Research progress of light irradiation stability of functional layers in perovskite solar cells

Li Yan; He Hong; Dang Wei-Wu; Chen Xue-Lian; Sun Can; Zheng Jia-Lu

doi:10.7498/aps.70.20201762

Abstract

The low-cost, high-efficiency and easy fabrication of perovskite solar cells make them an ideal candidate for replacing industrialized silicon solar cells, and thus reforming the current energy supply structure. However, the industrialization of perovskite solar cells is now restricted due to its poor stability. In this article, the intrinsic ion migration behavior in the perovskite film under light irradiation is introduced, which is mainly responsible for hysteresis, fluorescence quenching/enhancement and the failure of solar cell. In addition, the typical ultraviolet light instability of TiO₂/perovskite interface, and the light instability of hole transport layer and metal electrodes are also discussed subsequently. As a light-dependent device, improving its light radiation stability is essential for making it suitable to various environmental applications.

Keywords:

Authors and contacts

1.
School of Materials Science and Engineering, Xi’an Shiyou University, Xi’an 710065, China
2.
College of Intelligent Manufacturing, Shaanxi Institute of Technology, Xi’an 710300, China

Corresponding author: Li Yan, li1988yan@163.com

Funds: Project supported by the Natural Science Foundation Research Project of Shaanxi Province, China (Grant Nos. 2019JQ-286, 2018JQ-5130), the Scientific Research Program Funded by Shaanxi Provincial Education Department, China (Grant Nos. 19JK0660, 20JK0507), the State Key Laboratory of Metal Material Strength of Xi'an Jiaotong University, China, the Materials Science and Engineering of Provincial Advantage Disciplines in Xi’an Shiyou University, China (Grant No. YS37020203), and the Postgraduate Innovation and Practical Ability Training Program of Xi'an Shiyou University, China (Grant No. YCS20212115)

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图 1 PSCs的(a)正向和(c)反向基本结构; (b)钙钛矿材料的晶体结构; 在(d)短路和(e)开路状态下PSCs内部的能级结构; (f) PSCs不稳定的主要诱因示意图^[14]

Figure 1. Basic structure of PSCs in (a) regular and (c) inverted configurations; (b) crystalline structure of perovskite materials; general energy band diagram at (d) short circuit and (e) open circuit; (f) main contributing factors in the degradation processes of PSCs^[14].

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图 2 PSCs内部电荷-载流子动力学过程　(a)载流子动力学过程; (b)动力学过程发生的时间尺度^[37]

Figure 2. General charge-carrier processes within a PSC: (a) Carrier dynamics processes; (b) corresponding time scale of the cell^[37].

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图 3 ABX₃钙钛矿晶体结构的变化　(a), (b)标准钙钛矿结构; (c) BX₆八面体的扭曲和旋转引起的结构变化; (d)—(f)过大的A位原子对钙钛矿结构的破坏^[38]

Figure 3. Structure of the ABX₃: (a), (b) Standard perovskite structure; (c) structural changes caused by the twist and rotation of BX₆ octahedron; (d)–(f) destruction of perovskite structure by too large A atom^[38].

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图 4 固定电压下PSCs内部的能级结构对齐关系　(a)和(b)正向扫描; (c)和(d)反向扫描; 其中(a)和(c)不考虑离子迁移行为, (b)和(d)考虑离子迁移行为^[60]

Figure 4. Schematic illustration of the ion migration: (a) and (b) Electronic band structure alignments of the PSCs at a fixed bias under forward scan; (c) and (d) reverse scan; (a) and (c) without, (b) and (d) with consideration of ion migration^[60].

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图 5 离子和电子分布示意图(左侧)和相应的能级分布(右侧)　(a)黑暗中; (b)光照的瞬间; (c)光辐照一段时间后; 其中, 红色阴影区域为耗尽区域, 阴影等级表示电场强度, 由于光照下产生的内建电场, 图(b)和(c)中耗尽区域宽度逐渐减小, 在图(b)中, 左侧的虚线箭头代表离子迁移到平衡状态之前, 电子和空穴在萎缩的耗尽层区域的重新分布, 与此同时能带的弯曲减少了对外的静电流^[70]

Figure 5. Schematics of ionic and electronic carrier distributions (left) and corresponding band diagrams (right) for three situations of interest: (a) Dark equilibrium; (b) immediately after light turns on; (c) after prolonged illumination. Where the red-color shaded region is the depletion region with the shade grading indicating the electric field strength, note that the depletion region width reduces in panel (b) and (c), because of photovoltage bulid-up after illumination; in panel (b), dashed arrows on the left indicate redistribution of electrons and holes upon the shrinkage of the depletion region but before ions move to new equilibriums, while distortion of the band diagram on the right results in a reduction in the net currents^[70].

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图 6 光曝后碘的重新分布现象　(a)不同光曝时间下MAPbI₃薄膜的瞬态荧光淬灭结果, 其中脉冲激发光源为470 nm, 1.2 kJ/cm²; (b) ToF-SIMS采集的钙钛矿薄膜内碘元素在深度方向的信息, 标尺为10 μm; (c)是对图(b)中蓝线区域碘分布的线扫描结果(右轴), 照明激光的空间轮廓测试结果被显示在左轴^[49]

Figure 6. Iodide redistribution after light soaking: (a) A series of time resolved photoluminescence decays from a MAPbI₃ film measured over time under illumination before ToF-SIMS measurements, and the sample was photoexcited with pulsed excitation (470 nm, 1.2 kJ/cm²); (b) ToF-SIMS image of the iodide (I^–) distribution summed through the film depth (the image has been adjusted to show maximum contrast), scale bar, 10 μm; (c) line scan of the blue arrow in panel (b) to show the iodide distribution (right axis), where the measured spatial profile of the illumination laser (blue) is shown on the left axis^[49].

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图 7 SKPM在MAPbI₃/Au (a)−(c)和MAPbI₃/PMMA/SiO₂/Au (d)−(f)电极界面的单线扫描结果　(a)和(d)从左侧为两类样品加上+9 V的偏压; (b), (c), (e)和(f)是关掉+9 V正向偏压后接地; (g)是去掉+9 V偏压后MAPbI₃/PMMA/SiO₂/Au样品中的电荷密度分布; (h)是去掉偏压后, 两类样品中电子和离子的分布示意图^[54]

Figure 7. SKPM scan of a single line within the electrode gap of (a)−(c) MAPbI₃/Au and (d)−(f) MAPbI₃/PMMA/SiO₂/Au, measured (a), (d) with a +9 V bias applied to the right electrode and (b), (c), (e), (f) at 0 V bias after turning off the +9 V bias; the black line in (b) displays the SKPM CPD signal prior to biasing; (g) charge density in MAPbI₃/PMMA/SiO₂/Au after bias; (h) illustration of electronic and ionic charge distribution after electric biasing^[54].

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图 8 在Pb/MAPbI₃/AgI/Ag电池中(a)电场作用下带电离子的流动方向; (b)电池A, B面的图片; (c) B面的SEM图片; (d)在10 nA直流电下服役1周后A, B两面的XRD; (e) B面Pb元素的EDS^[19]

Figure 8. (a) Flow directions of the charged ion species in a Pb/MAPbI₃/AgI/Ag cell under electrical bias; (b) images for surfaces A and B; (c) SEM image of surface B on the Pb pellet; (d) XRD patterns of surfaces A and B of the Pb disk after applying a direct current of 10 nA for a week; (e) EDS spectrum for surface B of Pb^[19].

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图 9 紫外线照射下TiO₂材料的光催化(a)−(d)行为及机理(TiO₂材料中存在大量缺陷, 通过吸附和脱附O₂分子的过程, 形成深能级缺陷Ti⁴⁺, 它通过从卤素负离子中提取电子的方式破坏了钙钛矿结构的电平衡)^[98]

Figure 9. Photocatalysis of TiO₂ material under UV illumination: (a)−(d) there are abundant defects in TiO₂ material. During the absorption and deabsorption of the O₂ molecular, the positive charge (Ti⁴⁺) is formed, which will extract electrons from halogen negative ions, thus destroying the electrical balance of perovskite structure^[98].

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图 10 不同温度下(a) CsBr钝化后的电池和(b)无CsBr钝化的电池的界面电容数值; (c) CsBr钝化后的电池和(d)无CsBr钝化的电池在特定测试频率下的Arrhenius点, 基于此可获得缺陷的活化能^[117]

Figure 10. Temperature dependence of capacitance for (a) device with CsBr and (b) control device without CsBr. Arrhenius plot of the characteristic frequencies to extract the defect activation energy for (c) device with CsBr and (d) control device without CsBr^[117].

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图 11 在(a) 85 ℃下24 h处理之前和(b)处理之后, 断面内ToF-SIMS测试的元素分布; (c)热处理后不同温度下断面内Ag^–, I^–和CN分布^[126]

Figure 11. ToF-SIMS elemental depth profiles (a) before and (b) after a thermal treatment at 85 ℃ for 24 h; (c) depth profiles of Ag^–, I^– and CN^– after different temperature of thermal treatment^[126].

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表 1 钙钛矿材料的离子活化能

Table 1. Ion activation energy of the perovskite material

材料	迁移离子	E_A/eV	文献
MAPbI₃	I^–	0.58	[47]
	Pb²⁺	2.31
	MA⁺	0.84
MAPbI₃	I^–	0.19 ± 0.05	[49]
MAPbI₃	I^–	0.1	[50]
	Pb²⁺	0.8
	MA⁺	0.5
MAPbI₃	I^–	0.33	[16]
MAPbI₃	MA⁺	0.55	[16]
MAPbI₃	MA⁺	0.36	[18]
MAPbI₃	$ {\rm{I}}_{\rm{i}}^{0} $	0.06	[21]
	$ {\rm{I}}_{\rm{i}}^{-} $	0.08
	$ {\rm{I}}_{\rm{i}}^{-} $(e/h)	0.05
	$ {\rm{V}}_{\rm{I}}^{0} $	0.15
	$ {\rm{V}}_{\rm{I}}^{+} $	0.09
	$ {\rm{V}}_{\rm{I}}^{+} $(e/h)	0.15

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