Investigation of rapid thermal oxide/ silicon nitride passivation stack of n+ emitter

To anticipate the initial phosphorus diffusion parameters of silicon solar cells process fabrication, we report in this paper an overview of our experiments on silicon n⁺-emitters passivation by means of rapid thermal silicon oxide/silicon nitride stack. The process-induced changes have been evaluated and explained. We found that 900 °C and 80 s were the appropriate process parameters to grow 10 nm silicon oxide. Investigation of the effect of this oxidation on n⁺ multicrystalline silicon emitters revealed a large decrease (more than 25%) of the sheet resistance and around 12% increase of the junction depth. The experiments also revealed that the passivation effect of the optimal silicon oxide/silicon nitride stack is efficient only for higher emitter quality. In addition, we found that this stack reduces the surface reflection more than the optimal single silicon nitride layer.     

Passivation of black silicon boron emitters with atomic layer deposited aluminum oxide

The nanostructured surface – also called black silicon (b‐Si) – is a promising texture for solar cells because of its extremely low reflectance combined with low surface recombination obtained with atomic layer deposited (ALD) thin films. However, the challenges in keeping the excellent optical properties and passivation in further processing have not been addressed before. Here we study especially the applicability of the ALD passivation on highly boron doped emitters that is present in crystalline silicon solar cells. The results show that the nanostructured boron emitters can be passivated efficiently using ALD Al₂O₃ reaching emitter saturation current densities as low as 51 fA/cm². Furthermore, reflectance values less than 0.5% after processing show that the different process steps are not detrimental for the low reflectance of b‐Si. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electronic-beam evaporation processed titanium oxide as an electron selective contact for silicon solar cells

This work is dedicated to the study of electronic-beam (e-beam) evaporated titanium oxide (TiO_x) contact for polycrystalline silicon hetero-junction solar cells. A TiO_x material obtained by e-beam evaporation method is suggested as a possible alternative to the atomic layer deposition (ALD) process. The purpose is to achieve corresponding passivation efficiency between e-beam evaporation of TiOx and the ALD method. However, the TiOx in question achieved a relatively low passivation performance of S_eff = 113 cm⁻¹ in comparison to the reported ALD results. Nonetheless, as e-beam evaporation is well-established and an environmentally friendly deposition technology, e-beam evaporated TiO_x passivation layer has potential for improvement. What is clearly demonstrated in our work is how such an improvement in contact resistance dropped from >55 Ω/cm² to 2.29 Ω/cm². Indeed, our study established a correlation between the main process parameters of e-beam evaporation and their influence on the quality of electron selective TiO_x layer. Moreover, we reveal a possible scenario for the implementation of e-beam evaporated Titanium oxide as electron selective contact for asymmetrical hetero-junction solar cells.     

Solar cell fabrication using edge-defined film-fed growth (EFG) silicon wafers

The insufficient supply of polysilicon is limiting the growth of the segment of the photovoltaic industry using silicon materials. Because it is grown directly in the form of ribbon from a silicon melt, edge-defined film-fed growth (EFG) silicon ribbon is a promising alternative for cutting down wafer costs by reducing the polysilicon consumption and eliminating kerf loss. In this paper, we will discuss the various properties that can be achieved with for low cost and high-efficiency EFG silicon ribbon solar cell fabrication. Boron-doped p-type EFG ribbon silicon wafers with resistivities of 2-4 Ω cm and a size of 125 mm × 125 mm were used. The major fabrication steps we studied were mixed acid (HF, HNO₃, DI water) texturing, phosphorus diffusion with POCl₃, thermal oxide growth for surface passivation, laser process for edge isolation, and PECVD of SiN_x:H for surface passivation and antireflection coating. By optimizing the processing steps, we achieved a conversion efficiency, open circuit voltage, short circuit current, and fill factor as high as 14.5%, 584 mV, 32.1 mA/cm², and 77%, respectively.     

Silicon nitride/silicon oxide interlayers for solar cell passivating contacts based on PECVD amorphous silicon

This Letter demonstrates improved passivating contacts for silicon solar cells consisting of doped silicon films together with tunnelling dielectric layers. An improvement is demonstrated by replacing the commonly used silicon oxide interfacial layer with a silicon nitride/silicon oxide double interfacial layer. The paper describes the optimization of such contacts, including doping of a PECVD intrinsic a‐Si:H film by means of a thermal POCl₃ diffusion process and an exploration of the effect of the refractive index of the SiN_x. The n⁺ silicon passivating contact with SiN_x /SiO_x double layer achieves a better result than a single SiN_x or SiO_x layer, giving a recombination current parameter of ～7 fA/cm² and a contact resistivity of ～0.005 Ω cm², respectively. These self‐passivating electron‐selective contacts open the way to high efficiency silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

The effect of anti-reflection coating of porous silicon on solar cells efficiency

Anti-reflection coatings of solar cells have been fabricated using different techniques. The techniques used include SiO₂ thermal oxidation, ZnO/TiO₂ sputtering deposition and porous silicon prepared by electrochemical etching. Surface morphology and structural properties of solar cells were investigated by using scanning electron microscopy and atomic forces microscopy. Optical reflectance was obtained by using optical reflectometer. I-V characterizations were studied under 80 mW/cm² illumination conditions. Porous silicon was found to be an excellent anti-reflection coating against incident light when it is compared with another anti-reflection coating and exhibited good light-trapping of a wide wavelength spectrum which produced high efficiency solar cells.     

Extremely low surface recombination in 1 Ω cm n‐type monocrystalline silicon

A key requirement in the recent development of highly efficient silicon solar cells is the outstanding passivation of their surfaces. In this work, plasma enhanced chemical vapour deposition of a triple layer dielectric consisting of amorphous silicon, silicon oxide and silicon nitride, charged extrinsically using corona, has been used to demonstrate extremely low surface recombination. Assuming Richter's parametrisation for bulk lifetime, an effective surface recombination velocity S_eff = 0.1 cm/s at Δn = 10¹⁵ cm^–3 has been obtained for planar, float zone, n ‐type, 1 Ω cm silicon. This equates to a saturation current density J_0s = 0.3 fA/cm², and a 1‐sun implied open‐circuit voltage of 738 mV. These surface recombination parameters are among the lowest reported for 1 Ω cm c‐Si. A combination of impedance spectroscopy and corona‐lifetime measurements shows that the outstanding chemical passivation is due to the small hole capture cross section for states at the interface between the Si and a‐Si layer which are hydrogenated during nitride deposition. (© 2016 The Authors. Phys. Status Solidi RRL published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of SiNx:H film properties according to gas mixture ratios for crystalline silicon solar cells

The Hydrogenated silicon nitride (SiN_x:H) using plasma enhanced chemical vapor deposition is widely used in photovoltaic industry as an antireflection coating and passivation layer. In the high temperature firing process, the SiN_x:H film should not change the properties for its use as high quality surface layer in crystalline silicon solar cells. For optimizing surface layer in crystalline silicon solar cells, by varying gas mixture ratios (SiH₄ + NH₃ + N₂, SiH₄ + NH₃, SiH₄ + N₂), the hydrogenated silicon nitride films were analyzed for its antireflection and surface passivation (electrical and chemical) properties. The film deposited with the gas mixture of SiH₄ + NH₃ + N₂ showed the best properties in before and after firing process conditions.The single crystalline silicon solar cells fabricated according to optimized gas mixture condition (SiH₄ + NH₃ + N₂) on large area substrate of size 156 mm × 156 mm (Pseudo square) was found to have the conversion efficiency as high as 17.2%. The reason for the high efficiency using SiH₄ + NH₃ + N₂ is because of the good optical transmittance and passivation properties. Optimized hydrogenated silicon nitride surface layer and high efficiency crystalline silicon solar cells fabrication sequence has also been explained in this study.     

硅片及其太阳电池的光衰规律研究

采用氙灯模拟太阳光源,将光强调至1000 W/m2,研究常规太阳能级单晶硅片、多晶硅片和物理提纯硅片的原片、去损减薄片、热氧化钝化片、双面镀氮化硅(SiN x:H)膜钝化片、碘酒钝化片以及太阳电池的光衰规律.利用WT-2000少子寿命测试仪以及太阳电池I-V特性测试仪分别对硅片的少子寿命和太阳电池的I-V特性参数随光照时间的变化进行了测试.结果表明:所有硅片以及太阳电池在光照的最初60 min内衰减很快随后衰减变慢,180 min之后光衰速率变得很小,几乎趋于零.     

19.4%‐efficient large‐area fully screen‐printed silicon solar cells

We demonstrate industrially feasible large‐area solar cells with passivated homogeneous emitter and rear achieving energy conversion efficiencies of up to 19.4% on 125 × 125 mm² p‐type 2–3 Ω cm boron‐doped Czochralski silicon wafers. Front and rear metal contacts are fabricated by screen‐printing of silver and aluminum paste and firing in a conventional belt furnace. We implement two different dielectric rear surface passivation stacks: (i) a thermally grown silicon dioxide/silicon nitride stack and (ii) an atomic‐layer‐deposited aluminum oxide/silicon nitride stack. The dielectrics at the rear result in a decreased surface recombination velocity of S_rear = 70 cm/s and 80 cm/s, and an increased internal IR reflectance of up to 91% corresponding to an improved J_sc of up to 38.9 mA/cm² and V_oc of up to 664 mV. We observe an increase in cell efficiency of 0.8% absolute for the cells compared to 18.6% efficient reference solar cells featuring a full‐area aluminum back surface field. To our knowledge, the energy conversion efficiency of 19.4% is the best value reported so far for large area screen‐printed solar cells. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Role of a‐Si:H bulk in surface passivation of c‐Si wafers

The low thermal stability of hydrogenated amorphous silicon (a‐Si:H) thin films limits their widespread use for surface passivation of c‐Si wafers on the rear side of solar cells. We show that the thermal stability of a‐Si:H surface passivation is increased significantly by a hydrogen rich a‐Si:H bulk, which acts as a hydrogen reservoir for the a‐Si:H/c‐Si interface. Based on this mechanism, an excellent lifetime of 5.1 ms (at injection level of 10¹⁵ cm^–3) is achieved after annealing at 450 °C for 10 min. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Deposition of device quality amorphous silicon and solar cell from argon dilution of silane

In our present study hydrogenated amorphous silicon (a-Si:H) thin films and solar cells have been prepared in a conventional single chamber rf-PECVD unit from silane–argon mixture by varying radio frequency (rf) power densities from 6 mW/cm² to 50 mW/cm². By optimizing the properties of the intrinsic material we have chosen a material which is deposited at 6 mW/cm² rf power density, 0.2 Torr pressure, 175 ^oC substrate temperature and by 97% argon dilution. For this material minority carriers (holes) diffusion length (L_d) measured in the as deposited state is 180 nm and it degrades by 15% after light soaking. This high L_d value indicates that the material is of device quality. We have fabricated a single junction solar cell having the structure p-a-SiC:H/i-a-Si:H/n-a-Si:H without optimizing the doped layers. This set exhibits a mean open circuit voltage of 0.8 V and conversion efficiency of 7.7%. After light soaking conversion efficiency decreases by 15% which demonstrates that it is possible to deposit device grade material and solar cells from silane–argon mixture.     

Influence of experimental parameters on physical properties of porous silicon and oxidized porous silicon layers

This paper reports physical properties of porous silicon and oxidized porous silicon, manufactured by anodisation from heavily p-type doped silicon wafers as a function of experimental parameters. The growth rate and refractive index of the layers were studied at different applied current densities and glycerol concentrations in electrolyte. When the current density varied from 5 to 100 mA/cm², the refractive index was between 1.2 and 2.4 which corresponded to a porosity range from 42 to 85%. After oxidation, the porosity decreased and was between 2 and 45% for a refractive index range from 1.22 to 1.46. The thermal processing also induced an increase in thickness which was dependent on the initial porosity. This increase in thickness was more important for the lowest porosities. Lastly, the roughness of the porous layer/silicon substrate interface was studied at different applied current densities and glycerol concentrations in solution. Roughness decreased when the current density or glycerol concentration increased. Moreover, roughness was also reduced by thermal oxidation.     

Electrical and optical properties of nanowires based solar cell with radial p-n junction

In our studies the absorption, transmittance and reflectance spectra for periodic nanostructures with different parameters were calculated by the FDTD (Finite-Difference Time-Domain) method. It is shown that the proportion of reflected light in periodic structures is smaller than in case of thin films. The experimental results showed the light reflectance in the spectral range of 400–900 nm lower than 1% and it was significantly lower in comparison with surface texturing by pyramids or porous silicon.Silicon nanowires on p-type Si substrate were formed by the Metal-Assisted Chemical Etching method (MacEtch). At solar cells with radial p-n junction formation the thermal diffusion of phosphorus has been used at 790 °C. Such low temperature ensures the formation of an ultra-shallow p-n junction. Investigation of the photoelectrical properties of solar cells was carried out under light illumination with an intensity of 100 mW/cm². The obtained parameters of NWs' solar cell were I_sc = 22 mA/cm², U_oc = 0.62 V, FF = 0.51 for an overall efficiency η = 7%. The relatively low efficiency of obtained SiNWs solar cells is attributed to the excessive surface recombination at high surface areas of SiNWs and high series resistance.     

Alternating current surface photovoltage in thermally oxidized chromium-contaminated n-type silicon wafers

We investigated a variation of frequency-dependent alternating current (AC) surface photovoltages (SPVs) in thermally oxidized, chromium-contaminated, n-type silicon (Si) wafers. As previously reported, immediately after rinsing in Cr-contaminated solution, a Cr(OH)₃–Si contact causes a Schottky-barrier-type AC SPV on n-type Si. Upon oxidation at 373 K for 10 min, the Schottky barrier collapses and, with further oxidation, a metal-induced negative oxide charge, due to atomic bridging of (CrOSi)⁻ and/or CrO₂^-\mathrm{CrO}_{2}^{-} networks, definitely grows over time in SiO₂. For samples oxidized at temperatures between 823 and 1023 K for 30 min, the observed AC SPV gives evidence that the metal-induced negative oxide charge causes a strongly inverted state of the Si surface. At oxidation temperatures higher than 1023 K and /or for an oxidation time longer than 60 min, the level height of the AC SPV is reduced, implying that the strongly inverted state changes into a less depleted state, whilst, finally, the AC SPV disappears. In this case, the collapse of the (CrOSi)⁻ and/or CrO₂^-\mathrm{CrO}_{2}^{-} networks is anticipated, with a possible change into Cr₂O₃. The existence of the (CrOSi)⁻ and/or CrO₂^-\mathrm{CrO}_{2}^{-} networks has also been confirmed in p-type Si wafers.     

Low-porosity porous silicon nanostructures on monocrystalline silicon solar cells

In this work we present a study of low-porosity porous silicon (PS) nanostructures stain etched on monocrystalline silicon solar cells. The PS layers reduce the reflectance, improve the diffusion of dopants by rapid thermal processes, and increase the homogeneity of the sheet resistance. Some samples were subjected to chemical oxidation in HNO₃ to reduce the porosity of the surface layer. After the diffusion process, deposition of a SiN_x antireflection layer, and screen printing of the samples, an efficiency of 15.5% is obtained for low-porosity PS solar cells, compared with an efficiency of 10.0% for standard PS cells and 14.9% for the reference Cz cells.     

Theoretical investigation on the passivation layer with linearly graded bandgap for the amorphous/crystalline silicon heterojunction solar cell

Passivation layer with linearly graded bandgap (LGB) was proposed to improve the performance of amorphous/crystalline silicon heterojunction (SHJ) solar cell by eliminating the large abrupt energy band uncontinuity at the a‐Si:H/c‐Si interface. Theoretical investigation on the a‐Si:H(p)/the LGB passivation layer(i)/c‐Si(n)/a‐Si:H(i)/a‐Si:H(n⁺) solar cell via AFORS‐HET simulation show that such LGB passivation layer could improve the solar cell efficiency (η) by enhancing the fill factor (FF) greatly, especially when the a‐Si:H(p) emitter was not efficiently doped and the passivation layer was relatively thick. But gap defects in the LGB passivation layer could make the improvement discounted due to the open‐circuit voltage (V_OC) decrease induced by recombination. To overcome this, it was quite effective to keep the gap defects away from the middle of the bandgap by widening the minimum bandgap of the LGB passivation layer to be a little larger than that of the c‐Si base. The underlying mechanisms were analysed in detail. How to achieve the LGB passivation layer experimentally was also discussed. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

氧化随机织构硅表面对单晶硅太阳电池性能的影响研究

热氧化生长的SiO\-2 薄膜经常在高效单晶硅太阳电池中被用作扩散掩膜,化学镀掩膜,钝化层或者基本的减反射层.在这些高效太阳电池中,经常使用碱性溶液对单晶硅表面进行处理,得到随机分布的正金字塔结构的织绒表面,减少表面的光反射.表面氧化后的正金字塔太阳电池暗反向电流-电压呈现"软击穿"现象,并联电阻明显下降.研究结果表明引起这些现象的原因在于氧化正金字塔表面会导致在体内形成位错型缺陷,这些缺陷能够贯穿整个pn 结,导致太阳电池的并联电阻下降,同时载流子在位错型缺陷在能隙中引入的能级处发生复合,导致空间电荷区 关键词： 热氧化 随机织构 位错 太阳电池     

Selective laser induced melting of ultrathin nanoporous silicon layers

Short laser pulses (wavelength 337 nm, duration time 0.5 ns) are used for thermal processing of ultra thin nanoporous silicon layers (UPSL) prepared electrochemically on n- and p-type Si(1 1 1) in aqueous NH₄F solution. The theoretical threshold for melting (W _m ) of UPSL is about 0.01 J/cm². This is about one order of magnitude belowW _m of crystalline silicon. A selective laser induced melting regime can be realized for which an UPSL is practically completely molten on the top of an unmolten crystalline silicon substrate. Investigations with scanning and high resolution transmission electron microscopy show the formation of crystalline silicon spheres with diameters in the range of some of ten nm in this regime.     

Electrical and optical characterization of SiOxNy and SiO2 dielectric layers and rear surface passivation by using SiO2/SiOxNy stack layers with screen printed local Al-BSF for c-Si solar cells

In c-Si solar cells, surface recombination velocity increases as the wafer thickness decreases due to an increase in surface to volume ratio. For high efficiency, in addition to low surface recombination velocity at the rear side, a high internal reflection from the rear surface is also required. The SiO_xN_y film with low absorbance can act as rear surface reflector. In this study, industrially feasible SiO₂/SiO_xN_y stack for rear surface passivation and screen printed local aluminium back surface field were used in the cell structure. A 3 nm thick oxide layer has resulted in low fixed oxide charge density of 1.58 × 10¹¹ cm⁻² without parasitic shunting. The oxide layer capped with SiO_xN_y layer led to surface recombination velocity of 155 cm/s after firing. Using single layer (SiO₂) rear passivation, an efficiency of 18.13% has been obtained with V_oc of 625 mV, J_sc of 36.4 mA/cm² and fill factor of 78.7%. By using double layer (SiO₂/SiO_xN_y stack) passivation at the rear side, an efficiency of 18.59% has been achieved with V_oc of 632 mV, J_sc of 37.6 mA/cm², and fill factor of 78.3%. An improved cell performance was obtained with SiO₂/SiO_xN_y rear stack passivation and local BSF.