In this work, a novel dynamic cation exchange driven by an anion exchange procedure was used for incorporating Ni dopants into the Pb-site of CsPbBr3 and CsPb­(BrCl)3 perovskite nanocrystals under ambient conditions. Ni doping has significant merits in tuning the optical properties and introducing magnetic functionality. Moreover, Ni doping provides chemical and photochemical stability to a host phase with consequent importance for solar cell applications. The present work describes a thorough investigation of the Ni incorporation mechanism via structural, compositional, and optical characterizations. The results indicated the essential need for cation–anion coexchange, enabling control of the Ni concentration from <1% to about 12%, with uniform distribution across the host lattice. In addition, the doping improved the photoluminescence quantum yields beyond those of the undoped nanocrystals. The observations were corroborated by the density functional theory (DFT), confirming that the incorporation of Ni is energetically favorable.

NMR is a noninvasive, molecular-level spectroscopic technique widely used for chemical characterization. However, it lacks the sensitivity to probe the small number of spins at surfaces and interfaces. Here, we use nitrogen vacancy (NV) centers in diamond as quantum sensors to optically detect NMR signals from chemically modified thin films. To demonstrate the method’s capabilities, aluminum oxide layers, common supports in catalysis and materials science, are prepared by atomic layer deposition and are subsequently functionalized by phosphonate chemistry to form self-assembled monolayers. The surface NV-NMR technique detects spatially resolved NMR signals from the monolayer, indicates chemical binding, and quantifies molecular coverage. In addition, it can monitor in real time the formation kinetics at the solid–liquid interface. With our approach, we show that NV quantum sensors are a surface-sensitive NMR tool with femtomole sensitivity for in situ analysis in catalysis, materials, and biological research.

Characterization of the molecular properties of surfaces under ambient or chemically reactive conditions is a fundamental scientific challenge. Nuclear magnetic resonance (NMR) spectroscopy would be the ideal technique, however it lacks the sen-sitivity to probe the small number of spins at interfaces. Here we use nitrogen vacancy (NV) centers in diamond as quantum sensors to optically detect NMR signals from chemically modified thin films. Aluminum oxide (Al2O3) layers, common supports in catalysis and materials science, are prepared by atomic layer deposition and are subsequently functionalized by phosphonate chemistry to form self-assembled monolayers (SAMs). The surface NV-NMR technique detects NMR signals from the monolayer, indicates chemical binding, and quantifies molecular coverage. In addition, it can monitor in real-time the formation kinetics at the solid-liquid interface. This work demonstrates the capability of NV quantum sensors as a sur-face-sensitive (femtomole) NMR tool for in-situ analysis in catalysis, materials and biological research.

Hybrid organic–inorganic networks that incorporate chiral molecules have attracted great attention due to their potential in semiconductor lighting applications and optical communication. Here, we introduce a chiral organic molecule (R)/(S)-1-cyclohexylethylamine (CHEA) into bismuth-based lead-free structures with an edge-sharing octahedral motif, to synthesize chiral lead-free (R)/(S)-CHEA4Bi2Br x I10–x crystals and thin films. Using single-crystal X-ray diffraction measurements and density functional theory calculations, we identify crystal and electronic band structures. We investigate the materials’ optical properties and find circular dichroism, which we tune by the bromide–iodide ratio over a wide wavelength range, from 300 to 500 nm. We further employ transient absorption spectroscopy and time-correlated single photon counting to investigate charge carrier dynamics, which show long-lived excitations with optically induced chirality memory up to tens of nanosecond timescales. Our demonstration of chirality memory in a color-tunable chiral lead-free semiconductor opens a new avenue for the discovery of high-performance, lead-free spintronic materials with chiroptical functionalities.