Supporting Information

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1 Supporting Information Vacuum Referred Binding Energy Scheme, Electron-Vibrational Interaction and Energy Transfer Dynamics in BaMg 2 Si 2 O 7 : Ln (Ce 3+, Eu 2+ ) Phosphors Yiyi Ou, a, Weijie Zhou, a, Chunmeng Liu, a Litian Lin, a Mikhail G. Brik, b,c,d Pieter Dorenbos, e Ye Tao, f and Hongbin Liang*,a a MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 1027, China. b College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 40006, China. c Institute of Physics, University of Tartu, W. Ostwald Str 1, Tartu 0411, Estonia. d Institute of Physics, Jan Długosz University, Armii Krajowej 13/1, PL Częstochowa, Poland. e Faculty of Applied Sciences, Delft University of Technology, Mekelweg 1, 2629 JB Delft, The Netherlands. f Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing , China. * The corresponding author, cesbin@mail.sysu.edu.cn, Tel: These authors contributed equally to this work. S1

2 Experimental Section I. Synthesis The Ce 3+ /Eu 2+ /Gd 3+ /Eu 3+ singly-doped powder samples Ba 1-2x Ce x K x Mg 2 Si 2 O 7 (x = 0, 1, 2, 3), Ba 1-x Eu x Mg 2 Si 2 O 7 (x = 0, 1, 2, 3, ), Ba 0.98 Gd 1 K 1 Mg 2 Si 2 O 7, Ba Eu 01 K 01 Mg 2 Si 2 O 7 and co-doped samples Ba 0.99-x Ce 0 Eu x K 0 Mg 2 Si 2 O 7 (x= 0, 1) were synthesized by a conventional high-temperature solid-state reaction method. The BaCO 3 (analytical reagent, AR), MgO (AR), SiO 2 (AR), K 2 CO 3 (AR), CeO 2 (99.99 %), Eu 2 O 3 (99.99 %), and Gd 2 O 3 (99.99 %) are used as starting materials. Due to the different ionic charges between Ba 2+ and Ce 3+ /Eu 3+ /Gd 3+, K + ions were added as charge compensators. After the stoichiometric raw materials were weighed and grounded homogeneously in an agate mortar, the obtained mixture was pre-heated at 1373K in CO reducing atmosphere for 6 h, then re-grounded and sintered at 1473K in the same atmosphere for 10 h. The final products were obtained after cooling down to room temperature. II. Characterization The phase purity of powder samples was checked by a Rigaku D-MAX 2200 VPC X-ray diffractometer with Cu Kα radiation (λ = Å) at 40 kv and 26 ma. High-quality XRD data for Rietveld refinement were collected over a 2θ range from 10 to 110 at an interval of 2 with a Bruker D8 advanced X-ray diffractometer with Cu Kα radiation (λ = Å) at 40 kv and 40 ma. The Rietveld refinement of XRD data was performed using the TOPAS-Academic program S1. The excitation and emission spectra in UV-vis range and luminescence decay curves of samples under different temperatures were recorded on an Edinburgh Instrument FLS920 combined fluorescence lifetime and steady-state spectrometer. The excitation source for UV-visible spectra was a 40 W xenon lamp, and that for luminescence decay curves was a 10 W nf920 flash lamp with a pulse width of 1 ns and pulse repetition rate of 40 khz. The sample temperature was varied by a temperature controller (Oxford, S2

3 CRYTEMP). The internal quantum yield (QY) of samples at RT was measured using a barium sulphate coated integrating sphere (10 mm in diameter) attached to the FLS920. The VUV-UV excitation spectra and corresponding emission spectra were recorded on the beamline 4B8 of the Beijing Synchrotron Radiation Facility (BSRF). More details about the optical layout and the spectroscopic measurements can be found elsewhere S2. The X-ray excited luminescence spectra were recorded using a Philips PW223/20 X-ray tube and a Cu anode operating at 40 kv and 2 ma at Delft University of Technology, the Netherlands. References S1. A. A. Coelho, Coelho Software, Version 4, Topas Academic, Brisbane, Australia, 200. S2. Y. Tao, Y. Huang, Z. H. Gao, H. Zhang, A. Y. Zhou, Y. L. Tan, D. W. Li, S. S. Sun, J. Synchrotron Radiat., 2009, 16, S3

4 Figures and Tables Normalized intensity (a.u.) BMSO:0.%Ce 3+, 2 K = 310 nm = 323 nm = 332 nm BMSO:1%Gd 3+, 2 K = 313 nm = 24 nm = 276 nm = 297 nm Wavelength (nm) Normalized intensity (a.u.) Figure S1. The highest-height-normalized VUV-UV excitation ( = 310, 323, 332 nm) and emission ( = 24, 276, 297 nm) spectra of sample BMSO:0.Ce 3+ and excitation ( = 313 nm) spectrum of BMSO:1%Gd 3+ at 2 K. 6 BMSO:0.1%Eu 3+, RT 6 Relative intensity (10 ) 4 2 = 611 nm Eu 3+ - O 2- CTB ~ 284 nm, ~ 4.36 ev 7 F0 L 6 7 F0 D 2 D0 7 F 0 D0 7 F 1 = 284 nm = 393 nm D0 7 F 2 D0 7 F 3 D0 7 F Relative intensity (10 4 ) Wavelength (nm) 0 Figure S2. The excitation ( = 611 nm) and emission ( = 284, 393 nm) spectra of sample BMSO:0.1%Eu 3+ at RT. S4

5 Normalized intensity (a.u.) BMSO:0.%Eu 2+, RT = 38 nm 390 nm 396 nm 410 nm 430 nm = 300 nm 320 nm 30 nm FWHM ~ 147 cm -1 (~ 23 nm) Normalized intensity (a.u.) Wavelength (nm) Figure S3. The highest-height-normalized excitation ( = 38, 390, 396, 410, 430 nm) and emission ( = 300, 320, 30 nm) spectra of sample BMSO:0.%Eu 2+ at RT. Table S1. Refined Structural Parameters of compound BaMg 2 Si 2 O 7 at RT. a Atom Site X y z Occ. B iso (Å 2 ) Ba 8f (2) 168(1) (2) (2) Mg1 4e (9) (9) Mg2 4e (9) (9) Mg3 8f 37(9) 0.236(7) 98(6) (9) Si1 8f (8) (4) () 1 1(7) Si2 8f 0.328(8) (4) 0.379(6) 1 1(7) O1 8f 0.421() 0.776(4) 0.386(2) (10) O2 8f (3) 0.116(3) (3) (10) O3 8f (7) (6) 0.481(9) (10) O4 8f 18(9) (1) (2) (10) O 8f (4) 160(7) (4) (10) O6 8f (4) 0.888(2) 0.21(1) (10) O7 8f (9) () () (10) a The obtained Biso values of the constituent ions of host BMSO are similar to the reference S

6 results T1, which are all reasonable. Table S2. The FWHM Values of Narrow-Band-Emitting Phosphors at RT. Phosphor FWHM λ max Reference (Emission) BaMgAl 10 O 17 :Eu 2+ ~ 2698 cm -1 (~ 7 nm) ~ 40 nm T2 Sr (PO 4 ) 3 Cl:Eu 2+ ~ 1829 cm -1 (~ 36 nm) ~ 430 nm T3 β SiAlON:Eu 2+ ~ 1800 cm -1 (~ nm) ~ 3 nm T4 KSrPO 4 :Eu 2+ ~ 1731 cm -1 (~ 31 nm) ~ 424 nm T BaMg 2 Si 2 O 7 :Eu 2+ ~ 147 cm -1 (~23 nm) ~ 396 nm our work Sr[LiAl 3 N 4 ]:Eu 2+ ~ 1180 cm -1 (~ 0 nm) ~ 60 nm T6 CsPbBr 3 /SDDA@PMMA ~ 840 cm -1 (~ 23 nm) ~ 23 nm T7 Table S3. The Internal Quantum Efficiencies of Eu 2+ -Doped Samples. Concentration of Eu 2+ (at. %) Internal quantum efficiency (%) References T1. Park, C.-H.; Choi, Y.-N. Crystal Structure of BaMg 2 Si 2 O 7 and Eu 2+ Luminescence. J. Solid State Chem. 2009, 182, T2. Kim, K. B.; Kim, Y. I.; Chun, H. G.; Cho, T. Y.; Jung, J. S.; Kang, J. G. Structural and Optical Properties of BaMgAl 10 O 17 :Eu 2+ Phosphor. Chem. Mater. 2002, 14, T3. Zhou, L; Liang, H. B.; Tanner, P. A.; Zhang, S.; Hou, D. J.; Liu, C. M.; Tao, Y.; Huang, Y.; Li, L. N. Luminescence, Cathodoluminescence and Ce 3+ Eu 2+ Energy Transfer and Emission Enhancement in the Sr (PO 4 ) 3 Cl:Ce 3+,Eu 2+ Phosphor. J. Mater. Chem. C 2013, 1, T4. Xie, R. J.; Hirosaki, N.; Li, H. L.; Li, Y. Q.; Mitomo, M. Synthesis and Photoluminescence Properties of β sialon:eu 2+ (Si 6-z Al z O z N 8-z :Eu 2+ ). J. Electrochem. Soc. 2007, 14, J314 J319. T. Lin, C. C.; Xiao, Z. R.; Guo, G. Y.; Chan, T. S.; Liu, R. S. Versatile Phosphate Phosphors S6

7 ABPO 4 in White Light-Emitting Diodes: Collocated Characteristic Analysis and Theoretical Calculations. J. Am. Chem. Soc. 2010, 132, T6. Pust, P.; Weiler, V.; Hecht, C.; Tücks, A.; Wochnik, A. S.; Henß, A. K.; Wiechert, D.; Scheu, C.; Schmidt, P. J.; Schnick, W. Narrow-Band Red-Emitting Sr[LiAl 3 N 4 ]:Eu 2+ as a Next-Generation LED-Phosphors Material. Nat. Mater. 2014, 13, T7. Zhang, X. J.; Wang, H. C.; Tang, A. C.; Lin, S. Y.; Tong, H. C.; Chen, C. Y.; Lee, Y. C.; Tsai, T. L.; Liu, R. S. Robust and Stable Narrow-Band Green Emitter: An Option for Advanced Wide-Color-Gamut Backlighting Display. Chem. Mater. 2016, 28, S7