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WO2025172353A1 - Luminophore, composant optoélectronique et procédé de production d'un luminophore - Google Patents

Luminophore, composant optoélectronique et procédé de production d'un luminophore

Info

Publication number
WO2025172353A1
WO2025172353A1 PCT/EP2025/053709 EP2025053709W WO2025172353A1 WO 2025172353 A1 WO2025172353 A1 WO 2025172353A1 EP 2025053709 W EP2025053709 W EP 2025053709W WO 2025172353 A1 WO2025172353 A1 WO 2025172353A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphor
electromagnetic radiation
layer
ions
combinations
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.)
Pending
Application number
PCT/EP2025/053709
Other languages
German (de)
English (en)
Inventor
Juliane Kechele
Simon Dallmeir
Frauke PHILIPP
Christiane STOLL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ams Osram International GmbH
Original Assignee
Ams Osram International GmbH
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Filing date
Publication date
Application filed by Ams Osram International GmbH filed Critical Ams Osram International GmbH
Publication of WO2025172353A1 publication Critical patent/WO2025172353A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/77748—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • 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
    • 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
    • H10H20/8513—Wavelength conversion materials having two or more wavelength conversion materials

Definitions

  • a phosphor and an optoelectronic component are specified. Furthermore, a method for producing a phosphor is specified. One object is to specify a phosphor with increased efficiency. Furthermore, the phosphor has better light quality. Further objects are to provide a method for producing such a phosphor with increased efficiency and an optoelectronic component with increased efficiency. A phosphor is specified.
  • RE is selected from the group of trivalent rare earth elements or combinations thereof.
  • Rare earth elements in the present case include the chemical elements of the third subgroup of the periodic table as well as the lanthanides.
  • Rare earth elements 2023PF01062 February 12, 2025 P2023,1280 WO N - 2 - are in this case generally selected from the group formed by scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
  • A is selected from Ce, Eu, Mn, Bi, Tb, Dy, Ni, Cr, Er or combinations thereof.
  • A is an activator element.
  • the activator element changes the electronic structure of the host lattice in such a way that 2023PF01062 February 12, 2025 P2023,1280 WO N - 3 - electromagnetic radiation with an excitation spectrum is absorbed by the phosphor and excites an electronic transition in the activator element, which returns to the ground state by emitting electromagnetic radiation with an emission spectrum.
  • the activator element which is incorporated into the host lattice, is thus responsible for the wavelength-converting properties of the phosphor.
  • wavelength-converting in this case means that radiated electromagnetic radiation of a specific wavelength range, in this case the excitation spectrum or first wavelength range, is converted into electromagnetic radiation of another, preferably longer wavelength range, in this case the emission spectrum or second wavelength range .
  • a wavelength-converting component absorbs electromagnetic radiation of one incident wavelength range, converts it through electronic processes at the atomic and/or molecular level into electromagnetic radiation of a different wavelength range, and re-emits the converted electromagnetic radiation.
  • pure scattering or pure absorption is not understood here as wavelength-converting.
  • phosphors are described using molecular formulas. The elements listed in the molecular formulas are present in charged form.
  • elements and/or atoms in relation to the molecular formulas of the phosphors thus refer to ions in the form of cations and anions, even if this is not explicitly stated. This also applies to element symbols. 2023PF01062 February 12, 2025 P2023,1280 WO N - 4 - if these are given without a charge number for the sake of clarity.
  • the phosphor comprises further elements, for example in the form of impurities. Taken together, these impurities amount to a maximum of 5 mol%, in particular a maximum of 1 mol%, preferably a maximum of 0.1 mol%.
  • the phosphor is generally uncharged towards the outside.
  • the phosphor comprises a mixture.
  • the mixture comprises, for example, among others, the general formula EA 4-xad SE x+a M 1-bc Si 19-yx- 3c Al y+x+3c N 29-y+a-3b-2d O y-a+3b+2d :A.
  • Further components of the mixture can be, for example, reactants that did not react during the production of the phosphor, impurities and/or secondary phases that were formed during the reaction.
  • the phosphor has the general formula EA 4-xad SE x+a M 1-bc Si 19-yx-3c Al y+x+3c N 29-y+a-3b- 2d O y-a+3b+2d :A, where - EA is selected from Ca, Sr, Ba, Zn or combinations thereof, - SE is selected from the group of trivalent rare earth elements or combinations thereof, 2023PF01062 February 12, 2025 P2023,1280 WO N - 5 - - M is selected from Sc, Y, Lu, Tm, Er, Ho or combinations thereof, - A is selected from Ce, Eu, Mn, Bi, Tb, Dy, Ni, Cr, Er or combinations thereof, - 0 ⁇ d ⁇ 1; - 0 ⁇ x+a+d ⁇ 4; - 0 ⁇ b+c ⁇ 1; - 0 ⁇ y+x+3c ⁇ 19; and - 0 ⁇ y-a
  • the phosphor is free of monovalent ions such as sodium ions, potassium ions and/or lithium ions. This means that the phosphor has no monovalent ions.
  • 0 ⁇ d ⁇ 1; 0 ⁇ x+a+d ⁇ 4; 0 ⁇ b+c ⁇ 1; 0 ⁇ y+x+3c ⁇ 19; 0 ⁇ y-a+3b+2d ⁇ 10; and 2*(4-xad) + 3*(x+a) + 3*(1-bc)+ 4*(19-yx-3c) + 3*(y+x+3c)-3*(29-y+a-3b-2d)-2*(y-a+3b+2d) 0.
  • x + a 0. In other words, no SE is present in the phosphor.
  • A comprises cerium or consists of this element. Cerium is present in particular in the form Ce 3+ .
  • A represents the element cerium.
  • quenching occurs even at low irradiances of around 100 mW/mm2, which can lead to a reduction in quantum efficiency.
  • quenching means the presence of processes that lead to the absorption of a photon in the first wavelength range, but without the subsequent emission of a photon in the second wavelength range or emission spectrum.
  • the photon in the first wavelength range therefore does not trigger transitions in the visible spectral range, but is converted into lattice vibrations. This leads to a reduction in efficiency.
  • the quenching can be caused, for example, by an internal conversion or an energy transfer, for example to the host lattice.
  • Conventional applications of phosphors sometimes operate at significantly higher irradiances than 100 mW/mm2.
  • Ce 3+ Phosphors that contain Ce 3+ as an activator element exhibit lower quenching even at higher irradiances. Therefore, the use of Ce 3+ as activator element A is advantageous.
  • An excited state of Ce 3+ has a typical lifetime of usually less than 100 nanoseconds.
  • the typical lifetime of the excited state of Eu 2+ in contrast, is usually in the range of 1 to 10 microseconds. Due to the shorter lifetime of the excited state of Ce, a phosphor with Ce as the activator element exhibits lower quenching at high irradiances.
  • the conventional phosphor Y 3 Al 5 O 12 :Ce 3+ only shows significant radiation-induced quenching above an irradiance of 10 W/mm2 .
  • A has a molecular fraction of between 0.01% and 5% inclusive, based on EA, SE and M.
  • EA comprises Sr.
  • EA consists of strontium.
  • Strontium is present in particular in the form Sr 2+ .
  • SE and/or M comprises yttrium.
  • the yttrium is present in particular in the form Y 3+ .
  • SE consists of yttrium.
  • M consists of yttrium.
  • the elements SE and EA are crystallographically located on the same layers and the element M is located on a further layer.
  • the phosphor has the formula EA 4-m Y 1-n (Si,Al) 19 (N,O) 29 :Ce 3+ .
  • EA is selected from Ca, Sr, Ba, Zn or combinations thereof.
  • the phosphor has the formula Sr4-m-oY1-n-pSi19-t+2m+3nAlt-2m-3nN29-t-2o-3pOt+2o+3p:Ce 3+ , where 2023PF01062 February 12, 2025 P2023,1280 WO N - 8 - - 0 ⁇ t ⁇ 19; - t ⁇ 2m; - t ⁇ 3n; - 0 ⁇ m ⁇ 3; - 0 ⁇ o ⁇ 3; - 0 ⁇ n ⁇ 1; - 0 ⁇ p ⁇ 1; - 0 ⁇ m + o ⁇ 4; - 0 ⁇ n
  • m is between 0 and 1 inclusive. More preferably, o is between 0 and 1 inclusive.
  • the phosphor has the formula Sr 4-m Y 1-n (Si,Al) 19 (N,O) 29 :Ce 3+ .
  • the phosphor is therefore free of monovalent elements such as potassium, sodium, and lithium.
  • the phosphor preferably converts electromagnetic radiation in the UV to blue wavelength range into electromagnetic radiation in the blue-green to green wavelength range. The phosphor efficiently converts the electromagnetic radiation even at high irradiances.
  • the wavelength range of the emitted electromagnetic radiation depends, among other things, on the excitation wavelength.
  • the phosphor has a host lattice comprising a structure with a 2023PF01062 February 12, 2025 P2023,1280 WO N - 9 - trigonal space group.
  • the phosphor comprises a crystalline, for example, ceramic host lattice.
  • the phosphor is, for example, a ceramic material.
  • the crystalline host lattice is generally composed in particular of a three-dimensionally periodically repeating unit cell. In other words, the unit cell is the smallest recurring unit of the crystalline host lattice that reflects the symmetry of the crystal.
  • the elements EA, SE, M, Al, N, Si, O, and A each preferentially occupy defined, symmetrical sites, so-called atomic positions, within the three-dimensional unit cell of the host lattice.
  • the phosphor crystallizes in the trigonal space group P3. This corresponds to number 143.
  • a crystal structure of the host lattice of the phosphor comprises corner-sharing (Si,Al)(N,O) 4 tetrahedra.
  • the crystal structure of the host lattice of the phosphor is a framework (nitrido)silicate or belongs to the group of framework (nitrido)silicates.
  • the crystal structure exclusively comprises corner-sharing (Si,Al)(N,O) 4 tetrahedra.
  • the (Si,Al)(N,O)4 tetrahedra generally have a tetrahedral gap.
  • the tetrahedral gap is a region in the interior of the respective tetrahedron.
  • the term “tetrahedral gap” refers to the region in the interior of the 2023PF01062 February 12, 2025 P2023,1280 WO N - 10 - tetrahedron that remains free when touching spheres are placed at the corners of the tetrahedron.
  • the N,O atoms preferably span the (Si,Al)(N,O)4 tetrahedron , with the Si,Al atom located in the tetrahedral gap of the (Si,Al)(N,O) 4 tetrahedron spanned by the N,O atoms.
  • the tetrahedra are centered around the Si,Al atom.
  • all atoms that span the tetrahedron have a similar distance to the Si,Al atom that is located in the tetrahedral gap.
  • Corner-sharing means that at least two of the (Si,Al)(N,O) 4 tetrahedra are connected to each other via an N,O vertex.
  • the two (Si,Al)(N,O) 4 tetrahedra are vertex-shared.
  • the N,O atom is a common N,O atom of the corner-shared (Si,Al)(N,O)4 tetrahedra.
  • the N,O atom that links the (Si,Al)(N,O) 4 tetrahedra is preferably part of both the (Si,Al)(N,O) 4 tetrahedron and another (Si,Al)(N,O) 4 tetrahedron.
  • all four vertices are each linked to a vertex of another (Si,Al)(N,O) 4 tetrahedron.
  • the corner-shared (Si,Al)(N,O) 4 tetrahedra form a tetrahedral network.
  • the crystal structure of the host lattice of the phosphor comprises a first layer and a second layer, wherein the first layer and the second layer comprise (Si,Al)(N,O) 4 tetrahedra.
  • the first layer comprises three-membered rings.
  • the three-membered rings comprise three (Si,Al)(N,O) 4 tetrahedra sharing corners. In other words, three (Si,Al)(N,O) 4 - 2023PF01062 February 12, 2025 P2023,1280 WO N - 11 - Tetrahedron a three-membered ring.
  • Three three-membered rings are corner-linked to one another in such a way that they form a nine-membered unit, in the center of which is a first six-membered ring .
  • the first six-membered ring is formed by two (Si,Al)(N,O) 4 tetrahedra of each of the three three-membered rings. If the six-membered ring is located in the first layer, it is referred to as the first six-membered ring.
  • the shape of the first six-membered ring of the formed nine-membered unit is a triangle.
  • a channel is located in the center of the first six-membered ring.
  • the channel is preferably free of (Si,Al)(N,O) 4 tetrahedra and/or ions.
  • the channel can also be referred to as a tetrahedral defect.
  • the first layer has a plurality of nine-membered units. The nine units are each linked to each other via corners . In this case, three corners of the nine unit are linked to corners of further nine units. In other words, the three corners of the triangle of the first six-ring are linked to further corners of further triangles.
  • the second layer has, among other things, units consisting of four (Si,Al)(N,O)4 tetrahedra shared by each other via corners.
  • This four-unit is constructed by a (Si,Al)(N,O) 4 tetrahedron in the center of the unit, which is surrounded by three further (Si,Al)(N,O) 4 tetrahedra shared by each other via corners.
  • the second layer has, as a further structural element, six interconnected 2023PF01062 February 12, 2025 P2023,1280 WO N - 12 - corner-sharing (Si,Al)(N,O) 4 tetrahedra, which form a second six-membered ring.
  • the second six-membered ring differs from the first six-membered ring, among other things, in that the second six-membered ring is located in the second layer.
  • the second six-membered ring is linked to other second six-membered rings via the four-membered unit via shared corners.
  • Each four-membered unit is linked to three second six-membered rings via shared corners.
  • a second six-membered ring is in turn linked to three four-membered units.
  • the second layer preferably has at least one second six-ring made of (Si,Al)(N,O) 4 tetrahedra and at least one nine-ring made of (Si,Al)(N,O) 4 tetrahedra.
  • the (nitrido)silicate framework of the phosphor is formed exclusively from corner-sharing (Si,Al)(N,O)4 tetrahedra.
  • a framework structure is constructed from alternating first and second layers .
  • the first and second layers are connected to one another via common (Si,Al)(N,O) 4 tetrahedral corners.
  • the first layer has first gaps
  • the second layer has second gaps and third gaps.
  • EA ions or RE ions are embedded in the first gaps
  • EA ions and/or RE ions, as well as M ions are embedded in the second gaps of the second layer .
  • the first gaps contain exclusively EA ions or SE ions.
  • the EA ions can be replaced by SE ions.
  • the SE ions By substituting the SE ions at the same position as the EA ions, a mixed population is created in the phosphor.
  • the first layer contains exclusively EA ions, preferably strontium ions.
  • the first gaps differ from the channels in the first layer.
  • the channels in the first layer are located in the center of a first six-ring. In other words, the channel is located in the center of three three-rings.
  • the first gaps are located in the center of three corner-sharing nine-units. In other words, three nine-units with the first six-rings located in the center are linked together via corner sharing, forming a first gap in the center .
  • the first gap appears like a triangle in a sectional view.
  • EA ions and/or RE ions are located in the first gaps.
  • both EA ions and/or RE ions are located in the second gaps.
  • the third gaps are particularly rich in M ions.
  • strontium and Y ions are found exclusively in the second gaps.
  • the EA ions are located in the second gaps in the nine-membered rings.
  • the M ions are located particularly in the third gaps of the second six-membered rings.
  • the EA ions can be substituted by RE ions.
  • the A ions for example cerium, statistically preferentially occupy the same positions as the RE ions and/or M ions and EA ions. Thus, they can be found in the first, second, and third gaps.
  • the second gaps for the EA ion are fully occupied.
  • the position of the EA ion can also be partially occupied.
  • the EA ions and the SE ions crystallographically occupy, in particular, the same positions.
  • the M ions for example Y ions, are arranged in the third gaps of the second six-membered ring .
  • the M ion for example the yttrium ion, is five-fold coordinated by N,O ions . This is due to the ionic radius of the yttrium ion.
  • the phosphor absorbs electromagnetic radiation in the near ultraviolet to blue spectral range.
  • the phosphor is excitable between 350 nm and 470 nm inclusive.
  • the phosphor absorbs electromagnetic radiation with a wavelength of approximately 405 nm, approximately 440 nm, or approximately 448 nm. Other wavelengths for exciting the phosphor are conceivable.
  • the phosphor emits electromagnetic radiation.
  • the emitted electromagnetic radiation can be described in the form of an emission spectrum.
  • the emission spectrum has an emission peak with an emission maximum that lies between 450 nanometers and 550 nanometers inclusive.
  • the emission maximum of the phosphor is at an excitation of 440 nm or 448 nm. 2023PF01062 February 12, 2025 P2023,1280 WO N - 15 - between 504 nm and 550 nm. At an excitation wavelength of 405 nm, the emission maximum is in a range between 459 nm and 499 nm. The emission maximum of the phosphor is at an excitation wavelength of 405 nm at approximately 479 nm and at an excitation wavelength of 440 nm at approximately 524 nm and at an excitation wavelength of 448 nm at approximately 530 nm.
  • the emission spectrum is the intensity distribution of the electromagnetic radiation emitted by the phosphor after excitation with electromagnetic radiation of the first wavelength range.
  • the emission spectrum is usually represented in the form of a diagram in which a spectral intensity or a spectral radiant flux per wavelength interval (“spectral intensity/spectral radiant flux”) of the electromagnetic radiation emitted by the phosphor is plotted as a function of the wavelength ⁇ .
  • the emission spectrum represents a curve in which the wavelength is plotted on the x-axis and the spectral intensity or the spectral radiant flux is plotted on the y-axis.
  • a dominant wavelength ( ⁇ Dom ) of the electromagnetic radiation emitted by the phosphor lies between 470 nm and 575 nm inclusive.
  • a dominant wavelength ( ⁇ Dom ) of the electromagnetic radiation emitted by the phosphor at an excitation wavelength of 440 nm or 448 nm lies between 2023PF01062 February 12, 2025 P2023,1280 WO N - 16 - including 520 nanometers and 575 nanometers inclusive.
  • the dominant wavelength at an excitation wavelength of 440 nm is approximately 540 nm
  • the dominant wavelength at an excitation wavelength of 448 nm is approximately 555 nm.
  • a dominant wavelength ( ⁇ Dom ) of the electromagnetic radiation emitted by the phosphor at an excitation wavelength of 405 nanometers is between 479 nanometers and 519 nanometers inclusive.
  • the dominant wavelength at an excitation wavelength of 405 nm is approximately 499 nm.
  • the dominant wavelength is advantageously in the blue-green to green wavelength range.
  • a straight line is drawn in the CIE standard diagram, starting from the white point and passing through the chromaticity coordinate of the electromagnetic radiation.
  • the intersection of the straight line with the spectral color line delimiting the CIE standard diagram denotes the dominant wavelength of the electromagnetic radiation.
  • the dominant wavelength is the monochromatic wavelength that produces the same color impression as a polychromatic light source.
  • the dominant wavelength is therefore the wavelength perceived by the human eye.
  • the dominant wavelength differs from the wavelength of the emission maximum.
  • a half-width of the electromagnetic radiation emitted by the phosphor is between 50 nm and 125 nm inclusive.
  • the half-width of the electromagnetic radiation emitted by the phosphor preferably has a range from 80 nm to 110 nm inclusive.
  • the half-width of the electromagnetic radiation emitted by the phosphor particularly preferably has a range from 80 nm to 100 nm inclusive. For example, the half-width is approximately 90 nm.
  • the term half-width refers to a curve with a maximum, such as the emission spectrum, the half-width being the width of that region on the x-axis which corresponds to the two y-values which correspond to half the maximum.
  • An optoelectronic component is also specified.
  • the phosphor is particularly suitable and intended for use in an optoelectronic component.
  • Features and embodiments that are implemented solely in connection with the phosphor and/or the method can also be implemented in the optoelectronic component, and vice versa.
  • the optoelectronic component comprises a semiconductor chip that, during operation, emits electromagnetic radiation of a first wavelength range from a radiation exit surface.
  • the semiconductor chip is, for example, a light-emitting diode chip or a laser diode chip.
  • the semiconductor chip preferably has an epitaxially grown semiconductor layer sequence with an active zone configured to generate electromagnetic radiation.
  • the active zone has, for example, a pn junction, a double heterostructure, a single quantum well structure, or particularly preferably a multiple quantum well structure.
  • the semiconductor chip preferably emits electromagnetic radiation from the ultraviolet spectral range and/or from the visible spectral range, particularly preferably from the blue spectral range.
  • the optoelectronic component has a conversion element with a phosphor described here, which converts electromagnetic radiation of the first wavelength range into electromagnetic radiation of the emission spectrum.
  • the first wavelength range is preferably wholly or partially the excitation spectrum of the phosphor.
  • the phosphor converts electromagnetic radiation of the first wavelength range completely or partially into electromagnetic radiation of the emission spectrum.
  • the conversion element comprises, for example, in addition to the phosphor described here, a matrix material in which the phosphor is embedded in the form of particles.
  • the matrix material is preferably selected from the group of polysiloxanes, epoxides, glasses, and hybrid materials.
  • the matrix material contains one or more 2023PF01062 February 12, 2025 P2023,1280 WO N - 19 - further phosphors are embedded.
  • the further phosphors are preferably red- or yellow-emitting phosphors.
  • the further phosphors are, for example, garnet phosphors or nitride phosphors.
  • the garnet phosphor is particularly preferably a YAG phosphor with the chemical formula Y 3 Al 5 O 12 :Ce 3+ or a LuAG phosphor with the chemical formula Lu 3 Al 5 O 12 :Ce 3+ .
  • the nitride phosphors preferentially convert blue primary radiation into red secondary radiation.
  • the nitride phosphor can be, for example, an alkaline earth metal silicon nitride, an oxynitride, an aluminum oxynitride, a silicon nitride or a sialon.
  • the nitride phosphor is (Ca,Sr,Ba)AlSiN 3 :Eu 2+ (CASN).
  • the further phosphors are particularly preferably selected from the following group: Ce 3+ doped garnets such as YAG and LuAG, for example (Y, Lu, Gd, Tb) 3 (Al 1-x , Ga x ) 5 O 12 :Ce 3+ ; Eu 2+ doped nitrides, for example (Ca, Sr)AlSiN 3 :Eu 2+ , Sr(Ca, Sr)Si 2 Al 2 N 6 :Eu 2+ (SCASN), (Sr, Ca)AlSiN 3 *Si 2 N 2 O:Eu 2+ , (Ca, Ba, Sr) 2 Si 5 N 8 :Eu 2+ , SrLiAl 3 N 4 :Eu 2+ , SrLi 2 Al 2 O 2 N 2 :Eu 2+ ; Ce 3+ doped nitrides, for example (Ca,Sr)Al(1-4x/3)Si(1+x)N3:Ce
  • phosphors include, in particular, the following aluminum-containing and/or silicon-containing phosphor particles: 2023PF01062 February 12, 2025 P2023,1280 WO N - 20 - (Ba 2+ 1-x-ySrxCay)SiO4:Eu (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), (Ba1-x- S 2+ 2+ y rxCay)3SiO5:Eu (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), Li2SrSiO4:Eu, oxo- nitrides such as (Ba Sr Cay)Si2O 2+ 1-xy x 2N2:Eu (0 ⁇ x ⁇ 1; 0 ⁇ y ⁇ 1), SrSiAl ON :Eu2+, Ba -xC 2+ 2 3 2 4 axSi6ON10:Eu (0 ⁇ x ⁇ 1), (
  • the conversion element comprises at least one further phosphor that converts electromagnetic radiation of the first wavelength range into electromagnetic radiation of a further wavelength range.
  • the further phosphor is also embedded in the same conversion element as the first phosphor.
  • the further phosphor can also be arranged in a further conversion element, which is located on the conversion element.
  • the further phosphor preferably converts electromagnetic radiation of the first wavelength range into electromagnetic radiation of the third wavelength range, which differs from the emission spectrum.
  • the further phosphor emits yellow and/or red light.
  • the phosphor can be produced using the method described below. Features and embodiments that are only described in connection with the phosphor and the 2023PF01062 February 12, 2025 P2023,1280 WO N - 22 - optoelectronic component can also be formed in the method and vice versa.
  • EA 4-xad SE x+a M 1-bc Si 19-yx-3c Al y+x+3c N 29-y+a-3b-2d O y-a+3b+2d :A where - EA is selected from Ca, Sr, Ba, Zn or combinations thereof, - SE is selected from the group of trivalent rare earth elements or combinations thereof, - M is selected from Sc, Y, Lu, Tm, Er, Ho or combinations thereof, - A is selected from Ce, Eu, Mn, Bi, Tb, Dy, Ni, Cr, Er or combinations thereof, - 0 ⁇ d ⁇ 1; - 0 ⁇ x+a+d ⁇ 4; - 0 ⁇ b+c ⁇ 1; - 0 ⁇ y+x+3c ⁇ 19; - 0 ⁇ y-a+3b+2d ⁇ 10; - 2*(4-xad) +
  • a stoichiometric composition of the reactants is homogenized. This can 2023PF01062 February 12, 2025 P2023,1280 WO N - 23 - for example, in a hand mortar, a mortar mill, a ball mill, a multi-axis mixer, or the like.
  • the resulting reaction mixture of the reactants is transferred into a crucible.
  • the crucible can comprise, for example, corundum, tungsten, molybdenum, or tantalum.
  • the reaction mixture is heated in a further step to a temperature between 1500°C and 2000°C, preferably between 1650°C and 1850°C.
  • the temperature is maintained for 1 hour up to and including 20 hours.
  • the heating takes place under a nitrogen atmosphere or a reducing atmosphere, for example forming gas, at normal or elevated pressure .
  • the forming gas atmosphere comprises, for example, a mixture of nitrogen or argon with up to 10% hydrogen, or is formed from such a mixture.
  • the reaction mixture is preferably heated under an N2 atmosphere at 20 bar and at a temperature of 1750°C for four hours. Particularly preferably, the reaction mixture is heated under an N2 atmosphere at atmospheric pressure and at a temperature of 1650°C for four hours.
  • the reactants are selected from the following group: yttrium compound, 2023PF01062 February 12, 2025 P2023,1280 WO N - 24 - Strontium compound, silicon compound, cerium compound, aluminum compound, and combinations thereof.
  • the reactants are selected from the following group: yttrium nitride, yttrium oxide, strontium nitride, strontium subnitride, strontium carbonate, strontium oxide, silicon nitride, silicon oxide, aluminum nitride, aluminum oxide, cerium oxide, cerium nitride, cerium fluoride, and combinations thereof.
  • the reaction mixture is heated at atmospheric pressure.
  • One idea of the present phosphor is to reduce the proportion of yttrium to the proportion of the framework former, for example, silicon, to 1:19. This advantageously reduces a rarely occurring, expensive element in the phosphor . In other words, the rare earth content per mass of phosphor is reduced to 8 percent.
  • the phosphor is particularly well-suited for high irradiances, as only minimal quenching effects occur.
  • the phosphor described here is very well suited for the blue-green to green spectral range and contributes to more efficient and/or simpler, and thus more cost-effective, solutions for the application.
  • the phosphor described here emits blue-green to green light and can be used at high irradiances.
  • Figure 1 a schematic section of a first layer of a crystal structure of a host lattice of a phosphor according to an embodiment
  • Figure 2 a four-unit as a structural feature of a second layer of a crystal structure of a host lattice of a phosphor according to an embodiment
  • Figure 3 a schematic section of a second layer of a crystal structure of a host lattice of a phosphor with a four-unit and a second six-ring as structural features according to an embodiment
  • Figure 4 the linkage of the first layer and the second layer to a framework structure of a phosphor according to an embodiment, 2023PF01062 February 12, 2025 P2023,1280 WO N - 26 -
  • Figure 5 shows a schematic section of a first layer of a crystal structure of a host lattice of a phosphor according to an exemplary embodiment
  • Figure 6 shows a schematic section of a second layer of a crystal structure of a host lattice of a phosphor
  • the phosphor 1 according to one embodiment is in the form of particles.
  • the particles have a grain size of between 0.2 micrometers and 100 micrometers inclusive (not explicitly shown).
  • the phosphor 1 obeys the formula EA 4-xad SE x+a M 1-bc Si 19-yx-3c Al y+x+3c N 29-y+a-3b-2d O y- a+3b+2d:A
  • the phosphor 1 obeys the empirical formula Sr 4-mo Y 1-np Si 19-t+2m+3n Al t-2m-3n N 29-t-2o-3p O t+2o+3p :Ce 3+ .
  • the host lattice comprises a structure with a trigonal space group.
  • the phosphor 1 crystallizes in the trigonal space group P3.
  • the crystal structure of the host lattice of the phosphor 1 comprises corner-sharing (Si,Al)(N,O) 4 tetrahedra 2.
  • the crystal structure has a first layer 4, and the first layer 4 comprises (Si,Al)(N,O) 4 tetrahedra 2.
  • the first layer comprises three-membered rings 20.
  • the three-membered rings 20 comprise three corner-sharing (Si,Al)(N,O) 4 tetrahedra 2. In other words, three corner-sharing (Si,Al)(N,O) 4 tetrahedra 2 form a three-membered ring 20.
  • Three three-membered rings 20 are corner-sharing to form a nine-membered unit 23 with a first six-membered ring 17 at the center.
  • the first six-membered ring 17 is formed by two (Si,Al)(N,O) 4 tetrahedra 2 of each of the three three-membered rings 20.
  • a channel 21 is located in the center of the first six-membered ring 17.
  • the channel 21 is preferably free of tetrahedra and/or ions.
  • the channel 21 is a tetrahedral defect.
  • the first layer 4 has a plurality of nine-membered units 23 and thus of first six-membered rings 17.
  • the plurality of nine-membered units 23 are each connected to one another via common corners 3. 2023PF01062 February 12, 2025 P2023,1280 WO N - 28 - linked. In this case, three corners of the nine-unit 23 are each linked to corners of three further nine-units 23.
  • Figure 2 shows a section of a crystal structure of a host lattice of a phosphor 1 according to an exemplary embodiment.
  • Figure 2 shows part of the second layer 5 of the crystal structure.
  • the second layer 5 has, among other things, a four-unit 22 consisting of four (Si,Al)(N,O)4 tetrahedra 2 sharing corners.
  • the two right-hand figures in Figure 2 show two ordered variants that differ only in the precise orientation of the disordered N,O positions.
  • a (Si,Al)(N,O) 4 tetrahedron 2 is located at the center. This tetrahedron is corner-shared with three further (Si,Al)(N,O) 4 tetrahedra 2.
  • Figure 3 shows the second layer 5 of the crystal structure of the phosphor 1 according to an exemplary embodiment.
  • the second layer 5 has six corner-shared (Si,Al)(N,O) 4 tetrahedra 2, which form a second six-ring 18.
  • the second six-ring 18 is linked to the four-units 22.
  • Each four-unit 22 is linked to three second six-rings 18 via common corners.
  • a second six-ring 18 is in turn linked to three four -units 22.
  • Nine-rings 19 are formed, which are formed by three times two (Si,Al)(N,O)4 tetrahedra 2 of the second six-rings 18 and one (Si,Al)(N,O)4 tetrahedron 2 each of the three four-ring units 22.
  • the second layer comprises 5 second six-rings 18 and nine-rings 19. 2023PF01062 February 12, 2025 P2023,1280 WO N - 29 - Figure 4 shows a part of the first layer 4 and the second layer 5 of the crystal structure of the phosphor 1 according to an embodiment.
  • the first layer 4 and the second layer 5 form a framework structure 6.
  • the first layer 4 and the second layer 5 are connected to one another via common (Si,Al)(N,O) 4 tetrahedral corners to form a framework structure.
  • Figure 5 shows the first layer 4 of the crystal structure of the phosphor 1 according to an embodiment.
  • the first layer 4 has first gaps 71, and EA ions or SE ions 8 are embedded in the first gaps 71 of the first layer 4.
  • the first gaps 71 are located in the middle of three corner-sharing nine-units 23.
  • three EA ions 8, preferably strontium ions are each embedded in a first gap 71 of the first layer 4.
  • the first layer 4 contains exclusively EA ions or SE ions 8, preferably strontium ions.
  • the channels 21 in the center of the first six-rings 17 in the first layer 4 are free of ions and (Si,Al)(N,O) 4 tetrahedra 2.
  • Figure 6 shows a section of the second layer 5 of the crystal structure of the phosphor 1 according to an exemplary embodiment.
  • the second layer 5 has second gaps 72 and third gaps 73.
  • EA ions or SE ions 8 are embedded in the second gaps 72
  • M ions 9 are embedded in the third gaps 73.
  • strontium ions are present in the second gaps 72 of the second layer 5 2023PF01062 February 12, 2025 P2023,1280 WO N - 30 - embedded.
  • the second gaps 72 are located in the middle of the nine-rings 19.
  • the third gaps 73 are located in the middle of the second six-rings 18.
  • the strontium ions are located in the second gaps 72 of the nine-rings 19.
  • the M ions 9, preferably Y ions, are embedded in the third gaps 73 of the second six-rings 18.
  • the second gaps 72 of the nine-rings 19 there is preferably an EA ion 8, in this case the strontrium ion
  • the third gaps 73 of the second six-rings 18 there is preferably an M ion 9, in this case the Y ion.
  • the activator ion A occupies the same positions as the EA, SE or M ions, preferably Y and strontium ions, and can be located in the first layer 4 and in the second layer 5.
  • all Si layers could have a mixed Si/Al occupancy.
  • all terminal or doubly bridging layers could have a mixed N/O occupancy or a pure O occupancy. These layers are marked [1] or [2] in Table 2. 2023PF01062 February 12, 2025 P2023,1280 WO N - 31 - All other N layers are triply bridging layers. These are marked with [3] .
  • a mixed occupation of the Sr layers with other divalent or trivalent cations is conceivable, depending on the composition.
  • Table 1 Crystallographic data of Sr 4-mo Y 1-np Si 19-t+2m+3n Al t-2m-3n N 29-t-2o-3p O t+2o+3p :Ce 3+ .
  • Table 2 Crystallographic position parameters of Sr4-m-oY1-n-pSi19-t+2m+3nAl t-2m-3nN29-t-2o-3pO t+2o+3p:Ce 3+ .
  • the phosphor 1 was excited at a wavelength of 405 nm and 440 nm.
  • the emission spectrum is the spectral intensity I of the electromagnetic radiation emitted by the phosphor 1 as a function of the wavelength ⁇ .
  • the emission spectrum is in a wavelength range from 450 to 2023PF01062 February 12, 2025 P2023,1280 WO N - 33 - including 700 nanometers.
  • the emission spectrum E1 exhibits a dominant wavelength ⁇ Dom of 499 nanometers at an excitation wavelength of 405 nanometers .
  • the spectral full width at half maximum (FWHM) is 57 nanometers.
  • the emission spectrum is cut off on the short-wavelength side by a filter due to the measurement setup.
  • the emission maximum ⁇ max is 479 nanometers.
  • the emission spectrum E2 exhibits a dominant wavelength ⁇ Dom of 540 nanometers at an excitation wavelength of 440 nanometers.
  • the spectral full width at half maximum is 90 nanometers and the emission maximum ⁇ max is 524 nanometers.
  • the emission spectrum exhibits a dominant wavelength ⁇ Dom of 555 nanometers at an excitation wavelength of 448 nanometers.
  • the spectral full width at half maximum is 89 nanometers, and the emission maximum ⁇ max is 530 nanometers.
  • Tables 3 and 4. A shift in the emission curve depending on the excitation wavelength is clearly visible.
  • Table 3 Spectral data for Sr4-m-oY1-n-pSi19-t+2m+3nAlt-2m-3nN29-t-2o-3pOt+2o+3p:Ce 3+ .
  • Excitation at excitation at 4 05 nm 440 nm Dominant wavelength 499 nm 540 nm ⁇ dom Emission maximum ⁇ max 479 nm 524 nm Half width FWHM 57 nm (cut-off) 90 nm
  • Figure 8 shows the emission spectrum E-VB1 of the comparative example YAGaG:Ce and the emission spectrum E-VB2 of the comparative example ß-SiAlON:Eu as well as the 2023PF01062 February 12, 2025 P2023,1280 WO N - 34 - Emission spectrum E3 of the exemplary embodiment of the phosphor 1 with the empirical formula Sr4-m-oY1-n-pSi19-t+2m+3nA
  • the excitation wavelength is 448 nanometers.
  • the emission spectrum E3 of the phosphor 1 is shown as a solid line.
  • the emission spectrum E-VB1 of the comparison phosphor YAGaG:Ce is shown as a dotted line, and the emission spectrum E-VB2 of the comparison phosphor ß-SiAlON:Eu is shown as a dashed line.
  • the spectral data are summarized in Table 4.
  • Table 4 Spectral data for Sr4-m-oY1-n-pSi19-t+2m+3nAlt-2m-3nN29-t-2o-3pOt+2o+3p:Ce 3+ , embodiment 2, comparative example 1 (YAGaG:Ce) and comparative example 2 (ß-SiAlON:Eu) at excitation at 448 nm .
  • the semiconductor chip 11 comprises an active layer sequence and an active region (not explicitly 2023PF01062 February 12, 2025 P2023,1280 WO N - 35 - shown) which serves to generate the primary radiation.
  • the primary radiation is electromagnetic radiation of a first wavelength range. Preferably, it is electromagnetic radiation with wavelengths in the visible range, for example, in the blue spectral range.
  • a conversion element 13 is arranged in the beam path of the electromagnetic radiation emitted by the semiconductor chip 11 in the first wavelength range. The conversion element 13 is configured to absorb the electromagnetic radiation of the first wavelength range and to convert it at least partially into electromagnetic radiation of the emission spectrum. In particular, the emission spectrum has a longer wavelength than the absorbed first wavelength range.
  • the conversion element 13 has a phosphor 1 with the general formula EA 4-xad SE x+a M 1-bc Si 19-yx-3c Al y+x+3c N 29-y+a-3b-2d O y- a+3b+2d:A.
  • the conversion element 13 can have the phosphor 1 with the formula Sr 4-mo Y 1-np Si 19-t+2m+3n Al t-2m-3n N 29-t-2o- 3p O t+2o+3p :Ce 3+ .
  • the phosphor 1 can be embedded in a matrix material.
  • the matrix material is, for example, a silicone, a polysiloxane, an epoxy resin, or a glass.
  • the conversion element 13 can be free of a matrix material.
  • the conversion element 13 made of the phosphor 1 can, for example, consist of a ceramic of the phosphor 1. 2023PF01062 February 12, 2025 P2023,1280 WO N - 36 -
  • the conversion element 13 can have at least one further phosphor 1.
  • the further phosphor 1 converts electromagnetic radiation of the first wavelength range into electromagnetic radiation of a further wavelength range.
  • the further phosphor can, for example, convert the electromagnetic radiation of the first wavelength range into electromagnetic radiation of the yellow and/or red wavelength range.
  • the further phosphor can, for example, be a (Sr,Ca)AlSiN 3 :Eu and/or YAGaG:Ce.
  • the semiconductor chip 11 and the conversion element 13 are embedded in a recess 15 of a housing 14.
  • the recess 15 of the housing 14 can be filled with a potting compound 16, and the semiconductor chip 11 and the conversion element 13 are completely encased by the potting compound 16.
  • the conversion element 13 can be arranged in direct mechanical contact on the semiconductor chip 11, as shown in Figure 9.
  • the radiation exit surface 12 forms the common surface between the conversion element 13 and the semiconductor chip 11.
  • further layers, such as adhesive layers can be located between the semiconductor chip 11 and the conversion element 13.
  • the conversion element 13 is arranged at a distance from the semiconductor chip 11.
  • a potting compound 16 can be arranged between the semiconductor chip 11 and the conversion element 2023PF01062 February 12, 2025 P2023,1280 WO N - 37 - 13.
  • the recess 15 between the semiconductor chip 11 and the conversion element 13 can also be free of a potting 16 or further layers or components.
  • the conversion element 13 is arranged in a recess 15.
  • the semiconductor chip 11 is embedded in the conversion element 13.
  • the conversion element 13 has the phosphor 1 and the matrix material, which is, for example, silicone. Further phosphors can be introduced into the conversion element 13.
  • Figures 12 and 13 each show simulated LED emission spectra of phosphor solutions.
  • the phosphor solution of the emission spectrum SE1 comprises the phosphor 1, in this case Sr 4-mo Y 1-np Si 19-t+2m+3n Al t-2m-3n N 29-t-2o- O :Ce3+ 3p t+2o+3p , and the additional red phosphor (Sr,Ca)AlSiN3:Eu.
  • the simulated LED spectrum SE2 comprises the phosphor solution consisting of the reference phosphor YAGaG:Ce and the additional red phosphor (Sr,Ca) AlSiN3 :Eu.
  • the color temperature in Figure 12 is 4000 K and the color temperature in Figure 13 is 5000 K.
  • the relative intensity I is plotted against the wavelength ⁇ in nanometers .
  • LED emission spectra were simulated for the phosphor solutions consisting of phosphor 1 and the red phosphor (Sr,Ca) AlSiN3 :Eu, as well as for the reference phosphor solution consisting of YAGaG:Ce and the red phosphor (Sr,Ca)AlSiN3:Eu .
  • the dominant wavelength of the blue-emitting semiconductor chip 11 was 458 nanometers.
  • Table 5 compares the optical data of the simulated LED emission spectra of the phosphor solution comprising the phosphor 1 Sr 4-mo Y 1-np Si 19-t+2m+3n Al t-2m-3n N 29-t-2o-3p O t+2o+3p :Ce 3+ according to the exemplary embodiment and the red phosphor (Sr,Ca)AlSiN3:Eu, as well as a comparative example phosphor solution comprising the comparative phosphor YAGaG:Ce and the red phosphor (Sr,Ca) AlSiN3 :Eu.
  • the blue-emitting semiconductor chip 11 has a dominant wavelength of 458 nanometers.
  • Table 5 Comparison of solutions for white light generation with CRI> 90 using the phosphor according to the invention as the green component and CRI ⁇ 90 using a commercially available YAGaG:Ce as the green component.
  • Phosphor solution Phosphor solution 1 Comparative example Sr4-m-oY1-n-pSi19-t+2m+3nAlt- 1: 2 m-3n N 29-t-2o-3p O t+2o+3p :Ce 3+ YAGaG:Ce + (Sr,Ca)AlSiN:Eu + (Sr,Ca)AlSiN:Eu Color temperature CCT 4000 K 5000 K 4000 K 5000 K Color rendering CRI 90 90 86 87 R9 46 54 22 27
  • a stoichiometric composition of reactants is provided in a first method step S1.
  • the reactants can be an yttrium source, for example yttrium nitride, yttrium oxide; a strontium source, for example 2023PF01062 February 12, 2025 P2023,1280 WO N - 39 - Example stontium nitride, strontium subnitride, strontium oxide or strontium carbonate; a silicon source, for example silicon nitride or silicon oxide; an aluminum source, for example aluminum nitride or aluminum oxide and an activator, for example cerium in the form of cerium oxide, cerium nitride or cerium fluoride.
  • the reactants are weighed in a protective gas atmosphere and thoroughly mixed.
  • a next step S2 the reaction mixture is heated to a temperature between 1500 °C and 2000 °C inclusive.
  • the mixed reactants are transferred to a crucible for homogenization.
  • This crucible can be made of corundum, tungsten, molybdenum or tantalum, for example.
  • the maximum synthesis temperature is maintained for 1 to 20 hours .
  • Annealing takes place under a nitrogen or reducing atmosphere, such as forming gas, at atmospheric or elevated pressure.
  • the reactants are reacted under an N2 atmosphere at 20 bar and 1750 °C or under an N2 atmosphere at atmospheric pressure and 1650 °C for 4 hours.
  • the reaction mixture is cooled and ground in a hand mortar.
  • This can be done, for example, in a hand mortar, a mortar grinder, or a ball mill.
  • Table 6 summarizes the weight of the reactants used for the production of a phosphor 1 with the molecular formula Sr 4-mo Y 1-np Si 19-t+2m+3n Al t-2m- 3n N 29-t-2o-3p O t+2o+3p :Ce 3+ according to an embodiment.

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

Abstract

L'invention concerne un luminophore (1) de formule générale EA4-x-a-dSEx+aM1-b-cSi19-y-x-3cAly+x+3cN29-y+a-3b-2dOy-a+3b+2d:A , dans laquelle : - EA est choisi parmi Ca, Sr, Ba, Zn ou leurs combinaisons ; - SE est choisi dans le groupe d'éléments trivalents de terres rares ou de leurs combinaisons ; - M est choisi parmi Sc, Y, Lu, Tm, Er, Ho ou leurs combinaisons ; - A est choisi parmi Ce, Eu, Mn, Bi, Tb, Dy, Ni, Cr, Er ou leurs combinaisons ; - 0 ≤ d ≤ 1; - 0 ≤ x+a+d ≤ 4; - 0 ≤ b+c < 1 ; - 0 ≤ y+x+3c ≤ 19 ; - 0 ≤ y-a+3b+2d ≤ 10 ; et - 2*(4-x-a-d) + 3*(x+a) + 3* (1-b-c)+ 4*(19-y-x-3c) + 3*(y+x+3c)-3*(29-y+a-3b-2d)-2*(y-a+3b+2d) = 0. L'invention concerne également un composant optoélectronique (10) et un procédé de production d'un luminophore (1).
PCT/EP2025/053709 2024-02-14 2025-02-12 Luminophore, composant optoélectronique et procédé de production d'un luminophore Pending WO2025172353A1 (fr)

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US20180346808A1 (en) * 2017-06-06 2018-12-06 Panasonic Intellectual Property Management Co., Ltd. Phosphor that includes cerium

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WO2008146571A1 (fr) * 2007-05-22 2008-12-04 Showa Denko K.K. Substance fluorescente, procédé de production de celle-ci et dispositif émettant de la lumière utilisant celle-ci
CN103031127B (zh) * 2011-09-30 2014-10-29 有研稀土新材料股份有限公司 一种橙色荧光粉及其制备方法和用该荧光粉制成的电光源
CN103045257B (zh) * 2011-10-17 2015-09-23 有研稀土新材料股份有限公司 一种氮化物发光材料及采用该发光材料制成的发光器件
EP2784143B1 (fr) * 2011-11-07 2016-10-05 National Institute for Materials Science Phosphore, son procédé de production, dispositif d'émission de lumière et dispositif d'affichage d'images utilisant du phosphore
WO2015018474A1 (fr) * 2013-08-08 2015-02-12 Merck Patent Gmbh Substances luminescentes

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US20180346808A1 (en) * 2017-06-06 2018-12-06 Panasonic Intellectual Property Management Co., Ltd. Phosphor that includes cerium

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