Electrical properties of fine line printed and light‐induced plated contacts on silicon solar cells

The properties of fine‐line printed contacts on silicon solar cells, in combination with light‐induced plating (LIP), are presented. The seed layers are printed using an aerosol system and a new metallization ink called SISC developed at Fraunhofer ISE. The influence of multiple layer printing on the contact geometry is studied as well as the influence of the contact height on the line resistivity and on the contact resistance. The dependence between contact resistance and contact height is measured using the transfer length model (TLM). Further on, it is explained by taking SEM images of the metal–semiconductor interface, that a contact height of less than 1 µm or a minimum ink amount of only 4–6 mg is sufficient to contact a large area (15·6 cm × 15·6 cm) silicon solar cell on the front side and results in a contact resistance R_c × W < 0·5 Ω cm. As the line resistivity of fine‐line printed fingers needs to be reduced by LIP, three different plating solutions are tested on solar cells. The observed differences in line resistivity between ρ_f = 5 × 10⁻⁸ and 2 × 10⁻⁸ Ω m are explained by taking SEM pictures of the grown LIP‐silver. Finally, the optimum LIP height for different line resistivities is calculated and experimentally confirmed by processing solar cells with an increasing amount of LIP silver. Copyright © 2010 John Wiley & Sons, Ltd.     

Combining laser chemical processing and aerosol jet printing: a laboratory scale feasibility study

First results showing the viability of combining laser chemical processing (LCP) and aerosol jet printing (AJP) technologies to produce a high‐efficiency front side for silicon solar cells are presented. LCP simultaneously opens the anti‐reflection coating (ARC) and highly dopes the underlying silicon to create a selective emitter, while AJP is the first in a two‐step fine‐line contact formation procedure. The electrical properties as well as the morphology of the resulting structures are presented. Performance similar to that achieved with evaporated TiPdAg metallization is demonstrated. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermal oxidation for crystalline silicon solar cells exceeding 19% efficiency applying industrially feasible process technology

Thermal oxides are commonly used for the surface passivation of high‐efficiency silicon solar cells from mono‐ and multicrystalline silicon and have led to the highest conversion efficiencies reported so far. In order to improve the cost‐effectiveness of the oxidation process, a wet oxidation in steam ambience is applied and experimentally compared to a standard dry oxidation. The processes yield identical physical properties of the oxide. The front contact is created using a screen‐printing process of a hotmelt silver paste in combination with light‐induced silver plating. The contact formation on the front requires a short high‐temperature firing process, therefore the thermal stability of the rear surface passivation is very important. The surface recombination velocity of the fired oxide is experimentally determined to be below S ≤ 38 cm/s after annealing with a thin layer of evaporated aluminium on top. Monocrystalline solar cells are produced and 19·3% efficiency is obtained as best value on 4 cm² cell area. Simulations show the potential of the developed process to approach 20% efficiency. Copyright © 2008 John Wiley & Sons, Ltd.     

Shunting problems due to sub‐micron pinholes in evaporated solid‐phase crystallised poly‐Si thin‐film solar cells on glass

Recent progress in the metallisation of poly‐silicon thin‐film solar cells on glass, created by solid phase crystallisation (SPC) of evaporated amorphous silicon (EVA), revealed that shunting through sub‐micron holes (density 100–200 mm⁻²) in the films causes severe shunting problems when the air‐side metal contact is deposited onto these diodes, by creating effective shunting paths between the two highly doped layers of EVA cells. We present evidence of these pinholes by optical transmission and focussed ion beam (FIB) microscopic images and confirm the point‐like pinhole shunts using lock‐in thermographic images. The latter revealed that the Al rear electrode induces strong ohmic shunts below the grid lines and a high density of weak non‐linear shunts away from the grid lines. Two distinctly different approaches are shown to reduce the shunting problem to a negligible level: (i) to contact only a small fraction of the rear Si surface via a point contacting scheme, whereby the metal layer needs to be thin (<1 µm) and the fractional area coverage small (<5%), and (ii) to deposit line contacts in a bifacial interdigitated scheme, whereby a thick layer of metal is deposited followed by a wet‐chemical etching step that effectively reduces shunting by preferentially etching away the shunting paths. Test devices with an area of 1 cm² achieve pseudo fill factors ( pFF ) of above 75% and diode ideality factors of below 1·3, demonstrating that the proposed methods are well suited for the metallisation of the rear surface of EVA solar cells. Copyright © 2008 John Wiley & Sons, Ltd.     

High‐Temperature Contact Formation on n‐Type Silicon: Basic Reactions and Contact Model for Seed‐Layer Contacts

Contact formation on n‐type silicon, especially using a high‐temperature process, has been the subject of research for more than 40 years. After its application in microelectronics, n‐type silicon is widely used in silicon solar cells as the emitter layer. The formation of a low ohmic contact grid using an industrially feasible process step is one of the key features required to improve the solar‐cell efficiency. The contact materials, typically deposited in a printing step, have to fulfil several functions: opening the dielectric antireflection layer and forming an intimate metal‐semiconductor contact with good mechanical adhesion and low specific contact resistance. As the used contact inks typically contain several functional materials, such as silver and a glass frit, the detailed contact formation is still not entirely understood. Therefore, the chemical reactions during the contact firing process have been studied in detail by thermogravimetric differential thermal analysis in combination with mass spectroscopy. Based on these studies, a contact ink has been developed, optimized and tested on silicon solar cells. In this paper, the mechanism of the etching process, the opening of a dielectric layer, the influence of different atmospheres and the impact of the glass‐frit content are investigated. The observed microscopic contact structure, the resulting electrical solar‐cell parameters and the studied reactions are combined to clarify the physics behind the high‐temperature contact formation.     

Low‐temperature formation of local Al contacts to a‐Si:H‐passivated Si wafers

We have passivated boron‐doped, low‐resistivity crystalline silicon wafers on both sides by a layer of intrinsic, amorphous silicon (a‐Si:H). Local aluminum contacts were subsequently evaporated through a shadow mask. Annealing at 210°C in air dissolved the a‐Si:H underneath the Al layer and reduces the contact resistivity from above 1 Ω cm² to 14·9 m Ω cm². The average surface recombination velocity is 124 cm/s for the annealed samples with 6% metallization fraction. In contrast to the metallized regions, no structural change is observed in the non‐metallized regions of the annealed a‐Si:H film, which has a recombination velocity of 48 cm/s before and after annealing. Copyright © 2004 John Wiley & Sons, Ltd.     

Fine line printed silicon solar cells exceeding 20% efficiency

Silicon solar cells with passivated rear side and laser‐fired contacts were produced on float zone material. The front side contacts are built up in two steps, seed and plate. The seed layer is printed using an aerosol jet printer and a silver ink. After firing this seed layer through the silicon nitride layer, the conductive layer is grown by light induced plating. The contact formation is studied on different emitter sheet resistances, 55 Ω/sq, 70 Ω/sq, and on 110 Ω/sq. These emitters are passivated with a PECVD silicon nitride layer which also acts as an anti‐reflection coating. Even on the 110 Ω/sq emitters it was possible to reach a fill factor of 80·1%. The electrical properties i.e., the contact resistance of the front side contacts are studied by transfer length model (TLM) measurements. On a cell area of 4 cm² and emitter sheet resistance of 110 Ω/sq, a record efficiency of 20·3% was achieved. Excellent open‐circuit voltage (V_oc) and short‐circuit current (j_sc) values of 661 mV and 38·4 mA/cm² were obtained due to the low recombination in the 110 Ω/sq emitter and at the passivated rear surface. These results show impressively that it is possible to contact emitter profiles with a very high efficiency potential using optimized printing technologies. Copyright © 2008 John Wiley & Sons, Ltd.     

High‐efficiency (19%) screen‐printed textured cells on low‐resistivity float‐zone silicon with high sheet‐resistance emitters

High‐efficiency 4 cm² screen‐printed (SP) textured cells were fabricated on 100 Ω/sq emitters using a rapid single‐step belt furnace firing process. The high contact quality resulted in a low series resistance of 0·79 Ωcm², high shunt resistance of 48 836 Ωcm², a low junction leakage current of 18·5 nA/cm² (n₂ = 2) yielding a high fill factor (FF) of 0·784 on 100 Ω/sq emitter. A low resistivity (0·6 Ωcm) FZ Si was used for the base to enhance the contribution of the high sheet‐resistance emitter without appreciably sacrificing the bulk lifetime. This resulted in a 19% efficient (confirmed at NREL) SP 4 cm² cell on textured FZ silicon with SP contacts and single‐layer antireflection coating. This is apparently higher in performance than any other previously reported cell using standard screen‐printing approaches (i.e., single‐step firing and grid metallization). Detailed cell characterization and device modeling were performed to extract all the important device parameters of this 19% SP Si cell and provide guidelines for achieving 20% SP Si cells. Copyright © 2005 John Wiley & Sons, Ltd.     

Towards thinner and low bowing silicon solar cells: form the boron and aluminum co‐doped back surface field with thinner metallization film

Using thinner wafers can largely reduce the cost of silicon solar cells. One obstacle of using thinner wafers is that few methods can provide good dopant concentration for the back surface field (BSF) and good ohmic contact while generated only in low bowing. In this paper, we have demonstrated the screening–printing B and Al (B/Al) mixture metallization film technique, making use of the screen‐printing technique and the higher solubility of B in silicon to form a B/Al‐BSF. This technique can raise the carrier concentration in the BSF by more than one order of magnitude and reduce the back surface recombination at a low firing temperature (≤800 °C). We have also shown that through the new technique, the metallization paste thickness at the rear could be reduced largely, which however did not degrade the solar cell efficiency. All these efforts are aiming for pushing forward the application of thinner wafers. Copyright © 2011 John Wiley & Sons, Ltd.     

Silicon solar cells based on all‐laser‐transferred contacts

Crystalline silicon solar cells based on all‐laser‐transferred contacts (ALTC) have been fabricated with both front and rear metallization achieved through laser induced forward transferring. Both the front and rear contacts were laser‐transferred from a glass slide coated with a metal layer to the silicon substrate already processed with emitter formation, surface passivation, and antireflection coating. Ohmic contacts were achieved after this laser transferring. The ALTC solar cells were fabricated on chemically textured p‐type Cz silicon wafers. An initial conversion efficiency of over 15% was achieved on a simple cell structure with full‐area emitter. Further improvements are expected with optimized laser transferring conditions, front grid pattern design, and surface passivation. The ALTC process demonstrates the advantage of laser processing in simplifying the solar cell fabrication by a one‐step metal transferring and firing process. Copyright © 2013 John Wiley & Sons, Ltd.     

Selective laser ablation of SiNx layers on textured surfaces for low temperature front side metallizations

For an alternative front side metallization process without screen printing of metal paste the selective opening of the front surface anti‐reflection coating could be realized by laser ablation. A successful implementation of this scheme requires direct absorption of the laser light within the anti‐reflection coating, since the emitter underneath must not be damaged severely. Additionally, the ablation must be feasible on textured surfaces. In this paper, we show that laser light with a wavelength of 355 nm and a pulse length of approximately 30 ns is absorbed directly by a typical silicon nitride anti‐reflection coating. Based on lifetime measurements on ablated samples it is shown that a damage free laser ablation of SiN_x layers on planar surfaces is possible. The characteristic ablation structure on textured surfaces is explained and quantified by rigorous coupled wave analysis (RCWA) simulations. Finally, high efficiency solar cells with a standard emitter (R_sh approx. 50 Ω/sq) have been processed using laser ablation of the silicon nitride anti‐reflection coating. These cells show efficiencies of up to 19·1%, comparable to the reference solar cells using photolithographically opened contact areas. Copyright © 2008 John Wiley & Sons, Ltd.     

Evolution of metal plating for silicon solar cell metallisation

Increasing silver prices and reducing silicon wafer thicknesses provide incentives for silicon solar cell manufacturing to develop new metallisation strategies that do not rely on screen printing and preferably reduce silver usage. Recently, metal plating has re‐emerged as a metallisation process that may address these future requirements. This paper reports on the evolution of metal plating techniques, from their use in early silicon solar cells, to current light‐induced plating processes. Unlike screen‐printed metallisation, metal plating typically requires an initial patterning step to create openings in a masking layer for the subsequent self‐aligned metallisation. Consequently, relevant recently‐developed dielectric patterning methods are also reviewed because, in many cases, the plating process must be adapted to the properties of the patterning method used. The potential of new light‐induced plating processes to form cost‐effective copper metallisation is supported by the recent activity in the development of metal plating tools for commercial silicon solar cell manufacture. Copyright © 2012 John Wiley & Sons, Ltd.     

Screen‐printed Emitter‐Wrap‐Through solar cell with single step side selective emitter with 18.8% efficiency

A fabrication process for Emitter‐Wrap‐Through solar cells on monocrystalline material with high quality gap passivation by wet thermal silicon dioxide is investigated. Masking and structuring steps are performed by screen‐printing technology. Via‐holes are created by an industrially applicable high‐speed laser drilling process. The cell structure features a selective emitter structure fabricated in a single high temperature step: a highly doped emitter at the via‐holes and the rear side, allowing for a low via‐hole resistivity as well as a low resistivity contact to screen‐printed pastes, and a moderately doped front side emitter exhibiting high quantum efficiency in the low wavelength range. Therefore a novel approach is applied depositing either doped or undoped PECVD silicon dioxide layers on the front side. It is shown that doping profiles advantageous for the EWT‐cell structure can be achieved. The screen‐printed aluminum paste is found to penetrate the underlying thermal dioxide layer at appropriate contact firing conditions leading to a zone of high recombination in the overlap region of aluminum and silicon dioxide. It is shown that conventional PECVD‐anti‐reflection silicon nitride acts as effective protection layer reducing the recombination in this region. Designated area conversion efficiencies up to 18.8% on FZ material are obtained applying the single step side selective emitter fabrication technique. Copyright © 2010 John Wiley & Sons, Ltd.     

Stack system of PECVD amorphous silicon and PECVD silicon oxide for silicon solar cell rear side passivation

A stack of hydrogenated amorphous silicon (a‐Si) and PECVD‐silicon oxide (SiO_x) has been used as surface passivation layer for silicon wafer surfaces. Very good surface passivation could be reached leading to a surface recombination velocity (SRV) below 10 cm/s on 1 Ω cm p‐type Si wafers. By using the passivation layer system at a solar cell's rear side and applying the laser‐fired contacts (LFC) process, pointwise local rear contacts have been formed and an energy conversion efficiency of 21·7% has been obtained on p‐type FZ substrates (0·5 Ω cm). Simulations show that the effective rear SRV is in the range of 180 cm/s for the combination of metallised and passivated areas, 120 ± 30 cm/s were calculated for the passivated areas. Rear reflectivity is comparable to thermally grown silicon dioxide (SiO₂). a‐Si rear passivation appears more stable under different bias light intensities compared to thermally grown SiO₂. Copyright © 2008 John Wiley & Sons, Ltd.     

Add‐on laser tailored selective emitter solar cells

An elegant laser tailoring add‐on process for silicon solar cells, leading to selectively doped emitters increases their efficiency η by Δη = 0.5% absolute. Our patented, scanned laser doping add‐on process locally increases the doping under the front side metallization, thus allowing for shallow doping and less Auger recombination between the contacts. The selective laser add‐on process modifies the emitter profile from a shallow error‐function type to Gaussian type and enables excellent contact formation by screen printing, normally difficult to achieve for shallow diffused emitters. The significantly deeper doping profile of the laser irradiated samples widens the process window for the firing of screen printed contacts and avoids metal spiking through the pn‐junction. Copyright © 2010 John Wiley & Sons, Ltd.     

Laser‐fired contact for n‐type crystalline Si solar cells

Laser‐fired contacts to n‐type crystalline silicon were developed by investigating novel metal stacks containing Antimony (Sb). Lasing conditions and the structure of metals stacks were optimized for lowest contact resistance and minimum surface damage. Specific contact resistance for firing different metal stacks through either silicon nitride or p‐type amorphous silicon was determined using two different models and test structures. Specific contact resistance values of 2–7 mΩcm² have been achieved. Recombination loss due to laser damage was consistent with an extracted local surface recombination velocity of ~20 000 cm/s, which is similar to values for laser‐fired base contact for p‐type crystalline silicon. Interdigitated back contact silicon heterojunction cells were fabricated with laser‐fired base contact and proof‐of‐concept efficiencies of 16.9% were achieved. This localized base contact technique will enable low cost back contact patterning and innovative designs for n‐type crystalline solar cell. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation of laser‐fired rear‐side recombination properties using an analytical model

This paper presents the application of the analytical model for locally contacted rear sides recently published by Fischer to the determination of recombination losses of solar cells with fixed metallization fraction, but varying contact pitch. After the successful experimental validation of the model on oxide‐passivated solar cells with ohmic contacts, the model was used for a detailed investigation of rear sides prepared by the laser‐fired contacts (LFC) method. In this way the surface recombination velocity (SRV) at the very contact areas was extracted for a broad base doping range. The determined parameterization allows the calculation of the SRV of any LFC rear side concerning base doping and contact pitch. The excellent passivation quality of the alnealed oxide with LFC contacts is shown: on 1 (100) Ω cm FZ an effective SRV of only 35 (4·3) cm/s could be measured with 1000 µm contact pitch. Copyright © 2006 John Wiley & Sons, Ltd.     

Screen printing metallization of boron emitters

This paper analyzes the influence of the composition of screen printing metal pastes on contacting boron emitters for crystalline silicon solar cells, optimized on the basis of commercial Ag‐paste Ferro 3347 by adding silicon and aluminum. Aluminum provides a lower contact resistance, while silicon prevents the spiking and alloying of aluminum with the silicon of the substrate. The best pastes have turned out to be high Si‐concentrated, which have provided a final specific contact resistance of 3–4 mΩ cm² on screen printed boron emitters diffused at 1000°C for 8 min, with shunt conductance lower than 0.6 mS/cm². The final fill factors have been better than 77.5% and open circuit voltages have exceeded 605 mV on Czochralski (Cz) n type 0.7 Ω cm solar cells. These results have proven the feasibility of our screen printing process for p⁺nn⁺ structures. Copyright © 2009 John Wiley & Sons, Ltd.     

Enhanced lateral current transport via the front N+ diffused layer of n‐type high‐efficiency back‐junction back‐contact silicon solar cells

N‐type back‐contact back‐junction solar cells were processed with the use of industrially relevant structuring technologies such as screen‐printing and laser processing. Application of the low‐cost structuring technologies in the processing of the high‐efficiency back‐contact back‐junction silicon solar cells results in a drastic increase of the pitch on the rear cell side. The pitch in the range of millimetres leads to a significant increase of the lateral base resistance. The application of a phosphorus doped front surface field (FSF) significantly reduces the lateral base resistance losses. This additional function of the phosphorus doped FSF in reducing the lateral resistance losses was investigated experimentally and by two‐dimensional device simulations. Enhanced lateral majority carrier's current transport in the front n⁺ diffused layer is a function of the pitch and the base resistivity. Experimental data show that the application of a FSF reduces the total series resistance of the measured cells with 3.5 mm pitch by 0.1 Ω cm² for the 1 Ω cm base resistivity and 1.3 Ω cm² for the 8 Ω cm base resistivity. Two‐dimensional simulations of the electron current transport show that the electron current density in the front n⁺ diffused layer is around two orders of magnitude higher than in the base of the solar cell. The best efficiency of 21.3% was obtained for the solar cell with a 1 Ω cm specific base resistivity and a front surface field with sheet resistance of 148 Ω/sq. Copyright © 2008 John Wiley & Sons, Ltd.     

Autodiffusion: a novel method for emitter formation in crystalline silicon thin‐film solar cells

The in situ formation of an emitter in monocrystalline silicon thin‐film solar cells by solid‐state diffusion of dopants from the growth substrate during epitaxy is demonstrated. This approach, that we denote autodiffusion, combines the epitaxy and the diffusion into one single process. Layer‐transfer with porous silicon (PSI process) is used to fabricate n‐type silicon thin‐film solar cells. The cells feature a boron emitter on the cell rear side that is formed by autodiffusion. The sheet resistance of this autodiffused emitter is 330 Ω/□. An independently confirmed conversion efficiency of (14·5 ± 0·4)% with a high short circuit current density of (33·3 ± 0·8) mA/cm² is achieved for a 2 × 2 cm² large cell with a thickness of (24 ± 1) µm. Transferred n‐type silicon thin films made from the same run as the cells show effective carrier lifetimes exceeding 13 µs. From these samples a bulk diffusion length L > 111 µm is deduced. Amorphous silicon is used to passivate the rear surface of these samples after the layer‐transfer resulting in a surface recombination velocity lower than 38 cm/s. Copyright © 2006 John Wiley & Sons, Ltd.