process under mild conditions. The abovementioned advantages make perovskites a promising family of materials for the next-generation photovoltaic solar cells. Since the first report on the perovskite solar cell (PSC) by Miyasaka and coworkers in 2009, [1a] considerable efforts have been made to improve the power conversion efficiency (PCE) of the PSC to rival those of commercially available silicon solar panels. [1b-e] In a strikingly short period of time, the highest certified PCE has reached a value as high as 25.2% in a single-junction PSC. [2] Self-assembled monolayers (SAMs) are 2D nanomaterials with the thickness of one or few molecules. [3] Self-assembly of molecules on the surface is a thermodynamically favorable process where molecules interact with each other to form organized structures. Typically, molecules are vertically aligned on the surface with some tilt angle relative to the surface normal. The molecules are designed to have three parts: the anchoring, the spacer, and the terminal groups (Figure 1). 1) Anchoring group: the anchoring group is responsible for the interaction between the molecule and the surface. Various anchoring groups that bind to specific substrates are available, which provides users the option to select the type of electrode and molecule to suit their intended purpose. The most widely studied class of SAMs is derived from the anchoring chemistries between thiol and coinage metals or between silane and oxide substrates. In SAM-inserted PSCs, various oxide substrates are commonly used for bottom contacts, and few Brønsted-Lowry acids (e.g., carboxylic acid, phosphonic acid, and boronic acid) are extensively utilized (see below for details). Anchoring chemistry matters for the tilt angle of molecule with respect to the surface normal, work function (WF) of substrate, interfacial dipole, contact resistance, and energy offset between the Fermi level and energy of frontier molecular orbital. All of them are essential for the electronic function and performance of PSCs. These effects of SAMs on interfacial properties of PSCs are discussed below. 2) Spacer group: the spacer group is the backbone of the molecule, and it bridges terminal and anchoring groups. The length of the backbone is important for electronically isolating one contact from another. The spacer group is responsible for lateral interaction between molecules during the selfassembly process, which affects the final packing structure. Self-assembled monolayers (SAMs), owing to their unique and versatile abilities to manipulate chemical and physical interfacial properties, have emerged as powerful nanomaterials for improving the performance of perovskite solar cells (PSCs). Indeed, in the last six years, a collection of studies has shown that the application of SAMs to PSCs boosts the performance of devices compared to the pristine PSCs. This review describes recent studies that demonstrate the direct advantages of SAM-based interfacial engineering to power conversion efficiency (PCE) of PSCs. This review includes 1) a b...

studies have relied on homogeneous, pure SAMs, that is, SAMs composed of one type of molecules. Contamination or dilution of a homogenous SAM by different molecules has typically been considered to cause negative effects because increased heterogeneity can directly translate into (supra)molecular and electronic structural changes, which can hinder the achievement of desired device performance.Although the field of molecular and organic electronics has long utilized pure molecular systems, studies on how charges traverse across multicomponent molecular systems have only recently emerged. [8] This review article focuses on the emergence of, and recent advances in mixed molecular electronics, defined as an electronics field exploiting heterogeneous molecular systems such as mixed SAMs (Figure 1). In this article, we introduce and discuss charge transport behaviors in mixed SAMs and applications for mixed molecular electronics. We further aim to provide a rational perspective on the unique features of mixed molecular systems with an eye toward potential molecular and nanoelectronics applications. Supramolecular and Electronic Structures of Mixed SAMs Supramolecular Structure of Mixed SAMsDiluting a pure, single-component SAM with another molecule leads to a mixed SAM. Depending on the number of molecular species comprising a mixed SAM, such a molecular dilution can yield binary, ternary, quaternary mixed SAMs, and so on. Mixed SAMs can be formed by several methods. Among others, the following three methods are commonly employed.

Metal halide perovskites promise bright and narrowband light-emitting diodes (LEDs). To this end, reliable understanding on structure−property relations is necessary, yet singling out one effect from others is difficult because photophysical and electronic functions of perovskite LEDs are interwoven each other.To resolve this problem, we herein employ self-assembled monolayers (SAMs) for interfacial engineering nanomaterials. Four different molecules that have the same anchor (thiol), different backbone (aryl vs alkyl) and different terminal group (amine vs pyridine vs methyl) are used to form SAMs at the interface with the thin film of a green-color perovskite, CH 3 NH 3 PbBr 3 . SAM-engineered perovskite films are characterized with Xray diffraction (XRD), depth-profile X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscopy (KPFM), scanning electron microscopy (SEM), time-resolved laser spectroscopy, and UV−vis absorption and emission spectroscopies. This permits access to how the chemical structure of molecule comprising SAM is related to the various chemical and physical features such as quality and grain size, cross-sectional atomic composition (Pb(0) vs Pb(II)), charge carrier lifetime, and charge mobility of perovskite films, leading to inferences of structure−property relations in the perovskite. Finally, we demonstrate that the trends observed in the model system stem from the affinity of SAM over the undercoordinated Pb ions of perovskite, and these are translated into considerably enhanced EQE (from 2.20 to 5.74%) and narrow-band performances (from 21.3 to 15.9 nm), without a noticeable wavelength shift in perovskite LEDs. Our work suggests that SAM-based interfacial engineering holds a promise for deciphering mechanisms of perovskite LEDs.