Thick-Shell CuInS2/ZnS Quantum Dots with Suppressed “Blinking” and Narrow Single-Particle Emission Line Widths

Huidong Zang, Hongbo Li, Nikolay S. Makarov, Kirill A. Velizhanin, Kaifeng Wu, Young Shin Park, Victor I Klimov

Research output: Contribution to journalArticle

67 Citations (Scopus)

Abstract

Quantum dots (QDs) of ternary I-III-VI2 compounds such as CuInS2 and CuInSe2 have been actively investigated as heavy-metal-free alternatives to cadmium- and lead-containing semiconductor nanomaterials. One serious limitation of these nanostructures, however, is a large photoluminescence (PL) line width (typically >300 meV), the origin of which is still not fully understood. It remains even unclear whether the observed broadening results from considerable sample heterogeneities (due, e.g., to size polydispersity) or is an unavoidable intrinsic property of individual QDs. Here, we answer this question by conducting single-particle measurements on a new type of CuInS2 (CIS) QDs with an especially thick ZnS shell. These QDs show a greatly enhanced photostability compared to core-only or thin-shell samples and, importantly, exhibit a strongly suppressed PL blinking at the single-dot level. Spectrally resolved measurements reveal that the single-dot, room-temperature PL line width is much narrower (down to ∼60 meV) than that of the ensemble samples. To explain this distinction, we invoke a model wherein PL from CIS QDs arises from radiative recombination of a delocalized band-edge electron and a localized hole residing on a Cu-related defect and also account for the effects of electron-hole Coulomb coupling. We show that random positioning of the emitting center in the QD can lead to more than 300 meV variation in the PL energy, which represents at least one of the reasons for large PL broadening of the ensemble samples. These results suggest that in addition to narrowing size dispersion, future efforts on tightening the emission spectra of these QDs might also attempt decreasing the “positional” heterogeneity of the emitting centers.

Original languageEnglish
Pages (from-to)1787-1795
Number of pages9
JournalNano Letters
Volume17
Issue number3
DOIs
Publication statusPublished - Mar 8 2017

Fingerprint

blinking
particle emission
Linewidth
Semiconductor quantum dots
quantum dots
Photoluminescence
photoluminescence
Electrons
Polydispersity
radiative recombination
heavy metals
Heavy Metals
Cadmium
Nanostructured materials
cadmium
Heavy metals
positioning
Nanostructures
emission spectra
Lead

Keywords

  • copper indium sulfide
  • Core/shell quantum dot
  • photoluminescence line width
  • single-dot spectroscopy
  • suppressed blinking

ASJC Scopus subject areas

  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanical Engineering

Cite this

Thick-Shell CuInS2/ZnS Quantum Dots with Suppressed “Blinking” and Narrow Single-Particle Emission Line Widths. / Zang, Huidong; Li, Hongbo; Makarov, Nikolay S.; Velizhanin, Kirill A.; Wu, Kaifeng; Park, Young Shin; Klimov, Victor I.

In: Nano Letters, Vol. 17, No. 3, 08.03.2017, p. 1787-1795.

Research output: Contribution to journalArticle

Zang, Huidong ; Li, Hongbo ; Makarov, Nikolay S. ; Velizhanin, Kirill A. ; Wu, Kaifeng ; Park, Young Shin ; Klimov, Victor I. / Thick-Shell CuInS2/ZnS Quantum Dots with Suppressed “Blinking” and Narrow Single-Particle Emission Line Widths. In: Nano Letters. 2017 ; Vol. 17, No. 3. pp. 1787-1795.
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AB - Quantum dots (QDs) of ternary I-III-VI2 compounds such as CuInS2 and CuInSe2 have been actively investigated as heavy-metal-free alternatives to cadmium- and lead-containing semiconductor nanomaterials. One serious limitation of these nanostructures, however, is a large photoluminescence (PL) line width (typically >300 meV), the origin of which is still not fully understood. It remains even unclear whether the observed broadening results from considerable sample heterogeneities (due, e.g., to size polydispersity) or is an unavoidable intrinsic property of individual QDs. Here, we answer this question by conducting single-particle measurements on a new type of CuInS2 (CIS) QDs with an especially thick ZnS shell. These QDs show a greatly enhanced photostability compared to core-only or thin-shell samples and, importantly, exhibit a strongly suppressed PL blinking at the single-dot level. Spectrally resolved measurements reveal that the single-dot, room-temperature PL line width is much narrower (down to ∼60 meV) than that of the ensemble samples. To explain this distinction, we invoke a model wherein PL from CIS QDs arises from radiative recombination of a delocalized band-edge electron and a localized hole residing on a Cu-related defect and also account for the effects of electron-hole Coulomb coupling. We show that random positioning of the emitting center in the QD can lead to more than 300 meV variation in the PL energy, which represents at least one of the reasons for large PL broadening of the ensemble samples. These results suggest that in addition to narrowing size dispersion, future efforts on tightening the emission spectra of these QDs might also attempt decreasing the “positional” heterogeneity of the emitting centers.

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