【作者】 王宇航；

【导师】 邓先宇；

【作者基本信息】 哈尔滨工业大学 ， 材料工程（专业学位）， 2023， 硕士

【摘要】 金属酞菁配合物（MPc）具有特殊的光电性能,在光电器件中被广泛研究。酞菁铝（AlClPc）是MPc中具有特殊分子结构的有机材料,低的结合能、窄的带隙以及稳定的线性响应使得AlClPc在光电探测中不断被开发和应用。目前,制备AlClPc膜及其光电探测器还主要基于真空蒸镀的传统方式,在实际生产应用中受到很多限制。溶液加工的方式可以简单制备大面积器件,在柔性穿戴、健康监测等新兴领域有着非常大的发展潜力。为了有效利用AlClPc材料的绿色环保、成分稳定、简单易得以及光探测敏感等优势,开发一种基于溶液法制备AlClPc膜的方法,并用于制备高性能有机光电探测器变的十分重要。本文首先研究了影响AlClPc成膜过程中的热力学、动力学和后处理因素。通过调整AlClPc在不同有机溶剂中的溶解状态,调控二元溶剂比例,探究出能够有助于小分子成膜的最佳溶剂体系。将AlClPc与PC₆₁BM制备为具有体异质结的活性层,应用在ITO/Lys/AlClPc:PC₆₁BM/Mo O₃/Al倒置结构的有机光电二极管探测器（PD-OPD）中。随后通过研究活性层的退火和旋涂过程探究后处理工艺对器件性能的影响,确定最佳控制参数。进一步优化ITO和活性层之间的中间层材料,对比实验后使用Zn O作为新的电子传输层来提高载流子传输和降低反向暗电流。细化活性层成分比例,当给、受体占比为1:1时器件取得最佳性能,其零偏压下光开关比能达到10³,比探测率（D*）在360 nm-800 nm波段内大于10¹⁰Jones,且在-1 V偏压时该波段在近红外部分拓宽至914 nm。基于优化后的器件结构,研究线性聚合物对AlClPc成膜的辅助优化作用。通过对比不同分子结构的聚合物对AlClPc膜的形貌和光吸收性影响,筛选出具有支链结构的P3HT和PTB7-Th对活性层进行含量梯度掺杂实验,探究不同含量的聚合物对PD-OPD光电性能的影响。对比分析所有性能结果,分别掺杂10wt%P3HT和9.0 wt%PTB7-Th的活性层制备出的器件性能最好。与掺杂前的器件相比,P3HT优化后的器件在零偏压下提高了可见光范围内的比探测率,在470 nm实现2×10¹¹ Jones;PTB7-Th优化的器件几乎在整个波段都有所提高,在350 nm-756 nm范围内D*超过1×10¹¹Jones,在710 nm处取得最大值为2.14×10¹¹Jones。更多还原

【Abstract】 Metal phthalocyanine complexes（MPc）have been widely studied in optoelec-tronic devices because of their special photoelectric properties.Aluminum phthalo-cyanine（AlClPc）is an organic material with special molecular structure in MPc.Be-cause of its low binding energy narrow band gap and stable linear response,AlClPc has been continuously developed and applied in photoelectric detection.At present,the preparation and application in photodetector of AlClPc films are mainly based on the traditional method of vacuum evaporation,which is limited in practical produc-tion and application.Solution processing can simply prepare large-area devices,which has great development potential in emerging fields such as flexible wearing and health monitoring.In order to effectively utilize the advantages of AlClPc in en-vironmental protection,stable composition,easy to product and sensitive to light de-tection,it is very important to develop solution-based AlClPc films and use them to prepare high-performance organic photodetectors.In this paper,the thermodynamics,kinetics and post-treatment factors of affect-ing AlClPc films formation were studied firstly.By adjusting the dissolution state of AlClPc in different organic solvents and the ratio of binary solvents,the best solvent system which can help small molecules to form films was explored.The AlClPc and PC₆₁BM were fabricated as bulk heterojunction active layers,which was applied in organic photodiode detector（PD-OPD）with ITO/Lys/AlClPc:PC₆₁BM/Mo O₃/Al in-verted structure.Then through adjusting the annealing and spin coating process of the active layer,the influence of the post-treatment process of the films on the photode-tector performance was explored,and the best control parameters were determined.The interlayer material between ITO and active layer is further optimized.After com-parison experiment,Zn O is used as a new electron transport layer to improve carrier transport and reduce reverse dark current.When the ratio of donor to acceptor is 1:1,the photodetector achieves the best performance.The optical switching ratio can reach 10³ at zero bias voltage,the specific detection rate（D*）is greater than 10¹⁰Jones in the band of 360 nm-800 nm,and the band is widened to 914 nm in the near infrared at-1 V bias.Based on the optimized device structure,the optimization auxiliary effect of lin-ear polymers for AlClPc film formation was studied.By comparing the effects of polymers with different structures on the morphology and light absorption of AlClPc films,the P3HT and PTB7-Th with branched chain structure were selected to dope the active layer with content gradient.And the effects of different polymer contents on the photoelectric properties of PD-OPD were explored.Comparing and analyzing all the performance results,the active films doped with 10 wt%P3HT and 9.0 wt%PTB7-Th respectively have the best performance.Compared with the PD-OPD before doping,the PD-OPD optimized by P3HT improves the D*in the visible range under zero bias voltage and realizes 2×10¹¹ Jones at 470 nm;The PTB7-Th optimized device has an improvement in almost whole band,the D*exceeds 1×10¹¹ Jones in the range of 350 nm-756 nm,and the maximum value is 2.14×10¹¹ Jones at 710 nm.更多还原