倍增型全聚合物光电探测器及其在光电容积描记传感器上的应用  

Photomultiplication-Type All-Polymer Photodetectors and Their Applications in Photoplethysmography Sensor

作　　者：赵兴超 李晓明 刘明 赵子进 杨凯旋 刘蓬天 张皓岚 李金泰 马晓玲 姚琪[3] 孙艳明 张福俊[1] Xingchao Zhao;Xiaoming Li;Ming Liu;Zijin Zhao;Kaixuan Yang;Pengtian Liu;Haolan Zhang;Jintai Li;Xiaoling Ma;Qi Yao;Yanming Sun;Fujun Zhang(Key Laboratory of Luminescence and Optical Information,Ministry of Education,Beijing Jiaotong University,Beijing 100044,China;School of Chemistry,Beihang University,Beijing 100191,China;BOE Technology Group Co.,LTD.,Beijing 100176,China.)

机构地区：[1]北京交通大学,发光与光信息教育部重点实验室,北京100044 [2]北京航空航天大学化学学院,北京100191 [3]京东方科技集团股份有限公司,北京100176

出　　处：《物理化学学报》2025年第1期111-120,共10页Acta Physico-Chimica Sinica

基　　金：中央高校基本科研业务费(2023YJS080);北京市自然科学基金(4232073);国家自然科学基金(U22A6002,62105017)资助项目。

摘　　要：我们以宽带隙聚合物聚(3-己基噻吩)(P3HT)为给体,窄带隙聚合物聚{2,2'-((2Z,2'Z)-((12,13-双(2-癸基十四烷基)-6-(2-乙基己基)-4,8-二甲基-6,8,12,13-四氢-4氢-苯并[1,2,3]三唑并噻吩[2'',3'':4',5']并吡咯[2',3':4,5]并吡咯[3,2-g]并噻吩[2',3':4,5]并吡咯[3,2-b]并[4,5-e]吲哚-2,10-二基)双(甲烷亚甲基))双(5,5’-3-氧-2,3-二氢-1氢-2,1-二亚基茚))二丙二腈-连-2,5-二噻吩}(PTz-PT)为受体,研制了基于氧化铟锡(ITO)/聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS)/有源层/Al结构的倍增型全聚合物光电探测器(PM-APDs)。我们制备了P3HT:PTz-PT质量比为100:1、100:4、100:7和100:10的四种不同比例的二元PM-APDs。在黑暗条件下,由于Al的功函数和P3HT的最高已占据分子轨道(HOMO)之间存在0.8 eV的能级差距,空穴难以从铝电极注入到有源层中。有源层中的PTz-PT含量较低,缺乏连续的电子传输通道,导致有源层的电子传输能力较差。在光照条件下,由于有源层中PTz-PT含量较低,并且P3HT和PTz-PT的最低未占据分子轨道(LUMO)相差0.84 eV,光生电子会被孤立的PTz-PT捕获。Al电极附近的受陷电子会引起界面能带弯曲,实现空穴隧穿注入,从而导致外量子效率(EQE)值大于100%。在−8 V偏压下,基于P3HT:PTz-PT(100:4 wt/wt)的最优二元PMAPDs在300–1100 nm的光谱范围内具有超过100%的EQE。PM-APDs的EQE光谱形状取决于铝电极附近的受陷电子分布。通过引入聚合物聚(2-(4,8-双(4-(2-乙基己基)环戊二烯并-1,3-啶-1-基)苯并[1,2-b:4,5-b']二噻吩-2-基)-5,5-二氟-10-(5-(2-己基癸基)噻吩-2-基)-3,7-二甲基-5H-4λ4,5λ4-二吡咯[1,2-c:2',1'-f][1,3,2]二氮杂硼嗪)(PMBBDT)作为第三组分,PMAPDs的EQE光谱形状变得更平坦。我们制备了P3HT:PMBBDT:PTz-PT质量比分别为90:10:4和80:20:4的三元PM-APDs。三元PM-APDs的EQE值在420–600 nm的范围内提高,而在630–870 nm的范围内降低。三元PM-APDs具有更平坦的EQE光谱是由于其�Photomultiplication-type all-polymer photodetectors(PM-APDs)based on structure of ITO/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)/active layer/Al were developed with wide bandgap polymer poly(3-hexylthiophene)(P3HT)as donor and narrow bandgap polymer poly{2,2ʹ-((2Z,2ʹZ)-((12,13-bis(2-decyltetradecyl)-6-(2-ethylhexyl)-4,8-dimethyl-6,8,12,13-tetrahydro-4H-thieno[2ʹʹ,3ʹʹ:4ʹ,5ʹ]pyrrolo[2ʹ,3ʹ:4,5]pyrrolo[3,2-g]thieno[2ʹ,3ʹ:4,5]pyrrolo[3,2-b][1,2,3]triazolo[4,5-e]indole-2,10-diyl)bis(methaneylylidene))bis(5,5ʹ-3-oxo-2,3-dihydro-1Hindene-2,1-diylidene))dimalononitrile-alt-2,5-dithiophene}(PTz-PT)as acceptor.A series of binary PM-APDs were prepared with P3HT:PTz-PT weight ratios of 100:1,100:4,100:7,and 100:10.In the dark,the holes are difficultly injected from Al electrode into the active layer due to the 0.8 eV injection barriers from the work function of Al onto the highest occupied molecular orbital(HOMO)level of P3HT.The limited PTz-PT content in the active layer results in the absence of continuous electron transport channel,leading to poor electron transport ability.The photogenerated electrons are trapped in isolated PTz-PT under light illumination due to the scarce PTz-PT content in active layer and 0.84 eV difference between the lowest unoccupied molecular orbital(LUMO)of P3HT and PTz-PT.The trapped electrons near the Al electrode induce interfacial band bending for hole tunneling injection,leading to external quantum efficiency(EQE)values exceeding 100%.The optimal binary PM-APDs based on P3HT:PTz-PT(100:4 wt/wt)exhibit a spectral response range from 300 to 1100 nm with EQE values over 100%at-8 V bias.The EQE spectral shape of PMAPDs is determined by the distribution of trapped electrons near the Al electrode.The shape of EQE spectra is further flattened by introducing polymer poly(2-(4,8-bis(4-(2-ethylhexyl)cyclopenta-1,3-dien-1-yl)benzo[1,2-b:4,5-b']dithiophen-2-yl)-5,5-difluoro-10-(5-(2-hexyldecyl)thiophen-2-yl)-3,7-dimethyl-5H-4λ4,5λ4-dipyrrolo[1,2-c:2ʹ,1ʹ-f][1,3,2]

关 键 词：光电倍增 全聚合物光电探测器 空穴隧穿注入 受陷电子 PPG传感器 

分 类 号：O649.4[理学—物理化学]