铯掺杂提升反梯度结构二维(CMA)2MA8Pb9I28钙钛矿薄膜及太阳电池的性能

王仕东; 闫雅婷; 王瑞英; 朱志立; 谷锦华

doi:10.7498/aps.72.20230357

摘要

相对于3D钙钛矿材料, 二维(2D)有机-无机杂化钙钛矿材料具有更好的稳定性. 然而由于载流子输运性差, 2D钙钛矿太阳电池效率较低. 为了提高2D钙钛矿太阳电池的效率, 制备了铯掺杂的具有反梯度结构的二维(CMA)₂MA₈Pb₉I₂₈薄膜. 研究结果发现: CsI掺杂能够改善(CMA)₂MA₈Pb₉I₂₈薄膜的形貌、增加晶粒尺寸、降低缺陷态密度, 并且提高了(CMA)₂MA₈Pb₉I₂₈钙钛矿薄膜的热稳定性. 最后, CsI掺杂浓度为10%时制备(CMA)₂MA₈Pb₉I₂₈钙钛矿太阳电池效率最高, 达到了14.67 %, 相对于未掺杂的电池效率(10.06%)提高了45.8%.

关键词:

Abstract

Compared with three-dimensional (3D) perovskites, two-dimensional (2D) perovskites have excellent environmental stability. However, the efficiency of 2D perovskite solar cells is still lower than that of their 3D counterparts owing to the poor carrier transport. In order to improve the efficiency of 2D perovskite solar cells, the cesium (Cs) doping 2D (CMA)₂MA₈Pb₉I₂₈ films with an inverse gradient structure (small n quantum well (QW) located at the surface and large n QW at the bottom) are prepared. The inverse gradient QW structure has the advantages of being more moisture-resistant (small n QW protects the vulnerable large n QW from being attacked by water molecules) and favoring self-driven charge transport (type-II band alignment between different phases). The results show that the quality and thermal stability of 2D (CMA)₂MA₈Pb₉I₂₈ film can be effectively improved by using Cs doping. The SEM images show that the film grains become larger, and the surface is smoother and more compact with CsI content increasing. When CsI increases to 15%, the surface becomes coarse. From the XRD, it can be seen that the crystallinity of perovskite is improved with CsI doping, and it reaches saturation when CsI content increases to 10%. The PL intensity of the film with 5% CsI is higher than the others’, implying a relatively low non-radiative recombination loss and low defect state in that film. Therefore, the minority carrier average lifetime of film doped with 5% CsI is the longest. The absorption is almost unchanged when CsI is doped. The thermal stability of film can be effectively improved when CsI exceeds 10%. Considering the SEM images, crystallinity, PL intensity, light absorption and thermal stability of perovskite, the optimized CsI doped concentration is 10% in our work. Finally, the highest efficiency of (CMA)₂MA₈Pb₉I₂₈ perovskite solar cells doped with 10% CsI content reaches to 14.67%, with a short-circuit current density (J_SC) of 23.16 mA/cm², an open-circuit voltage (V_oc) of 1.05 V and a fill factor (FF) of 60.75%. The efficiency of the undoped cells is 10.06%, which is lower than that of CsI doped cells (10%). Therefore, CsI doping is an effective method to further improve the efficiency and thermal stability of 2D perovskite solar cells.

Keywords:

作者及机构信息

郑州大学物理学院(微电子学院), 材料物理教育部重点实验室, 郑州　450052

通信作者: 谷锦华, gujinh@zzu.edu.cn

基金项目: 国家自然科学基金(批准号: 12274375)资助的课题.

Authors and contacts

Key Laboratory of Materials Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China

Corresponding author: Gu Jin-Hua, gujinh@zzu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 12274375)

文章全文 : translate this paragraph

参考文献

[1]	Burschka J, Pellet N, Moon S J, Humphry-Baker R, Gao P, Nazeeruddin M K, Grätzel M 2013 Nature 499 316 Google Scholar
[2]	Stranks S D, Snaith Henry J 2015 Nat. Nanotechnol. 10 391 Google Scholar
[3]	Lee M M, Teuscher J, Miyasaka T, Murakami T N, Snaith H J 2012 Science 338 643 Google Scholar
[4]	Kim H S, Lee C R, Im J H, et al. 2012 Sci. Rep. 2 591 Google Scholar
[5]	Wang M, Tan S, Zhao Y, et al. 2021 Adv. Funct. Mater. 31 2007520 Google Scholar
[6]	Ponseca C S, Savenije T J, Abdellah M, et al. 2014 J. Am. Chem. Soc. 136 5189 Google Scholar
[7]	Brenner T M, Egger D A, Kronik L, Hodes G, Cahen D 2016 Nat. Rev. Mater. 1 15007 Google Scholar
[8]	Stoumpos C C, Malliakas C D, Kanatzidis M G 2013 Inorg. Chem. 52 9019 Google Scholar
[9]	Zhao Y, Zhu K 2016 Chem. Soc. Rev. 45 655 Google Scholar
[10]	Wolf S D, Holovsky J, Moon S J, et al. 2014 J. Phys. Chem. Lett. 5 1035 Google Scholar
[11]	Hao F, Stoumpos C C, Cao D H, Chang R P H, Kanatzidis M G 2014 Nat. Photonics 8 489 Google Scholar
[12]	Wu Z W, Bai S, Xiang J, Yuan Z C, Yang Y G, Cui W, Gao X Y, Liu Z, Jin Y Z, Sun B Q 2014 Nanoscale 6 10505 Google Scholar
[13]	Kim H S, Seo J Y, Park N G 2016 Chem. Sus. Chem 9 2528 Google Scholar
[14]	Leijtens T, Eperon G E, Noel N K, Habisreutinger S N, Petrozza A, Snaith H J 2015 Adv. Energy Mater. 5 1500963 Google Scholar
[15]	Jeon N, Noh J, Yang W, Kim Y, Ryu S, Seo J, Seok S 2015 Nature 517 476 Google Scholar
[16]	Tan H, Jain A, Voznyy O, et al. 2017 Science 355 722 Google Scholar
[17]	Raghavan C M, Chen T P, Li S S, et al. 2018 Nano Lett. 18 3221 Google Scholar
[18]	Wei Y, Chu H L, Tian Y Y, Chen B Q, Wu K F, Wang J H, Yang X C, Cai B, Zhang Y F, Zhao J J 2019 Adv. Energy Mater. 1 900612 Google Scholar
[19]	Wu Y H, Ding Y, Liu X Y, Ding X H, Liu X P, Pan X, Dai S Y 2020 Sci. China Mater. 63 47 Google Scholar
[20]	Chang R G, Yan Y T, Zhang J Y, Zhu Z L, Gu J H 2020 Thin Solid Films. 712 138279 Google Scholar

施引文献

图 1 钙钛矿太阳电池结构

Fig. 1. Structure of perovskite solar cell.

下载: 全尺寸图片幻灯片

图 2 从正面和背面激发的(CMA)₂(MA)₈Pb₉I₂₈薄膜的PL光谱

Fig. 2. PL spectra of (CMA)₂(MA)₈Pb₉I₂₈ film excited from front and back side.

下载: 全尺寸图片幻灯片

图 3 不同CsI掺杂浓度(CMA)₂MA₈Pb₉I₂₈薄膜的SEM图像　(a) Cs₀-2D; (b) Cs₃-2D; (c) Cs₅-2D; (d) Cs₁₀-2D; (e) Cs₁₅-2D

Fig. 3. SEM surface images of (CMA)₂MA₈Pb₉I₂₈ perovskite films doped with different CsI content: (a) Cs₀-2D; (b) Cs₃-2D; (c) Cs₅-2D; (d) Cs₁₀-2D; (e) Cs₁₅-2D.

下载: 全尺寸图片幻灯片

图 4 不同CsI掺杂浓度(CMA)₂MA₈Pb₉I₂₈薄膜　(a) XRD谱; (b) (111)衍射峰半高宽

Fig. 4. (CMA)₂MA₈Pb₉I₂₈ perovskite films doped with different CsI content: (a) XRD patterns; (b) full width of half maximum at (111) peak.

下载: 全尺寸图片幻灯片

图 5 FTO玻璃衬底上, 不同CsI掺杂浓度(CMA)₂MA₈Pb₉I₂₈薄膜　(a) PL谱; (b)归一化PL谱; (c)时间分辨PL谱

Fig. 5. (CMA)₂MA₈Pb₉I₂₈ perovskite films doped with different CsI content on FTO substrates: (a) PL spectra; (b) normalization of the PL spectra; (c) time-resolved PL spectra.

下载: 全尺寸图片幻灯片

图 6 不同CsI掺杂浓度(CMA)₂MA₈Pb₉I₂₈的吸收谱

Fig. 6. Absorption spectra of (CMA)₂MA₈Pb₉I₂₈ films doped with different CsI content.

下载: 全尺寸图片幻灯片

图 7 不同CsI掺杂浓度(CMA)₂MA₈Pb₉I₂₈ 薄膜在不同退火温度的照片

Fig. 7. Photographs of different CsI content doping (CMA)₂MA₈Pb₉I₂₈ films annealed at different temperatures.

下载: 全尺寸图片幻灯片

图 8 不同CsI掺杂浓度(CMA)₂MA₈Pb₉I₂₈钙钛矿太阳电池的J-V曲线

Fig. 8. J-V curves of (CMA)₂MA₈Pb₉I₂₈ perovskite solar cells doped with different CsI content.

下载: 全尺寸图片幻灯片

表 1 不同CsI掺杂浓度(CMA)₂MA₈Pb₉I₂₈钙钛矿太阳电池光伏参数

Table 1. Photovoltaic performance of (CMA)₂MA₈Pb₉I₂₈ perovskite solar cells doped with different CsI content.

Sample	J_sc/(mA·cm^–2)	V_oc/V	FF/%	PCE/%
Cs₀-2D	21.05	1.01	48.40	10.06 ^a)
Cs₀-2D	(21.33±0.28)	(1.00±0.01)	(45.67±2.73)	(9.43±0.63)^b)
Cs₃-2D	21.36	1.03	49.18	10.68 ^a)
Cs₃-2D	(20.74±1.29)	(1.02±0.01)	(45.66±3.52)	(9.66±1.02)^b)
Cs₅-2D	22.08	1.04	56.96	13.08 ^a)
Cs₅-2D	(22.62±0.54)	(1.04±0)	(49.39±7.57)	(11.56±1.52)^b)
Cs₁₀-2D	23.16	1.05	60.75	14.67 ^a)
Cs₁₀-2D	(21.90±1.26)	(1.04±0.01)	(56.07±4.68)	(13.49±1.18)^b)
Cs₁₅-2D	22.71	1.03	58.58	14.12 ^a)
Cs₁₅-2D	(21.59±1.12)	(1.00±0.03)	(55.20±3.38)	(12.23±1.89)^b)
注: a)为最高效率; b)为平均值.

下载: 导出CSV

[1]	Burschka J, Pellet N, Moon S J, Humphry-Baker R, Gao P, Nazeeruddin M K, Grätzel M 2013 Nature 499 316 Google Scholar
[2]	Stranks S D, Snaith Henry J 2015 Nat. Nanotechnol. 10 391 Google Scholar
[3]	Lee M M, Teuscher J, Miyasaka T, Murakami T N, Snaith H J 2012 Science 338 643 Google Scholar
[4]	Kim H S, Lee C R, Im J H, et al. 2012 Sci. Rep. 2 591 Google Scholar
[5]	Wang M, Tan S, Zhao Y, et al. 2021 Adv. Funct. Mater. 31 2007520 Google Scholar
[6]	Ponseca C S, Savenije T J, Abdellah M, et al. 2014 J. Am. Chem. Soc. 136 5189 Google Scholar
[7]	Brenner T M, Egger D A, Kronik L, Hodes G, Cahen D 2016 Nat. Rev. Mater. 1 15007 Google Scholar
[8]	Stoumpos C C, Malliakas C D, Kanatzidis M G 2013 Inorg. Chem. 52 9019 Google Scholar
[9]	Zhao Y, Zhu K 2016 Chem. Soc. Rev. 45 655 Google Scholar
[10]	Wolf S D, Holovsky J, Moon S J, et al. 2014 J. Phys. Chem. Lett. 5 1035 Google Scholar
[11]	Hao F, Stoumpos C C, Cao D H, Chang R P H, Kanatzidis M G 2014 Nat. Photonics 8 489 Google Scholar
[12]	Wu Z W, Bai S, Xiang J, Yuan Z C, Yang Y G, Cui W, Gao X Y, Liu Z, Jin Y Z, Sun B Q 2014 Nanoscale 6 10505 Google Scholar
[13]	Kim H S, Seo J Y, Park N G 2016 Chem. Sus. Chem 9 2528 Google Scholar
[14]	Leijtens T, Eperon G E, Noel N K, Habisreutinger S N, Petrozza A, Snaith H J 2015 Adv. Energy Mater. 5 1500963 Google Scholar
[15]	Jeon N, Noh J, Yang W, Kim Y, Ryu S, Seo J, Seok S 2015 Nature 517 476 Google Scholar
[16]	Tan H, Jain A, Voznyy O, et al. 2017 Science 355 722 Google Scholar
[17]	Raghavan C M, Chen T P, Li S S, et al. 2018 Nano Lett. 18 3221 Google Scholar
[18]	Wei Y, Chu H L, Tian Y Y, Chen B Q, Wu K F, Wang J H, Yang X C, Cai B, Zhang Y F, Zhao J J 2019 Adv. Energy Mater. 1 900612 Google Scholar
[19]	Wu Y H, Ding Y, Liu X Y, Ding X H, Liu X P, Pan X, Dai S Y 2020 Sci. China Mater. 63 47 Google Scholar
[20]	Chang R G, Yan Y T, Zhang J Y, Zhu Z L, Gu J H 2020 Thin Solid Films. 712 138279 Google Scholar

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铯掺杂提升反梯度结构二维(CMA)₂MA₈Pb₉I₂₈钙钛矿薄膜及太阳电池的性能

Cesium doping for improving performance of inverse-graded 2D (CMA)₂MA₈Pb₉I₂₈ perovskite film and solar cells

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Abstract

作者及机构信息

郑州大学物理学院(微电子学院), 材料物理教育部重点实验室, 郑州　450052

通信作者: 谷锦华, gujinh@zzu.edu.cn

Authors and contacts

Key Laboratory of Materials Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China

Corresponding author: Gu Jin-Hua, gujinh@zzu.edu.cn

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