JP2010232381A - Semiconductor light-emitting device, and image display and lighting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor light-emitting device which can utilize a phosphor that is superior in light-emitting characteristic but has a problem in chemical stability, and to provide an image display using the same, and a lighting device. <P>SOLUTION: The light-emitting device includes a light source and a phosphor absorbing at least a part of light from a light source and having a wavelength different from that of light from the light source, and also includes a semiconductor light-emitting element formed on a substrate having conductivity as a light source, and a fluorine complex phosphor activated by Mn<SP>4+</SP>as the phosphor. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a light emitting device using a semiconductor light emitting element and a phosphor, and an image display device and an illumination device using the light emitting device. More specifically, a semiconductor light-emitting device, a light-emitting device having a fluorine complex phosphor activated with Mn ⁴⁺ that generates light of different wavelengths by irradiation of light from the semiconductor light-emitting device, and the light-emitting device were used. The present invention relates to an image display device and an illumination device.

  Recently, a white light-emitting device composed of a combination of a gallium nitride (GaN) semiconductor light-emitting element and a phosphor as a wavelength conversion material takes advantage of the feature of low power consumption and long life. It attracts attention as a light source of the device. For example, a white light emitting device in which an In-doped GaN blue LED and a Ce-activated yttrium / aluminum / garnet yellow phosphor are combined can be cited as a typical light emitting device. In recent years, such white light-emitting devices are expected to be used for new applications such as backlights for displays, and accordingly, research and development of phosphors combined with semiconductor light-emitting elements are being promoted.

  A light-emitting device having a semiconductor light-emitting element (hereinafter sometimes referred to as “semiconductor light-emitting device”) often employs a form in which the periphery of the semiconductor light-emitting element is sealed with a resin containing a phosphor. In such a form, the phosphor is in a state of being easily affected by heat or the like emitted from the semiconductor light emitting element. For this reason, phosphors used in semiconductor light-emitting devices have been often selected as a first priority because they are less susceptible to the use environment such as moisture and are chemically stable.

On the other hand, in recent years, semiconductor light-emitting devices have been expected to be used for new applications such as displays as well as displays and lighting, and have desired emission characteristics within the range of conventional substances. However, the use of substances exceeding the conventional range has been studied.
Among them, a light emitting device using a Mn ⁴⁺ activated fluorine complex phosphor is known. For example, (1) a method of depositing a phosphor directly on a semiconductor light emitting element and sealing with a sealing member, (2) A method of uniformly dispersing the phosphor in the sealing member, and (3) a method of applying the phosphor to the surface or inner wall of the sealing capsule are exemplified (see Patent Documents 1 to 3). .

  In addition, in order to prevent the phosphor from deteriorating, there is known a method of forming a coating layer on the surface of the phosphor by a chemical vapor reaction method (CVD method) or by depositing a coating layer on the particle surface of the phosphor in a solution. (See Patent Document 4).

US Patent Publication 2006/0071589 US Patent Publication No. 2006/0169998 US Patent Publication No. 2007/0205712 JP 2005-82788 A

However, when the semiconductor light-emitting device is produced using the method described in the above-mentioned patent documents, it has been clarified by the inventors that the deterioration with time is severe and it cannot be put into practical use.
In addition, the method for coating the phosphor by the CVD method described in Patent Document 4 requires a special apparatus. Further, Patent Document 4 discloses another method of coating by depositing a coating layer on the surface of the phosphor particles in a solution, but is not suitable for a phosphor having low water resistance. Or difficult to apply to all phosphors.

Furthermore, as a result of preliminary investigations by the present inventors, even when a light-emitting device is manufactured using a host crystal of a phosphor that does not contain Mn ⁴⁺ that is an activating element, a semiconductor with time elapses. It has been found that the performance of the light emitting device is degraded. Was examined this phenomenon in more detail, in the semiconductor light-emitting device using activated with fluorine complex phosphor Mn ⁴⁺ is a deterioration of the semiconductor light-emitting element itself, fluorine complex phosphor itself is activated with Mn ⁴⁺ It turns out that there are two factors of deterioration.

  SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a semiconductor light emitting device capable of putting a phosphor having a problem in chemical stability to a practical use although it has excellent light emission characteristics, and the semiconductor. An object of the present invention is to provide an image display device and a lighting device using a light emitting device.

In view of the above problems, the present inventors have studied in detail the relationship between the structure of the semiconductor light emitting device itself and the Mn ⁴⁺ activated fluorine complex phosphor. As a result, when using a fluorine complex phosphor activated with Mn ⁴⁺ , the durability of the semiconductor light emitting device can be obtained by using a semiconductor light emitting element formed on a conductive substrate. It was found that can be improved.

In addition, the present inventors have found that the semiconductor light emitting device 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 (9).
(1) In a light emitting device including a light source and a phosphor that absorbs at least part of light from the light source and emits light having a wavelength different from that of the light from the light source, a conductive substrate as the light source It includes a semiconductor light emitting device formed above and characterized in that it comprises a fluorine complex phosphors activated with Mn ⁴⁺ as phosphor, the semiconductor light-emitting device.
(2) the ^{Mn 4+} activated with a fluorine complex phosphor, at 200 ° C., wherein the heating occurs fluorine amount per phosphor 1g is of more than 0.01 [mu] g / min, (1) The semiconductor light-emitting device described in 1.
(3) The fluorine complex phosphor activated with Mn ⁴⁺ has a solubility in 100 g of water at 20 ° C. of 0.005 g or more and 7 g or less, (1) or (2) The semiconductor light-emitting device described in the above.
(4) The fluorine complex phosphor activated by Mn ⁴⁺ has a main emission peak in a wavelength range of 610 nm or more and 650 nm or less, wherein any of (1) to (3) The semiconductor light-emitting device as described.
(5) The semiconductor light emitting device according to (4), wherein the half width of the main light emission peak is 10 nm or less.
(6) The rate of change of the emission peak intensity at 100 ° C. with respect to the emission peak intensity at 25 ° C. when the wavelength of the excitation light is 455 nm is 40% or less in the fluorine complex phosphor activated with Mn ⁴⁺ The semiconductor light-emitting device according to any one of (1) to (5), wherein
(7) The fluorine complex phosphor activated by Mn ⁴⁺ contains a crystal phase having a chemical composition represented by any one of the following formulas [1] to [8]. , (1)-(6) The semiconductor light-emitting device in any one of (6).

M ^I ₂ [M ^IV _1-x R _x F ₆ ] ... [1]
M ^I ₃ [M ^III _1-x R _x F ₆ ] ... [2]
M ^II [M ^IV _1-x R _x F ₆ ] ... [3]
M ^I ₃ [M ^IV _1-x R _x F ₇ ] ... [4]
M ^I ₂ [M ^III _1-x R _x F ₅ ] ... [5]
_{^{Zn 2 [M III 1-x}} R x F 7] ··· [6]
M ^I [M ^III _2-2x R _2x F ₇ ] ... [7]
Ba _0.65 Zr _0.35 F _2.70 : Mn ⁴⁺ ... [8]
(In the above formulas [1] to [8], M ^I represents one or more monovalent groups selected from the group consisting of Li, Na, K, Rb, Cs, and NH ₄ , and M ^II represents Represents an alkaline earth metal element, M ^III represents one or more metal elements selected from the group consisting of groups 3 and 13 of the periodic table, and M ^IV represents groups 4 and 14 of the periodic table And one or more metal elements selected from the group consisting of R and R represents an activating element containing at least Mn, and x is a numerical value in a range represented by 0 <x <1.)
(8) An image display device comprising the light-emitting device according to any one of (1) to (7).
(9) An illumination device comprising the light-emitting device according to any one of (1) to (7).

According to the present invention, it is possible to provide a semiconductor light emitting device with excellent durability even when a fluorine complex phosphor activated with Mn ⁴⁺ is used.
In addition, a semiconductor light emitting device having high color rendering properties can be provided by utilizing the light emission characteristics of the fluorine complex phosphor activated with Mn ⁴⁺ .
Furthermore, it is possible to provide an image display device and an illumination device with excellent durability using the semiconductor light emitting device of the present invention.

FIG. 1A is a cross-sectional view of a vertical semiconductor light emitting device. FIG. 1B is a cross-sectional view of a horizontal semiconductor light emitting device. It is sectional drawing of the light emitting element by one Embodiment (vertical structure) of this invention. It is a typical perspective view which shows one Example of the semiconductor light-emitting device of this invention. FIG. 4A is a schematic cross-sectional view showing an embodiment of the bullet-type light emitting device of the present invention, and FIG. 4B 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.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.
1) In addition, the numerical range represented using “to” in this specification means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
2) In addition, the relationship between the color name and the chromaticity coordinates in the specification is based on the JIS standard (JISZ8110).
3) In the phosphor composition formulas 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 “(Ba, Sr, Ca) Al ₂ O ₄ : Eu” has “BaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “CaAl ₂ O ₄ : Eu”. If: the _{"Ba 1-x Sr x Al 2} O 4 Eu ": the _{"Ba 1-x Ca x Al 2} O 4 Eu ": a _{"Sr 1-x Ca x Al 2} O 4 Eu " _{"Ba 1-x-y Sr x} Ca y Al 2 O 4: E
u ”are all shown comprehensively (where 0 <x <1, 0 <y <1, 0 <x + y <1).

[1. Semiconductor light emitting device]
The light emitting wavelength of the semiconductor light emitting device is not particularly limited as long as it overlaps with the absorption wavelength of the phosphor used, and a light emitting material in a wide light emitting wavelength region can be used. Among these, when blue light is used as excitation light, it is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, still more preferably 450 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm. Hereinafter, it is more preferable to use a light emitter having an emission peak wavelength of 460 nm or less. On the other hand, when using near ultraviolet light or ultraviolet light as excitation light, it is 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. It is desirable to use a light emitter having an emission peak wavelength.

The fluorine complex phosphor activated with Mn ⁴⁺ used in the present invention (hereinafter sometimes simply referred to as “fluorine complex phosphor”) is usually excited with blue light. Therefore, when using near-ultraviolet light or ultraviolet light, the fluorine complex phosphor is normally excited (indirectly excited) by blue light emitted by the blue phosphor excited by these lights. It is preferable to select excitation light having a wavelength that matches the excitation band of the blue phosphor.

  As the semiconductor light emitting device, for example, an InGaN-based, GaAlN-based, InGaAlN-based, ZnSeS-based semiconductor light-emitting device or the like grown on a substrate such as silicon carbide, sapphire, or gallium nitride by MOCVD or the like can be preferably used. . In order to achieve high output, the light source size may be increased or the number of light sources may be increased. Further, it may be an edge emitting type or a surface emitting type laser diode. Blue or near-ultraviolet LEDs are preferably used in that a light source with a large amount of light can be obtained because they have a wavelength that can excite phosphors efficiently.

Among these, GaN-based light emitting diodes (hereinafter sometimes referred to as “LEDs”) and LDs (laser diodes) using GaN-based compound semiconductors are preferable as the semiconductor light-emitting elements. 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, “ _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.

Only one semiconductor light emitting element may be used, or two or more semiconductor light emitting elements may be used in any combination and ratio.
As shown in FIGS. 1A and 1B, the semiconductor light emitting device includes a device having a vertical device structure and a device having a horizontal device structure. Among these, when a semiconductor light-emitting element having a vertical element structure formed on a conductive substrate is used, when a fluorine complex phosphor is used, the durability of the light-emitting device is improved. This is preferable in that deterioration of the light emitting device over time at 85 ° C. and humidity of 85% is suppressed.

Here, the vertical element structure means that a desired light emitting element structure is epitaxially grown on a conductive substrate, one electrode is formed on the substrate, and one electrode is further formed on the epitaxial growth layer. By doing so, it means a structure of a so-called vertical conduction type (vertical type) light emitting element in which current flows in the epitaxial growth direction.
A case where a semiconductor light emitting device is manufactured using a pn junction type element will be described below with reference to the drawings. FIG. 1A shows a vertical element structure and its current distribution, and FIG. 1B shows a horizontal element structure and its current distribution.

  In the vertical element structure shown in FIG. 1A, an n-type layer (104) and a p-type layer (103) are stacked on a conductive substrate (105), and a p-type electrode (101) is formed on the p-type layer (103). ) And a conductive substrate (105), and an n-type electrode (102) is formed. In this case, assuming that the direction perpendicular to the interface between the layers is the vertical direction, current flows only in the vertical direction in the conductive substrate (105), the n-type layer (104), and the p-type layer (103).

  The horizontal element structure shown in FIG. 1B is a structure taken when an element is formed on an insulating substrate such as sapphire. An n-type layer (104) and a p-type layer (103) are stacked on an insulating substrate (106), and the p-type layer (103) is exposed by a p-type electrode (101) and dry etching. The n-type electrode (102) is formed on (104). In this case, assuming that the horizontal direction to the interface between the layers is the horizontal direction, the current flows in the n-type layer (104) in the horizontal direction, so that the element resistance increases and the electric field is on the n-type electrode (102) side. The current distribution tends to be non-uniform due to concentration.

A typical example of the vertical element structure will be shown below.
As shown in FIG. 2, a semiconductor light emitting device (20) according to an embodiment of the present invention includes a substrate (21) and a compound semiconductor thin film crystal layer (hereinafter simply referred to as a thin film crystal layer) laminated on one of the substrates (21). Say). The thin film crystal layer includes, for example, a buffer layer (22), a first conductive type semiconductor layer including a first conductive type cladding layer (24), an active layer structure (25), and a second type including a second conductive type cladding layer (26). A conductive semiconductor layer and a contact layer (23) are laminated in this order from the substrate (21) side.

A second conductivity type side electrode (27) for current injection is disposed on a part of the surface of the contact layer (23), and the contact layer (23) and the second conductivity type side electrode (27) are in contact with each other. The part which becomes this becomes the 2nd electric current injection area | region (29) which inject | pours an electric current into a 2nd conductivity type semiconductor layer.
Moreover, the 1st conductivity type side electrode (28) is arrange | positioned at the surface on the opposite side to the said thin film crystal layer of a board | substrate (21), ie, a back surface.

By arrange | positioning a 2nd conductivity type side electrode (27) and a 1st conductivity type side electrode (28) as mentioned above, both are arrange | positioned on both sides of a board | substrate (21), and a semiconductor light-emitting device ( 20) is configured as a so-called vertical semiconductor light emitting device.
As the substrate (21), a conductive substrate or a part of an insulating substrate penetrated by a conductive material can be used. When using a conductive substrate, a GaN substrate, a ZnO substrate, etc. are mentioned besides a SiC substrate. In particular, an SiC substrate and a GaN substrate are preferable because the electrical resistance can be reduced and the conductivity can be increased.

The reason why the vertical element structure is preferable as the semiconductor light emitting element used in the light emitting device containing the Mn ⁴⁺ activated fluorine complex phosphor is not clear, but when the electrode surface after the durability test is observed with a microscope, it is compared with the horizontal element structure. It has been observed that LED chips having a vertical element structure have little electrode surface discoloration.
When the semiconductor light emitting device is energized, a corrosive substance (containing fluorine) is generated from the Mn ⁴⁺ activated fluorine complex phosphor, causing damage to the wire, and the damaged wire has increased resistance. It is considered a thing. A semiconductor light-emitting element having a vertical element structure is presumed to be preferable because it has one electrode on the upper side as compared with a horizontal element structure, so that damage to wires and electrodes is small and change in electrical conductivity is small. .

Furthermore, it is considered that the corrosive substance generated from the Mn ⁴⁺ activated fluorine complex phosphor when energized contains an ion conductive substance. In the case of having a horizontal element structure, since the distance between two electrodes is short, there is a high possibility that a leakage current flows between the electrodes. However, in a semiconductor light emitting element having a vertical element structure, the distance between two electrodes is high. Is likely to be less likely.

[2. Fluorine complex phosphor activated with Mn ⁴⁺ ]
The semiconductor light-emitting device of the present invention includes a phosphor that emits light when directly or indirectly excited by light emitted from the semiconductor light-emitting element. In the semiconductor light emitting device of the present invention, a fluorine complex phosphor activated with Mn ⁴⁺ is essential as the phosphor.
Fluorine complex phosphors activated with Mn ⁴⁺ tend to be poor in chemical stability, and in the structure of a conventionally known semiconductor light emitting device, various problems such as color misregistration occur when used for a long time. was there. On the other hand, the semiconductor light-emitting device of the present invention can be suitably used as a phosphor constituting a semiconductor light-emitting device together with a semiconductor light-emitting element, even if such a fluorine complex phosphor activated with Mn ⁴⁺ is used. Is.
The semiconductor light-emitting device of the present invention can be suitably used for a phosphor having the following characteristics among fluorine complex phosphors activated with Mn ⁴⁺ .

[2-1. Heat generated fluorine amount]
The fluorine complex phosphor has a heat generation fluorine amount per 1 g of the phosphor at 200 ° C. (hereinafter sometimes referred to as “heat generation F amount”) of 0.01 μg / min or more, particularly 0.1 μg / min or more. Furthermore, although it may be 1 μg / min or more, as described above, when combined with a semiconductor light emitting element having a vertical element structure, it is in a high temperature and high humidity state (for example, a temperature of 85 ° C. and a humidity of 85%). Thus, it is possible to suppress deterioration over time when the light emitting device is stored or lit. The amount of heat generated F per gram of the phosphor is preferably 2 μg / min or less from the environmental standard. Moreover, in order to reduce damage to the periphery of the phosphor, a phosphor of 1.5 μg / min or less can be preferably used.

The amount of F generated by heating can be measured by the following method.
A certain amount of phosphor is precisely weighed, placed in a platinum boat, and set in an alumina furnace core tube of a horizontal electric furnace. Next, while flowing argon gas at a flow rate of 400 ml / min, the temperature in the furnace is raised and the temperature of the phosphor reaches 200 ° C., and is held for 2 hours. Here, the entire amount of argon gas flowing through the furnace is absorbed in a KOH aqueous solution (concentration: 67 mM), and the absorbed solution is analyzed by a liquid chromatography method to determine the amount of F generated per minute per 1 g of phosphor.

[2-2. Solubility in water]
Further, the fluorine complex phosphor has a solubility in 100 g of water at room temperature of 20 ° C. of usually 0.005 g or more, preferably 0.010 g or more, more preferably 0.015 g or more, and usually 7 g or less, preferably 2g or less. As described above, even a phosphor having a relatively high solubility in water can be combined with a semiconductor light-emitting element having a vertical element structure as described above to achieve high temperature and high humidity (for example, temperature 85 ° C., humidity 85%), it is possible to suppress deterioration over time when the light emitting device is stored or lit.
For reference, the solubility of the hexafluoro complex is shown in the following table. The values listed in the table are based on the product safety data sheet (MSDS) attached to the reagent manufactured by Morita Chemical.

[2-3. Emission spectrum]
The fluorine complex phosphor used in 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, while if it is too long, it tends to be dark reddish, and 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.

  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.

[2-4. Quantum efficiency and absorption efficiency]
The fluorine complex phosphor used in 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.
The fluorine complex phosphor used in 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.
The fluorine complex phosphor used in the present invention is more preferable as its absorption efficiency is higher. The value is usually 25% or more, preferably 30% or more, more preferably 42% or more, and particularly preferably 50% or more. When the absorption efficiency is low, the light emission efficiency tends to decrease.
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.

[2-5. Particle size and shape of fluorine complex phosphor particles]
<Weight average median diameter _{D 50>}
Although there is no restriction | limiting in particular in the particle size of the fluorescent substance used for this invention, since the specific surface area is small and there exists a tendency for reaction with a water | moisture content to decrease, it is preferable that the particle size of fluorescent substance is large. Fluorine complex phosphor weight median diameter _{D 50} which is used in the present invention 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 fluorocomplex phosphor used in the present invention is usually 1.3 m ² / g or less, preferably 1.1 m ² / g or less, particularly preferably 1.0 m ² / g or less, and usually 0. .05m ² / g or more and among them 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 the present invention, the specific surface area of the phosphor is measured by the 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 fluorine complex phosphor used in 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 the present invention, the particle size distribution of the phosphor can be measured by, for example, a laser diffraction / scattering type particle size distribution measuring apparatus (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 about 1.

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 fluorine complex phosphor used in the present invention recognized from observation of a scanning microscope (hereinafter sometimes referred to as “SEM”) is preferably a granular shape that grows evenly 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).

[2-6. Temperature dependence of emission peak intensity]
The fluorine complex phosphor used in the present invention preferably has a small rate of change in emission peak intensity. Specifically, when the wavelength of the excitation light is 455 nm, the rate of change of the emission peak intensity at 100 ° C. with respect to the emission peak intensity when the phosphor temperature is 25 ° C. is usually 40% or less, preferably 30% or less. More preferably, it is 25% or less, more preferably 22% or less, particularly preferably 18% or less, most preferably 15% or less.

  The light emitted from the semiconductor light emitting element is absorbed by the phosphor and the binder holding the phosphor. As a result, the binder generates heat and heats the phosphor. In addition, the phosphor itself generates heat by the light emitted from the semiconductor light emitting element being absorbed by the phosphor. Furthermore, when the semiconductor light emitting element is energized to emit light, the light emitting element generates heat due to the electrical resistance inside the semiconductor light emitting element, and the temperature rises, whereby the phosphor is heated by heat transfer. The temperature of the phosphor reaches about 100 ° C. by these heating actions. The emission peak intensity of the phosphor depends on the temperature, and the emission peak intensity tends to decrease as the temperature of the phosphor increases.

On the other hand, the semiconductor light-emitting device of the present invention is usually combined with a fluorine complex phosphor having a light emission peak in the red region and other kinds of phosphors (for example, a green phosphor or a blue phosphor described later) in combination with a desired one. A light-emitting device having an emission color can be obtained.
Therefore, in order to prevent the overall color tone from changing even when light is continuously emitted from the semiconductor light emitting device, even if the emission peak intensity of each color phosphor changes due to a temperature rise, the balance is greatly lost. It is important not to.

For other types of phosphors used together with the fluorine complex phosphor, the change rate of the emission peak intensity at 100 ° C. with respect to the emission peak intensity at 25 ° C. is within the above range when the wavelength of the excitation light is 400 nm or 455 nm. It is preferable to prepare the composition and the like. As a result, even if the emission peak intensity of each color phosphor changes due to the temperature rise of each color phosphor, the change is relatively small between each color phosphor, so the color tone of the light emitted from the semiconductor light emitting device of the present invention is Overall, the change is small.
Here, specifically, the temperature dependence of the phosphor can be measured, for example, as follows.

[Temperature dependence measurement example]
The temperature dependence is measured by using, for example, a MCPD7000 multi-channel spectrum measurement device manufactured by Otsuka Electronics Co., Ltd. as an emission spectrum measurement device, a stage equipped with, for example, a color luminance meter BM5A, a cooling mechanism using a Peltier element, and a heating mechanism using a heater. Then, using a device equipped with a 150 W xenon lamp as the light source, the following procedure is performed.

  Place the cell containing the phosphor sample on the stage, change the temperature to 25 ° C and 100 ° C, check the surface temperature of the phosphor, and then remove the spectrum from the light source with a diffraction grating, wavelength 400nm or 455nm The phosphor is excited with the light, and the luminance value and the emission spectrum are measured. The emission peak intensity is obtained from the measured emission spectrum. Here, as a measured value of the surface temperature on the excitation light irradiation side of the phosphor, a value corrected by using a temperature measured value by a radiation thermometer and a thermocouple is used.

[2-7. Composition of Fluorine Complex Phosphor Activated with Mn ⁴⁺ ]
The fluorine complex phosphor activated with Mn ⁴⁺ used in the semiconductor light emitting device of the present invention is preferably at least one element selected from the group consisting of alkali metal elements, alkaline earth metal elements, and Zn. A phosphor containing at least one element selected from the group consisting of Group 3, Group 4, Group 13, and Group 14 of the Periodic Table and at least one element selected from a halogen element; Can be mentioned.

The fluorine complex phosphor activated with Mn ⁴⁺ is ^preferably a phosphor represented by the following formulas [1] to [8].
M ^I ₂ [M ^IV _1-x R _x F ₆ ] ... [1]
M ^I ₃ [M ^III _1-x R _x F ₆ ] ... [2]
M ^II [M ^IV _1-x R _x F ₆ ] ... [3]
M ^I ₃ [M ^IV _1-x R _x F ₇ ] ... [4]
M ^I ₂ [M ^III _1-x R _x F ₅ ] ... [5]
_{^{Zn 2 [M III 1-x}} R x F 7] ··· [6]
M ^I [M ^III _2-2x R _2x F ₇ ] ... [7]
Ba _0.65 Zr _0.35 F _2.70 : Mn ⁴⁺ ... [8]
(In the above formulas [1] to [8], M ^I represents one or more monovalent groups selected from the group consisting of Li, Na, K, Rb, Cs, and NH ₄ , and M ^II represents Represents an alkaline earth metal element, and M ^III represents one or more metal elements selected from the group consisting of Group 3 and Group 13 of the periodic table (hereinafter, description of the periodic table may be omitted). represents, M ^IV represents at least one metal element selected from the group consisting of group 4 and group 14, R represents, .x representing the activated element containing at least Mn is 0 <x <1 It is the numerical value of the range to be expressed.)
The M ^I, it is particularly preferable to contain one or more elements selected from the group consisting of K and Na.

The M ^II, preferably contains at least Ba, and particularly preferably Ba.
Preferable specific examples of M ^III include one or more metal elements selected from the group consisting of Al, Ga, In, Y, and Sc, and among these, selected from the group consisting of Al, Ga, and In. One or more metal elements are preferable, and at least Al is more preferable, and Al is particularly preferable.

Preferred examples of ^{M IV, Si, Ge, Sn} , Ti, and one or more metal elements selected from the group consisting of Zr, and among them Si, Ge, Ti, Zr are preferred, of which at least It is preferable to contain Si, and Si is particularly preferable.
x is preferably 0.004 or more, more preferably 0.010 or more, particularly preferably 0.020 or more, preferably 0.30 or less, more preferably 0.25 or less, and still more preferably 0. 0.08 or less, particularly preferably 0.06 or less.

Preferable specific examples of the compounds represented by the above formulas [1] to [8] include K ₂ [AlF ₅ ]: Mn ⁴⁺ , K ₃ [AlF ₆ ]: Mn ⁴⁺ , K ₃ [GaF ₆ ]: Mn ^{4+ _{, Zn 2 [AlF 7]:}} Mn 4+, K [In 2 F 7]: Mn 4+, K 2 [SiF 6]: Mn 4+, Na 2 [SiF 6]: Mn 4+, K 2 [TiF 6]: Mn ⁴⁺ , K ₃ [ZrF ₇ ]: Mn ⁴⁺ , Ba [TiF ₆ ]: Mn ⁴⁺ , K ₂ [SnF ₆ ]: Mn ⁴⁺ , Na ₂ [TiF ₆ ]: Mn ⁴⁺ , Na ₂ [ZrF ₅ ]: Mn ⁴⁺ , KRb [TiF ₆ ]: Mn ⁴⁺ , K ₂ [Si _0.5 Ge _0.5 F ₆ ]: Mn ⁴⁺ .

Among the phosphors represented by the above formulas [1] to [8], it is particularly preferable to contain a crystal phase having a chemical composition represented by the formula [1]. This is because the phosphor containing a crystal phase having the chemical composition represented by the formula [1] is less likely to cause crystal defects and is excellent in stability. Further, the _K 2 MnF ₆ containing ^{Mn 4+} complex ion _[MnF ^{6] 2-,} and _{K 2 TiF 6, K 2 SiF} 6, K 2 GeF 6, K 2 ZrF 6 maternal taking a similar crystal structure This is because these base materials are easily substituted in the state of [MnF ₆ ] ² -complex ion.

Among the compounds represented by the above formula [1], it contains a crystal phase having a chemical composition represented by the following formula [1 ′], and the ratio of Mn to the total number of moles of M ^IV ′ and Mn is 0.00. Use of a material having a specific surface area of not less than 1 mol% and not more than 40 mol% and having a specific surface area of 1.3 m ² / g or less is preferred from the viewpoint of the luminance of the obtained semiconductor light emitting device.
M ^I ' ₂ M ^IV ' F ₆ : R ... [1 ']
(In the formula [1 ′], M ^I ′ contains one or more elements selected from the group consisting of K and Na, and M ^IV ′ contains at least Si in the periodic table 4th. And represents one or more metal elements selected from the group consisting of Group 14 and Group 14, and R represents an activating element containing at least Mn.)
In the formula [1 ′], M ^I ′ contains one or more elements selected from the group consisting of K and Na. Any one of these elements may be contained alone, or two of them may be contained in any ratio. In addition to the above, an alkali metal element such as Li, Rb, and Cs or a part of (NH ₄ ) may be contained as long as the performance is not affected. The content of Li, Rb, Cs, or (NH ₄ ) is usually 10 mol% or less with respect to the total M ^I ′ amount.

Among these, M ^I ′ preferably contains at least K, and usually K is 90 mol% or more, preferably 97 mol% or more, more preferably 98 mol% or more, based on the total M ^I ′ amount. More preferably, it occupies 99 mol% or more, and it is particularly preferable to use only K.
In the above formula [1 ′], M ^IV ′ contains at least Si. Usually, Si is 90 mol% or more, preferably 97 mol% or more, more preferably 98 mol% or more, and even more preferably 99 mol% or more with respect to the total amount of M ^IV ′, and only Si is used. Is particularly preferred. That is, it is particularly preferable to contain a crystal phase having a chemical composition represented by the following formula [1 ″].

M ^I ′ ₂ SiF ₆ : R ... [1 ″]
(In Formula [1 ″], M ^I ′ and R have the same meanings as in Formula [1 ′] above.)
R is an activation element containing at least Mn, and R may be included in addition to Mn, and the activation element may be selected from the group consisting of Cr, Fe, Co, Ni, Cu, Ru, and Ag. 1 type, or 2 or more types.
R preferably contains 90 mol% or more of Mn relative to the total amount of R, more preferably 95 mol% or more, particularly preferably 98 mol% or more, and particularly preferably contains only Mn.

Phosphor of the present invention, (in the present invention, this ratio is referred to as the "Mn concentration".) The total proportion of Mn to moles of Mn and M ^{IV 'is} at least 0.1 mol% 40 mol% or less It is characterized by being. 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. More preferable Mn concentration is 0.4 mol or more, more preferably 1 mol% or more, particularly preferably 2 mol% or more, 30 mol% or less, more preferably 25 mol% or less, and still more preferably 8 mol%. Hereinafter, it is particularly preferably 6 mol% or less.

  In addition, 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, for the following reasons, There is a slight deviation from the composition of the phosphor obtained. 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.

Here, the ionic radius of ^{Mn 4+} (0.53 Å) is larger than the ionic radius (0.4 Å) of ^{Si 4+, Mn 4+} _is not totally dissolved in K 2 SiF _6, since the partial solid solution, In the phosphor of the present invention, the substantially activated Mn ⁴⁺ concentration is limited and reduced as compared with the charged composition. However, even when the concentration of Mn ⁴⁺ contained in the phosphor is low, according to the production method of the present invention, particle growth is promoted, so that sufficient absorption efficiency and luminance can be provided.

In addition, the chemical composition analysis of the Mn concentration contained in the phosphor in the present invention can be measured by, for example, SEM-EDX. In this method, in scanning electron microscope (SEM) measurement, the phosphor is irradiated with an electron beam (for example, an acceleration voltage of 20 kV), and characteristic X-rays emitted from each element contained in the phosphor are detected to detect the element. Analyze. 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.
In addition to the elements constituting the phosphor, the phosphor is one or two selected from the group consisting of Al, Ga, B, In, Nb, Mo, Zn, Ta, W, Re, and Mg. The above elements may be contained in a range that does not adversely affect the performance of the phosphor.

[2-8. Activated process for the preparation of fluorinated complex phosphor Mn ^4+]
The fluorine complex phosphor used in the present invention can be produced according to a known method by mixing raw materials containing each constituent element. Specifically, after dissolving each reagent in hydrofluoric acid, heating the solution and evaporating the phosphor to dryness (J. Electrochem. Soc. Vol. 120,
No.7, (1973), 942-947, US 2006169998A1) and a poor solvent precipitation method in which each reagent is dissolved in hydrofluoric acid and then a phosphor is precipitated by adding a poor solvent (US patent) No. 357
No. 6756) can be used.

In addition, in the case of the phosphor represented by the above formula [1 ′], those produced by the following method using no poor solvent are preferable to the above poor solvent precipitation method. Hereinafter, M ^{IV 'is} a typical example of the case of Si, a method will be described without using a poor solvent.
The method that does not use a poor solvent is “a mixture of two or more solutions containing one or more elements selected from the group consisting of K, Na, Si, Mn, and F, and then a precipitate ( In this method, it is preferable that all the elements constituting the target phosphor are contained in the solution to be mixed. Specific examples of the combination of the solutions to be mixed include the following 2-1) and the following 2-2).

2-1) A solution containing at least Si and F, and at least K (and / or Na)
And a solution containing Mn and F.
2-2) A method of mixing a solution containing at least Si, Mn and F with a solution containing at least K (and / or Na) and F.

Examples of the “solution containing at least Si and F” include hydrofluoric acid containing an SiF ₆ source (hereinafter referred to as “HF aqueous solution”), and the above “at least K (and / or Na)”. Examples of the “solution containing Mn, M and F” include an HF aqueous solution containing a K (and / or Na) source and a Mn source.

The “solution containing at least Si, Mn, and F” includes an HF aqueous solution containing a SiF ₆ source and a Mn source, and contains the above “at least K (and / or Na) and F. Examples of the “solution” include an aqueous HF solution containing a K (and / or Na) source.
Here, the SiF ₆ source is a compound containing Si and F, and any compound having excellent solubility in a solution may be used. H ₂ SiF ₆ , Na ₂ SiF ₆ , (NH ₄ ) ₂ SiF ₆ , Rb ₂ SiF ₆ , and Cs ₂ SiF ₆ can be used. Among these, H ₂ SiF ₆ is preferable because it has high solubility in water and does not contain an alkali metal element as an impurity. These SiF ₆ sources may be used alone or in combination of two or more thereof.

_The K source, KF, KHF 2, KOH, KCl, KBr, KI, potassium _acetate, may be a water-soluble potassium salts such as K 2 CO _3, dissolved without lowering the concentration of HF among others solution In addition, KHF ₂ is preferable because of its low heat of dissolution and high safety.
As the Mn source, K ₂ MnF ₆ , KMnO ₄ , K ₂ MnCl _6, etc. can be used, and among them, the Cl element that does not tend to destabilize the crystal lattice is not included. K ₂ MnF ₆ is preferable because it can stably exist in the HF acid aqueous solution as a MnF ₆ complex ion while maintaining the oxidation number (tetravalent) that can be obtained. Of the Mn sources, those containing K also serve as the K source.

The HF concentration of these HF aqueous solutions 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. The following is preferable.
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.

The total concentration of K source and Mn 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 35%. It is preferable that it is below wt%.
After the reaction, crystals of the target phosphor are precipitated. The crystals are recovered by solid-liquid separation by filtration or the like, washed with a solvent such as ethanol, water, acetone, etc., and usually 100 ° C. or higher, preferably 120 It is preferable to dry at a temperature of not less than 150 ° C, more preferably not less than 150 ° C, usually not more than 300 ° C, preferably not more than 250 ° C, more preferably not more than 200 ° C. The drying time is not particularly limited as long as the water adhering to the phosphor can be evaporated, but for example, it is dried for about 1 to 2 hours.

  When the phosphor represented by the above formula [1 '] is produced by the above method without using a poor solvent, the specific surface area tends to be small, which is preferable. In addition, the phosphor represented by the above formula [1 ′] produced by the method using no poor solvent has a tendency that the peak value of the particle size distribution becomes one, and the width of the peak of the particle size distribution. There is also a tendency to narrow. Specific numerical ranges such as specific surface area and particle size distribution in this case are as described in [2-5. This is the same as described in [Particle size and shape of fluorine complex phosphor particles].

[2-9. 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.

[3. Phosphors that can be used with fluorocomplex phosphors]
The semiconductor light-emitting device of the present invention may be used activated with fluorine complex phosphor Mn ⁴⁺ alone, two or more fluorine complex phosphor may be used together in any combination and in any ratio. Moreover, unless the effect of this invention is impaired remarkably, you may use together with a fluorine complex fluorescent substance other types of fluorescent substance by arbitrary combinations and a ratio. That is, the combination of phosphors to be used and the ratio thereof may be arbitrarily set according to the use of the semiconductor light emitting device.

Specifically, a semiconductor light emitting device, a fluorine complex phosphor activated with Mn ⁴⁺ , and a phosphor having an emission peak wavelength different from that of the fluorine complex phosphor so that a desired emission color can be obtained. Appropriate combinations are preferred.
For example, when the semiconductor light emitting device of the present invention is desired to emit red light, at least one fluorine complex phosphor activated with Mn ⁴⁺ may be used.

For example, when the semiconductor light-emitting device of the present invention is intended to emit white light, the fluorine complex phosphor activated with Mn ⁴⁺ usually emits red light. The blue phosphor and the green phosphor may be combined. When a blue light emitting semiconductor light emitting element is used, the green phosphor may be combined.
As will be described later, if necessary, an orange or red phosphor (same color combination phosphor) other than the fluorine complex phosphor activated with Mn ⁴⁺ may be used in combination.
Examples of phosphors that can be used in the semiconductor light emitting device of the present invention are shown below.

<Blue phosphor>
When a blue phosphor is used in addition to the fluorine complex phosphor activated with Mn ⁴⁺ , 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 fluorine complex phosphor activated by Mn ⁴⁺ , and the phosphor of the present invention is efficiently used by the blue light from the blue phosphor. This is because it can be excited well.
The following table shows phosphors that can be used as such blue phosphors.

以上の中でも、青色蛍光体としては、（Ｃａ，Ｓｒ，Ｂａ）ＭｇＡｌ_１０Ｏ_１７：Ｅｕ、（Ｓｒ，Ｃａ，Ｂａ，Ｍｇ）_１０（ＰＯ_４）_６（Ｃｌ，Ｆ）_２：Ｅｕ、（Ｂａ，Ｃａ，Ｍｇ，Ｓｒ）_２ＳｉＯ_４：Ｅｕ、（Ｓｒ，Ｃａ，Ｂａ，Ｍｇ）_１０（ＰＯ_４）_６（Ｃｌ，Ｆ）_２：Ｅｕ、（Ｂａ，Ｃａ，Ｓｒ）_３ＭｇＳｉ_２Ｏ_８：Ｅｕが好ましく、（Ｂａ，Ｓｒ）ＭｇＡｌ_１０Ｏ_１７：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）_１０（ＰＯ_４）_６（Ｃｌ，Ｆ）_２：Ｅｕ、Ｂａ_３ＭｇＳｉ_２Ｏ_８：Ｅｕがより好ましく、Ｓｒ_１０（ＰＯ_４）_６Ｃｌ_２：Ｅｕ、ＢａＭｇＡｌ_１０Ｏ_１７：Ｅｕが特に好ましい。

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 is preferred, (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 is more preferred, Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, BaMgAl ₁₀ O ₁₇ : Eu are particularly preferable.

<Green phosphor>
When a green phosphor is used in addition to the fluorine complex phosphor activated with Mn ⁴⁺ , 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.

以上の中でも、緑色蛍光体としては、Ｙ_３（Ａｌ，Ｇａ）_５Ｏ_１２：Ｃｅ、ＣａＳｃ_２Ｏ_４：Ｃｅ、Ｃａ_３（Ｓｃ，Ｍｇ）_２Ｓｉ_３Ｏ_１２：Ｃｅ、（Ｓｒ，Ｂａ）_２ＳｉＯ_４：Ｅｕ、（Ｓｉ，Ａｌ）_６（Ｏ，Ｎ）_８：Ｅｕ（β−ｓｉａｌｏｎ）、（Ｂａ，Ｓｒ）_３Ｓｉ_６Ｏ_１２：Ｎ_２：Ｅｕ、ＳｒＧａ_２Ｓ_４：Ｅｕ、ＢａＭｇＡｌ_１０Ｏ_１７：Ｅｕ，Ｍｎが好ましい。

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, Mn is 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 fluorine complex phosphor activated with Mn ⁴⁺ , 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.

以上の中でも、黄色蛍光体としては、Ｙ_３Ａｌ_５Ｏ_１２：Ｃｅ、（Ｙ，Ｇｄ）_３Ａｌ_５Ｏ_１２：Ｃｅ、（Ｓｒ，Ｃａ，Ｂａ，Ｍｇ）_２ＳｉＯ_４：Ｅｕ、（Ｃａ，Ｓｒ）Ｓｉ_２Ｎ_２Ｏ_２：Ｅｕが好ましい。

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.

<Orange to red phosphor>
If necessary, an orange to red phosphor (same color combination phosphor) other than the fluorine complex phosphor activated with Mn ⁴⁺ may be used in combination. Any orange or red phosphor that can be used in combination with the fluorine complex phosphor activated with Mn ⁴⁺ 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.

以上の中でも、赤色蛍光体としては、（Ｃａ，Ｓｒ，Ｂａ）_２Ｓｉ_５（Ｎ，Ｏ）_８：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）Ｓｉ（Ｎ，Ｏ）_２：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）ＡｌＳｉ（Ｎ，Ｏ）_３：Ｅｕ、（Ｓｒ，Ｂａ）_３ＳｉＯ_５：Ｅｕ、（Ｃａ，Ｓｒ）Ｓ：Ｅｕ、（Ｌａ，Ｙ）_２Ｏ_２Ｓ：Ｅｕ、Ｅｕ（ジベンゾイルメタン）_３・１，１０−フェナントロリン錯体等のβ−ジケトン系Ｅｕ錯体、カルボン酸系Ｅｕ錯体、Ｋ_２ＳｉＦ_６：Ｍｎが好ましく、（Ｃａ，Ｓｒ，Ｂａ）_２Ｓｉ_５（Ｎ，Ｏ）_８：Ｅｕ、（Ｓｒ，Ｃａ）ＡｌＳｉ（Ｎ，Ｏ）：Ｅｕ、（Ｌａ，Ｙ）_２Ｏ_２Ｓ：Ｅｕ、Ｋ_２ＳｉＦ_６：Ｍｎがより好ましい。
また、橙色蛍光体としては、（Ｓｒ，Ｂａ）_３ＳｉＯ_５：Ｅｕ、（Ｓｒ，Ｂａ）_２ＳｉＯ_４：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）_２Ｓｉ_５（Ｎ，Ｏ）_８：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）ＡｌＳｉ（Ｎ，Ｏ）_３：Ｃｅが好ましい。

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.

Specifically, in the case where the semiconductor light emitting device of the present invention is configured as a white light emitting device, an example of a preferable combination of a semiconductor light emitting element, a fluorine complex phosphor activated with Mn ⁴⁺ , and another phosphor. Examples of the combinations include the following combinations (A) to (C).
(A) A blue light emitter (blue LED or the like) is used as a semiconductor light emitting element, a fluorine complex phosphor activated with Mn ⁴⁺ is used as a red phosphor, and a green phosphor or a yellow phosphor is used as another phosphor. Is used. 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 is a kind 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 a semiconductor light-emitting element, a fluorine complex phosphor activated with Mn ⁴⁺ is used as a red phosphor, and a blue phosphor and a green phosphor are used as other phosphors. Use 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 two or more of the green phosphor selected from the group consisting of Eu is preferred.
A blue luminous body (blue LED or the like) as (C) the semiconductor light emitting element, using activated with fluorine complex phosphor Mn ⁴⁺ as a red phosphor, further using the orange phosphor. In this case, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

As described above, the fluorine complex phosphor activated with Mn ⁴⁺ is preferably a phosphor represented by the formula [1], more preferably a fluorescence represented by the formula [1 ′]. More preferably, the phosphor is combined with the phosphor represented by the formula [1 ″].
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.

また、表６に示した組み合わせの中でもより好ましい組み合わせを表７に示す。

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

さらに、特に好ましい組み合わせを表８に示す。

Further, particularly preferred combinations are shown in Table 8.

表６〜８に示す各色蛍光体は、青色領域の光で励起され、それぞれ赤色領域、および緑色領域の中でも狭帯域で発光し、かつ温度変化による発光ピーク強度の変化が少ないという優れた温度特性を有している。

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 solid light emitting element that emits light in the near ultraviolet to 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. Sealing material]
[4-1. Cured material]
The semiconductor light emitting element is preferably sealed with a sealing material. When the semiconductor light emitting element is sealed with a sealing material, the phosphor may be contained in the sealing material, and the sealing material may also serve as a binder.
The kind of the sealing material 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 secures the role of guiding the light emitted from the solid 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 poly (meth) acrylic acid methyl; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; Cellulose resins such as cellulose acetate and cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins and the like.

  Since the semiconductor light-emitting device of the present invention has a fluorine complex fluorescent substance, among these curable materials, there is little deterioration with respect to light emission from the semiconductor light-emitting element, and the silicon-containing material also has excellent alkali resistance, acid resistance, and heat resistance. Preference is given to using 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 in selection such as a curing speed 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.

[4-3. Phosphor content]
The amount of phosphor used in the semiconductor light emitting device of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, and can be freely selected according to the application form.
The ratio of the total weight of the phosphor to the total weight of the phosphor-containing part is usually 3% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and usually 50% by weight or less, preferably It is 28 wt% or less, more preferably 25 wt% or less.
In addition, when the curable material changes in weight in the curing step, such as when the curable material contains a solvent or the like, the phosphor content relative to the total weight of the curable material and the phosphor after the curing step The rate may be the same as the phosphor content in the phosphor-containing portion.

  The phosphor content is particularly suitable for obtaining white light. Accordingly, the specific phosphor content varies depending on the target color, the luminous efficiency of the phosphor, the color mixture format, the specific gravity of the phosphor, the coating film thickness, and the shape of the optical member, and is not limited thereto.

[5. Semiconductor 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.

  In the example of the light-emitting device of the present invention, a semiconductor light-emitting element serving as an excitation light source (hereinafter sometimes referred to as “first light-emitting body”) and a second phosphor configured as a phosphor-containing portion having a phosphor. A schematic perspective view showing the positional relationship with the light emitter is shown in FIG. In FIG. 3, reference numeral 1 denotes a phosphor-containing portion (second light emitter), reference numeral 2 denotes a surface-emitting GaN 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. 4A is a typical example of a light emitting device of a form generally referred to as a shell type, and includes a semiconductor 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 a light-emitting device. In the semiconductor light emitting device (4), reference numeral 5 is a mount lead, reference numeral 6 is an inner lead, reference numeral 7 is a semiconductor light emitting element (first light emitter) as an excitation light source, reference numeral 8 is a phosphor-containing portion, and reference numeral 9 is A conductive wire, code | symbol 10 points out a mold member, respectively.

  FIG. 4B is a typical example of a semiconductor light emitting device of a form called a surface mount type, and has 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 a light-emitting device. In the figure, reference numeral 7 is an excitation light source (first light emitter), reference numeral 8 is a phosphor-containing portion (second light emitter), reference numeral 15 is a frame, reference numeral 16 is a conductive wire, reference numerals 17 and 18 are electrodes. Respectively.

[6. Application of semiconductor light emitting device]
The application of the semiconductor light-emitting device of the present invention is not particularly limited, and can be used in various fields in which ordinary semiconductor light-emitting devices are used. However, since the color rendering property is high and the color reproduction range is wide, It is particularly preferably used as a light source for an illumination device or an image display device.
<6-1. 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 semiconductor light-emitting device (4) as shown in FIG. 5 can be mentioned.

  FIG. 5 is a cross-sectional view schematically showing an embodiment of the illumination device of the present invention. As shown in FIG. 5, 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. A semiconductor light emitting device (4) corresponds to the lid of the holding case (12), and is provided with a power supply and a circuit (not shown) for driving the light emitting device (13) provided outside thereof. A diffusion plate (14) such as an acrylic plate made of milky white is fixed at a place to be made 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.

<6-2. 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 this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.
Using the following semiconductor light-emitting elements, phosphors, and phosphor-containing layer forming liquids, semiconductor light-emitting devices of Examples and Comparative Examples to be described later were prepared, and durability was evaluated by lighting tests.

<Semiconductor light emitting device>
(Production Example 1-1) Vertical Semiconductor Light-Emitting Element As a semiconductor light-emitting element (A), a 290 μm square chip “C460EZ290” manufactured by Cree Co., Ltd. is a silicone resin-based transparent die-bond paste, and the bottom of the concave portion of the 3528 SMD type PPA resin package. Bonded to the terminal. At this time, one bonding wire was used.
(Production Example 1-2) Horizontal Semiconductor Light-Emitting Element As the semiconductor light-emitting element (A), a 350 μm square chip “GU35R460T” manufactured by Showa Denko KK is a silicone resin-based transparent die-bond paste, and the bottom of the concave portion of the 3528 SMD type PPA resin package is used. Bonded to the terminal. At this time, the number of bonding wires was two.

<Phosphor>
(Synthesis Example 1) Red phosphor K ₂ TiF ₆ : Mn ⁴⁺
As raw material compounds, 4.743 g of K ₂ TiF ₆ and 0.2596 g of K ₂ MnF ₆ were used so that the charged composition of the phosphor was K ₂ Ti _0.95 Mn _0.05 F ₆ . Under the conditions of atmospheric pressure and room temperature, these raw material compounds were added to 40 ml of hydrofluoric acid (concentration: 47.3% by weight) and dissolved by stirring. After confirming that each raw material compound was completely dissolved, 60 ml of acetone was added at a rate of 240 ml / hour while stirring the solution to precipitate the phosphor in a poor solvent. The obtained phosphor was washed with acetone and then dried at 100 ° C. for 1 hour.

From the X-ray diffraction pattern of the obtained phosphor, it was confirmed that K ₂ Ti _1-x Mn _x F ₆ was synthesized. Moreover, the peak wavelength of the obtained red phosphor main emission peak is 631 nm,
The half width of the main emission peak was 7 nm, and the internal quantum efficiency measured by the method described below was 65%.
Further, the amount of F generated by heating of this phosphor and the rate of change of the emission peak intensity were measured by the methods described below, and the results are shown in Table 9.

<Measurement method of quantum efficiency>
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 having the adjusted emission peak wavelength, 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. 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). In addition, the lower limit of the integration section of (Formula III) was set to 466 nm to 780 nm. Figures are calculated by the following (Formula III) is proportional to the number N _PL of photons originating from the fluorescence phenomenon.

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 .

<Measurement method of amount of F generated by heating>
After precisely weighing 1 g of the phosphor, it was placed in a platinum boat and set in an alumina furnace core tube of a horizontal electric furnace. Next, while circulating argon gas at a flow rate of 400 ml / min, the temperature in the furnace was increased and the phosphor was maintained at 200 ° C. for 2 hours.
Here, the total amount of argon gas flowing through the furnace was absorbed in a KOH aqueous solution (concentration: 67 mM), and the absorbed solution was analyzed by a liquid chromatography method to determine the amount of F generated per minute per 1 g of phosphor. .

<Measurement method of change rate of emission peak intensity>
The change rate of the emission peak intensity is measured by using an MCPD7000 multi-channel spectrum measurement device manufactured by Otsuka Electronics as a light emission spectrum measurement device, a stage equipped with a cooling mechanism using a Peltier element and a heating mechanism using a heater, and a device equipped with a 150 W xenon lamp as a light source. The following procedure was followed.

A cell containing a phosphor sample is placed on the stage, the temperature is changed from 25 ° C. to 150 ° C., the surface temperature of the phosphor is confirmed, and then light with a wavelength of 455 nm is extracted from the light source by a diffraction grating. The phosphor was excited with and the emission spectrum was measured. From the measured emission spectrum, the emission peak intensity at 25 ° C. and the emission peak intensity at 100 ° C. were obtained, and the change rate (%) of the emission peak intensity was obtained from the following formula [A].
{1- (luminescence peak intensity at 100 ° C.) / (Luminescence peak intensity at 25 ° C.)} × 100 (A)
In addition, as a measured value of the surface temperature on the excitation light irradiation side of the phosphor, a value corrected using a temperature measured value by a radiation thermometer and a thermocouple was used.
(Synthesis Example 2) the red phosphor _K 2 _SiF 6: ^{Mn 4+}
As raw material compounds, 1.7783 g of K ₂ SiF ₆ and 0.2217 g of K ₂ MnF ₆ were used so that the charged composition of the phosphor was K ₂ Si _0.9 Mn _0.1 F ₆ . Under the conditions of atmospheric pressure and room temperature, these raw material compounds were added to 70 ml of hydrofluoric acid (47.3% by weight) and dissolved by stirring. After confirming that all the raw material compounds were dissolved, 70 ml of acetone was added at a rate of 240 ml / hour while stirring the solution to precipitate the phosphor in a poor solvent.

The obtained phosphor was washed with ethanol and dried at 130 ° C. for 1 hour to obtain 1.7 g of the phosphor. From the X-ray diffraction pattern of the obtained phosphor, it was confirmed that K ₂ SiF ₆ : Mn was synthesized. Moreover, the peak wavelength of the obtained red phosphor main emission peak was 630 nm, the half width of the main emission peak was 7 nm, and the internal quantum efficiency measured by the method described above was 94%.

  In addition, Table 9 shows the amount of F generated by heating the phosphor and the rate of change of the emission peak intensity.

（製造例２） フッ素錯体蛍光体含有層形成液の製造
信越化学社製シリコーン樹脂ＳＣＲ１０１６を１００重量部と、前述の合成例１又は合成例２で合成した蛍光体それぞれ１２重量部とを、シンキー社製攪拌脱泡装置ＡＲ−１００にて混合して、蛍光体含有層形成液（１）及び（２）を製造した。
［実施例１］ 半導体発光装置の作製
手動ピペットを用いて、上述の製造例２で得られた蛍光体含有層形成液（１）を４μｌ計量し、上述の製造例１−１に記載の縦型半導体発光素子を設置した半導体発光装置に注液した。この半導体発光装置を、減圧することができるデシケーターボックス中、２５℃、１ｋＰａの条件下で５分間保持することにより、注液時に生じた巻き込み気泡や溶存空気・水分を除去した。その後、この半導体発光装置を、７０℃で１時間保持し、次いで、１５０℃で５時間保持することにより形成液を硬化させ、半導体発光装置を得た。得られた半導体発光装置について以下に記載の方法で点灯試験を行うことにより、耐久性の評価を行った。
［比較例１］
半導体発光素子を上述の製造例１−２に記載の横型半導体発光素子に変更したこと以外は、実施例１と同様の操作で半導体発光装置を得、耐久性の評価を行った。
［実施例２］
蛍光体含有層形成液（１）の代わりに、蛍光体含有層形成液（２）を使用したこと以外は、実施例１と同様の操作で半導体発光装置を得、耐久性の評価を行った。
［比較例２］
半導体発光素子を上述の製造例１−２に記載の横型半導体発光素子に変更したこと以外は、実施例２と同様の操作で半導体発光装置を得、耐久性の評価を行った。

(Production Example 2) Production of Fluorine Complex Phosphor-Containing Layer Forming Solution 100 parts by weight of Shin-Etsu Chemical Co., Ltd. silicone resin SCR1016 and 12 parts by weight of each of the phosphors synthesized in Synthesis Example 1 or Synthesis Example 2 The phosphor-containing layer forming liquids (1) and (2) were produced by mixing with a stirring deaerator AR-100 manufactured by the company.
Example 1 Production of Semiconductor Light-Emitting Device Using a manual pipette, 4 μl of the phosphor-containing layer forming solution (1) obtained in Production Example 2 described above was weighed, and the vertical direction described in Production Example 1-1 above. The liquid was injected into a semiconductor light emitting device provided with a type semiconductor light emitting element. This semiconductor light-emitting device was held 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 70 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the forming liquid, thereby obtaining a semiconductor light emitting device. The durability of the obtained semiconductor light emitting device was evaluated by performing a lighting test by the method described below.
[Comparative Example 1]
A semiconductor light emitting device was obtained in the same manner as in Example 1 except that the semiconductor light emitting element was changed to the horizontal semiconductor light emitting element described in Production Example 1-2 above, and durability was evaluated.
[Example 2]
A semiconductor light-emitting device was obtained in the same manner as in Example 1 except that the phosphor-containing layer forming liquid (2) was used instead of the phosphor-containing layer forming liquid (1), and durability was evaluated. .
[Comparative Example 2]
A semiconductor light-emitting device was obtained in the same manner as in Example 2 except that the semiconductor light-emitting element was changed to the horizontal semiconductor light-emitting element described in Production Example 1-2 above, and durability was evaluated.

<Lighting test>
A current of 20 mA is applied to the semiconductor light emitting device, and immediately after starting 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 to 1100 nm, light receiving method) : An emission spectrum was measured using an integrating sphere (diameter 1.5 inches).

  Next, using a aging device, LED AGING SYSTEM 100ch LED environmental test device (YEL-50005, manufactured by Yamakatsu Electronics Co., Ltd.), the semiconductor light emitting device is continuously energized at a drive current of 20 mA under conditions of 85 ° C. and 85% relative humidity. Then, emission spectra were measured in the same manner as in the case of 0 hour at each time point of 50 hours, 100 hours, 150 hours, and 200 hours from the start of energization. At the same time, the semiconductor light emitting device is stored without being energized under the conditions of 85 ° C. and relative humidity of 85%, and measurement is performed at each time point of 50 hours, 100 hours, 150 hours, and 200 hours after the start of energization. Only when electricity was supplied, the emission spectrum was measured in the same manner as in the case of 0 hour.

Table 10 shows the values of various emission characteristics (total luminous flux, luminance, chromaticity coordinates Cx, Cy) calculated from the emission spectrum obtained after 200 hours as relative values with the measured value at 0 hour as 100%.
In the 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.

In Example 1 and Example 2 using the vertical semiconductor light emitting element, the decrease in the total luminous flux and luminance was smaller and the color shift was less than those in Comparative Example 1 and Comparative Example 2 using the horizontal semiconductor light emitting element. .
Further, when Example 1 and Example 2 are compared, K ₂ Si _0.9 Mn _0.1 F ₆ as a phosphor may be more durable than K ₂ Ti _0.95 Mn _0.05 F _6. all right. It is presumed that K ₂ Si _0.9 Mn _0.1 F ₆ has a lower solubility in water and a smaller amount of F generated by heating.

  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 is used for image display devices of various electronic devices such as mobile phones, household appliances, and outdoor displays. It is preferable.

1 Phosphor-containing part (second light emitter)
2 Excitation light source (first light emitter) (LD)
3 Substrate 4 Semiconductor 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 Semiconductor light-emitting device 14 Diffusion plate 15 Frame 16 Conductive wire 17 Electrode 18 Electrode 20 Semiconductor light-emitting device
21 Substrate
22 Buffer layer
23 Contact Layer 24 First Conductive Clad Layer
25 Active layer structure
26 Second conductivity type cladding layer
27 Second conductivity type side electrode
28 First conductivity type side electrode 29 Second current injection region 101 p-type electrode 102 n-type electrode 103 p-type layer 104 n-type layer 105 conductive substrate 106 insulating substrate

Claims (9)

In a light emitting device comprising a light source and a phosphor that absorbs at least a part of light from the light source and emits light having a wavelength different from that of the light from the light source.
A semiconductor light-emitting element formed on a conductive substrate as the light source; and
A semiconductor light emitting device comprising: a fluorine complex phosphor activated with Mn ⁴⁺ as the phosphor. Fluorine complex phosphors activated with the Mn ⁴⁺ is at 200 ° C., wherein the heating occurs fluorine amount per phosphor 1g is of more than 0.01 [mu] g / min, according to claim 1 Semiconductor light emitting device. The fluorine complex phosphor activated by Mn ⁴⁺ has a solubility in 100 g of water at 20 ° C. of 0.005 g or more and 7 g or less. 3. Semiconductor light emitting device. 4. The semiconductor according to claim 1, wherein the phosphor complex phosphor activated by Mn ⁴⁺ has a main emission peak in a wavelength range of 610 nm or more and 650 nm or less. Light emitting device. The semiconductor light emitting device according to claim 4, wherein a half width of the main light emission peak is 10 nm or less. The fluorine complex phosphor activated by Mn ⁴⁺
The rate of change of the emission peak intensity at 100 ° C. with respect to the emission peak intensity at 25 ° C. when the wavelength of the excitation light is 455 nm is 40% or less. The semiconductor light emitting device according to item. The activated with fluorine complex phosphor Mn ^4+, characterized in that it is one containing the following formula [1] to crystal phase having a chemical composition represented by any one of [8], claim The semiconductor light-emitting device of any one of 1-6.
_{^{M I 2 [M IV 1-}} x R x F 6] ··· [1]
M ^I ₃ [M ^III _1-x R _x F ₆ ] ... [2]
M ^II [M ^IV _1-x R _x F ₆ ] ... [3]
M ^I ₃ [M ^IV _1-x R _x F ₇ ] ... [4]
M ^I ₂ [M ^III _1-x R _x F ₅ ] ... [5]
_{^{Zn 2 [M III 1-x}} R x F 7] ··· [6]
M ^I [M ^III _2-2x R _2x F ₇ ] ... [7]
Ba _0.65 Zr _0.35 F _2.70 : Mn ⁴⁺ ... [8]
(In the above formulas [1] to [8], M ^I represents one or more monovalent groups selected from the group consisting of Li, Na, K, Rb, Cs, and NH ₄ , and M ^II represents an alkaline earth metal element, M ^III represents one or more metal elements selected from the group consisting of group 3 and group 13 of the periodic table, M ^IV is from group 4 and group 14 of the periodic table And one or more metal elements selected from the group consisting of R and R represents an activating element containing at least Mn, and x is a numerical value in a range represented by 0 <x <1.) An image display device comprising the light-emitting device according to claim 1. An illumination device comprising the light-emitting device according to claim 1.

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