A simple model (the HTMT model) describing the interaction of excess mobile charge carriers with an exponential bandtail is presented. The new model differs from the commonly used intuitive thermalization (TROK) model only by the definition of the demarcation energy. By comparison of the results of the TROK and the HTMT model with numerical calculation of the interaction it is shown that the HTMT model yields an adequate description, whereas the TROK model does not reproduce the absolute values and also has a deviating time dependence at higher temperatures. The origin of these differences is discussed.

We review modulated photocurrent experiments which indicate that thermal emission rate for Do defects in intrinsic samples varies in response to changes in the Fermi-level or quasi-Fermi position. This apparent shift in energy threshold is confirmed using time resolved sub-band-gap spectroscopy. We also demonstrate that such a variation of emission rate with changes in the Fermi-level position, if present within the depletion region near a barrier junction, is consistent with the details of the temperature dependence of the junction capacitance in intrinsic samples.

Undoped microcrystalline silicon films of high crystalline volume fraction were studied by optically detected magnetic resonance (ODMR). Luminescence energies peak at 0.88 eV and emission at 1.3 eV arising from amorphous tissue is negligible. Recombination involving dangling bonds (g=2.0052, g=2.0043) in disordered regions or crystallites and shallow states near the conduction band (g= 1.998) in the crystalline parts of the material are observed. At temperatures below 30 K a very broad feature of approximately 1000 G width is observed, possibly originating from two separate resonances with high g-values of g=2.1 and g=2.08. We suggest the origin to be of hole-states near or in the valence band. No evidence for excitonic recombination was found. Frequency response indicates ODMR lifetimes of all resonances in the range of 10−5s to 10−4s.

We report on a study of ESR and conductivity on a series of hot-wire CVD microcrystalline silicon samples prepared with different hydrogen dilution of silane. We observe two different types of dangling bond defects in ESR in different microscopic environments. One type of defect is located at outer surfaces accessible to oxygen and/or chemicals, the other is located at inner boundaries presumably at columnar structures. We correlate changes of the defect density induced by either annealing, exposure to air or wet-chemical treatment with the morphology and electronic properties of the films. We find that annealing at 200 °C induces irreversible changes in donor concentration as monitored by an ESR signal at g = 1.9981±3.

We measured the response time zR and the ambipolar diffusion length Lamb in amorphous (a-Si:H) and microcrystalline silicon films (μ-Si:H) prepared by hot-wire chemical vapor deposition (HW-CVD). The response times in the amorphous and microcrystalline HW films were larger by factors of 100 and 1000, respectively, than in standard PE-CVD a-Si:H films (1-2 μs). The ambipolar diffusion length of the HW-CVD films was about twice as large as in conventional glow-discharge films. Strong doping of microcrystalline HW films with trimethylboron (TMB) led to a reduction of the response time. The results hint to a positive effect of the compact microstructure of HW-CVD films. We suggest the dark conductivity activation energy, Eact, and response time, τR, to be used as suitable parameters to describe optoelectronic film properties.

Light-induced electron spin resonance in a-Si:H films was measured using second harmonic detection over a wide range of excitation intensities. Second harmonic detection results in an undifferentiated absorption lineshape that saturates much less easily with increasing microwave power. The ratio of the spin densities of the broad line to the narrow line is approximately 3 at a generation rate of 1019 cm−3s−1, and this ratio increases only slightly with decreasing excitation intensity. The kinetics of the LESR after the light is turned on or off show dispersive behavior. The dispersive response of the LESR is related to the dispersive transport of carriers at low temperature. A model that assumes a bimolecular recombination fits the experimental results reasonably well.

Thin microcrystalline silicon-germanium films (μ-Sil.xGex:H) prepared by PECVD at 95 MHz have been investigated. The optical absorption of these films increases in the infrared spectral region with increasing germanium content. In addition to the shift of the indirect gap an increase of the absorption coefficient above the band edge is observed. The material shows high crystallinity and exhibits good structural quality similar to pure μ-Si:H films. The films are homogeneous on a macroscopic to a microscopic scale as confirmed by Raman spectroscopy and Electron Microscopy methods. p-i-n solar cells with pc-Sil-xGex:H i-layers have been prepared for the first time. An efficiency of η = 3.1 % under AM1.5 has been obtained for a cell with 150 nm thin i-layer.

The phenomenon of enhanced optical absorption in hot wire microcrystalline silicon (hw-μ-Si:H) has been investigated with respect to the structural properties of the as deposited as well as annealed films. The influence of the structural properties on the absorption behavior is explained within the framework of a model. In this model the μc-Si:H is assumed to consist of crystalline grains surrounded by grain boundaries embedded into an amorphous matrix. Because of the relaxation of the k-selection rule the absorption is supposed to be higher for the disordered grain boundaries than for the crystalline grains. The absorption coefficient α is derived from the superposition of the absorption coefficients for the amorphous, crystalline and grain boundary regions weighted by their appropriate volume fractions. According to experimental results it is furthermore assumed that the absorption of the grain boundary regions correlates with the hydrogen content of the films. The model is proven and confirmed by crucial experiments especially concerning the influence of the hydrogen content on the absorption coefficient. Other possible reasons that might influence the enhanced optical absorption such as strain induced changes of α and light scattering effects are also discussed and explicitely excluded by appropriate experiments to be the essential enhancement reasons.

The optical and electronic properties of a series of microcrystalline silicon (μ-Si) films, deposited by the hot wire (HW) technique, are reported. Preliminary results suggest, using moderate H2 /SiH4 dilution ratios and substrate temperatures (320°C), high filament temperatures, and no H gas purifier, that the subgap absorption for these films, measured using the constant photocurrent (CPM) method, can be as low as that obtained for films deposited by the very high frequency glow discharge (VHF-GD) technique. The film dark conductivities of the HW samples, ranging as low as 2.0 × 10−8 (ohm cm)−1, lend further credance to these low defect values. At the same time, the optical absorption in the region > 1.6 eV is higher than that previously observed for the VHF-GD deposited samples. The present results, discussed in the context of the film microcrystalline fraction, suggest that there is no unique, good quality, low defect density μ-Si material, and that different deposition techniques can be used to successfully deposit device quality gc-Si. We also present optical and structural data for films deposited at lower substrate temperatures and higher deposition rates, and suggest combinations of deposition parameters to be used that may further improve the electronic properties of these films.

This work deals with the role of hydrogen dilution and filament temperature on the morphology, structure and electrical properties of nanocrystalline boron doped silicon carbide thin films produced by hot-wire technique. The structural and morphological data obtained by XRD, SEM and micro-Raman show that for filament temperatures and hydrogen dilutions above 2100°C and 90%, respectively, the surface morphology of the films is granular with a needle shape, while for lower filament temperatures and hydrogen dilutions the surface morphology gets honeycomb like. The SIMS analysis reveals that films produced with filament temperatures of about 2200°C and hydrogen dilution of 99% present a higher hydrogen and carbon incorporation than the films produced at lower temperatures and hydrogen dilutions. These results agree with the electrical and optical characteristics recorded that show that the films produced exhibit optical gaps in the range from 1.8 to 2 eV and transverse conductivities ranging from 10−1S/cm to 10−3 S/cm, consistent with the degree of films crystallinity and carbon incorporation recorded.

We have investigated the structure of a-Si:H thin films using variable coherence transmission electron microscopy. Variable coherence is a new microscopy technique that is sensitive to higher-order atomic position correlations. We observe changes in the structure of α-Si:H with increasing hydrogen content and with light soaking. Based on these observations we conclude that a less ordered form of α-Si:H is more structurally stable than a more ordered form. This may have implications for understanding the Staebler-Wronski effect.

The role of hydrogen atoms in the formation process of hydrogenated microcrystalline silicon (μc-Si:H) by plasma enhanced chemical vapor deposition method has been investigated. Under the present conditions, the etching and the permeation of hydrogen atoms in the subsurface region do not cause the crystallization. The kinetics study of surface morphology and structure in the initial growth of μc-Si:H on an atomically flat substrate indicates that the onset thickness of island coalescence reduced under μc-Si:H formation condition. The results support the ‘surface diffusion model’ in which the surface diffusion of film precursors is enhanced by the sufficient hydrogen coverage of surface and by hydrogen atom recombination energy on the growing surface of the film.

Ultra clean plasma CVD process opens the doorway to clarify the role of impurities in the growth process of μc-Si:H. A reduction of impurity levels during the growth extends the temperature range for crystalline formation to lower side, i.e., high-crystallinity μc-Si:H formation even at room temperature, substantially reduces midgap defect density at 200°C, and enlarges crystalline grain size at 350°C. These results imply that impurities disrupt crystalline formation even on hydrogen covered surface. The crystalline-to-amorphous transition is induced by a loss of surface hydrogen coverage due to thermal hydrogen desorption at higher temperature of ∼450°C irrespective of the effect of oxygen impurity. Light-soaking experiments for the series of the films from a-Si:H to μc-Si:H films with different crystalline volume fraction indicate that the presence of small volume fraction of crystallite significantly suppresses light induced defect creation under the present light soaking condition of 3SUN 60°C 6hr. These results are explained in terms of preferential recombination of photo-excited carriers in the crystallite.

Solar cell using profiled poly-Si:H by HWCVD as i-layer in the configuration SS/n-µSi:H(PECVD)/i-poly-Si:H(HWCVD)/p-µc-Si:H(PECVD)/ITO showed 3.7% efficiency. A current of 23.6 mA/cm2 was generated in only 1.5 µm thick poly-Si:H i-layer grown at ∼5Å/s. TFTs made with the poly-Si:H films (grown at ≥ 9Å/s) exhibited remarkable stability to long duration of 23 hours of gate bias stress of ∼lMV/cm. A saturation mobility of 1.5 cm2/Vs for the TFT has been achieved. Films made at low hydrogen dilution (Poly2) showed device quality (purely intrinsic nature, ambipolar diffusion length of 568 nm, only (220) oriented growth and low ESR defect density of <1017/cm3with complete absence of signal due to conduction electrons) but with an incubation phase of amorphous initial growth, whereas the films made at high hydrogen dilution (Polyl) had a polycrystalline initial growth, though with higher defect density, incorporated oxygen and randomly oriented grains. Poly2 films are compact and hydrogen bonding is at compact Si-H sites manifested as 2000 cm−1IR vibration and high temperature hydrogen evolution peak. Exchange interaction of spins and spin pairing are observed while increasing defects in such a compact structure. A new approach has been used to integrate these two regimes of growth to make profiled poly-Si:H layers. The new layers show good electronic properties as well as complete elimination of incubation phase.

Plasma enhanced chemical vapor deposition of phosphorus-doped n+ silicon film over a wide range of process conditions has been studied. The deposited films were characterized with SIMS, Raman, and XRD. An unusually abrupt change of resistivity over a small SiH4(1% PH3) flow rate has been observed and was correlated to the variation of the film's morphology from amorphous to micrycrystalline. The grains are less than 50 Å in size and has strong <111> orientation. Amorphous silicon thin film transistors with microcrystalline n+ source and drain contacts have consistently good device characteristics. However, the contact resistance is comparable to the channel resistance when the channel length approaches 1 micrometer.

The growth of a-Si:H and the resulting weak bond and defect formation mechanism is analysed in terms of the adsorbed Sill3 model of growth. It is found that this model describes the surface processes well, but it needs further development to correctly describe the temperature dependence of the formation of defects and weak bonds, since the surface defect density decreases monotonically with temperature and does not show a minimum near 250C. We show that the experimentally observed increase in hydrogen content, weak bond and defect density at lower deposition temperatures can be accounted for by a hydrogen evolution reaction from H2* sites.

We describe a series of microcrystalline (μc) silicon n-i-p solar cell devices fabricated entirely by the hot-wire chemical vapor deposition technique. These devices are deposited on flat stainless-steel at a substrate temperature below 250°C, and are evaluated using solar-cell performance and quantum-efficiency (QE) measurements. We explore the effect of crystallite size, as examined by X-ray diffraction, by varying the hydrogen-to-silane ratio from 5 to 40, while keeping the μc-n and the μc-p layers the same. We find a significant blue shift of the QE peak and an enhancement of red response compared with a standard a-Si:H solar cell. The blue shift increases with increasing hydrogen-to-silane ratio. We attribute this shift to the i-layer becoming more n-type with increasing hydrogen dilution. We also use a hydrogen gas purifier and find a large improvement in device performance.

Bottom-gate thin film transistors (TFT) were fabricated with amorphous and microcrystalline silicon active layers deposited by hot-wire (HW) chemical vapor deposition using different levels of hydrogen dilution. As the hydrogen dilution was increased above 80%, the active layer made a transition from amorphous to microcrystalline. This transition resulted in an increase of the TFT off-current and in an increase of the TFT subthreshold slope. The TFT on- current and the TFT mobility remained at levels comparable to those of the a-Si:H HW TFTs. A comparison is made between TFTs with amorphous and microcrystalline silicon active layers prepared both by rf glow discharge and HW. HW TFTs with an active layer consisting of a thin layer deposited with high hydrogen dilution underlying a thicker amorphous silicon layer are also compared to TFTs with an active layer of the same total active layer thickness consisting only of the high hydrogen dilution film.

At the high temperatures during hot-wire assisted chemical vapor deposition, ther- mal emission of electrons from the filament occurs. We studied the effect of filament bias, and thus the filament-to-substrate current, on the structural, electronic and optical properties of amorphous and nanocrystalline silicon deposited by this method. The current drawn by the substrate can be varied by many orders of magnitude as thermally emitted electrons are increasingly collected with applied bias voltage. The crystallinity of the nanocrystalline samples is not affected by the bias voltage. The defect density in amorphous silicon is affected by the electron bombardment at high bias voltage only, for which we also find a significant reduction in the mobility-lifetime product from steady-state photoconductivity.

We compare the electronic properties of nanocrystalline silicon from hot-wire chemical vapor deposition in a high-vacuum and an ultra-high-vacuum deposition system, employing W and Ta as filament material. From the constant photocurrent method we identify a band gap around 1.15 eV while, in contrast, a Tauc plot from optical transmission data guides to a wide band gap above 1.9 eV. The sudden change-over from nanocrystalline to amorphous structure in a hydrogen dilution series is also find in the dark and photoconductivity measurements. The samples show a metastability effect in the dark conductivity upon annealing in vacuum with an increase in the dark conductivity, with the large dark conductivity decreasing slowly after the annealing cycle when the cryostat is flushed with air. We identify larger values for the mobility-lifetime products, which corresponds to the smaller defect density shoulder in constant photocur- rent spectra, for the ultra-high-vacuum deposited material compared to the high-vacuun counterpart.