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.     

Performance enhancement of membrane electrode assemblies with plasma etched polymer electrolyte membrane in PEM fuel cell

In this work, a surface modified Nafion 212 membrane was fabricated by plasma etching in order to enhance the performance of a membrane electrode assembly (MEA) in a polymer electrolyte membrane fuel cell. Single-cell performance of MEA at 0.7 V was increased by about 19% with membrane that was etched for 10 min compared to that with untreated Nafion 212 membrane. The MEA with membrane etched for 20 min exhibited a current density of 1700 mA cm⁻² at 0.35 V, which was 8% higher than that of MEA with untreated membrane (1580 mA cm⁻²). The performances of MEAs containing etched membranes were affected by complex factors such as the thickness and surface morphology of the membrane related to etching time. The structural changes and electrochemical properties of the MEAs with etched membranes were characterized by field emission scanning electron microscopy, Fourier transform-infrared spectrometry, electrochemical impedance spectroscopy, and cyclic voltammetry.     

Effectiveness of anisotropic etching of silicon in aqueous alkaline solutions

Optical effectiveness of anisotropic etching of (1 0 0) silicon in inorganic alkaline solution has been studied from the view point of its application in commercial silicon solar cells. The damage caused by ID saw or wire saw during slicing of the wafer is required to be removed for fabrication of solar cells. The etch rates for removal of the surface damages for boron doped Czochralski wafers of 1–2 Ω cm resistivity in 20% NaOH solution at 80°C was measured and was found to be 1.4 μm/min. After the damage removal, texturisation was obtained in 2% NaOH solution buffered with isopropyl alcohol at 80°C. An optical effectiveness parameter f_eff,λ was defined and its value was estimated from the study of reflectivity and topography of the wafers textured for different durations of time. The kinetics of anisotropic etching was studied which indicated that growth of pyramids begins at preferential sites which may arise due to crystalline defects or wetting. Silicon solar cells have been realized by standard process involving phosphorous diffusion and vacuum evaporated front and back contacts. The value of optical effectiveness parameter is found to have a direct correlation with the improvement in short circuit current density of the textured cells.     

Direct patterned etching of silicon dioxide and silicon nitride dielectric layers by inkjet printing

An inkjet method for the direct patterned etching of silicon dioxide and silicon nitride dielectric is described. The method involves fewer steps, lower chemical usage and generates less hazardous chemical waste than existing resist-based patterning methods (e.g., photolithography), which employ immersion etching. Holes of diameter 40–50 μm and grooves 50–60 μm wide were etched in 300 nm silicon dioxide layers. Grooves were also etched in 75 nm silicon nitride layers formed on textured silicon surfaces. The resulting patterned dielectric layers were used to facilitate masked etching, local diffusions and metal contacting of underlying silicon for solar cell applications.     

Controlled silica precipitation in geothermal brine at the reykjanes geo-chemicals plant

This article describes how silica was precipitated in an electromagnetic field from silica supersaturated brine. At the Reykjanes Geo-Chemicals plant deposition of silica was a serious problem. After acidification of brine to pH 2.5 before evaporation the silica can be kept in solution for a considerable time. In order to precipitate silica out of this brine caustic soda is added. To get an effective precipitation of silica, a pH of at least 8.2 has to be reached. By using an electromagnetic field, a pH of 7.3–7.8 is sufficient to precipitate silica and an increased settling rate is observed. Settling rates were found to be from 7.1–9.7 cm/min at 100°C and from 3.4–4.6 cm/min at 40°C, compared to 1.3 cm/min for silica which was only alkalized. Higher effluent purity is also achieved by using electromagnetic field to precipitate out slilica.     

High quality textured ZnO:Al surfaces obtained by a two-step wet-chemical etching method for applications in thin film silicon solar cells

ZnO:Al films deposited at 250 °C on Corning glass by radio frequency magnetron sputtering were studied for their use as front contact for thin film silicon solar cells. For this purpose, a two-step etching method combining different concentrations of diluted hydrochloric acid (from 0.1% to 3%) with different etching times was developed. Its influence on morphological, electrical and optical properties of the etched films was evaluated. This new etching method led to more uniform textured surfaces, where the electrical properties remained unchangeable after the etching process, and with adapted light scattering properties similar to those exhibited by commercial substrates.     

Investigation of Cu metallization for Si solar cells

For application of copper metallization to silicon solar cells, electrical resistivity of the electroplated Cu was investigated for different annealing conditions: the rapid thermal annealing (RTA) and the vacuum annealing at various temperatures. The characteristics of Ti as the diffusion barrier were also observed. The specific contact resistance between Si and Ti/Cu was measured using Kelvin test pattern. For 8-min electroplated sample, the lowest resistivity of 2.1 μΩ cm was obtained at 300°C RTA condition. For Cu with Ti barrier, 400°C 2 min vacuum-annealed sample showed etch pits whereas 400°C RTA showed no etch pits. A vacuum annealing at 450°C for 30 min reduced the specific contact resistance to 7.2×10⁻⁶ Ω cm².     

Experiments on anisotropic etching of Si in TMAH

Recently, TMAH has been widely studied due to its MOS compatibility, nontoxic, and good anisotropic etching characteristics. In this work, TMAH etching of Si was carried out at different temperatures (70°C, 80°C and 90°C) and concentrations (5, 15 and 25 wt%). From a patterned Si wafer, inverted pyramids with smooth surface and sharp pyramid vertices were obtained. Uniform random pyramids were obtained from a bare Si wafer, and optimum reflectanceas low as 0.2% was obtained by near normal incident reflectivity measurement.     

The effect of temperature on the power drop in crystalline silicon solar cells

The influence of temperature and wavelength on electrical parameters of crystalline silicon solar cell and a solar module are presented. At the experimental stand a thick copper plate protected the solar cell from overheating, the plate working as a radiation heat sink, or also as the cell temperature stabilizer during heating it up to 80°C. A decrease of the output power (−0.65%/K), of the fill-factor (−0.2%/K) and of the conversion efficiency (−0.08%/K) of the PV module with the temperature increase has been observed. The spectral characteristic of the open-circuit voltage of the single-crystalline silicon solar cell is also presented. It is shown that the radiation-rate coefficient of the short-circuit current-limit of the solar cell at 28°C is 1.2%/(mW/cm²).     

Effect of heat treatment on carbon in multicrystalline silicon

Effect of heat treatment on carbon in cast multicrystalline silicon (mc-Si) has been studied by means of Fourier Transmission Infrared Spectroscopy. Carbon is found to be involved in the formation of as-grown precipitates in mc-Si with higher oxygen content. The experimental results reveal that carbon is difficult to precipitate in mc-Si with lower oxygen or higher nitrogen concentration during annealing in the temperature range from 450°C to 1150°C. Carbon can enhance the nucleation of oxygen precipitates at lower temperature (<850°C). Although carbon does not affect the amount of oxygen precipitates at higher temperature (>950°C), it is suggested that carbon diffuses into oxygen precipitates by the enhancement of silicon self-interstitials. The experiments point out that preannealing at 750°C enhances the decrease of substitute carbon concentration during subsequent annealing at 1050°C. Dislocations and grain boundaries in mc-Si do not affect carbon thermal treatment properties.     

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.     

Effects of fluorine doping on the structural properties of the CdO films deposited by ultrasonic spray pyrolysis

The fluorine doped cadmium oxide samples have been deposited at 250 °C by ultrasonic spray pyrolysis method. X-ray diffraction patterns of the CdO:F samples have revealed that the samples are polycrystalline with cubic sodium chloride structure. The texture coefficients calculated for various planes at different fluorine concentrations indicate that the samples have exhibited (1 1 1) and (2 0 0) preferential orientations. The lattice parameters for cubic structure of each diffraction plane have been calculated. The crystallite size of the samples being nearly constant until 4% of fluorine doping showed reasonable decrease above this concentration value. The macro strain and dislocation density vary with fluorine concentrations.     

Correlation between reflectivity and photoluminescent properties of porous silicon films

Porous silicon (PS) layers were formed on p-type, 〈1 0 0〉 oriented, 1-5 Ω cm resistivity Cz silicon wafers by electrochemical etching in an HF:C₂H₅OH (1:2 by volume) electrolyte at room temperature at a constant current density 20 mA/cm². The etching duration was varied to achieve PS layers of different morphologies and thicknesses. Both the photoluminescence (PL) and the total diffused reflectivity spectra of the PS layers were measured. It was found that for the PS layers grown for etching durations of less than 90 s the PL emission is insignificant and reflectivity is quite low. Such PS layers can be used as antireflection coatings (ARC) on solar cells. The PS layers formed for etching durations greater than 90 s show a significant PL emission in 500-800 nm range with peak lying in 630-660 nm wavelength range. When etching duration increases from 90 s to 8 min the PL intensity increases and the PL peak shows a blue shift. With further increase in etching duration the PL intensity decreases and PL peak shows a red shift. The reflectivity of the photoluminescent layers increases with etching duration showing a highest value for a sample grown for 8 min. Further increase in etching duration up to 20 min the reflectivity decreases and then increases. Striking observation is that both the PL emission intensity and reflectivity in the wavelength range of 550-800 nm are maximum for the PS layer grown for the etching duration of 8 min.     

Novel etching method on high rate ZnO:Al thin films reactively sputtered from dual tube metallic targets for silicon-based solar cells

Highly transparent and conductive aluminum-doped zinc oxide thin films (ZnO:Al) were reactively sputtered from metallic targets at high rate of up to 90 nm m/min. For the application as transparent light scattering front contact in silicon thin film solar cells, a texture etching process is applied. Typically, it is difficult to achieve appropriate etch features in hydrochloric acid as the deposition process must be tuned and the interrelation is not well understood. We thus introduce a novel two-step etching method based on hydrofluoric acid. By tuning the etch parameters we varied the surface morphology and achieved a regular distribution of large craters with the feature size of 1-2 μm in diameter and about 250 nm in depth. Microcrystalline silicon single junction solar cells (μc-Si:H) and amorphous/microcrystalline silicon (a-Si:H/μc-Si:H) tandem solar cells with high efficiency of up to 8.2% and 11.4%, respectively, were achieved with optimized ZnO:Al films as light scattering transparent front contact.     

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.     

Oxygen in Czochralski silicon used for solar cells

Compared to the Czochralski (CZ) silicon used in microelectronic industry (M-CZ Si), the annealing behavior of oxygen in the CZ silicon used for solar cells (S-CZ Si) was investigated by means of FTIR and SEM. It was found that the oxygen concentration in S-CZ Si crystal was lower than in the M-CZ Si crystal. During single-step annealing in the temperature range of 800–1100°C, the oxygen in S-CZ Si was hard to precipitate, even if the material contained higher carbon concentrations. After pre-annealing at 750°C, many more oxygen precipitates were formed. The amount and density of the oxygen precipitates were almost the same as in M-CZ Si annealed in single step. It is considered that oxygen has no significant influence on the efficiency of solar cells made from Cz silicon if it is annealed only by a single step in the range of 800–1100°C.     

Phosphorus-doped, silver-based pastes for self-doping ohmic contacts for crystalline silicon solar cells

Undoped and phosphorus-doped Ag-based pastes were applied as circular contacts to the (1 1 1) surface of dendritic web n-type Si. Current–voltage characteristics of as-deposited contacts and contacts annealed at 780°C for 10 min, 950°C for 5 min, 1000°C for 10 min were measured and compared. Annealing above the Ag–Si eutectic temperature (835°C) yielded Si precipitation within the Ag matrix, resulting in increased current across the metal/semiconductor interface. The contact resistivity was significantly lower for P-doped (<0.04 Ω cm²) than for undoped (1.90 Ω cm²) Ag contacts, both of which were annealed at 1000°C. As supported by secondary ion mass spectrometry analyses, these results are attributed to an enhanced P doping level in the Si substrate after annealing the P-doped contacts. A p–n junction diode was demonstrated by alloying the Ag–P paste with p-type Si at 1000°C. The contact resistance was inferred from diode I–V data to be 0.013 Ω cm², a value which is comparable to the 0.010 Ω cm² target value for solar cell contacts.     

The influence of operation temperature on the output properties of amorphous silicon-related solar cells

The influence of the operation temperature on the output properties of solar cells with hydrogenated amorphous silicon (a-Si:H) and hydrogenated amorphous silicon germanium (a-SiGe:H) photovoltaic layers was investigated. The output power after longtime operation of an a-Si:H single junction, an a-Si:H/a-Si:H tandem, and an a-Si:H/a-SiGe:H tandem solar cell was calculated based on the experimental results of two types of temperature dependence for both conversion efficiency and light-induced degradation. It was found that the a-Si:H/a-SiGe:H tandem solar cell maintained a higher output power than the others even after longtime operation during which a temperature range of 25°C to 80°C. These results confirm the advantages of the a-Si:H/a-SiGe:H tandem solar cell for practical use, especially in high-temperature regions.     

A comparative study of CdS-based semiconductor photocatalysts for solar hydrogen production from sulphide + sulphite substrates

Different types of CdS-based photocatalysts have been prepared, characterized and tested for hydrogen evolution from a sulphide + sulphite solution. The benefit of the thermal treatment of CdS in air, argon, hydrogen sulphide or hydrogen atmospheres, as well as that of etching its surface, have been shown. The effects of adding to CdS a second semiconductor of smaller bandgap (Cu_xS) or larger bandgap (TiO₂), or/and a catalytic material (Pt or RuO_x), have been studied. The best results have been obtained using particles of CdS of ≈ 1.4 ωm, treated at 400°C in air atmosphere and etched with concentrated HNO₃, and on which 0.4% by weight of Pt was deposited.     

Improved anisotropic etching process for industrial texturing of silicon solar cells

An experimental study on the surface texturisation of monocrystalline wafers with solutions containing sodium-hydroxide and isopropanol was carried out. Both the composition and the temperature of the etching solution were optimised on the basis of etch-rate measurements on silicon samples having different crystallographic directions. It was found that the density and the size of the pyramids are influenced by the etch-rate of silicon in the 1 0 0 direction and also by the anisotropy factor of the solutions being the quotient of the etch rate in the 1 0 0 to 1 1 1 directions. Design of experiments and response surface methods were used to extract the etch rate as a function of different input parameters, such as the sodium hydroxide and isopropanol concentrations and the temperatures of the solutions. Optimum texturing conditions were found at a temperature of 80°C and a composition which causes a relatively high etch rate in the 1 0 0 direction with an anisotropy factor of 10. At the starting point of the etching process, the inhomogeneity of pyramid nucleation can be avoided by mixing an additive to the texturing solution. With such a solution, the pyramid size can be tuned by varying the etching time in order to obtain a low reflectivity from the textured silicon wafers. Based on our results the texturing process could be stabilised with respect to the reproducibility on a large scale of wafers.