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In this paper, P3HT∶PTB7∶PC61BM is used as an active layer to prepare a ternary heterojunction organic photodetector covering the visible light range. The effects of PTB7 added to P3HT∶PC61BM system on the optical and electrical properties of organic photodetectors (OPDs) are studied by atomic force microscopy, ultraviolet-visible absorption spectroscopy and fluorescence spectroscopy. It is found that when the mass ratio of P3HT∶PTB7∶PC61BM is 8∶2∶10, the response spectrum of the ternary mixed layer extends to 780 nm, and the responsivity (R) of OPDs reaches 178, 291, and 241 mA/W respectively under 630, 530, and 460 nm light and –1 V bias, and the specific detection rate (D*) reaches 1012 Jones, and the above results are compared with the research group’s previous results about P3HT∶PBDT-TT-C∶PC61BM as the active layer of ternary organic photodetector. The phenomenon of the device performance gap caused by adding two polymers PTB7 and PBDT-TT-C based on benzo[1, 2-b∶4, 5-b]dithiophene (BDT) units into the same system P3HT∶PC61BM is analyzed. The effect of PTB7 on the micro-morphology of the mixed film due to the introduction of fluorine atoms and the reason for the increase in the mobility of photogenerated carriers in the film are explained. This OPD with better preparation performance provides a theoretical basis and method.
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Keywords:
- organic photodetector /
- ternaryheterojunction /
- excitondissociation /
- micromorphology
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Zhu F Y 2018 M. S. Thesis (Chengdu: University of Electronic Science and Technology of China) (in Chinese)
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Zhao X S 2017 M. S. Thesis (Chongqing: Southwest University) (in Chinese)
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图 1 材料能级示意图结构图和器件结构图 (a)能级图; (b)结构图
Figure 1. Schematic diagram of material energy level structure diagram and device structure diagram: (a) Energy level diagram; (b) structure diagram.
图 2 (a) 聚合物分子结构; (b) 聚合物能级图; (c) 聚合物吸收光谱图
Figure 2. Molecular structure (a), energy diagram (b), and absorption spectrum (c) of two polymers.
图 3 两种聚合物对应的不同质量比的三元活性层薄膜对应的吸收光谱图
Figure 3. Absorption spectra of ternary active layer films with different mass ratios.
图 4 不同P3HT∶PTB7∶PC61BM质量比的三元混合活性层薄膜的2D和3D AFM图像 (a), (A) 质量比为10∶0∶10, Rq = 4.32; (b), (B) 质量比为9∶1∶10, Rq = 5.40; (c), (C) 质量比为8∶2∶10, Rq = 6.95; (d), (D) 质量比为7∶3∶10, Rq = 10.93
Figure 4. 2D and 3D AFM images of ternary mixed active layer films with different mass ratios of P3HT∶ PTB7∶ PC61BM∶ (a), (A) 质量比为10∶0∶10, Rq = 4.32; (b), (B) 质量比为9∶1∶10, Rq = 5.40; (c), (C) 质量比为8∶2∶10, Rq = 6.95; (d), (D) 质量比为7∶3∶10, Rq = 10.93.
图 5 P3HT∶PTB7∶PC61BM器件在三基色光照下的J-V曲线 (a)红光; (b)绿光; (c)蓝光; (d)暗光
Figure 5. The J-V curve of P3HT∶PTB7∶PCBM device under three primary colors: (a) Red light; (b) green light; (c) blue light; (d) dark light.
图 6 单空穴器件的ln(Jd3/V2)-(V/d)0.5曲线
Figure 6. ln(Jd3/V2)-(V/d)0.5 curve of single hole device.
图 7 不同质量比的三元活性层薄膜中的空穴迁移率
Figure 7. Hole mobility in ternary active layer films with different mass ratios.
图 8 525 nm激发光下不同质量比的三元薄膜的PL光谱
Figure 8. PL spectra of ternary thin films with different mass ratios under 525 nm excitation light.
图 9 –1 V偏压下, 三元OPD不同质量比的EQE光谱
Figure 9. EQE spectra of ternary OPDs at difffferent mass ratios at –1 V bias.
图 10 P3HT和PTB7薄膜的吸收光谱和PL光谱
Figure 10. Absorption spectrum and PL spectrum of P3HT and PTB7 films.
图 11 不同质量比的P3HT∶PTB7薄膜的PL光谱
Figure 11. PL spectra of P3HT∶PTB7 films with different mass ratios.
图 12 不同质量比的P3HT∶PTB7的OPDs的J-V曲线
Figure 12. J-V curves of P3HT∶PTB7 OPDs with different mass ratios.
图 13 –1 V偏压下器件P3HT∶PTB7∶PC61BM (8∶2∶10)的光电流与光功率的关系
Figure 13. Photocurrent-light intensity curves at –1 V bias for P3HT∶PTB7∶PC61 BM (8∶2∶10) devices.
图 14 在三基色的光脉冲以及偏压为–1 V下, P3HT∶PTB7∶PC61BM的质量比为8∶2∶10探测器的三基色瞬态响应曲线
Figure 14. The mass ratio of P3HT∶PTB7∶PC61BM is 8∶2∶10 in the three optical lights with the bias voltage is –1 V primary color transient response curve.
表 1 –1 V偏压以及三基色光照下P3HT∶PTB7∶PC61BM质量比为8∶2∶10的OPDs特性参数
Table 1. –1 V bias voltage and OPDs characteristic parameters of P3HT∶PTB7∶PC61BM with a mass ratio of 8∶2∶10 under the illumination of three primary colors.
活性层 偏压/V 光波长λ/nm 响应度R/mA·W–1 比探测率D*/Jones 外量子效率EQE/% P3HT∶PTB7∶PC61BM –1 630 178 1.75 × 1012 35 530 291 2.86 × 1012 68 460 241 2.37 × 1012 65 
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[1] Lochner C M, Khan Y, Pierre A, Arias A C 2014 Nat. Commun. 5 5745
Google Scholar
[2] Ross D, Ardalan A, Ajay K P, Paul L M, Paul M 2016 Adv. Mater. 28 4766
Google Scholar
[3] Wang W, Zhang F, Li L, Zhang M, An Q, Wang J, Sun Q 2015 J. Mater. Chem. C 3 7386
Google Scholar
[4] Wang W, Zhang F, Du M, Li L, Zhang M, Wang K, Wang Y, Hu B, Fang Y, Huang J 2017 Nano Lett. 17 1995
Google Scholar
[5] Gong X, Tong M, Xia Y, Cai W, Moon J, Cao Y, Yu G, Shieh C L, Nilsson B, Heeger A J 2009 Science 325 1665
Google Scholar
[6] Yoo J, Jeong S, Kim S, Je J H 2015 Adv. Mater. 27 1712
Google Scholar
[7] Hou J, Park M H, Zhang S, Yao Y, Chen L M, Li J H, Yang Y 2008 Macromolecules 41 6012
Google Scholar
[8] Zhang S, Ye L, Zhao W, Liu D, Yao H, Hou J 2014 Macromolecules 47 4653
Google Scholar
[9] Xu X, Li Z, Zhang W, Zou X, Di Carlo Rasi D, Ma W, Yartsev A, Andersson M R, Janssen R J, Wang E 2017 Adv. Energy Mater. 2018 8
[10] Liang Y, Feng D, Wu Y, Tsai S T, Li G, Ray C, Yu L 2009 J. Am. Chem. Soc. 131 7792
Google Scholar
[11] Liang Y, Wu Y, Feng D, Tsai S T, Son H J, Li G, Yu L 2009 J. Am. Chem. Soc. 131 56
Google Scholar
[12] 安涛, 王永强, 张俊 2019 光子学报 48 1004001
Google Scholar
An T, Wang Y Q, Zhang J, 2019 Acta Photon. Sin. 48 1004001
Google Scholar
[13] Shin H, Kim J, Lee C 2017 J. Korean Phys. Soc. 71 196
Google Scholar
[14] Arranz-Andres J, Blau W J 2008 Carbon 46 2067
Google Scholar
[15] Bhatia R, Kumar L 2017 J. Saudi Chem. Soc. 21 366
Google Scholar
[16] Robb M J, Ku S Y, Brunetti F G, Hawker C J 2013 J. Polym. Sci. Pol. Chem. 51 1263
[17] Noriega R, Rivnay J, Vandewal K, Koch F P V, Stingelin N, Smith P, Toney M F, Salleo A 2013 Nat. Mater. 12 1037
[18] Xiao M, Zhang K, Jin Y, Yin Q, Zhong W, Huang F, Cao Y 2018 Nano Energy 48 53
Google Scholar
[19] Ma X, Zhang F, An Q, Sun Q, Zhang M, Miao J, Hu Z, Zhang J 2017 J. Mater. Chem. A 5 13145
Google Scholar
[20] Meng H, Sun F, Goldfinger M B, Jaycox G D, Li Z, Marshall W J, Blackman G S 2005 J. Am. Chem. Soc. 127 2406
Google Scholar
[21] Geng Y, Wei Q, Hashimoto K, Tajima K 2011 Chem. Mater. 23 4257
Google Scholar
[22] Yuan J, Ford M J, Zhang Y, Dong H, Li Z, Li Y, Ma W 2017 Chem. Mate. 29 1758
Google Scholar
[23] Nam S, Seo J, Han H, Kim H, Bradley D D C, Kim Y 2017 Acs Appl. Mater. Inter. 9 14983
Google Scholar
[24] Jo J W, Jung J W, Jung E H, Ahn H, Shin T J, Jo W H 2015 Energ. Environ. Sci. 8 2427
Google Scholar
[25] Zhang D, Liu C, Li K, Guo W, Gao F, Zhou J, Zhang X, Ruan S 2018 Adv. Opt. Mater. 6 1701189
Google Scholar
[26] 朱方云 2018 硕士学位论文 (成都: 电子科技大学)
Zhu F Y 2018 M. S. Thesis (Chengdu: University of Electronic Science and Technology of China) (in Chinese)
[27] Thompson B C, Fréchet J M J 2008 Angew. Chem. Int. Edit. 39 58
[28] Lu L, Xu T, Chen W, Landry E S, Yu L 2014 Nat. Photonics 8 716
Google Scholar
[29] 赵旭生 2017 硕士学位论文 (重庆: 西南大学)
Zhao X S 2017 M. S. Thesis (Chongqing: Southwest University) (in Chinese)
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