We present a fully continuous chip microreactor‐based multistage platform for the synthesis of quantum dots with heterostructures. The use of custom‐designed chip reactors enables precise control of heating profiles and flow distribution across the microfluidic channels while conducting multistep reactions. The platform can be easily reconfigured by reconnecting the differently designed chip reactors allowing for screening of various reaction parameters during the synthesis of nanocrystals. III–V core/shell quantum dots are chosen as model reaction systems, including InP/ZnS, InP/ZnSe, InP/CdS and InAs/InP, which are prepared in flow using a maximum of six chip reactors in series.
A high-temperature continuous stirred-tank reactor cascade for the multistep synthesis of InP/ZnS quantum dots
The multistep and continuous production of core–shell III–V semiconductor nanocrystals remains a technological challenge. We present a newly designed high-temperature and miniature continuous stirred-tank reactor cascade, for the continuous and scalable synthesis of InP/ZnS core–shell quantum dots with a safer aminophosphine precursor comparing to standard protocols involving (TMS) 3 P . The resulting InP/ZnS QDs exhibit emissions between 520 and 610 nm, narrow emission linewidths in the range of 46–64 nm and photoluminescence quantum yields up to 42%.
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- Award ID(s):
- 1905164
- NSF-PAR ID:
- 10286956
- Date Published:
- Journal Name:
- Reaction Chemistry & Engineering
- Volume:
- 6
- Issue:
- 3
- ISSN:
- 2058-9883
- Page Range / eLocation ID:
- 459 to 464
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
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Abstract We present a fully continuous chip microreactor‐based multistage platform for the synthesis of quantum dots with heterostructures. The use of custom‐designed chip reactors enables precise control of heating profiles and flow distribution across the microfluidic channels while conducting multistep reactions. The platform can be easily reconfigured by reconnecting the differently designed chip reactors allowing for screening of various reaction parameters during the synthesis of nanocrystals. III–V core/shell quantum dots are chosen as model reaction systems, including InP/ZnS, InP/ZnSe, InP/CdS and InAs/InP, which are prepared in flow using a maximum of six chip reactors in series.
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Indium phosphide quantum dots (InP QDs) are nontoxic nanomaterials with potential applications in photocatalytic and optoelectronic fields. Post-synthetic treatments of InP QDs are known to be essential for improving their photoluminescence quantum efficiencies (PLQEs) and device performances, but the mechanisms remain poorly understood. Herein, by applying ultrafast transient absorption and photoluminescence spectroscopies, we systematically investigate the dynamics of photogenerated carriers in InP QDs and how they are affected by two common passivation methods: HF treatment and the growth of a heterostructure shell (ZnS in this study). The HF treatment is found to improve the PLQE up to 16–20% by removing an intrinsic fast hole trapping channel ( τ h,non = 3.4 ± 1 ns) in the untreated InP QDs while having little effect on the band-edge electron decay dynamics ( τ e = 26–32 ns). The growth of the ZnS shell, on the other hand, is shown to improve the PLQE up to 35–40% by passivating both electron and hole traps in InP QDs, resulting in both a long-lived band-edge electron ( τ e > 120 ns) and slower hole trapping lifetime ( τ h,non > 45 ns). Furthermore, both the untreated and the HF-treated InP QDs have short biexciton lifetimes ( τ xx ∼ 1.2 ± 0.2 ps). The growth of an ultra-thin ZnS shell (∼0.2 nm), on the other hand, can significantly extend the biexciton lifetime of InP QDs to 20 ± 2 ps, making it a passivation scheme that can improve both the single and multiple exciton lifetimes. Based on these results, we discuss the possible trap-assisted Auger processes in InP QDs, highlighting the particular importance of trap passivation for reducing the Auger recombination loss in InP QDs.more » « less
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Density functional theory calculations are combined with time-resolved photoluminescence experiments to identify the species responsible for the reversible trapping of holes following photoexcitation of InP/ZnSe/ZnS core/shell/shell quantum dots (QDs) having excess indium in the shell [P. Cavanaugh et al., J. Chem. Phys. 155, 244705 (2021)]. Several possible assignments are considered, and a substitutional indium adjacent to a zinc vacancy, In3+/VZn2−, is found to be the most likely. This assignment is consistent with the observation that trapping occurs only when the QD has excess indium and is supported by experiments showing that the addition of zinc oleate or acetate decreases the extent of trapping, presumably by filling some of the vacancy traps. We also show that the addition of alkyl carboxylic acids causes increased trapping, presumably by the creation of additional zinc vacancies. The calculations show that either a single In2+ ion or an In2+–In3+ dimer is much too easily oxidized to form the reversible traps observed experimentally, while In3+ is far too difficult to oxidize. Additional experimental data on InP/ZnSe/ZnS QDs synthesized in the absence of chloride demonstrates that the reversible traps are not associated with Cl−. However, a zinc vacancy adjacent to a substitutional indium is calculated to have its highest occupied orbitals about 1 eV above the top of the valence band of bulk ZnSe, in the appropriate energy range to act as reversible traps for quantum confined holes in the InP valence band. The associated orbitals are predominantly composed of p orbitals on the Se atoms adjacent to the Zn vacancy.
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The incorporation of quantum dots in display technology has fueled a renewed interest in InP-based quantum dots, but difficulty controlling the Zn chemistry during shelling has stymied thick, even ZnSe shell growth. The characteristic uneven, lobed morphology of Zn-based shells is difficult to assess qualitatively and measure through traditional methods. Here, we present a methodological study utilizing quantitative morphological analysis of InP/ZnSe quantum dots to analyze the impact of key shelling parameters on InP core passivation and shell epitaxy. We compare conventional hand-drawn measurements with an open-source semi-automated protocol to showcase the improved precision and speed of this method. Additionally, we find that quantitative morphological assessment can discern morphological trends in morphologies that qualitative methods cannot. In conjunction with ensemble fluorescence measurements, we find that changes to shelling parameters that promote even shell growth often do so at the cost of core homogeneity. These results indicate that the chemistry of passivating the core and promoting shell growth must be balanced carefully to maximize brightness while maintaining emission color-purity.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0re00454e
