We have applied a novel Ion-Assisted Sputter Deposition (IASD) method to deposit microcrystalline silicon (µc-Si) thin films with high deposition rates. An unbalanced magnetron sputter source together with an asymmetrical bipolar pulsed-DC plasma excitation operating in the frequency range 50-250 kHz was used for realizing high ion fluxes to the growing film. µc-Si films of high crystallinity are obtained at T > 400 °C with growth rates of up to 90 nm/min. The crystallinity of the films is characterized by the thickness-independent ratio of the optical thickness n·d determined by FTIR measurements and the atomic area density N·d as given by RBS analysis.

When an a-Si:H p-i-n structure is locally illuminated by a light spot, the non uniformity of light causes the appearance of a gradient in the carrier concentration between the illuminated and the dark zone. Carrier start to flow in agreement with such gradients, and when equilibrium is reached, the lateral diffusion process is counterbalanced by the appearance of a lateral component of the electric field vector in addition to the transverse usual one. The lateral fields act as a gate for the lateral flow of the carriers and small lateral currents appears at the transition region between the illuminated and the dark zone.

Such lateral photoeffect depends on the incident light wavelength, light intensity and on the device operation condition (mainly the applied bias). The introduction of carbon in the doped layers modifies the intensity and the extension of these lateral effects through the potential barriers deriving from the band banding at the interfaces.

We have used the 2D numerical simulator ASCA to analyze the behavior of an a-Si:H p-i-n structure under local illumination with the goal of observing the appearance of the lateral components of the electric field and current density vectors. Different homo and heterojunctions have been simulated, outlining how the band offset at the interfaces influences the induced lateral photoeffect and aiming to explain how a correct device design and engineering can, depending on the foreseen application, alternatively enhance or reduce the intensity of such lateral effects.

Undoped µc-Si:H film of the strong n-type character with the dark conductivity activation energy of about 0.28 eV was annealed. Annealing was carried out by slowly increasing the temperature from 25 °C to 450 °C at a constant rate of 12 °C/min (one annealing cycle). Annealing effects were monitored by measuring the changes in dark conductivity, oxygen and hydrogen concentrations, and photoluminescence (PL). Dark conductivity activation energy gradually increases with increasing the number of annealing cycles to a saturation value of about 0.6 eV. There is little or no change in the oxygen concentration, but the hydrogen concentration decreases with increasing the number of annealing cycles. The PL band near 1.2 eV disappears with annealing, while the low energy PL band near 0.85 eV dominates rather as the number of annealing cycles increases. A possible explanation will be discussed.

We characterized the electronic states and microstructure of high-growth-rate a-Si:H films by employing photoluminescence (PL) and Raman spectroscopies. The growth rate was from 50 to 115 Å/s compared to the standard rate of less than 10 Å/s. For the high-growth-rate a-Si:H films, we observed typical a-Si:H features in Raman but new features in PL. The new PL features are: a) the PL peak energy is as low as ∼1.15 eV compared to the standard ∼1.4 eV at 80 K; and b) the total intensity is more than one order of magnitude higher then the standard. We suggest that the nano-scale microstructure may be responsible for the anomalous PL features.

Substitution reactions of surface hydrogen in amorphous silicon at room temperature have been studied. After wet treatment of hydrogenated amorphous silicon thin films with Grignard reagent, surface hydrogen atoms have been substituted by organic groups. Wet treatment of amorphous silicon thin films in CH3(CH2)9-MgBr ether solution followed by quenching by diluted HCl changes infrared absorption spectra. After the treatment, new three peaks of C–H have been observed. In addition, the peaks did not disappeared after rising by hydrofluoric acid or various kinds of organic solvent. The spectra indicate that the Grignard reagent is enough reactive to form new covariant bonding of C and Si at the amorphous silicon surface by substitution reaction.

The performances of amorphous and nano-crystalline porous silicon thin films as gas detector are pioneer reported in this work. The films were produced by the hot wire chemical vapour deposition (HW-CVD). These films present a porous like-structure, which is due to the uncompensated bonds and oxidise easily in the presence of air. This behaviour is a problem when the films are used for solar cells or thin film transistors. For as gas detectors, the oxidation is a benefit, since the CO, H2 or O2 molecules replace the OH adsorbed group. In the present study we observe the behaviour of amorphous and nano-crystalline porous silicon thin films under the presence of ethanol, at room temperature. The data obtained reveal a change in the current values recorded by more than three orders of magnitude, depending on the film preparation condition. This current behaviouris due to the adsorption of the OH chemical group by the Si uncompensated bonds as can be observed in the infrared spectra. Besides that, the current response and its recover time are done in few seconds.

We report on the growth and electrical and optical properties of micro- and poly- crystalline Ge1−x Cxfilms. This is a new material which does not exist in nature. The films were grown using ECR plasma techniques under conditions of low pressure and high power from a mixture of germane, methane and hydrogen. The bandgap of the material could be varied from that of c-Ge (∼0.7 eV) to almost 1.15 eV by changing the methane/germane ratio. X ray diffraction and Raman measurements indicated good crystallinity in the film. The optical absorption spectrum of the film resembles that of c-Ge, with a near direct bandgap, implying that as C is added, both the central and the L valley in the conduction band move up simultaneously, while maintaining a small (∼0.15 eV) separation between the two. The Hall mobility was measured to be 70 cm2/V-sec. The films were doped n- type using phosphine, and p- type using diborane. P-n junctions with good rectification characteristics were fabricated. Because of its excellent optical absorption, this material may be suitable for photovoltaic applications, particularly for tandem junction cells. We have also observed that grain size can be controlled using H etching, and have observed distinct changes in optical properties related to quantum size effects in c-Ge films.

Electrical current induced joule heating method was applied to crystallization of 50 nm-thick amorphous silicon films formed on glass substrates. Voltages were applied to silicon films connected with a capacitance in parallel. Irradiation with 5 ns-pulsed-laser melted films partially and caused electrical current induced joule heating because of reduction of electrical resistance. Lateral grain growth with 12.6 µm was realized using the tapered-shaped-electrodes to apply voltages to silicon films with a capacitance of 0.33 µF. For 2.6×10 17 cm−3 phosphorus-doped films, analysis of temperature change in the electrical conductivity gave that defect states at grain boundaries was low of ∼1017 cm−3.

For the first time it is demonstrated that the surface defect density can be measured using the cavity ring down (CRD) absorption technique and it is shown that CRD is more sensitive for surface defects than dual beam photoconductivity (DBP) technique. Ex situ measurements have shown that the surface defects of the oxidized a-Si:H surface are distributed over a surface region with thickness W(d). The obtained surface defect density is 1.0 × 1012 up to 1.4 × 1012 cm-2. During growth the a-Si:H surface defect density region has at least a thickness of 15 nm. During deposition of 15 nm a-Si:H the surface density increases up to a not yet saturated value of 1×1013 cm-2.

Microcrystalline silicon solar cells were prepared at various substrate temperatures using a plasma enhanced chemical vapor deposition technique at 95 MHz. Devices in superstrate configuration, i.e. prepared on transparent glass/ZnO substrates with deposition sequence p-i-n, suffer from a reduction of short wavelength response upon increasing substrate temperature. As underlying mechanism adverse effects on the p-i interface region are discussed. For devices in substrate configuration (deposition sequence n-i-p on Ag/ZnO back-reflectors) a pronounced efficiency maximum with a highest value of 8.7 % is observed at substrate temperatures of about 250 °C. Comparing the dark J-V characteristics obtained for different device thicknesses at substrate temperatures of 200 °and 250 °C, respectively, improved i-layer material and transport properties are suggested in the latter case. The results illustrate the sensitivity ofmicrocrystalline silicon devices with respect to the employed substrate temperature by effects on the absorber layer material properties on the one hand and by effects related to the device design, e.g. the specific deposition sequence of the individual layers, on the other hand.

In this paper, changes in electrical properties of laser crystallized silicon films doped with 8.5×1017-cm−3-phosphorus atoms as a function of laser shot number are investigated. The samples are treated with plasma hydrogenation for 30 sec at 130 Pa at 250 °C and additional H2O vapor heat treatment at 260 °C for 3 hours with 1.3 MPa. The electrical conductivity at room temperature become about 10−6∼10−-5 S/cm as laser shot number increases from 1 to 100. After hydrogenation and additional H2O vapor heat treatment, electrical conductivity remarkably increases to 100∼101S/cm. At laser irradiation of 20 or 50 shots after both treatments, the density of defect at deep level states and tail states are determined 1.15×1017 cm−3 and 5.7×1017cm−3 using an analysis program. Potential barrier height at grain boundary is 0.048 eV. The effective carrier density and carrier mobility are markedly increased up to1017cm−3 and 209 cm2/Vs by hydrogenation and additional H2O vapor heat treatment.

Using a closed-form, time-dependent solution to the partial differential equation representing hydrogen diffusion in the frame of a growing silicon film we obtain considerable insight into processes controlled by mobile H in silicon. We apply this insight to quantitatively explain the limiting thickness for Si homoepitaxy and explain by analogy the incubation thickness before the transition from amorphous to nanocrystalline silicon growth.

The expanding thermal plasma (ETP) has been used to deposit microcrystalline silicon (µc-Si:H) with rates up to 2.7 nm/s. Typical material properties of well crystallised material are crystallite sizes of 20 nm, photo- and dark conductivity of 2×10−5 and 2x10−7 S/cm respectively, and an activation energy of 600 meV. The radical densities of SiH3, SiH, and Si present in the gas phase have been quantified. In conditions where [.proportional µc-Si:H is deposited the atomic hydrogen flux towards the surface is of the same magnitude or higher as the flux of deposited radicals. Furthermore, the abundance of radicals such as SiH and Si is large and may contribute several tens of percent to the deposition rate.

This paper deals with a novel structure of polycrystalline silicon (poly-Si) solar cell for terrestrial applications. Grain boundary (GB) in poly-Si degrades a conversion efficiency of poly-Si solar cell. To reduce the GB side-effect, we investigated various parameters such as the preferential GB etch, etchtime, ITO electrode, heat treatment, and emitter layer effect. Among various preferential etchants such as Sirtl, Yang, Secco, and Schimmel, a Schimmel etchant illustrated an excellent preferential etching property. We observed a 10μm deep trench along grain boundaries and randomly textured grain surface with pyramid structure. We used rf magnetron sputter grown tin doped indium oxide (ITO) film as a top contact metal. ITO films showed a resistivity of 1.14 ×10-4 Ω-cm and transmittance of 90.5% for the wavelength of 594 nm. ITO films served as a top electrode as well as an effective AR coating layer. ITO film properties were strongly influenced by the preparation temperatures. Substrate temperature of 400oC gave the highest conversion efficiency of poly-Si solar cell. With well-fabricated poly-Si solar cells, we were able to achieve conversion efficiency as high as 16% at the input power of 20 mW/cm2.

We review evidence for the vital role of H in metastability and defect equilibration in hydrogenated amorphous silicon. H pairs act both as an H reservoir that equilibrates with DB's and dopants and as the metastable H state of light-induced metastability. With ab initio pseudopotential theory, we calculate energies and configurations for two novel H pairing sites associated with small hydrogenated vacancies. We describe microscopic models of equilibration and metastability based on our calculations.

The low-temperature dynamics in amorphous silicon occurs through a sequence of discrete, activated events that reorganize the topology of the network. In this review, we present some recent work done to understand better the nature of these events and the associated dynamics ina-Si. Using the activation-relaxation technique (ART), we generated more than 8000 events in a 1000-atom model ofa-Si, providing an extensive database of relaxation and diffusion mechanisms. The generic properties of these events, such as the number of involved atoms and the activation energies, were investigated and foundto be in agreement with experimental data. As it turns out, the bond-transposition mechanism proposed by Wooten, Winer and Weaire (WWW) some time ago plays an important role in the events generated by ART. We have therefore turned to an optimized version of the WWW algorithm to generate the best overall configurations ofa-Si available today. We discuss the details of the optimization and present the structural and electronic properties of the resulting models.

We report experimental results that help settle apparent inconsistencies in earlier work on photoconductivity and light-induced defects in hydrogenated amorphous silicon (a-Si:H) and point toward a new understanding of this subject. After observing that light-induced photoconductivity degradation anneals out at much lower T than the light-induced increase in deep defect density, Han and Fritzsche[1] suggested that two kinds of defects are created during illumination of a-Si:H. In this view, one kind of defect degrades the photoconductivity and the other increases defect sub-bandgap optical absorption. However, the light-induced degradation model of Stutzmann et al.[2] assumes that photoconductivity is inversely proportional to the dangling-bond defect density. We observe two kinds of defects that are distinguished by their annealing activation energies, but because their densities remain in strict linear proportion during their creation, the two kinds of defects cannot be completely independent.

In our measurements of photoconductivity and defect absorption (constant photocurrent method) during 25°C light soaking and during a series of isochronal anneals between 25 < T < 190°C, we find that the absorption measured with E ≤1.1 eV, first increases during annealing, then exhibits the usual absorption decrease found for deeper defects. The maximum in this absorption at E ≤1.1eV occurs simultaneously with a transition from fast to slow recovery of photoconductivity. The absorption for E ≤1.1eV shows two distinct annealing activation energies: the signal rises with about 0.87 eV and falls with about 1.15 eV. The 0.87 eV activation energy roughly equals the activation energy for the dominant, fast, recovery of photoconductivity. The 1.15 eV activation energy roughly equals the single activation energy for annealing of the light-induced dangling bond absorption.

Proton NMR and proton-29Si double resonance NMR have been performed on hot wire a-Si:H films deposited from SiH4. Results are compared with those from conventional plasma enhanced chemical vapor deposition a-Si:H. Proton nutational angle studies and proton-29Si spin-echo double resonance (SEDOR) signals at 80 and 294 K indicate that a significant proton resonance population arises from T-site-trapped molecular H2. The hot wire films also display a ≥80 kHz FWHM uperbroad proton line and a sharp feature diamagnetically shifted by 25 ppm.

A novel concept of field aided lateral crystallization (FALC) and the effects of Cu on FALC of amorphous silicon (a-Si) were investigated. Cu was found to induce the lateral crystallization toward a metal-free region as well as the crystallization of a-Si in contact with Cu. In particular, the lateral crystallization caused by Cu was noticeably accelerated at the negative electrode side in every pattern with an aid of electric field, while it was retarded at the positive electrode side. The occurrence of Cu-FALC phenomenon was interpreted in terms of dominant diffusing species (DDS) in the reaction between metal and Si. The FALC velocity increased with the applied field intensity and the annealing temperature. The crystallization of a-Si was achieved at temperatures as low as 375°C when the annealing time increased in the presence of high electric field, above 30V/cm. Therefore, we could demonstrate the possibility of low temperature (<500°C) polycrystalline silicon (poly-Si) crystallization using Cu as a mediator in FALC technology.

This research is the first attempt at applying thermal plasma chemical vapor deposition (TPCVD) for the ultrafast deposition of Si films for solar cells. A conventional deposition process of Si films, such as plasma-enhanced chemical vapor deposition (PECVD), is capable of a maximum deposition rate of approximately 5 Å/s and it takes a relatively long time to deposit an intrinsic layer. In this paper we report a novel ultrafast deposition approach using dc-rf hybrid TPCVD. The extreme improvement of stability, controllability, and cleanliness of the process enabled the deposition of microcrystalline Si films at the ultrafast rate of over 1000 nm/s, which is about 2000 times faster than that by conventional CVD. Moreover, a minimum defect density of 7.2×1016 cm−3was achieved by post-treatment of the film in 2 Torr H2/Ar plasma. Monte-Carlo simulation and step coverage analysis suggested that the precursor is an approximately 1 nm cluster with a sticking probability of about 0.6. The success of this research will lead to the development of commercially viable technology in a roll-to-roll system in the near future, and will fundamentally change the established concepts of Si deposition technology.