Design of Strong and Weak Intermolecular Interactions to Engineer Buried Interfaces in Inverted Wide-Bandgap Perovskite Solar Cells

Abstract

The interfaces between the charge extraction layers and the perovskite layer are critical in defining the performance and stability of wide-bandgap (WBG) perovskite solar cells (PSCs). They govern multiple critical factors affecting the operation of photovoltaic devices such as the energetics of the contact, and the crystallization process of the thin film, thus its structural and electronic quality. Self-assembled monolayers (SAMs) have emerged as promising candidates as hole-selective materials for inverted PSCs, thanks to the flexibility provided by the large library of their functional groups. Herein, we outline a molecular hybridization strategy through the incorporation of the histamine molecule into the [4-(3,6-dimethyl-9H-carbazol-9yl)butyl]phosphonic acid (Me-4PACz), which is one of the most common hole extracting layers. Playing with intermolecular strong and weak interactions, we can contextually act on multiple processes. The proton transfer from the phosphonic acid group of the Me-4PACz to the ethylamine functional group of histamine enables the design of the interface dipole to facilitate hole extraction and minimize recombination losses. Then, the protonated amines balance the nucleation of halide components and stabilize the halide ions in the perovskite, avoiding their migration. Thus, three-dimensional nanovoids and tensile stress at the bottom surface were reduced, stabilizing the buried interface. Finally, the π-π interactions between the imidazole moiety and Me-4PACz improve the molecular assembling of the SAM, reducing disorder at the interfacial contact. The general impact of these results has been tested on PSCs based on lead mix-halide perovskites with two different bandgaps. The inverted WBG PSCs with 1.77 eV bandgap present a power conversion efficiency (PCE) of 20.34%, and maintains 95.5% of the initial PCE after 1000 hours of continuous illumination. The highly challenging WBG PSCs with 1.83 eV bandgap deliver a PCE of 18.99% with a Voc as high as 1.364 V-ranking among the highest reported PCEs and Voc values for such large bandgap.