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Title: Role of Interface Chemistry in Opening New Radiative Pathways in InP/CdSe Giant Quantum Dots with Blinking-Suppressed Two-Color Emission

Abstract

Abstract InP/CdSe core/thick‐shell “giant” quantum dots (gQDs) that exhibit blinking‐suppressed two‐color excitonic emission have been synthesized and optically characterized. These type II heterostructures exhibit photoluminescence from both a charge‐separated, near‐infrared type II excitonic state, and a shell‐localized visible‐color excitonic state. Infrared emission is intrinsic to the type II QD, while visible emission can either be eliminated or enhanced through chemical modification of the InP surface prior to CdSe shell growth. Single‐QD photoluminescence measurements confirm that the dual color emission is from individual nanocrystals. The probability of observing dual emission from individual QDs and the extent of blinking suppression increases with shell thickness. Visible emission can be stabilized by the addition of a second shell of CdS, where the resulting InP/CdSe/CdS core/shell/shell nanocrystals afford the strongest blinking suppression, determined by analysis of the Mandel Q parameter. Transient absorption spectroscopy verifies that dual emission arises when hole relaxation from the shell to the core is impeded, possibly as a result of enhanced interfacial hole trapping at F − or O 2− defect sites. Electron–hole recombination in the shell then competes with slower type II recombination, providing a different mechanism for breaking Kasha's rule and allowing two colors of light to be emittedmore » from one nanostructure.« less

Authors:
 [1];  [2];  [3];  [3];  [4];  [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3];  [5]; ORCiD logo [3]
+ Show Author Affiliations
  1. Boston Univ., Boston, MA (United States)
  2. United States Naval Academy, Annapolis, MD (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Center for Integrated NanotechnologiesMaterials Physics and Applications DivisionLos Alamos National Laboratory Los Alamos NM 87545 USA
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Comenius Univ., Bratislava (Slovakia)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Building Technologies Office
OSTI Identifier:
1569573
Alternate Identifier(s):
OSTI ID: 1529019
Report Number(s):
LA-UR-18-28614
Journal ID: ISSN 1616-301X
Grant/Contract Number:  
89233218CNA000001; 2009LANL1096
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 37; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Material Science; dual emission; giant quantum dots; nanoscale engineering; suppressed blinking

Citation Formats

Dennis, Allison M., Buck, Matthew R., Wang, Feng, Hartmann, Nicolai F., Majumder, Somak, Casson, Joanna L., Watt, John Daniel, Doorn, Stephen K., Htoon, Han, Sykora, Milan, and Hollingsworth, Jennifer Ann. Role of Interface Chemistry in Opening New Radiative Pathways in InP/CdSe Giant Quantum Dots with Blinking-Suppressed Two-Color Emission. United States: N. p., 2019. Web. doi:10.1002/adfm.201809111.
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Dennis, Allison M., Buck, Matthew R., Wang, Feng, Hartmann, Nicolai F., Majumder, Somak, Casson, Joanna L., Watt, John Daniel, Doorn, Stephen K., Htoon, Han, Sykora, Milan, & Hollingsworth, Jennifer Ann. Role of Interface Chemistry in Opening New Radiative Pathways in InP/CdSe Giant Quantum Dots with Blinking-Suppressed Two-Color Emission. United States. https://doi.org/10.1002/adfm.201809111
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Dennis, Allison M., Buck, Matthew R., Wang, Feng, Hartmann, Nicolai F., Majumder, Somak, Casson, Joanna L., Watt, John Daniel, Doorn, Stephen K., Htoon, Han, Sykora, Milan, and Hollingsworth, Jennifer Ann. Mon . "Role of Interface Chemistry in Opening New Radiative Pathways in InP/CdSe Giant Quantum Dots with Blinking-Suppressed Two-Color Emission". United States. https://doi.org/10.1002/adfm.201809111. https://www.osti.gov/servlets/purl/1569573.
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@article{osti_1569573,
title = {Role of Interface Chemistry in Opening New Radiative Pathways in InP/CdSe Giant Quantum Dots with Blinking-Suppressed Two-Color Emission},
author = {Dennis, Allison M. and Buck, Matthew R. and Wang, Feng and Hartmann, Nicolai F. and Majumder, Somak and Casson, Joanna L. and Watt, John Daniel and Doorn, Stephen K. and Htoon, Han and Sykora, Milan and Hollingsworth, Jennifer Ann},
abstractNote = {Abstract InP/CdSe core/thick‐shell “giant” quantum dots (gQDs) that exhibit blinking‐suppressed two‐color excitonic emission have been synthesized and optically characterized. These type II heterostructures exhibit photoluminescence from both a charge‐separated, near‐infrared type II excitonic state, and a shell‐localized visible‐color excitonic state. Infrared emission is intrinsic to the type II QD, while visible emission can either be eliminated or enhanced through chemical modification of the InP surface prior to CdSe shell growth. Single‐QD photoluminescence measurements confirm that the dual color emission is from individual nanocrystals. The probability of observing dual emission from individual QDs and the extent of blinking suppression increases with shell thickness. Visible emission can be stabilized by the addition of a second shell of CdS, where the resulting InP/CdSe/CdS core/shell/shell nanocrystals afford the strongest blinking suppression, determined by analysis of the Mandel Q parameter. Transient absorption spectroscopy verifies that dual emission arises when hole relaxation from the shell to the core is impeded, possibly as a result of enhanced interfacial hole trapping at F − or O 2− defect sites. Electron–hole recombination in the shell then competes with slower type II recombination, providing a different mechanism for breaking Kasha's rule and allowing two colors of light to be emitted from one nanostructure.},
doi = {10.1002/adfm.201809111},
journal = {Advanced Functional Materials},
number = 37,
volume = 29,
place = {United States},
year = {Mon Jun 24 00:00:00 EDT 2019},
month = {Mon Jun 24 00:00:00 EDT 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/adfm.201809111
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Cited by: 7 works
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Figures / Tables:

Figure 1 Figure 1: TEM images of InP/CdSe QDs for a representative shell-thickness series: (a) ~1 ML CdSe, (b) ~4 ML CdSe, (c) ~7 ML CdSe, and (d) ~10 ML CdSe. (e) Normalized PL spectra spanning visible and NIR spectral range for the same shell series (progressively from bottom to top). Spectramore » are offset for clarity. The measurement transitions from the visible to the NIR detector at ~1.5 eV; solvent absorption effects are responsible for the artifact at ~1 eV.« less
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