Research PaperNo Access

New viewpoint about the persistent luminescence mechanism of ${Mn}^{2 +} / {Eu}^{3 +}$ ${Mn}^{2 +} / {Eu}^{3 +}$ co-doped ${Zn}_{2} {GeO}_{4}$ ${Zn}_{2} {GeO}_{4}$

Zhou Wang

School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, P. R. China

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Zhiting Tang

School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, P. R. China

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Xueling Peng

School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, P. R. China

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Chuanhui Xia

School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, P. R. China

E-mail Address: chxia@cqjtu.edu.cn

Corresponding authors.

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, and

Feng Wang

http://orcid.org/0000-0002-4360-4475

School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, P. R. China

E-mail Address: wfbgc@cqjtu.edu.cn

Corresponding authors.

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https://doi.org/10.1142/S0217979219503892Cited by:5 (Source: Crossref)

Abstract

In this work, Mn $^{2 +} /$ $^{2 +} /$ Eu $^{3 +}$ $^{3 +}$ co-doped Zn₂GeO₄ (Zn₂GeO₄:Mn $^{2 +}, {Eu}^{3 +})$ $^{2 +}, {Eu}^{3 +})$ was prepared by high-temperature solid phase method. Compared with common fluorescent materials Zn₂GeO₄:Mn $^{2 +}$ $^{2 +}$ , Zn₂GeO₄:Mn $^{2 +}, {Eu}^{3 +}$ $^{2 +}, {Eu}^{3 +}$ could not only emit strong green fluorescence of 535 nm, but also maintain excellent persistent luminescence performance. Through Density Functional Theory calculation, we obtained the fine band structure of Zn₂GeO₄:Mn $^{2 +}, {Eu}^{3 +}$ $^{2 +}, {Eu}^{3 +}$ . The results of the band structure were consistent with the experimental spectral data. On this basis, we proposed a new luminescence mechanism model of Zn₂GeO₄:Mn $^{2 +}, {Eu}^{3 +}$ $^{2 +}, {Eu}^{3 +}$ to explain the phenomena observed in experiment reasonably, though which was not completely consistent with previous works. When Zn₂GeO₄:Mn $^{2 +}, {Eu}^{3 +}$ $^{2 +}, {Eu}^{3 +}$ was excited, electron–hole separation occurred in the valence band (VB), and the electron transitioned to the conduction band (CB) directly. Through CB, the electron was trapped by trap levels (⁷F $_{0} \sim^{7}$ $_{0} \sim^{7}$ F₅ of Eu $^{3 +})$ $^{3 +})$ and maintained metastable for a long time. Under the action of thermal stimulation, electron returned to CB from the trap level slowly. The electron was captured again by the ⁴T₂(D) level of Mn $^{2 +}$ $^{2 +}$ . Then the electron transitioned down toward VB and recombined with the previous hole and emitted a photon with 535 nm (afterglow). The samples were being irradiated, trap levels accommodated the excited electrons to saturation. More electrons excited into the CB could not be captured by the trap levels any more. They were captured directly by the ⁴T₂(D) and transitioned directly to VB, then emitted green fluorescence.

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PACS: 78.55.−m, 71.15.Mb

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