ABSTRACT
Carbon dots (CDs) are recognized as promising fluorescent nanomaterials with bright emission and large variations of photoluminescence quantum yield (PLQY). However, there is still no unique approach for explanation of mechanisms and recipes for synthetic procedures/chemical composition of CDs responsible for the enhancement of PLQY. Here, we compare photophysical behavior and PLQY of two types of CDs synthesized by different routes, leading to the different extent of oxidation and composition. The first type of CDs represents a conjugated carbon system oxidized by F, N and O heteroatoms, whereas the second type represents a non-conjugated carbon system oxidized by oxygen. Photophysical data, photoemission spectroscopy and microscopy data yield the suggestion that in the first case, a structure with a distinct carbon core and highly oxidized electron-accepting shell is formed. This leads to the excitonic type non-tunable emission with single-exponent decay and high PLQY with a strong dependence on the solvent polarity, being as high as 93% in dioxane and as low as 30% in aqueous medium, but which is vulnerable to photobleaching. In the second case, the oxidized CDs do not indicate a clear core-shell structure and show poor solvatochromism, negligible photobleaching, low PLQY varying in the range of 0.7-2.3% depending on the solvent used, and tunable emission with multi-exponent decay, which can be described by the model of multiple emission centers acting through a clustering-triggered emission mechanism. The obtained results lead to a strategy that allows one to design carbon nanomaterials with principally different PLQYs that differ by orders of magnitude.
ABSTRACT
Fungi produce and excrete various proteins, enzymes, polysaccharides, and secondary metabolites, which may be used as media for the "green" synthesis of metal and semiconductor nanoparticles (NPs). ZnO NPs with a flower-like morphology were synthesized by an affordable colloidal route, using an aqueous extract of Ganoderma lucidum as a reducing agent and stabilizer. Each individual "flower" has a large effective surface, which is preserved when the particles are close packed into a dense film, which is advantageous for numerous applications. The phonon Raman spectrum and X-ray diffraction (XRD) pattern prove the high crystallinity of the NPs, with the distinct pattern of a hexagonal (wurtzite) lattice, negligible residual stress, and a crystallite size of 12-14 nm determined from the XRD. The photoluminescence (PL) spectrum of the as-synthesized ZnO NPs contains a structured defect-related feature in the violet-blue range, while the green PL, common for nanostructures synthesized by "green" routes, is very weak. By applying dimethylsulfoxide as an additional passivating agent, the excitonic (UV) PL band was activated without enhancement of the defect-related features. Ag NP-decorated ZnO flowers were synthesized by subsequent silver reduction by pepper extract. The ZnO/Ag NPs exhibited efficient surface-enhanced Raman scattering (SERS) of a standard dye analyte, rhodamine 6G, ensuring the feasibility of other applications that require close contact of ZnO/Ag to other nanostructures or molecules to realize the energy of the charge transfer.
ABSTRACT
Luminescent carbon nanoparticles are a relatively new class of luminescent materials that have attracted the increasing interest of chemists, physicists, biologists and engineers. The present review has a particular focus on the synthesis and luminescent properties of carbon nanoparticles dispersed inside nanostructured silica of different natures: oxidized porous silicon, amorphous thin films, nanopowders, and nanoporous sol-gel-derived ceramics. The correlations of processing conditions with emission/excitation spectral properties, relaxation kinetics, and photoluminescence photodegradation behaviors are analyzed. Following the evolution of the photoluminescence (PL) through the "from-bottom-to-up" synthesis procedure, the transformation of molecular-like ultraviolet emission of organic precursor into visible emission of carbon nanoparticles is demonstrated. At the end of the review, a novel method for the synthesis of luminescent and transparent composites, in form of nanoporous silica filled with luminescent carbon nanodots, is presented. A prototype of white light emitting devices, constructed on the basis of such luminophores and violet light emitting diodes, is demonstrated.
ABSTRACT
The environment strongly affects both the fundamental physical properties of semiconductor nanocrystals (NCs) and their functionality. Embedding NCs in polymer matrices is an efficient way to create a desirable NC environment needed for tailoring the NC properties and protecting NCs from adverse environmental factors. Luminescent NCs in optically transparent polymers have been investigated due to their perspective applications in photonics and bio-imaging. Here, we report on the manifestations of photo-induced enhancement of photoluminescence (PL) of aqueous colloidal NCs embedded in water-soluble polymers. Based on the comparison of results obtained on bare and core/shell NCs, NCs of different compounds (CdSe, CdTe, ZnO) as well as different embedding polymers, we conclude on the most probable mechanism of the photoenhancement for these sorts of systems. Contrary to photoenhancement observed earlier as a result of surface photocorrosion, we do not observe any change in peak position and width of the excitonic PL. Therefore, we suggest that the saturation of trap states by accumulated photo-excited charges plays a key role in the observed enhancement of the radiative recombination. This suggestion is supported by the unique temperature dependence of the trap PL band as well as by power-dependent PL measurement.
