Photoinitiated Energy Transfer in Porous-Cage-Stabilised Silver Nanoparticles.

We report a new composite material consisting of silver nanoparticles decorated with three-dimensional molecular organic cages based on light-absorbing porphyrins. The porphyrin cages serve to both stabilize the particles and allow diffusion and trapping of small molecules close to the metallic surface. Combining these two photoactive components results in a Fano-resonant interaction between the porphyrin Soret band and the nanoparticle-localised surface-plasmon resonance. Time-resolved spectroscopy revealed the silver nanoparticles transfer up to 37 % of their excited-state energy to the stabilising layer of porphyrin cages. These unusual photophysics cause a 2-fold current increase in photoelectrochemical water-splitting measurements. The composite structure provides a compelling proof of concept for advanced photosensitiser systems with intrinsic porosity for photocatalytic and sensing applications.

Photoactive p-Type Spinel CuGa2O4 Nanocrystals.

Herein we report the synthesis and characterization of spinel copper gallate (CuGa2O4) nanocrystals (NCs) with an average size of 3.7 nm via a heat-up colloidal reaction. CuGa2O4 NCs have a band gap of ∼2.5 eV and marked p-type character, in agreement with ab initio simulations. These novel NCs are demonstrated to be photoactive, generating a clear and reproducible photocurrent under blue light irradiation when deposited as thin films. Crucially, the ability to adjust the Cu/Ga ratio within the NCs, and the effect of this on the optical and electronic properties of the NCs, was also demonstrated. These results position CuGa2O4 NCs as a novel material for optoelectronic applications, including hole transport and light harvesting.

SILAR Deposition of Metal Oxide Nanostructured Films.

Methods for the fabrication of thin films with well controlled structure and properties are of great importance for the development of functional devices for a large range of applications. SILAR, the acronym for Successive Ionic Layer Adsorption and Reaction, is an evolution and combination of two other deposition methods, the Atomic Layer Deposition and Chemical Bath Deposition. Due to a relative simplicity and low cost, this method has gained increasing interest in the scientific community. There are, however, several aspects related to the influence of the many parameters involved, which deserve further deepening. In this review article, the basis of the method, its application to the fabrication of thin films, the importance of experimental parameters, and some recent advances in the application of oxide films are reviewed. At first the fundamental theoretical bases and experimental concepts of SILAR are discussed. Then, the fabrication of chalcogenides and metal oxides is reviewed, with special emphasis to metal oxides, trying to extract general information on the effect of experimental parameters on structural, morphological and functional properties. Finally, recent advances in the application of oxide films prepared by SILAR are described, focusing on supercapacitors, transparent electrodes, solar cells, and photoelectrochemical devices.