Journal of Inorganic Materials ›› 2019, Vol. 34 ›› Issue (11): 1145-1155.DOI: 10.15541/jim20190045
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CAO Xun,CAO Cui-Cui,SUN Guang-Yao,JIN Ping-Shi
Received:2019-01-25
Revised:2019-03-18
Published:2019-11-20
Online:2019-05-29
Supported by:CLC Number:
CAO Xun, CAO Cui-Cui, SUN Guang-Yao, JIN Ping-Shi. Recent Progress of Single-phase White Light-emitting Diodes Phosphors[J]. Journal of Inorganic Materials, 2019, 34(11): 1145-1155.
Fig. 1 Development of WLED (a) InGaN蓝光芯片/YAG:Ce黄色荧光粉白光LED; (b) RGB混合荧光粉白光LED; (c)单基质白光LED[4] (a) blue light emitting InGaN chips/YAG:Ce yellow light emitting phosphor WLED; (b) WLED based on red-green-blue (RGB) emitting color phosphors; (c) WLED based on single-phase phosphor[4,5,6]
Fig. 3 EL spectra (a) of the white LED fabricated by using phosphors and 400 nm GaN-based LED chips, CIE (x, y) chromaticity diagram (b) with insets showing digital images of the fabricated white LED[22]
Fig. 4 (a) PLE and PL spectra of as-synthesized Ba3Y1.3Eu0.7B6O15 phosphors (λem=?593?nm and λex=?393?nm) at room temperature, (b) PL spectra of Ba3Y2-xEuxB6O15 (x?=?0.1, 0.3, 0.5, 0.6, 0.7, 0.9 and 1.0) phosphors with the inset illustrating the variation of the PL intensity (593?nm) on the concentration of Eu3+[23]
| Phosphor | UV/nm | Emission | CIE(x, y) | Ref. |
|---|---|---|---|---|
| BaSrMg(PO4)2: Eu2+ | 385 | 460 nm, 550 nm | (0.29, 0.35) | [25] |
| Sr3MgSi2O8: Eu2+ | 375 | 470 nm, 570 nm | (0.32, 0.33) | [26] |
| LaOF: Eu3+ | 274 | All the emissions from Eu3+ | (0.29, 0.34) | [27] |
| NaYF4: Eu3+ | 397 | 5DJ-7FJ’ (J,J’=0,1,2,3,4) | (0.29, 0.33) | [28] |
| CaIn2O4: Eu3+ | 397 | - | (0.32, 0.32) | [29] |
| BaY2ZnO5: Dy3+ | 355/351 | 489 nm, 579 nm | (0.32, 0.39) | [30] |
Table 1 Summary of single activator ion doped systems for single-phase white-emitting phosphors
| Phosphor | UV/nm | Emission | CIE(x, y) | Ref. |
|---|---|---|---|---|
| BaSrMg(PO4)2: Eu2+ | 385 | 460 nm, 550 nm | (0.29, 0.35) | [25] |
| Sr3MgSi2O8: Eu2+ | 375 | 470 nm, 570 nm | (0.32, 0.33) | [26] |
| LaOF: Eu3+ | 274 | All the emissions from Eu3+ | (0.29, 0.34) | [27] |
| NaYF4: Eu3+ | 397 | 5DJ-7FJ’ (J,J’=0,1,2,3,4) | (0.29, 0.33) | [28] |
| CaIn2O4: Eu3+ | 397 | - | (0.32, 0.32) | [29] |
| BaY2ZnO5: Dy3+ | 355/351 | 489 nm, 579 nm | (0.32, 0.39) | [30] |
Fig. 8 PL spectra of the CNPO:0.01Eu2+, nMn2+(n = 0, 0.1, 0.2, and 0.4) under the excitations at 276 (a), 320 (b), and 355 nm (c), respectively; The photos of the phosphors (d) excited by 365 nm UV lamp (bottom row), and photos obtained in daylight environment (upper row). The photos 1-4 correspond to n=0, 0.1, 0.2, and 0.4, respectively[33]
| Representative examples | Excitation/nm | Emission | CIE(x,y) | Ref. |
|---|---|---|---|---|
| Ca9Gd(PO4)7: Eu2+, Mn2+ | 380 | Eu2+: blue-greenish emission band (peaking at 494 nm) + Mn2+: red emission band (peaking at 652 nm) | (0.326, 0.328) | [34] |
| CaAl2Si2O8: Eu2+, Mn2+ | 354 | Eu2+: a broad band centered at 425 nm + Mn2+: a broad band centered at 568 nm | (0.33, 0.31) | [35] |
| MgY4Si3O13: Ce3+, Mn2+ | 328 | Ce3+: an asymmetric broad band peaking at 455 nm + Mn2+: orange-red emission band at 587 nm | (0.36, 0.26) | [36] |
| Ca3Sc2Si3O12: Ce3+, Mn2+, Y3+ | 450 | Ce3+: a green emission band peaked at 505 nm + Mn2+: a yellow band at around 574 nm and a red band at around 680 nm | (0.30, 0.33) | [37] |
| Sr2SiO4: Ce3+, Eu2+ | 354 | Ce3+: an asymmetric blue emission + Eu2+: a broad band covering the blue-green to yellow region | - | [38] |
| Sr3B2O6: Ce3+, Eu2+ | 351 | Ce3+: a broad asymmetric blue emission band centering at 434 nm + Eu2+: a broad yellow orange emission band centering at 574 nm | (0.31, 0.24) | [39] |
| Ca4Y6(SiO4)6O: Ce3+, Tb3+ | 352 | Ce3+: a blue band centered at 421 nm + Tb3+: characteristic emission lines ranging from 470 to 650 nm with yellow-greenish emission | (0.278, 0.353) | [40] |
| Ca2Al2SiO7: Ce3+, Tb3+ | 352 | Ce3+: a blue band centered at 419 nm + Tb3+: characteristic emission lines ranging from 470 to 650 nm with yellow-greenish emission | (0.316, 0.336) | [41] |
| Sr2Al2SiO7: Ce3+, Dy3+ | 335 | Ce3+: a blue emission band at 408 nm + Dy3+: the emission bands at 491 nm and 573 nm | - | [42] |
| 12CaO·7Al2O3: Ce3+, Dy3+ | 362 | Ce3+: a broad band centered at 430 nm + Dy3+: two narrow bands centered at 476 nm and 576 nm | (0.324, 0.323) | [43] |
Table 2 Summary of representative multi-ion doped single-phased white-emitting phosphors
| Representative examples | Excitation/nm | Emission | CIE(x,y) | Ref. |
|---|---|---|---|---|
| Ca9Gd(PO4)7: Eu2+, Mn2+ | 380 | Eu2+: blue-greenish emission band (peaking at 494 nm) + Mn2+: red emission band (peaking at 652 nm) | (0.326, 0.328) | [34] |
| CaAl2Si2O8: Eu2+, Mn2+ | 354 | Eu2+: a broad band centered at 425 nm + Mn2+: a broad band centered at 568 nm | (0.33, 0.31) | [35] |
| MgY4Si3O13: Ce3+, Mn2+ | 328 | Ce3+: an asymmetric broad band peaking at 455 nm + Mn2+: orange-red emission band at 587 nm | (0.36, 0.26) | [36] |
| Ca3Sc2Si3O12: Ce3+, Mn2+, Y3+ | 450 | Ce3+: a green emission band peaked at 505 nm + Mn2+: a yellow band at around 574 nm and a red band at around 680 nm | (0.30, 0.33) | [37] |
| Sr2SiO4: Ce3+, Eu2+ | 354 | Ce3+: an asymmetric blue emission + Eu2+: a broad band covering the blue-green to yellow region | - | [38] |
| Sr3B2O6: Ce3+, Eu2+ | 351 | Ce3+: a broad asymmetric blue emission band centering at 434 nm + Eu2+: a broad yellow orange emission band centering at 574 nm | (0.31, 0.24) | [39] |
| Ca4Y6(SiO4)6O: Ce3+, Tb3+ | 352 | Ce3+: a blue band centered at 421 nm + Tb3+: characteristic emission lines ranging from 470 to 650 nm with yellow-greenish emission | (0.278, 0.353) | [40] |
| Ca2Al2SiO7: Ce3+, Tb3+ | 352 | Ce3+: a blue band centered at 419 nm + Tb3+: characteristic emission lines ranging from 470 to 650 nm with yellow-greenish emission | (0.316, 0.336) | [41] |
| Sr2Al2SiO7: Ce3+, Dy3+ | 335 | Ce3+: a blue emission band at 408 nm + Dy3+: the emission bands at 491 nm and 573 nm | - | [42] |
| 12CaO·7Al2O3: Ce3+, Dy3+ | 362 | Ce3+: a broad band centered at 430 nm + Dy3+: two narrow bands centered at 476 nm and 576 nm | (0.324, 0.323) | [43] |
Fig. 9 Electroluminescence spectra of the WLED operated under various currents of 20 to 60 mA. Inset: the variation in CIE chromaticity coordinates of the WLED under various currents[57]
| Sample | KVO3 | RbVO3 | CsVO3 | Mg3V2O8 | Zn3V2O8 |
|---|---|---|---|---|---|
| η/% | 4 | 79 | 87 | 6 | 52 |
| CIE(x, y) | 0.362, 0.453 | 0.316, 0.424 | 0.306, 0.418 | 0.449, 0.475 | 0.432, 0.478 |
| CCT/K | 4859 | 5993 | 6334 | 3318 | 3583 |
Table 3 Luminescence property of AVO3 (A=K, Ru, Cs) and M3V2O8 (M=Mg, Zn)[60]
| Sample | KVO3 | RbVO3 | CsVO3 | Mg3V2O8 | Zn3V2O8 |
|---|---|---|---|---|---|
| η/% | 4 | 79 | 87 | 6 | 52 |
| CIE(x, y) | 0.362, 0.453 | 0.316, 0.424 | 0.306, 0.418 | 0.449, 0.475 | 0.432, 0.478 |
| CCT/K | 4859 | 5993 | 6334 | 3318 | 3583 |
| AVO3 phase | PLE peak/nm | PL peak/nm | FWHM/nm | CIE(x, y) | CCT/K |
|---|---|---|---|---|---|
| CsVO3 (W) | 356 | 487 | 151 | (0.2421, 0.3283) | 12050 |
| CsVO3 (Y) | 342 | 503 | 138 | (0.2671, 0.3855) | 8444 |
| RbVO3 (W) | 357 | 491 | 149 | (0.2462, 0.3379) | 11152 |
| RbVO3 (R) | 342 | 510 | 149 | (0.2797, 0.3960) | 7700 |
Table 4 Optical property of heterogeneous AVO3[63]
| AVO3 phase | PLE peak/nm | PL peak/nm | FWHM/nm | CIE(x, y) | CCT/K |
|---|---|---|---|---|---|
| CsVO3 (W) | 356 | 487 | 151 | (0.2421, 0.3283) | 12050 |
| CsVO3 (Y) | 342 | 503 | 138 | (0.2671, 0.3855) | 8444 |
| RbVO3 (W) | 357 | 491 | 149 | (0.2462, 0.3379) | 11152 |
| RbVO3 (R) | 342 | 510 | 149 | (0.2797, 0.3960) | 7700 |
Fig. 11 Controllable photoluminescence (a) Optical images of solution and film samples with different bandgaps under a 365 nm UV lamp; (b) Optical absorption; (c) Photoluminescence spectra of IPQDs with different composition[65]
| Phosphors | Advantages | Disadvantages | |
|---|---|---|---|
| Rare earth ion doped system | Single activator ion doped systems | High quantum conversion efficiency; wide emission spectrum range | Low color rendering index; high price; harmful to the environment |
| Multi-ions co-doping systems | |||
| Rare earth ion free systems | Semiconductor nanocrystal | Large absorption coefficient; wide excitation and emission band; high quantum yield; easy to be combined with packaging materials | Expensive raw materials; complex synthesis process; poor stability |
| Vanadate | High luminous efficiency; low preparation temperature | High color temperature; low intensity in red region | |
| Perovskite | Optical band gap adjustable; high quantum conversion efficiency | Pollution from soluble heavy metal Pb |
Table 5 Advantages and disadvantages of single-phase WLEDs phosphors
| Phosphors | Advantages | Disadvantages | |
|---|---|---|---|
| Rare earth ion doped system | Single activator ion doped systems | High quantum conversion efficiency; wide emission spectrum range | Low color rendering index; high price; harmful to the environment |
| Multi-ions co-doping systems | |||
| Rare earth ion free systems | Semiconductor nanocrystal | Large absorption coefficient; wide excitation and emission band; high quantum yield; easy to be combined with packaging materials | Expensive raw materials; complex synthesis process; poor stability |
| Vanadate | High luminous efficiency; low preparation temperature | High color temperature; low intensity in red region | |
| Perovskite | Optical band gap adjustable; high quantum conversion efficiency | Pollution from soluble heavy metal Pb |
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