Light-driven reversible charge transfers from ITO nanocrystals.

The combination of semiconductors and redox active molecules for light-driven energy storage systems has emerged as a powerful solution for the exploitation of solar batteries. On account of this, transparent conductive oxide (TCO) nanocrystals (NCs) demonstrated to be interesting materials, thanks to the photo-induced charge accumulation enabling light harvesting and storage. The charge transfer process after light absorption, at the base of the proper use of these semiconductors, is a key step, often resulting in non-reversible transformations of the chemicals involved. However, if considering the photocharging through TCO NCs not only as a charge provider for the system but potentially as part of the storage role, the reversible transformation of the redox compound represents a crucial aspect. In this paper, we explore the possible interaction of indium tin oxide (ITO) NCs and typical redox mediators commonly employed in catalytic applications with a twofold scope of enhancing or supporting the light-induced charge accumulation on the metal oxide NC side and controlling the reversibility of the whole process. The work presented focuses on the effect of the redox properties on the doped metal oxide response, both from the stability point of view and the photodoping performance, by monitoring the changes in the optical behavior of ITO/redox hybrid systems upon ultraviolet illumination.

Improving the stability of photodoped metal oxide nanocrystals with electron donating graphene quantum dots.

Doped metal oxide nanocrystals are emerging as versatile multi-functional materials with the potential to address several limitations of the current light-driven energy storage technology thanks to their unique ability to accumulate a large number of free electrons upon UV light exposure. The combination of these nanocrystals with a properly designed hole collector could lead to steady-state electron and hole accumulation, thus disclosing the possibility for light-driven energy storage in a single set of nanomaterials. In this framework, it is important to understand the role of the hole collector during UV light exposure. Here we show, via optical absorbance measurements under UV light, that well-defined graphene quantum dots with electron-donating character can act as hole acceptors and improve the stability of the photo-generated electrons in Sn-doped In2O3 nanocrystals. The results of this study offer new insight into the implementation of photo-charged storage devices based on hybrid organic/inorganic nanostructures.

Determination of the optical constants of ligand-free organic lead halide perovskite quantum dots.

Precise knowledge of the optical constants of perovskite lead halide quantum dots (QDs) is required to both understand their interaction with light and to rationally design and optimize the devices based on them. However, their determination from colloidal nanocrystal suspensions, or films made out of them, remains elusive, as a result of the difficulty in disentangling the optical constants of the organic capping ligands and those of the semiconductor itself. In this work, we extract the refractive index and extinction coefficient of ligand-free methylammonium lead iodide (MAPbI3) and bromide (MAPbBr3) nanocrystals. In order to prevent the use of organic ligands in the preparation, we follow a scaffold assisted synthetic procedure, which yields a composite film of high optical quality that can be independently and precisely characterized and modelled. In this way, the contribution of the guest nanocrystals can be successfully discriminated from that of the host matrix. Using a Kramers-Kronig consistent dispersion model along with an effective medium approximation, it is possible to derive the optical constants of the QDs by fitting the spectral dependence of light transmitted and reflected at different angles and polarizations. Our results indicate a strong dependence of the optical constants on the QD size. Small nanocrystals show remarkably large values of the extinction coefficient compared to their bulk counterparts. This analysis opens the door to the rigorous modelling of solar cells and light-emitting diodes with active layers based on perovskite QDs.

Multi-charge transfer from photodoped ITO nanocrystals.

Metal oxide nanocrystals are emerging as an extremely versatile material for addressing many of the current challenging demands of energy-conversion technology. Being able to exploit their full potential is not only an advantage but also a scientific and economic ambition for a more sustainable energy development. In this direction, the photodoping of metal oxide nanocrystals is a very notable process that allows accumulating multiple charge carriers per nanocrystal after light absorption. The reactivity of the photodoped electrons is currently the subject of an intense study. In this context, the possibility to extract efficiently the stored electrons could be beneficial for numerous processes, from photoconversion and sunlight energy storage to photocatalysis and photoelectrochemistry. In this work we provide, via oxidative titration and optical spectroscopy, evidence for multi-electron transfer processes from photodoped Sn : In2O3 nanocrystals to a widely employed organic electron acceptor (F4TCNQ). The results of this study disclose the potential of photodoped electrons to drive chemical reactions involving more than one electron.

Disentangling Electron-Phonon Coupling and Thermal Expansion Effects in the Band Gap Renormalization of Perovskite Nanocrystals.

The complex electron-phonon interaction occurring in bulk lead halide perovskites gives rise to anomalous temperature dependences, like the widening of the electronic band gap as temperature increases. However, possible confinement effects on the electron-phonon coupling in the nanocrystalline version of these materials remain unexplored. Herein, we study the temperature (ranging from 80 K to ambient) and hydrostatic pressure (from atmospheric to 0.6 GPa) dependence of the photoluminescence of ligand-free methylammonium lead triiodide nanocrystals with controlled sizes embedded in a porous silica matrix. This analysis allowed us to disentangle the effects of thermal expansion and electron-phonon interaction. As the crystallite size decreases, the electron-phonon contribution to the gap renormalization gains in importance. We provide a plausible explanation for this observation in terms of quantum confinement effects, showing that neither thermal expansion nor electron-phonon coupling effects may be disregarded when analyzing the temperature dependence of the optoelectronic properties of perovskite lead halide nanocrystals.

Highly Efficient and Environmentally Stable Flexible Color Converters Based on Confined CH3NH3PbBr3 Nanocrystals.

In this work, we demonstrate a synthetic route to attain methylammonium lead bromide (CH3NH3PbBr3) perovskite nanocrystals (nc-MAPbBr3, 1.5 nm < size < 3 nm) and provide them with functionality as highly efficient flexible, transparent, environmentally stable, and adaptable color-converting films. We use nanoparticle metal oxide (MOx) thin films as porous scaffolds of controlled nanopores size distribution to synthesize nc-MAPbBr3 through the infiltration of perovskite liquid precursors. We find that the control over the reaction volume imposed by the nanoporous scaffold gives rise to a strict control of the nanocrystal size, which allows us to observe well-defined quantum confinement effects on the photo-emission, being the luminescence maximum tunable with precision between λ = 530 nm (green) and λ = 490 nm (blue). This hybrid nc-MAPbBr3/MOx structure presents high mechanical stability and permits subsequent infiltration with an elastomer to achieve a self-standing flexible film, which not only maintains the photo-emission efficiency of the nc-MAPbBr3 unaltered but also prevents their environmental degradation. Applications as adaptable color-converting layers for light-emitting devices are envisaged and demonstrated.

Randomized prospective trial of early steroid withdrawal compared with low-dose steroids in renal transplant recipients using serial protocol biopsies to assess efficacy and safety.

BACKGROUND: Corticosteroid therapy after renal transplantation is associated with many adverse effects. Newer immunosuppressive agents may allow for safe and effective reductions in dose or early steroid withdrawal. METHODS: In this prospective, single-center clinical trial, 60 patients were randomized into 2 groups: control patients (n = 28), who received low doses of prednisone throughout, and study patients (n = 32), who were withdrawn from steroids 7 days posttransplant. Patients received a limited course of rabbit antilymphocyte globulin (rALG) induction therapy, tacrolimus (TAC), and mycophenolate mofetil (MMF). Patients were followed for clinical outcomes and renal function. Protocol biopsies were performed at 1, 6, and 12 months. RESULTS: Clinical rejections occurred in 11% of controls and 13% of study patients. Renal function was well maintained and equivalent in both groups. In all, 111 protocol biopsies were performed without complications. Subclinical rejection was noted in only 2 protocol biopsies, and borderline changes were seen in 12 biopsies, all of which were distributed equally between both groups. Unsuspected acute TAC toxicity was seen in 8 biopsies. Protocol biopsies led to changes in therapy in 10% of patients. In both groups, serial protocol biopsies demonstrated increased allograft fibrosis over time, which was significant at 1 year in the steroid withdrawal group. CONCLUSION: The immunosuppressive combination of rALG, TAC, and MMF prevents subclinical rejection and the need for high doses of steroids after transplantation. However, continual low-dose steroid therapy may aid in preventing chronic allograft fibrosis. Protocol biopsies help define the short-term and long-term risks of steroid withdrawal therapy.