Composition-Dependent Optical Properties of Cu-Zn-In-Se Colloidal Nanocrystals Synthesized via Cation Exchange

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Ankita Bora - , Chair of Physical Chemistry, TUD Dresden University of Technology (Author)
  • Josephine Lox - , Chair of Physical Chemistry, TUD Dresden University of Technology (Author)
  • René Hübner - , Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Nelli Weiß - , Chair of Physical Chemistry, TUD Dresden University of Technology (Author)
  • Houman Bahmani Jalali - , Italian Institute of Technology (Author)
  • Francesco Di Stasio - , Italian Institute of Technology (Author)
  • Christine Steinbach - , Leibniz Institute of Polymer Research Dresden (Author)
  • Nikolai Gaponik - , Chair of Physical Chemistry, TUD Dresden University of Technology (Author)
  • Vladimir Lesnyak - , Chair of Physical Chemistry, TUD Dresden University of Technology (Author)

Abstract

Copper chalcogenide-based nanocrystals (NCs) are a suitable replacement for toxic Cd/Pb chalcogenide-based NCs in a wide range of applications including photovoltaics, optoelectronics, and biological imaging. However, despite rigorous research, direct synthesis approaches of this class of compounds suffer from inhomogeneous size, shape, and composition of the NC ensembles, which is reflected in their broad photoluminescence (PL) bandwidths. A partial cation exchange (CE) strategy, wherein host cations in the initial binary copper chalcogenide are replaced by incoming cations to form ternary/quaternary multicomponent NCs, has been proven to be instrumental in achieving better size, shape, and composition control to this class of nanomaterials. Additionally, adopting synthetic strategies which help to eliminate inhomogeneities in the NC ensembles can lead to narrower PL bandwidths, as was shown by single-particle studies on I-III-VI2-based semiconductor NCs. In this work, we formulate a two-step colloidal synthesis of Cu-Zn-In-Se (CZISe) NCs via a partial CE pathway. The first step is the synthesis of Cu2-xSe NCs, which serve as a template for the subsequent CE reaction. The second step is the incorporation of the In3+and Zn2+guest cations into the synthesized Cu2-xSe NCs via simultaneous injection of both metal precursors, which results in gradient-alloyed CZISe NCs with a Zn-rich surface. The as-synthesized NCs exhibit near-infrared (NIR) PL without an additional shell growth, which is typically required in most of the developed protocols. The photoluminescence quantum yield (PLQY) of these Cu chalcogenide-based NCs reaches 20%. These NCs also exhibit intriguingly narrow PL bands, which challenges the notion of broad PL bands being an inherent property of this class of NCs. Additionally, a variation in the feed ratios of the incoming cations, i.e., In/Zn, results in the variation of the composition of the synthesized NCs. Henceforth, the optical properties of these NCs could be tuned by a simple variation of the composition of the NCs achieved by varying the feed ratios of the incoming cations. Within a narrow size distribution, the PL maxima range from 980 to 1060 nm, depending on the composition of the NCs. Post-synthetic surface modification of the synthesized NCs enabled the replacement of the parent long-chain organic ligands with smaller species, which is essential for their prospective applications requiring efficient charge transport. With PL emission extended into the NIR, the synthesized NCs are suitable for an array of potential applications, most importantly in the area of solar energy harvesting and bioimaging. The large Stokes shift inherent to these materials, their absorption in the solar range, and their NIR PL within the biological window make them suitable candidates.

Details

Original languageEnglish
Pages (from-to)4068-4077
Number of pages10
JournalChemistry of materials
Volume35
Issue number10
Publication statusPublished - 23 May 2023
Peer-reviewedYes

External IDs

ORCID /0000-0002-8827-2881/work/173051111