Michela Corricelli

Spectroscopic Insights into Carbon Dot Systems

The controversial nature of the fluorescent properties of carbon dots (CDs), ascribed either to surface states or to small molecules adsorbed onto the carbon nanostructures, is an unresolved issue. To date, an accurate picture of CDs and an exhaustive structure-property correlation are still lacking. Using two unconventional spectroscopic techniques, fluorescence correlation spectroscopy (FCS) and time-resolved electron paramagnetic resonance (TREPR), we contribute to fill this gap. Although electron micrographs indicate the presence of carbon cores, FCS reveals that the emission properties of CDs are based neither on those cores nor on molecular species linked to them, but rather on free molecules. TREPR provides deeper insights into the structure of carbon cores, where C sp2 domains are embedded within C sp3 scaffolds. FCS and TREPR prove to be powerful techniques, characterizing CDs as inherently heterogeneous systems, providing insights into the nature of such systems and paving the way to standardization of these nanomaterials.

Fabrication of flexible all-inorganic nanocrystal solar cells by room-temperature processing

We demonstrate the fabrication of all-inorganic heterostructured n–p junction devices made of colloidal PbS quantum dots (QDs) and TiO2 nanorods (NRs). The entire device fabrication procedure relies on room-temperature processing, which is compatible with flexible plastic substrates and low-cost production. Through Kelvin Probe Force Microscopy and femtosecond pump and probe spectroscopy we decipher the electron transfer process occurring at the interface between the colloidal PbS QDs and TiO2 anatase NRs. Overall we demonstrate a high power conversion efficiency of ∼3.6% on glass and ∼1.8% on flexible substrates, which is among the highest reported for entirely inorganic-nanocrystal based solar cells on plastic supports.

Self-organization of mono- and bi-modal PbS nanocrystal populations in superlattices

Here the synthesis of distinct monomodal and bimodal PbS nanocrystal (NC) populations, with narrow size-distribution, is reported. The ability to achieve careful control of NC size and size distribution allowed the preparation, in one single synthetic step, of two distinct populations of PbS NCs, with tuneable size ratio. The NC growth was carefully studied in order to gain insight into the mechanism underlying the formation of the mono and bimodal PbS NC families. The synthesized PbS NCs were structurally and chemically characterized, and subsequently used as building blocks for fabricating solid crystal assemblies by solvent evaporation. In particular the role played by different parameters, namely NC size and concentration, dispersing solvent and substrate, on crystallinity, geometry and structure of the obtained solids was systematically investigated. Interestingly the assembly of bimodal PbS NC samples leads to the formation of diverse superlattice structures, with a final geometry dependent on the NC size and the size ratio in the bimodal population. The synthetic procedure was then ultimately responsible of the superlattice structures, through the control of the PbS NC size and size ratio in the bimodal population.

Photoactive Hybrid Material Based on Pyrene Functionalized PbS Nanocrystals Decorating CVD Monolayer Graphene

A simple and facile solution-based procedure is implemented for decorating a large area, monolayer graphene film, grown by chemical vapor deposition, with size-tunable light absorbing colloidal PbS nanocrystals (NCs). The hybrid is obtained by exposing a large area graphene film to a solution of 1-pyrene butyric acid surface coated PbS NCs, obtained by a capping exchange procedure onto presynthesized organic-capped NCs. The results demonstrate that at the interface, multiple and cooperative π-π stacking interactions promoted by the pyrene ligand coordinating the NC surface lead to a successful anchoring of the nano-objects on the graphene platform which concomitantly preserves its aromatic structure. Interligand interactions provide organization of the nano-objects in highly interconnected nanostructured multilayer coatings, where the NCs retain geometry and composition. The resulting hybrid exhibits a sheet resistance lower than that of bare graphene, which is explained in terms of electronic communication in the hybrid, due to the interconnection of the NC film and to a hole transfer from photoexcited PbS NCs to graphene, channelled at the interface by pyrene. Such a direct electron coupling makes the manufactured hybrid material an interesting component for optoelectronics, sensors and for optical communication and information technology.

Polyelectrolyte multilayers as a platform for luminescent nanocrystal patterned assemblies.

The fabrication of uniform and patterned nanocrystal (NC) assemblies has been investigated by exploiting the possibility of carefully tailoring colloidal NC surface chemistry and the ability of polyelectrolyte (PE) to functionalize substrates through an electrostatic layer-by-layer (LbL) strategy. Appropriate deposition conditions, substrate functionalization, and post-preparative treatments were selected to tailor the substrate surface chemistry to effectively direct the homogeneous electrostatic-induced assembly of NCs. Water-dispersible luminescent NCs, namely, (CdSe)ZnS and CdS, were differently functionalized by (1) ligand-exchange reaction, (2) growth of a hydrophilic silica shell, and (3) formation of a hydrophilic inclusion complex, thus providing functional NCs stable in a defined pH range. The electrostatically charged functional NCs represent a comprehensive selection of examples of surface-functionalized NCs, which enables the systematic investigation of experimental parameters in NC assembly processes carried out by combining LbL procedures with microcontact printing and also exploiting NC emission, relevant for potential applications, as a prompt and effective probe for evaluating assembly quality. Thus, an ample showcase of combinations has been investigated, and the spectroscopic and morphological features of the resulting NC-based structures have been discussed.

Fabrication of photoactive heterostructures based on quantum dots decorated with Au nanoparticles

Abstract Silica based multifunctional heterostructures, exhibiting near infrared (NIR) absorption (650–1200 nm) and luminescence in the visible region, represent innovative nanosystems useful for diagnostic or theranostic applications. Herein, colloidal synthetic procedures are applied to design a photoactive multifunctional nanosystem. Luminescent silica (SiO2) coated quantum dots (QDs) have been used as versatile nanoplatforms to assemble on their surface gold (Au) seeds, further grown into Au spackled structures. The synthesized nanostructures combine the QD emission in the visible region, and, concomitantly, the distinctive NIR absorption of Au nanodomains. The possibility of having multiple QDs in a single heterostructure, the SiO2 shell thickness, and the extent of Au deposition onto SiO2 surface have been carefully controlled. The work shows that a single QD entrapped in 16 nm thick SiO2 shell, coated with Au speckles, represents the most suitable geometry to preserve the QD emission in the visible region and to generate NIR absorption from metal NPs. The resulting architectures present a biomedical potential as an effective optical multimodal probes and as promising therapeutic agents due to the Au NP mediated photothermal effect.

GISAXS and GIWAXS study on self-assembling processes of nanoparticle based superlattices

Organic capped Au nanoparticles (NPs) and PbS quantum dots (QDs), synthesized with high control on size and size distribution, were used as building blocks for fabricating solid crystals by solvent evaporation. The superlattice formation process for the two types of nano-objects was investigated as a function of concentration by means of electron microscopy and X-ray techniques. The effect of building block composition, size, geometry, and concentration and the role of the organic coordinating molecules was related to the degree of order in the superlattices. A convenient combination of different complementary X-ray techniques, namely in situ and ex situ GISAXS and GIWAXS, allowed elucidating the most reliable signatures of the superlattices at various stages of the self-assembly process, since their early stage of formation and up to few months of aging. Significantly different assembly behaviour was assessed for the two types of NPs, clearly explained on the basis of their chemical composition, ultimately reflecting on the assembling process and on the final structure characteristics.

Tuning light emission of PbS nanocrystals from infrared to visible range by cation exchange

Abstract Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700–850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices.

Three-Dimensional Self-Assembly of Networked Branched TiO2 Nanocrystal Scaffolds for Efficient Room-Temperature Processed Depleted Bulk Heterojunction Solar Cells

In this work, we report on ∼4% power conversion efficiency (PCE) depleted bulk heterojunction (DBH) solar cells based on a high-quality electrode with a three-dimensional nanoscale architecture purposely designed so as to maximize light absorption and charge collection. The newly conceived architecture comprises a mesoporous electron-collecting film made of networked anisotropic metal-oxide nanostructures, which accommodates visible-to-infrared light harvesting quantum dots within the recessed regions of its volume. The three-dimensional electrodes were self-assembled by spin-coating a solution of colloidal branched anatase TiO2 NCs (BNC), followed by photocatalytic removal of the native organic capping from their surface by a mild UV-light treatment and filling with small PbS NCs via infiltration. The PCE ∼ 4% of our TiO2 BNC/PbS QD DBH solar cell features an enhancement of 84% over the performance obtained for a planar device fabricated under the same conditions. Overall, the DBH device fabrication procedure is entirely carried out under mild processing conditions at room temperature, thus holding promise for low-cost and large-scale manufacturing.

Surface functionalized luminescent nanocrystals electrostatically assembled ont a patterned substrate

Background: In the last decades, the enormous interest in 2/3D nanocrystal (NC) architectures boosted the development of many and diverse techniques which allowed to precisely positioning the nanoparticles on substrates. The tremendous importance of such NC organizations is due to the novel collective properties arising from inter-particle interactions that emerge in these arti cial materials, with promising application in opto-electronics, photonics and biomedicines. Methods: Properly synthesized luminescent colloidal CdSe@ZnS NCs, coated by a silica shell, have been functionalized introducing specific chargeable moieties at their surface. At the same time, a patterned substrate has been fabricated by NanoImprint Lithography (NIL) on a polymer film deposited on a silicon substrate, resulting in polymeric structures alternating to bare silicon regions. Such “polymer-free” area have been further functionalized with charged bifunctional molecules to form a self-assembled monolayer (SAM), able to attract, by electrostatic interactions, the silanized NCs. Results: The directed self-assembly of the luminescent silica coated CdSe@ZnS NCs, onto a patterned substrate, has been shown. The functionalized NCs are organized onto appropriately functionalized and patterned substrates, by means of electrostatic interactions. The driven assembly of the NCs allows to obtain the formation of geometrically defined luminescent patterns on silicon substrates. Conclusion: The presented procedure ingeniously combine a top-down fabrication technique, NIL, with a bottom-up electrostatic self-assembly approach, achieving a versatile tool for fabricating original functional superstructures. Importantly, the surface functionalization, both of NCs and template substrate, has been shown to play a crucial role in the fabrication of the NC patterns, thus providing promptly integrable and versatile functional platforms, potentially useful for photonic and biosensing applications