Sergio Brovelli

Highly efficient large-area colourless luminescent solar concentrators using heavy-metal-free colloidal quantum dots

Luminescent solar concentrators serving as semitransparent photovoltaic windows could become an important element in net zero energy consumption buildings of the future. Colloidal quantum dots are promising materials for luminescent solar concentrators as they can be engineered to provide the large Stokes shift necessary for suppressing reabsorption losses in large-area devices. Existing Stokes-shift-engineered quantum dots allow for only partial coverage of the solar spectrum, which limits their light-harvesting ability and leads to colouring of the luminescent solar concentrators, complicating their use in architecture. Here, we use quantum dots of ternary I-III-VI2 semiconductors to realize the first large-area quantum dot-luminescent solar concentrators free of toxic elements, with reduced reabsorption and extended coverage of the solar spectrum. By incorporating CuInSexS2-x quantum dots into photo-polymerized poly(lauryl methacrylate), we obtain freestanding, colourless slabs that introduce no distortion to perceived colours and are thus well suited for the realization of photovoltaic windows. Thanks to the suppressed reabsorption and high emission efficiencies of the quantum dots, we achieve an optical power efficiency of 3.2%. Ultrafast spectroscopy studies suggest that the Stokes-shifted emission involves a conduction-band electron and a hole residing in an intragap state associated with a native defect.

Spectroscopic and Device Aspects of Nanocrystal Quantum Dots

The field of nanocrystal quantum dots (QDs) is already more than 30 years old, and yet continuing interest in these structures is driven by both the fascinating physics emerging from strong quantum confinement of electronic excitations, as well as a large number of prospective applications that could benefit from the tunable properties and amenability toward solution-based processing of these materials. The focus of this review is on recent advances in nanocrystal research related to applications of QD materials in lasing, light-emitting diodes (LEDs), and solar energy conversion. A specific underlying theme is innovative concepts for tuning the properties of QDs beyond what is possible via traditional size manipulation, particularly through heterostructuring. Examples of such advanced control of nanocrystal functionalities include the following: interface engineering for suppressing Auger recombination in the context of QD LEDs and lasers; Stokes-shift engineering for applications in large-area luminescent solar concentrators; and control of intraband relaxation for enhanced carrier multiplication in advanced QD photovoltaics. We examine the considerable recent progress on these multiple fronts of nanocrystal research, which has resulted in the first commercialized QD technologies. These successes explain the continuing appeal of this field to a broad community of scientists and engineers, which in turn ensures even more exciting results to come from future exploration of this fascinating class of materials.

Long-lived photoinduced magnetization in copper-doped ZnSe–CdSe core–shell nanocrystals

Nanoscale materials have been investigated extensively for applications in memory and data storage. Recent advances include memories based on metal nanoparticles, nanoscale phase-change materials and molecular switches. Traditionally, magnetic storage materials make use of magnetic fields to address individual storage elements. However, new materials with magnetic properties addressable via alternative means (for example, electrical or optical) may lead to improved flexibility and storage density and are therefore very desirable. Here, we demonstrate that copper-doped chalcogenide nanocrystals exhibit not only the classic signatures of diluted magnetic semiconductors--namely, a strong spin-exchange interaction between paramagnetic Cu(2+) dopants and the conduction/valence bands of the host semiconductor--but also show a pronounced and long-lived photoinduced enhancement of their paramagnetic response. Magnetic circular dichroism studies reveal that paramagnetism in these nanocrystals can be controlled and increased by up to 100% when illuminated with above-gap (blue/ultraviolet) light. These materials retain a memory of the photomagnetization for hour-long timescales in the dark, with effects persisting up to ∼80 K.

Dynamic Hole Blockade Yields Two-Color Quantum and Classical Light from Dot-in-Bulk Nanocrystals

Semiconductor nanocrystals (NCs) are an emerging class of color-tunable, solution-processable, room-temperature single-photon sources. Photon antibunching in NCs arises from suppression of multiphoton emission by nonradiative Auger recombination. Here, we demonstrate a new antibunching mechanism-dynamic Coulomb blockade-which allows for generating both quantum and classical light from the same NC without detrimental effects of Auger decay. This mechanism is realized in novel dot-in-bulk (DiB) nanostructures comprising a quantum-confined CdSe core overcoated with a thick, bulk-like CdS shell. The presence of one hole in the core suppresses the capture of the second hole forcing it to recombine in the shell region. Under weak excitation, these NCs emit red antibunched light (core emission). At higher pump levels they exhibit an additional green band (shell emission) with bulk-like, Poissonian photon statistics. The unusual versatility of these novel nanoscale light sources, that combine mutually correlated channels for quantum and classical emission and additionally allow for facile tunability of effective color, opens new interesting opportunities for a range of applications from quantum optics to sensing and nanoscale imaging.

Fully inorganic oxide-in-oxide ultraviolet nanocrystal light emitting devices

The development of integrated photonics and lab-on-a-chip platforms for environmental and biomedical diagnostics demands ultraviolet electroluminescent materials with high mechanical, chemical and environmental stability and almost complete compatibility with existing silicon technology. Here we report the realization of fully inorganic ultraviolet light-emitting diodes emitting at 390 nm with a maximum external quantum efficiency of ~0.3%, based on SnO(2) nanoparticles embedded in SiO(2) thin films obtained from a solution-processed method. The fabrication involves a single deposition step onto a silicon wafer followed by a thermal treatment in a controlled atmosphere. The fully inorganic architecture ensures superior mechanical robustness and optimal chemical stability in organic solvents and aqueous solutions. The versatility of the fabrication process broadens the possibility of optimizing this strategy and extending it to other nanostructured systems for designed applications, such as active components of wearable health monitors or biomedical devices.

Optical and Electroluminescent Properties of Conjugated Polyrotaxanes

Conjugated polyrotaxanes are conjugated polymeric semiconductors engineered at a supramolecular level by threading the conjugated moiety into molecular macrocycles, such as cyclodextrins (CD). CD-threaded rotaxanes thus provide a class of model compounds with reduced interchain interactions which enable us to explore the influence of such interactions on the fundamental photophysics of conjugated semiconductors. CD rotaxination also endows these materials with additional sites for functionalization, thus resulting in extremely versatile structures. Our current understanding of the photophysics of these materials is reviewed, both in solid/liquid solutions and in neat films, as a function of the relevant parameters, such as the threading ratio and the concentration, and with the help of rotaxanes incorporating a variety of different backbones.

Ultraviolet free-exciton light emission in Er-passivated SnO2 nanocrystals in silica

SnO2 nanocrystals are grown in silica starting from a sol-gel method and using Er doping to passivate the cluster boundaries. As a result, emission at 3.8eV from the decay of SnO2 free excitons is observed in nanostructured SnO2:SiO2, besides the extrinsic 2eV luminescence of defects in SnO2 and ascribable to substoichiometric nanocluster boundaries. The analysis of the extrinsic emission competitive with the ultraviolet (UV) luminescence evidences the involvement of a phonon mode at 210cm−1 from a SnO-like phase. The feasibility of passivated wide-band-gap nanocrystals in silica gives interesting perspectives for UV-emitting optical devices.

Influence of cyclodextrin size on fluorescence quenching in conjugated polyrotaxanes by methyl viologen in aqueous solution

Poly(4,4′-diphenylenevinylene) rotaxanes and [2]rotaxanes with α-, β-, γ-cyclodextrin macrocycles were synthesised and their sensitivities to fluorescence quenching by methyl viologen in aqueous solution were determined, relative to uninsulated analogues. Stern–Volmer analysis revealed that the fluorescence quenching response of polyrotaxanes is strongly dependent on the diameter of the cyclodextrins. Polyrotaxanes, composed of the smaller diameter α- or β-cyclodextrins, are the least easily quenched, with Stern–Volmer constants about two orders of magnitude smaller than from the wider γ-cyclodextrin polyrotaxane and the uninsulated polymer. Time-resolved photoluminescence results demonstrate the crucial role of interchain aggregation on the sensitivity to fluorescence quenchers. The materials with the highest Stern–Volmer constants exhibit the most biexponential photoluminescence decay, which is indicative of aggregation, and the emission spectra of solutions containing methyl viologen resemble the early-time emission spectra (0–3 ns after excitation) of the unquenched samples. The results show that the threaded α-cyclodextrin is effective in preventing aggregation, and in hindering fluorescence quenching, even when only a small fraction of the conjugated polymer is encapsulated. This conclusion is relevant to the application of these materials in optoelectonic devices, such as light-emitting diodes, where it is essential to prevent luminescence quenching without hindering charge transport.

A conjugated thiophene-based rotaxane: synthesis, spectroscopy, and modeling.

A dithiophene rotaxane 1 subsetbeta-CD and its shape-persistent corresponding dumbbell 1 were synthesized and fully characterized. 2D NOESY experiments, supported by molecular dynamics calculations, revealed a very mobile macrocycle (beta-CD). Steady-state and time-resolved photoluminescence experiments in solution were employed to elucidate the excited-state dynamics for both systems and to explore the effect of cyclodextrin encapsulation. The photoluminescence (PL) spectrum of 1 subsetbeta-CD was found to be blueshifted with respect to the dumbbell 1 (2.81 and 2.78 eV, respectively). Additionally, in contrast to previous observations, neither PL spectra nor the decay kinetics of both threaded and unthreaded systems showed changes upon increasing the concentration or changing the polarity of the solutions, thereby providing evidence for a lack of tendency toward aggregation of the unthreaded backbone.

Ultra-broad optical amplification and two-colour amplified spontaneous emission in binary blends of insulated molecular wires

Conjugated polymers are receiving growing consideration thanks to their potential as optically active materials in light-emitting diodes (LEDs), [ 1 ] fi eld-effect transistors, photovoltaic cells, [ 2 ] microcavities [ 3 ] and all-organic lasers. [ 4–6 ] Virtually all those applications that exploit luminescence as their principal functional property (e.g. LEDs, microcavities, and lasers) can benefi t from control of intermolecular interactions between polymer chains, that often lead to formation of interchain aggregates with lower effi ciency and red-shifted emission. Non-covalent encapsulation of conjugated polymers by means of cyclodextrins (rotaxination) has enabled control of the secondary interactions between long conjugated chains, [ 7–11 ] and suppression of photoinduced charge generation (polarons) in the threaded backbone. [ 12 , 13 ] Such a property can be exploited to achieve broadband optical amplifi cation from polymer blends in which the gain