Core/shell CdSe/ZnS quantum dots (QDs) are synthesized by a microfluidic reactor-assisted continuous reactor system. Photoluminescence and absorbance of synthesized CdSe/ZnS core/shell QDs are investigated by fluorescence spectrophotometry and online UV-Vis spectrometry. Three reaction conditions, namely; the shell coating reaction temperature, the shell coating reaction time, and the ZnS/CdSe precursor volume ratio, are combined in the synthesis process. The quantum yield of the synthesized CdSe QDs is determined for each condition. CdSe/ZnS QDs with a higher quantum yield are obtained compared to the discontinuous microfluidic reactor synthesis system. The maximum quantum efficiency is 98.3% when the reaction temperature, reaction time, and ZnS/CdSe ratio are 270℃, 10 s, and 0.05, respectively. Obtained results indicate that a continuous synthesis of the Core/shell CdSe/ZnS QDs with a high quantum efficiency could be achieved by isolating the reaction from the external environment.
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.
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.
Conjugated nanocrystals using CdSe/ZnS core/shell nanocrystal quantum dots modified by organic linkers and glucose oxidase (GOx) were prepared for use as biosensors. The trioctylphophine oxide (TOPO)-capped QDs were first modified to give them water-solubility by terminal carboxyl groups that were bonded to the amino groups of GOx through an EDC/NHS coupling reaction. As the glucose concentration increased, the photoluminescence intensity was enhanced linearly due to the electron transfer during the enzymatic reaction. The UV-visible spectra of the as-prepared QDs are identical to that of QDs-MAA. This shows that these QDs do not become agglomerated during ligand exchanges. A photoluminescence (PL) spectroscopic study showed that the PL intensity of the QDs-GOx bioconjugates was increased in the presence of glucose. These glucose sensors showed linearity up to approximately 15 mM and became gradually saturated above 15 mM because the excess glucose did not affect the enzymatic oxidation reaction past that amount. These biosensors show highly sensitive variation in terms of their photoluminescence depending on the glucose concentration.
We report on the light-emitting diode (LED) characteristics of core-shell CdSe/ZnS nanocrystal quantum dots (QDs) embedded in TiO2thin films on a Si substrate. A simple p-n junction could be formed when nanocrystal QDs on a p-type Si substrate were embedded in ~5 nm thick TiO2 thin film, which is inherently an n-type semiconductor. The TiO2 thin film was deposited over QDs at 200˚C using plasma-enhanced metallorganic chemical vapor deposition. The LED structure of TiO2/QDs/Si showed typical p-n diode currentvoltage and electroluminescence characteristics. The colloidal core-shell CdSe/ZnS QDs were synthesized via pyrolysis in the range of 220-280˚C. Pyrolysis conditions were optimized through systematic studies as functions of synthesis temperature, reaction time, and surfactant amount.