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.     

Extremely low surface recombination velocities on low‐resistivity n‐type and p‐type crystalline silicon using dynamically deposited remote plasma silicon nitride films

Extremely low upper‐limit effective surface recombination velocities (S_eff.max) of 5.6 and 7.4 cm/s, respectively, are obtained on ~1.5 Ω cm n‐type and p‐type silicon wafers, using silicon nitride (SiN_x) films dynamically deposited in an industrial inline plasma‐enhanced chemical vapour deposition (PECVD) reactor. SiN_x films with optimised antireflective properties in air provide an excellent S_eff.max of 9.5 cm/s after high‐temperature (>800 °C) industrial firing. Such low S_eff.max values were previously only attainable for SiN_x films deposited statically in laboratory reactors or after optimised annealing; however, in our case, the SiN_x films were dynamically deposited onto large‐area c‐Si wafers using a fully industrial reactor and provide excellent surface passivation results both in the as‐deposited condition and after industrial‐firing, which is a widely used process in the photovoltaic industry. Contactless corona‐voltage measurements reveal that these SiN_x films contain a relatively high positive charge of (4–8) × 10¹² cm⁻² combined with a relatively low interface defect density of ~5 × 10¹¹ eV⁻¹ cm⁻². 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.     

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.     

Comparison of TiO2 and other dielectric coatings for buried‐contact solar cells: a review

This paper compares the optical, electronic, physical and chemical properties of dielectric thin films that are commonly used to enhance the performance of bulk silicon photovoltaic devices. The standard buried‐contact (BC) solar cell presents a particularly challenging set of criteria, requiring the dielectric film to act as: (i) an anti‐reflection (AR) coating; (ii) a film compatible with surface passivation; (iii) a mask for an electroless metal plating step; (iv) a diffusion barrier for achieving a selective emitter; (v) a film with excellent chemical resistance; (vi) a stable layer during high‐temperature processing. The dielectric coatings reviewed here include thermally grown silicon dioxide (SiO₂), silicon nitride deposited by plasma‐enhanced chemical vapour deposition (a‐ SiN_x :H) and low‐pressure chemical vapour deposition (Si₃N₄), silicon oxynitride (SiON), cerium dioxide (CeO₂), zinc sulphide (ZnS), and titanium dioxide (TiO₂). While TiO₂ dielectric coatings exhibit the best optical performance and a simple post‐deposition surface passivation sequence has been developed, they require an additional sacrificial diffusion barrier to survive the heavy groove diffusion step. A‐ SiN_x :H affords passivation through its high fixed positive charge density and large hydrogen concentration; however, it is difficult to retain these electronic benefits during lengthy high‐temperature processing. Therefore, for the BC solar cell, Si₃N₄ films would appear to be the best choice of dielectric films common in industrial use. Copyright © 2004 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.     

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.     

Investigation of optical and chemical bond properties of hydrogenated amorphous silicon nitride for optoelectronics applications

The aim of this work is to determine optimal deposition parameters of silicon nitride for optical applications. The authors present the investigation of hydrogenated amorphous silicon nitride SiN_x:H deposited by the low temperature PECVD method in high frequency reactors. The study of hydrogen bonds in the SiN_x:H thin films were detailed. The impact of NH₃, SiH₄ and N₂ flow ratio and radio frequency power on optical coefficients in relation to chemical composition and roughness of the film is studied. The correlation between chemical bonds (N–H, Si–H) and refractive index and extinction coefficients is systematically verified. The experimental results show that the films with high refractive indexes superior to 2.05 and low roughness of about 0.35 nm can be achieved for optoelectronics applications by tuning the flow ratio or decreasing the RF power. A variety of processes have been suggested as compatible with low thermal budget (under 350 °C) in order to integrate optical waveguides with lower loss. In particular, the incorporation of N₂ as dilution gas is suited to the fabrication of SiN_x:H films optical waveguide requiring low N–H bonds, low concentration of hydrogen [H] and high refractive index.     

Boron‐doped hydrogenated silicon carbide alloys containing silicon nanocrystallites for highly efficient nanocrystalline silicon thin‐film solar cells

Boron‐doped hydrogenated silicon carbide alloys containing silicon nanocrystallites (p‐nc‐SiC:H) were prepared using a plasma‐enhanced chemical vapor deposition system with a mixture of CH₄, SiH₄, B₂H₆ and H₂ gases. The influence of hydrogen dilution on the material properties of the p‐nc‐SiC:H films was investigated, and their roles as window layers in hydrogenated nanocrystalline silicon (nc‐Si:H) solar cells were examined. By increasing the R_H (H₂/SiH₄) ratio from 90 to 220, the Si―C bond density in the p‐nc‐SiC:H films increased from 5.20 × 10¹⁹ to 7.07 × 10¹⁹/cm³, resulting in a significant increase of the bandgap from 2.09 to 2.23 eV in comparison with the bandgap of 1.95 eV for p‐nc‐Si:H films. For the films deposited at a high R_H ratio, the Si nanocrystallites with a size of 3–15 nm were formed in the amorphous SiC:H matrix. The Si nanocrystallites played an important role in the enhancement of vertical charge transport in the p‐nc‐SiC:H films, which was verified by conductive atomic force microscopy measurements. When the p‐nc‐SiC:H films deposited at R_H = 220 were applied in the nc‐Si:H solar cells, a high conversion efficiency of 8.26% (V_oc = 0.53 V, J_sc = 23.98 mA/cm² and FF = 0.65) was obtained compared to 6.36% (V_oc = 0.44 V, J_sc = 21.90 mA/cm² and FF = 0.66) of the solar cells with reference p‐nc‐Si:H films. Further enhancement in the cell performance was achieved using p‐nc‐SiC:H bilayers consisting of highly doped upper layers and low‐level doped bottom layers, which led to the increased conversion efficiency of 9.03%. Copyright © 2015 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.     

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.     

Reduction of charge injection into PECVD SiNxHy by control of deposition chemistry

The high rate of charge trapping in thin-film silicon nitride causes its electrical properties to change with stressing level and time. The rate of shift of the high-frequency CV curves of Al/SiN_xH_y/cSi capacitors was used here to measure nitride charging rate and to compare PECVD nitrides deposited under various conditions of plasma power and gas mixture in the same parallel-plate reactor. By operating the plasma under high power to activate the NH₃ or N₂ and under low SiH₄ flow to ensure that all of the SiH4 reacts with N, it is possible to deposit N-rich nitride that has no detectable Si—H bonding, which bonding others have correlated with charge trapping. Nitride deposited under these conditions using NH₃ and 13 MHz rf power had charging rates for both gate polarities that were 20 times lower than those of nitride that had a “stoichiometric” N/Si ratio of 4/3 and that had its H distributed among Si—H and N—H bonds. MIS capacitors made with the latter nitride also had a high negative initial flat-bond voltage, indicating the presence of grown-in positive charge. This charge was large enough to invert the surface ofp-Si substrates. N-rich nitride free of Si—H that was deposited either using N₂ or using low-frequency rf power (≤400 kHz) had higher charging rates than did that deposited from NH₃ at 13 MHz. Also, the low-frequency material contained grown-in positive charge that is attributed to H⁺ implanted by the high ion bombardment energy of the low-frequency plasma.     

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.     

Minimizing hydrogen content in silicon oxynitride by thermal oxidation of silicon-rich silicon nitride

This work reports a detailed study of the re-oxidation effects on the hydrogen content and optical properties of silicon oxynitride films grown by plasma enhanced chemical vapor deposition (PECVD) with N₂O, NH₃ and SiH₄ as the precursors. Results showed that the silicon oxynitride deposited with gas flow rates of NH₃/N₂O/SiH₄ = 20/500/20 (sccm) has favorable properties for integrated waveguide applications. The refractive index of this layer is about 1.57 at 632.8 nm wavelength and the layer has a comparative low density of NH bonds. With a high temperature re-oxidation of the as-deposited film, the hydrogen content of the oxynitride film was reduced from 2.255 × 10²² to 6.98 × 10²⁰ cm⁻³ which is attributed to the removal of excess silicon oxidation and hydrogen bonds.     

Experimental evidence of parasitic shunting in silicon nitride rear surface passivated solar cells

Many solar cells incorporating SiN_x films as a rear surface passivation scheme have not reached the same high level of cell performance as solar cells incorporating high‐temperature‐grown silicon dioxide films as a rear surface passivation. In this paper, it is shown by direct comparison of solar cells incorporating the two rear surface passivation schemes, that the performance loss is mainly due to a lower short‐circuit current while the open‐circuit voltage is equally high. With a solar cell test structure that features a separation of the rear metal contacts from the passivating SiN_x films, the loss in short‐circuit current can be reduced drastically. Besides a lower short‐ circuit current, dark I–V curves of SiN_x rear surface passivated solar cells exhibit distinct shoulders. The results are explained by parasitic shunting of the induced floating junction (FJ) underneath the SiN_x films with the rear metal contacts. The floating junction is caused by the high density of fixed positive charges in the SiN_x films. Other two‐dimensional effects arising from the injection level dependent SRV of the Si/SiN_x interfaces are discussed as well, but, are found to be of minor importance. Pinholes in the SiN_x films and optical effects due to a different internal rear surface reflectance can be excluded as a major cause for the performance loss of the SiN_x rear surface passivated cells. Copyright © 2002 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.     

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.     

原子层沉积氧化铝薄膜对多晶太阳能电池表面钝化的影响

A stack of Al2O3/SiNx dual layer was applied for the back side surface passivation of p-type multi-crystalline silicon solar cells, with laser-opened line metal contacts, forming a local aluminum back surface field （local Al-BSF） structure. A slight amount of Al2O3, wrapping around to the front side of the wafer during the thermal atomic layer deposition process, was found to have a negative influence on cell performance. The different process flow was found to lead to a different cell performance, because of the Al2O3 wrapping around the front surface. The best cell performance, with an absolute efficiency gain of about 0.6% compared with the normal full Al-BSF structure solar cell, was achieved when the Al2O3 layer was deposited after the front surface of the wafer had been covered by a SiNx layer. We discuss the possible reasons for this phenomenon, and propose three explanations as the Ag paste, being hindered from firing through the front passivation layer, degraded the SiNx passivation effect and the Al2O3 induced an inversion effect on the front surface. Characterization methods like internal quantum efficiency and contact resistance scanning were used to assist our understanding of the underlying mechanisms.     

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.