Abstract
A simple liquid-phase laser fragmentation approach, resulting in the rapid transformation of CdSe microcrystals into colloidal quantum dots (QDs), is presented. Laser fragmentation is achieved by irradiating a CdSe suspension in dimethylformamide with intense infrared, picosecond laser pulses followed by surface passivation with oleylamine or different types of phosphines. The generated QDs reveal perfect colloidal stability preventing agglomeration and precipitation, and show characteristic QD absorption and fluorescence characteristics, whereas their emission properties strongly depend on the surface states and applied capping ligands. These QDs show distinct photoemission under 405-nm single-photon and 800-nm multi-photon excitations in the 560- to 610-nm spectral region corresponding to the QDs size of about 1.5–2 nm in diameter which is confirmed by transmission electron microscopy.
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Acknowledgments
This work was conducted in the framework of German Academic Exchange Service grant A/14/02402. Additionally, the authors received financial support from the Deutsche Forschungsgemeinschaft within the excellence cluster REBRITH (Exc62/1), and the Collaborative Research Center/Transregio 123 “Planar Optronic Systems.” The authors would like to acknowledge Torben Kodanek and Andreas Wolf from the Laboratory of Nano and Quantum Engineering in Hannover for TEM and the excitation spectra measurements, respectively.
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Appendix: Stability of solvents towards laser irradiation
Appendix: Stability of solvents towards laser irradiation
Majority of organic solvents tested for stability towards laser irradiation in this work (toluene, chloroform, cyclohexane, dichloromethane, dimethylformamide, methanol, ethanol) showed certain signs of degradation. During 5 min of irradiation with pulse repetition rate of 5 kHz, the color of toluene, chloroform, cyclohexane, and dichloromethane changed drastically to colors between dark yellow and brownish yellow. Under the same conditions, dimethylformamide, methanol, and ethanol did not show essential color changes. At the same time, they showed raise of absorbance in the UV range (Figs. 2a, 8) with methanol exhibiting the lowest increase of absorbance. Except methanol and ethanol all other tested solvents after laser irradiation had rather strong fluorescence emission when excited by 405-nm laser diode. But lack of such emission in methanol and ethanol can be simply explained by the absence of absorbance at this excitation wavelength.
Absorbance spectra of ethanol (1) and methanol (2) after laser irradiation (5 min, fp = 5 kHz) and spectra of CdSe fragmentation products in ethanol (3) and methanol (4) (2 min, fp = 5 kHz)
When CdSe powder suspension was treated with laser radiation in ethanol and methanol there was observed essential and almost identical growth of absorbance in the whole visible range (Fig. 8) but without any distinct peaks typical for monodisperse QDs. The laser fragmentation products also did not show any noticeable fluorescence when excited at 405 nm. Such results could be explained either by formation of broad range of QD sizes that lack surface passivation and rich for surface defects leading to nonradiative excitons decay or by essential chemical degradation of fragmented CdSe products without formation of nanoparticles at all.
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Zholudov, Y.T., Sajti, C.L., Slipchenko, N.N. et al. Generation of fluorescent CdSe nanocrystals by short-pulse laser fragmentation. J Nanopart Res 17, 490 (2015). https://doi.org/10.1007/s11051-015-3303-z
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DOI: https://doi.org/10.1007/s11051-015-3303-z