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Title: Intervalence charge transfer luminescence: Interplay between anomalous and 5d − 4f emissions in Yb-doped fluorite-type crystals

In this paper, we report the existence of intervalence charge transfer (IVCT) luminescence in Yb-doped fluorite-type crystals associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. By means of embedded cluster, wave function theory ab initio calculations, we show that the widely studied, very broad band, anomalous emission of Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, usually associated with impurity-trapped excitons, is, rather, an IVCT luminescence associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. The IVCT luminescence is very efficiently excited by a two-photon upconversion mechanism where each photon provokes the same strong 4f{sup 14}–1A{sub 1g}→ 4f{sup 13}({sup 2}F{sub 7/2})5de{sub g}–1T{sub 1u} absorption in the Yb{sup 2+} part of the pair: the first one, from the pair ground state; the second one, from an excited state of the pair whose Yb{sup 3+} moiety is in the higher 4f{sup 13}({sup 2}F{sub 5/2}) multiplet. The Yb{sup 2+}–Yb{sup 3+} → Yb{sup 3+}–Yb{sup 2+} IVCT emission consists of an Yb{sup 2+} 5de{sub g} → Yb{sup 3+} 4f{sub 7/2} charge transfer accompanied by a 4f{sub 7/2} → 4f{sub 5/2} deexcitation within the Yb{sup 2+} 4f{sup 13} subshell: [{sup 2}F{sub 5/2}5de{sub g},{sup 2}F{sub 7/2}] → [{sup 2}F{sub 7/2},4f{sup 14}]. The IVCT vertical transition leaves the oxidized andmore » reduced moieties of the pair after electron transfer very far from their equilibrium structures; this explains the unexpectedly large band width of the emission band and its low peak energy, because the large reorganization energies are subtracted from the normal emission. The IVCT energy diagrams resulting from the quantum mechanical calculations explain the different luminescent properties of Yb-doped CaF{sub 2}, SrF{sub 2}, BaF{sub 2}, and SrCl{sub 2}: the presence of IVCT luminescence in Yb-doped CaF{sub 2} and SrF{sub 2}; its coexistence with regular 5d-4f emission in SrF{sub 2}; its absence in BaF{sub 2} and SrCl{sub 2}; the quenching of all emissions in BaF{sub 2}; and the presence of additional 5d–4f emissions in SrCl{sub 2} which are absent in SrF{sub 2}. They also allow to interpret and reproduce recent experiments on transient photoluminescence enhancement in Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, the appearance of Yb{sup 2+} 4f–5d absorption bands in the excitation spectra of the IR Yb{sup 3+} emission in partly reduced CaF{sub 2}:Yb{sup 3+} samples, and to identify the broadband observed in the excitation spectrum of the so far called anomalous emission of SrF{sub 2}:Yb{sup 2+} as an IVCT absorption, which corresponds to an Yb{sup 2+} 4f{sub 5/2} → Yb{sup 3+} 4f{sub 7/2} electron transfer.« less
Authors:
;  [1] ;  [2]
  1. Departamento de Química, Universidad Autónoma de Madrid, 28049 Madrid (Spain)
  2. (Spain)
Publication Date:
OSTI Identifier:
22413350
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 23; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; BARIUM FLUORIDES; CALCIUM FLUORIDES; CRYSTALS; DE-EXCITATION; DOPED MATERIALS; ELECTRON TRANSFER; EXCITATION; EXCITED STATES; EXCITONS; FLUORITE; GROUND STATES; PEAKS; PHOTOLUMINESCENCE; PHOTONS; SPECTRA; STRONTIUM CHLORIDES; STRONTIUM FLUORIDES; WAVE FUNCTIONS; YTTERBIUM IONS