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.     

Excellent boron emitter passivation for high‐efficiency Si wafer solar cells using AlOx/SiNx dielectric stacks deposited in an industrial inline plasma reactor

Excellent passivation of boron emitters is realised using AlO_x/SiN_x dielectric stacks deposited in an industrial inline plasma‐enhanced chemical vapour deposition reactor. Very low emitter saturation current density (J_0e) values of 10 and 45 fA/cm² are obtained for 180 and 30 Ω/sq planar p⁺ emitters, respectively. For textured p⁺ emitters, the J_0e was found to be 1.5–2 times higher compared with planar emitters. The required thermal activation of the AlO_x films is performed in a standard industrial fast‐firing furnace, making the developed passivation stack industrially viable. We also show that an AlO_x thickness of 5 nm in the AlO_x/SiN_x stack is sufficient for obtaining a J_0e of 18 fA/cm² for planar 80 Ω/sq p⁺ emitters, which corresponds to a 1‐sun open‐circuit voltage limit of the solar cell of 736 mV at 25 °C. Copyright © 2012 John Wiley & Sons, Ltd.     

Front and rear silicon‐nitride‐passivated multicrystalline silicon solar cells with an efficiency of 18.1%

A solar cell process designed to utilise low‐temperature plasma‐enhanced chemical vapour deposited (PECVD) silicon nitride (SiN_x) films as front and rear surface passivation was applied to fabricate multicrystalline silicon (mc‐Si) solar cells. Despite the simple photolithography‐free processing sequence, an independently confirmed efficiency of 18.1% (cell area 2 × 2 cm²) was achieved. This excellent efficiency can be predominantly attributed to the superior quality of the rear surface passivation scheme consisting of an SiN_x film in combination with a local aluminium back‐surface field (LBSF). Thus, it is demonstrated that low‐temperature PECVD SiN_x films are well suited to achieve excellent rear surface passivation on mc‐Si. Copyright © 2002 John Wiley & Sons, Ltd.     

Textured silicon surface passivation by high‐rate expanding thermal plasma deposited SiN and thermal SiO2/SiN stacks for crystalline silicon solar cells

Expanding thermal plasma (ETP) deposited silicon nitride (SiN) with optical properties suited for the use as antireflection coating (ARC) on silicon solar cells has been used as passivation layer on textured monocrystalline silicon wafers. The surface passivation behavior of these high‐rate (>5 nm/s) deposited SiN films has been investigated for single layer passivation schemes and for thermal SiO₂/SiN stack systems before and after a thermal treatment that is normally used for contact‐firing. It is shown that as‐deposited ETP SiN used as a single passivation layer almost matches the performance of a thermal oxide. Furthermore, the SiN passivation behavior improves after a contact‐firing step, while the thermal oxide passivation degrades which makes ETP SiN a better alternative for single passivation layer schemes in combination with a contact‐firing step. Moreover, using the ETP SiN as a part of a thermal SiO₂/SiN stack proves to be the best alternative by realizing very low dark saturation current densities of <20 fA/cm² on textured solar‐grade FZ silicon wafers and this is further improved to <10 fA/cm² after the anneal step. Optical and electrical film characterizations have also been carried out on these SiN layers in order to study the behavior of the SiN before and after the thermal treatment. Copyright © 2008 John Wiley & Sons, Ltd.     

Bulk passivation of multicrystalline silicon solar cells induced by high‐rate‐deposited (> 1 nm/s) silicon nitride films

Silicon nitride (a‐SiN_x:H) films deposited by the expanding thermal plasma at high rate (> 1 nm/s) have been studied for application as anti‐reflection coatings for multicrystalline silicon (mc‐Si) solar cells. Internal quantum efficiency measurements have revealed that bulk passivation is achieved after a firing‐through process of the a‐SiN_x:H as deposited from NH₃/SiH₄ and N₂/SiH₄ plasmas. However, the a‐SiN_x:H films deposited from N₂/SiH₄ show a lower passivation quality than those deposited from NH₃/SiH₄. This has been attributed to a poorer thermal stability of the films deposited from the N₂/SiH₄ plasma, resulting in structural changes within the film during the firing step. Copyright © 2002 John Wiley & Sons, Ltd.     

Diffusion‐free high efficiency silicon solar cells

Traditional POCl₃ diffusion is performed in large diffusion furnaces heated to ~850 C and takes an hour long. This may be replaced by an implant and subsequent 90‐s rapid thermal annealing step (in a firing furnace) for the fabrication of p‐type passivated emitter rear contacted silicon solar cells. Implantation has long been deemed a technology too expensive for fabrication of silicon solar cells, but if coupled with innovative process flows as that which is mentioned in this paper, implantation has a fighting chance. An SiOx/SiN_y rear side passivated p‐type wafer is implanted at the front with phosphorus. The implantation creates an inactive amorphous layer and a region of silicon full of interstitials and vacancies. The front side is then passivated using a plasma‐enhanced chemical vapor deposited SiN_xH_y. The wafer is placed in a firing furnace to achieve dopant activation. The hydrogen‐rich silicon nitride releases hydrogen that is diffused into the Si, the defect rich amorphous front side is immediately passivated by the readily available hydrogen; all the while, the amorphous silicon recrystallizes and dopants become electrically active. It is shown in this paper that the combination of this particular process flow leads to an efficient Si solar cell. Cell results on 160‐µm thick, 148.25‐cm² Cz Si wafers with the use of the proposed traditional diffusion‐free process flow are up to 18.8% with a V_oc of 638 mV, J_sc of 38.5 mA/cm², and a fill factor of 76.6%. Copyright © 2012 John Wiley & Sons, Ltd.     

SiOyNx/SiNx stack: a promising surface passivation layer for high‐efficiency and potential‐induced degradation resistant mc‐silicon solar cells

A thin SiO_yN_x film was inserted below a conventional SiN_x antireflection coating used in c‐Si solar cells in order to improve the surface passivation and the solar cell's resistance to potential‐induced degradation (PID). The effect of varying the flow ratio of the N₂O and SiH₄ precursors and the deposition temperature for the SiO_yN_x thin film upon material properties were systematically investigated. An excellent surface passivation was obtained on FZ p‐type polished silicon wafers, with the best results obtained with a SiO_yN_x film deposited at a very low temperature of 130 °C and with an optical refractive index of 1.8. In the SiO_yN_x/SiN_x stack structure, a SiO_yN_x film with ~6 nm thickness is sufficient to provide excellent surface passivation with an effective surface recombination velocity S_eff < 2 cm/s. Furthermore, we applied the optimized SiO_yN_x/SiN_x stack on multicrystalline Si solar cells as a surface passivation and antireflection coating, resulting in a 0.5% absolute average conversion efficiency gain compared with that of reference cells with conventional SiN_x coating. Moreover, the cells with the SiO_yN_x/SiN_x stack layers show a significant increase in their resistance to PID. Nearly zero degradation in shunt resistance was obtained after 24 h in a PID test, while a single SiN_x‐coated silicon solar cell showed almost 50% degradation after 24 h. Copyright © 2016 John Wiley & Sons, Ltd.     

Multi‐crystalline Si solar cells with very fast deposited (180 nm/min) passivating hot‐wire CVD silicon nitride as antireflection coating

Hot‐wire chemical vapor deposition (HWCVD) is a promising technique for very fast deposition of high quality thin films. We developed processing conditions for device‐ quality silicon nitride (a‐SiN_x:H) anti‐reflection coating (ARC) at high deposition rates of 3 nm/s. The HWCVD SiN_x layers were deposited on multicrystalline silicon (mc‐Si) solar cells provided by IMEC and ECN Solar Energy. Reference cells were provided with optimized parallel plate PECVD SiN_x and microwave PECVD SiN_x respectively. The application of HWCVD SiN_x on IMEC mc‐Si solar cells led to effective passivation, evidenced by a V_oc of 606 mV and consistent IQE curves. For further optimization, series were made with HW SiN_x (with different x) on mc‐Si solar cells from ECN Solar Energy. The best cell efficiencies were obtained for samples with a N/Si ratio of 1·2 and a high mass density of >2·9 g/cm³. The best solar cells reached an efficiency of 15·7%, which is similar to the best reference cell, made from neighboring wafers, with microwave PECVD SiN_x. The IQE measurements and high V_oc values for these cells with HW SiN_x demonstrate good bulk passivation. PC1D simulations confirm the excellent bulk‐ and surface‐passivation for HW SiN_x coatings. Interesting is the significantly higher blue response for the cells with HWCVD SiN_x when compared to the PECVD SiN_x reference cells. This difference in blue response is caused by lower light absorption of the HWCVD layers (compared to microwave CVD; ECN) and better surface passivation (compared to parallel plate PECVD; IMEC). The application of HW SiN_x as a passivating antireflection layer on mc‐Si solar cells leads to efficiencies comparable to those with optimized PECVD SiN_x coatings, although HWCVD is performed at a much higher deposition rate. Copyright © 2007 John Wiley & Sons, Ltd.     

Very low surface recombination velocity of crystalline silicon passivated by phosphorus‐doped a‐SicxNy:H(n) alloys

Hydrogenated and phosphorus‐doped amorphous silicon carbonitride films (a‐SiC_xN_y:H(n)) were deposited by plasma‐enhanced chemical vapor deposition (PECVD) on crystalline silicon surface in order to explore surface passivation properties. Very silicon‐rich films yielded effective surface recombination velocities at 1 sun‐illumination as low as 3 cm s⁻¹ and 2 cm s⁻¹ on 1 Ω cm p‐ and n‐type crystalline silicon substrates, respectively. In order to use them as anti‐reflection coating, we increased alternatively either the carbon or nitrogen content of these films. Also, a combination of passivation and antireflective films was analyzed. Finally, we explored the passivation stability under high‐temperature steps. Copyright © 2007 John Wiley & Sons, Ltd.     

High efficiency screen‐printed EFG Si solar cells through rapid thermal processing‐induced bulk lifetime enhancement

This paper shows that one second (1 s) firing of Si solar cells with screen‐printed Al on the back and SiN _x anti‐reflection coating on the front can produce a high quality Al‐doped back‐surface‐field (Al‐BSF) and significantly enhance SiN _x ‐induced defect hydrogenation in the bulk Si. Open‐circuit voltage, internal quantum efficiency measurements, and cross‐sectional scanning electron microscopy pictures on float‐zone silicon cells revealed that 1 s firing in rapid thermal processing at 750°C produces just as good a BSF as 60 s firing, indicating that the quality of Al‐BSF region is not a strong function of RTP firing time at 750°C. Analysis of edge‐defined film‐fed grown (EFG) Si cells showed that short‐term firing is much more effective in improving the hydrogen passivation of bulk defects in EFG Si. Average minority‐carrier lifetime in EFG wafers improved from ∼3 to ∼33 μs by 60 s firing but reached as high as 95μs with 1 s firing, resulting in 15·6% efficient screen‐printed cells on EFG Si. Copyright © 2004 John Wiley & Sons, Ltd.     

Laser‐fired contact optimization in c‐Si solar cells

In this work we study the optimization of laser‐fired contact (LFC) processing parameters, namely laser power and number of pulses, based on the electrical resistance measurement of an aluminum single LFC point. LFC process has been made through four passivation layers that are typically used in c‐Si and mc‐Si solar cell fabrication: thermally grown silicon oxide (SiO₂), deposited phosphorus‐doped amorphous silicon carbide (a‐SiC_x/H(n)), aluminum oxide (Al₂O₃) and silicon nitride (SiN_x/H) films. Values for the LFC resistance normalized by the laser spot area in the range of 0.65–3 mΩ cm² have been obtained. Copyright © 2011 John Wiley & Sons, Ltd.     

20.7% efficient ion‐implanted large area n‐type front junction silicon solar cells with rear point contacts formed by laser opening and physical vapor deposition

In this work, we report on ion‐implanted, high‐efficiency n‐type silicon solar cells fabricated on large area pseudosquare Czochralski wafers. The sputtering of aluminum (Al) via physical vapor deposition (PVD) in combination with a laser‐patterned dielectric stack was used on the rear side to produce front junction cells with an implanted boron emitter and a phosphorus back surface field. Front and back surface passivation was achieved by thin thermally grown oxide during the implant anneal. Both front and back oxides were capped with SiN_x, followed by screen‐printed metal grid formation on the front side. An ultraviolet laser was used to selectively ablate the SiO₂/SiN_x passivation stack on the back to form the pattern for metal–Si contact. The laser pulse energy had to be optimized to fully open the SiO₂/SiN_x passivation layers, without inducing appreciable damage or defects on the surface of the n⁺ back surface field layer. It was also found that a low temperature annealing for less than 3 min after PVD Al provided an excellent charge collecting contact on the back. In order to obtain high fill factor of ~80%, an in situ plasma etching in an inert ambient prior to PVD was found to be essential for etching the native oxide formed in the rear vias during the front contact firing. Finally, through optimization of the size and pitch of the rear point contacts, an efficiency of 20.7% was achieved for the large area n‐type passivated emitter, rear totally diffused cell. Copyright © 2014 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.     

High‐quality surface passivation of silicon solar cells in an industrial‐type inline plasma silicon nitride deposition system

We have studied the surface passivation of silicon by deposition of silicon nitride (SiN) in an industrial‐type inline plasma‐enhanced chemical vapor deposition (PECVD) reactor designed for the continuous coating of silicon solar cells with high throughput. An optimization study for the passivation of low‐resistivity p‐type silicon has been performed exploring the dependence of the film quality on key deposition parameters of the system. With the optimized films, excellent passivation properties have been obtained, both on undiffused p‐type silicon and on phosphorus‐diffused n⁺ emitters. Using a simple design, solar cells with conversion efficiencies above 20% have been fabricated to prove the efficacy of the inline PECVD SiN. The passivation properties of the films are on a par with those of high‐quality films prepared in small‐area laboratory PECVD reactors. Copyright © 2004 John Wiley & Sons, Ltd.     

Approach for Al2O3 rear surface passivation of industrial p‐type Si PERC above 19%

Atomic layer deposition (ALD) of thin Al₂O₃ (≤10 nm) films is used to improve the rear surface passivation of large‐area screen‐printed p‐type Si passivated emitter and rear cells (PERC). A blister‐free stack of Al₂O₃/SiO_x/SiN_x is developed, leading to an improved back reflection and a rear recombination current (J_0,rear) of 92 ± 6 fA/cm². The Al₂O₃/SiO_x/SiN_x stack is blister‐free if a 700°C anneal in N₂ is performed after the Al₂O₃ deposition and prior to the SiO_x/SiN_x capping. A clear relationship between blistering density and lower open‐circuit voltage (V_OC) due to increased rear contacting area is shown. In case of the blister‐free Al₂O₃/SiO_x/SiN_x rear surface passivation stack, an average cell efficiency of 19.0% is reached and independently confirmed by FhG‐ISE CalLab. Compared with SiO_x/SiN_x‐passivated PERC, there is an obvious gain in V_OC and short‐circuit current (J_SC) of 5 mV and 0.2 mA/cm², respectively, thanks to improved rear surface passivation and rear internal reflection. Copyright © 2012 John Wiley & Sons, Ltd.     

Improvement of charge minority‐carrier lifetime in p(boron)‐type Czochralski silicon by rapid thermal annealing

In p‐type Czochralski‐grown (Cz) silicon a light‐induced degradation of the minority‐carrier lifetime is well known in the literature. Reducing the extent of this degradation would significantly improve the stable effective lifetime and thus the related performance of solar cells. In this work, the reduction of the density of the metastable defect underlying the degradation is performed by rapid thermal annealing (RTA). For a proper analysis it is extremely important to avoid contamination by the RTA furnace. Both, SiN_x and SiO₂ were examined as a barrier layer. A 60 nm SiN_x layer was proven to act as the most effective barrier layer, allowing maintenance of a very high lifetime of 700 μs on 1.25 Ω cm p‐type FZ material. A design‐of‐experiments (DOE) study was used to analyze the effect of five process parameters on the stable effective lifetime. Especially, the plateau temperature shows a strong correlation with τ_d, the stable effective lifetime after light‐induced degradation. The effect of plateau temperature on τ_d of Cz‐ and FZ‐Si wafers is examined in the temperature range of 700–1050°C for plateau time 120 s. It was found that the stable effective lifetime of all RTA‐treated Cz‐wafers is increased compared with the initial stable effective lifetime before processing. The highest increase of stable effective lifetime (by a factor of around 2) is obtained at 900°C with a process time of 120 s. This increase in lifetime is reflected in a reduced concentration of the metastable defect. Copyright © 2001 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.     

Surface passivation of high‐efficiency silicon solar cells by atomic‐layer‐deposited Al2O3

Atomic‐layer‐deposited aluminium oxide (Al₂O₃) is applied as rear‐surface‐passivating dielectric layer to passivated emitter and rear cell (PERC)‐type crystalline silicon (c‐Si) solar cells. The excellent passivation of low‐resistivity p‐type silicon by the negative‐charge‐dielectric Al₂O₃ is confirmed on the device level by an independently confirmed energy conversion efficiency of 20·6%. The best results are obtained for a stack consisting of a 30 nm Al₂O₃ film covered by a 200 nm plasma‐enhanced‐chemical‐vapour‐deposited silicon oxide (SiO_x) layer, resulting in a rear surface recombination velocity (SRV) of 70 cm/s. Comparable results are obtained for a 130 nm single‐layer of Al₂O₃, resulting in a rear SRV of 90 cm/s. Copyright © 2008 John Wiley & Sons, Ltd.     

Light‐enhanced surface passivation of TiO2‐coated silicon

Titanium dioxide is shown to afford good passivation to non‐diffused silicon surfaces and boron‐diffused surfaces after a low‐temperature anneal. The passivation most likely owes to the significant levels of negative charge instilled in the films, and passivation is enhanced by illumination—advantageous for solar cells—indicating that a titanium dioxide photoreaction is at least partly responsible for the low surface recombination. We demonstrate a surface recombination velocity of less than 30 cm/s, on a 5‐Ω cm n‐type silicon, and an emitter saturation current density of 90 fA/cm² on a 200‐Ω/sq boron diffusion. If these titanium dioxide passivated boron‐diffused surfaces were employed in a crystalline silicon solar cell, an open‐circuit voltage as high as 685 mV could be achieved. Given that TiO₂ has a high refractive index and was deposited with atmospheric pressure chemical vapour deposition, an inexpensive technique, it has the potential as a passivating antireflection coating for industrial boron‐diffused silicon solar cells. Copyright © 2011 John Wiley & Sons, Ltd.