Ambient stability of wet chemically passivated germanium wafer for crystalline solar cells

Surface passivation has been recognized as a crucial step in the evaluation of minority carrier lifetime of photovoltaic materials as well as in the fabrication of high efficient solar cells. Dilute acids of HF and HCl are employed for germanium (Ge) surface passivation. An effective lifetime of passivated Ge wafers has been evaluated by a microwave photoconductive decay (μ-PCD) measurement. Surface recombination velocities, S, of H- and Cl-terminated Ge surfaces are 23 and 37 cm/s, respectively. The stability of passivated Ge surfaces against exposure to air has also been examined. The HCl-passivated Ge surfaces are found to be more robust than HF-passivated surfaces.     

Microwave detection of minority carriers in solar cell silicon wafers

Techniques measuring photoconductive decay by means of microwaves (μ-PCD) can be used to detect free carriers in semiconductors. The instrument as developed at ECN for characterization of the solar cell material is described. The experimental details of two measurement techniques and the theoretical background are discussed. In the decay method the effective mean lifetime of the minority carriers is measured. In the harmonic modulation technique information about the lifetime of the minorities is contained in the phase-shift of the microwave signal relative to the phase of the light intensity. The aim of this research is to determine the bulk mean lifetime of the minority carriers and the surface recombination velocities of solar cell silicon wafers by a non-destructive and contactless technique. Typical experiments will be presented.     

Electrical properties of multicrystalline silicon produced by electromagnetic casting process: Degradation and improvement

The electrical properties of boron-doped multicrystalline silicon for photovoltaic applications, elaborated by the cold crucible pulling process, are studied by the photoconductivity decay method and the electron beam-induced current measurement technique. The bulk lifetime mapping of the minority carriers in the as-grown silicon wafers is drawn up using both the techniques. Moreover, the consequence of phosphorus doping on the recombination properties of extended defects are studied using the EBIC measurements. Two different treatments are investigated in order to improve the electrical properties of the as-grown silicon wafers: (a) thermal phosphorus diffusion, for which the gettering efficiency is determined by the different treatment parameters; (b) remote plasma hydrogen passivation which leads to increase of the minority carrier lifetime.     

Extended high temperature Al gettering for improvement and homogenization of minority carrier diffusion lengths in multicrystalline Si

Multicrystalline Si for photovoltaic applications is a very inhomogeneous material with localized regions of high dislocation density and large impurity and precipitate concentrations which limit solar cell efficiency by acting as carrier recombination sites. Due to slow dissolution of precipitates in multicrystalline Si, these regions cannot be improved by conventional P and Al gettering treatments for removal of metal impurities which give good results for single crystal Si. It is shown that an extended high temperature Al gettering treatment can improve minority carrier diffusion lengths in these low quality regions and homogenize the electrical properties of multicrystalline Si wafers.     

Spatially resolved investigations of lifetime enhancement in vertically grown, multicrystalline silicon ribbons

The influence of gettering or defect passivation steps on recombination activity in the vertically grown, multicrystalline ribbon materials edge-defined film-fed growth and string ribbon silicon has been investigated with the help of photoconductance decay. In contrast to well-known results of integral measurements, spatially resolved lifetime mappings have been obtained by applying microwave detection technique.This aspect of spatial resolution has been found to be indispensable for investigating the impact of different processing steps on material quality in an accurate way. Apart from strong variations in as-grown lifetimes that have been found throughout vertically grown silicon wafers, this is due to areas of comparable starting lifetimes which have been revealed to react very differently to applied processing steps. After processing, some of them reach minority charge carrier lifetimes of more than 300 μs whereas others just show values of a few microseconds. As a consequence, the results of integral measurements strongly depend on the nature of areas incorporated in the specific sample. An impression of the corresponding uncertainties inherent to integral measurements has been obtained by statistical evaluation of spatially resolved lifetime data.     

Minority carrier lifetime in plasma-textured silicon wafers for solar cells

In this work a comparison between plasma-induced defects by two different SF₆ texturing techniques, reactive ion etching (RIE) and high-density plasma (HDP) is presented. It is found that without any defect-removal etching (DRE), the minority carrier lifetime is the highest for the HDP technique. After DRE, the minority carrier lifetime rises as high as 750 μs for both RIE- and HDP-textured wafers at an excess carrier density of 1×10¹⁵ cm⁻³. The measured lifetimes correspond to an implied one-sun open-circuit voltage of around 680 mV compared to about 640 mV before DRE for the HDP-textured wafers. FZ silicon 1 0 0 wafers were used in this study. We also noted that in the RIE process, the induced defect density was significantly lower for wafers etched at 300 K than those etched at 173 K.     

Surface passivation of crystalline silicon wafer via hydrogen plasma pre-treatment for solar cells

The carrier lifetime of crystalline silicon wafers that were passivated with hydrogenated silicon nitride (SiN_x:H) films using plasma enhanced chemical vapor deposition was investigated in order to study the effects of hydrogen plasma pre-treatment on passivation. The decrease in the native oxide, the dangling bonds and the contamination on the silicon wafer led to an increase in the minority carrier lifetime. The silicon wafer was treated using a wet process, and the SiN_x:H film was deposited on the back surface. Hydrogen plasma was applied to the front surface of the wafer, and the SiN_x:H film was deposited on the hydrogen plasma treated surface using an in-situ process. The SiN_x:H film deposition was carried out at a low temperature (<350 °C) in a direct plasma reactor operated at 13.6 MHz. The surface recombination velocity measurement after the hydrogen plasma pre-treatment and the comparison with the ammonia plasma pre-treatment were made using Fourier transform infrared spectroscopy and secondary ion mass spectrometry measurements. The passivation qualities were measured using quasi-steady-state photoconductance. The hydrogen atom concentration increased at the SiN_x:H/Si interface, and the minority carrier lifetime increased from 36.6 to 75.2 μs. The carbon concentration decreased at the SiN_x:H/Si interfacial region after the hydrogen plasma pre-treatment.     

Monitoring of silicon solar cell technology via the surface photovoltage method

The surface photovoltage (SPV) technique adapted to thin samples was used to monitor solar cell technology. The relatively short minority carrier diffusion length from 70 to 80 μm found in p-bulk of the cells results from the presence of a layer with structural defects near the surface. The measurement of successively etched samples reveals that freshly cut off silicon wafers are already strongly destroyed to a depth of at least 35 μm. A diffusion length of about 300 μm was evaluated in the samples after removing the disturbed layer.     

Dependence of the recombination in thin-film Si solar cells grown by ion-assisted deposition on the crystallographic orientation of the substrate

One promising strategy for achieving high-quality polycrystalline silicon thin-film solar cells on glass is based on low-temperature ion-assisted deposition for epitaxial thickening of a thin, large-grained seeding layer on glass. The crystal growth on the seeding layer is influenced by various factors, amongst which the crystal orientation of the grains plays a substantial role. In this paper we investigate how the electronic properties of solar cells grown on “ideal” seeding layers (Si wafers) are influenced by the crystallographic orientation of the substrate. The Si wafers are heavily doped p-type, ensuring that their contribution to the photogenerated current is small. The films grown on (1 0 0)-oriented Si substrates have a very low density of structural defects, while the films grown on (1 1 1)-oriented Si substrates display a high density of twin defects. The electronic properties of the thin-film solar cells were investigated by means of open-circuit voltage measurements as a function of the incident light intensity. The (1 0 0)-oriented diodes consistently exhibit a higher V_oc than the (1 1 1)-oriented diodes throughout the entire illumination range from 10⁻³ to 10³ Suns. We determine 7 μm as the bulk minority carrier diffusion length of the as-grown (1 0 0)-oriented Si film. A lower bound of 3 μm was found for the bulk minority carrier diffusion length in the as-grown (1 1 1)-oriented Si film. The performances of both types of solar cells were improved by hydrogenation in an ammonia plasma. At voltages around the 1-Sun maximum power point the improvement is due to a reduction of non-ideal current mechanisms. The diffusion length of the (1 0 0) diode remains unaffected by hydrogenation while the lower bound of the diffusion length of the (1 1 1) diode improves to 10 μm.     

A detailed study of H2 plasma passivation effects on GaAs/Si solar cell

The hydrogen plasma passivation effects of MOCVD-grown GaAs solar cell on Si substrate have been studied in detail. To get a more reproducible increase of conversion efficiency and test the thermal stability of the plasma-exposed GaAs/Si solar cell, both the plasma exposure and post-passivation annealing conditions were optimized. Annealing the H₂ plasma passivated GaAs/Si solar cell at 450°C in AsH₃/H₂ ambient seems a very essential parameter to restore the carrier concentration, especially, without losing the beneficial effects of H incorporation into GaAs on Si. For the H₂ plasma passivated GaAs/Si solar cell, a highest conversion efficiency of 18.3% was obtained compared with that of the as-grown cell (16.6%) due to the H passivation effects on nonradiative recombination centers, which increased the minority carrier lifetime.     

Impact of thermal processes on multi-crystalline silicon

Fabrication of modern multi-crystalline silicon solar cells involves multiple processes that are thermally intensive. These include emitter diffusion, thermal oxidation and firing of the metal contacts. This paper illustrates the variation and potential effects upon recombination in the wafers due to these thermal processes. The use of light emitter diffusions more compatible with selective emitter designs had a more detrimental effect on the bulk lifetime of the silicon than that of heavier diffusions compatible with a homogenous emitter design and screen-printed contacts. This was primarily due to a reduced effectiveness of gettering for the light emitter. This reduction in lifetime could be mitigated through the use of a dedicated gettering process applied before emitter diffusion. Thermal oxidations could greatly improve surface passivation in the intragrain regions, with the higher temperatures yielding the highest quality surface passivation. However, the higher temperatures also led to an increase in bulk recombination either due to a reduced effectiveness of gettering, or due to the presence of a thicker oxide layer, which may interrupt hydrogen passivation. The effects of fast firing were separated into thermal effects and hydrogenation effects. While hydrogen can passivate defects hence improving the performance, thermal effects during fast firing can dissolve precipitating impurities such as iron or de-getter impurities hence lower the performance, leading to a poisoning of the intra-grain regions.     

Characterisation of single crystalline silicon grown by Czochralski method

Abstract

The conversion efficiency of solar cells made from single crystalline Si is generally about 3–4% higher than those made from Si multicrystal by the casting method. In this paper, the single crystalline Si obtained by the Czochralski method using metallurgical grade silicon raw materials was characterised by minority carrier lifetime, optical microscopy, the concentration of impurities and the conversion efficiency. The influence of crystalline defects and impurity elements on the electrical property has been investigated. We can conclude that both defects and impurity elements play important roles in the deterioration of the minority carrier lifetime. The conversion efficiency of solar cell using the middle wafer can reach 11·39%.     

Gettering of impurities in solar silicon

Electrical properties of crystalline silicon wafers used for photovoltaïcs are degraded by metallic impurity atoms. Such atoms are introduced during the crystal growth or during the processing steps needed to prepare solar cells. External gettering treatments such as phosphorus diffusion from a POCl₃ source or Al–Si alloying are needed to restore or to improve the bulk electrical properties of the material. Monocrystalline wafers can be easily ugraded by such treatments. In multicrystalline silicon wafers, external gettering by phosphorus diffusion, as well as by Al–Si alloying are efficient, provided the temperature does not exceed 900°C. Longer treatments (2–4 h) are needed in order to increase the minority carrier diffusion length beyond the wafer thickness. So longer times are necessary to dissolve metallic atom containing precipitates. However, if the major part of the wafer is neatly improved, some regions containing dislocation tangles are poorly modified. In such regions, impurities could be involved in the formation of silicates which cannot be dissolved during the gettering treatment. Nevertheless, external gettering treatments are able to clean efficiently single crystalline and multicrystalline silicon wafers, provided the oxygen concentration and the defect density are not too high and are homogeneously distributed.     

Two-dimensional resolution of minority carrier diffusion constants in different silicon materials

Hall measurements are a common method to determine the majority charge carrier diffusion constant. But the diffusion constant of the minority carriers D_n, the more interesting parameter in photovoltaics, is rather hard to detect. In this paper we introduce a method to determine D_n locally resolved and mapped in two dimensions. For that purpose the local diffusion length L_diff, which can be calculated from LBIC (laser beam induced current) measurements, has been combined with the local bulk lifetime τ_b received by μ-PCD (microwave-detected photo conductance decay) measurements. We evaluated the diffusion constants of the minority charge carriers D_n for different p-type silicon materials with a resolution of 100 μm. The measurements were carried out on solar cells before and after remote plasma hydrogen passivation in order to get an impression of the diffusion constant dependency on hydrogen incorporation.     

Chemical surface passivation of low resistivity p-type Ge wafers for solar cell applications

The measurement of the bulk minority carrier lifetime of semiconductors requires efficient passivation of the recombination states at the surface. While numerous recipes have been published for Si-surface passivation, no adequate passivation methods are available for Ge. This paper presents a new and straightforward passivation method, based on a solution of iodine in polyvinyl acetate and acetone. The dependence of the carrier lifetime with time after passivation and with Ge resistivity has been investigated. It is found that the lifetime in this low resistivity material is strongly governed by Auger recombination.     

Effects of grain boundaries in polycrystalline silicon thin-film solar cells based on the two-dimensional model

The two-dimensional calculation for polycrystalline Si thin-film solar cells was performed. Two models, “stripe structure” and “columnar structure”, were applied for the solar cells composed of grains. For the stripe structure of 20 μm active layer, to keep the efficiency distribution within 5% for individual unit cells, the stripe width requires more than 500 μm for a minority-carrier lifetime of 1×10⁻⁵ s and recombination velocity at the grain boundary of 1×10⁴ cm/s. For the columnar structure of 10 μm active layer, to keep the efficiency independent of grain size, the recombination velocity should be kept less than 1×10³ cm/s. If imperfect passivation of a grain boundary is given, the way of decreasing carrier concentration to 10¹⁴ cm⁻³ in an active layer may realize insusceptible output. An appropriate device modeling is needed in the two-dimensional calculation for polycrystalline Si thin films with an electron diffusion length close to or more than grain size and with a poorly passivated grain boundary. The calculated efficiency using bad model will include an error of about 1% as overestimation.     

SiO2 passivation layer grown by liquid phase deposition for silicon solar cell application

Surface passivation is one of the primary requirements for high efficient silicon solar cells. Though the current existed passivation techniques are effective, expensive equipments are required. In this paper, a comprehensive understanding of the SiO₂ passivation layer grown by liquid phase deposition (LPD) was presented, which was cost-effective and very simple. It was found that the post-annealing process could significantly enhance the passivation effect of the LPD SiO₂ film. Besides, it was revealed that both chemical passivation and field-effect passivation mechanisms played important roles in outstanding passivation effect of the LPD SiO₂ film through analyzing the minority carrier lifetime and the surface recombination velocity of n-type and p-type silicon wafers. Although the deposition parameters had little influence on the passivation effect, they affected the deposition rate. Therefore, appropriate deposition parameters should be carefully chosen based on the compromise of the deposition rate and fabrication cost. By utilizing the LPD SiO₂ film as surface passivation layer, a 19.5%-efficient silicon solar cell on a large-scale wafer (156 mm × 156 mm) was fabricated.     

Characterization of multicrystalline silicon wafers by non-invasive measurements

Non-invasive transient photoconductance measurements of large grain multicrystalline silicon wafers (ρ=1 Ω cm) are presented. It is shown that the surfaces of untreated wafers can be characterized as infinite sinks for excess charge carriers. The value 24.5 cm² s⁻¹ for the minority carrier diffusion constant was determined in all samples. So in untreated wafers, surface recombination yields a known contribution to the decay time measured and the volume lifetime can be determined. Application of these measurements as a standard characterization of multicrystalline silicon wafers is discussed.     

Gettering impurities from crystalline silicon by phosphorus diffusion using a porous silicon layer

The possible benefits of phosphorus-based gettering applied to crystalline silicon wafers have been evaluated. The gettering process is achieved by forming porous silicon (PS) layers on both sides of the Si wafers. The PS layers were formed by the stain-etching technique, and phosphorus diffusion using liquid POCl₃-based source was done on both sides of the Si wafer. The realized phosphorus/PS/Si/PS/phosphorus structure undergoes a heat treatment in an infrared furnace under an O₂/N₂ controlled atmosphere. This heat treatment allows phosphorus to diffuse throughout the PS layer and to getter eventual metal impurities towards the phosphorus doped PS layer. The gettering effect was evaluated using four probe points, Hall effect measurements and the light beam induced current (LBIC) technique. These techniques enable to measure the density and the mobility of the majority carrier and the minority carrier diffusion length (L_d) of the Si substrate. We noticed that the best gettering is achieved at 900 °C for 90 min of heat treatment. After gettering impurities, we found an apparent enhancement of the mobility and the minority carrier diffusion length as compared to the reference substrate.     

UVCVD silicon nitride passivation and ARC layers for multicrystalline solar cells

This work intends to investigate the effectiveness of silicon nitride layers (SiN_x : H) deposited by photochemical vapor deposition (UVCVD) for antireflection and passivation purposes when applied to electromagnetically casted silicon solar cells (EMC). Effective reflectivity of 10.8% is achieved, as well as 66% increase of minority carrier lifetime.