Amorphous silicon/p-type crystalline silicon heterojunction solar cells with a microcrystalline silicon buffer layer

Undoped hydrogenated amorphous silicon (a-Si:H)/p-type crystalline silicon (c-Si) structures with and without a microcrystalline silicon (μc-Si) buffer layer have been investigated as a potential low-cost heterojunction (HJ) solar cell. Unlike the conventional HJ silicon solar cell with a highly doped window layer, the undoped a-Si:H emitter was photovoltaically active, and a thicker emitter layer was proven to be advantageous for more light absorption, as long as the carriers generated in the layer are effectively collected at the junction. In addition, without using heavy doping and transparent front contacts, the solar cell exhibited a fill factor comparable to the conventional HJ silicon solar cell. The optimized configuration consisted of an undoped a-Si:H emitter layer (700 Å), providing an excellent light absorption and defect passivation, and a thin μc-Si buffer layer (200 Å), providing an improved carrier collection by lowering barrier height at the interface, resulting in a maximum conversion efficiency of 10% without an anti-reflective coating.     

Intrinsic microcrystalline silicon: A new material for photovoltaics

Microcrystalline silicon (μc-Si:H) prepared by plasma-enhanced chemical vapor deposition (PECVD) has been investigated as material for absorber layers in solar cells. The deposition process has been adjusted to achieve high deposition rates and optimized solar cell performance. In particular, already moderate variations of the crystalline vs. amorphous volume fractions were found to effect the electronic material – and solar cell properties. Such variation is readily achieved by changing the process gas mixture of silane to hydrogen. Best cell performance was found for material near the transition to the amorphous growth regime. With this optimized material efficiencies of 7.5% for a 2 μm thick μc-Si:H single solar cell and 12% for an a-Si:H/μc-Si:H stacked solar cell have been achieved.     

Silicon-based thin-film solar cells fabricated near the phase boundary by VHF PECVD technique

The light-soaked and annealing behaviors for silicon (Si)-based thin-film single-junction solar cells fabricated near the phase boundary using a very-high-frequency plasma-enhanced chemical vapor deposition (VHF PECVD) technique are investigated. The hydrogen dilution ratio is changed in order to achieve wide band gap hydrogenated amorphous Si (a-Si:H) and narrow band gap hydrogenated microcrystalline Si (μc-Si:H) absorbers. Just below the a-Si:H-to-μc-Si:H transition, highly hydrogen-diluted a-Si:H solar cells with a good stability against light-soaking and fast annealing behavior are obtained. In contrast, the solar cell fabricated at the onset of the μc-Si:H growth is very unstable and its annealing behavior is slow. In the case of μc-Si:H solar cells with the crystal volume fraction of 43–53%, they show the lowest light-induced degradation among the fabricated solar cells. However, it is very difficult to recover the degraded μc-Si:H solar cells via thermal annealing.     

Microcrystalline silicon solar cell using p-a-Si:H window layer deposited by photo-CVD method

A p-a-Si:H layer, deposited by a photo-assisted chemical vapor deposition (photo-CVD) method, was adopted as the window layer of a hydrogenated microcrystalline silicon (μc-Si:H) solar cell instead of the conventional p-μc-Si:H layer. We verified the usefulness of p-a-Si:H for the p-layer of the μc-Si:H solar cell by applying it to SnO₂-coated glass substrate. It was found that the quantum efficiency (QE) characteristics and solar cell performance strongly depend on the p-a-Si:H layer thicknesses. We applied boron-doped nanocrystalline silion (nc-Si:H) p/i buffer layers to μc-Si:H solar cells and investigated the correlation of the p/i buffer layer B₂H₆ flow rate and solar cell performance. When the B₂H₆ flow rate was 0.2 sccm, there was a little improvement in fill factor (FF), but the other parameters became poor as the B₂H₆ flow rate increased. This is because the conductivity of the buffer layer decreases as the B₂H₆ flow rate increases above appropriate values. A μc-Si:H single-junction solar cell with ZnO/Ag back reflector with an efficiency of 7.76% has been prepared.     

Control of μc-Si/c-Si interface layer structure for surface passivation of Si solar cells

Outstanding passivation properties for p-type crystalline silicon surfaces were obtained by using very thin n-type microcrystalline silicon (μc-Si) layers with a controlled interface structure. The n-type μc-Si layers were deposited by the RF PE-CVD method with an insertion of an ultra-thin oxide (UTO) layer or an n-type amorphous silicon (a-Si : H) interface layer. The effective surface recombination velocity (SRV) obtained was very small and comparable to that obtained using thermal oxides prepared at 1000°C. The structural studies by HRTEM and Raman measurements suggest that the presence of UTO produces a very thin a-Si : H layer under the μc-Si. A crystal lattice discontinuity caused by these interface layers is the key to a small SRV.     

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     

High-efficiency μc-Si/c-Si heterojunction solar cells

P-type microcrystalline silicon (μc-Si (p)) on n-type crystalline silicon (c-Si(n)) heterojunction solar cells is investigated. Thin boron-doped μc-Si layers are deposited by plasma-enhanced chemical vapor deposition on CZ-Si and the V_oc of μc-Si/c-Si heterojunction solar cells is higher than that produced by a conventional thermal diffusion process. Under the appropriate conditions, the structure of thin μc-Si films on (1 0 0), (1 1 0), and (1 1 1) CZ-Si is ordered, so high V_oc of 0.579 V is achieved for 2×2 cm² μc-Si/multi-crystalline silicon (mc-Si) solar cells. The epitaxial-like growth is important in the fabrication of high-efficiency μc-Si/mc-Si heterojunction solar cells.     

Cell structures with low-high heterojunction of c-Si and μc-Si: H under rear contact for improvement of efficiencies

For a remarkable improvement of conversion efficiencies of single-crystalline silicon (c-Si) solar cells, we have been investigating rear surface structures. The structure has a highly conductive boron (B) doped hydrogenated microcrystalline silicon (μc-Si:H) film with a wide optical bandgap between a p-type c-Si substrate and a rear contact instead of a heavily diffused layer. The conditions of depositing the μc-Si:H film were investigated. Both short-circuit current density (J_sc) and open-circuit voltage (V_oc) of the cell with the μc-Si:H film are much higher than those without the film. The V_oc obtained was higher than 650 mV and the efficiency was 19.6% for a 5 cm × 5 cm cell. It is confirmed that a low-high heterojunction of the c-Si substrate and the μc-Si:H film is very effective in preventing minority carriers near the rear contact from recombining.     

Flexible amorphous and microcrystalline silicon tandem solar modules in the temporary superstrate concept

Encapsulated and series-connected amorphous silicon (a-Si:H) and microcrystalline silicon (μc-Si:H) based thin film silicon solar modules were developed in the superstrate configuration using an aluminum foil as temporary substrate during processing and a commodity polymer as permanent substrate in the finished module. For the development of μc-Si:H single junction modules, aspects regarding TCO conductivity, TCO reduction, deposition uniformity, substrate temperature stability and surface morphology were addressed. It was established that on sharp TCO morphologies where single junction μc-Si:H solar cells fail, tandem structures consisting of an a-Si:H top cell and a μc-Si:H bottom cell can still show a good performance. Initial aperture area efficiencies of 8.2%, 3.9% and 9.4% were obtained for fully encapsulated amorphous silicon (a-Si:H) single junction, microcrystalline silicon (μc-Si:H) single junction and a-Si:H/μc-Si:H tandem junction modules, respectively.     

Fabrication of microcrystalline silicon solar cells on a SnO2 coated substrate using seed layer insertion

We fabricated hydrogenated microcrystalline silicon (μc-Si:H) solar cells on SnO₂ coated glass using a seed layer insertion technique. Since rich hydrogen atoms from the μc-Si:H deposition process degrade the SnO₂ layer, we applied p-type hydrogenated amorphous silicon (p-a-Si:H) as a window layer. To grow the μc-Si:H layer on the p-a-Si:H window layer, we developed a seed layer insertion method. We inserted the seed layer between the p-a-Si:H layer and intrinsic bulk μc-Si:H. This seed layer consists of a thin hydrogen diluted silicon buffer layer and a naturally hydrogen profiled layer. We compared the characteristics of solar cells with and without the seed layer. When the seed layer was not applied, the fabricated cell showed the characteristics of a-Si:H solar cell whose spectral response was in a range of 400-800 nm. Using the seed layer, we achieved a μc-Si:H solar cell with performance of V_oc=0.535 V, J_sc=16.0 mA/cm², FF=0.667, and conversion efficiency=5.7% without any back reflector. The spectral response was in the range of 400-1100 nm. Also, the fabricated device has little substrate dependence, because a-Si:H has weaker substrate selectivity than μc-Si:H.     

Relationship between Raman crystallinity and open-circuit voltage in microcrystalline silicon solar cells

A series of nip-type microcrystalline silicon (μc-Si:H) single-junction solar cells has been studied by electrical characterisation, by transmission electron microscopy (TEM) and by Raman spectroscopy using 514 and 633 nm excitation light and both top- and bottom-illumination. Thereby, a Raman crystallinity factor indicative of crystalline volume fraction is introduced and applied to the interface regions, i.e. to the mixed amorphous-microcrystalline layers at the top and at the bottom of entire cells. Results are compared with TEM observations for one of the solar cells. Similar Raman and electrical investigations have been conducted also on pin-type μc-Si:H single-junction solar cells. Experimental data show that for all nip and pin μc-Si:H solar cells, the open-circuit voltage linearly decreases as the average of the Raman crystallinity factors for top and bottom interface regions increases.     

Application of real-time spectroscopic ellipsometry for characterizing the structure and optical properties of microcrystalline component layers of amorphous semiconductor solar cells

Over the past few years, we have applied real-time spectroscopic ellipsometry (RTSE) to probe hydrogenated amorphous silicon (a-Si:H)-based solar cell fabrication on the research scale. From RTSE measurements, the microstructural development of the component layers of the cell can be characterized with sub-monolayer sensitivity, including the time evolution of (i) the bulk layer thickness which provide the deposition rates, and (ii) the surface roughness layer thickness which provide insights into precursor surface diffusion. In the same analysis, RTSE also yields the optical properties of the growing films, including the dielectric functions and optical gaps. Results reported earlier have been confined to p-i-n and n-i-p cells consisting solely of amorphous layers, because such layers are found to grow homogeneously, making data analysis relatively straightforward. In this study, we report the first results of an analysis of RTSE data collected during the deposition of an n-type microcrystalline silicon (μc-Si:H) component layer in an a-Si:H p-i-n solar cell. Such an analysis is more difficult owing to (i) the modification of the underlying i-layer by the H₂-rich plasma used in doped μc-Si:H growth and (ii) the more complex morphological development of μc-Si:H, including surface roughening during growth.     

Thickness dependence of microcrystalline silicon solar cell properties

This paper addresses the performance of pin and nip solar cells with microcrystalline silicon (μc-Si:H) absorber layers of different thickness. Despite the reverse deposition sequence, the behavior of both types of solar cells is found to be similar. Thicker absorber layers yield higher short-circuit currents, which can be fully attributed to an enhanced optical absorption. Open-circuit voltage V_OC and fill factor FF decrease with increasing thickness, showing limitations of the bulk material. As a result of these two contrary effects the efficiency η varies only weakly for absorber layers of 1 to 4 μm thickness, yielding maximum values up to 8.1 %. For a-Si:H/μc-Si:H stacked solar cells an initial efficiency of 12% has been obtained.     

Amorphous and microcrystalline silicon solar cells prepared at high deposition rates using RF (13.56 MHz) plasma excitation frequencies

This paper presents a-Si:H and μc-Si:H p–i–n solar cells prepared at high deposition rates using RF (13.56 MHz) excitation frequency. A high deposition pressure was found as the key parameter to achieve high efficiencies at high growth rates for both cell types. Initial efficiencies of 7.1% and 11.1% were achieved for a μc-Si:H cell and an a-Si:H/μc-Si:H tandem cell, respectively, at a deposition rate of 6 Å/s for the μc-Si i-layers. A μc-Si:H cell prepared at 9 Å/s exhibited an efficiency of 6.2%.     

New materials and deposition techniques for highly efficient silicon thin film solar cells

This paper reviews recent efforts to provide the scientific and technological basis for cost-effective and highly efficient thin film solar modules based on amorphous (a-Si:H) and microcrystalline (μc-Si:H) silicon. Textured ZnO:Al films prepared by sputtering and wet chemical etching were applied to design optimised light-trapping schemes. Necessary prerequisite was the detailed knowledge of the relationship between film growth, structural properties and surface morphology obtained after etching. High rate deposition using plasma enhanced chemical vapour deposition at 13.56 MHz plasma excitation frequency was developed for μc-Si:H solar cells yielding efficiencies of 8.1% and 7.5% at deposition rates of 5 and 9 Å/s, respectively. These μc-Si:H solar cells were successfully up-scaled to a substrate area of 30×30 cm² and applied in a-Si:H/μc-Si:H tandem cells showing initial test cell efficiencies up to 11.9%.     

Influence of defects and band offsets on carrier transport mechanisms in amorphous silicon/crystalline silicon heterojunction solar cells

We have investigated the carrier transport mechanisms in undoped a-Si:H/p-type c-Si heterojunctions with and without a μc-Si buffer layer, as well as their effects on the photovoltaic properties of the junction. The conduction behavior of the junction is strongly affected by the defect state distribution and band offset at the hetero-interface. The recombination process involving the interface states on the thin film silicon (a-Si:H/μc-Si) side dominates at low forward bias (V<0.3 V), whereas multistep tunneling capture emission (MTCE) dominates in the higher bias region (0.3<V<0.55 V) until the conduction becomes space charge limited (V>0.55 V). The MTCE process seems to be more closely related to the bulk defects in the thin film silicon than the interface states. In addition, the position of a trapping level, where the tunneling process occurs, seems to be determined by the hole energy at the edge of the c-Si and the trap distribution in the thin film silicon. Despite the domination of MTCE in the indicated voltage range, the reduced band offset at the interface increases current levels by the enhanced diffusion and/or emission processes. The insertion of a 200 Å thick μc-Si buffer layer between the a-Si:H (700 Å)/c-Si increases the solar cell efficiency to 10%, without an antireflective coating, by improving both the carrier transport and the red response of the cell.     

Single-crystalline silicon solar cell with pp heterojunction of c-Si substrate and μc-Si : H film

Annealing effects of the single-crystalline silicon solar cells with hydrogenated microcrystaline silicon (μc-Si : H) film were studied to improve the conversion efficiency. Boron-doped (p⁺) μc-Si : H film was deposited in a RF plasma enhanced chemical vapor deposition system (RF plasma CVD) on the rear surface of the cell. With the optimized annealing conditions for the substrate, the conversion efficiency of 21.4% (AM1.5, 25°C, 100 mW/cm²) was obtained for 5 × 5 cm² area single crystalline-solar cell.     

Microcrystalline silicon films and solar cells deposited by PECVD and HWCVD

The application of microcrystalline silicon (μc-Si:H) in thin-film solar cells is addressed in the present paper. Results of different technologies for the preparation of μc-Si:H are presented, including plasma enhanced chemical vapour deposition (PECVD) using 13.56 MHz (radio frequency, rf) and 94.7 MHz (very high frequency, vhf) and hot-wire chemical vapour deposition (HWCVD). The influence of the silane concentration (SC) on the material and solar cell parameters is studied for the different techniques as the variation of SC allows to optimise the solar cell performance in each deposition regime. The best performance of μc-Si:H solar cells is always observed near the transition to amorphous growth. The highest efficiency obtained so far at a deposition rate of 5 Å/s is 9.4%, achieved with rf-PECVD in a deposition regime of using high pressure and high discharge power. High deposition rates and solar cell efficiencies could be also achieved by vhf-PECVD. An alternative approach represents the HWCVD which also demonstrated high deposition rates for μc-Si:H. However, good material quality and solar cell performance could only be achieved at low substrate temperatures and, consequently, low deposition rates. The μc-Si:H solar cells prepared by HWCVD exhibit comparably high efficiencies up to 9.4% and exceptionally high open circuit voltages up to 600 mV but at lower deposition rates (≈1 Å/s). The properties of PECVD and HWCVD solar cells are carefully compared.     

Absorption coefficient spectra of μc-Si in the low-energy region 0.4–1.2 eV

Optical absorption spectra in the low-energy region 0.4–1.2 eV is reported for μc-Si:H using a photothermal deflection spectroscopy technique. Absorption coefficient spectra in the low-energy region contain important information related to defects and hydrogen. It is demonstrated that there is a good correlation between electron spin densities and integrated absorption coefficient spectra from 0.7 to 1.2 eV. The amount of the hydrogen molecules in microvoids is much larger in μc-Si:H than that in a-Si:H. Light illumination effects in PDS spectra has also been studied from a view point of photo degradation of the μc-Si:H.     

Raman scattering analysis of SiH bond stretching modes in hydrogenated microcrystalline silicon for use in thin-film photovoltaics

The presence of a pair of peaks in the high wavenumber infrared (IR) absorption region of hydrogenated microcrystalline silicon (μc-Si:H) has been recently proposed as a strong indicator of poor quality material that is prone to oxidation and is therefore unsuitable for thin-film, photovoltaic applications. In this work, we show that these peaks located at 2083 and 2100 cm⁻¹ are also present in the Raman scattering spectra of μc-Si:H and therefore can be directly measured on substrates that are suitable for solar cells. We present results for material grown by matrix-distributed electron-cyclotron resonance (MD-ECR) plasma-enhanced chemical vapour deposition (PECVD) on both crystalline silicon and borosilicate glass substrates. The narrow, twinned peaks detected by Raman disappear with time—presumably due to oxidation—although a broad peak at 2100 cm⁻¹ remains.