KNbO3 photoelectrode for DSSC: a structural, optical and electrical approach.

In this work, we present the potassium niobate (KNbO3) nanoparticles as a suitable mesoporous photoelectrode for dye-sensitized solar cells (DSSCs). The KNbO3 particles were synthesized by the microwave-assisted hydrothermal method using mild conditions and characterized by SEM, XRD, Raman, and UV-Vis diffuse reflectance. The particles presented a pyramidal tower-like shape with an orthorhombic structure and an indirect bandgap of (3.0 ± 0.1) eV. Dye-sensitized solar cells were assembled using the synthesized KNbO3 nanoparticles, which were deposited as a photoelectrode on a TiO2 recombination charge blocking layer. It is noticeable that the synergistic operation of the TiO2 blocking layer and KNbO3 photoelectrode is essential to achieve photovoltaic behaviour in our solar cells. The short-circuit current density of Jsc = 2.82 mA, open-circuit voltage Voc = 669 mV, fill factor FF = 0.62, and a power conversion efficiency PCE = 1.17%, reports elevated parameters if compared to other DSSCs alternative materials, becoming potassium niobate suitable as photoelectrode.

Low recombination rates and improving charge transfer as decisive conditions for high current densities and fill factors in ZnS complex systems.

The growth of ZnS photoelectrodes on ZnO particles identified as ZnO/ZnS(ZC + TAA) by the microwave-assisted hydrothermal method showed excellent photovoltaic parameters of JSC = 1.2 mA cm-2 and FF = 0.66, even compared to ZnS(ZC + TAA) used as a reference sample with JSC = 0.15 mA cm-2 and FF = 0.52. A careful analysis indicates that the better charge transfer and the higher resistance to recombination present in the ZnO/ZnS(ZC + TAA) samples were the origin of the best photovoltaic behavior. These assertions are supported by a set of samples synthesized from different precursors resulting in different crystal structures, which can be directly associated with current densities and fill factors. All aspects about synthesis and optical/electronic parameters associated with structural features will be available in this article.

Properties of zinc titanates synthesized by microwave assisted hydrothermal method.

Zinc titanates are compounds that have shown great application versatility, including in the field of semiconductors. Solid state reactions, the polymeric precursor method and the hydrothermal method are the most mentioned synthesis of these compounds in the literature. In the present work, we use microwave assisted hydrothermal method (MAH) to synthesize zinc titanate and evaluate its potential for solar cell applications through structural and optical characterization techniques. The synthesized samples were also subjected to a variable temperature heat treatment in the range of 500 °C-800 °C. The analysis showed that the crystallization of the material starts at 500 °C and that samples submitted to temperatures of 600 °C-800 °C showed the formation of two phases of zinc titanates, being a cubic phase of ZnTiO3, considered rare in the literature, predominant up to a temperature of 800 °C. The optical characterization, based on the techniques of photoluminescence spectroscopy and UV-Visible spectroscopy, showed that the photoluminescent activity and the energy of the band gap increased with the increase of the temperature of the heat treatment, having the highest response in 700 °C, facts that can be linked to the predominant formation of the cubic phase of ZnTiO3 and simultaneous of the cubic and rhombohedral phases of ZnTiO3 at 700 and 800 °C. Finally, we highlight as the most important results, the fact that it was possible to obtain these titanates at a temperature lower than that reported in the literature, and that the heat-treated sample at 500 °C is the one with the lowest energy expenditure to be synthesized and the one with the greatest potential for application in dye-sensitized solar cells (DSSC's).

Influence of Eu valence on the optical activity of BaTiO3 decorated with CaF2 synthesized by microwave-assisted hydrothermal method.

Inorganic hybrid materials have promising applications in absorbers and for the photon harvesting of solar irradiation, such as in DSSC photoanodes. Moreover, investigation of the interactions between the photoanode constituent materials is extremely important, since it is known that the properties of the materials are strongly dependent on the nucleation and growth process. Therefore, the purpose of this work was to synthesize a system consisting of a synergic combination of two inorganic hosts, BaTiO3 and CaF2, synthesized together through a microwave-assisted hydrothermal method, which allows single-phase materials to be obtained after short synthesis times and at low temperatures. The increase in optical activity was investigated after the insertion of Eu ions. From the structural results, it was possible to observe that the method used to obtain the system was efficient, even using temperatures as low as 140 °C and a reaction time of one minute. The optical properties (emission and excitation) were evaluated in the visible and VUV region from 2.5 to 10.5 eV. The XANES Eu Liii edge differences associated with the XEOL results indicate that the synthesis method incorporated Eu3+ in the hosts and the surface of the two compounds, BaTiO3 and CaF2. Therefore, the combination between the Eu3+ activators and the F centers of the host increased the range for photon harvesting, making these systems a promising material for future applications in photoanodes for DSSCs.

Band alignment and charge transfer predictions of ZnO/ZnX (X = S, Se or Te) interfaces applied to solar cells: a PBE+U theoretical study.

The engineering of semiconductor materials for the development of solar cells is of great importance today. Two topics are considered to be of critical importance for the efficiency of Grätzel-type solar cells, the efficiency of charge separation and the efficiency of charge carrier transfer. Thus, one research focus is the combination of semiconductor materials with the aim of reducing charge recombination, which occurs by spatial charge separation. From an experimental point of view, the combining of materials can be achieved by decorating a core with a shell of another material resulting in a core-shell system, which allows control of the desired photoelectronic properties. In this context, a computational simulation is mandatory for the atomistic understanding of possible semiconductor combinations and for the prediction of their properties. Considering the construction of ZnO/ZnX (X = S, Se or Te) interfaces, we seek to investigate the electronic influence of the shell (ZnX) on the core (ZnO) and, consequently, find out which of the interfaces would present the appropriate properties for (Grätzel-type) solar cell applications. To perform this study, we have employed density functional theory (DFT) calculations, considering the Perdew-Burke-Ernzerhof (PBE) functional. However, it is well-known that plain DFT fails to describe strong electronic correlated materials where, in general, an underestimation of the band gap is obtained. Thus, to obtain the correct description of the electronic properties, a Hubbard correction was employed, i.e. PBE+U calculations. The PBE+U methodology provided the correct electronic structure properties for bulk ZnO in good agreement with experimental values (99.4%). The ZnO/ZnX interfaces were built and were composed of six ZnO layers and two ZnX layers, which represents the decoration process. The core-shell band gap was 2.2 eV for ZnO/ZnS, ∼1.71 eV for ZnO/ZnSe and ∼0.95 eV for ZnO/ZnTe, which also exhibited a type-II band alignment. Bader charge analysis showed an accumulation of charges in the 6th layer of ZnO for the three ZnO/ZnX interfaces. On the basis of these results, we have proposed that ZnO/ZnS and ZnO/ZnSe core-shell structures can be applied as good candidates (with better efficiency) for photovoltaic devices.

Functionalized pink Al2O3:Mn pigments applied in prosthetic dentistry.

STATEMENT OF PROBLEM: The color of dental poly(methyl methacrylate) (PMMA) is conventionally rendered by organic and inorganic pigments, which are usually not bonded to the polymer network. Functionalized ceramic pigments can be used to color PMMA, allowing improved chemical interaction with the resin matrix. PURPOSE: The purpose of this in vitro study was to synthesize, functionalize, and characterize pink manganese-doped alumina ceramic pigments. The hypothesis tested was that functionalized ceramic pigments would render pink coloration to a translucent PMMA without jeopardizing its mechanical properties. MATERIAL AND METHODS: Pink alumina powders doped with 1 or 2 mol% of manganese (Al2O3:Mn) were prepared by means of a polymeric precursor method. Pigment (Pig.) particles were functionalized with a silica coating method followed by silanation before preparation of PMMA-based composite resins (5 wt% pigment). The color of composite resins (Pig.1% and Pig.2%) and PMMA controls (Pink and translucent [Trans]) was evaluated (CIELab color coordinates), and their mechanical properties were tested (3-point bending). RESULTS: The microstructure of the pigment particles showed approximately 55-nm nanocrystals of manganese-doped α-alumina clustered into irregular porous particles up to 60 µm. The composite resins and pink PMMA showed similar color parameters (CIE a* pink=20.1, Pig.1%=14.6, Pig.2%=16.0, Trans=0.19, P<.001; CIE b* Pink=17.0, Pig.1%=18.6, Pig.2%=19.0, Trans=2.52, P<.001). No statistical differences were observed in mechanical properties among groups (σf pink=98.4, Pig.1%=98.1, Pig.2%=98.8, trans=89.1, P=.136). CONCLUSIONS: The addition of the functionalized pink ceramic pigments to a translucent PMMA yielded similar coloration to that of the regular pink PMMA used in dentistry and did not jeopardize its mechanical properties.

Fingerprints of short-range and long-range structure in BaZr(1-x)HfxO3 solid solutions: an experimental and theoretical study.

A microwave-assisted hydrothermal method was applied to synthesize BaZr1-xHfxO3, (BZHO) solid solutions at a low temperature, 140 °C, and relatively short times, 160 min. The detailed features of the crystal structure, at both short and long ranges, as well as the crystal chemistry doping process, are extensively analysed. X-ray diffraction measurements and Raman spectroscopy have been used to confirm that pure and Hf-doped BZO materials present a cubic structure. Extended X-ray absorption fine structure (EXAFS) spectra indicate that Hf(4+) ions have replaced the Zr(4+) ions on the 6-fold coordination and a subsequent change on the Ba(2+) 12-fold coordination can be sensed. X-ray absorption near-edge structure (XANES) spectroscopy measurements reveal a local symmetry breaking process, associated to overlap of the 4d-2p and 5d-2p orbitals of Zr-O and Hf-O bonds, respectively. Field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HRTEM) show the mesocrystalline nature of self-assembled BZHO nanoparticles under a dodecahedron shape. In addition first principle calculations were performed to complement the experimental data. The analysis of the band structures and density of states of the undoped BZO and doped BZHO host lattice allow deep insight into the main electronic features. The theoretical results help us to find a correlation between simulated and experimental Raman modes and allow a more substantial interpretation of crystal structure.

Joint experimental and theoretical analysis of order-disorder effects in cubic BaZrO3 assembled nanoparticles under decaoctahedral shape.

Periodic first-principles calculations based on density functional theory at the B3LYP level has been carried out to investigate the photoluminescence (PL) emission of BaZrO(3) assembled nanoparticles at room temperature. The defect created in the nanocrystals and their resultant electronic features lead to a diversification of electronic recombination within the BaZrO(3) band gap. Its optical phenomena are discussed in the light of photoluminescence emission at the green-yellow region around 570 nm. The theoretical model for displaced atoms and/or angular changes leads to the breaking of the local symmetry, which is based on the refined structure provided by Rietveld methodology. For each situation a band structure, charge mapping, and density of states were built and analyzed. X-ray diffraction (XRD) patterns, UV-vis measurements, and field emission scanning electron microscopy (FE-SEM) images are essential for a full evaluation of the crystal structure and morphology.