Indium–Poly(carboxylic acid) Ligand Interactions Modify InP Quantum Dot Nucleation and Growth

Larson, Helen; Cossairt, Brandi M.

doi:10.1021/acs.chemmater.3c01309

Indium–Poly(carboxylic acid) Ligand Interactions Modify InP Quantum Dot Nucleation and Growth

Journal Article · Wed Jul 26 00:00:00 EDT 2023 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.3c01309· OSTI ID:1993125

Larson, Helen ^[1]; ^[2]

University of Washington, Seattle, WA (United States); University of Washington
University of Washington, Seattle, WA (United States)

Size control through precursor reactivity in InP quantum dot (QD) synthesis has been difficult due to the presence of kinetically persistent InP clusters when using conventional indium carboxylate and tris(trimethylsilyl)phosphine chemistry. However, the advent of indium halide/aminophosphine-based synthesis creates new opportunities to harness precursor design to impact nucleation and growth. Driven to further explore indium coordination as a synthetic handle in InP QD synthesis, we examined the effect of a strongly chelating anion on the nucleation and growth of InP QDs. Increasing the equivalents of metal-chelating aminopoly(carboxylic acid) EDTA ([CH₂N(CH₂CO₂H)₂]₂) (0–0.75 equiv per indium) is found to decrease the final diameter of InP QDs from 4.5 to 2.3 nm by lowering the initial InP growth rate. This size trend is rationalized by invoking a continuous nucleation model. Control experiments carried out with substoichiometric equivalents of indium do not exhibit a drastic size decrease, pointing to complex effects of EDTA on the indium precursor reactivity. By ¹H NMR spectroscopy, EDTA is identified to form an octahedral complex with indium that is less reactive. Furthermore, this competitive decrease in reactivity and in the effective concentration of indium precursor is proposed to suppress the initial InP growth rates and consequently decrease the final size of the nanocrystals.

View Accepted Manuscript (DOE)

Research Organization:: University of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0019288

OSTI ID:: 1993125

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 15 Vol. 35; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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