150-mm layer transfer for monocrystalline silicon solar cells

We report on recent improvements concerning the transfer of monocrystalline silicon layers to plastic substrates for flexible solar cell applications. Finite element numerical modeling of the etching current density distribution allows for optimizing our electrochemical etching setup for separation layer formation. By modifying the setup according to the simulation results, we are now able to transfer 25 μm thick monocrystalline silicon sheets with up to 150 mm in diameter.     

Plasma-enhanced CVD silicon nitride antireflection coatings for solar cells

Multilayer plasma-enhanced chemical vapor deposition (PECVD) silicon nitride antireflection coatings were deposited on space quality silicon solar cells. Preliminary experiments indicated that multilayer coatings decreased the total reflectance of polished silicon from 35 per cent to less than 3 per cent over the spectral range 0.4–1.0 μm. The solar cell energy conversion efficiency was increased from an average of 8.84 per cent to an average of 12.63 per cent.     

Optimization of porous silicon reflectance for silicon photovoltaic cells

The antireflection properties of electrochemically formed porous silicon (PS) layers in the 0.3 μm thick n⁺ emitter of Si p–n⁺ junctions, have been optimized for application to commercial silicon photovoltaic cells. The porosity and thickness of the PS layers are easily adjusted by controlling the electrochemical formation conditions (current density and anodization time). The appropriate PS formation conditions were determined by carrying out a two steps experiment. A first set of samples allowed to determine the optimal porosity and a second one to adjust the thickness of the PS layers, by evaluating the interference features of the reflectance produced by the layers. A PS layer with optimal antireflection coating (ARC) characteristics was obtained in 30% HF in only 3.5 s. The effective reflectance is reduced to 7.3% between 400 and 1150 nm which leads to a gain of up to 33% in the theoretical short circuit current of a p–n⁺ shallow junction compared to a reference junction without a PS layer. The effective reflectance with optimized PS layers is significantly less than that obtained with a classical TiO₂ ARC on a NaOH pretextured multicrystalline surface (11%).     

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.     

Multicrystalline silicon wafers prepared from upgraded metallurgical feedstock

A solution to the problem of the shortage of silicon feedstock used to grow multicrystalline ingots can be the production of a feedstock obtained by the direct purification of upgraded metallurgical silicon by means of a plasma torch. It is found that the dopant concentrations in the material manufactured following this metallurgical route are in the 10¹⁷ cm⁻³ range. Minority carrier diffusion lengths L_n are close to 35 μm in the raw wafers and increases up to 120 μm after the wafers go through the standard processing steps needed to make solar cells: phosphorus diffusion, aluminium–silicon alloying and hydrogenation by deposition of a hydrogen-rich silicon nitride layer followed by an annealing. L_n values are limited by the presence of residual metallic impurities, mainly slow diffusers like aluminium, and also by the high doping level.     

Optimization of front surface texturing processes for high-efficiency silicon solar cells

This paper presents the results of an experimental study regarding the increase in the efficiency of the silicon solar cells by texturing the front surface. Designing, patterning and surface etching processes led to refined structures with very low losses of the incident optical radiation. Photolithography has been used to generate patterns (disc hole) through the silicon dioxide layer grown at the beginning on silicon wafers. The holes (4 μm in diameter) have been uniformly distributed on the entire surface (2×2) cm² and the distance between the hole centres was determined to be 20 μm. Semispherical walls have been defined in holes by isotropic etching up to join together of the wells.     

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.     

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.     

Polycrystalline silicon solar cells on mullite substrates

Polycrystalline silicon layers have been grown on various alumino-silicate substrates in a rapid thermal chemical vapor deposition (RTCVD) system at high temperatures (>1000°C). Structural analysis shows a columnar growth with grain sizes up to 15 μm and growth rates up to 5 μm/min. Solar cell devices on this fine-grained Si material result in a short-circuit current of about 13 mA/cm² but a poor open-circuit voltage (<0.4 V). Larger grains obtained by the zone melting recrystallization (ZMR) technique boosted the current up to 26.1 mA/cm², thanks to the light-trapping by the mullite substrate. Best efficiency is 8.2% on a 1 cm² cell made on a 20 μm thick poly-Si layer.     

Thin film polycrystalline silicon solar cells on mullite ceramics

In this work, we present the structural quality of polycrystalline silicon films formed by high-temperature chemical vapor deposition (CVD) on mullite ceramics coated with spin-on flowable oxides (FO_x) serving as intermediate layers (ILs). The average grain size and the size distribution were investigated by optical microscopy. It is found that more than 65% of the surface of polysilicon films grown on boron-doped FO_x is covered by large grains of 5–10 μm. The intra-grain and inner-grain defects as well as the grain orientation were analyzed with the electron backscattering diffraction (EBSD) technique. Twin-type defects such as Σ3 and Σ9 are frequently present in these silicon layers, which are slightly (1 1 0) preferentially oriented. Finally, we present the photovoltaic data on test solar cells made on these CVD polysilicon films. An efficiency of about 3.3% is reported. The limiting factors, as well as possible improvements, are discussed.     

Intrinsic microcrystalline silicon: A new material for photovoltaics

Microcrystalline silicon (μc-Si:H) prepared by plasma-enhanced chemical vapor deposition (PECVD) has been investigated as material for absorber layers in solar cells. The deposition process has been adjusted to achieve high deposition rates and optimized solar cell performance. In particular, already moderate variations of the crystalline vs. amorphous volume fractions were found to effect the electronic material – and solar cell properties. Such variation is readily achieved by changing the process gas mixture of silane to hydrogen. Best cell performance was found for material near the transition to the amorphous growth regime. With this optimized material efficiencies of 7.5% for a 2 μm thick μc-Si:H single solar cell and 12% for an a-Si:H/μc-Si:H stacked solar cell have been achieved.     

Photoluminescence from photochemically etched silicon

The photoluminescence (PL) of photochemically etched silicon is studied. In the photochemical etching process, an n-type silicon wafer is immersed in an etchant solution of hydrofluoric acid (HF) and H₂O₂. A low-power visible laser (typically He–Ne) is used to illuminate the samples. The etching process occurs through the photogeneration of carriers. Although no electrodes are used in this etching method, the final samples show PL similar to electrochemically etched porous silicon. The samples were prepared using (1 0 0) n-type silicon with a resistivity of 1.0–5.5 Ω cm. An He–Ne laser with 20 mW of maximum power output was used and the spot radius (on the samples) was varied from 1 to 4 mm. A strong emission in the red-yellow optical region can be present in the final samples depending on the HF:H₂O₂ concentration ratio, etching time and laser intensity of the etching process. The PL spectra excited with the monochromated output of an Xe light source as excitation is studied. The peak wavelength of the PL intensity shifts to the blue region of the spectrum when increasing the laser intensity. Quantum confinement can explain this blue shifting if smaller silicon nanocrystallites are formed with higher laser intensity. The peak PL intensity also decreases when increasing the laser intensity, although a “threshold” condition must be reached to have measurable PL. Each sample also exhibits a shifting in peak PL wavelength when varying the PL excitation wavelength. The corresponding dependence and the variations of the PL intensity are studied. Other experimental conditions are discussed.     

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.     

Thickness determination of thin (20 nm) microcrystalline silicon layers

For the development of thin, doped microcrystalline silicon (μc-Si) layers, it is necessary to have an accurate tool to determine the thickness and material properties of layers around 20 nm. Here, we report on the interpretation of UV-VIS-NIR spectroscopy (reflection/transmission) measurements using the O’Leary, Johnson, Lim (OJL) model in which we add extra information to compensate for the loss of density information due to the lack of fringes. Moreover, using this method we extract information that can be correlated to the crystalline ratio of μc-Si:H thin layers. We correlate thicknesses and material properties obtained from the optical method to the results obtained from various other techniques: Raman spectroscopy, Rutherford back scattering (RBS) and cross-sectional transmission electron microscopy (X-TEM).By analyzing the data of thin μc-Si:H layers (20 nm) as well as of thicker layers (100 nm) and comparing the results to thicknesses measured with X-TEM, we conclude that as long as the density of thin layers is identical to the thicker layers, with the optical method a good approximation of thickness of microcrystalline silicon layers is possible at a layer thickness down to 20 nm.     

High-rate microcrystalline silicon deposition for p–i–n junction solar cells

We have developed a high-rate plasma process based on high-pressure and silane-depletion glow discharge for highly efficient microcrystalline silicon (μc-Si:H) p–i–n junction solar cells. Under high-rate conditions (2–3 nm/s), we find that the deposition pressure becomes the dominant parameter in determining solar-cell performance. With increasing deposition pressure from 4 to 7–9 Torr, short-circuit current increases by 50% due to a remarkable improvement in quantum efficiencies at the visible and near infrared. As a result, the maximum efficiency of 9.13% has been achieved at an i-layer deposition rate of 2.3 nm/s. We attribute the improved performance of high-pressure-grown μc-Si:H solar cells to the structural evolution toward denser grain arrangement that prevents post-oxidation of grain boundaries.     

Black silicon layer formation for application in solar cells

Low-cost, large area, random and mask less texturing scheme independent of crystal orientation are some of the factors that significantly influence the success of terrestrial photovoltaic technology. This work is focused on the texturing of the silicon surface microstructures by reactive ion etching using a multi-hollow cathode system. Desirable texturing effect has been achieved by applying a radio-frequency power of about 20 W per hollow cathode glow. The etched silicon surface shows almost zero reflectance in the visible region as well as in near-IR region. The silicon surface is covered by columnar microstructures with diameters ranging from 50 to 100 nm and with a depth of about 500 nm. Solar cells with efficiencies of 11.7% and 10.2% with black mono-crystalline and multi-crystalline silicon wafers, respectively, were successfully fabricated and tested.     

Light trapping in layer-transferred quasi-monocrystalline porous silicon solar cell

Quasi-monocrystalline porous silicon (QMPS) layers have a top surface like crystalline silicon with small voids in the body. Such layers are reported to have significantly higher absorption coefficient compared to crystalline silicon at the wavelength of interest for solar cells. A model has been developed to account for higher absorption coefficient of QMPS layer. The model conforms to the experimental results. The model is then extended to predict absorption coefficient of QMPS layer for different thickness, porosity and void size. Interesting results are obtained, particularly regarding the dependence of absorption coefficient on thickness and void diameter of QMPS layers. Computed values of absorption coefficient and some experimental results relating to electronic properties of QMPS layers are used to investigate the solar cell potential of QMPS layers. Short circuit current density of about 31 mA/cm² is predicted for a QMPS layer of thickness 4 μm having average void radius of about 15 nm assuming effective diffusion length to be 5 μm.     

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.     

Defect passivation of industrial multicrystalline solar cells based on PECVD silicon nitride

Low surface recombination velocity and significant improvements in bulk quality are key issues for efficiency improvements of solar cells based on a large variety of multicrystalline silicon materials. It has been proven that PECVD silicon nitride layers provide excellent surface and bulk passivation and their deposition processes can be executed with a high throughput as required by the PV industry. The paper discusses the various deposition techniques of PECVD silicon nitride layers and also gives results on material and device properties characterisation. Furthermore the paper focuses on the benefits achieved from the passivation properties of PECVD SiN_x layers on the multi-Si solar cells performance. This paper takes a closer look at the interaction between bulk passivation of multi-Si by PECVD SiN_x and the alloying process when forming an Al-BSF layer. Experiments on state-of-the-art multicrystalline silicon solar cells have shown an enhanced passivation effect if the creation of the alloy and the sintering of a silicon nitride layer (to free hydrogen from its bonds) happen simultaneously. The enhanced passivation is very beneficial for multicrystalline silicon, especially if the defect density is high, but it poses processing problems when considering thin (<200 μm) cells.     

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.