Fluoride phosphor, method for producing same, and light-emitting device

Abstract

Provided is a fluoride phosphor which can further improve the reliability of a light-emitting device. A fluoride phosphor which contains fluoride particles and a fluorine compound that is disposed on at least a portion of the surface of the fluoride particles and contains zirconium. The fluoride particles have a composition including an element M including at least one element selected from group 4 elements, group 13 elements, and group 14 elements, at least one element selected from alkali metals and ammonium ions, manganese, and fluorine atoms, the element M including at least one element selected from group 4 elements, group 13 elements, and group 14 elements, and when the total number of moles of the alkali metals and ammonium ions is 2, the number of moles of the fluorine atoms is 2. The number of moles of manganese is more than 0 and less than 0.2, the total number of moles of element M is more than 0.8 and less than 1, and the number of moles of fluorine atoms is more than 5 and less than 7.

Description

Technical Field

[0001] The present disclosure relates to a fluoride phosphor, a method for manufacturing the same, and a light-emitting device. Background Art

[0002] Light-emitting devices that combine light-emitting elements and phosphors are used in a wide range of fields, including lighting, automotive lighting, displays, and LCD backlights. For example, phosphors used in light-emitting devices for LCD backlights require high color purity, that is, a narrow half-value width of their emission peak. Manganese-doped fluoride phosphors are known as red-emitting phosphors with a narrow half-value width of their emission peak.

[0003] For example, Patent Document 1 states that in order to reduce the instability problem caused by the degradation of the manganese-doped red phosphor, the manganese-doped red phosphor is coated with aluminum oxide or the like; and Patent Document 1 further states a light-emitting device having a fluorescent component including the coated manganese-doped red phosphor.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2019-525974 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] A light-emitting device including a wavelength conversion component containing a manganese-containing fluoride phosphor may experience reduced reliability depending on the environment in which the light-emitting device is used. One embodiment of the present disclosure aims to provide a fluoride phosphor and a method for producing the same, which can further improve the reliability of the light-emitting device.

[0009] Solutions to the Problem

[0010] A first embodiment relates to a fluoride phosphor comprising fluoride particles and a fluorine compound, the fluorine compound being disposed on at least a portion of the surface of the fluoride particles and containing zirconium. The fluoride particles have a composition comprising an element M, at least one selected from an alkali metal and an ammonium ion, manganese, and fluorine atoms, wherein the element M comprises at least one selected from a Group 4 element, a Group 13 element, and a Group 14 element, and wherein, when the total number of moles of the alkali metal and the ammonium ion is 2, the number of moles of manganese is greater than 0 and less than 0.2, the total number of moles of the element M is greater than 0.8 and less than 1, and the number of moles of the fluorine atoms is greater than 5 and less than 7.

[0011] A second embodiment relates to a method for producing a fluoride phosphor, the method comprising: preparing fluoride particles, and contacting the prepared fluoride particles with a solution containing complex ions containing zirconium and fluoride, and disposing a fluorine compound containing zirconium on at least a portion of the surface of the fluoride particles, wherein the fluoride particles have the following composition: an element M, at least one selected from alkali metals and ammonium ions, manganese, and fluorine atoms, the element M contains at least one selected from Group 4 elements, Group 13 elements, and Group 14 elements, and when the total molar number of the alkali metals and ammonium ions is 2, the molar number of manganese is greater than 0 and less than 0.2, the total molar number of the element M is greater than 0.8 and less than 1, and the molar number of the fluorine atoms is greater than 5 and less than 7.

[0012] A third aspect relates to a light-emitting device including: the fluoride phosphor according to the first aspect; and a light source having a peak emission wavelength in the range of 380 nm to 485 nm.

[0013] Effects of the Invention

[0014] According to one embodiment of the present disclosure, a fluoride phosphor capable of further improving the reliability of a light-emitting device and a method for manufacturing the same can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a schematic cross-sectional view showing an example of a light-emitting device using a fluoride phosphor.

[0016] Figure 2A This is an example of a scanning electron microscope image of the fluoride phosphor of Example 1.

[0017] Figure 2B This is an example of a scanning electron microscope image of the fluoride phosphor of Example 3.

[0018] Figure 3 This is an example of the X-ray diffraction spectrum of a fluoride phosphor.

[0019] Explanation of symbols

[0020] 10: Light-emitting element

[0021] 20: First wire

[0022] 30: Second wire

[0023] 40: Molded body

[0024] 50: Wavelength conversion component

[0025] 60: Wires

[0026] 70: Phosphor

[0027] 100: Light-emitting device DETAILED DESCRIPTION

[0028] In this specification, the term "process" is not only an independent process, but also includes it in this term as long as the intended purpose of the process can be achieved when it cannot be clearly distinguished from other processes. In addition, when there are multiple substances corresponding to each component in the composition, as long as there is no characteristic limitation, the content of each component in the composition represents the total amount of the multiple substances present in the composition. Furthermore, the upper and lower limits of the numerical ranges described in this specification can be arbitrarily selected and combined with the numerical values exemplified as numerical ranges. In the formula representing the composition of a phosphor or a luminescent material in this specification, the multiple elements described separated by commas (,) mean that at least one element of these multiple elements is included in the composition. In addition, in the formula representing the composition of a phosphor, the mother crystal is represented before the colon (:), and the activating element is represented after the colon (:). In this specification, the relationship between the color name and the chromaticity coordinates, the relationship between the wavelength range of light and the color name of monochromatic light, etc. are all based on JIS Z8110. The half-value width of a phosphor refers to the wavelength width of the emission spectrum where the emission intensity reaches 50% of the maximum emission intensity (full width at half maximum; FWHM) in the emission spectrum of the phosphor. The following describes embodiments of the present invention in detail. However, the fluoride phosphors, methods for manufacturing the same, and light-emitting devices illustrated in the embodiments below are intended to embody the technical concept of the present invention, and the present invention is not limited to the fluoride phosphors, methods for manufacturing the same, and light-emitting devices illustrated below.

[0029] Fluoride phosphor

[0030] A fluoride phosphor may include fluoride particles and a fluorine compound, the fluorine compound comprising zirconium, disposed on at least a portion of the surface of the fluoride particles. The fluoride particles may be composed of an element M, at least one selected from an alkali metal and an ammonium ion, manganese, and fluorine atoms, wherein the element M comprises at least one selected from Group 4 elements, Group 13 elements, and Group 14 elements. In the fluoride particles, when the total molar number of the alkali metal and ammonium ions is 2, the molar number of manganese may be greater than 0 and less than 0.2, the total molar number of the element M may be greater than 0.8 and less than 1, and the molar number of the fluorine atoms may be greater than 5 and less than 7.

[0031] A light-emitting device containing a fluoride phosphor composed of a fluoride compound containing zirconium disposed on the surface of fluoride particles as a fluorescent substance can reduce or prevent degradation of luminous flux, color tone changes, and the like, even under operating environments such as high temperature or high temperature and high humidity, thereby demonstrating excellent reliability. This can be considered, for example, in the following manner. It is believed that this is because the surface of the fluoride particles does not contain manganese ions that may cause luminous flux reduction and color tone changes, and the presence of a zirconium-containing fluorine compound having a different composition from that of the fluoride particles can suppress degradation of the fluoride phosphor under high temperature or high temperature and high humidity environments.

[0032] The fluoride particles constituting the fluoride phosphor may contain at least a fluorescent substance activated by manganese (Mn), or may contain only a fluorescent substance activated by Mn. With respect to the composition of the fluoride particles, when the total molar number of the alkali metal and the ammonium ion is 2, the molar number of Mn may be greater than 0 and less than 0.2, preferably greater than 0.01 and less than 0.12. In addition, with respect to the composition of the fluoride particles, when the total molar number of the alkali metal and the ammonium ion is 2, the molar number of the element M may be greater than 0.8 and less than 1, preferably greater than 0.88 and less than 0.99. With respect to the composition of the fluoride particles, when the molar number of the alkali metal is 2, the molar number of F may be greater than 5 and less than 7, preferably greater than 5.9 and less than 6.1. The composition of the fluoride particles can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry.

[0033] The alkali metal in the composition of the fluoride particles may include at least one selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs). In addition, the alkali metal includes at least potassium (K) and may include at least one selected from lithium (Li), sodium (Na), rubidium (Rb) and cesium (Cs). In the composition, the ratio of the number of moles of K to the total number of moles of alkali metals and ammonium ions may be, for example, greater than 0.90, preferably greater than 0.95, or may be greater than 0.97. The upper limit of the ratio of the number of moles of K is, for example, 1 or less than 0.995. The composition of the fluoride particles may include ammonium ions (NH4 + ) instead of the alkali metal. When ammonium ions are included, the ratio of the number of moles of ammonium ions to the total number of moles of the alkali metal and ammonium ions in the composition is, for example, 0.10 or less, preferably 0.05 or less, or 0.03 or less. The lower limit of the ratio of the number of moles of ammonium ions may be, for example, greater than 0, and preferably 0.005 or more.

[0034] Element M in the composition of the fluoride particles contains at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements. As Group 4 elements, examples include titanium (Ti), zirconium (Zr), hafnium (Hf), etc., and at least one element selected from these elements can be included. As Group 13 elements, examples include boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), etc., and at least one element selected from these elements can be included. As Group 14 elements, examples include carbon (C), silicon (Si), germanium (Ge), tin (Sn), etc., and at least one element selected from these elements can be included. Element M can contain at least one element from Group 14 elements, preferably at least one of Si and Ge, more preferably at least Si. In addition, element M can contain at least one element from Group 13 elements and at least one element from Group 14 elements, preferably at least one of Al, Si, and Ge, more preferably at least Al and Si.

[0035] Regarding the composition of the fluoride particles, the total molar number of element M and Mn can be 0.9 or more and 1.1 or less, preferably 0.95 or more and 1.05 or less, or can be 0.97 or more and 1.03 or less relative to the total molar number 2 of alkali metals and ammonium ions.

[0036] The composition of the fluoride particles can be the composition represented by the following formula (1).

[0037] A c [M 1-b Mn b F d (1)

[0038] In formula (1), A can contain at least one selected from Li, Na, K, Rb, Cs, and NH4 + . M contains at least Si and can further contain at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements. Mn can be a tetravalent Mn ion. b can satisfy 0 < b < 0.2, c is the absolute value of the charge of [M 1-b Mn b F d ions, and d can satisfy 5 < d < 7.

[0039] A in formula (1) contains at least K and can further contain at least one of Li, Na, Rb, Cs, and NH4 + . In the composition, the molar ratio of K to the total molar number of A can be, for example, 0.90 or more, preferably 0.95 or more, or can be 0.97 or more. The upper limit of the molar ratio of K can be, for example, 1 or 0.995 or less.

[0040] In formula (1), b is preferably 0.005 or more and 0.15 or less, 0.01 or more and 0.12 or less, or 0.015 or more and 0.1 or less. C can be, for example, 1.8 or more and 2.2 or less, preferably 1.9 or more and 2.1 or less, or can be 1.95 or more and 2.05 or less. D is preferably 5.5 or more and 6.5 or less, 5.9 or more and 6.1 or less, 5.95 or more and 6.05 or less, or 5.97 or more and 6.03 or less.

[0041] In addition, the fluoride particles may have a theoretical composition represented by the following formula (1a).

[0042] A2MF6:Mn (1a)

[0043] In formula (1a), A may include at least one selected from Li, Na, K, Rb, Cs, and NH4 + M includes at least Si and may further include at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements. Mn may be a tetravalent Mn ion.

[0044] As a mode of the composition of the fluoride particles, the first composition may include at least one selected from Group 4 elements and Group 14 elements as element M, preferably includes at least one selected from Group 14 elements, more preferably includes at least one selected from Si and Ge, and further preferably includes at least Si. In addition, with respect to the total molar number 2 of alkali metals and ammonium ions, the total molar number of Si, Ge, and Mn in the first composition of the fluoride particles may be 0.9 or more and 1.1 or less, preferably 0.95 or more and 1.05 or less, or may be 0.97 or more and 1.03 or less.

[0045] The first composition of the fluoride particles may be a composition represented by the following formula (2).

[0046] A 1 q [M 1 1-p Mn p F r (2)

[0047] In formula (2), A 1 may include at least one selected from Li, Na, K, Rb, Cs, and NH4 + M 1 includes at least one of Si and Ge and may further include at least one element selected from Group 4 elements and Group 14 elements. Mn may be a tetravalent Mn ion. p may satisfy 0 < p < 0.2, and q is [M 1 1-p Mn p Fr ]The absolute value of the charge of the ion, r can satisfy 5 <r<7。

[0048] A in formula (2) 1 Contains at least K and may further contain Li, Na, Rb, Cs and NH4 + At least one of the following. 1 When ammonium ions are included, the number of moles of ammonium ions in the composition relative to A 1 The total molar ratio of the ammonium ions may be, for example, 0.10 or less, preferably 0.05 or less, or 0.03 or less. The lower limit of the molar ratio of the ammonium ions may be, for example, greater than 0, preferably 0.005 or more.

[0049] In formula (2), p is preferably 0.005 to 0.15, 0.01 to 0.12, or 0.015 to 0.1. q may be, for example, 1.8 to 2.2, preferably 1.9 to 2.1, or 1.95 to 2.05. r is preferably 5.5 to 6.5, 5.9 to 6.1, 5.92 to 6.05, or 5.95 to 6.025.

[0050] Furthermore, the fluoride particles having the first composition may have a first theoretical composition represented by the following formula (2a).

[0051] A 1 2M 1 F6:Mn (2a)

[0052] In formula (2a), A 1 May contain Li, Na, K, Rb, Cs and NH4 + There is at least one group in M. 1 It contains at least one of Si and Ge, and may further contain at least one element selected from Group 4 elements and Group 14 elements. Mn may be a tetravalent Mn ion.

[0053] As a mode of the composition of fluoride particles, regarding the second composition, as the element M, it may contain at least one selected from Group 4 elements and Group 14 elements, and at least one of Group 13 elements. It preferably contains at least one selected from Group 14 elements and at least one of Group 13 elements, and more preferably contains at least Si and Al. In addition, with respect to the total molar number 2 of alkali metals and ammonium ions, the total molar number of Si, Al, and Mn in the second composition of fluoride particles may be 0.9 or more and 1.1 or less, preferably 0.95 or more and 1.05 or less, or may be 0.97 or more and 1.03 or less. Further, regarding the second composition of fluoride particles, with respect to the total molar number 2 of alkali metals and ammonium ions, the molar number of Al may exceed 0 and be 0.1 or less, preferably exceed 0 and be 0.03 or less, more preferably be 0.002 or more and 0.02 or less, or may be 0.003 or more and 0.015 or less.

[0054] The second composition of fluoride particles may be the composition represented by the following formula (3).

[0055] A 2 t [M 2 1-s Mn s F u (3)

[0056] In formula (3), A 2 contains at least K, and may further contain at least one selected from Li, Na, Rb, Cs, and NH4 + . M 2 contains at least Si and Al, and may further contain at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements. Mn is a tetravalent Mn ion. s may satisfy 0 < s < 0.2, t is the absolute value of the charge of [M 2 1-s Mn s F u ions, and u may satisfy 5 < u < 7.

[0057] When A in formula (3) <​​​​​In formula (3), s is preferably 0.005 or more and 0.15 or less, 0.01 or more and 0.12 or less, or may be 0.015 or more and 0.1 or less. t may be, for example, 1.8 or more and 2.2 or less, preferably 1.9 or more and 2.1 or less, or may be 1.95 or more and 2.05 or less. u is preferably 5.5 or more and 6.5 or less, 5.9 or more and 6.1 or less, 5.92 or more and 6.05 or less, or may be 5.95 or more and 6.025 or less.

[0059] In addition, the fluoride particles of the second composition may have a second theoretical composition represented by the following formula (3a).

[0060] A 2 2Si 1-v Al v F 6-v :Mn (3a)

[0061] In formula (3a), A 2 contains at least K and may further contain at least one selected from Li, Na, Rb, Cs, and NH4 + . v may satisfy 0 < v < 1, preferably satisfy 0.005 < v < 0.03. Mn may be tetravalent Mn ions.

[0062] The fluoride phosphor may contain a fluorine compound, which is disposed on at least a part of the surface of the fluoride particles and contains zirconium. The fluorine compound may coat the surface of the fluoride particles in a film form or may be disposed on the surface of the fluoride particles as a fluorine compound layer. The coating rate of the fluorine compound on the fluoride particles in the fluoride phosphor may be, for example, 50% or more, preferably 80% or more, or may be 90% or more. The coating rate of the fluorine compound on the fluoride particles can be calculated as the ratio of the area covered by the fluorine compound to the surface area of the fluoride particles.

[0063] The fluorine compound may be a compound containing zirconium and fluorine atoms in its composition, and may further contain at least one selected from alkali metals and ammonium ions in the composition. When the composition of the fluorine compound contains an alkali metal or an ammonium ion, it may contain at least potassium as the alkali metal. When the composition of the fluorine compound contains potassium, the molar ratio of potassium to alkali metals and ammonium ions may be, for example, 0.8 or more, preferably 0.9 or more, or may be 0.95 or more. In addition to zirconium, the composition of the fluorine compound may further contain Group 4 atoms such as titanium other than zirconium. When the composition of the fluorine compound contains Group 4 atoms other than zirconium, the molar ratio of Group 4 atoms other than zirconium to zirconium may be, for example, 0.1 or less, preferably 0.01 or less, or may be 0.001 or less.

[0064] The fluorine compound may include at least a compound having a composition represented by AZrF5. Here, A may include a compound selected from Li, Na, K, Rb, Cs, and NH4. + A contains at least K and may further contain Li, Na, Rb, Cs and NH4 + At least one of the above may be substantially K. "Substantially" here means that unavoidable impurities may be tolerated, and the impurity content may be, for example, 5 mol% or less, 1 mol% or less, or 0.1 mol% or less. The ratio of the number of moles of K to the total number of moles of A in the composition may be, for example, 0.90 or greater, preferably 0.95 or greater, or 0.97 or greater. The upper limit of the ratio of the number of moles of K may be, for example, 1 or 0.995 or less.

[0065] The content of the fluorine compound in the fluoride phosphor, calculated as zirconium, can be, for example, 0.1% by mass or more and 10% by mass or less, preferably 0.3% by mass or more, 0.5% by mass or more, or 0.8% by mass or more. Furthermore, the content of the fluorine compound is 5% by mass or less, or 2% by mass or less. When the content of the fluorine compound is within the above range, the reliability of the light-emitting device tends to be further improved. Furthermore, there is a tendency to suppress a decrease in the brightness of the powder.

[0066] From the viewpoint of improving brightness, the volume-based median particle size of the fluoride phosphor can be, for example, 5 μm or more and 90 μm or less, preferably 10 μm or more and 70 μm or less, or 15 μm or more and 50 μm or less. From the viewpoint of improving brightness, the particle size distribution of the fluoride phosphor can be, for example, a unimodal particle size distribution, preferably a unimodal particle size distribution with a narrow distribution width. Specifically, in the volume-based particle size distribution, if the particle size corresponding to 10% of the cumulative volume from the small particle size side is set as D 10 The particle size corresponding to 90% of the cumulative volume is set as D 90 , then D 90 Relative to D 10 The ratio (D 90 / D 10 ) can be, for example, 3.0 or less. It should be noted that, in the volume-based particle size distribution, the volume-based median particle size is the particle size corresponding to 50% of the cumulative volume from the small particle size side, and the volume-based particle size distribution is measured by a laser diffraction particle size distribution measuring device.

[0067] The fluoride phosphor is, for example, a phosphor activated by tetravalent manganese. This fluoride phosphor can absorb light in the short-wavelength region of visible light and emit red light. The light irradiating the fluoride phosphor can be primarily cyan light, with a peak wavelength within the wavelength range of, for example, 380 nm to 485 nm. The luminescence spectrum of the fluoride phosphor can have a peak wavelength within the wavelength range of, for example, 610 nm to 650 nm. The half-value width of the luminescence spectrum of the fluoride phosphor can be, for example, 10 nm or less.

[0068] Method for producing fluoride phosphor

[0069] A method for producing a fluoride phosphor includes: a first step of preparing fluoride particles having a specific composition; and a second step of contacting the prepared fluoride particles with a treatment solution containing complex ions containing zirconium and fluoride ions, thereby disposing a fluorine compound containing zirconium on at least a portion of the surface of the fluoride particles. The treatment solution contains complex ions containing zirconium and fluoride ions. The fluoride particles having the specific composition have the following composition: an element M, at least one selected from an alkali metal and an ammonium ion, manganese, and fluorine atoms, wherein the element M comprises at least one selected from a Group 4 element, a Group 13 element, and a Group 14 element, and when the total number of moles of the alkali metal and the ammonium ion is 2, the number of moles of manganese is greater than 0 and less than 0.2, the total number of moles of the element M is greater than 0.8 and less than 1, and the number of moles of the fluorine atoms is greater than 5 and less than 7.

[0070] By contacting fluoride particles having a predetermined composition with a treatment solution containing complex ions comprising zirconium and fluoride ions, a fluoride phosphor having a fluorine compound containing zirconium disposed on at least a portion of the surface of the fluoride particles can be efficiently produced. A light-emitting device comprising a wavelength conversion member comprising the resulting fluoride phosphor and a resin has improved reliability, for example, in high-temperature environments.

[0071] In the first step, fluoride particles having a predetermined composition are prepared. In the preparation step, fluoride particles can be prepared by transferring fluoride particles, or by manufacturing desired fluoride particles. The details of the prepared fluoride particles are as described above.

[0072] Fluoride particles can be produced, for example, by the following method. When the fluoride particles have the first composition, for example, they can be produced by a production method comprising mixing a solution a containing at least a first complex ion containing tetravalent manganese, a second complex ion containing at least one selected from Group 4 and Group 14 elements and a fluoride ion, and hydrogen fluoride, and a solution b containing at least an alkali metal including potassium and hydrogen fluoride.

[0073] Alternatively, for example, a fluoride phosphor can be produced by a manufacturing method comprising mixing a first solution containing at least a first complex ion comprising tetravalent manganese and hydrogen fluoride, a second solution containing at least an alkali metal containing at least potassium and hydrogen fluoride, and a third solution containing at least a second complex ion containing at least one selected from Group 4 elements and Group 14 elements and a fluoride ion. The manufacturing method of the fluoride phosphor having the first composition can be described, for example, in Japanese Patent Application Laid-Open No. 2014-141684, Japanese Patent Application Laid-Open No. 2015-143318, and Japanese Patent Application Laid-Open No. 2015-188075.

[0074] Furthermore, when the fluoride particles have the second composition, the fluoride particles having the second composition can be produced by, for example, a production method comprising the following steps: preparing fluoride particles having the first composition; preparing fluoride particles containing Al, an alkali metal, and F; and subjecting a mixture containing the fluoride particles and the fluoride particles having the first composition to a first heat treatment step at a first heat treatment temperature of 600°C to 780°C in an inert gas atmosphere. Here, in the composition of the fluoride particles containing Al, an alkali metal, and F, the ratio of the total number of moles of the alkali metal to 1 mole of Al may be 1 to 3, and the ratio of the number of moles of F may be 4 to 6. Alternatively, the ratio of the total number of moles of the alkali metal to 1 mole of Al may be 2 to 3, and the ratio of the number of moles of F may be 5 to 6. The method for producing the fluoride phosphor having the second composition can be referred to, for example, Japanese Patent Application Laid-Open No. 2010-254933 and Japanese Patent Application Laid-Open No. 2022-099232.

[0075] In the second step, the prepared fluoride particles are contacted with a treatment solution containing complex ions comprising zirconium and fluoride ions, and a fluoride compound containing zirconium is arranged on at least a portion of the surface of the fluoride particles. When the treatment solution containing complex ions comprising zirconium and fluoride ions contacts the fluoride particles, for example, a portion of the fluoride particles undergoes a dissolution reaction to generate at least one ion selected from alkali metal ions and ammonium ions, and a complex ion comprising element M and fluoride ions, which constitute the fluoride particles. It is believed that the generated at least one ion selected from alkali metal ions and ammonium ions reacts with the complex ions comprising zirconium and fluoride ions, thereby configuring the fluoride compound containing zirconium on the surface of the fluoride particles.

[0076] The treatment liquid comprises complex ions containing zirconium and fluoride ions, and a liquid medium. The liquid medium may contain at least water, and may be substantially water in addition to an organic solvent and the like described below.

[0077] Examples of complex ions containing zirconium and fluoride ions include: [ZrF6]2- 、[ZrF7] 3- 、[ZrF8] 4- 、[ZrF5] - 、[Zr2F 10 ] 2- 、[Zr2F 12 ] 4- 、[Zr2F 13 ] 5- 、[Zr2F 14 ] 6- 、[Zr6F 31 ] 7- The treatment liquid preferably contains at least [ZrF6] 2- The complex ion of the composition represented. Examples of the countercation of the complex ion comprising zirconium and fluoride ions include hydrogen ions, ammonium ions, and the like, and at least hydrogen ions may be included. Regarding the content of the complex ion comprising zirconium and fluoride ions in the treatment liquid, the zirconium content may be, for example, 0.01 mol / L or more, preferably 0.02 mol / L or more. In addition, the content of the complex ion may be, for example, 1 mol / L or less, preferably 0.5 mol / L or less.

[0078] In addition to the complex ions containing zirconium and fluoride ions, the treatment solution may further contain an oxygen-containing acid of boron. Examples of the oxygen-containing acid of boron include orthoboric acid (H3BO3), metaboric acid (HBO2), n ), perboric acid (HBO3), diboric acid (H4B2O4), boric acid (H3BO2), hydroxyborane (H3BO) (Borinic acid), etc. The oxyacid of boron contained in the treatment liquid may at least include orthoboric acid. By making the treatment liquid include oxyacid of boron, for example, hydrogen fluoride generated along with the formation of fluorine compounds containing zirconium can be removed in the form of fluoroboric acid (for example, HBF4), which can promote the formation of fluorine compounds containing zirconium. Specifically, when the treatment liquid contains orthoboric acid, it can be considered that a reaction similar to the following occurs. It should be noted that in the following formula, A contains at least one selected from alkali metals and ammonium ions.

[0079] 2H2ZrF6+A2SiF6→2AZrF5+H2SiF6+2HF

[0080] H3BO3+4HF→HBF4+3H2O

[0081] When the treatment liquid contains an oxyacid of boron, the content of the oxyacid of boron in the treatment liquid, as a boron content, may be, for example, 0.01 mol / L or more, preferably 0.02 mol / L, or 0.04 mol / L or more. Alternatively, the content of the oxyacid of boron may be, for example, 0.4 mol / L or less, preferably 0.2 mol / L or less.

[0082] The treatment liquid may further contain a reducing agent. By including a reducing agent, for example, tetravalent manganese ions dissolved from the fluoride particles can be reduced, thereby suppressing coloration caused by the tetravalent manganese ions. Examples of reducing agents include hydrogen peroxide and oxalic acid. The reducing agent preferably contains at least hydrogen peroxide. Hydrogen peroxide has little effect on fluoride particles and can effectively reduce tetravalent manganese ions. Furthermore, hydrogen peroxide ultimately decomposes into harmless water and oxygen, making it easy to use in the manufacturing process and reducing environmental impact.

[0083] When the treatment liquid contains a reducing agent, the content of the reducing agent in the treatment liquid can be, for example, 0.1% by mass or more and 20% by mass or less, preferably 0.5% by mass or more, or 5% by mass or less. Furthermore, the content of the reducing agent can be, for example, 0.02 mol / L or more and 4 mol / L or less, preferably 0.05 mol / L or more, or 0.1 mol / L or more, or preferably 2 mol / L or less, or 1 mol / L or less.

[0084] In the second step, the treatment liquid in contact with the fluoride particles may further contain an organic solvent. By making the treatment liquid contain an organic solvent, the solubility of the fluorine compound containing zirconium in the treatment liquid can be reduced, thereby more efficiently configuring the fluorine compound on the surface of the fluoride particles. In addition, the formation of the fluorine compound containing zirconium can be promoted. The organic solvent can be an organic solvent miscible with water, and examples include: alcohol solvents with a carbon number of 3 or less, such as methanol, ethanol, propanol, isopropanol; ketone solvents such as acetone and methyl ethyl ketone; nitrile solvents such as acetonitrile, etc. The organic solvent contained in the solution preferably contains at least an alcohol with a carbon number of 3 or less.

[0085] When the treatment liquid in the second step contains an organic solvent, the content of the organic solvent in the treatment liquid containing the organic solvent can be, for example, 5% by volume or more, preferably 10% by volume or more, or 15% by volume or more. Alternatively, the content of the organic solvent can be, for example, 80% by volume or less, preferably 70% by volume or less, 60% by volume or less, or 55% by volume or less. Here, the volume of the treatment liquid containing the organic solvent is defined as the sum of the volume of the treatment liquid without the organic solvent and the volume of the organic solvent added to the treatment liquid, and the volume change caused by the mixing of water and the organic solvent is disregarded.

[0086] The amount of the treatment liquid used in contact with the fluoride particles in the second step can be, for example, 100% by mass or more and 3000% by mass or less, preferably 300% by mass or more, preferably 500% by mass or more, or preferably 2500% by mass or less, or 2000% by mass or less, as a mass ratio relative to the fluoride particles. When the mass ratio of the treatment liquid is within the above range, the zirconium-containing fluoride compound tends to be more uniformly arranged on the surface of the fluoride particles.

[0087] The contact between the fluoride particles and the treatment liquid can be carried out, for example, by mixing the fluoride particles and the treatment liquid. Alternatively, the contact can be carried out while stirring the treatment liquid containing the fluoride particles. The contact temperature between the fluoride particles and the treatment liquid can be, for example, 10°C to 50°C, preferably 20°C to 35°C or less. In addition, the contact time can be, for example, 1 hour to 40 hours, preferably 2 hours to 30 hours or less. The contact atmosphere can be either an air atmosphere or an inert gas atmosphere.

[0088] The method for producing a fluoride phosphor may further include the following steps: after the second step, a step of recovering the fluoride phosphor obtained in the second step by solid-liquid separation; a step of drying the fluoride phosphor after the solid-liquid separation; etc.

[0089] Light-emitting device

[0090] The light emitting device includes a wavelength conversion member containing the fluoride phosphor and a resin, and a light source having a peak emission wavelength in the wavelength range of 380 nm to 485 nm. The light emitting device may further include other components as needed.

[0091] An example of a light emitting device will be described with reference to the drawings. Figure 1This is a schematic cross-sectional view showing an example of a light-emitting device according to this embodiment. This light-emitting device is an example of a surface-mounted light-emitting device. Light-emitting device 100 includes a light-emitting element 10, which is a light source that emits light having a peak wavelength on the short-wavelength side of visible light (e.g., within the range of 380 nm to 485 nm), and a molded body 40 on which light-emitting element 10 is mounted. Molded body 40 includes a first lead 20 and a second lead 30 and is integrally molded from a thermoplastic resin or a thermosetting resin. Molded body 40 is formed with a recess having a bottom surface and side surfaces corresponding to the substrate, and light-emitting element 10 is mounted on the bottom surface of the recess. Light-emitting element 10 includes a pair of positive and negative electrodes electrically connected to first lead 20 and second lead 30 via an electrical wire 60. Light-emitting element 10 is encased in a wavelength conversion member 50. Wavelength conversion member 50 contains a phosphor 70 comprising a fluoride phosphor that converts the wavelength of light emitted by light-emitting element 10. The phosphor 70 may include the above-mentioned fluoride phosphor and a light-emitting material that emits light having a peak emission wavelength in a wavelength range different from that of the fluoride phosphor due to the excitation light from the light-emitting element 10 .

[0092] The wavelength conversion component may contain a resin and a phosphor. Examples of the resin constituting the wavelength conversion component include silicone resin, epoxy resin, modified silicone resin, modified epoxy resin, acrylic resin, and the like. For example, the refractive index of the silicone resin may be in the range of 1.35 to 1.55, more preferably 1.38 to 1.43. When the refractive index of the silicone resin is within these ranges, it has excellent light transmittance and can be suitably used as a resin constituting the wavelength conversion component. Here, the refractive index of the silicone resin is the refractive index after curing, as measured in accordance with JIS K7142:2008. In addition to the resin and the phosphor, the wavelength conversion component may further include a light diffusing material. By including a light diffusing material, the directivity of the light-emitting element can be mitigated, thereby increasing the viewing angle. Examples of the light diffusing material include silicon oxide, titanium oxide, zinc oxide, zirconium oxide, aluminum oxide, and the like.

[0093] The light-emitting element emits light having a peak emission wavelength in the wavelength range of 380 nm to 485 nm in the short wavelength region of visible light. The light-emitting element can be a light source that excites a fluoride phosphor. The light-emitting element preferably has a peak emission wavelength in the range of 380 nm to 480 nm, more preferably in the range of 410 nm to 480 nm, and further preferably in the range of 430 nm to 480 nm. As the light-emitting element of the light source, a semiconductor light-emitting element is preferably used. By using a semiconductor light-emitting element as a light source, a light-emitting device with high efficiency, strong linearity of output relative to input, and strong stability against mechanical impact can be obtained. As the semiconductor light-emitting element, for example, a semiconductor light-emitting element using a nitride-based semiconductor can be used. The half-value width of the emission peak in the emission spectrum of the light-emitting element can be, for example, 30 nm or less.

[0094] The light-emitting device is constructed by including a fluoride phosphor. Details of the fluoride phosphor included in the light-emitting device are described above. For example, the fluoride phosphor is contained in a wavelength conversion member that covers the light source. In a light-emitting device where the light source is covered by a wavelength conversion member containing the fluoride phosphor, a portion of the light emitted by the light source is absorbed by the fluoride phosphor and emitted as red light. By using a light source that emits light with a peak emission wavelength within a range of 380 nm to 485 nm, the emitted light can be more efficiently utilized, and light loss from the light-emitting device can be reduced, thereby providing a highly efficient light-emitting device.

[0095] In addition to the fluoride phosphor, the light-emitting device preferably further includes a luminescent material other than the fluoride phosphor. The luminescent material other than the fluoride phosphor can absorb light emitted from the light source and convert the wavelength of the light to light with a wavelength different from that of the fluoride phosphor. Similar to the fluoride phosphor, the luminescent material can be included in a wavelength conversion member, for example.

[0096] The luminescent material may have an emission peak wavelength within the wavelength range of more than 495 nm and less than 573 nm, and is preferably at least one selected from β - sialon phosphors, halosilicate phosphors, silicate phosphors, rare - earth aluminate phosphors, perovskite - type luminescent materials, and nitride phosphors. The β - sialon phosphor may have a composition represented by, for example, the following formula (IIa). The halosilicate phosphor may have a composition represented by, for example, the following formula (IIb). The silicate phosphor may have a composition represented by, for example, the following formula (IIc). The rare - earth aluminate phosphor may have a composition represented by the following formula (IId). The perovskite - type luminescent material may have a composition represented by, for example, the following formula (IIe). The nitride phosphor may have a composition represented by, for example, the following formula (IIf), (IIg), or (IIh). When the light - emitting device is used as a light source for, for example, backlight, by making the wavelength - converting member contain a β - sialon phosphor or a perovskite - type luminescent material as a luminescent material other than the fluoride phosphor, the range of color reproducibility of the light - emitting device can be made wider. When the light - emitting device is used as a light source for, for example, illumination, by making the wavelength - converting member contain a halosilicate phosphor, a silicate phosphor, a rare - earth aluminate phosphor, or a nitride phosphor as a luminescent material other than the fluoride phosphor, the color rendering property of the light - emitting device can be higher, or the luminous efficiency can be higher.

[0097] Si 6-x Al x O x N 8-x :Eu (IIa)

[0098] (In formula (IIa), x is a number satisfying 0 < x ≤ 4.2.)

[0099] (Ca,Sr,Ba)8MgSi4O 16 (F,Cl,Br)2:Eu (IIb)

[0100] (Ba,Sr,Ca,Mg)2SiO4:Eu (IIc)

[0101] (Y,Lu,Gd,Tb)3(Al,Ga)5O 12 :Ce (IId)

[0102] CsPb(F,Cl,Br,I)3 (IIe)

[0103] (La,Y,Gd)3Si6N 11 :Ce (IIf)

[0104] (Sr,Ca)LiAl3N4:Eu (IIg)

[0105] (Ca,Sr)AlSiN3:Eu (IIh)

[0106] In addition to the fluoride phosphor, the wavelength conversion component may further include at least one quantum dot. The quantum dot can absorb light from the light source and convert its wavelength into light of a wavelength different from that of the fluoride phosphor, or convert its wavelength into light of the same wavelength. As quantum dots, there can be mentioned: quantum dots with a perovskite structure having a composition such as (Cs, FA, MA) (Pb, Sn) (Cl, Br, I) 3 (here, FA represents formamidine and MA represents methylammonium); quantum dots with a chalcopyrite structure having a composition such as (Ag, Cu, Au) (In, Ga) (S, Se, Te) 2; semiconductor quantum dots such as (Cd, Zn) (Se, S); InP-based semiconductor quantum dots, etc., and may include at least one selected from them. Here, in the formula representing the composition of the quantum dot, a plurality of elements or cations separated by commas (,) means that at least one of these multiple elements or cations is included in its composition.

[0107] The invention disclosed herein may include the following aspects, for example.

[0108] [1] A fluoride phosphor comprising fluoride particles and a fluorine compound,

[0109] The fluorine compound is disposed on at least a portion of the surface of the fluoride particles and contains zirconium,

[0110] The fluoride particles have the following composition:

[0111] Containing element M, at least one selected from alkali metals and ammonium ions, manganese, and fluorine atoms,

[0112] The element M includes at least one selected from Group 4 elements, Group 13 elements, and Group 14 elements,

[0113] When the total molar number of the alkali metal and ammonium ions is 2, the molar number of manganese is greater than 0 and less than 0.2, the total molar number of element M is greater than 0.8 and less than 1, and the molar number of fluorine atoms is greater than 5 and less than 7.

[0114] [2] The fluoride phosphor according to [1], wherein

[0115] The fluoride particles have a composition represented by the following formula (1):

[0116] A c [M 1-b Mn b F d ] (1)

[0117] In formula (1), A includes at least one selected from Li, Na, K, Rb, Cs, and NH4 + wherein M includes at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements, and at least includes Si, b satisfies 0 < b < 0.2, c is the absolute value of the charge of 1-b Mn b F d ions, and d satisfies 5 < d < 7.

[0118] [3] The fluoride phosphor according to [1] or [2], wherein

[0119] The content of the fluorine compound in terms of zirconium conversion is 0.1% by mass or more and 10% by mass or less.

[0120] [4] The fluoride phosphor according to any one of [1] to [3], wherein

[0121] The fluorine compound at least includes a compound having a composition represented by KZrF5.

[0122] [5] The fluoride phosphor according to any one of [1] to [4], wherein the fluoride particles have the following composition:

[0123] The alkali metal includes potassium, and the molar ratio of potassium to the total molar number of the alkali metal and ammonium ions is 0.9 or more and 1 or less;

[0124] The element M includes silicon, and the molar ratio of silicon to the total molar number of the element M is 0.9 or more and 1 or less.

[0125] [(6)] A method for manufacturing a fluoride phosphor, the method including:

[0126] Preparing fluoride particles; and

[0127] Making the prepared fluoride particles contact with a treatment solution containing a complex ion including zirconium and fluoride ions to dispose a fluorine compound including zirconium on at least a part of the surface of the fluoride particles,

[0128] wherein the fluoride particles have the following composition:

[0129] Including element M, at least one selected from alkali metals and ammonium ions, manganese, and fluorine atoms,

[0130] The element M includes at least one selected from Group 4 elements, Group 13 elements, and Group 14 elements,

[0131] When the total molar number of the alkali metal and ammonium ions is 2, the molar number of manganese exceeds 0 and is less than 0.2, the total molar number of element M exceeds 0.8 and is less than 1, and the molar number of fluorine atoms exceeds 5 and is less than 7.

[0132] [7] The method for manufacturing a fluoride phosphor according to [6], wherein

[0133] the fluoride particles have a composition represented by the following formula (1):

[0134] A c [M 1-b Mn b F d (1)

[0135] In formula (1), A includes at least one selected from Li, Na, K, Rb, Cs, and NH4 + M includes at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements, and at least includes Si, b satisfies 0 < b < 0.2, c is the absolute value of the charge of [M 1- b Mn b F d ions, and d satisfies 5 < d < 7.

[0136] [8] The method for manufacturing a fluoride phosphor according to [6] or [7], wherein

[0137] the treatment liquid further contains orthoboric acid.

[0138] [9] The method for manufacturing a fluoride phosphor according to [8], wherein

[0139] the concentration of orthoboric acid in the treatment liquid is 0.04 mol / L or more.

[0140]

[10] The method for manufacturing a fluoride phosphor according to any one of [6] to [9], wherein <00oooo398>

[0141] the treatment liquid further contains an organic solvent.

[0142]

[11] The method for manufacturing a fluoride phosphor according to

[10] , wherein

[0143] the content rate of the organic solvent is 15 vol% or more.

[0144]

[12] The method for manufacturing a fluoride phosphor according to

[10] or

[11] , wherein

[0145] the organic solvent contains an alcohol having 3 or less carbon atoms.

[0146]

[13] The method for producing a fluoride phosphor according to any one of [6] to

[12] , wherein:

[0147] The treatment fluid further comprises a reducing agent.

[0148]

[14] A light emitting device comprising:

[0149] The fluoride phosphor according to any one of [1] to [4], and

[0150] A light source with a peak emission wavelength in the range of 380nm to 485nm.

[0151]

[15] The light-emitting device according to

[14] further comprises a light-emitting material, wherein:

[0152] The light-emitting material has a light-emitting peak wavelength within a range of 495 nm to 573 nm.

[0153] Example

[0154] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

[0155] Production Example 1

[0156] Fluoride particles were obtained by a known method. The Mn content of the fluoride particles was 1.00 mass % and the particles had K2[Si 0.960 Mn 0.040 F6] represents the theoretical composition of the phosphor.

[0157] Example 1

[0158] 20 g of the fluoride particles produced in Production Example 1 were weighed and placed in a 250 ml cylindrical plastic bottle. A treatment solution was added to the treatment solution, which contained 60 g of a 1.0 mol / L aqueous hexafluorozirconic acid (H2ZrF6) solution, 15 g of a 1.0 mol / L aqueous orthoboric acid (H3BO3) solution, 30 g of a 1.47 mol / L aqueous hydrogen peroxide (H2O2) solution, 45 g of pure water, and 38 ml (30 g) of ethanol. The mixture was stirred at room temperature for 5 hours using a stirrer (product name: MIX ROTOR MR-5, manufactured by As One Co., Ltd.). The resulting precipitate was separated into solid and liquid, washed with ethanol, and then dried at 90°C for 10 hours to produce the fluoride phosphor of Example 1.

[0159] Example 2

[0160] A fluoride phosphor of Example 2 was produced by the same method as in Example 1 except that the amount of fluoride particles added was changed to 40 g.

[0161] Example 3

[0162] A fluoride phosphor of Example 3 was produced by the same method as in Example 1 except that the stirring time was changed to 20 hours.

[0163] Example 4

[0164] The fluoride phosphor of Example 4 was prepared by the same method as Example 1, except that the addition amount of H2ZrF6 aqueous solution was changed to 15 g, the addition amount of pure water was changed to 90 g, and the addition amount of ethanol was changed to 152 ml (120 g).

[0165] Comparative Example 1

[0166] The fluoride particles obtained in Production Example 1 were used as the fluoride phosphor of Comparative Example 1.

[0167] evaluate

[0168] The fluoride phosphors of Examples 1 to 4 and Comparative Example 1 obtained above were evaluated for relative brightness, manganese content, and zirconium content as shown below.

[0169] Relative brightness

[0170] The luminescence luminance of the fluoride phosphor of Comparative Example 1 was set to 100%, and the luminescence luminance of the fluoride phosphors of Examples 1 to 4 was calculated from the luminescence spectrum data measured for each fluoride phosphor, and the result was expressed as relative luminance. The results are shown in Table 1.

[0171] Manganese content

[0172] The manganese content of each fluoride phosphor was analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES), and the content (Mn content; mass %) relative to the fluoride phosphor was determined.

[0173] Zirconium content

[0174] The zirconium content of each fluoride phosphor was analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES), and the content (Zr content; mass %) relative to the fluoride phosphor was determined.

[0175]

[0176] The amount of Zr detected in the fluoride phosphor of Comparative Example 1 was below the detection limit. On the other hand, Zr was detected in the fluoride phosphors of Examples 1 to 4.

[0177] Scanning electron microscopy observation

[0178] The fluoride phosphors obtained in Examples 1 and 3 were imaged using a scanning electron microscope (SEM). The SEM image of the fluoride phosphor of Example 1 is shown in FIG. Figure 2A The SEM image of the fluoride phosphor of Example 3 is shown in Figure 2B .

[0179] X-ray diffraction spectroscopy

[0180] The X-ray diffraction (XRD) spectra of the fluoride phosphors obtained in Examples 1 and 3 were measured using a sample-level multifunctional X-ray diffractometer (product name: Ultima IV, manufactured by Rigaku Co., Ltd.) under the following measurement conditions: X-ray source: CuKα line (λ = 0.15418 nm, tube voltage 40 kV, tube current 40 mA), angle: 10° to 70°, scan width: 0.02°, scan speed: 20° / min. The results are shown together with the XRD spectrum of KZrF5. Figure 3 .

[0181] Manufacturing Example of Light-Emitting Device

[0182] The following method was used to manufacture the Figure 1 As the phosphor 70, the fluoride phosphor of Examples 1, 2 or Comparative Example 1 and the phosphor having Si 5.81 Al 0.19 O 0.19 N 7.81 :Eu and a β-sialon phosphor having a composition represented by Eu and having a peak emission wavelength near 540nm. The fluoride phosphor and the β-sialon phosphor are mixed with a silicone resin so that the chromaticity coordinates in the CIE1931 color system are x to 0.280 and y to 0.270, thereby obtaining a resin composition. Next, a molded body 40 having a recess is prepared. On the bottom surface of the recess, a light-emitting element 10 made of a gallium nitride compound semiconductor having a peak emission wavelength of 451nm is arranged on the first wire 20, and then the electrodes of the light-emitting element 10 are connected to the first wire 20 and the second wire 30 respectively with wires 60. Furthermore, a resin composition is injected into the recess of the molded body 40 with a syringe to cover the light-emitting element 10, and then the resin composition is cured to form a wavelength conversion component 50, thereby manufacturing a light-emitting device 100.

[0183] Durability test 1

[0184] Durability Test 1 was conducted by storing each light-emitting device using the fluoride phosphor obtained in Examples 1 and 2 or Comparative Example 1 for 500 hours in an environmental testing chamber at 85°C and 85% relative humidity. The lumen maintenance rate (%) of the light-emitting device after Durability Test 1 was calculated, assuming the luminous flux of the light-emitting device before storage in the environmental testing chamber was 100%. The results showed that a higher lumen maintenance rate (%) indicated superior durability against high heat and humidity. The results are shown in Table 2.

[0185] Durability test 2

[0186] Each light-emitting device using the fluoride phosphor obtained in Examples 1 and 2 or Comparative Example 1 was operated continuously at a current of 150 mA in an unhumidified environmental testing chamber at 85°C. After 500 hours, a durability test 2 was conducted. Δx was determined by taking the chromaticity x value of the light-emitting device in the CIE 1931 colorimetric system before Durability Test 2 as the initial value and calculating the absolute value of the change from the initial x value in the CIE 1931 colorimetric system for the light-emitting device after Durability Test 2. This absolute value was used as Δx. The Δx of the light-emitting device using the fluoride phosphor in Comparative Example 1 was set as a reference (100%). The relative Δx change rate (%) of the Δx obtained for each light-emitting device in the Examples relative to the reference (100%) was calculated. The results showed that the lower the relative Δx change rate (%), the smaller the chromaticity change and the higher the durability. The results are shown in Table 2.

[0187]

[0188] Compared to the light-emitting device using the fluoride phosphor of Comparative Example 1, the light-emitting devices using the fluoride phosphors of Examples 1 and 2 exhibited higher lumen maintenance in Durability Test 1 and lower Δx change rates in Durability Test 2, thus demonstrating superior durability. Furthermore, when comparing the light-emitting device using the fluoride phosphor of Example 1 with the light-emitting device using the fluoride phosphor of Example 2, the light-emitting device using the fluoride phosphor of Example 1, which has a higher Zr content, exhibited higher lumen maintenance in Durability Test 1 and lower Δx change rates in Durability Test 2 than the light-emitting device using the fluoride phosphor of Example 2. This demonstrates that light-emitting devices using a fluoride phosphor coated with a large amount of a fluorine compound containing at least zirconium and fluorine exhibit high durability.

Claims

1. A fluoride phosphor comprising fluoride particles and a fluorine compound, wherein the fluorine compound is disposed on at least a portion of a surface of the fluoride particles and contains zirconium. The fluoride particles have the following composition: Containing element M, at least one selected from alkali metals and ammonium ions, manganese, and fluorine atoms, The element M includes at least one selected from Group 4 elements, Group 13 elements, and Group 14 elements, When the total molar number of the alkali metal and ammonium ions is 2, the molar number of manganese is greater than 0 and less than 0.2, the total molar number of element M is greater than 0.8 and less than 1, and the molar number of fluorine atoms is greater than 5 and less than 7.

2. The fluoride phosphor according to claim 1, wherein The fluoride particles have the following formula (1): composition: A c [M 1-b Mn b F d ] (1) In formula (1), A includes at least one selected from Li, Na, K, Rb, Cs, and NH4 + ; M includes at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements, and at least includes Si; b satisfies 0 < b < 0.2; c is the absolute value of the charge of the 1-b Mn b F d ion; and d satisfies 5 < d < 7.

3. The fluoride phosphor according to claim 1, wherein The content of the fluorine compound is 0.1% by mass or more and 10% by mass or less in terms of zirconium.

4. The fluoride phosphor according to claim 1, wherein The fluorine compound at least includes a compound having a composition represented by KZrF5.

5. The fluoride phosphor according to claim 1, wherein The fluoride particles have the following composition: The alkali metal includes potassium, and the ratio of the molar number of potassium to the total molar number of the alkali metal and ammonium ions is 0.9 or more and 1 or less; The element M includes silicon, and a ratio of the number of moles of silicon to the total number of moles of the element M is 0.9 or more and 1 or less.

6. A method for producing a fluoride phosphor, the method comprising: preparing fluoride particles; as well as The prepared fluoride particles are brought into contact with a treatment solution containing complex ions, so that a fluorine compound containing zirconium is disposed on at least a portion of the surface of the fluoride particles, wherein the complex ions contain zirconium and fluoride ions. Wherein, the fluoride particles have the following composition: Containing element M, at least one selected from alkali metals and ammonium ions, manganese, and fluorine atoms, The element M includes at least one selected from Group 4 elements, Group 13 elements, and Group 14 elements, When the total molar number of the alkali metal and ammonium ions is 2, the molar number of manganese is greater than 0 and less than 0.2, the total molar number of element M is greater than 0.8 and less than 1, and the molar number of fluorine atoms is greater than 5 and less than 7.

7. The method for producing a fluoride phosphor according to claim 6, wherein: The fluoride particles have the following formula (1): composition: A c [M 1-b Mn b F d ] (1) In formula (1), A includes at least one selected from Li, Na, K, Rb, Cs, and NH4 + ; M includes at least one element selected from Group 4 elements, Group 13 elements, and Group 14 elements and contains at least Si; b satisfies 0 < b < 0.2; c is the absolute value of the charge of 1-b Mn b F d ions; d satisfies 5 < d < 7.

8. The method for producing a fluoride phosphor according to claim 6, wherein: The treatment solution further comprises orthoboric acid.

9. The method for producing a fluoride phosphor according to claim 8, wherein: The concentration of orthoboric acid in the treatment liquid is 0.04 mol / L or higher.

10. The method for producing a fluoride phosphor according to claim 6, wherein: The treatment liquid further comprises an organic solvent.

11. The method for producing a fluoride phosphor according to claim 10, wherein: The content of the organic solvent is 15% by volume or more.

12. The method for producing a fluoride phosphor according to claim 10, wherein: The organic solvent includes an alcohol having 3 or less carbon atoms.

13. The method for producing a fluoride phosphor according to claim 6, wherein: The treatment fluid further comprises a reducing agent.

14. A light-emitting device comprising: The fluoride phosphor according to any one of claims 1 to 4; and A light source having a light emission peak wavelength within a range of 380 nm to 485 nm.

15. The light-emitting device according to claim 14, further comprising a light-emitting material, wherein The light-emitting material has a light-emitting peak wavelength within a range of 495 nm to 573 nm.

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