The most developed approaches for the synthesis of InAs nanocrystals (NCs) rely on pyrophoric, toxic, and not readily available tris-trimethylsilyl (or tris-trimethylgermil) arsine precursors. Less toxic and commercially available chemicals, such as tris(dimethylamino)arsine, have recently emerged as alternative As precursors. Nevertheless, InAs NCs made with such compounds need to be further optimized in terms of size distribution and optical properties in order to meet the standard reached with tristrimethylsilyl arsine. To this aim, in this work we investigated the role of ZnCl 2 used as an additive in the synthesis of InAs NCs with tris(dimethylamino)arsine and alane N,N-dimethylethylamine as the reducing agent. We discovered that ZnCl 2 helps not only to improve the size distribution of InAs NCs but also to passivate their surface acting as a Z-type ligand. The presence of ZnCl 2 on the surface of the NCs and the excess of Zn precursor used in the synthesis enable the subsequent in situ growth of a ZnSe shell, which is realized by simply adding the Se precursor to the crude reaction mixture. The resulting InAs@ZnSe core@shell NCs exhibit photoluminescence emission at ∼860 nm with a quantum yield as high as 42±4%, which is a record for such heterostructures, given the relatively high mismatch (6%) between InAs and ZnSe. Such bright emission was ascribed to the formation, under our peculiar reaction conditions, of an In−Zn−Se intermediate layer between the core and the shell, as indicated by X-ray photoelectron spectroscopy and elemental analyses, which helps to release the strain between the two materials.

† These authors contributed equally to this work. 'Charge engineering' of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-lasting challenge in colloidal chemistry and holds promise for groundbreaking advancements in many optoelectronic, photonic and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviours and complicates the realization of advanced device concepts based on their advantageous functionalities. Here we aim to address these issues by realizing the first example of II-VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as 'quantized' dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II-VI NCs, are found to incorporate as nonmagnetic Au + species activating intense size-tuneable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au + to paramagnetic Au 2+ (5d 9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behaviour revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a new chemical approach towards NCs with physical functionalities tailored to the single impurity level and offer a versatile platform for future investigations and device exploitation of individual and collective impurity processes in quantum confined structures.

We report a detailed study on the first colloidal synthesis of NiAs nanocrystals. By optimizing the synthesis parameters, we were able to obtain trioctylphosphine-capped NiAs nanoplatelets with an average diameter of ∼10 nm and a thickness of ca. 4 nm. We then studied the performance of such NiAs nanocrystals as electrocatalysts for electrochemical water splitting reactions, namely, acidic hydrogen evolution reaction (HER) and alkaline oxygen evolution reaction (OER). These nanocrystals were found to be the most HER active ones among the transition metal arsenides reported to date despite exhibiting less than 40 h of stability under benchmark operative conditions (i.e., −10 mA cm geo −2 ). When tested as alkaline OER electrocatalysts, our NiAs nanocrystals behaved as a pre-catalyst and transformed superficially into an active Ni-oxy/hydroxide. As a result, NiAs nanocrystals featured an OER activity higher than that of benchmark Ni 0 nanocrystals. Noticeably, the OER performance, in terms of 10 mA cm OER geo 2 , was retained for up to 60 h of continuous operation. The present study highlights how transition metal arsenides, whose structural features could be successfully controlled through a proper tuning of the synthetic parameters, might represent an emerging class of materials for electrocatalytic applications.