近年来反式结构钙钛矿电池因具有稳定性高、迟滞效应小及易构成高效叠层器件等优点而受到广泛关注,空穴传输层的选择与优化对电池的性能至关重要。NiOx基空穴传输层具有化学稳定性好、空穴迁移率高、带隙宽度大等特点,在反式钙钛矿电池中得到广泛应用。系统介绍了相比其他空穴传输层材料,选择NiOx基空穴传输层材料的优劣势,重点阐述了氧气等离子体处理法和紫外臭氧处理法的研究进展及对薄膜质量、表面性能和能带排列的影响,详细论述了通过碱和碱土金属掺杂、过渡金属掺杂、稀土金属及有机分子掺杂以及共掺杂的方法提升NiOx基空穴传输层光、电性能的进展情况以及对器件转换效率和稳定性的影响,最后对未来NiOx基反式结构钙钛矿电池规模化制备应提升的关键点进行了展望。
In recent years,inverted perovskite solar cells (IPSCs) have garnered significant attention due to their high stability,low hysteresis and easy integration into tandem devices with high efficiency.The selection and optimization of hole transport layer (HTL) are crucial to the performance of these solar cells.Owing to its chemical stability,high hole mobility and wide bandgap,NiOx-based hole transport layer is widely applied in IPSCs.This paper systematically introduced the advantages and disadvantages of NiOx-based hole transport layer compared with other hole transport layer materials,and focused on the research progress of oxygen plasma treatment and ultraviolet ozone treatment,as well as their effects on film quality,surface properties and band alignment.It discussed in detail the advancements in enhancing the optical and electrical properties of NiOx-based hole transport layer by alkali and alkaline earth metal doping,transition metal doping,rare earth metal and organic molecule doping,and co-doping methods,as well as the impact on the conversion efficiency and stability of devices.Finally,it discussed the key points that need to be improved for the large-scale preparation of NiOx-based IPSCs in the future.
[1] Jiang Y,Xu T F,Du H Q,et al.Organic-inorganic hybrid nature enables efficient and stable CsPbI3-based perovskite solar cells[J].Joule,2023,7:2905-2922.
[2] Zhang X,Wu S F,Zhang H,et al.Advances in inverted perovskite solar cells[J].Nat Photon,2024,18:1243-1253.
[3] Liu Q J,Ding L,Fu J F,et al.Enhancing the efficiency and stability of inverted perovskite solar cells and modules through top interface modification with N-type semiconductors[J].Angewandte Chemie International Edition,2025,64(4):e202416390.
[4] Kojima A,Teshima K,Shirai Y,et al.Organometal halide perovskites as visible-light sensitizers for photovoltaic cells[J].Journal of the American Chemical Society,2009,131(17):6050-6051.
[5] Green M A,Dunlop E D,Yoshita M,et al.Solar cell efficiency tables (version 66)[J].Progress in Photovoltaics,2025,33(7):795-810.
[6] Zhu X L,Li M B,Mo K W,et al.A surface-reconstructed bilayer heterojunction enables efficient and stable inverted perovskite solar cells[J].Advanced Materials,2024,36:2409340.
[7] Zhang Q,Huang H,Yang Y Y,et al.A universal ternary solvent system of surface passivator enables perovskite solar cells with efficiency exceeding 26%[J].Advanced Materials,2024,36:2410390.
[8] Liu C,Yang Y,Chen H,et al.Bimolecularly passivated interface enables efficient and stable inverted perovskite solar cells[J].Science,2023,38:810-815.
[9] 张美荣,祝曾伟,杨晓琴,等.迈向效率大于30%的钙钛矿/晶硅叠层太阳能电池技术的研究进展[J].物理学报,2023,72(5):058801.
[10] Sahli F,Werner J,Kamino B A,et al.Fully textured monolithic perovskite/silicon tandem solar cells with 25.2% power conversion efficiency[J].Nature Materials,2018,17:820-826.
[11] Liang H M,Feng J G,Rodríguez-Gallegos C D,et al.29.9%-efficient,commercially viableperovskite/CuInSe2 thin-film tandem solar cells[J].Joule,2023,7:2859-2872.
[12] Liu X X,Zhang J J,Tang L T,et al.Over 28% efficiency perovskite/Cu(InGa)Se2 tandem solar cells:highly efficient sub-cells and their bandgap matching[J].Energy & Environmental Science,2023,16:5029-5042.
[13] Kwon Y S,Lim J,Yun H J,et al.A diketopyrrolopyrrole-containing hole transporting conjugated polymer for use in efficient stable organic-inorganic hybrid solar cells based on a perovskite[J].Energy & Environmental Science,2014,7:1454-1460.
[14] Kim G W,Kang G,Kim J,et al.Dopant-free polymeric hole transport materials for highly efficient and stable perovskite solar cells[J].Energy & Environmental Science,2016,9:2326-2333.
[15] Liu J W,Pathak S,Stergiopoulos T,et al.Employing PEDOT as the p-type charge collection layer in regular organic-inorganic perovskite solar cells[J].Journal of Physical Chemistry Letters,2015,6(9):1666-1673.
[16] Kranthiraja K,Gunasekar K,Kim H,et al.High-performance long-term-stable dopant-free perovskite solar cells and additive-free organic solar cells by employing newly designed multirole π-conjugated polymers[J].Advanced Materials,2017,29(23):1700183.
[17] Xie F X,Chen C C,Wu Y Z,et al.Vertical recrystallization for highly efficient and stable formamidinium-based inverted-structure perovskite solar cells[J].Energy & Environmental Science,2017,10:1942-1949.
[18] Tseng Z L,Chen L C,Chiang C H,et al.Efficient inverted-type perovskite solar cells using UV-ozone treated MoOx and WOx as hole transporting layers[J].Sol Energy,2016,139:484-488.
[19] Cheng M,Li Y Y,Safdari M,et al.Efficient perovskite solar cells based on a solution processable nickel(Ⅱ) phthalocyanine and vanadium oxide integrated hole transport layer[J].Advanced Energy Materials,2017,7(14):1602556.
[20] Qin P,Tanaka S,Ito S,et al.Inorganic hole conductor-based lead halide perovskite solar cells with 12.4% conversion efficiency[J].Nature Communications,2014,5:3834.
[21] Igbari F,Li M,Hu Y,et al.A room-temperature CuAlO2 hole interfacial layer for efficient and stable planar perovskite solar cells[J].Journal of Materials Chemistry A,2016,4:1326-1335.
[22] Son M K,Steier L,Schreier M,et al.A copper nickel mixed oxide hole selective layer for Au-free transparent cuprous oxide photocathodes[J].Energy & Environmental Science,2017,10:912-918.
[23] Ratcliff E L,Meyer J,Steirer K X,et al.Evidence for near-surface NiOOH species in solution-processed NiOx selective interlayer materials:impact on energetics and the performance of polymer bulk heterojunction photovoltaics[J].Chemistry of Materials,2011,23:4988-5000.
[24] Nishihara Y,Chikamatsu M,Kazaoui S,et al.Influence of O2 plasma treatment on NiOx layer in perovskite solar cells[J].Japanese Journal of Applied Physics,2018,57:04FS07.
[25] Zhao Q Q,Fang C,Tie F G,et al.Regulating the Ni3+/Ni2+ ratio of NiOx by plasma treatment for fully vacuum-deposited perovskite solar cells[J].Materials Science in Semiconductor Processing,2022,148:106839.
[26] Islam R,Chen G,Ramesh P,et al.Investigation of the changes in electronic properties of nickel oxide (NiOx) due to UV/ozone treatment[J].ACS Applied Materials & Interfaces Journal,2017,9(20):17201-17207.
[27] Wang T,Ding D,Zheng H,et al.Efficient inverted planar perovskite solar cells using ultraviolet/ozone-treated NiOx as the hole transport layer[J].Solar RRL,2019,3(6):1900045.
[28] Lian Q,Wang P L,Wang G L,et al.Doping free and amorphous NiOx film via UV irradiation for efficient inverted perovskite solar cells[J].Advanced Science,2022,9(18):2201543.
[29] Dutta T,Gupta P,Gupta A,et al.Effect of Li doping in NiO thin films on its transparent and conducting properties and its application in heteroepitaxial p-n junctions[J].Journal of Applied Physics,2010,108:083715.
[30] Qiu Z W,Gong H B,Zheng G H J,et al.Enhanced physical properties of pulsed laser deposited NiO films via annealing and lithium doping for improving perovskite solar cell efficiency[J].Journal of Materials Chemistry C,2017,5:7084-7094.
[31] Chen W,Liu F Z,Feng X Y,et al.Cesium doped NiOx as an efficient hole extraction layer for inverted planar perovskite solar cells[J].Advanced Energy Materials,2017,7(19):1700722.
[32] Chen P C,Yang S H,Potassium-doped nickel oxide as the hole transport layer for efficient and stable inverted perovskite solar cells[J].ACS Applied Energy Materials,2019,2(9):6705-6713.
[33] Fu Q X,Xiao S Q,Tang X L,et al.High-performance inverted planar perovskite solar cells based on solution-processed rubidium-doped nickel oxide hole-transporting layer[J].Organic Electronics,2019,69:34-41.
[34] Li G J,Jiang Y B,Deng S B,et al.Overcoming the limitations of sputtered nickel oxide for high-efficiency and large-area perovskite solar cells[J].Advanced Science,2017,4(12):1700463.
[35] Ge B,Qiao H W,Lin Z Q,et al.Deepening the valance band edges of NiOx contacts by alkaline earth metal doping for efficient perovskite photovoltaics with high open-circuit voltage[J].Solar RRL,2019,3(8):1900192.
[36] Jung W J,Chueh C C,Jen A K Y,A low-temperature,solution-processable,Cu-doped nickel oxide hole-transporting layer via the combustion method for high-performance thin-film perovskite solar cells[J].Advanced Materials,2015,27:7874-7880.
[37] Chen W,Wu Y H,Fan J,et al.Understanding the doping effect on NiO:toward high-performance inverted perovskite solar cells[J].Advanced Energy Materials,2018,8(19):1703519.
[38] Bashira A,Haura L J,Shuklaa S,et al.Cu-doped nickel oxide interface layer with nanoscale thickness for efficient and highly stable printable carbon-based perovskite solar cell[J].Solar Energy,2019,182:225-236.
[39] Xie Y L,Lu K,Duan J S,et al.Enhancing photovoltaic performance of inverted planar perovskite solar cells by cobalt-doped nickel oxide hole transport layer[J].ACS Applied Materials & Interfaces,2018,10(16):14153-14159.
[40] Yuan X B,Li H Y,Fan J,et al.Enhanced p-type conductivity of NiOx films with divalent Cd ion doping for efficient inverted perovskite solar cells[J].ACS Applied Materials & Interfaces,2022,14:17434-17443.
[41] Zhao J F,Yang X D,Zhang Z Q,et al.A novel silver-doped nickel oxide hole-selective contact for crystalline silicon heterojunction solar cells[J].Frontiers of Chemical Science and Engineering,2024,18(2):19.
[42] Wan X X,Jiang Y N,Qiu Z W,et al.Zinc as new dopant for NiOx based planar perovskite solar cells with stable efficiency near 20%[J].ACS Applied Energy Materials,2018,1(8):3947-3954.
[43] Chandrasekhar P S,Seo Y H,Noh Y J,et al.Room temperature solution-processed Fe doped NiOx as a novel hole transport layer for high efficient perovskite solar cells[J].Applied Surface Science,2019,481:588-596.
[44] Zhang W,Shen H L,Ge J W,et al.Magnetron sputtered Al-doped NiOx films as a holetransport layer for perovskite solar cells[J].Journal of Materials Science,2022,57:15889-15900.
[45] Hu Z J,Chen D,Yang P,et al.Sol-gel-processed yttrium-doped NiO as hole transport layer in inverted perovskite solar cells for enhanced performance[J].Applied Surface Science,2018,441:258-264.
[46] Teo S,Guo Z L,Xu Z H,et al.The role of lanthanum on a nickel oxide-based inverted perovskite solar cell for efficiency and stability improvement[J].ChemSusChem,2019,12(2):518-526.
[47] Bao H X,Du M Y,Wang H,et al.Samarium-doped nickel oxide for superior inverted perovskite solar cells:insight into doping effect for electronic applications[J].Advanced Functional Materials,2021,31(34):2102452.
[48] Zhou P C,Li B,Fang Z M,et al.Nitrogen-doped nickel oxide as hole transport layer for high-efficiency inverted planar perovskite solar cells[J].Solar RRL,2019,3(10):1900164.
[49] Ru P B,Bi E,Zhang Y,et al.High electron affinity enables fast hole extraction for efficient flexible inverted perovskite solar cells[J].Advanced Energy Materials,2020,10(12):1903487.
[50] Xia X F,Jiang Y H,Wan Q X,et al.Lithium and silver co-doped nickel oxide hole-transporting layer boosting the efficiency and stability of inverted planar perovskite solar cells[J].ACS Applied Materials & Interfaces,2018,10(51):44501-44510.
[51] Wang S X,Zhang B J,Feng D,et al.Achieving high performance and stable inverted planar perovskite solar cells by using lithium and cobalt codoped nickel oxide as hole transport layer[J].Journal of Materials Chemistry C,2019,7:9270-9277.
[52] Hou D G,Zhang J,Gan X L,et al.Pb and Li co-doped NiOx for efficient inverted planar perovskite solar cells[J].Journal of Colloid and Interface Science,2020,559:29-38.
基金资助
安徽省科技厅重大专项项目(201903a05020017);安徽省重点研究与开发计划项目(2023a05020003)
PDF
