Mechanism of photoluminescence in intrinsically disordered CaZrO3 crystals: First principles modeling of the excited electronic states

Abstract CaZrO3 (CZO) powders obtained by the polymeric precursor method at 400 °C, and then, the samples were annealed at different temperatures (400, 600, 800, and 1000 °C) and characterized by X-ray diffraction, Raman and ultraviolet–visible spectroscopic methods, along with photoluminescence (PL) emissions. First principle calculations based on the density functional theory (DFT), using a periodic cell models, provide a theoretical framework for understanding the PL spectra based on the localization and characterization of the ground and electronic excited states. Fundamental (singlet, s ) and excited (singlet, s* , and triplet, t* ) electronic states were localized and characterized us…

α- and β-AgVO3 polymorphs as photoluminescent materials: an example of temperature-driven synthesis

Abstract Controlling the synthesis of a given polymorph of an inorganic material is a further step in the design of property and function. In this letter, we report for the first time a simple procedure to effectively control the reversible transformation between the crystalline polymorphs α-AgVO3 and β-AgVO3. Photoluminescence emission (PL) performance is analyzed; at low temperatures (up to 35 °C) when α-AgVO3 is formed the PL emission is red, while at temperatures larger than 45 °C when β-AgVO3 is obtained the color of emission PL emission goes from green to blue. The findings highlight the ability of temperature to dramatically alter the nature of phase transformation at the atomic leve…

Structure, morphology and photoluminescence emissions of ZnMoO4: RE 3+=Tb3+ - Tm3+ - X Eu3+ (x = 1, 1.5, 2, 2.5 and 3 mol%) particles obtained by the sonochemical method

Made available in DSpace on 2018-12-11T17:36:34Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-06-25 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Ministerio de Economía y Competitividad ZnMoO4 and ZnMoO4: RE3+ = 1% Tb3+, 1% Tm3+, x Eu3+ (x = 1, 1.5, 2, 2.5 and 3 mol%) particles were prepared by a sonochemical method. The influence of the dopant content on photoluminescent behavior was investigated. The X-ray diffraction results confirmed the formation of the α-ZnMoO4 phase with a triclinic crystalline structure. The influence of th…

Computational chemistry meets experiments for explaining the geometry, electronic structure, and optical properties of Ca10V6O25

In this paper, we present a combined experimental and theoretical study to disclose, for the first time, the structural, electronic, and optical properties of Ca10V6O25 crystals. The microwave-assisted hydrothermal (MAH) method has been employed to synthesize these crystals with different morphologies, within a short reaction time at 120 °C. First-principle quantum mechanical calculations have been performed at the density functional theory level to obtain the geometry and electronic properties of Ca10V6O25 crystal in the fundamental and excited electronic states (singlet and triplet). These results, combined with the measurements of X-ray diffraction (XRD) and Rietveld refinements, confirm…

Surfactant-Mediated Morphology and Photocatalytic Activity of α‑Ag2WO4 Material

In the present work, the morphology (hexagonal rod-like vs cuboid-like) of an α-Ag2WO4 solid-state material is manipulated by a simple controlled-precipitation method, with and without the presence of the anionic surfactant sodium dodecyl sulfate (SDS), respectively, over short reaction times. Characterization techniques, such as X-ray diffraction analysis, Rietveld refinement analysis, Fourier-transform (FT) infrared spectroscopy, FT Raman spectroscopy, UV–vis spectroscopy, transmission electron microscopy (TEM), high-resolution TEM, selected area electron diffraction, energy-dispersive X-ray spectroscopy, field emission-scanning electron microscopy (FE-SEM), and photoluminescence emission…

Reading at exposed surfaces: theoretical insights into photocatalytic activity of ZnWO4

ZnWO4 nanocrystals: synthesis, morphology, photoluminescence and photocatalytic properties

The present joint experimental and theoretical work provides in-depth understanding on the morphology and structural, electronic, and optical properties of ZnWO4 nanocrystals. Monoclinic ZnWO4 nanocrystals were prepared at three different temperatures (140, 150, and 160 °C) by a microwave hydrothermal method. Then, the samples were investigated by X-ray diffraction with Rietveld refinement analysis, field-emission scanning electron microscopy, transmission electronic microscopy, micro-Raman and Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and photoluminescence measurements. First-principles theoretical calculations within the framework of density functional the…

Uncovering the metastable γ-Ag2WO4 phase: a joint experimental and theoretical study

The synthesis of metastable solid phases is a pivotal starting point for innovative materials research. Here, we report the synthesis by means of a precipitation method of the metastable cubic γ-Ag2WO4 phase under ambient conditions. Different experimental techniques such as X-ray diffraction (XRD) with Rietveld refinement, field emission scanning electron microscopy (FE-SEM), micro-Raman/ultraviolet-visible (UV-vis) diffuse reflectance, photoluminescence spectroscopies, and differential scanning calorimetry (DSC) were employed. To complement the experimental data, the geometry, morphology, vibrational and electronic structure of γ-Ag2WO4 were characterized and evaluated using first-princip…

Synthesis of Cuboctahedral CeO2 Nanoclusters and Their Assembly into Cuboid Nanoparticles by Oriented Attachment

Here, we describe a simple approach to control the oriented attachment process through selective ligand scavenging from the {100} facets of CeO2 nanoclusters. Aggregates of these nanoclusters smaller than 10 nm with controlled shapes and exposed facets were obtained. For the synthesis of the cuboctahedral CeO2 nanoclusters, we developed a solvent-controlled synthesis approach based on a non-hydrolytic sol–gel process and used an ester aminolysis reaction to control ligand scavenging from the {100} facets. First-principle calculations allowed us to understand and interpret, at the atomic level, the effects of shape control on the synthesis. Fine-tuning of the desired morphologies can be achi…

Understanding the White-Emitting CaMoO4 Co-Doped Eu3+, Tb3+, and Tm3+ Phosphor through Experiment and Computation

In this article, the synthesis by means of the spray pyrolysis method, of the CaMoO4 and rare-earth cation (RE3+)-doped CaMoO4:xRE3+ (RE3+ = Eu3+, Tb3+, and Tm3+; and x = 1, 2, and 4% mol) compounds, is presented. The as-synthesized samples were characterized using X-ray diffraction, Rietveld refinement, field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and photoluminescence (PL) spectroscopy. To complement and rationalize the experimental results, first-principles calculations, at the density functional theory level, have been performed to analyze the band structure and density of states. In addition, a theoretical method based on the calculations of surface energie…

Integrated experimental and theoretical study on the phase transition and photoluminescent properties of ZrO2:xTb3+ (x=1, 2, 4 and 8 mol %)

Abstract Zirconia (ZrO2) has been intensively studied as an important ceramic material, and numerous technological applications have been found. The present work deals with synthesizing and characterizing the phase transition (cubic vs tetragonal) and photoluminescence emissions of ZrO2:xTb3+ (x = 1,2,4 and 8 mol%). The samples formed by the complex polymerization were thoroughly characterized for physicochemical properties such powder by X-ray diffraction (XRD), and Raman and diffuse reflectance spectroscopies. First-principle calculations at the density functional theory level were performed to complement and rationalize the experimental results. An energy transfer mechanism which promote…

Experimental and theoretical study of the energetic, morphological, and photoluminescence properties of CaZrO3:Eu3+

In this study, we present a combined experimental and theoretical study of the geometry, electronic structure, morphology, and photoluminescence properties of CaZrO3:Eu3+ materials. The polymeric precursor method was employed to synthesize CaZrO3:Eu3+ crystals, while density functional theory calculations were performed to determine the geometrical and electronic properties of CaZrO3:Eu3+ in its ground and excited electronic states (singlet and triplet). The results were combined with X-ray diffraction (XRD) measurements to elucidate the local structural changes induced by the introduction of Eu3+ in the crystal lattice. This process results in the formation of intermediate levels in the ba…

Experimental and theoretical study to explain the morphology of CaMoO4 crystals

Abstract CaMoO 4 crystals were prepared by a controlled co-precipitation method and processed in a domestic microwave-assisted hydrothermal system with two different surfactants (ethyl 4-dimethylaminobenzoate and 1,2,4,5-benzenetetracarboxylic dianhydride). The corresponding structures were characterized by X-ray diffraction and Rietveld refinement techniques, Fourier transform infrared spectroscopy, ultraviolet–visible absorption spectroscopy, and photoluminescence measurements. Field emission scanning electron microscopy was used to investigate the morphology of the as-synthesized aggregates. The structure, the surface stability of the (001), (112), (100), (110), (101), and (111) surfaces…

First-Principles Study on Polymorphs of AgVO3: Assessing to Structural Stabilities and Pressure-Induced Transitions

In this paper, we present a comprehensive theoretical study, based on density-functional theory calculations, and which focuses on the structural and electronic properties of silver vanadium oxide (AgVO3) in the monoclinic [Cm (β-AgVO3), C2/c (α-AgVO3), and Cc], orthorhombic (Amm2), and cubic (Pm3̅m) phases from 0–30 GPa. The structural and electronic properties, the stability of different phases, and the pressure-induced solid–solid phase transitions of AgVO3 have been previously studied. The effects of pressure on the band structures, energy–gap values, density of states, and vibrational frequencies are also studied. Numerical and analytical calculations are conducted to obtain the lattic…

Theoretical approach for determining the relation between the morphology and surface magnetism of Co3O4

Abstract Precisely controlling the different aspects of the morphology and magnetic properties of metal oxides are fundamental to materials design. A theoretical approach, based on the Wulff construction and magnetization density (M) index, is presented to clarify the relation between the morphology and surface magnetism. The M index allows us to evaluate the uncompensated spins at the (1 0 0), (1 1 0), (1 1 1) and (1 1 2) surfaces of Co3O4 with a spinel structure. The investigated morphologies show an excellent agreement with the experimental results, with the main contribution coming from the (1 0 0) and (1 1 1) magnetic planes. The present results are also helpful in clarifying the intri…

Geometry, electronic structure, morphology, and photoluminescence emissions of BaW1-xMoxO4 (x = 0, 0.25, 0.50, 0.75, and 1) solid solutions: Theory and experiment in concert

Abstract The design of a solid solution with tunable electro-optical properties and multifunctionality is a promising strategy for developing novel materials. In this work, BaW1-xMoxO4 (x = 0, 0.25, 0.5, 0.75, and 1) solid solutions have been successfully prepared for the first time by a co-precipitation method. Their crystal structure and phase composition were determined by X-ray diffraction and Rietveld refinements. Fourier transform infrared and micro Raman spectroscopy in combination with field-emission scanning electron microscopy (FE-SEM) were used to describe the microstructures and chemical compositions of the synthesized materials. The influence of chemical composition on morpholo…

Mechanism of Antibacterial Activity via Morphology Change of α-AgVO3: Theoretical and Experimental Insights

The electronic configuration, morphology, optical features, and antibacterial activity of metastable α-AgVO3 crystals have been discussed by a conciliation and association of the results acquired by experimental procedures and first-principles calculations. The α-AgVO3 powders were synthesized using a coprecipitation method at 10, 20, and 30 °C. By using a Wulff construction for all relevant low-index surfaces [(100), (010), (001), (110), (011), (101), and (111)], the fine-tuning of the desired morphologies can be achieved by controlling the values of the surface energies, thereby lending a microscopic understanding to the experimental results. The as-synthesized α-AgVO3 crystals display a …

CSD 1851956: Experimental Crystal Structure Determination

Related Article: Mayara Mondego Teixeira, Regiane Cristina de Oliveira, Marisa Carvalho Oliveira, Renan Augusto Pontes Ribeiro, Sergio R. de Lazaro, M��ximo Siu Li, Adenilson J. Chiquito, Lourdes Gracia, Juan Andr��s, Elson Longo|2018|Inorg.Chem.|57|15489|doi:10.1021/acs.inorgchem.8b02807

CSD 1851955: Experimental Crystal Structure Determination

Related Article: Mayara Mondego Teixeira, Regiane Cristina de Oliveira, Marisa Carvalho Oliveira, Renan Augusto Pontes Ribeiro, Sergio R. de Lazaro, M��ximo Siu Li, Adenilson J. Chiquito, Lourdes Gracia, Juan Andr��s, Elson Longo|2018|Inorg.Chem.|57|15489|doi:10.1021/acs.inorgchem.8b02807

CSD 1851954: Experimental Crystal Structure Determination

Related Article: Mayara Mondego Teixeira, Regiane Cristina de Oliveira, Marisa Carvalho Oliveira, Renan Augusto Pontes Ribeiro, Sergio R. de Lazaro, M��ximo Siu Li, Adenilson J. Chiquito, Lourdes Gracia, Juan Andr��s, Elson Longo|2018|Inorg.Chem.|57|15489|doi:10.1021/acs.inorgchem.8b02807

CSD 1851953: Experimental Crystal Structure Determination

Related Article: Mayara Mondego Teixeira, Regiane Cristina de Oliveira, Marisa Carvalho Oliveira, Renan Augusto Pontes Ribeiro, Sergio R. de Lazaro, M��ximo Siu Li, Adenilson J. Chiquito, Lourdes Gracia, Juan Andr��s, Elson Longo|2018|Inorg.Chem.|57|15489|doi:10.1021/acs.inorgchem.8b02807