Polymethylmethacrylate (PMMA) microspheres were synthesized by surfactant-free emulsion polymerization. These microspheres were used to obtain opals by the self-assembly method. Monomer and initiator quantities were varied systematically to monitor the size of PMMA microspheres. From SEM and DLS measurements, a trend was observed showing as the monomer and initiator amounts increased the average diameter of PMMA microspheres increased except when a minimum monomer amount was reached, for which the size of the microspheres remained practically constant. Diffuse reflectance spectra were processed by the Kubelka–Munk treatment to estimate the energy band gap (Eg) of the PMMA microspheres. It was found that PMMA microspheres present an indirect transition. From SEM micrographs, it is seen that PMMA opals photonic crystals are formed by microspheres in a uniform periodic face-centered cubic (fcc) array. Variable-angle specular reflectance spectra show that the opals possess a pseudo photonic band gap (PBG) in the visible and near-IR regions. Furthermore, it was found that PBGs shift towards larger wavelengths as the average diameter of the PMMA microspheres increases.
The effect of Fe ion concentration on the morphological, structural, and optical properties of TiO2 films supported on silica (SiO2) opals has been studied. TiO2:Fe2O3 films were prepared by the sol-gel method in combination with a vertical dip coating procedure; precursor solutions of Ti and Fe were deposited on a monolayer of SiO2 opals previously deposited on a glass substrate by the same procedure. After the dip coating process has been carried out, the samples were thermally treated to obtain the TiO2:Fe2O3/SiO2 composites at the Fe ion concentrations of 1, 3, and 5 wt%. Scanning electron microscopy (SEM) micrographs show the formation of colloidal silica microspheres of about 50 nm diameter autoensembled in a hexagonal close-packed fashion. Although the X-ray diffractograms show no significant effect of Fe ion concentration on the crystal structure of TiO2, the μ-Raman and reflectance spectra do show that the intensity of a phonon vibration mode and the energy bandgap of TiO2 decrease as the Fe+3 ion concentration increases.
SERS substrates formed by spherical silver nanoparticles (Ag-NPs) with a 15 nm average diameter adsorbed on Si substrate at three different concentrations and Ag/PMMA composites formed by an opal of PMMA microspheres of 298 nm average diameter were synthesized. The Ag-NPs were varied at three different concentrations. We have observed from SEM micrographs, in the Ag/PMMA composites, the periodicity of the PMMA opals is slightly altered as the Ag-NP concentration is increased; as a consequence of this effect, the PBGs maxima shift toward longer wavelengths, decrease in intensity, and broaden as the Ag-NP concentration is increased in the composites. The performance of single Ag-NP and Ag/PMMA composites as SERS substrates was determined using methylene blue (MB) as a probe molecule with concentrations in the range of 0.5 µM to 2.5 µM. We found that in both single Ag-NP and Ag/PMMA composites as SERS substrates, the enhancement factor (EF) increases as the Ag-NP concentration is increased. We highlight that the SERS substrate with the highest concentration of Ag-NPs has the highest EF due to the formation of metallic clusters on the surface, which generates more “hot spots”. The comparison of the EFs of the single Ag-NP with those of Ag/PMMA composite SERS substrates shows that the EFs of the former are nearly 10-fold higher than those of Ag/PMMA composites. This result is obtained probably due to the porosity of the PMMA microspheres that decreases the local electric field strength. Furthermore, PMMA exerts a shielding effect that affects the optical efficiency of Ag-NPs. Moreover, the metal–dielectric surface interaction contributes to the decrease in the EF. Other aspect to consider in our results is in relation to the difference in the EF of the Ag/PMMA composite and Ag-NP SERS substrates and is due to the existing mismatch between the frequency range of the PMMA opal stop band and the LSPR frequency range of the Ag metal nanoparticles adsorbed on the PMMA opal host matrix.
2 September 2019 in European Journal of Engineering and Technology Research
In the present work, reduced graphene oxide/Titanium dioxide (rGO/TiO2) composites (1:1 and 1:2 wt %) have been synthesized by the hydrothermal method using graphene oxide (GO) and commercial TiO2 as precursors. Previously, we prepared the GO, in the way optimizing and making safer, the Hummers route. We have chosen the hydrothermal method to prepare the composites because it offers several advantages: 1) It consist of a very simple experimental setup, 2) it utilizes only water, instead of Hydrazine or Sulfonate used as chemical reductants in traditional methods, avoiding the incorporation of un-willing impurities into GO sheets, 3) the temperature and pressure condition reached in the closed hydrothermal system have promoted the recovery of π-conjugation after dehydration diminishing defects concentration and increasing the degree of reduction of the GO sheets, and 4) this system is compatible with industrial batch production. The structure, surface morphology, chemical composition and optical properties of GO, TiO2 and rGO/TiO2 composites have been analyzed using, TEM, FTIR, Raman- and XPS-spectroscopy. TEM micrographs show that the TiO2 nanoparticles are non-homogenously adsorbed onto the GO sheets. FTIR spectra of the rGO/TiO2 composites suggest that during the hydrothermal process the GO sheets get reduced. Raman spectra suggest that TiO2 remains with anatase structure even after the hydrothermal process. The C 1s XPS spectra of the rGO/TiO2 composites have shown a significant decrease of oxygenated carbon related signals, confirming that most of the oxygenated groups were successfully removed. Based on these characterization results we infer that, GO sheets of good quality have been successfully synthesized and the GO sheets have been partially reduced via the TiO2 nanoparticles anchored during the hydrothermal process.
In this work, colloidal solutions with silicon nanoparticles using different solvents were synthetized. Structural, morphological and optical characterizations were realized, and these were studied. X-ray diffraction (XRD) was used to measure the diffractograms of the colloidal solutions, which are composed of silicon nanocrystals (Si-ncs), with an average size of approximately 3 nm, and a preferential crystalline orientation (311). Atomic force microscopy (AFM) images show that the morphology of silicon nanoparticles (Si-nps) is agglomerated in a big amount, which is corroborated by means of the roughness. On the other hand, high resolution transmission electronic microscopy (HRTEM) images show on average size of the Si-nc ranging from 1.5 to 10 nm, which depends on the solvent used. Also, different preferential crystalline orientations of the Si-nc such as (311), (220) and (111) were obtained. A correlation between the optical and structural properties was realized in colloidal solutions with silicon nanoparticles and different solvents.