Title: Quantitative morphological analysis of InP-based quantum dots reveals new insights into the complexity of shell growth
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
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%.
Yang, Wenxing; Yang, Yawei; Kaledin, Alexey L.; He, Sheng; Jin, Tao; McBride, James R.; Lian, Tianquan
(, Chemical Science)
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.
Murray, Ian M; Choi, Sinil; Jemison, Henry M; Kim, Sunghu; Altman, Alison B; Jeong, Sohee; Son, Dong Hee
(, The Journal of Chemical Physics)
We investigated the pressure-dependent exciton absorption and photoluminescence (PL) properties of colloidal InAs/ZnSe core/shell quantum dots (QDs) emitting near-infrared (NIR) photons, an environmentally friendly alternative to heavy-metal-containing NIR QDs. A detailed analysis of exciton absorption and emission spectra was conducted in the pressure range of 0–10 GPa, focusing on the energy shifts, PL intensity, and lineshape changes with pressure. The pressure coefficients for exciton absorption and PL peaks were ∼70% of the bulk InAs value, with enhanced bandgap nonlinearity tentatively attributed to the higher bulk modulus of QDs compared to bulk material. The pressure-induced shifts in exciton absorption and PL peaks were reversible upon compression and decompression, with no indication of the semiconductor-to-metallic phase transition observed in bulk InAs around 7 GPa. However, PL intensity exhibited partial irreversibility, suggesting defect formation at the core/shell interface under pressure. From the findings of this study, along with previous high-pressure studies on molecular beam epitaxy-grown InAs QDs on GaAs, we infer the importance of the shell in determining the pressure response of exciton absorption and PL in core/shell QD structures with non-negligible interfacial strain and wave function spill into the shell.
Czyz, Magdalena H; Snee, Preston T
(, The Journal of Chemical Physics)
Charge carriers in a solid-state material are modeled as free particles with a variable “effective” mass that is derived from the curvature of the conduction/valence band. These effective masses of electrons and holes are unique to each material and are dependent on the internal band structure (e.g., heavy vs light holes). Quantum mechanical characterizations of nanomaterials employ effective mass theory using particle-in-a-box paradigms to calculate quantum confinement (i.e., localization) energies. However, semiconductor heterostructures, such as core/shell quantum dots, have spatially variant masses, and as a result, the Schrodinger equation must be solved via a numerical approach incorporating the Hermitian kinetic energy operator T̂∼∇m−1x∇. To this end, the split operator “spectral” method was modified with the variable mass kinetic energy operator to study a variety of core/shell quantum dots. The results reveal a preferential localization of charge carriers into regions of high effective mass, which has a non-negligible effect on structure/property relationships that are increasingly being used to guide the synthesis of semiconductor heterostructures, such as “giant” type II quantum dots.
Schuck, Christopher F.; Roy, Simon K.; Garrett, Trent; Yuan, Qing; Wang, Ying; Cabrera, Carlos I.; Grossklaus, Kevin A.; Vandervelde, Thomas E.; Liang, Baolai; Simmonds, Paul J.
(, Scientific Reports)
Abstract Driven by tensile strain, GaAs quantum dots (QDs) self-assemble on In0.52Al0.48As(111)A surfaces lattice-matched to InP substrates. In this study, we show that the tensile-strained self-assembly process for these GaAs(111)A QDs unexpectedly deviates from the well-known Stranski-Krastanov (SK) growth mode. Traditionally, QDs formed via the SK growth mode form on top of a flat wetting layer (WL) whose thickness is fixed. The inability to tune WL thickness has inhibited researchers’ attempts to fully control QD-WL interactions in these hybrid 0D-2D quantum systems. In contrast, using microscopy, spectroscopy, and computational modeling, we demonstrate that for GaAs(111)A QDs, we can continually increase WL thickness with increasing GaAs deposition, even after the tensile-strained QDs (TSQDs) have begun to form. This anomalous SK behavior enables simultaneous tuning of both TSQD size and WL thickness. No such departure from the canonical SK growth regime has been reported previously. As such, we can now modify QD-WL interactions, with future benefits that include more precise control of TSQD band structure for infrared optoelectronics and quantum optics applications.
Click, Sophia M., Koziel, Alexandra C., Torres, Ruben, Flores, Sebastian, McBride, James R., and Rosenthal, Sandra J. Quantitative morphological analysis of InP-based quantum dots reveals new insights into the complexity of shell growth. Retrieved from https://par.nsf.gov/biblio/10471619. The Journal of Chemical Physics 158.22 Web. doi:10.1063/5.0149097.
Click, Sophia M., Koziel, Alexandra C., Torres, Ruben, Flores, Sebastian, McBride, James R., & Rosenthal, Sandra J. Quantitative morphological analysis of InP-based quantum dots reveals new insights into the complexity of shell growth. The Journal of Chemical Physics, 158 (22). Retrieved from https://par.nsf.gov/biblio/10471619. https://doi.org/10.1063/5.0149097
Click, Sophia M., Koziel, Alexandra C., Torres, Ruben, Flores, Sebastian, McBride, James R., and Rosenthal, Sandra J.
"Quantitative morphological analysis of InP-based quantum dots reveals new insights into the complexity of shell growth". The Journal of Chemical Physics 158 (22). Country unknown/Code not available: Journal of Chemical Physics. https://doi.org/10.1063/5.0149097.https://par.nsf.gov/biblio/10471619.
@article{osti_10471619,
place = {Country unknown/Code not available},
title = {Quantitative morphological analysis of InP-based quantum dots reveals new insights into the complexity of shell growth},
url = {https://par.nsf.gov/biblio/10471619},
DOI = {10.1063/5.0149097},
abstractNote = {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.},
journal = {The Journal of Chemical Physics},
volume = {158},
number = {22},
publisher = {Journal of Chemical Physics},
author = {Click, Sophia M. and Koziel, Alexandra C. and Torres, Ruben and Flores, Sebastian and McBride, James R. and Rosenthal, Sandra J.},
}
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