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.     

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.     

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%.     

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.     

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%.     

Lowering of thickness of boron-doped microcrystalline hydrogenated silicon film by seeding technique

By using a seeding technique it has been possible to reduce the thickness of p-μc-Si:H film to 230 Å, with an improved electrical conductivity (0.93 S cm⁻¹) and lower optical absorption compared to those of conventional p-μc-Si:H layers without a seed layer, for use at the tunnel junction and as the top layer of a double junction n–i–p structured a-Si solar cell. Undoped-μc-Si:H has been used as the seed layer. The layers were prepared by the radio frequency plasma-enhanced chemical vapour deposition (RF-PECVD) method (13.56 MHz) at 40 mW/cm² rf power density and low substrate temperature (200 °C). The ultrathin seed layer (30 Å) enhances the growth of microcrystallinity of the p-type μc-Si:H film as confirmed by the results of transmission electron microscopy (TEM) analysis and Raman spectroscopy.     

Promotion of microcrystallization by argon in moderately hydrogen diluted silane plasma

Using argon as a diluent of SiH₄, undoped hydrogenated microcrystalline silicon (μc-Si:H) films, having σ_D10⁻⁵ S cm⁻¹, were prepared at a very high deposition rate of 36 Å/min. Micrograins were identified with several well-defined crystallographic orientations. The effect of variation of Ar-dilution on the electrical and structural properties of Si:H films were studied systematically. Addition of H₂ to the Ar-diluted SiH₄ plasma improved the network structure by eliminating defects, introducing structural reorientation and grain growth, although, reducing the deposition rate. Accordingly, highly conducting (σ_D10⁻³S cm⁻¹) undoped μc-Si:H film was achieved utilizing energy released by de-excitation of metastable state of Ar (denoted as Ar*), in association with network modulation by atomic hydrogen in the plasma.     

Microcrystalline silicon thin-film solar cells prepared at low temperature using PECVD

The low-temperature deposition of μc-Si:H has been found to be effective to suppress the formation of oxygen-related donors that cause a reduction in open-circuit voltage (V_oc) due to shunt leakage. We demonstrate the improvement of V_oc by lowering the deposition temperature down to 140°C. A high efficiency of 8.9% was obtained using an Aasahi-U substrate. Furthermore, by optimizing textured structures on ZnO transparent conductive oxide substrates, an efficiency of 9.4% was obtained. In addition, relatively high efficiency of 8.1% was achieved using VHF (60 MHz) plasma at a deposition rate of 12 Å s⁻¹. Thus, this low-temperature deposition technique for μc-Si:H is promising for obtaining both high efficiency and high-rate deposition technique for μc-Si:H solar cells.     

Microcrystallisation in Si:H: the effect of gas pressure in Ar-diluted SiH4 plasma

Using noble gas argon as a diluent of SiH₄ in RF glow discharge, undoped μc-Si:H thin films have been developed at a low power density of 30 mW/cm². It has been found that the gas pressure is a critical factor for the growth of μc-Si:H films. Undoped μc-Si:H films having σ_D10⁻⁶ S/cm and ΔE<0.57 eV have been obtained at and above a critical pressure of 0.8 Torr. When the RF power density is increased to 90 mW/cm², a more crystalline as well as highly conducting (σ_D10⁻⁴ S/cm) μc-Si:H film has been achieved at a deposition rate of 30 Å/min, which is much higher than that attained from H₂-diluted SiH₄ plasma, by conventional approach. The crystallinity of the films has been identified by the sharp Raman peak at 520 cm⁻¹ and a large number of micrograins in the TEM micrographs. The metastable state of Ar, denoted as Ar^*, plays the crucial role in inducing microcrystallisation by transferring its de-excitation energy at the surface of the growing film. A mechanism has been proposed to explain the dependence of the formation of μc-Si:H film on the working gas pressure in the plasma.     

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.     

Synthesis of a-Si:H/μc-Si:H multilayer structures by hot wire chemical vapor deposition (HW-CVD) technique: Study of opto-electronic and photovoltaic properties

Multilayer structures of the type a-Si:H/μc-Si:H were fabricated for the first time by hot wire chemical vapor deposition (HW-CVD) technique. These multilayers were studied for their opto-electronic and photovoltaic properties as a function of a-Si:H sublayer thickness. The microcrystalline phase of a-Si (μc-Si:H) of thickness 250 Å have been used to create drift field in these multilayer structures. The quantum size and photovoltaic effects are observed in these multilayer structures. The persistent photoconductivity measurements clearly indicate the existence of interface defects and spatial charge separation due to the formation of p-n junction field. The best photovoltaic performance was obtained with the fill factor 0.4062 and conversion efficiency (η) 2.08% over an active area of 0.0132 cm². The advantage in these multilayer structures is that no hazardous gases are involved in the fabrication process because no intentional doping is performed and all depositions were carried out in a single deposition chamber.     

Amorphous silicon/p-type crystalline silicon heterojunction solar cells

We have investigated the photovoltaic (PV) characteristics of both glow discharge deposited hydrogenated amorphous silicon (a-Si:H) on crystalline silicon (c-Si) in a n⁺ a-Si:H/undoped a-Si:H/p c-Si type structure, and DC magnetron sputtered a-Si:H in a n-type a-Si:H/p c-Si type solar cell structure. It was found that the PV properties of the solar cells were influenced very strongly by the a-Si/c-Si interface. Properties of strongly interface limited devices were found to be independent of a-Si thickness and c-Si resistivity. A hydrofluoric acid passivation prior to RF glow discharge deposition of a-Si:H increases the short circuit current density from 2.57 to 25.00 mA/cm² under 1 sun conditions.DC magnetron sputtering of a-Si:H in a Ar/H₂ ambient was found to be a controlled way of depositing n type a-Si:H layers on c-Si for solar cells and also a tool to study the PV response with a-Si/c-Si interface variations. 300 Å a-Si sputtered onto 1–10 ω cm p-type c-Si resulted in 10.6% efficient solar cells, without an A/R coating, with an open circuit voltage of 0.55 V and a short circuit current density of 30 mA/cm² over a 0.3 cm² area. High frequency capacitance-voltage measurements indicate good junction characteristics with zero bias depletion width in c-Si of 0.65 μm. The properties of the devices have been investigated over a wide range of variables like substrate resistivity, a-Si thickness, and sputtering power. The processing has focused on identifying and studying the conditions that result in an improved a-Si/c-Si interface that leads to better PV properties.     

Computer simulation of a-Si/c-Si heterojunction solar cell with high conversion efficiency

The p-type a-Si:H/n-type c-Si (P⁺ a-Si:H/N⁺ c-Si) heterojunction was simulated for developing solar cells with high conversion efficiency and low cost. The characteristic of such cells with different work function of transparent conductive oxide (TCO) were calculated. The energy band structure, quantum efficiency and electric field are analyzed in detail to understand the mechanism of the heterojunction cell. Our results show that the a-Si/c-Si heterojunction is hypersensitive to the TCO work function, and the TCO work function should be large enough in order to achieve high conversion efficiency of P⁺ a-Si:H/N⁺ c-Si solar cells. With the optimized parameters set, the P⁺ a-Si:H/N⁺ c-Si solar cell reaches a high efficiency (η) up to 21.849% (FF: 0.866, V_OC: 0.861 V, J_SC: 29.32 mA/cm²).     

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.     

Numerical analysis of bulk diffusion length in thin-film c-Si solar cells

We propose a novel technique of determining relationship between effective and bulk diffusion length of single-crystalline Si (c-Si) thin-film solar cells using two-dimensional device simulator. In addition, bulk diffusion length was obtained using the result of the simulation. Effective diffusion length was measured by LBIC method in order to presume bulk diffusion length of c-Si thin film. We obtained 6.7 μm for effective diffusion length of c-Si thin-film solar cell whose thickness was about 7 μm. We compared the result of measurement and simulation, bulk diffusion length of c-Si thin film prepared by CVD method was estimated more than 30 μm and recombination velocity was presumed <10⁴ cm/s for front surface and 10³ cm/s for rear surface of the cell.     

Deposition of microcrystalline silicon by electron beam excited plasma

Hydrogenated microcrystalline silicon (μc-Si:H) films were deposited by electron beam excited plasma (EBEP) CVD. As the SiH₄ flow rate increases, deposition rate steeply increases, however, crystalline fraction and grain size decrease. A high deposition rate of 69 nm/min is achieved using SiH₄ without H₂ dilution. It is shown that H atom plays key roll for μc-Si:H formation. Results show that deposition mechanism of μc-Si:H by EBEP is mainly controlled by the reaction in the plasma rather than the reaction on the film surface.     

Preparation of highly conductive p-type μc-Si:H window layer using lower concentration of hydrogen in the rf glow discharge plasma

Boron doped p-type hydrogenated microcrystalline silicon (μc-Si:H) films have been prepared by radio-frequency glow discharge method. Highly conductive p-type μc-Si:H films can be obtained even with lower concentration of hydrogen in the rf glow discharge plasma if chamber pressure is low. Effects of increase in hydrogen (H₂) flow rate and chamber pressure have been studied. The structural properties of the films have been studied by X-ray diffractometry. The electrical and optical characterization have been done by dark conductivity, Hall measurements and optical absorption measurements respectively. Film with conductivity 0.1(Ω-cm)⁻¹ with band gap 2.1 eV has been obtained.     

Low-temperature deposition of polycrystalline silicon thin films by hot-wire CVD

Polycrystalline silicon films have been prepared by hot-wire chemical vapor deposition (HWCVD) at a relatively low substrate temperature of 430°C. The material properties have been optimized for photovoltaic applications by varying the hydrogen dilution of the silane feedstock gas, the gas pressure and the wire temperature. The optimized material has 95% crystalline volume fraction and an average grain size of 70 nm. The grains have a preferential orientation along the (2 2 0) direction. The optical band gap calculated from optical absorption by photothermal deflection spectroscopy (PDS) showed a value of 1.1 eV, equal to crystalline silicon. An activation energy of 0.54 eV for the electrical transport confirmed the intrinsic nature of the films. The material has a low dangling bond-defect density of 10¹⁷ cm³. A photo conductivity of 1.9 × 10⁻⁵ Ω⁻¹cm⁻¹ and a photoresponse (σ_ph/σ_d) of 1.4 × 10² were achieved. A high minority-carrier diffusion length of 334 nm as measured by the steady-state photocarrier grating technique (SSPG) and a large majority-carrier mobility-lifetime (μτ) product of 7.1 × 10⁻⁷cm²V⁻¹ from steady-state photoconductivity measurement ensure that the poly-Si : H films possess device quality. A single junction n---i---p cell made in the configuration n⁺-c-Si/i-poly-Si: H/p-μc-Si : H/ITO yielded 3.15% efficiency under 100 mW/cm² AM 1.5 illumination.     

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.     

Dark I–V–T measurements and characteristics of (n) a-Si/(p) c-Si heterojunction solar cells

Heterojunction solar cells have been manufactured by depositing n-type a-Si:H on p-type 1–2 Ω cm Cz single-crystalline silicon substrates. An efficiency of 14.2% has been obtained for 1 cm² solar cells by using a simple (Al/(p) c-Si/(n) a-Si:H/ITO/metal grid) structure. With an additional surface texturing, we have reached an efficiency of 15.3% for 1 cm² solar cells. We have investigated the dark IV-curves in order to contribute to a better understanding of the basis of solar cells.