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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
  • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
  • C09K11/7774—Aluminates
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/851—Wavelength conversion means
  • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
  • H10H20/8512—Wavelength conversion materials
• • 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
  • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
  • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

• the invention relates to the field of lighting engineering and, in particular, to luminescent materials luminous when excited by blue light in the yellow-orange region of the spectrum and used in solid-state white light sources in which an intense white glow is obtained as a result of a combination of yellow-orange luminescence of a phosphor with primary blue radiation generated by an InGaN LED emitting in the blue region of the spectrum (440-480 nm).
• these devices have been used to create highly efficient white light sources with a light output of up to 150 lumens / watt, which is more than 10 times the light output of incandescent lamps and almost twice the light output of gas-discharge fluorescent light sources.
• the development of solid-state white light sources is currently determining the prospects for the development of lighting technology.
• SUBSTITUTE SHEET (RULE 26) groups Ga, In, Sc. The ratio between about rigidly
• ⁇ Me J + is fixed and equal to -.
• Ce - being an activator of luminescence, i.e. atom, optical transitions in which determine the color of the glow, and the concentration determines the brightness of the luminescence (related, but correcting functions can perform Pr 3 Yb);
• Gd, Tb, and Lu provide a shift in the position of the maximum in the luminescence spectrum to the long-wave (Gd, Tb) or short-wave (Lu) spectral regions (Ga, In, Sc can play a similar role);
• the half-width of the emission band is 110-125 nm
• T c color temperature
• SUBSTITUTE SHEET (RULE 26) A broadband phosphor with a yellow-orange glow based on yttrium-aluminum garnet activated by cerium (Y 5 Ce) 3 AbOi 2 and the method for its preparation was first patented in 1967 by Philips employees G. Blassse and A. .Brilem (A. Brille) in a number of countries, including the United States: Rat. US 3564322 (US Class: 313/468; Litern'1 Class: C09Kl 1/77) dated 04.29.1967.
• cerium-activated aluminum garnet [US Ratings ⁇ N ⁇ : JYo5998925 (US Class: 313/503; Intern'1 Class: H0 IJOO 1/62) dated 12/07/1997, ⁇ N26069440 (US Class: 313 / 486,489; Intern'1 Class: H01L 033/00) from 05/30/2000, I "6608332 (US Class: 257/98) from 08/19/2003, JVG2b614179 (US Class: 353/512; Intem'1 Class: H01L 33/00) from 08/19/2003, J7362048 (US Class: 313/512].
• SUBSTITUTE SHEET (RULE 26) composition stoichiometric composition in relation to a set of rare earth elements while maintaining the generalized formula "A 3 -Bs-Oi 2 ".
• US Pat. Pat. No. 6630077 US Class: 313/468; Intem'1 Class: C09K 11/27 of 10/07/2003 included in the list of claimed lanthanides all 14 f-elements, with their separation according to type of functional action on structure-forming (Tb, Lu, La, Gd, Yb), activating (Ce) and performing auxiliary functions (Pr, Nd, Sm, Eu, Dy, But, Er, Tm).
• the phosphor composition is given by the formula [Yi_ x . yz . q Gd x Lu y Yb 2 Eu q + activating additives Ce 5 Pr 5 Dy, Er 5 Sm] 3 Al 5 Oi 2 , where 9 out of 14 f-elements were included in the lanthanide group.
• garnet is understood to mean more than 10 minerals having the same crystalline structure, but different chemical composition.
• the minerals Mg 3 Al 3 Si 3 Oi 2 , Ca 3 Al 2 Si 3 Oi 2 , Mn 3 Al 2 Si 3 Oi 2 are well known.
• Type A 5 ions which may include lanthanides, calcium, magnesium, manganese, iron, etc., have
• SUBSTITUTE SHEET silicon garnet with partial replacement of two Al atoms (In 3 Ga 5 Sc) with Mg (Ca 5 Sr 5 Ba). The degree of substitution (x) did not exceed a concentration of 15%.
• An analogue of the invention is the application US20090153027 (US Class: 313/503; Intern'1 Class: C09KP / 78) dated 06/19/2009, in which a phosphor having the composition [Y2-xyz-qGd x Ce y Pr z DypO 3 ] i is proposed , 5 ⁇ . ⁇ + (Al2 ⁇ 3 ) 2.5 ⁇ ⁇ .
• the purpose of the patent was to obtain warm white radiation through the use of a phosphor, the emission spectrum of which was shifted to the red region as a result of the introduction of three activators, namely, cerium, praseodymium and dysprosium.
• the luminescent material was obtained as a result of a three-stage heat treatment of a mixture of hydroxides Gd, Y, Ce, Dy, Er, Yb, Al and Ga, coprecipitated by ammonia from a solution of mixtures of nitrates of these metals.
• the precursors were calcined in the presence of mineralizers in a hydrogen medium: first, at 500 K, then 900–1100 K, and finally, at 1400–1700 K, followed by gradual cooling to 400 K.
• the obtained product after heat treatment was strongly sintered and ground to particles ⁇ 1, 5 microns. Grinding to such a small size should inevitably lead to some decrease in the brightness and quality of the phosphor.
• the objective of the invention is to expand the range of inorganic luminescent materials for solid-state white light sources.
• the problem is solved by creating an inorganic luminescent material for solid-state white light sources based on blue-emitting InGaN LEDs, including yttrium oxide, rare-earth metal oxides, as well as aluminum oxide, while the composition of the inorganic luminescent material corresponds to the general formula ( ⁇ i- ⁇ - y Ce ⁇ Ln y ) s + ⁇ Al 5 O 12 + 1; 5 ⁇ ,
• ⁇ is a value characterizing the increase in the stoichiometric index in comparison with the known for yttrium gadolinium garnet and varying in the range from 0.033 to 2;
• x is the atomic fraction of cerium, equal to 0.001-0.1;
• Ln one or more lanthanides from the group Gd, Tb, La, Yb, which together with yttrium and cerium form an yttrium sublattice.
• Pr, Nd, Sm, Eu, Dy, Er, Lu can be included in its composition
• the proposed material is a phase of a cubic structure, the lighting characteristics of which for a given composition of rare-earth elements weakly depend on the value of the stoichiometric index, while for a given stoichiometric index, the variation in cationic composition can lead to a change in color coordinates and the position of the maximum in the luminescence spectrum in the range from 550 to 590 nm, which allows you to change the color temperature of solid state of a white light source from 2700 - 4500K.
• the proposed luminescent material is a mixed composition of two phases, one of which has a cubic structure and composition
• SUBSTITUTE SHEET (RULE 26) yttrium composition (Y 1- ⁇ y Ce x ] T Ln J Al 5 O 15 doped with Gd, Tb, La, Yb and activated by cerium, and for a given cationic composition, the lighting parameters of two-phase compositions depend on the index value (3 + ⁇ ) due to increasing the relative content of the orthorhombic modification of yttrium aluminate, so that the color temperature of a solid-state white light source can vary from 3000 to 6000 K.
• Phosphors the composition of which is shown in the list of examples, were obtained by heat treatment of a mixture of oxides of yttrium, cerium, gadolinium, terbium, lanthanum, ytterbium and aluminum hydroxide (or a mixture of hydroxides, coprecipitated from aqueous solutions of nitrates).
• the prepared mixtures were calcined in the presence of mineralizers (fluxes), contributing to an increase in the mass transfer rate due to the formation of a liquid phase on the surface of reacting solids, and thereby leading to an increase in the rate of formation of the target product by reactions:
• the starting materials (lanthanide oxides and aluminum hydroxide) with a known particle size distribution (laser particle size analyzer) were mixed in a dry form on a vibrating stand or in a drunken barrel type mixer in closed polyethylene containers using metal balls with a polyethylene coating.
• Calcination was carried out in alundum crucibles (Al 2 O 3 ) with gradual heating of the reagents in a reducing medium (N 2 + H 2 ) at a speed of 7-10 deg / min to a temperature of 1350-1450 0 C.
• the exposure time at high temperature was 3-5 hours, after which the crucibles were cooled to 400 0 C for 2.5 hours.
• SUBSTITUTE SHEET (RULE 26) particle size distribution of the precursors, the average particle size of the phosphor was about 3.5 - 5.0 microns.
• the prepared samples were washed several times with a large volume of distilled water and dried in an oven at 15O 0 C.
• the synthesis of the sample composition (Yo, 555Gdo, 4 Lao, oo5Ce o , o4) s, 5 Al 5 O 12 7S was carried out using Y 2 O 3 , Gd 2 O 3 , La 2 O 3 , CeO 2 and Al (OH) 3 . Annealing temperature 145O 0 C. Duration of exposure at high temperature for 4 hours.
• Lighting parameters of samples N ° 1-7 were measured in certified installations by two methods. In the first of them, the spectra of the white radiation spectrum were recorded when blue radiation was reflected from the synthesized phosphor powders with a yellow-orange glow. Using the second technique, the spectra were measured after blue radiation passed through a solid organic matrix with a dispersed phosphor, i.e. in conditions that mimic the operation of white lamps based on blue-emitting diodes (whit Indian LED lamper). The results of spectral measurements by the second method are shown in table N "1 in italics. For comparison, the data on the lighting characteristics of industrial samples of phosphors manufactured by Nichiya are also presented there.
• the nonstoichiometric phase (Yi_ x _ y ⁇ Ln] Al 5 O 12 + I5Sa ' which composition corresponds to index variations from 3 to 3.45 can be considered as a homogeneous solid solution of cubic yttrium aluminate Y 5 Al 5 Oi 5 in the phase doped with lanthanides of yttrium aluminum garnet.
• index variation for given concentrations and composition of the yttrium sublattice
• SUBSTITUTE SHEET (RULE 26) the region is detected by the appearance of a set of reflections belonging to the orthorhombic modification of YAlO 3 against the background of diffraction reflections from the cubic phase.
• Sample composition (Y 0.95 It was also biphasic due to the presence of both cubic and orthorhombic modifications of subsidized yttrium-aluminum perovskite.
• the blue radiation passes through a polymer organic matrix with a suspended phosphor, which forms the shell of the lamp with a blue LED (white LED lamper), then changing the thickness of the absorbing layer or the concentration of the phosphor in the photo-converting the scattering medium can almost completely “utilize” the blue radiation and lower the color temperature of the white radiation to 4500-6000 K even for a sample of the composition (Yo, 95 Tb O; oiCeo, o4) 5, oo AIsO 15 .
• the luminescence brightness in the range of indices from 3.5 to 4.5 decreased by less than ⁇ 20-25% in comparison with the cubic phase.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Luminescent Compositions (AREA)

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• 2009
  • 2009-07-28 WO PCT/RU2009/000374 patent/WO2011014091A1/ru not_active Ceased
  • 2009-07-28 KR KR1020127002326A patent/KR101423249B1/ko not_active Expired - Fee Related
  • 2009-07-28 CN CN200980160642.5A patent/CN102473803B/zh not_active Expired - Fee Related
  • 2009-07-28 US US13/148,723 patent/US8388862B2/en not_active Expired - Fee Related
  • 2009-07-28 EP EP09847877A patent/EP2461377A4/en not_active Withdrawn
  • 2009-07-28 IN IN1509DEN2012 patent/IN2012DN01509A/en unknown

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