Microcrystalline/micromorph silicon thin-film solar cells prepared by VHF-GD technique

Hydrogenated microcrystalline silicon prepared at low temperatures by the glow discharge technique is examined here with respect to its role as a new thin-film photovoltaic absorber material. XRD and TEM characterisations reveal that microcrystalline silicon is a semiconductor with a very complex morphology. Microcrystalline p–i–n cells with open-circuit voltages of up to 560–580 mV could be prepared. “Micromorph” tandem solar cells show under outdoor conditions higher short-circuit currents due to the enhanced blue spectra of real sun light and therefore higher efficiencies than under AM1.5 solar simulator conditions. Furthermore, a weak air mass dependence of the short-circuit current density could be observed for such micromorph tandem solar cells. By applying the monolithic series connection based on laser patterning a first micromorph mini-module (total area of 23.6 cm²) with 9% cell conversion efficiency could be fabricated.     

High-Ts amorphous top cells for increased top cell currents in micromorph tandem cells

In the present paper, the authors discuss the application of amorphous p–i–n solar cells containing i-layers which are deposited at high substrate temperatures as top cells in amorphous silicon/microcrystalline silicon tandem (“micromorph”) solar cells. Increasing the substrate temperature for the deposition of intrinsic a-Si : H results in a reduced optical gap. The optical absorption is enhanced and thereby the current generation. A high-current generation within a relatively thin amorphous top cell is very interesting in the context of micromorph tandem cells, where the amorphous top cell should contribute a current of at least 13 mA/cm² for a total cell current density of 26 mA/cm². A detailed study of the intrinsic material deposited by VHF-GD at 70 MHz at substrate temperatures between 220°C and 360°C is presented, including samples deposited from hydrogen-diluted silane plasmas. The stability of the films against light soaking is investigated employing the μ₀τ₀ parameter, which has been shown to be directly correlated to the cell performance. The paper discusses in detail the technological problems arising from the insertion of i-layers deposited at high substrate temperatures into solar cells. These problems are specially pronounced in the case of cells in the p–i–n (superstrate) structure. The authors demonstrate that an appropriate interface layer at the p/i-interface can largely reduce the detrimental effects of i-layer deposition at high temperatures. Finally, the application of such optimized high-temperature amorphous cells as top cells in micromorph tandem cells is discussed. Current densities of 13 mA/cm² in the top cell are available with a top cell i-layer thickness of only 250 nm.     

Towards high-efficiency thin-film silicon solar cells with the “micromorph” concept

Tandem solar cells with a microcrystalline silicon bottom cell (1 eV gap) and an amorphous-silicon top cell (1.7 eV gap) have recently been introduced by the authors; they were designated as “micromorph” tandem cells. As of now, stabilised efficiencies of 11.2% have been achieved for micromorph tandem cells, whereas a 10.7% cell is confirmed by ISE Freiburg. Micromorph cells show a rather low relative temperature coefficient of 0.27%/K. Applying the grain-boundary trapping model so far developed for CVD polysilicon to hydrogenated microcrystalline silicon deposited by VHF plasma, an upper limit for the average defect density of around 2 × 10¹⁶/cm³ could be deduced; this fact suggests a rather effective hydrogen passivation of the grain-boundaries. First TEM investigations on μc-Si : H p-i-n cells support earlier findings of a pronounced columnar grain structure. Using Ar dilution, deposition rates of up to 9 Å/s for microcrystalline silicon could be achieved.     

Highly and quickly stabilized p–i–n/p–i–n-type protocrystalline silicon multilayer tandem solar cells

We have developed p–i–n/p–i–n-type protocrystalline silicon (pc-Si:H) multilayer tandem solar cells. The purpose of this work is to make a thin film silicon solar cell with low degradation by combining the virtues of a pc-Si:H multilayer and tandem structure. The usefulness of the pc-Si:H multilayer as a low degradation top and bottom cell was confirmed when we achieved a low degradation ratio of 10.0%. Notably, this tandem cell stabilized rapidly, within 1 h. Nanocrystalline silicon (nc-Si) grains embedded in a pc-Si:H multilayer were detected with the aid of a planer transmission electron microscope. The isolated nc-Si grains may suppress the photocreation of dangling bonds due to non-radiative recombination in an a-Si:H matrix. Because of these embedded nc-Si grains, the pc-Si:H multilayer has a fast and high light-induced metastability.     

Microcrystalline silicon thin film solar modules on glass

We developed microcrystalline silicon (μc-Si:H) thin film solar modules on textured ZnO-coated glass. The single junction (p–i–n) cell structure was prepared by plasma-enhanced chemical vapour deposition (PECVD) at substrate temperatures below 250 °C. Front ZnO and back contacts were prepared by sputtering. A process for the monolithic series connection of μc-Si:H cells by laser scribing was developed. These microcrystalline p–i–n modules showed aperture area efficiencies up to 8.3% and 7.3% on aperture areas of 64 and 676 cm², respectively. The temperature coefficient of the efficiency was −0.4%/K.     

Realization of high efficiency micromorph tandem silicon solar cells on glass and plastic substrates: Issues and potential

High conversion efficiency for (amorphous/microcrystalline) "micromorph" tandem solar cells requires both a dedicated light management, to keep the absorber layers as thin as possible, and optimized growth conditions of the microcrystalline silicon (μc-Si:H) material. Efficient light trapping is achieved here by use of textured front and back contacts as well as by implementing an intermediate reflecting layer (IRL) between the individual cells of the tandem. This paper discusses the latest developments of IRLs at IMT Neuchâtel: SiO_x based for micromorphs on glass and ZnO based IRLs for micromorphs on flexible substrates were successfully incorporated in micromorph tandem cells leading to high, matched, current above 13.8 mA/cm² for p-i-n tandems. In n-i-p configuration, asymmetric intermediate reflectors were employed to achieve currents of up to 12.5 mA/cm². On glass substrates, initial and stabilized efficiencies exceeding 13% and 11%, respectively, were thus obtained on 1 cm² cells, while on plastic foils with imprinted gratings, 11.2% initial and 9.8% stable efficiency could be reached. Recent progress on the development of effective front and back contacts will be described as well.     

Deposition pressure effects on material structure and performance of micromorph tandem solar cells

Tandem solar cells represent an elegant way of overcoming the efficiency limits of single-junction solar cells and reducing the light-induced degradation of amorphous silicon films. Stacked structures consisting of an amorphous silicon top cell and a microcrystalline silicon bottom cell allow a good utilization of the solar spectrum due to the band gap values of the two materials. These devices, firstly introduced by the IMT research group, were designated as “micromorph” tandem solar cells. To better exploit this concept, it is important to tune parameters like the band gaps and the short-circuit currents.In this work, we have realized micromorph tandem solar cells on Asahi U-type TCO-covered glass substrates. The intrinsic layer of both the amorphous top cell and the microcrystalline bottom cell is grown by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) at 100 MHz at low substrate temperature (150 °C). Finally, a ZnO reflector and a metal contact complete the structure. No intermediate optical mirror between the two cells is used at this stage. Undiluted a-Si:H, with reduced band gap when compared to H₂-diluted amorphous silicon, is used as absorber layer in the top cell. As for the bottom cell, the high-pressure–high-power regime (up to 267 Pa–80 W) has been explored aiming at growing high-quality microcrystalline silicon at large deposition rates. The effect of the structural composition of the microcrystalline absorber layer on the current–voltage characteristic and spectral response of tandem devices has been investigated. An efficiency of 11.3% has been obtained with short-circuit current densities around 13 mA/cm², open-circuit voltages 1.34 V and fill factors 66%.     

Development of highly efficient thin film silicon solar cells on texture-etched zinc oxide-coated glass substrates

ZnO films prepared by magnetron sputtering on glass substrates and textured by post-deposition chemical etching are applied as substrates for p–i–n solar cells. Using both rf and dc sputtering, similar surface textures can be achieved upon etching. Excellent light trapping is demonstrated by high quantum efficiencies at long wavelengths for microcrystalline silicon solar cells. Applying an optimized microcrystalline/amorphous p-layer design, stacked solar cells with amorphous silicon top cells yield similarly high stabilized efficiencies on ZnO as on state-of-the-art SnO₂ (9.2% for a-Si/a-Si). The efficiencies are significantly higher than on SnO₂-coated float glass as used for module production.     

Preparation of microcrystalline single junction and amorphous–microcrystalline tandem silicon solar cells entirely by hot-wire CVD

The hot-wire chemical vapour deposition (HWCVD) has been used to prepare highly conducting p- and n-doped microcrystalline silicon thin layers as well as highly photoconducting, low defect density intrinsic microcrystalline silicon films. These films were incorporated in all-HWCVD, all-microcrystalline nip and pin solar cells, achieving conversion efficiencies of η=5.4% and 4.5%, respectively. At present, only the nip-structures are found to be stable against light-induced degradation. Furthermore, microcrystalline nip and pin structures have been successfully incorporated as bottom cells in all-hot-wire amorphous–microcrystalline nipnip- and pinpin-tandem solar cells for the first time. So far, the highest conversion efficiencies of the “micromorph” tandem structures are η=5.7% for pinpin-solar cells and 7.0% for nipnip solar cells.     

Applying analytical and numerical methods for the analysis of microcrystalline silicon solar cells

The results of numerical device simulations for p–i–n diodes and the closed-form expression of the current–voltage characteristics developed for p–n diodes are compared. It is shown that the closed-form expression correctly predicts the functional relationship between material parameters and device performance of p–i–n diodes. The ideality factor between 1 and 2 is analyzed in detail. The effect of the defect density, the intrinsic carrier concentration, the mobility and the built-in potential on device performance are demonstrated. These insights are applied to analyze microcrystalline silicon thin-film solar cells deposited by chemical vapor deposition at temperatures below 250 °C.     

Microdoping compensation of microcrystalline silicon obtained by hot-wire chemical vapour deposition

Undoped hydrogenated microcrystalline silicon was obtained by hot-wire chemical vapour deposition at different silane-to-hydrogen ratios and low temperature (<300°C). As well as technological aspects of the deposition process, we report structural, optical and electrical characterisations of the samples that were used as the active layer for preliminary p–i–n solar cells. Raman spectroscopy indicates that changing the hydrogen dilution can vary the crystalline fraction. From electrical measurements an unwanted n-type character is deduced for this undoped material. This effect could be due to a contaminant, probably oxygen, which is also observed in capacitance–voltage measurements on Schottky structures. The negative effect of contaminants on the device was dramatic and a compensated p–i–n structure was also deposited to enhance the cell performance.     

Rough ZnO layers by LP-CVD process and their effect in improving performances of amorphous and microcrystalline silicon solar cells

Doped ZnO layers deposited by low-pressure chemical vapour deposition technique have been studied for their use as transparent contact layers for thin-film silicon solar cells.Surface roughness of these ZnO layers is related to their light-scattering capability; this is shown to be of prime importance to enhance the current generation in thin-film silicon solar cells. Surface roughness has been tuned over a large range of values, by varying thickness and/or doping concentration of the ZnO layers.A method is proposed to optimize the light-scattering capacity of ZnO layers, and the incorporation of these layers as front transparent conductive oxides for p–i–n thin-film microcrystalline silicon solar cells is studied.     

High-rate microcrystalline silicon deposition for p–i–n junction solar cells

We have developed a high-rate plasma process based on high-pressure and silane-depletion glow discharge for highly efficient microcrystalline silicon (μc-Si:H) p–i–n junction solar cells. Under high-rate conditions (2–3 nm/s), we find that the deposition pressure becomes the dominant parameter in determining solar-cell performance. With increasing deposition pressure from 4 to 7–9 Torr, short-circuit current increases by 50% due to a remarkable improvement in quantum efficiencies at the visible and near infrared. As a result, the maximum efficiency of 9.13% has been achieved at an i-layer deposition rate of 2.3 nm/s. We attribute the improved performance of high-pressure-grown μc-Si:H solar cells to the structural evolution toward denser grain arrangement that prevents post-oxidation of grain boundaries.     

Silicon thin films prepared in the transition region and their use in solar cells

Diphasic silicon films (nc-Si/a-Si:H) have been prepared by a new regime of plasma enhanced chemical vapour deposition in the region adjacent of phase transition from amorphous to microcrystalline state. Comparing to the conventional amorphous silicon (a-Si:H), the nc-Si/a-Si:H has higher photoconductivity (σ_ph), better stability, and a broader light spectral response range in the longer wavelength range. It can be found from Raman spectra that there is a notable improvement in the medium range order. The blue shift for the stretching mode and red shift for the wagging mode in the IR spectra also show the variation of the microstructure. By using this kind of film as intrinsic layer, a p–i–n junction solar cell was prepared with the initial efficiency of 8.51% and a stabilized efficiency of 8.01% (AM1.5, 100 mw/cm²) at room temperature.     

Amorphous solar cells, the micromorph concept and the role of VHF-GD deposition technique

During the last two decades, the Institute of Microtechnology (IMT) has contributed in two important fields to future thin-film silicon solar cell processing and design:

(1) In 1987, IMT introduced the so-called “very high frequency glow discharge (VHF-GD)” technique, a method that leads to a considerable enhancement in the deposition rate of amorphous and microcrystalline silicon layers. As a direct consequence of reduced plasma impedances at higher plasma excitation frequencies, silane dissociation is enhanced and the maximum energy of ions bombarding the growing surface is reduced. Due to softer ion bombardment on the growing surface, the VHF process also favours the formation of microcrystalline silicon. Based on these beneficial properties of VHF plasmas, for the growth of thin silicon films, plasma excitation frequencies f_exc in the range 30–300 MHz, i.e. clearly higher than the standard 13.56 MHz, are indeed scheduled to play an important role in future production equipment.

(2) In 1994, IMT pioneered a novel thin-film solar cell, the microcrystalline silicon solar cell. This new type of thin-film absorber material––a form of crystalline silicon––opens up the way for a new concept, the so-called “micromorph” tandem solar cell concept. This term stands for the combination of a microcrystalline silicon bottom cell and an amorphous silicon top cell. Thanks to the lower band gap and to the stability of microcrystalline silicon solar cells, a better use of the full solar spectrum is possible, leading, thereby, to higher efficiencies than those obtained with solar cells based solely on amorphous silicon.

Both the VHF-GD deposition technique and the “micromorph” tandem solar cell concept are considered to be essential for future thin-film PV modules, as they bear the potential for combining high-efficiency devices with low-cost manufacturing processes.     

Device simulation and modeling of microcrystalline silicon solar cells

Device modeling for p–i–n junction basis thin film microcrystalline Si solar cells has been examined with a simple model of columnar grain structure utilizing two-dimensional device simulator. The simulation results of solar cell characteristics show that open-circuit voltage (V_oc) and fill factor considerably depend on structural parameters such as grain size and acceptor doping in intrinsic layer, while short-circuit current density (J_sc) is comparatively stable by built-in electric field in the i-layer. It is also found that conversion efficiency of more than 16% could be expected with 1 μm grain size and well-passivated condition with 10 μm thick i-layer and optical confinement.     

Microcrystalline silicon solar cells fabricated by VHF plasma CVD method

A series of systematic investigations on microcrystalline silicon (μc-Si:H) solar cells at high deposition rates has been studied. The effect of high deposition pressure and narrow cathode-substrate (CS) distance on the deposition rate and quality of microcrystalline silicon is discussed. The microcrystalline silicon solar cell is adopted as middle cell and bottom cell in a three-stacked junction solar cell. The characteristics of large area three-stacked junction solar cells, whose area is 801.6 cm² including grid electrode areas, are studied in various deposition rates from 1 to 3 nm/s of microcrystalline silicon. An initial efficiency of 13.1% is demonstrated in the three-stacked junction solar cell with microcrystalline silicon deposited at 3 nm/s.     

Hydrogenated nanocrystalline silicon p-layer in amorphous silicon n–i–p solar cells

This paper describes an investigation into the impacts of hydrogenated nanocrystalline silicon (nc-Si:H) p-layer on the photovoltaic parameters, especially on the open-circuit voltage (V_oc) of n–i–p type hydrogenated amorphous silicon (a-Si:H) solar cells. Raman spectroscopy and transmission electron microscopy (TEM) analyses indicate that this p-layer is a diphasic material that contains nanocrystalline grains with size around 3–5 nm embedded in an amorphous silicon matrix. Optical transmission measurements show that the nc-Si:H p-layer has a wide band gap of 1.9 eV. Using this nanocrystalline p-layer in n–i–p a-Si:H solar cells, the cell performances were improved with a V_oc of 1.042 V, whereas the solar cells deposited under similar conditions but incorporating a hydrogenated microcrystalline silicon (μc-Si:H) p-layer exhibit a V_oc of 0.526 V.     

Low-temperature growth of thick intrinsic and ultrathin phosphorous or boron-doped microcrystalline silicon films: Optimum crystalline fractions for solar cell applications

The growth kinetics and optoelectronic properties of intrinsic and doped microcrystalline silicon (μc-Si:H) films deposited at low temperature have been studied combining in situ and ex situ techniques. High deposition rates and preferential crystallographic orientation for undoped films are obtained at high pressure. X-ray and Raman measurements indicate that for fixed plasma conditions the size of the crystallites decreases with the deposition temperature. Kinetic ellipsometry measurements performed during the growth of p-(μc-Si:H) on transparent conducting oxide substrates display a remarkable stability of zinc oxide, while tin oxide is reduced at 200°C but stable at 150°C. In situ ellipsometry, conductivity and Kelvin probe measurements show that there is an optimum crystalline fraction for both phosphorous- and boron-doped layers. Moreover, the incorporation of p-(μc-Si:H) layers produced at 150°C in μc-Si:H solar cells shows that the higher the crystalline fraction of the p-layer the better the performance of the solar cell. On the contrary, the optimum crystalline fraction of the p-layer is around 30% when hydrogenated amorphous silicon (a-Si:H) is used as the intrinsic layer of p–i–n solar cells. This is supported by in situ Kelvin probe measurements which show a saturation in the contact potential of the doped layers just above the percolation threshold. In situ Kelvin probe measurements also reveal that the screening length in μc-Si:H is much higher than in a-Si:H, in good agreement with the good collection of microcrystalline solar cells     

Light soaking effect in a-Si:H based n–i–p and p–i–n solar cells

Hydrogenated amorphous silicon solar cells have been realised in both a p–i–n configuration on a Corning glass substrate as well as in a n–i–p configuration on stainless-steel substrate. The performance degradation of the two kinds of cell under solar illumination has been examined for a 140 h period. During degradation, the two devices were kept under load in the maximum power condition that is normally used in a solar plant. The performance of the Corning glass deposited device exhibited a higher rate of degradation with respect to the other cell. A discussion on the possible reasons for this behaviour is given.