Metal aerosol jet printing for solar cell metallization

Metal aerosol jet printing is a new non‐contact direct‐write technique for the front side metallization of highly efficient industrial silicon solar cells. With this technique the first layer of a two‐layer contact structure is created. It features a low contact resistance and good mechanical adhesion to the silicon surface. The second layer is formed by light‐induced silver plating (LIP) to increase the line conductivity. To form the first layer a metal‐containing aerosol is created in the printer and focused via a second surrounding gas stream through a nozzle and deposited onto the substrate. The focussing gas avoids the contact between the aerosol and the nozzle tip. In addition, line widths significantly smaller than the outlet diameter of the nozzle tip can be reached. Fine and continuous lines with a width of 14 µm were printed using a metal organic ink. As the adhesion of these layers was not sufficient, a commercially available screen‐printing paste for solar cell metallization was modified and tested. Monocrystalline silicon solar cells of 12·5 cm × 12·5 cm with an aluminum back surface field were processed, achieving energy conversion efficiencies up to 17·8%. Copyright © 2007 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.     

Inkjet printed metallizations for Cu(In1−x Ga x )Se2 photovoltaic cells

This study reports the inkjet printing of Ag front contacts on Aluminum doped Zinc Oxide (AZO)/intrinsic Zinc Oxide (i‐ZnO)/CdS/Cu(In_1−xGa_x)Se₂ (CIGS)/Mo thin film photovoltaic cells. The printed Ag contacts are being developed to replace the currently employed evaporated Ni/Al bi‐layer contacts. Inkjet deposition conditions were optimized to reduce line resistivity and reduce contact resistance to the Al:ZnO layer. Ag lines printed at a substrate temperature of 200°C showed a line resistivity of 2.06 µΩ · cm and a contact resistance to Al:ZnO of 8.2 ± 0.2 mΩ · cm² compared to 6.93 ± 0.3 mΩ · cm² for thermally evaporated contacts. These deposition conditions were used to deposit front contacts onto high quality CIGS thin film photovoltaic cells. The heating required to print the Ag contacts caused the performance to degrade compared to similar devices with evaporated Ni/Al contacts that were not heated. Devices with inkjet printed contacts showed 11.4% conversion efficiency compared to 14.8% with evaporated contacts. Strategies to minimize heating, which is detrimental for efficiency, during inkjet printing are proposed. Copyright © 2011 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.     

Series resistance characterization of industrial silicon solar cells with screen‐printed contacts using hotmelt paste

This work presents the results of a detailed series resistance characterization of silicon solar cells with screen‐printed front contacts using hotmelt silver paste. Applying the hotmelt technology energy conversion efficiencies up to 18·0% on monocrystalline wafers with a size of 12·5 cm × 12·5 cm have been achieved, an increase of 0·3% absolute compared to cells with conventional screen‐printed contacts. This is mainly due to the reduction in the finger resistance to values as low as 14 Ω/m, which reduces the series resistance of the solar cell significantly. To retrieve the lumped series resistance as accurately as possible under the operating condition, different determination methods have been analyzed. Methods under consideration were fitting of the two‐diode equation function to a dark IV‐curve, integration of the area A under an IV‐curve, comparison of a j_sc–V_oc with a one‐sun IV‐curve, comparison of the j_sc and V_oc points of a shaded curve with the one‐sun IV‐curve as well as comparison of a dark IV‐curve with a one‐sun IV‐curve, and comparison of IV‐curves measured at different light intensities. The performed investigations have shown that the latter four methods all resulted in reliable series resistance values. Copyright © 2007 John Wiley & Sons, Ltd.     

Comprehensive analysis of advanced solar cell contacts consisting of printed fine‐line seed layers thickened by silver plating

This work presents a detailed analysis of a new two‐layer process to contact industrial solar cells. However, most of the results seem to be transferable to standard screen print paste contacts. The seed layer was created by a pad or screen printer and thickened by light‐induced plating (LIP) of silver. These contact structures were investigated microscopically to gain a better understanding of the observed electrical parameters. A review of the present microscopic contact formation model for flat surfaces is presented. This model was extended and applied to surfaces textured with random pyramids. This analysis has revealed two new types of silver crystallites which can be described by a crystallographic model. The dependence of the silver crystallite density on the surface doping concentration was investigated. Next, the dependence of the contact resistance on the width of the seed layer was measured showing that the contact resistivity increases with a reduction of the seed layer width. These results have been further approved by an analysis of SEM images of wet‐chemically etched contacts examining the density of crystallites and the fraction of removed SiN_x layer. Contact resistance R_C measurements before and after LIP of silver showed surprisingly a positive influence of the plating process on R_C. A detailed microscopical analysis revealed four new possible current flow paths due to the LIP of a conventional contact or a seed layer. The results led to an extension of the existing model for a screen‐printed contact. Copyright © 2008 John Wiley & Sons, Ltd.     

Low‐Temperature‐Processed Printed Metal Oxide Transistors Based on Pure Aqueous Inks

Additive patterning of transparent conducting metal oxides at low temperatures is a critical step in realizing low‐cost transparent electronics for display technology and photovoltaics. In this work, inkjet‐printed metal oxide transistors based on pure aqueous chemistries are presented. These inks readily convert to functional thin films at lower processing temperatures (T ≤ 250 °C) relative to organic solvent‐based oxide inks, facilitating the fabrication of high‐performance transistors with both inkjet‐printed transparent electrodes of aluminum‐doped cadmium oxide (ACO) and semiconductor (InO_x ). The intrinsic fluid properties of these water‐based solutions enable the printing of fine features with coffee‐ring free line profiles and smoother line edges than those formed from organic solvent‐based inks. The influence of low‐temperature annealing on the optical, electrical, and crystallographic properties of the ACO electrodes is investigated, as well as the role of aluminum doping in improving these properties. Finally, the all‐aqueous‐printed thin film transistors (TFTs) with inkjet‐patterned semiconductor (InO_x ) and source/drain (ACO) layers are characterized, which show ideal low contact resistance (R _c < 160 Ω cm) and competitive transistor performance (µ _lin up to 19 cm² V^?1 s^?1, Subthreshold Slope (SS) ≤150 mV dec^?1) with only low‐temperature processing (T ≤ 250 °C).     

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.     

Resistivity and lifetime variation along commercially grown Ga‐ and B‐Doped Czochralski Si ingots and its effect on light‐induced degradation and performance of solar cells

A systematic study of the variation in resistivity and lifetime on cell performance, before and after light‐induced degradation (LID), was performed along ∼900‐mm‐long commercially grown B‐ and Ga‐doped Czochralski (Cz) ingots. Manufacturable screen‐printed solar cells were fabricated and analyzed from different locations on the ingots. Despite the large variation in resistivity (0·57–2·5 Ω cm) and lifetime (100–1000 µ s) in the Ga‐doped Cz ingot, the efficiency variation was found to be ≤ 0·5% with an average efficiency of ∼17·1%. No LID was observed in these cells. In contrast to the Ga‐doped ingot, the B‐doped ingot showed a relatively tight resistivity range (0·87–1·22 Ω cm), resulting in smaller spread in lifetime (60–400 µ s) and efficiency (16·5–16·7%) along the ingot. However, the LID reduced the efficiency of these B‐doped cells by about 1·1% absolute. Additionally, the use of thinner substrate and higher resistivity (4·3 Ω cm) B‐doped Cz was found to reduce the LID significantly, resulting in an efficiency reduction of 0·5–0·6%, as opposed to >1·0% in ∼1 Ω cm ∼17% efficient screen‐printed cells. As a result, Ga‐doped Cz cells gave 1·5 and 0·7% higher stabilized efficiency relative to 1 and 4·3 Ω cm B‐doped Cz Si cells, respectively. Copyright © 2005 John Wiley & Sons, Ltd.     

Effect of carbon containing SiNx antireflection coating on the screen‐printed contact and low illumination performance of silicon solar cell

Screen‐printed metal contact formation through a carbon containing antireflection coating was investigated for silicon solar cells by fabricating conventional carbon‐free SiN_x and carbon‐rich SiC_xN_y film. An appreciable difference was found in the average shunt resistance (R_sh), which was about an order of magnitude higher for SiC_xN_y‐coated solar cells relative to the counterpart SiN_x‐coated solar cells. Series resistance (R_s) and fill factor (FF) were comparable for both antireflection coatings but the starting efficiency of SiC_xN_y‐coated cell was ~0·2% lower because of slightly inferior surface passivation. However, SiC_xN_y‐coated solar cells showed less degradation under lower illumination (<1000 W/m²) compared with the SiN_x‐coated cells due to reduced FF degradation under low illumination. Theoretical calculations in this paper support that this is a direct result of high R_sh. Detailed photovoltaic system and cost modeling is performed to quantify the enhanced energy production and the reduced levelized cost of electricity due to higher shunt resistance of the SiC_xN_y‐coated cells. It is shown that R_sh value below 30 Ω (7000 Ω cm² for 239 cm² cell) can lead to appreciable loss in energy production in regions of low solar insolation. Copyright © 2011 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.     

Industrial high‐rate (∼5 nm/s) deposited silicon nitride yielding high‐quality bulk and surface passivation under optimum anti‐reflection coating conditions

High‐quality surface and bulk passivation of crystalline silicon solar cells has been obtained under optimum anti‐reflection coating properties by silicon nitride (a‐SiN_x:H) deposited at very high deposition rates of ∼5 nm/s. These a‐SiN_x:H films were deposited using the expanding thermal plasma (ETP) technology under regular processing conditions in an inline industrial‐type reactor with a nominal throughput of 960 solar cells/hour. The low surface recombination velocities (50–70 cm/s) were obtained on p‐type silicon substrates (8·4 Ω cm resistivity) for as‐deposited and annealed films within the broad refractive index range of 1·9–2·4, which covers the optimum bulk passivation and anti‐reflection coating performance reached at a refractive index of ∼2·1. Copyright © 2005 John Wiley & Sons, Ltd.     

Electroless‐Plated Gold Contacts for High‐Performance,Low Contact Resistance Organic Thin Film Transistors

Deposition of metallic electrodes on a semiconductor medium is an indispensable factor in governing carrier injection, and a metal/semiconductor contact that can be formed via solution process is highly desired in printed electronics. However, fine‐patterning the solution processes of metallic electrodes without damaging the excellent electronic properties of organic semiconductors (OSCs) is still a challenge. In this work, electroless plating, a metal coating technique that involves auto‐catalytic reaction in an aqueous solution, is used to fabricate top‐contact organic thin‐film transistors (OTFTs). An electroless‐plated gold pattern with a spatial resolution of 10 micrometers is transferred and laminated on a monolayer of OSCs to serve as a hole‐injection electrode. The fabricated OTFTs exhibit reasonably high field‐effect mobility of up to 13 cm² V^?1 s^?1 and decent contact resistance as low as 120 Ω · cm, which implies that an ideal metal/semiconductor contact can be realized. This electroless plating technique can provide possibilities for practical mass production of organic integrated circuits because it is in principle cost‐effective, capable of covering large areas, high‐vacuum free, and environmentally friendly.     

Belt furnace gettering and passivation of n‐web silicon for high‐efficiency screen‐printed front‐surface‐field solar cells

Six different resistivities (0.32, 0.57, 1.2, 2.2, 9.1 and 20 Ω cm) were investigated to understand the dopant–defect interaction in n‐type, antimony‐doped, dendritic web silicon ribbon, and to study its response to gettering and passivation during belt furnace processing (BFP). The as‐grown lifetime was found to be a strong function of resistivity with higher resistivity displaying higher lifetime. Phosphorus gettering at 925° C/6 min raised the as‐grown lifetime of ∼1 μs in 20 Ω cm n‐web to 5.4 μs. A combination of phosphorus gettering followed by simultaneous Al gettering and SiN hydrogenation raised the 20 Ω cm n‐web lifetime to 78 μs. Unlike the as‐grown web, the processed lifetime was greater than 75 μs for all resistivities, with no clear doping dependence. This is attributed to the very effective gettering and passivation during the belt furnace processing. Front surface field (FSF) n⁺–n–p⁺ cells were fabricated by spin‐on phosphorus diffusion on the front and screen‐printed Al on the back. A lifetime value of over 100 μs was obtained in a 14.2% screen‐printed FSF n‐web solar cell fabricated on 100‐μm‐thick 20 Ω cm substrate. The screen‐printed FSF cell fabricated on (111) FZ gave an efficiency of 14.9% with a fill factor of 77.6%. These results are supported by model calculations, which revealed a maximum efficiency of ∼15% for 100‐μm‐thick planar screen‐printed FSF cells and their insensitivity to bulk lifetime above 60 μs. Copyright © 2001 John Wiley & Sons, Ltd.     

A masked process for the industrial production of buried contact solar cells on multi‐crystalline silicon

This paper reports on the development of a masked process for the production of buried contact solar cells on multi‐crystalline silicon. The process results in high efficiencies, and only includes steps that would be feasible in an industrial environment. We report here on different mask candidates and on the importance of hydrogenation with the new process. Using the developed process, we produced 111 large area (12 × 12 cm²) cells and achieved an average cell efficiency of 16·2%. The best cell had an efficiency of 16·9%, a V_oc of 616 mV, a J_sc of 35·0 mA/cm² and a fill factor of 78·3%. Copyright © 2008 John Wiley & Sons, Ltd.     

Material development for dye solar modules: results from an integrated approach

In this paper, we report on the outcome of a German network project conducted with 12 partners from universities and research institutes on the material development of dye solar cells (DSC). We give an overview in the field and evaluate the concept of monolithic DSC further with respect to upscaling and producibility on glass substrates. We have developed a manufacturing process for monolithic DSC modules which is entirely based on screen printing. Similar to our previous experience gained in the sealing of standard DSC, the encapsulation of the modules is achieved in a fusing step by soldering of glass frit layers. For use in monolithic DSC, a platinum free, conductive counter electrode layer, showing a charge transfer resistance of R_CT < 1·5 Ω cm², has been realized by firing a graphite/carbon black composite under an inert atmosphere. Glass frit sealed monolithic test cells have been prepared using this platinum‐free material. A solar efficiency of 6% on a 2·0 cm² active cell area has been achieved in this case. Various types of non‐volatile imidazolium‐based binary ionic liquid electrolytes have been synthesized and optimized with respect to diffusion‐limited currents and charge transfer resistances in DSC. In addition, quasi‐solid‐state electrolytes have been successfully tested by applying inorganic (SiO₂) physical gelators. For the use in semi‐transparent DSC modules, a polyol process has been developed which resulted in the preparation of screen printed, transparent catalytic platinum layers showing an extremely low charge transfer resistance (0·25 Ω cm²). Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Laser ablation of SiO2 for locally contacted Si solar cells with ultra‐short pulses

We apply ultra‐short pulse laser ablation to create local contact openings in thermally grown passivating SiO₂ layers. This technique can be used for locally contacting oxide passivated Si solar cells. We use an industrially feasible laser with a pulse duration of τ_pulse ∼ 10 ps. The specific contact resistance that we reach with evaporated aluminium on a 100 Ω/sq and P‐diffused emitter is in the range of 0·3–1 mΩ cm². Ultra‐short pulse laser ablation is sufficiently damage free to abandon wet chemical etching after ablation. We measure an emitter saturation current density of J_0e = (6·2 ± 1·6) × 10⁻¹³ A/cm² on the laser‐treated areas after a selective emitter diffusion with R_sheet ∼ 20 Ω/sq into the ablated area; a value that is as low as that of reference samples that have the SiO₂ layer removed by HF‐etching. Thus, laser ablation of dielectrics with pulse durations of about 10 ps is well suited to fabricate high‐efficiency Si solar cells. Copyright © 2007 John Wiley & Sons, Ltd.     

20.1%‐efficient crystalline silicon solar cell with amorphous silicon rear‐surface passivation

We have developed a crystalline silicon solar cell with amorphous silicon (a‐Si:H) rear‐surface passivation based on a simple process. The a‐Si:H layer is deposited at 225°C by plasma‐enhanced chemical vapor deposition. An aluminum grid is evaporated onto the a‐Si:H‐passivated rear. The base contacts are formed by COSIMA (contact formation to a‐Si:H passivated wafers by means of annealing) when subsequently depositing the front silicon nitride layer at 325°C. The a‐Si:H underneath the aluminum fingers dissolves completely within the aluminum and an ohmic contact to the base is formed. This contacting scheme results in a very low contact resistance of 3.5 ±0.2 mΩ cm² on low‐resistivity (0.5 Ω cm) p‐type silicon, which is below that obtained for conventional Al/Si contacts. We achieve an independently confirmed energy conversion efficiency of 20.1% under one‐sun standard testing conditions for a 4 cm² large cell. Measurements of the internal quantum efficiency show an improved rear surface passivation compared with reference cells with a silicon nitride rear passivation. Copyright © 2005 John Wiley & Sons, Ltd.     

High efficiency screen printed bifacial solar cells on monocrystalline CZ silicon

We present industrialized bifacial solar cells on large area (149 cm²) 2 cm CZ monocrystalline silicon wafers processed with industrially relevant techniques such as liquid source BBr₃ and POCl₃ open‐tube furnace diffusions, plasma enhanced chemical vapor deposition (PECVD) SiN_x deposition, and screen printed contacts. The fundamental analysis of the paste using at boron‐diffused surface and the bifacial solar cell firing cycle has been investigated. The resulting solar cells have front and rear efficiencies of 16.6 and 12.8%, respectively. The ratio of the rear J_SC to front J_SC is 76.8%. It increases the bifacial power by 15.4% over a conventional solar cell at 20% of 1‐sun rear illumination, which equals to the power of a conventional solar cell with 19.2% efficiency. We also present a bifacial glass–glass photovoltaic (PV) module with 30 bifacial cells with the electrical characteristics. Copyright © 2010 John Wiley & Sons, Ltd.