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.     

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%.     

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%.     

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.     

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.     

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.     

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.     

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.     

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.     

Surface textured MF-sputtered ZnO films for microcrystalline silicon-based thin-film solar cells

Highly conductive and transparent aluminum-doped zinc oxide (ZnO:Al) films were prepared by reactive mid-frequency (MF) magnetron sputtering at high growth rates. By varying the deposition pressure, pronounced differences with respect to film structure and wet chemical etching behavior were obtained. Optimized films develop good light-scattering properties upon etching leading to high efficiencies when applied to amorphous (a-Si:H) and microcrystalline (μc-Si:H) silicon-based thin-film solar cells and modules. Initial efficiencies of 7.5% for a μc-Si:H single junction and 9.7% for an a-Si:H/μc-Si:H tandem module were achieved on an aperture area of 64 cm².     

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.     

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.     

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.     

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.     

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.     

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.     

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     

Heterogeneous growth of microcrystalline silicon germanium

Microcrystalline silicon germanium films showing excellent opto-electronic properties have been prepared at a substrate temperature of 195°C by radio frequency plasma enhanced chemical vapor deposition at 13.56 MHz. A white light (AM 1.5) photoconductivity of 5×10⁻⁵/Ω cm and ambipolar diffusion length of 114 nm (from SSPG) established the device quality. Films are intrinsic (Fermi level near midgap; activation energy E_a (0.49 eV) is approximately half the band gap (1.01 eV)). Performance of preliminary n–i–p solar cells (with μc-SiGe:H i-layer) on stainless steel and molybdenum substrates justify their photosensitivities. A current density of 9.44 mA/cm² has been generated in an i-layer of only 150 nm thick without any back-reflector. A deposition rate of 0.75 Å/s for such a thin layer gives this material much advantage than a μc-Si cell, where a thickness of >2 μm is needed. A high V_oc of 0.43 eV has been achieved for such a low mobility gap cell (Ge fraction 60%).     

Spatial distribution of high-density microwave plasma for fast deposition of microcrystalline silicon film

The high-density microwave plasma utilizing a spokewise antenna was successfully applied to fast deposition of highly crystallized and photoconductive microcrystalline silicon (μc-Si:H) film at low temperatures. Among various deposition parameters, spatial distribution of ion energy (IDF) mainly determines film crystallinity. The best crystallinity was obtained at the axial distance, Z from the quartz glass plate, where the spread of mean ion energy is minimum. By optimizing the axial distance, Z and total pressure, highly crystallized and photoconductive μc-Si:H film could be fabricated with a high deposition rate of 47 Å/s at 50 mTorr in SiH₄ and Ar plasma.     

Structural and electrical studies of plasma-deposited polycrystalline silicon thin-films for photovoltaic application

Plasma-deposited polycrystalline Si films [or microcrystalline Si (μc-Si) films] produced by plasma enhanced chemical vapor deposition (PECVD) have attracted considerable attention as novel, low-cost and stable materials for the photovoltaic i-layer in p–i–n junction thin-film solar cells. The μc-Si films prepared under various deposition conditions show widely various microstructures, from a crystalline–amorphous mixed state to an almost perfect crystalline state, with different crystallographic orientations. These structural changes directly influence the carrier transport properties that play a dominant role in determining photovoltaic performance. Furthermore, obtaining a uniform built-in electric field throughout the i-layer is a crucial issue for achieving excellent photovoltaic performance. To obtain a uniform electric field, the following terms should be required for the i-layer: ‘truly’ intrinsic characteristic (or not n-type characteristics) as well as structural uniformity in the growth direction without an incubation layer. Here, structural properties of μc-Si for achieving truly intrinsic characteristics are reviewed with an emphasis on collations with the crystalline volume function and the degree of (2 2 0) crystallographic preferential orientation in the crystalline phase. In addition, we reviewed a growth mechanism for the μc-Si film that is actually used in the photovoltaic i-layer in highly efficient solar cells: hybrid-phase growth consisting of conventional vapor-phase growth at the surface and the solid-phase crystallization that simultaneously occurs in the film. That growth is very effective in producing structural uniformity along the growth direction and for formation of crystallites directly on the underlying doped layer.