Deciphering hot- and multi-exciton dynamics in core-shell QDs by 2D electronic spectroscopies

Although the harnessing of multiple and hot excitons is a prerequisite for many of the groundbreaking applications of semiconductor quantum dots (QDs), the characterization of their dynamics through conventional spectroscopic techniques is cumbersome. Here, we show how a careful analysis of 2DES maps acquired in different configurations (BOXCARS and pump–probe geometry) allows the tracking and visualization of intraband Auger relaxation mechanisms, driving the hot carrier cooling, and interband bi- and tri-exciton recombination dynamics. The results obtained on archetypal core– shell CdSe/ZnS QDs suggest that, given the global analysis of the resulting datasets, 2D electronic spectroscopy techniques can successfully and efficiently dispel the intertwined dynamics of fast and ultrafast recombination processes in nanomaterials. Hence, we propose this analysis scheme to be used in future research on novel quantum confined systems

CsPbBr3 Nanocrystals-Based Polymer Nanocomposite Films: Effect of Polymer on Spectroscopic Properties and Moisture Tolerance

Metal halide perovskites nanocrystals (NCs) represent an emerging class of materials that find increasing application in optoelectronic and photovoltaic devices, thanks to their intriguing optical properties, including high absorption coefficient, high fluorescence quantum yield (PL QY) and fast charge carrier separation. However, their opening to market is still hindered by their limited reliability, due to an intrinsic structural instability and degradation of their photophysical properties upon air, moisture, and light exposure. The incorporation of perovskite NCs in polymer matrix can limit some of the NC instability issues, with advantages in film processability, device fabrication and mechanical performance, being also useful for fundamental studies. In this regard, here, nanocomposites based on polymethylmethacrylate or polystyrene embedding all-inorganic CsPbBr3 NCs have been prepared and processed in the form of flexible free-standing films. A systematic spectrofluorimetric study, comprising steady state photoluminescence (PL), PL quantum yield (QY) and PL decay of the free-standing films before and after exposure to relative humidity condition (RH% 85%, at 25 °C) is performed and discussed. Phase segregation phenomena, changes in NC passivation and recombination dynamics are evaluated as a function of polymer loading and its molecular structure and finally the efficacy of the polymer as moisture barrier investigate

Luminescent Oil-Soluble Carbon Dots toward White Light Emission: A Spectroscopic Study

Carbon dots (C-dots) are emerging as new emitting nanomaterials for optoelectronics, bioimaging, and biosensing thanks to their high quantum yield (QY), biocompatibility, low toxicity, and cost-effective sources. Although the origin of their photoluminescence (PL) mechanism (i.e., their strong blue-green emission and excitation dependent fluorescence) is still controversial, it has been demonstrated to depend on the synthetic protocols and experimental conditions, able to modify the surface properties. Here oil-dispersible C-dots, synthesized by carbonization of citric acid in the presence of hexadecylamine in high boiling organic solvent, are thoroughly investigated by systematically controlling the synthetic reaction parameters. Similarly to what was found for water-soluble C-dots, citric acid in the presence of amine-containing passivating agents improves the PL emission of C-dots via the formation of molecular fluorescent derivatives alongside the carbonization process. We demonstrate that at growth temperature of 200 °C such C-dots exhibit an interesting and intense white emission, when excited in the blue region, thus resulting in a biocompatible colloidal white emitting single nano-objects. The incorporation of the nanoparticles in a poly(methyl methacrylate) (PMMA) host matrix, to obtain free-standing nanocomposite films, is demonstrated not to affect the color point, which still falls in the white color region of the 1931 CIE diagram. Remarkably, the emission properties are retained even after several months of films exposure to air and sunlight, thus confirming the color stability of the nanoparticles against aging

Coupling effects in QD dimers at sub-nanometer interparticle distance

AbstractCurrently, intensive research efforts focus on the fabrication of meso-structures of assembled colloidal quantum dots (QDs) with original optical and electronic properties. Such collective features originate from the QDs coupling, depending on the number of connected units and their distance. However, the development of general methodologies to assemble colloidal QD with precise stoichiometry and particle-particle spacing remains a key challenge. Here, we demonstrate that dimers of CdSe QDs, stable in solution, can be obtained by engineering QD surface chemistry, reducing the surface steric hindrance and favoring the link between two QDs. The connection is made by using alkyl dithiols as bifunctional linkers and different chain lengths are used to tune the interparticle distance from few nm down to 0.5 nm. The spectroscopic investigation highlights that coupling phenomena between the QDs in dimers are strongly dependent on the interparticle distance and QD size, ultimately affecting the exciton dissociation efficiency

Dye-Derived Red-Emitting Carbon Dots for Lasing and Solid-State Lighting

Carbon dots are carbon-based nanoparticles renowned for their intense light-emitting capabilities covering the whole visible light range. Achieving carbon dots emitting in the red region with high efficiency is extremely relevant due to their huge potential in biological applications and in optoelectronics. Currently, photoluminescence in such an energy interval is often associated with polyheterocyclic molecular domains forming during the synthesis that, however, present low emission efficiency and issues in controlling the optical features. Here, we overcome these problems by solvothermally synthesizing carbon dots starting from Neutral Red, a common red-emitting dye, as a molecular precursor. As a result of the synthesis, such molecular fluorophore is incorporated into a carbonaceous core while retaining its original optical properties. The obtained nanoparticles are highly luminescent in the red region, with a quantum yield comparable to that of the starting dye. Most importantly, the nanoparticle carbogenic matrix protects the Neutral Red molecules from photobleaching under ultraviolet excitation while preventing aggregation-induced quenching, thus allowing solid-state emission. These advantages have been exploited to develop a fluorescence-based color conversion layer by fabricating polymer-based highly concentrated solid-state carbon dot nanocomposites. Finally, the dye-based carbon dots demonstrate both stable Fabry-Perot lasing and efficient random lasing emission in the red region

A fast and effective procedure for the optical efficiency determination of luminescent solar concentrators

We introduce a new method for the prompt and effective evaluation of the optical efficiency of different sets of luminescent solar concentrators (LSC) based on dye-doped poly(methyl methacrylate) thin films. The procedure founded on the realization of a home-build apparatus (PeryRoom), which allowed for a fast and reliable measurement of the generated photocurrents profiting of the use of a photodiods system. The photocurrents were analyzed by means of a simple model inspired by the work of Goetzberger and Greube (1977) and rationalized in terms of different dye characteristics and film thickness. The procedure was eventually validated by comparing the optical efficiencies measured by using a Si-based photovoltaic module. Overall, the present results support the use of PeryRoom for the optimization of the current state-of-art LSC systems

Colloidal Inorganic Nanocrystal Based Nanocomposites: Functional Materials for Micro and Nanofabrication

The unique size- and shape-dependent electronic properties of nanocrystals (NCs) make them extremely attractive as novel structural building blocks for constructing a new generation of innovative materials and solid-state devices. Recent advances in material chemistry has allowed the synthesis of colloidal NCs with a wide range of compositions, with a precise control on size, shape and uniformity as well as specific surface chemistry. By incorporating such nanostructures in polymers, mesoscopic materials can be achieved and their properties engineered by choosing NCs differing in size and/or composition, properly tuning the interaction between NCs and surrounding environment. In this contribution, different approaches will be presented as effective opportunities for conveying colloidal NC properties to nanocomposite materials for micro and nanofabrication. Patterning of such nanocomposites either by conventional lithographic techniques and emerging patterning tools, such as ink jet printing and nanoimprint lithography, will be illustrated, pointing out their technological impact on developing new optoelectronic and sensing devices

One-Pot Synthesis of Dual Color-Emitting CDs: Numerical and Experimental Optimization towards White LEDs

Carbon Dots (CDs) are fluorescent carbon-based nanoparticles that have attracted increasing attention in recent years as environment-friendly and cost-effective fluorophores. An application that can benefit from CDs in a relatively short-term perspective is the fabrication of color-converting materials in phosphor-converted white LEDs (WLEDs). In this work we present a one-pot solvothermal synthesis of polymer-passivated CDs that show a dual emission band (in the green and in the red regions) upon blue light excitation. A purposely designed numerical approach enables evaluating how the spectroscopic properties of such CDs can be profitable for application in WLEDs emulating daylight characteristics. Subsequently, we fabricate nanocomposite coatings based on the dual color-emitting CDs via solution-based strategies, and we compare their color-converting properties with those of the simulated ones to finally accomplish white light emission. The combined numerical and experimental approach can find a general use to reduce the number of experimental trial-and-error steps required for optimization of CD optical properties for lighting application

One-Pot Synthesis of Dual Color-Emitting CDs: Numerical and Experimental Optimization towards White LEDs

Carbon Dots (CDs) are fluorescent carbon-based nanoparticles that have attracted increasing attention in recent years as environment-friendly and cost-effective fluorophores. An application that can benefit from CDs in a relatively short-term perspective is the fabrication of color-converting materials in phosphor-converted white LEDs (WLEDs). In this work we present a one-pot solvothermal synthesis of polymer-passivated CDs that show a dual emission band (in the green and in the red regions) upon blue light excitation. A purposely designed numerical approach enables evaluating how the spectroscopic properties of such CDs can be profitable for application in WLEDs emulating daylight characteristics. Subsequently, we fabricate nanocomposite coatings based on the dual color-emitting CDs via solution-based strategies, and we compare their color-converting properties with those of the simulated ones to finally accomplish white light emission. The combined numerical and experimental approach can find a general use to reduce the number of experimental trial-and-error steps required for optimization of CD optical properties for lighting application