LUMINESCENCE OF RE OVERSATURATED CRYSTALS A. Gektin a *, N. Shiran a, V. Nesterkina a, G. Stryganyuk b, K. Shimamura c, E. Víllora c, K. Kitamura c a Institute for Scintillation Materials, NAS of Ukraine, Kharkov b HASYLAB at Deutsches Elektronensynchrotron DESY, Hamburg, Germany c Advanced Materials Lab., Nat. Inst. for Materials Science, Tsukuba, Japan
Fluorides allows to modify properties Scintillator phosphor storage dosimetry Broad variety of crystal lattices What is the RE doping optimum? Motivation LiCaAlF 6 LiSrAlF 6 LiCaAlF 6 / LiSrAlF 6 colquiriite LiBaF 3 LiBaF 3 perovskite ВаМgF 4 orthorhombic LiF LiF cubic BaF 2 fluorite LiF – dosimeter KMgF 3 (Eu) –UV dosimeter BaFBr(Eu) – screen phosphor BaF 2 – fast scintillator LiBaF 3 (Ce)– n/ discriminator CaF 2 (Eu) – scintillator
New phosphors M 1-x RE x F 2+x (M=Ca, Sr, Ba) Structure of fluorite MF 2 (М=Ca, Sr, Ba) FiFi V Fc {F 12 } Defect cluster [RE 6 F 36 ] Supercluster {M 8 [RE 6 F ]} RE 3+ -F i ¯ dipole dimer, trimer, etc. M 1-x RE x F 2+x REF 3 phase increase of RE 3+ concentration in fluoride matrix It is supposed that defect clusters and fluoride phases of non-stoichiometric crystals can form nanostructures that opens an possibility to engineering materials with various kinds of properties. detect clusters ~0.1%~1-2%~3-5%~10% 20-50%
Phase Diagrams of Ba 0.65 Pr 0.35 F 2.35 Systems Internal structure is not still clear but single crystals are available *)Rodnyi, Phys.Rev. (2005) BaF 2 BaF 2 –Pr (0.3 mol%) *) BaF 2 –Pr (3 mol%) *) BaF 2 –Pr (35 mol%) BaF 2 –Pr (35mol%) Ba 0.65 Pr 0.35 F 2.35
RE oversaturated crystals Which properties will dominates? crystala, Å CaF (8) CaF 0.65 Eu 0.35 F (8) CaF 0.65 Pr 0.35 F (4) SrF Sr 0.65 Pr 0.35 F (2) BaF BaF 0.65 Pr 0.35 F (6) Me 1–x Pr x F 2+x M= Ca,Sr,Ba 0.22 < x < 0.5 ionR, Å Ca Eu Pr Sr Ba F–F– 1.19 Me 1–x Pr x F 2+x MeF 2 –Pr PrF 3
Fluorides phase structure, superlattice Non coherent inclusions nano phases Gleiter, Acta Met. (2000) Coherent inclusions M 2+ R 3+ Sobolev, Crystallography (2003) M 1-x R x F 2+x with R 3+ to 40%
Fluorides phase structure, superlattice Non coherent inclusions Coherent inclusions nano phases Coincidence lattice with R 3+ content 42.86% (Ba 4 Yb 3 F 17 ). Other step is 15.38% Sobolev, Crystallography (2003) Model of non stoichiometric crystal with R 3+ content 40%
Eu 2+ Eu 3+ transformation by “lattice engineering” 1. At energies E < 6.5 eV only interconfigurational 4f-4f transitions are observed; 2. Intraconfigurational 4f-5d and charge transfer (F – →Eu 3+ ) transitions occur in range of eV; CaF 2 (Eu) phosphor Ca 0.65 Eu 0.35 F 2.35 Eu 2+ emission in CaF 2 (Eu) Eu 3+ emission in Ca 0.65 Eu 0.35 F 2.35 CCD camera sensitivity
BaF 2 –Pr photon cascade emission Cascade emission: 1 step: 1 S 0 → 1 I 6 (~400 нм) 2 step: 3 P 0 → 3 H 4 (~482 нм) Second step only Energy levels and Pr 3+ transitions (Rodnyi, Phys.Rev., 2005) BaF 0.65 Pr 0.35 F 2.35
Pr absorption in different hosts Ca 0.65 Pr 0.35 F 2.35 Sr 0.65 Pr 0.35 F 2.35 Ba 0.65 Pr 0.35 F 2.35 Absorption peaks structure is similar for different hosts
Clasters structure and Pr 3+ excitation spectra Excitation for em = 250 нм 1. CaF 2 –Pr (0.1%) 2. Ca 0.65 Pr 0.35 F 2.35 Broad excitation spectra due to Pr 3+ cluster structure and peaks overlapping 300K 8K
Hexagonal, space group Emission spectra, 8K Ca 0.65 Pr 0.35 F 2.35 Sr 0.65 Pr 0.35 F 2.35 Ba 0.65 Pr 0.35 F 2.35
Emission spectra (photoexcitation), 300K Ca 0.65 Pr 0.35 F 2.35 Sr 0.65 Pr 0.35 F 2.35
Multi cluster structure Decay curves for different cluster peak excitation Ca 0.65 Pr 0.35 F 2.35
– luminescence and glow curve CaPrF 223 nm o < 5 ns, 250 nm 1 =25 ns and 2 =262 ns 273 nm 1 =54 ns and 2 =300 ns 400 nm 1 =71 ns and =330 ns SrPrF 230 and 275 nm o <5 ns 325 nm 1 =35 ns 400 nm 1 =34 ns 475 nm 1 =23 нс and 2 =139 ns. BaPrF 250 nm o < 1 ns 325 nm 1 =37 ns 480 nm 2 =101 ns and 3 =549 ns Glow curve
Hexagonal, space group Properties Crystal CaF 2 :0.1%PrCa 0.65 Pr 0.35 F 2.35 PrF 3 StructureCubic fluorite Lattice constant, Å (8) (4)7.078 / Coordination number 8>89 X-ray emission 77K 5d–4f, UV 1 S o - 1 I o 3 P H 4 233, 251, 272nm ― 482nm 233, 251, 272nm 400 nm ― 233, 251, 272nm 400 nm ― Photoluminescence Pr 3+ 5d–4f 1 S o - 1 I o 3 P H 4 233, 251, 272nm ― 482nm 233, 251, 272nm 400 nm ― 233, 251, 272nm 400 nm ― Excitation of d f Pr 3+ emission C 4v site154, , , , Cluster τ 1 (5d–4f), ns τ 2 ( 1 S 0 – 1 I 6 ), ns 20~ ~ Ca–Pr–F compound emission
CompoundSrF %PrSr 0.65 Pr 0.35 F 2.35 PrF 3 Structurefluoride distorted hexagonal Lattice constant a, Å (2) Coordination number 8>89 X-ray emission 5d–4f, UV 1 S o - 1 I o 3 P H 4 233, 251, 272nm ― 482nm 233, 251, 272nm 400nm 482nm 233, 251, 272nm 400 nm ― Photoluminescence 5d–4f, UV 1 S o - 1 I o 3 P H 4 233, 251, 272nm ― 482nm 233, 251, 272nm 400 nm 482nm 233, 251, 272nm 400 nm ― Excitation of d f, nm single Pr , 218 cluster―223, 160 −190223, Decay time 1, (5d–4f) 2, ( 1 S o - 1 I o ) 2, ( 3 P H 4 ) 25 ― < , ― Sr–Pr–F compound emission
Photon cascade conditions 1. S level should be separated from f-d level 2. Minimal influence of cross relaxation This has to corresponds to: * coordination number more then 8-9 * large distance between Pr and anion ions CaF 2 :Pr 0.2% Ca 0.65 Pr 0.35 F 2.35
Conclusions 1. Me 1–x RE x F 2+x – is a stable crystal lattice with RE content to 50% 2. RE ions aggregation gives a lot of clasters 3. Photon cascade emission is typical for all Me 0.65 Pr 0.35 F 2.35 compound but yield is still very low 4. Is it possible to make the same lattice with F substitution by Cl, Br or I ?