Recent advances in energy transfer in bulk and nanoscale. luminescent materials: From spectroscopy to applications
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1 Electronic Supplementary Material (ESI) for Chemical Society Reviews. This journal is The Royal Society of Chemistry 215 Electronic supplementary information Recent advances in energy transfer in ulk and nanoscale luminescent materials: From spectroscopy to applications Xiaofeng Liu a* and Jianrong Qiu a,* a School of Materials Science and Engineering, Zhejiang University, Hangzhou 3127, P. R. China. xfliu@zju.edu.cn. College of Materials Science and Engineering, South China University of Technology, Guangzhou, 516, P. R. China. qjr@zju.edu.cn. a R L R Fig. S1 Resonance ET y (a) dipole and multipole interaction, and () exchange interaction. It shows that the exchange interaction requires the overlap of wavefunctions of the two centers while the dipole or multipole interactions do not.
2 a 1. R =.5R =.985 Intensity (a. u.) D excitation A excitation D emission A emission.5 R = R =.5 R = 2R =.15 Wavelength (nm) 1 2 c R/R I D A (t)d t η E T = 1 I D (t)d t Intensity (a. u.) Donor only Donor+acceptor Time Fig. S2 Experimental oservation of sensitized luminescence in donor-acceptor pair. (a) Typical experimental spectra for donor (D) and acceptor (A). The overlap in the excitation spectra of D and A is regarded as a direct evidence of sensitized emission, ecause the excitation of D leads to the emission of A. () Dependence on ET efficiency ( ) on D-A separation. R is the critical distance where ET rate equals radiative rate of D. (c) Fluorescence decay curves for the donor in the asence and presence of acceptor. The energy transfer efficiency can e calculated from the curves. Conduction and 5 Dj 7 Fj Valence and Fig. S3 Representative mechanism for host sensitized luminescence of Eu 3+ emission y the transition of 5 D j 7 F j. UV excitation promote an electron from the valence and to the conduction and. Followed y energy migration (mediated y excitons), the excitation energy is then transferred to f levels of Eu 3+ ions, finally giving the reddish emission.
3 Tale S1 Selected examples of host sensitized luminescence in practical luminescence materials activated with RE or TM metal ions*. Phosphor Host asorption Emission color/position nm YVO :Eu < 2 nm Red / 62 nm CaMoO :Eu < 35 nm Red/ 6 nm, 61 nm Y 2 O 2 S:Eu < nm Orange/Multiple peaks from 5 to 65 nm PWO Blue / 2 nm Bi Ge 3 O 12 < 32 nm Blue / 85 nm ZnS:Cu +,Al 3+ <2 nm Blue/ 52 nm ZnS:Mn 2+ < nm Orange-yellow / 59 nm ZnSe:Cu +,Cl < nm Red / 65 nm CdSe:Y 3+2 < 6 nm NIR / 985 nm *Spectra data are adapted from Ref. 1 unless otherwise indicated. Tale S2 Selected examples of ET in ion pairs of RE or non-re ions for enhanced Stocks emission Sensit Transition/position* Activator: resonance energy level Transition/position Ref. izer Ce 3+ f( 2 FJ) 5d(A1g) / T 3+ : 5 Dj (j=, 1, 2, 3,..) 5 D 7 F5,,3 / 55 nm 3 32 nm (in most oxides) Nd 3+ : 2 Hj (j=9/2, 11/2), Dj (j=1/2, 3/2, F3/2 I11/2 / 888 nm 5 nm (in YAG) 5/2) or higher F3/2 I9/2 / 162 nm 25 nm, 35 nm (in CaF2) Er 3+ : 3 P3/2, 2 Gj (j=7/2, 9/2) I13/2 I15/2 / 155 nm 5 Mn 2+ : T2, A1 T1 6 A1 / 5-57 nm 1,6 Eu 2+ Eu 2+ in Sr3MgSi2O8 Mn 2+ : T2, A1 T1 6 A1 / 68 nm 7 f-5d transition / nm Y 3+ 2 F7/2 2 F5/2 / 98 nm Er 3+ : I11/2 I13/2 I15/2 / 155 nm 8 Tm 3+ : 3 H5 3 H 3 F / 1 nm 3 F 3 H6 / 18 nm 8 Pr 3+ : 1 G 1 G 3 H5 / 13 nm 9 Bi-center Center: 125 nm 1 Ni 2+ : 3 T2( 3 F) 3 T2 3 A2 / 13 nm 11 Cu 2+ 2 B1g 2 B2g / 6 8 nm Y 3+ : 2 F5/2 Nd 3+ I9/2 2 H9/2, F7/2 / 8 nm Y 3+ : 2 F5/2 2 F5/2 2 F7/2 / 15 nm 12 2 F5/2 2 F7/2 / 12 nm 9 Nd 3+ I9/2 2 H9/2, F7/2 / 8 nm Er 3+ : I9/2 I11/2 I13/2 / 27 nm 13 Tm 3+ 3 F / 175 nm Dy 3+ : 6 H11/2 *f-f transition energies are almost independent of the types of host. 6 H11/2 6 H13/2/3 nm 6 H13/2 6 H15/2 29 nm 1
4 Tale S3 Selected examples of sensitizer ions for the NIR emission of Y 3+ for QC in NIR range. (remove to SI) ion host Excitation / emission wavelength (transition) Mechanism a. Coop.: cooperative energy transfer; CR: cross relaxation energy transfer.. The assignment of a cooperative has een questioned y other authors. c. Both cooperative and CR have een proposed to explain the ET to Y 3+. d. High possiility of a one-to-one ET, not QC. Coop. / CR a YAG 7 nm / 55 nm (f-5d transition) Coop. 15 Ce 3+ Y 2 SiO 5 36 nm / 31 nm Coop. 16 Pr 3+ oxide 2 nm, 89 nm ( 3 H 3 P 2,1, ) / 67 nm ( 3 P 3 H 6 ) Both c Nd 3+ YF 3 35 nm ( D 1/2 ), 52 ( G 11/2 ) / 88 nm ( F 3/2 I 9/2 ) 133 nm ( F 3/2 I 13/2 ) Eu 3+ CR 2 Oxyfluoride 39 nm (5 D ) / 59 nm, 615 nm (5 L 6 /5 D F 2,1,) Coop. 21 GC, ZrO 2 T 3+ LaPO 89 nm ( 7 F 6 5 D ) /5, 57, 62 nm ( 5 D 7 F j ) Coop. 22 Ho 3+ Tellurite GC 36 nm ( 5 G 5 ), 9 nm ( 5 G 6 ) / 55 nm, 66 nm ( 5 S 2 5 I 8, 5 F 5 5 I 8 ) Er 3+ La 2 O 2 S 523 nm ( 2 H 11/2 ) / 5 nm, 65 nm ( S 3/2, F 9/2 I 15/2 ), 155 nm ( I 13/2 I 15/2 ) CR 23 CR 2 Tm nm ( 1 G ) / 65 nm ( 1 G 3 F ), 78 nm ( 1 G 3 H 5 ) Both c 18 Eu 2+ Borate glass 32nm / nm (f7-f65d transition) Coop. 25 Cr 3+ YAG 5 nm ( T 1 ), 59 nm ( T 2 ) / 2 E A nm Coop. d 26 Mn 2+ Zn 2 GeO 37 nm ( A 1 (G), T 2 (G))/ 535 nm ( T 1 6 A 1 ) Coop. d 27 MoO 2+ CaMO Charge transfer transition at 35 nm Coop. 28 Bi 3+ Gd 2 O 3 35 nm / 5 nm ( 3 P 1 1 S ) Coop. 29 YVO 35 nm/ 5-55 nm ( 3 P 1 1 S ) Coop. 3 Ref. References: 1 W. M. Yen, M. J. Weer, Inorganic phosphors: compositions, preparation, and optical properties, CRC Press, Boca Raton, Florida, 2. 2 R. Martín-Rodríguez, R. Geiteneek and A. Meijerink, J. Am. Chem. Soc., 213, 135, J. C. Bourcet and F. K. Fong, J. Chem. Phys., 197, 6, J. X. Meng, J. Q. Li, Z. P. Shi, K. W. Cheah, Appl. Phys. Lett., 28, 93, 22198/ J. X. Meng, K. W. Cheah, Z. P. Shi and J. Q. Li, Appl. Phys. Lett., 27, 91, 15117/ R. J. Ginther, J. Electrochem. Soc., 195, 11, J. S. Kim, P. E. Jeon, J. C. Choi, H. L. Park, S. I. Mho and G. C. Kim, Appl. Phys. Lett., 2, 8, Y. H. Won, H. S. Jang, W. B. Im, D. Y. Jeon and J. S. Lee, Appl. Phys. Lett., 26, 89, 23199/ S. Tanae, T. Kouda and T. Hanada, Opt. Mater., 1999, 12, J. Ruan, E. Wu, H. P. Zeng, S. F. Zhou, G. Lakshminarayana and J. R. Qiu, Appl. Phys. Lett., 28, 92, 11121/ B. T. Wu, J. Ruan, J. J. Ren, D. P. Chen, C. S. Zhu, S. F. Zhou and J. R. Qiu, Appl. Phys. Lett., 28, 92, 111/ Y. X. Zhuang and S. Tanae, J. Appl. Phys., 212, 112, 93521/ H. Y. Zhong, B. J. Chen, G. Z. Ren, L. H. Cheng, L. Yao and J. S. Sun, J. Appl. Phys., 29, 16, H. T. Guo, L. Liu, Y. Q. Wang, C. Q. Hou, W. N. Li, M. Lu, K. S. Zou and B. Peng, Opt. Express, 29, 17, X. F. Liu, Y. Teng, Y. X. Zhuang, J. H. Xie, Y. B. Qiao, G. P. Dong, D. P. Chen and J. R. Qiu, Opt. Lett., 29, 3, W. L. Zhou, Y. Li, R. H. Zhang, J. Wang, R. Zou and H. B. Liang, Opt. Lett., 212, 37, Q. Y. Zhang, G. F. Yang and Z. H. Jiang, Appl. Phys. Lett., 27, 91, 5193/ X. F. Liu, Y. B. Qiao, G. P. Dong, S. Ye, B. Zhu, G. Lakshminarayana, D. P. Chen and J. R. Qiu, Opt. Lett., 28, 33, B. M. van der Ende, L. Aarts and A. Meijerink, Adv. Mater., 29, 21, J. M. Meijer, L. Aarts, B. M. van der Ende, T. J. H. Vlugt and A. Meijerink, Phys. Rev. B, 21, 81, 3517/ Q. Luo, X. S. Qiao, X. P. Fan, H. Y. Fu, J. L. Huang, Y. J. Zhang, B. Fan and X. H. Zhang, J. Am. Ceram. Soc., 212, 95,
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