EP2536809A1 - Luminescent compounds - Google Patents
Luminescent compoundsInfo
- Publication number
- EP2536809A1 EP2536809A1 EP11712897A EP11712897A EP2536809A1 EP 2536809 A1 EP2536809 A1 EP 2536809A1 EP 11712897 A EP11712897 A EP 11712897A EP 11712897 A EP11712897 A EP 11712897A EP 2536809 A1 EP2536809 A1 EP 2536809A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zero
- compound
- compounds
- radiation
- varies
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 121
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 230000005855 radiation Effects 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 description 29
- 238000004020 luminiscence type Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000005284 excitation Effects 0.000 description 12
- 229910052691 Erbium Inorganic materials 0.000 description 11
- 238000000295 emission spectrum Methods 0.000 description 10
- -1 rare earth ions Chemical class 0.000 description 10
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 7
- 229910052769 Ytterbium Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 5
- 230000009102 absorption Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960001506 brilliant green Drugs 0.000 description 2
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- 239000011707 mineral Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Definitions
- the present invention relates to the field of luminescent materials, more particularly so-called “up-conversion” materials, capable of emitting a higher energy radiation (of shorter wavelength) than that of the incident radiation.
- luminescent compounds have the particularity, when they are subjected to radiation of a given wavelength, to re-emit a second radiation of higher wavelength, therefore of lower energy than that of the incident radiation. .
- Up-conversion compounds are crystalline solids of the oxide or halide type (especially fluoride) doped with lanthanide ions (also called “rare earths").
- lanthanide ions also called “rare earths”
- the compound Y 2 0 3 doped with Er + ions is known which makes it possible to convert radiation in the near infrared range into radiation in the visible range.
- the known compounds is also yttrium fluoride YF 3 doped with ions Yb 3+ and Er 3+ (denoted YF 3 : Yb 3+ / Er 3+ ).
- Gd 2 BaZn0 5 Yb 3+ / Er 3+
- Gd 2 BaZn0 5 Yb 3+ / Tm 3+ .
- These compounds exhibit an up-conversion phenomenon in the sense that they are capable of converting radiation whose wavelength is located in the infrared (typically 975 nm) into visible radiation, mainly in the fields of green (approximately 550 nm) and red (about 660 nm).
- the luminescence yield is high, and can even reach values greater than 1% for the Gd 2 BaZnO 5 compound doped with Yb 3+ / Er 3+ containing 1% of erbium and 10% of ytterbium, of formula Gdi, 78 bo, 2 Ero, o 2 BaZn0 5 .
- the object of the invention is to propose novel up-conversion compounds based on oxides whose luminescence yield is even higher.
- the subject of the invention is a crystalline compound of formula
- Ln is or Gd
- t1 + t2 + t3 + t4 varies from 0.001 to 0.3, preferably from 0.007 to 0.2, or even from 0.01 to 0.2
- tl + t3 + t4 is non-zero if Ln is Gd and if t3 + t4 is zero, then tl varies from
- the compound is then of the Ln 2 BaZnO 5 type , more precisely of the Y 2 BaZnO 5 or Gd 2 BaZnOs type, each of these compounds being doped with at least one or even two, three or even four rare earth ions, Er 3+. , Yb 3+ , Tm 3+ or Ho 3+ .
- the doping ion (Yb 3+ , Er 3+ , Tm 3+ , Ho 3+ ) partially replaces the Ln 3+ ion (Y 3+ , Gd 3+ ).
- the parameters t1 to t4 correspond to the molar fraction of Ln 3+ ion substituted by the corresponding doping ion. These parameters are also called “contents” or "concentrations" of doping ions.
- Ln is chosen from Y and Gd, because these ions make it possible to obtain the highest luminescence yields.
- Ln is preferably Y, because this element has proved to be capable of obtaining better crystallized compounds for a time of equivalent synthesis.
- the compound according to the invention is therefore preferably of the type Gd 2 BaZnO 5 , and more preferably Y 2 BaZnO 5 .
- t1 + t2 + t3 is greater than or equal to 0.05 and / or t1 + t4 is greater than or equal to 0.05.
- the compound according to the invention preferably contains the Yb 3+ ion, which has an absorption cross section around 980 nm approximately ten times higher than that of erbium, thulium or holmium ions.
- the parameter t1 is therefore advantageously greater than or equal to 0.01, or even to 0.05.
- Ln is preferably Y
- These compounds are in particular of the Y 2 BaZnO 5 and Gd 2 BaZnO 5 type co-doped with Er 3+ and Yb 3+ ions, and have, thanks to the specific choice of the erbium and ytterbium concentrations, much higher luminescence yields.
- Particularly effective compounds have the following formula: Y 1 , 8 Yb 0 , i Er 0 , osBaZnOs and
- the compounds of this family emit very intensively in the green (around 550 nm) and in the red (around 670 nm). These compounds also exhibit up-conversion phenomena when they are excited in other ranges of wavelengths. For example, excitation in the red (around 660 nm) gives a luminescence in the green (around 550 nm) and in the ultraviolet. An excitation in the near infrared (around 800 nm) makes it possible to obtain an emission in the red (around 670 nm) and the green (around 550 nm). The yields observed are, however, lower than those obtained by irradiation in the infrared.
- the indicated doping ranges make it possible to reach extremely high luminescence yields, above 3%, and even 5%.
- the increase in the Yb 3+ content makes it possible to accentuate the red component to the detriment of the green component.
- tl and t3 are non-zero.
- tl preferably varies from 0.03 to 0.2, in particular from 0.05 to 0.2, or even from 0.05 to 0.1, and t3 preferably varies from 0.001 to 0.05, in particular from 0.001 to 0, 01, or even 0.001 to 0.005.
- These compounds are in particular of the type Y 2 Ba Z n0 5 co-doped with ions Yb 3+ and Tm 3+ .
- the compounds of this family emit at 800 nm (infrared), 650 nm (red) and 480 nm (blue), with luminescence efficiency exceeding 1%. The color perceived with the eye is blue. These compounds also exhibit up-conversion phenomena when they are excited in other ranges of wavelengths. For example, near-infrared excitation (around 800 nm) produces emission in the red (around 650 nm) and blue (around 480 nm). The yields observed are, however, lower than those obtained by irradiation in the infrared.
- the intensity ratio between blue emission and infrared emission decreases as the Tm 3+ content increases.
- tl and t4 are non-zero.
- These compounds are in particular of the Y 2 BaZnO 5 or Gd 2 BaZnO 5 type co-doped with Yb 3+ and Ho 3+ ions.
- the compounds of this family emit strongly around 550 nm (green), and more weakly around 660 nm and 760 nm (red and near infrared), with a luminescence yield that can exceed 2 %.
- the coloration perceived with the eye is of a very brilliant green.
- These compounds also exhibit up-conversion phenomena when they are excited in other wavelength ranges. For example, excitation in the red (around 660 nm) also makes it possible to obtain luminescence in the green (around 550 nm). An excitation in the near infrared (around 800 nm) makes it possible to obtain an emission in red and green.
- t4 may be zero or non-zero, preferably zero.
- These compounds are in particular of the Y 2 BaZnO 5 or Gd 2 BaZnO 5 type , co-doped with at least three ions: Yb 3+ , Er 3+ and Tm 3+ .
- the Ho 3+ ion can also be added to these compounds.
- the choice of Y is preferred.
- Ln 2 BaZn0 5 : Yb 3+ / Tm 3+ with or without addition of compounds of the type Ln 2 BaZn0 5 : Yb 3+ / Ho 3+ also makes it possible to obtain any desired color, and in particular a white light emission, under irradiation in the infrared (in the range 890-1100 nm, and more particularly around 975 nm).
- the invention therefore also relates to a mixture of at least two different compounds according to the invention. In particular, a mixture of two different compounds or of three different compounds is preferred.
- Y 2 BaZnO 5 Yb 3+ / Tm 3+
- a white light is typically obtained for a second compound mass 20 to 35 times (especially 25 to 30 times) higher than the mass of the first compound.
- the subject of the invention is also the processes for obtaining the compounds according to the invention.
- These compounds can be obtained by a solid phase process, that is to say a process comprising the steps of mixing powders, typically oxides or carbonates powders, to grind the mixture, optionally to press it for forming a pellet and then heating the mixture so as to chemically react the powders together.
- the powders are, for example, Gd 2 O 3 , Y 2 O 3 , Yb 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , ZnO, BaCO 3 .
- Nanoparticles can be obtained by grinding the powders obtained, for example by a ball milling technique.
- the compounds according to the invention can also be obtained by a sol-gel type process, comprising the steps of dissolving precursors (typically nitrates, acetates, or even carbonates) in water or in a predominantly aqueous solvent, to add a complexing agent (typically an ⁇ -hydroxycarboxylic acid such as citric acid) and optionally a crosslinking agent (typically a polyhydroxy alcohol such as ethylene glycol) so as to obtain a gel and then to heat the gel obtained, normally at a temperature of at least 1000 ° C.
- a sol-gel method generally makes it possible to obtain a better homogeneity. Heating at least 1000 ° C overcomes the disadvantages associated with this process, including a higher content of impurities (C0 2 , water ...) which generates a probability of occurrence of structural defects higher.
- the subject of the invention is also the use of the compounds according to the invention for converting infrared radiation into visible radiation, in particular for converting radiation of wavelength in the range from 890 to 1100 nm, especially for about 975 nm, in wavelength radiation of about 550 nm and / or 660 nm and / or 480 nm and / or 800 nm.
- This up-conversion phenomenon which converts infrared radiation into visible radiation (blue, green, red, or any type of color, especially white, by mixing several different compounds or by doping a compound with three different dopants) can be used in many applications, particularly in the areas of display, imaging (including medical), lasers, photovoltaic energy production, the fight against counterfeiting or identification.
- the compounds according to the invention can convert infrared laser radiation (around 980 nm for example) into green, blue or red laser radiation, or of any desired color. They can advantageously replace the doubling compounds of frequency currently employed, which are based on second harmonic generation phenomena.
- the compounds according to the invention can serve as luminescent markers in fluorescence imaging techniques.
- the advantage over existing methods lies in the possibility of using an excitation light source emitting in the infrared, and not in the ultraviolet, because the ultraviolet radiation is capable of creating lesions in the tissues and generates an unwanted background related to the endogenous fluorescence of biological tissues.
- the compounds according to the invention can be incorporated into coatings deposited on any substrates. These coated substrates can advantageously be used in the fields of photovoltaic power generation and display.
- the subject of the invention is therefore a substrate coated on at least a part of at least one of its faces with a coating incorporating at least one compound according to the invention and a display device or a device for the production of photovoltaic energy comprising at least one such coated substrate.
- the substrate may be transparent, opaque, or even translucent. It may be an organic substrate, metallic, mineral, for example of the glass, ceramic, glass-ceramic type, comprising a hydraulic binder (plaster, cement, lime ).
- the substrate may be flat or curved.
- the compounds according to the invention can be incorporated into the coating by various techniques.
- the thin layer may in particular comprise the compounds according to the invention within a binder.
- This binder can in particular be of an organic nature (for example of the ink, paint, lacquer, varnish type) or mineral (for example a glaze, an enamel, a sol-gel type binder).
- different methods of form are possible: sputter deposition, curtain, coating, scouring, screen printing, spray gunsing etc.
- the coating may also consist of at least one compound according to the invention, and may be deposited by various CVD techniques (deposit chemical vapor phase) or PVD (especially sputtering).
- a clear glass substrate coated on one of its faces with a coating incorporating at least one compound according to the invention may for example be used as a front-face substrate of a photovoltaic cell.
- the term "front-face substrate” is intended to mean the substrate traversed first by solar radiation.
- a substrate coated on one of its faces with a coating incorporating at least one compound according to the invention may alternatively or cumulatively be used as a backside substrate of a photovoltaic cell, possibly associated with a device providing reflection (diffuse or specular) towards the photovoltaic material.
- the presence of the compounds according to the invention makes it possible to convert part of the infrared radiation into visible radiation at wavelengths in which the quantum efficiency of the photovoltaic material is higher.
- the maximum quantum efficiency is around 640 nm for cadmium telluride, 540 nm for amorphous silicon and 710 nm for microcrystalline silicon.
- a substrate coated on one of its faces with a coating incorporating at least one compound according to the invention may also be used in a display device, the selective irradiation by an infrared laser making it possible to reveal visible light, of different colors.
- the display device may for example be a screen or a "head-up display” (HUD) device used for example in transport vehicles, land, air, rail or sea.
- the coated substrate according to the invention can therefore be glazing, for example a vehicle windshield, or to be incorporated in such a glazing.
- Some currently marketed systems use fluorescent compounds incorporated in laminated windshields (they are generally deposited on or within the lamination interlayer), which emit visible radiation when irradiated by a laser emitting in the laminated windshield. 'ultraviolet.
- the compounds according to the invention can advantageously replace these fluorescent compounds, which makes it possible to use a laser emitting in the infrared, for example a laser diode, which is considerably less expensive and dangerous than a laser emitting in the ultraviolet.
- Figure 1 is a typical emission spectrum of a compound of the type Y 2 a-ti-t 2 ) Yb 2t iEr 2t 2 BaZnO 5 when irradiated with radiation of about 975 nm wavelength.
- Figure 2 superimposes several emission spectra of compounds Y 2 a-ti-t2) Yb2tiEr 2t2 BaZn0 5 , for a content tl + t2 constant, with a content t2 ranging from 0.03 to 0.08.
- Figure 3 is a map showing the luminescence yield obtained for compounds Y 2 ( i_ti_t2 ) Yb 2t iEr 2t2 BaZn0 5 as a function of the concentrations of Yb 3+ (tl) and Er 3+ (t2).
- Figure 4 is an experimental curve showing the ordinate the red / green intensity ratio with respect to the pulse duration of the laser.
- Figure 5 is a typical emission spectrum of a Y 2 compound (i-t 1 -t 3 > Yb 2 tiTm 2t 3 BaZnO 5 when irradiated with infrared radiation of about 975 nm wavelength .
- Figures 6a and 6b are mappings showing the luminescence yield obtained for Y 2 ( i-t 1 -t 3 ) Yb 2 tiTm 2t 3 BaZnO 5 compounds as a function of the concentrations of Yb + (tl) and Tm 3+ (t3). ) in the emission range of 420 to 870 nm ( Figure 6a) and 420 to 530 nm ( Figure 6b).
- Figure 7 is a typical emission spectrum of a compound of type Y 2 (i-ti-t4> Yb 2t iHo 2T4 BaZn0 5 when irradiated by infrared radiation of about 975 nm wavelength .
- Figure 8 is a map showing the luminescence yield obtained for compounds of the type Y 2 (i- t i -t4) Yb 2t iHo 2 t 4 BaZ n0 5 as a function of the concentrations of Yb 3+ (tl) and Ho 3 + (t4).
- Figure 9 a typical emission spectrum of a compound of formula Yi, 8 Ybo, Er i 4 0 o 6 BaZ n0 5 incorporated in a coating deposited on a glass substrate when irradiated with infrared radiation about 975 nm wavelength.
- the phenomenon of up-conversion is characterized by the determination, using a spectrophotometer, of the emission spectrum of the compound when it is subjected to a coherent radiation whose wavelength is around 975 nm.
- the compounds are ground and the powder obtained is held between two quartz plates.
- Samples are excited using a continuous laser diode (Thorlabs, L980P100 and TCLDM9) driven by a laser controller (ILX-Lightwave LDC-3742), pulsed using a function generator (Agilent Hewlett Packard 33120A) or a pulsed power source (ILX Lightwave LDP-3811).
- the emission in the visible is recorded using a conventional device comprising a monochromator and detected using a silicon photodiode (Newport Si 818-UV).
- the up-conversion luminescence phenomenon is also characterized by determining the luminescence efficiency.
- the compounds are ground and the powder obtained is held in a sample holder composed of two quartz plates, one of which is coated with a reflective layer of aluminum.
- the sample holder is then placed on the backside of an integrating sphere (Instruments Systems, ISP-150-100).
- the excitation signal is focused at the center of the sample with a lens.
- the measurement is carried out in two stages. In a first step, the sample holder is empty (no powder is present), and the signal is collected by an optical fiber and analyzed using a spectrometer (Instruments Systems, CAS 140B). In a second step, the powder is placed in the sample holder and both the excitation light fraction which has not been absorbed by the sample and the emitted up-conversion light are measured. The luminescence yield, which corresponds to the ratio between the emission in the range 380-780 nm relative to the power absorbed between 950 and 1000 nm, is calculated from these two steps.
- the samples show a luminescence ranging from green to orange, characterized by a strong emission in the red (around 673 nm, due to a transition between levels 4 F 9 / 2 and i 4 I 5/2 erbium) and green (around 548 nm, due to a transition between levels 4 S 3/2 and 4 II5 / 2 of erbium).
- Figure 1 shows the emission spectrum obtained.
- the variation of the ytterbium ion content from 3% to 11% makes it possible to pass the ratio of red / green intensity (defined as the ratio of the intensity of the emission band centered around 673 nm to the intensity of the emission band centered around 550 nm), from 4 to 8.
- Figure 3 shows the value of the luminescence yield as a function of the concentration of erbium (t2) and ytterbium (tl) ions. It can be seen that when t1 (concentration of Yb 3+ ions) varies from 0.05 to 0.1 and t2 (concentration of Er 3+ ions) varies from 0.02 to 0.07, the Luminescence efficiency is generally at least 3%, and exceeds 4% or even 5% when tl varies from 0.07 to 0.09 and t2 ranges from 0.03 to 0.04.
- the red / green intensity ratio can also be adjusted or modified by varying the pulse duration of the laser.
- the red / green intensity ratio increases continuously with the pulse duration (between 0.05 and 1 millisecond), then stabilizes for longer pulses.
- the red / green intensity ratio is less than 1, so that the light emitted is mainly green.
- the emitted light turns orange and then red.
- Figure 4 illustrates this phenomenon by showing the evolution of the red / green intensity ratio as a function of the duration of the pulses.
- EXAMPLE 2 Y 2 BaZnO 5 : Yb 3+ / Tm 3+
- Y 2 BaZnO 5 Yb 3+ / Tm 3+ are prepared by solid phase reaction. Powders of Y 2 O 3 , Yb 2 O 3 , Tm 2 O 3 (Alfa Aesar, 99.99%), ZnO (Fischer Scientific 99.5%) and BaCO 3 (Fisher Scientific 99 +%) are mixed together, ground together and then sintered at room temperature. 1200 ° C for 3 days, with intermediate grinding steps.
- Figure 5 shows the typical emission spectrum obtained for these compounds when subjected to radiation of about 975 nm wavelength.
- the main emission band is mostly located in the infrared, around 800 nm.
- Two less intense bands are located around 480 nm (blue) and 650 nm (red). In the eye, the light emitted appears blue.
- Figures 6a and 6b show the value of the luminescence yield as a function of the concentrations of Yb 3+ (tl) and Tm 3+ (t3) in the emission range of 420 to 870 nm ( Figure 6a) and 420 to 530 nm (FIG. 6b).
- the compound has the formula Y1, 78 Ybo, 2Tm 0 , o2BaZn0 5 .
- the luminescence yield obtained is 1.7% at room temperature. room.
- the compound has the formula Y 1, 83 Ybo, i 2 Tm 0 , o 5 BaZnO 5 .
- Y 2 BaZnO 5 Yb 3+ / Ho 3+ are prepared by solid phase reaction. Powders of Y 2 O 3 , Yb 2 O 3 , H0 2 O 3 (Alfa Aesar, 99.99%), ZnO (Fisher Scientific 99.5%) and BaCO 3 (Fisher Scientific 99 +%) are mixed, milled together and then sintered at room temperature. 1200 ° C for 3 days, with intermediate grinding steps.
- Figure 7 shows the typical emission spectrum obtained for these compounds when subjected to radiation of about 975 nm wavelength.
- the main emission band is mainly located in the green, around 550 nm.
- Two distinctly less intense bands are located around 760 nm (red and near infrared) and 660 nm (red).
- the light emitted is of a very brilliant green.
- Figure 8 is a map showing the evolution of the luminescence yield at room temperature as a function of the dopant contents Yb 3+ (tl) and Ho 3+ (t4). The highest yields are obtained for Yb 3+ contents ranging from 6% to 12% (tl ranging from 0.06 to 0.12) and Ho 3+ contents ranging from 0.25% to 2% (t4). ranging from 0.0025 to 0.02).
- the efficiency changes as a function of the temperature of the laser diode, the optimum being at a temperature of about 75 ° C.
- EXAMPLE 4 Ln 2 BaZnO s : Yb 3+ / Er 3+ / Tm 3+
- Y 2 of the formula compounds are prepared (t i-t2 t i- 3) 2 Yb2tiEr t2Tm 2 t3BaZn05 by solid phase reaction. Powders of Y 2 O 3 , Yb 2 O 3 , Er 2 O 3 , Tm 2 O 3 (Alfa Aesar, 99.99%), ZnO (Fisher Scientific 99.5%) and BaCO 3 (Fisher Scientific 99 +%) are mixed, milled together then sintered at 1200 ° C for 3 days, with intermediate milling steps.
- Table 1 indicates, as a function of the values of t1, t2, t3 and the power of the laser diode, the colorimetric coordinates in the x, y colorimetric system of the radiation emitted in response to an excitation at a length of wave of about 975 nm.
- Table 1 White light is characterized by a pair where x and y are both 1/3. It can be seen from Table 1 that the gradual increase in the erbium content makes it possible to go from blue to green, passing through the white.
- Modulating the power of the laser diode also makes it possible to vary the hue obtained, as shown by the comparison between Examples 1 to 3, or 4 to 7 or 8 to 11, or again 12 to 13.
- EXAMPLE 5 Mixtures of Compounds
- Table 2 presents, as a function of the ratio R and the power of the laser diode, the colorimetric coordinates in the x, y colorimetric system of the radiation emitted in response to an excitation at a wavelength of about 975. nm.
- the mixture of compounds A and B makes it possible to pass from an emission in orange to a blue emission by passing through white light for a ratio R between 20 and 35, in particular of the order of 25 to 30.
- a decrease in the power of the diode generally increases the value x
- Luminescent coatings 0.1 mm thick were obtained on soda-lime glass substrates in the following manner.
- Luminescent particles according to the invention were mixed with an organic medium (typically castor oil) and with a glass frit.
- organic medium typically castor oil
- the luminescent compounds were Yi formula 8 Ybo, i4Ero, o 6 BaZ n0 5 or Yi, esYbo, 2:00 p.m., Oiba Z n0 5.
- the glass frit consisted of SiO 2 (12% by weight), Z 2 O (40%), Bi 2 O 3 (29%), Na 2 O (19%).
- the samples were baked at 600 ° C. for 6 minutes.
- the emission spectrum after irradiation with laser radiation of about 980 nm wavelength is shown in Figure 9. It comprises a main band at 680 nm (red) and a secondary band at about 550 nm (green).
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Abstract
The aim of the invention is to provide a crystalline compound of formula Lnx.
(1-t1-t2-t3-t4) Ybx.t1Erx. t2Tmx. t3Hox. t4BayZnzO1. 5x+y+z where: Ln is Y, Gd or La, t1+t2+t3+t4 varies from 0.001 to 0.3, preferably from 0.01 to 0.2, and such that when x=2, y=1, z=1, t1+t3+t4 is nonzero if Ln is La or Gd and if t3+t4 is zero, then t1 varies from 0.05 to 0.1 and t2 varies from 0.02 to 0.07 if Ln is Gd, then t2+t4 is nonzero.
Description
COMPOSES LUMINESCENTS LUMINESCENT COMPOUNDS
La présente invention concerne le domaine des matériaux luminescents, plus particulièrement des matériaux dits « up-conversion », capables d'émettre un rayonnement d'énergie plus élevée (de longueur d'onde plus courte) que celle du rayonnement incident. The present invention relates to the field of luminescent materials, more particularly so-called "up-conversion" materials, capable of emitting a higher energy radiation (of shorter wavelength) than that of the incident radiation.
La plupart des composés luminescents ont la particularité, lorsqu'ils sont soumis à un rayonnement d'une longueur d'onde donnée, de réémettre un second rayonnement de longueur d'onde plus élevée, donc d'énergie plus faible que celle du rayonnement incident. Most luminescent compounds have the particularity, when they are subjected to radiation of a given wavelength, to re-emit a second radiation of higher wavelength, therefore of lower energy than that of the incident radiation. .
Il a toutefois été récemment découvert des composés, appelés composés « up-conversion », capables d'émettre un rayonnement d'énergie plus élevée que le rayonnement incident. Ce phénomène, qui s'explique par des absorptions successives de plusieurs photons par un même ion ou par des absorptions par des ions différents suivies de transferts d'énergie entre lesdits ions, est extrêmement rare. Il ne se produit en effet que pour quelques ions, en particulier des ions de terres rares ou de métaux de transition, lorsque ces derniers sont dans un environnement favorable. En outre, le rendement de luminescence associé est généralement très faible car la probabilité d'occurrence du phénomène est elle-même très faible. On définit le rendement de luminescence comme le rapport entre la quantité d'énergie lumineuse émise à une longueur d'onde plus faible que la longueur d'onde d'excitation et la quantité d'énergie lumineuse absorbée par le matériau. However, compounds known as up-conversion compounds have recently been discovered capable of emitting higher energy radiation than incident radiation. This phenomenon, which is explained by successive absorptions of several photons by the same ion or by absorptions by different ions followed by energy transfers between said ions, is extremely rare. In fact, only a few ions, in particular rare earth ions or transition metal ions, occur when the ions are in a favorable environment. In addition, the associated luminescence efficiency is generally very low because the probability of occurrence of the phenomenon is itself very low. The luminescence efficiency is defined as the ratio between the amount of light energy emitted at a wavelength lower than the excitation wavelength and the amount of light energy absorbed by the material.
Le phénomène qui permet d'obtenir les plus forts rendements est appelé « addition de photons par transferts d'énergie » (APTE) ou encore « energy transfer upconversion » (ETU) . Ce phénomène met en œuvre deux ions (identiques ou différents) initialement dans un niveau
d'énergie excité et un transfert non-radiatif d'énergie entre ces deux ions. The phenomenon that makes it possible to obtain the highest yields is called "addition of photons by energy transfer" (APTE) or "energy transfer upconversion" (ETU). This phenomenon implements two ions (identical or different) initially in a level of excited energy and a non-radiative transfer of energy between these two ions.
La plupart des composés « up-conversion » sont des solides cristallisés du type oxyde ou halogénure (notamment fluorure) dopés par des ions lanthanides (aussi appelés « terres rares ») . On connaît par exemple le composé Y203 dopé par des ions Er + qui permet de convertir des rayonnements dans le domaine du proche infrarouge en rayonnements dans le domaine du visible. Parmi les composés connus figure également le fluorure d' yttrium YF3 dopé par des ions Yb3+ et Er3+ (noté YF3 :Yb3+/Er3+) . Most "up-conversion" compounds are crystalline solids of the oxide or halide type (especially fluoride) doped with lanthanide ions (also called "rare earths"). For example, the compound Y 2 0 3 doped with Er + ions is known which makes it possible to convert radiation in the near infrared range into radiation in the visible range. Among the known compounds is also yttrium fluoride YF 3 doped with ions Yb 3+ and Er 3+ (denoted YF 3 : Yb 3+ / Er 3+ ).
La demande WO 2009/056753, au nom de la présente demanderesse, décrit des oxydes présentant pour certains d'entre eux de forts rendements de luminescence : Y2BaZn05 :Er3+, La2BaZn05 :Er3+, Gd2BaZn05 :Er3+,The application WO 2009/056753, in the name of the present applicant, describes oxides having, for some of them, high luminescence yields: Y 2 BaZnO 5 : Er 3+ , La 2 BaZnO 5 : Er 3+ , Gd 2 BaZn0 5 : Er 3+ ,
Gd2BaZn05 :Yb3+/Er3+, Gd2BaZn05 :Yb3+/Tm3+. Ces composés présentent un phénomène d' up-conversion au sens où ils sont capables de convertir un rayonnement dont la longueur d'onde est située dans l'infrarouge (typiquement 975 nm) en un rayonnement visible, principalement dans les domaines du vert (environ 550 nm) et du rouge (environ 660 nm) . Le rendement de luminescence est élevé, et peut même atteindre des valeurs supérieures à 1% pour le composé Gd2BaZn05 dopé Yb3+/Er3+ contenant 1% d'erbium et 10% d' ytterbium, de formule Gdi,78 bo,2Ero,o2BaZn05. Gd 2 BaZn0 5 : Yb 3+ / Er 3+ , Gd 2 BaZn0 5 : Yb 3+ / Tm 3+ . These compounds exhibit an up-conversion phenomenon in the sense that they are capable of converting radiation whose wavelength is located in the infrared (typically 975 nm) into visible radiation, mainly in the fields of green (approximately 550 nm) and red (about 660 nm). The luminescence yield is high, and can even reach values greater than 1% for the Gd 2 BaZnO 5 compound doped with Yb 3+ / Er 3+ containing 1% of erbium and 10% of ytterbium, of formula Gdi, 78 bo, 2 Ero, o 2 BaZn0 5 .
L'invention a pour but de proposer de nouveaux composés up-conversion à base d'oxydes dont le rendement de luminescence est encore plus élevé. The object of the invention is to propose novel up-conversion compounds based on oxides whose luminescence yield is even higher.
A cet effet, l'invention a pour objet un composé cristallin de formule For this purpose, the subject of the invention is a crystalline compound of formula
Lnx. (i-ti-t2-t3-t ) bx.tiErx.t2Tmx.t3Hox.t BayZnzOi.5X+y+z dans lequel : Ln x . (i-t1-t2-t3-t) b x . t iEr x .t 2 Tm x .t 3 Ho x .t Ba y Zn z Oi.5 X + y + z in which:
Ln est ou Gd,
tl+t2+t3+t4 varie de 0,001 à 0,3, de préférence de 0,007 à 0,2, voire de 0,01 à 0,2, Ln is or Gd, t1 + t2 + t3 + t4 varies from 0.001 to 0.3, preferably from 0.007 to 0.2, or even from 0.01 to 0.2,
et tel que lorsque x=2, y=l, z=l, and such that when x = 2, y = 1, z = 1,
tl+t3+t4 est non-nul si Ln est Gd et si t3+t4 est nul, alors tl varie de tl + t3 + t4 is non-zero if Ln is Gd and if t3 + t4 is zero, then tl varies from
0,05 à 0,1 et t2 varie de 0,02 à 0,07 0.05 to 0.1 and t2 varies from 0.02 to 0.07
si Ln est Gd, alors t2+t4 est non-nul. if Ln is Gd, then t2 + t4 is non-zero.
Le composé selon l'invention est de préférence tel que x=2, y=l, z=l . Le composé est alors du type Ln2BaZn05, plus précisément du type Y2BaZn05 ou Gd2BaZnOs, chacun de ces composés étant dopé par au moins un, voire deux, trois ou même quatre ions de terre rare, Er3+, Yb3+, Tm3+ ou Ho3+. The compound according to the invention is preferably such that x = 2, y = 1, z = 1. The compound is then of the Ln 2 BaZnO 5 type , more precisely of the Y 2 BaZnO 5 or Gd 2 BaZnOs type, each of these compounds being doped with at least one or even two, three or even four rare earth ions, Er 3+. , Yb 3+ , Tm 3+ or Ho 3+ .
D'autres combinaisons sont également possibles, parmi lesquelles x=8, y=5, z=4 (composé du type Ln8Ba5Zn402i) ou x=2, y=2, z=8 (composé du type Ln2Ba2Zn80i3 ) . Other combinations are also possible, among which x = 8, y = 5, z = 4 (compound of the type Ln 8 Ba 5 Zn 4 0 2 i) or x = 2, y = 2, z = 8 (compound of type Ln 2 Ba 2 Zn 8 0i 3 ).
Ces composés du type LnxBayZnzOi.5x+y+z sont avantageux, notamment au regard des fluorures tels que par exemple NaYF , car l'apparition du phénomène d' up-conversion se manifeste pour des densités de puissance beaucoup plus faibles, typiquement de l'ordre de 10 mW/mm2 , voire moins. Dans certains cas, des densités de puissance de seulement 0,2 mW/mm2 se sont révélées suffisantes. These compounds of the type Ln x Ba y Zn z Oi. 5x + y + z are advantageous, especially with regard to fluorides such as for example NaYF, because the appearance of the up-conversion phenomenon is manifested for much lower power densities, typically of the order of 10 mW / mm 2 or less. In some cases, power densities of only 0.2 mW / mm 2 have been found to be sufficient.
Dans les structures cristallines des composés selon l'invention, l'ion dopant (Yb3+, Er3+, Tm3+, Ho3+) se substitue partiellement à l'ion Ln3+ (Y3+, Gd3+) . Les paramètres tl à t4 correspondent à la fraction molaire d'ion Ln3+ substituée par l'ion dopant correspondant. Ces paramètres sont aussi appelés « teneurs » ou « concentrations » en ions dopants. In the crystalline structures of the compounds according to the invention, the doping ion (Yb 3+ , Er 3+ , Tm 3+ , Ho 3+ ) partially replaces the Ln 3+ ion (Y 3+ , Gd 3+ ). The parameters t1 to t4 correspond to the molar fraction of Ln 3+ ion substituted by the corresponding doping ion. These parameters are also called "contents" or "concentrations" of doping ions.
Ln est choisi parmi Y et Gd, car ces ions permettent d'obtenir les plus forts rendements de luminescence. Ln est de préférence Y, car cet élément s'est révélé apte à obtenir des composés mieux cristallisés pour un temps de
synthèse équivalent. Le composé selon l'invention est donc de préférence du type Gd2BaZn05, et mieux encore Y2BaZn05. Ln is chosen from Y and Gd, because these ions make it possible to obtain the highest luminescence yields. Ln is preferably Y, because this element has proved to be capable of obtaining better crystallized compounds for a time of equivalent synthesis. The compound according to the invention is therefore preferably of the type Gd 2 BaZnO 5 , and more preferably Y 2 BaZnO 5 .
De préférence, tl+t2+t3 est supérieur ou égal à 0,05 et/ou tl+t4 est supérieur ou égal à 0,05. Preferably, t1 + t2 + t3 is greater than or equal to 0.05 and / or t1 + t4 is greater than or equal to 0.05.
Le composé selon l'invention contient de préférence l'ion Yb3+, qui présente une section efficace d'absorption vers 980 nm environ dix fois plus élevée que celle des ions erbium, thulium ou holmium. Le paramètre tl est donc avantageusement supérieur ou égal à 0,01, voire à 0,05. De tels composés présentent une absorption dans l'infrarouge dans une gamme de longueurs d'onde relativement large, entre 890 et 1100 nm, préférentiellement entre 970 et 980 nm. C'est particulièrement le cas pour les composés tels que x=2, y=l et z=l. The compound according to the invention preferably contains the Yb 3+ ion, which has an absorption cross section around 980 nm approximately ten times higher than that of erbium, thulium or holmium ions. The parameter t1 is therefore advantageously greater than or equal to 0.01, or even to 0.05. Such compounds have an infrared absorption over a relatively wide wavelength range, between 890 and 1100 nm, preferably between 970 and 980 nm. This is particularly the case for compounds such that x = 2, y = 1 and z = 1.
Une première famille de composés préférés est telle que, notamment lorsque x=2, y=l, z=l: A first family of preferred compounds is such that, especially when x = 2, y = 1, z = 1:
Ln est de préférence Y, Ln is preferably Y,
- t3+t4 est nul t3 + t4 is zero
tl varie de 0,05 à 0,1, de préférence de 0,07 à 0,09 - t2 varie de 0,02 à 0,07, de préférence de 0,03 à 0,04. It varies from 0.05 to 0.1, preferably from 0.07 to 0.09, and varies from 0.02 to 0.07, preferably from 0.03 to 0.04.
Ces composés sont notamment du type Y2BaZn05 et Gd2BaZn05 co-dopés avec des ions Er3+ et Yb3+, et présentent, grâce au choix spécifique des concentrations en erbium et ytterbium, des rendements de luminescence bien plus élevés que les composés connus de la demande WO 2009/056753 susmentionnée. Des composés particulièrement efficaces ont la formule suivante : Yi, 8Yb0, i Er0, osBaZnOs etThese compounds are in particular of the Y 2 BaZnO 5 and Gd 2 BaZnO 5 type co-doped with Er 3+ and Yb 3+ ions, and have, thanks to the specific choice of the erbium and ytterbium concentrations, much higher luminescence yields. that the known compounds of the aforementioned WO 2009/056753 application. Particularly effective compounds have the following formula: Y 1 , 8 Yb 0 , i Er 0 , osBaZnOs and
Gdi,8Ybo,i4Ero,o6BaZn05 (tl=0,07 et t2=0,03). Gdi, 8 Ybo, i4Ero, o6BaZn0 5 (tl = t2 = 0.07 and 0.03).
Excités par un rayonnement infrarouge (entre 890 et 1100 nm, et surtout autour de 975 nm de longueur d'onde), les composés de cette famille émettent de manière très intense dans le vert (autour de 550 nm) et dans le rouge (autour de 670 nm) . Ces composés présentent également des phénomènes d' up-conversion lorsqu'ils sont excités dans
d'autres gammes de longueurs d'onde. Par exemple, une excitation dans le rouge (vers 660 nm) permet d'obtenir une luminescence dans le vert (autour de 550 nm) et dans l'ultraviolet. Une excitation dans le proche infrarouge (autour de 800 nm) permet d'obtenir une émission dans le rouge (autour de 670 nm) et le vert (autour de 550 nm) . Les rendements observés sont toutefois plus faibles que ceux obtenus par irradiation dans l'infrarouge. Excited by infrared radiation (between 890 and 1100 nm, and especially around 975 nm wavelength), the compounds of this family emit very intensively in the green (around 550 nm) and in the red (around 670 nm). These compounds also exhibit up-conversion phenomena when they are excited in other ranges of wavelengths. For example, excitation in the red (around 660 nm) gives a luminescence in the green (around 550 nm) and in the ultraviolet. An excitation in the near infrared (around 800 nm) makes it possible to obtain an emission in the red (around 670 nm) and the green (around 550 nm). The yields observed are, however, lower than those obtained by irradiation in the infrared.
Les gammes de dopage indiquées permettent d' atteindre des rendements de luminescence extrêmement élevés, au-delà de 3%, et même 5%. L'augmentation de la teneur en Yb3+ permet d'accentuer la composante rouge au détriment de la composante verte. The indicated doping ranges make it possible to reach extremely high luminescence yields, above 3%, and even 5%. The increase in the Yb 3+ content makes it possible to accentuate the red component to the detriment of the green component.
Une deuxième famille de composés préférés est telle que, notamment lorsque x=2, y=l, z=l: A second family of preferred compounds is such that, especially when x = 2, y = 1, z = 1:
- Ln est Y - Ln is Y
- t2+t4 est nul t2 + t4 is zero
tl et t3 sont non-nuls. tl and t3 are non-zero.
tl varie de préférence de 0,03 à 0,2, notamment de 0,05 à 0,2, voire de 0,05 à 0,1 et t3 varie de préférence de 0,001 à 0,05, notamment de 0,001 à 0,01, voire de 0,001 à 0, 005. tl preferably varies from 0.03 to 0.2, in particular from 0.05 to 0.2, or even from 0.05 to 0.1, and t3 preferably varies from 0.001 to 0.05, in particular from 0.001 to 0, 01, or even 0.001 to 0.005.
Ces composés sont notamment du type Y2Ba Z n05 co-dopé avec des ions Yb3+ et Tm3+. Des composés particulièrement efficaces présentent les formules suivantes : Yi,78Y 0 , 2 m0 , 02Ba ZnO5 (tl=0,l et t3=0,01) ouThese compounds are in particular of the type Y 2 Ba Z n0 5 co-doped with ions Yb 3+ and Tm 3+ . Particularly effective compounds have the following formulas: Yi, 78 Y 0 , 2 m 0 , 02Ba ZnO 5 (t1 = 0, 1 and t3 = 0.01) or
Y1, 875Ybo , i2 Tm0 r 0 o5Ba Zn05 (tl=0,06 et t3=0, 0025) . Y 1, 875 Ybo, i Tm 2 0 r 0 o 5 Zn0 Ba 5 (t = 0.06, and t3 = 0, 0025).
Excités par un rayonnement infrarouge (dans la gamme 890-1100 nm, et plus particulièrement autour de 975 nm) , les composés de cette famille émettent vers 800 nm (infrarouge), 650 nm (rouge) et 480 nm (bleu), avec un rendement de luminescence dépassant 1%. La coloration perçue à l'œil est bleue. Ces composés présentent également des phénomènes d' up-conversion lorsqu'ils sont excités dans
d'autres gammes de longueurs d'onde. Par exemple, une excitation dans le proche infrarouge (autour de 800 nm) permet d'obtenir une émission dans le rouge (autour de 650 nm) et le bleu (autour de 480 nm) . Les rendements observés sont toutefois plus faibles que ceux obtenus par irradiation dans l'infrarouge. Excited by infrared radiation (in the range 890-1100 nm, and more particularly around 975 nm), the compounds of this family emit at 800 nm (infrared), 650 nm (red) and 480 nm (blue), with luminescence efficiency exceeding 1%. The color perceived with the eye is blue. These compounds also exhibit up-conversion phenomena when they are excited in other ranges of wavelengths. For example, near-infrared excitation (around 800 nm) produces emission in the red (around 650 nm) and blue (around 480 nm). The yields observed are, however, lower than those obtained by irradiation in the infrared.
Outre un rendement plus élevé, le choix de Y par rapport à Gd permet d'obtenir des composés mieux cristallisés pour un temps de synthèse équivalent. In addition to a higher yield, the choice of Y with respect to Gd makes it possible to obtain better crystallized compounds for an equivalent synthesis time.
A teneur en Yb3+ constante (par exemple telle que tl=0,l), le rapport d'intensité entre l'émission dans le bleu et l'émission infrarouge diminue lorsque la teneur en Tm3+ augmente. At a constant Yb 3+ content (e.g., such that tl = 0.1), the intensity ratio between blue emission and infrared emission decreases as the Tm 3+ content increases.
Une troisième famille de composés préférés est telle que, notamment lorsque x=2, y=l, z=l: A third family of preferred compounds is such that, especially when x = 2, y = 1, z = 1:
- t2+t3=0 - t2 + t3 = 0
tl et t4 sont non-nuls. tl and t4 are non-zero.
Ces composés sont notamment du type Y2BaZn05 ou Gd2BaZn05 co-dopés avec des ions Yb3+ et Ho3+. These compounds are in particular of the Y 2 BaZnO 5 or Gd 2 BaZnO 5 type co-doped with Yb 3+ and Ho 3+ ions.
Excités par un rayonnement infrarouge (entre 890 et Excited by infrared radiation (between 890 and
1100 nm, et plus particulièrement autour de 975 nm) , les composés de cette famille émettent fortement vers 550 nm (vert), et plus faiblement vers 660 nm et 760 nm (rouge et proche infrarouge) , avec un rendement de luminescence pouvant dépasser 2%. La coloration perçue à l'œil est d'un vert très brillant. Ces composés présentent également des phénomènes d' up-conversion lorsqu'ils sont excités dans d'autres gammes de longueurs d'onde. Par exemple, une excitation dans le rouge (vers 660 nm) permet aussi d'obtenir une luminescence dans le vert (autour de 550 nm) . Une excitation dans le proche infrarouge (autour de 800 nm) permet d'obtenir une émission dans le rouge et le vert. Les rendements observés sont toutefois plus faibles que ceux obtenus par irradiation dans l'infrarouge.
Les plus forts rendements de luminescence sont obtenus, notamment pour des composés de formule Y2BaZn05 et Gd2BaZn05 co-dopés avec des ions Yb3+ et Ho3+, lorsque tl varie de 0,06 à 0,12 et t4 varie de 0,001 à 0,02, notamment de 0,003 à 0,012. Les composés de formule Yi,85Ybo,i Hoo,0iBaZn05 (tl=0,07 et t4=0, 005) ou1100 nm, and more particularly around 975 nm), the compounds of this family emit strongly around 550 nm (green), and more weakly around 660 nm and 760 nm (red and near infrared), with a luminescence yield that can exceed 2 %. The coloration perceived with the eye is of a very brilliant green. These compounds also exhibit up-conversion phenomena when they are excited in other wavelength ranges. For example, excitation in the red (around 660 nm) also makes it possible to obtain luminescence in the green (around 550 nm). An excitation in the near infrared (around 800 nm) makes it possible to obtain an emission in red and green. The yields observed are, however, lower than those obtained by irradiation in the infrared. The highest luminescence yields are obtained, in particular for compounds of formula Y 2 BaZnO 5 and Gd 2 BaZnO 5 co-doped with ions Yb 3+ and Ho 3+ , when tl varies from 0.06 to 0.12 and t4 ranges from 0.001 to 0.02, especially from 0.003 to 0.012. Compounds of formula Y 1, 85 Ybo, H 0 , 0 iBaZnO 5 (t 1 = 0.07 and t 4 = 0.005) or
Yi,8iYbo,i8Hoo,0iBaZn05 (tl=0,09 et t4=0, 005) présentent un rendement de luminescence supérieur à 2%. Yi, 8iYbo, 18Hoo, 0 iBaZn0 5 (t1 = 0.09 and t4 = 0.005) have a luminescence efficiency greater than 2%.
Une quatrième famille de composés préférés est telle que, notamment lorsque x=2 , y=l, z=l, tl, t2 et t3 sont non-nuls. t4 peut être nul ou non-nul, de préférence nul. A fourth family of preferred compounds is such that, especially when x = 2, y = 1, z = 1, t1, t2 and t3 are non-zero. t4 may be zero or non-zero, preferably zero.
Ces composés sont notamment du type Y2BaZn05ou Gd2BaZn05, co-dopés avec au moins trois ions : Yb3+, Er3+ et Tm3+. L'ion Ho3+ peut également être ajouté à ces composés. Ici encore, le choix de Y est préféré. These compounds are in particular of the Y 2 BaZnO 5 or Gd 2 BaZnO 5 type , co-doped with at least three ions: Yb 3+ , Er 3+ and Tm 3+ . The Ho 3+ ion can also be added to these compounds. Here again, the choice of Y is preferred.
Ces composés émettent à la fois dans le vert (grâce à l'ion Er3+, et optionnellement à l'ion Ho3+) , le rouge (grâce à l'ion Er3+) et le bleu (grâce à l'ion Tm3+) . Les différentes composantes (rouge, vert, bleu) peuvent être réglées par la teneur en dopants afin d' obtenir toute couleur désirée. Un bon mélange des trois couleurs d'émission permet d'émettre de la lumière blanche. Une lumière blanche est typiquement obtenue pour tl=0,l, t3=0,01 et t2 entre 0,002 et 0,005. These compounds emit both green (thanks to the Er 3+ ion, and optionally the Ho 3+ ion), red (thanks to the Er 3+ ion) and blue (thanks to the Tm 3+ ion). The different components (red, green, blue) can be adjusted by the dopant content to obtain any desired color. A good mix of the three emission colors makes it possible to emit white light. White light is typically obtained at tl = 0.1, t3 = 0.01 and t2 between 0.002 and 0.005.
Un mélange de composés du type Ln2BaZn05 :Yb3+/Er3+ etA mixture of compounds of the type Ln 2 BaZn0 5 : Yb 3+ / Er 3+ and
Ln2BaZn05 :Yb3+/Tm3+, avec ou sans ajout de composés du type Ln2BaZn05 :Yb3+/Ho3+ permet également d'obtenir toute couleur désirée, et notamment une émission de lumière blanche, sous irradiation dans l'infrarouge (dans la gamme 890-1100 nm, et plus particulièrement autour de 975 nm) . L'invention a donc aussi pour objet un mélange d'au moins deux composés différents selon l'invention. En particulier un mélange de deux composés différents ou de trois composés différents est préféré. Parmi les mélanges préférés figurent les mélanges suivants :
un mélange comprenant (ou consistant en) un premier composé de la première famille préférée (t3+t4=0, tl et t2 non-nuls, notamment Y2BaZn05 :Yb3+/Er3+) et un deuxième composé de la deuxième famille préférée (t2+t4=0, tl et t3 non nuls, notammentLn 2 BaZn0 5 : Yb 3+ / Tm 3+ , with or without addition of compounds of the type Ln 2 BaZn0 5 : Yb 3+ / Ho 3+ also makes it possible to obtain any desired color, and in particular a white light emission, under irradiation in the infrared (in the range 890-1100 nm, and more particularly around 975 nm). The invention therefore also relates to a mixture of at least two different compounds according to the invention. In particular, a mixture of two different compounds or of three different compounds is preferred. Among the preferred mixtures are the following mixtures: a mixture comprising (or consisting of) a first compound of the first preferred family (t3 + t4 = 0, t1 and t2 non-zero, in particular Y 2 BaZnO 5 : Yb 3+ / Er 3+ ) and a second compound of the second preferred family (t2 + t4 = 0, t1 and t3 non-zero, in particular
Y2BaZn05 : Yb3+/Tm3+) , Y 2 BaZnO 5 : Yb 3+ / Tm 3+ ),
un mélange comprenant (ou consistant en) un premier composé de la première famille préférée (t3+t4=0, tl et t2 non-nuls, notamment Y2BaZn05 :Yb3+/Er3+), un deuxième composé de la deuxième famille préféréea mixture comprising (or consisting of) a first compound of the first preferred family (t3 + t4 = 0, t1 and t2 non-zero, in particular Y 2 BaZnO 5 : Yb 3+ / Er 3+ ), a second compound of the second favorite family
(t2+t4=0, tl et t3 non-nuls, notamment(t2 + t4 = 0, t1 and t3 non-zero, in particular
Y2BaZn05 :Yb3+/Tm3+) et un troisième composé de la troisième famille préférée (t2+t3=0, tl et t4 non- nuls, notamment Y2BaZn05 : Yb3+/Ho3+) . Y 2 BaZnO 5 : Yb 3+ / Tm 3+ ) and a third compound of the third preferred family (t2 + t3 = 0, t1 and t4 non-zero, in particular Y 2 BaZn0 5 : Yb 3+ / Ho 3+ ) .
Dans le cas du premier mélange préféré, une lumière blanche est typiquement obtenue pour une masse de deuxième composé 20 à 35 fois (notamment 25 à 30 fois) plus élevée que la masse du premier composé. In the case of the first preferred mixture, a white light is typically obtained for a second compound mass 20 to 35 times (especially 25 to 30 times) higher than the mass of the first compound.
L'invention a également pour objet les procédés d'obtention des composés selon l'invention. The subject of the invention is also the processes for obtaining the compounds according to the invention.
Ces composés peuvent être obtenus par un procédé en phase solide, c'est-à-dire un procédé comprenant les étapes consistant à mélanger des poudres, typiquement des poudres d'oxydes ou de carbonates, à broyer le mélange, éventuellement à le presser pour former une pastille, puis à chauffer le mélange de manière à faire réagir chimiquement les poudres entre elles. Les poudres sont par exemple Gd203, Y203, Yb203, Er203, Tm203, Ho203, ZnO, BaC03. These compounds can be obtained by a solid phase process, that is to say a process comprising the steps of mixing powders, typically oxides or carbonates powders, to grind the mixture, optionally to press it for forming a pellet and then heating the mixture so as to chemically react the powders together. The powders are, for example, Gd 2 O 3 , Y 2 O 3 , Yb 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , ZnO, BaCO 3 .
Des nanoparticules peuvent être obtenues en broyant les poudres obtenues, par exemple par une technique de broyage à boulets. Nanoparticles can be obtained by grinding the powders obtained, for example by a ball milling technique.
Les composés selon l'invention peuvent également être obtenus par un procédé du type sol-gel, comprenant les étapes consistant à dissoudre des précurseurs (typiquement des nitrates, acétates, ou encore carbonates) dans l'eau ou
dans un solvant majoritairement aqueux, à ajouter un agent complexant (typiquement un acide α-hydroxycarboxylique tel que l'acide citrique) et éventuellement un agent réticulant (typiquement un polyhydroxyalcool tel que 1 ' éthylèneglycol ) de manière à obtenir un gel, puis à chauffer le gel obtenu, normalement à une température d'au moins 1000 °C. Par rapport au procédé en phase solide, le procédé sol-gel permet généralement d'obtenir une meilleure homogénéité. Le chauffage à au moins 1000°C permet de s'affranchir des inconvénients liés à ce procédé, notamment une teneur en impuretés plus élevée (C02, eau...) qui engendre une probabilité d'occurrence de défauts structurels plus élevée . The compounds according to the invention can also be obtained by a sol-gel type process, comprising the steps of dissolving precursors (typically nitrates, acetates, or even carbonates) in water or in a predominantly aqueous solvent, to add a complexing agent (typically an α-hydroxycarboxylic acid such as citric acid) and optionally a crosslinking agent (typically a polyhydroxy alcohol such as ethylene glycol) so as to obtain a gel and then to heat the gel obtained, normally at a temperature of at least 1000 ° C. Compared with the solid phase process, the sol-gel method generally makes it possible to obtain a better homogeneity. Heating at least 1000 ° C overcomes the disadvantages associated with this process, including a higher content of impurities (C0 2 , water ...) which generates a probability of occurrence of structural defects higher.
L'invention a également pour objet l'utilisation des composés selon l'invention pour convertir un rayonnement infrarouge en un rayonnement visible, notamment pour convertir un rayonnement de longueur d'onde comprise dans la gamme allant de 890 à 1100 nm, notamment d'environ 975 nm, en un rayonnement de longueur d'onde d'environ 550 nm et/ou 660 nm et/ou 480 nm et/ou 800 nm. The subject of the invention is also the use of the compounds according to the invention for converting infrared radiation into visible radiation, in particular for converting radiation of wavelength in the range from 890 to 1100 nm, especially for about 975 nm, in wavelength radiation of about 550 nm and / or 660 nm and / or 480 nm and / or 800 nm.
Ce phénomène d' up-conversion, qui convertit un rayonnement infrarouge en rayonnement visible (bleu, vert, rouge, ou tout type de couleurs, notamment du blanc, en mélangeant plusieurs composés différents ou en dopant un composé avec trois dopants différents) peut être mis à profit dans de nombreuses applications, en particulier dans les domaines de l'affichage, de l'imagerie (notamment médicale), des lasers, de la production d'énergie photovoltaique, de la lutte contre la contrefaçon ou de l'identification. This up-conversion phenomenon, which converts infrared radiation into visible radiation (blue, green, red, or any type of color, especially white, by mixing several different compounds or by doping a compound with three different dopants) can be used in many applications, particularly in the areas of display, imaging (including medical), lasers, photovoltaic energy production, the fight against counterfeiting or identification.
Dans le domaine des lasers, les composés selon l'invention peuvent convertir un rayonnement laser infrarouge (vers 980 nm par exemple) en rayonnement laser vert, bleu, rouge, ou de toute couleur désirée. Ils peuvent avantageusement remplacer les composés doubleurs de
fréquence actuellement employés, qui sont basés sur les phénomènes de génération de seconde harmonique. In the field of lasers, the compounds according to the invention can convert infrared laser radiation (around 980 nm for example) into green, blue or red laser radiation, or of any desired color. They can advantageously replace the doubling compounds of frequency currently employed, which are based on second harmonic generation phenomena.
Dans le domaine de l'imagerie médicale, les composés selon l'invention peuvent servir de marqueurs luminescents dans des techniques d'imagerie de fluorescence. L'avantage par rapport aux méthodes existantes réside dans la possibilité d'employer une source lumineuse d'excitation émettant dans l'infrarouge, et non dans l'ultraviolet, car le rayonnement ultraviolet est susceptible de créer des lésions au niveau des tissus et génère un bruit de fond indésirable lié à la fluorescence endogène des tissus biologiques . In the field of medical imaging, the compounds according to the invention can serve as luminescent markers in fluorescence imaging techniques. The advantage over existing methods lies in the possibility of using an excitation light source emitting in the infrared, and not in the ultraviolet, because the ultraviolet radiation is capable of creating lesions in the tissues and generates an unwanted background related to the endogenous fluorescence of biological tissues.
Les composés selon l'invention peuvent être incorporés à des revêtements déposés sur des substrats quelconques. Ces substrats revêtus peuvent avantageusement être utilisés dans les domaines de la production d'énergie photovoltaïque et de l'affichage. L'invention a donc aussi pour objet un substrat revêtu sur au moins une partie d'au moins une de ses faces d'un revêtement incorporant au moins un composé selon l'invention et un dispositif d'affichage ou un dispositif de production d'énergie photovoltaïque comprenant au moins un tel substrat revêtu. The compounds according to the invention can be incorporated into coatings deposited on any substrates. These coated substrates can advantageously be used in the fields of photovoltaic power generation and display. The subject of the invention is therefore a substrate coated on at least a part of at least one of its faces with a coating incorporating at least one compound according to the invention and a display device or a device for the production of photovoltaic energy comprising at least one such coated substrate.
Selon les applications visées, le substrat peut être transparent, opaque, ou encore translucide. Il peut s'agir d'un substrat organique, métallique, minéral, par exemple du type verre, céramique, vitrocéramique, comprenant un liant hydraulique (plâtre, ciment, chaux...) . Le substrat peut être plan ou bombé. Depending on the targeted applications, the substrate may be transparent, opaque, or even translucent. It may be an organic substrate, metallic, mineral, for example of the glass, ceramic, glass-ceramic type, comprising a hydraulic binder (plaster, cement, lime ...). The substrate may be flat or curved.
Les composés selon l'invention peuvent être incorporés dans le revêtement par différentes techniques. La couche mince peut notamment comprendre les composés selon l'invention au sein d'un liant. Ce liant peut notamment être de nature organique (par exemple du type encre, peinture, laque, vernis) ou minérale (par exemple une glaçure, un émail, un liant de type sol-gel) . En fonction de la nature du liant, différentes méthodes de mise en
forme sont possibles : dépôt par pulvérisation, au rideau, par enduction, chiffonnage, sérigraphie, pistolettage etc.. Le revêtement peut également être constitué d'au moins un composé selon l'invention, et peut être déposé par diverses techniques de CVD (dépôt chimique en phase vapeur) ou PVD (notamment la pulvérisation cathodique) . The compounds according to the invention can be incorporated into the coating by various techniques. The thin layer may in particular comprise the compounds according to the invention within a binder. This binder can in particular be of an organic nature (for example of the ink, paint, lacquer, varnish type) or mineral (for example a glaze, an enamel, a sol-gel type binder). Depending on the nature of the binder, different methods of form are possible: sputter deposition, curtain, coating, scouring, screen printing, spray gunsing etc. The coating may also consist of at least one compound according to the invention, and may be deposited by various CVD techniques (deposit chemical vapor phase) or PVD (especially sputtering).
Un substrat en verre clair revêtu sur une de ses faces par un revêtement incorporant au moins un composé selon 1' invention peut par exemple être utilisé comme substrat de face avant d'une cellule photovoltaïque . On entend par substrat de face avant le substrat traversé en premier par le rayonnement solaire. Un substrat revêtu sur une de ses faces par un revêtement incorporant au moins un composé selon l'invention peut alternativement ou cumulativement être utilisé comme substrat de face arrière d'une cellule photovoltaïque, éventuellement associé à un dispositif assurant une réflexion (diffuse ou spéculaire) vers le matériau photovoltaïque. Quelle que soit la configuration, la présence des composés selon l'invention permet de convertir une partie du rayonnement infrarouge en rayonnement visible, à des longueurs d'onde où l'efficacité quantique du matériau photovoltaïque est plus élevée. Par exemple l'efficacité quantique maximale se situe vers 640 nm pour du tellure de cadmium, 540 nm pour du silicium amorphe et 710 nm pour du silicium microcristallin. A clear glass substrate coated on one of its faces with a coating incorporating at least one compound according to the invention may for example be used as a front-face substrate of a photovoltaic cell. The term "front-face substrate" is intended to mean the substrate traversed first by solar radiation. A substrate coated on one of its faces with a coating incorporating at least one compound according to the invention may alternatively or cumulatively be used as a backside substrate of a photovoltaic cell, possibly associated with a device providing reflection (diffuse or specular) towards the photovoltaic material. Whatever the configuration, the presence of the compounds according to the invention makes it possible to convert part of the infrared radiation into visible radiation at wavelengths in which the quantum efficiency of the photovoltaic material is higher. For example, the maximum quantum efficiency is around 640 nm for cadmium telluride, 540 nm for amorphous silicon and 710 nm for microcrystalline silicon.
Un substrat revêtu sur une de ses faces par un revêtement incorporant au moins un composé selon l'invention peut aussi être utilisé dans un dispositif d'affichage, l'irradiation sélective par un laser infrarouge permettant de faire apparaître de la lumière visible, de différentes couleurs. Le dispositif d'affichage peut a titre d'exemple être un écran ou un dispositif « d'affichage tête haute » (HUD) utilisé par exemple dans des véhicules de transport, terrestre, aérien, ferroviaire ou maritime. Le substrat revêtu selon l'invention peut donc être un vitrage, par exemple un pare-brise de véhicule, ou
être incorporé à un tel vitrage. Certains systèmes actuellement commercialisés mettent en œuvre des composés fluorescents incorporés à des pare-brise feuilletés (ils sont généralement déposés sur ou au sein de l'intercalaire de feuilletage) , qui émettent un rayonnement visible lorsqu'ils sont irradiés par un laser émettant dans l'ultraviolet. Les composés selon l'invention peuvent avantageusement remplacer ces composés fluorescents, ce qui permet d'utiliser un laser émettant dans l'infrarouge, par exemple une diode laser, nettement moins onéreuse et dangereuse qu'un laser émettant dans l'ultraviolet. A substrate coated on one of its faces with a coating incorporating at least one compound according to the invention may also be used in a display device, the selective irradiation by an infrared laser making it possible to reveal visible light, of different colors. The display device may for example be a screen or a "head-up display" (HUD) device used for example in transport vehicles, land, air, rail or sea. The coated substrate according to the invention can therefore be glazing, for example a vehicle windshield, or to be incorporated in such a glazing. Some currently marketed systems use fluorescent compounds incorporated in laminated windshields (they are generally deposited on or within the lamination interlayer), which emit visible radiation when irradiated by a laser emitting in the laminated windshield. 'ultraviolet. The compounds according to the invention can advantageously replace these fluorescent compounds, which makes it possible to use a laser emitting in the infrared, for example a laser diode, which is considerably less expensive and dangerous than a laser emitting in the ultraviolet.
L'invention sera mieux comprise à la lecture des exemples qui suivent, illustrés par les Figures 1 à 8. The invention will be better understood on reading the examples which follow, illustrated by FIGS. 1 to 8.
La Figure 1 est un spectre d'émission typique d'un composé de type Y2 a-ti-t2) Yb2tiEr2t2BaZn05 lorsqu'il est irradié par un rayonnement d'environ 975 nm de longueur d'onde. Figure 1 is a typical emission spectrum of a compound of the type Y 2 a-ti-t 2 ) Yb 2t iEr 2t 2 BaZnO 5 when irradiated with radiation of about 975 nm wavelength.
La Figure 2 superpose plusieurs spectres d'émission de composés du type Y2 a-ti-t2) Yb2tiEr2t2BaZn05, pour une teneur tl+t2 constante, avec une teneur t2 variant de 0,03 à 0,08. Figure 2 superimposes several emission spectra of compounds Y 2 a-ti-t2) Yb2tiEr 2t2 BaZn0 5 , for a content tl + t2 constant, with a content t2 ranging from 0.03 to 0.08.
La Figure 3 est une cartographie présentant le rendement de luminescence obtenu pour des composés du type Y2 (i_ti_t2) Yb2tiEr2t2BaZn05 en fonction des concentrations en Yb3+ (tl) et Er3+ (t2) . Figure 3 is a map showing the luminescence yield obtained for compounds Y 2 ( i_ti_t2 ) Yb 2t iEr 2t2 BaZn0 5 as a function of the concentrations of Yb 3+ (tl) and Er 3+ (t2).
La Figure 4 est une courbe expérimentale présentant en ordonnée le rapport d'intensité rouge/vert par rapport à la durée d'impulsion du laser. Figure 4 is an experimental curve showing the ordinate the red / green intensity ratio with respect to the pulse duration of the laser.
La Figure 5 est un spectre d'émission typique d'un composé de type Y2 (i-ti-t3> Yb2tiTm2t3BaZn05 lorsqu'il est irradié par un rayonnement infrarouge d'environ 975 nm de longueur d' onde . Figure 5 is a typical emission spectrum of a Y 2 compound (i-t 1 -t 3 > Yb 2 tiTm 2t 3 BaZnO 5 when irradiated with infrared radiation of about 975 nm wavelength .
Les Figures 6a et 6b sont des cartographies présentant le rendement de luminescence obtenu pour des composés du type Y2 (i-ti-t3) Yb2tiTm2t3BaZn05 en fonction des concentrations en Yb + (tl) et Tm3+ (t3) dans la gamme d'émission allant de 420 à 870 nm (Figure 6a) et de 420 à 530 nm (Figure 6b) .
La Figure 7 est un spectre d'émission typique d'un composé de type Y2 (i-ti-t4> Yb2tiHo2t4BaZn05 lorsqu'il est irradié par un rayonnement infrarouge d'environ 975 nm de longueur d' onde . Figures 6a and 6b are mappings showing the luminescence yield obtained for Y 2 ( i-t 1 -t 3 ) Yb 2 tiTm 2t 3 BaZnO 5 compounds as a function of the concentrations of Yb + (tl) and Tm 3+ (t3). ) in the emission range of 420 to 870 nm (Figure 6a) and 420 to 530 nm (Figure 6b). Figure 7 is a typical emission spectrum of a compound of type Y 2 (i-ti-t4> Yb 2t iHo 2T4 BaZn0 5 when irradiated by infrared radiation of about 975 nm wavelength .
La Figure 8 est une cartographie présentant le rendement de luminescence obtenu pour des composés du type Y2(i-ti-t4) Yb2tiHo2 t 4BaZ n05 en fonction des concentrations en Yb3+ (tl) et Ho3+ (t4) . Figure 8 is a map showing the luminescence yield obtained for compounds of the type Y 2 (i- t i -t4) Yb 2t iHo 2 t 4 BaZ n0 5 as a function of the concentrations of Yb 3+ (tl) and Ho 3 + (t4).
La Figure 9 un spectre d'émission typique d'un composé de formule Yi, 8Ybo,i4Er0 , o6BaZ n05 incorporé dans un revêtement déposé sur un substrat de verre, lorsqu'il est irradié par un rayonnement infrarouge d'environ 975 nm de longueur d' onde . Figure 9 a typical emission spectrum of a compound of formula Yi, 8 Ybo, Er i 4 0 o 6 BaZ n0 5 incorporated in a coating deposited on a glass substrate when irradiated with infrared radiation about 975 nm wavelength.
Pour tous les exemples, le phénomène d' up-conversion est caractérisé par la détermination, à l'aide d'un spectrophotomètre , du spectre d'émission du composé lorsqu'il est soumis à un rayonnement cohérent dont la longueur d'onde est autour de 975 nm. For all the examples, the phenomenon of up-conversion is characterized by the determination, using a spectrophotometer, of the emission spectrum of the compound when it is subjected to a coherent radiation whose wavelength is around 975 nm.
Plus précisément, les composés sont broyés et la poudre obtenue est maintenue entre deux plaques de quartz. Les échantillons sont excités à l'aide d'une diode laser continue (Thorlabs, L980P100 et TCLDM9) pilotée par un contrôleur laser ( ILX-Lightwave LDC-3742), puisée à l'aide d'un générateur de fonction (Agilent Hewlett Packard 33120A) ou une source de courant puisé (ILX Lightwave LDP- 3811) . L'émission dans le visible est enregistrée à l'aide d'un dispositif conventionnel comprenant un monochromateur et détectée à l'aide d'une photodiode au silicium (Newport Si 818-UV) . More precisely, the compounds are ground and the powder obtained is held between two quartz plates. Samples are excited using a continuous laser diode (Thorlabs, L980P100 and TCLDM9) driven by a laser controller (ILX-Lightwave LDC-3742), pulsed using a function generator (Agilent Hewlett Packard 33120A) or a pulsed power source (ILX Lightwave LDP-3811). The emission in the visible is recorded using a conventional device comprising a monochromator and detected using a silicon photodiode (Newport Si 818-UV).
Le phénomène de luminescence up-conversion est également caractérisé par détermination du rendement de luminescence . The up-conversion luminescence phenomenon is also characterized by determining the luminescence efficiency.
Pour ce faire, un rayonnement issu d'une diode laser, de longueur d'onde centrée autour de 977 nm, est focalisé et amené à traverser l'échantillon. L'intensité émise par
l'échantillon est alors mesurée à l'aide d'une sphère intégrante, et ramenée à l'intensité absorbée par 1' échantillon . To do this, radiation from a laser diode, wavelength centered around 977 nm, is focused and passed through the sample. The intensity emitted by the sample is then measured using an integrating sphere, and reduced to the intensity absorbed by the sample.
Plus précisément, les composés sont broyés et la poudre obtenue est maintenue dans un porte-échantillon composé de deux plaques de quartz, dont l'une est revêtue d'une couche réfléchissante en aluminium. Le porte- échantillon est ensuite placé sur la face arrière d'une sphère intégrante (Instruments Systems, ISP-150-100) . Le signal d'excitation est focalisé au centre de l'échantillon à l'aide d'une lentille. La mesure est réalisée en deux étapes. Dans une première étape, le porte-échantillon est vide (aucune poudre n'est présente), et le signal est collecté par une fibre optique et analysé à l'aide d'un spectromètre (Instruments Systems, CAS 140B) . Dans une deuxième étape, on place la poudre dans le porte- échantillon et l'on mesure à la fois la fraction de lumière d'excitation qui n'a pas été absorbée par l'échantillon et la lumière d' up-conversion émise. Le rendement de luminescence, qui correspond au rapport entre l'émission dans la gamme 380-780 nm par rapport à la puissance absorbée entre 950 et 1000 nm, est calculée à partir de ces deux étapes. More specifically, the compounds are ground and the powder obtained is held in a sample holder composed of two quartz plates, one of which is coated with a reflective layer of aluminum. The sample holder is then placed on the backside of an integrating sphere (Instruments Systems, ISP-150-100). The excitation signal is focused at the center of the sample with a lens. The measurement is carried out in two stages. In a first step, the sample holder is empty (no powder is present), and the signal is collected by an optical fiber and analyzed using a spectrometer (Instruments Systems, CAS 140B). In a second step, the powder is placed in the sample holder and both the excitation light fraction which has not been absorbed by the sample and the emitted up-conversion light are measured. The luminescence yield, which corresponds to the ratio between the emission in the range 380-780 nm relative to the power absorbed between 950 and 1000 nm, is calculated from these two steps.
EXEMPLE 1 : Y2BaZn05 : Yb /Er3+ et Gd2BaZnOs : Yb3+/Er: EXAMPLE 1 Y 2 BaZn0 5: Yb / Er 3+ and Gd 2 BaZnO s: Yb 3+ / Er:
On prépare des composés de formule Y2BaZn05 : Yb +/Er + (formule A) et Gd2BaZn05 : Yb3+/Er3+ (formule B) par réaction en phase solide. Des poudres de Y203 ou Gd203, Yb203, Er203 (Alfa Aesar, 99.99%), ZnO (Fischer Scientific 99.5%) et BaC03 (Fisher Scientific 99+%) sont mélangées, broyées ensemble puis frittées à 1200°C pendant 3 jours, avec des étapes de broyage intermédiaires.
La structure cristalline est orthorhombique , et appartient au groupe d'espace Pnma. Pour une teneur en dopant de 7% en Yb3+ et 3% en Er3+ (ce qui correspond à tl=0,07 et t2=0,03), les paramètres de maille sont les suivants : a=l.23354 nm, b=0.570897 nm, c=0.706887 nm (formule A) et a=l.24861 nm, b=0.57713 nm, c=0.71720 nm (formule B) . Compounds of formula Y 2 BaZnO 5 : Yb + / Er + (formula A) and Gd 2 BaZnO 5 : Yb 3+ / Er 3+ (formula B) are prepared by solid phase reaction. Powders of Y 2 0 3 or Gd 2 0 3 , Yb 2 O 3 , Er 2 O 3 (Alfa Aesar, 99.99%), ZnO (Fisher Scientific 99.5%) and BaCO 3 (Fisher Scientific 99 +%) are mixed, milled together then sintered at 1200 ° C for 3 days, with intermediate milling steps. The crystalline structure is orthorhombic, and belongs to the Pnma space group. For a dopant content of 7% in Yb 3+ and 3% in Er 3+ (which corresponds to tl = 0.07 and t2 = 0.03), the mesh parameters are as follows: a = l.23354 nm, b = 0.570897 nm, c = 0.706887 nm (formula A) and a = l.24861 nm, b = 0.57713 nm, c = 0.71720 nm (formula B).
Soumis à un rayonnement d'excitation d'environ 977 nm, les échantillons présentent une luminescence allant du vert à l'orange, caractérisée par une forte émission dans le rouge (autour de 673 nm, due à une transition entre les niveaux 4F9/2 et 4 I i5 / 2 de l'erbium) et dans le vert (autour de 548 nm, due à une transition entre les niveaux 4S3/2 et 4Ii5/2 de l'erbium) . La Figure 1 représente le spectre d'émission obtenu. With an excitation radiation of about 977 nm, the samples show a luminescence ranging from green to orange, characterized by a strong emission in the red (around 673 nm, due to a transition between levels 4 F 9 / 2 and i 4 I 5/2 erbium) and green (around 548 nm, due to a transition between levels 4 S 3/2 and 4 II5 / 2 of erbium). Figure 1 shows the emission spectrum obtained.
Il est possible de faire varier à la fois le rendement de luminescence et le rapport d'intensité rouge/vert en modifiant les teneurs en dopants. It is possible to vary both the luminescence yield and the red / green intensity ratio by modifying the dopant contents.
Ainsi, pour une teneur en ion erbium de 3% (t2=0,03), la variation de la teneur en ions ytterbium de 3% à 11% (tl de 0,03 a 0,11) permet de faire passer le rapport d' intensité rouge/vert (défini comme le rapport de l'intensité de la bande d'émission centrée autour de 673 nm à l'intensité de la bande d'émission centrée autour de 550 nm) , de 4 à 8. Thus, for an erbium ion content of 3% (t2 = 0.03), the variation of the ytterbium ion content from 3% to 11% (tl of 0.03 to 0.11) makes it possible to pass the ratio of red / green intensity (defined as the ratio of the intensity of the emission band centered around 673 nm to the intensity of the emission band centered around 550 nm), from 4 to 8.
On peut voir en Figure 2 qu'à teneur tl+t2 constante (égale à 0,1), l'augmentation de la teneur t2 (concentration en ion erbium) réduit considérablement l'émission dans le rouge (bande vers 670 nm) au profit de l'émission dans le vert (bande vers 550 nm) . It can be seen in FIG. 2 that at a constant t1 + t2 content (equal to 0.1), the increase in the t2 content (erbium ion concentration) considerably reduces the emission in the red (band around 670 nm) at benefit of green emission (band around 550 nm).
La Figure 3 indique la valeur du rendement de luminescence en fonction de la concentration en ions erbium (t2) et ytterbium (tl) . On peut voir que lorsque tl (concentration en ions Yb3+) varie de 0,05 à 0,1 et t2 (concentration en ions Er3+) varie de 0,02 à 0,07, le
rendement de luminescence est généralement d'au moins 3%, et dépasse 4%, voire 5% lorsque tl varie de 0,07 à 0,09 et t2 varie de 0,03 à 0,04. Figure 3 shows the value of the luminescence yield as a function of the concentration of erbium (t2) and ytterbium (tl) ions. It can be seen that when t1 (concentration of Yb 3+ ions) varies from 0.05 to 0.1 and t2 (concentration of Er 3+ ions) varies from 0.02 to 0.07, the Luminescence efficiency is generally at least 3%, and exceeds 4% or even 5% when tl varies from 0.07 to 0.09 and t2 ranges from 0.03 to 0.04.
Pour une teneur en dopant de 7% en Yb3+ (tl=0,07) et 3% en Er+ (t2=0,03), le rendement de luminescence à température ambiante est de 5,2% +/- 0,2%, à la fois pour la formule A et la formule B. Ces composés particulièrement efficaces ont la formule suivante : Yi,8Ybo,i4Ero,o6BaZn05 et Gdi,8Ybo,i4Ero,o6BaZn05. For a dopant content of 7% Yb 3+ (tl = 0.07) and 3% Er + (t2 = 0.03), the luminescence yield at room temperature is 5.2% +/- 0 , 2%, both for formula A and formula B. These particularly effective compounds have the following formula: Yi, 8 Ybo, i 4 Ero, o 6 BaZn0 5 and Gdi, 8 Ybo, i 4 Ero, o6BaZn0 5 .
Pour une même teneur en dopants, le rapport d' intensité rouge/vert peut également être réglé ou modifié en faisant varier la durée des impulsions du laser. Le rapport d'intensité rouge/vert augmente continûment avec la durée d'impulsions (entre 0,05 et 1 milliseconde), puis se stabilise pour des impulsions plus longues. Pour des impulsions très courtes (inférieure à 0,25 milliseconde), le rapport d'intensité rouge/vert est inférieur à 1, si bien que la lumière émise est principalement verte. Pour des impulsions plus longues, la lumière émise devient orange puis rouge. La Figure 4 illustre ce phénomène en représentant l'évolution du rapport d'intensité rouge/vert en fonction de la durée des impulsions. For the same dopant content, the red / green intensity ratio can also be adjusted or modified by varying the pulse duration of the laser. The red / green intensity ratio increases continuously with the pulse duration (between 0.05 and 1 millisecond), then stabilizes for longer pulses. For very short pulses (less than 0.25 millisecond), the red / green intensity ratio is less than 1, so that the light emitted is mainly green. For longer pulses, the emitted light turns orange and then red. Figure 4 illustrates this phenomenon by showing the evolution of the red / green intensity ratio as a function of the duration of the pulses.
EXEMPLE 2 : Y2BaZn05 : Yb3+/Tm3+ EXAMPLE 2: Y 2 BaZnO 5 : Yb 3+ / Tm 3+
On prépare des composés de formule Y2BaZn05 : Yb3+/Tm3+ par réaction en phase solide. Des poudres de Y2O3, Yb203, Tm203 (Alfa Aesar, 99.99%), ZnO (Fischer Scientific 99.5%) et BaC03 (Fisher Scientific 99+%) sont mélangées, broyées ensemble puis frittées à 1200°C pendant 3 jours, avec des étapes de broyage intermédiaires. Compounds of formula Y 2 BaZnO 5 : Yb 3+ / Tm 3+ are prepared by solid phase reaction. Powders of Y 2 O 3 , Yb 2 O 3 , Tm 2 O 3 (Alfa Aesar, 99.99%), ZnO (Fischer Scientific 99.5%) and BaCO 3 (Fisher Scientific 99 +%) are mixed together, ground together and then sintered at room temperature. 1200 ° C for 3 days, with intermediate grinding steps.
La Figure 5 représente le spectre d'émission typique obtenu pour ces composés lorsqu'ils sont soumis à un rayonnement d'environ 975 nm de longueur d'onde. La
principale bande d'émission est majoritairement située dans l'infrarouge, vers 800 nm. Deux bandes moins intenses sont situées vers 480 nm (bleu) et 650 nm (rouge) . A l'œil, la lumière émise paraît de couleur bleue. Figure 5 shows the typical emission spectrum obtained for these compounds when subjected to radiation of about 975 nm wavelength. The main emission band is mostly located in the infrared, around 800 nm. Two less intense bands are located around 480 nm (blue) and 650 nm (red). In the eye, the light emitted appears blue.
Les Figures 6a et 6b indiquent la valeur du rendement de luminescence en fonction des concentrations en Yb3+ (tl) et Tm3+ (t3) dans la gamme d'émission allant de 420 à 870 nm (Figure 6a) et de 420 à 530 nm (Figure 6b) .Pour une teneur en Yb3+ de 10% (tl=0,l) et une teneur en Tm3+ de 1% (t3=0,01), on a pu obtenir un rendement de luminescence de 1,33% à température ambiante. Le composé présente la formule Yi,78Ybo, 2Tm0, o2BaZn05 . Figures 6a and 6b show the value of the luminescence yield as a function of the concentrations of Yb 3+ (tl) and Tm 3+ (t3) in the emission range of 420 to 870 nm (Figure 6a) and 420 to 530 nm (FIG. 6b). For a Yb 3+ content of 10% (tl = 0.1) and a Tm 3+ content of 1% (t3 = 0.01), it was possible to obtain a luminescence yield. 1.33% at room temperature. The compound has the formula Y1, 78 Ybo, 2Tm 0 , o2BaZn0 5 .
Pour une teneur en Yb3+ de 6% (tl=0,06) et une teneur en Tm3+ de 0,25% (t3=0,0025), le rendement de luminescence obtenu est de 1,7% à température ambiante. Le composé présente l a formule Yi,83Ybo,i2Tm0, o5BaZn05 . For a Yb 3+ content of 6% (tl = 0.06) and a Tm 3+ content of 0.25% (t3 = 0.0025), the luminescence yield obtained is 1.7% at room temperature. room. The compound has the formula Y 1, 83 Ybo, i 2 Tm 0 , o 5 BaZnO 5 .
EXEMPLE 3 : Y2BaZn05 : Yb /Ho EXAMPLE 3: Y 2 BaZnO 5 : Yb / Ho
On prépare des composés de formule Y2BaZn05 : Yb3+/Ho3+ par réaction en phase solide. Des poudres de Y2O3, Yb203, H02O3 (Alfa Aesar, 99.99%), ZnO (Fischer Scientific 99.5%) et BaC03 (Fisher Scientific 99+%) sont mélangées, broyées ensemble puis frittées à 1200°C pendant 3 jours, avec des étapes de broyage intermédiaires. Compounds of formula Y 2 BaZnO 5 : Yb 3+ / Ho 3+ are prepared by solid phase reaction. Powders of Y 2 O 3 , Yb 2 O 3 , H0 2 O 3 (Alfa Aesar, 99.99%), ZnO (Fisher Scientific 99.5%) and BaCO 3 (Fisher Scientific 99 +%) are mixed, milled together and then sintered at room temperature. 1200 ° C for 3 days, with intermediate grinding steps.
La Figure 7 représente le spectre d'émission typique obtenu pour ces composés lorsqu'ils sont soumis à un rayonnement d'environ 975 nm de longueur d'onde. La principale bande d'émission est majoritairement située dans le vert, vers 550 nm. Deux bandes nettement moins intenses sont situées vers 760 nm (rouge et proche infrarouge) et 660 nm (rouge) . A l'œil, et compte tenue de la plus forte sensibilité de l'œil humain pour le vert, la lumière émise est d'un vert très brillant.
La Figure 8 est une cartographie montrant l'évolution du rendement de luminescence à température ambiante en fonction des teneurs en dopants Yb3+ (tl) et Ho3+ (t4) . Les plus forts rendements sont obtenus pour des teneurs en Yb3+ allant de 6% à 12% (tl allant de 0,06 à 0,12) et des teneurs en Ho3+ allant de 0,25% à 2% (t4 allant de 0,0025 à 0, 02) . Figure 7 shows the typical emission spectrum obtained for these compounds when subjected to radiation of about 975 nm wavelength. The main emission band is mainly located in the green, around 550 nm. Two distinctly less intense bands are located around 760 nm (red and near infrared) and 660 nm (red). In the eye, and given the strongest sensitivity of the human eye to the green, the light emitted is of a very brilliant green. Figure 8 is a map showing the evolution of the luminescence yield at room temperature as a function of the dopant contents Yb 3+ (tl) and Ho 3+ (t4). The highest yields are obtained for Yb 3+ contents ranging from 6% to 12% (tl ranging from 0.06 to 0.12) and Ho 3+ contents ranging from 0.25% to 2% (t4). ranging from 0.0025 to 0.02).
Un rendement de 2,6% à température ambiante a été obtenu pour des composés de formule Yi,85Ybo,i4Ho0,oiBaZn05 et Yi,8iYbo,i8Hoo,oiBaZn05. A 2.6% yield at room temperature was obtained for compounds of the formula Y 1, 85 Ybo, 14 Ho 0 , o 16BaZnO 5 and Yi, 8 iYbo, 18Hoo, oiBaZnO 5 .
Le rendement évolue en fonction de la température de la diode laser, l'optimum se situant à une température d' environ 75 °C . The efficiency changes as a function of the temperature of the laser diode, the optimum being at a temperature of about 75 ° C.
EXEMPLE 4 : Ln2BaZnOs : Yb3+/Er3+/Tm3+ EXAMPLE 4: Ln 2 BaZnO s : Yb 3+ / Er 3+ / Tm 3+
On prépare des composés de formule Y2 (i-ti-t2- t3) Yb2tiEr2t2Tm2t3BaZn05 par réaction en phase solide. Des poudres de Y203, Yb203, Er203, Tm203 (Alfa Aesar, 99.99%), ZnO (Fischer Scientific 99.5%) et BaC03 (Fisher Scientific 99+%) sont mélangées, broyées ensemble puis frittées à 1200°C pendant 3 jours, avec des étapes de broyage intermédiaires . Y 2 of the formula compounds are prepared (t i-t2 t i- 3) 2 Yb2tiEr t2Tm 2 t3BaZn05 by solid phase reaction. Powders of Y 2 O 3 , Yb 2 O 3 , Er 2 O 3 , Tm 2 O 3 (Alfa Aesar, 99.99%), ZnO (Fisher Scientific 99.5%) and BaCO 3 (Fisher Scientific 99 +%) are mixed, milled together then sintered at 1200 ° C for 3 days, with intermediate milling steps.
Le Tableau 1 ci-après indique, en fonction des valeurs de tl, t2, t3 et de la puissance de la diode laser, les coordonnées colorimétriques dans le système colorimétrique x,y du rayonnement émis en réponse à une excitation à une longueur d'onde d'environ 975 nm.
o Table 1 below indicates, as a function of the values of t1, t2, t3 and the power of the laser diode, the colorimetric coordinates in the x, y colorimetric system of the radiation emitted in response to an excitation at a length of wave of about 975 nm. o
n %Yb3+ %Er3+ %Tm3+ Puissance X y n% Yb 3 + % Er 3 + % Tm 3+ Power X y
(tl) (t2) (t3) (mW) (tl) (t2) (t3) (mW)
1 0,1 0, 005 0,01 45 0,3369 0, 3646 1 0.1 0, 005 0.01 45 0.3369 0, 3646
2 0,1 0, 005 0,01 29 0,3516 0,36892 0.1 0, 005 0.01 29 0.3516 0.3689
3 0,1 0, 005 0,01 13 0, 3636 0, 36503 0.1 0, 005 0.01 13 0, 3636 0, 3650
4 0,1 0, 004 0,01 45 0, 3259 0,34484 0.1 0, 004 0.01 45 0, 3259 0.3448
5 0,1 0, 004 0,01 29 0,3315 0,34120.1 0, 004 0.01 29 0.3315 0.3412
6 0,1 0, 004 0,01 13 0, 3348 0, 32226 0.1 0, 004 0.01 13 0, 3348 0, 3222
7 0,1 0, 004 0,01 2,7 0,3445 0, 31677 0.1 0, 004 0.01 2.7 0.3445 0, 3167
8 0,1 0, 002 0,01 45 0, 2935 0,30318 0.1 0, 002 0.01 45 0, 2935 0.3031
9 0,1 0, 002 0,01 29 0,3021 0, 30979 0.1 0, 002 0.01 29 0.3021 0, 3097
10 0,1 0, 002 0,01 13 0,3103 0,30490.1 0, 002 0.01 13 0.3103 0.3049
11 0,1 0, 002 0,01 2,7 0, 3296 0,307111 0.1 0, 002 0.01 2.7 0, 3296 0.3071
12 0,1 0, 001 0,01 12 0, 2931 0, 264412 0.1 0, 001 0.01 12 0, 2931 0, 2644
13 0,1 0, 001 0,01 2 0,2850 0,2669 13 0.1 0, 001 0.01 2 0.2850 0.2669
Tableau 1 La lumière blanche est caractérisée par un couple où x et y ont tous deux la valeur 1/3. On peut déduire du tableau 1 que l'augmentation progressive de la teneur en erbium permet de passer du bleu au vert, en passant par le blanc . Table 1 White light is characterized by a pair where x and y are both 1/3. It can be seen from Table 1 that the gradual increase in the erbium content makes it possible to go from blue to green, passing through the white.
Une modulation de la puissance de la diode laser permet également de faire varier la teinte obtenue, comme le montre la comparaison entre les exemples 1 à 3, ou 4 à 7 ou 8 à 11, ou encore 12 et 13.
EXEMPLE 5 : mélanges de composés Modulating the power of the laser diode also makes it possible to vary the hue obtained, as shown by the comparison between Examples 1 to 3, or 4 to 7 or 8 to 11, or again 12 to 13. EXAMPLE 5 Mixtures of Compounds
On mélange un premier composé A de formule Yi, 8Ybo,i4Er0 , o6BaZn05 (tl=0,07 et t2=0,03) et un deuxième composé B de formule Yi, 78Ybo,2Tm0,02BaZn05 (tl=0,l et t3=0,01) . Le rapport de la masse du composé B à la masse du composé A est noté R. Mixing a first compound A of formula Yi, 8 Ybo, i4Er 0 o 5 6 BaZn0 (tl = t2 = 0.07 and 0.03) and a second compound B of formula Yi, 78 Ybo, Tm 2 0, 02 BaZnO5 (t1 = 0, 1 and t3 = 0.01). The ratio of the mass of compound B to the mass of compound A is denoted R.
Le Tableau 2 ci-après présente, en fonction du rapport R et de la puissance de la diode laser, les coordonnées colorimétriques dans le système colorimétrique x,y du rayonnement émis en réponse à une excitation à une longueur d'onde d'environ 975 nm.
Table 2 below presents, as a function of the ratio R and the power of the laser diode, the colorimetric coordinates in the x, y colorimetric system of the radiation emitted in response to an excitation at a wavelength of about 975. nm.
no R Puissance y no R Power y
d' essai diode (mW) diode test (mW)
14 0 45 0, 4764 0,4966 14 0 45 0, 4764 0.4966
15 0 13 0,4883 0,4843 15 0 13 0.4883 0.4843
16 5 45 0, 4221 0,4506 16 5 45 0, 4221 0.4506
17 5 13 0, 4353 0,4388 17 5 13 0, 4353 0.4388
18 10 45 0,3773 0,4019 18 10 45 0.3773 0.4019
19 10 13 0, 3927 0, 3949 19 10 13 0, 3927 0, 3949
20 20 45 0, 3571 0, 3662 20 20 45 0, 3571 0, 3662
21 20 13 0, 3667 0, 3582 21 20 13 0, 3667 0, 3582
22 25 45 0,3319 0,3398 22 25 45 0.3319 0.3398
23 25 13 0,3468 0,3387 23 25 13 0.3468 0.3387
24 30 45 0,3136 0, 3260 24 30 45 0.3136 0, 3260
25 30 29 0, 3281 0,3476 25 30 29 0, 3281 0.3476
26 30 13 0,3381 0,3440 26 30 13 0.3381 0.3440
27 30 2,7 0, 3732 0, 3641 27 30 2.7 0, 3732 0, 3641
28 35 45 0,2886 0,3031 28 35 45 0.2886 0.3031
29 35 13 0, 3201 0, 3250 29 35 13 0, 3201 0, 3250
30 45 0,2053 0,1891 30 45 0.2053 0.1891
31 13 0, 2272 0,2084 31 13 0, 2272 0.2084
Tableau 2 Table 2
Le mélange de composés A et B permet de passer d'une émission dans l'orange vers une émission dans le bleu en passant par la lumière blanche pour un rapport R entre 20 et 35, notamment de l'ordre de 25 à 30.
Une diminution de la puissance de la diode entraîne généralement une augmentation de la valeur x The mixture of compounds A and B makes it possible to pass from an emission in orange to a blue emission by passing through white light for a ratio R between 20 and 35, in particular of the order of 25 to 30. A decrease in the power of the diode generally increases the value x
EXEMPLE 6 : mise en forme EXAMPLE 6: Formatting
Des revêtements luminescents de 0,1 mm d'épaisseur ont été obtenus sur des substrats de verre silico-sodo-calcique de la manière suivante. Luminescent coatings 0.1 mm thick were obtained on soda-lime glass substrates in the following manner.
Des particules luminescentes selon l'invention ont été mélangées avec un médium organique (typiquement de l'huile de ricin) et avec une fritte de verre. Luminescent particles according to the invention were mixed with an organic medium (typically castor oil) and with a glass frit.
Plus précisément, les composés luminescents étaient de formule Yi , 8Ybo,i4Ero, o6BaZ n05 ou Yi , esYbo , 14H00, oiBa Z n05. La fritte de verre était constituée de Si02 (12% en masse), Z nO (40%) , Bi203 (29%) , Na20 (19%) . More specifically, the luminescent compounds were Yi formula 8 Ybo, i4Ero, o 6 BaZ n0 5 or Yi, esYbo, 2:00 p.m., Oiba Z n0 5. The glass frit consisted of SiO 2 (12% by weight), Z 2 O (40%), Bi 2 O 3 (29%), Na 2 O (19%).
Après dépôt du mélange obtenu sur le verre au moyen d'un tire-film, les échantillons ont subi une étape de cuisson à 600°C pendant 6 minutes. After depositing the mixture obtained on the glass by means of a film-puller, the samples were baked at 600 ° C. for 6 minutes.
Le spectre d'émission après irradiation par un rayonnement laser d'environ 980 nm de longueur d'onde est représenté en Figure 9. Il comprend une bande principale vers 680 nm (rouge) et une bande secondaire vers 550 nm (vert) .
The emission spectrum after irradiation with laser radiation of about 980 nm wavelength is shown in Figure 9. It comprises a main band at 680 nm (red) and a secondary band at about 550 nm (green).
Claims
1. Composé cristallin de formule 1. Crystalline compound of formula
Lnx. (i-ti-t2-t3-t ) Ybx.tiErx.t2Tmx.t3Hox.t4BayZnzOi.5X+y+z dans lequel : Ln x . (i-ti-t2-t3-t) Yb x . t iEr x .t 2 Tm x . t3 Ho x .t 4 Ba y Zn z O1.5 X + y + z in which:
Ln est Y ou Gd, Ln is Y or Gd,
- tl+t2+t3+t4 varie de 0,001 à 0,3, de préférence de 0,01 à 0,2, t1 + t2 + t3 + t4 varies from 0.001 to 0.3, preferably from 0.01 to 0.2,
et tel que lorsque x=2, y=l, z=l, and such that when x = 2, y = 1, z = 1,
tl+t3+t4 est non-nul tl + t3 + t4 is non-zero
si Ln est Gd et si t3+t4 est nul, alors tl varie de 0,05 à 0,1 et t2 varie de 0,02 à 0,07 if Ln is Gd and if t3 + t4 is zero, then tl varies from 0.05 to 0.1 and t2 varies from 0.02 to 0.07
si Ln est Gd, alors t2+t4 est non-nul. if Ln is Gd, then t2 + t4 is non-zero.
2. Composé selon la revendication 1, tel que x=2, y=l, z=l . 2. A compound according to claim 1, such that x = 2, y = 1, z = 1.
3. Composé selon la revendication 1, tel que x=8, y=5, z=4 ou x=2, y=2, z=8. 3. A compound according to claim 1, such that x = 8, y = 5, z = 4 or x = 2, y = 2, z = 8.
4. Composé selon l'une des revendications précédentes, et notamment selon la revendication 2, tel que : 4. Compound according to one of the preceding claims, and in particular according to claim 2, such that:
- t3+t4 est nul t3 + t4 is zero
tl varie de 0,05 à 0,1, notamment de 0,07 à 0,09 t2 varie de 0,02 à 0,07, notamment de 0,03 à 0,04. It varies from 0.05 to 0.1, in particular from 0.07 to 0.09, and varies from 0.02 to 0.07, especially from 0.03 to 0.04.
5. Composé selon l'une des revendications précédentes, et notamment selon la revendication 2, tel que : 5. Compound according to one of the preceding claims, and in particular according to claim 2, such that:
Ln est Y Ln is Y
- t2+t4 est nul t2 + t4 is zero
tl et t3 sont non-nuls, tl variant notamment de 0,05 à 0,2 et t3 variant notamment de 0,001 à 0,05. t1 and t3 are non-zero, t1 varying in particular from 0.05 to 0.2 and t3 varying in particular from 0.001 to 0.05.
6. Composé selon l'une des revendications précédentes, et notamment selon la revendication 2, tel que : 6. Compound according to one of the preceding claims, and in particular according to claim 2, such that:
t2+t3 est nul t2 + t3 is zero
tl et t4 sont non-nuls, tl variant notamment de 0,06 à 0,12 et t4 variant notamment de 0,001 à 0,02. t1 and t4 are non-zero, t1 varying in particular from 0.06 to 0.12 and t4 varying in particular from 0.001 to 0.02.
7. Composé selon l'une des revendications précédentes, et notamment selon la revendication 2, tel que tl, t2 et t3 sont non-nuls. 7. Compound according to one of the preceding claims, and in particular according to claim 2, such that tl, t2 and t3 are non-zero.
8. Mélange d'au moins deux composés différents selon l'une des revendications précédentes. 8. Mixture of at least two different compounds according to one of the preceding claims.
9. Mélange selon la revendication précédente, comprenant un premier composé tel que t3+t4=0 et tl et t2 sont non- nuls et un second composé tel que t2+t4=0 et tl et t3 sont non-nuls . 9. Mixture according to the preceding claim, comprising a first compound such that t3 + t4 = 0 and t1 and t2 are non-zero and a second compound such that t2 + t4 = 0 and t1 and t3 are non-zero.
10. Procédé d'obtention des composés selon l'une des revendications 1 à 7, comprenant les étapes consistant à mélanger des poudres, à broyer le mélange, puis à chauffer le mélange de manière à faire réagir chimiquement les poudres entre elles. 10. Process for obtaining compounds according to one of claims 1 to 7, comprising the steps of mixing powders, grinding the mixture, and then heating the mixture so as to chemically react the powders together.
11. Procédé d'obtention des composés selon l'une des revendications 1 à 7, comprenant les étapes consistant à dissoudre des précurseurs, notamment des nitrates, acétates, ou encore carbonates, dans l'eau ou dans un solvant majoritairement aqueux, à ajouter un agent complexant, notamment un acide α-hydroxycarboxylique tel que l'acide citrique et éventuellement un agent réticulant, notamment un polyhydroxyalcool tel que 1 ' éthylèneglycol de manière à obtenir un gel, puis à chauffer le gel obtenu à une température d'au moins 1000°C. 11. Process for obtaining compounds according to one of claims 1 to 7, comprising the steps of dissolving precursors, including nitrates, acetates, or carbonates, in water or in a predominantly aqueous solvent, to be added. a complexing agent, especially an α-hydroxycarboxylic acid such as citric acid and optionally a crosslinking agent, in particular a polyhydroxy alcohol such as ethylene glycol so as to obtain a gel, and then to heat the gel obtained at a temperature of at least 1000 ° C.
12. Substrat revêtu sur au moins une partie d'au moins une de ses faces d'un revêtement incorporant au moins un composé selon l'une des revendications de composé précédentes . 12. Substrate coated on at least a portion of at least one of its faces with a coating incorporating at least one compound according to one of the preceding compound claims.
13. Dispositif d'affichage ou de production d'énergie photovoltaïque comprenant au moins un substrat selon la revendication précédente. 13. Display device or photovoltaic power production comprising at least one substrate according to the preceding claim.
14. Utilisation de composés selon l'une des revendications de composé précédentes pour convertir un rayonnement infrarouge en un rayonnement visible, notamment pour convertir un rayonnement de longueur d'onde comprise dans la gamme allant de 890 à 1100 nm, notamment d'environ 975 nm, en un rayonnement de longueur d'onde d'environ 550 nm et/ou 660 nm et/ou 480 nm et/ou 800 nm. 14. Use of compounds according to one of the preceding compound claims for converting infrared radiation into visible radiation, especially for converting radiation of wavelength in the range of 890 to 1100 nm, including about 975 nm, in wavelength radiation of about 550 nm and / or 660 nm and / or 480 nm and / or 800 nm.
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FR1051126A FR2956407B1 (en) | 2010-02-17 | 2010-02-17 | LUMINESCENT COMPOUNDS |
PCT/FR2011/050303 WO2011101584A1 (en) | 2010-02-17 | 2011-02-14 | Luminescent compounds |
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EP (1) | EP2536809A1 (en) |
JP (1) | JP2013519774A (en) |
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US20110266457A1 (en) * | 2010-04-29 | 2011-11-03 | Eads Construcciones Aeronauticas, S.A. | System for night vision of selected objects |
CN102690654A (en) * | 2012-06-06 | 2012-09-26 | 大连海事大学 | High-efficiency up-conversion emission phosphor and preparation method thereof |
WO2014175550A1 (en) * | 2013-04-25 | 2014-10-30 | 동우 화인켐 주식회사 | Optical film and pointing display device |
US9209597B2 (en) * | 2013-06-06 | 2015-12-08 | Gokhan Bilir | Method and device for producing white light from Y2O3 nano-powders |
CN105473528A (en) * | 2013-09-27 | 2016-04-06 | 积水化学工业株式会社 | Intermediate film for laminated glass, and laminated glass |
DE102014112681A1 (en) | 2014-09-03 | 2016-03-03 | Osram Opto Semiconductors Gmbh | Optoelectronic semiconductor device and flashlight |
EP3431570B1 (en) * | 2017-07-21 | 2019-10-02 | Karlsruher Institut für Technologie | New composition with enhanced luminescence |
CN109037461B (en) * | 2018-07-13 | 2021-12-14 | 京东方科技集团股份有限公司 | Blue-light organic light-emitting diode, display substrate and display device |
KR102298723B1 (en) | 2018-11-16 | 2021-09-06 | 세종대학교산학협력단 | Marker for discrimination of resistance to tomato yellow leaf curl virus and discrimination method using the same marker |
CN110335532A (en) * | 2019-05-30 | 2019-10-15 | 南京萃智激光应用技术研究院有限公司 | A method of it is anti-fake using long phosphorescence |
RU2730491C1 (en) * | 2019-06-27 | 2020-08-24 | Акционерное общество Научно-производственное предприятие "Интеграл" | Inorganic luminescent compound, marking using inorganic luminescent compound and information medium using inorganic luminescent compound |
RU2754001C1 (en) * | 2020-08-18 | 2021-08-25 | Акционерное общество Научно-производственное предприятие "Интеграл" | Luminescent compound based on rare earth metal ions |
CN112382684A (en) * | 2020-09-28 | 2021-02-19 | 希腊布莱特公司 | Transparent solar glass panel with luminescent solar concentrator nanomaterial coating |
FR3118156B1 (en) | 2020-12-23 | 2022-12-30 | Nexter Systems | HARMONIZATION DEVICE FOR SIGHTING MEANS COMPRISING AT LEAST ONE ILLUMINATION MEANS AND HARMONIZATION METHOD FOR IMPLEMENTING SUCH A DEVICE |
CN114315156B (en) * | 2021-11-30 | 2023-12-29 | 无锡极电光能科技有限公司 | Perovskite quantum dot glaze, photovoltaic glass, preparation method of perovskite quantum dot glaze and photovoltaic assembly |
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CN1277901C (en) * | 2005-05-27 | 2006-10-04 | 王锦高 | Luminescent powder of light emitting diode for semiconductor white light illumination, and preparation method thereof |
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2010
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US20130043406A1 (en) | 2013-02-21 |
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FR2956407B1 (en) | 2013-03-08 |
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