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金属卤化物钙钛矿因其颜色可调、颜色纯度高、光电性能好而备受关注, 因而广泛应用于显示、照明等领域. 近年来, 对于钙钛矿发光二极管(perovskite light emitting doides, PeLEDs)的研究也越来越热门, 要获得高性能PeLEDs, 其发光层-钙钛矿薄膜的质量是关键因素之一. 本工作采用离子化合物四苯基氯化膦(tetraphenylphosphinium chloride, TPPCl)作准二维钙钛矿薄膜的添加剂, 制作了具有双电子传输层的高性能准二维PeLEDs. 其最佳器件的最大亮度(25285 cd/m2)、最大电流效率(65.9 cd/A)和最大外量子效率(17.3%)分别是控制器件的4.1, 7.2和7.2倍. 通过对其光电性能提高的物理机理进行研究, 发现TPPCl的引入不仅可以提高钙钛矿薄膜的质量, 减少缺陷, 还可以调节结晶相的分布, 从而更好地将激子限制在发光层中, 最终在能量漏斗效应的辅助下获得更好的光致发光和电致发光性能 .Metal halide perovskite has attracted much attention due to its adjustable color, high color purity, and excellent photoelectric properties. The quality of the perovskite film is one of the key factors that affect the performance of device. Here, PEA2Csn–1PbnBr3n+1 thin films are prepared by directly doping the ionic compound additive tetraphenylphosphine chloride (TPPCl) into the perovskite precursor of the light-emitting layer based on additive assisted technology. High-quality perovskite films with uniform, less pinholes and smaller grains are obtained. Not only is the photoluminescence (PL) performance of PeLEDs improved but the electroluminescence (EL) performance of PeLEDs with a double electron transport layer also turns better. The maximum brightness is 25285 cd/m2. The maximum current efficiency is 65.9 cd/A. And the maximum EQE is 17.3%. The method of adding ionic compounds to the perovskite precursor can not only improve the carrier transport behavior, but also make the formed small n crystal phases and large n crystal phase more balance, leading to the energy funnel effect to be enhanced. Further investigation by FTIR proves that the TPPCl can passivate the perovskite film, and thus greatly improving the EQE value of the PeLED. This researchpresents a simple and efficient method of developing high-performance quasi-two-dimensional green PeLEDs.
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Keywords:
- perovskite light emitting doides /
- tetraphenylphosphine chloride /
- photoluminescence /
- electroluminescence
[1] Cheng L, Jiang T, Cao Y, Yi C, Wang N, Huang W, Wang J 2020 Adv. Mater. 32 1904163
Google Scholar
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Google Scholar
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Wang R, Jia Y L, Zhang Y, Ma X J, Xu Q, Zhu Z X, Deng Y H, Xiong Z H, Gao C H 2020 Acta. Phys. Sin. 69 038501
Google Scholar
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Google Scholar
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Google Scholar
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图 1 不含/含TPPCl钙钛矿薄膜的光学性质 (a) XRD图谱, TPPCl的化学分子结构和相应的三维图; (b) 紫外-可见吸收光谱; (c) 归一化光致发光强度光谱, 及部分放大图(左)和荧光照片(右); (d) 时间分辨光致发光光谱
Fig. 1. Optical properties of perovskite films w/o TPPCl and with TPPCl: (a) XRD patterns, the chemical molecule structure of TPPCl and the corresponding 3D diagram; (b) UV-vis absorption spectra; (c) normalized PL intensity spectra, partial enlarged image (left) and fluorescence photo (right); (d) TRPL spectra.
图 2 (a) PEA2Csn–1PbnBr3n+1, TPPCl、含TPPCl的PEA2Csn–1PbnBr3n+1的傅里叶变换红外光谱; (b) 不含/含TPPCl的钙钛矿薄膜在不同激光强度下的PLQY
Fig. 2. (a) FTIR spectra of PEA2Csn–1PbnBr3n+1, TPPCl, PEA2Csn–1PbnBr3n+1 with TPPCl; (b) PLQY of perovskite films w/o and with TPPCl under different laser intensities.
图 3 (a), (b) 不含TPPCl和含TPPCl钙钛矿薄膜的顶部SEM图像, 红色圈标记的是孔洞; (c) 钙钛矿发光二极管的器件结构示意图; (d) 器件C的SEM剖面图
Fig. 3. (a), (b) The top-view SEM image of perovskite films w/o TPPCl and with TPPCl. The pinholes are circled in red; (c) the structure sketch map of quasi-2D PeLEDs; (d) the cross-sectional SEM images of device C.
图 4 不同浓度TPPCl的准二维PeLEDs的EL性能 (a) 电流密度-电压; (b) 亮度-电压; (c) 电流效率-电压-外部量子效率; (d) 在6 V下的归一化EL光谱
Fig. 4. EL performance of all the PeLEDs with different concentration of TPPCl: (a) Current density-voltage (J-V); (b) luminance-voltage (L-V); (c) current efficiency-voltage-external quantum efficiency (CE-V-EQE); (d) normalized EL spectra under an applied voltage of 6 V.
图 6 (a) 电子主导器件EDD 1和EDD 2的电流密度-电压曲线图; (b) 空穴主导器件HDD 1和HDD 2的电流密度-电压曲线图
Fig. 6. (a) J-V curves of electron dominated devices EDD 1 and EDD 2; (b) J-V curves of hole dominant devices HDD 1 and HDD 2
图 7 器件A (不含TPPCl) (a)和器件C (TPPCl浓度为2 mg/mL) (b)的电致发光机理图
Fig. 7. The diagram of EL mechanism of device A (without TPPCl) (a) and device C (with TPPCl of 2 mg/mL)(b).
表 1 不含/含TPPCl钙钛矿薄膜的TRPL拟合参数
Table 1. Summary of TRPL fitting parameters for perovskite films w/o TPPCl and with TPPCl.
Perovskite films $ {\tau _1} $/ns A1 $ {\tau _2} $/ns A2 $ {\tau _3} $/ns A3 ${\tau _{\rm ave} }$/ns w/o TPPCl 1.441±
0.0200.492±
0.0010.422±
0.0041.050±
0.0017.109±
0.0010.069±
0.0011.020±
0.001with TPPCl 4.677±
0.0800.394±
0.0011.027±
0.0082.705±
0.00125.007±
0.7100.048±
0.0011.849±
0.001
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表 2 不同浓度TPPCl的准二维PeLEDs的EL性能的参数
Table 2. Summary of EL performance parameters of quasi-2D PeLEDs with different TPPCl concentrations.
TPPCl
/(mg·mL–1) aVturn on
/(V) bLmax
/(cd·m–2) cCEmax
/(cd·A–1) dEQEmax
/% eFWHM
/nm f0 3.8 6212 9.2 2.4 18 1 3.6 16502 32.9 8.7 18 2 3.2 25285 65.9 17.3 18 4 3.2 13785 42.4 11.2 18 注: a钙钛矿薄膜中TPPCl的掺杂浓度; b器件亮度为1 cd/m2时的开启电压; c最大亮度; d最大电流效率; e最大外部量子效率; f 6 V电压下的半峰全宽.
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[1] Cheng L, Jiang T, Cao Y, Yi C, Wang N, Huang W, Wang J 2020 Adv. Mater. 32 1904163
Google Scholar
[2] Kim Y H, Cho H, Lee T W 2016 Proc. Natl. Acad. Sci. U. S. A. 113 11694
Google Scholar
[3] 瞿子涵, 储泽马, 张兴旺, 游经碧 2019 68 158504
Google Scholar
Qu Z H, Chu Z M, Zhang X W, You J B 2019 Acta Phys. Sin. 68 158504
Google Scholar
[4] Gao X, Zhang X, Yin W, Wang H, Hu Y, Zhang Q, Shi Z, Colvin V L, Yu W W, Zhang Y 2019 Adv. Sci. 6 1900941
Google Scholar
[5] Kim Y H, Kim S, Jo S H, Lee T W 2018 Small Methods 2 1800093
Google Scholar
[6] Zhou Y Y, Zhao Y X 2019 Energy Environ. Sci. 12 1495
Google Scholar
[7] 王润, 贾亚兰, 张月, 马兴娟, 徐强, 朱志新, 邓艳红, 熊祖洪, 高春红 2020 69 038501
Google Scholar
Wang R, Jia Y L, Zhang Y, Ma X J, Xu Q, Zhu Z X, Deng Y H, Xiong Z H, Gao C H 2020 Acta. Phys. Sin. 69 038501
Google Scholar
[8] Era M, Morimoto S, Tsutsui T, Saito S 1994 Appl. Phys. Lett. 65 676
Google Scholar
[9] Tan Z K, Moghaddam R S, Lai M L, et al. 2014 Nat. Nanotechnol. 9 687
Google Scholar
[10] Jiang Y, Wei J, Yuan M 2021 J. Phys. Chem. Lett. 12 2593
Google Scholar
[11] Zhang L, Sun C, He T, Jiang Y, Wei J, Huang Y, Yuan M 2021 Light Sci. Appl. 10 61
Google Scholar
[12] Chu Z, Ye Q, Zhao Y, Ma F, Yin Z, Zhang X, You J 2021 Adv. Mater. 33 2007169
Google Scholar
[13] Liu Z, Qiu W, Peng X, Sun G, Liu X, Liu D, Li Z, He F, Shen C, Gu Q, Ma F, Yip H L, Hou L, Qi Z, Su S J 2021 Adv. Mater. 33 2103268
Google Scholar
[14] Wang R, Zhang Y, Ma X J, Deng Y H, Shi J W, Wang X C, Jia Y L, Xu Q, Xiong Z H, Gao C H 2020 J. Mater. Chem. C 8 9845
Google Scholar
[15] Kim Y H, Kim S, Kakekhani A, et al. 2021 Nat. Photonics 15 148
Google Scholar
[16] Xu Q, Wang R, Jia Y L, He X L, Deng Y H, Yu F X, Zhang Y, Ma X J, Chen P, Zhang Y, Xiong Z H, Gao C H 2021 Org. Electron. 98 106295
Google Scholar
[17] Kim B W, Heo J H, Park J K, Lee D S, Park H, Kim S Y, Kim J H, Im S H 2021 J. Ind. Eng. Chem. 97 417
Google Scholar
[18] Cheng T, Qin C J, Watanabe S, Matsushima T, Adachi C 2020 Adv. Funct. Mater. 30 2001816
Google Scholar
[19] Zhao B, Lian Y, Cui L, et al. 2020 Nat. Electron. 3 704
Google Scholar
[20] Li T, Xiang T, Wang M S, Zhang W, Shi J S, Shao M, Xu T F, Ahmadi M, Wu X Y, Gao Z, Xu L, Chen P 2021 Laser Photonics Rev. 15 2000495
Google Scholar
[21] Shi D, Adinolfi V, Comin R, et al. 2015 Science 347 519
Google Scholar
[22] Li W J, Lynch V, Thompson H, Fox M A 1997 J. Am. Chem. Soc. 119 7211
Google Scholar
[23] Gao C H, Cai S D, Gu W, Zhou D Y, Wang Z K, Liao L S 2012 ACS Appl. Mater Interfaces 4 5211
Google Scholar
[24] Gao C H, Yu F X, Xiong Z Y, Dong Y J, Ma X J, Zhang Y, Jia Y L, Wang R, Chen P, Zhou D Y, Xiong Z H 2019 Org. Electron. 70 264
Google Scholar
[25] Jia Y L, Wang R, Zhang Y, Ma X J, Yu F X, Xiong Z Y, Zhou D Y, Xiong Z H, Gao C H 2019 J. Lumin. 209 251
Google Scholar
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