where the application of the gas pipe leak can also result in an increase of the oxygen concentration to 1 × 10²⁰ cm^? 3.     

Role of interfacial crystallites in the crystallization of α-Fe2O3/α-Al2O3(0 0 0 1) thin films

In situ crystallization of α-Fe₂O₃/α-Al₂O₃(0 0 0 1) thin films was studied in real-time synchrotron X-ray scattering experiments. We find the coexistence of α-Fe₂O₃ (hexagonal) and Fe₃O₄ (cubic) interfacial crystallites (∼50-Å-thick), well aligned [0.02° full-width at half-maximum (FWHM)] to the α-Al₂O₃[0 0 0 1] direction, in the sputter-grown amorphous films. As the annealing temperature increases up to 750°C, the cubic stacking of the Fe₃O₄ crystallites gradually changes to the hexagonal α-Fe₂O₃ stacking, together with the growth of the well-aligned (WA) (0.02° FWHM) grains from the α-Fe₂O₃ crystallites. In the meanwhile, heterogeneous nucleation starts to occur on the substrate at ∼600°C, resulting in the formation of misaligned (1.39° FWHM) α-Fe₂O₃ grains. Our study reveals that the interfacial crystallites act as a template for the growth of the WA α-Fe₂O₃ grains.     

A simple quality factor for characterization of thin silicon films

Four series of intrinsic thin Si films were prepared by plasma enhanced chemical vapor deposition at standard and high growth rate conditions. We suggest a simple ‘μc-Si:H layer quality factor’ based on the ratio of subgap optical absorption coefficient values: α(1.4 eV)/α(1 eV). This ratio minimizes the light scattering effects for rough films and can serve as a reliable detection of the amorphous/microcrystalline structure transition and also as a figure of merit for the microcrystalline layer. The quality factor is evaluated for series of our samples with well known structure and also compared with samples from other laboratories with different deposition and measurement techniques.     

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.     

Optical properties of microcrystalline 3C–SiC:H films measured by resonant photothermal bending spectroscopy

Optical absorption coefficient spectra of hydrogenated microcrystalline cubic silicon carbide (μc-3C–SiC:H) films prepared by Hot-Wire CVD method have been estimated for the first time by resonant photothermal bending spectroscopy (resonant-PBS). The optical bandgap energy and its temperature coefficient of μc-3C–SiC:H film is found to be about 2.2 eV and 2.3 × 10⁻⁴ eV K⁻¹, respectively. The absorption coefficient spectra of localized states, which are related to grain boundaries, do not change by exposure of air and thermal annealing. The localized state of μc-3C–SiC:H has different properties for impurity incorporation compared with that of hydrogenated microcrystalline silicon (μc-Si:H) film.