Optical Absorbance Spectroscopy.
In Fig. 1, the absorbance spectrum of both CdTe/ZnS quantum dot samples is exhibited. Both the reference sample and Sample 1 (it which contains an equimolar concentration of ZnCl2 and thiourea of 0.04 M), have an excitonic peak with well-defined line shape, and with a mean width at maximum intensity of the order of 40 nm, which indicates that the size distribution is nearly monodisperse. Different case resulted for Sample 2, prepared with an equimolar concentration of ZnCl2 and thiourea of 0.08 M, whose excitonic peak has a widened line shape compared to the other two samples, possibly due to a dispersed size distribution [26–27]. We can also observe that the position of the excitonic peaks of the samples varies slightly with respect to the reference sample, possibly these variations are due to temperature gradients present during the heating process.
Dynamic Light Scattering
Results of DLS measurements are exhibited in Fig. 2, for Sample 1, and Fig. 3, for Sample 2, respectively. The hydrodynamic diameter obtained for Sample 1 was of 4.4 nm, and in the case of Sample 2, the value was 4.9nm. The larger value of the particle size obtained for both samples compared with theoretical calculations for samples whose excitonic peaks are localized in the interval of 400–500 nm [28] (nearly green luminescence), is related to the deposition of a ZnS shell layer and the solvation of the CdTe/ZnS system surface. According to the graphs, there is a distribution of homogeneously sized nanocrystals, with a single mean size population in the case of Sample 1 and with two mean size populations in the case of Sample 2, where one distribution is the majority and the other one is the minority. This result was verified with the DLS results based on size distribution by volume shown in Figs. 2b) and 3 b), respectively.
The second population of particles seen in Fig. 3a) can corresponds to a slight number of agglomerated particles due to the growth of the solvation layer associated with the increase in temperature and concentration due to the functional groups present in the QDs surface. In addition, the presence of ZnS nanocrystals is also possible, whose excitonic peaks are below 400 nm [28.] and have a weak luminescence [29]. However, these bands were not observed in the absorbance and fluorescence spectra of the samples.
On the other hand, Sample 1 exhibited a nearly monodisperse distribution compared to Sample 2, so that a 0.04 M equimolar concentration of ZnCl2 and thiourea allowed uniform deposition of a ZnS layer on the surface of CdTe QDs. For this reason, the excitonic peak of sample 1 resulted in a closely symmetrical line shape, with a mean width at maximum intensity less than that corresponding to Sample 2. This nearly monodisperse feature was also observed in the fluorescence spectrum.
Molecular Fluorescence
The line shape of the photoluminescent emission spectra is also a characteristic measure of the quality, and size distribution of the prepared nanocrystals. The photoluminescence spectra obtained for the studied samples are showed in Fig. 4. Both spectra exhibit a well-defined and intense line shape, within the interval of 480 and 550nm and with peaks of maximum intensity centered at 527nm and 525nm, respectively, producing a nearly green emission. Since samples 1 and 2 exhibit the same luminescent wavelength as the reference sample, in spite quantum dots have hydrodynamic sizes of 4.4 and 4.9 nm, respectively.It follows that the emitting center of CdTe maintains its initial size and therefore an ultra-thin film of ZnS was deposited on its surface. It is well known that the hydrodynamic size includes the CdTe/ZnS core/shell size and part of the ionic atmosphere that moves with it [30].
Making a comparison between both samples, it is possible to conclude that the solvation layer that surrounds and moves with Sample 2 is greater than the one that surrounds Sample 1, and this affects its fluorescence intensity, due the tendency to the molecules agglomeration and therefore there are larger particles inside, which were not excited and therefore did not emit radiation [29]. It must be taken into account that the pH of both samples is different, due to the fact that the concentrations of the ZnS precursors vary. This has an impact on the photoluminescent intensity [31] and is expected to also influence the hydrodynamic surface of the sample, changing its size.
Finally, emission bands relative to ZnS nanocrystals, localized in the blue region of the electromagnetic spectrum, were not observed in the spectra of Fig. 4. We can deduce the second population of nanoparticles exhibited in the size distribution by volume curve corresponding to Sample 2, consist of CdTe/ZnS agglomerates.
Fourier Transform Infrared Spectroscopy
The FT-IR spectra corresponding to 3-MPA and both samples are shown in the Fig. 5, and the Table 1 summarizes the main absorption bands, characteristics of functional groups of 3-MPA molecule. The characteristic absorption band of the C = O vibration of 3-MPA (1726 cm-1) for the case of both samples has been displaced to lower frequencies. This can be due to the inductive (-I) and mesomeric (+ M) effects of the functional R-SH- [31], or also due to the presence of carboxylate ions (R-COO-) on the surface of both samples. [32] This hydrophilic group is responsible for the negative charge on said surface, making the nanoparticle an excellent candidate for realize another external bonds [33], that is, functionalize. In addition, it is observed how the ionization of the COOH makes the two C-O bonds equivalent, which gives rise to an intense condenser of oscillators. Indeed, this shift occurs when the thiol group, through sulphur ion (R-S) had some chemical activity, such as the formation of a bond with a zinc since the synthesis is considered to result in a CdTe/ZnS core/shell system ion located on the surface of the CdTe/ZnS core/shell. It is also possible to identify in the samples a mode which is not observed in the FT-IR of 3-MPA. It is the asymmetric mode of the C-O-H anion, around 1398 cm-1, this may be due to QDs dispersion effects in the aqueoussolution. [34] With these results it is verified that the 3-MPA molecule binds to the surface of the quantum dot, possibly through a superficial zinc ion and the other end of the molecule provides solubility in aqueous solution to the nanostructure.
The bond corresponding to the H-S thiol group is a weak bond, which is easily broken once the 3-MPA is dissolved in water, so the H-S vibrational mode disappears before the 3-MPA molecule anchors to the nanocrystal surface.[35]
Zeta Potential
The results of the Z potential measurements for the samples are presented in Fig. 6. According to FT-IR spectroscopy results discussed in the previous section, we expect that QDs surface gets negatively charged, since the carboxyl group provides a negative charge when is dissociating in carboxylate ions. Therefore, the carboxyl functional remains outside the sphere of coordination and is available to conjugate with any molecule of the biological type, while, inside the quantum dot, the R-SH- group is found coordinating the zinc ions (Zn-S) in excess on QDs surface.in Fig. 6, the distribution of the Zeta Potential is showed, and its corresponding negative values are reported in Table 2. The different concentration values of charges in Sample 2 with respect to Sample 1 are due to the difference in charges existing between the surface, that is, the solvation layer, and the interior of the nanoparticle. The value of the distribution peak for Sample 1 is positive due to a higher concentration of Cd2+ and Zn2+ ions that remained in excess once coordination was established. These results are consistent with what was obtained by Carrasco, D.E in 2021 with his work on the synthesis and characterization of QDs of g-C3N4 and its application in fluorescence detection systems [36].
Both the position of the distribution peak, as well as the negative zeta potential values for the samples indicate that they meet the requirements to be functionalized for biological labeling. These results corroborate the presence mostly of carboxylate groups responsible for the negative charges on the surface.
Table 2: Measurement statistics for samples 1 and 2.