Cross-contamination in single-chamber processes for thin-film silicon solar cells

Boron (B) and phosphorus (P) cross-contamination for single-chamber deposited a-Si:H, μc-Si:H, and a-Si:H/μc-Si:H tandem solar cells has been investigated by studying their impact on the different layers of solar cells. To reduce the B and P cross-contamination into the i-layer and p-layer, respectively, to a tolerable level, for a-Si:H and μc-Si:H cells a 15' evacuation cycle prior to the i-layer deposition is applied. The effect of P cross-contamination into the i-layer is strongly reduced by the p-layer deposition and a 15’ evacuation cycle prior to the i-layer deposition. The p-layer is assumed to cover up or to fix (in form of P-B complexes) most of the P at the chamber walls. This leads to high quality μc-Si:H cells and a-Si:H cells with only slightly reduced performance. Here, a soft-start of the a-Si:H i-layer led to high quality cells, presumably due to reduced P recycling. Further, there is no need to clean the process chamber with, e.g. NF₃, after each p-layer, as applied in many industrial processes. Instead, many cells are deposited without cleaning the process chamber. We established a single-chamber tandem cell process with 15' evacuation cycles prior to the μc-Si:H p-layer and to each i-layer with a cell efficiency of ~ 11.1%.     

Drift-mobility characterization of silicon thin-film solar cells using photocapacitance

We have applied the photocapacitance method to the measurements of hole drift-mobilities in silicon solar cells. We found a simple analysis that yields drift-mobilities even in the presence of anomalously dispersive transport. On one thick sample we measured the hole drift-mobility using both the photocapacitance and the time-of-flight methods; the two methods gave results that were consistent with each other and with the established bandtail multiple-trapping model. We then applied the method to thinner samples that are more characteristic of the conditions in solar modules, but are not generally usable for the time-of-flight method. These samples showed much smaller hole drift-mobilities than expected from the bandtail trapping model. We speculate that the hole drift-mobility has smaller values in regions close to the substrate during deposition than has been reported for thicker samples.     

Improved light absorption in thin-film silicon solar cells by integration of silver nanoparticles

Silver nanoparticles, produced by thermal evaporation and a subsequent annealing treatment, were integrated at the back side of thin-film silicon solar cells. Metallic nanoparticles can lead to (i) a strong enhancement of the electric field in their surrounding when they are irradiated by light and (ii) significant scattering of the light when they have the proper diameter (>100 nm). In this study, we investigated the optical properties of two types of substrates, one with large and well separated ellipsoidal silver nanoparticles (with average lateral size of 300 nm), and the other with silver nanostructures connected to each other. Furthermore, these substrates were used as back reflectors in microcrystalline silicon solar cells in substrate (n–i–p) configuration.     

Improvement of amorphous silicon n-i-p solar cells by incorporating double-layer hydrogenated nanocrystalline silicon structure

We develop a double-layer p-type hydrogenated nanocrystalline silicon (p-nc-Si:H) structure consisting of a low hydrogen diluted i/p buffer layer and a high hydrogen diluted p-layer to improve the hydrogenated amorphous silicon (a-Si:H) n-i-p solar cells. The electrical, optical and structural properties of p-nc-Si:H films with different hydrogen dilution ratio (R_H) are investigated. High conductivity, low activation energy and wide band gap are achieved for the thin films. Raman spectroscopy and high-resolution transmission electron microscopy (HRTEM) analyses indicate that the thin films contain nanocrystallites with grain size around 3-5 nm embedded in the amorphous silicon matrix. By inserting a p-nc-Si:H buffer layer at the i/p interface, the overall performance of the solar cell is improved significantly compared to the bufferless cell. The improvement is correlated with the reduction of the density of defect states at the i/p interface.     

Properties of thin-film silicon solar cells at very high irradiance

The focussed beam of a low-power helium–neon laser is used to study accelerated light-induced degradation (Staebler–Wronski effect) and high steady-state photocarrier generation rates in amorphous and microcrystalline silicon thin-film solar cells, at up to 13 MW m^? 2 irradiance. Even at these high power densities, COMSOL® simulations indicate that heat diffusion into the substrate, aided by spreading conduction via the Ag back-contact, restricts the temperature rise to less than 14 °C. Short-circuit current may be measured directly, and the I–V characteristic estimated by taking into account shunting by the inactive part of the cell. The improved resistance to degradation of microcrystalline silicon cells is shown to persist to high irradiance. Computer simulations of an amorphous silicon solar cell are presented that are consistent with measured un-degraded and degraded properties, and offer insight into prevailing defect creation processes and carrier recombination mechanisms.     

Micro-Raman mapping on layers for crystalline silicon thin-film solar cells

Micro-Raman mappings have been used for characterization of our layers system developed for thin-film silicon solar cells. For the cubic SiC barrier layer a preferential orientation of the grains in 〈1 1 1〉 direction normal to the substrate was revealed. A high density of stacking faults resulted in the splitting of transversal optical (TO)-phonon modes, usually only observed in several non-cubic SiC polytypes. Within the silicon layers, which were obtained by zone melting recrystallization (ZMR) and subsequent epitaxial growth, a high residual stress of about 625 MPa was measured near the boundary towards the SiC layer. Outside of this boundary no residual stress could be detected, in spite of commonly found twin boundaries. Thus the main origin of residual stress in the silicon layers is due to the different expansion coefficients of the respective layers, while grain boundaries have no dominant effect.     

Structural characterization of amorphous silicon nitride by molecular dynamics simulation

Computer simulation, using the molecular dynamics (MD) technique, has been carried out on amorphous silicon nitride (a-Si₃N₄) with simple Busing-type potentials. From the MD simulation, the following points have been deduced. (1) The average Si---N bond length obtained from MD results is r_Si---N=1.74 Å, and its coordination number, N_Si---N, is 3.95. The bond angles around a Si and a N atom, N---Si---N and Si---N---Si, are found to be 109.8° ± 12.36° and 127.08° ± 16.63°, respectively. The N---Si---N value obtained is in very good agreement with the tetrahedral bond angle (= 109.47°). Hence, the short-range structural arrangement of a-Si₃N₄ comprises tetrahedral SiN₄ units. The MD results presented in this study also indicate that there exist only a small number of defects such as dangling bonds. (2) These MD results are in good agreement with the reported X-ray and neutron data. The a-Si₃N₄ structure can be reproduced by the MD simulation given in this study.     

Hole mobilities and the physics of amorphous silicon solar cells

The effects of low hole mobilities in the intrinsic layer of pin solar cells are illustrated using general computer modeling; in these models electron mobilities are assumed to be much larger than hole values. The models reveal that a low hole mobility can be the most important photocarrier transport parameter in determining the output power of the cell, and that the effects of recombination parameters are much weaker. Recent hole drift-mobility measurements in a-Si:H are compared. While hole drift mobilities in intrinsic a-Si:H are now up to tenfold larger than two decades ago, even with recent materials a-Si:H cells are low-mobility cells. Computer modeling of solar cells with parameters that are consistent with drift-mobility measurements give a good account for the published initial power output of cells from United Solar Ovonic Corp.; deep levels (dangling bonds) in the intrinsic layer were not included in this calculation. Light-soaking creates a sufficient density of dangling bonds to lower the power from cells below the mobility limit, but in contemporary a-Si:H solar cells degradation is not large. We discuss the speculation that light-soaking is ‘self-limiting’ in such cells.     

Design and application of dielectric distributed Bragg back reflector in thin-film silicon solar cells

A dielectric distributed Bragg reflector (DBR) formed by four pairs of hydrogenated amorphous silicon/silicon nitride layers is used as the back reflector in thin-film silicon solar cells. The DBR was designed to perform in a broad wavelength range with the peak reflectance at 600 nm. The DBR was fabricated at low substrate temperature (172 °C) and applied at the rear side of flat and textured amorphous silicon single-junction solar cells in both superstrate (pin) and substrate (nip) configurations. The spectral response and electrical I–V characteristics were measured. Solar cells with optimized DBR exhibit an enhanced external quantum efficiency in the long wavelength range and the electrical performance is comparable to solar cells having conventional Ag back reflector.     

Inline deposited thin-film silicon solar cells on imprinted foil using linear PECVD sources

The standard way to improve the light management of thin film solar cells is to introduce a light scattering structure, either on the front window or at the back reflector. Usually, growth conditions of TCO layers are adjusted to get random surface roughness on the front window. In this paper we present an alternative method, which can be applied both on the front window and at the back reflector. It involves imprinting a UV curable coating layer allowing full control on the texture (random or periodic) to fully optimise the light trapping. Light trapping is even more important for microcrystalline Si solar cells. We have fabricated thin film nip Si solar cells with sputtered Ag/ZnO back contacts on embossed barrier layers on steel foil. We show that the UV curable coating is well-suited as imprintable barrier layer between the steel foil and the active layers. For nip a-Si cells we can obtain light trapping, as measured by the short-circuit current, that is almost as good as that of nip a-Si cells made on Asahi U-type glass, covered with a Ag/ZnO back reflector. Furthermore, we show that dynamically processed a-Si nip cells on foil realised efficiencies of over 7%, which are only slightly less than for cells made in a UHV lab-scale cluster tool in static processing. Finally, a-Si/a-Si tandems and μc-Si/a-Si tandems have been fabricated. Initial efficiencies of around 8% on textured barrier layer on steel foil have been achieved.     

Short-range order in non-stoichiometric amorphous silicon oxynitride and silicon-rich nitride

By de-convoluting the Si 2p X-ray photoelectronic spectra, it was found that the short-range order in amorphous silicon oxynitride (SiO_xN_y) films with different compositions can be quantitatively described by the random bonding model. In this model the SiO_xN_y consists of five types of randomly distributed tetrahedra and it indicates that metal-oxide-semiconductor transistor with this gate dielectric will not result in any gigantic potential fluctuation in the conduction channel. On the contrary, the structure of silicon-rich silicon nitride SiN_x can only be described by the random mixture model where the local composition fluctuations in this film will result in gigantic potential contra-variant fluctuation.     

Improving the performance of amorphous and crystalline silicon heterojunction solar cells by monitoring surface passivation

The influence of thermal annealing on the crystalline silicon surface passivating properties of selected amorphous silicon containing layer stacks (including intrinsic and doped films), as well as the correlation with silicon heterojunction solar cell performance has been investigated. All samples have been isochronally annealed for 1 h in an N₂ ambient at temperatures between 150 °C and 300 °C in incremental steps of 15 °C. For intrinsic films and intrinsic/n-type stacks, an improvement in passivation quality is observed up to 255 °C and 270 °C, respectively, and a deterioration at higher temperatures. For intrinsic/n-type a-Si:H layer stacks, a maximum minority carrier lifetime of 13.3 ms at an injection level of 10¹⁵ cm^? 3 has been measured. In contrast, for intrinsic/p-type a-Si:H layer stacks, a deterioration in passivation is observed upon annealing over the whole temperature range. Comparing the lifetime values and trends for the different layer stacks to the performance of the corresponding cells, it is inferred that the intrinsic/p-layer stack is limiting device performance. Furthermore, thermal annealing of p-type layers should be avoided entirely. We therefore propose an adapted processing sequence, leading to a substantial improvement in efficiency to 16.7%, well above the efficiency of 15.8% obtained with the ‘standard’ processing sequence.     

Light-induced changes in hydrogenated amorphous silicon solar cells deposited at the edge of crystallinity

A series of hydrogenated amorphous silicon (a-Si:H) films were deposited in the transition region from amorphous to nanocrystalline phases by changing hydrogen dilution ratio R, deposition gas pressure, and RF power. Single junction a-Si:H solar cells were made using these materials as the intrinsic layers in the structure of n–i–p type on ZnO/Ag/stainless steel substrates. Light-induced degradations in the photovoltaic parameters were characterized on these cells after 1 Sun solar illumination for 150 h. The stabilized efficiencies were compared in conjunction with the structures in the intrinsic layers, which were revealed by high resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectrometry (FTIR). It was found that the solar cells incorporated protocrystalline intrinsic layer as the i-layer give a better initial efficiency, while solar cells made from nanostructured i-layers have a better stability of ～7% degradation against light soaking, as a result, both have nearly the same final stabilized efficiency. The best device stabilized efficiency reaches ～10.2% (0.25 cm², AM1.5G) for the intrinsic layer deposited at a high pressure of 2 Torr.     

Comparison of photocurrent spectra measured by FTPS and CPM for amorphous silicon layers and solar cells

Fourier Transform Photocurrent Spectroscopy (FTPS) has been recently introduced as a fast and highly sensitive method for the evaluation of the optical absorption coefficient of photoconductive thin films such as microcrystalline silicon layers. This contribution represents the first study of FTPS utilization for amorphous silicon layers and cells. FTPS spectra are compared with results of Constant Photocurrent Method (CPM) and Dual Beam Photoconductivity (DBP) measured at different chopping frequencies. We will concentrate to highlight the appropriate measuring conditions and evaluation procedures for correct data interpretation. Moreover, we will present our novel approach for the interference free determination of absorption coefficients of thin films grown on transparent substrates, which is mainly important for very thin layers where broad interference fringes do not allow correct evaluation of parameters such as a slope of the Urbach tail and the defect density.     

Preparation of amorphous composites with polymer-derived silicon nitride matrix reinforced by three-dimensional silica fiber

Perhydropolysilazane, a low viscosity preceramic polymer with good infiltration efficiency and high char yield, was used to prepare amorphous composites with polymer-derived silicon nitride matrix reinforced by three-dimensional silica fiber, and the mechanical properties and microstructures were investigated. The composites without fiber coating showed a typical brittle fracture behavior with a smooth fracture surface, and a flexural strength of just 33.5 MPa. While the composites with fiber coating exhibited a non-brittle fracture behavior with distinct fiber pull-out in the fracture surface, and a high flexural strength of 144.9 MPa. It was the controlled fiber/matrix interface by precoating treatment that contributed to the high mechanical property of the composites.     

Heat treatment of amorphous silicon p-i-n solar cells with high-pressure H2O vapor

We report improvement in characteristics of hydrogenated amorphous silicon (a-Si:H ) p-i-n structured solar cells by high-pressure H₂O vapor heat treatment. a-Si:H p-i-n solar cells were formed on glass substrates coated with textured SnO₂ layer. P-, i-, and n-type a-Si:H layers were subsequently formed by plasma enhanced chemical vapor deposition. Finally an indium-tin-oxide layer was coated on the n-type a-Si:H surface. Heat treatment at 210 °C with 2 × 10⁵ Pa H₂O vapor for 1 h was applied to the a-Si:H p-i-n solar cells. Electrical characteristics were measured when samples were kept in dark and illuminated with light of AM 1.5 at 100 mW/cm². The heat treatment with H₂O vapor increased fill factor (FF) and the conversion efficiency from 0.54 and 7.7% (initial) to 0.57 and 8.4%, respectively. Marked improvement in solar cell characteristics was also observed in the case of a poor a-Si:H p-i-n solar cell. FF and the conversion efficiency were increased from 0.29 and 3.2% (initial) to 0.56 and 7.7%, respectively.     

Charge collection in amorphous silicon solar cells: Cell analysis and simulation of high-efficiency pin devices

The drift length L_drift = μτE within the i layer of a-Si:H solar cells is a crucial parameter for charge collection and efficiency. It is strongly reduced not only by light-induced reduction of μτ, but also by electric field deformation ΔE by charges near the p–i and i–n interfaces. Here, a simple model is presented to estimate contributions of free carriers, charges trapped in band tails and charged dangling bonds to ΔE. It is shown that the model reproduces correctly trends observed experimentally and by ASA simulations: charged dangling bonds contribute most to ΔE of meta-stable cells. Electrons trapped in the conduction band tail near the i–n interface lead to the strongest field deformation in the initial state, while positively charged dangling bonds near the p–i interface get more important with degradation under AM1.5g spectrum. The measurable parameter V_coll is proposed as an indirect parameter to estimate the electric field, and an experimental technique is presented that could enable the distinction of defects near the p–i and the i–n interfaces.     

Optimization and characterization of i/p buffer layer in hydrogenated nanocrystalline silicon solar cells

The effect of a-Si:H i/p buffer layer on the performance of nc-Si:H solar cells is studied systematically. The results show that for thin nc-Si:H cells, an optimized i/p buffer layer significantly reduces the dark current thus increases the open-circuit voltage. We believe that the carrier recombination at the i/p interface is one of the determining factors for the nc-Si:H cell performance, especially for cells with a thin intrinsic layer. Therefore, optimizing the i/p buffer layer is one of the key factors for achieving high efficiency nc-Si:H solar cells. This interface effect is less pronounced as the nc-Si:H intrinsic layer thickness increases, where the recombination in the bulk becomes a dominant factor. Combining the improved nc-Si:H intrinsic layer with a proper hydrogen dilution and an optimized a-Si:H i/p buffer layer, the performance of nc-Si:H single-junction and a-Si:H/a-SiGe:H/nc-Si:H triple-junction cells is significantly improved.     

Impurities in thin-film silicon: Influence on material properties and solar cell performance

The influence of oxygen and nitrogen impurities on the material properties of a-Si:H and μc-Si:H films and on the corresponding solar cell performances was studied. For intentional contamination of the i-layer the impurities were inserted by two contamination sources: (i) directly into the plasma through a leak at the chamber wall or (ii) into the gas supply line. The critical oxygen and nitrogen concentrations for silicon solar cells were determined as the lowest concentration of these impurities in the i-layer causing a deterioration of the cell performance. Similar critical concentrations for a-Si:H and μc-Si:H cells in the range of 4–6 × 10¹⁸ cm^? 3 for nitrogen and 1–5 × 10¹⁹ cm^? 3 for oxygen by applying a chamber leak are observed. Similar increase of conductivity with increasing impurity concentration in the a-Si:H and μc-Si:H films is found. A more detailed study shows that the critical oxygen concentration depends on the contamination source and the deposition parameters. For a-Si:H cells, the application of the gas pipe leak leads to an increased critical oxygen concentration to 2 × 10²⁰ cm^? 3. Such an effect was not observed for nitrogen. For μc-Si:H, a new deposition regime with reduced discharge power was found where the application of the gas pipe leak can also result in an increase of the oxygen concentration to 1 × 10²⁰ cm^? 3.     

Characteristics of p-type nanocrystalline silicon thin films developed for window layer of solar cells

Different rf-power and chamber pressures have been used to deposit boron doped hydrogenated silicon films by the PECVD method. The optoelectronic and structural properties of the silicon films have been investigated. With the increase of power and pressure the crystallinity of the films increases while the absorption decreases. As a very thin p-layer is needed in p–i–n thin film solar cells the variation of properties with film thickness has been studied. The fraction of crystallinity and thus dark conductivity vary also with the thickness of the film. Conductivity as high as 2.46 S cm⁻¹ has been achieved for 400 Å thin film while for 3000 Å thick film it is 21 S cm⁻¹. Characterization of these films by XRD, Raman Spectroscopy, TEM and SEM indicate that the grain size, crystalline volume fraction as well as the surface morphology of p-layers depend on the deposition conditions as well as on the thickness of the film. Optical band gap varies from 2.19 eV to 2.63 eV. The thin p-type crystalline silicon film with high conductivity and wide band gap prepared under high power and pressure is suitable for application as window layer for Silicon thin film solar cells.