Unique challenges accompany thick-shell CdSe/nCdS (n > 10) nanocrystal synthesis

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2011-12-23
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Guo, Yijun
Marchuk, Kyle
Sampat, Siddharth
Abraham, Rachel
Fang, Ning
Malko, Anton
Vela, Javier
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Vela, Javier
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Ames National Laboratory

Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.

For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.

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Chemistry

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The Department of Chemistry was founded in 1880.

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Abstract

Thick-shell CdSe/nCdS (n >10) nanocrystals were recently reported that show remarkably suppressed fluorescence intermittency or "blinking" at the single-particle level as well as slow rates of Auger decay. Unfortunately, whereas CdSe/nCdS nanocrystal synthesis is well-developed up to n < 6 CdS monolayers (MLs), reproducible syntheses for n > 10 MLs are less understood. Known procedures sometimes result in homogeneous CdS nucleation instead of heterogeneous, epitaxial CdS nucleation on CdSe, leading to broad and multimodal particle size distributions. Critically, obtained core/shell sizes are often below those desired. This article describes synthetic conditions specific to thick-shell growth (n> 10 and n> 20 MLs) on both small (sub2 nm) and large (>4.5 nm) CdSe cores. We find added secondary amine and low concentration of CdSe cores and molecular precursors give desired core/shell sizes. Amine-induced, partial etching of CdSe cores results in apparent shell-thicknesses slightly beyond those desired, especially for very-thick shells (n >20 MLs). Thermal ripening and fast precursor injection lead to undesired homogeneous CdS nucleation and incomplete shell growth. Core/shells derived from small CdSe (1.9 nm) have longer PL lifetimes and more pronounced blinking at single-particle level compared with those derived from large CdSe (4.7 nm). We expect our new synthetic approach will lead to a larger throughput of these materials, increasing their availability for fundamental studies and applications.

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Reprinted (adapted) with permission from Journal of Physical Chemistry C 116 (2012): 2791, doi: 10.1021/jp210949v. Copyright 2011 American Chemical Society.

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Sat Jan 01 00:00:00 UTC 2011
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