最新效率记录：钙钛矿-硅叠层太阳能电池

LONGi set in October 2023The latest efficiency record for perovskite/silicon tandem solar cells (Figure 1) has reached an impressive 33.9%, This is the culmination of a significant leap forward in the field of photovoltaics. The record surpassed the benchmark set earlier this year by the King Abdullah University of Science and Technology (KAUST) and is one of several records set since late 2022 that exceeded the Shockley-Quissar (S-Q) limit for single-junction silicon solar cells.

So, why is it important to break this limit? Due to optical, thermal, and electronic losses, commercially viable single-junction silicon solar cells are highly unlikely to have efficiencies close to the S-Q limit. Continuous improvements in silicon solar cell technology (e.g., passivation, advanced light capture, etc.) are driving improvements in their efficiency, but it is unlikely to exceed the S-Q limit.

This article will explore the fundamentals of multi-junction solar cells and explain how optical and electrical simulations can be used to understand how to optimize the performance of tandem solar cells.

Figure 1.The increase in solar cell efficiency from the 1980s to 2023 highlights the performance of perovskite/silicon tandem cells over monocrystalline silicon cells in recent years.

The Limitations of Silicon Solar Cells 

Figure 2.Optical (green), thermal (yellow), and electronic (blue) losses in silicon solar cells.

Silicon-based single-junction PV modules account for 95% of the PV market. The efficiency of the most efficient solar cells currently is 26.8%, while the theoretical limit, known as the Shockley-Queisser limit, is about 32%. The nature of the band gap (direct-indirect) affects the number of absorbed photons. The indirect bandgap of silicon is a strong limitation of the ideal efficiency of these solar cells. Three types of losses limit the efficiency of solar cells:

1. Optical: Photons with energies below the band gap are not absorbed. The higher the band gap, the higher the amount of unabsorbed photons (about 19% of the total loss of silicon solar cells).

1. Heat: Photons with energy exceeding the band gap (E>Eg) are absorbed and heated. Excess energy is released into the solar cell in the form of heat (about 33% of the total loss of silicon solar cells)

1. Electrons: Losses during the collection of electron-hole pairs, which, if not collected, recombine and re-emit photons. (Approximately 15% of the total loss of silicon solar cells)

Overall, these losses result in about 68% of sunlight not being converted into electricity. The efficiency of commercial silicon solar panels is further limited to around 20%, which is parasitic loss due to the non-ideality of the large cell area. Large area.

Methods beyond the Shockley-Queisser limit

本博客重点介绍多结太阳能电池。在这里，我们仅列出社区提出的几种解决方案，以减少硅太阳能电池的损耗。如果对这个主题感兴趣，我们邀请读者搜索更详细的分析：  

1. 热载流子太阳能电池在多余的能量转化为热量之前提取高能电荷。  

1. 中间带隙太阳能电池在不降低电压的情况下吸收能量小于带隙的光子。中间带 （IB） 能级介于导带和价带之间。IB允许能量小于带隙的光子激发从价带到传导的电荷。 

1. 太阳能电池中的多个激子世代从单个高能光子产生多个电荷载流子。  

尽管从理论上讲，提出的解决方案应该可以提高硅太阳能电池的效率，但它们很少用于商业光伏。  

图 4.光伏电池的能带图，显示了随着能量的增加，吸收的光子产生的开路电压以及由此产生的电子从价带到导带的运动。 

图 3.三种先进的太阳能电池机制：热载流子吸收、中间带跃迁和多激子产生，每一种机制都提高了电子激发和能量转换效率。 

多结太阳能电池的兴起 

传统的太阳能电池具有单个PN结，即p和n掺杂半导体层的组合。相反的掺杂会产生一个内部电场，促进光生电荷的提取。多结太阳能电池有两个或多个结，每个结吸收的波长不同。结越多，被吸收的太阳光谱部分就越大，从而产生更高的理论效率。 

具有无限多结的太阳能电池的理论效率高达86.8%。-目前，世界上最高效的太阳能电池在聚光照明下的效率为47.6%，由4个结组成。在标准Global Spectrum下，三结太阳能电池的创纪录效率为39.5%。这两种创纪录的太阳能电池都具有由三五半导体构成的吸光材料。这些先进的太阳能电池比硅太阳能电池贵一千倍。它们的使用主要限于特殊应用，例如空间应用，在这些应用中，成本问题不如重量等其他方面。 

图 5.各种串联太阳能电池配置及其相应的电路图，展示了光管理和连接如何影响太阳能电池的整体效率和性能。 

优化串联太阳能电池 

只有两种吸收材料的多结太阳能电池是所谓的串联太阳能电池，它是“标准”商业用途最有趣的选择。它们可以用四个或两个电极制造，也称为四端子和两端串联配置。三端串联是第三种鲜为人知但正在迎头赶上的接触变体。在四端串联太阳能电池中，两个子电池是独立制造的，并且彼此电隔离，子电池要么机械堆叠，要么与光谱分光器耦合，光谱分光器本质上是一组透镜，用于将光引导到适当的子电池。然而，这种配置具有相当大的寄生吸收和反射，来自非活性层，并且由于多个基板、复杂的组装和布线，总材料成本更高。 

Figure 6.A solar energy system in which a holographic spectral beamsplitter splits incident sunlight into high- and low-energy photons, which are absorbed by the corresponding high and low bandgap solar cells, thereby improving photovoltaic efficiency.

In double-ended series solar cells, the sub-cells are electrically connected and must be current-matched to avoid compound losses. This configuration is obtained by mechanically stacking subcells, or most efficiently by adding a transparent conductive layer, also known as a composite layer, which is essential to create ohmic contact between the subcells. This configuration requires less wiring and is simpler to install, but the manufacturing process is challenging as the top battery must be deposited without damaging the bottom cell. In addition, due to the diurnal and seasonal variations of the solar spectrum, current matching requirements are not always met.

The three terminals in series have an intermediate point of contact between the two subunits, avoiding the tandem junction and current matching as in the case of two terminals in series. However, these devices are less explored than 2- and 4-terminal solar cells. We won't discuss it here.

Figure 7.Contour plot comparing the performance of tandem solar cells, with the axis representing the bandgap of the top and bottom cells and the contour representing the percentage of efficiency.

At standard light intensity and AM1.5 G, the highest theoretical efficiencies of four-terminal and two-terminal tandem solar cells are 46% and 45.7%, respectively. TWP-end tandem PV has fewer bandgap combinations for maximum efficiency as they require electrical and optical matching, while 4-terminal tandem PV only requires light matching, allowing for greater bandgap variation for the top cell. It's unclear which of the two solutions is likely to be the winner. They can all have several benefits, but they have problems that need to be addressed before we see them on the market.

So far, we have assumed that the lighting only hits the top subunit. It is also worth mentioning bifacial tandem solar cells. These intriguing solutions collect the light exposure that hits the back side of the solar cell, increasing the total amount of photons absorbed by the active layer.

Figure 8.A bifacial tandem solar cell setup in which sunlight is captured by the top and bottom cells, which also use the reflected light (albedo) to generate electricity.

Maximize efficiency with lighting management

The most widely studied tandem solar cell is silicon/perovskite, where silicon is the bottom daughter cell. Silicon has a bandgap of 1.12 eV. To maximize efficiency, the ideal bandgap for a top cell should be between 1.67 and 1.75 eV. Perovskites are an excellent solution for top-of-the-line cells because they can be designed to have a bandgap between 1.15 and 3.1 eV. They can be deposited at low temperatures by solution processes such as spin coating, thus avoiding any damage to the bottom cell during the manufacture of double-ended solar cells. In addition, perovskites have a direct band gap and a strong light absorption coefficient. Therefore, a thickness of about 500 nm is sufficient for the needs of perovskite subcells. In contrast, due to its indirect bandgap and low absorption coefficient, the silicon layer is almost a thousand times thicker than perovskite.

Figure 10.Cross-sectional view of a tandem solar cell, showing the layering from the upper layer to the package. Perovskites and silicon daughter cells are separated by transparent contacts and optocoupled.

Several strategies have been developed to increase the light absorption of silicon daughter cells. The use of textured surfaces (Figure 11) is one of the most commonly used techniques. However, determining the optimal roughness of these surfaces is a complex process that cannot be achieved through experimental trial and error alone. This is where computer simulations come in handy. For example, from the optical simulation, we can see how much current can be recovered from a silicon perovskite tandem solar cell at both ends by adding a textured interface. The simulation is shown in Figure 12 and is used Setfos 软件执行。  

图 12.光与太阳能电池的相互作用，显示出波和射线光学现象，光线被反射和吸收，而波在电池结构内衍射。 

图 11.具有金字塔状结构的纹理硅表面的电子显微镜视图，旨在增强硅亚电池内的光吸收，说明了为太阳能应用优化表面粗糙度的复杂性。 

我们使用了一个光学仿真模型，该模型结合了波动光学来计算相干薄膜组件的反射和透射，使用射线光学来评估纹理界面的角度散射特性，并使用净辐射算法来量化整个层堆栈中的光传播。 

图 13.钙钛矿/硅串联太阳能电池的详细层叠，指定了从空气界面到基板的每一层的材料和厚度。 

钙钛矿/硅串联太阳能电池的独立光学仿真和组合光电仿真对于这种创新光伏技术的发展极为重要。仿真还有助于理解串联光伏的光学特性和电学特性之间的关系。从全栈的模拟吸收率中，我们可以计算出器件的光电流。从没有纹理界面的平面器件开始，添加抗反射涂层可改善钙钛矿和硅吸收剂在 500 至 1000 nm 波长下的吸收。硅子电池两侧的纹理在大于 750 nm 的波长下显着改善了光吸收。与平面器件相比，电流增加了近 23%。硅特别受益于光管理策略，而钙钛矿由于吸收系数高，不需要这种处理。  

图 14.平面钙钛矿硅串联太阳能电池正面和背面的横截面扫描电子显微镜（SEM）。资料来源： © D. Türkay （洛桑联邦理工学院）， C. Wolff （洛桑联邦理工学院）， F. Sahli （CSEM）， Q. Jeangros （CSEM）.计算出的全钙钛矿/硅串联PV的吸收率。  

然而，在纹理表面上旋涂钙钛矿会导致不均匀沉积和形成孔洞。可能的解决方案包括减小织构尺寸并沉积较厚的钙钛矿层或将钙钛矿保形沉积到硅子电池的织构上。  

这两种方法在 2022 年创下了硅钙钛矿叠层太阳能电池的最高效率记录。在两个子电池之间具有纳米纹理的平坦化串联太阳能电池获得了创纪录的32.5%的效率，改善了光管理和钙钛矿吸收剂的沉积质量。对于具有微米级纹理和共形沉积钙钛矿的串联电池，最高认证效率为 31.3%。 

图 15.左图绘制了太阳能电池中不同缺陷密度的电流-电压特性，右图显示了钙钛矿层厚度随着缺陷密度的增加而增加，突出显示了最低缺陷浓度下的光学最佳。 

解决重组损失问题  

要充分利用太阳能电池，需要良好的光管理，并通过界面上的复合来限制损耗。钙钛矿和传输层电荷之间界面处的非辐射复合是性能损失的典型来源。 

使用SETFOS的电气仿真  （图15）表明，随着钙钛矿界面缺陷密度的增加，开路电压（Voc）显著降低。为了补偿载流子的损失，钙钛矿厚度应从光学模拟推断的最佳厚度值增加 30 nm（图 15）。 

探索更多太阳能电池主题 

在总结对叠层太阳能电池的广泛概述时，很明显，该领域已经成熟，充满了创新和进一步探索的机会。以下是正在进行的研究的一些关键领域的快速浏览： 

三端串联太阳能电池：三端串联设计的引入标志着一个重大的飞跃，克服了顶部子电池带隙的局限性，并有望实现更高的能量产量，具有强劲的经济前景并减少对环境的影响。 

减少寄生虫吸收的创新：解决寄生虫吸收问题至关重要。最近局部选择性接触材料的转变旨在最大限度地减少这些损失，提高串联电池的整体效率。 

增强光吸收： 调整钙钛矿材料的带隙可以显着提高光吸收和光电转换效率，使其成为未来低成本太阳能电池的有前途的候选者。 

钙钛矿吸收材料的进展： 卤化物钙钛矿材料改变了游戏规则，导致更高效的串联太阳能电池具有可调和强大的光吸收能力。研究仍在进行中，我们期待一些新的发展，这些发展可以继续提高太阳能电池的效率，但最重要的是，提高其运行稳定性。  

这些发展只是串联太阳能电池可能性的开始。随着研究的不断推进，我们可以期待看到太阳能电池技术的更多创新解决方案和改进，推动我们走向更可持续和更高效的能源未来。 

如果您想尝试来自瑞士Fluxim Ag的模拟软件Setfos，或者了解我们的特性测试工具和用于钙钛矿及有机太阳能电池或LED的放大软件，请联系我们在中国的经销商：

Beijing Hua Tong Terui Photon Technology Co., Ltd.
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Apartment No. 8, Beichen E. Rd.
100101 Beijing, China
Tel: +86-10-8497-2140
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