%0 Journal Article %T Stabilization of ultra-small [Ag2](2+) and [Agm](n+) nano-clusters through negatively charged tetrahedrons in oxyfluoride glass networks: To largely enhance the luminescence quantum yields %+ Department of Materials Science and Engineering %+ Department of Materials Science and Engineering (Dallas, USA) %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Ma, Ronghua %A Zhao, Junjie %A Chen, Xiaotong %A Qiao, Xvsheng %A Fan, Xianping %A Du, Jincheng %A Zhang, Xianghua %Z The authors gratefully acknowledge the financial support from the National Nature Science Foundation of China (No. 51672243), the Zhejiang Provincial Natural Science Foundation of China (No. LY16E020003), and the Fundamental Research Funds for the Central Universities (No. 2016QNA4005 %Z 2016FZA4007). %< avec comité de lecture %@ 1463-9076 %J Physical Chemistry Chemical Physics %I Royal Society of Chemistry %V 19 %N 34 %P 22638-22645 %8 2017-08-30 %D 2017 %R 10.1039/c7cp02531a %M 28853746 %Z Chemical SciencesJournal articles %X Herein, three different silver species were stably formed in SiO-AlO-BO-NaO-ZnF-CaF glasses and were identified by their characteristic luminescence bands: violet blue luminescence (Ag: 4d5s → 4d), green white molecular fluorescence (molecule-like [Ag], named ML-Ag) and orange molecular fluorescence ([Ag] pairs). Due to the relatively low aggregation degrees of [Ag] and [Ag], non-radiative transitions were highly suppressed, and the PL quantum yields (QYs) of ML-Ag and [Ag] pairs reached 73.7% and 89.7%, respectively. The substitution of 0.5BO-0.5NaO with SiO promoted the partial reduction of Ag to Ag and the subsequent aggregation of Ag and Ag to form [Ag] (ML-Ag). The absence of NaO also resulted in an increasing amount of Ag-Ag pairs with closing interionic distance to form [Ag] in glass. According to the X-ray photoelectron spectra (XPS) and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra, a solubility strategy and a charge compensation model were proposed to describe the transformations between different silver species. The formation of ML-Ag was further controlled via the solubility of Ag in glass, whereas [Ag] centers could be effectively produced by lowering the total amount of other competitive charge compensators, such as Na, or by introducing negatively charged [BO], [AlO], and [ZnO] tetrahedrons into the glass matrix. %G English %L hal-01579655 %U https://univ-rennes.hal.science/hal-01579655 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR_VC %~ STATS-UR1 %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ IVER %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ TEST-HALCNRS %~ UR1-MMS %~ TEST2-HALCNRS