JP5446432B2 - Phosphor, phosphor-containing composition and light emitting device using the phosphor, and image display device and illumination device using the light emitting device - Google Patents

Description

  The present invention relates to a phosphor emitting red fluorescence, a phosphor-containing composition and a light emitting device using the phosphor, and an image display device and an illumination device using the light emitting device.

  2. Description of the Related Art Recently, a white light-emitting device configured by combining a GaN (gallium nitride) -based semiconductor light-emitting element (hereinafter, “semiconductor light-emitting element” may be referred to as “LED”) and a phosphor as a wavelength conversion material has been developed. Taking advantage of the feature of low power consumption and long life, it has been attracting attention as a light emitting source for image display devices and lighting devices. Among them, a white light emitting device in which an In-added GaN blue LED and a Ce-activated yttrium / aluminum / garnet yellow phosphor are combined can be cited as a typical light emitting device.

Such white light emitting devices are expected to be used for new applications such as display backlights, and accordingly, research and development of phosphors to be combined with semiconductor light emitting elements are being promoted.
For example, Patent Documents 1 to 3 disclose a light emitting device in which a semiconductor light emitting element is combined with a fluorine complex phosphor activated with Mn ⁴⁺ . The fluorine complex phosphors exemplified in Patent Documents 1 to 3 have trivalent, tetravalent, or pentavalent ions as metal ions that are coordinate centers of fluorine ions.

US Patent Publication 2006/0071589 US Patent Publication No. 2006/0169998 US Patent Publication No. 2007/0205712

However, in the light emitting devices described in Patent Documents 1 to 3, the luminance of the phosphor is still insufficient, and in addition, the fluorine complex phosphor activated by Mn ⁴⁺ used tends to deteriorate over time. Therefore, it has been clarified by examination of the present inventors that the product cannot be put into practical use.
In order to put a light emitting device using a fluorine complex phosphor activated with Mn ⁴⁺ into practical use, it is desired to improve the durability of the fluorine complex phosphor activated with Mn ⁴⁺ .

In view of the above problems, the present inventors have studied in detail the composition of the fluorine complex phosphor. As a result, when a specific metal element ( trivalent metal element) is added to the phosphor having the chemical composition represented by the following formula [2] in addition to the tetravalent metal element essential for Si, the durability is improved. The present invention has been completed.
_{^{M 1 2 + x M 2 '}} y R z F n ··· formula [2]
(Wherein, M ¹ is, .M 2 ^'is representative of the alkali metal elemental containing at least K, .R representing a tetravalent metal element containing at least Si represents the activated element containing at least Mn .

Moreover, x, y, z, and n represent the number which satisfy | fills the following formula | equation.
-1 ≦ x ≦ 1
0.9 ≦ y + z ≦ 1.1
0.001 ≦ z ≦ 0.4
5 ≦ n ≦ 7)
Further, the present inventors have found that the phosphor can be suitably used for applications such as a display device and a lighting device, and have completed the present invention.

That is, the gist of the present invention resides in the following (1) to ( 10 ).
(1) A phosphor having a chemical composition represented by the following formula [1].
^{_{M 1 2 + x M 2 y}} R z F n ··· formula [1]
(Wherein, M ¹ is, the .M ² representing an alkali metal elemental containing at least K, and essential tetravalent metal elements containing at least Si, the trivalent metal source element further containing at least Al Represents a metal element to be contained, and R represents an activation element containing at least Mn.

Moreover, x, y, z, and n represent the number which satisfy | fills the following formula | equation.
-1 ≦ x ≦ 1
0.9 ≦ y + z ≦ 1.1
0.001 ≦ z ≦ 0.4
5 ≦ n ≦ 7)
(2) In the above formula [1], wherein the content of K to the total ^{M 1} content of 90 mol% or more, the phosphor according to (1).

In (3) the formula [1], ^{M 1} is contained Na as the alkali metal element other than K, and the content of Na relative to all ^{M 1} content is 10 mol% or less, (1 ) Or the phosphor according to (2) .
(4) The phosphor according to any one of (1) to (3), wherein in the formula [1], the content of the trivalent metal with respect to the total amount of M ² is 10 mol% or less.
(5) In the above formula [1], wherein the content of Si to the total tetravalent metal amount contained in M ² is 90 mol% or more, according to any one of (1) to (4) Phosphor.
( 6 ) A phosphor-containing composition comprising the phosphor according to any one of (1) to ( 5 ) and a liquid medium.

( 7 ) A light emitting device including a first light emitter and a second light emitter that emits visible light by irradiation of light from the first light emitter, wherein the second light emitter is (1) A light emitting device comprising a first phosphor containing one or more of the phosphors according to any one of ( 5 ) to ( 5 ).
( 8 ) The second phosphor includes a second phosphor including one or more phosphors having emission peak wavelengths different from those of the first phosphor. ( 7 ) The light-emitting device of description.

( 9 ) An illumination device comprising the light-emitting device according to ( 7 ) or ( 8 ).
( 10 ) An image display device comprising the light-emitting device according to ( 7 ) or ( 8 ).

According to the present invention, it is possible to improve the durability of the fluorine complex phosphor while maintaining practical luminance.
In addition, by using the phosphor of the present invention, it is possible to provide a light emitting device, an image display device, and a lighting device with high efficiency and high color rendering properties.

It is a typical perspective view which shows one Example of the semiconductor light-emitting device of this invention. FIG. 2A is a schematic cross-sectional view showing an embodiment of a bullet-type light emitting device of the present invention, and FIG. 2B is a schematic view showing an embodiment of the surface-mounted light-emitting device of the present invention. It is sectional drawing. It is typical sectional drawing which shows one Example of the illuminating device of this invention. It is the excitation spectrum of the fluorescent substance of Example 1-1, and an emission spectrum. It is a SEM observation image of Example 1-1. It is a SEM observation image of Example 1-2. It is a SEM observation image of Example 1-3. It is a SEM observation image of comparative example 1-1.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
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 separated by commas (,), one or two or more of the listed elements may be included 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 " and all assumed to generically indicated (in the above formula, 0 <x <1,0 <y <1,0 <X + y <1).

[1. Phosphor]
[1-1. Composition of phosphor]
The phosphor of the present invention is a phosphor characterized in that the chemical composition of the phosphor particles is represented by the following formula [1].
^{_{M 1 2 + x M 2 y}} R z F n ··· formula [1]
(However, M ¹ represents at least one monovalent metal element selected from the group consisting of alkali metal elements.

M ² represents a metal element containing at least a tetravalent metal element containing at least Si and further containing at least one metal element selected from the group consisting of a trivalent metal element and a pentavalent metal element. .
R represents an activation element containing at least Mn.
Moreover, x, y, z, and n represent the number which satisfy | fills the following formula | equation.
-1 ≦ x ≦ 1
0.9 ≦ y + z ≦ 1.1
0.001 ≦ z ≦ 0.4
5 ≦ n ≦ 7)
In addition, the fluorescent substance particle in this specification means a single particle. Here, the single particle refers to a particle that can clearly distinguish the boundary between the particle in SEM observation.

In the above formula [1], M ¹ represents at least one monovalent metal element selected from the group consisting of alkali metal elements. Here, the alkali metal element means Li, Na, K, Rb, Cs, or Fr. M ¹ may contain ^one of these alkali metal elements alone, or may contain two or more of them in an arbitrary ratio.
M ¹ preferably contains one or more elements selected from the group consisting of K and Na, and preferably contains at least K. Usually, K is 90 mol% or more based on the total ^{M 1} volume, preferably 93 mol% or more, more preferably 95 mol% or more, more preferably 97 mol% or more.

M ¹ preferably contains at least K and contains an alkali metal element other than K in addition to K because durability is improved. Here, as an alkali metal element other than K, one or more elements selected from the group consisting of Li, Na, Rb, and Cs are preferable, and Na is particularly preferable. This is because the durability improvement effect is remarkable.
The content of the alkali metal element other than K, usually, 0.001 mol% or more based on the total ^{M 1} volume, preferably 0.01 mol% or more, more preferably 0.1 mol% or more, more preferably It is 0.5 mol% or more, and is usually 10 mol% or less, preferably 8 mol% or less, more preferably 5 mol% or less.

In addition to the above, (NH ₄ ) may be partially contained as long as the performance is not affected. The content of (NH ₄ ) is usually 10 mol% or less with respect to the total amount of M ¹ .
In the above formula [1], M ² essentially includes at least a tetravalent metal element containing Si, and at least one metal element selected from the group consisting of a trivalent metal element and a pentavalent metal element. Is a metal element containing

Examples of the trivalent metal element contained in M ² include one or more selected from the group consisting of B, Al, Ga, In, Y, Sc, and rare earth elements. Among these, Al is preferable because it is closest to the ionic radius of Si.
Examples of the pentavalent metal element contained in M ² include one or more elements selected from the group consisting of V, P, Nb, and Ta. Among these, Ta is preferable in view of safety.

Among the above, M ² preferably contains a trivalent metal element together with a tetravalent metal element containing at least Si, and more preferably the trivalent metal element is Al.
Trivalent metal element, and the content of at least one metal element selected from the group consisting of pentavalent metallic element, the total M ² content, 0.001 mol% or more, preferably 0.01 Mol% or more, more preferably 0.1 mol% or more, further preferably 0.5 mol% or more, and usually 10 mol% or less, preferably 8 mol% or less, more preferably 5 mol% or less. .

M ² may contain one or more elements selected from the group consisting of Ge, Sn, Ti, Zr, Re, and Hf in addition to Si as a tetravalent metal element.
The content of Si is usually, Si is 90 mol% or more based on the total amount of tetravalent metal elements contained in M ^2, preferably 93 mol% or more, more preferably 95 mol% or more, more preferably Is 97 mol% or more, and it is particularly preferable that all of the tetravalent metal elements contained in M ² are Si.

In the above formula [1], R is an activation element containing at least Mn. As R, the activation element that may be contained other than Mn includes one or more selected from the group consisting of Cr, Fe, Co, Ni, Cu, Ru, and Ag.
R preferably contains 90 mol% or more, more preferably 95 mol% or more, more preferably 98 mol% or more, and more preferably contains only Mn, based on the total amount of R. preferable.

F in the above formula [1] represents fluorine. However, halogen elements other than fluorine may be included to such an extent that the light emission characteristics are not affected.
“2 + x” in the formula [1] is a number representing the number of moles of M ¹ . x is usually −1 or more, preferably −0.5 or more, and usually represents a number of 1 or less, preferably 0.5 or less. If the value of x is too large or too small, the light emission characteristics tend to deteriorate.

Z in the above formula [1] is a number representing the number of moles of R. z is usually 0.001 or more, preferably 0.005 or more, more preferably 0.01 or more, and usually represents a number of 0.4 or less, preferably 0.2 or less. If the value of z is too large or too small, the light emission characteristics tend to deteriorate.
N in the above formula [1] is a number representing the number of moles of F (fluorine). n is usually 5 or more, preferably 5.5 or more, and usually represents a number of 7 or less, preferably 6.5 or less, and n is particularly preferably 6. If the value of z is too large or too small, the durability tends to decrease.

Further, the value of “y + z” in the above formula [1] is usually 0.9 or more, preferably 0.95 or more, and usually 1.1 or less, preferably 1.05 or less. If the value of “y + z” is too large or too small, the light emission characteristics tend to deteriorate.
Fluorine complex phosphors in which trivalent or pentavalent ions coexist in addition to tetravalent ions as metal ions that serve as the coordination center of fluorine ions are also described in the aforementioned Patent Documents 1 to 3. It is a novel phosphor without suggestion.

  The phosphor of the present invention is preferably manufactured by the method described in the phosphor manufacturing method described later. In the phosphor manufacturing method, the phosphor raw material charge composition is obtained for the following reason. There is a slight deviation from the composition of the phosphor. The phosphor of the present invention is characterized by having the above-mentioned specific composition as the composition of the obtained phosphor, not the raw material composition at the time of phosphor production.

In the phosphor of the present invention, it is not yet clear how the trivalent metal element or the pentavalent metal element is present in the phosphor particles.
However, as described below, the phosphor particles are scanned using a scanning electron microscope and an energy dispersive X-ray analyzer (hereinafter referred to as “SEM-EDX”). By performing composition analysis, the elements contained in the phosphor particles can be identified. The phosphor of the present invention can detect elements (Na, Al, Ta, etc.) other than K, Si, and Mn from phosphor particles by SEM-EDX. That is, the phosphor particles constituting the phosphor of the present invention are considered to have elements (Na, Al, Ta, etc.) other than K, Si, and Mn in their chemical composition.

In the phosphor of the present invention, the ratio of Mn to the total number of moles of M ² and Mn obtained by SEM-EDX (in the present invention, this ratio is hereinafter referred to as “Mn concentration”) is 0.1 mol%. It is preferable that it is 40 mol% or less. If the Mn concentration is too low, the absorption efficiency of the excitation light by the phosphor decreases, so the luminance tends to decrease. If it is too high, the absorption efficiency increases, but the internal quantum efficiency and luminance decrease due to concentration quenching. Tend to. The preferred Mn concentration is 0.4 mol% or more, more preferably 1 mol% or more, particularly preferably 2 mol% or more, and 30 mol% or less, more preferably 25 mol% or less, and still more preferably 8 mol%. The mol% or less, particularly preferably 6 mol% or less.

In the phosphor of the present invention, the ratio of Na to the total number of moles of all M ¹ determined by SEM-EDX (in the present invention, this ratio is hereinafter referred to as “Na concentration”) is 0.001 mol% or more. Preferably it is 0.01 mol% or more, More preferably, it is 0.1 mol% or more, More preferably, it is 0.5 mol% or more, and it is 10 mol% or less normally, Preferably it is 8 mol% or less, More preferably, it is 5 mol% or more. It is less than mol%.

In the phosphor of the present invention, the ratio of Al to the total number of moles of M ² and Mn determined by SEM-EDX (in the present invention, this ratio is hereinafter referred to as “Al concentration”) is 0.001 mol%. Or more, preferably 0.01 mol% or more, more preferably 0.1 mol% or more, further preferably 0.5 mol% or more, and usually 10 mol% or less, preferably 8 mol% or less, more preferably Is 5 mol% or less.

  In the SEM-EDX method, in scanning electron microscope (SEM) measurement, a phosphor is irradiated with an electron beam (for example, acceleration voltage 20 kV), and characteristic X-rays emitted from each element contained in the phosphor are emitted. It detects and performs elemental analysis. As the measuring device, for example, an SEM (S-3400N) manufactured by Hitachi, Ltd. and an energy dispersive X-ray analyzer (EDX) (EX-250x-act) manufactured by Horiba, Ltd. can be used.

[1-2. Characteristics of phosphor
<Emission spectrum>
The phosphor of the present invention preferably has the following characteristics when the emission spectrum is measured by excitation with light having a peak wavelength of 455 nm.
The peak wavelength λp (nm) in the above-mentioned emission spectrum is usually larger than 600 nm, preferably 605 nm or more, more preferably 610 nm or more, and usually 660 nm or less, especially 650 nm or less. If the emission peak wavelength λp is too short, it tends to be yellowish, whereas if it is too long, it tends to be dark reddish, which is not preferable because the characteristics as orange or red light may be deteriorated.

In addition, the phosphor of the present invention has a full width at half maximum (hereinafter, abbreviated as “FWHM” where appropriate) in the above-described emission spectrum, which is usually larger than 1 nm, particularly 2 nm or more, and more preferably 3 nm. In addition, it is usually less than 50 nm, particularly 30 nm or less, more preferably 10 nm or less, and even more preferably 8 nm or less. Among these, a range of 7 nm or less is preferable. If this half-value width (FWHM) is too narrow, the emission peak intensity may decrease, and if it is too wide, the color purity may decrease.
Since the phosphor of the present invention uses Mn ⁴⁺ as an activation element, it has a spectral shape having a plurality of sharp emission peaks. The description of the emission peak wavelength and the half width is for each emission peak, but it is sufficient that at least the main emission peak satisfies this.

  In order to excite the phosphor with light having a peak wavelength of 455 nm, for example, a xenon light source can be used. The emission spectrum of the phosphor of the present invention can be measured by, for example, a fluorescence measuring apparatus (manufactured by JASCO Corporation) equipped with a 150 W xenon lamp as an excitation light source and a multichannel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measuring apparatus. ) Or the like. The emission peak wavelength and the half width of the emission peak can be calculated from the obtained emission spectrum.

<Quantum efficiency and absorption efficiency>
The phosphor of the present invention is more preferable as its internal quantum efficiency is higher. The value is usually 50% or more, preferably 75% or more, more preferably 85% or more, and particularly preferably 90% or more. If the internal quantum efficiency is low, the light emission efficiency tends to decrease, which is not preferable.
The phosphor of the present invention is more preferable as its external quantum efficiency is higher. The value is usually 20% or more, preferably 25% or more, more preferably 30% or more, and particularly preferably 35% or more. If the external quantum efficiency is low, the light emission efficiency tends to decrease, which is not preferable.

The phosphor of the present invention is preferably as its absorption efficiency is high. The value is usually 25% or more, preferably 30% or more, more preferably 42% or more, and particularly preferably 50% or more. If the absorption efficiency is low, the light emission efficiency tends to decrease, which is not preferable.
In addition, the said internal quantum efficiency, external quantum efficiency, and absorption efficiency can be measured by the method as described in the below-mentioned Example.

<Weight average median diameter _{D 50>}
Phosphor of the present invention, the weight-average median diameter _{D 50} is usually 3μm or more and preferably 10μm or more, and usually 50μm or less, and preferably among them 30μm or less. When the weight-average median diameter D ₅₀ is too small, and if the luminance is lowered, there is a case where phosphor particles tend to aggregate. On the other hand, when the weight-average median diameter D ₅₀ is too large, there is a tendency for blockage, such as uneven coating or a dispenser.

The weight-average median diameter D ₅₀ of the phosphor in the present invention, for example, can be measured using a device such as a laser diffraction / scattering particle size distribution measuring apparatus.
<Specific surface area>
The specific surface area of the phosphor of the present invention is usually 1.3 m ² / g or less, preferably 1.1 m ² / g or less, particularly preferably at 1.0 m ² / g or less, typically 0.05 m ² / g or more, In particular, it is preferably 0.1 m ² / g or more. If the specific surface area of the phosphor is too small, the phosphor particles are large, which tends to cause coating unevenness and clogging of the dispenser, etc. If too large, the phosphor particles are small, so the contact area with the outside increases and durability It becomes inferior.

In addition, the specific surface area of the phosphor in the present invention is measured by a BET one-point method, for example, using a fully automatic specific surface area measuring device (flow method) (AMS1000A) manufactured by Okura Riken.
<Particle size distribution>
The phosphor of the present invention preferably has one peak value in the particle size distribution.
A peak value of 2 or more indicates that there are a peak value due to single particles and a peak value due to aggregates thereof. Therefore, a peak value of 2 or more means that single particles are very small.

Therefore, a phosphor having a single particle size distribution peak value has large single particles and very few aggregates. As a result, the luminance is improved, and the specific surface area is reduced due to the large growth of single particles, thereby improving the durability.
In addition, the particle size distribution of the phosphor in the present invention can be measured by, for example, a laser diffraction / scattering particle size distribution measuring device (LA-300) manufactured by Horiba, Ltd. In the measurement, ethanol was used as a dispersion solvent, the phosphor was dispersed, the initial transmittance on the optical axis was adjusted to around 90%, and the influence of aggregation was minimized while stirring the dispersion solvent with a magnet rotor. It is preferable to perform measurement while suppressing the pressure to a minimum.

Further, the peak width of the particle size distribution is preferably narrow. Specifically, the quadrature deviation (QD) of the particle size distribution of the phosphor particles is usually 0.18 or more, preferably 0.20 or more, and usually 0.60 or less, preferably 0.40 or less. More preferably, it is 0.35 or less, More preferably, it is 0.30 or less, Most preferably, it is 0.25.
In addition, the quarter deviation of the particle size distribution becomes smaller as the particle diameters of the phosphor particles are uniform. That is, the fact that the quarter deviation of the particle size distribution is small means that the peak width of the particle size distribution is narrow and the sizes of the phosphor particles are uniform.

The quadrant deviation of the particle size distribution can be calculated using a particle size distribution curve measured using a laser diffraction / scattering particle size distribution measuring device.
<Particle shape>
The particle shape of the phosphor of the present invention recognized from the observation of the SEM photograph of the present invention is preferably a granular shape that grows uniformly in the triaxial direction. When the particle shape grows evenly in the triaxial direction, the specific surface area becomes small, and the contact area with the outside is small, so the durability is excellent.

In addition, this SEM photograph can be image | photographed, for example by Hitachi Ltd. SEM (S-3400N).
<Durability>
The phosphor of the present invention is excellent in durability. Specifically, a light-emitting device is manufactured using the phosphor of the present invention, and the luminance maintenance rate after leaving for 150 hours without lighting at room temperature of 85 ° C. and relative humidity of 85% is usually 75% or more, Preferably it is 85% or more, more preferably 90% or more.

The luminance maintenance rate can be obtained by the method described in the examples.
[1-3. Method for producing phosphor]
The method for producing the phosphor of the present invention is not particularly limited, but a method using a poor solvent as in the following method (1) and a method not using a poor solvent as in the following method (2). It is divided roughly into.

Each manufacturing method will be described below by taking as a representative example a case where M ¹ has K and Na, and M ² has Si as a tetravalent metal element and Al as a trivalent metal element.
(1) Poor solvent precipitation method.
(2) Two or more types of solutions containing one or more elements selected from the group consisting of K, Al, Na, Si, Mn, and F are mixed and supersaturated in the mixed solution to precipitate the phosphor. How to make.

In the method (2), it is preferable that the solution to be mixed contains all the elements constituting the phosphor to be produced. For example, there is a method of mixing a solution containing at least Na, Si, Mn, and F with a solution containing at least K, Al, and F.
However, it is not limited to the above combination, and after adding an aqueous solution containing a raw material of the target composition at room temperature without adding a poor solvent, the constituent elements are such that the fluoride is supersaturated and precipitated in the mixed solution May be combined.

(1) This method antisolvent precipitation method, for example, the ^M ₁ 2 SiF ₆ as the starting compound, the _{^{M 1 3 AlF 6, M 1}} 2
Using RF ₆ (wherein M ¹ and R have the same meanings as in the above formula [1]), these are added to hydrofluoric acid at a predetermined ratio and dissolved under stirring to react. Then, a phosphor poor solvent is added to deposit the phosphor. For example, it can be performed in the same manner as the method described in US Pat. No. 3,576,756.

  The method described in US Pat. No. 3,576,756 has a problem that the obtained phosphor particles are fine, have low luminance, and are not practical. On the other hand, the present inventors do not add the poor solvent at a time when adding the poor solvent to precipitate the phosphor, but slow down the addition rate of the poor solvent or add it separately. Thus, it has been found that a phosphor with higher luminance can be obtained.

As a combination of raw material compounds used in this poor solvent precipitation method,
1) A combination of K ₂ SiF ₆ , K ₂ NaAlF ₆ and K ₂ MnF ₆ ,
₂₎ a combination of K 2 SiF ₆ and _K 3 AlF _6, NaF, _K 2 MnF _6,
3) a combination of K 2 SiF ₆ and _K 3 AlF ₆ and _Na 3 AlF ₆ and _K 2 MnF _6,
4) a combination of K 2 SiF _6, KF, and _Na 3 AlF ₆ and _K 2 MnF _6,
5) A combination of K ₂ SiF ₆ , K ₂ NaAlF ₆ and KMnO ₄ ,
₆₎ a combination of K 2 SiF ₆ and _K 3 AlF _6, NaF, KMnO _4,
7) K ₂ SiF ₆ , K ₃ AlF ₆ , Na ₃ AlF ₆ and KMnO ₄ ,
8) A combination of K ₂ SiF ₆ , KF, Na ₃ AlF ₆ and KMnO ₄ ,
9) A combination of K ₂ SiF ₆ and K ₂ MnCl ₆ ,
₁₀₎ a combination of K 2 SiF ₆ and _K 3 AlF _6, NaF, _K 2 MnCl _6,
11) A combination of K ₂ SiF ₆ , K ₃ AlF ₆ , Na ₃ AlF ₆ and K ₂ MnCl ₆ , 12) A combination of K ₂ SiF ₆ , KF, Na ₃ AlF ₆ and K ₂ MnCl ₆ ,
Etc.

Here, instead of K ₂ SiF ₆ , a water-soluble potassium salt (KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO _3, etc.), hydrofluoric acid and H ₂ Combination with SiF ₆ aqueous solution, combination of water-soluble potassium salt, hydrofluoric acid and silicates (SiO ₂ , Si alkoxide, etc., the same shall apply hereinafter), potassium silicate (K ₂ SiO ₃ ) and fluoride A combination with hydroacid may be used.

The water-soluble potassium salt means a potassium salt having a solubility in water at 15 ° C. of 10% by weight or more (the same applies to the method (2) described later).
These raw material compounds are used in such a ratio that a phosphor having the desired composition can be obtained, but as described above, there is a slight difference between the composition of the phosphor raw material and the composition of the obtained phosphor. It is important to adjust the composition of the obtained phosphor so that it becomes the target composition.

The concentration of hydrogen fluoride is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight. It is used as the following aqueous solution. For example, when the hydrofluoric acid concentration is 40 to 50% by weight, it is used so that the ratio of hydrofluoric acid (concentration 40 to 50% by weight) to 1 g of K ₂ SiF ₆ is about 30 to 60 ml. preferable.

The reaction can be carried out at atmospheric pressure and room temperature (20-30 ° C.).
Usually, a raw material compound is added to and mixed with hydrofluoric acid at a predetermined ratio, and when all of the raw material compound is dissolved, a poor solvent is added.
As the poor solvent, an organic solvent having a solubility parameter of 10 or more and less than 23.4, preferably 10 to 15 is usually used. Here, the solubility parameter is defined as follows.

(Definition of dissolution parameters)
In the regular solution theory, the force acting between the solvent and the solute is modeled as only the intermolecular force, so it can be considered that the interaction causing the liquid molecules to aggregate is only the intermolecular force. Since the cohesive energy of the liquid is equivalent to the enthalpy of evaporation, the solubility parameter is defined as δ = √ (ΔH / V−RT) from the heat of molar evaporation ΔH and the molar volume V. That is, it is calculated from the parallel root (cal / cm ³ ) ^{1/2 of the} heat of evaporation required for evaporating a 1 molar volume of liquid.

  It is rare that the actual solution is a regular solution, and forces other than intermolecular forces such as hydrogen bonds also act between the solvent and solute molecules, and whether the two components mix or phase separate is a mixture of those components It is determined thermodynamically by the difference between enthalpy and mixed entropy. However, empirically, a substance having a solubility parameter (Solubility Parameter; hereinafter referred to as “SP value”) is likely to be mixed easily. Therefore, the SP value also serves as a standard for determining the ease of mixing of the solute and the solvent.

In regular solution theory, the force acting between the solvent and the solute is assumed to be only an intermolecular force, so the solubility parameter is used as a measure of the intermolecular force. Although an actual solution is not necessarily a regular solution, it is empirically known that the smaller the difference between the SP values of the two components, the greater the solubility.
Such poor solvents include acetone (solubility parameter: 10.0), isopropanol (solubility parameter: 11.5), acetonitrile (solubility parameter: 11.9), dimethylformamide (solubility parameter: 12.0), acetic acid. (Dissolution parameter: 1
2.6), ethanol (solubility parameter: 12.7), cresol (solubility parameter: 13.3), formic acid (solubility parameter: 13.5), ethylene glycol (solubility parameter: 14.2), phenol (solubility parameter) : 14.5), methanol (solubility parameter: 14.5 to 14.8) and the like. Among these, acetone is preferable because it does not contain a hydroxyl group (—OH) and dissolves well in water. These poor solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The amount of the poor solvent used varies depending on the type, but is usually 50% by volume or higher, preferably 60% by volume or higher, more preferably 70% by volume or higher, and usually 70% by volume with respect to the phosphor raw material-containing hydrofluoric acid. It is preferable to set it to 200 volume% or less, preferably 150 volume% or less, more preferably 120 volume% or less.
The addition of the poor solvent may be divided addition or continuous addition, but the addition rate of the poor solvent to the phosphor raw material-containing hydrofluoric acid is usually 400 ml / hour or less, preferably 100 to 350 ml / hour, which is a relatively slow addition. The speed is preferable for obtaining a high-luminance phosphor with a small specific surface area. However, if this rate of addition is too slow, productivity is impaired.

  The phosphor deposited by the addition of the poor solvent is recovered by solid-liquid separation by filtration or the like, and washed with a solvent such as ethanol, water, or acetone. Thereafter, the water adhering to the phosphor is evaporated at a temperature of usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. Although there is no restriction | limiting in particular in drying time, For example, it is about 1-2 hours.

(2) A method of precipitating a product (phosphor) by mixing a solution containing at least Na, Si, Mn, and F and a solution containing at least K, Al, and F. Since no flammable organic solvent is used as a poor solvent, safety is improved industrially; no organic solvent is used; therefore, the cost can be reduced; the same amount of fluorescence Since the hydrofluoric acid necessary for synthesizing the body is reduced to about one-half that of the method (1), the cost can be further reduced; In comparison, particle growth is further promoted, a specific surface area is small, a particle size is large, and a high-luminance phosphor excellent in durability can be obtained.

Examples of the solution containing at least Na, Si, Mn, and F (hereinafter sometimes referred to as “solution I”) include hydrofluoric acid containing Na, SiF ₆ source, and Mn source.
The SiF ₆ source of the solution I may be a compound containing Si and F and has excellent solubility in the solution. H ₂ SiF ₆ , Na ₂ SiF ₆ , (NH ₄ ) ₂ SiF ₆ , Rb ₂ SiF ₆ , Cs ₂ SiF ₆ or the like can be used. Of these, H ₂ SiF ₆ is preferred because of its high solubility in water and the absence of alkali metal elements as impurities. These SiF ₆ sources may be used alone or in combination of two or more thereof.

The Na source is a compound containing water-soluble Na and has only to be excellent in solubility in a solution. NaF, NaHF ₂ , NaOH, NaCl, NaBr, NaI, sodium acetate, Na ₂ CO ₃ etc. can be used. These Na sources may be used individually by 1 type, and may use 2 or more types together.
Further, as the Mn source, K ₂ MnF ₆ , KMnO ₄ , K ₂ MnCl ₆ or the like can be used. Among these, K ₂ MnF ₆ is preferable. Since it does not contain Cl element which tends to be destabilized by distorting the crystal lattice, it maintains MnF ₆ complex ion in hydrofluoric acid while maintaining the oxidation number (tetravalent) that can be activated. It is because it can exist stably.

Of the Mn sources, those containing K also serve as the K source.
The hydrogen fluoride concentration of hydrofluoric acid in Solution I is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, More preferably, it is 50% by weight or less. The SiF ₆ source concentration is usually 10% by weight or more, preferably 20% by weight or more, and usually 60% by weight or less, preferably 40% by weight or less. If the hydrogen fluoride concentration in the solution I is too low, Mn ions are easily hydrolyzed when a solution containing a Mn source described later is added to the solution I, and the activated Mn concentration is changed and synthesized. Since it becomes difficult to control the amount of Mn activation in the phosphor, the variation in the luminous efficiency of the phosphor tends to increase, and when it is too high, the risk of work tends to increase. Further, if the SiF ₆ source concentration is too low, the phosphor yield tends to decrease and the particle growth of the phosphor tends to be suppressed, and if too high, the phosphor particles tend to be too large.

On the other hand, examples of the solution containing at least K, Al, and F (hereinafter sometimes referred to as “solution II”) include hydrofluoric acid containing a K source and a Mn source.
As the K source of the solution II, water-soluble potassium salts such as KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO _{3 and the} like can be used. Among these, KHF ₂ is preferable. This is because it can be dissolved without lowering the concentration of hydrogen fluoride in the solution, and because the heat of dissolution is small, the safety is high.

As the Al source, AlF ₃ , K ₂ AlF ₅ , Na ₂ AlF ₅ , K ₃ AlF ₆ , and Na ₃ AlF ₆ can be used.
Each of these K source and Al source may be used alone or in combination of two or more.
The hydrogen fluoride concentration of hydrofluoric acid in Solution II is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight. % Or less, more preferably 50% by weight or less. The total concentration of K source and Al source is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and usually 45% by weight or less, preferably 40% by weight or less, more preferably. Is preferably 35% by weight or less. If the hydrogen fluoride concentration is too low, the raw material K ₂ MnF ₆ of the activation element contained in the solution I is unstable and easily hydrolyzed, and the Mn concentration changes drastically, so that the Mn activation in the synthesized phosphor Since it becomes difficult to control the amount, the variation in the luminous efficiency of the phosphor tends to increase, and when it is too high, the risk of work tends to increase. Further, if the K source and Al source concentrations are too low, the phosphor yield tends to decrease, and the phosphor particle growth tends to be suppressed. If it is too high, the phosphor particles tend to be too large. .

The mixing method of the solution I and the solution II is not particularly limited, and the solution II may be added and mixed while stirring the solution I, or the solution I may be added and mixed while stirring the solution II. good. Alternatively, the solution I and the solution II may be put into a container at a time and stirred and mixed.
By mixing the solution I and the solution II, the SiF ₆ source, the K source, the Na source, the Al source, and the Mn source react with each other at a predetermined ratio to precipitate the target phosphor crystal. The solid is separated and collected by filtration or the like, and washed with a solvent such as ethanol, water, or acetone. Thereafter, the water adhering to the phosphor is evaporated at a temperature of usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. Although there is no restriction | limiting in particular in drying time, For example, it is about 1-2 hours.

In mixing the solution I and the solution II, the composition of the phosphor as a product is changed to the target composition in consideration of the difference between the above-described composition of the phosphor raw material and the composition of the obtained phosphor. Therefore, it is necessary to adjust the mixing ratio of the solution I and the solution II.
[1-4. Surface treatment of phosphor]
The phosphor used in the present invention may be subjected to a surface treatment by applying a known method for the purpose of preventing unnecessary aggregation of the phosphor particles. However, care must be taken so that the phosphor is not deteriorated by such surface treatment.

[1-5. Use of phosphor]
The phosphor of the present invention can be used for any application using the phosphor. In addition, the phosphor of the present invention can be used alone, but two or more of the phosphors of the present invention can be used together, or the phosphor of the present invention and other phosphors It is also possible to use as a phosphor mixture of any combination.

  In addition, the phosphor of the present invention can be suitably used for various light-emitting devices (hereinafter referred to as “light-emitting device of the present invention”) taking advantage of the characteristic that it can be excited by blue light. Since the phosphor of the present invention is usually a red light-emitting phosphor, for example, when an excitation light source that emits blue light is combined with the phosphor of the present invention, a purple to pink light-emitting device can be manufactured. . In addition, the phosphor of the present invention is combined with an excitation light source that emits blue light and a phosphor that emits green light, or an excitation light source that emits near-ultraviolet light, a phosphor that emits blue light, and a fluorescence that emits green light. If the body is combined, the phosphor of the present invention emits red light when excited by blue light from an excitation light source that emits blue light or a phosphor that emits blue light, and thus a white light emitting device is manufactured. be able to.

The emission color of the light-emitting device is not limited to white, and by appropriately selecting the combination and content of phosphors, a light-emitting device that emits light in any color such as light bulb color (warm white) or pastel color is manufactured. can do. The light-emitting device thus obtained can be used as a light-emitting portion (particularly a liquid crystal backlight) or an illumination device of an image display device.
[2. Phosphor-containing composition]
The phosphor of the present invention can be used by mixing with a liquid medium. In particular, when the phosphor of the present invention is used for applications such as a light emitting device, it is preferably used in a form dispersed in a liquid medium. The phosphor of the present invention dispersed in a liquid medium will be referred to as “the phosphor-containing composition of the present invention” as appropriate.

[2-1. Phosphor]
There is no restriction | limiting in the kind of fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention, It can select arbitrarily from what was mentioned above. Moreover, the fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention 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 invention may contain a phosphor other than the phosphor of the present invention as long as the effects of the present invention are not significantly impaired.

[2-2. Liquid medium]
The kind of the liquid medium used for the phosphor-containing composition of the present invention is not particularly limited, and a curable material that can be molded over the semiconductor light emitting element can be used. The curable material is a fluid material that is cured by performing some kind of curing treatment. Here, the fluid state means, for example, a liquid state or a gel state. The curable material is not particularly limited as long as it ensures the role of guiding light emitted from the semiconductor light emitting element to the phosphor. Moreover, only 1 type may be used for a curable material and it may use 2 or more types together by arbitrary combinations and a ratio. Therefore, as the curable material, any of inorganic materials, organic materials, and mixtures thereof can be used.

As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof is solidified (for example, a siloxane bond). Inorganic materials having
On the other hand, examples of the organic material include a thermosetting resin and a photocurable resin. Specific examples include (meth) acrylic resins such as methyl poly (meth) acrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; Cellulose resins such as cellulose acetate and cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins.

  Since the phosphor-containing composition of the present invention has a fluorine complex phosphor, among these curable materials, there is little deterioration with respect to light emission from the semiconductor light emitting device, and it is excellent in alkali resistance, acid resistance, and heat resistance. Preference is given to using silicon-containing compounds. The silicon-containing compound is a compound having a silicon atom in the molecule, organic materials such as polyorganosiloxane (silicone compound), inorganic materials such as silicon oxide, silicon nitride, silicon oxynitride, borosilicate, phosphosilicate Examples thereof include glass materials such as salts and alkali silicates. Of these, silicone materials are preferred from the viewpoints of transparency, adhesion, ease of handling, mechanical and thermal adaptability relaxation characteristics, and the like.

The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and for example, condensation-type, addition-type, improved sol-gel type, photo-curing type silicone-based materials can be used.
As the condensed silicone material, for example, semiconductor light-emitting device members described in JP-A-2007-112973 to 112975, JP-A-2007-19459, JP-A-2008-34833, and the like can be used. Condensation-type silicone materials have excellent adhesion to components such as packages, electrodes, and light-emitting elements used in semiconductor light-emitting devices, so the addition of adhesion-improving components can be minimized, and crosslinking is mainly due to siloxane bonds. There is an advantage of excellent heat resistance and light resistance.

  Examples of the addition-type silicone material include potting silicone materials described in JP-A-2004-186168, JP-A-2004-221308, JP-A-2005-327777, JP-A-2003-183881, Organically modified silicone materials for potting described in JP-A-2006-206919, silicone materials for injection molding described in JP-A-2006-324596, silicone materials for transfer molding described in JP-A-2007-231173, etc. Can be suitably used. The addition-type silicone material has advantages such as a high degree of freedom of selection such as a curing rate and a hardness of a cured product, a component that does not desorb during curing, hardly shrinking due to curing, and excellent deep part curability.

  Moreover, as an improved sol-gel type silicone material that is one of the condensation types, for example, the silicone materials described in JP-A-2006-077234, JP-A-2006-291018, JP-A-2007-119569 and the like can be used. It can be used suitably. The improved sol-gel type silicone material has an advantage that it has a high degree of crosslinking, heat resistance, light resistance and durability, and is excellent in the protective function of a phosphor having low gas permeability and low moisture resistance.

As the photocurable silicone material, for example, silicone materials described in JP 2007-131812 A, JP 2007-214543 A, and the like can be suitably used. The ultraviolet curable silicone material has advantages such as excellent productivity because it cures in a short time, and it is not necessary to apply a high temperature for curing, so that the light emitting element is hardly deteriorated.
These silicone materials may be used alone, or a mixture of a plurality of silicone materials may be used if curing inhibition does not occur when mixed.

[2-3. Content ratio of liquid medium and phosphor]
The content of the liquid medium is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 25% by weight or more, preferably 40% by weight or more, based on the entire phosphor-containing composition of the present invention. The amount is usually 99% by weight or less, preferably 95% by weight or less, more preferably 80% by weight or less. When the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is desirable to use a liquid medium. On the other hand, when there is too little liquid medium, fluidity | liquidity may fall and it may become difficult to handle.

  The liquid medium mainly serves as a binder in the phosphor-containing composition of the present invention. The liquid medium may be used alone or in combination of two or more in any combination and ratio. For example, when using a silicon-containing compound for the purpose of improving heat resistance, light resistance, etc., other thermosetting resins such as an epoxy resin are contained so as not to impair the durability of the silicon-containing compound. Also good. In this case, the content of the other thermosetting resin is usually 25% by weight or less, preferably 10% by weight or less based on the total amount of the liquid medium as the binder.

  The content of the phosphor in the phosphor-containing composition of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 1% by weight or more with respect to the entire phosphor-containing composition of the present invention, Preferably it is 5 weight% or more, More preferably, it is 20 weight% or more, and is 75 weight% or less normally, Preferably it is 60 weight% or less. The proportion of the phosphor of the present invention in the phosphor in the phosphor-containing composition is also arbitrary, but is usually 30% by weight or more, preferably 50% by weight or more, and usually 100% by weight or less. If the phosphor content in the phosphor-containing composition is too high, the flowability of the phosphor-containing composition may be inferior and difficult to handle, and if the phosphor content is too low, the light emission efficiency of the light-emitting device decreases. There is a tendency.

[2-4. Other ingredients]
In the phosphor-containing composition of the present invention, other than the phosphor and the liquid medium, for example, a metal oxide for adjusting the refractive index described later, or a diffusing agent, unless the effect of the present invention is significantly impaired. Additives such as fillers, viscosity modifiers, and UV absorbers may be included. Only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

[3. Light emitting device]
The light-emitting device of the present invention (hereinafter referred to as “light-emitting device” as appropriate) includes a first light-emitting body (excitation light source), and a second light-emitting body that emits visible light when irradiated with light from the first light-emitting body. A light-emitting device having the above-described [1. It contains a first phosphor containing one or more of the phosphors of the present invention described in the section [Phosphor].

  As the phosphor of the present invention, a phosphor that emits fluorescence in the red region under irradiation of light from an excitation light source (hereinafter sometimes referred to as “the red phosphor of the present invention”) is usually used. The red phosphor of the present invention preferably has an emission peak in a wavelength range of 600 nm or more and 650 nm or less. Any one of the red phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.

By using the red phosphor of the present invention, the light-emitting device of the present invention exhibits high luminous efficiency with respect to an excitation light source (first light-emitting body) that emits light in a blue region. When used in a white light emitting device such as a display light source, the light emitting device is excellent.
Moreover, as a preferable specific example of the red phosphor of the present invention used in the light emitting device of the present invention, [1. Examples include the phosphor of the present invention described in the “Phosphor” column and the phosphor used in each Example in the “Example” column described below.

The light-emitting device of the present invention has a first light emitter (excitation light source), and at least the phosphor of the present invention is used as the second light emitter. It is possible to arbitrarily adopt the apparatus configuration. A specific example of the device configuration will be described later.
The light emission peak in the red region of the light emission spectrum of the light emitting device of the present invention preferably has a light emission peak in the wavelength range of 600 nm to 650 nm.

  The emission spectrum of the light-emitting device is measured by energizing 20 mA with a color / illuminance measurement software manufactured by Ocean Optics and a USB2000 series spectrometer (integral sphere specification) in a room maintained at a temperature of 25 ± 1 ° C. Can be done. Chromaticity values (x, y, z) can be calculated as chromaticity coordinates in the XYZ color system defined by JIS Z8701 from data in the wavelength region of 380 nm to 780 nm of the emission spectrum. In this case, the relational expression x + y + z = 1 holds. In the present specification, in the XYZ color system, those indicating only the chromaticity values x and y are normally expressed as (x, y).

  The light emitting device of the present invention preferably has a light emission efficiency of usually 10 lm / W or more, particularly 30 lm / W or more, particularly 50 lm / W or more. The luminous efficiency is obtained by obtaining the total luminous flux from the result of the emission spectrum measurement using the light emitting device as described above and dividing the lumen (lm) value by the power consumption (W). The power consumption is obtained by measuring a voltage using a True RMS Multimeters Model 187 & 189 manufactured by Fluke in a state in which 20 mA is energized, and obtaining the product of the current value and the voltage value.

  Among the light emitting devices of the present invention, in particular, as a white light emitting device, specifically, an excitation light source as described later is used as the first light emitter, and in addition to the red phosphor as described above, a blue light source as described later is used. A phosphor that emits fluorescence (hereinafter referred to as “blue phosphor” as appropriate), a phosphor that emits green fluorescence (hereinafter referred to as “green phosphor” as appropriate), and a phosphor that emits yellow fluorescence (hereinafter referred to as “yellow fluorescence” as appropriate). It is obtained by using known phosphors such as “body”) in any combination and adopting a known device configuration.

Here, the white color of the white light emitting device means all of (yellowish) white, (greenish) white, (blueish) white, (purple) white and white defined by JIS Z 8701 Of these, white is preferred.
[3-1. Configuration of light emitting device]
<3-1-1. First luminous body>
The 1st light-emitting body in the light-emitting device of this invention light-emits the light which excites the 2nd light-emitting body mentioned later.

The emission peak wavelength of the first illuminant is not particularly limited as long as it overlaps with the absorption wavelength of the second illuminant described later, and an illuminant having a wide emission wavelength region can be used. Usually, an illuminant having an emission wavelength from the ultraviolet region to the blue region is used, and it is particularly preferable to use an illuminant having an emission wavelength in the blue region.
As a specific numerical value of the emission peak wavelength of the first illuminant, 200 nm or more is usually desirable. Among these, when blue light is used as excitation light, the emission peak wavelength is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 480 nm or less, preferably 470 nm or less, more preferably 460 nm or less. It is desirable to use a luminescent material having the same. On the other hand, when near-ultraviolet light is used as excitation light, the phosphor of the present invention is excited by blue light from a phosphor that emits blue light when excited by near-ultraviolet light. It is preferable to select excitation light (near ultraviolet light) having a wavelength suitable for the band. Specifically, it is desirable to use a luminescent material having an emission peak wavelength of usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less, preferably 410 nm or less, more preferably 400 nm or less. .

  As the first light emitter, a semiconductor light emitting element is generally used, and specifically, a light emitting diode (LED), a laser diode (LD), or the like can be used. In addition, as a light-emitting body which can be used as a 1st light-emitting body, an organic electroluminescent light emitting element, an inorganic electroluminescent light emitting element, etc. are mentioned, for example. However, what can be used as a 1st light-emitting body is not restricted to what is illustrated by this specification.

Among these, as the first light emitter, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and emit very bright light with low power when combined with the phosphor. It is because it is obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. As the GaN-based LED and LD, those having an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer are preferable. Among them, since the emission intensity is very high, the GaN-based LED is particularly preferably one having an In _X Ga _Y N light emitting layer, and more preferably a multiple quantum well structure having an In _X Ga _Y N layer and a GaN layer. preferable.

In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is an n-type and p-type Al _X Ga _Y N layer, GaN layer, or In _X Those having a heterostructure sandwiched between Ga _Y N layers and the like are preferable because of high light emission efficiency, and those having a heterostructure having a quantum well structure are more preferable because of high light emission efficiency.

Note that only one first light emitter may be used, or two or more first light emitters may be used in any combination and ratio.
<3-1-2. Second luminous body>
The second light emitter in the light emitting device of the present invention is a light emitter that emits visible light when irradiated with light from the first light emitter described above, and contains the first phosphor including the red phosphor of the present invention. In addition, a second fluorescent material (a blue fluorescent material, a green fluorescent material, a yellow fluorescent material, an orange fluorescent material, etc.), which will be described later, is appropriately contained in accordance with the application. Further, for example, the second light emitter is configured by dispersing the first and second phosphors in a sealing material.

Used for the in the second luminescent material is not particularly limited to the phosphor composition other than the phosphor of the present invention, the host _{crystal, Y 2 O 3, YVO 4} , Zn 2 SiO 4, Y 3 Metal oxides typified by Al ₅ O ₁₂ , Sr ₂ SiO ₄ , metal nitrides typified by Sr ₂ Si ₅ N ₈ , phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl, and the like Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, sulfide represented by ZnS, SrS, CaS, etc., oxysulfide represented by Y ₂ O ₂ S, La ₂ O ₂ S, etc. A combination of rare earth metal ions such as Ho, Er, Tm, and Yb, and metal ions such as Ag, Cu, Au, Al, Mn, and Sb as activators or coactivators.

  Specific examples of preferred crystal matrixes are shown in the following table.

However, the matrix crystal and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.
Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the following examples, as described above, phosphors that differ only in part of the structure are omitted as appropriate.

<3-1-2-1. First phosphor>
The 2nd light-emitting body in the light-emitting device of this invention contains the 1st fluorescent substance containing the fluorescent substance of the above-mentioned this invention at least. Any one of the phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.
In addition to the phosphor of the present invention, a phosphor that emits fluorescence of the same color as the phosphor of the present invention (same color combined phosphor) may be used as the first phosphor. Usually, the phosphor of the present invention is a red phosphor. Therefore, as the first phosphor, other types of red phosphors or phosphors emitting orange fluorescence (hereinafter referred to as “orange phosphors” as appropriate). Can be used in combination.

  The weight median diameter of the first phosphor used in the light emitting device of the present invention is usually in the range of 2 μm or more, especially 5 μm or more, and usually 30 μm or less, especially 20 μm or less. When the weight median diameter is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

Any orange or red phosphor that can be used in combination with the phosphor of the present invention can be used as long as the effects of the present invention are not significantly impaired.
At this time, the emission peak wavelength of the orange to red phosphor, which is the same color combination phosphor, is usually 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm. It is preferable to be in the following wavelength range.

  The phosphors that can be used as such orange or red phosphors are shown in the following table.

Among these, as red phosphors, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, (La, Y) ₂ O ₂ S: Eu, Eu (dibenzoylmethane) ) ₃ · 1,10-phenanthroline complexes of β- diketone Eu complex, a carboxylic acid Eu _complex, K 2 _SiF 6: Mn is _{preferred, (Ca, Sr, Ba)} 2 Si 5 (N, O) 8: Eu, (Sr, Ca) AlSi (N, O): Eu, (La, Y) ₂ O ₂ S: Eu, and K ₂ SiF ₆ : Mn are more preferable.

As the orange phosphor, (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ba) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, ( Ca, Sr, Ba) AlSi (N, O) ₃ : Ce is preferred.
<3-1-2-2. Second phosphor>
The second light emitter in the light emitting device of the present invention may contain a phosphor (that is, a second phosphor) in addition to the first phosphor described above, depending on the application. The second phosphor is one or more phosphors having different emission peak wavelengths from the first phosphor. Usually, since these second phosphors are used to adjust the color tone of light emitted from the second light emitter, the second phosphor emits fluorescence having a color different from that of the first phosphor. Often phosphors are used. As described above, since a red phosphor is usually used as the first phosphor, examples of the second phosphor include phosphors other than the red phosphor such as a blue phosphor, a green phosphor, and a yellow phosphor. Is used.

Second phosphor weight-average median diameter D ₅₀ of which is used for the light emitting device of the present invention is usually 2μm or more and preferably 5μm or more, and usually 30μm or less is preferably in a range of inter alia 20μm or less. When the weight-average median diameter D ₅₀ is too small, and the luminance decreases tends to phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

<Blue phosphor>
When a blue phosphor is used in addition to the phosphor of the present invention, any blue phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, and further preferably 460 nm or less. It is preferable to be in the wavelength range. When the emission peak wavelength of the blue phosphor used is within this range, it overlaps with the excitation band of the phosphor of the present invention, and the phosphor of the present invention can be efficiently excited by the blue light from the blue phosphor. Because.

  The following table shows phosphors that can be used as such blue phosphors.

Among these, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba , Ca,
Mg, Sr) ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu are preferable (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Ca, Sr, Ba) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu, Ba ₃ MgSi ₂ O ₈ : Eu are more preferable, and Sr ₁₀ ( PO ₄ ) ₆ Cl ₂ : Eu, BaMgAl ₁₀ O ₁₇ : Eu are particularly preferred.

<Green phosphor>
When a green phosphor is used in addition to the phosphor of the present invention, any green phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 542 nm or less, and further preferably 535 nm or less. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and the characteristics as green light may deteriorate.

  The phosphors that can be used as such green phosphors are shown in the table below.

Among these, as the green phosphor, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr, Ba) ₂ SiO ₄ :
Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu, SrGa ₂ S ₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu and Mn are preferred.

When the obtained light-emitting device is used for a lighting device, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, (Sr , Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, Sr) ₃ Si ₆ O ₁₂ : N ₂ : Eu are preferable.

When the obtained light emitting device is used for an image display device, (Sr, Ba) ₂ SiO ₄ : Eu, (Si, Al) ₆ (O, N) ₈ : Eu (β-sialon), (Ba, _{sr) 3 Si 6 O 12:} N 2: Eu, SrGa 2 S 4: Eu, BaMgAl 10 O 17: Eu, Mn are preferable.
<Yellow phosphor>
When a yellow phosphor is used in addition to the phosphor of the present invention, any yellow phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred.

  The phosphors that can be used as such yellow phosphors are shown in the table below.

More in even, as the yellow _{phosphor, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, (Sr, Ca, Ba, Mg) 2 SiO 4: Eu, (Ca, Sr) Si ₂ N ₂ O ₂ : Eu is preferred.
Specifically, as an example of a preferable combination of a semiconductor light emitting element, a fluorine complex phosphor activated with Mn ⁴⁺ , and another phosphor when the light emitting device of the present invention is configured as a white light emitting device. Includes the following combinations (A) to (C).

(A) A blue light emitter (blue LED or the like) is used as a semiconductor light emitting element, the phosphor of the present invention is used as a red phosphor, and a green phosphor or a yellow phosphor is used as another phosphor. As the green phosphor, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu phosphor, (Ca, Sr) Sc ₂ O ₄ : Ce phosphor, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce-based phosphor, SrGa ₂ S ₄ : Eu-based phosphor, Eu-activated β-sialon-based phosphor, (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu-based phosphor, and M _One or two or more green phosphors selected from the group consisting of ₃ Si ₆ O ₁₂ N ₂ : Eu (where M represents an alkaline earth metal element) are preferred. The yellow phosphor may be one selected from the group consisting of Y ₃ Al ₅ O ₁₂ : Ce phosphor, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu phosphor, and α-sialon phosphor. Two or more yellow phosphors are preferred. A green phosphor and a yellow phosphor may be used in combination.

(B) A near-ultraviolet light emitter (near-ultraviolet LED or the like) is used as the semiconductor light-emitting element, the phosphor of the present invention is used as the red phosphor, and the blue phosphor and the green phosphor are used as the other phosphors. In this case, blue phosphors include (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu, and (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ). ) ₆ (Cl, F) ₂ : One or more blue phosphors selected from the group consisting of Eu are preferable. Further, as the green phosphor, in addition to the green phosphor exemplified in the above section (A), (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, Mn, (Ba, Sr, Ca) ₄ Al ₁₄ O ₂₅ : Eu and (Ba, Sr, Ca) Al ₂ O ₄ : One or more green phosphors selected from the group consisting of Eu are preferable.

(C) A blue light emitter (blue LED or the like) is used as the semiconductor light emitting element, the phosphor of the present invention is used as the red phosphor, and an orange phosphor is further used. In this case, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.
Further, the combination of the phosphors described above will be described more specifically below.
When a blue light emitting element such as a blue LED is used as a semiconductor light emitting element and used for a backlight of an image display device, the combinations shown in the following table are preferable.

  Table 7 shows more preferable combinations among the combinations shown in Table 6.

  Further, particularly preferred combinations are shown in Table 8.

Each color phosphor shown in Tables 6 to 8 is excited by the light in the blue region, emits light in a narrow band in the red region and the green region, respectively, and has excellent temperature characteristics that change in emission peak intensity due to temperature change is small. have.
Therefore, by combining two or more kinds of phosphors including these color phosphors with a semiconductor light emitting element that emits light in the blue region, the light emission efficiency for the color image display device of the present invention can be set higher than before. It can be set as the semiconductor light-emitting device suitable for the light source used for a light.

When a semiconductor light emitting element that emits light in the near ultraviolet or ultraviolet region and a phosphor are used in combination, the phosphor combinations shown in Tables 6 to 8 above are further combined with (Sr, Ca, Ba, Mg) ₁₀ ( PO ₄ ) ₆ (Cl, F): Eu, and (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu selected from the group consisting of Eu It is preferable to combine phosphors, and it is more preferable to combine (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F): Eu or (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu. preferable. At this time, it is preferable to combine BaMgAl ₁₀ O ₁₇ : Eu, Mn as the green phosphor.

[4. Embodiment of Light Emitting Device]
[4-1. Embodiment of Light Emitting Device]
Hereinafter, the light-emitting device of the present invention will be described in more detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and does not depart from the gist of the present invention. It can be implemented with arbitrary modifications.

  FIG. 1 is a schematic perspective view showing a positional relationship between a first light emitter serving as an excitation light source and a second light emitter configured as a phosphor containing portion having a phosphor in an example of the light emitting device of the present invention. Shown in In FIG. 1, reference numeral 1 denotes a phosphor-containing portion (second light emitter), reference numeral 2 denotes a surface-emitting GaN-based LD as an excitation light source (first light emitter), and reference numeral 3 denotes a substrate. In order to create a state in which they are in contact with each other, LD (2) and phosphor-containing portion (second light emitter) (1) are produced separately, and their surfaces are brought into contact with each other by an adhesive or other means. Alternatively, the phosphor-containing portion (second light emitter) may be formed (molded) on the light emitting surface of the LD (2). As a result, the LD (2) and the phosphor-containing portion (second light emitter) (1) can be brought into contact with each other.

When such an apparatus configuration is employed, the light loss is such that light from the excitation light source (first light emitter) is reflected by the film surface of the phosphor-containing portion (second light emitter) and oozes out. Therefore, the light emission efficiency of the entire device can be improved.
FIG. 2A is a typical example of a light emitting device of a form generally referred to as a shell type, and has a light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the light emitting device (4), reference numeral 5 denotes a mount lead, reference numeral 6 denotes an inner lead, reference numeral 7 denotes an excitation light source (first light emitter), reference numeral 8 denotes a phosphor-containing portion, reference numeral 9 denotes a conductive wire, reference numeral 10 Indicates a mold member.

  FIG. 2B is a representative example of a light-emitting device in a form called a surface-mount type, and light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the figure, reference numeral 22 is an excitation light source (first light emitter), reference numeral 23 is a phosphor-containing portion (second light emitter), reference numeral 24 is a frame, reference numeral 25 is a conductive wire, reference numerals 26 and 27 are electrodes. Respectively.

[4-2. Application of light emitting device]
The use of the light-emitting device of the present invention is not particularly limited, and can be used in various fields in which ordinary light-emitting devices are used. However, since the color rendering property is high and the color reproduction range is wide, the illumination device is particularly preferable. And as a light source for image display devices.
<4-2-1. Lighting device>
When the light-emitting device of the present invention is applied to a lighting device, the above-described light-emitting device may be appropriately incorporated into a known lighting device. For example, a surface-emitting illumination device (11) incorporating the above-described light-emitting device (4) as shown in FIG. 3 can be mentioned.

  FIG. 3 is a cross-sectional view schematically showing one embodiment of the illumination device of the present invention. As shown in FIG. 3, the surface-emitting illumination device has a number of light-emitting devices (13) (described above) on the bottom surface of a rectangular holding case (12) whose inner surface is light-opaque such as a white smooth surface. The light emitting device (4) corresponds to the lid portion of the holding case (12) by arranging a power source and a circuit (not shown) for driving the light emitting device (13) on the outside thereof. A diffuser plate (14) such as a milky white acrylic plate is fixed at a location for uniform light emission.

  Then, the surface emitting illumination device (11) is driven to apply light to the excitation light source (first light emitter) of the light emitting device (13) to emit light, and part of the light emission is converted into the phosphor. The phosphor in the phosphor-containing resin part as the containing part (second light emitter) absorbs and emits visible light, while having high color rendering due to color mixing with blue light or the like that is not absorbed by the phosphor. Luminescence is obtained, and this light is transmitted through the diffusion plate (14) and emitted upward in the drawing, so that illumination light with uniform brightness can be obtained within the surface of the diffusion plate (14) of the holding case (12). Become.

<4-2-2. Image display device>
When the light emitting device 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 it is preferably used together with a color filter. For example, when the image display device is a color image display device using color liquid crystal display elements, the light emitting device is used as 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, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
[Measurement method of physical properties]
The physical property values of the phosphors obtained in Examples and Comparative Examples described later were measured and calculated by the following methods.

{Luminescent properties}
<Emission spectrum>
The emission spectrum was measured at room temperature (25 ° C.) using a 150 W xenon lamp as an excitation light source and a fluorescence measuring apparatus (manufactured by JASCO Corporation) equipped with a multi-channel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measuring apparatus. did.

  More specifically, the light from the excitation light source was passed through a diffraction grating spectrometer having a focal length of 10 cm, and only the excitation light having a wavelength of 455 nm or less was irradiated to the phosphor through the optical fiber. The light generated from the phosphor by the irradiation of the excitation light is dispersed by a diffraction grating spectroscope having a focal length of 25 cm, the emission intensity of each wavelength is measured by a spectrum measuring device in a wavelength range of 300 nm to 800 nm, and a personal computer is used. An emission spectrum was obtained through signal processing such as sensitivity correction. In the measurement, the slit width of the light-receiving side spectroscope was set to 1 nm.

<Luminance>
The relative luminance is a range obtained by removing the excitation wavelength range from the emission spectrum in the visible range obtained by the above-described method, and similarly, from the stimulus value Y calculated in accordance with JIS Z8724 in the XYZ color system, excitation at a wavelength of 455 nm. Stimulus obtained in the same manner as the emission spectrum obtained by exciting the yellow phosphor Y ₃ Al ₅ O ₁₂ : Ce (product number: P46-Y3) manufactured by Kasei Optonics Co., Ltd. with light. The value Y was calculated as a relative value (hereinafter, sometimes simply referred to as “luminance”) with 100%.

<Excitation spectrum>
The excitation spectrum was measured using a fluorescence spectrophotometer F-4500 manufactured by Hitachi, Ltd. at room temperature (25 ° C.). More specifically, the red emission peak at 630 nm was monitored to obtain an excitation spectrum in the wavelength range of 300 nm to 550 nm.

{Phosphor particle shape}
<Scanning electron microscope (SEM) photograph>
The shape of the phosphor particles was observed using an SEM (S-3400N) manufactured by Hitachi, Ltd.
{Analysis of chemical composition}
<SEM-EDX method>
Chemical composition analysis of the Mn concentration contained in the phosphor is performed by using SEM (S-3400N) manufactured by Hitachi, Ltd., and energy dispersive X-ray analyzer (EDX) EX-250 x-act manufactured by Horiba, Ltd. Was measured by the SEM-EDX method. Specifically, in scanning electron microscope (SEM) measurement, the phosphor is irradiated with an electron beam at an accelerating voltage of 20 kV, and elemental analysis is performed by detecting characteristic X-rays emitted from each element contained in the phosphor. went.

<X-ray photoelectron spectroscopy (hereinafter referred to as “XPS”)>
{Analysis of surface chemical composition}
(XPS analysis)
The sample (phosphor) was measured using a Quantum 2000 manufactured by PHI under the following measurement conditions.
-X-ray source: Monochromatic Al-Kα, output 16 kV-34 W (X-ray generation area 170 μmφ)
・ Charge neutralization: Electron gun 2μA, combined use with ion gun
・ Spectroscopic system: Path energy
187.85 eV = wide spectrum
58.7 eV = Narrow spectrum [O1s, Na1s, Al2p, Mn2p]
29.35 eV = Narrow spectrum [C1s, F1s, Si2p, K2p]
・ Measurement area: 300μmφ
・ Extraction angle: 45 ° (from the surface)
{Quantum efficiency}
<Absorption efficiency α _q , internal quantum efficiency η _i , and external quantum efficiency η _o >
When obtaining the quantum efficiency (absorption efficiency α _q , internal quantum efficiency η _i and external quantum efficiency η _o ), first, the measurement accuracy of the phosphor sample (for example, phosphor powder) to be measured is maintained. Then, the surface was sufficiently smoothed and packed in a cell, and attached to a condenser such as an integrating sphere.

An Xe lamp was attached to the condensing device as an emission source for exciting the phosphor sample. In addition, adjustment was performed using a filter, a monochromator (diffraction grating spectrometer), or the like so that the emission peak wavelength of the emission source was monochromatic light of 455 nm.
The phosphor sample to be measured was irradiated with light from the light emission source whose emission peak wavelength was adjusted, and a spectrum including light emission (fluorescence) and reflected light was measured with a spectrometer (MCPD7000 manufactured by Otsuka Electronics Co., Ltd.). .

<Absorption efficiency α _q >
The absorption efficiency α _q was calculated as a value obtained by dividing the number of photons N _abs of excitation light absorbed by the phosphor sample by the total number of photons N of excitation light.
The specific calculation procedure is as follows.
First, the total photon number N of the latter excitation light was obtained as follows.

That is, a white reflector such as a “Spectralon” manufactured by Labsphere (having a reflectivity R of 98% for 455 nm excitation light) such as a material having a reflectivity R of almost 100% with respect to the excitation light is measured. The sample was attached to the above-described light collecting device in the same arrangement as the phosphor sample, and the reflection spectrum was measured using the spectrometer (this reflection spectrum is hereinafter referred to as “I _ref (λ)”).

From this reflection spectrum I _ref (λ), a numerical value represented by the following (formula I) was obtained. In addition, the integration interval of the following (Formula I) was 435 nm-465 nm. The numerical value represented by the following (formula I) is proportional to the total photon number N of the excitation light.

Moreover, the numerical value represented by the following (formula II) was calculated | required from the reflection spectrum I ((lambda)) when the fluorescent substance sample used as the measuring object of absorption efficiency (alpha) _q was attached to the condensing apparatus. Note that the integration interval in the above (formula II) is the same as the integration interval defined in the above (formula I). The numerical value obtained by the following (formula II) is proportional to the number of photons _Nabs of the excitation light absorbed by the phosphor sample.

From the above, the absorption efficiency α _q was calculated by the following equation.
Absorption efficiency α _q = N _abs / N = (Formula II) / (Formula I)
<Internal quantum efficiency η _i >
The internal quantum efficiency η _i was calculated as a value obtained by dividing the number of photons N _PL derived from the fluorescence phenomenon by the number of photons N _abs absorbed by the phosphor sample.

A numerical value represented by the following formula (III) was determined from the above I (λ). Note that the lower limit of the integration interval of (Formula III) was 466 nm to 780 nm. The numerical value calculated by the following (formula III) is
The number of photons derived from the fluorescence phenomenon is proportional to _NPL .

From the above, the internal quantum efficiency η _i was calculated by the following equation.
η _i = (Formula III) / (Formula II)
<External quantum efficiency η _o >
The external quantum efficiency η _o was calculated by taking the product of the absorption efficiency α _q obtained by the above procedure and the internal quantum efficiency η _i .

{Powder X-ray diffraction measurement for general identification}
Powder X-ray diffraction was precisely measured with a powder X-ray diffractometer X'Pert manufactured by PANalytical. The measurement conditions are as follows.
Using CuKα tube X-ray output = 45 kV, 40 mA
Divergence slit = automatic, irradiation width 10mm x 10mm
Detector = Semiconductor array detector X'Celerator used, Cu filter used Scanning range 2θ = 10 to 65 degrees Reading width = 0.0167 degrees Counting time = 10 seconds
[Raw materials]
The raw materials used in Examples and Comparative Examples described below are shown in the following table.

Producing K ₂ MnF ₆ for (Synthesis Example ₁₎ K 2 MnF ₆ can be obtained by the reaction formula shown below.

That is, after the KF powder was dissolved in hydrofluoric acid (47.3% by weight), the KMnO ₄ powder was dissolved in the solution. While stirring the solution, hydrogen peroxide water was added dropwise, and a yellow precipitate was obtained when the molar ratio of KMnO ₄ and H ₂ O ₂ reached 1.5. The precipitate was washed with acetone and dried at 130 ° C. for 1 hour to obtain K ₂ MnF ₆ .
In the following examples and comparative examples, K ₂ MnF ₆ synthesized as described above was used.

[Examples and Comparative Examples of Phosphor Production]
<Example 1-1>
4.73 g of KHF ₂ and 2.04 g of K ₃ AlF ₆ were weighed and dissolved in 80 ml of hydrofluoric acid (47.3 wt%).
On the other hand, 0.8678 g of K ₂ MnF ₆ and 0.3318 g of NaF were weighed and added to a mixed solution of 10 ml of an H ₂ SiF ₆ aqueous solution (33 wt%) and 40 ml of hydrofluoric acid (47.3% wt). And dissolved to prepare a solution.

While this solution was stirred at 26 ° C., hydrofluoric acid in which KHF ₂ and K ₃ AlF ₆ were dissolved was added to this solution to precipitate yellow crystals. The obtained crystals were designated as No. 1 After filtering with 5C filter paper, it was washed 3 times with 30 ml of ethanol and dried at 150 ° C. for 2 hours to obtain 4.8 g of a phosphor.
<Example 1-2>
0.6509 g of K ₂ MnF ₆ and 0.3317 g of NaF were weighed and added to a mixed solution of 5 ml of H ₂ SiF ₆ aqueous solution (33 wt%) and 20 ml of hydrofluoric acid (47.3% wt) to dissolve. To prepare a solution.

On the other hand, 2.2627 g of KHF ₂ and 2.0407 g of K ₃ AlF ₆ were weighed and dissolved in 40 ml of hydrofluoric acid (47.3 wt%).
While this solution was stirred at 26 ° C., a mixed solution of H ₂ SiF ₆ aqueous solution (33 wt%) in which K ₂ MnF ₆ and NaF were dissolved and hydrofluoric acid was added to this solution, and yellow solution was added. Crystal was precipitated. The obtained crystals were designated as No. 1 After filtering with 5C filter paper, it was washed with 30 ml of ethanol three times and dried at 150 ° C. for 2 hours to obtain 2.4 g of a phosphor.

<Example 1-3>
3.412 g of K ₂ MnF ₆ and 1.3252 g of NaF were weighed and added to a mixed solution of 40 ml of H ₂ SiF ₆ aqueous solution (33 wt%) and 160 ml of hydrofluoric acid (47.3% wt) to dissolve. A prepared solution was prepared.
On the other hand, 18.92 g of KHF ₂ and 8.16 g of K ₃ AlF ₆ were weighed and dissolved in 320 ml of hydrofluoric acid (47.3% by weight).

While this solution was stirred at 26 ° C., a mixed solution of 33 wt% H ₂ SiF ₆ aqueous solution and hydrofluoric acid in which K ₂ MnF ₆ and NaF were dissolved was added to this solution, and yellow crystals were added. Was precipitated. The obtained crystals were designated as No. 1 After filtering with 5C filter paper, it was washed 3 times with 50 ml of ethanol and dried at 150 ° C. for 2 hours to obtain 19.6 g of a phosphor.
<Comparative Example 1-1>
K ₂ SiF ₆ (1.77783 g) and K ₂ MnF ₆ (0.2217 g) are used as the raw material compounds so that the raw material composition of each phosphor becomes K ₂ Si _0.9 Mn _0.1 F _6. Under atmospheric pressure and room temperature, it was dissolved in 70 ml of hydrofluoric acid (47.3% by weight) with stirring. After all the raw material compounds were dissolved, 70 ml of acetone was added all at once while stirring the solution to precipitate the phosphor in a poor solvent. Each of the obtained phosphors was washed with ethanol and dried at 130 ° C. for 1 hour to obtain 1.7 g of the phosphor.

<Comparison of phosphors obtained in Examples 1-1, 1-2, 1-3, and Comparative Example 1-1>
For the phosphors obtained in Examples 1-1, 1-2, and 1-3 and Comparative Example 1-1, the Na, Al, and Mn concentrations obtained as a result of the composition analysis by SEM-EDX (“ (Analytical concentration (mol%))) The luminance (relative value when the yellow phosphor P46-Y3 manufactured by Kasei Optonix Co., Ltd. is set to 100) obtained from an emission spectrum obtained by excitation with light having a wavelength of 455 nm. Table 10 shows. About Example 1-3, the surface composition analysis value by XPS method was also performed. The results are shown in Table 10. From Table 10, it can be seen that the phosphor of Example 1-3 has a large amount of Na and Al on the surface.

Moreover, the emission spectrum and excitation spectrum of the phosphor of Example 1-1 are shown in FIG.
Further, in order to observe the shape of phosphor particles, etc., in each example and comparative example, SEM (manufactured by Hitachi, S-3400N) was used 1000 times (Example 1-1), 500 times (Example). SEM photographs were taken at 1-2, 1-3) or 5000 times (Comparative Example 1-1). The result is shown in FIG. FIG. 5 shows that each phosphor particle of the phosphor of the present embodiment example is larger than that of Comparative Example 1-1.

From the above results, it can be seen that the phosphors obtained in the examples contain Na ions and Al ions in the composition of the phosphor particles. Moreover, it turns out that the brightness | luminance which the phosphor obtained in the Example has improved notably compared with the phosphor of the comparative example which is manufactured by the conventionally well-known manufacturing method and does not contain Na ion or Al ion.
[Example of manufacturing light-emitting device]
<Example 2-1>
(Manufacture of phosphor-containing layer forming liquid)
Using the phosphor synthesized in Example 1-1, a phosphor-containing layer forming solution was produced. Specifically, the sealing agent liquid and the phosphor were weighed at the blending ratio shown in Table 11 below, and then mixed with a stirring deaerator “Awatake Rentaro AR-100” manufactured by Shinky Corporation.

(Production of light emitting device)
A 350 μm square chip GU35R460T manufactured by Showa Denko KK was used as a blue light emitting diode (hereinafter abbreviated as “LED” as appropriate). Specifically, this LED is bonded to the terminal at the bottom of the recess of the 3528 SMD type PPA resin package with a silicone resin-based transparent die bond paste, and then heated at 150 ° C. for 2 hours to cure the transparent die bond paste. A blue LED and a package electrode were wire-bonded using a gold wire with a diameter of 25 μm. This LED emits light with a dominant emission wavelength of 455 nm to 465 nm (emission peak wavelength of 451 nm to 455 nm) and a half width of the emission peak of 22 to 28 nm.

  Using a manual pipette, 4 μl of the phosphor-containing layer forming solution (including the phosphor synthesized in Example 1-1 as a red phosphor) obtained in the above (manufacturing the phosphor-containing layer forming solution). Weighed and poured into a light emitting device provided with the above-mentioned LED. This light-emitting device was kept in a desiccator box capable of reducing pressure under conditions of 25 ° C. and 1 kPa for 5 minutes to remove entrained bubbles, dissolved air, and moisture generated during injection. Thereafter, the semiconductor light-emitting device was held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the forming liquid, thereby obtaining a light-emitting device 2-1.

<Example 2-2>
The same as Example 2-1 except that the phosphor synthesized in Example 1-2 was used instead of the phosphor synthesized in Example 1-1 in the above (Manufacturing of phosphor-containing layer forming solution). Thus, a light emitting device of Example 2-2 was obtained.
<Example 2-3>
The same as in Example 2-1 except that the phosphor synthesized in Example 1-3 was used instead of the phosphor synthesized in Example 1-1 in the above (manufacturing the phosphor-containing layer forming solution). Thus, the light emitting device of Example 2-3 was obtained.

[Evaluation of Light Emitting Devices of Examples 2-1, 2-2, and 2-3]
About the light emitting device of each Example and each Comparative Example obtained as described above, durability was evaluated by performing a non-lighting test by the method described below.
<Non-lighting test>
A current of 20 mA was applied to the light-emitting device obtained in the example, and immediately after the start of lighting (this time point is hereinafter referred to as “0 hour”), a fiber multichannel spectrometer (USB2000 manufactured by Ocean Optics (integrated wavelength range: 200 nm)). The emission spectrum was measured using a light receiving system: integrating sphere (diameter: 1.5 inches).

Next, using the aging device, LED AGING SYSTEM 100ch LED environment test device (YEL-51005, manufactured by Yamakatsu Electronics Co., Ltd.), the light emitting device was not energized under the conditions of a temperature of 85 ° C. and a relative humidity of 85%. In the case of 150 hours, electricity was supplied only at the time of measurement, and the emission spectrum was measured in the same manner as in the case of 0 hour.
The values of various emission characteristics (luminance (lm)) calculated from the obtained emission spectrum are shown in Table 12 as relative values with the measured value at 0 hour as 100%.

  In the non-lighting test, the emission spectrum was measured by holding the spectrometer in a thermostatic chamber at 25 ° C. in order to prevent data disturbance due to the temperature change of the spectrometer main body.

  From the above results, it can be seen that the light emitting device using the phosphor of the present invention has high durability. This is considered due to the improvement in durability of the phosphors of Examples 1-1, 1-2, and 1-3 used in the light emitting device. That is, the phosphor of the present invention is a phosphor having both excellent light emission characteristics and durability.

  The present invention can be used in any field where light is used. For example, in addition to indoor and outdoor lighting, the present invention can be applied to image display devices for various electronic devices such as mobile phones, household appliances, and outdoor displays. It can be used suitably.

1 Phosphor-containing part (second light emitter)
2 Excitation light source (first light emitter) (LD)
3 Substrate 4 Light-emitting device 5 Mount lead 6 Inner lead 7 Excitation light source (first light emitter)
DESCRIPTION OF SYMBOLS 8 Fluorescent substance containing part 9 Conductive wire 10 Mold member 11 Surface emitting illuminating device 12 Holding case 13 Light emitting apparatus 14 Diffusion plate 23 Fluorescent substance containing part (2nd light emitter)
24 frame 25 conductive wire 26 electrode 27 electrode

Claims (10)

The chemical composition of the phosphor particles, wherein the benzalkonium represented by the following formula [1], the phosphor.
^{_{M 1 2 + x M 2 y}} R z F n ··· formula [1]
(Wherein, ^{M 1} is, an alkali metal elemental containing at least K.
M ² represents a metal element containing a trivalent metallic elemental containing at least Al is an essential tetravalent metallic element containing at least Si, further.
R represents an activation element containing at least Mn.
Moreover, x, y, z, and n represent the number which satisfy | fills the following formula | equation.
-1 ≦ x ≦ 1
0.9 ≦ y + z ≦ 1.1
0.001 ≦ z ≦ 0.4
5 ≦ n ≦ 7)   In the formula [1], all M ¹ The phosphor according to claim 1, wherein the content of K with respect to the amount is 90 mol% or more. In the formula [1], ^{M 1} is contained Na as the alkali metal element other than K, and the content of Na relative to all ^{M 1} content is 10 mol% or less, according to claim 1 or 2 The phosphor according to 1.   In the formula [1], all M ² The phosphor according to any one of claims 1 to 3, wherein the content of the trivalent metal with respect to the amount is 10 mol% or less.   In the formula [1], M ² The phosphor according to any one of claims 1 to 4, wherein the content of Si with respect to the amount of all tetravalent metals contained in said is 90 mol% or more. A phosphor-containing composition comprising the phosphor according to any one of claims 1 to 5 and a liquid medium. A light emitting device comprising: a first light emitter; and a second light emitter that emits visible light by irradiation of light from the first light emitter,
A light emitting device comprising a first phosphor containing one or more of the phosphors according to any one of claims 1 to 5 as the second phosphor. 8. The light emitting device according to claim 7 , wherein the second phosphor includes a second phosphor including one or more phosphors having emission peak wavelengths different from those of the first phosphor. 9. apparatus. Lighting apparatus comprising: a light-emitting device according to claim 7 or 8. The image display apparatus comprising: a light-emitting device according to claim 7 or 8.