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Fast epitaxial growth of several microns thick Si at glass-compatible temperatures by the hot-wire CVD technique is investigated, for film Si photovoltaic and other applications. Growth temperature determines the growth phase (epitaxial or disordered) and affects the growth rate, possibly due to the different hydrogen coverage. Stable epitaxy proceeds robustly in several different growth chemistry regimes at substrate temperatures above 600°C. The resulting films exhibit low defect concentrations and high carrier mobilities.
Solid-phase crystallization (SPC) rates are compared in amorphous silicon films prepared by three different methods: hot-wire chemical vapor deposition (HWCVD), plasma-enhanced chemical vapor deposition (PECVD), and electron-beam physical vapor deposition (e-beam). Random SPC proceeds approximately 5 and 13 times slower in PECVD and e-beam films, respectively, as compared to HWCVD films. Doping accelerates random SPC in e-beam films but has little effect on the SPC rate of HWCVD films. In contrast, the crystalline growth front in solid-phase epitaxy experiments propagates at similar speed in HWCVD, PECVD, and e-beam amorphous Si films. This strongly suggests that the observed large differences in random SPC rates originate from different nucleation rates in these materials while the grain growth rates are relatively similar. The larger grain sizes observed for films that exhibit slower random SPC support this suggestion.
We incorporate narrow-gap amorphous silicon germanium (a-SiGe:H) alloys grown by hot-wire chemical vapor deposition (HWCVD) into single-junction n-i-p solar cells, and improve both fill factor (FF) and open-circuit voltage (Voc) by bandgap grading. The Tauc bandgap (ET) of the a-SiGe:H is as low as about 1.25 eV. Previously , we obtained a short-circuit current density (Jsc) up to 20 mA/cm2 in an n-i-p device incorporating an ungraded 120-nm i-layer of 1.25-eV a-SiGe:H. However, without buffer layers or bandgap profiling, the fill factor was only 38%, likely due to an abrupt bandgap transition and poor hole collection. To overcome these problems, we have used composition bandgap profiling throughout the i-layer and improved both Voc and FF significantly without any Jsc loss. The solar cell efficiency is improved from 3.55% to 5.85% and Voc rises from 0.475 to 0.550 eV. This improved single-junction a-SiGe:H solar cell has a quantum efficiency of about 48% at l=800 nm and about 15% at l=900 nm. We present details of the bandgap profiling and its effect on device performance.
We have found that narrow-bandgap—1.25 < Tauc Gap < 1.50 eV—amorphous silicon germanium (a-SiGe:H) alloys grown by hot-wire chemical vapor deposition (hot-wire CVD) can be improved by lowering both substrate and filament temperatures. We systematically study films deposited using a one-tungsten filament, decreasing filament temperature (Tf) from our standard temperature of 2150° down to 1750°C, and fixing all other deposition parameters. By decreasing Tf at the fixed substrate temperature (Ts) of 180°C, the Ge-H bonding increases, whereas the Si-H2 bonding is eliminated. Films with higher Ge-H bonding and less Si-H2 have improved photoconductivity. For the series of films deposited using the same germane gas fraction at 35%, the energy where the optical absorption is 1x104 (E04) drops from 1.54 to 1.41 eV with decreasing Tf. This is mainly due to the combination of an increasing Ge solid fraction (x) in the film, and an improved homogeneity and compactness due to significant reduction of microvoids, which was confirmed by small angle X-ray scattering (SAXS). We also studied a series of films grown by decreasing the Ts from our previous standard temperature of 350°C down to 125°C, fixing all other deposition parameters including Tf at 1800°C. By decreasing Ts, both the total hydrogen content (CH) and the Ge-H bonding increased, but the Si-H2 bonding is not measurable in the Ts range of 180°-300°C. The E04 increases from 1.40 to 1.51 eV as Ts decreased from 350° to 125°C, mainly due to the increased total hydrogen content (CH). At the same time, the photo-to-dark conductivity ratio increases almost three orders of magnitude over this range of Ts.
We find that hydrogen diffuses as H+, H0, or H- in hydrogenated amorphous silicon depending on its location within the i-layer of a p-i-n device. We annealed a set of five p-i-n devices, each with a thin deuterium-doped layer at a different location in the i-layer, and observed the D-diffusion using secondary ionmass spectrometry (SIMS). When H-diffuses in a charged state, electric fields in the device strongly influence the direction and distance of diffusion. When D is incorporated into a device near the p-layer, almost all of the D-diffusion occurs as D+, and when the D is incorporated near the n-layer, most of the D-diffusion occurs as D-. We correlate the preferential direction of D-motion at given depth within the i-layer, with the local Fermi level (as calculated by solar cell simulations), to empirically determine an effective correlation energy for mobile-H electronic transitions of 0.39 ± 0.1 eV. Using this procedure, the best fit to the data produces a disorder broadening of the transition levels of ∼0.25 eV. The midpoint between the H0/+ and the H0/- transition levels is ∼0.20 ± 0.05 eV above midgap.
Measurements of cosmogenic nuclides made in situ in the Earth's surface are being used to help resolve a wide range of geologic and chronologic questions. Cosmogenic nuclides (3He, 10Be, 14C, 21Ne, 26Al 36C1 are presently used) can reveal rock exposure history information leading to estimates of timing of surface forming events, rates and styles of erosion, and timing and durations of episodes of burial. Depending on the problems being tackled, a significant source of error (±10–25%) for any cosmogenic nuclide method is the present uncertainty in the spatial and temporal variability of the rates of production of these in-situ nuclides.
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