Light Emission Mechanisms in CuInS2 Quantum Dots Evaluated by Spectral Electrochemistry

Addis S. Fuhr, Hyeong Jin Yun, Nikolay S. Makarov, Hongbo Li, Hunter McDaniel, Victor I Klimov

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Luminescent CuInS2 (CIS) quantum dots (QDs) exhibit highly efficient intragap emission and long, hundreds-of-nanoseconds radiative lifetimes. These spectral properties, distinct from structurally similar II-VI QDs, can be explained by the involvement of intragap defect states containing a localized hole capable of coupling with a conduction band electron for a radiative transition. However, the absolute energies of the intragap and band-edge states, the structure of the emissive defect(s), and the role and origin of nonemissive decay channels still remain poorly understood. Here, we address these questions by applying methods of spectral electrochemistry. Cyclic voltammetry measurements reveal a well-defined intragap state whose redox potential is close to that of the Cux defect state (where x = 1+ or 2+). The energy offset of this state from the valence band accounts well for the apparent photoluminescence Stokes shift observed in optical spectra. These results provide direct evidence that Cu-related defects serve as emission centers responsible for strong intragap emission from CIS QDs. We then use in situ spectroelectrochemistry to reveal two distinct emission pathways based on the differing oxidation states of Cu defects, which can be controlled by altering QD stoichiometry (1+ for stoichiometric QDs and 2+ for Cu-deficient QDs).

Original languageEnglish
Pages (from-to)2425-2435
Number of pages11
JournalACS Photonics
Volume4
Issue number10
DOIs
Publication statusPublished - Oct 18 2017

Fingerprint

Electrochemistry
Quantum Dots
Light emission
electrochemistry
Semiconductor quantum dots
light emission
quantum dots
Light
Defects
defects
Spectroelectrochemistry
radiative lifetime
Electron transitions
Valence bands
Conduction bands
Stoichiometry
Cyclic voltammetry
Oxidation-Reduction
optical spectrum
stoichiometry

Keywords

  • CuInS
  • defect photoluminescence
  • electron trapping
  • hole trapping
  • quantum dot
  • spectral electrochemistry

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Biotechnology
  • Atomic and Molecular Physics, and Optics
  • Electrical and Electronic Engineering

Cite this

Light Emission Mechanisms in CuInS2 Quantum Dots Evaluated by Spectral Electrochemistry. / Fuhr, Addis S.; Yun, Hyeong Jin; Makarov, Nikolay S.; Li, Hongbo; McDaniel, Hunter; Klimov, Victor I.

In: ACS Photonics, Vol. 4, No. 10, 18.10.2017, p. 2425-2435.

Research output: Contribution to journalArticle

Fuhr, Addis S. ; Yun, Hyeong Jin ; Makarov, Nikolay S. ; Li, Hongbo ; McDaniel, Hunter ; Klimov, Victor I. / Light Emission Mechanisms in CuInS2 Quantum Dots Evaluated by Spectral Electrochemistry. In: ACS Photonics. 2017 ; Vol. 4, No. 10. pp. 2425-2435.
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