WO2024028387A1 - Leuchtstoff, verfahren zur herstellung eines leuchtstoffs und strahlungsemittierendes bauelement - Google Patents
Leuchtstoff, verfahren zur herstellung eines leuchtstoffs und strahlungsemittierendes bauelement Download PDFInfo
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- WO2024028387A1 WO2024028387A1 PCT/EP2023/071407 EP2023071407W WO2024028387A1 WO 2024028387 A1 WO2024028387 A1 WO 2024028387A1 EP 2023071407 W EP2023071407 W EP 2023071407W WO 2024028387 A1 WO2024028387 A1 WO 2024028387A1
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- 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
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- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/77928—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
Definitions
- a phosphor, a method for producing a phosphor and a radiation-emitting component are specified.
- the task of at least one embodiment is to provide a phosphor with improved properties.
- the object of at least one further embodiment is to provide a method for producing a phosphor with improved properties.
- the object of at least one further embodiment is to provide a radiation-emitting component with improved properties.
- the phosphor has the general formula A 4 L 3-x M 1+x N 9-x O x :RE, where 0 ⁇ x ⁇ 3.
- A is an element or a combination of elements from the group of rare earth elements
- L an element or a combination of elements from the group of tetravalent elements
- M an element or a combination of elements from the group of trivalent elements
- RE an activator element.
- a phosphor described here can convert electromagnetic radiation of a specific wavelength or a specific wavelength range, hereinafter referred to as primary radiation, into electromagnetic radiation of a second 2022PF00115 August 2, 2023 P2022,0732 WO N - 2 - wavelength or a second wavelength range, hereinafter referred to as secondary radiation.
- the conversion of primary radiation into secondary radiation is also known as wavelength conversion.
- primary radiation is absorbed by a wavelength-converting element containing the phosphor, converted into secondary radiation by electronic processes at the atomic and/or molecular level and emitted again.
- Primary and secondary radiation therefore have wavelength ranges that are at least partially different from one another, with the secondary radiation having a longer wavelength range according to one embodiment.
- the term “wavelength conversion” does not mean pure scattering or pure absorption of electromagnetic radiation in this case.
- the phosphor can in particular have a crystalline, for example ceramic, host material into which RE is introduced as an activator element.
- the phosphor is, for example, a ceramic material.
- an activator element is to be understood as an element that changes the electronic structure of the host material in such a way that electromagnetic radiation of the first wavelength range can be absorbed by the phosphor. This primary radiation can stimulate an electronic transition in the phosphor, which can return to the ground state by emitting electromagnetic radiation in the second wavelength range.
- the activator element RE which is introduced into the host material, is therefore for 2022PF00115 August 2, 2023 P2022,0732 WO N - 3 - wavelength converting properties of the phosphor.
- phosphors are described using molecular formulas. The elements listed in the molecular formulas are in charged form.
- elements and/or atoms in relation to the molecular formulas of the phosphors mean ions in the form of cations and anions, even if this is not explicitly stated. This also applies to element symbols if they are given without a charge number for the sake of clarity.
- A, L, M and RE exist as cations, while O and N exist as anions.
- RE has a triple positive charge and can therefore also be specified as RE 3+ .
- the phosphor has other elements, for example in the form of impurities. Taken together, these impurities have at most 5 mol%, in particular at most 1 mol%, preferably at most 0.1 mol%.
- the present phosphor can be externally uncharged. This means that there can be a complete charge balance between positive and negative charges in the phosphor to the outside. However, it is also possible that the phosphor does not formally have a complete charge balance to a small extent.
- rare earth elements include the chemical elements of the 3rd subgroup of the periodic table as well as the lanthanoids.
- rare earth elements are generally selected from the group formed by scandium, yttrium, lanthanum, cerium, 2022PF00115 August 2, 2023 P2022,0732 WO N - 4 - Praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
- the term “valence” in relation to a specific element means how many elements with a simple opposite charge are required in a chemical compound to achieve charge balance. The term “valence” therefore includes the charge number of the element.
- Trivalent elements are elements with a valence of three. Trivalent elements are often triple positively charged in chemical compounds and have a charge number of +3. For example, charge balancing in a chemical compound can occur via an element that is triple negatively charged or through three elements that are single negatively charged. Tetravalent elements are elements with a valence of four. Tetravalent elements are often four times positively charged in chemical compounds and have a charge number of +4. For example, charge balancing in a chemical compound can occur via one element that is four times negatively charged, two elements that are doubly negatively charged, or four elements that are single negatively charged.
- a phosphor described here has an emission position that can be adjusted over a wide wavelength range and can therefore be used and used in a variety of ways.
- the phosphor can be stimulated with primary radiation from the blue or UV (UV: ultraviolet) 2022PF00115 August 2, 2023 P2022,0732 WHERE N - 5 - spectral range emit secondary radiation in the blue-green to red spectral range.
- UV ultraviolet
- the phosphor described here can also be used for full conversion into LEDs if it completely converts the primary radiation into secondary radiation.
- the phosphor emits, for example, in the orange spectral range, an LED with full conversion can then be used, for example, for flashing lights in automobiles. If the phosphor emits in the blue-green or yellow-green spectral range, it is also suitable for Human Centric Lighting (HCL) applications where the effects of light on people are important. Since the spectral position of an electromagnetic radiation emitted by the phosphor in the blue-green or green-yellow range has a high overlap with the melanopic curve, the alertness of the viewer can be influenced in particular.
- the phosphor described here has an extended color temperature (CCT, correlated color temperature) range and improved color rendering index (CRI) values compared to conventional phosphors.
- CCT extended color temperature
- CRI color rendering index
- representatives of the garnet system (Y,Gd,Tb) 3 (Al,Ga) 5 O 12 :Ce 3+ are usually used for conversion into the green and yellow spectral range, with dominance wavelengths ( ⁇ dom ) of 555 nm to 575 nm can be realized.
- the systems (Ca,Sr,Ba) 2 Si 5 N 8 :Eu 2+ and (Ca,Sr)AlSiN 3 :Eu 2+ are known.
- dominance wavelengths of 580 nm to 610 nm can usually be achieved.
- the phosphor described here has adjustability over a broad wavelength range from the blue-green to red spectral range.
- a controlled displaceability or adaptability of the emission position over such a large wavelength range with only one phosphor system is advantageous for various applications because they represent efficient and/or simple and therefore inexpensive solutions for the application.
- the emission position can be controlled, for example, via the composition and/or the content of activator element.
- the emission position can be shifted towards red as the content of the activator element RE increases.
- RE is an element or a combination of elements from the group Ce, Eu, Tb, Sm and Pr.
- RE is Ce.
- Ce is then triple 2022PF00115 August 2, 2023 P2022,0732 WO N - 7 - positively charged in the phosphor and can also be specified as Ce 3+ .
- the use of Ce as an activator element can result in a phosphor that is particularly stable to quenching.
- L is Si.
- M is Al.
- the phosphor has the general formula La 4 Si 3-x Al 1+x N 9-x O x :RE with 0 ⁇ x ⁇ 3.
- Si is used for L and Al for M and La for A.
- x is chosen to be greater than 0, so that O is necessarily present.
- RE may be selected as explained above.
- RE is Ce.
- the phosphor has the general formula La 4 Si 3-x Al 1+x N 9-x O x :Ce.
- a phosphor emits, in particular broadband, in the blue-green to red spectral range and can therefore be used without combination with other phosphors for solutions that require broadband emission in these spectral ranges, for example in warm white lighting devices.
- the phosphor comprises a crystalline, for example ceramic, host lattice.
- the phosphor is, for example, a ceramic material.
- the crystalline host lattice is constructed in particular from a generally periodically repeating three-dimensional elementary cell.
- the unit cell is the smallest repeating unit 2022PF00115 August 2, 2023 P2022,0732 WO N - 8 - of the crystalline host lattice.
- the elements L, M, N and O each occupy fixed positions, so-called point positions, in the three-dimensional unit cell of the host lattice.
- six lattice parameters are required, three lengths a, b and c and three angles ⁇ , ⁇ and ⁇ .
- the three lattice parameters a, b and c are the lengths of the lattice vectors that span the unit cell.
- the other three grid parameters ⁇ , ⁇ and ⁇ are the angles between these grid vectors.
- the phosphor described here crystallizes in a monoclinic space group.
- the phosphor crystallizes in the monoclinic space group P2 1 /n. This can be determined, for example, using single crystal X-ray diffraction.
- the phosphor crystallizes in the monoclinic space group P2 1 /n and has lattice parameters which have the following ranges: 650 pm ⁇ a ⁇ 700 pm, 530 pm ⁇ b ⁇ 580 pm, 1250 pm ⁇ c ⁇ 1310 pm, 85 ° ⁇ ⁇ ⁇ 95°, 95° ⁇ ⁇ ⁇ 115°, 85° ⁇ ⁇ ⁇ 95°.
- the phosphor has first L-centered L(N,O) 4 tetrahedra, first M-centered M(N,O) 4 tetrahedra, second L-centered L(N,O) 4 tetrahedra and second M-centered M(N,O) 4 tetrahedra.
- first L-centered L(N,O) 4 tetrahedra first M-centered M(N,O) 4 tetrahedra
- second L-centered L(N,O) 4 tetrahedra second M-centered M(N,O) 4 tetrahedra.
- the phosphor has first and second Si-centered Si(N,O) 4 tetrahedra and first and second Al-centered Al(N,O) 4 tetrahedra.
- the tetrahedrons each have a tetrahedral gap.
- the tetrahedral gap is an area inside the respective tetrahedron.
- the term “tetrahedral gap” refers to the area inside the tetrahedron that remains free when touching balls are placed in the corners of the tetrahedron.
- the N and/or O atoms of the tetrahedra span the tetrahedron, with the L or M atom located in the tetrahedral gap of the spanned tetrahedron.
- the L or M atom is surrounded by four N and/or O atoms in a tetrahedron shape.
- all atoms that span the tetrahedron are at a similar distance to the L or M atom that is in the tetrahedral gap.
- the first L-centered L(N,O) 4 tetrahedra and M-centered M(N,O) 4 tetrahedra are corner-linked on all sides. Corner-linked on all sides means that each tetrahedron is linked to one corner of another tetrahedron across all four corners.
- the second L-centered L(N,O) 4 tetrahedra and M-centered M(N,O) 4 tetrahedra each have a terminal N or O.
- the tetrahedra of the second type are thus linked to form further tetrahedra via a total of three corners.
- the first and second tetrahedra thus together form one 2022PF00115 August 2, 2023 P2022,0732 WO N - 10 - three-dimensional space network structure made of corner-linked tetrahedra.
- the first L-centered L(N,O) 4 tetrahedra and M-centered M(N,O) 4 tetrahedra are two first L-centered L(N,O) 4 tetrahedra and/or M-centered M(N,O) 4 tetrahedra and linked to two second L-centered L(N,O) 4 tetrahedra and/or M-centered M(N,O) 4 tetrahedra.
- the tetrahedra of the first type are corner-connected on all sides to two further tetrahedra of the first type and to two tetrahedra of the second type.
- the second L-centered L(N,O) 4 tetrahedra and M-centered M (N,O) 4 - Tetrahedra to two first L-centered L(N,O) 4 tetrahedra and/or M-centered M(N,O) 4 tetrahedra and to a second L-centered L(N,O ) 4 tetrahedron or M-centered M(N,O) 4 tetrahedron.
- the tetrahedra of the second type are linked via a total of three corners to form two tetrahedra of the first type and one tetrahedron of the second type.
- the first L-centered L(N,O) 4 tetrahedra, first M-centered M(N,O) 4 tetrahedrons, second L-centered L(N,O) 4 tetrahedrons and second M -centered M(N,O) 4 tetrahedron four-membered rings.
- the tetrahedra of the first kind and the tetrahedra of the second kind form four-rings.
- These rings of four can each contain two tetrahedra of the first type and two tetrahedra of the second type, with a tetrahedron of one type within the ring of four only being linked to two tetrahedra of the other type.
- the four-rings are connected to further four-rings via corners of the tetrahedrons.
- the connection to the next four-ring can be done to form a tetrahedron of the same type.
- the tetrahedra of the first type bridge to form two further tetrahedra of the first type, each of which is part of two further four-rings.
- the tetrahedrons of the second type only link to form another tetrahedron of the second type, which is part of another ring of four.
- the fourth corner of the tetrahedron of the second type has a terminal anion, i.e. N or O.
- a terminal anion i.e. N or O.
- cavities or channels can arise in which the A atoms, for example La, are arranged.
- the A atoms are distributed over two crystallographic layers, i.e. symmetrically different layers. In both positions, the A atom can be surrounded by seven anions, i.e. N and/or O, with the anions each forming distorted, simply capped octahedra.
- the phosphor has an absorption range at least in the UV to blue wavelength range of the electromagnetic spectrum.
- the phosphor can thus be stimulated to emit radiation, for example with blue or UV radiation-emitting semiconductor chips.
- the phosphor emits in the blue-green to red wavelength range of the electromagnetic spectrum.
- a phosphor described here that emits in the yellow-orange spectral range can be used well as a single conversion phosphor solution for warm white LEDs.
- electromagnetic radiation emitted by the phosphor has a dominance wavelength ( ⁇ dom ) between 500 nm and 600 nm inclusive, in particular between 510 nm and 590 nm inclusive. This range is significantly expanded compared to conventional phosphors.
- ⁇ dom dominance wavelength
- This range is significantly expanded compared to conventional phosphors.
- a straight line is drawn in the CIE standard diagram starting from the white point through the color locus 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.
- an electromagnetic radiation emitted by the phosphor has an emission maximum of at least one emission peak between 480 nm and 630 nm inclusive, in particular between 485 nm and 625 nm inclusive. 2022PF00115 August 2, 2023 P2022,0732 WO N - 13 - According to at least one embodiment, an electromagnetic radiation emitted by the phosphor has a spectral half-width between 70 nm and 160 nm inclusive, in particular between 75 and 150 nm inclusive. The phosphor therefore emits in a broad band and can therefore be used without combining with other phosphors for solutions that require broad band emission in certain spectral ranges.
- a process for producing a phosphor is also specified.
- the method can be used to produce a phosphor as described above. All features and embodiments disclosed in connection with the phosphor therefore also apply to the method and vice versa.
- the method produces a phosphor with the general formula A 4 L 3-x M 1+x N 9-x O x :RE where 0 ⁇ x ⁇ 3, A is an element or a combination of elements from the group of rare earth elements, L is an element or a combination of elements from the group of tetravalent elements, M is an element or a combination of elements from the group of trivalent elements, and RE is an activator element.
- the method comprises the steps - providing educts, - mixing the educts to form an educt mixture, and - heating the educt mixture.
- the starting materials are selected from a group consisting of oxides, nitrides, carbonates, nitrates, oxalates, citrates and hydroxides each of A, L, M and RE and combinations included from it.
- LaN, Si 3 N 4 , AlN, Al 2 O 3 and CeO 2 can be selected as starting materials.
- the mixing is carried out in a hand mortar, a mortar mill, a ball mill or a multi-axis mixer. Other devices suitable for mixing the starting materials are also conceivable.
- the educt mixture is transferred to a crucible before heating.
- the crucible can be made of tungsten, for example.
- the educt mixture is caused to react and the phosphor is formed.
- the educt mixture is heated to a temperature in the range between 1500 ° C and 1900 ° C inclusive.
- the educt mixture is heated to a temperature of 1700°C.
- the educt mixture is heated for a period of 10 hours to 14 hours inclusive.
- the educt mixture is heated for 12 hours.
- the educt mixture is heated under a forming gas atmosphere or N 2 atmosphere.
- the forming gas atmosphere can be composed of N 2 and H 2 , for example with a ratio of 95/5.
- the educt mixture is heated under a pressure of up to 12 bar, in particular under a pressure of 1 bar up to and including 10 bar. Following heating, the product obtained can be cooled and ground.
- a radiation-emitting component is also specified.
- the phosphor described above is particularly suitable and intended for use in a radiation-emitting component. Features and embodiments that are described in connection with the phosphor and the method for producing a phosphor therefore also apply to the radiation-emitting component and vice versa.
- the radiation-emitting component comprises - a semiconductor chip which, during operation, emits electromagnetic radiation of a first wavelength range, and - a conversion element which has a phosphor described here, which converts electromagnetic radiation of the first wavelength range into electromagnetic radiation of a second wavelength range, which is from dem 2022PF00115 August 2, 2023 P2022,0732 WO N - 16 - first wavelength range is at least partially different.
- the electromagnetic radiation of the first wavelength range forms the emission spectrum of the semiconductor chip and is also referred to as primary radiation.
- the semiconductor chip is, for example, a light-emitting diode chip or a laser diode chip.
- the component can therefore be a light-emitting diode (LED) or a laser.
- the semiconductor chip preferably has an epitaxially grown semiconductor layer sequence with an active zone that is suitable for generating electromagnetic radiation.
- the active zone has, for example, a pn junction, a double heterostructure, a single quantum well or a multiple quantum well structure.
- the semiconductor chip can emit electromagnetic radiation, for example from the ultraviolet spectral range and/or from the visible spectral range, in particular from the blue spectral range.
- the primary radiation therefore has, for example, wavelengths in the range 400 nm to 500 nm, in particular 400 nm to 480 nm.
- the conversion element is arranged on the semiconductor chip, in particular on a radiation exit surface of the semiconductor chip, for example in the beam path of the semiconductor chip.
- the phosphor in the conversion element converts electromagnetic radiation of the first wavelength range into electromagnetic radiation of a second wavelength range.
- the electromagnetic radiation of the second wavelength range forms the emission spectrum of the phosphor and is also referred to as secondary radiation.
- the electromagnetic radiation of the second wavelength range is at least partially different from the first wavelength range.
- the phosphor that is contained in the conversion element or of which the conversion element consists gives the conversion element wavelength-converting properties. For example, the conversion element only partially converts the electromagnetic radiation of the semiconductor chip into electromagnetic radiation of the second wavelength range, while a further part of the electromagnetic radiation of the semiconductor chip is transmitted by the conversion element.
- the radiation-emitting component emits mixed light, which is composed of electromagnetic radiation of the first wavelength range and electromagnetic radiation of the second wavelength range.
- the mixed light includes, for example, white, in particular warm white, light. If the primary radiation is completely converted by the conversion element and/or if there is no transmission of primary radiation through the conversion element, this is referred to as full conversion.
- the radiation-emitting component emits the secondary radiation emitted by the conversion element, in particular 2022PF00115 August 2, 2023 P2022,0732 WO N - 18 - from the blue-green to red, for example from the yellow-orange range. Due to the nature of the phosphor described here, the radiation-emitting component can be used for a wide range of applications.
- the broadband emission of the phosphor in the blue-green to red spectral range allows it to be used solely in the conversion element, for example in warm white lighting devices. If the phosphor emits, for example, in the yellow-orange-red spectral range, the radiation-emitting component can be used if, in addition to brightness, a slight red component in the emitted radiation is important, as is the case, for example, with lighting solutions for general lighting, automobile headlights or indicators.
- a radiation-emitting component that contains the phosphor described here can also be used well for HCL applications if the phosphor emits, for example, in the blue-green or green-yellow spectral range and the radiation emitted by the radiation-emitting component therefore has a high overlap with the melanopic curve.
- the conversion element is free of another phosphor. Due to its nature, the phosphor described here can be used well without combination with other phosphors, for example if broadband emission in blue-green or green-yellow to red spectral ranges is desired.
- At least one further phosphor can be present in the conversion element.
- the at least one further phosphor can, for example, be selected from the group comprising 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 :Eu2+ (SCASN), (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
- the conversion element is designed as a conversion layer.
- the conversion layer can be applied in direct or indirect contact with the semiconductor chip, in particular with the radiation exit surface of the semiconductor chip. In the case of indirect contact, it can be applied to the semiconductor chip using, for example, an adhesive layer, or a potting can be applied between the semiconductor chip and the conversion element.
- Semiconductor chip, optionally the conversion layer and optionally an adhesive layer can be surrounded by a potting according to a further embodiment. For example, the semiconductor chip, conversion element and, if necessary, an adhesive layer are all surrounded by a potting. Then the semiconductor chip, conversion layer and 2022PF00115 August 2, 2023 P2022,0732 WO N - 20 - if necessary, an adhesive layer may be arranged in the recess of a housing, in which the potting is also arranged.
- a potting can have a permeability for the primary radiation and/or the secondary radiation and/or the radiation emitted by other phosphors present, which is at least 85%, preferably 95%.
- a casting can have silicone or epoxy resin as a material, for example.
- the phosphor in the conversion element is present as ceramic.
- the conversion layer can consist of the phosphor forming the ceramic.
- the phosphor is embedded in a matrix in the conversion element.
- the phosphor is in particle form embedded in a matrix.
- the matrix may, for example, comprise a material selected from a group including polymers and glass.
- polymers examples include polystyrene, polysiloxane, polysilazane, PMMA, polycarbonate, polyacrylate, polytetrafluoroethylene, polyvinyl, silicone resin, silicone, epoxy resin and transparent synthetic rubber.
- silicates, water glass and quartz glass can be selected as glass.
- Figure 3 shows a section of the crystal structure of a phosphor according to an exemplary embodiment.
- Figure 4 shows emission spectra of phosphors according to exemplary embodiments.
- Figure 5 shows the emission spectrum of a comparative example.
- Identical, similar or identically acting elements are provided with the same reference numerals in the figures.
- the figures and the size relationships between the elements shown in the figures should not be considered to scale. Rather, individual elements, in particular layer thicknesses, can be shown exaggeratedly large for better representation and/or better understanding.
- Figure 1 shows a schematic sectional view of a radiation-emitting component 100 according to an exemplary embodiment.
- the radiation-emitting component 100 has a semiconductor chip 10.
- the semiconductor chip 10 emits electromagnetic radiation of a first wavelength range (primary radiation) from a radiation exit surface 11.
- the semiconductor chip 10 has 2022PF00115 August 2, 2023 P2022,0732 WO N - 22 - an epitaxially grown semiconductor layer sequence with an active zone 12, which is suitable for generating electromagnetic radiation.
- the primary radiation has wavelengths in the blue and/or UV range.
- the component has a conversion element 20.
- the conversion element 20 either contains a matrix in which the phosphor 1, in particular particles of the phosphor 1, is embedded, or the conversion element 20 has a ceramic formed from the phosphor 1 or consists of it.
- the conversion element 20, which is designed here as a conversion layer, is applied directly to the semiconductor chip 10 in this exemplary embodiment, in particular on its radiation exit surface 11.
- the conversion element 20 can also be attached to the semiconductor chip 10, for example by means of an adhesive layer (not explicitly shown here).
- the semiconductor chip 10 with the conversion element 20 arranged thereon is arranged in the recess of a housing 30.
- the housing 30 has side surfaces that are beveled towards the semiconductor chip 10 and can be designed to be reflective.
- the semiconductor chip 10 and the conversion element 20 can be surrounded in the housing 30 by a potting 40 (not shown here). However, the presence of a potting 40 is not absolutely necessary.
- the housing 30 can also have no side walls and therefore no recess and can be designed as a carrier (not shown here).
- the conversion element 20 is not arranged directly on the semiconductor chip 10, but rather spaced therefrom on the side of a potting 40 facing away from the semiconductor chip 10, which is arranged in the recess of the housing 30.
- the conversion element 20 is again designed as a conversion layer.
- the potting 40 can be formed, for example, from a silicone or epoxy resin and has a permeability to electromagnetic radiation of the semiconductor chip 10 which is at least 85%, preferably 95%.
- the components shown in Figures 1 and 2 are, for example, LEDs.
- additional elements present, such as electrical contacts, are not shown in Figures 1 and 2.
- the phosphor 1 can be a phosphor of the general formula A 4 L 3-x M 1+x N 9-x O x :RE, where 0 ⁇ x ⁇ 3, A is an element or a combination of elements from the group of rare earth elements, L is an element or a combination of elements from the group of tetravalent elements, M is an element or a combination of elements from the group of trivalent elements, and RE is an activator element.
- exemplary embodiments 1 to 5 with the composition La 4 Si 3- x Al 1+x N 9-x O x :Ce.
- La is selected as A
- Si is selected as L
- Al is M
- Ce is variable.
- the starting materials LaN, Si 3 N 4 , AlN, optionally Al 2 O 3 and CeO 2 are mixed together. This can be done, for example, in a hand mortar, a mortar mill, a ball mill, a multi-axis mixer or similar.
- the educt mixture obtained is then transferred to a crucible, which can be made of tungsten, for example.
- the educt mixture is then heated under a forming gas atmosphere at 1700 ° C and a pressure of 1 bar to 10 bar for 12 hours and thus reacted.
- the product obtained is ground, which can again be done, for example, in a hand mortar, a mortar mill or a ball mill.
- the phosphor 1 thus obtained is then characterized.
- a dark reddish-brown powder is obtained which fluoresces blue-greenish or green-yellow to reddish under ultraviolet or blue light.
- Table 1 lists the exemplary weights of the starting materials for the individual exemplary embodiments 1 to 5.
- Table 1 also lists values for the parameter x, which was determined from the nominal ratio of the elements Si and Al and represents a good initial estimate of the actual ratio of Si:Al.
- Figure 3 shows a section of the crystal structure of the phosphor 1 with the composition La 4 Si 3-x Al 1+x N 9-x O x :Ce.
- the open circles represent the La ions, the hatched areas represent the (N,O) 4 tetrahedra, which either surround Si, i.e. are Si-centered, or surround Al, i.e. are Al-centered.
- the four-rings which are formed by the tetrahedra and actually lie diagonally in the plane.
- the first Si(N,O) 4 tetrahedra and the first Al(N,O)4 tetrahedra are connected at all sides to two further first Si(N,O) 4 tetrahedra and/or the first Al(N,O) 4 - Tetrahedra and two second Si(N,O) 4 tetrahedra and/or second Al(N,O) 4 tetrahedra.
- the second Si(N,O) 4 tetrahedra and second Al(N,O) 4 tetrahedra are connected to two first Si(N,O) 4 tetrahedra and/or first Al(N,O) 4 over a total of three corners -tetrahedrons and one 2022PF00115 August 2, 2023 P2022,0732 WO N - 26 - second Si(N,O) 4 tetrahedron or second Al(N,O) 4 tetrahedron.
- the rings of four shown in Figure 3 each contain two tetrahedra of the first type and two tetrahedra of the second type, with a tetrahedron of one type within the ring of four only being linked to two tetrahedra of the other type, i.e. within the ring of four an alternating sequence of the first and second tetrahedron is present (not explicitly shown).
- the four-rings are connected to other four-rings via corners of the tetrahedrons. The connection to the next ring of four takes place to form a tetrahedron of the same type.
- the tetrahedra of the first type bridge to form two further tetrahedra of the first type, each of which is part of two further four-rings.
- the tetrahedrons of the second type only link to form another tetrahedron of the second type, which is part of another ring of four.
- the fourth corner of the tetrahedron of the second type has a terminal anion (N or O).
- N or O terminal anion
- a three-dimensional network of corner-linked tetrahedrons is created.
- cavities or channels arise in which the La ions (open circles in Figure 3) are arranged.
- the La ions are distributed over two crystallographic layers. This means that there are two symmetrically different layers in the structure on which La can be found. Both La layers are surrounded by seven anions, i.e. N and/or O.
- the anions each form distorted, simply capped octahedra.
- the structure of the phosphor 1 based on the exemplary embodiments is determined using single crystal X-ray diffraction 2022PF00115 August 2, 2023 P2022,0732 WO N - 27 - determined.
- Table 2 shows the lattice parameters, crystallographic data and the basic quality parameters of the X-ray determination of exemplary embodiment 5.
- the lattice parameters a, b, c, ⁇ , ⁇ , and ⁇ of the unit cell and the associated volume the measured section of the reciprocal space over the Limits of the associated Miller indices (hkl) are given.
- the conventional R value of all reflections R all is given, which indicates the mean percentage deviation between observed and calculated structure factors.
- the weighted R value wR ref contains a weighting factor that weights the reflexes according to a defined scheme depending, among other things, on their standard deviation. For a good structural model, R all should be below 5% and wR ref should be below 10%. Another quality feature for the agreement between the calculated and measured structure is the goodness of fit (GooF), which should be close to 1. 2022PF00115 August 2, 2023 P2022,0732 WO N - 28 - Table 2
- the further determined crystallographic position parameters of exemplary embodiment 5 are summarized in Table 3.
- the Wyckoff position describes the symmetry of the point positions according to RWG Wyckoff. x, y and z indicate the atomic positions.
- U ani is the radius of the anisotropic deflection parameters of the respective atom.
- Table 3 Using the crystallographic position parameters in Table 3, the first and second tetrahedra can be distinguished. 2022PF00115 August 2, 2023 P2022,0732 WO N - 29 - While Si4 can be assigned to the first Si(N,O) 4 tetrahedra, Si3 and Al3 belong to the second Si(N,O) 4 tetrahedra and Al( N,O) 4 tetrahedra.
- Table 4 summarizes the spectral data determined for exemplary embodiments 1 to 5 with peak wavelength, dominance wavelength and half-width FWHM. The spectral data were obtained under combined excitation with a combination of monochromatic radiation of 405 nm and 440 nm, respectively.
- Table 4 The associated emission spectra of exemplary embodiments 1 to 5 (marked A1 to A5) are shown in Figure 4.
- the wavelength ⁇ in nm is plotted against the relative intensity I/I max .
- Figure 5 shows the emission spectrum of the comparative example YAG.
- YAG is Y 3 Al 5 O 12 :Ce, one of the longest wavelength Ce 3+ -activated phosphors in use today, with which dominant wavelengths of 555 nm to 574 nm can be achieved.
- one exemplary embodiment is used as the only phosphor in the conversion element 20 and a blue-emitting LED chip is used as the semiconductor chip 10.
- the numbering of the application examples corresponds to the numbering of the exemplary embodiments used.
- Table 5 The CRI values of the application examples are in the range of CRI 81 to 84. Compared to comparative example YAG with a CRI of 63, the application examples of the phosphor described here achieve significantly better CRI values. The achievable color temperature depends directly on the emission level.
- the simulated color temperature is 4369 K, which is one of the lowest color temperatures available with conventional Ce 3+ activated 2022PF00115 August 2, 2023 P2022,0732 WHERE N - 31 - phosphors can be reached. Color temperatures CCT ⁇ 4000 K are usually not achievable with these conventional phosphors.
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Abstract
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| DE112023002392.1T DE112023002392A5 (de) | 2022-08-04 | 2023-08-02 | Leuchtstoff, verfahren zur herstellung eines leuchtstoffs und strahlungsemittierendes bauelement |
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| DE102022119601.1A DE102022119601A1 (de) | 2022-08-04 | 2022-08-04 | Leuchtstoff, verfahren zur herstellung eines leuchtstoffs und strahlungsemittierendes bauelement |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040155225A1 (en) * | 2003-02-06 | 2004-08-12 | Ube Industries, Ltd., A Corporation Of Japan | Sialon-based oxynitride phosphor, process for its production, and use thereof |
| US20070018567A1 (en) * | 2003-08-22 | 2007-01-25 | National Institute For Material Science | Oxynitride phosphor and light-emitting instrument |
| US20090105065A1 (en) * | 2006-03-23 | 2009-04-23 | Koninklijke Philips Electronics N.V. | Light emitting device with a ceramic garnet material |
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| DE102021203336A1 (de) * | 2021-04-01 | 2022-10-06 | OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung | Leuchtstoff, verfahren zur herstellung eines leuchtstoffs und strahlungsemittierendes bauelement |
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2022
- 2022-08-04 DE DE102022119601.1A patent/DE102022119601A1/de not_active Withdrawn
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2023
- 2023-08-02 DE DE112023002392.1T patent/DE112023002392A5/de active Pending
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040155225A1 (en) * | 2003-02-06 | 2004-08-12 | Ube Industries, Ltd., A Corporation Of Japan | Sialon-based oxynitride phosphor, process for its production, and use thereof |
| US20070018567A1 (en) * | 2003-08-22 | 2007-01-25 | National Institute For Material Science | Oxynitride phosphor and light-emitting instrument |
| US20090105065A1 (en) * | 2006-03-23 | 2009-04-23 | Koninklijke Philips Electronics N.V. | Light emitting device with a ceramic garnet material |
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| DE112023002392A5 (de) | 2025-03-06 |
| DE102022119601A1 (de) | 2024-02-15 |
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