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Title: A novel approach to obtain highly intense self-activated photoluminescence emissions in hydroxyapatite nanoparticles

Abstract

Defect-related photoluminescence (PL) in materials have attracted interest for applications including near ultraviolet (NUV) excitable light-emitting diodes and in biomedical field. In this paper, hydroxyapatite [Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}] nanorods with intense PL bands (bluish- and yellowish-white emissions) were obtained when excited under NUV radiation at room temperature. These nanoparticles were synthesized via chemical precipitation at 90 °C followed by distinct heat treatments temperatures (200–800 °C). Intense and broad emission profiles were achieved at 350 °C (380–750 nm) and 400 °C (380–800 nm). UV–Vis spectroscopy revealed band gap energies (5.58–5.78 eV) higher than the excitation energies (~3.54 and ~2.98 eV at 350 and 415 nm, respectively), confirming the contribution of defect energy levels within the forbidden zone for PL emissions. The structural features were characterized by X-ray diffraction, Rietveld refinement, thermogravimetric analysis, and Fourier transform infrared spectroscopy. By means of these techniques, the relation between structural order-disorder induced by defects, chemical reactions at both lattice and surface of the materials as well as the PL, without activator centers, was discussed in details. - Graphical abstract: The self-activated photoluminescence emissions of chemically precipitated hydroxyapatite nanorods were improved by different heat treatment temperatures. - Highlights: • HA nanorods were synthesized withmore » improved self-activated PL at room temperature. • PL profile and intensity dependents on the temperature of posterior heat treatments. • Bluish- and yellowish-white emissions under NUV excitation (350 and 415 nm). • Broad and intense profiles achieved at 350 °C (380–750 nm) and 400 °C (380–800 nm). • PL from the e′–h{sup •} recombination between defect energy levels within the band gap.« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [5];  [6];  [3];  [1]
  1. CDMF-UFSCar, Universidade Federal de São Carlos, P.O. Box 676, 13565-905 São Carlos, São Paulo (Brazil)
  2. (Spain)
  3. QIO-UJI, Universitat Jaume I, 12071 Castellón (Spain)
  4. PPGEM-IFMA, Instituto Federal de Educação, Ciência e Tecnologia do Maranhão, 65030-005 São Luís, MA (Brazil)
  5. IFSC-USP, Universidade de São Paulo, P.O. Box 369, 13560-970 São Carlos, SP (Brazil)
  6. QFA-UJI, Universitat Jaume I, 12071 Castellón (Spain)
Publication Date:
OSTI Identifier:
22658262
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 249; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; APATITES; CHEMICAL REACTIONS; CRYSTAL DEFECTS; ELECTRONIC STRUCTURE; EXCITATION; EXPERIMENTAL DATA; FOURIER TRANSFORM SPECTROMETERS; FOURIER TRANSFORMATION; HEAT TREATMENTS; NANOPARTICLES; NANOSTRUCTURES; PHOTOLUMINESCENCE; SYNTHESIS; TEMPERATURE RANGE 0273-0400 K; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION

Citation Formats

Machado, Thales R., QIO-UJI, Universitat Jaume I, 12071 Castellón, Sczancoski, Júlio C., Beltrán-Mir, Héctor, Nogueira, Içamira C., Li, Máximo S., Andrés, Juan, Cordoncillo, Eloisa, and Longo, Elson, E-mail: elson.liec@gmail.com. A novel approach to obtain highly intense self-activated photoluminescence emissions in hydroxyapatite nanoparticles. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2016.12.018.
Machado, Thales R., QIO-UJI, Universitat Jaume I, 12071 Castellón, Sczancoski, Júlio C., Beltrán-Mir, Héctor, Nogueira, Içamira C., Li, Máximo S., Andrés, Juan, Cordoncillo, Eloisa, & Longo, Elson, E-mail: elson.liec@gmail.com. A novel approach to obtain highly intense self-activated photoluminescence emissions in hydroxyapatite nanoparticles. United States. doi:10.1016/J.JSSC.2016.12.018.
Machado, Thales R., QIO-UJI, Universitat Jaume I, 12071 Castellón, Sczancoski, Júlio C., Beltrán-Mir, Héctor, Nogueira, Içamira C., Li, Máximo S., Andrés, Juan, Cordoncillo, Eloisa, and Longo, Elson, E-mail: elson.liec@gmail.com. Mon . "A novel approach to obtain highly intense self-activated photoluminescence emissions in hydroxyapatite nanoparticles". United States. doi:10.1016/J.JSSC.2016.12.018.
@article{osti_22658262,
title = {A novel approach to obtain highly intense self-activated photoluminescence emissions in hydroxyapatite nanoparticles},
author = {Machado, Thales R. and QIO-UJI, Universitat Jaume I, 12071 Castellón and Sczancoski, Júlio C. and Beltrán-Mir, Héctor and Nogueira, Içamira C. and Li, Máximo S. and Andrés, Juan and Cordoncillo, Eloisa and Longo, Elson, E-mail: elson.liec@gmail.com},
abstractNote = {Defect-related photoluminescence (PL) in materials have attracted interest for applications including near ultraviolet (NUV) excitable light-emitting diodes and in biomedical field. In this paper, hydroxyapatite [Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}] nanorods with intense PL bands (bluish- and yellowish-white emissions) were obtained when excited under NUV radiation at room temperature. These nanoparticles were synthesized via chemical precipitation at 90 °C followed by distinct heat treatments temperatures (200–800 °C). Intense and broad emission profiles were achieved at 350 °C (380–750 nm) and 400 °C (380–800 nm). UV–Vis spectroscopy revealed band gap energies (5.58–5.78 eV) higher than the excitation energies (~3.54 and ~2.98 eV at 350 and 415 nm, respectively), confirming the contribution of defect energy levels within the forbidden zone for PL emissions. The structural features were characterized by X-ray diffraction, Rietveld refinement, thermogravimetric analysis, and Fourier transform infrared spectroscopy. By means of these techniques, the relation between structural order-disorder induced by defects, chemical reactions at both lattice and surface of the materials as well as the PL, without activator centers, was discussed in details. - Graphical abstract: The self-activated photoluminescence emissions of chemically precipitated hydroxyapatite nanorods were improved by different heat treatment temperatures. - Highlights: • HA nanorods were synthesized with improved self-activated PL at room temperature. • PL profile and intensity dependents on the temperature of posterior heat treatments. • Bluish- and yellowish-white emissions under NUV excitation (350 and 415 nm). • Broad and intense profiles achieved at 350 °C (380–750 nm) and 400 °C (380–800 nm). • PL from the e′–h{sup •} recombination between defect energy levels within the band gap.},
doi = {10.1016/J.JSSC.2016.12.018},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 249,
place = {United States},
year = {Mon May 15 00:00:00 EDT 2017},
month = {Mon May 15 00:00:00 EDT 2017}
}
  • We synthesized the ZnS:Mn{sup 2+} nanoparticles passivated by biocompatible layer, namely, biotin by chemical precipitation route and studied their temporal evolution for size, structure, optical, and photoluminescence stability. To monitor the structural and optoelectronic properties of the nanoparticles with time, we have characterized the grown product by x-ray diffraction, small angle x-ray scattering, UV visible, and photoluminescence spectroscopic techniques at a regular interval for a period of three months. Results showed that the properties of nanophosphors capped with biotin are remaining the same even after 3 months. Energy dispersive x-ray analysis of 3 month aged sample shows long time compatibilitymore » between ZnS:Mn{sup 2+} nanoparticles and the biotin. This is also confirmed by electron microscopy that the growth of the nanoparticles is strongly arrested by the biotin. X-ray photoelectron spectra were also recorded to show the chemical state of the elements. Enhanced ratio of Zn 2p to Mn 2p peaks in the x-ray photoelectron spectra of ZnS:Mn{sup 2+} nanoparticles shows that the Mn{sup 2+} ions are incorporated within ZnS host matrix. We found that biotin capping will enhance the luminescence from ZnS:Mn{sup 2+} nanoparticles as compared to without capped particles. Absence of biotin will gradually degrade the luminescence upon aging while drastic degradation in luminescence intensity was observed after annealing. Properties show that biotin also protected the nanoparticles from any environmental attack.« less
  • White light emission of self-activated photoluminescence (PL) in Sr{sub 3}AlO{sub 4}F under 254 nm light is only observed after annealing in a reducing atmosphere of 5%H{sub 2}/95%Ar. High-resolution neutron powder diffraction reveals that the FSr{sub 6} octahedrons and AlO{sub 4} tetrahedrons in this anti-perovskite structure are closer packed in reduced than in air-annealed samples which show no PL. Careful analysis of temperature-dependent neutron powder diffraction data establishes smaller isotropic displacement parameters for Sr(1) and O in Sr{sub 3}AlO{sub 4}F annealed in a reducing atmosphere indicating that the denser packing of the polyhedral sub-units leads to a slightly deeper potential formore » the Sr(1) and O atoms. Both the air- and reductively-annealed samples have identical thermal expansion within the temperature range between 3 and 350 K. The Debye temperatures were calculated using the atomic displacement parameters and show no significant differences between the air and reductively annealed samples making the Debye temperature a bad proxy for self-activated PL. - Graphical abstract: Annealing Sr{sub 3}AlO{sub 4}F under reducing conditions results in an intense self-activated photoluminescence which is correlated with a denser packing of FSr{sub 6} and AlO{sub 4} polyhedra. - Highlights: • Sr{sub 3}AlO{sub 4}F made in air does not show self-activated photoluminescence. • Only when annealing Sr{sub 3}AlO{sub 4}F in a reducing gas is photoluminescence observed. • FSr{sub 6} and AlO{sub 4} polyhedra in reduced Sr{sub 3}AlO{sub 4}F structure are packed more efficient. • Smaller displacement parameters are found for under-bonded Sr(1) and O sites.« less
  • Cited by 1
  • Core–shell nanoparticles have potential for a wide range of applications due to the tunability of their magnetic, catalytic, electronic, optical, and other physicochemical properties. A frequent drawback in the design of core–shell nanoparticles and nanocrystals is the lack of control over an extensive, disordered, and compositionally distinct interface that occurs due to the dissimilarity of structural and compositional phases of the core and shell. In this work, we demonstrate a new hydrothermal nanophase epitaxy (HNE) technique to synthesize highly structurally ordered α-Cr 2O 3@α-Co 0.38Cr 1.62O 2.92 inverted core–shell nanoparticles (CSNs) with evidence for the nanoscale growth of corundum structuremore » beginning from the core and extending completely into the shell of the CSNs with minimal defects at the interface. The high-resolution TEM results show a sharp interface exhibiting epitaxial atomic registry of shell atoms over highly ordered core atoms. The XPS and Co K-edge XANES analyses indicate the +2 oxidation state of cobalt is incorporated in the shell of the CSNs. Our XPS and EXAFS results are consistent with oxygen vacancy formation in order to maintain charge neutrality upon substitution of the Co 2+ ion for the Cr 3+ ion in the α-Co 0.38Cr 1.62O 2.92 shell. Furthermore, the CSNs exhibit the magnetic exchange bias effect, which is attributed to the exchange anisotropy at the interface made possible by the nanophase epitaxial growth of the α-Co 0.38Cr 1.62O 2.92 shell on the α-Cr 2O 3 core of the nanoparticles. The combination of a well-structured, sharp interface and novel nanophase characteristics is highly desirable for nanostructures having enhanced magnetic properties.« less