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We report on our systematic study of light trapping effects using Ag/ZnO BRs for nc-Si:H solar cells. The texture of Ag and ZnO was optimized to achieve enhancement in photocurrent. The light trapping effect on photocurrent enhancement in solar cells was carefully investigated. Comparing to single-junction solar cells deposited on flat stainless steel substrates, the gain in Jsc by using Ag/ZnO BRs is 57% for nc-Si:H solar cells. This gain in Jsc is much higher than what has been achieved by advanced light trapping approaches using photonic structures or plasmonic light trapping reported in the literature. We achieved a Jsc of 29-30 mA/cm2 in a nc-Si:H single-junction solar cell with an intrinsic layer thickness of ∼2.5 μm. We compared the quantum efficiency of single-junction cells to the classical limit of fully randomized scattering and found that there is a 6-7 mA/cm2 difference between the measured Jsc and the classical limit, in which 3-4 mA/cm2 is in the long wavelength region. However, by taking into consideration the losses from reflection of the top contact, absorption in the doped layers, and imperfect reflection in the BRs, the difference disappears. This implies we have reached the practical limit if the scattering from randomly textured substrates is the only mechanism of light trapping. Therefore, we believe future research for improving photocurrent should be directed toward reducing (i) reflection loss by the top contact, the absorption in ZnO and at the Ag/ZnO interface, and (ii) p layer absorption.
We report the results of using n-type hydrogenated nanocrystalline silicon oxide alloy (nc-SiOx:H) in hydrogenated nanocrystalline silicon (nc-Si:H) and amorphous silicon germanium alloy (a-SiGe:H) single-junction solar cells. We used VHF glow discharge to deposit nc-SiOx:H layers on various substrates for material characterizations. We also used VHF glow discharge to deposit the intrinsic layer in nc-Si:H solar cells. RF glow discharge was used for the deposition of the doped layers and the intrinsic layer in a-SiGe:H solar cells. Various substrates such as stainless steel (SS), Ag coated SS, and ZnO/Ag coated SS were used for different cell structures. We found that by using nc-SiOx:H to replace the ZnO and the a-Si:H n-layer in nc-Si:H solar cells, the cell structure is greatly simplified, while the cell performances remain nearly identical to those made using the conventional n-i-p structure on standard ZnO/Ag BR’s. Solar cells with nc-SiOx:H as the n layer directly deposited on textured Ag show similar quantum efficiency (QE) as the n-i-p cells on ZnO/Ag BRs. In both cases, QE is higher than that in the n-i-p cells made directly on Ag coated SS. This effect is probably caused by the shift of surface plasmon-polariton resonance frequency due to the difference in index of refraction of ZnO, nc-SiOx:H, and Si.
Multi-junction solar cells incorporating hydrogenated nanocrystalline silicon (nc-Si:H) exhibit a high current capability and low light-induced degradation. In this paper, we report our recent progress in developing nc-Si:H solar cells using a modified very-high-frequency glow discharge technique. We achieved a short-circuit current density >30 mA/cm2and 10.6% conversion efficiency from single-junction solar cells. Using the improved nc-Si:H cells in an a-Si:H/nc-Si:H/nc-Si:H triple-junction structure, we attained initial and stabilized efficiencies of 13.9% and 13.6%, respectively. Issues related to improving material properties and device structures are addressed. Besides using the conventional techniques, such as hydrogen dilution profiling, optimized Ag/ZnO back reflector, and buffer layers, we found that compensation from Boron and Oxygen micro-doping is also critical in obtaining the above achievements.
We have measured electron drift in amorphous silicon-germanium nip photodiodes using the photocarrier time-of-flight technique. The samples show electron deep-trapping shortly after photogeneration, which is generally attributed to capture by a neutral dangling bond (D0) to form a negatively charged center (D-). An unusual feature is that electron re-emission from the trap is also clearly seen in the transients. Temperature-dependent measurements on the emission yield an activation energy of about 0.8 eV and the remarkably large value of 1015 Hz for the emission prefactor frequency. We also compiled results on electron emission from deep traps in a-Si:H, a-SiGe:H, and a-SiC:H from six previous publications. Collectively, these measurements exhibit "Meyer Neldel" behavior for electron emission over a range of activation energies from 0.2–0.8 eV and a prefactor range extending over nine decades, from 106 to 1015 Hz. The Meyer-Neldel behavior is consistent with the predictions of the multi-excitation entropy model. We extract a ionization entropy of 20kB from the measurements, which is very large compared to crystal silicon. We discuss this result in terms of a bond charge model.
The last decade has witnessed tremendous progress in the science and technology of thin film silicon (amorphous and nanocrystalline) photovoltaic. The shipment of solar panels using this technology was about 200 MW in 2009; based on announcement of new or expanded production capacity, the shipment is projected to grow ten-times in the next 3-5 years. The key factor that will determine the wide-scale acceptance of the products will be the cost of solar electricity achieved using this technology. Efficiency of solar modules and throughput of production equipment will play a key role. In this paper, we discuss our roadmap to improve the product efficiency and machine throughput.
We have examined a series of a Si,Ge:H alloy devices deposited using both RF and VHF glow discharge in two configurations: SS/n+/i (a-SiGe:H)/p+/ITO nip devices and SS/n+/i (a-SiGe:H)/Pd Schottky contact devices, over a range of deposition rates. We employed drive-level capacitance profiling (DLCP), modulated photocurrent (MPC), and transient junction photo-current (TPI) measurement methods to characterize the electronic properties in these materials. The DLCP profiles indicated quite low defect densities (mid 1015 cm-3. to low 1016 cm-3 depending on the Ge alloy fraction) for the low rate RF (∼1Å/s) deposited a-SiGe:H materials. In contrast to the RF process, the VHF deposited a-SiGe:H materials did not exhibit nearly as rapid an increase of defect density with the deposition rate, remaining well below 1017 cm-3. up to rates as high as 10Å/s. Simple examination of the TPI spectra on theses devices allowed us to determine valence band-tail widths.. Modulated photocurrent (MPC) obtained for several of these a-SiGe:H devices allowed us to deduce the conduction band-tail widths. In general, the a-Si,Ge:H materials exhibiting narrower valence band-tail widths and lower defect densities correlated with the best device performance.
We report recent progress on hydrogenated nanocrystalline silicon (nc-Si:H) solar cells prepared at different deposition rates. The nc-Si:H intrinsic layer was deposited, using a modified very high frequency (MVHF) glow discharge technique, on Ag/ZnO back reflectors (BRs). The nc-Si:H material quality, especially the evolution of the nanocrystallites, was optimized using hydrogen dilution profiling. First, an initial active-area efficiency of 10.2% was achieved in a nc-Si:H single-junction cell deposited at ~5 Å/s. Using the improved nc-Si:H cell, we obtained 14.5% initial and 13.5% stable active-area efficiencies in an a-Si:H/nc-Si:H/nc-Si:H triple-junction structure. Second, we achieved a stabilized total-area efficiency of 12.5% using the same triple-junction structure but with nc-Si:H deposited at ~10 Å/s; the efficiency was measured at the National Renewable Energy Laboratory (NREL). Third, we developed a recipe using a shorter deposition time and obtained initial 13.0% and stable 12.7% active-area efficiencies for the same triple-junction design.
We present the progress made in attaining high-efficiency large-area nc-Si:H based multi-junction solar cells using Modified Very High Frequency technology. We focused our effort on improving the spatial uniformity and homogeneity of nc-Si:H film growth and cell performance. We also conducted both indoor and outdoor light soaking studies and achieved 11.2% stabilized efficiency on large-area (≥400 cm2) encapsulated a-Si:H/nc-Si:H/nc-Si:H triple-junction cells.
We investigate the effect of hydrogenation of grain boundaries on the performance of solar cells for hydrogenated nanocrystalline silicon (nc-Si:H) thin films. Using hydrogen effusion, we found that the amplitude of the lower temperature peak in the H-effusion spectra is strongly correlated to the open-circuit voltage in solar cells. This is attributed to the hydrogenation of grain boundaries in the nc-Si:H films.
A layer of silver nanoparticles created by thermal annealing of evaporated silver films can increase the photocurrents in silicon-on-insulator (SOI) devices by fivefold or more, but significant enhancements have been restricted to wavelengths greater than 800 nm. Here we report a significant enhancement of photoconductance at shorter wavelengths (500-750 nm) by using a monolayer of silver nanoparticles transferred from a colloidal suspension. Photocurrents on SOI increased in the 500-750 nm spectral range with the addition of silver nanoparticles, with enhancements more than two times; enhancements at longer wavelengths were small, in contrast to results with annealed silver films. We prepared similar colloidal silver nanoparticle monolayers layers on nanocrystalline silicon solar cells with conducting oxide top layers. There is an overall decrease in the quantum efficiency of these cells with the deposition of silver nanoparticles. We attribute these effects to the substantial substrate-mediated changes in the localized surface plasmon resonance frequencies of the differing nanoparticle configurations.
Quantum efficiency measurements in (nc-Si:H) solar cells deposited onto textured substrates indicate that these cells are close to the “stochastic light-trapping limit“ proposed by Yablonovitch in the 1980s. An interesting alternative to texturing is “plasmonic“ light-trapping based on non-textured cells and using an overlayer of metallic nanoparticles to produce light-trapping. While this type of light-trapping has not yet been demonstrated for nc-Si:H solar cells, significant photocurrent enhancements have been reported on silicon-on-insulator devices with similar optical properties to nc-Si:H. Here we report our work on the measurerements of quantum efficiencies in nc-Si:H solar cells and normalized photoconductance spectra in SOI photdetectors with and without silver nanoparticle layers. As was done previously, the silver nanoparticles were created by thermal annealing of evaporated silver thin films. We observed enhancement in the normalized photoconductance spectra of SOI photodetectors at longer wavelengths with the silver nanoparticles. For nc-Si:H solar cells, we have not yet observed significant improvement of the quantum efficiency with the addition of annealed silver films.
We have used small-angle x-ray scattering (SAXS) in conjunction with X-ray diffraction (XRD) to study the nanostructure of hydrogenated nanocrystalline silicon (nc-Si:H). The crystallite size in the growth direction, as deduced from XRD data, is 24 nm with a preferred  orientation in the growth direction of the film. Fitting the SAXS intensity shows that the scattering derives from electron density fluctuations of both voids in the amorphous phase and H-rich clusters in the film, probably at the crystallite interfaces. The SAXS results indicate ellipsoidal shaped crystallites about 6 nm in size perpendicular to the growth direction. We annealed the samples, stepwise, and then measured the SAXS and ESR. At temperatures below 350◦C, we observe an overall increase in the size of the scattering centers on annealing but only a small change in the spin density, which suggests that bond reconstruction on the crystallite surfaces takes place with high efficacy.
Hydrogenated nano-crystalline silicon (nc-Si:H) is a promising material for multi-junction solar cells. We investigated the local hydrogen environments in nano-crystalline silicon thin films by nuclear-magnetic-resonance (NMR). At room temperature, 1H NMR spectra have broader components than those observed in standard device grade hydrogenated amorphous silicon (a-Si:H). As the temperature decreases, the 1H NMR exhibits a broadening of the line shape attributed to hydrogen atoms at the interfaces between the amorphous silicon (a-Si) and the crystalline silicon (c-Si) regions. These results suggest that the local hydrogen structure in nc-Si:H is very different from that in a-Si:H. In particular, the hydrogen clusters contributing to broadened spectra may exist on the surfaces of the a-Si/c-Si interfaces which do not exist in the more dense matrix of a-Si:H and may contribute to certain unique optoelectronic properties of these nc-Si:H thin films. The dependence of the spin-lattice relaxation time (T1) on temperature, however, is very similar to that in a-Si:H, which indicates the spin-lattice relaxation mechanism, i.e via spin diffusion through molecular hydrogen, is common to both systems.
Sparse arrays of evaporated silver nanodiscs were fabricated with nanosphere lithography (NSL) on glass substrates and on hydrogenated nanocrystalline silicon solar cells. The optical transmittance spectra for arrays on glass vary substantially with film thickness, and were reasonably consistent with previous work. The quantum efficiency spectra of hydrogenated nanocrystalline silicon solar cells show spectral shifts due to coupling of surface plasmons in the metal nanodiscs to the planar waveguide modes of the cells, with overall photocurrent enhancement up to 10%.
We report our investigations of large area multi-junction solar cells based on hydrogenated nano-crystalline silicon (nc-Si:H). We compared results from cells deposited by RF (13.56 MHz) at lower deposition rate (˜3 Å/s) and by Modified Very High Frequency (MVHF) at higher rate (≥ 10 Å/s). With optimized process conditions and cell structures, we have obtained ˜12% initial small active-area (˜0.25 cm2) efficiency for both RF and MVHF cells and 10˜11% large aperture-area (˜400 cm2) encapsulated MVHF cell efficiency for both a-Si:H/nc-Si:H double-junction and a-Si:H/nc-Si:H/nc-Si:H triple-junction structures on Ag/ZnO coated stainless steel substrate.
We report our recent progress on nc-Si:H single-junction and a-Si:H/nc-Si:H/nc-Si:H triple-junction cells made by a modified very-high-frequency (MVHF) technique at deposition rates of 10-15 Å/s. First, we studied the effect of substrate texture on the nc-Si:H single-junction solar cell performance. We found that nc-Si:H single-junction cells made on bare stainless steel (SS) have a good fill factor (FF) of ˜0.73, while it decreased to ˜0.65 when the cells were deposited on textured Ag/ZnO back reflectors. The open-circuit voltage (Voc) also decreased. We used dark current-voltage (J-V), Raman, and X-ray diffraction (XRD) measurements to characterize the material properties. The dark J-V measurement showed that the reverse saturated current was increased by a factor of ˜30 when a textured Ag/ZnO back reflector was used. Raman results revealed that the nc-Si:H intrinsic layers in the two solar cells have similar crystallinity. However, they showed a different crystallographic orientation as indicated in XRD patterns. The material grown on Ag/ZnO has more random orientation than that on SS. These experimental results suggested that the deterioration of FF in nc-Si:H solar cells on textured Ag/ZnO was caused by poor nc-Si:H quality. Based on this study, we have improved our Ag/ZnO back reflector and the quality of nc-Si:H component cells and achieved an initial and stable active-area efficiencies of 13.4% and 12.1%, respectively, in an a-Si:H/nc-Si:H/nc-Si:H triple-junction cell.
We have developed high efficiency large area a-Si:H and a-SiGe:H multi-junction solar cells using a Modified Very High Frequency (MVHF) glow discharge process. We conducted a comparative study for different cell structures, and compared the initial and stable performance and light-induced degradation of solar cells made using MVHF and RF techniques. Besides high efficiency, the MVHF cells also demonstrate superior light stability, showing <10% degradation after 1000 hour of one-sun light soaking at 50 °C. We also studied light-induced defect level and hydrogen evolution characteristics of MVHF deposited a-SiGe:H films and compared them with the RF deposited films.
Significant advances have been made in increasing the deposition rate of hydrogenated silicon germanium alloys (a-SiGe:H) using a modified VHF glow discharge deposition method while also maintaining good electronic properties important for its application in photovoltaic devices. We examine the electrical and optical properties of these alloys deposited either by RF (13.56MHz) or the modified VHF methods over deposition rates varying from 1 to 10 Å/s. The electronic properties of a series of 1.4 eV optical gap a-SiGe:H i-layers, in many cases in solar cell device configurations, were characterized. Drive-level capacitance profiling was used to determine the deep defect densities, and transient photocapacitance measurements allowed us to determine the Urbach energies. Results were obtained for both the annealed and light-soaked degraded states and these results were correlated to the cell performance parameters. In general the a-SiGe:H layers deposited using the modified VHF excitation exhibited improved electronic properties at higher growth rates than the RF deposited samples.
Light trapping effect in hydrogenated amorphous silicon-germanium alloy (a-SiGe:H) and nano-crystalline silicon (nc-Si:H) thin film solar cells deposited on stainless steel substrates with various back reflectors is reviewed. Structural and optical properties of the Ag/ZnO back reflectors are systematically characterized and correlated to solar cell performance, especially the enhancement in photocurrent. The light trapping method used in our current production lines employing an a-Si:H/a-SiGe:H/a-SiGe:H triple-junction structure consists of a bi-layer of Al/ZnO back reflector with relatively thin Al and ZnO layers. Such Al/ZnO back reflectors enhance the short-circuit current density, Jsc, by ˜20% compared to bare stainless steel. In the laboratory, we use Ag/ZnO back reflector for higher Jsc and efficiency. The gain in Jsc is about ˜30% for an a-SiGe:H single-junction cell used in the bottom cell of a multi-junction structure. In recent years, we have also worked on the optimization of Ag/ZnO back reflectors for nano-crystalline silicon (nc-Si:H) solar cells. We have carried out a systematic study on the effect of texture for Ag and ZnO. We found that for a thin ZnO layer, a textured Ag layer is necessary to increase Jsc, even though the parasitic loss is higher at the Ag and ZnO interface due to the textured Ag. However, a flat Ag can be used for a thick ZnO to reduce the parasitic loss, while the light scattering is provided by the textured ZnO. The gain in Jsc for nc-Si:H solar cells on Ag/ZnO back reflectors is in the range of ˜60-75% compared to cells deposited on bare stainless steel, which is much larger than the enhancement observed for a-SiGe:H cells. The highest total current density achieved in an a-Si:H/a-SiGe:H/nc-Si:H triple-junction structure on Ag/ZnO back reflector is 28.6 mA/cm2, while it is 26.9 mA/cm2 for a high efficiency a-Si:H/a-SiGe:H/a-SiGe:H triple-junction cell.
Phosphorus and Boron doping effects on the microstructure of nanocrystallites in hydrogenated amorphous and nanocrystalline mixed-phase silicon films were investigated using Raman spectroscopy, secondary ion mass spectrometry, cross-sectional transmission electron microscopy, atomic force microscopy, and conductive atomic force microscopy. The characterizations revealed the following observations. First, the mixed-phase Si:H films can be heavily doped in ˜1021/cm3 by adding PH3 and BF3 in the precursor gases. Second, the intrinsic and doped films can be made in a similar crystalline volume fraction by adjusting hydrogen dilution ratio. The hydrogen dilution ratio is much higher for P-doped films than for the intrinsic film with the similar crystallinity. Third, the doping impacts the nanostructures in the films significantly. Nanograins aggregate to form cone-shaped clusters in the intrinsic and B-doped films but isolate and randomly distribute in amorphous tissues in the P-doped films. The cones in the intrinsic and B-doped films are also different. The cone-angle is smaller and the nanograin density is lower in the B-doped films than in the intrinsic films. These P- and B-doping effects on the nanocrystalline formation are interpreted in terms of diffusions of Si-related radicals during the film growth.