Stoichiometric control of DNA-grafted colloid self-assembly
[1];
- Department of Chemical Engineering, Columbia University, New York, NY 10027,
- Department of Chemical Engineering, Indian Institute of Technology, Gandhinagar 382424, India, and
- Department of Chemical Engineering, Columbia University, New York, NY 10027,, Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973
- Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973
In this study, there has been considerable interest in understanding the self-assembly of DNA-grafted nanoparticles into different crystal structures, e.g., CsCl, AlB₂, and Cr₃Si. Although there are important exceptions, a generally accepted view is that the right stoichiometry of the two building block colloids needs to be mixed to form the desired crystal structure. To incisively probe this issue, we combine experiments and theory on a series of DNA-grafted nanoparticles at varying stoichiometries, including noninteger values. We show that stoichiometry can couple with the geometries of the building blocks to tune the resulting equilibrium crystal morphology. As a concrete example, a stoichiometric ratio of 3:1 typically results in the Cr₃Si structure. However, AlB₂ can form when appropriate building blocks are used so that the AlB₂ standard-state free energy is low enough to overcome the entropic preference for Cr₃Si. These situations can also lead to an undesirable phase coexistence between crystal polymorphs. Thus, whereas stoichiometry can be a powerful handle for direct control of lattice formation, care must be taken in its design and selection to avoid polymorph coexistence.
- Research Organization:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- FG02-12ER46909; AC02-98CH10886; SC00112704
- OSTI ID:
- 1235164
- Alternate ID(s):
- OSTI ID: 1188276
- Report Number(s):
- BNL-108126-2015-JA
- Journal Information:
- Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 112 Journal Issue: 16; ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of SciencesCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
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