Localized surface plasmon resonance (LSPR) is a subwavelength optical phenomenon that has found widespread use in bio- and chemical- sensing applications thanks to the possibility to efficiently transduce refractive index changes into wavelength shifts. However, is it very hard to transpose the successes demonstrated in liquid and physiological environment toward the detection of gasous molecules. In fact, the latter typically adsorb in an unspecific manner and induce very minute refractive index changes tipicaly below the sensor sensitivity.
Here, we show first insights on the aerosol large-scale self-assembly of metasurfaces made of monocrystalline Au nanoislands with uniform disorder over large scale. Notably, these architectures show tuneable disorder levels and demonstrate high-quality LSPR, enabling the fabrication of highly performing optical gas sensors detecting down to 10−5 variations in refractive index.
Next, we use our aerosol synthesis method to integrate tailored fractals of dielectric TiO2 nanoparticles onto resonant plasmonic metasurfaces. We show how this integration strongly enhances the interaction between the plasmonic field and volatile organic molecules and provides a means for their selective detection. Interesting, the improved performance is the result of a synergetic behavior between the dielectric fractals and the plasmonic metasurface: in fact, upon this integration, the enhancement of plasmonic field is drastically extended, all the way up to a maximum thickness of 1.8 μm.
Optimal dielectric-plasmonic structures allow measurements of changes in the refractive index of the gas mixture down to <8x10-6 at room temperature and selective identification of three exemplary volatile organic compounds (VOCs). These findings provide a basis for the development of a novel family of hybrid dielectric-plasmonic materials with application extending from light harvesting and photo-catalysts to contactless sensors for non-invasive medical diagnostics.
Adequate amount of graphene oxide (GO) was firstly prepared by oxidation of graphite and GO/epoxy nanocomposites were subsequently prepared by typical solution mixing technique. X-ray diffraction (XRD) pattern, X-ray photoelectron (XPS), Raman and Fourier transform infrared (FTIR) spectroscopy indicated the successful preparation of GO. Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) images of the graphite oxide showed that they consist of a large amount of graphene oxide platelets with a curled morphology containing of a thin wrinkled sheet like structure. AFM image of the exfoliated GO signified that the average thickness of GO sheets is ~1.0 nm which is very similar to GO monolayer. Mechanical properties of as prepared GO/epoxy nanocomposites were investigated. Significant improvements in both Young’s modulus and tensile strength were observed for the nanocomposites at very low level of GO loading. The Young’s modulus of the nanocomposites containing 0.5 wt% GO was 1.72 GPa, which was 35 % higher than that of the pure epoxy resin (1.28 GPa). The effective reinforcement of the GO based epoxy nanocomposites can be attributed to the good dispersion and the strong interfacial interactions between the GO sheets and the epoxy resin matrices.
Molecular-resolved real-space images of self-assembled structures of the conductive polymer regioregular poly(3-
hexylthiophene) (rrP3HT) on single-walled carbon nanotubes (SWNT) were obtained using scanning tunneling
microscopy (STM). The STM images revealed that the adsorbed polymer typically formed a 10 nm thick coating on
SWNT's. This is in agreement with transmission electron microscopy (TEM) results for drop-cast composite films that
provided strong evidence that SWNTs were isolated in a polymer matrix and coated with rrP3HT multilayers. A 10 nm
thick deposit corresponds to a coating of ~25 layers of polymer on SWNT, assuming that π-π interactions between
rrP3HT layers determine deposition and that the underlying SWNT directs the polymer self-assembly process. STM
measurements of adsorbed monolayers and multilayers of rrP3HT on SWNT surfaces were compared to rrP3HT
monolayer and multilayer deposition on highly ordered pyrolytic graphite (HOPG) surfaces. The average inter-lamellar
distances of adsorbed polymer was greater for both rrP3HT monolayer and multilayer films adsorbed onto the curved
surfaces of SWNTs than on the flat surfaces of HOPG samples. Analysis of STM images yielded the interchain spacings
of adsorbed macromolecules, dcc = 1.55 - 1.68 ± 0.02 nm. The polymer was observed to wrap around some SWNTs at an
angle with respect to the SWNT long-axis, which indicated that the rrP3HT self-assembly is hierarchical. The conductive
polymer's deposition appears to occur with epitaxy and is directed by the underlying SWNT chiral structure.
A detailed study of poly(alkylthiophene) self-assembly and organization on single-walled carbon nanotubes (SWNTs) is presented. Experimental evidence for self-assembly and organization of regioregular poly(3-hexyl thiophene) (rrP3HT) on single-walled carbon nanotubes was obtained using scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). TEM images of drop-cast rrP3HT/SWNT composites displayed strong evidence that SWNTs were isolated from each other in a polymer matrix and coated with between 1-3 layers rrP3HT. STM measurements of adsorbed monolayers of rrP3HT on SWNT surfaces were compared to rrP3HT monolayer deposition on highly ordered pyrolytic graphite (HOPG) surfaces. The results show that average inter-lamellar distances of adsorbed polymer are greater for rrP3HT monolayers adsorbed onto the curved surfaces of SWNTs than on the flat surfaces of HOPG samples. Analysis of STM images yielded the chiral angles at which the thiophene polymer chains wrap around individual carbon nanotubes (41-48° with respect to nanotube axis) while the interchain spacings of adsorbed macromolecules was 1.68 ± 0.02 nm. Comparisons between the native polymer deposited on graphite and the composite structure confirmed that the presence of carbon nanotubes in rrP3HT produces a material with a high degree of order at the molecular level. This high level of order and close coupling of the two components of the composite are prerequisites for its use as the active layer of an organic photovoltaic.
Quantum dots (QDs) grown on semiconductors surfaces are actually the main researchers' interest for applications in the forecoming nanotechnology era. New frontiers in nanodevice technology rely on the precise positioning of the nucleation site and on controlling the shape and size of the dots. Novel approaches to form ordered patterns of homogeneous nanostructures are explored: natural patterning induced by surface instabilities (as step bunching of Si(111) or misoriented Si(001) surfaces), standard patterning with high resolution lithographic techniques, implantation of Ga+ ions by Focused Ion Beam (FIB), or in situ substrate patterning by Scanning Tunneling Microscopy (STM). Based on the analysis of STM images we report on growth and arrangement of Ge islands on Si(001) substrates nanopatterned using several different approaches. The first is a natural method based on the regular step bunching that occurs on Si(111) surfaces with different annealing treatments. The second is based on the self organization of a Si(001) misoriented surface covered by a thin layer of a GeSi alloy. The third exploit an array of holes produced by STM lithography. The forth is a tight pattern created by FIB. We analyze the resulting distribution of islands resulting from all these approaches.
We studied composites of single walled carbon nanotubes and poly(3hexylthiophene) by optical absorption, X-ray diffraction and transmission electron and scanning tunneling microscopy. Dispersing single walled carbon nanotubes in poly(3hexylthiophene) leads to sharpening of vibronic structure and enhanced optical absorbance near the band edge. We show that the enhanced order in the polymer is due to templating of the polymer chains by the surface of the carbon
nanotubes leading to increased electronic delocalization.
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