Crystalline Si thin-film solar cells: a review

The present review summarizes the results of research efforts in the field of crystalline silicon thin-film solar cells on foreign substrates. The large number of competing approaches can be broadly classified according to the grain size of the crystalline Si films and the doping of the crystalline absorber. Currently, solar cells based on microcrystalline Si films on glass with an intrinsic or moderately doped absorber film achieve efficiencies around 10%, whereas thin-film cells fabricated from large-grained polycrystalline Si on high-temperature-resistant substrates have efficiencies in the range of 15%. The paper discusses the limitations of various approaches and describes recent developments in the area of thin, monocrystalline Si films that may open the way towards 20% efficient thin-film Si solar cells. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

硅异质结太阳电池的物理机制和优化设计

硅异质结太阳电池是一种由非晶硅薄膜层沉积于晶硅吸收层构成的高效低成本的光伏器件,是一种具有大面积规模化生产潜力的光伏产品.异质结界面钝化品质、发射极的掺杂浓度和厚度以及透明导电层的功函数是影响硅异质结太阳电池性能的主要因素.针对这些影响因素已经有大量的研究工作在全世界范围内展开,并且有诸多研究小组提出了器件效率限制因素背后的物理机制.洞悉物理机制可为今后优化设计高性能的器件提供准则.因此及时总结硅异质结太阳电池的物理机制和优化设计非常必要.本文主要讨论了晶硅表面钝化、发射极掺杂层和透明导电层之间的功函数失配以及由此形成的肖特基势垒;讨论了屏蔽由功函数失配引起的能带弯曲所需的特征长度,即屏蔽长度;介绍了硅异质结太阳电池优化设计的数值模拟和实践;总结了硅异质结太阳电池的研究现状和发展前景.     

Effect of hydrogen on surface texturing and crystallization of a-Si:H thin film irradiated by excimer laser

Hydrogenated amorphous silicon (a-Si:H) thin films have been considered for use in solar cell applications because of their significantly reduced cost compared to crystalline bulk silicon. However, their overall efficiency and stability are lower than that of their bulk crystalline counterpart. Limited work has been performed on simultaneously solving the efficiency and stability issues of a-Si:H. Previous work has shown that surface texturing and crystallization on a-Si:H thin film can be achieved through a single-step laser processing, which can potentially alleviate the disadvantages of a-Si:H in solar cell applications. In this study, hydrogenated and dehydrogenated amorphous silicon thin films deposited on glass substrates were irradiated by KrF excimer laser pulses and the effect of hydrogen on surface morphologies and microstructures is discussed. Sharp spikes are focused only on hydrogenated films, and the large-grained and fine-grained regions caused by two crystallization processes are also induced by presence of hydrogen. Enhanced light absorptance is observed due to light trapping based on surface geometry changes of a-Si:H films, while the formation of a mixture of nanocrystalline silicon and original amorphous silicon after crystallization suggests that the overall material stability can potentially improve. The relationship between crystallinity, fluence and number of pulses is also investigated. Furthermore, a step-by-step crystallization process is introduced to prevent the hydrogen from diffusing out in order to reduce the defect density, and the relationship between residue hydrogen concentration, fluence and step width is discussed. Finally, the combined effects show that the single-step process of surface texturing and step-by-step crystallization induced by excimer laser processing are promising for a-Si:H thin-film solar cell applications.     

High-temperature processing of crystalline silicon thin-film solar cells

The crystalline silicon thin-film solar cell combines, in principle, the advantages of crystalline silicon wafer-based solar cells and of thin-film solar cell technologies. Its efficiency potential is the highest of all thin-film cells. In the “high-temperature approach” thin silicon layers are deposited on substrates that withstand processing temperatures higher than 1000 °C. The basic features of the high-temperature crystalline silicon thin-film cell technology are described and some important results are discussed. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Amorphous thin-film solar cells

This report gives an overview of the present status of thin-film solar cells made from hydrogenated amorphous semiconductors (a-Si:H, a-Ge:H) together with new results emphasizing the physics of amorphous materials and devices. Preparation techniques, quality and performances of a-Si:H and a-Ge:H films as well as solar cells with pin structures are reviewed. Dark and light current-voltage I(V) characteristics and spectral response measurements give information about photovoltaic diodes and allow further insights into the physics of these kinds of materials and solar cells. Simulation calculations and device modelling of such solar cells have increased our understanding of amorphous semiconductors and their devices. The introduction of pin/pin stacked and/or tandem structures has improved the long-term stability and conversion efficiency of amorphous solar cells.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

Microcrystalline silicon and micromorph tandem solar cells

“Micromorph” tandem solar cells consisting of a microcrystalline silicon bottom cell and an amorphous silicon top cell are considered as one of the most promising new thin-film silicon solar-cell concepts. Their promise lies in the hope of simultaneously achieving high conversion efficiencies at relatively low manufacturing costs. The concept was introduced by IMT Neuchatel, based on the VHF-GD (very high frequency glow discharge) deposition method. The key element of the micromorph cell is the hydrogenated microcrystalline silicon bottom cell that opens new perspectives for low-temperature thin-film crystalline silicon technology. According to our present physical understanding microcrystalline silicon can be considered to be much more complex and very different from an ideal isotropic semiconductor. So far, stabilized efficiencies of about 12% (10.7% independently confirmed) could be obtained with micromorph solar cells. The scope of this paper is to emphasize two aspects: the first one is the complexity and the variety of microcrystalline silicon. The second aspect is to point out that the deposition parameter space is very large and mainly unexploited. Nevertheless, the results obtained are very encouraging and confirm that the micromorph concept has the potential to come close to the required performance criteria concerning price and efficiency. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 1 July 1999     

N-type amorphous silicon-based bilayers for cost-effective thin-film silicon photovoltaic devices

We investigate the improvement of p–i–n type thin-film silicon (Si) solar cells by employing a hydrogenated n-type amorphous Si (n-a-Si:H)-based bilayer. The initial conversion efficiency (η) of a-Si:H single-junction solar cells is improved from 9.2 to 10.0%. The developed n-a-Si:H-based bilayer is also suitable for a-Si:H/hydgrogenated microcrystalline Si (μc-Si:H) double-junction solar cells, and thus initial η is improved from 10.4 to 10.8%. With a further optimization, initial η of 11.3% and stabilized η of 10.1% are achieved. Since the n-a-Si:H-based bilayer is easily formed using a conventional process, it can be a promising option for cost-effective mass production of large-area thin-film Si solar modules.     

非晶硅界面缓冲层对非晶硅锗电池性能的影响

针对非晶硅锗电池本征层高锗含量时界面带隙失配以及高界面缺陷密度造成电池开路电压和填充因子下降的问题,通过在PI界面插入具有合适带隙的非晶硅缓冲层,不仅有效缓和了带隙失配,降低界面复合,同时也通过降低界面缺陷密度改善内建电场分布,从而提高了电池的收集效率. 进一步引入IN界面缓冲层以及对非晶硅锗本征层进行能带梯度设计,在仅采用Al背电极时,单结非晶硅锗电池转换效率达8.72%. 关键词： 非晶硅缓冲层 非晶硅锗薄膜太阳电池 带隙 界面     

高压射频等离子体增强化学气相沉积制备高效率硅薄膜电池的若干关键问题研究

报道了采用高压射频等离子体增强化学气相沉积(RF-PECVD) 制备高效率单结微晶硅电池和非晶硅/微晶硅叠层电池时几个关键问题的研究结果, 主要包括: 1)器件质量级本征微晶硅材料工艺窗口的确定及其结构和光电性能表征; 2)孵化层的形成机理以及减小孵化层的有效方法; 3)氢稀释调制技术对本征层晶化率分布及其对提高电池性能的作用; 4)高电导、高晶化率的微晶硅p型窗口层材料的获得, 及其对减小微晶硅电池p/i界面孵化层厚度和提高电池性能的作用等. 在解决上述问题的基础上, 采用高压RF-PECVD制备的单结微晶硅电池效率达8.16%, 非晶硅/微晶硅叠层电池效率11.61%.     

Superstrate p-i-n a-Si:H solar cells on textured ZnO:Al front transparent conduction oxide

Superstrate p-i-n amorphous silicon thin-film (a-Si:H) solar cells are prepared on SnO₂:F and ZnO:Al transparent conducting oxides (TCOs) in order to see the effect of TCO/p-layers on a-Si:H solar cell operation. The solar cells prepared on textured ZnO:Al have higher open circuit voltage V_oc than cells prepared on SnO₂:F. The presence of a thin microcrystalline p-type silicon layer (μc-Si:H) between ZnO:Al and p a-SiC:H plays a major role by causing an improvement in the fill factor as well as in V_oc of a-Si:H solar cells prepared on ZnO:Al TCO. Without any treatment of the p-i interface, we could obtain a high V_oc of 994 mV while keeping the fill factor (72.7%) and short circuit current density J_sc at the same level as for the cells on SnO₂:F TCO. This high V_oc value can be attributed to modification in the current transport in this region due to creation of a potential barrier.     

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     

非晶硅太阳电池结构模拟设计

为了从理论上分析提高非晶硅太阳能电池的转化效率,运用微电子和光子结构分析一维器件模拟程序模拟非晶硅太阳电池a-SiC∶H/a-Si∶H/a-Si∶H结构,分析比较了不同前端接触透明导电层的功函数ФITO、禁带宽度、本征层厚度、掺杂浓度、缺陷态密度等因素对太阳电池性能的影响.模拟得到,在功函数达到5.1 eV,禁带宽度1.8 eV,本征层厚度265 nm等最优化条件下,非晶硅太阳能电池转化效率达到9.855%,比一般非晶硅太阳能电池转化效率高近2%.     

P/i interfacial engineering in semi-transparent silicon thin film solar cells for fabrication at a low temperature of 150 °C

In this study, we aimed to develop semitransparent solar cells (STSCs) using hydrogenated amorphous silicon (a-Si:H) at a low temperature of 150 °C to support the fabrication of flexible solar modules, applicable in building-integrated photovoltaics (BIPV). To compensate for the presumable loss of device performance at such a low processing temperature, careful control of the p/i interface is proposed. We fabricated buffer layers with hydrogen (H₂)/silane (SiH₄) gas flow ratios (R) ranging from 4 to 16 (R₄–R₁₆) to investigate their characteristics and incorporate them at the p/i interface by considering energy band matching. By employing this buffer, the power conversion efficiency (PCE) of a STSC was improved from 4.83% to 5.57% which is the best record in a-Si:H STSCs processed at a low temperature of 150 °C. This p/i interfacial buffer can support the realization of flexible a-Si:H-based BIPV systems using plastic- or polymer-based substrates.     

Top PV market solar cells 2016

Photovoltaic (PV) technologies which play a role in PV market are divided into basic two types: wafer-based (1st generation PV) and thin-film cell (2nd generation PV). To the first category belong mainly crystalline silicon (c-Si) cells (both mono- and multi-crystalline). In 2015 around 90% of the solar market belonged to crystalline silicon. To the 2nd generation solar cells belongs thin film amorphous silicon (a-Si) or a combination of amorphous and microcrystalline silicon (a-Si/μc-Si), compound semiconductor cadmium telluride (CdTe), compound semiconductor made of copper, indium, gallium and selenium (CIS or CIGS) and III–V materials. The PV market for thin film technology is dominated by CdTe and CIGS solar cells. Thin film solar cells’ share for all thin film technologies was only 10% in 2015. New emerging technologies, called 3rd generation solar cells, remain the subject of extensive R&D studies but have not been used in the PV market, so far.In this review the best laboratory 1st and 2nd generation solar cells that were recently achieved are described. The scheme of the layer structure and energy band diagrams will be analyzed in order to explain the boost of their efficiency with reference to the earlier standard designs.     

Role of heterogeneities in Staebler–Wronski effect

The effect of light soaking (LS) on the properties of hydrogenated amorphous silicon (a-Si:H) presents many challenging puzzles. We look at some of them, along with their present understanding. In particular, the role of the heterogeneities in LS is examined. We find that for most of the solved as well as unsolved puzzles, the long-range potential fluctuations arising from the heterogeneities in the films, afford an alternative view which looks quite plausible. The implications of such considerations are used to speculate on the possibility of making stable a-Si:H solar cells.     

Three dimensional a-Si:H thin-film solar cells with silver nano-rod back electrodes

We present three dimensional (3-D) amorphous silicon (a-Si:H) thin-film solar cells with silver nano-rods as back electrodes, which are fabricated by low cost nano imprint lithography (NIL). After conformal deposition of thin metal and semiconductor layers, we can achieve a dome-shaped geometry, which is shown to be effective in reducing the reflectance at the front surface due to the graded refractive index effect. In addition, the enhancement of the diffused reflectance over a broad wavelength in this dome-shaped geometry provides light trapping due to the increase in the effective light propagation length. Using this 3-D solar cell, we achieved 54% increase in short circuit current density and 45% increase in the conversion efficiency compared to the control cells with flat Ag surfaces. This 3-D structure can be also used for improving light harvesting in various photovoltaic devices regardless of materials and structures.     

钙钛矿/硅叠层太阳电池中平面a-Si:H/c-Si异质结底电池的钝化优化及性能提高

最近,旋涂法制备的钙钛矿/平面硅异质结高效叠层太阳电池引起人们广泛关注,主要原因是相比于绒面硅衬底制备的钙钛矿/硅叠层太阳电池,其制备工艺简单、制备成本低且效率高.对于平面a-Si:H/c-Si异质结电池, a-Si:H/c-Si界面的良好钝化是获得高转换效率的关键,进而决定了钙钛矿/硅异质结叠层太阳电池的性能.本文主要从硅片表面处理、a-Si:H钝化层和P型发射极等方面展开研究,通过对硅片表面的氢氟酸(HF)浸泡时间和氢等离子体预处理气体流量、a-Si:H钝化层沉积参数、钝化层与P型发射极(I/P)界面富氢等离子体处理的综合调控,获得了相应的优化工艺参数.对比研究了p-a-Si:H和p-nc-Si:H两种缓冲层材料对I/P界面的影响,其中高电导、宽带隙的p-nc-Si:H缓冲层既能够降低I/P界面的缺陷态,又可以增强P型发射层的暗电导率,提高了前表面场效应钝化效果.通过上述优化,制备出最佳的P-type emitter layer/aSi:H(i)/c-Si/a-Si:H(i)/N-type layer (inip)结构样品的少子寿命与implied-Voc分别达到2855μs和709 mV,表现出良好的钝化效果.应用于平面a-Si:H/c-Si异质结太阳电池,转换效率达到18.76%,其中开路电压达到681.5 mV,相对于未优化的电池提升了34.3 mV.将上述平面a-Si:H/c-Si异质结太阳电池作为底电池,对应的钙钛矿/硅异质结叠层太阳电池的开路电压达到1780 mV,转换效率达到21.24%,证明了上述工艺优化能够有效地改善叠层太阳电池中的硅异质结底电池的钝化及电池性能.     

椭圆偏振光谱表征单晶硅衬底上生长的非晶硅和外延硅薄膜

本文采用射频等离子体增强化学气相沉积(rf-PECVD)技术在单晶硅衬底上沉积了两个系列的硅薄膜. 通过对样品进行固定角度椭圆偏振测试, 结果表明第一个系列硅薄膜为非晶硅, 形成了突变的a-Si:H/c-Si异质结构, 此结构在HIT电池中有利于形成好的界面特性, 对于非晶硅薄膜采用通常的Tauc-Lorentz摇摆模型(Genosc)拟合结果很好; 第二个系列硅薄膜为外延硅, 对于外延硅薄膜, 随着膜厚增加晶化率降低, 当外延硅薄膜厚度为46 nm时开始非晶硅生长. 对于外延硅通常采用EMA模型(即将硅薄膜体层看成由非晶硅和c-Si构成的混合层)拟合结果较好, 当硅薄膜中出现非晶硅生长时, 将体层分成混合层和非晶硅两层, 采用三层模型拟合结果很好. 本文证实了椭偏光谱分析采用不同的模型可对单晶硅衬底上不同结构的硅薄膜进行有效表征.     

Photo-induced electrical instability in hydrogenated amorphous silicon based thin-film transistors and the effect of its phase transition

We investigate the origin of photo-induced electrical instability in hydrogenated amorphous silicon based thin-film transistors (a-Si:H TFTs). Photo instability alone was accompanied by a positive shift in the threshold voltage (V_TH) caused by photo irradiation, and even larger positive or negative shift further exacerbated the instability caused by photo-induced electrical bias stress. Such phenomena can occur as a result of extended charge trapping and/or the creation of defect-states at the semiconductor/dielectric interface or in the gate dielectric. The mechanism for such is difficult to describe through chemical interactions of electron-donating and -withdrawing molecules that exhibit a shift in V_TH in only one direction. We also prove that a transition from an amorphous to a protocrystalline phase improves the photo-induced electrical stability. Such results originate from a reduction in the density of the localized states in protocrystalline-Si:H films relative to that of a-Si:H. We believe that this study provides significant information on the device physics of optoelectronics, which commonly exhibit photo-induced instability and charge transport, as a result of prolonged exposure to photo irradiation.     

硅锗量子阱结构在硅异质结太阳电池中应用的数值模拟

利用半导体工艺和器件仿真软件silvaco TCAD(Technology Computer Aided Design),模拟研究了采用硅/硅锗合金(silicon/silicon germanium alloy,Si/Si_(1-x)Ge_x)量子阱结构作为吸收层的薄膜晶体硅异质结太阳电池各项性能.模拟结果显示,长波波段光学吸收随锗含量的增加而增加,而开路电压则因Si_(1-x)Ge_x)层带隙的降低而下降.锗含量为0.25时,短路电流密度的增加补偿了开路电压的衰减,效率提升0.2%.氢化非晶硅/晶体硅(a-Si:H/c-Si)界面空穴密度以及Si_(1-x)Ge_x)量子阱的体空穴载流子浓度制约着空穴费米能级的位置,进而影响到开路电压的大小.随着锗含量增加,a-Si:H/c-Si界面缺陷对开压的影响降低,Si_(1-x)Ge_x)量子阱的体缺陷对开压的影响则相应增加.高效率含Si_(1-x)Ge_x)量子阱结构的硅异质结太阳电池的制备需要a-Si:H/c-Si界面缺陷的良好钝化以及高质量Si_(1-x)Ge_x)量子阱的生长.