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 EP2026052139_13082026_PF_FP_ABST
Abstract
Description
[0001] 2024PF01460 January 28, 2026
[0002] P2024, 1102 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 entry: 2024PF01460 28 January 2026]
[0008] P2024, 1102 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 listed elements exist 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 formulation, the phosphor has the chemical formula EA. 4-v-x-y-z Li x+y SE v+z D 6-w+y-z E w-y+z N 10+v-w-x O 1-v+w+x :R. In particular, the phosphor has the molecular formula (M,Li)4(D,E)6(N,O) 11 :R, where M is the elements EA and SE2024PF01460, January 28, 2026
[0016] P2024, 1102 WO N - 3 -
[0017] includes. In other words, the phosphor can have the chemical formula (EA,SE,Li)4(D,E)6(N,O) 11 exhibit :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 third group.
[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. 2024PF01460 January 28, 2026
[0024] P2024, 1102 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 via 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 2024PF01460 28 January 2026
[0029] P2024, 1102 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 proportion of 0.01 mol% to 30 mol% inclusive, based on the elements EA and SE. In particular, R has a proportion of 0.01 mol% to 15 mol% inclusive, based on the elements EA and SE. For example, R has a molecular proportion between 0.01 mol% and 5 mol% inclusive, based on EA and SE.
[0032] According to at least one implementation form, the following hold: 0 < x+y < 4, -4 < -vxyz < 0, 0 < v+z < 4, 0 < w-y+z < 6 and
[0033] -10 ≤ vwx ≤ 1. According to at least one embodiment, lithium is therefore contained in the phosphor.
[0034] According to at least one embodiment: 2*(4-vxyz)+1*(x+y)+3*(v+z)+4*(6-w-x+yz)+3*(w-y+z)-3*(10+vwx)-2*(1-v+w+x) = 0.
[0035] According to at least one embodiment, the phosphor has the chemical formula EA 4-v-x-y-z Li x+y SE v+z D6-w+y-z E w-y+z N 10+v-w-x O 1-v+w+x :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 2024PF01460 28 January 2026
[0036] P2024, 1102 WO N - 6 -
[0037] a combination of elements selected from the group of four-valued elements, E is an element or a combination of elements selected from the group of three-valued elements, R includes an activator element, 0 < x+y < 4, -4 < -vxyz < 0, 0 < v+z < 4, 0 < w-y+z < 6, -10 < vwx < 1 and 2*(4-vxyz)+1*(x+y)+3*(v+z)+4*(6-w-x+yz)+3*(w-y+z)-3*(10+vwx)-2*(1-v+w+x) = 0.
[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 combination of elements selected from the group formed by Ca, Sr, and Ba. For example, EA includes or is Ba.
[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.2024PF01460 28 January 2026
[0043] P2024, 1102 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, Cr, 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, Cr 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 is or comprises 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+ For example, it is less than 100 nanoseconds, while typical 2024PF01460 is January 28, 2026.
[0053] P2024, 1102 WO N 8
[0054] Lifetimes of excited states 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 irradiance levels. For example, studies have shown that...
[0056] Y3Al5O 12 :Ce 3+ Quenching effects only occur 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 effects observed. Ce 3+ -activated phosphors only exhibit quenching effects at more than an order of magnitude above the irradiance at which phosphors with Eu 2+ The phosphor already exhibits quenching effects as an activator element. Therefore, the phosphor described here can be advantageously used in applications with higher irradiance.
[0057] According to at least one embodiment, the phosphor has the chemical formula EA 4-v-x-z Li xSE v+z Si 6-w-z Al w+z N 10+v-w-x O 1-v+w+x :R, where 0 < x < 4, -4 < -vxz < 0, 0 < v+z < 4, 0 < w+z < 6, -10 < vwx < 1, and 2*(4-vxz)+1*(x)+3*(v+z)+4*(6-wxz)+3*(w+z)-3*(10+vwx)-2*(1-v+w+x) = 0. In other words, D Si, E Al, and y = 0. The sum formula can also be expressed as (M,Li)4(Si,Al)6(N,O) 11 :R, where M is SE and EA, are represented.
[0058] According to at least one embodiment, the phosphor has the chemical formula EA4- v-x Li x SE v Si6N 10 + v -xOi-v+x: R, where 0 < x < 4, -4 < -vx do, 0 < v < 4, -10 < vx < 1 and 2* (4-vx) +1* (x) +3* (v) +4* ( 6) -3* ( 10+vx) -2* ( 1-v+x) = 0. In other words, D Si, y = 0 and z = 0. Therefore, the phosphor does not contain the element E. The sum formula can be 2024PF01460 January 28, 2026
[0059] P2024, 1102 WO N 9
[0060] also known as (M,Li)4Si6(N,O) 11:R, where M is SE and EA, are represented.
[0061] 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 P213 (No. 198).
[0062] For example, the phosphor has the same crystal structure as (Ba,Eu)3YbSi6N 11 , Ba 1,8 Approx 2,2 Si6N 10 and EA 3-3 / 2u SE 1+u (Si,Al)6(N,O) 11 :A. For example, in the phosphor described here, Li, EA and SE partially occupy the same positions in the crystal structure of the host lattice.
[0063] 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, known as point positions, within the three-dimensional unit cell of the host lattice.
[0064] 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. 2024PF01460 January 28, 2026
[0065] P2024, 1102 WO N 10
[0066] In a cubic space group, a = b = c and a = ß = y = 90°.
[0067] According to at least one embodiment of the phosphor, the lattice parameter a of the cubic crystal structure is less than 10.45 Å. In other words, the lattice vectors that span the unit cell of the host lattice crystal structure have a length of at most 10.450 Å.
[0068] According to at least one embodiment of the phosphor, the phosphor has an excitation wavelength in the range between and including 250 nanometers and inclusive 600 nanometers. In other words, the phosphor can be excited by electromagnetic radiation from the ultraviolet to yellow region of the electromagnetic spectrum.
[0069] In particular, the phosphor exhibits at least two, and in particular three, excitation maxima. For example, a first excitation maximum of the phosphor lies in the ultraviolet region of the electromagnetic spectrum, in particular in the region between and including 250 nanometers and 325 nanometers. A second excitation maximum of the phosphor may lie in the ultraviolet to blue region of the electromagnetic spectrum, for example in the region between and including 325 nanometers and 450 nanometers. A third excitation maximum of the phosphor lies, for example, in the green to yellow region of the electromagnetic spectrum, for example in the region between and including 450 nanometers and 600 nanometers. 2024PF01460 January 28, 2026
[0070] P2024, 1102 WO N 11
[0071] 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, in particular, electromagnetic radiation of the second wavelength range.
[0072] The emission spectrum is an intensity distribution of the electromagnetic radiation emitted by the phosphor after excitation with electromagnetic radiation of the excitation wavelength.
[0073] 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 X. In other words, the emission spectrum is a curve in a diagram where the wavelength is plotted on the x-axis and the spectral intensity or spectral flux is plotted on the y-axis.
[0074] The emission maximum lies particularly in the range between 500 and 600 nanometers, for example, between 560 and 590 nanometers. In other words, the phosphor can emit in the green to orange region of the electromagnetic spectrum. The emission maximum depends specifically on the composition of the phosphor.
[0075] The emission maximum can also be in the range between and including 425 nanometers and including 6502024PF01460 28 January 2026
[0076] P2024, 1102 WO N 12
[0077] The emission maximum lies in the nanometer range. In other words, the phosphor can emit in the blue to orange wavelength range of the electromagnetic spectrum. Specifically, the emission maximum depends on the composition of the phosphor. For example, the emission maximum lies in the range between 450 and 500 nanometers. The emission maximum can also lie in the range between 550 and 600 nanometers.
[0078] Emission in the cyan wavelength range can be obtained, for example, with a phosphor containing EA = Ca and / or Ba and with v+z = 0, i.e., without SE.
[0079] 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 exhibits, in particular, at least two or at least three local emission maxima. A first local emission maximum is located, for example, in the range between and including 425 nanometers and 525 nanometers. A second local emission maximum is located, for example, in the range between and including 525 nanometers and 625 nanometers, and in particular in the range between and including 560 nanometers and 580 nanometers. A third local emission maximum is located, for example, in the range between and including 625 nanometers and 650 nanometers.
[0080] According to at least one embodiment, the electromagnetic radiation emitted by the phosphor exhibits a 2024PF01460 28 January 2026
[0081] P2024, 1102 WO N 13
[0082] 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.
[0083] 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 coordinate 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.
[0084] According to at least one embodiment of the phosphor, the emission maximum has a full width at half maximum (FWHM) in the range between 100 nanometers and 170 nanometers inclusive, in particular between 100 nanometers and 160 nanometers inclusive, for example, between 100 nanometers and 150 nanometers inclusive. It is also possible to specify the FWHM in electron volts (eV). For example, the FWHM of the emission maximum of the phosphor is in the range between 0.400 eV and 0.550 eV inclusive. In particular, the FWHM of the emission maximum of the phosphor is at most 0.520 eV, for example, at most 0.450 eV. 2024PF01460 January 28, 2026
[0085] P2024, 1102 WO N 14
[0086] The term half-width refers to a curve with a maximum, such as the emission spectrum, where the half-width is the area on the x-axis that corresponds to the two y-values that represent half of the maximum.
[0087] According to at least one embodiment of the phosphor, the electromagnetic radiation emitted by the phosphor has a center-of-mass wavelength X. cen t in the range from 500 nanometers inclusive to 700 nanometers inclusive, in particular in the range from 570 nanometers inclusive to 700 nanometers inclusive.
[0088] 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(X):
[0089] QA ■ s(A)dA
[0090] J-cent — ßV TT VJT- '
[0091]
[0092] 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 2024PF01460 January 28, 2026
[0093] P2024, 1102 WO N - 15 -
[0094] Irradiance reaches a maximum emission brightness.
[0095] The phosphor described here therefore represents a more efficient alternative to the EU phosphors. 2+ -activated phosphors are available. The phosphor described here is also suitable as a more efficient alternative to cyan-emitting phosphors.
[0096] 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
[0097] 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
[0098] λ dom > 580 nm. In contrast, with the phosphor described here, dominance wavelengths in the same range or even below 580 nanometers can be achieved.
[0099] 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 Y3Al5O 12:Ce 3+ (YAG: Ce) for application. Typical spectral values for YAG are between 565 nanometers and 574 nanometers for the dominance wavelength and between 110 nanometers and 125 nanometers for the full width at half maximum (FWHM). Longer-wavelength emissions, such as Ce, are described in the literature. 3+ -activated phosphors, e.g. in Tb3Al50i2: Ce 3+ (TbAG: Ce) or Gd3Al50i2: Ce 3+ (GdAG: Ce). However, these are not suitable for the application because they exhibit strong thermal quenching. 2024PF01460 January 28, 2026
[0100] P2024, 1102 WO N - 16 -
[0101] Due to its emission properties, the phosphor described here is therefore suitable as an alternative to TbAG: Ce, GdAG: Ce and orange-emitting Eu. 2+ -doped phosphors in radiation-emitting components.
[0102] To produce LEDs with a color rendering index (CRI) of 70 or more, a mixture of Ce is typically used. 3+ -activated green to yellow fluorescent materials and EU 2+ -activated orange to red phosphors are used. Due to its properties, the phosphor described here is advantageously suited for use as an orange-emitting component 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.
[0103] According to at least one embodiment of the phosphor, it has a photometric radiation equivalent in the range between 270 lm / W and 350 lm / W.
[0104] 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 at a given power. The phosphor described here has a higher photometric luminous efficacy compared to other phosphors. 2024PF01460 January 28, 2026
[0105] P2024, 1102 WO N 17
[0106] Furthermore, a method for producing a phosphor is described. In particular, the previously described phosphor is produced by this method.
[0107] The design features and other characteristics described in connection with the phosphor also apply to the process and vice versa.
[0108] According to at least one implementation of the process, the phosphor has the chemical formula EA4- v-x-y-z Li x+y SE v+z D 6-w + y-z E w - y+z Nio +v-w-xOi-v+w+x: 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 is an activator element, 0 < x+y < 4, -4 < -vxyz < 0, 0 < v+z < 4, 0 < w-y+z < 6, -10 < vwx < 1 and 2* (4-vxyz ) +1* (x+y) +3* (v+z) +4* ( 6-w-x+yz ) +3* (w-y+z) -3* ( 10+ vwx) -2* ( 1-v+w+x) = 0.
[0109] 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.
[0110] In particular, the steps are performed in the specified order.
[0111] 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, starting materials used in the production of the phosphor. 2024PF01460 28 January 2026
[0112] P2024, 1102 WO N 18
[0113] The phosphor may not have reacted, or it may be impurities and / or side phases that were formed during manufacturing.
[0114] 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.
[0115] For example, the starting materials are selected from the group formed by: BaN 1-y, where y lies between and including -0.5 and 0.5, BaO, BaCO3, Ca3N2, CaCO3, Sr3N2, SrN2, SrCO3, Li3N, Li2O, Li2CO3, YN, Y2O3, LaN, La2O3, LuN, Lu2O3, Si3N4, SiO2, AIN, A12O3, CeN, Ce2O3, CeO2, CeF3 and combinations thereof. In particular, the reactants each comprise a reactant for EA, Li, SE, D, E and R, insofar as present in the phosphor.
[0116] 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 inclusive, in particular in the range between 1600 °C and 1950 °C inclusive.
[0117] 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. In particular, 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. 2024PF01460 January 28, 2026
[0118] P2024, 1102 WO N - 19 -
[0119] 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.
[0120] 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.
[0121] 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.
[0122] 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.
[0123] In particular, the semiconductor chip comprises an epitaxially grown sequence of semiconductor layers, which includes an active 2024PF01460 28 January 2026
[0124] P2024, 1102 WO N 20
[0125] The component has a region that generates electromagnetic radiation of the first wavelength range during operation. The semiconductor chip is, for example, a light-emitting diode (LED) 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 located at least on the radiation emission surface of the semiconductor chip.
[0126] 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.
[0127] The radiation-emitting component exhibits a CRI of at least 70. 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 70 in this configuration. Advantageously, such radiation-emitting components are used for street lighting.
[0128] According to at least one embodiment of the radiation-emitting component, the conversion element includes an additional phosphor that converts the electromagnetic radiation of the first wavelength range into electromagnetic radiation of a third wavelength range. Conversion element 2024PF01460, January 28, 2026
[0129] P2024, 1102 WO N 21
[0130] It therefore features, in particular, two different phosphors. For example, the phosphor converts the electromagnetic radiation of the third wavelength range into the electromagnetic radiation of the second wavelength range. Alternatively or additionally, it is possible that the phosphor converts the electromagnetic radiation of the first wavelength range into the electromagnetic radiation of the second wavelength range.
[0131] 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 Y3Al5O 12 :Ce 3+ (YAG: Ce).
[0132] 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.
[0133] For example, the radiation-emitting component can be used with the additional phosphor in a turning signal lamp or to generate amber-colored light. 2024PF01460 January 28, 2026
[0134] P2024, 1102 WO N 22
[0135] 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.
[0136] Figure 1 shows a schematic representation of a phosphor according to an exemplary embodiment.
[0137] Figure 2 schematically shows steps of a process for producing a phosphor according to an exemplary embodiment.
[0138] Figure 3 shows excitation spectra of a phosphor according to one embodiment and according to a comparative example.
[0139] Figures 4 to 7 show emission spectra of phosphors according to different embodiments and various comparative examples.
[0140] Figure 8 shows the thermal quenching behavior of phosphors according to one embodiment and according to comparative examples.
[0141] Figure 9 shows a schematic sectional view of a radiation-emitting component 10 according to an exemplary embodiment.
[0142] Figure 10 shows simulated emission spectra of a radiation-emitting component according to an exemplary embodiment and a comparative example. 2024PF01460 January 28, 2026
[0143] P2024, 1102 WO N - 23 -
[0144] Figure 11 shows a color locus diagram.
[0145] Figure 12 shows a simulated emission spectrum of a radiation-emitting component according to an exemplary embodiment.
[0146] Figure 13 shows a simulated emission spectrum of a radiation-emitting component according to a comparative example.
[0147] Figure 14 shows a powder diffractogram of a phosphor according to an exemplary embodiment.
[0148] Figures 15 and 16 show emission spectra of phosphors according to different embodiments.
[0149] Figures 17 to 19 each show a powder diffractogram of a phosphor according to an exemplary embodiment.
[0150] 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.
[0151] The phosphor 1 of the embodiment shown in Figure 1 has the chemical formula EA4- v-x -y- z Li x +ySE v + z D6- w +y-z E w -y+ z N 10+v-w-x O 1-v +w+x • 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 2024PF01460 28 January 2026
[0152] P2024, 1102 WO N 24
[0153] 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 is an activator element or includes, 0 < x+y < 4, -4 < -vxyz < 0, 0 < v+z < 4, 0 < w-y+z < 6, -10 < vwx < 1 and 2* (4-vxyz ) +1* (x+y ) +3* (v+z) +4* ( 6-w-x+yz ) +3* (w-y+z) -3* ( 10+ vwx) -2* ( 1-v+w+x) = 0. In other words, phosphor 1 has the formula (M, Li ) 4 (D, E )6(N, 0) g: R, where M includes EA and SE. In particular, EA is Ba, Ca and / or Sr. D can be Si and E can be Al. R is or includes, for example, Ce. 3+ SE is specifically Y. In the crystal structure of phosphor 1, EA, Li, and SE partially occupy the same positions. D and E can also occupy the same positions in the crystal structure. Phosphor 1 can be free of aluminum. However, phosphor 1 always contains Li.
[0154] The phosphor 1 is present in the form of particles. For example, the particle size is between 500 nanometers and 100 micrometers.
[0155] Phosphor 1 has a host lattice in which the activator element R is embedded. Phosphor 1 crystallizes in the cubic space group P2i3 and is isostructural to the crystal structures of EA3_.
[0156] 3 / 2USEI+ U (Si, Al )6(N, 0) u: A, ( Ba, Eu ) 3 YbS i gNn and Bai f 3 Ca2,2Si gN3QO.
[0157] Table 1 summarizes important crystallographic data for embodiment 1-1. Table 1 shows the measured portion of the reciprocal space across the limits of the corresponding Miller indices (hkl). Furthermore, the conventional R-value of all reflections R is given. all 2024PF01460 January 28, 2026
[0158] P2024, 1102 WO N - 25 -
[0159] The weighted R-value (wR) indicates the mean percentage deviation between observed and calculated structural factors. ref It includes a weighting factor that weights the reflexes according to a defined scheme, depending, among other things, on their standard deviation. The goodness of fit (GooF), which should be close to 1, is given as a quality indicator for the agreement between the calculated and measured structure.
[0160] Table 1: Crystallographic data of
[0161] (Ba, Ca, Y, Li )4Si6(0, N) ii: Ce (Exemplary 1-1 )
[0162] Sum formula (Ba, Ca, Y, Li) 4Sie (O, N) n: Ce Example 1-1
[0163] Z 4
[0164] cubic crystal system
[0165] Space group P213
[0166] Grid parameters
[0167] a / Ä 10, 38510 ( 10 )
[0168] Volume V / Ä 3 1120, 04 ( 3 )
[0169] T / K 296 (2 )
[0170] Bruker D8 Quest diffractometer
[0171] CuKa radiation
[0172] Measuring range
[0173] Measured / independent 4541 / 653
[0174] Reflexes
[0175] Measured reciprocal -12
[0176]
[0177] h 11 Room
[0178]
[0179] -10 k 12
[0180] -12 < 1 < 11
[0181] R all / wR ref 2.09% / 4.79%
[0182] GooF 1,086
[0183] Table 2 shows the crystallographic position parameters of (Ba, Ca, Y, Li)4Sie (0, N) ii: Ce of embodiment 1-1. The Wyckoff position describes the symmetry of the point positions according to RWG Wyckoff; x, y, and z indicate the atomic positions. ani ist2024PF01460 January 28, 2026
[0184] P2024, 1102 WO N - 26 -
[0185] the radius of the anisotropic displacement parameters of the
[0186] each atom. Due to their low concentration, Ca and Ce are not mentioned in the crystallographic positional parameters. However, Ca and Ce occupy the same positions as Y, Ba, and Li.
[0187] Table 2: Crystallographic positional parameters of
[0188] (Ba, Ca, Y, Li )4Si6( 0, N) ii: Ce (From example 1- 1 )
[0189] Atom- Wyckoff so f
[0190] Name X yz U ani type -location
[0191] Bal Ba 4a 0, 21986 ( 4 ) 0, 28014 ( 4 ) 0, 71986 ( 4 ) 0, 0217 ( 2 ) Ba2 Ba 12b 0, 4067 ( 4 ) 0, 8845 ( 18 ) 0, 6274 ( 15 ) 0, 0264 ( 15 ) Y3 Y 4a 0, 42237 ( 7 ) 0, 42237 ( 7 ) 0, 42237 ( 7 ) 0, 0232 ( 3 ) Y4 Y 4a 0, 57991 ( 19 ) 0, 57991 ( 19 ) 0, 57991 ( 19 ) 0.232 ( 8 ) 0.0151 ( 16 ) Li4 Li 4a 0.57991 ( 19 ) 0.57991 ( 19 ) 0.57991 ( 19 ) 0.768 ( 8 ) 0.0151 ( 16 ) Si5 Si 12b 0.31887 ( 14 ) 0.44239 ( 14 ) 1.00447 ( 14 ) 0.0101 ( 3 ) Si6 Si 12b 0.33604 ( 15 ) 0.59547 ( 14 ) 0.74553 ( 13 ) 0.0098 ( 3 ) N7 N 4a 0.2375 ( 5 ) 0. 7375 ( 5 ) 0. 7625 ( 5 ) 0. 0120 ( 16 ) N8 N 12b 0. 3212 ( 5 ) 0. 5377 ( 5 ) 0. 5934 ( 4 ) 0. 0142 ( 10 ) N9 N 12b 0. 4945 ( 5 ) 0.6322 ( 5 ) 0.7830 ( 5 ) 0.0126 ( 9 ) N10 N 12b 0. 2754 ( 5 ) 0. 4902 ( 5 ) 0. 8549 ( 4 ) 0. 0123 ( 9 ) Ni l N 4a 0. 4512 ( 5 ) 0.5488 ( 5 ) 1.0488 ( 5 ) 0.0137 ( 16 ) 0
[0192] Table 3 shows a comparison of the grating parameter a of the phosphor fs 1 according to example 1-1 with the grating parameters a of the compounds EA3_
[0193] 3 / 2 U SE 1+U ( Si, Al )6(N, 0) ii: A, like (Ba, Y)4( Si, Al )6( 0, N) n,
[0194] 5 (Ba, Eu) 3 YbS i gNu and Bai f gCa2, 2Si gNi QO.
[0195] Table 3: Comparison of the grid parameter a
[0196] (Ba, Ca, Y, Li)4(Si, Al) e (Ba, Y)4(Si, A1)6(Ba, Eu)3Yb Bai,8Ca2,2(O, N) n (O, N) n SieNn Si6Ni0O a in Ä 10, 38510 ( 10 ) 10, 411 ( 1 ) 10, 436 ( 1 ) 10, 402 ( 2 )2024PF01460 January 28, 2026
[0197] P2024, 1102 WO N - 27 -
[0198] Figure 2 schematically shows the steps of a process for producing a phosphor 1 according to an exemplary embodiment. The phosphor 1 has the chemical formula EA4-v- x -y- z Li x+y SE v+zDe-w+y-zEw-y+zNlO+vw-xOl-v+w+x • R up.
[0199] In a first process step S1, reactants are provided. The reactants each comprise one 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 BaN 1-y, where y lies between and including -0.5 and 0.5, BaO, BaCO3, Ca3N2, CaCO3, Sr3N2, SrN2, SrCO3, Li3N, Li2O, Li2CO3, YN, Y2O3, LaN, La2O3, LuN, Lu2O3, Si3N4, SiO2, AIN, A12O3, 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 out under protective gas and intimately mixed in a second process step S2. The resulting starting material mixture is transferred in process step S3 to a crucible made of tungsten, tantalum, or molybdenum and heated to a temperature in the range of 1400°C to 2100°C, particularly between 1600°C and 1950°C. This heating takes place, for example, in a tube furnace, chamber furnace, high-pressure furnace, or retort furnace. The temperature is maintained for a period of 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. (Additional information: 2024PF01460, January 28, 2026)
[0200] P2024, 1102 WO N - 28 -
[0201] The resulting mixture can be acid-washed to increase the phase fraction. In particular, the process produces a mixture containing the phosphor f 1.
[0202] The quantities of materials required for the synthesis of examples 1 to 10 are summarized in Table 4. Although no calcium source was used in the synthesis, calcium may be present in phosphor f 1, as demonstrated by EDX measurement (see Table 8). The calcium was introduced into phosphor f 1 primarily through contamination of the starting materials and / or the crucible. However, a controlled synthesis is possible using a calcium source, such as CaCO3 or Ca2N2.
[0203] Table 4: Sample weights for the synthesis of
[0204] (Ba, Ca, Y, Li )4Si6( O, N) u : Ce
[0205] BaNi-y YN Si3N4SiO2Li3N CeO2Aus example 4, 460g 0, 766g 3, 544g 0, 8678g 0, 259g 0, 104g
[0206] From example 4, 216g 1, 448g 3, 682g 0, 393g 0, 163g 0, 098g
[0207] From examples 3.994g 2.058g 3.778g 0.077g 0.093g 3 to 5
[0208] From examples 5, 459g 0, 938g 3, 299g 0, 184g 0, 035g 0, 084g 6 and 7
[0209] From examples 5, 591g 0, 640g 3, 232g 0, 378g 0, 072g 0, 087g 8 and 9
[0210] From examples 5, 730g 0, 328g 3, 162g 3, 162g 0, 111g 0, 089g 10 and 11
[0211] The heating of the reactant mixture for examples 1, 2, 4, 6, 8 and 10 took place at a temperature of 1750 °C for a period of 4 hours at a pressure of 20 bar. Heating of the reactant mixture 2024PF01460 January 28, 2026
[0212] P2024, 1102 WO N - 29 -
[0213] For embodiments 7, 9, and 11, the reactant mixture was heated at a temperature of 1750 °C for 48 hours at a pressure of 20 bar N₂. For embodiment 5, the reactant mixture was heated at a temperature of 1850 °C for 4 hours at a pressure of 20 bar N₂. For embodiment 3, the reactant mixture was heated at a temperature of 1850 °C for 48 hours at a pressure of 20 bar N₂. In all embodiments, BaBaN was used as the reactant. 1-y with y = 0, 11.
[0214] Furthermore, embodiments 12 and 13 of the phosphor were produced using the following method: The starting materials BaN 1-y(y=0, ll ), AIN, Si3N4, Li3N, YN were mixed with the dopant under a protective gas atmosphere to form a reactant mixture 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 reactants are summarized in Tables 5 and 6.
[0215] Table 5: Weights for the production of embodiment 12
[0216] Product weight
[0217] Bank 1-y 18,951 g
[0218] AIN 0.409 g
[0219] Si3N418, 215 g
[0220] L i3N 0.367 g
[0221] YN 9, 765 g
[0222] CeO22, 292 g
[0223] Table 6: Weights for the production of embodiment 132024PF01460 28 January 2026
[0224] P2024, 1102 WO N - 30 -
[0225] Product weight
[0226] Bank 1-y 18,449 g
[0227] AIN 0.570 g
[0228] Si3N417, 927 g
[0229] L i3N 0.357 g
[0230] YN 9, 506 g
[0231] CeO23, 191 g
[0232] Figure 3 shows excitation spectra of embodiment 3 (A3) and a comparative example 1 (A-VB1) of the phosphor 1. Embodiment 3 corresponds to the powder sample synthesized for embodiment 3 using the conditions described above. The phosphor 1 of embodiment 3 has the molecular formula (Ba, Ca, Y, Li)₄Si₃(O, N)₂ 21 : Ce. Comparison example 1 has the molecular formula BasYSieNu: Ce. Comparison example 1 is therefore a compound of class EA. 3-3 / 2u SE 1+u (Si, Al)6(N, 0) n: A. The excitation spectra are shown in a wavelength range from 250 nanometers to 550 nanometers. The excitation spectra were obtained for an emission wavelength of X emdetermined by 575 nanometers. Exemplary embodiment 3 exhibits excitation maxima at approximately 295 nanometers, 375 nanometers, and 527 nanometers. In comparison to example 1 with the sum formula BasYSieNu: Ce 3+ With a corresponding lithium-free compound, excitation in the deep blue spectral range between approximately 400 and 430 nanometers becomes possible. The phosphor 1 described here is therefore advantageously more flexible with respect to its excitation wavelength.
[0233] Figure 4 shows that the phosphor 1 has the chemical formula (Ba, Ca, Y, Li )4Si3(0, N) 21 : Ce narrowband im2024PF01460 January 28, 2026
[0234] P2024, 1102 WO N 31
[0235] orange region of the electromagnetic spectrum is emitted. Figure 4 shows emission spectra of exemplary embodiments of phosphor 1. The emission spectra are shown in a wavelength range from 400 nanometers to 900 nanometers. The emission spectra were recorded at an excitation wavelength of 408 nanometers. Important spectral data for phosphor 1 with the molecular formula (Ba, Ca, Y, Li)₄Si₆(O, N)₂ 11 The values for Ce are shown in Table 7. The embodiments in Table 7 result from the embodiments of the previously described process for the synthesis of phosphor 1. For example, embodiments 1-1 and 1-3 are two different crystals obtained from the synthesis under the conditions listed above according to embodiment 1.
[0236] Table 7: Important spectral data of embodiments 1 to 4, 6, 8, and 10
[0237] Execution- Spectrum
[0238]
[0239] λ dom / λ peak / FWHM / LER / example nm nm nm Im / W 1-1 El-1 0, 423 0, 419 579 566 122 311
[0240] 1-3 0, 449 0, 428 581 567 123 311
[0241] 2-1 E2-1 0, 499 0, 452 582 569 111 341
[0242] 2-2 0, 508 0, 453 583 570 115 331
[0243] 3-1 E3-1 0, 409 0, 391 581 568 113 308
[0244] 3-2 0, 490 0, 430 584 572 114 321
[0245] 3-3 0, 493 0, 428 585 572 114 317
[0246] 4-1 E4-1 0, 494 0, 449 582 569 112 343
[0247] 4-2 0, 367 0, 381 574 564 119 302
[0248] 6-1 E6-1 0, 530 0, 442 586 574 114 315
[0249] 8-1 E8-1 0, 475 0, 428 583 569 124 304
[0250] 10-1 E10-1 0, 522 0, 433 586 573 130 279
[0251] 10-2 0, 483 0, 428 584 570 131 2862024PF01460 28. January 2026
[0252] P2024, 1102 WO N - 32 -
[0253] The data in Table 7 show that the phosphor 1 of embodiments 1 to 4, 6, 8 and 10 at an excitation wavelength λ ex of 408 nanometers with a dominance wavelength λ dom in the range between and including 574 nanometers and inclusive 586 nanometers and with an emission maximum λ max The emission range is between 564 nanometers and 574 nanometers (inclusive). The full width at half maximum (FWHM) for the emission of the exemplary embodiments is between 112 nanometers and 131 nanometers (inclusive), or between 0.440 eV and 0.513 eV (inclusive).
[0254] The emission of phosphor 1 with the chemical formula
[0255] (Ba, Ca, Y, Li )4Si6(O, N) 11 Ce is therefore comparable to the emission of the corresponding Li-free phosphor Ba3YSi6N 11However, with the phosphor described here, lower half-widths can be achieved.
[0256] Table 8 shows the half-value widths for phosphor 1 according to embodiment 2-1 and two comparative examples. Comparative example 1 is phosphor 1 with the molecular formula Ba3YSi6N 11 : Ce. Comparison example 2 is Y3Al5O 12 :Ce 3+ (YAG: Ce).
[0257] Table 8: Comparison of half-widths
[0258] FWHM / eV Example 2-1 0, 440
[0259] Comparative example 1 0,453
[0260] Comparative example 2 0, 518
[0261] Figure 5 shows emission spectra of embodiment 2-1 (E2-1) and comparison example 1 (E-VB1) in the wavelength range from 400 nanometers to 900 nanometers at an excitation wavelength of 408 nanometers. Figure 6 shows 2024PF01460 28 January 2026
[0262] P2024, 1102 WO N - 33 -
[0263] Emission spectra of embodiment 2-1 (E2-1), comparative example 1 (E-VB1) and comparative example 2 (E-VB2) in the range from 1.5 eV to 2.7 eV. The emission spectra of Figure 6 are therefore shown on the energy scale.
[0264] Figure 7 shows emission spectra of embodiment 3-2 (E3-2), comparison example 1 (E-VB1), and comparison example 3 (E-VB3) in the wavelength range from 400 nanometers to 900 nanometers. Comparison example 3 is Gd-YAG:Ce. Important spectral data for embodiment 3-2, comparison example 1, and comparison example 3 are summarized in Table 9.
[0265] Table 9: Important spectral data of phosphors 1 according to embodiment 3-2, comparative example 1 and comparative example 3.
[0266] Comparative embodiment example 3 3-2 example 1 Gd-YAG: Ce ( Ba, Ca, Y, Li )4Si6(O, N)11 : Ce Ba3YSi6N 11 : Ce λ ex / nm 448 408 448
[0267] 0, 440 0, 490 0, 526 y CIE 0, 535 0, 430 0, 465
[0268] λ dom / nm 571 584 583
[0269] λ peak / nm 556 572 571
[0270] λ cent / nm 583 607 627
[0271] FWHM / nm 125 114 121
[0272] LER / Im / W 432 321 303
[0273] It is expected that different spectral properties will result for phosphor 1 with the chemical formula EA when using other alkaline earth and rare earth ions and when incorporating aluminum. 4-v-x-y-z Li x+y SE v+z D 6-w+y-z E w-y+z N 10+v-w-x O 1-v+w+x : R compared to the example with the sum formula
[0274] (Ba, Ca, Y, Li )4Si6(O, N) 11: Ce can be obtained. For example, for a rare-earth element-free compound with M = Ca, Ba at low Ce content, cyan-emitting phosphors are produced with 2024PF01460 28 January 2026
[0275] P2024, 1102 WO N 34
[0276] a dominance wavelength of approximately 485 nanometers is obtained. By incorporating aluminum or using lutetium or lanthanum, it is possible to achieve emissions with a larger 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.
[0277] For embodiments 1-1, 6-1, 8-1, and 10-2, the compositions were determined using EDX. The results of these measurements are summarized in Table 10. The Si content was normalized to 6. Since the lithium content cannot be determined by EDX, it was calculated as the difference between the sum of the contents of all alkaline earth and rare earth element ions and the stoichiometric factor of 4, i.e., 4 - (content (Ba) + content (Y) + content (Ce) + content (Ca) ) = content (Li).
[0278] Table 10: EDX results
[0279] Ba Y Ca Li Ce Si Exemplary embodiment 1-1 2.30 1.11 0.05 0.47 0.07 6 Exemplary embodiment 6-1 1.96 1.32 0.15 0.57 not 6 detectable Exemplary embodiment 8-1 1.95 1.30 0.11 0.62 0.02 6 Exemplary embodiment 10- 1.65 1.20 0.08 0.99 0.08 6 2
[0280] Figure 8 shows the thermal quenching behavior of phosphors 1 according to embodiment 3 and comparative examples 1 (Ba3YSi6N11 : Ce ) and 3 (Gd-YAG: Ce). The y-axis of the diagram in Figure 8 shows the relative brightness B in % relative to the brightness at 25 °C. The x-axis shows the temperature T in °C. 2024PF01460 January 28, 2026
[0281] P2024, 1102 WO N 35
[0282] The relative brightness was measured in 25 °C increments. The thermal quenching behavior of embodiment 3 was determined at an excitation wavelength of 525 nanometers. The thermal quenching behavior of comparison example 1 was determined at an excitation wavelength of 375 nanometers. The excitation wavelength was selected based on the maximum excitability of the respective phosphor.
[0283] Figure 8 shows that the phosphor 1 according to embodiment 3 ( (Ba, Ca, Y, Li )4Si6(O, N) 11: Ce ) above 125 °C exhibits better thermal behavior than the Li-free phosphor of comparison example 1 (Ba3YSi6N ). 11 : Ce ) and shows significantly better thermal behavior than comparison example 3 (Gd-YAG: Ce).
[0284] 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.
[0285] The radiation-emitting component 10 also includes a conversion element 12. The conversion element 12 contains a phosphor 1 as described herein. The conversion element 12 may also contain another phosphor 13. (2024PF01460, January 28, 2026)
[0286] P2024, 1102 WO N 36
[0287] The further phosphor 13 can also be a mixture of at least two different phosphors.
[0288] Phosphor 1 emits electromagnetic radiation in a second wavelength range. Phosphor 13 emits electromagnetic radiation in a third wavelength range. The three wavelength ranges differ, at least partially. Phosphor 1 converts the electromagnetic radiation of the first and / or third wavelength range into the electromagnetic radiation of the second wavelength range. Phosphor 13 converts the electromagnetic radiation of the first wavelength range into the electromagnetic radiation of the third wavelength range.
[0289] 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.
[0290] Simulated emission spectra S10-1 and S-VB1 of a radiation-emitting device 10 according to a first embodiment (S10-1) and a first comparative example (S-VB1) are shown in Figure 10. The simulated emission spectra S-VB1 and S10-1 are shown in a wavelength range from 400 nanometers to 800 nanometers.
[0291] The conversion element 12 of the radiation-emitting component 10 according to the first embodiment has the 2024PF01460 28 January 2026
[0292] P2024, 1102 WO N - 37 -
[0293] Fluorescent material 1 of embodiment 10-1
[0294] ( (Ba, Ca, Y, Li )4Si6(O, N) 11 : Ce ) and another phosphor 13, which in this case is YAG: Ce. A blue-emitting LED chip with a dominant wavelength λ is used as the radiation-emitting semiconductor chip 11. domemitted from 453 nanometers. The radiation-emitting component 10 according to the comparison example has the same structure, however, phosphor 1 and further phosphor 13 are used.
[0295] (Sr, Ca) AlSiN3: Eu and YAG: Ce are used. With the radiation-emitting components 10 according to the first comparative example and the first embodiment, a color coordinate of x is achieved. CIE = 0, 567 and y CIE = 0.430 reached.
[0296] 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.
[0297] 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.
[0298] Besides achieving a pure Ce 3+ -activated fluorescent solution for turn signal lights can be used with 2024PF01460 28 January 2026
[0299] P2024, 1102 WO N - 38 -
[0300] The phosphor 1, according to the exemplary embodiments, can also be used to implement a single-phosphor f-CRI70 solution, for example, for use in street lighting. A corresponding radiation-emitting component 10, according to a second exemplary embodiment, has the phosphor 1 described here in the conversion element 12, for example, with the chemical formula (Ba, Ca, Y, Li)4Si6(N, O) 11 : Ce according to embodiment 1-1, and no further phosphor 13. A blue LED with a dominance wavelength λ is used as the radiation-emitting semiconductor chip 11. domof 448 nanometers. Figure 12 shows a simulated emission spectrum Sl-1 of the second embodiment of the radiation-emitting component 10 in the wavelength range from 420 nanometers to 920 nanometers.
[0301] Figure 13 shows a simulated emission spectrum S-VB2 of a second comparative example of a radiation-emitting component 10 in the wavelength range from 420 nanometers to 820 nanometers. In the second comparative example, YAG:Ce is used as the phosphor 1. As in the second embodiment, no further phosphor 13 is present in the conversion element 12.
[0302] The radiation-emitting component 10 according to the second embodiment achieves a higher color rendering value CRI = 72 compared to CRI = 63 for the radiation-emitting component 10 according to the comparison example.
[0303] In the second comparative example, one of the longest-wavelength Ce currently in use is used. 3+ -activated phosphors are used. Since the achievable color temperature depends directly on the emission position, the simulated color temperature of 2024PF01460 is January 28, 2026.
[0304] P2024, 1102 WO N - 39 -
[0305] 4370 K for the radiation-emitting component 10 according to the second comparison example is one of the lowest color temperatures achievable with conventional Ce 3+ -activated phosphors. Color temperatures below 4000 K (CCT < 4000 K) are not usually achievable with these phosphors. The radiation-emitting component 10 according to the second embodiment, however, achieves a color temperature of 3527 K.
[0306] Figure 14 shows a powder diffractogram P1 of embodiment 1-1. The powder diffractogram was measured with Cu-Ka radiation and is shown in an angular range from 20° (10°) to 40°.
[0307] Figures 15 and 16 show emission spectra E12-1, E12-2, E12-3, E13-1, E13-2, and E13-3 of embodiments 12 and 13. To obtain the emission spectra, individual crystals were isolated from the prepared samples, resulting in the respective emission spectra. The emission spectra are shown in a wavelength range from 400 nm to 900 nm. Important optical data of the embodiments are summarized in Table 11.
[0308] Table 11: Important optical data of the phosphors 1 according to embodiments 12-1 to 12-3 (based on embodiment 12) and 13-1 to 13-3 (based on embodiment 13)
[0309] Implementation example 12-1 12-2 12-3 13-1 13-2 13-3 CIE x 0.469 0.492 0.573 0.594 0.591 0.626 CIE y 0.400 0.399 0.386 0.371 0.373 0.352 λ dom / nm 586, 8 588, 8 595, 7 599, 3 598, 9 604, 5 λ peak / nm 582, 9 594, 4 639, 4 641, 2 641, 7 644, 5 λ cent / nm 621, 8 632, 3 669, 3 679, 4 679, 1 690, 5 FWHM / nm 151, 6 159, 0 157, 9 154, 8 157, 7 156, 32024PF01460 January 28, 2026 P2024, 1102 WO N - 40 -
[0310] LER / Im / W 246, 3 229, 6 158, 2 132, 4 133, 2 104, 8
[0311] EDX measurements confirm that the phosphor 1 of embodiments 12 and 13 contains aluminum and therefore element E. The phosphor 1 of embodiments 12 and 13 thus has the molecular formula (Ba, Y, Li)⁴(Si, Al)⁶(N, O) 11 : Ce 3+The EDX measurements are summarized in Table 12. Si + Al is normalized to 6. Since the lithium content cannot be determined by EDX, it was calculated from the difference between the sum of the contents of all alkaline earth and rare earth element ions and the stoichiometric factor of 4, i.e., according to 4 - (Content (Ba) + Content (Y) + Content (Ce) + Content (Ca)) = Content (Li).
[0312] Table 12: Results of the EDX measurements of the phosphors 1 according to embodiments 12 and 13
[0313] Execution - 12-1 12-2 12-3 13-1 13-2 13-3 example
[0314] Ba 1, 9 1, 9 2, 0 1, 73 2, 2 1, 9 Ce 0, 1 0, 2 0, 2 0, 2 0, 3 0, 2 Y 1, 4 1, 3 1, 3 1, 25 1, 2 1, 3 sum
[0315] 3, 4 3, 3 3, 5 3, 2 3, 7 3, 4 (Ba+Ce+Y)
[0316] Si 5, 9 5, 8 5, 9 5, 8 5, 9 5, 9 Al 0, 1 0, 2 0, 1 0, 2 0, 1 0, 1 SE or SE or SE or SE or SE or SE or Li-Position
[0317] EA EA EA EA EA EA
[0318] Calculated
[0319] 0, 6 0, 7 0, 5 0, 8 0, 3 0, 6 Li content
[0320] Figures 17 to 19 show powder diffractograms P2, P3 and P4 of phosphors 1 according to one embodiment each. Embodiment 13 leads to powder diffractogram P2, embodiment 12 leads to powder diffractogram P3 and embodiment 3 leads to 2024PF01460 January 28, 2026
[0321] P2024, 1102 WO N 41
[0322] Regarding powder diffractogram P4: The powder diffractograms were each recorded using Cu-Kα radiation and are shown in an angular range 2θ from 10° to 80°. Figures 17 to 19 each show a measured powder diffractogram G1 and a calculated powder diffractogram G2. Line G3 represents the difference between the values of curve G2 and curve G1. In other words, it is a difference diagram G3.
[0323] In Figure 17, the black markings G4 correspond to the theoretical reflex positions of BaY. 0.97 Si4N7 (above) and of the phosphor 1 of embodiment 13
[0324] ((Ba,Y,Li)4(Si,Al)6(N,O) 11 :Ce 3+ , below). In Figure 18, the black markings G4 correspond to the theoretical reflex positions of BaY. 0.97 Si4N7(above) and of the phosphor 1 of embodiment 12((Ba,Y,Li)4(Si,Al)6(N,O) 11 :Ce 3+ , below). In Figure 19, the black markings G4 correspond to the theoretical reflex positions of BaY. 0.97 Si4N7 (above) and from the phosphor 1 of embodiment 3
[0325] ((Ba,Ca,Y,Li)4Si6(N,O) 11 :Ce 3+ , below).
[0326] 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.
[0327] Furthermore, the embodiments described in connection with the figures may alternatively or additionally have further features as described in the general section. 2024PF01460 January 28, 2026
[0328] P2024, 1102 WO N - 42 -
[0329] This patent application claims priority over German patent application 10 2025 104 567.4, the disclosure content of which is hereby incorporated by reference.
[0330] The invention is not limited to the description provided by means of the exemplary embodiments. 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 that feature or combination itself is not explicitly stated in the claims or exemplary embodiments. 2024PF01460 January 28, 2026
[0331] P2024, 1102 WO N
[0332] 43
[0333] Reference symbol list
[0334] 1 Fluorescent
[0335] 10 radiation-emitting components
[0336] 11 radiation-emitting semiconductor chip 111 semiconductor layer stack
[0337] 112 active area
[0338] 12 Conversion element
[0339] 13 more fluorescent materials
Claims
1. 2024PF01460 January 28, 2026 P2024, 1102 WO N - 44 - Patent claims 1. Fluorescent material ( 1 ) with the chemical formula E A 4-v-x-y-z Li x+y SE v+z D 6-w+y-z E w-y+z N 10+v-w-x O 1-v+w+x :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, - 0 < x+y < 4, -4 < -vxyz < 0, 0 < v+z < 4, 0 < w-y+z < 6, -10 < vwx < 1, - 2*(4-vxyz)+1*(x+y)+3*(v+z)+4*(6-w-x+yz)+3*(w-y+z)-3*(10+vwx)-2*(1-v+w+x) = 0, and - a host lattice of the phosphor has a cubic crystal structure with the space group P2i3 and / or the same crystal structure as (Ba,Eu)3YbSi6N 11 exhibits.
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 combination of elements selected from the group formed by Al, B, Ga and In, and / or 2024PF01460 28 January 2026 P2024, 1102 WO N 45 - R is an element or a combination of elements selected from the group formed by Ce, Eu, Mn, Bi, Tb, Dy, Ni, Cr, Cu and Er.
3. Fluorescent material (1) according to one of the preceding claims having the molecular formula EA 4-v-x-z Li x SE v+z Si6-w-z Al w+z N 10+v-w-x O 1-v+w+x :R, where - 0 < x < 4, -4 < -vx- z < 0, 0 < v+ z < 4, 0 < w+ z < 6, - 10 < vwx < 1, and - 2*(4-vxz)+1*(x)+3*(v+z)+4*(6-wxz)+3*(w+z)-3*(10+vwx)-2*(1-v+w+x)=0.
4. Fluorescent material (1) according to any one of the preceding claims having the molecular formula EA 4-v-x Li x SE v Si6N 10+v-x O 1-v+x :R, where - 0 < x < 4, -4 < -vx do, 0 < v < 4, - 10 < vx < 1, and - 2*(4-vx)+1*(x)+3*(v)+4*(6)-3*(10+vx)-2*(1-v+x)=0.
5. Phosphor (1) according to the preceding claim, wherein a lattice parameter a of the cubic crystal structure is less than 10.45 Å.
6. 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.
7. Phosphor (1) according to any of the preceding claims, wherein electromagnetic radiation emitted by the phosphor (1) has an emission spectrum with an emission maximum in the range between and including 425 nanometers and inclusive 650 nanometers. 2024PF01460 January 28, 2026 P2024, 1102 WO N 46 8. Phosphor ( 1 ) according to any of the preceding claims, wherein electromagnetic radiation emitted by the phosphor ( 1 ) has an emission spectrum with an emission maximum in the range between 500 nanometers and 600 nanometers.
9. 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.
10. 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 100 nanometers and inclusive 170 nanometers.
11. Method for the production of a phosphor ( 1 ) with the molecular formula E A4- v-x -y- z Li x +ySE v + z D6- w +y- z E w -y+ z N 10+v-w-x O 1-v +w+x • 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 is an activator element, - 0 < x+y < 4, -4 < -vxyz < 0, 0 < v+z < 4, 0 < w-y+z < 6, -10 < vwx < 1, and2024PF01460 January 28, 2026 P2024, 1102 WO N 47 - 2*(4-vxyz)+1*(x+y)+3*(v+z)+4*(6-w-x+yz)+3*(w-y+z)-3*(10+vwx)-2*(1-v+w+x) = 0, showing the steps: - Providing starting materials, - Mixing the reactants to form a reactant mixture, - Heating the reactant mixture.
12. 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.
13. Method according to one of claims 11 and 12, wherein the reactant mixture is heated to a temperature in the range between and including 1400 °C and 2100 °C.
14. Method according to any one of claims 11 to 13, wherein the reactant mixture is heated in an inert and / or reducing atmosphere.
15. 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.
16. Radiation-emitting component (10) according to claim 15, wherein the phosphor (1) converts the electromagnetic radiation of the first wavelength range into the electromagnetic radiation of the second wavelength range. 2024PF01460 January 28, 2026 P2024, 1102 WO N 48 17. Radiation-emitting component ( 10) according to claim 15, wherein - 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.