Intrinsic Formamidinium Tin Iodide Nanocrystals by Suppressing the Sn(IV) Impurities.

The long search for nontoxic alternatives to lead halide perovskites (LHPs) has shown that some compelling properties of LHPs, such as low effective masses of carriers, can only be attained in their closest Sn(II) and Ge(II) analogues, despite their tendency toward oxidation. Judicious choice of chemistry allowed formamidinium tin iodide (FASnI3) to reach a power conversion efficiency of 14.81% in photovoltaic devices. This progress motivated us to develop a synthesis of colloidal FASnI3 NCs with a concentration of Sn(IV) reduced to an insignificant level and to probe their intrinsic structural and optical properties. Intrinsic FASnI3 NCs exhibit unusually low absorption coefficients of 4 × 103 cm-1 at the first excitonic transition, a 190 meV increase of the band gap as compared to the bulk material, and a lack of excitonic resonances. These features are attributed to a highly disordered lattice, distinct from the bulk FASnI3 as supported by structural characterizations and first-principles calculations.

Assessing the Charge Carrier Dynamics at Hybrid Interfaces of Organic Photoanodes for Solar Fuels.

Organic semiconductors (OSCs) have emerged as promising active layers for photoanodes to drive photoelectrochemical (PEC) oxidation reactions. Interfacing an OSC with an inorganic electron transport layer (ETL) is key to enabling both high performance and stability. While spectroelectrochemical techniques have been established for the evaluation of inorganic interfaces, allowing rational optimization toward higher performances, a similar level of understanding for hybrid organic-inorganic interfaces remains elusive. To close this knowledge gap, we first perform a systematic parameter study (ETL thickness, potential dependency, and light intensity) on a state-of-the-art organic photoanode to establish factors determining the photoelectrochemical impedance spectroscopy (PEIS) response. Coupled with in situ UV-Vis characterizations, key charge transfer processes are clearly assigned to the PEIS features.

Advancing high-throughput combinatorial aging studies of hybrid perovskite thin films via precise automated characterization methods and machine learning assisted analysis.

To optimize material stability, automated high-throughput workflows are of increasing interest. However, many of those workflows either employ synthesis techniques not suitable for large-area depositions or are carried out in ambient conditions, which limits the transferability of the results. While combinatorial approaches based on vapour-based depositions are inherently scalable, their potential for controlled stability assessments has yet to be exploited. Based on MAPbI3 thin films as a prototypical system, we demonstrate a combinatorial inert-gas workflow to study intrinsic materials degradation, closely resembling conditions in encapsulated devices. Specifically, we probe the stability of MAPbI3 thin films with varying residual PbI2 content. A comprehensive set of automated characterization techniques is used to investigate the structure and phase constitution of pristine and aged thin films. A custom-designed in situ UV-Vis aging setup is used for real-time photospectroscopy measurements of the material libraries under relevant aging conditions, such as heat or light-bias exposure. These measurements are used to gain insights into the degradation kinetics, which can be linked to intrinsic degradation processes such as autocatalytic decomposition. Despite scattering effects, which complicate the conventional interpretation of in situ UV-Vis results, we demonstrate how a machine learning model trained on the comprehensive characterization data before and after the aging process can link changes in the optical spectra to phase changes during aging. Consequently, this approach does not only enable semi-quantitative comparisons of material stability but also provides detailed insights into the underlying degradation processes which are otherwise mostly reported for investigations on single samples.

Covalent grafting of molecular catalysts on C3N x H y as robust, efficient and well-defined photocatalysts for solar fuel synthesis.

The covalent attachment of molecules to 2D materials is an emerging area as strong covalent chemistry offers new hybrid properties and greater mechanical stability compared with nanoparticles. A nickel bis-aminothiophenol catalyst was grafted onto a range of 2D carbon nitrides (C3N x H y ) to form noble metal-free photocatalysts for H2 production. The hybrids produce H2 beyond 8 days with turnover numbers reaching 1360 based on nickel, a more than 3 fold higher durability than reported molecular catalyst-carbon nitride mixtures, and under longer wavelengths (>475 nm). Time-resolved spectroscopy reveals sub-microsecond electron transfer to the grafted catalyst, six orders of magnitude faster compared with similar reports of non-grafted catalysts. The photoelectrons on the catalyst have a ca. 1000 times longer half-time (7 ms) compared with bare carbon nitride (10 µs). The grafting strategy operates across a range of molecular catalyst-carbon nitride combinations, thus paving the way for robust efficient photocatalysts based on low-cost tunable components.