Role of hydrazine monohydrate during texturization of large-area crystalline silicon solar cell fabrication

Reduction of optical losses in monocrystalline silicon solar cells by surface texturing is one of the important issues of modern silicon photovoltaic. For texturization during commercial monocrystalline silicon solar cell fabrication, a mixture of NaOH or KOH and isopropyl alcohol (IPA) is generally used in order to achieve good uniformity of pyramidal structure on the silicon surface. The interfacial energy between silicon and electrolyte should be reduced in order to achieve sufficient wettability for the silicon surface which in turn will enhance the pyramid nucleation. In this work, we have investigated the role of hydrazine monohydrate as a surface-active additive, which supplies OH⁻ ions after dissociation. This cuts down the IPA consumption during texturing without any loss of uniformity of textured pyramid. We are probably the first group to report such a novel idea of using hydrazine monohydrate addition in NaOH solution for texturization of solar cell. We were able to fabricate monocrystalline silicon solar cells with more than 85% yield in the range of 14–15% efficiency.     

Investigation of texturization for crystalline silicon solar cells with sodium carbonate solutions

We investigate a new texturization technique for crystalline silicon solar cells with sodium carbonate (Na₂CO₃) solutions. We show the dependence of the hemispherical surface reflectance on solution temperature, the etching time and the Na₂CO₃ concentration. Furthermore, we investigate what element in Na₂CO₃ solution influences the texturing for reducing the texturing time. As a result of experiments, we find it possible to get low reflectance in a shorter texturing time by the addition of NaHCO₃. The size of texture becomes smaller by the addition of NaHCO₃ but the etching rate does not change. We conclude carbonic ion and/or its compound seems to play an important role as the initiator of pyramidal structure. This texturing method is cost effective because there is no need of expensive IPA, and the surface reflectance is reduced sufficiently in a short time. This method is promising for a large-scale production of crystalline silicon solar cells.     

Efficiency improved by acid texturization for multi-crystalline silicon solar cells

In this paper, we will show that efficiency of multi-crystalline silicon (mc-Si) solar cells may be improved by acid texturization. In order to enhance overall efficiency of mc-Si for solar-cell applications, the surface treatment of texturization with wet etching using appropriate solutions can improve incident light into the cell. Alkali etchant cannot produce uniformly textured surface to generate enough open circuit voltage (V_OC) and high efficiency of the mc-Si due to the unavoidable grain randomly oriented with higher steps formed during etching process. Optimized acid etching conditions can be obtained by decreasing the reflectance (R) for mc-Si substrate below levels generated by alkali etching. Short-circuit current (I_SC) measurements on acid textured cells reveal that current gain can be significantly enhanced by reducing reflection. The optimal acid etching ratio HF:HNO₃:H₂O = 15:1:2.5 with etching time of 60 s and lowering 42.7% of the R value can improve 112.4% of the conversion efficiency (η) of the developed solar cell. In order to obtain more detailed information of different defect region, high-resolution light beam induced current (LBIC) is applied to measure the internal quantum efficiency (IQE) and the lifetime of minority carriers. Thus, the acid texturing approach is instrumental to achieve high efficiency in mass production using relatively low-cost mc-Si as starting material with proper optimization of the fabrication steps.     

A novel low cost texturization method for large area commercial mono-crystalline silicon solar cells

Texturization of mono-crystalline silicon for solar cell fabrication is still a key issue due to consumption of large amount of costly isopropyl alcohol (IPA) in conventional NaOH/KOH solution. The need of IPA arises due to the improvement in the uniformity of pyramidal structures and elimination of spots caused by bubbles sticking on the wafer surface during the texturization process. We investigated a new texturization technique for mono-crystalline silicon solar cells with tribasic sodium phosphate (Na₃PO₄, 12H₂O) solution with much less amount of IPA. The proposed texturization method of this paper is cost effective due to reduction in the consumption of expensive IPA. The cost comparison of our novel texturization approach with conventional NaOH texturization has also been reported in this paper. We are reporting for the first time such a novel approach of using tribasic sodium phosphate for texturization of mono-crystalline silicon surface with which solar cells of efficiency 14–14.8% are fabricated with more than 90% yield.     

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.     

Optimization of sodium carbonate texturization on large-area crystalline silicon solar cells

This work describes a texturization method for monocrystalline silicon solar cells based on a mixture of sodium carbonate and sodium hydrogen carbonate solutions. A specific solution has been found that results in an optimal etching rate, the lowest surface reflectance and a homogeneous density of pyramidal structures on the silicon surface. The subsequent phosphorus diffusion with rapid thermal processes has been modified in order to drastically reduce the process time and, simultaneously, to obtain a high homogeneity of the sheet resistance values and improved photocarriers lifetimes. 100×100 mm solar cells with an efficiency of 15.8% have been obtained compared to an efficiency of 14.7% for the reference cell.     

Classification of shunting mechanisms in crystalline silicon solar cells

The efficiency of a solar cell is given by its average electrical parameters. On inhomogeneous materials and especially on large-area solar cells the inhomogeneity of the short circuit current, the open circuit voltage and the fill factor are important factors to reach high and stable efficiencies and may limit the overall performance of the device.A locally increased dark forward current (shunt) reduces the fill factor and the open circuit voltage of the whole cell. The inhomogeneity of the forward current in a solar cell can be measured using lock-in thermography. The quantitative and voltage-dependent evaluation of these thermographic investigations of various solar cell types on mono- or multi-crystalline silicon enables the classification of the different shunting mechanisms found. By further microscopic investigations the physical reasons for the increased dark forward currents can be determined.It turns out that a high density of crystallographic defects like dislocation tangles or microdefects can be responsible for an increased dark forward current. Unexpectedly, grain boundaries in solar cells on multicrystalline silicon do not show any measurable influence on the local dark forward current. In most cases shunts caused by process-induced defects are dominating the current–voltage characteristic at the maximum power point of the solar cell. In commercial solar cells shunts at the edges are most important, followed by shunts beyond the grid lines.     

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.     

Novel low-cost approach for removal of surface contamination before texturization of commercial monocrystalline silicon solar cells

This paper reports a novel approach on the surface treatment of monocrystalline silicon solar cells using an inorganic chemical, sodium hypochlorite (NaOCl) that has some remarkable properties. The treatment of contaminated crystalline silicon wafer with hot NaOCl helps the removal of organic contaminants due to its oxidizing properties. The objective of this paper is to establish the effectiveness of this treatment using hot NaOCl solution before the saw damage removal step of the conventional NaOH texturing approach. A comparative study of surface morphology and FTIR analyses of textured monocrystalline silicon surfaces with and without NaOCl pre-treatment is also reported. The process could result in a significant low cost approach viable for cleaning silicon wafers on a mass production scale.     

Investigation of texturization for monocrystalline silicon solar cells with different kinds of alkaline

In this paper, monocrystalline silicon was textured with different kind of etchants for solar cells, respectively. It was found that, only with sodium hydroxide (NaOH) or sodium acetate anhydrous (CH₃COONa) solution, the textural results were very weak, resulting in high reflectance of silicon surface. However, if using the mixture solution of NaOH and CH₃COONa, the reflectance was noticeably decreased. Moreover, the dependence of reflectance on the etching time showed that longer etching time was necessary for texturization in the NaOH+CH₃COONa+H₂O system. And it was also found that the addition of isopropyl alcohol (IPA) to this mixture solution had a detrimental effect on the texturization. All these results suggested that acetate (CH₃COO⁻) plays a similar role as IPA for alkaline texturization, but they cannot coexist. Finally, the mechanisms of texturization with different kinds of etchant were discussed in detail.     

Reactive ion etching (RIE) technique for application in crystalline silicon solar cells

Saw damage removal (SDR) and texturing by conventional wet chemical processes with alkali solution etch about 20 micron of silicon wafer on both sides, resulting in thin wafers with which solar cell processing is difficult. Reactive ion etching (RIE) for silicon surface texturing is very effective in reducing surface reflectance of thin crystalline silicon wafers by trapping the light of longer wavelength. High efficiency solar cells were fabricated during this study using optimized RIE. Saw damage removal (SDR) with acidic mixture followed by RIE-texturing showed the decrease in silicon loss by ∼67% and ∼70% compared to conventional SDR and texturing by alkaline solution. Also, the crystalline silicon solar cells fabricated by using RIE-texturing showed conversion efficiency as high as 16.7% and 16.1% compared with 16.2%, which was obtained in the case of the cell fabricated with SDR and texturing with NaOH solution.     

Thin crystalline silicon solar cells

A 50 μm thin layer of high quality crystalline silicon together with efficient light trapping and well passivated surfaces is in principle all that is required to achieve stable solar cell efficiencies in the 20% range. In the present work, we propose to obtain these layers by directly cutting 50 μm thin wafers from an ingot with novel cutting techniques. This development is discussed in the frame of a defect tolerant mass production scenario and aims at obtaining twice the amount of wafers as compared to present wire/slurry technology. The ability to process such mechanically flexible wafers into solar cells with standard laboratory equipment is experimentally verified.     

Zone melting recrystallization of silicon films for crystalline silicon thin-film solar cells

Coarse-grained silicon films for crystalline silicon thin-film solar cells have been prepared by zone melting recrystallization. A zone melting heater was modified to obtain better temperature homogeneity of the sample and higher reproducibility of the melt process. Various substrate materials of different purity and surface roughness have been tested concerning their suitability for, silicon deposition, zone melting and solar cell process. Solar cell efficiencies up to 10.5% could be achieved on silicon sheets from powder, capped by an intermediate layer. Silicon films on SiAlON ceramics were successfully processed to solar cells by a completely dry solar cell process.     

Rapid thermal technologies for high-efficiency silicon solar cells

This paper shows that rapidly formed emitters in less than 6 min in the hot zone of a conveyor belt furnace or in 3 min in an rapid thermal processing (RTP) system, in conjunction with a screen-printed (SP) RTP Al-BSF and passivating oxide formed simultaneously in 2 min can produce very simple high-efficiency n⁺-p-p⁺ cells with no surface texturing, point contacts, or selective emitter. It is shown for the first time that an 80 Ω/□ emitter and SP Al-back surface field (BSF) formed in a high throughput belt furnace produced 19% FZ cells and greater than 17% CZ cells with photolithography (PL) contacts. Using PL contacts, we also achieved 19% efficient cells on FZ, >18% on MCZ, and 17% boron-doped CZ by emitter and SP Al-BSF formation in <10 min in a single wafer RTP system. Finally, manufacturable cells with 45 Ω/□ emitter and SP Al-BSF and Ag contacts formed in the conveyor belt furnace gave 17% efficient cells on FZ silicon. Compared to the PL cells, the SP cell gave 2% lower efficiency along with a decrease in J_sc and fill factor. This loss in performance is attributed to a combination of the poor blue response, higher series resistance and higher contact shading in the SP devices     

Comparison between normal and reverse thin crystalline silicon solar cells

The newly developed ingot growing techniques, as the three-grain and the columnar multigrain ingot processes, are now offering the possibility of slicing thinner wafers (≤ 100 μm). In this paper we present the results obtained on p type large area (≥ 100 cm²) and 100 μm thick wafers by using both conventional and reverse cell manufacturing technologies.The conventional cells are provided with aluminium or boron BSF plus screen-printed silver mirror or a silver-aluminium net; the reverse cells have a FSF and the deep back junction completely covered by a screen-printed or CVD silver layer.The constructing parameters have been chosen on the base of one and two dimensions modeling and both raw material and devices have been completely characterized.This work shows that very thin wafers do not introduce serious problems for the conventional manufacturing of solar cells. The efficiencies of the normal and of the reverse cells are found to be comparable and are of the same order than those of thicker cells, however at a significant lower cost. The main obtained result has to be related to the demonstration of a cell manufacturing feasibility starting from very thin wafers.     

Industrial manufacturing of semitransparent crystalline silicon POWER solar cells

This paper gives an extract of the state of the art of the manufacturing of semitransparent crystalline silicon POWER solar cells in an industrial environment. A short introduction of the POWER devices concept (see Fig. 1) will be given followed by an insight in the applied production process. Finally, examples effecting the efficiency distribution in the cell production and their solutions are given. It is believed that the lessons we learned in optimising the manufacturing process and production line of transparent POWER solar cells can be helpful for the increasing activities in the direction of thin wafers as well as novel solar cell devices.     

New concepts for high-efficiency silicon solar cells

This paper gives an overview about recent activities in the industrial application of high-efficiency monocrystalline silicon solar cells. It also presents the latest results achieved at Fraunhofer ISE, especially a new patented process for the formation of back-contact points on dielectrically passivated cells called laser-fired contacts and its application to thin wafers.     

Full process for integrating silicon nanowire arrays into solar cells

A novel process was developed for integrating silicon nanowire arrays into solar cells. n-Type silicon nanowires were grown by chemical-vapour deposition via the gold-catalysed vapour-liquid-solid method, on a p-type silicon substrate. After the growth, the nanowire array was planarized, by embedding the nanowires in a spin-on glass matrix and subsequent chemical-mechanical polishing of the front surface. This planarization step allows to deposit a continuous and uniform conductive film on top of the nanowire array, and thus to form a high-quality front electrical contact. For an illumination intensity of 100 mW/cm², our devices exhibit an energy conversion efficiency of 1.9%. The main performance limiting factor is a high pn junction reverse current, due to contamination by the growth catalyst or to a lack of passivation of surface electronic defects.     

Minority carrier lifetime of silicon solar cells from quasi-steady-state photoluminescence

Minority carrier lifetime is the most crucial material parameter for the performance of a silicon solar cell. While numerous methods exist to determine carrier lifetime on solar cell precursors prior to metallization, only very few techniques are capable of implicitly extracting effective minority carrier lifetimes from metallized silicon samples. In this paper, a measurement technique for effective minority carrier lifetime on silicon solar cells and metallized cell precursors via quasi-steady-state photoluminescence is presented. The setup requirements for this measurement technique are elaborated, experimental evidence of the reliability of such measurements down to carrier lifetimes in the range of a microsecond is provided, and a lifetime calibration of spatially resolved photoluminescence images of solar cells via the presented measurement technique is sketched. Finally, the very good agreement between the obtained effective carrier lifetime and the corresponding open circuit voltage of a solar cell is demonstrated.     

Present status and future of crystalline silicon solar cells in Japan

Crystalline silicon solar cells show promise for further improvement of cell efficiency and cost reduction by developing process technologies for large-area, thin and high-efficiency cells and manufacturing technologies for cells and modules with high yield and high productivity.In this paper, Japanese activities on crystalline Si wafers and solar cells are presented. Based on our research results from crystalline Si materials and solar cells, key issues for further development of crystalline Si materials and solar cells will be discussed together with recent progress in the field. According to the Japanese PV2030 road map, by the year 2030 we will have to realize efficiencies of 22% for module and 25% for cell technologies into industrial mass production, to reduce the wafer thickness to 50–100 μm, and to reduce electricity cost from 50 Japanese Yen/kWh to 7 Yen/kWh in order to increase the market size by another 100–1000 times.