Conductive metal organic frameworks (MOFs) represent a promising class of porous crystalline materials that have demonstrated potential in photo-electronics and photocatalytic applications. However, the lack of fundamental understanding on charge transport (CT) mechanism as well as the correlation of CT mechanism with their structure hampered their further development. Herein, we report the direct evidence of CT mechanism in 2D Cu-THQ MOFs and the correlation of temporal and spatial behaviors of charge carriers with their photoconductivity by combining three advanced spectroscopic methods, including time resolved optical and X-ray absorption spectroscopy and terahertz spectroscopy. In addition to Cu-THQ, the CT in Cu/Zn-THQ after incorporating Zn 2+ guest metal was also examined to uncover the contribution of through space pathway, as the presence of the redox inactive 3d 10 Zn 2+ is expected to perturb the long range in-plane CT. We show that the hot carriers in Cu-THQ generated after photoexcitation are highly mobile and undergo fast localization to a lower energy state (cool carriers) with electrons occupying Cu center and holes in ligands. The cool carriers, which have super long lifetime (>17 ns), are responsible for the long-term photoconductivity in Cu-THQ and transport through the O− Cu−O motif with negligible contribution from interlayer ligand π−π stacking, as incorporation of Zn 2+ in Cu-THQ significantly reduced photoconductivity. These unprecedented results not only demonstrate the capability to experimentally probe CT mechanism but also provide important insight in the rational design of 2D MOFs for photoelectronic and photocatalytic applications.

Light‐emitting diodes (LEDs) made with quasi‐2D/3D and layered perovskites have undergone an unprecedented surge as their external quantum efficiency (EQE) is rapidly approaching other lighting technologies. Manipulating the charge recombination pathway in semiconductors is highly desirable for improving the device performance. This study reports high‐performance layered perovskites LEDs with benzyl ring as spacer where radiative recombination lifetime is longer, compared with much shorter alkyl chain spacer yields. Based on detailed optical and X‐ray absorption spectroscopy measurements, direct signature of charges localization is observed near the band edge in exchange with the shallow traps in benzyl organics containing layered perovskites. As a result, it boosts the photoluminescence intensity by 7.4 times compared to that made with the alkyl organics. As a demonstration, a bright LED made with the benzyl organics with current efficiency of 23.46 ± 1.52 cd A−1 is shown when the device emits at a high brightness of 6.6 ± 0.93 × 104 cd m−2. The average EQE is 9.2% ± 1.43%, two orders of magnitude higher than the device made with alkyl organics. The study suggests that the choices of organic spacers provide a path toward the manipulation of charge recombination, essential for efficient optoelectronic device fabrications.

Efficient photovoltaic cells based on thin films of solution-processed 2D Ruddlesden–Popper hybrid perovskites (RPPs) represent an exciting breakthrough due to their enhanced tunability and chemical stability relative to those fabricated from 3D phases. However, reports of efficient charge separation and current collection are in apparent contradiction with the well-known enhancement of the exciton binding energy in multilayered halide perovskites, which should lower the device’s internal quantum efficiency and voltage. This controversy has led to various proposals for the electronic and physical structure of RPP thin films, including phase inhomogeneity as the driving force for exciton dissociation and transport. We address this apparent paradox in high-quality hot-cast RPP films by correlating ultrafast transient absorption spectroscopy with X-ray scattering measurements. We show that a hot-casting fabrication method produces highly phase pure n = 3 (BA)2(MA) n−1Pb n I3n+1 RPP structures. The high-phase purity and large grain sizes allow us to observe vertical transport of excitons via a diffusive process and allow us to determine that charge separation is primarily driven by dissociation at surface localized subgap electronic states. We analyze the differential absorption kinetics in films of varying thickness to directly determine that the excitonic diffusion constant is ∼0.18 cm2 s–1. We propose that a surface localized structural distortion, observed using surface selective grazing incidence X-ray scattering measurements, is responsible for the creation of the surface localized defect states. We find that the density and spatial distribution of these defect states is a function of preparation conditions.

Metal organic frameworks (MOFs) have emerged as promising photocatalytic materials for solar energy conversion. However, the fundamental understanding of light harvesting and charge separation (CS) dynamics in MOFs remain underexplored,...