可溶性不对称锌酞菁作为钙钛矿太阳能电池空穴传输层的研究

SOLUBLE ASYMMETRIC ZINC(II) PHTHALOCYANINES AS HOLE TRANSPORT LAYERS IN PEROVSKITE SOLAR CELLS

王峰

11649174

硕士

化学工程

许宗祥

2018

2018.7.10

哈尔滨工业大学

深圳

钙钛矿太阳能电池因其结构简单，制备成本低，开路电压理想，转换效率高而受到广泛关注。空穴传输层是提高电池效率及寿命的关键因素，传统空穴传输材料的研究主要是利用苯胺或噻吩进行分子构建，合成步骤复杂，制备成本高，而关于-共轭金属配合物类型的空穴传输材料的系统研究仍处于起步阶段。酞菁分子具有优良的半导体特性及热和化学稳定性、合成提纯简单、价格低廉、载流子迁移率高，与钙钛矿材料能级相匹配，被视为理想的钙钛矿太阳能电池空穴传输材料。本论文着眼于非掺杂的高性能空穴传输材料的开发研究，提出了以-共轭金属配合物-酞菁分子为主体来设计锌酞菁，在锌酞菁环β 位引入不同取代基来进行功能化修饰。首先，合成前驱体亚酞菁（SubPc）和六甲基取代亚酞菁（Me6-SubPc），再通过两种亚酞菁扩环反应得到不对称单丁基锌酞菁（Bu-ZnPc）和六甲基一丁基锌酞菁（Me6Bu-ZnPc）。结果表明，单丁基的引入提高了酞菁分子的有机溶解性、水氧稳定性，增强了酞菁分子成膜后分子间-共轭堆积作用；与此同时，Me6Bu-ZnPc 的分子设计实现了分子在钙钛矿表面成膜后的face-on 堆积方式，从而有效提高空穴提取及传输效率。本论文同时探索了Me6-SubPc、Me6Bu-ZnPc 的成膜工艺，采用全液相法制备了非掺杂的太阳能电池器件，分别获得6.96%和11.4%的光电转换效率，并对器件的工作机理进行了研究。本研究同时利用了亚酞菁和酞菁类空穴传输材料对于热和化学的稳定性，实现了对钙钛矿层的封装保护，有效改善了太阳能电池的稳定性。

Perovskite solar cells have attracted widespread attention and research effort due to their simple structure, low fabrication cost, ideal open circuit voltage and high photoelectric conversion efficiency (PCE). It has been found that hole transport layer (HTL) plays an important role in enhancing devices’ performance as well as stability. However, the ongoing effort on HTL materials mainly focus on the molecules containing aniline or thiophene units. The synthesis of these materials involves complicated procedures and tremendous purification effort, typically resulting in high production cost. As an important class macrocyclic metal complexes, metal phthalocyanines (MPcs) hold the advantages of excellent semiconducting property, high thermal/chemical stabilities, simple synthesis and purification, low cost, high charge carrier mobility and suitable energy levels, and are regarded as ideal HTL materials for perovskite solar cells. However, the study of the HTL materials based on MPcs is still in its infancy.In this thesis, a new series of zinc(II) phthalocyanine derivtives, with different functional groups attaced at β position, were designed and synthesized for ues as HTL materials in perovskite solar cells. The subphthalocyanine (SubPc) and hexamethyl-substituted subphthalocyanine (Me6-SubPc) were firstly synthesized as precusors for the further synthesis of the asymmetrical monobutyl zinc(II) phthalocyanine (Bu-ZnPc) and hexamethy monobutyl zinc (II) phthalocyanine (Me6Bu-ZnPc) via ring expansion reaction. It has been found that the introduction of monobutylate to the MPc ring not only enhanced the solubility of these zinc(II) phthalocyanines in common organic solvents, but also increased their stabilities in ambient condition as well as intermolecular π-π stack interaction between phthalocyanine molecules. Also, the Me6Bu-ZnPc molecules have been found to adopt a face-on orientation in the thin film on top of the perovskite layer, resulting in the enhanced hole mobility and device performance. The perovskite solar cells fabricated via total liquid phase method based on the Me6-SubPc and Me6Bu-ZnPc HTLs gave the PCEs of 6.96% and 11.4%, respectively，and we studied the working mechanism of the device. Thanks to the excellent chemical and thermal stabilities of the MPcs, the perovskite layer can be well encapsulated by these SubPc or MPc materials, giving rise to the significant enhancement in device stabilities.

钙钛矿太阳能电池 空穴传输材料 非掺杂 不对称锌酞菁

Perovskite solar cells hole transport materials dopant-free asymmetrical zinc phthalocyanine

中文

联合培养

南方科技大学

王峰. 可溶性不对称锌酞菁作为钙钛矿太阳能电池空穴传输层的研究[D]. 深圳. 哈尔滨工业大学,2018.