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
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%.
more »
« less
- Award ID(s):
- 1905164
- 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
More Like this
-
-
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.more » « less
-
Quantum Dot downconverters will enable high-resolution, bright, and wide color gamut displays for all display formats. We have developed a method to directly photopattern densely packed InP/ZnS Quantum Dots that achieve an optical density of 2 at sub 10 μm thicknesses while preserving the photoluminescent quantum yield.more » « less
-
Abstract The actual incorporation of dopant species into the ZnS Quantum Dots (QDs) host lattice will induce structural defects evidenced by a red shift in the corresponding exciton. The doping should create new intermediate energetic levels between the valence and conduction bands of the ZnS and affect the electron-hole recombination. These trap states would favour the energy transfer processes involved with the generation of cytotoxic radicals, so-called Reactive Oxygen Species, opening the possibility to apply these nanomaterials in cancer research. Any synthesis approach should consider the direct formation of the QDs in biocompatible medium. Accordingly, the present work addresses the microwave-assisted aqueous synthesis of pure and doped ZnS QDs. As-synthesized quantum dots were fully characterized on a structural, morphological and optical viewpoint. UV-Vis analyzes evidenced the excitonic peaks at approximately 310 nm, 314 nm and 315 nm for ZnS, Cu-ZnS and Mn-ZnS, respectively, Cu/Zn and Mn/Zn molar ratio was 0.05%. This indicates the actual incorporation of the dopant species into the host lattice. In addition, the Photoluminescence spectrum of non-doped ZnS nanoparticles showed a high emission peak that was red shifted when Mn 2+ or Cu 2+ were added during the synthesis process. The main emission peak of non-doped ZnS, Cu-doped ZnS and Mn-doped ZnS were observed at 438 nm, 487 nm and 521 nm, respectively. Forthcoming work will address the capacity of pure and Cu-, Mn-ZnS quantum dots to generate cytotoxic Reactive Oxygen Species for cancer treatment applications.more » « less
-
Abstract We investigate the effect of bis(imino)pyridine (BIP) ligands in guiding self-assembly of semiconducting CdSe/ZnS quantum dots (QDs) into three-dimensional multi-layered shells with diameters spanning the entire mesoscopic range, from 200 nm to 2 μm. The assembly process is directed by guest–host interactions between the BIP ligands and a thermotropic liquid crystal (LC), with the latter’s phase transition driving the process. Characterization of the shell structures, through scanning electron microscopy and dynamic light scattering, demonstrates that the average shell diameter depends on the BIP structure, and that changing one functional group in the chemical scaffold allows systematic tuning of shell sizes across the entire range. Differential scanning calorimetry confirms a relationship between shell sizes and the thermodynamic perturbation of the BIP molecules to the LC phase transition temperature, allowing analytical modeling of shell assembly energetics. This novel mechanism to controllably tune shell sizes over the entire mesoscale via one standard protocol is a significant development for research on in situ cargo/drug delivery platforms using nano-assembled structures.more » « less
An official website of the United States government

