Wet-chemical passivation of atomically flat and structured silicon substrates for solar cell application

Special sequences of wet-chemical oxidation and etching steps were optimised with respect to the etching behaviour of differently oriented silicon to prepare very smooth silicon interfaces with excellent electronic properties on mono- and poly-crystalline substrates. Surface photovoltage (SPV) and photoluminescence (PL) measurements, atomic force microscopy (AFM) and scanning electron microscopy (SEM) investigations were utilised to develop wet-chemical smoothing procedures for atomically flat and structured surfaces, respectively. Hydrogen-termination as well as passivation by wet-chemical oxides were used to inhibit surface contamination and native oxidation during the technological processing. Compared to conventional pre-treatments, significantly lower micro-roughness and densities of surface states were achieved on mono-crystalline Si(100), on evenly distributed atomic steps, such as on vicinal Si(111), on silicon wafers with randomly distributed upside pyramids, and on poly-crystalline EFG (Edge-defined Film-fed-Growth) silicon substrates.The recombination loss at a-Si:H/c-Si interfaces prepared on c-Si substrates with randomly distributed upside pyramids was markedly reduced by an optimised wet-chemical smoothing procedure, as determined by PL measurements. For amorphous-crystalline hetero-junction solar cells (ZnO/a-Si:H(n)/c-Si(p)/Al) with textured c-Si substrates the smoothening procedure results in a significant increase of short circuit current I_sc, fill factor and efficiency η. The scatter in the cell parameters for measurements on different cells is much narrower, as compared to conventional pre-treatments, indicating more well-defined and reproducible surface conditions prior to a-Si:H emitter deposition and/or a higher stability of the c-Si surface against variations in the a-Si:H deposition conditions.     

Passivation of structured p-type silicon interfaces: Effect of surface morphology and wet-chemical pre-treatment

The effect of both surface morphology and wet-chemical pre-treatment on electronic surface and interface properties was investigated for mono- and polycrystalline silicon substrates with special surface structures. Surface charge, energetic distribution, and density of rechargeable states on these surfaces were determined by surface photovoltage (SPV) measurements. These results were correlated to previously reported findings on atomically flat Si(111) and Si(100) surfaces of monocrystalline wafers. In this paper, a specially optimised sequence of cleaning, wet-chemical oxidation, and oxide removal procedures is described in detail for the first time. This method was successfully applied in order to remove contaminations and damaged surface layers and to obtain atomically flat areas on substrates with evenly distributed atomic steps, polycrystalline and monocrystalline substrates with randomly distributed pyramids. A significant reduction in surface micro-roughness, interface state density, and recombination loss was achieved. Using passivation by wet-chemical oxidation or H-termination, respectively, the optimised surface state can be preserved by the time of following preparation steps and during subsequent a-Si:H plasma enhanced chemical vapour deposition (PECVD).     

PIN型和NIP型硅薄膜太阳电池中绒面陷光结构和陷光性能研究

对于硅薄膜太阳电池来说, 无论是PIN型还是NIP型太阳电池, 采用绒面陷光结构来提高入射光的有效利用率是提高太阳电池效率的重要方法之一.本文采用标度相干理论对PIN和NIP型电池的绒面结构的陷光性能进行了数值模拟. 结果表明: PIN电池中前电极和NIP电池中背电极衬底粗糙度分别为160和40 nm时可获得理想的陷光效果; 在不同粗糙度背电极衬底上制备a-SiGe:H电池发现, 使用40和61.5 nm 背电极可获得相当的短路电流密度, 理论分析和实验得到了一致的结果. 关键词： 陷光结构 光散射能力 标量相干理论 硅基薄膜太阳电池     

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)     

单晶硅表面均匀小尺寸金字塔制备及其特性研究

表面织构是一种通过有效的光俘获增加短路电流从而提高太阳电池效率的主要途径之一.在加入间隙式超声和NaClO添加剂的碱性四甲基氢氧化铵(TMAH)溶液中对单晶硅表面进行织构化处理,研究超声与NaClO在织构过程中对金字塔成核和生长的影响,以及金字塔大小对高温工艺之后的单晶硅少子寿命的影响.研究表明,通过在织构溶液中加入间隙式超声控制气泡停留在硅片表面的时间和脱离硅片表面速度,增强了小尺寸金字塔的均匀分布.织构之后硅片在AM1.5G光谱下的加权平均反射率能够达到12.4%,在高温扩散和氧化之后少子寿命的大小与金字塔大小之间存在近似于指数衰减函数的关系. 关键词： 表面织构化 反射率 少子寿命 单晶硅太阳电池     

Excitonic photoluminescence characteristics of amorphous silicon nanoparticles embedded in silicon nitride film

We have investigated the photoluminescence (PL) properties of amorphous silicon nanoparticles (a-Si NPs) embedded in silicon nitride film (Si-in-SiN_x) grown by helicon wave plasma-enhanced chemical vapor deposition (HWP-CVD) technique. The PL spectrum of the film exhibits a broad band constituted of two Gaussian components. From photoluminescence excitation (PLE) measurements, it is elucidated that the two PL bands are associated with the a-Si NPs and the silicon nitride matrix surrounding a-Si NPs, respectively. The existence of Stokes shift between PL and absorption edge indicates that radiative recombination of carriers occurs in the states at the surface of the Si NPs, whereas their generation takes place in the a-Si NPs cores and the silicon nitride matrix, respectively. The visible PL of the film originates from the radiative recombination of excitons trapped in the surface states. At decreasing excitation energy (E_ex), the PL peak energy was found to be redshifted, accompanied by a narrowing of the bandwidth. These results are explained by surface exciton recombination model taking into account there existing a size distribution of a-Si NPs in the silicon nitride matrix.     

Nanoimprint texturing of transparent flexible substrates for improved light management in thin‐film solar cells

We present a nanoimprint based approach to achieve efficient light management for solar cells on low temperature transparent polymer films. These films are particularly low‐priced, though sensitive to temperature, and therefore limiting the range of deposition temperatures of subsequent solar cell layers. By using nanoimprint technology, we successfully replicated optimized light trapping textures of etched high temperature ZnO:Al on a low temperature PET film without deterioration of optical properties of the substrate. The imprint‐textured PET substrates show excellent light scattering properties and lead to significantly improved incoupling and trapping of light in the solar cell, resulting in a current density of 12.9 mA/cm², similar to that on a glass substrate. An overall efficiency of 6.9% was achieved for a flexible thin‐film silicon solar cell on low cost PET substrate. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

a-C: Fe/AlOx/Si基异质结的光伏效应

使用脉冲激光沉积(PLD)依次沉积氧化铝和碳膜制备了a-C: Fe/AlO_x/Si基异质结,研究了其光伏效应及其在太阳能电池上的应用.该太阳能电池在标准日光照射(AM1.5,100 mW/cm²)下,可获得0.33 V的开路电压和4.5 mA/cm²的电流密度,太阳能电池的转换效率为0.35%.通过C-V测量,证明了氧化铝层的引入降低了界面能级数目,增加了界面势垒高度.界面能级数目降低减少了光生载流子在界面复合的 关键词： 光伏效应 非晶碳膜 异质结 氧化铝     

Nanocrystalline ZnO film deposited by ultrasonic spray on textured silicon substrate as an anti-reflection coating layer

A ZnO thin film was successfully synthesized on glass, flat surface and textured silicon substrates by chemical spray deposition. The textured silicon substrate was carried out using two solutions (NaOH/IPA and Na₂CO₃). Textured with Na₂CO₃ solution, the sample surface exhibits uniform pyramids with an average height of 5 μm. The properties and morphology of ZnO films were investigated. X-ray diffraction (XRD) spectra revealed a preferred orientation of the ZnO nanocrystalline film along the c-axis where the low value of the tensile strain 0.26% was obtained. SEM images show that all films display a granular, polycrystalline morphology. The morphology of the ZnO layers depends dramatically on the substrate used and follows the contours of the pyramids on the substrate surface. The average reflectance of the textured surface was found to be around 13% and it decreases dramatically to 2.57% after deposition of a ZnO antireflection coating. FT-IR peaks arising from the bonding between Zn–O are clearly represented using a silicon textured surface. A very intense photoluminescence (PL) emission peak is observed for ZnO/textured Si, revealing the good quality of the layer. The PL peak at 380.5 nm (UV emission) and the high-intensity PL peak at 427.5 nm are observed and a high luminescence occurs when using a textured Si substrate.     

Development of surface-textured hydrogenated ZnO:Al thin-films for μc-Si solar cells

This study addresses the optimization of rf magnetron-sputtered hydrogenated ZnO:Al (HAZO) films as front contacts in microcrystalline silicon solar cells. The front contact of a solar cell has to be highly conductive and highly transparent to visible and infrared radiation. Furthermore, it has to scatter the incident light efficiently in order for the light to be effectively trapped in the underlying silicon layers. In this research, HAZO films were rf-magnetron-sputtered on glass substrates from a ceramic (98 wt% ZnO, 2 wt% Al₂O₃) target. Various compositions of AZO films on glass substrates were prepared by changing the H₂/(Ar + H₂) ratio of the sputtering gas. The resulting smooth films exhibited high transparencies (T  85% for visible light including all reflection losses) and excellent electrical properties (ρ = 2.7 × 10⁻⁴ Ω · cm). Depending on their structural properties, these films developed different surface textures upon post-deposition etching using diluted hydrochloric acid. The light-scattering properties of these films could be controlled simply by varying the etching time. Moreover, the electrical properties of the films were not affected by the etching process. Therefore, within certain limits, it is possible to optimize the electro-optical and light-scattering properties separately. The microcrystalline silicon (μc-Si:H)-based p–i–n solar cells prepared using these new texture-etched AZO:H substrates showed high quantum efficiencies in the long wavelength range, thereby demonstrating effective light trapping. Using the optimum AZO:H thin-film textured surface, we achieved a p–i–n μc-Si solar cell efficiency of 7.78%.     

基于BiFeO_3/ITO复合膜表面钝化的黑硅太阳电池性能研究

采用金属银辅助化学刻蚀法在制绒的硅片表面刻蚀纳米孔形成微纳米双层结构,以期获得高吸收率的太阳能电池用黑硅材料.鉴于微纳米结构会在晶硅表面引入大量的载流子复合中心,利用磁控溅射技术在黑硅太阳电池表面制备了BiFeO_3/ITO复合膜,并对其表面性能和优化效果进行了探索.实验制备的具有微纳米双层结构的黑硅纳米线长约180—320 nm,在300—1000 nm波长范围内入射光反射率均在5%以下.沉积BiFeO_3/ITO复合薄膜后的黑硅太阳能电池反射率略有提高,但仍然具有较强的光吸收性能;采用BiFeO_3/ITO复合膜的黑硅太阳能电池开路电压和短路电流密度分别由最初的0.61 V和28.42 mA/cm~2提升至0.68 V和34.57 mA/cm~2,相应电池的光电转化效率由13.3%上升至16.8%.电池综合性能的改善主要是因为沉积BiFeO_3/ITO复合膜提高了电池光生载流子的有效分离,从而增强了黑硅太阳电池短波区域的光谱响应,表明具有自发极化性能的BiFeO_3薄膜对黑硅太阳能电池的表面性能可起到较好的优化作用.     

Theoretical analysis on the limitations of the open-circuit voltage of a hydrogenated amorphous silicon p-i-n solar cell

We have made theoretical studies on the limitation of the open-circuit voltageV _oc of a hydrogenated amorphous silicon (a-Si:H) p-i-n type solar cell. The effects of the tail states in the a-Si:H i layer and of the interface recombination are discussed in detail. The opencircuit voltage increases when the distribution of the tail states is sharp and/or the capture cross sections of these states are small. This is because the recombination rate of photogenerated carriers and/or the density of space charge due to trapped carriers in these states become low in these conditions. These effects of the tail states on the value ofV _oc become pronounced when the built-in potential of the p-i-n junction is high. The decrease in the effective recombination velocity of carriers at the p/i and n/i interfaces results in an increase ofV _oc. This increase becomes remarkable when the effects of the tail states on the value ofV _oc are small. Both the sharp distribution of tail states and the small value of the interface recombination velocity are necessary to increase considerably the value ofV _oc. We show the conditions of the material parameters necessary to obtain an open-circuit voltage of 1.0 V.     

单室沉积p-i-n型微晶硅薄膜太阳电池性能优化的研究

采用原位的氢等离子体处理技术和微晶覆盖技术来降低单室沉积p-i-n型微晶硅薄膜太阳电池中的硼污染问题.通过对不同处理技术所制备电池的电流密度-电压和量子效率测试结果的比较发现,一定的氢处理时间和合适的覆盖层技术都可以在一定程度上提高电池的性能,但每种方法的影响程度各异、文中对此异同进行了分析.通过对电池陷光结构和氢等离子体处理时间的优化,在单室中获得了效率为6.39%的单结微晶硅太阳电池.     

Influence of surface recombination and interface states on the performance of β-FeSi2/c-Si heterojunction solar cells

To explore the origin of low conversion efficiency for novel β-FeSi₂/c-Si heterojunction solar cells, the effect of surface recombination and interface states on the cell performance has been investigated by numerical simulation. The present results show that surface recombination of β-FeSi₂ film plays an important role in limiting the cell property since the photovoltaic behavior of β-FeSi₂ is quite sensitive to surface recombination due to its especial characteristic of very high optical absorption coefficient. Surface quality of β-FeSi₂ film should be much improved for better cell performance. In addition, it is shown that interface states between β-FeSi₂ film and crystalline silicon are critical to device characterization. Interface states should be minimized to obtain higher conversion efficiency. If surface recombination and interface states can be best suppressed, potential conversion efficiency for the cell may be up to 28.12% at 300 K under illumination of AM 1.5, 100 mW/cm².     

Laser machined macro and micro structures on glass for enhanced light trapping in solar cells

In order to increase the efficiency of solar cell modules it is necessary to make the optimum use of light incident upon them. Much research has been done on improving light absorption through front surface texturisation and light trapping schemes. Laser light is commonly used in industry for various applications including marking and texturisation. By controlling laser parameters, it is possible to tailor macro and micro structures in most materials. The CO₂ laser used in this investigation emits radiation at 10.6 μm with the ability to pulse in the micro-second range. The laser was used to ablate grooved textures in the fused quartz material, used in this study as the light trapping medium, following which an analysis of the effects of the laser parameters on the texture geometry and surface morphology was performed through a combination of cross sectioning and scanning electron microscopy. Transmission through the textured glass was improved for most samples after acid etching. The light trapping effects of the best performing textures were analysed by investigating the effects on a silicon solar cell’s performance at varying angles of incidence. Results indicated a significant increase in light trapping when light was incident at acute angles. For an angle of incidence of 10^° a relative increase in efficiency of up to 51 % was observed.     

Near-field study of optical modes in randomly textured ZnO thin films

We report on near-field scanning optical microscopy measurements on randomly textured ZnO thin films. These films are commonly used as transparent conducting oxide in thin-film solar cells. Textured interfaces are used to increase the scattering of light, which leads to a better light trapping in the solar cell. Here, both the topography and the local transmission are measured with a tapered fiber tip with very high spatial resolution. By varying the distance of the tip and the wavelength of the incident light, the optical profile is visualized and reveals a strong confinement of light on a subwavelength scale which corresponds to ridges in the surface structure. The confinement of light results from guided optical modes in the ZnO which are accompanied by a modulated evanescent field in air. No corresponding structure to this modulation is found in the topography. These results give new insight for further improvement of light trapping in solar cells.     

Effect of surface morphology on screen printed solar cells

Surface texturing is well known as one of the major paths to improving the efficiency of silicon solar cells by increasing the short circuit current through effective photon trapping. However, the effects of the pyramids created after surface texturing on the other properties remain obscure. In this work, we studied the effect of the surface morphologies on the formation of both the emitter layer and metal electrode using the screen printing method, which is a cost-effective method of fabricating silicon solar cells. Various textured surfaces, such as with large, small, sharp or smooth pyramids, were investigated in comparison with a flat surface. The contact resistance was measured from a TLM patterned cell by I–V measurement under dark conditions and SEM, TEM and UV–vis spectrophotometer were used to evaluate the surfaces.     

Impact of rough silicon buffer layer on electronic quality of GaAs grown on Si substrate

The electronic and the structural properties of n-GaAs layers grown on rough surface of silicon substrate by molecular beam epitaxy (MBE) has been investigated by photoluminescence (PL), time resolved photoluminescence (TRPL) and high resolution X-ray diffraction (HRXRD). The relationship between electronic and structural properties of the n-GaAs layer was checked, showing that the defect density is a strong cause for trapping the minority carriers. The impact of introducing intermediate rough silicon layer between silicon substrate and n-GaAs layer on the electronic properties was observed, showing that the structure grown on rough Si involves higher lifetime than those developed on flat silicon substrate. Such structure could be used for economic solar cells fabrication.     

Light trapping for a‐Si:H/µc‐Si:H tandem solar cells using direct pulsed laser interference texturing

We present a‐Si:H/µc‐Si:H tandem solar cells on laser textured ZnO:Al front contact layers. Direct pulsed laser interference patterning (DLIP) was used for writing arrays of one‐dimensional micro gratings of submicron period into ZnO:Al films. The laser texture provides good light trapping which is indicated by an increase in short‐circuit current density of 20% of the bottom cell limited device compared to cells on planar ZnO:Al. The open‐circuit voltage of the cells on laser textured ZnO:Al is almost the same as for cells on planar substrates, indicating excellent growth conditions for amorphous and microcrystalline silicon on the U‐shaped grating grooves. DLIP is a simple, single step and industrially applicable method for large area periodic texturing of ZnO:Al thin films. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Photoluminescence analyses of hydrogenated amorphous silicon nitride thin films

Silicon-rich hydrogenated amorphous silicon nitride (a-SiN_x:H) films were grown by plasma enhanced chemical vapor deposition (PECVD) with different r=NH₃/SiH₄ gas flow ratios. The optical absorption characteristics were analyzed by Fourier transform infrared (FTIR) and UV-visible transmittance spectroscopies. The recombination properties were investigated via photoluminescence (PL) measurements. As r was increased from 2 to 9, the PL emission color could be adjusted from red to blue with the emission intensity high enough to be perceived by naked eye at room temperature. The behaviors of the PL peak energy and the PL band broadness with respect to the optical constants were discussed in the frame of electron-phonon coupling and band tail recombination models. A semiquantitative analysis supported the band tail recombination model, where the recombination was found to be favored when the carriers thermalize to an energy level at which the band tail density of states (DOS) reduces to some fraction of the relevant band edge DOS. For the PL efficiency comparison of the samples with different nitrogen contents, the PL intensity was corrected for the absorbed intensity fraction of the incident PL excitation source. The resulted correlation between the PL efficiency and the subgap absorption tail width further supported the band tail recombination model.