JP2002359404A - Light emitting device using phosphor - Google Patents

Abstract

(57) [Summary] An object of the present invention is to provide a light emitting device having a phosphor and having high light emission luminance. The light emitting device includes a light source and a phosphor that converts at least a part of an emission spectrum from the light source, wherein the emission spectrum from the light source is at least three.
The phosphor has an emission peak in the range of 00 nm to 430 nm, and the phosphor has at least E
A light emitting device characterized by being a phosphate and / or borate phosphor having an element represented by M ′ containing one selected from u, Mn, Sn, Fe, and Cr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting device which can be used for a signal light, a lighting, a display, an indicator, various light sources, and the like. To provide.

[0002]

2. Description of the Related Art Today, a light emitting diode (LED) or a laser diode (LD) using a semiconductor light emitting element as a light source.
Is being developed. Semiconductor light-emitting devices have the advantages of low voltage operation, small size, light weight, thin, long life, high reliability, and low power consumption. The part is being replaced.

In particular, a light-emitting element using a nitride semiconductor has been developed as a light-emitting element capable of efficiently emitting light from the ultraviolet region to the short wavelength side of visible light. For example, in a quantum well structure in which a nitride semiconductor made of an InGaN mixed crystal is used as an active layer (light emitting layer), blue and green light emitting LEDs having high luminance of 10 candela or more are being developed and commercialized.

[0004] Further, by using light from such a semiconductor light emitting element, mixed color display including white can be realized by combination with a phosphor which emits fluorescence when excited by the light.
For example, JP-A-5-152609 and JP-A-9-15
No. 3645 and JP-A-10-242513.

[0005] As such a phosphor, a blue-emitting _{phosphor, BaMg 2 Al 16 O 2 7} : Eu, (Sr,
Ca, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, BaMg ₂ Al ₁₆ O ₂₇ : Eu, Mn as a green light emitting phosphor
Zn ₂ GeO ₄ : Mn, Y ₂ O ₂ as a red light emitting phosphor
S: Eu and the like. In addition, various intermediate colors can be emitted by mixing the phosphors of these emission colors, and the mixture is used for lighting or the like so as to be particularly white.

A light emitting device using such a phosphor is also used for a light emitting screen, a decorative plate and the like.
When used as a decorative plate, for example, it is used by being mixed into concrete or glass, etc., and is effective under outdoor sunlight or indoor fluorescent light under long-wavelength ultraviolet irradiation from a UV lamp. A display effect is exhibited by the display effect.

[0007]

However, in a light-emitting device using the above-described phosphor, the red-light-emitting phosphor Y ₂ O ₂ S: Eu has lower luminous efficiency than phosphors of other colors. Therefore, in order to obtain white light by mixing, it is necessary to increase the mixing ratio. Further, this phosphor is expensive because it contains a rare earth element as a main component, and increasing the mixing ratio makes the mixed phosphor expensive. Furthermore, in the method of obtaining white light emission by mixing phosphors having three different emission colors as described above, it is difficult to adjust a mixing ratio for obtaining a target color tone, and workability is poor even in a manufacturing process. There is. Therefore, a single phosphor capable of emitting white light is desired. Further, when used for a decorative plate, a light source, or the like, a phosphor having a higher emission luminance is required to exhibit the effect.

[0008]

Accordingly, the present inventor has solved the above-mentioned problems and has used a phosphor having a high emission luminance and capable of emitting red light or a single phosphor capable of emitting white light. And a light-emitting device with high luminance. That is, the present invention is a light-emitting device including a light source and a phosphor that converts at least a part of an emission spectrum from the light source, wherein the emission spectrum from the light source is at least three.
The phosphor has an emission peak wavelength in the range of 00 nm to 430 nm, and the phosphor includes at least an element represented by M including at least one selected from Mg, Ca, Sr, Ba, and Zn;
It is a phosphate and / or borate phosphor having an element represented by M ′ containing one selected from u, Mn, Sn, Fe, and Cr. Thus, a light-emitting element having high emission luminance can be obtained.

In the light emitting device of the present invention, the phosphor is a phosphate phosphor containing at least Sr and containing Eu and / or Mn. Thus, a light emitting device capable of emitting white light can be obtained.

[0010] In the light emitting device of the present invention, the phosphor is preferably 2
(M_1-x, M '_x) O ・ aP₂O ₅・ BB₂O₃In table
Is done. However, M is Mg, Ca, Sr, Ba, Zn
M ′ is Eu, M
at least one selected from n, Sn, Fe, and Cr
is there. Also, 0.001 ≦ x ≦ 0.5, 0 ≦ a ≦ 2, 0
≦ b ≦ 3, 0.3 <a + b. This allows
A light emitting device having a wide range of emission colors can be provided.
You.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION A light emitting device using a phosphor of the present invention is a light emitting device having a light source and a phosphor for converting at least a part of an emission spectrum from the light source. In particular, the emission spectrum is at least 300 nm to 430 nm.
And a phosphor that converts at least a part of the emission spectrum.

Here, in the present invention, the phosphor is composed of at least Eu, M
It is a phosphate and / or borate phosphor having an element represented by M ′ including one selected from n, Sn, Fe, and Cr.

The above-mentioned phosphor can change the emission wavelength by changing the ratio of M and M ', and can change the emission wavelength from a red color to a white color (for example, white in a conventional color of JIS Z8110 or a system color name). Various luminescent colors can be reproduced, from white as a basic color in the figure) to further blue. Moreover, since the emission spectrum from the light-emitting layer is excited by light in a wide range from the ultraviolet region to the visible light region as described above, color mixing with light from a light source is also possible, and a wider range of wavelengths can be obtained. An emission color can be obtained. Further, among them, at least Sr is contained, and Eu and / or
Alternatively, since the phosphate phosphor containing Mn can emit white light alone, it is possible to provide a high-luminance and stable light-emitting device as compared with a case where mixed color light is obtained using phosphors of a plurality of emission colors. be able to.

When a phosphor capable of emitting visible light when excited by ultraviolet rays is used, the color of light emitted from the phosphor can be visually recognized as the color of emitted light. When a phosphor that can emit visible light when excited by visible light is used, a mixed color of the excitation wavelength from the excitation source and the emission wavelength from the phosphor can be visually recognized.

Further, the phosphor of the present invention has 2 (M_1-x,
M '_x) O ・ aP₂O₅・ BB₂O ₃Can be represented by
it can. However, M is Mg, Ca, Sr, Ba, Zn
M ′ is Eu, M
at least one selected from n, Sn, Fe, and Cr
is there. Also, 0.001 ≦ x ≦ 0.5, 0 ≦ a ≦ 2, 0
≦ b ≦ 3, 0.3 <a + b. x is the activator
Some Eu, Mn, Sn, Fe, Cr
It indicates the composition ratio of at least one kind of element, and 0.001 ≦
x ≦ 0.5 is preferred. x is less than 0.001
Degree, and when it exceeds 0.5,
It is not preferable because sufficient light emission luminance cannot be obtained. Also,
a and b indicate the composition ratio of the phosphoric acid component and the boric acid component
0 ≦ a ≦ 2, 0 ≦ b ≦ 3, 0.3 <a + b
Good. a is a range exceeding 2 and b is a range exceeding 3
Is preferable because a phosphor with high emission luminance cannot be obtained.
Absent. Light emission is possible even when a = 0 and b = 0,
When a = b = 0, no light is emitted. 0.3 <a + b is preferable.
Most preferably, a + b = 1. This
Thus, a phosphor having excellent luminous efficiency can be obtained.

FIG. 1 shows Embodiment 1 used in the present invention.
FIG. 7 is a CIE chromaticity diagram showing an example of emission colors of the phosphors obtained in 2, 5, and 47 when excited by 365 nm. From this figure, it can be seen that, by changing the composition ratio of the phosphor of the present invention, the color tone can be adjusted by variously changing the phosphor so as to have an emission spectrum of blue, white, and red.

That is, when M is Sr and M 'is Eu, E having a peak around 430-490 nm
The emission color is bluish green due to the emission of u ²⁺ , but M ′ is changed to M
n, and by changing the concentration,
It shows a red emission color.

FIG. 4 shows an emission spectrum of the phosphor obtained in Example 1 of the present invention when excited by 400 nm, and FIG.
Shows the excitation spectrum of the phosphor obtained in Example 1 of the present invention. From this figure, it can be seen that the phosphor of Example 1 of the present invention has a relatively long wavelength range of ultraviolet rays (for example, 300 nm to 330 nm).
m), a relatively short wavelength of visible light (for example, 400 nm to
430 nm) and the emission color is JIS
It can be seen that the basic color name in Z8110 is included in the white area. In addition, since this phosphor is efficiently excited in the whole region of ultraviolet rays, it can be effectively used as a phosphor for short wavelength ultraviolet rays.

The phosphor of the present invention has a particle size of 1 μm to
The range of 100 μm is preferred, and more preferably 5 μm to
50 μm. More preferably, it is 10 μm to 30 μm. Phosphors having a particle size smaller than 1 μm are relatively easy to form aggregates. Further, depending on the particle size range, the light absorptivity and the light conversion efficiency are high and the width of the excitation wavelength is wide. As described above, by using a phosphor having a large particle diameter having excellent optical characteristics, a light-emitting device using the phosphor can have high luminance.

Here, the particle size is a value obtained from a deposition standard particle size distribution curve. The sedimentation standard particle size distribution curve is obtained by measuring the particle size distribution by a laser diffraction / scattering method. The phosphor is dispersed in an aqueous solution of sodium, and the particle size range is set to 0.
It can be measured from 03 μm to 700 μm. In this volume-based particle size distribution curve, the particle size when the integrated value is 50% is defined as the particle size (center particle size) in the present invention. The phosphor of the present invention exhibits higher brightness when the particle size is in the range of 10 μm to 50 μm. In addition, it is preferable that the particle size contains a phosphor having a particle size near the center particle size with high frequency, and the frequency value is preferably 20% to 50%. By using a phosphor having a small variation in particle diameter in this manner, a light-emitting device with less emission color unevenness and stable color tone can be obtained.

The phosphor of the present invention can be obtained by the following method. Predetermined amounts of oxides of the constituent elements of the phosphor of the present invention or various compounds that can be converted into oxides by thermal decomposition are weighed and sufficiently mixed by a ball mill or the like. The obtained mixture is placed in a crucible and placed in a reducing atmosphere of N ₂ / H ₂ for 800 to 1 μm.
Bake at a temperature of 300 ° C. for 3-7 hours. After cooling, the obtained calcined product is taken out of the crucible and pulverized, and then passed through a sieve to remove coarse particles and the like. Next, it can be obtained by washing with pure water to remove unreacted raw materials, followed by dehydration and drying.

(Light Source) The phosphor of the present invention has an excitation wavelength of 3
It is 00 to 430 nm. As a light source (excitation source) capable of emitting light having such an excitation wavelength, an ultraviolet lamp, a semiconductor light emitting element, and the like can be given. In the present invention, by using a semiconductor light emitting element, a light emitting device integrated with a light source such as a light emitting diode or a laser diode can be obtained.

(Semiconductor Light-Emitting Element) In the present invention, the semiconductor light-emitting element is preferably a semiconductor light-emitting element having a light-emitting layer capable of emitting an emission wavelength capable of efficiently exciting a phosphor. As a material of such a semiconductor light emitting device, BN, SiC,
ZnSe, GaN, InGaN, InAlGaN, Al
Various semiconductors such as GaN, BAlGaN, and BInAlGaN can be given. Similarly, these elements may contain Si, Zn, or the like as an impurity element to serve as a light emission center. In particular, nitride semiconductors (for example, nitride semiconductors containing Al and Ga, nitrides containing In and Ga, etc.) can be used as a material for a light emitting layer capable of efficiently emitting short wavelengths of visible light from the ultraviolet region where phosphors can be efficiently excited. I as a semiconductor
_{n X Al Y Ga 1-X} -Y N, 0 ≦ X, 0 ≦ Y, X + Y
≦ 1) is more preferable. When the mixed crystal ratio of In or Al is increased, the emission wavelength can be shifted to a longer wavelength, so that light emission in a wide range from the ultraviolet region (about 365 nm) to the visible region (about 450 nm) is possible. .

Further, as the structure of the semiconductor, a homo structure having a MIS junction, a PIN junction, a pn junction or the like, a hetero structure, or a double hetero structure is preferably exemplified. Various emission wavelengths can be selected depending on the material of the semiconductor layer and its mixed crystal ratio. The output can be further improved by using a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed as a thin film in which a quantum effect occurs.

When a nitride semiconductor is used, sapphire, spinel, SiC, Si, ZnO,
Materials such as GaAs and GaN are preferably used. In order to form a nitride semiconductor having good crystallinity with good productivity, it is preferable to use a sapphire substrate. A nitride semiconductor can be formed on the sapphire substrate by using the HVPE method, the MOCVD method, or the like. A non-single-crystal buffer layer is formed on a sapphire substrate by growing at a low temperature such as GaN, AlN, and GaAIN, and a nitride semiconductor having a pn junction is formed thereon.

Having a pn junction using a nitride semiconductor
As an example of a light-emitting element that can efficiently emit light in the ultraviolet region,
On the sapphire substrate in a direction substantially perpendicular to the orientation flat surface
iO _TwoAre formed in a stripe shape. HV on stripe
GaN is converted to ELOG (Epitaxial) using the PE method.
 Lateral Growth GaN)
Let it grow. Subsequently, the n-type nitride
First contact layer made of lithium, n-type aluminum nitride
First cladding layer formed of GaN
Indium, aluminum and gallium well layers and nitrided aluminum
High weight with multiple layers of Luminium / Gallium barrier layers
Active layer having a well structure, p-type aluminum nitride
A second cladding layer formed of lithium, p-type gallium nitride
Double layer in which the second contact layers formed by
Examples include a configuration such as a hetero configuration. Ridges active layer
It has a triple shape and is sandwiched between guide layers,
The semiconductor laser device that can be used in the present invention
it can.

The nitride semiconductor shows n-type conductivity without being doped with impurities. When a desired n-type nitride semiconductor is formed, for example, to improve luminous efficiency, it is preferable to appropriately introduce Si, Ge, Se, Te, C, or the like as an n-type dopant. On the other hand, when forming a p-type nitride semiconductor, Zn, Mg, Be, C
It is preferable to dope a, Sr, Ba and the like. Since it is difficult to make a nitride semiconductor p-type only by doping it with a p-type dopant, it is preferable to reduce the resistance by heating the furnace or irradiating plasma after introducing the p-type dopant. When a sapphire substrate is not used, each contact layer is exposed by performing etching from the p-type side to the surface of the first contact layer. After each electrode is formed on each contact layer, the semiconductor wafer is cut into chips to form a light emitting element made of a nitride semiconductor.

(Light Emitting Device Using Phosphor) Hereinafter, a specific configuration of a light emitting device using the phosphor of the present invention will be described using a surface mount type light emitting device as shown in FIG. 2 as an example. An LED chip as a light emitting element has an emission peak wavelength of about 370 nm as an emission layer as shown in FIG.
A nitride semiconductor device having a GaN semiconductor is used. On a sapphire substrate as a more specific LED element structure,
An n-type GaN layer, which is an undoped nitride semiconductor, and Ga, which forms an n-type contact layer by forming an Si-doped n-type electrode
An N layer, an undoped nitride semiconductor n-type GaN layer,
This is a single quantum well structure of an n-type AlGaN layer that is a nitride semiconductor and then an InGaN layer that constitutes a light emitting layer. On the light emitting layer, a p-type clad layer doped with Mg
The structure is such that an lGaN layer and a GaN layer which is a p-type contact layer doped with Mg are sequentially stacked. (Note that
On the sapphire substrate, a GaN layer is formed at a low temperature to serve as a buffer layer. In addition, the p-type semiconductor is 400
Annealed above ℃. ) The surface of each pn contact layer is exposed on the same side of the nitride semiconductor on the sapphire substrate by etching. Positive and negative pedestal electrodes are respectively formed on each contact layer using a sputtering method.

Next, a Kovar package 5 having a concave portion in the center and a base portion having a Kovar lead electrode 2 inserted and fixed in a hermetically insulating manner 3 on both sides of the concave portion is used. Ni on the surfaces of the package and the lead electrodes
/ Ag layer is provided. A in the recess of the package
The above-mentioned LED chip is die-bonded with a g-Sn alloy. With this configuration, all the components of the light emitting device can be made inorganic, and even if the light emitted from the LED chip is in an ultraviolet region or a short wavelength region of visible light, the reliability is dramatically improved. A high light emitting device can be obtained.

Next, each electrode of the die-bonded LED chip and each lead electrode exposed from the bottom surface of the concave portion of the package are electrically connected to each other by the Ag wire 4. After the moisture in the concave portion of the package is sufficiently removed, the package is sealed with a Kovar lid 6 having a glass window 7 at the center, and seam welding is performed. In the glass window, the phosphor is previously contained in a slurry composed of 90 wt% of nitrocellulose and 10 wt% of γ-alumina, applied to the back of the light transmitting window of the lid, and cured by heating at 220 ° C. for 30 minutes. Constitute a color conversion member. When the light emitting device thus formed emits light, a light emitting diode capable of emitting white light with high luminance can be obtained. Hereinafter, each configuration of the present invention will be described in detail.

In the light-emitting device of the present invention, it is preferable to use a resin in order to form the light-emitting device with good mass productivity. In order to further improve the luminous efficiency, it is necessary to use a wavelength of 360 nm or more and 410
nm or less is more preferable.

The phosphor can be arranged at various locations in relation to the semiconductor light emitting element. That is, the light emitting element may be contained in a die bonding material for die bonding, or may be contained in a mold material for covering the light emitting element. Further, it may be arranged with a gap from the semiconductor light emitting element or may be directly mounted.

The fluorescent substance can be attached with various binders such as resin which is an organic material and glass which is an inorganic material. When an organic substance is used as the binder, a transparent resin having excellent weather resistance such as an epoxy resin, an acrylic resin, or silicone is preferably used as a specific material.
In particular, it is preferable to use silicone because it is excellent in reliability and can improve the dispersibility of the phosphor.

It is preferable to use an inorganic substance having a coefficient of thermal expansion close to that of the window as the binder, since the phosphor can be satisfactorily adhered to the window. As a specific method, a sedimentation method, a sol-gel method, or the like can be used. For example,
Phosphor, silanol _{(Si (OEt) 3 OH)} , and ethanol are mixed to form a slurry, after discharging the slurry from the nozzle, silanol and SiO ₂ was heated for 3 hours at 300 ° C., phosphor Can be fixed at a desired place.

Further, an inorganic binder can be used as a binder. The binder is a so-called low-melting glass, is preferably a fine particle, and it is preferable that it is extremely stable in a binder with little absorption for radiation from the ultraviolet to the visible region, and is obtained by a precipitation method. Alkaline earth borates, which are fine particles, are suitable.

When a phosphor having a large particle size is to be adhered, a binder in which the particles are ultrafine even if the melting point is high, for example, silica, alumina, or a fine particle size alkali obtained by a precipitation method. It is preferable to use an earth metal pyrophosphate, orthophosphate or the like. These binders can be used alone or as a mixture with one another.

Here, a method of applying the binder will be described. In order to sufficiently enhance the binding effect, the binder is preferably wet-pulverized in a vehicle and made into a slurry to be used as a binder slurry. The vehicle is a high-viscosity solution obtained by dissolving a small amount of a binder in an organic solvent or deionized water. For example, an organic vehicle can be obtained by adding 1% by weight of nitrocellulose as a binder to butyl acetate as an organic solvent.

A phosphor is added to the binder slurry thus obtained to prepare a coating solution. The addition amount of the slurry in the coating solution can be such that the total amount of the binder in the slurry is about 1 to 3% wt with respect to the phosphor mass in the coating solution. In order to suppress a decrease in the luminous flux maintenance rate, a method in which the amount of the binder added is small is preferable. Such a coating liquid is applied to the back of the window. After that, hot air or hot air is blown to dry. Finally, baking is performed at a temperature of 400 ° C. to 700 ° C., and the vehicle is scattered to attach a phosphor layer to a desired place with a binder.

(Diffusing Agent) In the present invention, a diffusing agent may be contained in addition to the phosphor. As a specific diffusing agent, barium titanate, titanium oxide, aluminum oxide, silicon oxide, or the like is suitably used. As a result, a light emitting device having good directivity characteristics can be obtained. The particle size of the diffusing agent is preferably 1 nm to 5 μm. A diffusing agent having a particle diameter in this range is preferable because light from the phosphor can be satisfactorily irregularly reflected, and color unevenness that tends to occur when a phosphor having a large particle diameter is used can be suppressed. On the other hand, a diffusing agent having a thickness of 1 nm to 1 μm has a low interference effect on the light wavelength from the semiconductor light emitting element, but can increase the resin viscosity without lowering the luminous intensity. Thereby, when disposing the phosphor-containing resin or the like by potting or the like, it becomes possible to substantially uniformly disperse the phosphor in the resin in the syringe and maintain the state, and to treat particles having a particle size that is relatively difficult to handle. Even when a large phosphor is used, it is possible to produce with good yield. As described above, the function of the diffusing agent in the present invention differs depending on the particle size range, and can be selected or combined in accordance with the method of use.

(Filler) In the present invention, a filler may be contained in addition to the phosphor. The specific material is the same as the diffusing agent, but the central particle size differs from the diffusing agent,
Those having a size of 5 μm to 100 μm are preferred. When a filler having such a particle diameter is contained in the light-transmitting resin, the chromaticity variation of the light-emitting device can be improved by the light scattering action, and the thermal shock resistance of the light-transmitting resin can be increased. Accordingly, even when used under high temperature, reliability can be prevented such that disconnection of a wire for electrically connecting the semiconductor light emitting element and the external electrode and separation of the bottom of the semiconductor light emitting element from the bottom of the concave portion of the package can be prevented. A light emitting device having a high level can be obtained. Further, the fluidity of the resin can be adjusted to be constant for a long time, so that the sealing member can be formed in a desired place, and mass production can be performed with high yield. Further, the filler preferably has a particle size and / or shape similar to that of the phosphor. Here, in the present specification, the term “similar particle size” refers to a case where the difference between the respective center particle sizes of the respective particles is less than 20%. This refers to a case where the difference between the values of the expressed circularity (circularity = perimeter of a perfect circle equal to the projected area of the particle / perimeter of the projection of the particle) is less than 20%. By using such a filler, the phosphor and the filler interact with each other, the phosphor can be favorably dispersed in the resin, and color unevenness is suppressed.

For example, both the phosphor and the filler have a center particle diameter of 15 μm to 50 μm, more preferably 20 μm to 50 μm.
It can be 50 μm. By adjusting the particle diameter in this way, it is possible to arrange the particles at a preferable interval. As a result, a light extraction path is secured, and the directional characteristics can be improved while suppressing a decrease in luminous intensity due to mixing of the filler. Hereinafter, examples of the present invention will be described in detail.

[0042]

(Example 1) 2 (Sr, Eu,
Mn) O.1.0P ₂ O ₅ is used. This phosphor uses SrCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (NH
_{4) 2} PO ₄ was used ₂ (Sr _{0.96, Eu 0.01,}
Mn _0.03 ) O.1.0 Adjust and mix so as to have a composition ratio of P ₂ O ₅ (SrCO ₃ : 283.4 g, Eu ₂
O ₃ : 3.52 g, MnCO ₃ : 6.90 g, (N
_{H 4) 2 HPO 4: 263.9g} ).

The raw materials are weighed and thoroughly mixed dry by a mixer such as a ball mill. This mixed material is packed in a crucible made of SiC, quartz, alumina, or the like, heated to 1200 ° C. at 960 ° C./hr in a reducing atmosphere of N ₂ / H ₂ , and fired at 1200 ° C. in a constant temperature section for 3 hours. After cooling, the obtained fired product is pulverized and dispersed in water, separated through a sieve, washed with water, and dried to obtain the phosphor of the present invention.

In this embodiment, the light emission luminance indicates a relative light emission luminance with respect to the reference phosphor. As the reference phosphor, B
aMg ₂ Al ₁₆ O ₂₇ ; Eu (blue), BaMg ₂ A
_{l 1 6 O 27; Eu,} Mn ( _{green), Y 2 O 2 S;} Eu
(Red) is mixed and mixed in such a ratio as to give a color tone according to the embodiment of the present invention. With this value taken as 100%, a relative value is obtained by simultaneous measurement at each excitation wavelength.

(Semiconductor Light Emitting Element) An LED chip using a nitride semiconductor element having a 365 nm GaN semiconductor having an emission peak in an ultraviolet region as a light emitting layer is prepared. More specifically, in the LED chip, a TMG (trimethyl gallium) gas, a TMI (trimethyl indium) gas, a nitrogen gas, and a dopant gas are flowed together with a carrier gas on a cleaned sapphire substrate, and a nitride semiconductor is formed by MOCVD. This can be formed. By switching between SiH ₄ and Cp ₂ Mg as the dopant gas, a layer to be an n-type nitride semiconductor or a p-type nitride semiconductor is formed.

The element structure of the LED chip is such that n-type Ga which is an undoped nitride semiconductor is formed on a sapphire substrate.
An N layer, a GaN layer on which a Si-doped n-type electrode is formed to be an n-type contact layer, and n which is an undoped nitride semiconductor
A containing Si to be a n-type GaN layer and an n-type cladding layer
1GaN layer, then a GaN layer as a light emitting layer, and a Mg-doped p-type cladding layer on the light emitting layer.
The structure is such that an lGaN layer, a GaN layer for increasing electrostatic withstand voltage, and a GaN layer serving as a p-type contact layer doped with Mg are sequentially laminated. (Note that a GaN layer is formed on the sapphire substrate at a low temperature to serve as a buffer layer.
The p-type semiconductor is annealed at 400 ° C. or higher after film formation. )

The surface of each pn contact layer is exposed on the same side of the nitride semiconductor on the sapphire substrate by etching. Positive and negative pedestal electrodes were formed on the respective contact layers by using a sputtering method. A metal thin film is formed as a light-transmitting electrode on the entire surface of the p-type nitride semiconductor, and then a pedestal electrode is formed on a part of the light-transmitting electrode. After a scribe line is drawn on the completed semiconductor wafer, the semiconductor wafer is divided by external force to form LED chips as semiconductor light emitting elements. This LED chip emits light having a peak wavelength of 365 nm.

On the other hand, as the housing of the light emitting device, a Kovar package having a concave portion in the center and a base portion in which Kovar lead electrodes are inserted and fixed on both sides of the concave portion in an insulating and airtight manner is used. A Ni / Ag layer is provided on the surfaces of the package and the lead electrode. Ag-Sn is placed in the recess of the package thus configured.
Die bond the LED chip with alloy. Next, each of the electrodes of the die-bonded LED chip and each of the lead electrodes exposed from the bottom surface of the concave portion of the package are electrically connected to each other by an Ag wire.

The above-obtained phosphor and SiO ₂ filler or diffusing agent are contained in a slurry composed of 90% by weight of nitrocellulose and 10% by weight of γ-alumina, and applied to the back of the light-transmitting window of the lid. The color conversion member is formed by heating and curing at 30 ° C. for 30 minutes. After the moisture in the concave portion of the package is sufficiently removed, the concave portion is sealed with a Kovar lid having a glass window at the center, and seam welding is performed to form a light emitting device.
The chromaticity coordinates of such a light emitting device are (x, y) = (0.3
05, 0.242), and the emission luminance was 125%.

The light emitting layer of the semiconductor light emitting device is
Instead of aN, an AlInGaN layer constituting the well layer and an AlInG layer serving as a barrier layer having a higher Al content than the well layer
The light emission luminance of a semiconductor light emitting device having a light emitting wavelength of 400 nm, which is a multiple quantum well structure in which a set of aN layers is formed as one set and five sets are stacked, is 176%. there were.

Hereinafter, in the light emitting device of the first embodiment,
The light emitting device of the present invention is obtained by changing the body as described below. (Example 2) SrCO as raw material₃, Eu₂O₃, Mn
CO₃, (NH₄)₂PO₄2 (Sr_0.97,
Eu_0.01, Mn_0.02) O ・ 1.0P₂O ₅Pair of
Same as Example 1 except that the composition ratio was adjusted and mixed.
To obtain the phosphor of the present invention. Such a phosphor
Chromaticity coordinates (x, y) = (0.1
82, 0.125).
%. The emission luminance is 132 at 400 nm excitation.
%.

(Example 3) SrCO as raw material₃, Eu
₂O₃, MnCO₃, (NH₄)₂PO₄And 2 (S
r_0.97, Eu_0.01, Mn_0.02) O ・ 1.0
P₂O ₅Except that they are adjusted and mixed so that the composition ratio becomes
The same procedure as in Example 1 is performed to obtain the phosphor of the present invention. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.235,0.186)
The brightness becomes 110%. In addition, the emission luminescence at 400 nm excitation
The degree is 154%.

Example 4 SrCO as raw material₃, Eu
₂O₃, MnCO₃, (NH₄)₂PO₄And 2 (S
r_0.95, Eu_0.01, Mn_0.04) O ・ 1.0
P₂O ₅Except that they are adjusted and mixed so that the composition ratio becomes
The same procedure as in Example 1 is performed to obtain the phosphor of the present invention. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.332, 0.266), and light emission
The luminance becomes 132%. In addition, the emission luminescence at 400 nm excitation
The degree becomes 181%.

Example 5 SrCO was used as a raw material.₃, Eu
₂O₃, MnCO₃, (NH₄)₂PO₄And 2 (S
r_0.94, Eu_0.01, Mn_0.05) O ・ 1.0
P₂O ₅Except that they are adjusted and mixed so that the composition ratio becomes
The same procedure as in Example 1 is performed to obtain the phosphor of the present invention. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.357,0.301)
The luminance becomes 137%. In addition, the emission luminescence at 400 nm excitation
The degree is 190%.

Example 6 SrCO was used as a raw material.₃, Eu
₂O₃, MnCO₃, (NH₄)₂PO₄And 2 (S
r_0.95, Eu_0.02, Mn_0.03) O ・ 1.0
P₂O ₅Except that they are adjusted and mixed so that the composition ratio becomes
The same procedure as in Example 1 is performed to obtain the phosphor of the present invention. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.325, 0.271), and the light emission
The luminance becomes 132%. In addition, the emission luminescence at 400 nm excitation
The degree becomes 185%.

(Example 7) SrCO as raw material₃, Eu
₂O₃, MnCO₃, (NH₄)₂PO₄And 2 (S
r_0.94, Eu_0.03, Mn_0.03) O ・ 1.0
P₂O ₅Except that they are adjusted and mixed so that the composition ratio becomes
The same procedure as in Example 1 is performed to obtain the phosphor of the present invention. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.345, 0.311), and light emission
The luminance becomes 145%. In addition, the emission luminescence at 400 nm excitation
The degree is 201%.

[2 (Ca, Eu, Mn) O · 1.0P₂
O₅Example 8 CaCO as Raw Material₃, Eu₂O₃, Mn
CO₃, (NH₄)₂PO₄2 (Ca_0.96,
Eu_0.01, Mn_0.03) O ・ 1.0P₂O ₅Pair of
Same as Example 1 except that the composition ratio was adjusted and mixed.
(CaCO₃192.2 g, Eu₂O₃:
3.52 g, MnCO₃: 6.90 g, (NH₄)₂H
PO₄: 263.9 g). Such a phosphor is known as 365
For nm excitation, chromaticity coordinates (x, y) = (0.286,0.
231), and the light emission luminance is 106%.
Further, the emission luminance becomes 155% when excited by 400 nm.

Example 9 CaCO was used as a raw material.₃, Eu
₂O₃, MnCO₃, (NH₄)₂PO₄2 (C
a_0.98, Eu_0.01, Mn_0.01) O ・ 1.0
P₂O ₅Except that they are adjusted and mixed so that the composition ratio becomes
This is performed in the same manner as in the eighth embodiment. Such a phosphor has 365n
In the case of m excitation, chromaticity coordinates (x, y) = (0.151, 0.1)
05), and the light emission luminance is 92%. Ma
In addition, the emission luminance becomes 112% when excited by 400 nm.

(Example 10) As raw materials, CaCO ₃ , E
using u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄
(Ca _0.97 , Eu _0.01 , Mn _0.02 ) O
The same operation as in Example 8 is performed, except that the composition is adjusted and mixed so as to have a composition ratio of 1.0P ₂ O ₅ . Such phosphors are 3
At 65 nm excitation, chromaticity coordinates (x, y) = (0.210,
0.161), resulting in a light emission luminance of 98%. In addition, the emission luminance becomes 134% when excited by 400 nm.

(Example 11) As raw materials, CaCO ₃ , E
using u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄
(Ca _0.95 , Eu _0.01 , Mn _0.04 ) O
The same operation as in Example 8 is performed, except that the composition is adjusted and mixed so as to have a composition ratio of 1.0P ₂ O ₅ . Such phosphors are 3
For 65 nm excitation, chromaticity coordinates (x, y) = (0.307,
0.260), resulting in a light emission luminance of 115%. In addition, the emission luminance becomes 152% when excited by 400 nm.

(Example 12) As raw materials, CaCO ₃ , E
using u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄
(Ca _0.94 , Eu _0.01 , Mn _0.05 ) O
The same operation as in Example 8 is performed, except that the composition is adjusted and mixed so as to have a composition ratio of 1.0P ₂ O ₅ . Such phosphors are 3
In the case of 65 nm excitation, chromaticity coordinates (x, y) = (0.332,
0.281), resulting in a light emission luminance of 120%. In addition, the emission luminance is 171% when excited by 400 nm.

Example 13 As raw materials CaCO ₃ , E
using u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄
(Ca _0.95 , Eu _0.02 , Mn _0.03 ) O
The same operation as in Example 8 is performed, except that the composition is adjusted and mixed so as to have a composition ratio of 1.0P ₂ O ₅ . Such phosphors are 3
At 65 nm excitation, chromaticity coordinates (x, y) = (0.305,
0.256), and the light emission luminance becomes 115%. In addition, the emission luminance is 165% when excited by 400 nm.

(Example 14) As raw materials, CaCO ₃ , E
using u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄
(Ca _0.94 , Eu _0.03 , Mn _0.03 ) O
The same operation as in Example 8 is performed, except that the composition is adjusted and mixed so as to have a composition ratio of 1.0P ₂ O ₅ . Such phosphors are 3
At 65 nm excitation, chromaticity coordinates (x, y) = (0.321,
0.292), which gives a light emission luminance of 127%. In addition, the emission luminance becomes 181% when excited by 400 nm.

[2 (Ba, Eu, Mn) O · 1.0P ₂
O ₅ ] (Example 15) BaCO ₃ , Eu ₂ O ₃ , M
2 (B) using nCO ₃ and (NH ₄ ) ₂ PO ₄
a _0.94 , Eu _0.03 , Mn _0.03 ) O · 1.0
Except for adjusting and mixing to have a composition ratio of P ₂ O ₅ ,
Performed in the same manner as in Example 1 (BaCO ₃ : 378.9 g, E
u ₂ O ₃ : 10.6 g, MnCO ₃ : 6.90 g, (N
_{H 4) 2 HPO 4: 263.9g} ). Such a phosphor has a chromaticity coordinate (x, y) = (0.1) at 365 nm excitation.
82, 0.105), and an emission luminance of 82%
Becomes The emission luminance is 101% when excited by 400 nm.
Becomes

[2 (Sr, Ba, Ca, Eu, Mn) O
・ 1.0P₂O₅(Example 16) SrCO as raw material₃, BaCO₃, C
aCO₃, Eu₂O₃, MnCO₃, (NH₄)₂PO
₄2 (Sr_0.70, Ba_0.21, Ca
_0.05, Eu_0.01, Mn_0.03) O ・ 1.0P
₂O₅Except that they were adjusted and mixed so that the composition ratio was
Performed in the same manner as in Example 1₃: 206.7 g, Ba
CO₃: 82.9 g, CaCO₃10.0 g, Eu₂
O₃: 3.52 g, MnCO₃: 6.90 g, (N
H₄)₂HPO₄: 263.9 g). Such a phosphor
Chromaticity coordinates (x, y) = (0.3
02, 0.241), and an emission luminance of 129
%. In addition, the emission luminance is 181 at 400 nm excitation.
%.

Example 17 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, Eu₂O₃, MnCO₃, (N
H₄)₂PO₄2 (Sr_0.72, B
a_0.21, Ca _0.05, Eu_0.01, Mn
_0.01) O ・ 1.0P₂O₅So that the composition ratio becomes
The same operation as in Example 16 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.171, 0.121), and light emission
The luminance becomes 107%. In addition, the emission luminescence at 400 nm excitation
The degree is 139%.

Example 18 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, Eu₂O₃, MnCO₃, (N
H₄)₂PO₄2 (Sr_0.71, B
a_0.21, Ca _0.05, Eu_0.01, Mn
_0.02) O ・ 1.0P₂O₅So that the composition ratio becomes
The same operation as in Example 16 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.230, 0.185)
The luminance becomes 113%. In addition, the emission luminescence at 400 nm excitation
The degree is 161%.

Example 19 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, Eu₂O₃, MnCO₃, (N
H₄)₂PO₄2 (Sr_0.69, B
a_0.21, Ca _0.05, Eu_0.01, Mn
_0.04) O ・ 1.0P₂O₅So that the composition ratio becomes
The same operation as in Example 16 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.325,0.261), and light emission
The luminance becomes 135%. In addition, the emission luminescence at 400 nm excitation
The degree is 191%.

Example 20 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, Eu₂O₃, MnCO₃, (N
H₄)₂PO₄2 (Sr_0.68, B
a_0.21, Ca _0.05, Eu_0.01, Mn
_0.05) O ・ 1.0P₂O₅So that the composition ratio becomes
The same operation as in Example 16 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.352, 0.295)
The luminance becomes 141%. In addition, the emission luminescence at 400 nm excitation
The degree becomes 199%.

Example 21 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, Eu₂O₃, MnCO₃, (N
H₄)₂PO₄2 (Sr_0.69, B
a_0.21, Ca _0.05, Eu_0.02, Mn
_0.03) O ・ 1.0P₂O₅So that the composition ratio becomes
The same operation as in Example 16 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.321, 0.269), and the light emission
The luminance becomes 140%. In addition, the emission luminescence at 400 nm excitation
The degree becomes 195%.

[2 (Sr, Ba, Ca, Eu, Mn, S
n) O.1.0P ₂ O ₅ ] (Example 22) SrCO ₃ , BaCO ₃ , C
aCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
₄ , using SnO ₂ , 2 (Sr _0.70 , B
a _{0 . 20} , Ca _0.05 , Eu _0.01 , Mn
_0.03 , Sn _0.01 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 1 was carried out, except that the composition ratio was adjusted and mixed so as to have a composition ratio. Such a phosphor can have chromaticity coordinates (x, y) = (0.332, 0.261) when excited at 365 nm, and has an emission luminance of 131%. In addition, the emission luminance becomes 192% when excited by 400 nm.

[2 (Sr, Ba, Ca, Eu, Mn, F
e) O ・ 1.0P₂O₅(Example 23) SrCO as raw material₃, BaCO₃, C
aCO₃, Eu₂O₃, MnCO₃, (NH₄)₂PO
₄, Fe₂O₃And 2 (Sr_0.70, Ba
_0.20, Ca_0.05, Eu_0.01, M
n_0.03, Fe_0.01) O ・ 1.0P₂O₅Composition of
Same as Example 1 except that the mixture was adjusted and mixed so as to obtain a ratio.
To do. Such a phosphor has a chromaticity at 365 nm excitation.
Coordinates (x, y) = (0.329, 0.270)
And the light emission luminance is 119%. Also, 400 nm
Upon excitation, the emission luminance is 163%.

[2 (Sr, Ba, Ca, Eu, Mn, C
r) O ・ 1.0P₂O₅(Example 24) SrCO as raw material₃, BaCO₃, C
aCO₃, Eu₂O₃, MnCO₃, (NH₄)₂PO
₄, Cr₂O₃And 2 (Sr_0.70, Ba
_0.20, Ca_0.05, Eu_0.01, M
n_0.03, Cr_0.01) O ・ 1.0P₂O₅Composition of
Same as Example 1 except that the mixture was adjusted and mixed so as to obtain a ratio.
To do. Such a phosphor has a chromaticity at 365 nm excitation.
Coordinates (x, y) = (0.352, 0.250)
And the light emission luminance is 127%. Also, 400 nm
Upon excitation, the emission luminance is 181%.

[2 (Sr, Ba, Ca, Eu, Mn,
Zn) O.1.0P ₂ O ₅ ] (Example 25) SrCO ₃ , BaCO ₃ , C
aCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
_4, ZnO, ₂ (Sr 0.65 _{using, Ba 0. 20,}
Ca _0.05 , Eu _0.01 , Mn _0.03 , Zn
_0.06 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 1 was carried out except that the composition ratio was adjusted and mixed so as to have a composition ratio of P ₂ O ₅ . Such a phosphor has a chromaticity coordinate (x, y) =
(0.372, 0.242), and the light emission luminance is 135%. In addition, the emission luminance is 201% when excited by 400 nm.

[2 (Sr, Eu, Mn) O · 0.84P
_{2 O 5 · 0.16B 2 O 3} ] ( Example 26) SrCO ₃ as a raw material, _Eu 2 _O 3, M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Sr _0.96 , Eu _0.01 , Mn _0.03 ) O
The same procedure as in Example 1 was performed except that the composition ratio was adjusted and mixed so that the composition ratio was 0.84P ₂ O ₅ · 0.16B ₂ O ₃ (S
rCO ₃ : 283.4 g, Eu ₂ O ₃ : 3.52 g, M
nCO ₃ : 6.90 g, (NH ₄ ) ₂ HPO ₄ : 22
_{1.7g, H 3 BO 3: 19.78g} ). Such a phosphor has a chromaticity coordinate (x, y) =
(0.304, 0.322), and the emission luminance is 137%. In addition, the emission luminance is 189% when excited by 400 nm.

Example 27 SrCO ₃ , E as raw materials
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Sr _0.98 , Eu _0.01 , Mn
Example 26 except that the composition ratio was adjusted and mixed so that the composition ratio became _0.01 ) O · 0.84P ₂ O ₅ · 0.16B ₂ O _3.
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.181, 0.275) when excited at 365 nm, and has a light emission luminance of 115%. Also, 40
At 0 nm excitation, the emission luminance becomes 145%.

Example 28 SrCO ₃ , E
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Sr _0.97 , Eu _0.01 , Mn
_{0.02) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 26
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.231, 0.280) when excited at 365 nm, and has a light emission luminance of 123%. Also, 40
At 0 nm excitation, the emission luminance is 166%.

Example 29 SrCO ₃ , E as raw materials
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Sr _0.95 , Eu _0.01 , Mn
Example 26 except that the composition ratio was adjusted and mixed so as to have a composition ratio of _0.04 ) O · 0.84P ₂ O ₅ · 0.16B ₂ O _3.
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.329, 0.342) when excited at 365 nm, and has a light emission luminance of 142%. Also, 40
At 0 nm excitation, the emission luminance is 198%.

(Example 30) SrCO ₃ , E
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Sr _0.94 , Eu _0.01 , Mn
Example 26 except that the composition ratio was adjusted and mixed so that the composition ratio became _0.05 ) O · 0.84P ₂ O ₅ · 0.16B ₂ O _3.
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.350, 0.371) when excited at 365 nm, and has an emission luminance of 150%. Also, 40
At 0 nm excitation, the emission luminance is 210%.

(Example 31) SrCO ₃ , E as raw materials
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Sr _0.95 , Eu _0.02 , Mn
_{0.03) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 26
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.320, 0.351) when excited at 365 nm, and has an emission luminance of 143%. Also, 40
At 0 nm excitation, the emission luminance is 203%.

(Example 32) SrCO ₃ , E as raw materials
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Sr _0.94 , Eu _0.03 , Mn
_{0.03) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 26
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.361, 0.381) when excited at 365 nm, and has an emission luminance of 162%. Also, 40
At 0 nm excitation, the emission luminance becomes 223%.

[2 (Ca, Eu, Mn) O · 0.84P
_{2 O 5 · 0.16B 2 O 3} ] ( Example 33) CaCO ₃ as a raw material, _Eu 2 _O 3, M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Ca _0.96 , Eu _0.01 , Mn _0.03 ) O
The same operation as in Example 1 was carried out except that the composition ratio was adjusted and mixed so that the composition ratio was 0.84P ₂ O ₅ · 0.16B ₂ O ₃ (C
aCO ₃ : 192.2 g, Eu ₂ O ₃ : 3.52 g, M
nCO ₃ : 6.90 g, (NH ₄ ) ₂ HPO ₄ : 22
_{1.7g, H 3 BO 3: 19.78g} ). Such a phosphor has a chromaticity coordinate (x, y) =
(0.291, 0.331), and the emission luminance is 125%. In addition, the emission luminance becomes 159% when excited by 400 nm.

(Example 34) As raw materials, CaCO ₃ , E
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Ca _0.98 , Eu _0.01 , Mn
Example 33 except that the composition ratio was adjusted to be _0.01 ) O · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ and mixed.
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.161, 0.285) when excited at 365 nm, and has a light emission luminance of 102%. Also, 40
At 0 nm excitation, the emission luminance is 129%.

(Example 35) As raw materials, CaCO ₃ , E
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
_{Using 3} and 2 (Ca _0.97 , Eu _0.01 , Mn
_{0.02) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 33
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.213, 0.301) when excited at 365 nm, and has a light emission luminance of 108%. Also, 40
At 0 nm excitation, the emission luminance is 139%.

(Example 36) CaCO ₃ , E as raw materials
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Ca _0.95 , Eu _0.01 , Mn
Example 33 except that the composition ratio was adjusted and mixed so as to have a composition ratio of _0.04 ) O · 0.84P ₂ O ₅ · 0.16B ₂ O _3.
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.311, 0.351) when excited at 365 nm, and has a light emission luminance of 127%. Also, 40
At 0 nm excitation, the emission luminance is 172%.

Example 37 As raw materials CaCO ₃ , E
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
_{Using 3} and 2 (Ca _0.94 , Eu _0.01 , Mn
_{0.05) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 33
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.330, 0.361) when excited at 365 nm, and has an emission luminance of 135%. Also, 40
The emission luminance is 182% when excited by 0 nm.

(Example 38) As raw materials, CaCO ₃ , E
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ (Ca _0.95 , Eu _0.02 , Mn
_{0.03) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 33
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.310, 0.341) when excited by 365 nm, and has a light emission luminance of 138%. Also, 40
At 0 nm excitation, the emission luminance is 175%.

(Example 39) As raw materials, CaCO ₃ , E
u ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄ , H ₃ BO
₃ and 2 (Ca _0.94 , Eu _0.03 , Mn
_{0.03) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 33
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.319, 0.365) when excited at 365 nm, and has an emission luminance of 155%. Also, 40
At 0 nm excitation, the emission luminance becomes 211%.

[2 (Ba, Eu, Mn) O · 0.84P
_{2 O 5 · 0.16B 2 O 3} ] ( Example 40) BaCO ₃ as raw material, _Eu 2 _O 3, M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Ba _0.94 , Eu _0.03 , Mn _0.03 ) O
The same procedure as in Example 1 was carried out except that the composition ratio was adjusted to be 0.84P ₂ O ₅ · 0.16B ₂ O ₃ and mixed (B
aCO ₃ : 378.9 g, Eu ₂ O ₃ : 10.6 g, M
nCO ₃ : 6.90 g, (NH ₄ ) ₂ HPO ₄ : 22
_{1.7g, H 3 BO 3: 19.78g} ). Such a phosphor has a chromaticity coordinate (x, y) =
(0.192, 0.285), and the light emission luminance is 99%. In addition, the emission luminance becomes 110% when excited by 400 nm.

[2 (Sr, Ba, Ca, Eu, Mn) O
・ 0.84P₂O₅・ 0.16B₂O ₃(Example 41) SrCO as raw material₃, BaCO₃, C
aCO₃, Eu₂O₃, MnCO₃, (NH₄)₂PO
₄, H₃BO₃2 (Ba_0.70, B
a_{0 . 21}, Ca_0.05, Eu_0.01, Mn
_0.03) O ・ 0.84P₂O₅・ 0.16B₂O₃of
Example 1 was repeated except that the composition ratio was adjusted and mixed.
Do the same (SrCO₃: 206.7 g, BaCO₃:
82.9 g, CaCO₃10.0 g, Eu₂O₃:
3.52 g, MnCO₃: 6.90 g, (NH₄)₂H
PO₄: 221.7 g, H₃BO₃: 19.78 g).
Such phosphors have chromaticity coordinates at 365 nm excitation.
(X, y) = (0.296, 0.321)
As a result, the light emission luminance becomes 138%. 400 nm excitation
In this case, the emission luminance becomes 192%.

Example 42 SrCO ₃ , B as raw materials
aCO ₃ , CaCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (N
Using H ₄ ) ₂ PO ₄ and H ₃ BO ₃ , 2 (Sr _0.72 ,
Ba _{0 . 21} , Ca _0.05 , Eu _0.01 , Mn
Example 41 except that the composition ratio was adjusted and mixed so that the composition ratio became _0.01 ) O · 0.84P ₂ O ₅ · 0.16B ₂ O _3.
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.185, 0.281) when excited at 365 nm, and has a light emission luminance of 121%. Also, 40
At 0 nm excitation, the emission luminance becomes 150%.

(Example 43) SrCO ₃ , B
aCO ₃ , CaCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (N
Using H ₄ ) ₂ PO ₄ and H ₃ BO ₃ , 2 (Sr _0.71 ,
Ba _{0 . 21} , Ca _0.05 , Eu _0.01 , Mn
_{0.02) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 41
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.235, 0.282) when excited at 365 nm, and has a light emission luminance of 130%. Also, 40
At 0 nm excitation, the emission luminance is 171%.

Example 44 SrCO ₃ and B as raw materials
aCO ₃ , CaCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (N
Using H ₄ ) ₂ PO ₄ and H ₃ BO ₃ , 2 (Sr _0.69 ,
Ba _{0 . 21} , Ca _0.05 , Eu _0.01 , Mn
_{0.04) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 41
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.328, 0.337) at 365 nm excitation, and has a light emission luminance of 151%. Also, 40
At 0 nm excitation, the emission luminance becomes 211%.

Example 45 SrCO ₃ , B
aCO ₃ , CaCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (N
Using H ₄ ) ₂ PO ₄ and H ₃ BO ₃ , 2 (Sr _0.68 ,
Ba _{0 . 21} , Ca _0.05 , Eu _0.01 , Mn
Example 41 except that the composition ratio was adjusted and mixed so that the composition ratio became _0.05 ) O · 0.84P ₂ O ₅ · 0.16B ₂ O _3.
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.355, 0.368) when excited at 365 nm, and has an emission luminance of 165%. Also, 40
At 0 nm excitation, the emission luminance is 230%.

(Example 46) SrCO ₃ , B as raw materials
aCO ₃ , CaCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (N
Using H ₄ ) ₂ PO ₄ and H ₃ BO ₃ , 2 (Sr _0.69 ,
Ba _{0 . 21} , Ca _0.05 , Eu _0.02 , Mn
_{0.03) O · 0.84P 2 O 5} · 0.16B adjusted to a composition ratio of ₂ O _3, except that the mixing, Example 41
Perform in the same manner as described above. Such a phosphor can have chromaticity coordinates (x, y) = (0.327, 0.351) when excited at 365 nm, and has an emission luminance of 156%. Also, 40
At 0 nm excitation, the emission luminance is 213%.

[2 (Sr, Ba, Ca, Eu, Mn, S
n) O · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ ] (Example 47) SrCO ₃ , BaCO ₃ , C as raw materials
aCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
_{4, H} 3 _BO 3, using a _{SnO 2 2 (Sr 0.7 0,} B
a _0.20 , Ca _0.05 , Eu _0.01 , Mn
_{0.03, Sn 0.01) O · 0.84P} 2 O 5 · 0.
The same operation as in Example 1 is performed except that the composition ratio is adjusted to 16B ₂ O ₃ and mixed. Such phosphors have 36
For 5 nm excitation, chromaticity coordinates (x, y) = (0.321,
0.331), resulting in a light emission luminance of 125%. In addition, the emission luminance becomes 162% when excited by 400 nm.

[2 (Sr, Ba, Ca, Eu, Mn, F
_{e) O · 0.84P 2 O 5} · 0.16B 2 O 3] ( Example 48) SrCO ₃ as a raw material, BaCO _3, C
aCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
_{4, H 3 BO 3, Fe} 2 O 3 was used _{2 (Sr 0. 70,}
Ba _0.20 , Ca _0.05 , Eu _0.01 , Mn
_{0.03, Fe 0.0 1) O ·} 0.84P 2 O 5 · 0.
The same operation as in Example 1 is performed except that the composition ratio is adjusted to 16B ₂ O ₃ and mixed. Such phosphors have 36
At 5 nm excitation, chromaticity coordinates (x, y) = (0.342,
0.311), and the emission luminance is 115%. In addition, the emission luminance becomes 142% when excited by 400 nm.

[2 (Sr, Ba, Ca, Eu, Mn, C
_{r) O · 0.84P 2 O 5} · 0.16B 2 O 3] ( Example 49) SrCO _3, BaCO ₃ as raw materials, C
aCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
_{4, H 3 BO 3, Cr} 2 O 3 was used _{2 (Sr 0. 70,}
Ba _0.20 , Ca _0.05 , Eu _0.01 , Mn
_{0.03, Cr 0.0 1) O ·} 0.84P 2 O 5 · 0.
The same operation as in Example 1 is performed except that the composition ratio is adjusted to 16B ₂ O ₃ and mixed. Such phosphors have 36
At 5 nm excitation, chromaticity coordinates (x, y) = (0.361,
0.281), resulting in a light emission luminance of 122%. In addition, the emission luminance becomes 162% when excited by 400 nm.

[2 (Sr, Ba, Ca, Eu, Mn, Z
_{n) O · 0.84P 2 O 5} · 0.16B 2 O 3] ( Example 50) SrCO _3, BaCO ₃ as raw materials, C
aCO ₃ , Eu ₂ O ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
₄ , H ₃ BO ₃ , and ZnO using 2 (Sr _0.65 , Ba
_0.20 , Ca _0.05 , Eu _0.01 , M
n _0.03 , Zn _0.06 ) O.0.84 P ₂ O _5.
The same procedure as in Example 1 is performed, except that the composition ratio is adjusted to 0.16B ₂ O ₃ and mixed. Such a phosphor is
With 365 nm excitation, chromaticity coordinates (x, y) = (0.35
2,0.292), and a light emission luminance of 115%
Becomes In addition, the emission luminance is 138% at 400 nm excitation.
Becomes

[2 (Sr, Mn) O.1.0P ₂ O ₅ ] (Example 51) SrCO ₃ , MnCO ₃ ,
Using (NH ₄ ) ₂ PO ₄ , 2 (Sr _0.97 , Mn
_0.03 ) O.1.0 Performed in the same manner as in Example 1 except that adjustment and mixing were performed so as to obtain a composition ratio of P ₂ O ₅ (SrCO 2
₃ : 286.4 g, MnCO ₃ : 6.90 g, (N
_{H 4) 2 HPO 4: 263.9g} ). Such a phosphor has a chromaticity coordinate (x, y) = (0.4
60, 0.450), and the emission luminance is 138.
%. The emission luminance is 198 at 400 nm excitation.
%.

(Example 52) SrCO ₃ , M
2 (S) using nCO ₃ and (NH ₄ ) ₂ PO ₄
(r _0.99 , Mn _0.01 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 51 was carried out, except that the composition ratio was adjusted and mixed. Such a phosphor can have chromaticity coordinates (x, y) = (0.440, 0.442) when excited at 365 nm, and has an emission luminance of 106%. Also, 400n
With m excitation, the emission luminance is 152%.

Example 53 SrCO ₃ , M
2 (S) using nCO ₃ and (NH ₄ ) ₂ PO ₄
r _0.98 , Mn _0.02 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 51 was carried out, except that the composition ratio was adjusted and mixed. Such a phosphor can have chromaticity coordinates (x, y) = (0.452, 0.446) when excited by 365 nm, and has a light emission luminance of 127%. Also, 400n
With m excitation, the emission luminance is 180%.

(Example 54) SrCO ₃ , M
2 (S) using nCO ₃ and (NH ₄ ) ₂ PO ₄
r _0.96 , Mn _0.04 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 51 was carried out, except that the composition ratio was adjusted and mixed. Such a phosphor can have chromaticity coordinates (x, y) = (0.462, 0.453) when excited at 365 nm, and has an emission luminance of 143%. Also, 400n
With m excitation, the emission luminance is 206%.

Example 55 SrCO ₃ , M
2 (S) using nCO ₃ and (NH ₄ ) ₂ PO ₄
(r _0.95 , Mn _0.05 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 51 was carried out, except that the composition ratio was adjusted and mixed. Such a phosphor can have chromaticity coordinates (x, y) = (0.466, 0.455) when excited at 365 nm, and has an emission luminance of 145%. Also, 400n
With m excitation, the emission luminance is 215%.

(Example 56) SrCO ₃ , M
2 (S) using nCO ₃ and (NH ₄ ) ₂ PO ₄
r _0.93 , Mn _0.07 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 51 was carried out, except that the composition ratio was adjusted and mixed. Such a phosphor can be set to chromaticity coordinates (x, y) = (0.470, 0.458) when excited at 365 nm, and has an emission luminance of 142%. Also, 400n
With m excitation, the emission luminance is 208%.

(Example 57) SrCO ₃ , M
2 (S) using nCO ₃ and (NH ₄ ) ₂ PO ₄
r _0.90 , Mn _0.10 ) O · 1.0 P ₂ O ₅ The same procedure as in Example 51 was carried out, except that the composition ratio was adjusted and mixed. Such a phosphor can have chromaticity coordinates (x, y) = (0.471, 0.459) when excited at 365 nm, and has an emission luminance of 117%. Also, 400n
With m excitation, the emission luminance is 172%.

[2 (Sr, Mn) O · 0.84P ₂ O ₅
0.16B ₂ O ₃ ] (Example 58) SrCO ₃ , MnCO ₃ ,
2 (Sr) using (NH ₄ ) ₂ PO ₄ and H ₃ BO _{3
0.97, Mn 0.03) O · 0.84P} 2 O 5 · 0.
The same operation as in Example 1 was performed except that the composition ratio was adjusted to 16B ₂ O ₃ and mixed (SrCO ₃ : 286.4).
g, MnCO ₃ : 6.90 g, (NH ₄ ) ₂ HPO ₄ :
_{221.7g, H 3 BO 3: 19.78g} ). Such a phosphor has a chromaticity coordinate (x, y) =
(0.459, 0.448), and the light emission luminance is 135%. In addition, the emission luminance becomes 192% when excited by 400 nm.

Example 59 SrCO ₃ , M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Sr _0.99 , Mn _0.01 ) O · 0.84P ₂ O ₅
Except that the composition ratio was adjusted to 0.16B ₂ O ₃ and mixed, the same procedure as in Example 58 was carried out. Such a phosphor has a chromaticity coordinate (x, y) = (0.4
39, 0.440), and the emission luminance is 10
3%. In addition, the emission luminance is 14 at 400 nm excitation.
8%.

Example 60 SrCO ₃ , M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO _{3
(Sr 0.98, Mn 0.02) O} · 0.84P 2 O 5
Except that the composition ratio was adjusted to 0.16B ₂ O ₃ and mixed, the same procedure as in Example 58 was carried out. Such a phosphor has a chromaticity coordinate (x, y) = (0.4
50, 0.444), and the emission luminance is 12
It becomes 4%. In addition, the emission luminance is 17 at 400 nm excitation.
2%.

Example 61 SrCO ₃ , M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Sr _0.96 , Mn _0.04 ) O · 0.84 P ₂ O ₅
Except that the composition ratio was adjusted to 0.16B ₂ O ₃ and mixed, the same procedure as in Example 58 was carried out. Such a phosphor has a chromaticity coordinate (x, y) = (0.4
61, 0.451), and the emission luminance is 13
9%. In addition, the emission luminance is 19 at 400 nm excitation.
8%.

Example 62 SrCO ₃ , M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Sr _0.95 , Mn _0.05 ) O · 0.84P ₂ O ₅
Except that the composition ratio was adjusted to 0.16B ₂ O ₃ and mixed, the same procedure as in Example 58 was carried out. Such a phosphor has a chromaticity coordinate (x, y) = (0.4
62, 0.451), and the emission luminance is 14
2%. Also, the emission luminance is 20 when excited by 400 nm.
3%.

Example 63 SrCO ₃ , M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Sr _0.93 , Mn _0.07 ) O · 0.84P ₂ O ₅
Except that the composition ratio was adjusted to 0.16B ₂ O ₃ and mixed, the same procedure as in Example 58 was carried out. Such a phosphor has a chromaticity coordinate (x, y) = (0.4
68, 0.456), and the emission luminance is 13
8%. Also, the emission luminance is 18 at 400 nm excitation.
9%.

Example 64 SrCO ₃ , M
Using nCO ₃ , (NH ₄ ) ₂ PO ₄ , and H ₃ BO ₃
(Sr _0.90 , Mn _0.10 ) O · 0.84P ₂ O ₅
Except that the composition ratio was adjusted to 0.16B ₂ O ₃ and mixed, the same procedure as in Example 58 was carried out. Such a phosphor has a chromaticity coordinate (x, y) = (0.4
70, 0.458), and the emission luminance is 11
8%. In addition, the emission luminance is 14 at 400 nm excitation.
8%.

[2 (Sr, Ba, Ca, Mn) O.1.
0P ₂ O ₅ ] (Example 65) SrCO ₃ , BaCO ₃ , C
aCO ₃ , MnCO ₃ , (NH ₄ ) ₂ PO ₄
(Sr _0.71 , Ba _0.21 , Ca _0.05 , Mn
_0.03 ) O.1.0 Performed in the same manner as in Example 1 except that adjustment and mixing were performed so as to obtain a composition ratio of P ₂ O ₅ (SrCO 2
₃ : 209.6 g, BaCO ₃ : 82.9 g, CaCO _{3
3: 10.0g, MnCO 3: 6.90g} , (NH 4)
₂ HPO _{4: 263.9g).} Such phosphors are 3
At 65 nm excitation, chromaticity coordinates (x, y) = (0.440,
0.430), resulting in a light emission luminance of 136%. In addition, the emission luminance is 194% when excited by 400 nm.

Example 66 SrCO ₃ , B as raw materials
aCO ₃ , CaCO ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
₄ and 2 (Sr _0.73 , Ba _0.21 , Ca
_The procedure is the same as that of Example 65, except that the composition ratio is adjusted and mixed so that the composition ratio becomes _0.05 , Mn _0.01 ) O.1.0P ₂ O ₅ . Such a phosphor can have chromaticity coordinates (x, y) = (0.420, 0.422) when excited at 365 nm, and has an emission luminance of 106%. Also, 400 nm
Upon excitation, the emission luminance is 151%.

(Example 67) SrCO ₃ , B
aCO ₃ , CaCO ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
₄ and 2 (Sr _0.72 , Ba _0.21 , Ca
_{The same} operation as in Example 65 was performed, except that the composition ratio was adjusted and mixed so that the composition ratio became _0.05 , Mn _0.02 ) O.1.0P ₂ O ₅ . Such a phosphor can have chromaticity coordinates (x, y) = (0.432, 0.428) when excited at 365 nm, and has a light emission luminance of 124%. Also, 400 nm
Upon excitation, the emission luminance becomes 168%.

Example 68 SrCO ₃ , B
aCO ₃ , CaCO ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
₄ and 2 (Sr _0.70 , Ba _0.21 , Ca
_{The same} operation as in Example 65 is performed except that the composition ratio is adjusted and mixed so that the composition ratio becomes _0.05 , Mn _0.04 ) O.1.0P ₂ O ₅ . Such a phosphor can have chromaticity coordinates (x, y) = (0.442, 0.432) when excited at 365 nm, and has an emission luminance of 135%. Also, 400 nm
Upon excitation, the emission luminance becomes 189%.

Example 69 SrCO ₃ , B
aCO ₃ , CaCO ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
₄ and 2 (Sr _0.69 , Ba _0.21 , Ca
_The procedure is the same as that of Example 65, except that the composition is adjusted and mixed so as to have a composition ratio of _0.05 , Mn _0.05 ) O.1.0P ₂ O ₅ . Such a phosphor can be set to chromaticity coordinates (x, y) = (0.445, 0.434) when excited at 365 nm, and has an emission luminance of 140%. Also, 400 nm
In the case of excitation, the emission luminance becomes 205%.

(Example 70) SrCO ₃ , B
aCO ₃ , CaCO ₃ , MnCO ₃ , (NH ₄ ) ₂ PO
₄ and 2 (Sr _0.64 , Ba _0.21 , Ca
_The procedure is the same as that of Example 65, except that the composition ratio is adjusted and mixed so as to have a composition ratio of _0.05 , Mn _0.10 ) O.1.0P ₂ O ₅ . Such a phosphor can have chromaticity coordinates (x, y) = (0.458, 0.448) when excited at 365 nm, and has an emission luminance of 121%. Also, 400 nm
Upon excitation, the emission luminance becomes 158%.

[2 (Sr, Ba, Ca, Mn) O.0.
84P₂O₅・ 0.16B₂O₃(Example 71) SrCO as raw material₃, BaCO₃, C
aCO₃, MnCO₃, (NH₄)₂PO₄, H₃BO
₃2 (Sr_0.71, Ba_0.20, Ca
_0.05, Mn_0.03) O ・ 0.84P₂O₅・ 0.
16B₂O₃Other than adjusting and mixing so that the composition ratio becomes
Is performed in the same manner as in Example 1 (SrCO₃: 209.6
g, BaCO₃: 82.9 g, CaCO₃10.0
g, MnCO₃: 6.90 g, (NH₄)₂HPO₄:
221.7 g, H₃BO₃: 19.78 g). like this
Phosphor has a chromaticity coordinate (x, y) =
(0.438, 0.440).
Degree is 130%. Also, the emission luminance at 400 nm excitation
Is 186%.

Example 72 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, MnCO₃, (NH₄)₂PO
₄, H₃BO₃2 (Sr_0.73, B
a_0.20, Ca _0.05, Mn_0.01) O · 0.8
4P₂O₅・ 0.16B₂O₃So that the composition ratio becomes
The same operation as in Example 71 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.448,0.443)
The luminance becomes 100%. In addition, the emission luminescence at 400 nm excitation
The degree becomes 140%.

Example 73 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, MnCO₃, (NH₄)₂PO
₄, H₃BO₃2 (Sr_0.72, B
a_0.20, Ca _0.05, Mn_0.02) O · 0.8
4P₂O₅・ 0.16B₂O₃So that the composition ratio becomes
The same operation as in Example 71 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.460, 0.450)
The luminance becomes 122%. In addition, the emission luminescence at 400 nm excitation
The degree is 161%.

Example 74 SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, MnCO₃, (NH₄)₂PO
₄, H₃BO₃2 (Sr_0.70, B
a_0.20, Ca _0.05, Mn_0.04) O · 0.8
4P₂O₅・ 0.16B₂O₃So that the composition ratio becomes
The same operation as in Example 71 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.463,0.450)
The luminance becomes 130%. In addition, the emission luminescence at 400 nm excitation
The degree becomes 181%.

(Example 75) SrCO was used as a raw material.₃, B
aCO₃, CaCO₃, MnCO₃, (NH₄)₂PO
₄, H₃BO₃2 (Sr_0.69, B
a_0.20, Ca _0.05, Mn_0.05) O · 0.8
4P₂O₅・ 0.16B₂O₃So that the composition ratio becomes
The same operation as in Example 71 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.467,0.456)
The luminance becomes 139%. In addition, the emission luminescence at 400 nm excitation
The degree is 192%.

(Example 76) As a raw material, SrCO₃, B
aCO₃, CaCO₃, MnCO₃, (NH₄)₂PO
₄, H₃BO₃2 (Sr_0.64, B
a_0.20, Ca _0.05, Mn_0.10) O · 0.8
4P₂O₅・ 0.16B₂O₃So that the composition ratio becomes
The same operation as in Example 71 is performed except for adjusting and mixing. This
Such a phosphor has chromaticity coordinates (x, y) at 365 nm excitation.
= (0.468,0.457)
The luminance becomes 119%. In addition, the emission luminescence at 400 nm excitation
The degree becomes 152%.

According to the present invention, it is possible to realize a light-emitting device using a phosphor capable of emitting light with high luminance at an excitation wavelength from ultraviolet light having a relatively long wavelength to visible light having a relatively short wavelength. Can be. Therefore, it is possible to obtain better luminance and mass productivity as a light source including lighting while taking advantage of the semiconductor light emitting element.

[Brief description of the drawings]

FIG. 1 is a CIE chromaticity diagram of a phosphor obtained in Examples 1, 2, 5, and 47 of the present invention.

FIG. 2 is a schematic plan view (a) and a schematic cross-sectional view (b) of a surface-mounted light emitting device that is a light emitting device of the present invention.

FIG. 3 is an excitation spectrum of a phosphor obtained in Example 1 of the present invention.

FIG. 4 shows a phosphor 400 obtained in Example 1 of the present invention.
Emission spectrum by nm excitation.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Semiconductor light emitting element 2 ... Lead electrode 3 ... Insulation sealing material 4 ... Conductive wire 5 ... Package 6 ... Lid 7 ... Translucent window part 8 ... Phosphor

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09K 11/70 CPU C09K 11/70 CPU CPW CPW CQC CQC 11/78 11/78 11/81 11/81

Claims (3)

[Claims] 1. A light emitting device comprising: a light source; and a phosphor for converting at least a part of an emission spectrum from the light source, wherein the emission spectrum from the light source is at least 300n.
m to 430 nm, and the phosphor contains at least Mg, Ca, Sr, Ba, Z
a phosphate and / or borate having an element represented by M containing one selected from n and at least an element represented by M 'containing one selected from Eu, Mn, Sn, Fe, and Cr; A light-emitting device, which is a phosphate phosphor. 2. The phosphor includes at least Sr,
The light emitting device according to claim 1, wherein the phosphor is a phosphate phosphor containing Eu and / or Mn. 3. The method according to claim 1, wherein the phosphor is 2 (M_1-x, M '_x)
O ・ aP₂O₅・ BB ₂O₃Claim 1 or contract represented by
The light emitting device according to claim 2. Where M is Mg, Ca, S
r, Ba, at least one selected from Zn,
M ′ is a small number selected from Eu, Mn, Sn, Fe, and Cr.
At least it is kind. Also, 0.001 ≦ x ≦ 0.5,
0 ≦ a ≦ 2, 0 ≦ b ≦ 3, 0.3 <a + b
You.