Electron spin resonance study of hydrogenated microcrystalline silicon–germanium alloy thin films

Paramagnetic defects of undoped hydrogenated microcrystalline silicon–germanium alloys (μc-Si_1?xGe_x:H) grown by low temperature (200 °C) plasma-enhanced chemical vapor desposition (PECVD) have been measured by electron spin resonance (ESR) and compared with those of hydrogenated amorphous silicon–germanium (a-Si_1?xGe_x:H). The spin density of μc-Si_1?xGe_x:H increases with Ge content and shows a broad maximum of ～10¹⁷ cm^?3 at x ～ 0.5, which reasonably accounts for the decreased photoconductivity. While the Ge dangling bond defects prevail in a-Si_1?xGe_x:H for Ge-rich compositions, we detected no ESR signal in μc-Si_1?xGe_x:H for x > 0.75 where an electrical change occurs from weak n- to strong p-type conduction. These results indicate that dangling bonds are charged in large densities due to the presence of the acceptor-like states in undoped μc-Si_1?xGe_x:H.     

Metastability effects in hydrogenated microcrystalline silicon thin films investigated by the dual beam photoconductivity method

Metastability effects in microcrystalline silicon (μc-Si:H) thin films have been investigated using dark conductivity, σ_D, photoconductivity, σ_ph, and sub-bandgap absorption methods. Nitrogen and inert gasses can cause reversible aging effect in conductivities but not in the sub-bandgap absorption. However, DI water and O₂ gas treatment result in both reversible and nonreversible effects in conductivities as well as in the sub-bandgap absorption. Only oxygen affected the dark conductivity reversibly in amorphous silicon, a-Si:H, films, other results were unaffected from the aging and annealing processes applied.     

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.     

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.     

Deposition of microcrystalline Ge films using hot-wire technique without toxic gases

To investigate the deposition of Ge films without toxic gas such as germane, we have studied the Ge films prepared by the hot-wire technique, which utilize the reaction between a Ge target and hydrogen atoms generated by the hot-wire decomposition of H₂ gas. The films deposited on Si substrate were microcrystalline Ge films and the mean crystallite size of the films increased from 13.3 to 24.8 nm with increasing the substrate temperature from 300 to 500 °C. Moreover, the deposition rate of Ge films deposited on Si substrate was higher than that of Ge films deposited on Corning 1737 substrate. It was found that the substrate temperature and the kind of substrate are key parameters for the preparation of microcrystalline Ge films by the hot-wire technique.     

Determination of Raman emission cross-section ratio in hydrogenated microcrystalline silicon

The determination of the crystalline volume fraction from the Raman spectra of microcrystalline silicon involves the knowledge of a material parameter called the Raman emission cross-section ratio y. This value is still debated in the literature. In the present work, the determination of y has been carried out on the basis of quantitative analysis of medium-resolution transmission electron microscopy (TEM) micrographs performed on one layer deposited by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) close to the amorphous/microcrystalline transition. Subsequent comparison of these data with the crystallinity as evaluated from measured Raman spectra yields a surprisingly high value of y = 1.7. This result is discussed in relation to previously published values (that range from 0.1 to 0.9).     

Optical properties of hydrogenated amorphous silicon films doped with fluorinated gases

Doped amorphous silicon films were prepared by plasma-enhanced chemical vapour deposition of silane and hydrogen mixtures, using phosphorus pentafluoride (PF₅) and boron trifluoride (BF₃) as dopant precursors. The films were studied by UV-vis spectroscopy and their photo and dark conductivity were measured, the latter as a function of temperature. The optical gap of the n-type samples, doped with PF₅, diminished as the concentration of this gas in the plasma was increased. However, the optical gap of p-type samples, doped with BF₃, did not show any appreciable optical gap decrease as the concentration of BF₃ was varied from 0.04% to 4.7%. The dark conductivity of the p-type films at these extremes of the doping range were 7.6 × 10⁻¹⁰ and 3.5 × 10⁻¹ Ω⁻¹ cm⁻¹, respectively.     

On the oxidation mechanism of microcrystalline silicon thin films studied by Fourier transform infrared spectroscopy

Insight into the oxidation mechanism of microcrystalline silicon thin films has been obtained by means of Fourier transform infrared spectroscopy. The films were deposited by using the expanding thermal plasma and their oxidation upon air exposure was followed in time. Transmission spectra were recorded directly after deposition and at regular intervals up to 8 months after deposition. The interpretation of the spectra is focused on the Si-H_x stretching (2000-2100 cm⁻¹), Si-O-Si (1000-1200 cm⁻¹), and O_xSi-H_y modes (2130-2250 cm⁻¹). A short time scale (< 3 months) oxidation of the crystalline grain boundaries is observed, while at longer time scales, the oxidation of the amorphous tissue and the formation of O-H groups on the grain boundary surfaces play a role. The implications of this study on the quality of microcrystalline silicon exhibiting no post-deposition oxidation are discussed: it is not sufficient to merely passivate the surface of the crystalline grains and fill the gap between the grains with amorphous silicon. Instead, the quality of the amorphous silicon tissue should also be taken into account, since this oxidation can affect the passivating properties of the amorphous tissue on the surface of the crystalline silicon grains.     

Effect of illumination on hydrogenated amorphous silicon thin films doped with chalcogens

Hydrogenated amorphous silicon thin films doped with chalcogens (Se or S) were prepared by the decomposition of silane (SiH₄) and H₂Se/H₂S gas mixtures in an RF plasma glow discharge on 7059 corning glass at a substrate temperature 230 °C. The illumination measurements were performed on these samples as a function of doping concentration, temperature and optical density. The activation energy varied with doping concentration and is higher in Se-doped than S-doped a-Si:H thin films due to a low defect density. From intensity versus photoconductivity data, it is observed that the addition of Se and S changes the recombination mechanism from monomolecular at low doping concentration films to bimolecular at higher doping levels. The photosensitivity (σ_ph/σ_d) of a-Si, Se:H thin films decreases as the gas ratio H₂Se/SiH₄ increased from 10^?4 to 10^?1, while the photosensitivity of a-Si, S:H thin films increases as the gas ratio H₂S/SiH₄ increased from 6.8 × 10^?7 to 1.0×10^?4.     

ESR study of the hydrogenated nanocrystalline silicon thin films

We studied the stability and light-induced paramagnetic centers in hydrogenated nanocrystalline silicon thin films (nc-Si:H) by electron-spin-resonance (ESR) and photothermal-deflection-spectroscopy (PDS). There is no measurable change in defect density upon illumination with white light with a light intensity of 300 mW cm^?2 for 300 h. At low temperatures, upon illumination with sub-bandgap light, a light-induced ESR signal appears. This signal is similar to that in hydrogenated micro-crystalline silicon (μc-Si:H).     

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.     

Transformation of microcrystalline state of hydrogenated silicon to amorphous one due to presence of more electronegative impurities

When a slight fraction (～ 2 mol %) of N₂ is added into H₂, sputtering atmosphere for microcrystalline hydrogenated Si films, without changing other fabrication parameters, the amorphous film rather than microcrystalline one forms. The stabilization mechanism of the amorphous film of Si is discussed through TEM and IR observations of this kind of transformation from microcrystal to amorphous state.     

Influence of the deposition parameters on the microstructure and opto-electrical properties of hydrogenated nanocrystalline silicon films by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) films were prepared at high deposition rates (> 13 Å/s) from pure silane without hydrogen dilution by hot wire deposition method by varying filament-to-substrate distance (d_s-f). In this study we have systematically and carefully investigated the effect of filament-to-substrate distance on structural, optical and electrical properties of the Si:H films. A variety of characterization techniques, including Raman spectroscopy, low angle X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Atomic Force Microscopy (AFM), Field Emission Scanning Electron Microscopy (FE-SEM), UV-Visible-NIR spectroscopy and electrical dark and photoconductivity measurement were used to characterize these films. Films deposited at d_s-f > 5 cm are amorphous while those deposited at d_s-f < 5 cm are biphasic; a crystalline phase and an amorphous phase with nano-sized crystallites embedded in it. Low angle X-ray diffraction analysis showed that the crystallites in the films have preferential orientation along (111) directions. Decrease in d_s-f, the crystallinity and crystalline size increases whereas hydrogen bonding shifts from mono-hydride (SiH) to di-hydride (SiH₂) and poly-hydride (SiH₂)_n complexes. The band gaps of nc-Si:H films (~ 1.9-2.0 eV) are high compared to the a-Si:H films, while hydrogen content remains < 10 at.%. We attribute the high band gap to the quantum size effect. A correlation between electrical and structural properties has been established. Finally, from the present study it has been concluded that the filament-to-substrate distance is a key process parameter to induce the crystallinity in the films by hot wire method. The ease of depositing films with variable crystallite size and its volume fraction, and tunable band gap is useful for fabrication of tandem/micro-morph solar cells.     

Laser crystallization of compensated hydrogenated amorphous silicon thin films

Raman backscattering and hydrogen effusion measurements were performed on compensated, highly P- and B-doped laser crystallized polycrystalline silicon. From hydrogen effusion spectra the hydrogen chemical potential, μ_H, is determined as a function of hydrogen concentration, which can be related to the hydrogen density-of-states distribution. Interestingly, hydrogen bonding is affected by doping of the amorphous starting material. Below the hydrogen transport states, four peaks are observed in the hydrogen density-of-states at 2.0, 2.2, 2.5 and 2.8 eV. The latest peak is not observed in B-doped samples. The hydrogen effusion results will be correlated with the results obtained from Raman backscattering measurements.     

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.     

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.     

The nanostructural analysis of hydrogenated silicon films based on positron annihilation studies

Due to the complex nature of hydrogenated amorphous and microcrystalline silicon (a-Si:H; μc-Si:H) a profound understanding of the Si:H nanostructure and its relation to the Staebler–Wronski effect (SWE) is still lacking. In order to gain more insight into the nanostructure we present a detailed study on a set of Si:H samples with a wide variety of nanostructural properties, including dense up to porous films and amorphous up to highly crystalline films, using Doppler broadening positron annihilation spectroscopy (DB-PAS) and Fourier Transform infrared (FTIR) spectroscopy. The results obtained from these material characterisation techniques show that they are powerful complementary methods in the analysis of the Si:H nanostructure. Both techniques indicate that the dominant type of open volume deficiency in device grade a-Si:H seems to be the divacancy, which is in line with earlier positron annihilation lifetime spectroscopy (PALS), Doppler broadening (DB) PAS and FTIR studies.     

Hydrogen passivation of ultra-thin low-temperature polycrystalline silicon films for electronic applications

We have investigated the influence of hydrogen passivation on the electronic properties of ultra-thin polycrystalline silicon layers prepared by the aluminum-induced layer exchange process. Hall effect measurements reveal high hole carrier concentrations in the as-grown poly-Si layers up to several times 10¹⁹ cm^?3. We find a drastic increase of the resistivity after hydrogenation for very thin samples, which is attributed to a combination of two effects: (1) the reduction of free holes due to acceptor passivation and (2) compensation of free holes remaining after H-passivation by interface trap states. Temperature-dependent measurements show that the activation energy of the dark conductivity increases strongly after the hydrogenation process. The origin of the compensation was investigated by spin-dependent transport measurements. In addition, the potential of the passivated poly-Si layers for electronic applications was studied. We have demonstrated a normally ON back-gate depletion mode transistor with a two mask process, which exhibits a field-effect mobility of 21 cm²/Vs for holes in the 20 nm thin channel layer.     

Characterization of hydrogenated amorphous silicon thin films prepared by magnetron sputtering

Magnetron sputtered hydrogenated amorphous silicon (a-Si:H) thin films have been characterized. Hydrogen (H₂) with argon (Ar) was introduced into the sputtering chamber to create the plasma. A sudden increase in the deposition rate occurred when the hydrogen was added. The maximum hydrogen content of 16 atomic percent (at.%) was achieved and a bandgap of about 2.07 eV was determined from the spectral investigations of the hydrogenated films. The effect of radio frequency (RF) power on the deposition rate, as well as on the hydrogen content was investigated. To change the hydrogen content in the films, the hydrogen flow rate was varied while keeping the argon flow rate constant. The hydrogen content in the films increased with increasing hydrogen flow rate up to the maximum content of 16 at.% and then decreased for further increases in hydrogen flow.