Physico-Chemical Transformation and Toxicity of Multi-Shell InP Quantum Dots under Simulated Sunlight Irradiation, in an Environmentally Realistic Scenario
Résumé
Quantum dots (QDs) are widely used in optoelectronics, lighting, and photovoltaics leading
to their potential release into the environment. The most promising alternative to the highly toxic
cadmium selenide (CdSe) QDs are indium phosphide (InP) QDs, which show reduced toxicity and
comparable optical and electronic properties. QD degradation leads to the release of toxic metal ions
into the environment. Coating the QD core with robust shell(s) composed of another semi-conductor
material enhances their properties and protects the QD from degradation. We recently developed
double-shelled InP QDs, which proved to be less toxic than single-shell QDs. In the present study,
we confirm their reduced cytotoxicity, with an LC50 at 77 nM for pristine gradient shell QDs and
>100 nM for pristine thin and thick shell QDs. We also confirm that these three QDs, when exposed
to simulated sunlight, show greater cytotoxicity compared to pristine ones, with LC50 ranging from
15 to 23 nM. Using a combination of spectroscopic and microscopic techniques, we characterize the
degradation kinetics and transformation products of single- and double-shell QDs, when exposed
to solar light at high temperature, simulating environmental conditions. Non-toxic pristine QDs
degrade to form toxic In–phosphate, In–carboxylate, Zn–phosphate, and oxidized Se, all of which
precipitate as heterogeneous deposits. Comparison of their degradation kinetics highlights that the
QDs bearing the thickest ZnS outer shell are, as expected, the most resistant to photodegradation
among the three tested QDs, as gradient shell, thin shell, and thick shell QDs lose their optical
properties in less than 15 min, 60 min, and more than 90 min, respectively. They exhibit the highest
photoluminescence efficiency, i.e., the best functionality, with a photoluminescence quantum yield in
aqueous solution of 24%, as compared to 18% for the gradient shell and thin shell QDs. Therefore,
they can be considered as safer-by-design QDs.
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