Hole-Conductor-Free Fully Printable Mesoscopic Solar Cell with Mixed-Anion Perovskite CH3NH3PbI(3-x)(BF4)x
Hole-Conductor-Free Fully Printable Mesoscopic Solar Cell with Mixed-Anion Perovskite CH3NH3PbI(3-x)(BF4)x
复制标题
混合阴离子钙钛矿CH3NH3PbI(3-x)(BF4)(x)无空穴导体完全可印刷介观太阳能电池
DOI：
10.1002/aenm.201502009
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发表时间：
2016-03-09
影响因子：
27.8
通讯作者：
Han, Hongwei
中科院分区：
文献类型：
--
作者：
Chen, Jiangzhao;Rong, Yaoguang;Han, Hongwei
这种基于三层介观层的器件已经实现了可比的PCE。[16, 17]然而，TiO 2 层和碳层之间的微米厚的ZrO 2 层（1–2 µm）对电荷传输提出了挑战，并阻碍了器件性能的进一步提高。简单地减小ZrO 2 层的厚度会导致短路并显着影响器件制造的再现性。因此，有必要提高有机金属三卤化物钙钛矿的空穴电导率以提高器件性能。使用混合阴离子代替单一阴离子似乎是优化钙钛矿电性能的有效方法。据报道，氟由于其高电负性和比其他阴离子更强的吸电子性质，在半导体材料的光电性能中起着至关重要的作用。值得注意的是，Kanatzidis 及其同事在全固态染料敏化太阳能电池中应用了 F 掺杂 CsSnI 2.95F 0.05 作为空穴导体。由于钙钛矿晶体结构中分子间堆积的增加，空穴电导率的增强导致器件性能显着提高。 [19]这份关于成功地将F元素掺入CsSnI 3 的报告鼓励我们将F掺入铅卤钙钛矿MAPbI 3 中。然而，由于基于I−和F−离子的混合卤化物钙钛矿体系的不稳定性，周期表VIIA列中离子半径最小的F元素不能用来代替PSCs MAPbI 3 中的碘。[20]据信，混合卤化物钙钛矿MAPbI (3−x) F x 的容差因子t不在稳定钙钛矿材料所需的0.7至1的范围内。这里，t表示为：t=(RA+RX)/[2 1/2(RB+RX)]，其中RA、RB和RX对应于A、B和X的离子半径，八面体因子μ定义为RB/RX之比。为了克服这种不稳定问题，Ogale 和同事报道了一种有趣的策略，即通过用离子半径相似的 BF 4− 部分取代 I−，将 F 离子纳入 MAPbI 3 中。 [20]不幸的是，这种混合阴离子钙钛矿与 BF 4− 在 MPSC 中的应用尚未被研究。在此，首先开发了一种用于无空穴导体MPSC的混合阴离子钙钛矿MAPbI (3− x)(BF 4) x 。受益于 BF 4− 和 I− 相似的离子半径，MAPbI 3 的基本特性可以保持，并且电性能得到特别改善。由于光捕获能力、载流子浓度和电导率等光学和电学性能的提高，与典型的基于MAPbI 3 的器件相比，基于MAPbI (3− x)(BF 4) x 的器件的光伏性能显着提高。 PCE 为 13.24%，增强 Jsc 为 18.15 mA cm− 2，Voc 为 957 mV，FF 为 0.76 自 Miyasaka 及其同事的开创性报告以来，杂化有机-无机金属卤化物钙钛矿因其高消光系数、优异的双极性电荷迁移率、小激子结合能和低介电常数等优点而迅速被认为是光伏应用中的杰出吸收剂。 [1-3]然而，钙钛矿在液态电解质中溶解导致的不稳定性阻碍了其作为钙钛矿敏化太阳能电池吸收剂的进一步发展。为了解决这个问题，固态空穴传输材料（HTM），如2, 2′, 7, 7′-四（N, N-二对甲氧基苯胺）-9, 9′-螺二芴（spiro-OMeTAD）被用来代替液态电解质并组装全固态器件。[4, 5]几年之内，这种全固态钙钛矿就出现了。太阳能…
This triple mesoscopic layer-based device has achieved comparable PCEs.[16, 17] However, the micrometer-thick ZrO 2 layer (1–2 µm) between TiO 2 layer and carbon layer challenges the charge transportation and hinders the further improvement of device performance. It will cause a short-circuit and significantly affect the reproducibility of the fabrication of devices to simply reduce the thickness of ZrO 2 layer. Thus, it is necessary to enhance the hole conductivity of the organometal trihalide perovskites to improve the device performance. Using mixedanion instead of single-anion seems to be an effective method to optimize the electric properties of the perovskites. It has been reported that fluorine plays a crucial role in the optoelectronic properties of semiconducting materials because of its high electro-negativity and stronger electron withdrawing nature than other anions. Notably, Kanatzidis and co-workers applied F doped CsSnI 2.95F 0.05 as hole conductor in all-solidstate dye-sensitized solar cells. Due to the increased intermolecular packing in the crystal structure of the perovskite, the enhanced hole conductivity led to a dramatic improvement in device performance.[19] This report on successfully incorporating F element into CsSnI 3 encourages us to incorporate F into lead halogen perovskite MAPbI 3. However, F element with the smallest ionic radius in the column VIIA in the periodic table cannot be employed to take the place of iodine in MAPbI 3 for PSCs because of the instability of mixed halide perovskite systems based on I− and F− ions.[20] It is believed that the tolerance factor t of mixed halide perovskite MAPbI (3− x) F x is not in the range of 0.7 to 1 which is required for stable perovskite materials. Here, t is expressed as: t=(RA+ RX)/[2 1/2 (RB+ RX)], where RA, RB, and RX correspond to the ionic radiuses of A, B, and X, and octahedral factor µ is defined as the ratio RB/RX. In order to overcome such instability issue, an interesting strategy to incorporate F ion in MAPbI 3 via partial substitution of I− by BF 4− with similar ionic radius was reported by Ogale and co-workers.[20] Unfortunately, the application of this mixedanion perovskite with BF 4− in MPSC has not been studied. Herein, a mixed-anion perovskite MAPbI (3− x)(BF 4) x was firstly developed for hole-conductor-free MPSCs. Benefiting from similar ionic radius of BF 4− and I−, the fundamental characteristics of MAPbI 3 could be maintained along with specifically improved electric properties. Due to the improved optical and electrical properties, such as light harvesting ability, carrier concentration and conductivity, the photovoltaic performance of MAPbI (3− x)(BF 4) x-based device was dramatically improved, compared with typical MAPbI 3-based device. PCE of 13.24% with enhanced Jsc of 18.15 mA cm− 2, Voc of 957 mV and FF of 0.76Since the path breaking report from Miyasaka and co-workers, hybrid organic–inorganic metal halide perovskite has been rapidly recognized as an outstanding absorber for the application in photovoltaics on account of their advantages of high extinction coefficient, excellent ambipolar charge mobility, small exciton binding energy, and tunable bandgap.[1–3] However, the instability resulted from the dissolution of perovskites in liquid-state electrolyte hinders its further development as the absorber in perovskite-sensitized solar cells. To solve this problem, solid-state hole-transporting-materials (HTMs), such as 2, 2′, 7, 7′-Tetrakis (N, N-di-p-methoxyphenyl amine)-9, 9′-spirobifluorene (spiro-OMeTAD), were employed to replace the liquid-state electrolyte and assemble all-solid-state devices.[4, 5] Within few years, such all-solid-state perovskite solar …