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In the past years, numerous alternative cations to replace Pb2+ in perovskite solar cells have been investigated. In terms of toxicity and chemical stability, methylammonium bismuth iodide [(CH3NH3)3Bi2I9 or MBI] containing the Bi3+ cation has been considered as a promising material. However, fabrication of coherent MBI films remains challenging. Recently, significant progress has been achieved by using vapor deposition processes. Compared with solution-processed ones, vapor-deposited MBI solar cells show higher fill factors and efficiencies. In this work, chemical vapor deposition (CVD) of MBI is investigated. Employing nitrogen as carrier gas, the precursors bismuth iodide (BiI3) and methylammonium iodide (MAI) are deposited sequentially over several cycles and form MBI during the process. In order to form dense and coherent layers, the lengths of the deposition cycles as well as the substrate temperature have been optimized. Scanning electron microscopy reveals the strong influence of both parameters on growth and crystal properties. Optimized films of MBI integrated into solar cells show that CVD of MBI is a promising method for fabricating large-area solar cells.
Although Pb-based perovskite solar cells already achieve power conversion efficiencies (PCE) beyond 20 %, the use of toxic Pb is causing considerable environmental concern. As a consequence, a variety of alternative cations have been investigated to replace Pb2+ in the perovskite structure. Methylammonium bismuth iodide (MA3Bi2I9, MBI) has shown promising results for environmentally benign and chemically stable devices. While the PCE of MBI-based solar cells are still comparably low, structural improvements have been made by using chemical vapor deposition (CVD). CVD allows for the well-controlled formation of coherent and dense MBI layers in contrast to solution-processing. In this work, CVD as a possible MBI fabrication method for efficient and size-scalable solar cells is discussed. The precursors MA iodide (MAI) and Bi iodide (BiI3) are deposited in an alternating deposition process forming the desired MBI perovskite on the heated substrate. Substrate temperatures as well as deposition times of each precursor are varied with the aim of forming coherent and dense MBI layers. Optimized films are further processed to solar cell prototypes and compared with solution-processed reference devices. The results reveal that CVD possesses great potential to enable the manufacture of MBI photovoltaic (PV) devices processed in a solvent-free environment.
Typical electron transport (2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi)) and injection (Cs2CO3) materials are successfully replaced by zirconium tetrakis(8-hydroxyquinolinolate) (Zrq4) and lithium 2-((o-tolylimino)methyl)-phenolate (EI-111) in simplified OLED (organic light-emitting diodes) processed by organic vapor phase deposition (OVPD). The performance of combining Zrq4 and EI-111 is analyzed in unipolar devices and compared to devices with configurations of Zrq4/Cs2CO3, TPBi/EI-111 and TPBi/Cs2CO3. Current density-voltage (J-V) measurements are performed and correlated to different carrier injection and transport properties. The investigated material combinations are implemented in the simplified OLED structures and compared to each other. To account for the high HOMO level of Zrq4, 5 nm of TPBi are added to confine holes and excitons in the emissive layer (EML) and to improve device performance. After tailoring the organic stack for OLED with Zrq4, a remarkable boost in device efficiency is observed. The luminous efficacy increased from 3.0 to 21.9 lm/W and the EQE from 2.1 to 11.0 % for a device with Zrq4/EI-111. Furthermore, OLED having Zrq4/Cs2CO3 show an even greater enhancement to 26.3 lm/W and 11.7 %.
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