Emerging Strategies for the Rational Synthesis of Copper-Chalcogenide Based Hetero-Nanorods

Celso de Mello Donega^a

^aDebye Institute for Nanomaterials Science, Utrecht University, Heidelberglaan, 8, Utrecht, Netherlands

Materials for Sustainable Development Conference (MATSUS)
Proceedings of nanoGe Spring Meeting 2022 (NSM22)

#SNI22. Semiconductor Nanocrystals I: Basic Science (synthesis, spectroscopy, electronic structure, device and application)

Online, Spain, 2022 March 7th - 11th

Organizers: Emmanuel Lhuillier, Sandrine Ithurria and Angshuman Nag

Invited Speaker, Celso de Mello Donega, presentation 087
DOI: https://doi.org/10.29363/nanoge.nsm.2022.087
Publication date: 7th February 2022

Colloidal semiconductor heteronanocrystals (HNCs) exhibit unique optoelectronic properties that are inaccessible to single-component NCs, making them promising materials for a wide range of applications. The optoelectronic properties of HNCs are determined not only by the bandgap and band alignment of its constituent materials but also by their morphology and heteroarchitecture [1]. Applications requiring efficient charge separation (e.g., photovoltaics and photocatalysis) greatly benefit from anisotropic morphologies, such as heteronanorods. Most of the work on heteronanorods has focused on Cd-chalcogenide-based HNCs. However, given the toxicity of Cd, the potential of these materials for large scale applications is limited.

Copper-chalcogenide based NCs have attracted increasing attention as promising alternatives for Cd- and Pb-chalcogenide NCs due to their low toxicity, large absorption cross-sections across a broad spectral range, composition-dependent band gaps in the 1 to 2.5 eV range, and photoluminescence tunability, spanning a spectral window that extends from the UV to the NIR depending on the NC size and composition [2,3].

Several synthetic strategies have been used in the quest for high-quality colloidal copper chalcogenide based HNCs. The most promising ones are based on the multistage approach, which allows the combination of different synthesis techniques (e.g., cation exchange [4,5] or seeded growth [6-9]) in a sequential manner in order to achieve the targeted preparation of colloidal HNCs. In this talk, I will discuss a selection of recent examples, chosen in order to provide an overview of the current status of the quest for Cd- and Pb-free HNCs and to illustrate specific synthesis strategies: CuInSe₂/CuInS₂ dot core/rod shell heteronanorods [4], Cu_1.8S-based multicomponent axially segmented heteronanorods [5], CuInS₂/ZnS dot core/rod shell heteronanorods [6], and Janus-type Cu_2‒xS/CuInS₂ and Cu_2−xS/ZnS heteronanorods [8,9]. I will show that by combining the design principles of post-synthetic heteroepitaxial seeded growth and nanoscale cation exchange into multistage synthesis strategies one can potentially gain access to a plethora of Cu-chalcogenide-basedmulticomponent heteronanorods with diameters in the quantum confinement regime.

References:

[1] de Mello Donega, C. Synthesis and Properties of Colloidal Heteronanocrystals. Chem. Soc. Rev. 2011, 40, 1512–1546.

[2] van der Stam, W.; Berends, A. C.; de Mello Donegá, C. Prospects of Colloidal Copper Chalcogenide Nanocrystals. ChemPhysChem 2016, 17, 559–581

[3] Berends, A. C.; Mangnus, M. J. J.; Xia, C.; Rabouw, F. T.; de Mello Donega, C. Optoelectronic Properties of Ternary I-III-VI2 Semiconductor Nanocrystals: Bright Prospects with Elusive Origins. J. Phys. Chem. Lett. 2019, 10, 1600-1616.

[4] van der Stam, W.; Bladt, E.; Rabouw, F. T.; Bals, S.; de Mello Donega, C. Near-Infrared Emitting CuInSe2/CuInS2 Dot Core/Rod Shell Heteronanorods by Sequential Cation Exchange. ACS Nano 2015, 9, 11430–11438.

[5] Steimle, B. C.; Fenton, J. L.; Schaak, R. E., Rational Construction of a Scalable Heterostructured Nanorod Megalibrary. Science 2020, 367, 418–424

[6] Xia, C.; Winckelmans, N.; Prins, P. T.; Bals, S.; Gerritsen, H. C.; de Mello Donega, C. NIR-Emitting CuInS2/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth. J. Am. Chem. Soc. 2018, 140, 5755-5763

[7] Berends, A. C.; van der Stam, W.; Hofmann, J. P.; Bladt, E.; Meeldijk, J. D.; Bals, S.; de Mello Donega, C. Interplay Between Surface Chemistry, Precursor Reactivity and Temperature Determines Outcome of ZnS Shelling Reactions on CuInS2 Nanocrystals. Chem. Mater. 2018, 30, 2400-2413.

[8] Xia, C.; van Oversteeg, C. H. M.; Bogaards, V. C. L.; Spanjersberg, T. H. M.; Visser, N. L.; Berends, A. C.; Meeldijk, J. D.; de Jongh, P. E.; de Mello Donega, C. Synthesis and Formation Mechanism of Colloidal Janus-Type Cu2‒xS/CuInS2 Heteronanorods via Seeded-Injection. ACS Nano 2021, 15, 9987-9999

[9] Xia, C.; Pedrazo-Tardajos, A.; Wang, D.; Meeldijk, J. D.; Gerritsen, H. C.; Bals, S.; de Mello Donega, C. Seeded Growth Combined with Cation Exchange for the Synthesis of Anisotropic Cu2−xS/ZnS, Cu2−xS, and CuInS2 Nanorods. Chem. Mater. 2021, 33, 102-116

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