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Photoluminescence of Ag-In-S/ZnS quantum dots: Excitation energy dependence and low-energy electronic structure

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Abstract

Cd-free I-III-VI group semiconductor quantum dots (QDs) like Ag-In-S and Cu-In-S show unstructured absorption spectra with a pronounced Urbach tail, rendering the determination of their band gap energy (Eg) and the energy structure of the exciton difficult. Additionally, the origin of the broad photoluminescence (PL) band with lifetimes of several hundred nanoseconds is still debated. This encouraged us to study the excitation energy dependence (EED) of the PL maxima, PL spectral band widths, quantum yields (QYs), and decay kinetics of AIS/ZnS QDs of different size, composition, and surface capping ligands. These results were then correlated with the second derivatives of the corresponding absorption spectra. The excellent match between the onset of changes in PL band position and spectral width with the minima found for the second derivatives of the absorption spectra underlines the potential of the EED approach for deriving Eg values of these ternary QDs from PL data. The PL QY is, however, independent of excitation energy in the energy range studied. From the EED of the PL features of the AIS/ZnS QDs we could also derive a mechanism of the formation of the low-energy electronic structure. This was additionally confirmed by a comparison of the EED of PL data of as-synthesized and size-selected QD ensembles and the comparison of these PL data with PL spectra of single QDs. These results indicate a strong contribution of intrinsic inhomogeneous PL broadening to the overall emission features of AIS/ZnS QDs originating from radiative transitions from a set of energy states of defects localized at different positions within the quantum dot volume, in addition to contributions from dimensional and chemical broadening. This mechanism was confirmed by numerically modelling the absorption and PL energies with a simple mass approximation for spherical QDs and a modified donor-acceptor model, thereby utilizing the advantages of previously proposed PL mechanisms of ternary QDs. These findings will pave the road to a deeper understanding of the nature of PL in quantum confined I-III-VI group semiconductor nanomaterials.

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Acknowledgements

U. Resch-Genger gratefully acknowledges financial support from the grants RE1203/17-1 (M-Eranet project ICENAP; financial support of F. Weigert) and RE1203/12-3 (financial support of L. Dhamo) from the German Research Council (DFG). A. Baimuratov, I. Rukhlenko and A. Baranov gratefully acknowledge support from the Federal Target Program for Research and Development of the Ministry of Science and Higher Education of the Russian Federation (No. 14.587.21.0047, project identifier RFMEFI58718X0047). I. Martynenko acknowledges support from an Adolf-Martens fellowship granted by BAM. The authors gratefully acknowledge fruitful discussions with J. Santos, University of Porto and performance of first DMA measurements by A. Schmidt, BAM (Division 4.2).

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Authors and Affiliations

  1. Federal Institute for Materials Research and Testing (BAM), Unter den Eichen 87, 12205, Berlin, Germany

    Irina V. Martynenko, Florian Weigert, Lorena Dhamo, Philip Nickl, Ilona Doerfel, Jutta Pauli & Ute Resch-Genger

  2. ITMO University, 49 Kronverksky Pr., St. Petersburg, 197101, Russia

    Anvar S. Baimuratov, Ivan D. Rukhlenko & Alexander V. Baranov

  3. University of Porto, Rua de Jorge Viterbo Ferreira, 228, 4050-313, Porto, Portugal

    José X. Soares

  4. Institute of Photonics and Optical Sciences (IPOS), School of Physics, The University of Sydney, Camperdown 2006, NSW, Australia

    Ivan D. Rukhlenko

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  1. Irina V. Martynenko
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Martynenko, I.V., Baimuratov, A.S., Weigert, F. et al. Photoluminescence of Ag-In-S/ZnS quantum dots: Excitation energy dependence and low-energy electronic structure. Nano Res. 12, 1595–1603 (2019). https://doi.org/10.1007/s12274-019-2398-4

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