Over the last decade, the study of the synthesis of semiconductor colloidal quantum dots has progressed at a tremendous rate. Colloidal quantum dots, which possess unique spectral-luminescent characteristics, are of great interest in the development of novel materials and devices, which are promising for use in various fields. Several studies have been carried out on hot injection synthesis methods. However, these methods have been found to be unsuitable for large-capacity synthesis. Therefore, this review paper introduces synthesis methods other than the hot injection synthesis method, to synthesize quantum dots with excellent optical properties, through continuous synthesis and large capacity synthesis. In addition, examples of the application of synthesized colloid quantum dots in displays, solar cells, and bio industries are provided.
Colloidally synthesized luminescent nanocrystals (NCs) have attracted tremendous attention due to their unique nanoscale optical and electronic properties. The emission properties of these NCs can be precisely tuned by controlling their size, shape, and composition as well as by introducing appropriate dopant impurities. Nowadays, these NCs are actively utilized for various applications such as optoelectronic devices including light emitting diodes (LEDs), lasers, and solar cells, and bio-medical applications such as imaging agents and bio-sensors. In this review, we classify luminescent nanomaterials into quantum dots (QDs), upconversion nanoparticles (UCNPs), and perovskite NCs and present their intrinsic emission mechanism. Furthermore, the recently emerging issues of efficiency, toxicity, and durability in these materials are discussed for better understanding of industry demands. As well, the future outlook will be offered for researchers to guide the direction of future research.
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In this study, the surface passivation process for InP-based quantum dots (QDs) is investigated. Surface coating is performed with poly(methylmethacrylate) (PMMA) and thioglycolic acid. The quantum yield (QY) of a PMMA-coated sample slightly increases by approximately 1.3% relative to that of the as-synthesized InP/ZnS QDs. The QYs of the uncoated and PMMA-coated samples drastically decrease after 16 days because of the high defect state density of the InP-based QDs. PMMA does not have a significant effect on the defect passivation. Thioglycolic acid is investigated in this study for the effective surface passivation of InP-based QDs. Surface passivation with thioglycolic acid is more effective than that with the PMMA coating, and the QY increases from 1.7% to 11.3%. ZnS formed on the surface of the InP QDs and S in thioglycolic acid show strong bonding property. Additionally, the QY is further increased up to 21.0% by the photochemical reaction. Electron–hole pairs are formed by light irradiation and lead to strong bonding between the inorganic and thioglycolic acid sulfur. The surface of the InP core QDs, which does not emit light, is passivated by the irradiated light and emits green light after the photochemical reaction.
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In this study, we investigate the optical properties of InP/ZnS core/shell quantum dots (QDs) by controlling the synthesis temperature of InP. The size of InP determined by the empirical formula tends to increase with temperature: the size of InP synthesized at 140oC and 220oC is 2.46 nm and 4.52 nm, respectively. However, the photoluminescence (PL) spectrum of InP is not observed because of the formation of defects on the InP surface. The growth of InP is observed during the deposition of the shell (ZnS) on the synthesized InP, which is ended up with green-red PL spectrum. We can adjust the PL spectrum and absorption spectrum of InP/ZnS by simply adjusting the core temperature. Thus, we conclude that there exists an optimum shell thickness for the QDs according to the size.
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This study investigates the main growth mechanism of InP during InP/ZnS reaction of quantum dots (QDs). The size of the InP core, considering a synthesis time of 1-30 min, increased from the initial 2.56 nm to 3.97 nm. As a result of applying the proposed particle growth model, the migration mechanism, with time index 7, was found to be the main reaction. In addition, after the removal of unreacted In and P precursors from bath, further InP growth (of up to 4.19 nm (5%)), was observed when ZnS was added. The full width at half maximum (FWHM) of the synthesized InP/ZnS quantum dots was found to be relatively uniform, measuring about 59 nm. However, kinetic growth mechanism provides limited information for InP / ZnS core shell QDs, because the surface state of InP changes with reaction time. Further study is necessary, in order to clearly determine the kinetic growth mechanism of InP / ZnS core shell QDs.
In this study, simple chemical synthesis of green emitting Cd-free InP/ZnS QDs is accomplished by reacting In, P, Zn, and S precursors by one-pot process. The particle size and the optical properties were tailored, by controlling various experimental conditions, including [In]/[MA] (MA: myristic acid) mole ratio, reaction temperature and reaction time. The results of ultraviolet–visible spectroscopy (UV-vis), and of photoluminescence (PL), reveal that the exciton emission of InP was improved by surface coating, with a layer of ZnS. We report the correlation between each experimental condition and the luminescent properties of InP/ZnS core/shell QDs. Transmission electron microscopy (TEM), and X-ray powder diffraction (XRD) techniques were used to characterize the as-synthesized QDs. In contrast to core nanoparticles, InP/ZnS core/shell treated with surface coating shows a clear ultraviolet peak. Besides this work, we need to study what clearly determines the shell kinetic growth mechanism of InP/ZnS core shell QDs.
We have investigated the washing method of as-synthesized CdSe/ZnS core/shell structure quantum dots (QDs) and the effective surface passivation method of the washed QDs using PMMA. The quantum yield (QY%) of assynthesized QDs decreases with time, from 79.3% to 21.1%, owing to surface reaction with residual organics. The decreased QY% is restored to the QY% of as-synthesized QDs by washing. However, the QY% of washed QDs also decreases with time, owing to the absence of surface passivation layer. On the other hand, the PMMA-treated QDs maintained a relatively higher QY% after washing than that of the washed QDs that were kept in toluene solution for 30 days. Formation of the PMMA coating layer on CdSe/ZnS QD surface is confirmed by HR-TEM and FT-IR. It is found that the PMMA surface coating, when combined with washing, is useful to be applied in the storage of QDs, owing to its long-term stability.
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Quantum dots (QDs) are capable of controlling the typical emission and absorption wavelengths because of the bandgap widening effect of nanometer-sized particles. These phosphor particles have been used in optical devices, photovoltaic devices, advanced display devices, and several biomedical complexes. In this study, we synthesize ZnSe QDs with controlled surface defects by a heating-up method. The optical properties of the synthesized particles are analyzed using UV-visible and photoluminescence (PL) measurements. Calculations indicate nearly monodisperse particles with a size of about 5.1 nm at 260°C (full width at half maximum = 27.7 nm). Furthermore, the study results confirm that successful doping is achieved by adding Eu3+ preparing the growth phase of the ZnSe:Eu QDs when heating-up method. Further, we investigate the correlation between the surface defects and the luminescent properties of the QDs.
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High-quality colloidal CdSe/ZnS (core/shell) is synthesized using a continuous microreactor. The particle size of the synthesized quantum dots (QDs) is a function of the precursor flow rate; as the precursor flow rate increases, the size of the QDs decreases and the band gap energy increases. The photoluminescence properties are found to depend strongly on the flow rate of the CdSe precursor owing to the change in the core size. In addition, a gradual shift in the maximum luminescent wave (λmax) to shorter wavelengths (blue shift) is found owing to the decrease in the QD size in accordance with the quantum confinement effect. The ZnS shell decreases the surface defect concentration of CdSe. It also lowers the thermal energy dissipation by increasing the concentration of recombination. Thus, a relatively high emission and quantum yield occur because of an increase in the optical energy emitted at equal concentration. In addition, the maximum quantum yield is derived for process conditions of 0.35 ml/min and is related to the optimum thickness of the shell material.
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