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dc.contributor.authorZhao, Qing
dc.contributor.authorKulik, Heather J.
dc.date.accessioned2020-05-14T19:45:08Z
dc.date.available2020-05-14T19:45:08Z
dc.date.issued2018-09
dc.identifier.issn0897-4756
dc.identifier.issn1520-5002
dc.identifier.urihttps://hdl.handle.net/1721.1/125250
dc.description.abstractIndium phosphide quantum dots (QDs) have emerged as a promising candidate to replace more toxic II-VI CdSe QDs, but production of high-quality III-V InP QDs with targeted properties requires a better understanding of their growth. We develop a first-principles-derived model that unifies InP QD formation from isolated precursor and early stage cluster reactions to 1.3 nm magic sized clusters and rationalize experimentally observed properties of full sized >3 nm QDs. Our first-principles study on realistic QD models reveals large surface-dependent reactivity for all elementary growth process steps, including In-ligand bond cleavage and P precursor addition. These thermodynamic trends correlate well to kinetic properties at all stages of growth, indicating the presence of labile and stable spots on cluster and QD surfaces. Correlation of electronic or geometric properties to energetics identifies surprising sources for these variations: short In···In separation on the surface produces the most reactive sites, at odds with conventional understanding of strain (i.e., separation) in bulk metallic surfaces increasing reactivity and models for ionic II-VI QD growth. These differences are rationalized by the covalent, directional nature of bonding in III-V QDs and explained by bond order metrics derived directly from the In-O bond density. The unique constraints of carboxylate and P precursor bonding to In atoms rationalize why all sizes of InP clusters and QDs are In-rich but become less so as QDs mature. These observations support the development of alternate growth recipes that take into account strong surface-dependence of kinetics as well as the shapes of both In and P precursors to control both kinetics and surface morphology in III-V QDs.en_US
dc.description.sponsorshipNational Science Foundation (U.S.) (Grant ECCS1449291)en_US
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)en_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/ACS.CHEMMATER.8B03125en_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourceOther repositoryen_US
dc.titleElectronic Structure Origins of Surface-Dependent Growth in III–V Quantum Dotsen_US
dc.typeArticleen_US
dc.identifier.citationZhao, Qing, and Heather J. Kulik. “Electronic Structure Origins of Surface-Dependent Growth in III–V Quantum Dots.” Chemistry of Materials 30, 20 (October 2018): 7154–65.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemical Engineeringen_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Mechanical Engineeringen_US
dc.relation.journalChemistry of Materialsen_US
dc.eprint.versionAuthor's final manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dc.date.updated2019-08-22T15:32:55Z
dspace.date.submission2019-08-22T15:33:04Z
mit.journal.volume30en_US
mit.journal.issue20en_US
mit.metadata.statusComplete


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