期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 6, 期 13, 页码 2406-2412出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.5b00946
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资金
- Robert A. Welch Foundation [F-1464]
- National Science Foundation [CBET-140378]
- NSF
- NIH/NIGMS via NSF [DMR-0936384, DMR-1332208]
- NSF IGERT [DGE-0549417]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1308813] Funding Source: National Science Foundation
- Directorate For Engineering
- Div Of Chem, Bioeng, Env, & Transp Sys [1403768] Funding Source: National Science Foundation
This paper addresses the assembly of body centered-cubic (bcc) superlattices of organic ligand-coated nanocrystals. First, examples of bcc superlattices of dodecanethiol-capped Au nanocrystals and oleic acid-capped PbS and PbSe nanocrystals are presented and examined by transmission electron microscopy (TEM) and grazing incidence small-angle X-ray scattering (GISAXS). These superlattices tend to orient on their densest (110) superlattice planes and exhibit a significant amount of {112} twinning. The same nanocrystals deposit as monolayers with hexagonal packing, and these thin films can coexist with thicker bcc superlattice layers, even though there is no hexagonal plane in a bcc lattice. Both the preference of bcc in bulk films over the denser face-centered cubic (fcc) superlattice structure and the transition to hexagonal monolayers can be rationalized in terms of packing frustration of the ligands. A model is presented to calculate the difference in entropy associated with capping ligand packing frustration in bcc and fcc superlattices.
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