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The incorporation of substitutional Co2+ impurities in [Cd10S4(SPh)16]4– (Cd10) molecular clusters prepared by the self-assembly method where Na2S is the sulfur precursor and a redox method where elemental S is the sulfur precursor is studied. The Co2+ ions provide unique spectroscopic and chemical handles to monitor dopant speciation during cluster formation and determine what role, if any, other cluster species play during Cd10 cluster formation. In contrast to the redox method that produces exclusively surface-exchanged Co2+-doped Cd10 (Co:Cd10), the preparation of Cd10 by the self-assembly method in the presence of Co2+ ions results in Co2+ incorporation at both the surface and core sites of the Cd10 cluster. Electrospray ionization mass spectrometry (ESI–MS) analysis of the dopant distribution for the self-assembly synthesis of Co:Cd10 is consistent with a near-Poissonian distribution for all nominal dopant concentrations albeit with reduced actual Co2+ incorporation. At a nominal Co2+ concentration of 50%, we observe incorporation of up to seven Co2+ ions within the Cd10 self-assembled cluster compared to a maximum of only four Co2+ dopants in the Cd10 redox clusters. The observation of up to seven Co2+ dopants must involve substitution of at least three core sites within the Cd10 cluster. Electronic absorption spectra of the Co2+ ligand field transition in the heavily doped Co:Cd10 clusters display clear deviation with the surface-doped Co2+-doped Cd10 clusters prepared by the redox method. We hypothesize that the coordination of Co2+ and S2– ions in solution prior to cluster formation, which is possible only with the self-assembly method, is critical to the doping of Co2+ ions within the Cd10 cores. 

Controlling the surface chemistry of colloidal semiconductor nanocrystals is critical to exploiting their rich electronic structures for various technologies. We recently demonstrated that the hydrothermal synthesis of colloidal nanocrystals of SrTiO 3 , a technologically-relevant electronic material, provided a strong negative correlation between the presence of an O 2 -related surface defect and hydrazine hydrate [W. L. Harrigan, S. E. Michaud, K. A. Lehuta, and K. R. Kittilstved, Chem. Mater. , 2016, 28 (2), 430]. When hydrazine hydrate is omitted during the aerobic hydrothermal synthesis, the surface defect is observed. However, it can be removed by either the addition of hydrazine hydrate or by purging the reaction solution with argon gas before the hydrothermal synthesis. We also propose that the formation of the O 2 -related defect is mediated by the reduction of dissolved O 2 by lactate anions that are present from the titanium precursor. This work helps elucidate the nature of the O 2 -related defect as a superoxide anion and presents a mechanism to explain its formation during the hydrothermal synthesis of SrTiO 3 and related BaTiO 3 nanocrystals. 

A viable qubit must have a long coherence time T 2 . In molecular nanomagnets, T 2 is often limited at low temperatures by the presence of dipole and hyperfine interactions, which are often mitigated through sample dilution, chemical engineering and isotope substitution in synthesis. Atomic-clock transitions offer another route to reducing decoherence from environmental fields by reducing the effective susceptibility of the working transition to field fluctuations. The Cr7Mn molecular nanomagnet, a heterometallic ring, features a clock transition at zero field. Both continuous-wave and spin-echo electron-spin resonance experiments on Cr7Mn samples, diluted via co-crystallization, show evidence of the effects of the clock transition with a maximum T 2 ∼ 390 ns at 1.8 K. We discuss improvements to the experiment that may increase T 2 further.