Al2O3钝化及其在晶硅太阳电池中的应用

介绍了Al₂O₃的材料性质及其原子层沉积制备方法, 详细阐述了该材料的钝化机制(化学钝化和场效应钝化), 并从薄膜厚度、热稳定性及叠层钝化等角度阐释其优化方案. 概述了Al₂O₃钝化在晶体硅太阳电池中的应用, 主要包括钝化发射极及背面局部扩散电池和钝化发射极及背表面电池. 最后, 对Al₂O₃钝化工艺的未来研究方向和大规模的工业应用进行了展望.     

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)     

Enhancement of photoluminescence intensity from Si nanodots using Al2O3 surface passivation layer grown by atomic layer deposition

Temperature-dependent photoluminescence (PL) from Si nanodots with Al₂O₃ surface passivation layers was studied. The Si nanodots were grown by low pressure chemical vapor deposition and the Al₂O₃ thin films were prepared by atomic layer deposition (ALD), respectively. The BOE (Buffer-Oxide-Etch) treatment resulted in the damaged surface of Si nanodots and thus caused dramatic reduction in the PL intensity. Significant enhancement of the PL intensity from Si nanodots after the deposition of Al₂O₃ thin films was observed over a wide temperature range, indicating the remarkable surface passivation effect to suppress the non-radiative recombination at the surface of Si nanodots. The results demonstrated that the Al₂O₃ surface passivation layers grown by ALD are effectually applicable to nanostructured silicon devices.     

Surface passivation of phosphorus‐diffused n+‐type emitters by plasma‐assisted atomic‐layer deposited Al2O3

In recent years Al₂O₃ has received tremendous interest in the photovoltaic community for the application as surface passivation layer for crystalline silicon. Especially p‐type c‐Si surfaces are very effectively passivated by Al₂O₃, including p‐type emitters, due to the high fixed negative charge in the Al₂O₃ film. In this Letter we show that Al₂O₃ prepared by plasma‐assisted atomic layer deposition (ALD) can actually provide a good level of surface passivation for highly doped n‐type emitters in the range of 10–100 Ω/sq with implied‐V_oc values up to 680 mV. For n‐type emitters in the range of 100–200 Ω/sq the implied‐V_oc drops to a value of 600 mV for a 200 Ω/sq emitter, indicating a decreased level of surface passivation. For even lighter doped n‐type surfaces the passivation quality increases again to implied‐V_oc values well above 700 mV. Hence, the results presented here indicate that within a certain doping range, highly doped n‐ and p‐type surfaces can be passivated simultaneously by Al₂O₃. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stacked and nanolaminated Al2O3/TiO2 for surface passivation and encapsulation of silicon

Silicon solar cells passivated with Al₂O₃ require a capping layer that protects the passivation layer from humidity because of sensitivity of Al₂O₃ to moisture. Al₂O₃/TiO₂ stacks obtained by atomic layer deposition have been known to provide a high level of passivation layers because of their excellent field‐effect passivation. In this work, degradation of this Al₂O₃/TiO₂ stack, when exposed to humidity, is examined, and an attempt is made for a humidity‐resistant encapsulation layer by adding Al₂O₃/TiO₂ nanolaminates that can be deposited in‐situ without breaking vacuum. Placing the nanolaminate on top of the TiO₂ and Al₂O₃ stack is found to lead to almost no degradation even after 10 days of humidity exposure. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effective surface passivation of crystalline silicon using ultrathin Al2O3 films and Al2O3/SiNx stacks

We measure surface recombination velocities (SRVs) below 10 cm/s on p‐type crystalline silicon wafers passivated by atomic–layer–deposited (ALD) aluminium oxide (Al₂O₃) films of thickness ≥10 nm. For films thinner than 10 nm the SRV increases with decreasing Al₂O₃ thickness. For ultrathin Al₂O₃ layers of 3.6 nm we still attain a SRV < 22 cm/s on 1.5 Ω cm p‐Si and an exceptionally low SRV of 1.8 cm/s on high‐resistivity (200 Ω cm) p‐Si. Ultrathin Al₂O₃ films are particularly relevant for the implementation into solar cells, as the deposition rate of the ALD process is extremely low compared to the frequently used plasma‐enhanced chemical vapour deposition of silicon nitride (SiN_x). Our experiments on silicon wafers passivated with stacks composed of ultrathin Al₂O₃ and SiN_x show that a substantially improved thermal stability during high‐temperature firing at 830 °C is obtained for the Al₂O₃/SiN_x stacks compared to the single‐layer Al₂O₃ passivation. Al₂O₃/SiN_x stacks are hence ideally suited for the implementation into industrial‐type silicon solar cells where the metal contacts are made by screen‐printing and high‐temperature firing of metal pastes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silicon solar cells with Al2O3 antireflection coating

The paper presents the possibility of using Al₂O₃ antireflection coatings deposited by atomic layer deposition ALD. The ALD method is based on alternate pulsing of the precursor gases and vapors onto the substrate surface and then chemisorption or surface reaction of the precursors. The reactor is purged with an inert gas between the precursor pulses. The Al₂O₃ thin film in structure of the finished solar cells can play the role of both antireflection and passivation layer which will simplify the process. For this research 50×50 mm monocrystalline silicon solar cells with one bus bar have been used. The metallic contacts were prepared by screen printing method and Al₂O₃ antireflection coating by ALD method. Results and their analysis allow to conclude that the Al₂O₃ antireflection coating deposited by ALD has a significant impact on the optoelectronic properties of the silicon solar cell. For about 80 nm of Al₂O₃ the best results were obtained in the wavelength range of 400 to 800 nm reducing the reflection to less than 1%. The difference in the solar cells efficiency between with and without antireflection coating was 5.28%. The LBIC scan measurements may indicate a positive influence of the thin film Al₂O₃ on the bulk passivation of the silicon.     

Effective silicon surface passivation by atomic layer deposited Al2O3/TiO2 stacks

In this work atomic layer deposition of Al₂O₃ and TiO₂ has been used to obtain dielectric stacks for passivation of silicon surfaces. Our experiments on n‐ and p‐type silicon wafers deposited by thin Al₂O₃/TiO₂ stacks show that a considerably improved passivation is obtained compared to the Al₂O₃ single layer. For Al₂O₃ films thinner than 20 nm the emitter saturation current density decreases with increasing TiO₂ thickness. Especially the passivation of ultrathin (～5 nm) Al₂O₃ is very effectively enhanced by TiO₂ due to a decreased interface defect density as well as an increased fixed negative charge in the stacks. Hence, the thin Al₂O₃/TiO₂ stacks developed in this work can be used as a passivation coating for Si‐based solar cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optimized emitter contacting on multicrystalline silicon thin film solar cells

We present an optimized contacting scheme for multicrystalline silicon thin film solar cells on glass based on epitaxially crystallized emitters with a thin Al₂O₃ layer and a silver back reflector. In a first step a 6.5 µm thick amorphous silicon absorber layer is crystallized by a diode laser. In a second step a thin silicon emitter layer is epitaxially crystallized by an excimer laser. The emitter is covered by an Al₂O₃ layer with a thickness ranging from 1.0 nm to 2.5 nm, which passivates the surface and acts as a tunnel barrier. On top of the Al₂O₃ layer a 90–100 nm thick silver back reflector is deposited. The Al₂O₃ layer was found to have an optimal thickness of 1.5 nm resulting in solar cells with back reflector that achieve a maximum open‐circuit voltage of 567 mV, a short‐circuit current density of 27.9 mA/cm², and an efficiency of 10.9%. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhanced rear‐side reflection and firing‐stable surface passivation of silicon solar cells with capping polymer films

Low refractive index polymer materials have been investigated with a view to form the back surface mirror of advanced silicon solar cells. SiO_x:H or AlO_y SiO_x:H polymer films were spun on top of an ultra‐thin (<10 nm) atomic‐layer‐deposited (ALD) Al₂O₃ layer, itself deposited on low‐resistivity (1 Ω cm) p‐type crystalline silicon wafers. These double‐layer stacks were compared to both ALD Al₂O₃ single layers and ALD Al₂O₃/plasma‐enhanced chemical vapour deposited (PECVD) SiN_x stacks, in terms of surface passivation, firing stability and rear‐side reflection. Very low surface recombination velocity (SRV) values approaching 3 cm/s were achieved with ALD Al₂O₃ layers in the 4–8 nm range. Whilst the surface passivation of the single ALD Al₂O₃ layer is maintained after a standard firing step typical of screen printing metallisation, a harsher firing regime revealed an enhanced thermal stability of the ALD Al₂O₃/SiO_x:H and ALD Al₂O₃/AlO_y SiO_x:H stacks. Using simple two‐dimensional optical modelling of rear‐side reflection it is shown that the low refractive index exhibited by SiO_x:H and AlO_y SiO_x:H results in superior optical performance as compared to PECVD SiN_x, with gains in photogenerated current of ～0.125 mA/cm² at a capping thickness of 100 nm. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Excellent Si surface passivation by low temperature SiO2 using an ultrathin Al2O3 capping film

It is demonstrated that the application of an ultrathin aluminum oxide (Al₂O₃) capping film can improve the level of silicon surface passivation obtained by low‐temperature synthesized SiO₂ profoundly. For such stacks, a very high level of surface passivation was achieved after annealing, with S_eff < 2 cm/s for 3.5 Ω cm n‐type c‐Si. This can be attributed primarily to a low interface defect density (D_it < 10¹¹ eV^–1 cm^–2). Consequently, the Al₂O₃ capping layer induced a high level of chemical passivation at the Si/SiO₂ interface. Moreover, the stacks showed an exceptional stability during high‐temperature firing processes and therefore provide a low temperature (≤400 °C) alternative to thermally‐grown SiO₂. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Al2O3增强的Co2-C98/Al2O3/Si异质结的光伏效应

随着能源危机的加剧,太阳能电池作为开发和利用太阳能的一种普遍形式, 日益受到世界各国的重视.随着太阳能电池向着高效率、薄膜化、无毒性和原材料丰富的方向发展, 单纯的硅系太阳能电池已经无法达到这样的要求,因此新的材料和工艺的开发利用迫在眉睫. 本文研究了碳材料在硅异质节上实现光伏效应的改善及其可能在太阳能电池上的应用. 采用脉冲激光沉积方法制备的Co₂-C₉₈/Al₂O₃/Si异质结构在标准日光照射 (AM1.5, 100 mW/cm²)条件下,可获得0.447 V的开路电压和18.75 mA/cm²的电流密度, 转换效率可达3.27%.通过电容电压特性和暗条件下的电输运性能测量, 证明了氧化铝层的引入不但对单晶硅的表面起到了物理钝化作用,减小了反向漏电流, 使异质结界面缺陷、界面能级和复合中心减少,还起到了场效应钝化作用, 增加了异质结界面的势垒高度,增加了开路电压,使异质结的光伏效应显著增强.     

Silicon surface passivation by atomic‐layer‐deposited Al2O3 facilitated in situ by the combination of H2O and O3 as reactants

We investigate the effect of O₃ and H₂O oxidant pre‐pulse prior to Al₂O₃ atomic layer deposition for Si surface passivation. Interfacial oxide SiO_x formed by the O₃ pre‐pulse is more beneficial than that by H₂O to a high level of surface passivation. The passivation of thinner H₂O–Al₂O₃ films is more improved by this O₃ pre‐pulse. O₃ pre‐pulse for 10 nm H₂O–Al₂O₃ reduces saturation current density in boron emitter to 18 fA cm^–2 by a factor of 1.7. Capacitance–voltage measurements reveal this interfacial oxide plays a role of decreasing interface trap density without detrimental effect to negative charge density of Al₂O₃. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Investigation of interface characteristics of Al2O3/Si under various O2 plasma exposure times during the deposition of Al2O3 by PA-ALD

Plasma-assisted atomic layer deposition (PA-ALD) is more suitable than thermal atomic layer deposition (ALD) for mass production because of its faster growth rate. However, controlling surface damage caused by plasma during the PA-ALD process is a key issue. In this study, the passivation characteristics of Al₂O₃ layers deposited by PA-ALD were investigated with various O₂ plasma exposure times. The growth per cycle (GPC) during Al₂O₃ deposition was saturated at approximately 1.4?Å/cycle after an O₂ plasma exposure time of 1.5?s, and a refractive index of Al₂O₃ in the range of 1.65–1.67 was obtained. As the O₂ plasma exposure time increased in the Al₂O₃ deposition process, the passivation properties tended to deteriorate, and as the radio frequency (RF) power increased, the passivation uniformity and the thermal stability of the Al₂O₃ layer deteriorated. To study the Al₂O₃/Si interface characteristics, the capacitance-voltage (C-V) and the conductance-voltage (G-V) were measured using a mercury probe, and the fixed charge density (Q_f) and the interface trap density (D_it) were then extracted. The Q_f of the Al₂O₃ layer deposited on a Si wafer by PA-ALD was almost unaffected, but the D_it increased with O₂ plasma exposure time. In conclusion, as the O₂ plasma exposure time increased during Al₂O₃ layer deposition by PA-ALD, the Al₂O₃/Si interface characteristics deteriorated because of plasma surface damage.     

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     

Plasma enhanced atomic layer deposition of gallium oxide on crystalline silicon: demonstration of surface passivation and negative interfacial charge

Herein we report on the passivation of crystalline silicon by gallium oxide (Ga₂O₃) using oxygen plasma as the oxidizing reactant in an atomic layer deposition (ALD) process. Excess carrier lifetimes of 2.1 ms have been measured on 1.75 Ω cm p‐type silicon, from which a surface recombination current density J₀ of 7 fA cm^–2 is extracted. From high frequency capacitance‐voltage (HF CV) measurements it is shown that, as in the case of Al₂O₃, the presence of a high negative charge density Q_tot/q of up to –6.2 × 10¹² cm^–2 is one factor contributing to the passivation of silicon by Ga₂O₃. Defect densities at midgap on the order of ～5 × 10¹¹ eV^–1 cm^–2 are extracted from the HF CV data on samples annealed at 300 °C for 30 minutes in a H₂/Ar ambient, representing an order of magnitude reduction in the defect density compared to pre‐anneal data. Passivation of a boron‐diffused p⁺ surface (96 Ω/□) is also demonstrated, resulting in a J₀ of 52 fA cm^–2. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

XPS study of the surface chemistry on AZ31 and AZ91 magnesium alloys in dilute NaCl solution

The surface chemistry on AZ31 and AZ91 magnesium alloys was characterized by X-ray photoelectron spectroscopy (XPS) in the corrosion and the passivation zones. In the corrosion zone, the presence of Mg(OH)₂ and MgCO₃ species was found in the outer surface, whereas, in the inner layer, the co-existence of Mg(OH)₂, MgO and MgCO₃ species was observed for both alloys. The presence of Al³⁺ in the surface electrolyte to form Al₂O₃/Al(OH)₃ and the formation of carbonate product provide a better passivation on the surfaces and retard the chloride-induced corrosion on the materials in the passivation zone.     

X-ray spectral analysis of the interface of a thin Al<Subscript>2</Subscript>O<Subscript>3</Subscript> film prepared on silicon by atomic layer deposition

The extent and phase chemical composition of the interface forming under atomic layer deposition (ALD) of a 6-nm-thick Al₂O₃ film on the surface of crystalline silicon (c-Si) has been studied by depthresolved, ultrasoft x-ray emission spectroscopy. ALD is shown to produce a layer of mixed Al₂O₃ and SiO₂ oxides about 6–8 nm thick, in which silicon dioxide is present even on the sample surface and its concentration increases as one approaches the interface with the substrate. It is assumed that such a complex structure of the layer is the result of interdiffusion of oxygen into the layer and of silicon from the substrate to the surface over grain boundaries of polycrystalline Al₂O₃, followed by silicon oxidation. Neither the formation of clusters of metallic aluminum near the boundary with c-Si nor aluminum diffusion into the substrate was revealed. It was established that ALD-deposited Al₂O₃ layers with a thickness up to 60 nm have similar structure.     

A study of GaN MOSFETs with atomic-layer-deposited Al2O3 as the gate dielectric

Accumulation-type GaN metal-oxide-semiconductor field-effect transistors (MOSFETs) with atomic-layer-deposited Al₂O₃ gate dielectrics are fabricated. The device, with atomic-layer-deposited Al₂O₃ as the gate dielectric, presents a drain current of 260 mA/mm and a broad maximum transconductance of 34 mS/mm, which are better than those reported previously with Al₂O₃ as the gate dielectric. Furthermore, the device shows negligible current collapse in a wide range of bias voltages, owing to the effective passivation of the GaN surface by the Al₂O₃ film. The gate drain breakdown voltage is found to be about 59.5 V, and in addition the channel mobility of the n-GaN layer is about 380 cm²/Vs, which is consistent with the Hall result, and it is not degraded by atomic-layer-deposition Al₂O₃ growth and device fabrication.