JP6964524B2 - Fluoride phosphor and light emitting device using it - Google Patents

Description

The present invention relates to a fluoride phosphor that is excited by blue light and emits red light, and a light emitting device using the same.

In recent years, as a white light source, a white light emitting diode (white LED), which is a combination of a light emitting diode (LED) and a phosphor, has been applied to a backlight light source of a display and a lighting device. Among them, white LEDs using InGaN-based blue LEDs as an excitation source are widely used.

The phosphor used for the white LED needs to be efficiently excited by the light emission of the blue LED and emit the fluorescence of visible light. A typical example of the fluorescent substance for a white LED is a cerium-activated yttrium aluminum garnet (YAG) phosphor that is efficiently excited by blue light and exhibits broad yellow emission. Pseudo-white color can be obtained by combining the YAG phosphor alone with a blue LED, and it exhibits light emission in a wide visible light region. For this reason, white LEDs containing YAG phosphors are used for lighting and backlight light sources, but there is a problem that the color rendering property is low in lighting applications and the color reproduction range is narrow in backlight applications due to the small amount of red components. be.

For the purpose of improving color rendering and color reproducibility, a white LED that combines a red phosphor that can be excited by a blue LED and a green phosphor such as Eu-activated β-type sialon or orthosilicate has also been developed.

As a red phosphor for such a white LED, since the fluorescence conversion efficiency is high, the brightness does not decrease at high temperatures, and the chemical stability is excellent, a nitride or oxynitride phosphor centered on ^{Eu 2+ is emitted.} Are often used, and typical examples include phosphors _{represented by the chemical formulas Sr 2} Si ₅ N ₈ : Eu ²⁺ , CaAlSiN ₃ : Eu ²⁺ , and (Ca, Sr) AlSiN ₃ : Eu ^2+. Be done. However, ^{the emission spectrum of the phosphor using Eu 2+} is broad and contains many emission components with low luminous efficiency. Therefore, the brightness of the white LED is the brightness of the YAG phosphor alone for its high fluorescence conversion efficiency. It will be much lower than in the case. In addition, since a phosphor used for a display application is required to be compatible with a color filter, a phosphor having a broad (unsharp) emission spectrum has a problem that it is not preferable.

Examples of the emission center of the red phosphor having a sharp emission spectrum include Eu ³⁺ and Mn ⁴⁺ . Above all, the ^{red phosphor obtained by solid-solving Mn 4+ in} a fluoride crystal such as _{K 2} SiF ₆ and activating it is efficiently excited by blue light and produces a sharp emission spectrum with a narrow half-value width. Have. Therefore, excellent color rendering and color reproducibility can be realized without lowering the brightness of the white LED. Therefore, in recent years, _{the application of K 2} SiF ₆ : Mn ⁴⁺ phosphor to the white LED has been actively studied. There is. (See Non-Patent Document 1)

Further, Patent Document 1 discloses a fluoride phosphor having a predetermined composition containing silicon, having a weight median diameter of 35 μm or more and a bulk density of 0.80 g / cm ³ or more.

Japanese Patent No. 60248550

A. G. Paulusz, Journal of The Electrochemical Society, 1973, Vol. 120, No. 7, p. 942-947

In light emitting devices such as backlights and lighting of liquid crystal displays, improvement of light emitting characteristics is always required, and for that purpose, improvement of characteristics of each member is required, and improvement of light emitting characteristics of phosphors is also required. Further, in _{the white LED using the K 2} SiF ₆ : Mn ⁴⁺ phosphor, there is a problem that the light emission characteristics vary widely.

Further, the present inventors have also stated that even with the fluoride phosphor disclosed in Patent Document 1, sufficient brightness cannot be stably obtained in practice, and there arises a problem that the yield as a white LED product is poor. I found it.

Therefore, there is a demand for a fluoride phosphor having good external quantum efficiency and suitable for stably producing a white LED.

As a result of various studies on the physical properties of the fluoride phosphor, the present inventors can stably produce a white LED having excellent external quantum efficiency by using a fluoride phosphor having specific powder characteristics. And came to the present invention.

That is, the present invention provides the following.

[1]
A fluoride phosphor having a composition represented by the following general formula (1) and having an angle of repose of 30 ° or more and 60 ° or less.
General formula: A ₂ M _(1-n) F ₆ : Mn ^{4 +} _n ... (1)
(Note that 0 <n ≦ 0.1, element A is one or more alkali metal elements containing at least K, and element M is Si alone, Ge alone, or Si and Ge, Sn, Ti, Zr and Hf. It is a combination with one or more elements selected from the group consisting of.)

[2] The fluoride phosphor according to [1], wherein the element A is a simple substance K and the element M is a simple substance Si in the general formula (1).

[3]
Bulk density 0.80 g / cm ³ or more and is 1.40 g / cm ³ or less [1] or [2] fluoride phosphor according.

[4]
The span value calculated by the following formula (2) from the 10% diameter (D10), the mass median diameter (D50), and the 90% diameter (D90) obtained from the mass-based cumulative distribution curve is 1.5 or less. The fluoride phosphor according to [1] to [3].
Equation: (span value) = (D90-D10) / D50 ... (2)

[5]
The fluoride phosphors according to [1] to [4] and
A light emitting device including a light source.

[6]
The light emitting device according to [5], wherein the peak wavelength of the light emitting light source is 420 nm or more and 480 nm or less.

[7]
The light emitting device according to [5] or [6], which is a white LED device.

According to the present invention, it is possible to provide a fluoride phosphor suitable for stably producing a white LED having good light emitting characteristics.

It is a figure which shows the X-ray diffraction pattern of the phosphor obtained in Example 1 in comparison with that of Comparative Example 1 and K ₂ SiF ₆ (ICSD-29407) which is a control. The vertical axis of the figure is the number of signal counts. It is a figure which shows the excitation / fluorescence spectrum of the phosphor obtained in Example 1. FIG. It is a cumulative distribution curve of the phosphor according to Examples 1 and 2. It is a cumulative distribution curve of the phosphor according to Comparative Examples 1 to 4. It is a frequency distribution curve of the phosphor which concerns on Examples 1 and 2. It is a frequency distribution curve of the phosphor which concerns on Comparative Examples 1 to 4.

In the present specification, unless otherwise specified, the upper limit value and the lower limit value thereof are included when indicating a numerical range.

The present invention is a fluoride phosphor represented by the general formula: A ₂ M _(1-n) F ₆ : Mn ^{4 +} _n. In the general formula, the element A is an alkali metal element containing at least potassium (K), and specifically, potassium alone, or potassium and lithium (Li), sodium (Na), rubidium (Rb), and cesium (Cs). It is a combination with at least one kind of alkali metal element selected from the above. From the viewpoint of chemical stability, it is preferable that the content ratio of potassium in the element A is high, and most preferably, potassium alone can be used as the element A.

Further, in the general formula, the element M is a tetravalent element containing at least silicon (Si), and specifically, silicon alone, germanium (Ge) alone, or silicon and germanium, tin (Sn), and titanium (Ti). ), Zirconium (Zr), and hafnium (Hf) in combination with one or more elements selected from the group. From the viewpoint of chemical stability, it is preferable that the content ratio of silicon in the element M is high, and most preferably, silicon alone can be used as the element M. Further, F in the general formula is fluorine and Mn is manganese.

In the fluoride phosphor according to the embodiment of the present invention, the angle of repose measured according to JIS R9301-2-2: 1999 needs to be 30 ° or more and 60 ° or less. Since the angle of repose indicates the fluidity of the fluoride phosphor, that is, it is an index indicating the degree of dispersion of the fluoride phosphor during use in the LED. If the angle of repose is less than 30 °, the fluidity of the fluoride phosphor is not sufficient, and if the angle of repose is more than 60 °, the fluidity of the fluoride phosphor is too high. There arises a problem that it is not preferable because the variation in the external quantum efficiency of the manufactured LED becomes large. In a more preferable embodiment, the angle of repose may be in the range of 32 ° or more and 58 ° or less, more preferably in the range of 34 ° or more and 56 ° or less.

In the fluoride phosphor according to the embodiment of the present invention, the bulk density is ^{preferably 0.80 g / cm 3} or more. If the bulk density is ^{less than 0.80 g / cm 3} , the external quantum efficiency may decrease, and the variation in the external quantum efficiency of the LED produced by using this phosphor may increase. Further, the bulk density is preferably 1.40 g / cm ³ or less, and if the bulk density ^{exceeds 1.40 g / cm 3} , the variation in the external quantum efficiency of the LED tends to be large, so that the performance may be inferior. be. In a further preferred embodiment, the bulk density can be 0.90 g / cm ³ or more and 1.40 g / cm ³ or less of the range, more preferably 1.00 g / cm ³ or more and 1.30 g / cm ³ or less It can also be in the range of.

The bulk density can be changed depending on the surface condition of the powder and the post-treatment method at the time of production, and cannot be immediately determined only from the particle size distribution. That is, the present invention is based on the effect obtained from a novel combination of a predetermined bulk density and mass median diameter.

In the fluoride phosphor according to the embodiment of the present invention, the span value is preferably 1.5 or less. In the present specification, the span value means a value calculated by (D90-D10) / D50, where D10, D50, and D90 are based on JIS R1622: 1995 and R1629: 1997, respectively. It refers to the 10% diameter, 50% diameter (mass median diameter), and 90% diameter obtained from the mass-based cumulative distribution curve converted from the volume-based cumulative distribution curve measured by the laser diffraction / scattering method. Further, D100 refers to a 100% diameter as described above. The span value is an index showing the distribution width of the particle size distribution, that is, the variation in the particle size of the fluoride phosphor. If the span value is too large, the variation in the external quantum efficiency of the manufactured LED may become large. That is, when the span value is 1.5 or less, it means that the fluoride phosphor has a characteristic that the particle size distribution is sharp and the particles are uniform as a powder, and the dispersibility in the sealing resin is high. It is thought that it will be possible to exert even better effects. In a preferred embodiment, the span value is in the range of 0.1 or more and 1.4 or less, in the range of 0.1 or more and 1.3 or less, in the range of 0.1 or more and 1.2 or less, or 0.1 or more and 1.1. It may be in the following range.

Further, in a preferred embodiment, the mass median diameter (D50) may be 30 μm or less. If D50 exceeds 30 μm, the dispersibility in the sealing resin when manufactured as a white LED is deteriorated, the brightness is lowered, and the manufacturing stability may be lowered. Further, it is preferable that D50 is 15 μm or more, and if D50 is less than 15 μm, the external quantum efficiency may decrease. In a more preferred embodiment, D50 can be in the range of 15 μm or more and 30 μm or less, and more preferably 16 μm or more and 29 μm or less.

In the fluoride phosphor according to the embodiment of the present invention, it is preferable that the frequency distribution curve based on the mass is monomodal. Further, the single peak (mode diameter) is more preferably 10 μm or more, and more preferably 10 μm or more and 100 μm.

In a preferred embodiment, the fluoride phosphor can have a combination of an angle of repose of 30 ° or more and 60 ° or less, ^{a bulk density of 0.80 g / cm 3} or more, and a span value of 1.5 or less. .. In a more preferred embodiment, the fluoride phosphors 34 and ° to 56 ° less the angle of repose, and bulk density of 0.80 g / cm ³ or more 1.40 g / cm ³ or less, 0.1 or 1.4 It can also have a combination with the following span values:

The fluoride phosphor according to the embodiment of the present invention can be prepared, for example, by a method including the following steps so that the fluoride phosphor has predetermined powder characteristics (bulk density, mass median diameter, etc.). A step of mixing hydrofluoric acid and an alkali metal hydrofluoric acid compound to obtain a solution. A step of adding an oxide of a tetravalent element and an alkali metal hexafluoromanganate compound to the solution to obtain a precipitate. A step of collecting, washing, and drying the precipitate to obtain a fluoride phosphor (powder).

In adjusting the powder properties, the compounding ratio of the above-mentioned hydrofluoric acid, alkali metal fluoride compound, tetravalent element oxide, and alkali metal hexafluoromanganate compound, and the oxide of tetravalent element and It can be controlled by the addition rate of the alkali metal hexafluoromanganate compound. Further, in the field of phosphors, it is known that different main components of a phosphor have different physical properties (morphology as a substance, peak wavelength of emission spectrum, spectral shape, etc.). That is, the fluoride phosphor according to the embodiment of the present invention behaves when used in a light emitting device even if the powder characteristics are seemingly the same as those of other phosphors such as YAG phosphor and Sialon phosphor. Note that of course it is quite different.

Further, the obtained fluoride phosphor powder may be further classified by means such as a sieve or a classifier, and adjusted so as to obtain desired powder characteristics. Further, the above step group is preferably performed at room temperature. In the present specification, "normal temperature" refers to a temperature in the temperature range defined by JIS Z8703: 1983, that is, in the range of 20 ± 15 ° C.

Further, in the embodiment of the present invention, it is possible to provide a light emitting device (LED or the like) including the above-mentioned fluoride phosphor and a light emitting light source. In such a light emitting device, it is preferable to use the fluoride phosphor sealed in a sealing material. Such a sealing material is not particularly limited, and examples thereof include silicone resin, epoxy resin, perfluoropolymer resin, and glass. In applications where high output and high brightness are required, such as display backlight applications, a sealing material having durability even when exposed to high temperature or strong light is preferable, and from this viewpoint, a silicone resin is particularly preferable.

Further, as the emission light source, it is preferable to emit light having a wavelength of a color that complements the red emission of the fluoride phosphor or light having a wavelength that can efficiently excite the fluoride phosphor. For example, a blue light source (blue LED or the like) is used. It is possible. Preferably, the peak wavelength of the light from the light emitting light source can be a wavelength in a range including blue (for example, a range of 420 nm or more and 560 nm or less), and more preferably a range of 420 nm or more and 480 nm or less.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention.

<Manufacturing process of _{K 2} MnF _{6>
K 2} MnF ₆ used in carrying out the method for producing a fluoride phosphor of Examples and Comparative Examples was prepared in accordance with the method described in Non-Patent Document 1. Specifically, 800 ml of hydrofluoric acid having a concentration of 40% by mass was placed in a beaker made of fluororesin having a capacity of 2000 ml, and 260.00 g of potassium bifluoride powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) and potassium permanganate powder were added. 12.00 g (manufactured by Wako Pure Chemical Industries, Ltd., reagent first grade) was dissolved. While stirring this hydrofluoric acid solution with a magnetic stirrer, 8 ml of 30% hydrogen peroxide solution (special grade reagent) was added dropwise little by little. When the amount of hydrogen peroxide solution dropped exceeded a certain amount, yellow powder began to precipitate, and the color of the reaction solution began to change from purple. After dropping a certain amount of hydrogen peroxide solution and continuing stirring for a while, the stirring was stopped and the precipitated powder was precipitated. After precipitation, the operation of removing the supernatant liquid, adding methanol, stirring, allowing to stand, removing the supernatant liquid, and further adding methanol was repeated until the liquid became neutral. Then, the precipitated powder was recovered by filtration, further dried, and the methanol was completely evaporated and removed to obtain 19.00 g of _{K 2} MnF _{6 powder.} All of these operations were performed at room temperature.

<Example 1>
As Example 1, a method for producing a fluoride phosphor represented by _{K 2} SiF _{6: Mn is shown below.} At room temperature, put 200 ml of 55% by mass hydrofluoric acid in a fluororesin beaker with a capacity of 500 _{ml, dissolve 25.6 g of KHF 2} powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent), and add an aqueous solution (B). Prepared. To this solution was _{added 6.9 g of silica (SiO 2} , manufactured by Denka, trade name FB-50R) and _{1.1 g of K 2} MnF ₆ powder. When silica powder was added to the aqueous solution, the temperature of the aqueous solution increased due to the generation of heat of solution. The solution temperature reached the maximum temperature about 3 minutes after the addition of silica, and then the solution temperature decreased because the dissolution of silica was completed. It was visually confirmed that the yellow powder began to be formed in the aqueous solution immediately after the addition of the silica powder.

After the silica powder was completely dissolved, the aqueous solution was stirred for a while to complete the precipitation of the yellow powder, and then the aqueous solution was allowed to stand to precipitate the solid content. After confirming the precipitation, the supernatant is removed, the yellow powder is washed with hydrofluoric acid and methanol having a concentration of 20% by mass, and the yellow powder is further filtered to separate and recover the solid portion, and the residual methanol is further dried. Was removed by evaporation. After the drying treatment, a nylon sieve having a mesh size of 75 μm was used, and only the yellow powder that had passed through the sieve was classified and recovered to finally obtain 19.9 g of yellow powder.

<Confirmation of yellow powder mother crystal by crystal phase measurement>
The X-ray diffraction pattern of the yellow powder obtained in Example 1 was measured using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., trade name Ultra4, using a CuKα tube). The obtained X-ray diffraction pattern is shown in FIG. As a result, since the X-ray diffraction pattern of the sample obtained in Example 1 was the same as that of the K ₂ SiF ₆ crystal, _{it was confirmed that K 2} SiF ₆ : Mn was obtained in a single phase.

<Example 2, Comparative Examples 1 to 4>
It was produced in the same manner as in Example 1 except that the preparation composition of Example 1 was changed to the formulation shown in Table 1 below, and Examples 2 and Comparative Examples 1 to 4 were obtained. When the X-ray diffraction pattern of the obtained yellow powder was measured, all showed the same pattern as the _{K 2} SiF _{6 crystal.}

<Evaluation of luminescence characteristics of fluoride phosphor>
The emission characteristics of each of the fluoride phosphors of Examples 1 and 2 and Comparative Examples 1 to 4 were evaluated by measuring the absorption rate, the internal quantum efficiency, and the external quantum efficiency by the following methods. That is, a standard reflector (manufactured by Labsphere, trade name Spectralon) having a reflectance of 99% was set in the side opening (φ10 mm) of the integrating sphere (φ60 mm). Monochromatic light dispersed at a wavelength of 455 nm was introduced into this integrating sphere by an optical fiber, and the spectrum of the reflected light was measured by a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., trade name MCPD-7000). At that time, the number of excited photons (Qex) was calculated from the spectrum in the wavelength range of 450 to 465 nm. Next, a concave cell filled with a phosphor so as to have a smooth surface is set in the opening of the integrating sphere, monochromatic light having a wavelength of 455 nm is irradiated, and the spectrum of the reflected light of excitation and the fluorescence is spectrophotometer. Measured by meter. The excitation / fluorescence spectra obtained from the fluoride phosphor of Example 1 are shown in FIG. 2 as a representative. From the obtained spectral data, the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) were calculated. The number of excited reflected light photons was calculated in the same wavelength range as the number of excited light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm. External quantum efficiency (= Qem / Qex × 100), absorption rate (= (Qex-Qref) / Qex × 100), internal quantum efficiency (= Qem / (Qex-Qref) × 100) from the obtained three types of photon numbers. ) Was asked.

<Evaluation of the angle of repose of fluoride phosphor>
The angle of repose of each fluoride phosphor of Examples 1 and 2 and Comparative Examples 1 to 4 was evaluated by an injection method according to JIS R 9301-2-2: 1999. That is, from a height of 2 to 4 cm on the upper edge of a commercially available glass funnel having a nozzle inner diameter of 6 mm, 200 g of the powder to be measured was dropped onto the substrate through the funnel at a speed of 20 to 60 g per minute to generate the powder. The angle of repose was calculated from the diameter and height of the conical deposit.

<Bulk density of fluoride phosphor>
The bulk density of each fluoride phosphor of Examples 1 and 2 and Comparative Examples 1 to 4 was evaluated according to JIS R 1628: 1997. That is, a constant volume container (100 cc) was used as the measurement container, and the mass thereof was weighed with a scale. The sample was placed through a measuring container through a sieve until the sample overflowed, taking great care not to apply vibration or pressure. The powder raised from the upper end surface of the measuring container was ground using a scraping plate. At this time, the fray plate was used by inclining it backward from the direction in which the powder was scraped so as not to compress the powder. The mass of each measuring container was weighed, and the mass of the sample was calculated by subtracting the mass of the measuring container. This measurement was performed 3 times. The average value of the mass of the sample calculated in each measurement divided by the volume of the measuring container was calculated as the bulk density.

<Evaluation of span value of fluoride phosphor>
The span values of each of the fluoride phosphors of Examples 1 and 2 and Comparative Examples 1 to 4 were evaluated by the following methods. That is, 30 ml of ethanol was weighed in a 50 ml beaker, and 0.03 g of the phosphor was placed therein. Next, the container was set in a homogenizer (manufactured by Nissei Tokyo Office, trade name US-150E) whose output was adjusted to "Altitude: 100%" in advance, and pretreatment was carried out for 3 minutes. D10, D50 (mass median diameter), D90, and D100 were obtained from the solution prepared as described above using a laser diffraction / scattering particle size distribution measuring device (manufactured by Microtrac Bell, trade name MT3300EXII). rice field. Using the obtained D10, D50, and D90, the span value was calculated as (D90-D10) / D50.

The evaluation results of each fluoride phosphor of Examples 1 and 2 and Comparative Examples 1 to 4 are summarized in Table 2 below. In addition, FIGS. 3 and 5 show the cumulative distribution curve and the frequency distribution curve of Examples 1 and 2, respectively. Further, FIGS. 4 and 6 show the cumulative distribution curve and the frequency distribution curve of Comparative Examples 1 to 4, respectively.

<Evaluation of LED emission characteristics using fluoride phosphor>
The fluoride phosphor of Example 1 was added to the silicone resin together with the β-sialon green fluorescent substance (manufactured by Denka Co., Ltd., trade name GR-MW540K). After defoaming and kneading, the white LED of Example 3 was produced by potting it in a surface mount type package to which a blue LED element having a peak wavelength of 455 nm was bonded and then thermosetting it. The addition amount ratio of the fluoride phosphor and the β-sialon green phosphor was adjusted so that the chromaticity coordinates (x, y) of the white LED became (0.28, 0.27) at the time of energized light emission.

Example 4 was prepared in the same manner as in Example 3 except that the fluorescent material of Example 2 was used instead of the fluorescent material of Example 1. Further, the white LEDs of Comparative Examples 5 to 8 were also produced in the same manner as in Example 3 except that the phosphors of Comparative Examples 1 to 4 were used. The addition amount ratios of the fluoride phosphor and the β-sialon green phosphor were adjusted so that the chromaticity coordinates (x, y) of the white LED would be (0.28, 0.27) at the time of energized light emission.

<Evaluation of variation in light emission characteristics>
White LEDs were produced 10 times in the same manner as in Examples 3 and 4 and Comparative Examples 5 to 8, and the emission characteristics (external quantum efficiency) of the obtained sample were measured every 10 times of production, and fluoride fluorescence was measured. The variation in external quantum efficiency due to the difference in body was compared and evaluated. Table 3 below shows the brightness, average value, and standard deviation of each white LED when the brightness of the first white LED produced in Example 3 is 100. It was found that in Example 3, the external quantum efficiency was higher than that in Comparative Example 5, and the standard deviation at the time of 10 measurements was small, so that the quality variation was small, the yield was excellent, and the yield was stable. Further, in Example 4, the same excellent results as in Example 3 were obtained. In all of Comparative Examples 5 to 8, the external quantum efficiency was low and the variation was large.

From the results of Examples and Comparative Examples shown in Tables 2 and 3, the angle of repose of the fluoride phosphor represented by _{A 2} M _(1-n) F ₆ : Mn ^{4 +} _{n of the present invention is in a specific range.} It can be seen that there is an effect that a high external quantum efficiency can be stably obtained when used as an LED. It is also understood that if the angle of repose is not within a certain range, it will not be effective.

_{By using the fluoride phosphor represented by A 2} M _(1-n) F ₆ : Mn ^{4 +} _n of the present invention for the LED, an LED having good light emitting characteristics can be stably obtained. The fluoride phosphor according to the present invention can be suitably used as a phosphor for white LEDs using blue light as a light source, and can be suitably used for a light emitting device such as a lighting fixture or an image display device.

Claims (7)

The composition is represented by the following general formula (1), the angle of repose is 30 ° or more, and the 10% diameter (D10), the mass median diameter (D50), and the 90% diameter (D90) obtained from the mass-based cumulative distribution curve. from the span value calculated by the following equation (2) is 1.5 Ri der less and is the internal quantum efficiency of 80% or more, the fluoride phosphors.
General formula: A ₂ M _(1-n) F ₆ : Mn ^{4 +} _n ... (1)
(Note that 0 <n ≦ 0.1, element A is one or more alkali metal elements containing at least K, and element M is Si alone, Ge alone, or Si and Ge, Sn, Ti, Zr and Hf. It is a combination with one or more elements selected from the group consisting of.)
Equation: (span value) = (D90-D10) / D50 ... (2) The fluoride phosphor according to claim 1, wherein the element A is a simple substance K and the element M is a simple substance Si in the general formula (1). Claim 1 or 2 fluoride phosphor according bulk density of 0.80 g / cm ³ or more and 1.40 g / cm ³ or less. The fluoride phosphor according to any one of claims 1 to 3, wherein the external quantum efficiency is 56% or more. The fluoride phosphor according to claims 1 to 4 and
A light emitting device including a light source. The light emitting device according to claim 5, wherein the peak wavelength of the light emitting light source is 420 nm or more and 480 nm or less. The light emitting device according to claim 5 or 6, which is a white LED device.

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