Synergistic Engineering of Conduction Band, Conductivity, and Interface of Bilayered Electron Transport Layers with Scalable TiO₂ and SnO₂ Nanoparticles for High-Efficiency Stable Perovskite Solar Cells

A simple, synergistic engineering of the conduction band (CB), conductivity, and interface of TiO2-based bilayered electron transport layers (ETLs) via scalable TiO2 and SnO2 nanoparticles processed at low temperature (≤ 100 °C) for regular planar perovskite solar cells (PSCs) was developed. The bottom layer (Lt-TiO2:SnO2 nanocomposite film) was prepared by spin coating from the ethanol suspension of small ground TiO2 nanoparticles with big ground SnO2 nanoparticles as the additive. The top C-SnO2 layer (spin-coated from the concentrated commercial SnO2 nanoparticles (C-SnO2 NPs, 20 wt %, 7 nm in size suspended in H2O)) can be regarded as an interlayer between Lt-TiO2:SnO2 and perovskite (Psk) absorbers. Bilayered Lt-TiO2:SnO2/C-SnO2 ETLs are dense films with a cascade CB, good conductivity, facile electron extraction/transport ability, and a highly hydrophilic surface for depositing high-quality Psk films. Regular planar PSCs based on Lt-TiO2:SnO2/C-SnO2 ETLs combined with a (FAI)0.90(PbI2)0.94(MABr)0.10(PbBr2)0.10 absorber and a spiro-OMeTAD hole transporter achieved the highest power conversion efficiency of 22.04% with a negligible current hysteresis. The champion cell lost less than 3% of the initial efficiency under continuous room lighting (1000 lux) for 1000 h (lost 10% after 2184 h) without encapsulation under an inert atmosphere. Four related low-temperature-processed ETLs (Lt-TiO2/C-SnO2, Lt-C-SnO2, Lt-TiO2:SnO2, and Lt-TiO2) were fabricated using the same metal oxide nanoparticle suspensions and studied simultaneously to reveal the function of each metal oxide in the bilayered Lt-TiO2:SnO2/C-SnO2 ETLs. In the bottom Lt-TiO2:SnO2 layer, small TiO2 nanoparticles were needed for making a dense film, and highly conducting big SnO2 nanoparticles are used to increase the conductivity of ETLs and a handy electron transport path for reducing the charge accumulation and series resistance of the cell. A top C-SnO2 layer (regarded as an interlayer between Psk and Lt-TiO2:SnO2) was used to extract/transport electrons facilely, to form a bilayered ETL with a cascade CB, and to create a hydrophilic surface to deposit high-quality Psk films to enhance the photovoltaic performance of the PSCs. This study provides a blueprint for designing good-performance ETLs for high-efficiency, stable regular planar PSCs using various sized nanoparticles prepared in a very simple and low-cost way.