Luminescent material, method for producing a luminescent material, and radiation-emitting component
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2026-01-28
- Publication Date
- 2026-08-13
Smart Images
Figure EP2026052126_13082026_PF_FP_ABST
Abstract
Description
[0001] 2024PF01673 January 28, 2026
[0002] P2024, 1179 WO N - 1 -
[0003] Description
[0004] Fluorescent material, method for producing a fluorescent material and radiation-emitting component
[0005] A phosphor, a method for producing a phosphor, and a radiation-emitting component are specified.
[0006] One of the tasks is to provide a phosphor with improved properties. In addition, a process for manufacturing a phosphor with improved properties and an improved radiation-emitting component are to be provided.
[0007] A phosphor is specified. The phosphor can convert electromagnetic radiation of a first wavelength range into electromagnetic radiation of a second wavelength range. The conversion of electromagnetic radiation of the first wavelength range into electromagnetic radiation of the second wavelength range is also called wavelength conversion. In particular, during wavelength conversion, the electromagnetic radiation of the first wavelength range is absorbed by a wavelength-converting element, converted into electromagnetic radiation of the second wavelength range by electronic processes at the atomic and / or molecular level, and then re-emitted. The electromagnetic radiation of the first wavelength range and the electromagnetic radiation of the second wavelength range are thus at least partially different from each other. [This is followed by a separate document:] 2024PF01673 January 28, 2026
[0008] P2024, 1179 WO N 2
[0009] It is possible that the electromagnetic radiation of the second wavelength range has longer wavelengths.
[0010] In particular, the term "wavelength conversion" does not refer to pure scattering or pure absorption of electromagnetic radiation.
[0011] Here and in the following, phosphors are described using their molecular formulas. The molecular formulas
[0012] The elements listed are present in charged form. Here and in the following, elements and / or atoms in relation to the molecular formulas of the phosphors therefore refer to ions in the form of cations and anions, even if this is not explicitly stated. This also applies to element symbols when, for the sake of clarity, they are given without the charge number.
[0013] Phosphors are generally neutrally charged externally. This means that there can be a complete balance of positive and negative charges within the phosphor. However, it is also possible that the phosphor may not have a complete charge balance to a small extent.
[0014] With the given molecular formulas, it is possible that the phosphor contains further elements, for example in the form of impurities. Taken together, these impurities constitute at most 5 mol%, in particular at most 1 mol%, preferably at most 0.1 mol%.
[0015] According to at least one embodiment, the phosphor has the molecular formula EA4+3v-y-zSE-3v+y+zD6-tvx-yEx+yLit+vN10-3t-x+zO1+3t+xz·R. In particular, the phosphor has the molecular formula M4(D, E, Li )6(N, 0) ii: R, where M represents the elements EA and SE2024PF01673 January 28, 2026
[0016] P2024, 1179 WO N - 3 -
[0017] includes. In other words, the phosphor can have the chemical formula (EA, SE )4(D, E, Li )6(N, 0) n: R.
[0018] According to at least one definition, EA is an element or a combination of elements selected from the group of binary elements.
[0019] The term "valence" in relation to a specific element refers to how many elements with a simple opposite charge are needed in a chemical compound to achieve charge balance. Thus, the term "valence" encompasses the element's charge number.
[0020] Elements with a valence of two are called divalent elements. Divalent elements are often doubly positively charged in chemical compounds and have a charge of +2. Charge balance in a chemical compound can be achieved, for example, through two other elements that are singly negatively charged, or through another element that is doubly negatively charged.
[0021] According to at least one embodiment of the phosphor, SE is an element or a combination of elements selected from the group of rare earth elements. Rare earth elements in this context comprise the chemical elements of the 3rd genome.
[0022] Subgroups of the periodic table as well as the lanthanides.
[0023] Rare earth elements are generally selected from the group consisting of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In particular, these rare earth elements have a valence of three. 2024PF01673 January 28, 2026
[0024] P2024, 1179 WO N - 4 -
[0025] According to at least one embodiment of the phosphor, D is an element or a combination of elements selected from the group of tetravalent elements. Tetravalent elements are elements with a valence of four. Tetravalent elements are frequently positively charged four times in chemical compounds and have a charge of +4. Charge balance in a chemical compound can occur, for example, via an element that is negatively charged four times, by two elements that are negatively charged twice, or by four elements that are negatively charged once.
[0026] According to at least one embodiment of the phosphor, E is an element or a combination of elements selected from the group of trivalent elements. Trivalent elements are elements with a valence of three. Trivalent elements are frequently triply positively charged in chemical compounds and have a charge of +3. Charge balance in a chemical compound can occur, for example, via an element that is triply negatively charged or by three elements that are singly negatively charged.
[0027] According to at least one embodiment of the phosphor, R is or comprises an activator element.
[0028] In particular, the phosphor has a host grid into which foreign elements are introduced as activator elements. The host grid modifies the electronic structure of the activator element in such a way that electromagnetic radiation of an excitation wavelength, that is, electromagnetic radiation of the first wavelength range, which is emitted by the 2024PF01673 28 January 2026
[0029] P2024, 1179 WO N 5
[0030] When the phosphor is absorbed, it undergoes a transition from a ground state to an excited state. By emitting electromagnetic radiation with an emission spectrum, that is, electromagnetic radiation in the second wavelength range, the phosphor returns to its ground state. For example, this electronic transition takes place in the activator element.
[0031] According to one embodiment of the phosphor, R has a content of 0.01 mol% to 30 mol% inclusive of the elements EA and SE. In particular, R has a content of 0.01 mol% to 15 mol% inclusive of the elements EA and SE. For example, R has a molecular content between 0.01 mol% and 5 mol% inclusive of EA and SE, preferably inclusive.
[0032] According to at least one embodiment of the phosphor, the following apply: -4 < +3v-yz < 0, -6 < -tvxy < 0, 0 < x+y < 6, 0 < t+v < 6 and -10 < -3t-x+z < 1. According to at least one
[0033] According to the formulation, lithium is therefore present in the phosphor.
[0034] According to at least one embodiment of the phosphor, the following applies: 2* (4+3v-yz) +3* (-3v+y+z) +4* ( 6-tvxy) +3* (x+y) +1* (t+v) -3* ( 10-3 t-x+ z ) -2 * ( 3 t+x- z ) = 0.
[0035] According to at least one embodiment, the phosphor has the chemical formula EA4+3 V -y-zSE-3v+y+zD6-tvx-yEx+yLit+vN10-3t-x+zO1+3t+xz·R, where EA is an element or combination of elements selected from the group of binary elements, SE is an element or combination of elements selected. 2024PF01673 January 28, 2026
[0036] P2024, 1179 WO N 6
[0037] from the group of rare earth elements, D is an element or a combination of elements selected from the group of tetravalent elements, E is an element or a combination of elements selected from the group of trivalent elements, R comprises an activator element, and -4 < +3v-yz < 0, -6 < -tvxy < 0, 0 < x+y < 6, 0 < t+v < 6, -10 < -3t-x+z < 1 and 2* (4+3v-yz) +3* (-3v+y+z) +4* ( 6-tvxy) +3* (x+y) +1* ( t+v) -3* ( 10-3t-x+z ) -2* ( 3t+xz ) = 0 holds.
[0038] Advantageously, the phosphor described here is characterized by increased temperature stability compared to other phosphors emitting in the same or similar wavelength range. In particular, this increased temperature stability can be explained by the presence of lithium in the phosphor.
[0039] For example, the relative brightness of the electromagnetic radiation emitted by the phosphor at 175 °C is at least 80% of the brightness of the radiation emitted by the phosphor at 25 °C. At 225 °C, the relative brightness is, for example, at least 70% of the brightness of the radiation emitted by the phosphor at 25 °C.
[0040] According to at least one embodiment of the phosphor, EA is an element or a combination of elements selected from the group formed by Mg, Ca, Sr, Ba and Zn.
[0041] In particular, EA is an element or a combination of elements selected from the group formed by Ca, Sr, and Ba. For example, EA includes or is Ba and / or Ca.
[0042] According to at least one embodiment of the phosphor, SE comprises or is an element or a combination of elements selected from the group formed by Y, La, and Lu. In particular, SE is or comprises Y.2024PF01673 28 January 2026
[0043] P2024, 1179 WO N 7
[0044] According to at least one embodiment of the phosphor, D is an element or a combination of elements selected from the group formed by Si, Ge, Sn, Ti and Zr.
[0045] In particular, D Si is or includes.
[0046] According to at least one embodiment of the phosphor, E is an element or a combination of elements selected from the group consisting of Al, B, Ga, and In. In particular, E is or comprises Al.
[0047] According to at least one embodiment of the phosphor, R is an element or a combination of elements selected from the group consisting of Ce, Eu, Mn, Bi, Tb, Dy, Ni, Gr, Cu, and Er. For example, Ce is in the form Ce 3+ before.
[0048] For example, Eu is in the form Eu 2+ or EU 3+ before.
[0049] For example, Mn is in the form Mn 2+ or Mn 4+ before.
[0050] For example, Bi is in the form Bi 3+ For example, Tb exists in the form Tb 3+ For example, Dy is in the form Dy 3+ For example, Ni exists in the form Ni 2+ For example, Gr exists in the form Cr. 3+ For example, Cu exists in the form Cu + for example, it is in the form He 3+ before.
[0051] According to at least one embodiment of the phosphor, R contains or includes Ce. Advantageously, phosphors with Ce as the activator element exhibit lower quenching effects, even at high irradiances, than, for example, phosphors with Eu. 2+ as an activator element.
[0052] In particular, this can be seen in the shorter lifetime of the excited state of Ce. 3+ explain. A typical lifetime of the excited state of Ce 3+ lies2024PF01673 January 28, 2026
[0053] P2024, 1179 WO N - 8 -
[0054] for example, less than 100 nanoseconds, while typical lifetimes of excited states are of Eu 2+ in the range between 1 microsecond and 10 microseconds.
[0055] Investigations of phosphors with Ce 3+Studies using activator elements have shown that such phosphors only exhibit quenching effects relevant to applications at very high irradiances. For example, for Y3Al5O12: Ce 3+ Quenching effect only occurs at irradiances greater than 10 W / mm² 2 observed. For phosphors with EU 2+ However, they are already used as activator elements at irradiances around 100 mW / mm². 2 Quenching effect observed. Ce 3+ -activated phosphors only exhibit quenching effects at more than an order of magnitude above the irradiance at which phosphors with Euclidean fluorescence (EU) do not. 2+ The phosphor already exhibits quenching effects when used as an activator element. Therefore, the phosphor described here can advantageously be used in applications with higher irradiance.
[0056] According to at least one embodiment, the phosphor has the sum form 1 EA4+3v-y-zSE-3v+y+zSi6-tvx-yAlx+yLit+vN10-3t-x+zO1+3t+xz:R. In other words, D Si and E Al.
[0057] According to at least one embodiment, the phosphor has the chemical formula EA4+3v-zSE-3v+zSi6-t-vLit+vN10-3t+zO1+3t-z:R, where -4 < 3v-z < 0, -6 < -tv < 0, 0 < t+v < 6, -10 < -3t+z < 1, and 2 * ( 4+3v- z ) +3* ( -3v+ z ) +4 * ( 6- tv) + 1 * ( t+v) -3* ( 10-3 t+ z ) -2* (3t-z) = 0. In other words, D is Si, and x = 0 and y = 0. The chemical formula of the phosphor in this embodiment can also be expressed as M4( Si, Li )6(N, 0) u: R or
[0058] (EA, SE) 4 (Si, Li) 6(N, 0) 11: R can be represented. 2024PF01673 January 28, 2026
[0059] P2024, 1179 WO N - 9 -
[0060] According to at least one embodiment, the phosphor has the chemical formula EA4+3vSE-3vSi6-t-vLit+vN10-3tO1+3t:R, where -4 < 3v < 0, -6 < -tv < 0, 0 < t+v < 6, -10 < -3t < 1 and
[0061] 2 * ( 4 + 3v) + 3 * ( -3v) + 4 * ( 6 - tv) + 1 * ( t + v) - 3 * ( 10 - 31 ) - 2 * ( 31 ) = 0 holds true. In other words, D Si and x = 0, y = 0 and z = 0.
[0062] According to at least one embodiment, the phosphor has the chemical formula M4(Si,Al,Li)6(N,O)n:R or
[0063] M4(Si,Li)6(N,O)ii: R, where M comprises EA and SE. In other words, the phosphor can have the molecular formula
[0064] (EA, SE)4(Si, Al, Li)6(N, 0) u: R or (EA, SE)4(Si, Li)6(N, 0) u: R.
[0065] According to at least one embodiment of the phosphor, the host lattice of the phosphor has a crystal structure with a cubic space group. In particular, the space group of the crystal structure is P2i3 (No. 198).
[0066] For example, the phosphor has the same crystal structure as (Ba,Eu)3YbSi6N11, Ba1-xCaxSi6N8O and EA3-3 / 2uSE1+u(Si,N)6(N,O)11:A. For example, in the phosphor described here, Li, D and E occupy the same positions in the crystal structure of the host lattice.
[0067] The host lattice is primarily composed of a three-dimensional unit cell that typically repeats periodically. In other words, the unit cell is the smallest recurring unit of the host lattice's crystal structure. The elements EA, SE, Li, D, E, N, and O each occupy specific positions within this unit cell, known as point positions. 2024PF01673 January 28, 2026
[0068] P2024, 1179 WO N 10
[0069] Six lattice parameters are needed to describe the three-dimensional unit cell of the host lattice's crystal structure: three lengths a, b, and c, and three angles a, β, and y. The three lattice parameters a, b, and c are the lengths of the lattice vectors that span the unit cell. The other three lattice parameters a, β, and y are the angles between these lattice vectors: a is the angle between b and c, β is the angle between a and c, and y is the angle between a and b.
[0070] In a cubic space group, a = b = c and a = ß = y = 90°.
[0071] According to at least one embodiment of the phosphor, the lattice parameter a of the cubic crystal structure is in the range between 10,390 Å and 10,420 Å, including inclusive. In other words, the lattice vectors that span the unit cell of the host lattice crystal structure have a length in the range between 10,390 Å and 10,420 Å, including inclusive.
[0072] According to at least one embodiment of the phosphor, the unit cell volume of the crystal structure of the host lattice is in the range between and including 1050 Å. 3 and including 1250 Ä 3 .
[0073] According to at least one embodiment of the phosphor, the phosphor has an excitation wavelength in the range between 250 nanometers and 600 nanometers. In other words, the phosphor can be excited by electromagnetic radiation from the ultraviolet to orange region of the electromagnetic spectrum. 2024PF01673 January 28, 2026
[0074] P2024, 1179 WO N - 11 -
[0075] In particular, the phosphor exhibits two excitation maxima. For example, a first excitation maximum of the phosphor lies in the ultraviolet to blue region of the electromagnetic spectrum, specifically in the range between and including 350 nanometers and 450 nanometers. A second excitation maximum of the phosphor can lie in the blue to orange region of the electromagnetic spectrum, for example, in the range between and including 450 nanometers and 600 nanometers.
[0076] According to at least one embodiment of the phosphor, the electromagnetic radiation emitted by the phosphor exhibits an emission spectrum with an emission maximum. The emitted electromagnetic radiation is primarily that of the second wavelength range. For example, the emission maximum depends on the excitation wavelength.
[0077] The emission spectrum is an intensity distribution of the electromagnetic radiation emitted by the phosphor after excitation with electromagnetic radiation of the excitation wavelength.
[0078] The emission spectrum is usually represented as a diagram showing the spectral intensity or spectral flux per wavelength interval ("spectral intensity / spectral flux") of the electromagnetic radiation emitted by the phosphor as a function of wavelength λ. In other words, the emission spectrum is a curve in a diagram where the wavelength is on the x-axis.
[0079] P2024, 1179 WO N 12
[0080] and the spectral intensity or spectral radiant flux is plotted on the y-axis.
[0081] The emission maximum lies specifically in the range between 425 nanometers and 650 nanometers. In other words, the phosphor can emit in the blue to orange region of the electromagnetic spectrum. The emission maximum depends particularly on the composition of the phosphor. For example, the emission maximum lies in the range between 450 nanometers and 500 nanometers. The emission maximum can also lie in the range between 550 nanometers and 600 nanometers.
[0082] According to at least one embodiment of the phosphor, the emission spectrum exhibits at least two emission peaks, and in particular three emission peaks. In other words, the phosphor can exhibit at least two emission bands. The emission spectrum, in particular, exhibits at least two local emission maxima. A first local emission maximum is located, for example, in the range between 425 nanometers and 525 nanometers inclusive. A second local emission maximum is located, for example, in the range between 525 nanometers and 625 nanometers inclusive, and in particular in the range between 560 nanometers and 580 nanometers inclusive. A third local emission maximum is located, for example, in the range between 625 nanometers and 650 nanometers inclusive.
[0083] According to at least one embodiment, the electromagnetic radiation emitted by the phosphor exhibits a 2024PF01673 28 January 2026
[0084] P2024, 1179 WO N 13
[0085] Dominance wavelength λ dom in the range between 460 nanometers and 620 nanometers including inclusive, in particular in the range between 570 nanometers and 590 nanometers including inclusive, or in the range between 470 nanometers and 500 nanometers including inclusive.
[0086] To determine the dominant wavelength of the electromagnetic radiation emitted by the phosphor, a straight line is drawn in the CIE standard diagram starting from the white point (x = 0.333, y = 0.333) and passing through the chromaticity coordinates of the electromagnetic radiation. The intersection of this straight line with the spectral chromaticity line that defines the CIE standard diagram indicates the dominant wavelength of the electromagnetic radiation. Generally, the dominant wavelength differs from the wavelength of the emission maximum.
[0087] According to at least one embodiment of the phosphor, the emission maximum has a full width at half maximum (FWHM) in the range between 80 nanometers and 170 nanometers, and in particular between 80 nanometers and 140 nanometers. It is also possible to specify the FWHM in electron volts (eV). For example, the FWHM of the emission maximum of the phosphor lies in the range between 0.400 eV and 0.550 eV. In particular, the FWHM of the emission maximum of the phosphor is at most 0.500 eV.
[0088] The term half-width refers to a curve with a maximum, such as the emission spectrum, where the 2024PF01673 January 28, 2026
[0089] P2024, 1179 WO N 14
[0090] The half-width is the area on the x-axis that corresponds to the two y-values that represent half of the maximum.
[0091] According to at least one embodiment of the phosphor, the electromagnetic radiation emitted by the phosphor has a center wavelength λ. cent in the range from 570 nanometers inclusive to 670 nanometers inclusive.
[0092] The center-of-mass wavelength denotes the center of a spectral distribution within an emission spectrum. In other words, the center-of-mass wavelength indicates where the midpoint of the emission spectrum is located. The center-of-mass wavelength is calculated as the weighted arithmetic mean of the wavelengths X, weighted by their amplitudes using the distribution function s(λ):
[0093] ∫λ · s(λ)dλ
[0094] J-cent — ßV TT VJT- '
[0095]
[0096] For example, blue to green emitting phosphors are currently used in the EU. 2+ -activated phosphors such as BaSi2O2N2: Eu 2+ or β-SiAlON: Eu 2+ deployed. With EU 2+ However, as previously described, strong quenching effects are observed at higher irradiances when used as an activator element. Therefore, the use of such phosphors is particularly limited to low irradiances. For example, with β-SiAlON: Eu 2+ due to saturation and quenching effects already at about 0.7 W / mm 2 Irradiance reaches a maximum emission brightness. 2024PF01673 January 28, 2026
[0097] P2024, 1179 WO N - 15 -
[0098] The phosphor described here therefore represents, in particular with Ce 3+ as an activator element, a more efficient alternative to the EU 2+ -activated phosphors ready.
[0099] Only a few phosphors are known to efficiently convert electromagnetic radiation from the blue range into electromagnetic radiation from the yellow-orange to red range. The system (Ca, Sr, Ba)₂Si₃N₈: Eu 2+ are typically dominance wavelengths of
[0100] λ dom > 580 nanometers achievable, with (Ca, Sr ) AlSiN3: Eu 2+ even just λ dom > 587 nanometers. The orange a-SiA10Ne also typically achieve dominance wavelengths of
[0101] λ dom > 580 nm. In comparison, the phosphor described here can advantageously achieve dominance wavelengths in the same range or even below 580 nanometers.
[0102] For the conversion of electromagnetic radiation from the blue range to electromagnetic radiation from the yellow range, conversion-based LED solutions currently almost exclusively use Ce. 3+-activated Y3Al5O12 (YAG: Ce) is used. Typical spectral values for YAG are between 565 and 574 nanometers for the dominance wavelength and between 110 and 125 nanometers for the full width at half maximum (FWHM). Longer-wavelength emissions, such as Ce, are also described in the literature. 3+ -activated phosphors, e.g. in Tb3Al5O 12 : Ce 3+ (TbAG: Ce) or Gd3Al5O 12 : Ce 3+ (GdAG: Ce). However, these are not suitable for the application because they exhibit strong thermal quenching.
[0103] Due to its emission properties, the phosphor described here is advantageously suitable as an alternative. 2024PF01673 January 28, 2026
[0104] P2024, 1179 WO N - 16 -
[0105] Regarding TbAG: Ce, GdAG: CE and orange-emitting EU 2+ -doped phosphors in radiation-emitting components.
[0106] To produce LEDs with a color rendering index (CRI) of 70 or more, especially 80 or more, a mixture of cerium-activated green to yellow phosphors and Euchromium is typically used. 2+ -activated orange to red phosphors were used.
[0107] Due to its properties, the phosphor described here is advantageously suited for use in such applications. This can be achieved through the use of Ce. 3+ The efficiency of the applications can be increased as an activator element.
[0108] According to at least one embodiment, the phosphor has a photometric radiation equivalent in the range between 230 Im / W and 370 Im / W.
[0109] For example, the photometric radiation equivalent is determined at an excitation wavelength of 408 nanometers.
[0110] The photometric luminous efficacy of radiation (LER) of a phosphor is the quotient of the luminous flux of the electromagnetic radiation emitted by the phosphor and the radiant power of the electromagnetic radiation emitted by the phosphor. The higher the photometric luminous efficacy, the greater the luminous flux usable by the eye for a given power. The phosphor described here has a higher photometric luminous efficacy compared to other phosphors.
[0111] A process for producing a phosphor is further specified. In particular, process 2024PF01673, dated January 28, 2026, describes this process.
[0112] P2024, 1179 WO N - 17 -
[0113] the previously described phosphor was produced.
[0114] Therefore, the design features and other characteristics described in connection with the phosphor also apply to the process and vice versa.
[0115] According to at least one implementation of the process, the phosphor has the chemical formula EA4. +3v-y-z SE-3 V+y+z D6-t- -x- y E x+y L it +v Ni o-3t-x+zOi +3t+xz: R, where EA is an element or combination of elements selected from the group of divalent elements, SE is an element or combination of elements selected from the group of rare earth elements, D is an element or combination of elements selected from the group of tetravalent elements, E is an element or combination of elements selected from the group of trivalent elements, R comprises an activator element, and -4 < +3v-yz < 0, -6 < -tvxy < 0, 0 < x+y < 6, 0 < t+v < 6, -10 < -3t-x+z < 1 and 2* (4+3v-yz) +3* (-3v+y+z) +4* (6-tvxy) +3* (x+y) +l* (t+v) -3* (10-3t-x+z ) -2* (3t+xz ) = 0.
[0116] According to at least one embodiment, the process comprises the steps of providing reactants, mixing the reactants to form a reactant mixture, and heating the reactant mixture.
[0117] In particular, the steps are performed in the specified order.
[0118] In particular, it is possible that the process produces a mixture that includes or consists of the phosphor. Other components of the mixture may include, for example, reactants that did not react during the production of the phosphor, impurities, and / or by-phases that were formed during production. 2024PF01673 January 28, 2026
[0119] P2024, 1179 WO N - 18 -
[0120] According to at least one embodiment of the process, the reactants are selected from the following group: nitrides, oxides, nitrates, citrates, oxalates, halides, carbonates, hydroxides of each of EA, Li, SE, D, E, R and combinations thereof.
[0121] For example, the starting materials are selected from the group formed by: Ba3N 2-y, where y is between inclusive -0.5 and inclusive 0.5, BaO, BaCO3, Ca3N2, CaCO3, Sr3N2, SrN2, SrCO3, Li3N, Li2O, Li2CO3, YN, Y2O3, LaN, La2O3, LuN, Lu2O3, Si3N4, SiO2, AIN, Al2O3, CeN, Ce2O3, CeO2, CeF3 and combinations thereof. In particular, the reactants each comprise one reactant for EA, Li, SE, D, E and R, if present in the phosphor.
[0122] According to at least one embodiment of the process, the reactant mixture is heated to a temperature in the range between 1400 °C and 2100 °C, in particular in the range between 1600 °C and 1950 °C.
[0123] According to at least one embodiment of the process, the reactant mixture is heated in an inert and / or reducing atmosphere. For example, heating takes place in a nitrogen atmosphere or a forming gas atmosphere. Advantageously, when using a reducing atmosphere, reactants can be used in which the oxidation state of EA, SE, and / or R does not correspond to the oxidation state of EA, SE, and / or R in the phosphor. For example, cerium oxide (CeO2) can be used as a reactant for Ce.
[0124] According to at least one embodiment of the process, the reactant mixture is heated for a period of time ranging from 2 hours inclusive to 60 hours inclusive. 2024PF01673 January 28, 2026
[0125] P2024, 1179 WO N - 19 -
[0126] According to at least one embodiment of the process, heating takes place under increased pressure. Here and in the following, increased pressure is any pressure that exceeds normal pressure, that is, approximately 1013 hPa (1.013 bar). It is also possible for heating to take place at normal pressure.
[0127] A radiation-emitting component containing a phosphor is further specified. Preferably, the phosphor described above is suitable and intended for use in a radiation-emitting component described herein. Features and embodiments described in connection with the phosphor and / or the method also apply to the radiation-emitting component and vice versa.
[0128] According to one embodiment, the radiation-emitting component comprises a semiconductor chip that emits electromagnetic radiation of a first wavelength range during operation, and a conversion element containing the phosphor described above. The phosphor emits electromagnetic radiation of a second wavelength range. The second wavelength range is, in particular, at least partially different from the first wavelength range. The radiation-emitting component is, for example, a light-emitting diode (LED) or a laser.
[0129] In particular, the semiconductor chip comprises an epitaxially grown sequence of semiconductor layers that includes an active region which, during operation of the device, generates electromagnetic radiation in the first wavelength range. The semiconductor chip is, for example, a 2024PF01673 dated January 28, 2026.
[0130] P2024, 1179 WO N 20
[0131] A light-emitting diode chip or a laser diode chip. The electromagnetic radiation of the first wavelength range is emitted through a radiation emission surface of the semiconductor chip. In particular, the conversion element is arranged at least on the radiation emission surface of the semiconductor chip.
[0132] According to at least one embodiment of the radiation-emitting component, the phosphor converts the electromagnetic radiation of the first wavelength range into the electromagnetic radiation of the second wavelength range. In particular, the first wavelength range includes wavelengths from the ultraviolet to blue region of the electromagnetic spectrum.
[0133] The radiation-emitting component exhibits a CRI of at least 80. The conversion element can contain only the phosphor described here as the converting substance. Therefore, the conversion element can be free of other phosphors and still achieve a CRI of at least 80 in this configuration. Advantageously, such radiation-emitting components are used for general lighting.
[0134] According to at least one embodiment of the radiation-emitting component, the conversion element includes a further phosphor that converts the electromagnetic radiation of the first wavelength range into electromagnetic radiation of a third wavelength range. The conversion element therefore includes, in particular, two different phosphors. The further phosphor can also be a mixture of different phosphors. (2024PF01673, January 28, 2026)
[0135] P2024, 1179 WO N 21
[0136] The conversion element can therefore have at least three different phosphors, each emitting in at least partially different wavelength ranges.
[0137] For example, the phosphor converts electromagnetic radiation of the third wavelength range into electromagnetic radiation of the second wavelength range. Alternatively or additionally, it is possible for the phosphor to convert electromagnetic radiation of the first wavelength range into electromagnetic radiation of the second wavelength range.
[0138] The first, second, and third wavelength ranges are, in particular, at least partially different. The third wavelength range, for example, includes wavelengths from the green to yellow region of the electromagnetic spectrum. For instance, the other phosphor is a ce-based fluorescent material. 3+-activated phosphor, such as Y3Al5O12: Ce 3+ (YAG: Ce).
[0139] In particular, the radiation-emitting component is configured with the additional phosphor for full conversion. In other words, the radiation-emitting component emits little or no electromagnetic radiation in the first wavelength range. Here, "little" specifically means that at most 10%, at most 5%, or at most 1% of the electromagnetic radiation in the first wavelength range generated in the active region is emitted by the radiation-emitting component. 2024PF01673 January 28, 2026
[0140] P2024, 1179 WO N 22
[0141] For example, the radiation-emitting component can be used with the additional phosphor in a turning signal light or to generate amber-colored light.
[0142] Further advantageous embodiments, configurations and further developments of the phosphor, the method for producing a phosphor and the radiation-emitting component result from the following exemplary embodiments shown in conjunction with the figures.
[0143] Figure 1 shows a schematic representation of a phosphor according to an exemplary embodiment.
[0144] Figure 2 schematically shows steps of a process for producing a phosphor according to an exemplary embodiment.
[0145] Figure 3 shows excitation spectra of a phosphor according to one embodiment and according to a comparative example.
[0146] Figures 4 to 7 show emission spectra of phosphors according to different embodiments and various comparative examples.
[0147] Figure 8 shows the thermal quenching behavior of phosphors according to one embodiment and according to comparative examples.
[0148] Figure 9 shows a schematic sectional view of a radiation-emitting component 10 according to an exemplary embodiment. 2024PF01673 January 28, 2026
[0149] P2024, 1179 WO N - 23 -
[0150] Figure 10 shows simulated emission spectra of a radiation-emitting component according to an exemplary embodiment and a comparative example.
[0151] Figure 11 shows a color locus diagram.
[0152] Figure 12 shows a simulated emission spectrum of a radiation-emitting component according to an exemplary embodiment.
[0153] Figure 13 shows a simulated emission spectrum of a radiation-emitting component according to a comparative example.
[0154] Figure 14 shows an emission spectrum of a phosphor according to an exemplary embodiment.
[0155] Figures 15 and 16 each show a powder diffractogram of a phosphor according to an exemplary embodiment.
[0156] Identical, similar, or similarly functioning elements are marked with the same reference symbols in the figures. The figures and the relative sizes of the elements depicted within them are not to be considered to scale. Rather, individual elements, particularly layer thicknesses, may be exaggerated for clarity and / or better understanding.
[0157] Figure 1 shows a phosphor 1 with the chemical formula EA 4+3v-y-z SE -3v+y+z D 6-t-v-x-y E x+y Li t+v N 10-3t-x+z O 1+3t+x-z• R • EA is an element or combination of elements selected from the group of divalent elements, in particular Ba, Ca, and / or Sr. SE is an element or combination of 2024PF01673 28 January 2026
[0158] P2024, 1179 WO N 24
[0159] Elements selected from the group of rare earth elements, in particular Y. D is an element or a combination of elements selected from the group of tetravalent elements, in particular Si. E is an element or a combination of elements selected from the group of trivalent elements, in particular Al. R comprises an activator element, in particular Ce. 3+ Furthermore, -4 < +3v-yz do, -6 < -tvxy < 0, 0 < x+y < 6, 0 < t+v < 6, -10 < -3t-x+z < 1 and 2* (4+3v-yz) +3* (-3v+y+z) +4* ( 6-tvxy) +3* (x+y) +1* ( t+v) -3* ( 10-3t-x+z ) -2* ( 3t+xz ) = 0. In other words, the phosphor 1 can be expressed using the formula
[0160] M4( Si, Al, Li )6(N, 0) u: Ce3+ with M comprehensive SE and EA.
[0161] The phosphor 1 is present in the form of particles. For example, the particle size ranges from 500 nanometers to 100 micrometers. The phosphor 1 also has a host lattice. The activator element R is embedded in the host lattice. Specifically, the activator element occupies the same sites as SE and EA in the host lattice. Furthermore, Si, Al, and Li occupy the same sites in the host lattice.
[0162] The phosphor 1 can be produced using the method shown schematically in Figure 2 according to an exemplary embodiment.
[0163] In a first process step S1, reactants are provided. The reactants each comprise a source of EA, Li, SE, D, E, and R. For example, one source of EA, one source of Li, one source of SE, one source of D, one source of E, and one source of R are used as reactants. For example, the reactants are selected from the group formed by BaNx-y, where y is between and including 2024PF01673 28 January 2026
[0164] P2024, 1179 WO N 25
[0165] -0.5 and including 0.5, BaO, BaCO3, Ca3N2, CaCO3, Sr3N2, SrN2, SrCO3, Li3N, Li2O, Li2CO3, YN, Y2O3, LaN, La2O3, LuN, Lu2O3, Si3N4, SiO2, AIN, Al2O3, CeN, Ce2O3, CeO2, CeF3 and combinations thereof. In particular, the reactants each comprise one reactant for EA, Li, SE, D, E and R, insofar as present in the phosphor. The reactants are weighed under protective gas and intimately mixed in a second process step S2. The resulting starting material mixture is transferred in process step S3 into a crucible made of tungsten, molybdenum, or tantalum and heated to a temperature in the range of 1400°C to 2100°C inclusive, particularly between 1600°C and 1950°C inclusive. This heating takes place, for example, in a tube furnace, a chamber furnace, a high-pressure furnace, or a retort furnace. The temperature is maintained for a period of time ranging from 2 to 60 hours.Heating can take place under a nitrogen or reducing atmosphere, such as forming gas, at normal or elevated pressure. After the reaction and cooling, the product obtained after heating is ground. This can be done, for example, in a hand mortar, a mortar mill, or a ball mill. Additionally, the resulting mixture can be acid-washed to increase the phase fraction. In particular, the process produces a mixture containing phosphor 1.
[0166] Weights for the synthesis of embodiments 1 to 5 with the molecular formula (Ba, Ca, Y)4( Si, Li )6(N, 0) n: Ce 3+ are summarized in Table 1. Although no calcium source was used in the synthesis, calcium may be present in phosphor 1, as demonstrated by EDX measurement (see Table 4). The calcium was introduced into phosphor 1 primarily through contamination of the starting materials and / or contamination of the crucible. 12024PF01673 28 January 2026
[0167] P2024, 1179 WO N - 26 -
[0168] introduced. However, targeted synthesis is possible through the use of a Ca source, such as CaCO3 or Ca3N2.
[0169] Table 1: Sample weights for the synthesis of
[0170] (Ba, Ca, Y)4( Si, Li )6(N, O) u: Ce 3+
[0171] Bank 1-y YN Si3N4SiO2Li3N CeO2Example 1 5.385g 1.233g 2.711g 0.516g 0.070g 0.083g Example 2 5.410g 1.239g 2.368g 0.793g 0.106g 0.084g Example 3 5.435g 1.245g 2.022g 1.072g 0.142g 0.084g Example 4 5.622g 1.288g 0.615g 2.248g 0.141g 0.087g Example 5 4.460g 0.766g 3, 544g 0.867g 0.259g 0.104g
[0172] The synthesis of embodiments 1 to 3 and 5 was carried out at a temperature of 1750 °C with a holding time of 4 hours and a pressure of 20 bar N₂. The synthesis of embodiment 4 was carried out at a temperature of 1850 °C with a holding time of 48 hours and a pressure of 20 bar N₂. Ba₃N₂ was used as the starting material for Ba in each case. 2-y with y = 0, 11.
[0173] Individual crystals were isolated from embodiments 1 to 5 of the process for producing phosphor 1 and examined by X-ray diffraction. The investigations showed that phosphor 1 has the molecular formula
[0174] (Ba, Ca, Y) 4 ( Si, Li )6(N, 0) ii: Ce 3+ crystallizes in the cubic space group P2i3 and is isostructural to the crystal structures of EA3_ 3 / 2U BE +U ( Si, Al )6( N, 0 ) H: A, ( Ba, Eu )3YbS i gNu and Bai f 3 Approx 2 f 2Si gNi QO is. In the present phosphor 1, lithium occupies the same positions as silicon in the previously mentioned compounds. 2024PF01673 January 28, 2026
[0175] P2024, 1179 WO N 27
[0176] Table 2 contains crystallographic data of the unit cell of phosphor 1 with the molecular formula
[0177] (Ba, Ca, Y) 4 ( Si, Li )6(N, 0) ii: Ce 3+ In summary, embodiments 1-1 and 1-2 involve two different crystals of phosphor 1 obtained from the process of embodiment 1. The naming of the other embodiments was analogous.
[0178] Table 2: Crystallographic data of the unit cell of (Ba, Ca, Y)4(Si, Li)6(N, O) u: Ce 3+
[0179] Execution - Crystal system a / Ä Cell volume / Radiation at play and centering Ä 3
[0180] 1- 1 cP 10, 4092 ( 14 ) 1127, 86 ( 15 ) Cu-Ka
[0181] ( A = 1, 542 Ä) 1-2 cP 10, 4152 ( 7 ) 1129, 79 ( 7 ) Cu-Ka
[0182] ( A = 1, 542 Ä) 2- 1 cP 10, 413 ( 8 ) 1129, 0 ( 9 ) Cu-Ka
[0183] ( A = 1, 542 Ä) 2-2 cP 10, 4118 ( 9 ) 1128, 69 ( 10 ) Cu-Ka
[0184] ( A = 1, 542 Ä) 3- 1 cP 10, 3939 ( 8 ) 1122, 89 ( 9 ) Cu-Ka
[0185] ( A = 1, 542 Ä) 3-2 cP 10, 4041 ( 5 ) 1126, 19 ( 5 ) Cu-Ka
[0186] ( A = 1, 542 Ä) 4- 1 cP 10, 397 ( 3 ) 1125, 2 ( 7 ) Cu-Ka
[0187] ( A = 1, 542 Ä) 5- 1 cP 10, 3913 ( 7 ) 1122, 04 ( 7 ) Cu-Ka
[0188] ( A = 1.542 Ä)
[0189] A comparison of the lattice parameter a of air 1 with the sum formula (Ba, Ca, Y)4( Si, Li )6(N, 0) n: Ce 3+ with the lattice parameters a of (Ba, Y, Li )4( Si, Al )6( 0, N) u: Ce 3+ ,
[0190] (Ba, Y)4( Si, Al )6( 0, N) y: Ce 3+, (Ba, Eu)3YbSi6Nu and Ba 1,8 Approx 2,2 Si6N 10 O is shown in Table 3. 2024PF01673 January 28, 2026
[0191] P2024, 1179 WO N - 28 -
[0192] Table 3: Comparison of the grid parameters a
[0193] Connection a in Ä
[0194] (Ba, Ca, Y)4(Si, Li)6(O, N) u : Ce 3+ 10, 3913 ( 7 ) (Exemplary 5- 1 )
[0195] (Ba, Y, Li )4( Si, Al )6( O, N ) u : Ce 3+ 10, 38510 (10) (Ba, Y)4(Si, Al)6(O, N) u : Ce 3+ 10,411 (1)
[0196] ( Ba, Eu )3YbSi6N 11 10,436 (1) Ba 1; 8 Ca2, 2Si6N 10 O 10, 402 ( 2 )
[0197] The presence of Ba, Y, Ca, and Ce in the phosphor was verified by EDX measurements. The EDX data for selected application examples are summarized in Table 4. Due to the low concentration of Ce 3+As an activator element, the Ce content for embodiments 3-1, 3-2 and 4-1 is below the detection limit.
[0198] Table 4: EDX measurement results given in atomic %. Execution Ba Y Ca Ce
[0199] example
[0200] 1- 1 0, 5675 0, 42 0, 01 0, 0025
[0201] 1-2 0, 6275 0, 3525 0, 015 0, 075
[0202] 3-1 0, 5400 0, 4500 0, 010 Not detectable
[0203] 3-2 0, 5950 0, 3850 0, 0175 Not detectable
[0204] 4- 1 0, 4225 0, 3050 0, 2725 Not detectable
[0205] 5- 1 0, 7000 0, 2500 0, 025 0, 025
[0206] For embodiment 5-1, a specific sum formula was calculated based on the EDX results. The Li content was calculated for this purpose, as it cannot be determined via EDX measurement. To calculate the Li content, the contents of SE, R, and EA (in this case, Ba, Ca, Ce, and Y) were first weighted so that their sum totaled 4. The determined silicon content was then multiplied by the same factor. The Li content was then calculated using 2024PF01673 28 January 2026
[0207] P2024, 1179 WO N 29
[0208] The equation content (Si) + content (Li) = 6 was determined. The ratio of nitrogen to oxygen also cannot be precisely determined by EDX measurement. Therefore, this ratio was also calculated based on the charge neutrality of the chemical formula and the equation content (N) + content (O) = 11. Thus, the following chemical formula results for embodiment 5-1: Ba 2,8 Approx 0,1 Y 1,0 Ce0,1 Si 5,7 Li 0,3 N 10,2 O 0,8 •
[0209] Due to the activator element R, the phosphor 1 according to the embodiment with the sum formula
[0210] (Ba, Ca, Y) 4 ( Si, Li )6(N, 0) ii: Ce 3+ Phosphor properties. Figure 3 shows excitation spectra A5-1 and A-VB1 of phosphors 1 according to embodiment 5-1 and a comparative example 1. Embodiment 5-1 has the molecular formula (Ba, Ca, Y)4(Si, Li)6(N, O)n:Ce 3+ , especially Ba 2,8 Approx 0,1 Y 1,0 Ce 0,1 Si 5,7 Li 0,3 N 10,2 O 0,8 The comparative example 1 shows the sum formula Ba3YSi6N 11 :Ce 3+ The excitation spectra A5-1 and A-VB1 are each shown in the wavelength range from 350 nanometers to 550 nanometers and were determined for an emission wavelength λ. emrecorded at 570 nanometers. The phosphor 1 of embodiment 5-1 exhibits excitation maxima λ ex at 408 nanometers and 530 nanometers. Compared to the lithium-free phosphor 1Ba3YSi6N 11 :Ce 3+ An improved excitation in the deep blue spectral range between approximately 400 nanometers and approximately 430 nanometers is observed. The phosphor 1 is therefore more flexible with respect to its excitation wavelength.
[0211] The emission properties of phosphors 1 according to various embodiments and comparative examples are illustrated by the emission spectra shown in Figures 4 to 7. From these figures, 2024PF01673 28 January 2026
[0212] P2024, 1179 WO N 30
[0213] It is evident that the phosphor 1 described here emits in the cyan or orange range of the electromagnetic spectrum, depending on its composition.
[0214] Figure 4 shows an emission spectrum E4-1 of the phosphor according to embodiment 4-1 with the chemical formula Ba 1,7 Approx 1,1 Y 1,2 (Si,Li)6(N,O) 11 :Ce 3+ and an emission spectrum E-VB2 of comparison example 2 is shown. Comparison example 2 of phosphor 1 has the molecular formula Ba1CaYSi6N 11 :Ce 3+ The emission spectra E4-1 and E-VB2 were recorded at an excitation wavelength of 408 nanometers and are shown in a wavelength range from 400 nanometers to 800 nanometers.
[0215] In contrast to the other embodiments, embodiment 4-1 is Ca-rich and has an emission spectrum that is comparable to the Li-free embodiment 2 Ba1CaYSi6N 11 :Ce 3+ is similar. The phosphor 1 of embodiment 4-1 emits at an excitation wavelength X ex = 408 nanometers with a dominance wavelength λ dom= 486 nanometers and an emission maximum X max = 467 nanometers at a full width at half maximum (FWHM) of 92 nanometers or 0.537 eV. The embodiment 4-1 thus emits in the cyan region of the electromagnetic spectrum.
[0216] Figure 5 shows the emission spectra El-1, El-2, E2-1, E2-2, E3-1, E3-2 and E5-1 of embodiments 1-1, 1-2, 2-1, 2-2, 3-1, 3-2 and 5-1 of the phosphor 1 with the molecular formula (Ba, Ca, Y) 4 ( Si, Li )6(N, 0) ii: Ce 3+ The emission spectra are shown in a wavelength range from 425 nanometers to 825 nanometers and were recorded at an excitation wavelength of 408 nanometers. (2024PF01673, January 28, 2026)
[0217] P2024, 1179 WO N - 31 -
[0218] The exemplary embodiments are Ba / Y-rich compositions. Each of these embodiments emits in the yellow to orange region of the electromagnetic spectrum. The dominant wavelength λ is... dom in the range between and including 575 nanometers and inclusive 587 nanometers, the emission maximum X max in the range between and including 565 nanometers and 577 nanometers, and the full width at half maximum (FWHM) in the range between and including 111 nanometers and 129 nanometers, respectively, in the range between and including 0.448 eV and 0.499 eV.
[0219] Selected spectral data of the exemplary embodiments of phosphor 1 with the chemical formula
[0220] (Ba, Ca, Y) 4 ( Si, Li )6(N, 0) ii: Ce 3+ are summarized in Table 5.
[0221] Table 5: Selected spectral data from
[0222] (Ba, Ca, Y)4(Si, Li)6(N, O) and: Ce3+
[0223] Design range
[0224]
[0225] λ dom / λ peak / FWHM / LER / example nm nm nm Im / W 1-1 El-1 0, 520 0, 441 585 573 119 313 1-2 El-2 0, 536 0, 431 587 577 129 276 2-1 E2-1 0, 491 0, 459 581 568 111 365 2-2 E2-2 0, 496 0, 446 583 570 124 315 3-1 E3-1 0, 369 0, 379 575 565 124 295 3-2 E3-2 0, 483 0, 417 585 572 115 308 4-1 E4-1 0, 179 0, 265 486 467 92 234 5-1 E5-1 0, 442 0, 428 580 566 123 311
[0226] Table 6 shows a comparison of the half-value widths of the phosphor 1 according to embodiment 3-2 with those of the phosphors 1 according to comparison example 12024PF01673 28 January 2026
[0227] P2024, 1179 WO N - 32 -
[0228] (BaaYSieNu: Ce 3+ ) and a comparative example 3 (Y3AI5O12: Ce 3+ , YAG).
[0229] Table 6: Comparison of half-widths
[0230] Connection FWHM / eV Example 3-2 0, 448
[0231] ( ( Ba, Ca, Y)4( Si, Li )6(N, 0) xl : Ce 3+ )
[0232] Comparative example 1 0,453
[0233] ( Ba3YSi6N 11 : Ce 3+ )
[0234] Comparative example 3 (YAG: Ce 3+ ) 0, 518
[0235] The corresponding emission spectra, plotted on the energy scale, are shown in Figure 6 in the range of 1.5 to 3 eV. The emission spectrum E-VB3 was determined for phosphor 1 according to comparative example 3 with the chemical formula Y3Al5O12:Ce 3+ (YAG: Ce 3+ ) recorded.
[0236] Figure 7 shows the emission spectrum E3-2 in comparison with emission spectra E-VB1 and E-VB4. The emission spectra are shown in the wavelength range from 400 nanometers to 900 nanometers. The emission spectrum E3-2 corresponds to embodiment 3-2 of the phosphor 1 with the molecular formula (Ba, Ca, Y)₄(Si, Li)₆(N, O)ₙ:Ce 3+ The emission spectrum E-VB1 is based on comparison example 1 of phosphor 1 with the chemical formula Ba3YSi6N. 11 :Ce 3+ The emission spectrum E-VB4 is based on a comparative example 4 of phosphor 1. Comparative example 4 is a Gd-YAG: Ce 3+ .
[0237] Table 7 shows important spectral data of embodiment 3-2 in comparison with comparison examples 1 and 4. 2024PF01673 January 28, 2026
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[0239] Table 7: Important spectral data of embodiment 3-2, comparative example 1 and comparative example 4.
[0240] Comparison - Execution - Comparison - example 4 example 3-2 example 1 Gd-YAG: Ce 3+ (Ba, Ca, Y)4(Si, Li)6(N, 0) 41 : Ce 3+ Ba3YSi6N 11 : Ce 3+ A ex / nm 448 408 448
[0241] 0. 440 0. 483 0. 526 yciE 0. 535 0. 417 0. 465 Adom / nm 571 585 583 Apeak / nm 556 572 571 Acent / nm 583 607 627 FWHM / nm 125 115 121 LER / Im / W 432 308 303
[0242] For other compositions of the phosphor 1 described here, especially when using other alkaline earth and rare earth ions and when incorporating aluminum, other spectral properties are obtained.
[0243] For example, a rare-earth-free compound with M = Ca, Ba and a low Ce content yields cyan-emitting phosphors with a dominance wavelength of approximately 485 nanometers. Incorporating aluminum or using lutetium or lanthanum can result in emissions with a wider full width at half maximum (FWHM). If only small amounts of Al, Lu, or La are present in the phosphor 1, this change in composition may have no or only a negligible effect on the FWHM.
[0244] Figure 8 shows the thermal quenching behavior of phosphors 1 according to embodiment 3-2 with the molecular formula (Ba, Ca, Y)4( Si, Li )6(N, 0) n: Ce 3+ and the comparative examples 1 (BaaYSieNu: Ce 3+ ) and 4 (Gd-YAG: Ce 3+The y-axis of the diagram in Figure 8 plots the relative brightness B in % relative to the brightness at 25 °C. The x-axis represents the temperature T in °C. The relative brightness was measured in 25 °C increments. 2024PF01673 January 28, 2026
[0245] P2024, 1179 WO N - 34 -
[0246] The thermal quenching behavior of embodiment 3-2 was determined at an excitation wavelength of 380 nanometers. The thermal quenching behavior of comparison example 1 was determined at an excitation wavelength of 375 nanometers. The thermal quenching behavior of comparison example 4 was determined at an excitation wavelength of 460 nanometers.
[0247] Figure 8 shows that the phosphor 1 according to embodiment 3-2 ( (Ba, Ca, Y)4(Si, Li)6(N, 0) u: Ce 3+) above 125 °C, it exhibits better thermal behavior than the Li-free phosphor of comparison example 1 (BaaYSieNu: Ce). 3+ ) and significantly better thermal behavior than comparison example 4 (Gd-YAG: Ce 3+ ) shows.
[0248] An embodiment of a radiation-emitting device 10 is shown in Figure 9. The radiation-emitting device 10 comprises a radiation-emitting semiconductor chip 11 with an epitaxially grown semiconductor layer sequence 111. The semiconductor layer sequence 111 has an active region 112, which is configured to generate and emit electromagnetic radiation of a first wavelength range. The first wavelength range is, for example, the ultraviolet to blue wavelength range of the electromagnetic spectrum.
[0249] The radiation-emitting component 10 also includes a conversion element 12. The conversion element 12 includes a phosphor 1 as described herein. The conversion element 12 may also include a further phosphor 13. The phosphor 1 emits electromagnetic radiation from a second 2024PF01673 January 28, 2026
[0250] P2024, 1179 WO N 35
[0251] wavelength range. The additional phosphor 13 emits electromagnetic radiation in a third wavelength range. This additional phosphor 13 can also be a mixture of different phosphors.
[0252] The first, second, and third wavelength ranges differ at least partially. Phosphor 1 converts the electromagnetic radiation of the first wavelength range and / or the third wavelength range into the electromagnetic radiation of the second wavelength range. The additional phosphor 13 converts the electromagnetic radiation of the first wavelength range into the electromagnetic radiation of the third wavelength range.
[0253] A mixed light emitted by the radiation-emitting component 10 consists at least of electromagnetic radiation from the second and third wavelength ranges. It is also possible that the mixed light contains electromagnetic radiation from the first wavelength range.
[0254] Simulated emission spectra S1-2 and S1-VB1 of a radiation-emitting device 10 according to a first embodiment (S1-2) and a first comparative example (S1-VB1) are shown in Figure 10. The emission spectra are shown in a wavelength range from 400 nanometers to 800 nanometers. The radiation-emitting semiconductor chip 11 of the underlying radiation-emitting devices 10 emits with a dominant wavelength of λ. dom = 453 nanometers. The radiation-emitting semiconductor chip 11 is 2024PF01673, January 28, 2026
[0255] P2024, 1179 WO N - 36 -
[0256] so a blue-emitting LED. The conversion element 12 of the radiation-emitting components 10 has YAG:Ce as a further phosphor 13. 3+ In the first embodiment of the radiation-emitting component 10, the phosphor 1 is embodiment 1-2 with the chemical formula (Ba, Ca, Y)4( Si, Li )6(N, 0) n: Ce. 3+The radiation-emitting component 10 according to the first comparison example exhibits (Sr, Ca)AlSiN3: Eu 2+ as phosphor 1. The first embodiment and the first comparative example achieve the color point with the color coordinates X. C IE = 0, 567, y C iE = 0.430.
[0257] In the radiation-emitting component 10 according to the first embodiment, the phosphor 1 is excited by the further phosphor 13. In other words, the phosphor 1 partially converts the electromagnetic radiation of the third wavelength range, which is generated by the conversion of the electromagnetic radiation of the first wavelength range by the further phosphor 13. Due to the achieved color coordinate, the radiation-emitting component 10 according to the first embodiment can be used in a turning signal lamp.
[0258] Figure 11 shows a CIE diagram in which a color coordinate region F of turning signal lamps is plotted. The color coordinate region F can advantageously be achieved with radiation-emitting components 10 containing the phosphor 1 described here. It is possible to use only cerium-activated phosphors in the conversion element 12.
[0259] Besides achieving a pure Ce 3+ -activated fluorescent solution for turn signal lights can also be used with fluorescent material 1 according to the exemplary embodiments 2024PF01673 28 January 2026
[0260] P2024, 1179 WO N - 37 -
[0261] A single phosphor with a CRI of 8 O-solution, for example for use in general lighting, can be implemented. A corresponding radiation-emitting component 10 according to a second embodiment has the phosphor 1 described here in the conversion element 12, for example with the chemical formula (Ba, Ca, Y)⁴(Si, Li)⁶(N, O)n:Ce 3+ according to embodiment 3-1, and no further phosphor 13. A blue LED with a dominance wavelength λ is used as the radiation-emitting semiconductor chip 11. dom of 448 nanometers. Figure 12 shows a simulated emission spectrum S3-1 of the second embodiment of the radiation-emitting component 10 in the wavelength range from 420 nanometers to 920 nanometers.
[0262] Figure 13 shows a simulated emission spectrum S-VB2 of a second comparative example of a radiation-emitting device 10 in the wavelength range from 420 nanometers to 820 nanometers. In the second comparative example, YAG:Ce is used. 3+ as phosphor 1. As in the second embodiment of the radiation-emitting component 10, no further phosphor 13 is present in the conversion element 12. In the second comparative example, YAG:Ce is used. 3+ one of the longest-wavelength cerium-activated phosphors currently in use was employed.
[0263] The radiation-emitting component 10 according to the second embodiment achieves a higher color rendering index (CRI) of 80 compared to CRI 63 for the radiation-emitting component 10 according to the second comparative example. Therefore, with the phosphor 1 described here, it is possible to create a purely Ce-based light source. 3+to implement conversion element 12 based on an activator element, with which 2024PF01673 January 28, 2026
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[0265] even using a single phosphor, a CRI of at least 80 is achieved.
[0266] Furthermore, embodiment 6 of the phosphor 1 was produced using the following method: The starting materials BaNx-y (y=0, ll), AIN, Si3N4, Li3N, YN were mixed together with the dopant under a protective gas atmosphere and then annealed in a tungsten crucible at 1850°C for 4 hours under 20 bar nitrogen in a high-pressure furnace. The weights of the starting materials are summarized in Table 8.
[0267] Table 8: Weighings for the synthesis of embodiment 6
[0268] Product weight
[0269] Bank 1-y 18,951 g
[0270] AIN 0.409 g
[0271] Si3N418, 215 g
[0272] L i3N 0.367 g
[0273] YN 9, 765 g
[0274] CeO22, 292 g
[0275] A crystal was isolated from a powder sample of embodiment 6 (embodiment 6-1). The corresponding emission spectrum E6-1 is shown in Figure 14 in a wavelength range from 400 nanometers to 900 nanometers inclusive. The optical data of the phosphor 1 of embodiment 6 are summarized in Table 9.
[0276] Table 9: Optical data of embodiment 6-1
[0277] Execution
[0278] game 6-1
[0279] XciE 0, 5662024PF01673 January 28, 2026
[0280] P2024, 1179 WO N - 39 -
[0281] YCIE 0, 386
[0282] Xdom / nm 595, 3
[0283] Apeak / nm 637.5
[0284] Acent / nm 663.8
[0285] FWHM / nm 157.6
[0286] LER / Im / W 169, 9
[0287] A powder diffractogram PI of the phosphor 1 according to embodiment 6 is shown in Figure 15, a powder diffractogram P2 of the phosphor 1 according to embodiment 1 in Figure 16.
[0288] Powder diffractograms were recorded using Cu-Ka radiation and are shown over an angular range of 10° to 80°. Figures 15 and 16 each show a measured powder diffractogram (Gl) and a calculated powder diffractogram (G2). Lines G3 and markings G4 are also shown. Line G3 represents the difference between the values of curve G2 and curve Gl. In other words, it is a difference diagram (G3).
[0289] The markings G4 in Figure 15 show the theoretical reflection positions of BaY0.97Si4N7 (top) and of the phosphor 1 of embodiment 6.
[0290] ( (Ba, Y) 4 ( Si, Al, Li )6(N, 0) ii: Ce3+ , below). The markings G4 in Figure 16 show the theoretical reflection positions of the phosphor 1 of embodiment 1.
[0291] ( (Ba, Y)4(Si, Li)6(N, O) u: Ce 3+ ).
[0292] An EDX measurement of embodiment 6-1 confirms the incorporation of aluminum. In other words, element E is contained in the phosphor 1 of embodiment 6-1. The phosphor 1 according to embodiment 6-1 thus has the molecular formula (Ba, Y)⁴(Si, Al, Li)⁶(N, O)n:Ce 3+ EDX-2024PF01673, January 28, 2026
[0293] P2024, 1179 WO N - 40 -
[0294] Measurements are summarized in Table 10. Ba + Y + Ce is normalized to 4. The Li content was calculated based on the missing amount of Si + Al.
[0295] Table 10: EDX results of embodiment 6-1
[0296] Example 6-1 Ba 2, 4
[0297] Ce 0, 2
[0298] Y 1, 4
[0299] Sum (Si+Al) 5.7
[0300] Si 5, 5
[0301] Al 0, 2
[0302] Left position D and / or E
[0303] Calculated Li content 0.3
[0304] The features and embodiments described in connection with the figures can be combined with each other according to further embodiments, even if not all combinations are explicitly described.
[0305] Furthermore, the embodiments described in connection with the figures may alternatively or additionally have further features as described in the general part.
[0306] This patent application claims priority over German patent application 10 2025 104 568.2, the disclosure content of which is hereby incorporated by reference.
[0307] The invention is not limited to the exemplary embodiments described therein. Rather, the invention encompasses every new feature and every combination of features, which in particular includes every combination of features in the claims, even if this feature is 2024PF01673 28 January 2026
[0308] P2024, 1179 WO N - 41 -
[0309] or this combination itself is not explicitly specified in the patent claims or embodiments. 2024PF01673 January 28, 2026
[0310] P2024, 1179 WO N
[0311] 42
[0312] Reference symbol list
[0313] 1 Fluorescent
[0314] 10 radiation-emitting components
[0315] 11 radiation-emitting semiconductor chip 111 semiconductor layer stack
[0316] 112 active area
[0317] 12 Conversion element
[0318] 13 more fluorescent materials
Claims
2024PF01673 January 28, 2026 P2024, 1179 WO N - 43 - Patent claims 1. Fluorescent material ( 1 ) with the chemical formula EA4 + 3 v -y-zSE-3 v +y+ z D6-tvx-yEx+yLit+vN10-3t-x+zOi + 3t+xz • Where - EA is an element or combination of elements selected from the group of divalent elements, - SE is an element or combination of elements selected from the group of rare earth elements, - D is an element or combination of elements selected from the group of four-valued elements, - E is an element or combination of elements selected from the group of three-valued elements, - R comprises an activator element, - -4 < +3v-yz do, -6 < -tvxy < 0, 0 < x+y < 6, 0 < t+v < 6, -10 < -3t-x+z < 1, and - 2* (4+3v-yz) +3* (-3v+y+z) +4* ( 6-tvxy) +3* (x+y) +l* (t+v) - 3* ( 10-3 t-x+ z ) -2 * ( 3 t+x- z ) = 0.
2. Fluorescent material ( 1 ) according to the preceding claim, wherein - EA is an element or a combination of elements selected from the group formed by Mg, Ca, Sr, Ba, Zn, - D is an element or a combination of elements selected from the group formed by Si, Ge, Sn, Ti and Zr, - E is an element or a combination of elements selected from the group formed by Al, B, Ga and In, and / or - R is an element or combination of elements selected from the group formed by Ce, Eu, Mn, Bi, Tb, Dy, Ni, Gr, Cu and Er. 2024PF01673 28 January 2026 P2024, 1179 WO N 44 3. Fluorescent material ( 1 ) according to one of the preceding claims having the molecular formula EA4 + 3 V-y-z SE-3 V+y+z Si6-tvx-yAlx+yLit+vNio-3t- x+zOi + 3t+xz • R • 4. Fluorescent material ( 1 ) according to any of the preceding claims having the molecular formula EA4 + 3 V-z SE-3 V+z Si6-t-vLit+vNio-3t+zOi + 3t-z: R, where - -4 < 3v-z < 0, -6 < -tv < 0, 0 < t+v < 6, -10 < -3t+z < 1, and - 2* (4 + 3v-z) +3* (-3v+z) +4* ( 6- tv) +1* (t+v) -3* ( 10-3t+z) -2* (3t-z) = 0.
5. Fluorescent material ( 1 ) according to any of the preceding claims having the molecular formula EA4 +3v SE-3 V Si6-t-vLit+vNio-3tOi + 3t: R, where - -4 < 3v < 0, -6 < -tv < 0, 0 < t+v < 6, -10 < -3t < 1, and - 2 * ( 4 + 3v) +3* ( -3v) +4 * ( 6- tv) + 1 * ( t+v) -3* ( 10-31 ) -2 * ( 31 ) = 0.
6. Phosphor ( 1 ) according to any of the preceding claims, wherein a host lattice of the phosphor ( 1 ) has a crystal structure with a cubic space group.
7. Phosphor ( 1 ) according to the preceding claim, wherein a unit cell volume of the crystal structure of the host lattice of the phosphor ( 1 ) in the range between inclusive 1050 Å 3 and including 1250 Ä 3 is.
8. Phosphor ( 1 ) according to any of the preceding claims, wherein the phosphor ( 1 ) has an excitation wavelength in the range between inclusive 250 nanometers and inclusive 600 nanometers.
9. Fluorescent material (1) according to one of the preceding claims, wherein a light emitted by the phosphor (1) 2024PF01673 28 January 2026 P2024, 1179 WO N 45 electromagnetic radiation has an emission spectrum with an emission maximum that lies in the range between 425 nanometers and 650 nanometers.
10. Phosphor ( 1 ) according to any of the preceding claims, wherein the electromagnetic radiation emitted by the phosphor ( 1 ) has a dominance wavelength λ dom in the range between 460 nanometers and 620 nanometers.
11. Phosphor ( 1 ) according to any of the preceding claims, wherein the emission maximum of the phosphor ( 1 ) has a half-width in the range between inclusive 80 nanometers and inclusive 170 nanometers.
12. Method for the production of a phosphor ( 1 ) with the sum formula EA4 + 3 v -y- z SE-3 v +y+ z D6-tvx-yEx+yLit+vN10-3t-x+zOi + 3t+xz • R, Where - EA is an element or combination of elements selected from the group of divalent elements, - SE is an element or combination of elements selected from the group of rare earth elements, - D is an element or combination of elements selected from the group of four-valued elements, - E is an element or combination of elements selected from the group of three-valued elements, - R comprises an activator element, - -4 < +3v-yz do, -6 < -tvxy < 0, 0 < x+y < 6, 0 < t+v < 6, -10 < -3t-x+z < 1, and - 2* (4+3v-yz) +3* (-3v+y+z) +4* ( 6-tvxy) +3* (x+y) +l* (t+v) - 3* ( 10-3 t-x+ z ) -2 * ( 3 t+x- z ) = 0, showing the steps: 2024PF01673 January 28, 2026 P2024, 1179 WO N 46 - Providing starting materials, - Mixing the reactants to form a reactant mixture, - Heating the reactant mixture.
13. The method of claim 11, wherein the reactants are selected from the following group: nitrides, oxides, nitrates, citrates, oxalates, halides, carbonates, hydroxides of EA, Li, SE, D, E, R and combinations thereof.
14. Method according to one of claims 12 and 13, wherein the reactant mixture is heated to a temperature in the range between and including 1400 °C and 2100 °C.
15. Method according to any one of claims 12 to 14, wherein the reactant mixture is heated in an inert and / or reducing atmosphere.
16. Radiation-emitting component ( 10) with - a radiation-emitting semiconductor chip ( 11 ) which emits electromagnetic radiation of a first wavelength range, and - a conversion element ( 12 ) with a phosphor ( 1 ) according to one of claims 1 to 10, which emits electromagnetic radiation of a second wavelength range.
17. Radiation-emitting component ( 10) according to claim 16, wherein the phosphor ( 1 ) converts the electromagnetic radiation of the first wavelength range into the electromagnetic radiation of the second wavelength range.
18. Radiation-emitting component (10) according to claim 16, wherein 2024PF01673 28 January 2026 P2024, 1179 WO N - 47 - - the conversion element ( 12 ) comprises a further phosphor ( 13) which converts the electromagnetic radiation of the first wavelength range into electromagnetic radiation of a third wavelength range, and - the phosphor ( 1 ) converts the electromagnetic radiation of the third wavelength range into the electromagnetic radiation of the second wavelength range.