RESUMEN
Photocatalysis and photoelectrochemical (PEC) reactions are complex processes involving both the physical properties and surface chemistry of the semiconductor photocatalyst. Their interplay applies specific limitations on the performance of different materials in light-driven reactions, often despite their optimal band structure and optical absorption. One of the ways to properly characterize the photocatalytic and PEC properties of semiconductors remains the measurement of the photopotential, which characterizes a driving force of photoinduced processes in the material. In this work, we give a general scope on the photopotential in PEC reactions that finds its origin in semiconductor physics. It is shown that the photopotential does not always play an interchangeable role with the photocurrent in comparative analysis of the photocatalytic performance of different materials. Furthermore, a correlation between the photopotential and the kinetics of methylene blue dye photocatalysis is shown for anatase-TiO2, CeO2and WO3as photocatalysts. Fermi level pinning (FLP) in the bandgap of CeO2is observed limiting the photoactivity of the compound, which is attributed to the high defectivity of CeO2. A short review is given on the possible origins of FLP in metal oxides and ways to overcome it. It is pointed out that the shift of the Fermi level after illumination of CeO2can trigger the chemical instability of the material accompanied by the FLP process.
RESUMEN
In this paper, we present a study of silicon surface passivation based on the use of spin-coated hybrid composite layers. We investigate both undoped poly(3,4-ethylenedioxythiophene)/poly-(styrenesulfonate) (PEDOT:PSS), as well as PEDOT:PSS functionalized with semiconducting oxide nanomaterials (TiO2 and SnO2). The hybrid compound was deposited at room temperature by spin coating-a potentially lower cost, lower processing time and higher throughput alternative compared with the commonly used vacuum-based techniques. Photoluminescence imaging was used to characterize the electronic properties of the Si/PEDOT:PSS interface. Good surface passivation was achieved by PEDOT:PSS functionalized by semiconducting oxides. We show that control of the concentration of semiconducting oxide nanoparticles in the polymer is crucial in determining the passivation performance. A charge carrier lifetime of about 275 µs has been achieved when using SnO2 nanoparticles at a concentration of 0.5 wt.% as a filler in the composite film. X-ray diffraction (XRD), scanning electron microscopy, high resolution transmission electron microscopy (HRTEM), energy dispersive x-ray in an SEM, and µ-Raman spectroscopy have been used for the morphological, chemical and structural characterization. Finally, a simple model of a photovoltaic device based on PEDOT:PSS functionalized with semiconducting oxide nanoparticles has been fabricated and electrically characterized.
RESUMEN
Based on the combination of density functional theory and theory-group methods, we performed systematic modeling of γ-CuI structural design at the atomistic level. Being started from the metallic copper lattice, we treated a crystal assembly as a stepwise iodination process characterized in terms of a sequence of intermediate lattice geometries. These geometries were selected and validated via screening of possible structural transformations. The genesis of chemical bonding was studied for three structural transformations by analyzing the relevant changes in the topology of valence electron densities. We determined structural trends driven by metal-ligand coupling. This allowed us to suggest the improved scenario of chemical bonding in γ-CuI. In particular, the unconventional effect of spatial separation of metallic and covalent interactions was found to be very important with respect to the preferred arrangements of valence electrons in the iodination process. We rigorously showed that useful electronic and optical properties of γ-CuI originate from the combination of two separated bonding patterns-strong covalency established in I-Cu tetrahedral connections and noncovalent interactions of copper cores is caused by the 3d10 closed-shell electron configurations. The other finding of ours is that the self-consistency of the GW calculations is crucial for correctly determining the dynamic electronic correlations in γ-CuI. Detail reinvestigation of the quasi-particle energy structure by means of the self-consistent GW approach allowed us to explain how p-type electrical conductivity can be engineered in the material.
RESUMEN
Using density functional total energy calculations the structural phase stability and pressure-induced structural transition in different polymorphs of ZnSiO(3) and Zn(2)SiO(4) have been studied. Among the considered monoclinic phase with space groups (P 2(1)/c) and (C 2/c), rhombohedral [Formula: see text] and orthorhombic (Pbca) modifications the monoclinic phase (P 2(1)/c) of ZnSiO(3) is found to be the most stable one. At high pressure monoclinic ZnSiO(3) (C 2/c) can co-exist with orthorhombic (Pbca) modification. Differences in equilibrium volume and total energy of these two polymorphs are very small, which indicates that it is relatively easier to transform between these two phases by temperature, pressure or chemical composition. It can also explain the experimentally established result of metastability of the orthorhombic phase under all conditions. The following sequence of pressure-induced structural phase transitions is found for ZnSiO(3) polymorphs: monoclinic [Formula: see text] monoclinic [Formula: see text] rhombohedral [Formula: see text]. Among the rhombohedral ([Formula: see text]), tetragonal [Formula: see text], orthorhombic (Pbca), orthorhombic (Imma), cubic [Formula: see text] and orthorhombic (Pbnm) modifications of Zn(2)SiO(4), the rhombohedral phase is found to be the ground state. For this chemical composition of zinc silicate the following sequence of structural phase transitions is found: rhombohedral [Formula: see text] tetragonal [Formula: see text] orthorhombic [Formula: see text] orthorhombic (Imma) [Formula: see text] cubic [Formula: see text] orthorhombic (Pbnm). Based on the analogy of crystal structures of magnesium and zinc silicates and using the lattice and positional parameters of Mg(2)SiO(4) as input, structural properties of spinel Zn(2)SiO(4) have also been studied.