Fluoride phosphors, their manufacturing methods and light-emitting devices

Abstract

The objective of this invention is to provide a fluoride phosphor that can further improve the reliability of a light-emitting device. This invention relates to a fluoride phosphor, comprising fluoride particles having the composition represented by formula (1) and a zirconium-containing fluorine compound disposed on at least a portion of the surface of the fluoride particles. The fluoride particles comprise an element M selected from the group consisting of elements of Group 4, Group 13 and Group 14, at least one element selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms. When the total mole number of alkali metals and ammonium ions is set to 2, the fluoride particles have a composition in which the mole number of manganese is greater than 0 and less than 0.2, the total mole number of element M is greater than 0.8 and less than 1, and the mole number of fluorine atoms is greater than 5 and less than 7. Ac[M1-bMnbFd] (1)

Description

Technical Field

[0001] The present invention relates to a fluoride phosphor, a manufacturing method thereof and a light-emitting device. Prior Art

[0002] Light-emitting devices combining 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, meaning a narrow half-width at half-maximum (FWHM) of their peak emission. Manganese-doped fluoride phosphors are known as red-emitting phosphors with narrow FWHM peaks.

[0003] For example, Patent Document 1 describes coating a manganese-doped red phosphor with aluminum oxide or the like to reduce the instability problem caused by degradation of the manganese-doped red phosphor, and further describes a light-emitting device having a fluorescent component including the coated manganese-doped red phosphor. [Prior Art Literature] [Patent Document]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-525974 Summary of the Invention

[0005] [Problems to be solved by the invention] In a light-emitting device having a wavelength conversion component including a manganese fluoride phosphor, the reliability of the light-emitting device may decrease depending on the environment in which the light-emitting device is used. One aspect of the present invention is to provide a fluoride phosphor and a method for manufacturing the same that can further improve the reliability of the light-emitting device. [Technical means to solve the problem]

[0006] The first embodiment is a fluoride phosphor comprising fluoride particles and a fluoride compound containing zirconium disposed on at least a portion of the surface of the fluoride particles. The fluoride particles comprise an element M comprising at least one selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements, at least one selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms. When the total molar number of the alkali metals and ammonium ions is 2, the fluoride particles have a composition in which the molar number of manganese exceeds 0 and is less than 0.2, the total molar number of the element M exceeds 0.8 and is less than 1, and the molar number of the fluorine atoms exceeds 5 and is less than 7.

[0007] The second aspect is a method for producing a fluoride phosphor, comprising: preparing fluoride particles, the fluoride particles comprising at least one element M selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements, at least one element selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms, wherein, when the total molar number of the alkali metals and ammonium ions is 2, the fluoride particles have a composition in which 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; contacting the prepared fluoride particles with a solution containing zirconium ions and fluoride ions, and disposing a fluorine compound containing zirconium on at least a portion of the surface of the fluoride particles.

[0008] The third aspect is a light-emitting device comprising the fluoride phosphor of the first aspect and a light source having a peak emission wavelength in the range of 380 nm to 485 nm. [Effects of the Invention]

[0009] According to one aspect of the present invention, a fluoride phosphor and a method for manufacturing the same can be provided, which can further improve the reliability of a light-emitting device. Simple diagram description

[0010] FIG1 is a schematic cross-sectional view showing an example of a light-emitting device using a fluoride phosphor. FIG. 2A is an example of a scanning electron microscope image of the fluoride phosphor of Example 1. FIG. FIG. 2B is an example of a scanning electron microscope image of the fluoride phosphor of Example 3. FIG. FIG3 is an example of the X-ray diffraction spectrum of a fluoride phosphor. Implementation Method

[0011] In this specification, the term "step" refers not only to individual steps but also to steps that achieve their intended purpose, even if they cannot be clearly distinguished from other steps. Furthermore, when a composition contains multiple substances corresponding to components, the content of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. Furthermore, the upper and lower limits of the numerical ranges described in this specification can be arbitrarily selected and combined to represent the numerical values ​​shown as examples of the numerical ranges. In this specification, multiple elements separated by commas (,) in formulas representing the composition of phosphors or luminescent materials mean that at least one of these multiple elements is contained in the composition. Furthermore, in formulas representing the composition of phosphors, the element before the colon (:) indicates the main crystal, and the element after the colon (:) indicates the activating element. In this specification, the relationship between color names and chromaticity coordinates, and the relationship between the wavelength range of light and the color name of monochromatic light, are based on JIS Z8110. The full width at half maximum (FWHM) of a phosphor refers to the wavelength width of the phosphor's emission spectrum where the emission intensity reaches 50% of the maximum emission intensity (full width at half maximum). The following describes embodiments of the present invention in detail. However, the embodiments described below are merely examples of fluoride phosphors, their manufacturing methods, and light-emitting devices used to embody the technical concepts of the present invention. The present invention is not limited to the fluoride phosphors, their manufacturing methods, and light-emitting devices described below.

[0012] Fluoride phosphor A fluoride phosphor may include fluoride particles and a fluoride compound containing zirconium disposed on at least a portion of the surface of the fluoride particles. The fluoride particles may contain an element M comprising at least one selected from the group consisting of Group 4, Group 13, and Group 14 elements, at least one selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms. In the composition of the fluoride particles, when the total molar number of alkali metals and ammonium ions is set to 2, the molar number of manganese may be greater than 0 and less than 0.2, the total molar number of element M may be greater than 0.8 and less than 1, and the molar number of fluorine atoms may be greater than 5 and less than 7.

[0013] A light-emitting device comprising a fluoride phosphor composed of a zirconium-containing fluoride compound disposed on the surface of fluoride particles (a fluorescent substance) can reduce or prevent light flux drop and color change, even in high-temperature, high-humidity, and other operating environments, and exhibits excellent reliability. This is believed to be due to the following: The fluoride particles do not contain manganese ions, which can cause light flux drop and color change, but rather a zirconium-containing fluoride compound having a different composition than the fluoride particles, thereby suppressing degradation of the fluoride phosphor in high-temperature or high-humidity environments.

[0014] The fluoride particles constituting the fluoride phosphor need only contain a fluorescent material activated by manganese (Mn), and may contain only a fluorescent material activated by Mn. In the composition of the fluoride particles, when the total molar number of alkali metal and ammonium ions is set to 2, the molar number of Mn can be greater than 0 and less than 0.2, and is preferably between 0.01 and 0.12. Furthermore, in the composition of the fluoride particles, when the total molar number of alkali metal and ammonium ions is set to 2, the molar number of the element M can be greater than 0.8 and less than 1, and is preferably between 0.88 and 0.99. In the composition of the fluoride particles, when the total molar number of alkali metal is set to 2, the molar number of F can be greater than 5 and less than 7, and is preferably between 5.9 and 6.1. The composition of the fluoride particles can be determined, for example, by inductively coupled plasma (ICP) emission spectroscopy.

[0015] The alkali metal in the fluoride particles may include at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs). Furthermore, the alkali metal, including at least potassium (K), may include at least one selected from the group consisting of lithium (Li), sodium (Na), rubidium (Rb), and cesium (Cs). The molar ratio of K to the total molar ratio of alkali metals and ammonium ions 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 molar ratio of K may be, for example, 1 or less than 0.995. The fluoride particles may also include ammonium ions (NH 4 + ) in place of the alkali metals. When ammonium ions are included, the molar ratio of ammonium ions to the total molar ratio of alkali metals and ammonium ions in the composition 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 ammonium ions may be, for example, greater than 0, and preferably 0.005 or greater.

[0016] Element M in the composition of the fluoride particles includes at least one selected from the group consisting of 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 selected from the group consisting of these may be included. As Group 13 elements, examples include boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), etc., and at least one selected from the group consisting of these may be included. As Group 14 elements, examples include carbon (C), silicon (Si), germanium (Ge), tin (Sn), etc., and at least one selected from the group consisting of these may be included. Element M may at least include at least one of Group 14 elements, preferably at least one of Si and Ge, more preferably at least include Si. Also, element M may at least include at least one of Group 13 elements and at least one of Group 14 elements, preferably at least one of Al, Si, and Ge, more preferably at least include Al and Si.

[0017] In the composition of the fluoride particles, relative to the total number of moles of alkali metal and ammonium ions being 2, the total number of moles of element M and Mn may be 0.9 or more and 1.1 or less, preferably 0.95 or more and 1.05 or less, or 0.97 or more and 1.03 or less.

[0018] The composition of the fluoride particles may be the composition represented by the following formula (1). A c[M 1-bMn bF d] (1) In formula (1), A may include at least one selected from the group consisting of Li, Na, K, Rb, Cs, and NH 4 +. M at least includes Si and may further include at least one element selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements. Mn may be a tetravalent Mn ion. b may satisfy 0 < b < 0.2, c is the absolute value of the charge of the [M 1-bMn bF d] ion, and d may satisfy 5 < d < 7.

[0019] In A in formula (1), at least K is included and may further include at least one selected from the group consisting of Li, Na, Rb, Cs, and NH 4 +. The ratio of the number of moles of K in the composition to the total number of moles of A may be 0.90 or more, preferably 0.95 or more, or 0.97 or more. The upper limit of the ratio of the number of moles of K may be 1 or 0.995 or less.

[0020] 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 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.

[0021] Furthermore, the fluoride particles may have a theoretical composition represented by the following formula (1a). A 2MF 6:Mn (1a) In formula (1a), A may include at least one selected from the group consisting of Li, Na, K, Rb, Cs, and NH 4 +. M includes at least Si, and may further include at least one element selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements. Mn may be a tetravalent Mn ion.

[0022] As a first composition as one form of the composition of the fluoride particles, it may include at least one selected from the group consisting of Group 4 elements and Group 14 elements as element M, preferably may include at least one selected from the group consisting of Group 14 elements, more preferably may include at least one of Si and Ge, and even more preferably may include at least Si. Also, with respect to the total number of moles 2 of the alkali metal and ammonium ion, the total number of moles 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 0.105 or less, or 0.97 or more and 1.03 or less.

[0023] The first composition of the fluoride particles may be a composition represented by the following formula (2). A 1 q[M 1 1-pMn pF r] (2)

[0024] In formula (2), A 1 may include at least one selected from the group consisting of Li, Na, K, Rb, Cs, and NH 4 +. M 1 includes at least one of Si and Ge, and may further include at least one element selected from the group consisting of Group 4 elements and Group 14 elements. Mn may be a tetravalent Mn ion. p may satisfy 0 < p < 0.2, q is the absolute value of the charge of the [M 1 1-pMn pF r] ion, and r may satisfy 5 < r < 7.

[0025] In formula (2), A1 includes at least K and may further include at least one selected from the group consisting of Li, Na, Rb, Cs, and NH4+. When A1 includes ammonium ions, the ratio of the molar number of ammonium ions in the composition to the total molar number of A1 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 ammonium ions may be, for example, greater than 0, and preferably 0.005 or greater.

[0026] In formula (2), p is preferably 0.005 to 0.15, 0.01 to 0.12, or 0.015 to 0.1. q can 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.

[0027] Furthermore, the fluoride particles of the first composition may have a first theoretical composition represented by the following formula (2a). A 1 2M 1F 6:Mn (2a)

[0028] In formula (2a), A1 may include at least one element selected from the group consisting of Li, Na, K, Rb, Cs, and NH4+. M1 may include at least one of Si and Ge, and may further include at least one element selected from the group consisting of Group 4 elements and Group 14 elements. Mn may be a tetravalent Mn ion.

[0029] The second component, as one embodiment of the composition of the fluoride particles, may include at least one element selected from the group consisting of Group 4 elements and Group 14 elements, and at least one element from Group 13 as the element M. Preferably, it includes at least one element selected from the group consisting of Group 14 elements and at least one element from Group 13, and more preferably includes at least Si and Al. Furthermore, the total molar number of Si, Al, and Mn in the second component relative to the total molar number 2 of the alkali metal and ammonium ions may be 0.9 to 1.1, preferably 0.95 to 1.05, or 0.97 to 1.03. Furthermore, the molar number of Al in the second component relative to the total molar number 2 of the alkali metal and ammonium ions may be greater than 0 and less than 0.1, preferably greater than 0 and less than 0.03, 0.002 to 0.02, or 0.003 to 0.015.

[0030] The second composition of the fluoride particles may be the composition represented by the following formula (3). A 2 t[M 2 1 - sMn sF u] (3)

[0031] In formula (3), A 2 contains at least K and may further contain at least one selected from the group consisting of Li, Na, Rb, Cs, and NH 4 +. M 2 contains at least Si and Al and may further contain at least one element selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements. Mn may be a tetravalent Mn ion. s may satisfy 0 < s < 0.2, t is the absolute value of the charge of the [M 2 1 - sMn sF u] ion, and u may satisfy 5 < u < 7.

[0032] When A 2 in formula (3) contains an ammonium ion, the ratio of the number of moles of the ammonium ion in the composition to the total number of moles of A 2 may be 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 the ammonium ion may exceed 0, preferably 0.005 or more.

[0033] 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 0.015 or more and 0.1 or less. t may be 1.8 or more and 2.2 or less, preferably 1.9 or more and 2.1 or less, or 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 5.95 or more and 6.025 or less.

[0034] Furthermore, the fluoride particles of the second composition may have a second theoretical composition represented by the following formula (3a). A 2 2Si 1-vAl vF 6-v:Mn (3a)

[0035] In formula (3a), A 2 contains at least K and may further contain at least one selected from the group consisting of Li, Na, Rb, Cs, and NH 4 +. v may satisfy 0 < v < 1, preferably 0.005 < v < 0.03. Mn may be a tetravalent Mn ion.

[0036] A fluoride phosphor may include a zirconium-containing fluoride compound disposed on at least a portion of the surface of fluoride particles. The fluoride compound may cover the surface of the fluoride particles in the form of a film, or may be disposed on the surface of the fluoride particles as a fluoride compound layer. The coverage rate of the fluoride particles in the fluoride phosphor with the fluoride compound may be, for example, 50% or greater, preferably 80% or greater or 90% or greater. The coverage rate of the fluoride particles with the fluoride compound is calculated as the ratio of the area covered by the fluoride compound to the surface area of ​​the fluoride particles.

[0037] The fluorine compound may be any compound containing zirconium and fluorine atoms, and may further contain at least one selected from the group consisting of alkali metals and ammonium ions. When the fluorine compound contains an alkali metal or ammonium ion, it may contain at least potassium as the alkali metal. When the fluorine compound contains potassium, the molar ratio of potassium to the alkali metal and ammonium ion may be, for example, 0.8 or greater, preferably 0.9 or greater or 0.95 or greater. In addition to zirconium, the fluorine compound may further contain a Group 4 atom other than zirconium, such as titanium. When the fluorine compound contains a Group 4 atom other than zirconium, the molar ratio of zirconium to the Group 4 atom other than zirconium may be, for example, 0.1 or less, preferably 0.01 or less or 0.001 or less.

[0038] For example, the fluorine compound may include at least a compound having a composition represented by AZrF 5. Here, A may include at least one selected from the group consisting of Li, Na, K, Rb, Cs, and NH 4 +. A includes at least K, and may further include at least one selected from the group consisting of Li, Na, Rb, Cs, and NH 4 +, or may be substantially K. Here, "substantially" means that unavoidable impurities are allowed, meaning that the impurity content is, for example, 5 mol% or less, 1 mol% or less, or 0.1 mol% or less. The ratio of the molar number of K to the total molar number 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 molar ratio of K may be, for example, 1 or 0.995 or less.

[0039] The content of the fluorine compound in the fluoride phosphor, calculated as zirconium, can be, for example, 0.1% by mass to 10% by mass, preferably 0.3% by mass, 0.5% by mass, or 0.8% by mass. Alternatively, the content of the fluorine compound can be 5% by mass or 2% by mass. When the content of the fluorine compound falls within this range, the reliability of the light-emitting device tends to be further improved. Furthermore, a decrease in the brightness of the powder tends to be suppressed.

[0040] From the perspective of improving brightness, the volume-based median diameter of the fluoride phosphor can be, for example, 5 μm to 90 μm, preferably 10 μm to 70 μm or 15 μm to 50 μm. From the perspective of improving brightness, the particle size distribution of the fluoride phosphor can exhibit, for example, a single-peak particle size distribution, preferably a single-peak 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 smaller diameter side is D10 and the particle size corresponding to 90% of the cumulative volume is D90, the ratio of D90 to D10 (D90 / D10) can be, for example, 3.0 or less. Furthermore, in the volume-based particle size distribution, the volume-based median diameter is the particle size corresponding to 50% of the cumulative volume from the smaller diameter side. The volume-based particle size distribution is measured using a laser diffraction particle size distribution analyzer.

[0041] Fluoride phosphors, for example, are activated by tetravalent manganese and can absorb light in the short wavelength region of the visible spectrum and emit red light. Light irradiating the fluoride phosphor can be primarily blue light, with a peak wavelength within the range of 380 nm to 485 nm. The peak wavelength of the fluoride phosphor's emission spectrum can be within the range of 610 nm to 650 nm, for example. The full width at half maximum of the fluoride phosphor's emission spectrum can be less than 10 nm, for example.

[0042] Method for producing fluoride phosphor A method for manufacturing 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 zirconium ions and fluoride ions, thereby disposing a fluorine compound containing zirconium on at least a portion of the surface of the fluoride particles. The fluoride particles having the specific composition include at least one element M selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements, at least one element selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms. When the total molar number of alkali metals and ammonium ions is 2, the fluoride particles have a composition in which 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.

[0043] By contacting fluoride particles having a predetermined composition with a treatment solution containing zirconium ions 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. This improves the reliability of a light-emitting device comprising a wavelength conversion member comprising the obtained fluoride phosphor and a resin, for example, in high-temperature environments.

[0044] In the first step, fluoride particles having a predetermined composition are prepared. In the preparation step, the fluoride particles can be prepared by transfer, etc., or the desired fluoride particles can be manufactured and prepared. The details of the prepared fluoride particles are as described above.

[0045] Fluoride particles can be produced, for example, as follows. When the fluoride particles have the first composition, they can be produced, for example, by a production method comprising mixing solution a and solution b, wherein solution a contains at least a first aluminum ion, a second aluminum ion, and hydrogen fluoride; solution b contains at least an alkali metal and hydrogen fluoride; the first aluminum ion contains tetravalent manganese; the second aluminum ion contains at least one element selected from the group consisting of Group 4 elements and Group 14 elements and a fluoride ion; and the alkali metal contains at least potassium.

[0046] Alternatively, for example, a fluoride phosphor can be produced by a method comprising mixing a first solution containing at least a first aluminum ion and hydrogen fluoride, a second solution containing at least an alkali metal and hydrogen fluoride, and a third solution containing at least a second aluminum ion. The first aluminum ion contains tetravalent manganese, the alkali metal contains at least potassium, and the second aluminum ion contains at least one element selected from the group consisting of Group 4 elements and Group 14 elements, and a fluoride ion. Methods for producing a fluoride phosphor having the first composition can be found, for example, in Japanese Patent Application Laid-Open Nos. 2014-141684, 2015-143318, and 2015-188075.

[0047] Furthermore, when the fluoride particles have a second composition, the fluoride particles having the second composition can be produced by, for example, a method comprising the following steps: preparing fluoride particles having the first composition; preparing fluoride particles comprising Al, an alkali metal, and F; and a first heat treatment step, wherein the first heat treatment step comprises subjecting a mixture comprising the fluoride particles and the fluoride particles having the first composition to a first heat treatment temperature of 600°C to 780°C in an inert gas atmosphere. Here, the composition of the fluoride particles comprising Al, an alkali metal, and F can have a ratio of the total molar number of alkali metals to a molar number of Al of 1 of 1 to a molar number of 3, and a ratio of the molar number of F of 4 to 6. Alternatively, the ratio of the total molar number of alkali metals to a molar number of Al of 1 of 1 to a molar number of 2 to a molar number of 3, and a ratio of the molar number of F of 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.

[0048] In the second step, the prepared fluoride particles are brought into contact with a treatment solution containing aluminum ions containing zirconium and fluoride ions, thereby disposing a fluoride compound containing zirconium on at least a portion of the surface of the fluoride particles. When the treatment solution containing aluminum ions containing zirconium and fluoride ions is brought into contact with the fluoride particles, a dissolution reaction occurs in a portion of the fluoride particles, generating at least one ion selected from the group consisting of alkali metal ions and ammonium ions that constitute the fluoride particles, and aluminum ions containing element M and fluoride ions. It is believed that the generated at least one ion selected from the group consisting of alkali metal ions and ammonium ions reacts with the aluminum ions containing zirconium and fluoride ions, thereby disposing a fluoride compound containing zirconium on the surface of the fluoride particles.

[0049] The treatment liquid comprises zirconium ions containing zirconium and fluoride ions and a liquid medium. The liquid medium only needs to contain water and can be substantially water, excluding the organic solvent described below.

[0050] Examples of aluminum ions containing zirconium and fluoride ions include [ZrF6]2-, [ZrF7]3-, [ZrF8]4-, [ZrF5]-, [Zr2F10]2-, [Zr2F12]4-, [Zr2F13]5-, [Zr2F14]6-, and [Zr6F31]7-. The treatment solution preferably contains at least aluminum ions having a composition represented by [ZrF6]2-. Examples of countercations for the aluminum ions containing zirconium and fluoride ions include hydrogen ions and ammonium ions, with hydrogen ions being at least possible. The content of aluminum ions containing zirconium and fluoride ions in the treatment solution, calculated as zirconium content, can be, for example, 0.01 mol / liter or greater, preferably 0.02 mol / liter or greater. Furthermore, the content of zinc ions may be, for example, less than 1 mol per liter, preferably less than 0.5 mol per liter.

[0051] In addition to 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 (H 3BO 3), metaboric acid ((HBO 2) n), perboric acid (HBO 3), hypoboric acid (H 4B 2O 4), boric acid (H 3BO 2), Acid (H₃BO), etc. The boron-containing oxyacid contained in the treatment liquid may include at least orthoboric acid. By including a boron-containing oxyacid in the treatment liquid, for example, hydrogen fluoride generated during the formation of a fluorine compound containing zirconium can be removed in the form of fluoroboric acid (e.g., HBF₄), thereby promoting the formation of the fluorine compound containing zirconium. Specifically, when the treatment liquid contains orthoboric acid, it is believed that the following reaction occurs, for example. Furthermore, in the following formula, A comprises at least one member selected from the group consisting of alkali metals and ammonium ions.

[0052] 2H 2ZrF 6+A 2SiF 6→2AZrF 5+H 2SiF 6+2HF H 3BO 3+4HF→HBF 4+3H 2O

[0053] When the treatment liquid contains a boron oxyacid, the boron oxyacid content in the treatment liquid, calculated as the boron content, may be, for example, 0.01 mol / L or greater, preferably 0.02 mol / L or 0.04 mol / L or greater. Alternatively, the boron oxyacid content may be, for example, 0.4 mol / L or less, preferably 0.2 mol / L or less.

[0054] The treatment liquid may further contain a reducing agent. By including a reducing agent, for example, tetravalent manganese ions that may dissolve from 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 minimal effect on fluoride particles and effectively reduces tetravalent manganese ions. Furthermore, it ultimately decomposes into harmless water and oxygen, making it easy to use in the manufacturing process and reducing environmental impact.

[0055] When the treatment liquid contains a reducing agent, the reducing agent content in the treatment liquid may be, for example, 0.1% to 20% by mass, preferably 0.5% to 5% by mass. Furthermore, the reducing agent content may be, for example, 0.02 mol / L to 4 mol / L, preferably 0.05 mol / L or 0.1 mol / L or more, and more preferably 2 mol / L or 1 mol / L or less.

[0056] In step 2, the treatment liquid that contacts the fluoride particles may further contain an organic solvent. Including an organic solvent in the treatment liquid can, for example, reduce the solubility of the zirconium-containing fluoride compound in the treatment liquid, allowing the fluoride compound to be more effectively positioned on the surface of the fluoride particles. This can also promote the formation of the zirconium-containing fluoride compound. The organic solvent can be any water-miscible organic solvent, such as alcoholic solvents with a carbon number of 3 or less, such as methanol, ethanol, propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; and nitrile solvents such as acetonitrile. The organic solvent contained in the solution is preferably an alcohol that can contain at least 3 carbon atoms or less.

[0057] In the second step, when the treatment liquid contains an organic solvent, the organic solvent content in the treatment liquid containing the organic solvent can be, for example, 5% by volume or greater, preferably 10% by volume or greater, or 15% by volume or greater. Alternatively, the organic solvent content 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. The volume of the treatment liquid containing the organic solvent is defined as the sum of the volume of the treatment liquid excluding the organic solvent and the volume of the organic solvent added to the treatment liquid, ignoring any volume changes caused by the miscibility of water and the organic solvent.

[0058] In the second step, the amount of the treatment liquid used in contact with the fluoride particles can be, for example, 100% by mass to 3000% by mass, preferably 300% by mass or 500% by mass, and more preferably 2500% by mass or 2000% by mass, relative to the mass ratio of the fluoride particles. If the mass ratio of the treatment liquid is within this range, the zirconium-containing fluoride compound tends to be more uniformly distributed on the surface of the fluoride particles.

[0059] The fluoride particles can be brought into contact with the treatment liquid by, for example, mixing the fluoride particles with the treatment liquid. 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, from 10°C to 50°C, preferably from 20°C to 35°C. Furthermore, the contact time can be, for example, from 1 hour to 40 hours, preferably from 2 hours to 30 hours. The contact atmosphere can be either air or an inert gas atmosphere.

[0060] The method for manufacturing the fluoride phosphor may further include, 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 solid-liquid separated fluoride phosphor, etc.

[0061] Light-emitting device The light-emitting device includes a wavelength conversion component comprising 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.

[0062] An example of a light-emitting device will be described with reference to the accompanying drawings. Figure 1 is a schematic cross-sectional view of an example of a light-emitting device according to this embodiment. This light-emitting device is an example of a surface-mount light-emitting device. The light-emitting device 100 includes a light-emitting element 10 and a molded body 40 on which the light-emitting element 10 is mounted. The light-emitting element 10 is a light source that emits light with a peak wavelength on the short wavelength side of visible light (e.g., within a range of 380 nm to 485 nm). The molded body 40 includes a first spring 20 and a second spring 30 and is integrally molded from a thermoplastic resin or a thermosetting resin. The molded body 40 is formed with a recess having a bottom and side surfaces corresponding to the substrate, and the light-emitting element 10 is mounted on the bottom surface of the recess. The light-emitting element 10 has a pair of positive and negative electrodes electrically connected to the first spring 20 and the second spring 30 via a wire 60. The light-emitting element 10 is covered by a wavelength conversion member 50. The wavelength conversion member 50 includes a phosphor 70 including a fluoride phosphor that converts the wavelength of light from the light emitting element 10. The phosphor 70 may include the fluoride phosphor and a luminescent material that emits light having a peak wavelength in a wavelength range different from that of the fluoride phosphor due to excitation light from the light emitting element 10.

[0063] The wavelength conversion component may include 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, and acrylic resin. For example, the refractive index of the silicone resin may be in the range of 1.35 to 1.55, and more preferably in the range of 1.38 to 1.43. If the refractive index of the silicone resin is within this range, 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 refers to the refractive index after curing and is measured in accordance with JIS K7142:2008. In addition to the resin and phosphor, the wavelength conversion component may further include a light diffusing material. By including a light diffusing material, the directivity from the light-emitting element can be mitigated and the viewing angle can be increased. Examples of the light diffusing material include silicon oxide, titanium oxide, zinc oxide, zirconium oxide, and aluminum oxide.

[0064] The light-emitting element emits light having a peak wavelength in the wavelength range of 380 nm to 485 nm, which is 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 wavelength in the range of 380 nm to 480 nm, more preferably in the range of 410 nm to 480 nm, and even more preferably in the range of 430 nm to 480 nm. A semiconductor light-emitting element is preferably used as the light source. By using a semiconductor light-emitting element as a light source, a stable light-emitting device with high efficiency, high linearity of output relative to input, and strong resistance to mechanical shock can be obtained. For example, a semiconductor light-emitting element using a nitride-based semiconductor can be used as the semiconductor light-emitting element. The full width at half maximum of the emission peak in the emission spectrum of the light-emitting element is preferably 30 nm or less.

[0065] The light-emitting device includes 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 covering a light source. A light-emitting device, whose light source is covered by a wavelength conversion member containing the fluoride phosphor, absorbs a portion of the light emitted by the light source and emits it as red light. By using a light source that emits light with a peak wavelength within the range of 380 nm to 485 nm, the emitted light can be more efficiently utilized, reducing light loss from the light-emitting device and providing a highly efficient light-emitting device.

[0066] The light-emitting device preferably includes a luminescent material other than a fluoride phosphor in addition to the fluoride phosphor. The luminescent material other than the fluoride phosphor can absorb light from the light source and convert the wavelength of light to a wavelength different from that of the fluoride phosphor. For example, the luminescent material can be included in a wavelength conversion component, similar to the fluoride phosphor.

[0067] The luminescent material may have an emission peak wavelength in the wavelength range of more than 495 nm and less than 573 nm, and preferably may be at least one selected from the group consisting of β-sialon phosphors, halogenosilicate phosphors, silicate phosphors, rare earth aluminate phosphors, perovskite-based luminescent materials, and nitride phosphors. The β-sialon phosphor may have, for example, a composition represented by the following formula (IIa). The halogenosilicate phosphor may have, for example, a composition represented by the following formula (IIb). The silicate phosphor may have, for example, a composition represented by the following formula (IIc). The rare earth aluminate phosphor may have a composition represented by the following formula (IId). The perovskite-based luminescent material may have, for example, a composition represented by the following formula (IIe). The nitride phosphor may have, for example, a composition represented by the following formula (IIf), (IIg), or (IIh). By making the wavelength conversion member contain a β-sialon phosphor or a perovskite-based luminescent material as a luminescent material other than a fluoride phosphor, when the light-emitting device is used as a light source for a rear combination lamp, for example, a light-emitting device with a wider range of color reproducibility can be manufactured. By making the wavelength conversion member contain a halogenosilicate phosphor, a silicate phosphor, a rare earth aluminate phosphor, or a nitride phosphor as a luminescent material other than a fluoride phosphor, when the light-emitting device is used as a light source for illumination, for example, a light-emitting device with higher color rendering properties or higher luminous efficiency can be manufactured.

[0068] Si 6-xAl xO xN 8-x:Eu (IIa) (In formula (IIa), x is a number satisfying 0 < x ≤ 4.2) (Ca,Sr,Ba) 8MgSi 4O 16(F,Cl,Br) 2:Eu (IIb) (Ba,Sr,Ca,Mg) 2SiO 4:Eu (IIc) (Y,Lu,Gd,Tb) 3(Al,Ga) 5O 12:Ce (IId) CsPb(F,Cl,Br,I) 3(IIe) (La,Y,Gd) 3Si 6N 11:Ce (IIf) (Sr,Ca)LiAl 3N 4:Eu (IIg) (Ca,Sr)AlSiN 3:Eu (IIh)

[0069] In addition to the fluoride phosphor, the wavelength conversion member may further include at least one kind of quantum dots. The quantum dots absorb light from a light source, can be wavelength-converted into light with a wavelength different from that of the fluoride phosphor, and can also be wavelength-converted into light with the same wavelength. Examples of the quantum dots include: quantum dots having a perovskite structure with a composition such as (Cs,FA,MA)(Pb,Sn)(Cl,Br,I)3 (where FA means formamidinium and MA means methylammonium), quantum dots having a chalcopyrite structure with 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 kind selected from the group consisting of them. Here, in the formula representing the composition of the quantum dots, plural kinds of elements or cations described separated by a comma (,) mean that at least one of the plural kinds of elements or cations is contained in the composition.

[0070] The invention of the present invention may include the following forms, for example. [1] A fluoride phosphor comprising fluoride particles and a zirconium-containing fluoride compound disposed on at least a part of the surface of the fluoride particles, The fluoride particles include an element M selected from at least one kind of the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements, at least one kind of the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms, and when the total molar number of the alkali metals and ammonium ions is 2, the fluoride particles have a composition in which 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.

[0071] [2] The fluoride phosphor according to [1], wherein the fluoride particles have a composition represented by the following formula (1). A c[M 1-bMn bF d] (1)

[0072] In formula (1), A includes at least one kind selected from the group consisting of Li, Na, K, Rb, Cs, and NH 4 +. M includes at least one kind of element selected from the group consisting of 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 [M 1-bMn bF d] ion, and d satisfies 5 < d < 7.

[0073] [3] The fluoride phosphor according to [1] or [2], wherein the content of the above fluoride compound is 0.1% by mass or more and 10% by mass or less in terms of zirconium conversion.

[0074] [4] The fluoride phosphor according to any one of [1] to [3], wherein the above fluoride compound at least contains a compound having a composition represented by KZrF5.

[0075] [5] The fluoride phosphor according to any one of [1] to [4], wherein the above fluoride particles have the following composition: the above alkali metal contains potassium, and the molar ratio of potassium to the total molar number of the above alkali metal and ammonium ion is 0.9 or more and 1 or less, the above element M contains silicon, and the molar ratio of silicon to the total molar number of element M is 0.9 or more and 1 or less.

[0076] [6] A method for manufacturing a fluoride phosphor, which includes: preparing fluoride particles, the above fluoride particles containing at least one element M selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements, at least one selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms, and when the total molar number of the above alkali metal and ammonium ion is set to 2, the above fluoride particles have a composition in which 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; bringing the prepared above fluoride particles into contact with a treatment liquid containing a complex ion having zirconium and fluoride ions, and disposing a fluoride compound containing zirconium on at least a part of the surface of the above fluoride particles.

[0077] [7] The method for manufacturing a fluoride phosphor according to [6], wherein the above fluoride particles have a composition represented by the following formula (1). A c[M 1-bMn bF d] (1)

[0078] In formula (1), A contains at least one selected from the group consisting of Li, Na, K, Rb, Cs, and NH 4 +. M contains at least one element selected from the group consisting of Group 4 elements, Group 13 elements, and Group 14 elements and at least contains Si. b satisfies 0 < b < 0.2, c is the absolute value of the charge of the [M 1-bMn bF d] ion, and d satisfies 5 < d < 7.

[0079] [8] A method for manufacturing a fluoride phosphor as described in [6] or [7], wherein the treatment solution further contains orthoboric acid.

[0080] [9] A method for producing a fluoride phosphor as described in [8], wherein the concentration of orthoboric acid in the treatment solution is greater than 0.04 mol / L.

[0081]

[10] The method for producing a fluoride phosphor as described in any one of [6] to [9], wherein the treatment liquid further contains an organic solvent.

[0082]

[11] A method for producing a fluoride phosphor as described in

[10] , wherein the content of the organic solvent is greater than 15% by volume.

[0083]

[12] A method for producing a fluoride phosphor as described in

[10] or

[11] , wherein the organic solvent contains an alcohol having 3 or less carbon atoms.

[0084]

[13] A method for manufacturing a fluoride phosphor as described in any one of [6] to

[12] , wherein the treatment solution further contains a reducing agent.

[0085]

[14] A light-emitting device comprising a fluoride phosphor as described in any one of [1] to [4], and a light source having a peak emission wavelength in the range of not less than 380 nm and not more than 485 nm.

[0086]

[15] The light-emitting device as described in

[14] further comprises a light-emitting material having a peak emission wavelength in the range of not less than 495 nm and not more than 573 nm. [Example]

[0087] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0088] Production Example 1 Fluoride particles as a phosphor having a Mn content of 1.00 mass % and a theoretical composition represented by K 2 [Si 0.960Mn 0.040F 6] were obtained by a known method.

[0089] Example 1 20 g of the fluoride particles produced in Preparation Example 1 were weighed and placed in a 250 ml cylindrical plastic bottle. 60 g of an aqueous solution of zirconium hydrofluoride (H2ZrF6) adjusted to 1.0 mol / liter, 15 g of an aqueous solution of orthoboric acid (H3BO3) adjusted to 1.0 mol / liter, 30 g of an aqueous solution of hydrogen peroxide (H2O2) adjusted to 1.47 mol / liter, 45 g of pure water, and 38 ml (30 g) of ethanol were added to the mixed treatment solution. The mixture was stirred at room temperature for 5 hours using a stirrer (Rotary Mixer MR-5, manufactured by AS ONE Co., Ltd.). The resulting precipitate was separated into solid and liquid, washed with ethanol, and dried at 90°C for 10 hours to produce the fluoride phosphor of Example 1.

[0090] Example 2 The fluoride phosphor of Example 2 was prepared by the same method as Example 1, except that the added amount of fluoride particles was set to 40 g.

[0091] Example 3 The fluoride phosphor of Example 3 was prepared by the same method as Example 1 except that the stirring time was set to 20 hours.

[0092] Example 4 The fluoride phosphor of Example 4 was prepared by the same method as Example 1, except that the amount of H 2 ZrF 6 aqueous solution was changed to 15 g, the amount of pure water was changed to 90 g, and the amount of ethanol added was changed to 152 ml (120 g).

[0093] Comparative Example 1 The fluoride particles obtained in Preparation Example 1 were used as the fluoride phosphor of Comparative Example 1.

[0094] Evaluate The relative brightness, manganese content, and zirconium content of the fluoride phosphors of Examples 1 to 4 and Comparative Example 1 obtained above were evaluated in the following manner.

[0095] Relative brightness Based on the luminescence spectrum data obtained for each fluoride phosphor, the luminance of the fluoride phosphor of Comparative Example 1 was set to 100%, and the luminance of the fluoride phosphors of Examples 1 to 4 was calculated as relative luminance. The results are shown in Table 1.

[0096] Manganese content The manganese content of each fluoride phosphor was analyzed using inductively coupled plasma atomic emission spectrometry (ICP-AES) to determine the Mn content relative to the fluoride phosphor (Mn content; mass %). The results are shown in Table 1.

[0097] Zirconium content The zirconium content of each fluoride phosphor was analyzed using inductively coupled plasma atomic emission spectrometry (ICP-AES) to determine the zirconium content relative to the fluoride phosphor (Zr content; mass %). The results are shown in Table 1.

[0098] [Table 1] Fluoride particles (g) Treatment fluid Contact time (h) Relative brightness (%) Mn content (mass %) Zr content (mass %) Liquid volume (mL) H2O2 (mol / L) H 2ZrF 6 (mol / L) H 3BO 3 (mol / L) ethanol (volume%) Example 1 20 188 0.23 0.32 0.08 20 5 100.2 0.98 1.0 Example 2 40 188 0.23 0.32 0.08 20 5 100.7 0.98 0.6 Example 3 20 188 0.23 0.32 0.08 20 20 87.3 0.90 4.8 Example 4 20 302 0.15 0.05 0.05 50 5 96.9 0.98 1.4 Comparative Example 1 - - 100.0 1.00 <0.001

[0099] 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.

[0100] Scanning electron microscopy observation Scanning electron microscope (SEM) images were obtained for the fluoride phosphors obtained in Examples 1 and 3. The SEM image of the fluoride phosphor of Example 1 is shown in FIG2A , and the SEM image of the fluoride phosphor of Example 3 is shown in FIG2B .

[0101] X-ray diffraction spectroscopy X-ray diffraction (XRD) spectra of the fluoride phosphors obtained in Examples 1 and 3 were measured using a horizontal multipurpose X-ray diffraction spectrometer (Ultima IV, manufactured by Rigaku Co., Ltd.) with a CuKα X-ray source (λ = 0.15418 nm, tube voltage 40 kV, tube current 40 mA) at an angle of 10° to 70°, a scan width of 0.02°, and a scan speed of 20° / min. The results are shown in Figure 3 along with the XRD spectrum of KZrF5.

[0102] Example of manufacturing a light-emitting device The light-emitting device 100 shown in FIG1 was manufactured as follows. As the phosphor 70, the fluoride phosphor of Examples 1, 2, or Comparative Example 1 and a β-sialon phosphor having a composition represented by Si 5.81Al 0.19O 0.19N 7.81:Eu and having a peak emission wavelength near 540 nm were used. The fluoride phosphor and the β-sialon phosphor were mixed with a silicone resin so that the chromaticity coordinates in the CIE 1931 color system were approximately 0.280 and 0.270, respectively, to obtain a resin composition. Next, a molded body 40 having a recess was prepared. A light-emitting element 10 made of a gallium nitride compound semiconductor and having a peak emission wavelength of 451 nm at the bottom of the recess was placed on the first spring 20. The electrodes of the light-emitting element 10 were connected to the first spring 20 and the second spring 30 via wires 60, respectively. Furthermore, a resin composition is injected into the concave portion of the molded body 40 using a syringe so as to cover the light-emitting element 10 , and then the resin composition is cured to form the wavelength conversion member 50 , thereby manufacturing the light-emitting device 100 .

[0103] Durability test 1 Each light-emitting device using the fluoride phosphor obtained in Examples 1 and 2 or Comparative Example 1 was stored in an environmental testing chamber at 85°C and 85% relative humidity for 500 hours, undergoing Durability Test 1. The luminous flux maintenance (%) of the light-emitting device after Durability Test 1 was determined, assuming the luminous flux of the light-emitting device before storage in the environmental testing chamber was 100%. A higher luminous flux maintenance (%) indicates better durability against high heat and humidity. The results are shown in Table 2.

[0104] Durability test 2 Each light-emitting device using the fluoride phosphors obtained in Examples 1 and 2 or Comparative Example 1 was subjected to Durability Test 2. Durability Test 2 consisted of continuous emission at a current of 150 mA in an unhumidified, 85°C environmental testing chamber for 500 hours. Evaluation was conducted. The chromaticity x value of the light-emitting device in the CIE 1931 colorimetric system before Durability Test 2 was used as the initial value. The absolute value of the change in x value from the initial value in the CIE 1931 colorimetric system after Durability Test 2 was calculated as Δx. The Δx value of the light-emitting device using the fluoride phosphor of Comparative Example 1 was used as the reference (100%). The relative Δx change rate (%) of the Δx values ​​obtained for each light-emitting device in the Examples relative to the reference (100%) was calculated. A lower relative Δx change rate (%) indicates a smaller change in chromaticity and higher durability. The results are shown in Table 2.

[0105] [Table 2] Zr content (mass %) Durability test 1 Durability test 2 Beam maintenance rate (%) ⊿x change rate (%) Example 1 1.0 91.5 78.7 Example 2 0.6 91.0 83.9 Comparative Example 1 <0.001 87.4 100.0

[0106] Compared to the light-emitting device using the fluoride phosphor of Comparative Example 1, the light-emitting device using the fluoride phosphors of Examples 1 and 2 exhibited higher luminous flux maintenance in Durability Test 1 and lower Δx change rate in Durability Test 2, 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 luminous flux maintenance in Durability Test 1 and lower Δx change rate in Durability Test 2 than the light-emitting device using the fluoride phosphor of Example 2. Therefore, it is clear that light-emitting devices using fluoride phosphors with a higher coverage of fluorine compounds containing at least zirconium and fluorine exhibit higher durability.

[0107] 10: Light-emitting element 20: First reed 30: Second reed 40: Molded body 50: Wavelength conversion component 60: Wire 70: Phosphor 100: Light-emitting device

Claims

1. A fluoride phosphor comprising fluoride particles and a zirconium-containing fluorine compound disposed on at least a portion of the surface of the fluoride particles, wherein the fluorine compound is a compound having a composition represented by KZrF5, wherein the fluoride particles comprise element M, at least one selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms, wherein element M is silicon (Si), and when the total mole number of the alkali metals and ammonium ions is set to 2, the fluoride particles have a composition in which the mole number of manganese is greater than 0 and less than 0.2, the total mole number of element M is greater than 0.8 and less than 1, and the mole number of fluorine atoms is greater than 5 and less than 7.

2. The fluoride phosphor of claim 1, wherein the fluoride particles have the composition represented by the following formula (1): Ac[M1-bMnbFd] (1) (in formula (1), A contains at least one element selected from the group consisting of Li, Na, K, Rb, Cs and NH4+; M contains at least one element selected from the group consisting of Group 4, Group 13 and Group 14 elements and contains at least Si; b satisfies 0 < b < 0.2, c is the absolute value of the charge of the [M1-bMnbFd] ion, and d satisfies 5 < d < 7).

3. The fluoride phosphor of claim 1, wherein the content of the fluorine compound is more than 0.1% by mass and less than 10% by mass when converted to zirconium.

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

5. A method for manufacturing a fluoride phosphor, comprising: Prepare fluoride particles comprising element M, at least one selected from the group consisting of alkali metals and ammonium ions, manganese, and fluorine atoms. Element M is silicon (Si). When the total mole number of the alkali metal and ammonium ions is set to 2, the fluoride particles have a composition in which the mole number of manganese is greater than 0 and less than 0.2, the total mole number of element M is greater than 0.8 and less than 1, and the mole number of fluorine atoms is greater than 5 and less than 7. Contact the prepared fluoride particles with a treatment liquid containing zirconium ions and fluoride ions. Deposit a fluorine compound containing zirconium on at least a portion of the surface of the fluoride particles. The fluorine compound is a compound having the composition represented by KZrF5.

6. The method for manufacturing a fluoride phosphor as claimed in claim 5, wherein the fluoride particles have the composition represented by the following formula (1): Ac[M1-bMnbFd] (1) (in formula (1), A contains at least one element selected from the group consisting of Li, Na, K, Rb, Cs and NH4+; M contains at least one element selected from the group consisting of 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 the [M1-bMnbFd] ion, and d satisfies 5 < d < 7).

7. The method for manufacturing a fluorinated phosphor as claimed in claim 5, wherein the above-mentioned processing solution further comprises orthoboric acid.

8. The method for manufacturing a fluorinated phosphor as claimed in claim 7, wherein the concentration of orthoboric acid in the above-mentioned treatment solution is 0.04 moles / liter or more.

9. The method for manufacturing a fluorinated phosphor as claimed in claim 5, wherein the above-mentioned processing liquid further comprises an organic solvent.

10. The method for manufacturing a fluorinated phosphor as claimed in claim 9, wherein the content of the aforementioned organic solvent is 15% by volume or more.

11. The method for manufacturing a fluorinated phosphor as claimed in claim 9, wherein the organic solvent comprises an alcohol having 3 or fewer carbon atoms.

12. The method for manufacturing a fluoride phosphor as claimed in claim 5, wherein the above-mentioned processing liquid further comprises a reducing agent.

13. A light-emitting device comprising a fluoride phosphor as described in any one of claims 1 to 3, and a light source having a peak emission wavelength in the range of 380 nm to 485 nm.

14. The light-emitting device of claim 13 further includes a light-emitting material having a peak emission wavelength in the range of 495 nm to 573 nm.

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