Multicrystalline silicon solar cells with porous silicon emitter

A review of the application of porous silicon (PS) in multicrystalline silicon solar cell processes is given. The different PS formation processes, structural and optical properties of PS are discussed from the viewpoint of photovoltaics. Special attention is given to the use of PS as an antireflection coating in simplified processing schemes and for simple selective emitter processes as well as to its light trapping and surface passivating capabilities. The optimization of a PS selective emitter formation results in a 14.1% efficiency mc-Si cell processed without texturization, surface passivation or additional ARC deposition. The implementation of a PS selective emitter into an industrially compatible screenprinted solar cell process is made by both the chemical and electrochemical method of PS formation. Different kinds of multicrystalline silicon materials and solar cell processes are used. An efficiency of 13.2% is achieved on a 25 cm² mc-Si solar cell using the electrochemical technique while the efficiencies in between 12% and 13% are reached for very large (100–164 cm²) commercial mc-Si cells with a PS emitter formed by chemical method.     

Study of electrical properties of oxidized porous silicon for back surface passivation of silicon solar cells

Back surface passivation becomes a key issue for the silicon solar cells made with thin wafers. The high surface recombination due to the metal contacts can be lowered by reducing the back contact area and forming local back surface field (LBSF) in conjunction with the passivation with dielectric layer. About 3×10^-7 m thick porous silicon (PS) layer with pore diameter mostly of 1×10^-8–5×10^-8 m was formed by chemical etching of silicon using the acidic solution containing hydrofluoric acid (HF), nitric acid (HNO₃) and De-ionized water in the volume ratio 1:3:5 at 298 K for which etching time was kept constant for 360 s. Electrical properties of oxidized PS was studied through the current–voltage (I–V) and capacitance–voltage (C–V) characteristics of the metal–insulator–semiconductor (MIS) device in which the oxidized PS was used as an insulating layer and the results were further analyzed. The C–V curves of all the studies MIS devices showed the negative flatband voltage varying from -2 to , confirming that the oxidized layer of PS has fixed positive charge.     

The influence of porous silicon on junction formation in silicon solar cells

In this work the results of a structural investigation by SEM of porous silicon (PS) before and after diffusion processes are reported. The formation of PS n⁺/p structures were carried out on PS p/p silicon wafers with two methods: from POCl₃ in a conventional furnace and from a phosphorous doped paste in an infrared furnace. Sheet resistance was found to be a strong function of PS structure. Further details on sheet resistance distribution are reported. The electrical contacts in prepared solar cells were obtained by screen printing process, with a Du Ponte photovoltaic silver paste for front contacts and home-prepared silver with 3% aluminium paste for the back ones. Metallization was done in the infrared furnace. Solar cell current–voltage characteristics were measured under an AM 1.5 global spectrum sun simulator. The average results for multi-crystalline silicon solar cells without antireflection coating are: I_sc=720 (mA), V_oc=560 (mV), FF=69%, Eff=10.6% (area 25 cm²).     

Two-dimensional LBIC and internal quantum efficiency investigations of porous silicon-based gettering procedure in multicrystalline silicon

In this work, a porous silicon-based gettering technique was applied to multicrystalline silicon (mc-Si) wafers. Porous silicon (PS) was formed by the stain-etching technique and was used as a sacrificial layer for efficient external purification technique. The gettering procedure consists of achieving a PS/mc-Si/PS structure that undergoes a heat treatment at 900 °C for 90 min in an infrared furnace under a N₂ ambient. After removing the PS layers, mc-Si solar cells were realized. The effect of the gettering procedure was evaluated by means of the laser beam-induced current (LBIC) mapping, the internal quantum efficiency (IQE) mapping and the dark current-voltage (I-V) characteristic. Consequently, LBIC and IQE images show an enhancement of the gettered sample as compared to a reference untreated one. The serial resistance and the shunt resistance carried out from the dark I-V curves confirm this gettering-related solar cell improvement.     

Double porous silicon layer on multi-crystalline Si for photovoltaic application

Double porous silicon (d-PS) layers formed by acid chemical etching on a top surface of n⁺/p multi-crystalline silicon solar cells were investigated with the aim to improve the performance of standard screen-printed silicon solar cells. First a macro-porous layer is formed on mc-Si. The role of this layer is texturization of surface. Next, the cells have been manufactured using standard technology based on screen-printing metallization. Finally, a second mezo-porous layer in n⁺ emitter of cell has been produced. The role of this PS layer is to serve as an antireflection coating. In this way, we have obtained d-PS layers on these solar cells. The paper present observation of d-PS microstructure with SEM as well as measurements of its effective reflectance at the level of 2.5% in the 400–1000 nm length wave range. The efficiency of the solar cells with this structure is about 12%.     

Performance improvements of crystalline silicon by iterative gettering process for short duration and with the use of porous silicon as sacrificial layer

In this work, we demonstrate that an efficient purification method of silicon wafers where iterative sequences were used. Each sequence consists of forming porous silicon (PS) on both sides of the samples, followed by thermal annealing in an infrared furnace under N₂/SiCl₄ ambient. Improvements of the electronic parameters were obtained by optimizing the heat treatments temperatures and the number and duration of the iteration sequences. Best results were obtained for temperatures below 980 °C and for three sequences of 20 min each one. After three sequences the mobility of the majority carrier improved from 94 cm² V⁻¹ s⁻¹ (for untreated wafer) to about 374 cm² V⁻¹ s⁻¹. The observed results were explained taking into account the transport properties of the impurities in the porous media and their concentration at the walls at each iteration. It was found that short iterative sequences give almost the same results than one long sequence duration. Silicon solar cells based on iterative gettered silicon wafers exhibit an increase in the short-circuit current and the open-circuit voltage. This fact seems to be important to ameliorate solar grade silicon (SGS) based solar cells performances.     

Enhancement of photovoltaic properties of multicrystalline silicon solar cells by combination of buried metallic contacts and thin porous silicon

Photovoltaic properties of buried metallic contacts (BMCs) with and without application of a front porous silicon (PS) layer on multicrystalline silicon (mc-Si) solar cells were investigated. A Chemical Vapor Etching (CVE) method was used to perform front PS layer and BMCs of mc-Si solar cells. Good electrical performance for the mc-Si solar cells was observed after combination of BMCs and thin PS films. As a result the current-voltage (I-V) characteristics and the internal quantum efficiency (IQE) were improved, and the effective minority carrier diffusion length (Ln) increases from 75 to 110 μm after BMCs achievement. The reflectivity was reduced to 8% in the 450-950 nm wavelength range. This simple and low cost technology induces a 12% conversion efficiency (surface area = 3.2 cm²). The obtained results indicate that the BMCs improve charge carrier collection while the PS layer passivates the front surface.     

Texturing of large area multi-crystalline silicon wafers through different chemical approaches for solar cell fabrication

Surface texturing of silicon can reduce the reflectance of incident light and hence increase the conversion efficiency of solar cells. Comparatively lesser concentrated (10%) standard alkaline (NaOH/KOH) solution does not give good textured multi-crystalline silicon (mc-Si) surface, which could give satisfactory open-circuit voltage. This is due to grain-boundary delineation with steps formed between successive grains of different orientations. In this work an attempt has been made to obtain a well-textured mc-Si surface through three different approaches. The first two are with two different types of acid solutions and the third with concentrated alkaline NaOH. Solutions of HF–HNO₃–CH₃COOH/H₂O system with different concentrations of HF and HNO₃ were used for texturing. The results on the effect of texturing of these three solutions on the surface morphology of very large area (125 mm×125 mm) mc-Si wafer as well as on the performance parameters of solar cell are presented in this paper. Attempts have been made to study extensively the surface morphologies of mc-Si wafers in two effective regions of the isoetch curves of the HF:HNO₃:diluent's system. Also we studied the reflectance, uniformity, spectral response, short-circuit current, open-circuit voltage, fill factor and dark current–voltage of the cells fabricated using wafers textured with the three different methods. Short-circuit current of the solar cells fabricated using acid-textured wafers were measured to be in the range of 4.93 A. This value is 0.37 and 0.14 A higher than the short-circuit current values measured in the cells fabricated with isotextured and alkaline-textured wafers, respectively.     

Comparison of the properties of porous silicon films with different back contacts (Ag, Al) for possible photovoltaic applications

In this work, porous silicon (PS) films were prepared by anodization on polished substrates of (1 0 0) Si for a fixed current density (I_d)20 mA cm⁻² and for a fixed anodization time of 30 min using different screen-printed (SP) back contacts, namely Ag and Al. The properties of PS formed using Ag as the back contact were found to be superior compared to the corresponding film using Al as the back contact. The PS formed with Ag-back contact exhibits higher porosity, negligible photoluminescence (PL) decay, better adherence to the substrate and smooth surface morphology compared to that formed with Al as the back contact for the same current density and time of anodization. Fourier transform infrared (FTIR) studies indicated significant presence of Si–O related features at 1050–1150 cm⁻¹ for PS films formed with Al as back contact, which could be responsible for traps and interface (PS–Si) defect densities as compared to corresponding PS films with Ag as the back contact. Measurements of capacitance–voltage (C–V) and current–voltage (I–V) were used for the investigation of the electrical properties of PS films with different back contacts. The frequency-dependent C–V characteristics were analysed to understand the effects of interface states and traps on the properties of PS films. The results have been analysed in terms of eutectic temperature and back surface field (BSF) across the metal–silicon interface.     

The influence of porous silicon coating on silicon solar cells with different emitter thicknesses

The influence of the emitter thickness on the photovoltaic properties of monocrystalline silicon solar cells with porous silicon was investigated. The measurements were carried out on n⁺p silicon junction whose emitter depth was varied between 0.5 and 2.2 μm. A thin porous silicon layer (PSL), less than 100 nm, was formed on the n⁺ emitter. The electrical properties of the samples with PS were improved with decrease of the n⁺p junction depth. Our results demonstrate short-circuit current values of about 35–37 mA/cm² using n⁺ region with 0.5 μm depth. The observed increase of the short-circuit current for samples with PS and thin emitter could be explained not only by the reduction of the reflection loss and surface recombination but also by the additional photogenerated carriers within the PSL. This assumption was confirmed by numerical modeling. The spectral response measurements were performed at a wavelength range of 0.4–1.1 μm. The relative spectral response showed a significant increase in the quantum efficiency of shorter wavelengths of 400–500 nm as a result of the PS coating. The obtained results point out that it would be possible to prepare a solar cell with 19–20% efficiency by the proposed simple technology.     

Analysis of anomalous current–voltage characteristics of silicon solar cells

The current–voltage characteristics of solar cells, under illumination and in the dark, represent a very important tool for characterizing the performance of the solar cell.The PC-1D computer program has been used to analyze the deviation of the dark current–voltage characteristics of p–n junction silicon solar cells from the ideal two-diode model behavior of the cell, namely the appearance of “humps” in the I–V characteristics. The effects of the surface recombination velocity, the minority-carrier lifetimes in the base — and emitter regions of the solar cell, as well as the temperature dependence of the I–V characteristics have been modeled using PC-1D.It is shown that the “humps” in the I–V characteristics arise as a result of recombination within the space-charge region of the solar cell, occurring when conditions for recombination are different from the simple assumptions of the Sah–Noyce–Shockley theory.     

Comparative study of different approaches of multicrystalline silicon texturing for solar cell fabrication

Alkali etchant cannot produce uniformly textured surface to generate satisfactory open circuit voltage as well as the efficiency of the multi-crystalline silicon (mc-Si) solar cell due to the unavoidable grain boundary delineation with higher steps formed between successive grains of different orientations during alkali etching of mc-Si. Acid textured surface formed by using chemicals with HNO₃–HF–CH₃COOH combination generally helps to improve the open circuit voltage but always gives lower short circuit current due to high reflectivity. Texturing mc-Si surface without grain boundary delineation is the present key issue of mc-Si research. We report the isotropic texturing with HF–HNO₃–H₂O solution as an easy and reliable process for mc-Si texturing. Isotropic etching with acidic solution includes the formation of meso- and macro-porous structures on mc-Si that helps to minimize the grain-boundary delineation and also lowers the reflectivity of etched surface. The study of surface morphology and reflectivity of different mc-Si etched surfaces has been discussed in this paper. Using our best chemical recipe, we are able to fabricate mc-Si solar cell of 14% conversion efficiency with PECVD AR coating of silicon nitride film. The isotropic texturing approach can be instrumental to achieve high efficiency in mass production using relatively low-cost silicon wafers as starting material with the proper optimization of the fabrication steps.     

Concentrator silicon solar cells from silicon industry rejects

Two types of silicon (Si) substrates (40 n-type with uniform base doping and 40 n/n⁺ epitaxial wafers) from the silicon industry rejects were chosen as the starting material for low-cost concentrator solar cells. They were divided into four groups, each consisting of 20 substrates: 10 are n/n⁺ and 10 are n substrates, and the solar cells were prepared for different diffusion times (45, 60, 75 and 90 min). The fabricated solar cells on n/n⁺ substrates (prepared with a diffusion time of 75 min) showed better parameters. In order to improve their performances, particularly the fill factor, 20 new solar cells on n/n⁺ substrates were fabricated using the same procedure (the diffusion time was 75 min)—but with four new front contact patterns. Investigation of current–voltage (I–V) characteristics under AM 1.5 showed that the parameters of these 20 new solar cells have improved in comparison to previous solar cells' parameters, and were as follows: open-circuit voltage (V_OC=0.57 V); short circuit current (I_SC=910 mA), and efficiency (η=9.1%). Their fill factor has increased about 33%. The I–V characteristics of these solar cells were also investigated under different concentration ratios (X), and they exhibited the following parameters (under X=100 suns): V_OC=0.62 V and I_SC=36 A.     

Formation of porous silicon for large-area silicon solar cells: A new method

Luminescent porous silicon (PS) was prepared for the first time using a spraying set-up, which can diffuse in a homogeneous manner HF solutions, on textured or untextured (1 0 0) oriented monocrystalline silicon substrate. This new method allows us to apply PS onto the front-side surface of silicon solar cells, by supplying very fine HF drops. The front side of N⁺/P monocrystalline silicon solar cells may be treated for long periods without altering the front grid metallic contact. The monocrystalline silicon solar cells (N⁺/P, 78.5 cm²) which has undergone the HF-spraying were made with a very simple and low-cost method, allowing front-side Al contamination. A poor but expected 7.5% conversion efficiency was obtained under AM1 illumination. It was shown that under optimised HF concentration, HF-spraying time and flow HF-spraying rate, Al contamination favours the formation of a thin and homogeneous hydrogen-rich PS layer. It was found that under optimised HF-spraying conditions, the hydrogen-rich PS layer decreases the surface reflectivity up to 3% (i.e., increase light absorption), improves the short circuit current (I_sc), and the fill factor (FF) (i.e., decreases the series resistance), allowing to reach a 12.5% conversion efficiency. The dramatic improvement of the latter is discussed throughout the influence of HF concentration and spraying time on the I–V characteristics and on solar cells parameters. Despite the fact that the thin surfae PS layer acts as a good anti-reflection coating (ARC), it improves the spectral response of the cells, especially in the blue-side of the solar spectrum, where absorption becomes greater, owing to surface band gap widening and conversion of a part of UV and blue light into longer wavelengths (that are more suitable for conversion in a Si cell) throughout quantum confinement into the PS layer.     

Degradation and annealing of amorphous silicon solar cells by current injection: experiment and modeling

In this paper we report in detail on the effect of current injection in amorphous silicon solar cells. A set of devices has been degraded and then annealed at different current intensities. Device performances during the whole experiment have been monitored by current–voltage characteristics and quantum efficiency curves. It has been found that annealing rate increases with current intensity, while stabilized photovoltaic parameters decrease. Time evolution of efficiency and short-circuit current during degradation has been reproduced by a numerical device modeling, resulting in a pronounced increase of defects near the p–i interface. The model also demonstrated that annealing results are not well reproduced if current-induced annealing is not energy selective.     

Improvement of multicrystalline silicon solar cell performance via chemical vapor etching method-based porous silicon nanostructures

In this paper, we report on the effect of chemical vapor etching-based porous silicon (PS) on the performance of multicrystalline silicon solar cells performed via deep n⁺/p junction-type structures. Chemical vapor etching of silicon leads to the formation of porous silicon (PS) nanostructures that dramatically decrease the surface reflectivity from 30% to about 8%, and increase the minority carrier diffusion lengths from 90 μm to 170 μm. As a result, the short-circuit current density was improved by more than 20% and the fill factor (FF) by about a 10%. An enhancement of the photovoltaic conversion energy efficiency of the solar cells from 7% to 10% was observed. This low-cost PS formation process can be applied in the photovoltaic cell technology as a standard procedure.     

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.     

Gettering effects by aluminum upon the dark and illuminated I–V characteristics of N–P–P silicon solar cells

Impurity gettering is an essential process step in silicon solar cell technology. A widely used technique to enhance silicon solar cell performance is the deposition of an aluminum layer on the back surface of the cell, followed by a thermal annealing. The aluminum thermal treatment is typically done at temperatures around 600°C for short times (10–30 min). Seeking a new approach of aluminum annealing at the back of silicon solar cells, a systematic study about the effect the above process has on dark and illuminated I–V cell characteristics is reported in this paper. We report results on silicon solar cells where annealing of aluminum was done at two different temperatures (600°C and 800°C), and compare the results for cells with and without aluminum alloying. We have shown that annealing of the aluminum in forming gas at temperatures around 800°C causes improvement of the electrical cell characteristics. We have also made evident that for temperatures below 250 K, the predominant recombination process for our cells is trap-assisted carrier tunneling for both annealing temperatures, but it is less accentuated for cells with annealing of aluminum at 800°C. For temperatures above 250 K, the recombination proceeds through Shockley–Read–Hall trap levels, for cells annealed at both temperatures. Furthermore, it seems from DLTS measurements that there is gettering of iron impurities introduced during the fabrication processes. The transport of impurities from the bulk to the back surface (alloyed with aluminum) reduces the dark current and increases the effective diffusion length as determined from dark I–V characteristics and from spectral response measurements, respectively. All these effects cause a global efficiency improvement for cells where aluminum is annealed at 800°C as compared to conventional cells where the annealing was made at 600°C.     

Porous silicon as an intermediate layer for thin-film solar cell

The potential of porous silicon (PS) with dual porosity structure as an intermediate layer for ultra-thin film solar cells is described. It is shown that a double-layered PS with a porosity of % allows to grow epitaxial Si film at medium temperature (725°–800°C) and at the same time serves as a gettering/diffusion barrier for impurities from potentially contaminated low-cost substrate. A 3.5 μm thin-film cell with reasonable efficiency is realized using such a PS intermediate layer.     

Formation and characterization of porous silicon layers for application in multicrystalline silicon solar cells

The electrochemical formation of porous silicon (PS) layers in the n⁺ emitter of silicon p–n⁺ homojunctions for solar energy conversion has been investigated. During the electrochemical process under constant polarization, a variation of the current density occurs. This effect is explained by considering the doping impurity gradient in the emitter and by TEM characterization of the PS layer structure. Optical transmission measurements indicate that modifications of the refractive index and absorption coefficient of PS are mainly related to the porosity value. Reflectivity measurements, spectral response and I–V characteristics show that PS acts as an efficient antireflection coating layer. However, beyond a critical layer thickness, i.e. when PS reaches the p–n⁺ interface, the junction properties are degraded.