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The elucidation of structure-to-function relationships for two-dimensional (2D) hybrid perovskites remains a primary challenge for engineering efficient perovskite-based devices. By combining insights from theory and experiment, we describe the introduction of bifunctional ligands that are capable of making strong hydrogen bonds within the organic bilayer. We find that stronger intermolecular interactions draw charge away from the perovskite layers, and we have formulated a simple and intuitive computational descriptor, the charge separation descriptor (CSD), that accurately describes the relationship between the Pb-I-Pb angle, band gap, and in-plane charge transport with the strength of these interactions. A higher CSD value correlates to less distortion of the Pb-I-Pb angle, a reduced band gap, and higher in-plane mobility of the perovskite. These improved material properties result in improved device characteristics of the resulting solar cells.

2D Ruddlesden–Popper metal‐halide perovskites exhibit structural diversity due to a variety of choices of organic ligands. Incorporating bifunctional ligands in such materials is particularly intriguing since it can result in novel electronic properties and functions. However, an in‐depth understanding of the effects of bifunctional ligands on perovskite structures and, consequently, their electronic and excitonic properties, is still lacking. Here,n = 1 2D perovskites built with organic ligands containing ─CN, ─OH, ─COOH, ─phenyl (Ph), and ─CH₃functional groups are investigated using ultraviolet and inverse photoemission spectroscopies, density functional theory calculations, and tight‐binding model analyses. The experimentally determined electronic gaps of the ─CN, ─COOH, ─Ph, and ─CH₃based perovskites exhibit a strong correlation with the in‐plane Pb─I─Pb bond angle, while the ─OH based perovskite deviates from the linear trend. Based on the band structure calculations, this anomaly is attributed to the out‐of‐plane dispersion, caused predominantly by significant interlayer electronic coupling that is present in ─OH based perovskites. These results highlight the complex and diverse impacts of organic ligands on electronic properties, especially in terms of the involvement of strong interlayer electronic coupling. The impact of the bifunctional ligands on the evolution of the exciton binding energy is also addressed.

Perovskite solar cells (PSCs) have rapidly emerged as one of the hottest topics in the photovoltaics community owing to their high power‐conversion efficiencies (PCE), and the promise to be produced at low cost. Among various PSCs, typical 3D perovskite‐based solar cells deliver high PCE but they suffer from severe instability, which restricts their practical applications. In contrast to 3D perovskites, 2D perovskites that incorporate larger, less volatile, and generally more hydrophobic organic cations exhibit much improved thermal, chemical, and environmental stability. 2D perovskites can have different roles within a solar cell, either as the primary light absorber (2D PSCs), or as a capping layer atop a 3D perovskite absorbing layer (2D/3D PSCs). Tradeoffs between PCE and stability exist in both types of PSCs—2D PSCs are more stable but exhibit lower efficiency while 2D/3D PSCs deliver exciting efficiency but show relatively poor stability. To address this PCE/stability tradeoff, the challenges both the 2D and 2D/3D PSCs face are identified and select works the community has undertaken to overcome them are highlighted in this review. It is ended with several recommendations on how to further improve PSCs so their performance and stability can be commensurate with application requirements.

Transparent photovoltaics (TPVs) can be integrated into the surfaces of buildings and vehicles to provide point‐of‐use power without impacting aesthetics. Unlike TPVs that target the photon‐rich near‐infrared portion of the solar spectrum, TPVs that harvest ultraviolet (UV) photons can have significantly higher transparency and color neutrality, offering a superior solution for low‐power electronics with stringent aesthetic tolerance. In addition to being highly transparent and colorless, an ideal UV‐absorbing TPV should also be operationally stable and scalable over large areas while still outputting sufficient power for its specified application. None of today's TPVs meet all these criteria simultaneously. Here, the first UV‐absorbing TPV is demonstrated that satisfies all four criteria by using CsPbCl_2.5Br_0.5as the absorber. By precisely tuning the halide ratio during thermal co‐evaporation, high‐quality large‐area perovskite films can be accessed with an ideal absorption cutoff for aesthetic performance. The resulting TPVs exhibit a record average visible transmittance of 84.6% and a color rendering index of 96.5, while maintaining an output power density of 11 W m⁻²under one‐sun illumination. Further, the large‐area prototypes up to 25 cm²are demonstrated, that are operationally stable with extrapolated lifetimes of >20 yrs under outdoor conditions.

Organic semiconductors (OSCs) have shown great promise in a variety of applications. Although solution processing of OSCs has resulted in high‐quality films, exquisite control of structural development to minimize defect formation during large‐scale fabrication remains formidable. Compounding this challenge is the use of halogenated organic solvents, which poses significant health and environmental hazards. However, the solvent‐free techniques introduced thus far impose additional limitations on solidification kinetics; the resulting OSC thin films are often more defective than those processed from solution. Here, a solvent‐free technique is reported to prepare OSC membranes with centimetric crystalline domains. Leveraging the tendency for liquid crystalline materials to preferentially orient, OSCs are “prealigned” by depositing them from the melt over a metal frame to form a freely suspended membrane. Crystallization from this prealigned phase affords membranes with unprecedented structural order across macroscopic distances. Field‐effect transistors comprising membranes of dioctyl[1]‐benzothieno[3,2‐b][1]benzothiophene (C8BTBT) and didodecyl[1]‐benzothieno[3,2‐b][1]benzothiophene (C12BTBT) having centimeter‐sized domains as active layers exhibit a hole mobility of ≈8.6 cm²V⁻¹s⁻¹, superseding the mobility of any transistors whose active layers are deposited from melt. This technique is scalable to yield membranes with large crystalline domains over wafer dimensions, making it amenable for broad applications in large‐area organic electronics.

Typical lead‐based perovskites solar cells show an onset of photogeneration around 800 nm, leaving plenty of spectral loss in the near‐infrared (NIR). Extending light absorption beyond 800 nm into the NIR should increase photocurrent generation and further improve photovoltaic efficiency of perovskite solar cells (PSCs). Here, a simple and facile approach is reported to incorporate a NIR‐chromophore that is also a Lewis‐base into perovskite absorbers to broaden their photoresponse and increase their photovoltaic efficiency. Compared with pristine PSCs without such an organic chromophore, these solar cells generate photocurrent in the NIR beyond the band edge of the perovskite active layer alone. Given the Lewis‐basic nature of the organic semiconductor, its addition to the photoactive layer also effectively passivates perovskite defects. These films thus exhibit significantly reduced trap densities, enhanced hole and electron mobilities, and suppressed illumination‐induced ion migration. As a consequence, perovskite solar cells with organic chromophore exhibit an enhanced efficiency of 21.6%, and substantively improved operational stability under continuous one‐sun illumination. The results demonstrate the potential generalizability of directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates surface traps in perovskite active layers to yield highly efficient and stable NIR‐harvesting PSCs.