JP2011054958A - Semiconductor light emitting device, image display device, and lighting system - Google Patents

Abstract

The present invention provides a semiconductor light-emitting device that enables practical use of a phosphor having excellent light-emitting properties but having a problem in chemical stability, and an image display device and an illumination device using the semiconductor light-emitting device.
In a semiconductor light emitting device comprising a semiconductor light emitting element A and a phosphor that emits light having a different wavelength by absorbing at least part of light from the semiconductor light emitting element, the semiconductor light emitting element and Mn ⁴⁺ are used. Between the layer C containing the activated fluorine complex phosphor, the water vapor transmission rate at 40 ° C. when the phosphor is not contained and the thickness is 0.4 mm is 10 g / m ² · day or less. Layer D is provided.
[Selection] Figure 6

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 containing 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 are used. The present invention relates to an image display device and a lighting 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. It is 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, it has been found that when the fluorine complex phosphor activated with Mn ⁴⁺ is used, the durability of the semiconductor light emitting device can be improved by devising the layer structure of the semiconductor light emitting device.
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 (10).
(1) In a semiconductor light emitting device comprising: a semiconductor light emitting element (A); and a phosphor (B) that emits light having a different wavelength by absorbing at least part of the light from the semiconductor light emitting element (A).
Water vapor at 40 ° C. when the phosphor (B) is not contained and the thickness is 0.4 mm between the semiconductor light emitting element (A) and the layer (C) containing the phosphor (B). Having a layer (D) having a transmittance of 10 g / m ² · day or less,
A semiconductor light emitting device characterized in that the phosphor (B) contains a fluorine complex phosphor activated with Mn ⁴⁺ .

(2) In a semiconductor light emitting device comprising: a semiconductor light emitting element (A); and a phosphor (B) that emits light having a different wavelength by absorbing at least part of light from the semiconductor light emitting element (A).
A part or all of the surface of the semiconductor light emitting device is coated with a layer (E) having a water vapor transmission rate at 40 ° C. of 10 g / m ² · day or less when the thickness is 0.4 mm,
A semiconductor light emitting device characterized in that the phosphor (B) contains a fluorine complex phosphor activated with Mn ⁴⁺ .

(3) In a semiconductor light emitting device comprising: a semiconductor light emitting element (A); and a phosphor (B) that emits light having a different wavelength by absorbing at least part of the light from the semiconductor light emitting element (A).
The layer (C) containing the phosphor (B) is covered with a layer (F) having a water vapor transmission rate at 40 ° C. of 10 g / m ² · day or less when the thickness is 0.4 mm,
A semiconductor light emitting device characterized in that the phosphor (B) contains a fluorine complex phosphor activated with Mn ⁴⁺ .

(4) 40 when the phosphor (B) is not included and the thickness is 0.4 mm between the semiconductor light emitting element (A) and the layer (C) including the phosphor (B). Water vapor permeability at 10 ° C is 10
The semiconductor light-emitting device according to (3), comprising a layer (D) of g / m ² · day or less.
(5) The amount of heat-generated fluorine at 200 ° C. of the phosphor (B) is 0.01 μg / min or more per 1 g of phosphor, (1) to (4), Semiconductor light emitting device.

(6) The semiconductor according to any one of (1) to (5), wherein the phosphor (B) has a solubility in 100 g of water at 20 ° C. of 0.005 g or more and 7 g or less. Light emitting device.
(7) The semiconductor light-emitting device according to any one of (1) to (6), wherein the phosphor (B) has a main light emission peak in a wavelength range of 610 nm to 650 nm.

(8) The phosphor (B) contains a crystal phase having a chemical composition represented by any one of the following formulas [1] to [8]. 7) The semiconductor light-emitting device according to any one of 7).
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.)
(9) An image display device comprising the semiconductor light emitting device according to any one of (1) to (8) as a light source.

  (10) An illumination device comprising the semiconductor light emitting device according to any one of (1) to (8) as a light source.

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. 6A shows an example of the first structure of the semiconductor light emitting device of the present invention. FIGS. 6B, 6C, and 6D show the semiconductor light emitting device of the present invention. FIG. 6E is an example of the second structure, and FIG. 6E is an example of the third structure of the semiconductor light emitting device of the present invention. 2 is an emission spectrum of the semiconductor light emitting device obtained in Example 1.

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 of the present invention.
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: Eu " and all assumed to generically indicated (in the above formula, 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 light emission intensity is very high, a GaN-based LED is particularly preferably one having an In _X Ga _Y N light emitting layer, and further having a multiple quantum well structure of 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. In the present invention, a vertical element structure or a horizontal element structure can be used, but 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, it is preferable in that the durability of the light emitting device is improved, specifically, the deterioration with time of the light emitting device at a temperature of 85 ° C. and a humidity of 85% can be 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, it may be 1 μg / min or more. 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 2 g or less.
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 is abbreviated as “FWHM” as appropriate in the full width at half maximum (hereinafter referred to as “FWHM”).
) Is usually larger than 1 nm, especially 2 nm or more, further 3 nm or more, and usually less than 50 nm, especially 30 nm or less, more preferably 10 nm or less, and further 8 nm or less, and in this range, it should be 7 nm or less. 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.
The external quantum efficiency can be obtained as a product of the internal quantum efficiency and the absorption efficiency.

[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. The weight median diameter D ₅₀ of the fluorocomplex phosphor used in the present invention is usually 3 μm or more, preferably 10 μm or more, and usually 50 μm or less, preferably 30 μm 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 preferably 1.3 m ² / g or less, more preferably 1.1 m ² / g or less, and particularly preferably 1.0 m ² / g or less. , and usually 0.05 m 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. 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 a minimum.

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

The quadrant deviation of the particle size distribution can be calculated using a particle size distribution curve measured using a laser diffraction / scattering particle size distribution measuring device.
<Particle shape>
The particle shape of the 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. . If 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 that 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 device is absorbed by the phosphor and the sealing material holding the phosphor. As a result, the sealing material 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. Further, when the semiconductor light emitting element is energized to emit light, the light emitting element generates heat due to the electric 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. And using the apparatus provided with a 150W xenon lamp as a light source, it carries out in the following procedure.

  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 selected from the group consisting of alkali metal elements, NH ₄ , alkaline earth metal elements, and Zn. And 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 halogen elements The phosphor to contain is 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.)
As M ^I , it is particularly preferable to contain one or more elements selected from the group consisting of K and Na.

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, K ₂ MnF ₆ containing Mn ⁴⁺ complex ion [MnF ₆ ] ²⁻ and the base K ₂ TiF ₆ , K ₂ SiF ₆ , K ₂ GeF ₆ , and K ₂ ZrF ₆ have a similar crystal structure. This is because these base materials are easily substituted in the state of [MnF ₆ ] ^2- complex ions.

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.

Of these, M ^I 'preferably contains at least K, and usually all M ^I '
This is a case where K accounts for 90 mol% or more, preferably 97 mol% or more, more preferably 98 mol% or more, and still more preferably 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.
In the phosphor represented by [1 ′], the ratio of Mn to the total number of moles of M ^IV ′ and Mn (in the present invention, this ratio is hereinafter referred to as “Mn concentration”) is 0.1 mol%. It is preferable that it is 40 mol% or less. If the Mn concentration is too small, the absorption efficiency of the excitation light by the phosphor decreases, so the luminance tends to decrease. If it is too large, 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.

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

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 described later, since the particle growth is promoted, sufficient absorption efficiency and luminance can be provided.

  The chemical composition analysis of the Mn concentration contained in the phosphor 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. Method for producing fluorine complex phosphor activated with 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, a method in which a poor solvent is not used will be described by taking M ^IV ′ as Si as a representative example.
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 method of mixing a solution containing at least Si and F and a solution containing at least K (and / or Na), 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.

As the K source, water-soluble potassium salts such as KF, KHF ₂ , KOH, KCl, KBr, KI, potassium acetate, K ₂ CO _{3 and the} like can be used. 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. 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 less than weight%.
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 not lower than 150 ° C., more preferably not lower than 150 ° C., usually not higher than 300 ° C., preferably not higher than 250 ° C., more preferably not higher 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]
In the semiconductor light emitting device of the present invention, a fluorine complex phosphor activated by Mn ⁴⁺ may be used alone, or two or more kinds of fluorine complex phosphors may be used in any combination and 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.

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.

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 : CeCa 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.

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.

Among these, as the red phosphor, (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, 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 more green phosphors selected from the group consisting of Eu are preferable.

(C) A blue light emitter (blue LED or the like) is used as a semiconductor light emitting element, a fluorine complex phosphor activated with Mn ⁴⁺ is used as a red phosphor, and an orange phosphor is further used. 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.

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

  Further, particularly preferred combinations are shown in Table 8.

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

When a 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. Curable 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 ensures the role of guiding light emitted from the semiconductor light emitting element to the phosphor. Moreover, only 1 type may be used for a curable material and it may use 2 or more types together by arbitrary combinations and a ratio. Therefore, as the curable material, any of inorganic materials, organic materials, and mixtures thereof can be used.

As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof is solidified (for example, a siloxane bond). Inorganic materials having
On the other hand, examples of the organic material include a thermosetting resin and a photocurable resin. Specific examples include (meth) acrylic resins such as 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, the silicone materials described in JP2007-131812A, JP2007-214543A, 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.

Among the materials exemplified above, the layer (D), the layer (E) in the semiconductor light emitting device of the present invention,
And as a material used for a layer (F), it is preferable to use a thing with a low water-vapor-permeation rate. Specifically, water vapor permeability at 40 ° C. when the thickness of 0.4mm is usually 10g ^/ m 2 · day or less, preferably 9.5g ^/ m 2 · day, more preferably 8.5 g / m ² · day or less, particularly preferably 5.0 g / m ² · day or less.

When the water vapor transmission rate is low, an effect of improving the durability of the semiconductor light emitting device can be obtained.
[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.

[5-1. Structure of semiconductor light emitting device]
Below, the preferable structural example of the semiconductor light-emitting device of this invention is demonstrated. Moreover, although the conceptual diagram of this invention is shown in FIG. 6, it is a representative example and is not limited to this.
[First structure]
The first structure of the semiconductor light emitting device of the present invention includes a semiconductor light emitting element (A) and a phosphor (B) that emits light having a different wavelength by absorbing at least part of light from the semiconductor light emitting element (A). The phosphor (B) is not contained between the semiconductor light emitting element (A) and the layer (C) containing the phosphor (B), and the thickness is 0. The water vapor permeability at 40 ° C. at 4 mm has a layer (D) having a viscosity of 10 g / m ² · day or less (see FIG. 6A).

By providing a layer (D) that does not contain the phosphor (B) between the semiconductor light emitting element (A) and the layer (C), a layer that contains the semiconductor light emitting element (A) and the phosphor (B) (C ), The durability of the semiconductor light-emitting device can be improved.
The thickness of the layer (D) is not particularly limited, but is usually 1/10 or more, preferably 1/4 or more, and usually ½ or less, preferably 1 or more times the thickness of the package of the semiconductor light emitting device. 1/3 or less.

The package of the semiconductor light emitting device is usually about 0.85 mm.
Such a semiconductor light emitting device can be manufactured, for example, as follows. After fixing the semiconductor light emitting device (A) to the bottom of the package, the composition constituting the layer (D) is injected onto the semiconductor light emitting device (A) and cured as necessary. Next, the composition constituting the layer (C) is injected and cured as necessary. As an injection method, an injection device such as a commonly used dispenser can be used.

[Second structure]
The second structure of the semiconductor light emitting device of the present invention includes a semiconductor light emitting element (A) and a phosphor (B) that emits light having a different wavelength by absorbing at least a part of light from the semiconductor light emitting element (A). A part or all of the surface of the semiconductor light emitting device is covered with a layer (E) having a water vapor transmission rate at 40 ° C. of 10 g / m ² · day or less when the thickness is 0.4 mm. (See FIGS. 6B and 6D).

By coating part or all of the semiconductor light emitting device with a light-transmitting material (E) having a low water vapor transmission rate, moisture can penetrate from the surrounding environment such as the atmosphere into the phosphor (B). Thus, the durability of the semiconductor light emitting device can be improved.
In the second structure, a portion corresponding to the layer (D) in the first structure may be further provided (see FIG. 6C).

Such a semiconductor light emitting device can be manufactured, for example, as follows.
As a manufacturing method for covering a part of the semiconductor light emitting device, after fixing the semiconductor light emitting element (A) to the bottom of the package, the composition constituting the layer (C) is injected onto the semiconductor light emitting element (A), Cure if necessary. Next, a curing material constituting the layer (E) is injected and cured as necessary. As the injection method, a commonly used injection device such as a dispenser can be used.

As a manufacturing method for covering the entire semiconductor light emitting device, the semiconductor light emitting element (A) is fixed to the bottom of the package, and then the composition constituting the layer (C) is injected onto the semiconductor light emitting element (A). Harden accordingly. Next, the semiconductor light-emitting device is covered with the layer (E) by immersing the semiconductor light-emitting device in the curable material constituting the layer (E) and then curing the semiconductor light-emitting device.
[Third structure]
The third structure of the semiconductor light emitting device of the present invention includes a semiconductor light emitting element (A) and a phosphor (B) that emits light having a different wavelength by absorbing at least part of light from the semiconductor light emitting element (A). The layer (C) containing the phosphor (B) is a layer (F) having a water vapor transmission rate at 40 ° C. of 10 g / m ² · day or less when the thickness is 0.4 mm. It is characterized by being covered (see FIG. 6E).

Such a semiconductor light emitting device can be manufactured, for example, as follows.
The phosphor-containing layer forming liquid is dropped on a fluorine-coated heat-resistant sheet and cured in the form of a water droplet to form a layer (C). Thereafter, a fluororesin is dropped from above the layer (C) and cured. Next, the fluorine-coated heat-resistant sheet contact surface of the layer (C) is faced up, and the fluorine resin is dropped and cured from above to form a layer (F) around the layer (C).

After injecting the composition constituting the layer (D) into the semiconductor light emitting device provided with the semiconductor light emitting element, the layer (C) covered with the layer (F) is put, and the layer (D) is further added thereon. The constituent composition is injected and cured to form layer (D).
[5-2. Layer (D), materials constituting layers (E) and (F)]
When the thickness of the curable material constituting the layers (D), (E), and (F) is 0.4 mm, the water vapor permeability at 40 ° C. is usually 10 g / m ² · day (40 ° C.). or less, preferably 9.5g ^/ m 2 · day or less, more preferably 8.5g ^/ m 2 · day or less, even more preferably at most 5.0g ^/ m 2 · day.

When the layer (D) is formed using a material having a high water vapor transmission rate, it has been confirmed that the durability of the semiconductor light-emitting device is reduced, and when the water vapor transmission rate exceeds 10 g / m ² · day, the light-emitting device There is a tendency for the durability of the to decrease. In addition, the measurement of water-vapor-permeability can be measured by the method as described in an Example.
Specifically, as the curing material constituting the layers (D), (E), and (F), [4-1. Among the materials described in [Curing Material], a material having a low water vapor transmission rate can be used. For example, silicone resin, epoxy resin, fluorine resin and the like can be mentioned, among which silicone resin or fluorine resin is preferable.

The thickness of layers (E) and (F) is not particularly limited, but is usually 1 μm or more, preferably 50 μm or more, more preferably 80 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm is as follows.
[5-3. Compounding amount of phosphor (B) in layer (C)]
The blending amount of the phosphor (B) is usually 3 parts by weight or more, preferably 10 parts by weight or more, more preferably 20 parts by weight or more with respect to 100 parts by weight of the resin constituting the layer (C). Usually, it is 100 parts by weight or less, 80 parts by weight or less, more preferably 60 parts by weight or less. If the blending amount of the phosphor (B) is too small, the luminance tends to be low, and if it is too large, the production operation may be difficult due to high viscosity.

In addition, as a material which comprises a layer (C), the above-mentioned [4-1. Materials described in [Curing Material] can be used. [4-1. Among the materials described in [Curing Material], it is preferable to use a material having a low water vapor transmission rate.
[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 as the semiconductor light-emitting element, phosphor, and phosphor-containing layer forming liquid, light emitting devices of Examples and Comparative Examples described later were prepared and evaluated.
[Semiconductor light emitting device]
A 350 μm square chip “GU35R460T” manufactured by Showa Denko Co., Ltd. was used as a semiconductor light emitting device, and it was bonded to a 3528 (3428) SMD type resin package with a transparent die bond paste (silicone resin base). Two bonding wires were used.

[Phosphor]
<Synthesis Example 1 Red Phosphor Phosphor K ₂ TiF ₆ : Mn ⁴⁺ >
K ₂ TiF ₆ (4.743 g) and K ₂ MnF ₆ (0.2596 g) were used as raw material compounds so that the raw material synthesis of the phosphors was K ₂ Ti _0.95 Mn _0.05 F _6. Under atmospheric pressure and room temperature, it was slowly added to 40 ml of hydrofluoric acid (47.3% by weight) with stirring and dissolved. After 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 phosphors were washed with pure water and acetone, respectively, and dried at 100 ° C. for 1 hour. From the X-ray diffraction pattern of the obtained phosphor, it was confirmed that K ₂ TiF ₆ : Mn was synthesized. In addition, the amount of fluorine generated by heating of the obtained phosphor was determined and shown in Table 9.

The amount of fluorine generated by heating was measured by the following method.
<Measurement method of the amount of fluorine 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 obtain the amount of fluorine generated per minute per 1 g of phosphor. .

[Phosphor-containing layer forming solution]
Using the phosphor synthesized in Synthesis Example 1 described above, the sealant solution and the phosphor were weighed at the blending ratio shown in Table 10 below, and then mixed with “V-mini300” manufactured by EME to contain the phosphor. A layer forming liquid (1) was obtained.

In addition, the said Table 10 means that 12 weight% of red fluorescent substance was added with respect to 100 weight% of sealing material liquids.
[Fabrication of semiconductor light emitting device]
<Example 1-1>
Using a manual pipette, the main component of the two-part silicone resin SCR1016 manufactured by Shin-Etsu Chemical Co., Ltd. and a curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μm of the resulting mixture
L was poured into a semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the forming liquid, thereby forming a layer (D).

  Next, using a manual pipette, 2 μL of the phosphor-containing layer forming solution (1) prepared from the two-part silicone resin SCR1016 manufactured by Shin-Etsu Chemical Co., Ltd. was poured into the semiconductor light emitting device and held at 100 ° C. for 1 hour. Then, the layer (C) containing the phosphor was cured by holding at 150 ° C. for 5 hours to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

In addition, a stereomicroscope (Keyence's "Digital Microscope VH-5000". For the lens, Keyence's "VH-Z25" was used, and for the software, Keyence's "VH Analyzer" was used.
), The thickness of each layer was measured at 100 magnification, and the (C) layer was about 0.57 mm and the (D) layer was about 0.28 mm.
<Example 1-2>
Using a manual pipette, the main component of 2-pack type epoxy resin YL7301 manufactured by Japan Epoxy Resin Co., Ltd. and a curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 1 μL of the obtained mixed solution is poured into a semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, held at 100 ° C. for 3 hours, then held at 140 ° C. for 3 hours to cure the forming solution, and layer (D) is formed. Formed.

Next, using a manual pipette, 2 μL of the phosphor-containing layer forming solution (1) prepared from the two-part silicone resin SCR1016 manufactured by Shin-Etsu Chemical Co., Ltd. was poured into the semiconductor light emitting device and held at 100 ° C. for 1 hour. After that, the layer (C) was cured by maintaining at 150 ° C. for 5 hours.
Thereafter, using a manual pipette, the main component of the two-part silicone resin SCR1016 manufactured by Shin-Etsu Chemical Co., Ltd. and the curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME, and 1 μL of the obtained mixed solution was added to the above-mentioned mixture. The solution was poured into the semiconductor light emitting device, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the layer (E) to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

Further, when the thickness of each layer was measured under the same conditions as in Example 1, the (C) layer was about 0.28 mm, the (D) layer was about 0.24 mm, and the (E) layer was about 0.33 mm. Met.
<Example 1-3>
Using a manual pipette, 2 μL of the phosphor-containing layer forming solution (1) is injected into the semiconductor light emitting device in which the above-described semiconductor light emitting element is installed, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours. Then, the phosphor layer (C) was cured.

Next, using a manual pipette, the main component of the two-part silicone resin SCR1016 manufactured by Shin-Etsu Chemical Co., Ltd. and the curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μL of the obtained mixed solution was poured into the semiconductor light emitting device, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to form a layer (E) to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

<Example 1-4>
0.5 μL of the phosphor-containing layer forming liquid (1) is dropped onto a fluorine-coated heat-resistant sheet, held in the form of a water drop at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to be cured. (C) was formed.
0.5 μL of fluororesin (“Eight Seal 3000” manufactured by Taihei Kasei Co., Ltd.) from the top of the layer (C)
Was dropped and held at 120 ° C. for 20 minutes to be cured. Next, the fluorine-coated heat-resistant sheet contact surface of layer (C) is faced up, and 0.5 μL of the above-mentioned fluorine resin (“Eight Seal 3000” manufactured by Taihei Kasei Co., Ltd.) is dropped thereon, and held at 120 ° C. for 20 minutes. Then, the layer (F) was formed around the layer (C) by curing.

A main component and a curing agent of a two-part silicone resin SCR1016 manufactured by Shin-Etsu Chemical Co., Ltd. as a semiconductor device forming liquid were vacuum defoamed and mixed with “V-mini300” manufactured by EME. After injecting 1 μL of the obtained mixed solution into the semiconductor light emitting device in which the semiconductor light emitting element is installed, the layer C covered with the layer F is put, and further 1 μL of the mixed solution is injected from above, and 1 μL is added at 100 ° C. After maintaining the time, the layer (D) was formed by maintaining at 150 ° C. for 5 hours. The configuration of this semiconductor light emitting device corresponds to FIG.

<Example 1-5>
100 parts by weight of two-part silicone resin SCR1016A manufactured by Shin-Etsu Chemical Co., Ltd. and 100 parts by weight of curing agent SCR1016B were subjected to vacuum defoaming mixing with “V-mini300” manufactured by EME. 1 μL of the obtained mixed solution was poured into a light-emitting device provided with the above-described semiconductor light-emitting element, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the silicone resin layer. ) Was formed.

Next, using a manual pipette, 2 μL of the phosphor-containing layer forming solution (1) is injected into the light-emitting device, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to form layer (C). Cured.
Furthermore, by injecting 1 μL of the above-mentioned mixed liquid of SCR1016A and SCR1016B on the layer (C), holding at 100 ° C. for 1 hour, and holding at 150 ° C. for 5 hours to cure the silicone resin layer. A layer (E) was formed to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

Further, when the thickness of each layer was measured under the same conditions as in Example 1-1, the layer (C) was about 0.
. 28 mm, the (D) layer was about 0.24 mm, and the (E) layer was about 0.33 mm.
<Comparative Example 1-1>
Using a manual pipette, 4 μl of the phosphor-containing layer forming liquid (1) was poured into the semiconductor light emitting device provided with the semiconductor light emitting element, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours. The layer (C) was cured to obtain a semiconductor light emitting device (white LED).

[Measurement of water vapor transmission rate]
Using “Permatran-W 3/31” manufactured by MOCON, the water vapor permeability of the sealant liquid (SCR1016) used in Examples 1-1 to 1-5 and Comparative Example 1-1 was measured. .
In addition, it carried out based on JIS K7129B.

As a result, the two-part silicone resin SCR1016 manufactured by Shin-Etsu Chemical Co., Ltd. was 8.0 g / m ² · day when the thickness was 0.47 mm. The relationship between the thickness and the water vapor transmission rate is inversely proportional when the thickness is 0 (zero), and when the thickness is infinite, the transmittance is 0 (zero). Therefore, when the thickness is 0.4 mm, it can be estimated as 9.4 g / m ² · day.

Moreover, the two-pack type epoxy resin YL7301 manufactured by Japan Epoxy Resin Co., Ltd. was 9.3 g / m ² · day when the thickness was 0.32 mm. When the thickness is 0.4 mm, it is estimated that the value (7.4 g / m ² · day) is smaller than the data (9.3 g / m ² · day) when the thickness is 0.37 mm.
[Durability test]
Durability tests were performed on the semiconductor light emitting devices obtained in the above-described examples and comparative examples by the following method.

A current of 20 mA is applied to the semiconductor light emitting device, and before starting lighting (this time point is hereinafter referred to as “0 hour”), a fiber multi-channel 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 energization under conditions of 85 ° C. and relative humidity 85%, and each time point before storage (before starting lighting), 50 hours, 100 hours, 150 hours, and 200 hours. In Fig. 2, the light emission spectrum was measured in the same manner as in the case of 0 hour, with electricity applied only during the measurement.

Relative values of various emission characteristics values (radiant flux (μW) total luminous flux (lm), chromaticity coordinates Cx, Cy) calculated from the emission spectrum obtained after 200 hours, with the measured value at 0 hours as 100% Table 11 shows.
During the lighting test, the emission spectrum was measured by holding the spectrometer in a constant temperature room at 25 ° C. in order to prevent data disturbance due to temperature changes in the spectrometer body.

Further, FIG. 7 shows an emission spectrum of the semiconductor light emitting device manufactured in Example 1-1. From FIG. 7, it can be seen that the semiconductor light emitting device of Example 1-1 can observe a narrow emission peak peculiar to the fluorine complex phosphor activated by Mn ⁴⁺ in the red region.

When Example 1-1 and Comparative Example 1-1 are compared, it can be seen that the durability of the semiconductor light-emitting device is improved by the presence of the layer (D) using the silicone resin not containing the phosphor.
Example 1-2 is an experiment using an epoxy resin for the layer (D). It can be seen that when epoxy resin is used, durability is improved under non-lighting conditions. On the other hand, in Examples 1-1 and 1-3 to 1-5 using the silicone resin, it can be seen that the durability is improved in the lighting condition in addition to the non-lighting condition.

Further, from Example 1-3, even if the layer (D) is not present, the formation of the layer (E) can suppress the transmission of water vapor to the phosphor (B) to a low level. It can be seen that the durability is improved.
Further, from Example 1-4, even when the layer (E) is not present, the layer (F) that directly covers the entire surface of the layer (C) is formed, and the layer (D) is further formed, thereby forming a semiconductor light emitting device. It can be seen that the durability of the device is improved.

Further, from Example 1-5, by simultaneously forming the layer (E) in addition to the layer (D), the semiconductor light emission is more than when the layer is only one (Example 1-1, Example 1-3). It can be seen that the durability is improved for the total luminous flux of the apparatus.
<Example 2-1>
Using a manual pipette, the main component and curing agent of two-part silicone resin SCR1011 manufactured by Shin-Etsu Chemical Co., Ltd. were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μm of the resulting mixture
L was poured into the semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, and held at 70 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the forming liquid, thereby forming a layer (D).

  Next, using a manual pipette, 2 μL of the phosphor-containing layer forming solution (2) prepared from the two-part silicone resin SCR1011 manufactured by Shin-Etsu Chemical Co., Ltd. was poured into the semiconductor light emitting device and held at 70 ° C. for 1 hour. Then, the layer (C) containing the phosphor was cured by holding at 150 ° C. for 5 hours to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

<Example 2-2>
Using a manual pipette, the main component and curing agent of two-part silicone resin SCR1011 manufactured by Shin-Etsu Chemical Co., Ltd. were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 1 μm of the obtained mixture
L was poured into the semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, and held at 70 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the forming liquid, thereby forming a layer (D).

Next, using a manual pipette, 2 μL of the phosphor-containing layer forming solution (2) prepared from the two-part silicone resin SCR1011 manufactured by Shin-Etsu Chemical Co., Ltd. was poured into the semiconductor light emitting device and held at 70 ° C. for 1 hour. Then, the layer (C) was cured by maintaining at 150 ° C. for 5 hours.
Thereafter, using a manual pipette, the main component of the two-part silicone resin SCR1011 manufactured by Shin-Etsu Chemical Co., Ltd. and the curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME, and 1 μL of the obtained mixed solution was added to the above-mentioned mixture. The liquid was poured into the semiconductor light emitting device, held at 70 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to cure the layer (E) to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

<Example 2-3>
Using a manual pipette, 2 μL of the phosphor-containing layer forming liquid (2) is injected into the semiconductor light emitting device provided with the semiconductor light emitting element described above, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours. Then, the phosphor layer (C) was cured.
Next, using a manual pipette, the main component of the two-part silicone resin SCR1011 manufactured by Shin-Etsu Chemical Co., Ltd. and a curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μL of the obtained mixed solution was poured into the semiconductor light emitting device, held at 70 ° C. for 1 hour, and then held at 150 ° C. for 5 hours to form a layer (E) to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.
<Comparative Example 2-2>
Using a manual pipette, 4 μl of the phosphor-containing layer forming solution (2) was poured into the semiconductor light emitting device provided with the semiconductor light emitting element, held at 100 ° C. for 1 hour, and then held at 150 ° C. for 5 hours. The layer (C) was cured to obtain a semiconductor light emitting device (white LED).

[Measurement of water vapor transmission rate]
In the same measurement method as in Examples 1-1 to 5 and Comparative Example 1-1, the water vapor transmission rate of the sealant liquid SCR1011 used in Examples 2-1 to 2-3 and Comparative Example 2-1. Measurements were made.
As a result, the two-part silicone resin SCR1011 manufactured by Shin-Etsu Chemical Co., Ltd. was 1.0 g / m ² · day when the thickness was 0.40 mm.
[Durability test]
Examples 1-1 to 1-5 and Comparative Examples except that the measurement points (elapsed time) were changed to the times shown in the table for the semiconductor light-emitting devices obtained in the above-described Examples and Comparative Examples. A durability test was performed in the same manner as in 1-1.
Table 13 shows values of various light emission characteristics (radiant flux (μW), total luminous flux (lm), chromaticity coordinates Cx, Cy) as relative values with a measured value at 0 hour being 100%.

In addition, Comparative Example 2-2 (calculation 282 hr) * is a value calculated based on an approximate curve equation from actual measurements at 219 hr (hours) and other times.
The lighting sample tends to be less susceptible to water vapor even when a highly water-soluble phosphor is used because the water vapor evaporates by the light source around 110 ° C. to 120 ° C. due to the light source and water vapor does not come close. . On the other hand, since the non-lighted sample is 85 ° C. in the test environment, the moisture is not evaporated and is directly affected by the water vapor, so that the deterioration is likely to occur. Comparing the comparative example and the example with respect to the non-lighting sample which is easily affected by the water vapor, it can be seen that the deterioration is improved in the example.

<Comparative Example 3-1>
Using a manual pipette, the main component and curing agent of two-part silicone resin LPS2410 manufactured by Shin-Etsu Chemical Co., Ltd. are vacuum defoamed and mixed with “V-mini300” manufactured by EME, and the phosphor-containing layer by the resulting liquid preparation 4 μl of the forming liquid (3) is poured into the semiconductor light emitting device provided with the semiconductor light emitting element, and held at 150 ° C. for 1 hour to cure the forming liquid and cure the layer (C). LED).

<Comparative Example 3-2>
Using a manual pipette, the main component of 2-part silicone resin LPS2410 manufactured by Shin-Etsu Chemical Co., Ltd. and a curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μm of the resulting mixture
L was poured into a semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, and held at 150 ° C. for 1 hour to cure the forming liquid, thereby forming a layer (D).

Next, using a manual pipette, 2 μL of the phosphor-containing layer forming liquid (3) prepared from the two-part silicone resin LPS2410 manufactured by Shin-Etsu Chemical Co., Ltd. was poured into the semiconductor light emitting device and held at 150 ° C. for 1 hour. Then, the layer (C) containing the phosphor was cured to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.
<Comparative Example 3-3>
Using a manual pipette, the main component of 2-part silicone resin LPS2410 manufactured by Shin-Etsu Chemical Co., Ltd. and a curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 1 μm of the obtained mixture
L was poured into a semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, and held at 150 ° C. for 1 hour to cure the forming liquid, thereby forming a layer (D).

Next, using a manual pipette, 2 μL of the phosphor-containing layer forming liquid (3) prepared from the two-part silicone resin LPS2410 manufactured by Shin-Etsu Chemical Co., Ltd. was poured into the semiconductor light emitting device and held at 150 ° C. for 1 hour. And layer (C) was cured.
Then, using a manual pipette, the main component and curing agent of Shin-Etsu Chemical Co., Ltd. two-part silicone resin LPS2410 were vacuum defoamed and mixed with “V-mini300” made by EME, and 1 μL of the resulting mixture was added to the above-mentioned mixture The solution was poured into the semiconductor light emitting device and held at 150 ° C. for 1 hour to cure the layer (E) to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

<Comparative Example 3-4>
Using a manual pipette, 2 μL of the phosphor-containing layer forming liquid (3) was poured into the semiconductor light-emitting device in which the semiconductor light-emitting element was installed, and held at 150 ° C. for 1 hour to cure the phosphor layer. .
Next, using a manual pipette, the main component of 2-pack type silicone resin LPS2410 manufactured by Shin-Etsu Chemical Co., Ltd. and a curing agent were vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μL of the obtained mixed solution was poured into the semiconductor light emitting device, and held at 150 ° C. for 1 hour to form a layer (E), thereby obtaining a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

[Measurement of water vapor transmission rate]
The water vapor permeability of the sealant liquid LPS2410 used in Comparative Examples 3-1 to 3-4 was measured by the same measurement method as in Examples 1-1 to 5 and Comparative Example 1-1.
As a result, the two-part silicone resin LPS2410 manufactured by Shin-Etsu Chemical Co., Ltd. was 17 g / m ² · day when the thickness was 0.40 mm.
[Durability test]
Examples 1-1 to 1-5 and Comparative Examples except that the measurement points (elapsed time) were changed to the times shown in the table for the semiconductor light-emitting devices obtained in the above-described Examples and Comparative Examples. A durability test was performed in the same manner as in 1-1.

  Table 15 shows values of various light emission characteristics (radiant flux (μW), total luminous flux (lm), chromaticity coordinates Cx, Cy) as relative values with a measured value of 0 hours being 100%.

It can be seen from Table 15 that when a sealant solution having a high water vapor transmission rate is used, the durability test results in significant deterioration, particularly in non-lighting. Also in the lighting samples, remarkable deterioration is recognized in Comparative Examples 3-1, 3-2 and 3-4.
<Comparative Example 4-1>
Using a manual pipette, 1-pack type silicone resin JCR6101 manufactured by Toray Dow Corning Co., Ltd. was vacuum degassed and mixed with “V-mini300” manufactured by EME, and a phosphor-containing layer forming solution (4) by the resulting preparation 4 μl is poured into the semiconductor light emitting device provided with the semiconductor light emitting element, held at 70 ° C. for 1 hour, and then held at 150 ° C. for 2 hours to cure the forming liquid and cure the layer (C). A device (white LED) was obtained.

<Comparative Example 4-2>
Using a manual pipette, 1-pack type silicone resin JCR6101 manufactured by Toray Dow Corning Co., Ltd. was vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μL of the obtained mixed solution is poured into a semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, held at 70 ° C. for 1 hour, then held at 150 ° C. for 2 hours to cure the forming solution, and layer (D) is formed. Formed.

  Next, using a manual pipette, 2 μL of the phosphor-containing layer forming solution (1) prepared from Toray Dow Corning 1-component silicone resin JCR6101 was poured into the semiconductor light emitting device and held at 70 ° C. for 1 hour. Subsequently, the layer (C) containing the phosphor was cured by maintaining at 150 ° C. for 2 hours to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

<Comparative Example 4-3>
Using a manual pipette, 1-pack type silicone resin JCR6101 manufactured by Toray Dow Corning Co., Ltd. was vacuum defoamed and mixed with “V-mini300” manufactured by EME. 1 μL of the obtained mixed solution is poured into a semiconductor light-emitting device provided with the above-described semiconductor light-emitting element, held at 70 ° C. for 1 hour, and then held at 150 ° C. for 2 hours to cure the forming solution, and layer (D) is formed. Formed.

Next, using a manual pipette, 2 μL of the phosphor-containing layer forming solution (4) prepared from Toray Dow Corning Co., Ltd. 1-pack type silicone resin JCR6101 was poured into the semiconductor light emitting device and held at 70 ° C. for 1 hour. Then, the layer (C) was cured by maintaining at 150 ° C. for 2 hours.
Thereafter, using a manual pipette, 1-pack type silicone resin JCR6101 manufactured by Toray Dow Corning Co., Ltd. was vacuum degassed and mixed with “V-mini300” manufactured by EME, and the resulting mixed solution 1 μL.
Was poured into the semiconductor light emitting device, held at 70 ° C. for 1 hour, and then held at 150 ° C. for 2 hours to cure the layer (E) to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

<Comparative Example 4-4>
Using a manual pipette, 2 μL of the phosphor-containing layer forming solution (4) is injected into the semiconductor light emitting device provided with the semiconductor light emitting element described above, and held at 70 ° C. for 1 hour, and then held at 150 ° C. for 2 hours. The phosphor layer was cured.
Next, using a manual pipette, 1-pack type silicone resin JCR6101 manufactured by Toray Dow Corning Co., Ltd. was vacuum defoamed and mixed with “V-mini300” manufactured by EME. 2 μm of the resulting mixture
L was poured into the semiconductor light emitting device, held at 70 ° C. for 1 hour, and then held at 150 ° C. for 2 hours to form a layer (E) to obtain a semiconductor light emitting device. The configuration of this semiconductor light emitting device corresponds to FIG.

[Measurement of water vapor transmission rate]
The water vapor permeability of the sealant liquid JCR6101 used in Comparative Examples 3-1 to 3-4 was measured by the same measurement method as in Examples 1-1 to 5 and Comparative Example 1-1. As a result, the one-pack type silicone resin JCR6101 manufactured by Toray Dow Corning Co., Ltd. was 330 g / m ² · day when the thickness was 0.30 mm. When the thickness is 0.4 mm, it is estimated to be 247.5 g / m ² · day.

[Durability test]
Examples 1-1 to 1-5 and Comparative Examples except that the measurement points (elapsed time) were changed to the times shown in the table for the semiconductor light-emitting devices obtained in the above-described Examples and Comparative Examples. A durability test was performed in the same manner as in 1-1.
Table 17 shows values of various light emission characteristics (radiant flux (μW), total luminous flux (lm), chromaticity coordinates Cx, Cy) as relative values with a measured value of 0 hour being 100%.

Note that Comparative Example 4-1 (calculation 190 hr) * is a value calculated based on an approximate curve equation from actual measurements at 282 hr and other times.
From Table 17, it can be seen that when a sealant solution having a high water vapor transmission rate is used, the durability test results in significant deterioration, particularly in non-lighting samples. In addition, also about the lighting sample, remarkable deterioration is recognized in Comparative Examples 4-1, 4-2, and 4-4.

Since the non-lighted sample is at 85 ° C in the test environment, the moisture is not evaporated and is directly affected by water vapor, so it is easily affected and deteriorates easily. As for the non-lighting samples that are easily affected by the above, the above-mentioned comparative examples are all markedly deteriorated.
In any field where light emitted from a phosphor is used with the phosphor sealed with a sealing material, when using a highly water-soluble phosphor, it is important that the phosphor does not deteriorate particularly when the lamp is not lit. . There are few products that are always lit, and many products such as home appliances and mobile phones are in a non-lighting condition except during use. For example, mobile phones placed in humid environments such as in the summer or in pockets, and traffic signals during rainy weather are susceptible to water vapor, and durability when not lit is important.

Further, for example, even if the result of the durability test at the time of lighting is good as in Comparative Example 3-3 and Comparative Example 4-3, in the durability test of around 200 hours, the radiant flux at the time of non-lighting If the total luminous flux is 60% or less, it is considered that practical application is difficult.

  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 (10)

In a semiconductor light emitting device comprising: a semiconductor light emitting element (A); and a phosphor (B) that emits light having a different wavelength by absorbing at least part of the light from the semiconductor light emitting element (A).
Water vapor at 40 ° C. when the phosphor (B) is not contained and the thickness is 0.4 mm between the semiconductor light emitting element (A) and the layer (C) containing the phosphor (B). Having a layer (D) having a transmittance of 10 g / m ² · day or less,
The phosphor (B) contains a fluorine complex phosphor activated with Mn ⁴⁺ . In a semiconductor light emitting device comprising: a semiconductor light emitting element (A); and a phosphor (B) that emits light having a different wavelength by absorbing at least part of the light from the semiconductor light emitting element (A).
A part or all of the surface of the semiconductor light emitting device is coated with a layer (E) having a water vapor transmission rate at 40 ° C. of 10 g / m ² · day or less when the thickness is 0.4 mm,
The phosphor (B) contains a fluorine complex phosphor activated with Mn ⁴⁺ . A semiconductor light emitting device. In a semiconductor light emitting device comprising: a semiconductor light emitting element (A); and a phosphor (B) that emits light having a different wavelength by absorbing at least part of the light from the semiconductor light emitting element (A).
The layer (C) containing the phosphor (B) is covered with a layer (F) having a water vapor transmission rate at 40 ° C. of 10 g / m ² · day or less when the thickness is 0.4 mm,
The phosphor (B) contains a fluorine complex phosphor activated with Mn ⁴⁺ . A semiconductor light emitting device. Water vapor at 40 ° C. when the phosphor (B) is not contained and the thickness is 0.4 mm between the semiconductor light emitting element (A) and the layer (C) containing the phosphor (B). The semiconductor light emitting device according to claim 3, further comprising a layer (D) having a transmittance of 10 g / m ² · day or less. The amount of fluorine generated by heating the phosphor (B) at 200 ° C is 0.01 µg / min or more per gram of phosphor. The semiconductor light-emitting device according to any one of claims 1 to 4, apparatus. The semiconductor light-emitting device according to claim 1, wherein the phosphor (B) has a solubility in 100 g of water at 20 ° C. of 0.005 g or more and 7 g or less. The semiconductor phosphor according to any one of claims 1 to 6, wherein the phosphor (B) has a main emission peak in a wavelength range of 610 nm or more and 650 nm or less. The phosphor (B) contains a crystal phase having a chemical composition represented by any one of the following formulas [1] to [8]. 2. The semiconductor light emitting device according to item 1.
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.)   An image display device comprising the semiconductor light-emitting device according to claim 1 as a light source.   An illumination device comprising the semiconductor light-emitting device according to claim 1 as a light source.

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