Electronics with semiconductors rely strongly on defect concentrations and on the properties of these defects. Here we study ZnO thin films which were grown by atomic layer deposition. An interesting mechanism of build-up and of self-healing of Zn interstitial defects as a function of layer thickness d was found, based on measurements of photoabsorption (PA), photoluminescence (PL) and x-ray diffraction as a function of d. The concentration of Zn interstitial defects increases up to d = 19 nm, coupled with a corresponding increase of the Urbach energy, Eu, in PA. At this layer thickness, the growth mode changes from the formation of a homogeneous layer to a layer of nano-crystals, where the nano-crystals grow in size with d. Surprisingly, the Zn interstitial concentration decreases spontaneously once the layer thickness exceeds d = 38 nm. We explain this behavior by a reduction of diffusion barriers for Zn interstitials as a function of average ZnO particle size leading to spontaneous diffusion to the particle surface and subsequent oxidation therein. At the same time, the concentration of oxygen vacancies, mostly located at the particle surface, is greatly reduced with increasing film thickness. The study is of importance in designing opto- and nano-electronic devices by means of appropriate selection of ZnO film thickness, for targeted quality, property and further practical applications.

Bi-layer epitaxial graphene (BLG) on 6H-SiC(0001) (EG/SiC) was grown and modified by thermal deposition of the molecular electron acceptor tetrafluoro-tetra cyano quinodimethane (F4-TCNQ). The surface-modified system, F4-TCNQ/EG/SiC, was studied by X-ray photoelectron spectroscopy (XPS) and angle-resolved polarized Raman spectroscopy (ARPRS). XPS results indicate that bonding of deposited F4-TCNQ molecules depends on their concentration. Although bonding through the cyano groups is present at all concentrations, charge transfer from graphene to fluorine is evident only at sub-monolayer concentrations. The corresponding change in bond character is coupled with a change in molecular orientation. Raman spectroscopy not only provides results consistent with the findings from the XPS study but also reveals a significant degree of molecular stacking above the monolayer concentration. Thus, both the variation of the acceptor concentration and the number of graphene layers provide further handles to manipulate charge and doping that may be useful in device applications.

Covalent-organic frameworks (COFs), being a new member of the crystalline porous materials family, have emerged as important materials for energy storage/conversion/generation devices. They possess high surface areas, ordered micro/mesopores, designable structures and an ability to precisely control electro-active groups in their pores, which broaden their application window. Thanks to their low weight density, long range crystallinity, reticular nature and tunable synthesis approach towards two and three dimensional (2D and 3D) networks, they have been found suitable for a range of challenging electrochemical applications. Our review focuses on the progress made on the design, synthesis and structure of COFs and their composites for various energy applications, such as metal-ion batteries, supercapacitors, water-splitting and solar cells. Additionally, attempts have been made to correlate the structural and mechanistic characteristics of COFs with their applications.

Mixed-metal metal-organic frameworks (M-MOFs) consist of at least two different metal ions as nodes in the same framework. The incorporation of a second or more metal ions provides structural/compositional diversity, multi-functionality and stability to the framework. Moreover, the periodical array of different metal ions in the framework may alter the physical/chemical properties of M-MOFs and result in fascinating applications. M-MOFs with exciting structural features offer superior supercapacitor performances compared to single metal MOFs due to the synergic effect of different metal ions. In this review, we summarize several synthetic methods to construct M-MOFs by employing various organic ligands or metalloligands. Further, we discuss the electrochemical performance of several M-MOFs and their derived composite materials for supercapacitor applications.

A dysprosium metal-organic framework, {[Dy(μ2-FcDCA)1.5(MeOH)(H2O)]·0.5H2O}n (1), where FcDCA = 1,1'-ferrocene dicarboxylic acid, was prepared by slow-diffusion technique at room temperature. The crystal structure analysis of 1 by single-crystal X-ray diffraction reveals different binding modes of FcDCA linkers coordinated with Dy(III) metal ions, which forms continuous porous two-dimensional (2D) infinite framework. The resulting 2D layers are linked by π···π interactions to build three-dimensional (3D) supramolecular framework. Observably, this thermally stable 3D architecture was topologically simplified as a three-connected uninodal net with fes topology. Furthermore, the practical applicability of 1 was investigated as a fluorescence sensor for the sensitive detection of picric acid in aqueous medium with an impressive detection limit of 0.71 μM with quenching constant (KSV) quantified to be 8.55 × 104 M-1. The distinguished selectivity in the presence of other nitroaromatics suggests the possible incorporation of 1 in real-world futuristic diagnostic kits. Additionally, the electrochemical behavior of 1 exhibits reversible in nature attributed to the ferrocene/ferrocenium cation.