We have demonstrated real-time process control of a-Si:H growth in an a-Si:H/c-Si heterojunction solar cell by spectroscopic ellipsometry (SE). Accurate thickness control of a-Si:H p-i layers with a precision better than ± Å has been realized by this technique. From real-time attenuated total reflection spectroscopy (ATR), we find the formation of a porous interface layer with a maximum SiH2-hydrogen content of 27 at.% at the a-Si:H/c-Si interface, although a rather high conversion efficiency of 14.6 % has been obtained in the solar cell. We found that an optimum i-layer thickness for the a-Si:H/c-Si solar cells is consistent with the thickness at which the a-Si:H i-layer growth reaches a steady state after the H-rich interface-layer formation. We have applied SE further to determine the dielectric functions of In2O3:Sn and ZnO:Ga with different carrier concentrations. From the dielectric function analysis, the effective mass m is extracted. We find linear increases in m as the carrier concentration of In2O3:Sn and ZnO:Ga increases. The validity of our analyses has been confirmed from excellent agreement between carrier concentrations determined by SE and Hall measurements. The construction of the optical database further enabled us to calculate a reflectance spectrum of the a-Si:H/c-Si solar cell accurately.

Based on various implanted standards, we have used SIMS (Secondary Ion Mass Spectrometry) to characterize amorphous Si thin films with high hydrogen content. SIMS and HFS (Hydrogen Forward Scattering) showed good agreement on the measured total H doses for H-implanted Si samples and the a-Si thin films. For the H-implanted Si samples, in the dose range of 2e15 atoms/cm2 to 2e17 atoms/cm2 (corresponding to peak H concentration from 0.32 at.% to 32 at.%), SIMS results showed that the calibration curve is a straight line. In other words, no correction for SIMS quantification is needed when moving from low to high hydrogen content samples. Analysis of P (Phosphorus) in a-Si thin films requires the use of high mass resolution magnetic sector SIMS to separate P and a mass interference from (30Si+H). Using a magnetic sector SIMS instrument, P-doped a-Si thin layers (˜ 50nm thick) were analyzed using 3keV O2 beam with oxygen leak for better depth resolution and improved detection limits. For the analysis of C, N, O in a-Si thin films (again approximately 50nm thick) the profiling energy typically needs to be lowered down to 3keV and the material needs to be sputtered at a high rate in order to reach real background levels. In this work, a-Si thin films were also analyzed using a 3keV Cs+ primary ion beam with (Cs2M)+ (M= C, N, O) detection for good depth resolution and detection limits.

In our previous publications [1, 2] nickel diffusion and spreading resistance probe (SRP) measurements for quality control of metal induced lateral crystallization (MILC) of amorphous silicon (a-Si) were studied. Now we present TCAD modeling and an explanation of experimental results. By using ISE TCAD the Ni concentration distributions were calculated and compared with results obtained by experiments using SIMS analysis.

In this work, we report on next-generation hot wire chemical vapor deposition technique, we call it ceramics hot-wire CVD. Using a new concept of rectangular ceramics filament holder and “confinement of thermal radiation from the filament”, a “new form” of polycrystalline silicon thin films has been developed at low temperature (˜ 250°C). The grains are found to be symmetrically distributed in array along the parallel lines, in (111) direction. On the surface of individual grains, “five-fold” and “six-fold” symmetries have been observed and we suspect that we developed “buckyball” type “giant silicon molecular solids” with different crystalline silicon lattice other than standard single-crystal silicon structure. We observed rarely found “icosaderal” symmetry in silicon thin films. This hypothesis has been supported by multiple Raman active transverse optical modes and the crystallographic structure analyzed by X-ray diffraction.

Nanocrystalline Ge and its alloys with C are potentially useful materials for solar cells, thin film transistors and image sensors. In this paper, we discuss the growth and properties of these materials using remote, low pressure ECR plasma deposition. The materials and devices were grown from mixtures of germane, methane and hydrogen. It was found that high hydrogen dilutions (>40:1) were needed to crystallize the films. Studies of x-ray spectra revealed that the grains were primarily <220> oriented. The grain size was a strong function of hydrogen dilution and growth temperature. Higher growth temperatures resulted in larger grain size. High hydrogen dilution tended to reduce grain size. These results can be explained by recognizing that excessive amounts of bonded H can inhibit the growth of <220> grain, which is the thermodynamically favorable direction for grain growth. Grain sizes as large as 80 nm were obtained in nc-Ge. Addition of C reduced the crystallinity. Mobility and carrier concentrations in nc-Ge were measured using Hall effect. Mobility values of ˜5 cm2/V-s and carrier concentrations of ˜1x1016/cm3 were obtained in larger grains. p+nn+ devices were fabricated on stainless steel substrates and compared with similar devices deposited in nc-Si:H. It was found that the voltage decreased and current increased in nc-Ge devices, in comparison with devices in nc-Si:H. Addition of C to Ge devices increased the open circuit voltage and shifted the quantum efficiency to larger photon energies, as expected.

In this paper we demonstrate a simple computational procedure for the simulation of transport in a disordered semiconductor in which both multi-trapping and hopping processes are occurring simultaneously. We base the simulation on earlier work on hopping transport, which used a Monte-Carlo method. Using the same model concepts, we now employ a stochastic matrix approach to speed computation, and include also multi-trapping transitions between localised and extended states. We use the simulation to study the relative contributions of extended state conduction (with multi-trapping) and hopping conduction (via localised states) to transient photocurrents, for various distributions of localised gap states, and as a function of temperature. The implications of our findings for the interpretation of transient photocurrents are examined.

In this paper, we present the results of Plasma Enhanced Chemical Vapor Deposition gate oxide (SiO2) integrity on ELC (excimer laser crystallized), MILC (metal induced lateral crystallized) and SPC (solid phase crystallized) polysilicon films. We observed that gate oxide strength of poly Si TFT strongly depends on the crystallization method for the active silicon layer. In the case of ELC films, asperities on the silicon surface reduce the SiO2 breakdown field significantly. The metallic contaminants in MILC films are responsible for a deleterious impact on gate oxide integrity. Among the three cases, the SiO2 breakdown field was the highest for the SPC silicon films. The breakdown fields at the 50% failure points in Weibull plots for the ELC, MILC and SPC cases were 5.1MV/cm, 6.2MV/cm, 8.1MV/cm, respectively. We conclude that the roughness and metallic contamination of the poly Si films are the main factors that cause en-hanced breakdown of SiO2 films.

Changes in the electrical conductivity of thin (< 300 nm) silicon films following prolonged exposure to atmosphere, are reported. Both reversible (by annealing at 150 °C under vacuum) and irreversible (annealing-resistant) effects are found to occur, which are larger in thinner films. The conductivity prefactor and thermal activation energy obey the Meyer-Neldel rule, although detailed behaviour depends on film thickness and microstructure. Irreversible changes may result from oxidation of thinner, more porous films, with water and/or oxygen adsorption and desorption responsible for reversible changes. The need to identify and account for these effects when discussing and formulating transport mechanisms in these materials is underlined.

Micro-crystalline silicon-germanium (μc-SiGe) films were prepared by the multi-target RF sputtering system using Ar and Ar-H2 mixture gases. The crystallization temperature of Si0.3Ge0.7 films is reduced from 600 °C to 400 °C by the introduction of H2 into the sputtering gases. The dark conductivity of 1.7x10-7 S/cm and one order of magnitude of photosensitivity are obtained with the H2/Ar flow ratio of 2. The activation energy of dark conductivity is 0.42 eV, which is a half of the energy gaps of Si0.3Ge0.7, and show that the films have intrinsic nature. Besides, the absorption coefficients are similar to those of single crystalline Si0.3Ge0.7. The results suggest that the H2 introduction is effective both to reduce the dangling bond defects and to decrease the crystallization temperature of the μc-SiGe films.

In undoped a-Si:H thin films, light soaking (LS) decreases dark current and photocurrent and increases the electron spin resonance signal monotonically with increasing exposure time, (Staebler-Wronski Effect, SWE). On the other hand, in porous silicon (PS) the light-soaking effect is non-monotonic. For short durations, LS increases dark current, photo current and photoluminescence and decreases the ESR signal. Long exposures of PS, however, have the opposite effect, which is similar to the SWE observed in a-Si:H. All metastabilities in PS as well as in a-Si:H can be removed by annealing, but not by exposure to infrared light. We find that the combined effect of NH3 vapor exposure and LS on PS yields a final state that depends upon the order in which the two steps are performed. This is in contrast to the corresponding observation in a-Si:H. We could arrest the light-induced degradation of PS over long times by coating with a thin polystyrene, which resulted in constant PL and ESR intensities. However, in the case of a-Si:H the polymer coating decreases the SWE, but does not eliminate it. The results can be understood, if we were to propose that LS affects the surface in PS, but affects mainly the bulk in a-Si:H.

We report on the growth of nanocrystalline Si:H films using both plasma CVD and remote hot wire deposition under systematically varied growth conditions. The films were grown from mixtures of silane and hydrogen. It was found that when the films were grown under low pressure VHF plasma growth conditions, the orientation of the film changed as the pressure increased. At the lowest pressures, the films were mainly <111> oriented, but changed to <220> orientation as the pressure increased. The grain size increased as the growth temperature increased. When the films were grown using remote hot wire deposition, the orientation depended upon both hydrogen dilution and growth temperature. As the hydrogen dilution increased, the <220> grain size became smaller. Grain size as large as 36 nm was obtained by controlling the growth conditions in hot wire deposition. As the growth temperature increased, the size of <220> grains increased. Growth rates also increased with increasing temperature. The data can be explained by invoking a growth model which recognizes that the natural growth direction for Si is <220>, since the surface energy is highest for (220) plane. Random nucleation leads to <220> grains. Bonded H is believed to inhibit the growth of <220> grains.

Growth of microcrystalline silicon (μc-Si) thin films with different preferential orientations has been studied employing XRD measurements versus thickness. The focus of this study is on the influence of preferential orientation on the film growth process. The (220) preferential orientation and randomly oriented μc-Si films studied here were prepared by VHF-PECVD at 180 °C. The thickness evolution revealed that the crystallinity was improved in the μc-Si with (220) preferential orientation μc-Si particularly in the first 0.5-μm of growth, while that in the randomly oriented μc-Si was almost completely unchanged. The difference in the crystallinity in the initial growth region arises from a difference in the growth mechanisms. Specifically, the growth of μc-Si with (220) preferential orientation can be elucidated by a hybrid-phase mode consisting of vapor- and solid-phase growth, whereas the growth of randomly oriented μc-Si can be achieved only by vapor-phase growth as occurs conventionally. Based on the growth mechanisms, the microstructures of μc-Si with both orientations and their influence on the photovoltaic performance are discussed.

Intrinsic microcrystalline silicon (μc-Si:H ) was prepared at high deposition rates (RD) by very high frequency plasma-enhanced chemical vapor deposition (PECVD) working at high-pressure high-power (hphP). The material has similar electrical and optical properties as μc-Si:H material deposited at low rates by low-pressure low-power PECVD, apart from a more pronounced structure in-homogeneity along the growth axis for material deposited on glass substrates. With optimized deposition conditions high efficiency solar cells can be grown with deposition rates of up to 15 Å/s without deterioration of the performance as a function of RD. A high conversion efficiency of 9.8 % was obtained for a single junction μc-Si:H p-i-n solar cell at a deposition rate of RD = 11 Å/s.

New types of transparent conductive oxides with low indices of refraction have been developed for use in optical stacks for the amorphous silicon (a-Si) solar cell and other thin film applications. The alloys are ZnO based with Si and MgF added to reduce the index of the materials through the creation of SiO2 or MgF2, with n=1.3-1.4, or the addition of voids in the materials. Alloys with 12-14% Si or Mg have indices of refraction at λ=800nm between 1.6 and 1.7. These materials are presently being used in optical stacks to enhance light scattering by Al/multi-layer/ZnO back reflectors in a-Si based solar cells to increase light absorption in the semiconductor layers and increase open circuit currents and boost device efficiencies. In contrast to Ag/ZnO back reflectors which have long term stability issues due to electromigration of Ag, these Al based back reflectors should be stable and usable in manufactured PV products. In this manuscript, structural properties for the materials will be reported as well as the performance of solar cell devices made using these new types of materials.

RF glow discharge deposited hydrogenated amorphous silicon films containing silicon nanocrystalline inclusions (a/nc-Si:H) films are investigated as a function of a thermal gradient applied across the silane plasma during film growth. The a/nc-Si:H films are synthesized from hydrogen-diluted silane plasmas when a capacitively-coupled plasma enhanced chemical vapor deposition reactor is operated at high gas chamber pressures. Plasma diagnostics and transmission electron microscopy image analysis of films deposited with and without a thermal gradient suggest that nanoparticle formation occurs within the plasma, rather than resulting from solid-state nucleation at the growing film surface.

Microcrystalline silicon carbide (μc-SiC) was prepared at substrate temperatures between 300°C and 450°C using Hot Wire Chemical Vapour Deposition (HWCVD). The SiC films were deposited from monomethylsilane (MMS) diluted in hydrogen on glass and crystalline silicon substrates. The influence of the hydrogen dilution on the deposition rate and the structural and the optoelectronic properties was investigated. Infrared and Raman spectroscopy and transmission electron microscopy (TEM) were applied to study the structural properties. Highly crystalline material with large columnar grains was obtained at high hydrogen dilutions. The optical absorption below the band gap is high and the dark conductivities are far above the values expected for intrinsic SiC. At lower hydrogen dilution, less crystalline or amorphous Si1-xCx is growing, showing broader IR- and Raman peaks, lower dark conductivity and higher absorption above the band gap energy. An extended nucleation zone with large structural disorder was observed even for highly crystalline material.

The photoluminescence spectra due to Er ions doped in a-Si:H were decomposed into several lines. The 19-K spectrum was reproduced by adding four Gaussian lines whose linewidths were increased with decreasing the photon energy. Since only the lowest energy level of 4I13/2 contributes to the radiative transition at this low temperature, the energy levels in 4I15/2 split by the Stark effect can be determined. These splittings are not largely different from those for Er in aluminosilicate glass. This implies that the all nearest neighbors of Er are oxygens which have been introduced unintentionally in the sample during preparation. The change in the photoluminescence intensity by annealing is discussed in relation with the spectral change and the results of ESR measurements.

We have studied silicon films grown epitaxially on silicon wafers using hot-wire chemical vapor deposition (HWCVD) with a tantalum filament. Silicon films were grown on (100)-oriented hydrogen terminated silicon wafers at temperatures from 175°C to 480°C, using a Ta filament 5 cm from the substrate to decompose pure SiH4 gas. The progression of epitaxy was monitored using real-time spectroscopic ellipsometry (RTSE). Analysis using RTSE, transmission electron microscopy (TEM), and scanning electron microscopy shows that at a characteristic thickness, hepi all of the films break down into a-Si:H cones. Below 380°C, both hepi and the thickness of the transition to pure a-Si:H increase with increasing temperature. Above 380°C, hepi was not observed to increase further but TEM images show fewer defects in the epitaxial regions. Secondary ion-mass spectrometry shows that the oxygen concentration remains nearly constant during growth (<1018 cm-3). The hydrogen concentration is found to increase substantially with film thickness from 5·1018 to 5·1019 cm-3, likely due to the incorporation of hydrogen into the a-Si:H cones that grow after the breakdown of epitaxy.

We measure times for complete solid phase crystallization (SPC) of hydrogenated amorphous silicon (a-Si:H) thin films that vary eight orders of magnitude, from a few ms to a few days. The time-to-crystallization activation energy is consistent with literature values of approximately 3.4 eV but the prefactor is markedly different for hot-wire chemical vapor deposition (HWCVD) films than for plasma-enhanced (PE) CVD films. The crystallized films were 0.3 – 2 μm thick, and deposited by high deposition rate (10-100 Å/s) HWCVD or standard PECVD onto glass substrates. We annealed these a-Si:H films over a wide temperature range (500 to 1100 °C) using techniques including simple hot-plates and tube furnaces, rapid thermal annealing by a tungsten-halogen lamp, and microwave electromagnetic heating at 2.45 GHz (magnetron) and 110 GHz (gyrotron).

We studied the correlation of in and ex situ stress to microstructures during Al-induced crystallization for structures of Al on top (AOT) and Al on bottom (AOB) of amorphous Si (a-Si) on 3000 Å SiO2 coated on Si wafers and found that a-Si deposited on PECVD SiO2 and Al increases the stress compressively, and Al deposited on PECVD SiO2 and on a-Si decreases the stress tensilely. In addition, the stress of AOB structures is in general less than that of AOT structures. Correlation of stress to microstructures indicated that the difference in microstructures between AOT and AOB results from the nature of the layer structures themselves. By using modified Stoney's equation, the lower stress of AOB structures than AOT could be explained with existence of oxide between a-Si and Al for both AOT and AOB structures.