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.     

Er-doped hydrogenated amorphous silicon: structural and optical properties

The effect of erbium-doping on the structural and optical properties of hydrogenated amorphous silicon (a-Si:H) is investigated. Optical absorption and Raman spectra indicate that erbium doping introduces defect states, and that above a concentration of 0.27 at.%, induces strong structural disorder. The photoluminescence measurements show that erbium doping introduces non-radiative decay paths for carriers in a-Si:H, leading to decrease in both the Er³⁺ and intrinsic a-Si:H luminescence intensity when the Er concentration is increased to more than 0.04 at.%. The results are compared to that of Er-doped crystalline Si, and the possible excitation mechanisms of Er in a-Si:H are discussed.     

Deviations from square-root distributions of electronic states in hydrogenated amorphous silicon and their impact upon the resultant optical properties

We study the distributions of conduction band and valence band electronic states associated with hydrogenated amorphous silicon. We find that there are substantial deviations from square-root distributions, particularly deep within the bands and within the gap region. The impact of these deviations is assessed through a determination of the spectral dependence of both the joint density of states function and the imaginary part of the dielectric function. These deviations are found to have a considerable effect upon the determination of the corresponding Tauc optical gap, the optical gap obtained for the case of hydrogenated amorphous silicon being 220 meV lower than the energy difference between the valence band and conduction band band edges. We suggest that the standard interpretation for the Tauc optical gap, as the energy difference between these band edges, should be reconsidered in light of these results.     

Photoluminescence of hydrogenated amorphous silicon

Photoluminescence has beeb proven to be a powerful technique in the characterization of a-Si:H. In particular, it has contributed to the elucidation of some aspects of the electronic structure. However, there is a set of controversial topics still under discussion including the idenntity of the luminescent transition and the origin of broadening of the emission spectrum. In this paper we study these problems and show that the specified width has its origin in both disorder and electron-phonon interaction.Luminescent decay at low temperature has been studied and lifetimes from 10^?8 to 10^?2 s have been confirmed.Photoconductivity and photoluminescence are shown to behave in a complementary way and activation energies for both processes are obtained. Also, the photoluminescence quenching and photoconductivity enhanced under an applied electric field have been measured an interpreted.     

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.     

Transport properties of hydrogenated amorphous silicon deposited by dc glow discharge decomposition

Conductivity and thermoelectric power measurements have been made as a function of temperature on a series of hydrogenated amorphous silicon samples. The samples were prepared by the dc glow discharge decomposition of silane and silane phosphine mixtures. The activation energy for conduction varied with the substrate temperature and discharge condition for undoped specimens. The difference in the activation energy for conduction as well as the dependence of photoconductivity and optical gap on the activation energy for conduction among undoped specimens can be explained by introducing centers acting as donors or by change transfer between the island and hydrogen rich interfacial region. The kinks in the log σ versus inverse temperature curves always appear at about 430 K for the undoped specimens prepared at 300°C, while they are absent for low substrate temperature specimens. The downward kinks with increasing temperature can be explained by a two-phase material model. A revised two-channel conduction path model including material heterogeneity is applied to interpret the conductivity and thermopower versus inverse temperature curves of doped a-Si:H films, and to determine the position of phosphorus donor levels. The levels are found to lie at about 0.47 eV below E_c, the mobility edge at the conduction band.     

Optical and electrical properties of chlorinated and hydrogenated amorphous silicon prepared by glow discharge

Chlorinated and hydrogenated amorphous silicon films were prepared by glow discharge of a SiCl₄/H₂ mixture. Infrared spectra of these films show that, in addition to the hydrogen induced bands, two new modes appear at 545 cm^?1 (SiCl stretching) and 500 cm^?1 (Si TO modes induced by chlorine). Observation of the 545 cm^?1 band proves that chlorine is able to act as a dangling bond terminator in an amorphous silicon matrix. A good agreement is found between the total amount of chlorine determined by electron microprobe analysis and the value estimated from the integrated strength of the SiCl stretching mode. The relatively high value of the optical band gap (1.80 eV) of our material containing only 5 at.% bonded hydrogen shows that chlorine plays a major role in the optical gap value. Electrical conductivity, photoconductivity and luminescence properties are qualitatively similar to that of a: SiH films.     

Luminescence gap in hydrogenated amorphous silicon

The “luminescence gap” is used instead of the thermalization gap and the hopping-gap because the gap is obtained from the luminescence measurement. The luminescence gaps in hydrogenated amorphous silicon (a-Si:H) are observed in the temperature range from 4.2 to 225 K for the films prepared at different substrate temperatures 170 to 300 °C by plasma CVD. It is shown from the temperature dependence of the luminescence gap that the luminescence edges are at the localized band tail states at which the waiting time for the hopping is equal to the life time of the luminescence. The excitation energy dependence of the luminescence peak energy similar to that of the porous Si has been observed.     

Network structure and dynamics of hydrogenated amorphous silicon

In this paper we discuss the application of current ab initio computer simulation techniques to hydrogenated amorphous silicon (a-Si:H). We begin by discussing thermal fluctuation in the number of coordination defects in the material, and its temperature dependence. We connect this to the ‘fluctuating bond-center detachment’ mechanism for liberating H bonded to Si atoms. Next, from extended thermal MD simulation, we illustrate various mechanisms of H motion. The dynamics of the lattice is then linked to the electrons, and we point out that the squared electron-lattice coupling (and the thermally-induced mean square variation in electron energy eigenvalues) is robustly proportional to the localization of the conjugate state, if localization is measured with inverse participation ratio. Finally we discuss the Staebler–Wronski effect using these methods, and argue that a sophisticated local heating picture (based upon reasonable calculations of the electron-lattice coupling and molecular dynamic simulation) explains significant aspects of the phenomenon.     

Voids in hydrogenated amorphous silicon materials

Effusion measurements of hydrogen and of implanted helium are used to characterize the presence of voids in hydrogenated amorphous silicon (a-Si:H) materials as a function of substrate temperature, hydrogen content, etc. For undoped plasma-grown a-Si:H, interconnected voids are found to prevail at hydrogen concentrations exceeding 15–20 at.%, while isolated voids which act as helium traps appear at hydrogen concentrations ≤ 15 at.%. The concentration of such isolated voids is estimated to some 10¹⁸/cm³ for device-grade undoped a-Si:H deposited at a substrate temperature near 200 °C. Higher values are found for, e.g., doped material, hot wire grown a-Si:H and hydrogen-implanted crystalline Si. The results do not support recent suggestions of predominant incorporation of hydrogen in a-Si:H in (crystalline silicon type) divacancies, since such models predict a concentration of voids (which act as helium traps) in the range of 10²¹/cm³ and a correlation between void and hydrogen concentrations which is not observed.     

Modification of amorphous hydrogenated silicon by co-sputtered aluminum

The electronic and optical properties of a-Si_1?xH_x have been modified by the incorporation of aluminum. Samples were prepared by rf sputtering in a hydrogenated atmosphere from a composite silicon-aluminum target. This paper reports on several modified material parameters including the optical band gap, electrical conductivity, and thermal activation energy. Aluminum concentrations up to 10.6% in the target have been investigated. It is observed that the optical band gap remains constant at 1.83 eV for Al concentrations up to 2.7%. For higher concentrations there is a marked decrease in optical gap. The conductivity initially decreases with small Al concentration and the activation energy increases, characteristic of compensation of the inherently n-type material. For higher Al concentrations the conductivity increases by seven orders of magnitude and the activation energy decreases to a minimum of about 0.2 eV. The increase in conductivity can be explained by both the movement of the Fermi level and the shrinking band gap. Microprobe analyses have also been performed to determine the amount of Al actually incorporated into the films. Finally, implications of these results are discussed and compared to previously reported results on gas phase doping and ion implantation.     

Luminescence decay in hydrogenated amorphous silicon and silicon nanostructures

The stretched exponential luminescence decay observed at temperatures lower than 20 K transits to the power law decay due to the electron-hopping at localized band tail states near 60 K in the hydrogenated amorphous silicon (a-Si:H). The luminescence decay at 4.2 K in a-Si:H is quite similar to that of Si-nanoparticles in the porous Si (p-Si). It is explained from the comparison with p-Si that the slow luminescence of the life time of ~ 1 ms is due to the recombination of excitonic electron–hole pairs at the spin triplet state quantum-confined in the hydrogen-free Si nanostructure in a-Si:H. The fast luminescence of the life time of ~ 1 μs is due to the recombination of the pairs at the spin-singlet state and the life time is explained as due to the indirect optical transition.     

Films thickness effect on structural and optoelectronic properties of hydrogenated amorphous germanium (a-Ge:H)

Thin films of hydrogenated amorphous germanium (a-Ge:H) deposited at high growth rate by radiofrequency (RF) glow discharge with 1 sccm GeH₄ diluted in 40 sccm H₂ have been studied. The effect of the films thicknesses on the defect density and on the structural parameters was carefully investigated by means of infrared spectroscopy, optical transmission measurements, and the photothermal deflection spectroscopy (PDS) technique. The results of this investigation show that when the films thicknesses increase, the total hydrogen content (C_H) decreases and the hydrogen-bonding configuration changes. The results of these changes appear clearly on the defects density and on the microstructure parameter of the films, while the disorder parameter E_OV and the optical gap E_T remain practically constant (E_OV ≈ 45 ± 2 meV, E_T = 1.08 ± 0.02 eV). The improvement of these parameters is mainly due to the incorporation of the hydrogen in the bulk of the material as the monohydride groups (Ge-H) rather than the polyhydride groups (Ge-H₂ and Ge-H_2n) when the films thicknesses increase.     

Formation of hydrogenated amorphous carbon films containing fullerene-like structures

Hydrogenated amorphous carbon films containing fullerene-like structures were obtained by magnetron sputtering of a titanium target in methane and argon atmosphere. The microstructure of the film was investigated by transmission electron microscopy and Raman spectra. Additionally, the three stage model proposed by Ferrari and Robertson was used to explain the formation process of fullerene-like structures. The results show that titanium target was covered by a hydrocarbon layer, and the new-produced hydrocarbon layer on titanium target rather than the titanium surface was sputtered during deposition. The product of the sputtering can serve as ‘seeds’ for the formation of fullerene-like structures. These ‘seeds’ or nuclei are proposed to be open graphene structures, at the effect of ions bombardment, more defects are introduced and the curved structure arises due to incorporation of odd member rings into the graphene sheets, which resulted in the formation of curved planes with small radii of curvature and closed fullerene-like structure.     

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.