Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes

doi:10.1021/acs.jpclett.8b01451

Title: Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes

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Abstract

We studied the optical absorption enhancement in colloidal suspensions of PbS quantum dots (QD) upon ligand exchange from oleate to a series of cinnamate ligands. By combining experiments and ab initio simulations, we elucidate physical parameters that govern the optical absorption enhancement. We find that within the cinnamate/PbS QD system the optical absorption enhancement scales linearly with the electronic gap of the ligand, indicating that the ligand/QD coupling occurs equally efficient between the QD and ligand HOMO and their respective LUMO levels. Disruption of the conjugation that connects the aromatic ring and its substituents to the QD core causes a reduction of the electronic coupling. Our results further support the notion that the ligand/QD complex should be considered as a distinct chemical system with emergent behavior rather than a QD core with ligands whose sole purpose is to passivate surface dangling bonds and prevent agglomeration.

Authors:

^[1];

^[2];

^[3];

^[4]; McNichols, Brett W. ^[5]; Castaneda, Chloe V. ^[4];

^[1];

^[6]; Galli, Giulia ^[2];

^[4]

National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
Univ. of Chicago, Chicago, IL (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)

Publication Date:: 2018-06-01

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Advanced Solar Photophysics (CASP); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1457664

Report Number(s):: NREL/JA-5900-70974
Journal ID: ISSN 1948-7185

Grant/Contract Number:: AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; quantum dots; quantum dot/ligand interactions; tunable properties; ligand exchange

Citation Formats


                    Kroupa, Daniel M., Voros, Marton, Brawand, Nicholas P., Bronstein, Noah, McNichols, Brett W., Castaneda, Chloe V., Nozik, Arthur J., Sellinger, Alan, Galli, Giulia, and Beard, Matthew C. Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.jpclett.8b01451.

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                    Kroupa, Daniel M., Voros, Marton, Brawand, Nicholas P., Bronstein, Noah, McNichols, Brett W., Castaneda, Chloe V., Nozik, Arthur J., Sellinger, Alan, Galli, Giulia, & Beard, Matthew C. Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes.  United States.  doi:10.1021/acs.jpclett.8b01451.

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                    Kroupa, Daniel M., Voros, Marton, Brawand, Nicholas P., Bronstein, Noah, McNichols, Brett W., Castaneda, Chloe V., Nozik, Arthur J., Sellinger, Alan, Galli, Giulia, and Beard, Matthew C. Fri .  
        "Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes".  United States.  doi:10.1021/acs.jpclett.8b01451.  https://www.osti.gov/servlets/purl/1457664.

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@article{osti_1457664,

  title        = {Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes},

  author       = {Kroupa, Daniel M. and Voros, Marton and Brawand, Nicholas P. and Bronstein, Noah and McNichols, Brett W. and Castaneda, Chloe V. and Nozik, Arthur J. and Sellinger, Alan and Galli, Giulia and Beard, Matthew C.},

  abstractNote = {We studied the optical absorption enhancement in colloidal suspensions of PbS quantum dots (QD) upon ligand exchange from oleate to a series of cinnamate ligands. By combining experiments and ab initio simulations, we elucidate physical parameters that govern the optical absorption enhancement. We find that within the cinnamate/PbS QD system the optical absorption enhancement scales linearly with the electronic gap of the ligand, indicating that the ligand/QD coupling occurs equally efficient between the QD and ligand HOMO and their respective LUMO levels. Disruption of the conjugation that connects the aromatic ring and its substituents to the QD core causes a reduction of the electronic coupling. Our results further support the notion that the ligand/QD complex should be considered as a distinct chemical system with emergent behavior rather than a QD core with ligands whose sole purpose is to passivate surface dangling bonds and prevent agglomeration.},

  doi          = {10.1021/acs.jpclett.8b01451},

  journal      = {Journal of Physical Chemistry Letters},

  number       = 12,

  volume       = 9,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

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DOI: 10.1021/acs.jpclett.8b01451

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