JP2019006861A - Phosphor, light emitting device, illumination device and image display device - Google Patents

Abstract

To provide a narrow band red phosphor that has a high content of light emission components in a short wavelength range (590-650 nm) with a short afterglow time and a high red luminosity, and has excellent durability, a method for producing the same, a high-quality light emitting device including the phosphor, and high-quality illumination devices and image display devices including the light emitting device.SOLUTION: A phosphor has a crystal phase including a composition represented by formula [1]. The phosphor 1 g is heated from room temperature to 600°C to generate moisture (HO), the total amount of which is 1.0 mg or less. ADMnF[1] (A is at least one element selected from Li, Na, K, Rb, Cs; D is two or more elements selected from Si, Ge, Ti; 1.5≤x≤2.5; 0.50≤y<1.00; y+z=1.00; 5.0≤w≤7.0).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a phosphor, a light emitting device, a lighting device, and an image display device.

A light emitting device that emits white light (hereinafter referred to as “LED” as appropriate) by combining a light source for excitation that emits light in the near-ultraviolet or short-wavelength visible region and a phosphor has become commonplace. It has been put into practical use. In particular, a phosphor that emits red fluorescence (hereinafter, referred to as “red phosphor” as appropriate) is used in a light-emitting device for an image display device or a lighting device, and its light emission characteristics are variously improved. Among these, in order to achieve both efficiency and color rendering properties, development of a phosphor having a narrow half-value width in a specific wavelength band is regarded as important.
In order to realize both high efficiency and color rendering of the image display device and the lighting device, for example, the emission peak wavelength of the emission spectrum is 590 nm to 650 nm and the half width of the emission spectrum is 1 nm to 80 nm. It is effective to use a red phosphor. Therefore, red phosphors having the above-mentioned light emission characteristics have been developed.
As such a phosphor, Non-Patent Document 1 discloses a Mn ⁴⁺ activated oxyfluoride phosphor such as Mg ₂₈ Ge _7.5 O ₃₈ F ₁₀ : Mn ⁴⁺ . For example, Patent Document 1 discloses a Mn ⁴⁺ activated fluoride phosphor such as a fluorogermanate phosphor.

Special table 2009-528429 gazette

J. SOLID STATE Chem., Vol.4, 269-274 (1972)

However, since the emission peak wavelength of the phosphor described in Non-Patent Document 1 is in the long wavelength region near 660 nm and the red visibility is low, there is a problem that the emission luminance of the phosphor is lowered. . In addition, the phosphor described in Patent Document 1 has a narrow half-value width of the emission spectrum, but there are cases where a long afterglow time becomes a problem. When the afterglow time is long, the amount of phosphor used in the light emitting device tends to increase. Further, when displaying an image, an image having a fast operation tends to be difficult to be displayed. Therefore, a phosphor having an emission peak wavelength of 590 nm or more and 650 nm or less and a narrow half-value width of the emission spectrum (hereinafter referred to as “narrow band red phosphor” as appropriate), and a short wavelength region (590 nm or more, There has been a demand for a phosphor having a large amount of luminescent components (650 nm or less) and a short afterglow time. These Mn-activated fluoride phosphors are required to have improved durability.
The present invention relates to a narrow-band red phosphor excellent in durability, having a long afterglow time, a high red luminous efficiency and a large amount of light emitting components in a short wavelength region, a method for producing the same, and high-quality light emission including the phosphor. It is an object of the present invention to provide a device, and a high-quality lighting device and an image display device including the light-emitting device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a phosphor having a specific composition and generating less moisture when heated can solve the above-mentioned problems. did.

That is, the present invention is as follows.
[1] A phosphor including a crystal phase having a composition represented by the following formula [1], wherein the total amount of moisture (H ₂ O) generated when 1 g of the phosphor is heated from room temperature to 600 ° C. The phosphor is characterized by being 1.0 mg or less.
_{A x D y Mn z F w} [1]
(In Formula [1],
The A element represents one or more elements selected from the group consisting of Li, Na, K, Rb, and Cs, and the D element represents two or more elements selected from the group consisting of Si, Ge, and Ti. X, y, z, and w are values that satisfy the following formulas independently.
1.5 ≦ x ≦ 2.5
0.50 ≦ y <1.00
y + z = 1.00
5.0 ≦ w ≦ 7.0)
[2] The phosphor according to [1], wherein the phosphor has an oxygen content of 0.50% by weight or less based on 1 g of the phosphor.
[3] The fluorescence according to [1] or [2], wherein the crystal phase has a peak in the following regions 1 to 5 in a powder X-ray diffraction pattern measured using CuKα rays (1.5418 Å). body.
Region 1 20.7 ° ≦ 2θ ≦ 21.0 °
Region 2 26.1 ° ≦ 2θ ≦ 26.7 °
Region 3 34.6 ° ≦ 2θ ≦ 35.6 °
Region 4 38.3 ° ≦ 2θ ≦ 39.4 °
Region 5 49.6 ° ≦ 2θ ≦ 50.7 °
[4] The phosphor according to any one of [1] to [3], wherein the A element is Na.
[5] The phosphor according to any one of [1] to [4], wherein the D element is Si and Ti.
[6] A first light emitter and a second light emitter that emits visible light when irradiated with light from the first light emitter, wherein the second light emitter is as described in [1] to [5]. A light emitting device comprising the phosphor according to any one of the above.
[7] An illumination device including the light emitting device according to [6] as a light source.
[8] An image display device comprising the light-emitting device according to [6] as a light source.
[9] A gas introduction step of introducing a fluorine-containing gas and an inert gas into a processing chamber in which a Mn-activated fluoride containing a crystal phase having a composition represented by the following formula [2] is installed; A phosphor manufacturing method, comprising: a first heating step of heating to a temperature equal to or higher than ° C .; and a first high temperature holding step of holding the processing chamber at the temperature for 10 minutes or more.
_{A x D y Mn z F w} [2]
(In Formula [2],
The A element represents one or more elements selected from the group consisting of Li, Na, K, Rb, and Cs, and the D element represents two or more elements selected from the group consisting of Si, Ge, and Ti. X, y, z, and w are values that satisfy the following formulas independently.
1.5 ≦ x ≦ 2.5
0.50 ≦ y <1.00
y + z = 1.00
5.0 ≦ w ≦ 7.0)
[10] A second heating step for heating the processing chamber to a temperature equal to or higher than the temperature in the first high temperature holding step after the first high temperature holding step, and a second high temperature holding step for holding the processing chamber at the temperature. [9] The production method according to [9].
[11] The production method according to [9] or [10], wherein in the first high temperature holding step and / or the second high temperature holding step, the fluorine-containing gas is circulated in a state where the pressure in the processing chamber is kept constant. .
[12] The production method according to [9] or [10], wherein in the first high temperature holding step and / or the second high temperature holding step, the fluorine-containing gas is sealed in a state where the pressure in the processing chamber is kept constant. .
[13] The manufacturing method according to any one of [9] to [12], wherein the temperature in the processing chamber is 700 ° C. or lower in the first high temperature holding step and / or the second high temperature holding step.
[14] The manufacturing method according to any one of [9] to [13], wherein in the first heating step and / or the second heating step, the processing chamber is heated at a rate of temperature increase of 20 ° C./min or less. .
[15] The manufacturing method according to any one of [9] to [14], wherein in the first high temperature holding step and / or the second high temperature holding step, the pressure in the processing chamber is 500 kPa or less.

  According to the present invention, a narrow-band red phosphor excellent in durability having a long afterglow time and a large amount of light-emitting component in a short wavelength region (590 nm or more and 650 nm or less) with high red visibility, and a method for producing the same, A high-quality light-emitting device including the phosphor, and a high-quality illumination device and image display device including the light-emitting device can be provided.

FIG. 3 is a diagram showing an XRD pattern of the phosphor obtained in Example 1. FIG. 3 is a diagram showing an emission spectrum of the phosphor obtained in Example 1.

Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified without departing from the gist of the present invention. Can be implemented.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. Further, in the phosphor composition formula in this specification, each composition formula is delimited by a punctuation mark (,). In addition, when a plurality of elements are listed by separating them with commas (,), one or two or more of the listed elements may be contained in any combination and composition. For example, the composition formula “(Ca, Sr, Ba) Al ₂ O ₄ : Eu” has “CaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “BaAl ₂ O ₄ : Eu”. “Ca _1−x Sr _x Al ₂ O ₄ : Eu”, “Sr _1−x Ba _x Al ₂ O ₄ : Eu”, “Ca _1−x Ba _x Al ₂ O ₄ : Eu”, _{"Ca 1-x-y Sr x} Ba y Al 2 O 4: Eu " (. in the formula, 0 <x <1,0 <y <1,0 < a x + y <1) all the comprehensive It shall be shown in
In the present specification, “Mn ⁴⁺ ” and “tetravalent manganese” are synonymous.

  The present invention includes a phosphor (first embodiment), a method for producing a phosphor (second embodiment), a light emitting device (third embodiment), and an image display device (fourth embodiment). .

{About phosphor}
[Regarding Formula [1]]
The phosphor according to the first embodiment of the present invention includes a crystal phase having a composition represented by the following formula [1].
_{A x D y Mn z F w} [1]
(In Formula [1],
A element represents one or more elements selected from the group consisting of Li, Na, K, Rb, Cs,
The D element represents two or more elements selected from the group consisting of Si, Ge, and Ti.
X, y, z, and w are values that satisfy the following formulas independently.
1.5 ≦ x ≦ 2.5
0.50 ≦ y <1.00
y + z = 1.00
5.0 ≦ w ≦ 7.0)

In formula [1], A (element A) represents one or more elements selected from the group consisting of Li (lithium), Na (sodium), K (potassium), Rb (rubidium), and Cs (cesium). . Among them, the element A is preferably Na in that it easily becomes a single-phase compound rather than a mixture and emits light uniformly.
The A element may be partially substituted with other elements as long as the effects of the present embodiment are not impaired. Examples of other elements include Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), and the like.

In formula [1], D (D element) represents two or more elements selected from the group consisting of Si, Ge, and Ti. Especially, it is preferable that D element is Si and Ti at the point which is easy to activate Mn4 ⁺ which is light emission ion.
When the element D is Si and Ti, the ratio (Ti) / (Si + Ti) is preferably 0.3 or more, more preferably 0.5 or more, in that the afterglow of the obtained phosphor is shortened. .
The D element may be partially substituted with other elements as long as the effects of the present embodiment are not impaired. Examples of other elements include Sn (tin), Zr (zirconium), Hf (hafnium), Nb (niobium), Ta (tantalum), and the like.

  In formula [1], Mn represents manganese. Unless the effect of the present embodiment is impaired, Mn is other activator element, for example, Eu (europium), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Tb (terbium). , Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium) and Yb (ytterbium) may be partially substituted.

  In formula [1], F represents fluorine. F may be partially substituted with other halogen elements such as Cl (chlorine), Br (bromine), I (iodine), and oxygen.

x represents the content of the element A, and the range thereof is usually 1.5 ≦ x ≦ 2.5, and the lower limit is preferably 1.7, more preferably 1.9, and the upper limit is Preferably it is 2.3, more preferably 2.1.
y represents the content of element D, and the range thereof is usually 0.50 ≦ y <1.00, and the lower limit is preferably 0.70 or more, more preferably 0.90 or more, and the upper limit. Is preferably 0.99 or less, more preferably 0.98 or less.
z represents the content of Mn.
The mutual relationship between y and z is usually
y + z = 1.00
Meet.
w represents the content of F, and the range thereof is usually 5.0 ≦ w ≦ 7.0, and the lower limit is preferably 5.5, more preferably 5.8, and the upper limit is preferably Is 6.5, more preferably 6.2.

  The composition of the phosphor can be confirmed by a generally known method. For example, inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), atomic absorption spectrometry (AAS), ion chromatography (IC), X-ray fluorescence analysis (XRF) Energy dispersive X-ray spectroscopy (EDX), wavelength dispersive X-ray spectroscopy (WDX), electron microanalyzer analysis (EPMA), and the like.

[About moisture content]
The total amount of moisture (H ₂ O) detected when the phosphor of this embodiment is heated from room temperature (for example, 25 ° C.) to 600 ° C. is usually 1.0 mg or less with respect to 1 g of the phosphor, Preferably it is 0.7 mg or less, More preferably, it is 0.5 mg or less. Since it is preferable that the total amount of moisture is small, there is no particular lower limit, but it is usually a value greater than 0 mg.
When the total amount of moisture detected when the phosphor is heated from room temperature (for example, 25 ° C.) to 600 ° C. is within the above range, that is, when the total amount of moisture contained in the phosphor is small, Mn contained in the phosphor Is preferable because it can prevent a decrease in phosphor characteristics caused by a reaction with moisture, resulting in a decrease in valence and no longer functioning as an emission center. Further, Mn contained in the phosphor reacts with moisture to become Mn hydrate, which is preferable because it can prevent the phosphor characteristics from being deteriorated due to blackening of the phosphor particles.

[About oxygen content]
The oxygen content in the phosphor of this embodiment is preferably 0.50% by weight or less, more preferably 0.45% by weight or less, still more preferably 0.40% by weight or less based on 1 g of the phosphor. Since the lower oxygen content is preferable, the lower limit is not particularly set, but it is usually greater than 0% by weight.
When the oxygen content is within the above range, that is, when the amount of oxygen contained in the phosphor is small, the symmetry of the octahedron formed by F ⁻ ions coordinated around Mn that is the emission center is kept high. This is preferable because the emission characteristics are improved.

[Surface Mn content]
[Mn] / [D + Mn], which is the surface Mn analysis value in the phosphor of the present embodiment, is preferably 0.01% or more, more preferably 0.05% or more, and still more preferably in terms of increasing the emission intensity. Is 0.10% or more.
[Mn] / [D + Mn] is preferably 4.5% or less, more preferably 4.0% or less, and further preferably 3.5% or less, from the viewpoint of increasing water resistance.
[Mn] represents the content (mol) of Mn contained in the phosphor, and [D + Mn] represents the total content (mol) of the D element and Mn contained in the phosphor.

[Powder X-ray diffraction (XRD) pattern]
The phosphor of this embodiment preferably has a peak in the following regions 1 to 5 in a powder X-ray diffraction pattern measured using CuKα rays (1.5418 Å).
Region 1 20.7 ° ≦ 2θ ≦ 21.0 °
Region 2 26.1 ° ≦ 2θ ≦ 26.7 °
Region 3 34.6 ° ≦ 2θ ≦ 35.6 °
Region 4 38.3 ° ≦ 2θ ≦ 39.4 °
Region 5 49.6 ° ≦ 2θ ≦ 50.7 °
In this embodiment, having a peak in the regions 1 to 5 means that the peak top is in the range of the regions 1 to 5. Specifying the regions 1 to 5 in this embodiment is merely a selection of peaks characteristic of the phosphor of this embodiment. In the phosphor of this embodiment, depending on the crystal shape, it may be oriented at the time of measurement, and a peak that can be confirmed by an X-ray diffraction pattern and a peak that cannot be confirmed may occur. The peaks appearing in the regions 1 to 5 in this embodiment are peaks that can be confirmed characteristically even if they are oriented.

[Emission spectrum]
The phosphor of this embodiment preferably has the following characteristics when the emission spectrum is measured by excitation with light having an excitation peak wavelength of 350 nm or more and 460 nm or less.
The emission peak wavelength in the above-mentioned emission spectrum is usually 590 nm or more, more preferably 600 nm or more, further preferably 610 nm or more, and usually 650 nm or less.
It is preferable at the point which has suitable red light emission as it is in the said range.

In the phosphor of this embodiment, the half-value width of the emission peak in the above-described emission spectrum is usually 80 nm or less, preferably 50 nm or less, more preferably 40 nm or less, still more preferably 20 nm or less, particularly preferably 10 nm or less. Usually, it is in the range of 1 nm or more.
It is preferable that the half-value width of the emission peak in the above-described emission spectrum is within the above range because the color purity tends to be high and the emission intensity tends to be high.

  In order to excite the phosphor with light having an excitation peak wavelength, for example, a xenon light source can be used. Moreover, the measurement of the emission spectrum of the phosphor of this embodiment can be performed using, for example, a fluorescence spectrophotometer F-4500 (manufactured by Hitachi, Ltd.). The emission peak and the half width of the emission peak can be calculated from the obtained emission spectrum.

{Phosphor production method}
The second embodiment of the present invention is a method for producing a phosphor.
The phosphor manufacturing method according to this embodiment includes a gas for introducing a fluorine-containing gas and an inert gas into a processing chamber in which a Mn-activated fluoride including a crystal phase having a composition represented by the following formula [2] is installed. It includes an introduction step, a first heating step for heating the processing chamber to 150 ° C. or higher, and a first high temperature holding step for maintaining the processing chamber at the temperature for 10 minutes or more. .
_{A x D y Mn z F w} [2]
(In Formula [2],
A element represents one or more elements selected from the group consisting of Li, Na, K, Rb, Cs,
The D element represents two or more elements selected from the group consisting of Si, Ge, and Ti.
X, y, z, and w are values that satisfy the following formulas independently.
1.5 ≦ x ≦ 2.5
0.50 ≦ y <1.00
y + z = 1.00
5.0 ≦ w ≦ 7.0)

  The manufacturing method of this embodiment includes a second heating step for heating the processing chamber to a temperature equal to or higher than the temperature in the first high temperature holding step after the first high temperature holding step, and a second high temperature for holding the processing chamber at the temperature. Including a holding step.

[Mn-activated fluoride]
The manufacturing method of this embodiment uses a Mn-activated fluoride containing a crystal phase having the composition represented by the formula [2].
In the Mn-activated fluoride used in the production method of this embodiment, each phosphor raw material is hydrofluoric acid (hereinafter sometimes referred to as “HF acid”) so as to have the composition of the formula [2]. It is possible to manufacture by dissolving the phosphor raw material solution obtained by mixing in HF acid.
Specific examples and preferred ranges of each element in the formula [2] are the same as the corresponding elements in the formula [1].

  As a raw material for the Mn-activated fluoride, a metal compound or a metal is used. For example, when producing a phosphor having the composition represented by the formula [2], a raw material for element A (hereinafter referred to as “A source” as appropriate) and a raw material for element D (hereinafter referred to as “D source” as appropriate). ), A raw material of Mn element (hereinafter referred to as “Mn source” as appropriate) and a raw material of F element (hereinafter referred to as “F source” as appropriate). Hereinafter, for example, the raw material of element Na may be referred to as “Na source”, and the raw material of element Si may be referred to as “Si source”.

  The production method of this embodiment is a step of dissolving a combination of the above raw materials in HF acid (dissolution step), and mixing and reacting the obtained raw material solution in HF acid to produce a slurry containing Mn-activated fluoride ( A step of heating the obtained Mn-activated fluoride-containing slurry (hydrothermal treatment step), a step of washing (washing step), and a step of dispersion / classification (dispersion / classification step) It is preferable to include a drying step. Moreover, a gas treatment process is included as will be described later.

  Although an example of the manufacturing method of the Mn activation fluoride used with the manufacturing method of this embodiment is shown below, this embodiment is not limited to these.

[Mn-activated fluoride raw material]
As a raw material of the Mn activated fluoride used in the manufacturing method of this embodiment, a known material can be used.
Specific examples of the Na source in the A source include NaF and NaHF ₂ .
Specific examples of the Li source, the K source, the Rb source, and the Cs source include compounds in which Na is replaced with Li, K, Rb, and Cs in each of the compounds listed as specific examples of the Na source.

Specific examples of the Si source in the D source include hexafluorosilicic acid (H ₂ SiF ₆ ), sodium hexafluorosilicate (Na ₂ SiF ₆ ), silicon oxide (SiO ₂ ), and silicon (Si).
Further, specific examples of the raw materials for the Ge source and Ti source include compounds in which Si is replaced by Ge and Ti, respectively, in the compounds listed as specific examples of the Si source.

Examples of the Mn source include potassium permanganate (KMnO ₄ ), potassium hexachloromanganate (K ₂ MnCl ₆ ), potassium hexafluoromanganate (K ₂ MnF ₆ ), and the like. Among these, potassium hexafluoromanganate (K ₂ MnF ₆ ) is preferable.

  In addition, specific examples of raw materials for other activation elements such as Eu source and Ce source include chloride, fluoride, oxide, hydroxide, carbonate, acetate, nitrate, sulfuric acid containing Eu or Ce. Examples of the compound include salts.

Specific examples of the F source include hydrofluoric acid (HF) and fluorine (F ₂ ).
Furthermore, any of these carbonates, oxides, oxalates, metals, chlorides, and the like that can be converted into a fluoride after being dissolved in HF acid can be used as a raw material.

  The F source (fluorine) in the formula [2] may be supplied from an A source, a D source, or a Mn source, or may be supplied from HF acid as a reaction solution. Each raw material may contain inevitable impurities.

[Dissolution process]
The production method of this embodiment is a step of obtaining a Mn-activated fluoride raw material solution by sufficiently dissolving the Mn-activated fluoride raw materials in HF acid using a stirrer or the like in a necessary combination so that the target composition is obtained. (Dissolution step).
What is necessary is just to design suitably the density | concentration which can form a fluoride after melt | dissolving a raw material, and melt | dissolving the density | concentration of HF acid used for melt | dissolution of a raw material. When the concentration of HF acid is lowered, the possibility of formation of a compound other than fluoride such as hydroxide is increased. Therefore, the concentration of HF acid is preferably higher. However, from the viewpoint of handling HF acid, the concentration of HF acid is preferably about 40 to 55%.

[Precipitation process]
The production method of the present embodiment includes a step (precipitation step) of mixing and reacting the obtained raw material solution in HF acid to produce a Mn-activated fluoride-containing slurry.
The method of producing a slurry containing Mn-activated fluoride by mixing and reacting the raw material solution includes, for example, a raw material solution composed of HF acid and Na source, and a raw material solution composed of HF acid, Si source and Ti source From a HF acid, Na source, Si source, and Ti source, a raw material solution comprising HF acid and Mn source is added to a 45% HF acid solution and reacted to produce a slurry containing Mn activated fluoride. A raw material solution consisting of HF acid, Na source, and Mn source is added to the raw material solution and reacted to produce a Mn-activated fluoride-containing slurry, or vice versa. If the activated fluoride-containing slurry is generated, the reaction may be performed by any method.

  The concentration of the HF acid used when mixing the raw material reaction liquid to produce the Mn-activated fluoride-containing slurry is particularly as long as the raw material solution reacts and the precipitate obtained after the reaction can become a fluoride. Not limited. When the concentration of HF acid is lowered, the possibility of formation of compounds other than fluorides such as hydroxide is increased. Therefore, it is preferable that the concentration of HF acid is high. However, from the viewpoint of handling HF acid, Mn-activated fluoride is preferred. Since the solubility of the fluoride-containing slurry in HF acid increases and the yield decreases, the concentration of HF acid is preferably about 30 to 55%.

[Hydrothermal treatment process]
In the production method of this embodiment, in order to make the Mn-activated fluoride-containing slurry more uniform, the Mn-activated fluoride-containing slurry is put in a Teflon container, sealed, and then heated at a predetermined temperature. It is preferable to include a process (hydrothermal treatment process). The container to be used is not limited to the one made of Teflon, but may have any resistance to HF acid and heat resistance at a predetermined temperature. Since the internal pressure of the sealed Teflon container increases as the temperature increases, the Teflon container may be enclosed with a SUS container to provide pressure resistance.
In order to make it more uniform, the slurry containing Mn-activated fluoride may be stirred with a stirrer or the entire processing vessel may be rotated during the hydrothermal treatment step.
If the hydrothermal treatment temperature is too low, homogenization does not proceed sufficiently, and if it is too high, the valence of Mn ions that are luminescent ions tends to change and the luminescent properties tend to deteriorate, so the range of 40 to 200 ° C. is preferred.
In the hydrothermal treatment step, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or the like may be added to the Mn-activated fluoride-containing slurry solution in addition to HF acid as necessary.

[Washing process]
The production method of this embodiment preferably includes a step of washing (washing step) after producing the Mn-activated fluoride-containing slurry and then filtering and separating the Mn-activated fluoride-containing slurry.
Unreacted residue due to HF acid, Na source, Si source, Ti source, Mn source, or fluoride produced when dissolved in HF acid, etc., used in manufacturing the slurry containing Mn-activated fluoride There is a tendency that unreacted components such as impurities and raw materials remain in the Mn-activated fluoride-containing slurry, or side-reacted components are generated in the Mn-activated fluoride-containing slurry.
In order to improve the characteristics of the phosphor, it is necessary to remove as much as possible the residual material and impurities generated during dissolution. There is no particular limitation on the cleaning method as long as impurities can be removed. For example, the produced Mn-activated fluoride-containing slurry such as HF acid, a mixture of potassium hydrogen fluoride and HF acid, or a mixture of hexafluorosilicic acid and HF acid becomes a compound other than fluoride such as hydroxide. If not, it can be washed with any liquid.
Considering removal of unreacted Mn, Si, Ti, and Na in particular, it is preferable to wash using a solution containing HF acid. When the concentration of HF acid is lowered, the possibility of formation of compounds other than fluorides such as hydroxide is increased and the emission characteristics are deteriorated. Therefore, the concentration of HF acid is preferably higher. In view of the above, and the solubility of the Mn-activated fluoride-containing slurry in HF increases and the yield may be lowered, the concentration of HF acid is preferably about 40 to 50%.

The weight of the HF acid when washing the Mn-activated fluoride-containing slurry is usually 0.1 times or more, preferably 3 times or more, more preferably 5 times or more, and usually 5 times the weight of the Mn-activated fluoride-containing slurry. 100 times or less, preferably 50 times or less.
The time for immersing the Mn-activated fluoride-containing slurry in HF acid varies depending on the stirring conditions and the like, but is usually 10 minutes or more, preferably 1 hour or more, and usually 24 hours or less, preferably 12 hours or less. is there. Moreover, you may wash | clean several times using HF acid, and may change the kind and density | concentration of the liquid to wash | clean.
In the washing step, after the work of immersing the Mn-activated fluoride-containing slurry in a washing solution containing HF acid and washing it, the Mn-activated fluoride-containing slurry can be produced by performing filtration and drying. . Further, washing using ethanol, acetone, methanol or the like may be put in between.

[Dispersion / classification process]
The production method of this embodiment preferably includes a step of dispersing and classifying the phosphor. The dispersion / classification step may be performed before or after the first heating step to the second high temperature holding step described later.
The phosphor produced in this embodiment preferably has a weight median diameter D50 in the range of usually 3 μm or more, particularly 10 μm or more, and usually 50 μm or less, especially 30 μm or less. If the weight median diameter D50 is too small, the luminance may decrease or the phosphor particles may aggregate. On the other hand, when the weight median diameter D50 is too large, there is a tendency that coating unevenness, blockage of a dispenser, etc. occur.
The weight median diameter D50 of the phosphor manufactured in this embodiment can be measured using an apparatus such as a laser diffraction / scattering particle size distribution measuring apparatus.

[Drying process]
The production method of this embodiment preferably includes a step of drying the phosphor. The atmosphere of the drying step includes air, dry air, nitrogen; rare gas such as argon (Ar), neon (Ne), helium (He). The drying temperature is preferably 50 ° C. or more and 300 ° C. or less. If the drying temperature is too low, moisture tends not to be removed, and if it is too high, the light emission characteristics of the phosphor tend to be lowered.

[Gas treatment process]
The manufacturing method of this embodiment includes a gas introduction step, a first heating step, and a first high temperature holding step as the gas treatment step. Moreover, it is preferable that a 2nd heating process and a 2nd high temperature holding process are included.
The production method of the present embodiment is not particularly limited as long as the effects of the present embodiment are not impaired. For example, International Publication No. 2009/09211 pamphlet, Japanese Patent Application Laid-Open No. 2015-028148, Special Table 2009-528429, etc. The methods described in each of the publications can be referred to as appropriate.

[Gas introduction process]
The manufacturing method of this embodiment includes a gas introduction step of introducing a fluorine-containing gas and an inert gas into a processing chamber in which a Mn-activated fluoride including a crystal phase having the composition represented by the formula [2] is installed. .

In the gas introduction step, the fluorine-containing gas and the inert gas are introduced so that the processing chamber has a predetermined pressure. The order of introducing the fluorine-containing gas and the inert gas is not particularly limited as long as the effect of the present embodiment is not impaired. It may be introduced into the processing chamber at the same time, or the fluorine-containing gas and the inert gas may be introduced one by one or a plurality of times alternately, or the fluorine-containing gas and the inert gas are mixed in advance and then introduced into the processing chamber. May be. Further, before introducing the gas, the processing chamber may be evacuated to less than 1 Torr, or a fluorine-containing gas atmosphere may be set.

As the fluorine-containing gas is not particularly limited, for _{example, F 2, HF, NF 3} , SiF 4, SF 6, NH 4 HF 2, NH 4 F, SbF 5, ClF 3, BrF 3, XeF 2, CF 4 One or more selected from C ₂ F ₆ , CHF ₃ , CH ₃ F, BF ₃ , PF ₃ , and C ₃ F ₆ are preferred.
The fluorine-containing gas can be introduced into the processing chamber in an activated state. As a method for activating the fluorine-containing gas, for example, one or more methods selected from plasma, microwaves, ultraviolet rays, a method using a catalyst, and the like are preferable.

The inert gas is preferably one or more selected from nitrogen (N ₂ ), helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe).
In the gas introduction step, when two or more types are mixed and introduced, the mixing method is not particularly limited. For example, a method in which a mixed gas filled in a container is introduced into the processing chamber, and two or more types are introduced upstream of the processing chamber. One or more methods selected from a method in which the gases are mixed in advance and introduced into the processing chamber, and a method in which each gas species is individually introduced and mixed in the processing chamber are preferable. As the mixing ratio, for example, when F ₂ is used, the F ₂ concentration is preferably 10% by volume or more, more preferably 20% by volume or more.

[First heating step]
The manufacturing method of this embodiment includes a first heating step of heating the processing chamber to 150 ° C. or higher after introducing the gas into the processing chamber in the gas introducing step.

[First high temperature holding step]
The manufacturing method of this embodiment includes a first high temperature holding step of holding the processing chamber heated to 150 ° C. or higher in the first heating step at that temperature for 10 minutes or more.

[Second heating step]
It is preferable that the manufacturing method of this embodiment includes the 2nd heating process of heating the said process chamber more than the temperature in this 1st high temperature holding process after the said 1st high temperature holding process.

[Second high temperature holding step]
It is preferable that the manufacturing method of this embodiment includes the 2nd high temperature holding process which hold | maintains the said process chamber at the temperature after a said 2nd heating process.

  The heating rate in the processing chamber in the first heating step and the second heating step is usually 20 ° C./min or less, preferably 10 ° C./min or less, preferably 1 ° C./min or more, preferably in any step. Is 3 ° C./min or more.

The upper limit of the temperature in the first heating step, the first high temperature holding step, the second heating step, and the second high temperature holding step is usually 700 ° C. or lower, preferably 650 ° C. or lower, more preferably in any step. Is 600 ° C. or lower.
In any step, the holding time in the first high temperature holding step and the second high temperature holding step is usually 10 minutes or longer, preferably 30 minutes or longer, and usually 50 hours or shorter, preferably 20 hours or shorter.
By setting both the upper limit of the temperature and the holding time within the above ranges, impurity elements such as oxygen contained in the Mn-activated fluoride are removed by the fluorine-containing gas, and the emission characteristics of the phosphor are improved. Since the phosphor does not grow as much as it becomes extremely difficult to handle as a body, it is preferable.

  In each of the first heating step, the first high temperature holding step, the second heating step, and the second high temperature holding step, the fluorine-containing gas is maintained in the processing chamber while maintaining a constant pressure in the processing chamber. However, it is also possible to change the pressure as appropriate. It is also preferable to enclose the fluorine-containing gas in the processing chamber while keeping the pressure in the processing chamber constant. “Distribution” means that gas is introduced into and discharged from the processing chamber at the same time. For example, when the pressure in the processing chamber is kept constant, for example, the amount of gas introduced and the amount of discharge are the same. Just make it into quantity. “Encapsulation” is to stop the introduction of gas after introducing it into the processing chamber and seal the processing chamber.

  Moreover, the pressure in the processing chamber in the first heating step, the first high temperature holding step, the second heating step, and the second high temperature holding step is usually 500 kPa or less, preferably 250 kPa or less, in any step. More preferably, it is 150 kPa or less, Preferably it is 10 kPa or more, More preferably, it is 30 kPa or more.

{Phosphor-containing composition}
The phosphor according to the first embodiment of the present invention and the phosphor manufactured by the manufacturing method according to the second embodiment can be used by mixing with a liquid medium. In particular, when the phosphor is used for applications such as a light emitting device, it is preferably used in a form dispersed in a liquid medium. A material in which the phosphor is dispersed in a liquid medium is appropriately referred to as “a phosphor-containing composition according to an embodiment of the present invention” or the like.

[Phosphor]
There is no restriction | limiting in the kind of the said fluorescent substance contained in the fluorescent substance containing composition of this embodiment, It can select arbitrarily from what was mentioned above. Moreover, the said fluorescent substance contained in the fluorescent substance containing composition of this embodiment may be only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Furthermore, the phosphor-containing composition of the present embodiment may contain a phosphor other than the phosphor as long as the effects of the present embodiment are not significantly impaired.

[Liquid medium]
The liquid medium used in the phosphor-containing composition of the present embodiment is not particularly limited as long as the effect of the phosphor is not impaired within the intended range. For example, any inorganic material and / or organic material can be used as long as it exhibits liquid properties under the desired use conditions, suitably disperses the phosphor, and does not cause an undesirable reaction. For example, a silicone resin, an epoxy resin, a polyimide silicone resin, etc. are mentioned.

[Content of liquid medium and phosphor]
The contents of the phosphor and the liquid medium in the phosphor-containing composition of the present embodiment are arbitrary as long as the effects of the present embodiment are not significantly impaired, but for the liquid medium, the phosphor-containing composition of the present embodiment. It is usually 50% by weight or more, preferably 75% by weight or more, and usually 99% by weight or less, preferably 95% by weight or less based on the whole product.

[Other ingredients]
The phosphor-containing composition of the present embodiment may contain other components in addition to the phosphor and the liquid medium as long as the effects of the present embodiment are not significantly impaired. Moreover, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

{Light emitting device}
A third embodiment of the present invention includes a first light emitter (excitation light source) and a second light emitter that emits visible light when irradiated with light from the first light emitter. The light emitting device is a light emitting device including the phosphor according to the first embodiment of the present invention or the phosphor manufactured by the manufacturing method according to the second embodiment. Here, any one of the phosphors may be used alone, or two or more may be used in any combination and ratio.
As the phosphor, for example, a phosphor that emits fluorescence in a green region or a red region under irradiation of light from an excitation light source is used. Specifically, the green or yellow phosphor preferably has an emission peak in the wavelength range of 500 nm to 600 nm, and the red phosphor has an emission peak in the wavelength range of 590 to 650 nm.
As the excitation source, one having an emission peak in the wavelength range of 350 nm to less than 500 nm is used.

Hereinafter, the phosphor according to the first embodiment of the present invention or the phosphor manufactured by the manufacturing method according to the second embodiment has an emission peak in a wavelength range of 590 nm to 650 nm, and the first Although the aspect of the light-emitting device in the case where a light-emitting body having an emission peak in a wavelength range of 350 nm to 500 nm is described, this embodiment is not limited to these.
In the above case, the light-emitting device of this embodiment can be set to the following embodiment (A) or (B), for example.
(A) The first illuminant having an emission peak in the wavelength range of 350 nm to 500 nm is used, and the first phosphor of the second illuminant has an emission peak in the wavelength range of 560 nm to less than 600 nm. The phosphor according to the first embodiment of the present invention or the manufacturing method according to the second embodiment is used as the second phosphor of the second luminous body, with at least one kind of phosphor (yellow phosphor) having Embodiment using the manufactured phosphor.
(B) A first phosphor having a light emission peak in a wavelength range of 350 nm to 500 nm is used, and a light emission peak in a wavelength range of 500 nm to less than 560 nm is used as the first phosphor of the second light emitter. The phosphor according to the first embodiment of the present invention or the manufacturing method according to the second embodiment is used as the second phosphor of the second luminous body as at least one kind of phosphor (green phosphor) having Embodiment using the manufactured phosphor.

(Yellow phosphor)
As yellow fluorescent substance in said aspect, the following fluorescent substance is used suitably, for example.
Examples of the garnet phosphor include (Y, Gd, Lu, Tb, La) ₃ (Al, Ga) ₅ O ₁₂ : (Ce, Eu, Nd),
Examples of the orthosilicate include (Ba, Sr, Ca, Mg) ₂ SiO ₄ : (Eu, Ce),
Examples of (acid) nitride phosphors include (Ba, Ca, Mg) Si ₂ O ₂ N ₂ : Eu (SION phosphor), (Li, Ca) ₂ (Si, Al) ₁₂ (O, N ₁₆ : (Ce, Eu) (α-sialon phosphor), (Ca, Sr) AlSi ₄ (O, N) ₇ : (Ce, Eu) (1147 phosphor), (La, Ca, Y) ₃ ( Al, Si) ₆ N ₁₁ : Ce (LSN phosphor)
Etc.
The phosphor is preferably a garnet phosphor, and more preferably a YAG phosphor represented by Y ₃ Al ₅ O ₁₂ : Ce.
Further, LSN phosphors preferable, _La 3 _Si 6 _N 11: LSN phosphor represented by Ce are more preferred.

(Green phosphor)
As the green phosphor in the above aspect, for example, the following phosphors are preferably used.
Examples of the garnet phosphor include (Y, Gd, Lu, Tb, La) ₃ (Al, Ga) ₅ O ₁₂ : (Ce, Eu, Nd), Ca ₃ (Sc, Mg) ₂ Si ₃ O _12. : (Ce, Eu) (CSMS phosphor),
Examples of the silicate phosphor include (Ba, Sr, Ca, Mg) ₃ SiO ₁₀ : (Eu, Ce), (Ba, Sr, Ca, Mg) ₂ SiO ₄ : (Ce, Eu) (BSS phosphor). ),
As the oxide phosphor, for example, (Ca, Sr, Ba, Mg) (Sc, Zn) ₂ O ₄ : (Ce, Eu) (CASO phosphor),
Examples of (acid) nitride phosphors include (Ba, Sr, Ca, Mg) Si ₂ O ₂ N ₂ : (Eu, Ce), Si _6-z Al _z O _z N _8−z : (Eu, Ce) (β-sialon phosphor) (0 <z ≦ 1), (Ba, Sr, Ca, Mg, La) ₃ (Si, Al) ₆ O ₁₂ N ₂ : (Eu, Ce) (BSON phosphor) ,
As the aluminate phosphor, for example, (Ba, Sr, Ca, Mg) ₂ Al ₁₀ O ₁₇ : (Eu, Mn) (GBAM phosphor)
Etc.

(Red phosphor)
In the light emitting device of this embodiment, other red phosphors may be used in combination with the phosphor according to the first embodiment or the phosphor produced by the production method according to the second embodiment. For example, the following phosphors are preferably used.
Examples of sulfide phosphors include (Sr, Ca) S: Eu (CAS phosphor), La ₂ O ₂ S: Eu (LOS phosphor),
Examples of the garnet phosphor include (Y, Lu, Gd, Tb) ₃ Mg ₂ AlSi ₂ O ₁₂ : Ce,
Examples of nanoparticles include CdSe,
Examples of the nitride or oxynitride phosphor include (Sr, Ca) AlSiN ₃ : Eu (S / CASN phosphor), (CaAlSiN ₃ ) _1-x · (SiO ₂ N ₂ ) _x : Eu (CASON fluorescence). Body), (La, Ca) ₃ (Al, Si) ₆ N ₁₁ : Eu (LSN phosphor), (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu (258 phosphor), ( _{Sr, Ca) Al 1 + x} Si 4-x O x N 7-x: Eu (1147 _{phosphors), M x (Si, Al} ) 12 (O, N) 16: Eu (M is, Ca, Sr, etc.) ( α-sialon phosphor), Li (Sr, Ba) Al ₃ N ₄ : Eu (wherein x is 0 <x <1).

[Configuration of light emitting device]
The light-emitting device of this embodiment has a first light emitter (excitation light source) and at least the phosphor according to the first embodiment of the present invention or the second embodiment as the second light emitter. The configuration is not limited except that the phosphor manufactured by the manufacturing method is used, and a known device configuration can be arbitrarily adopted.
Examples of the device configuration and the light emitting device include those described in Japanese Patent Application Laid-Open No. 2007-291352.
In addition, examples of the form of the light emitting device include a shell type, a cup type, a chip on board, a remote phosphor, and the like.

{Use of light emitting device}
The use of the light-emitting device according to the second embodiment of the present invention is not particularly limited and can be used in various fields where a normal light-emitting device is used, but has a wide color reproduction range and color rendering properties. In particular, it is particularly preferably used as a light source for illumination devices and image display devices.

[Lighting device]
A third embodiment of the present invention is an illumination device including the light emitting device according to the second embodiment of the present invention as a light source.
When the light-emitting device according to the second embodiment of the present invention is applied to a lighting device, the light-emitting device as described above may be appropriately incorporated into a known lighting device. For example, a surface emitting illumination device in which a large number of light emitting devices are arranged on the bottom surface of the holding case can be used.

[Image display device]
The fourth embodiment of the present invention is an image display device including the light emitting device according to the second embodiment of the present invention as a light source.
When the light emitting device according to the second embodiment of the present invention is used as a light source of an image display device, the specific configuration of the image display device is not limited, but is preferably used together with a color filter. For example, when the image display device is a color image display device using a color liquid crystal display element, the light emitting device is a backlight, a light shutter using liquid crystal and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

{Measuring method}
[Measurement of luminous characteristics]
For measurement of the emission spectrum of the phosphor, a fluorescence measuring apparatus (manufactured by JASCO Corporation) equipped with a 150 W xenon lamp as an excitation light source and a multi-channel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measuring apparatus was used. The emission peak wavelength and the half width of the emission peak were calculated from the obtained emission spectrum.

[Powder X-ray diffraction measurement]
Powder X-ray diffraction was precisely measured with a powder X-ray diffractometer D8 ADVANCE ECO (manufactured by BRUKER).
The measurement conditions are as follows.
Using CuKα tube X-ray output = 40 kV, 25 mA
Divergence slit = automatic detector = semiconductor array detector LYNXEYE, Cu filter used Scanning range 2θ = 5-65 degrees Reading width = 0.025 degrees

[Emission spectrum]
The emission spectrum was measured using a fluorescence spectrophotometer F-7000 (manufactured by Hitachi, Ltd.). More specifically, an emission spectrum within a wavelength range of 500 nm to 700 nm was obtained by irradiation with excitation light of 455 nm at room temperature (25 ° C.).

[Excitation spectrum]
The excitation spectrum was measured using a fluorescence spectrophotometer F-7000 (manufactured by Hitachi, Ltd.). More specifically, the red emission peak was monitored at room temperature (25 ° C.), and an excitation spectrum within a wavelength range of 300 nm to 550 nm was obtained.

[Measurement of afterglow time]
The afterglow time was measured using a fluorescence spectrophotometer F-7000 (manufactured by Hitachi, Ltd.). The excitation light of 455 nm was irradiated once at room temperature (25 ° C.), and the intensity change of the red emission peak after the irradiation was stopped was measured. The initial intensity was 1.0, and the intensity change up to 20 ms was measured.

[Analysis of moisture generated during heating]
The amount of released gas was analyzed by temperature programmed desorption mass spectrometry. Q-1500 (manufactured by JEOL Ltd.) was used as a mass spectrometer.
The sample was weighed in a platinum boat, set in a measurement container (quartz tube), heated while circulating pure He, and the generated gas was drawn into a mass spectrometer and observed. The quantitative value is a value compared with an integrated value of molecular weight 18 obtained by temperature programmed desorption of calcium oxalate monohydrate.

[Inorganic composition analysis]
For composition analysis, Si (silicon), Ti (titanium), Mn (manganese), and Na (sodium) were dissolved by adding an acid after the sample was alkali melted, and the resulting sample solution was appropriately diluted. Inductively coupled plasma optical emission spectrometer iCAP7600 Duo (Thermo F)
isher Scientific).
For fluorine (F), the sample was dissolved in an aqueous sodium carbonate solution, and appropriately diluted and filtered, and then performed using an ion chromatograph ICS-2000 (manufactured by Thermo Fisher Scientific).

[Surface Mn concentration analysis]
Surface Mn concentration analysis (X-ray Photoelectron Spectroscopy: X-ray photoelectron spectroscopy) was measured using an X-ray photoelectron spectrometer Quantum 2000 (manufactured by PHI). The measurement conditions are shown below.
-X-ray source: Monochromatic Al-Kα, output 16kV-34W (X-ray generation area 170umφ)
-Spectral system: path energy-187.85 eV @ wide spectrum-93.90 eV @ narrow spectrum (C1s, Mn2p3)
58.70 eV @ narrow spectrum (O1s, Si2p, FKLL)
29.35 eV @ narrow spectrum (F1s, Na1s, Ti2p)
・ Measurement area: 170umφspot (<340umφ)
・ Extraction angle: 45 ° (from the surface)

[Residual oxygen analysis]
Quantification was performed by an inert gas melting infrared analysis method (GFA) using an oxygen-nitrogen hydrogen analyzer (LECO, TCH600).
In addition to GFA, it can be measured by charged particle activation analysis (CPAA).

{Manufacture of phosphor}
(Comparative Example 1)
H ₂ SiF ₆ (33 wt%), H ₂ TiF ₆ (60 wt%) so that the charged composition ratio of each element is Na: Si: Ti: Mn = 2: 0.34: 0.66: 0.04. , K ₂ MnF ₆ , and HF acid mixed raw material, NaHF ₂ powder is added and stirred at room temperature (25 ° C.) for 10 minutes. The slurry after the reaction is filtered, washed with ethanol, and filtered again. And dried at 150 ° C. for 2 hours to obtain a Mn-activated fluoride of Comparative Example 1.

  The Mn concentration in the entire Mn-activated fluoride of Comparative Example 1 was 3.6 mol% with respect to the (Si + Ti) concentration. On the other hand, the Mn concentration present on the surface was 4.5 mol% with respect to the (Si + Ti) concentration.

Example 1
The phosphor of Example 1 was obtained by performing the following steps using the Mn-activated fluoride of Comparative Example 1. -Process (gas introduction process) It heated at 100 degreeC in the state which installed the Mn activation fluoride in the processing chamber. Next, a mixed gas of F ₂ and N ₂ (F ₂ concentration: 20% by volume, N ₂ concentration: 80% by volume) was supplied, and the inside of the processing chamber was placed in a fluorine-containing gas atmosphere.
(1st heating process) It heated to 500 degreeC over about 60 minutes.
(First high temperature holding step) While maintaining the temperature at 500 ° C., a mixed gas of F ₂ and N ₂ (F ₂ concentration: 20% by volume, N ₂ concentration: 80% by volume) was circulated in the 10 sccm processing chamber, 240 The 500 ° C. was held for a minute. Note that the pressure in the processing chamber was maintained at 80 kPa during the first high temperature holding step.
(Post-processing step) After the heat treatment, the furnace was cooled.

  As in Comparative Example 1, the Mn concentration present on the surface was analyzed and found to be 2.7 mol% with respect to the (Si + Ti) concentration.

(Example 2)
In the same manner as in Example 1 except that the Mn-activated fluoride of Comparative Example 1 was heated to 530 ° C. in the first heat treatment step, and the temperature was maintained at 530 ° C. in the first high temperature holding step. The phosphor of Example 2 was obtained.
Table 1 shows peak regions obtained by powder X-ray diffraction measurement of Example 1 and Example 2.

Table 2 shows the total amount of moisture (H ₂ O) detected when the Mn-activated fluoride of Comparative Example 1 and the phosphor of Example 2 were heated from room temperature (25 ° C.) to 600 ° C. As shown in Table 2, it can be seen that the phosphor of Example 2 generates significantly less moisture when heated.

  Table 3 shows the oxygen content contained in 1 g of the phosphors of Comparative Example 1 and Example 2. As shown in Table 3, it can be seen that the phosphor of Example 2 has an extremely low oxygen content.

Table 4 shows the afterglow time (ms) (time required to reach 1/10 of the initial intensity) in the phosphors of Example 1 and Example 2.
As shown in Table 4, the phosphors of Examples 1 and 2 have a short afterglow time. Therefore, when the phosphor of the present invention is used in a light emitting device or an image display device, the amount of use can be reduced. Furthermore, when the light emitting device using the phosphor of the present invention is applied to an image display device or the like, it is possible to display even a fast-moving image satisfactorily.

Subsequently, a durability test (lighting test) of the light emitting device was performed as follows.
The emission spectrum was measured before the lighting of the light emitting device was started (this time point is hereinafter referred to as “0 hour”). The luminance of the light emitting device using the phosphor of Comparative Example 1 is assumed to be 100, and Table 5 shows the luminance of the light emitting device when the phosphors of Example 1 and Example 2 are used.
Next, the semiconductor light emitting device was continuously energized with a driving current of 150 mA under the condition of 85 ° C., and after 20 hours had elapsed from the start of energization, the emission spectrum was measured in the same manner as in the case of 0 hour.
The chromaticity coordinates CIEx were calculated from the emission spectrum obtained after 20 hours, and the deviation (ΔCx) from the chromaticity coordinates CIEx obtained at 0 hours was evaluated.
Table 5 shows the results of the durability test of the light-emitting device using the phosphor of Comparative Example 1, Example 1, or Example 2.

  As shown in Table 5, the phosphors of Example 1 and Example 2 have improved brightness when used in a light-emitting device compared to the phosphor of Comparative Example 1, and the chromaticity change in the durability test is small. It can be seen that the durability is remarkably improved.

Claims (15)

The phosphor includes a crystal phase having a composition represented by the following formula [1], and the total amount of moisture (H ₂ O) generated when 1 g of the phosphor is heated from room temperature to 600 ° C. is 1. A phosphor characterized by being 0 mg or less.
_{A x D y Mn z F w} [1]
(In Formula [1],
A element represents one or more elements selected from the group consisting of Li, Na, K, Rb, Cs,
The D element represents two or more elements selected from the group consisting of Si, Ge, and Ti.
X, y, z, and w are values that satisfy the following formulas independently.
1.5 ≦ x ≦ 2.5
0.50 ≦ y <1.00
y + z = 1.00
5.0 ≦ w ≦ 7.0)   The phosphor according to claim 1, wherein the phosphor has an oxygen content of 0.50% by weight or less based on 1 g of the phosphor. The phosphor according to claim 1 or 2, wherein the crystalline phase has a peak in the following regions 1 to 5 in a powder X-ray diffraction pattern measured using CuKα rays (1.5418 Å).
Region 1 20.7 ° ≦ 2θ ≦ 21.0 °
Region 2 26.1 ° ≦ 2θ ≦ 26.7 °
Region 3 34.6 ° ≦ 2θ ≦ 35.6 °
Region 4 38.3 ° ≦ 2θ ≦ 39.4 °
Region 5 49.6 ° ≦ 2θ ≦ 50.7 °   The phosphor according to any one of claims 1 to 3, wherein the A element is Na.   The phosphor according to any one of claims 1 to 4, wherein the D element is Si and Ti.   A first light emitter and a second light emitter that emits visible light by irradiation of light from the first light emitter, the second light emitter according to any one of claims 1 to 5. A light emitting device comprising the phosphor described above.   An illumination device comprising the light-emitting device according to claim 6 as a light source.   An image display device comprising the light emitting device according to claim 6 as a light source. A gas introduction step of introducing a fluorine-containing gas and an inert gas into a treatment chamber in which a Mn-activated fluoride including a crystal phase having a composition represented by the following formula [2] is installed;
A first heating step of heating the processing chamber to 150 ° C. or higher;
And a first high-temperature holding step of holding the processing chamber at the temperature for 10 minutes or more.
_{A x D y Mn z F w} [2]
(In Formula [2],
A element represents one or more elements selected from the group consisting of Li, Na, K, Rb, Cs,
The D element represents two or more elements selected from the group consisting of Si, Ge, and Ti.
X, y, z, and w are values that satisfy the following formulas independently.
1.5 ≦ x ≦ 2.5
0.50 ≦ y <1.00
y + z = 1.00
5.0 ≦ w ≦ 7.0) A second heating step for heating the processing chamber to a temperature equal to or higher than the temperature in the first high temperature holding step after the first high temperature holding step;
The manufacturing method of Claim 9 including the 2nd high temperature holding process which hold | maintains this process chamber at the temperature.   The manufacturing method according to claim 9 or 10, wherein in the first high temperature holding step and / or the second high temperature holding step, the fluorine-containing gas is circulated in a state where the pressure in the processing chamber is kept constant.   11. The manufacturing method according to claim 9, wherein in the first high temperature holding step and / or the second high temperature holding step, the fluorine-containing gas is sealed in a state where the pressure in the processing chamber is kept constant.   The manufacturing method according to any one of claims 9 to 12, wherein in the first high temperature holding step and / or the second high temperature holding step, the temperature in the processing chamber is 700 ° C or lower.   The manufacturing method according to any one of claims 9 to 13, wherein in the first heating step and / or the second heating step, the processing chamber is heated at a temperature increase rate of 20 ° C / min or less.   The manufacturing method according to any one of claims 9 to 14, wherein, in the first high temperature holding step and / or the second high temperature holding step, a pressure in the processing chamber is 500 kPa or less.

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