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溶液法是新型光电器件制备的重要手段, 然而以钙钛矿半导体材料为代表的薄膜样品制备通常需要在手套箱环境下完成, 传统的实验表征大多在空气环境下进行, 这显然很难反映薄膜结构与器件性能间的真实关联, 因此急需对溶液成膜过程的微结构演变开展原位实时研究. 为了实现溶液法成膜中的结构与形貌的同步辐射掠入射广角散射实时观测, 本文结合上海同步辐射光源线站布局, 报道了一种基于手套箱的原位成膜观测装置, 可实现标准手套箱环境(c(H2O, O2) < 1×10–6)下远程控制薄膜旋涂、涂布及样品后处理, 并实时可视化监测微结构和形貌演变. 基于该装置进行的钙钛矿薄膜狭缝涂布大面积成膜结晶过程的原位GIWAXS/GISAXS (grazing incidence wide and small angle X-ray scattering)可视化测试揭示了薄膜微结构转变的内在驱动力: 钙钛矿薄膜沉积界面层的优化对提升钙钛矿成核速率、诱导结晶择优取向、形成晶粒有序堆叠等具有“共性作用”, 同时在成膜过程中的新生中间相显著提升软晶格薄膜质量和稳定性. 基于各层均采用卷对卷全溶液狭缝涂布方法制备的大面积全柔性三维钙钛矿薄膜太阳能电池转换效率提升至5.23% (单个器件面积约15 cm2), 为迄今报道的这一体系该尺寸的全溶液狭缝涂布柔性钙钛矿器件的最高器件效率之一. 因而, 基于该同步辐射原位GIWAXS/S/GISAXS装置可以获得控制薄膜生长界面特性和薄膜品质的关键工艺, 指导优化制备薄膜的最佳工艺条件.
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关键词:
- 同步辐射掠入射X射线散射 /
- 手套箱环境 /
- 钙钛矿薄膜 /
- 软晶格 /
- 微结构演化
Solution method is an important means of fabricating optoelectronic devices. During the thin film sample preparation, organic or inorganic perovskite semiconductor material usually needs to be finished in a glove box. However, most of the traditional experimental characterizations under the air environment, it is hard to reflect the reality of the structure and performance between film and device, therefore it is urgently needed to solve the microstructure evolutions of these semiconductor films based on in situ real-time representation technique. In this work, we report a synchrotron-based grazing incidence wide and small-angle scattering (GIWAXS and GISAXS) in situ real-time observation technique combined with a mini glove box, thereby realizing the standard glove box environment (H2O, O2 content all reached below 1×10–6) under remote control film spin coating or slot-die preparation and various sample post-processing. Meanwhile, this technique can real-time monitor the microstructure and morphology evolution of semiconductor film during fabrication. Based on the in situ device and GIWAXS, SnO2 ETL interface induced perovskite growth crystallization process shows that CQDs additive can result in three-dimensional perovskite, with the random orientation growth changing into highly ordered vertical orientation, meanwhile can effectively restrain the low-dimensional perovskite domain formation, helping to reveal the film microstructure transformation of inner driving force and providing the perovskite device preparation process optimized with experimental and theoretical basis. The conversion efficiency of large-area fully flexible three-dimensional perovskite thin film solar cells prepared by the roll-to-roll total solution slit coating method is increased to 5.23% (the area of a single device is ~15 cm2). Therefore, using the in situ synchrotron-based glove box device, the microstructure evolution and the associated device preparation conditions of perovskite and organic semiconductor thin films can be controlled, and the thin film growth interface characteristics and film quality can be further controlled, which is the key technology to control the optimization process conditions of semiconductor thin films and devices.-
Keywords:
- grazing incidence wide-angle angle scattering /
- glove box enviromental /
- perovskite film /
- soft lattice /
- microstructure evolution
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图 1 基于定制小型标准手套箱(c (H2O, O2) ~ 1×10–6)的同步辐射原位涂布成膜观测装置 (a) 原位装置布局; (b) 手套箱效果图; (c) 原位装置实物图; (d) 实时涂布
Fig. 1. A custom small standard glove box (c (H2O, O2< 1×10–6) of synchrotron radiation in situ slot-die film-forming observation device: (a) Schematic of in situ device; (b) glove box; (c) automatic drip system and the photo picture of in situ device object; (d) the photo picture of drip system.
图 2 (a) 原位涂布和同步辐射观测示意图; (b)—(e) 沉积在SnO2电子传输层上的3D钙钛矿涂布60 s过程中0, 10, 30, 60 s四个时间点的原位GIWAXS图; (f)—(i) 沉积在CQDs-SnO2 电子传输层上3D钙钛矿旋涂60 s过程中0, 10, 30, 60 s四个时间点的原位GIWAXS图
Fig. 2. (a) In situ slot-die coating synchrotron radiation observation. (b)–(e) In situ GIWAXS patterns of 3D perovskite thin films deposited on SnO2 electron transport layer (ETL) during the slot-die coating process from 0 to 60 s: (b) 0 s; (c) 10 s; (d) 30 s; (e) 60 s. (f)–(i) In situ GIWAXS patterns of 3D perovskite thin films deposited on CQDs-SnO2 ETL during the slot-die coating process from 0 to 60 s: (f) 0 s; (g) 10 s; (h) 30 s; (i) 60 s.
图 3 (a)—(d) 沉积在SnO2 电子传输层上的3D钙钛矿涂布60 s过程中0, 10, 30, 60 s四个时间点的原位GISAXS图; (e)—(h) 沉积在CQDs-SnO2 电子传输层上3D钙钛矿涂布60 s过程中0, 10, 30, 60 s四个时间点的原位GISAXS图; (i)—(k) 钙钛矿涂布60 s过程中0, 30, 60 s三个时间点的GISAXS一维积分数据
Fig. 3. (a)–(d) In situ GISAXS patterns of 3D perovskite thin films deposited on SnO2 ETL during the slot-die coating process from 0 to 60 s: (a) 0 s; (b) 10 s; (c) 30 s; (d) 60 s. (e)–(h) In situ GISAXS patterns of 3D perovskite thin films deposited on CQDs-SnO2 ETL during the slot-die coating process from 0 to 60 s: (e) 0 s; (f) 10 s; (g) 30 s; (h) 60 s. (i)–(k) 1D integrated GISAXS of 3D perovskite (Per) thin films deposited on CQDs-SnO2 ETL during the slot-die coating process: (i) 0 s; (j) 30 s; (k) 60 s.
图 4 基于卷对卷全溶液狭缝涂布方法制备的全柔性钙钛矿太阳能电池(器件结构为PET/ITO/SnO2 ETL/3D perovskite (2MOE)/Spiro/Au) (a) SnO2 电子传输层上制备的器件; (b) CQDs-SnO2 电子传输层上制备的器件, 单个器件有效面积为~15 cm2; (c)大面积全柔性3D钙钛矿太阳能电池
Fig. 4. Fully roll-to-roll (R2R) slot-die printed flexible perovskite solar cells with device structure of PET/ITO/SnO2 ETL/3D perovskite (2MOE)/Spiro/Au: (a) Prepared on the SnO2 electron transport layer and (b) prepared on CQDs-SnO2 electron transport layer, with an effective area of ~15 cm2 per unit cell; (c) the printed flexible perovskite solar cells with device structure of PET/ITO/SnO2 ETL/3D perovskite (2MOE)/Spiro/Au.
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[1] Ajay K J, Ashish K, Tsutomu M 2019 Chem. Rev. 119 3036
Google Scholar
[2] https://www.nrel.gov/pv/cell-efficiency.html [2023-11-22]
[3] Han T H, Tan S, Xue J J, Meng L, Lee J W, Yang Y 2019 Adv. Mater. 31 1803515
Google Scholar
[4] Luo D Y, Su R, Zhang W, Gong Q H, Zhu R 2020 Nat. Rev. Mater. 5 44
[5] Snaith H J 2013 J. Phys. Chem. Lett. 4 3623
Google Scholar
[6] Zhang H, Wang H, Williams S, Xiong D H, Zhang W J, Chueh C C, Chen W, Alex K J 2017 Adv. Mater. 29 1606608
Google Scholar
[7] Yang Y, Feng S L, Xu W D, Li M, Li L, Zhang X M, Ji G W, Zhang X N, Wang Z K, Xiong Y M, Cao L, Sun B Q, Gao X Y 2017 ACS Appl. Mater. interfaces 9 23141
Google Scholar
[8] Li F C, Yuan J Y, Ling X, Zhang Y, Yang Y G, Cheun S H, Carr H, Gao X F, Ma W L 2018 Adv. Funct. Mater. 28 1706377
Google Scholar
[9] Li H, Zuo C T, Angmo D, Weerasinghe H, Gao M, Yang J L 2022 Nano-Micro Lett. 14 79
Google Scholar
[10] Tan H, Jain A, Voznyy O, Lan X, Arquer F P, Fan J, Quintero-Bermudez R, Yuan M J, Zhang B, Zhao Y C, Fan F J, Li P C, Quan L, Zhao Y B, Lu Z H, Yang Z Y, Hoogland S, Sargent E H 2017 Science 355 722
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Google Scholar
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Google Scholar
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