Yb3+/Er3+ co-doped Dion–Jacobson niobium layered perovskites as NIR-to-green upconversion materials

Here, the upconversion behaviour of Yb3+/Er3+-codoped layered Dion–Jacobson calcium-niobium perovskites was investigated. This lanthanide pair is majorly responsible for the efficient green and red anti-Stokes-like emissions in rare-earth fluorides. Layered perovskites of the composition KCa2Nb3O10...

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Veröffentlicht in:New journal of chemistry 2020-06, Vol.44 (24), p.10165-10171
Hauptverfasser: Vendruscolo, Victor, Giordano, Luidgi, Vera Regina Leopoldo Constantino, Lucas Carvalho Veloso Rodrigues
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container_issue 24
container_start_page 10165
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creator Vendruscolo, Victor
Giordano, Luidgi
Vera Regina Leopoldo Constantino
Lucas Carvalho Veloso Rodrigues
description Here, the upconversion behaviour of Yb3+/Er3+-codoped layered Dion–Jacobson calcium-niobium perovskites was investigated. This lanthanide pair is majorly responsible for the efficient green and red anti-Stokes-like emissions in rare-earth fluorides. Layered perovskites of the composition KCa2Nb3O10 were synthesized by the ceramic method by replacing 1% per mol of Ca2+ by lanthanide ions in such a way that the Yb3+:Er3+ molar proportion varied from 2 : 1 to 20 : 1. Non-doped and four doped materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and emission spectroscopy. All materials showed similar XRD profiles, which indicated the isolation of well crystalline single phases. On the other hand, the morphologies accessed by SEM were different: microparticles with well-defined edges were replaced by particles with poorly defined edges, rounded features, and intergrowth aspect when the niobate was doped. The Raman spectra showed modifications in the bands below 200 cm−1 attributed to low-phonon-energy transitions. The doped layered niobates presented almost pure-green emission (excitation at 980 nm), which could be related to the low energy values of the vibrational levels, precluding energy loss. Additionally, the results indicated that the defects generated by the lanthanide ion isomorphic-aliovalent substitution in Ca2+ sites were mainly in the interlayer region. This coupled behaviour reduced the non-radiative decays of the upconversion centres, leading to the formation of an efficient emitting material. The spectroscopic emission data showed a two-photon major mechanism to excite the emitting levels via an energy transfer upconversion (ETU) population process. The lifetime results indicated that increasing the Yb3+ concentration did not lead to non-radiative decay paths. The high efficiency and the versatility of the layered niobate hosts can provide new insights into the design of efficient morphology-controlled materials.
doi_str_mv 10.1039/d0nj00261e
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This lanthanide pair is majorly responsible for the efficient green and red anti-Stokes-like emissions in rare-earth fluorides. Layered perovskites of the composition KCa2Nb3O10 were synthesized by the ceramic method by replacing 1% per mol of Ca2+ by lanthanide ions in such a way that the Yb3+:Er3+ molar proportion varied from 2 : 1 to 20 : 1. Non-doped and four doped materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and emission spectroscopy. All materials showed similar XRD profiles, which indicated the isolation of well crystalline single phases. On the other hand, the morphologies accessed by SEM were different: microparticles with well-defined edges were replaced by particles with poorly defined edges, rounded features, and intergrowth aspect when the niobate was doped. The Raman spectra showed modifications in the bands below 200 cm−1 attributed to low-phonon-energy transitions. The doped layered niobates presented almost pure-green emission (excitation at 980 nm), which could be related to the low energy values of the vibrational levels, precluding energy loss. Additionally, the results indicated that the defects generated by the lanthanide ion isomorphic-aliovalent substitution in Ca2+ sites were mainly in the interlayer region. This coupled behaviour reduced the non-radiative decays of the upconversion centres, leading to the formation of an efficient emitting material. The spectroscopic emission data showed a two-photon major mechanism to excite the emitting levels via an energy transfer upconversion (ETU) population process. The lifetime results indicated that increasing the Yb3+ concentration did not lead to non-radiative decay paths. 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The doped layered niobates presented almost pure-green emission (excitation at 980 nm), which could be related to the low energy values of the vibrational levels, precluding energy loss. Additionally, the results indicated that the defects generated by the lanthanide ion isomorphic-aliovalent substitution in Ca2+ sites were mainly in the interlayer region. This coupled behaviour reduced the non-radiative decays of the upconversion centres, leading to the formation of an efficient emitting material. The spectroscopic emission data showed a two-photon major mechanism to excite the emitting levels via an energy transfer upconversion (ETU) population process. The lifetime results indicated that increasing the Yb3+ concentration did not lead to non-radiative decay paths. 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This lanthanide pair is majorly responsible for the efficient green and red anti-Stokes-like emissions in rare-earth fluorides. Layered perovskites of the composition KCa2Nb3O10 were synthesized by the ceramic method by replacing 1% per mol of Ca2+ by lanthanide ions in such a way that the Yb3+:Er3+ molar proportion varied from 2 : 1 to 20 : 1. Non-doped and four doped materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and emission spectroscopy. All materials showed similar XRD profiles, which indicated the isolation of well crystalline single phases. On the other hand, the morphologies accessed by SEM were different: microparticles with well-defined edges were replaced by particles with poorly defined edges, rounded features, and intergrowth aspect when the niobate was doped. The Raman spectra showed modifications in the bands below 200 cm−1 attributed to low-phonon-energy transitions. The doped layered niobates presented almost pure-green emission (excitation at 980 nm), which could be related to the low energy values of the vibrational levels, precluding energy loss. Additionally, the results indicated that the defects generated by the lanthanide ion isomorphic-aliovalent substitution in Ca2+ sites were mainly in the interlayer region. This coupled behaviour reduced the non-radiative decays of the upconversion centres, leading to the formation of an efficient emitting material. The spectroscopic emission data showed a two-photon major mechanism to excite the emitting levels via an energy transfer upconversion (ETU) population process. The lifetime results indicated that increasing the Yb3+ concentration did not lead to non-radiative decay paths. The high efficiency and the versatility of the layered niobate hosts can provide new insights into the design of efficient morphology-controlled materials.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0nj00261e</doi><tpages>7</tpages></addata></record>
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source Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection
subjects Calcium ions
Crystal defects
Emission spectroscopy
Energy dissipation
Energy transfer
Erbium
Fluorides
Interlayers
Microparticles
Morphology
Niobates
Niobium
Perovskites
Raman spectra
Raman spectroscopy
Rare earth elements
Scanning electron microscopy
Spectrum analysis
Upconversion
X-ray diffraction
Ytterbium
title Yb3+/Er3+ co-doped Dion–Jacobson niobium layered perovskites as NIR-to-green upconversion materials
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