# Fileset

[Gd2MoO6_Supporting_TohokuUniv_Hangai_Ver5.pdf](https://mdr.nims.go.jp/filesets/27af5f69-b077-42a5-bae4-fdbcb8081ebb/download)

## Creator

Taisei Hangai, Takuya Hasegawa, [Jian Xu](https://orcid.org/0000-0002-1040-5090), [Takayuki Nakanishi](https://orcid.org/0000-0003-3412-2842), [Takashi Takeda](https://orcid.org/0000-0003-2510-4562), [Kosuke Nakano](https://orcid.org/0000-0001-7756-4355), [Kenta Hongo](https://orcid.org/0000-0002-2580-0907), Ryo Maezono, Tomoyo Goto, Yasushi Sato, Ayahisa Okawa, Shu Yin

## Rights

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Key Role of Metal-to-Metal Charge Transfer Transition between Mo6+ and Bi3+ for Enhancement in NIR Luminescence of Gd2MoO6:Bi,Yb Nanophosphor, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpcc.3c07501[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[Key Role of Metal-to-Metal Charge Transfer Transition between Mo<sup>6+</sup> and Bi<sup>3+</sup> for Enhancement in NIR Luminescence of Gd<sub>2</sub>MoO<sub>6</sub>:Bi,Yb Nanophosphor](https://mdr.nims.go.jp/datasets/07e3255b-4ec1-4715-939d-3fdd53154e01)

## Fulltext

S1 Supporting information Key Role of Metal-to-Metal Charge Transfer Transition between Mo6+ and Bi3+ for Enhancement in NIR Luminescence of Gd2MoO6:Bi,Yb Nanophosphor  Taisei Hangai,1 Takuya Hasegawa,*,1 Jian Xu,2 Takayuki Nakanishi,3 Takashi Takeda,3 Kosuke Nakano,4 Kenta Hongo,4 Ryo Maezono,4 Tomoyo Goto,5,6 Yasushi Sato,7 Ayahisa Okawa,1 and Shu Yin1,8  1 Institute of Multidisciplinary Research for Advanced Material (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan 2 International Center for Young Scientists (ICYS), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0044, Japan 3 Advanced Phosphor Group, National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, 305-0044, Japan 4 School of Information Science, Japan Advanced Institute of Science and Technology (JAIST), Asahidai 1-1, Nomi, Ishikawa 923-1292, Japan 5 SANKEN (The Institute of Scientific and Industrial Research), Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan 6 Institute for Advanced Co-Creation Studies, Osaka University, 1-1 Yamadaoka, Suita, Osaka, 565-0871, Japan 7 Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan 8 Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan  *Corresponding author: Takuya Hasegawa: hase@tohoku.ac.jp    S2 Figure and Table content Figure S1. Narrow scan analysis of XPS for (a) Gd 4d, and (b) Mo 3d for all GMO nanophosphors Figure S2. XANES spectra for all GMO nanophosphors of (a) Gd L3-, (b) Mo K-, (c) Bi L3-, and (d) Yb L3-edge with the reference samples (Gd2O3, MoO3, Bi2O3, and Yb2O3). Figure S3. TG-DTA curve for GMO:Bi,Yb, and from 330 K to 1000 K under ambient air. Figure S4. ∆E values calculated by the total energy obtained after structural relaxation. Figure S5. Fourier transformed EXAFS radial distribution function spectra of Mo K-edge in all GMO nanophosphors. Figure S6. (a)DOS/pDOS of GMO:Bi substituted in Gd3 site, and (b) enlarged one. Figure S7. Kubelka-Munk spectra of all GMO nanophosphors around 500 nm. Figure S8. Decay curve of GMO:Yb and GMO:Bi,Yb at 300 K (𝜆ex= 360 nm and 𝜆em= 975 nm). Figure S9. (a) PL spectra (𝜆ex= 363 nm) and (b) decay curve (𝜆ex= 360 nm and 𝜆em= 975 nm) of GMO:Bi,yYb (y = 5, 7, 8, 9, and 10 mol%) nanophosphors at 300 K. Figure S10. Gaussian fit of the PLE spectra (𝜆em= 670 nm) for GMO and GMO:Bi at 77 K. Figure S11. (a) PL spectra (𝜆ex= 360 nm) and (b) integrated intensity of GMO:xBi, (x = 0, 0.5, 1, 2, and 3 mol%) nanophosphors at 77 K. Figure S12. Enlarged DOS/pDOS of GMO:Bi substituted in Gd1 around conduction band minimum. Table S1. Molar ratios of Gd/Bi/Yb for all GMO nanophosphors calculated from XPS. Table S2. Lattice parameters for each GMO nanophosphor refined by Rietveld analysis. Table S3. Lattice parameters and bond length between cation (Gd, Mo) and oxygen obtained from optimized by DFT, Rietveld refined, and CIF.  Table S4. Calculated total energy after structural relaxation and ∆E values. Table S5. Fitting parameters of decay curves for GMO:Yb and GMO:Bi,Yb measured at 300 K. Table S6. Fitting parameters of decay curves for GMO:Bi,yYb (y = 5, 7, 8, 9, and 10 mol%) nanophosphors measured at 300 K (𝜆ex= 360 nm and 𝜆em= 975 nm).  S3 Table S7. Fitting parameters of decay curves for GMO:Bi,yYb (y = 0, 0.5, and 1 mol%) nanophosphors measured at 77 K (𝜆ex= 360 nm and 𝜆em= 670 nm).    S4  Figure S1. Narrow scan analysis of XPS for (a) Gd 4d and (b) Mo 3d.    S5  Figure S2. XANES spectra for all GMO nanophosphors of (a) Gd L3-, (b) Mo K-, (c) Bi L3-, and (d) Yb L3-edge with the reference samples (Gd2O3, MoO3, Bi2O3, and Yb2O3).    S6  Figure S3. TG-DTA curve for GMO:Bi,Yb, and from 330 K to 1000 K under ambient air.    S7  Figure S4. ∆E values calculated from the total energy obtained after structural relaxation.    S8  Figure S5. Fourier transformed EXAFS radial distribution function spectra of Mo K-edge in all GMO nanophosphors.    S9  Figure S6. (a) DOS/pDOS of GMO:Bi substituted in Gd3 site, and (b) enlarged one.   (a) (b)-6 -5 -4 -3 -2 -1  0  1  2Gd8Mo4O16Gd7BiMo4O16,(Gd3)DOS [a.u.]Energy [eV]Gd 4fMo 4dO 2pBi 6sDOS [a.u.]Energy [eV]-10-5 0 5 10-3 -2.5 -2 -1.5 -1 S10  Figure S7. Kubelka-Munk spectra of all GMO nanophosphors around 500 nm.    S11  Figure S8. Decay curves of GMO:Yb and GMO:Bi,Yb at 300 K (𝜆ex= 360 nm and 𝜆em= 975 nm).    S12  Figure S9. (a) PL spectra (𝜆ex= 363 nm) and (b) decay curve (𝜆ex= 360 nm and 𝜆em= 975 nm) of GMO:Bi,yYb (y = 5, 7, 8, 9, and 10 mol%) nanophosphors at 300 K.    S13  Figure S10. Gaussian fit of PLE spectra for GMO and GMO:Bi at 77 K.    S14  Figure S11. (a) PL spectra (𝜆ex= 360 nm) and (b) integrated intensity of GMO:xBi, (x = 0, 0.5, 1, 2, and 3 mol%) nanophosphors at 77 K.    S15  Figure S12. Enlarged DOS/pDOS of GMO:Bi substituted in Gd1 around conduction band minimum.    S16 Table S1. Molar ratios of Gd/Bi/Yb for all GMO nanophosphors calculated from XPS.  GMO GMO:Bi GMO:Yb GMO:Bi,Yb Gd [mol%] 100 94.6 96.2 90.4 Bi [mol%] 0 5.33 - 7.92 Yb [mol%] 0 - 3.80 1.67    S17 Table S2 Lattice parameters for each GMO nanophosphor refined by Rietveld analysis.  GMO GMO:Bi GMO:Yb GMO:Bi,Yb a [Å] 16.54(1) 17.13(1) 17.13(1) 16.508(4) b [Å] 11.183(6) 10.796(4) 10.741(5) 11.161(3) c [Å] 5.408(3) 5.417(5) 5.395(2) 5.394(1) β [°] 108.50(3) 108.50(7) 108.50(3) 108.247(1) V [Å3] 949(1) 950(1) 941.2(8) 942.7(4) Rwp [%] 9.788 10.48 8.252 9.133 Rp [%] 7.463 7.710 6.234 7.218 S 3.013 2.727 1.729 2.231    S18 Table S3. Lattice parameters and average bond length for each GMO nanophosphor refined by Rietveld analysis.   CIF DFT Rietveld Lattice parameter a [Å] 9.959 9.904 10.004 b [Å] 9.959 9.903 10.004 c [Å] 5.418 5.393 5.412 α [°] 105.06 104.78 105.25 β [°] 105.06 104.79 105.25 γ [°] 68.223 68.292 67.877 Average bond length Gd1-O 2.449 2.430 2.451 Gd2-O 2.442 2.417 2.425 Gd3-O 2.405 2.395 2.406 Mo-O 1.884 1.876 1.896    S19 Table S4. Calculated total energy after structural relaxation and ∆E values.  Total energy [Ry] ∆E [Ry] GMO -11949.258 - Bi Gd1 -11653.825 295.433 Gd2 -11653.826 295.432 Gd3 -11653.837 295.421 Yb Gd1 -12525.176 -575.918 Gd2 -12525.160 -575.902 Gd3 -12525.160 -575.902    S20 Table S5. Fitting parameters of decay curves for GMO:Yb and GMO:Bi,Yb measured at 300 K. Sample 𝜏! [µs] 𝜏" [µs] 𝐴! [-] 𝐴! [-] 𝜏#$% [µs] GMO:Yb 58.3 239 461 454 203 GMO:Bi,Yb 97.3 265 583 410 207    S21 Table S6. Fitting parameters of decay curves for GMO:Bi,yYb (y= 5, 7, 8, 9, and 10 mol%) measured at 300 K. y [mol%] 𝜏1 [µs] 𝜏2 [µs] 𝐴1 [-] 𝐴2 [-] 𝜏ave [µs] 5 95.3 340 441 496 291 7 102 299 557 420 238 8 97.3 265 583 410 207 9 73.4 229 611 402 178 10 50.1 265 674 302 201    S22 Table S7. Fitting parameters of decay curves for GMO:Bi,yYb (y = 0, 0.5, and 1 mol%) nanophosphors measured at 77 K (𝜆ex= 360 nm and 𝜆em= 670 nm). y [mol%] 𝜏1 [µs] 𝜏2 [µs] 𝐴1 [-] 𝐴2 [-] 𝜏ave [µs] 0 6.61 34.3 0.0240 0.00378 19.1 0.5 3.11 28.8 0.0322 0.00305 15.1 1 2.28 23.2 0.0375 0.00290 11.5