JP4999783B2 - Light emitting device - Google Patents

Description

The present invention relates to a light-emitting device using a phosphor, and more particularly, to a light-emitting device having high color rendering properties and a high luminous flux using a phosphor that is efficiently excited and emitted by ultraviolet light or short-wavelength visible light.

Various light-emitting elements configured to obtain light of a desired color by combining a light-emitting element and a phosphor that is excited by light generated by the light-emitting element and generates light having a wavelength region different from that of the light-emitting element. The device is known.
In particular, in recent years, as a white light-emitting device with long life and low power consumption, semiconductor light-emitting diodes such as light-emitting diodes (LEDs) and laser diodes (LD) that emit ultraviolet light or short-wavelength visible light, and phosphors using these as light sources for excitation A light-emitting device configured to obtain white light by combining the above is drawing attention.
Specific examples of such a white light emitting device include (1) a method of combining an LED that emits blue light and a phosphor that emits yellow light when excited by blue light, and (2) emits purple light or ultraviolet light. A method is known in which an LED and a plurality of phosphors that emit light of colors such as red, green, blue, and yellow are excited by violet light or ultraviolet light.
Japanese Patent No. 3503139 JP 2005-126777 A JP 2003-110150 A

However, in the white light emitting device of the method (1), the color rendering property is low because there is almost no light in the middle wavelength region of blue and yellow and there is little light in the red region obtained from the phosphor. There was a problem. In addition, since the white light is obtained by mixing the light of the LED and the phosphor, for example, if the amount of the phosphor applied varies in the manufacturing process of the white light emitting device, the balance of the amount of light emitted by the LED and the phosphor As a result, the spectrum of white light obtained varies.
On the other hand, although the white light emitting device of the method (2) is excellent in color rendering, no phosphor having a strong excitation band in the ultraviolet region or the short wavelength visible light region has been found, and a high output white light device. Realization of a light emitting device was difficult. Therefore, there has been a strong demand for the development of a phosphor that has a strong excitation band in the ultraviolet region or the short wavelength visible light region and can efficiently emit visible light. In particular, the conventionally known indium-containing gallium nitride-based (InGaN-based) LEDs have good emission characteristics in the wavelength region near 400 nm, and thus are excited efficiently in the wavelength region near 400 nm and have high emission intensity. Development of a phosphor capable of emitting visible light has been strongly desired.
In addition, in order to realize a light emitting device with high color rendering properties, it has been strongly desired to develop a phosphor having a broad emission spectrum.

The present invention has been made in view of the circumstances as described above, and an object of the present invention is to provide a light emitting device with high color rendering properties and high luminous flux using a phosphor that is efficiently excited and emitted by ultraviolet light or short wavelength visible light. The purpose is to provide.

As a result of repeated studies to solve the above-mentioned problems, the inventors have a general formula of M ¹ O ₂ .aM ² O.bM ³ X ₂ : M ⁴ (where M ¹ is Si, Ge, Ti, Zr And at least one element selected from the group consisting of Sn, M ² is at least one element selected from the group consisting of Ca, Sr, Mg, Ba and Zn, and M ³ is Mg, Ca, Sr, Ba and Zn at least one element selected from the group consisting of, X is at least one halogen element, M ⁴ is .a indicating at least one element essentially including Eu ²⁺ selected from the group consisting of rare earth elements and Mn The phosphor represented by 0.1 ≦ a ≦ 1.3 and b is in the range of 0.1 ≦ b ≦ 0.25) is effective in the ultraviolet or short wavelength visible light, particularly in the wavelength region near 400 nm. Emits visible light with high emission intensity when excited. As a result, the present invention has been completed by using this phosphor in a light emitting device.

That is, a light-emitting device according to claim 1 of the present invention includes a light-emitting element that emits ultraviolet or short-wavelength visible light, and at least one phosphor that emits visible light when excited by the ultraviolet or short-wavelength visible light. In the light emitting device, the phosphor has a general formula of M ¹ O ₂ .aM ² O.bM ³ X ₂ : M ⁴ (where M ¹ is at least selected from the group consisting of Si, Ge, Ti, Zr and Sn) One element, M ² is at least one element selected from the group consisting of Ca, Sr, Mg, Ba and Zn, and M ³ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba and Zn X represents at least one halogen element, M ⁴ represents at least one element essential to Eu ²⁺ selected from the group consisting of rare earth elements and Mn, and a represents 0.1 ≦ a ≦ 1.3. , B Is a range of 0.1 ≦ b ≦ 0.25).

According to a second aspect of the present invention, a light emitting device includes a light emitting element that emits ultraviolet light or short wavelength visible light, and at least two or more phosphors that are excited by the ultraviolet light or short wavelength visible light to emit visible light. In the light-emitting device configured to obtain white light by adding and mixing light from these phosphors in a complementary color relationship, visible light emitted from each phosphor has a general formula of M ¹ O ₂ · aM ² O · bM ³ X ₂ : M ⁴ (where M ¹ is at least one element selected from the group consisting of Si, Ge, Ti, Zr and Sn, and M ² is Ca, Sr, Mg, At least one element selected from the group consisting of Ba and Zn, M ³ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba and Zn, X is at least one halogen element, M ⁴ Are rare earth elements and In .a is 0.1 ≦ a ≦ 1.3 which represents at least one element is mandatory and the ^{Eu 2+} selected from the group consisting of Mn, b is in the range of 0.1 ≦ b ≦ 0.25) And a second phosphor that emits visible light in a complementary color relationship with the visible light emitted by the first phosphor.

In the first phosphor, when the content of M ^{4 in} the general formula is c (molar ratio), the range of c is more preferably 0.03 <c / (a + c) <0.8. .

In the first phosphor, M ^{1 in the} general formula requires at least Si, the proportion of Si is 80 mol% or more, and M ² in the general formula requires at least Ca and / or Sr. , Ca and / or Sr is 60 mol% or more, M ^{3 in the} general formula is at least Sr essential, Sr is 30 mol% or more, X in the general formula is at least Cl essential, The ratio is more preferably 50 mol% or more.

In the first phosphor, a in the general formula is in the range of 0.3 ≦ a ≦ 1.2, b is in the range of 0.1 ≦ b ≦ 0.2, and the content c of M ⁴ Is more preferably 0.05 ≦ c / (a + c) ≦ 0.5.

The production method of the first phosphor is not particularly limited, but at least the compounds represented by the following composition formulas (1) to (4) are included in the starting materials. The molar ratio of (1) :( 2) = 1: 0.1 to 1.0, (2) :( 3) = 1: 0.2 to 12.0, (2) :( 4) = 1: It can be obtained by mixing and firing the starting material, including 0.05 to 4.0.
(1) M ¹ O ₂
(2) M ² O
(3) M ³ X ₂
(4) M ⁴
(Where ^{M 1} is at least one element of Si, Ge, Ti, at least one element selected from the group consisting of Zr and Sn, ^{M 2} is selected from the group consisting of Mg, Ca, Sr, Ba and Zn , M ³ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba and Zn, X is at least one halogen element, M ⁴ is Eu ²⁺ selected from the group consisting of rare earth elements and Mn. (Indicates at least one element that is essential.)

In the starting material, M ^{1 in the} composition formula (1) requires at least Si, the proportion of Si is 80 mol% or more, and M ^{2 in the} composition formula (2) requires at least Ca and / or Sr. And the ratio of Ca and / or Sr is 60 mol% or more, M ^{3 in the} composition formula (3) is at least Sr essential, Sr is 30 mol% or more, and X in the general formula is at least It is preferable that Cl is essential and the proportion of Cl is 50 mol% or more.

In the above starting materials, the molar ratio of each compound of the composition formulas (1) to (4) is (1) :( 2) = 1: 0.25 to 1.0, (2) :( 3) = 1. : It is preferable to weigh in the range of 0.3-6.0, (2) :( 4) = 1: 0.05-3.0.
Furthermore, the molar ratio of each compound is (1) :( 2) = 1: 0.25-1.0, (2) :( 3) = 1: 0.3-4.0, (2): (4) = 1: More preferably in the range of 0.05 to 3.0.

In addition, in the said starting material, it is preferable to weigh the excess of the raw material of said compositional formula (3) more than a stoichiometric ratio. This excessive addition takes into consideration that a part of the halogen element evaporates and evaporates during firing of the raw material mixture, and it is possible to prevent the occurrence of crystal defects of the phosphor due to the lack of the halogen element.
Further, this excessive addition also acts as a flux, contributing to reaction promotion and crystallinity improvement.

Further, in the first phosphor, the measurement result of the X-ray diffraction is not particularly limited. However, at least a part of the crystal contained in the first phosphor exhibits the Kα characteristic X-ray of Cu. In the X-ray diffraction pattern used, the diffraction angle 2θ is 28.0 when the diffraction intensity of the diffraction peak with the highest intensity existing in the range of 29.0 ° or more and 30.5 ° or less is 100. There is a diffraction peak showing a diffraction intensity of 50 or more in the range of from 0 ° to 29.5 °, and a peak showing a diffraction intensity of 8 or more in the range of the diffraction angle 2θ of from 19.0 ° to 22.0 °, There is a peak having a diffraction intensity of 15 or more in the range of diffraction angle 2θ of 25.0 ° or more and 28.0 ° or less, and a diffraction intensity of 15 or more in the range of diffraction angle 2θ of 34.5 ° or more and 37.5 ° or less. And a diffraction angle 2θ of 40.0 ° or more and 42.5 Indicates diffraction intensity of 10 or more in the following ranges, it is preferable diffraction angle 2θ is phosphor with a peak having a diffraction intensity of 10 or more in the range of 13.0 ° or 15.0 ° or less.

Further, in the first phosphor, the measurement result of the X-ray diffraction is not particularly limited, but at least a part of the crystals contained in the first phosphor exhibits Mo Kα characteristic X-rays. In the diffraction pattern used, the diffraction angle 2θ is 12.0 ° or more when the diffraction intensity of the highest diffraction peak existing in the range of diffraction angle 2θ of 12.5 ° or more and 15.0 ° or less is 100. A diffraction peak showing a diffraction intensity of 50 or more exists in a range of 14.5 ° or less, a peak showing a diffraction intensity of 8 or more exists in a range of diffraction angle 2θ of 8.0 ° or more and 10.5 ° or less, and a diffraction angle. There is a peak showing a diffraction intensity of 15 or more in the range of 2θ of 11.0 ° or more and 13.0 ° or less, and a peak showing a diffraction intensity of 15 or more in the range of the diffraction angle 2θ of 15.5 ° or more and 17.0 ° or less. And the diffraction angle 2θ is 17.5 ° or more and 19.5 ° or less Range shows a diffraction intensity of 10 or more, it is preferable that the diffraction angle 2θ exists peaks indicating more diffraction intensity 10 in the following ranges 8.0 ° 5.0 ° or more.

The crystal structure of the first phosphor is not particularly limited, but at least a part of the crystals contained in the first phosphor is a crystal having a pyroxene type crystal structure. Is preferred.

Moreover, it is preferable that at least a part of the crystal contained in the first phosphor is a crystal belonging to crystal system: monoclinic crystal, Brave lattice: bottom-centered monoclinic lattice, space group: C2 / m.
In order to obtain higher emission intensity in the first phosphor, it is desirable that the amount of the crystal contained in the phosphor is as large as possible, preferably a single phase. The amount is desirably 20% by mass or more. More preferably, the emission intensity is remarkably improved at 50% by mass or more.

Incidentally, it is also possible that a characteristic composed of a mixture of the other crystal phase or amorphous phase within the range not lowering, in particular, the mixing ratio of the starting materials, SiO ₂ is excessively added, the crystal consists of SiO ₂ In the case of a phosphor in which quartz, tridymite, cristobalite or the like is synthesized as a slight byproduct, the emission intensity may be improved.

The light emitting device according to the present invention uses a light emitting element that emits ultraviolet light or short wavelength visible light as an excitation light source. Therefore, the first phosphor preferably has a strong excitation band in the wavelength range of 350 to 430 nm from the viewpoints of light emission efficiency, light emission luminance, and the like of the light emitting device.

From the viewpoint of color rendering properties of the light emitting device, the emission spectrum of the first phosphor preferably has a peak wavelength in the wavelength range of 560 to 590 nm and a half width of 100 nm or more.

The emission spectrum of the second phosphor is not particularly limited as long as it emits visible light complementary to the visible light emitted from the first phosphor, but it emits white light. For the purpose of obtaining an apparatus, it is preferable to use a phosphor that emits blue light, which is complementary color light, because the first phosphor mainly emits yellow light.
For the same purpose, from the viewpoint of color rendering properties, the emission spectrum of the second phosphor preferably has a peak wavelength in the wavelength range of 440 nm to 470 nm and a half width of 30 to 60 nm.

As an example of such a preferable second phosphor, the general formula Ca _x-yz Mg _y (PO ₄ ) ₃ Cl: Eu ²⁺ _z (where x is 4.95 <x <5.50, y is 0 <y <1.50, z is in the range of 0.02 <z <0.20, and y + z is in the range of 0.02 ≦ y + z ≦ 1.7).

The emission spectrum of the light-emitting element is not particularly limited as long as it emits at least ultraviolet light or short-wavelength visible light. However, from the viewpoint of the light emission efficiency of the light-emitting device, the emission spectrum has a peak of 350 nm to 430 nm. It is preferable that it exists in a wavelength range.

Specific examples of the light emitting element include various light sources such as a semiconductor light emitting element such as an LED or LD, a light source for obtaining light emission from vacuum discharge or thermoluminescence, and an electron beam excitation light emitting element. .
Here, by using a semiconductor light emitting element as the light emitting element, a light emitting device with a small size, power saving, and long life can be obtained.
As a suitable example of such a semiconductor light emitting device, an InGaN-based LED or LD having good light emission characteristics in a wavelength region near 400 nm can be given.

By configuring the light emitting device as described above, it is possible to obtain a light emitting device capable of emitting white light with high color rendering properties or light of other colors with high output.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples.

FIG. 1 is a schematic cross-sectional view showing a first embodiment of the light-emitting device of the present invention.
In the light emitting device 1 shown in FIG. 1, a pair of electrodes 3 a (anode) and 3 b (cathode) are formed on a substrate 2. A semiconductor light emitting element 4 is fixed on the electrode 3 a by a mount member 5. The semiconductor light emitting element 4 and the electrode 3 a are energized by the mount member 5, and the semiconductor light emitting element 4 and the electrode 3 b are energized by the wire 6. A fluorescent layer 7 is formed on the semiconductor light emitting device.

The substrate 2 is preferably formed of a material that has no electrical conductivity but high thermal conductivity. For example, a ceramic substrate (aluminum nitride substrate, alumina substrate, mullite substrate, glass ceramic substrate), a glass epoxy substrate, or the like is used. be able to.

The electrodes 3a and 3b are conductive layers formed of a metal material such as gold or copper.

The semiconductor light-emitting element 4 is an example of a light-emitting element used in the light-emitting device of the present invention. For example, an LED or LD that emits ultraviolet light or short-wavelength visible light can be used. Specific examples include InGaN-based compound semiconductors. The emission wavelength range of the InGaN-based compound semiconductor varies depending on the In content. When the In content is large, the emission wavelength becomes long, and when it is small, the wavelength tends to be short. However, the InGaN-based compound semiconductor containing In at such an extent that the peak wavelength is around 400 nm is a quantum efficiency in light emission. Has been confirmed to be the highest.

The mount member 5 is, for example, a conductive adhesive such as silver paste or gold-tin eutectic solder, and the lower surface of the semiconductor light emitting element 4 is fixed to the electrode 3a. The electrode 3a is electrically connected.

The wire 6 is a conductive member such as a gold wire, and is bonded to the upper surface side electrode of the semiconductor light emitting element 4 and the electrode 3b by, for example, ultrasonic thermocompression bonding, and electrically connects both.

In the fluorescent layer 7, a first phosphor, which will be described later, or the first phosphor and the second phosphor are sealed in a film shape covering the upper surface of the semiconductor light emitting element 4 with a binder member. For example, such a phosphor layer 7 is prepared by preparing a phosphor paste in which a phosphor is mixed in a liquid or gel binder member, and then applying the phosphor paste on the upper surface of the semiconductor light emitting element 4. It can be formed by curing the binder member of the phosphor paste.
As the binder member, for example, a silicone resin or a fluorine resin can be used. In particular, since the light-emitting device of the present invention uses ultraviolet light or short-wavelength visible light as an excitation light source, a binder member having excellent ultraviolet resistance is preferable.

The fluorescent layer 7 can be mixed with one or more types of phosphors having emission characteristics different from those of the first phosphor and the second phosphor. As a result, light of various colors can be obtained by combining light of various wavelength ranges.

The fluorescent layer 7 can also be mixed with substances other than phosphors having various physical properties. For example, the refractive index of the fluorescent layer 7 can be increased by mixing the fluorescent layer 7 with a substance having a higher refractive index than that of a binder member such as a metal oxide, a fluorine compound, or a sulfide. As a result, it is possible to reduce the total reflection that occurs when the light generated from the semiconductor light emitting element 4 enters the fluorescent layer 7 and to improve the efficiency of taking excitation light into the fluorescent layer 7. Furthermore, the refractive index can be increased without reducing the transparency of the fluorescent layer 7 by making the particle size of the substance to be mixed nanosize. In addition, average particle size of alumina, zirconia, titanium oxide, etc. 0.3-3 μm
About white powder can be mixed in the phosphor layer 7 as a light scattering agent. Thereby, uneven brightness and chromaticity in the light emitting surface can be prevented.

FIG. 2 is a schematic cross-sectional view showing a second embodiment of the light-emitting device of the present invention.
The second embodiment is a semiconductor light emitting device called a can package type. In the first embodiment, the fluorescent layer 7 is formed on the surface of the semiconductor light emitting element 4, whereas the second embodiment is a semiconductor light emitting device. In the second embodiment, the fluorescent layer 7 and the semiconductor light emitting element 4 are arranged apart from each other.
In addition, about the same part as the component of 1st embodiment shown in FIG. 1, the same code | symbol is attached | subjected and description is abbreviate | omitted.

In the light emitting device 1 shown in FIG. 2, an inert gas is sealed in an airtight space formed by a metal stem 8 and a can cap 9, and the semiconductor light emitting element 4 is attached to the metal stem 8 and the substrate 2 in the airtight space. It is housed in a form that is fixed via. The ceramic block 13 is fitted and fixed to the opening of the metal stem 8. A pair of electrode terminals 10a (anode) and 10b (cathode) extend through the ceramic block 13 into and out of the airtight space, and the electrode terminals 10a and 10b and the semiconductor light emitting element 4 are energized by wires 6 respectively. Yes. An opening 11 is formed at the center of the upper surface of the can cap 9, and a transparent plate 12 is sealed so as to close the opening 11 from the inner surface side of the can cap 9. A fluorescent layer 7 is formed in the opening 11.

The metal stem 8 and the can cap 9 are formed with an airtight space by joining their peripheral portions by welding or the like.
The metal stem 8 and the can cap are preferably made of the same material. For example, various metals and alloys such as Kovar and copper-tungsten can be used. Since the metal stem 8 supports the semiconductor light emitting element 4 in the airtight space and also plays a role of releasing the heat generated by the semiconductor light emitting element 4 to the outside of the airtight space, a material having a high thermal conductivity is preferable.

The inert gas sealed in the hermetic space is at least one kind of inert gas selected from, for example, nitrogen, helium, argon, and the like, thereby suppressing deterioration of the semiconductor light emitting element 4.

The ceramic block 13 is a non-conductive member such as alumina or aluminum nitride, and is fitted and fixed to an opening formed in the metal stem 8 to electrically insulate the electrode terminals 10a and 10b from the metal stem 8. keeping.

The semiconductor light emitting element 4 is fixed to the substrate using solder or the like, and the substrate 2 is fixed to the metal stem using solder or the like.

The electrode terminals 10a and 10b are metal conductive members, and are obtained, for example, by punching a metal flat plate.

The transparent plate 12 is a plate-like member formed of a translucent material, such as glass or resin, and can be formed in a convex shape or a concave shape as necessary to have a lens effect.

The fluorescent layer 7 is formed on the surface of the transparent plate in the opening 11, and the formation method is the same as in the first embodiment.

FIG. 3 is a schematic cross-sectional view showing a third embodiment of the light-emitting device of the present invention.
In addition, the same code | symbol is attached | subjected about the part similar to the component of 1st embodiment shown in FIG. 1, and description is abbreviate | omitted.

In the light emitting device 1 shown in FIG. 3, an electrode terminal 10 a (anode) is installed on the bottom of a cup-shaped vessel 13, and an electrode terminal 10 b (cathode) is installed on the side of the vessel.
The semiconductor light emitting element 4 is mounted on the upper surface of the electrode terminal 10 a via the mount member 5 at the bottom of the container 13. The lower surface electrode of the semiconductor light emitting element 4 and the electrode terminal 10 a are electrically connected by a mount member, and the upper surface electrode of the semiconductor light emitting element 4 and the electrode terminal 10 b are electrically connected by a wire 6.
The inner space of the container body 13 is filled with a filling member 14 so as to cover the semiconductor light emitting element 4, and the upper surface of the container body 13 is sealed with a transparent plate 12. A fluorescent layer 7 is formed on the side surface of the transparent plate 12.

The container 13 is made of a resin such as polyphthalamide, aromatic nylon, polysulfone, polyamideimide, liquid crystal polymer, and polycarbonate, and can be formed integrally with the electrode terminals 10a and 10b by insert molding or the like.
The inner space of the vessel body 13 is formed with an inner surface of the opening so that the diameter increases from the bottom toward the top, and the inner surface of the opening is subjected to a reflection treatment to reflect light from the semiconductor light emitting element 4. You can also

The filling member 14 is, for example, a transparent resin such as a silicone resin or a fluororesin, and preferably exhibits good light resistance.

The fluorescent layer 7 is formed on the inner surface of the transparent plate by the same formation method as in the first embodiment.

In the light emitting device configured as described above, when a driving current is applied to the electrodes 3a, 3b or the electrode terminals 10a, 10b, the semiconductor light emitting element 4 is energized, and the semiconductor light emitting element 4 is directed toward the fluorescent layer 7 with ultraviolet light or Irradiates light in a specific wavelength range including short-wavelength visible light. The phosphor in the phosphor layer 7 is excited by this light, and the phosphor emits light in a specific wavelength region. By utilizing such a mechanism, the light emitting device that emits desired light can be obtained by variously selecting the semiconductor light emitting element 4 and / or the phosphor.

Next, the first phosphor and the second phosphor used in the light emitting device of the present invention will be described in detail.

The first phosphor can be obtained, for example, as follows.
For the first phosphor, compounds represented by the following composition formulas (1) to (4) can be used as raw materials.
(1) M ¹ O ₂ (M ¹ represents a tetravalent element such as Si, Ge, Ti, Zr, or Sn.)
(2) M ² O (M ² represents a divalent element such as Mg, Ca, Sr, Ba, Zn, etc.)
(3) M ³ X ₂ (M ³ is a divalent element such as Mg, Ca, Sr, Ba, Zn, etc., and X is a halogen element.)
(4) M ⁴ (M ⁴ represents a rare earth element such as Eu ²⁺ and / or Mn.)

As the raw material of the composition formula (1), for example, SiO ₂ , GeO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ or the like can be used.
As a raw material of the composition formula (2), for example, a carbonate, oxide, hydroxide or the like of a divalent metal ion can be used.
As the raw material of the composition formula (3), for example, SrCl _2, SrCl ₂ .6H ₂ O, MgCl ₂ , MgCl ₂ .6H ₂ O, CaCl ₂ , CaCl ₂ .2H ₂ O, BaCl ₂ , BaCl _{2. 2H 2 O, ZnCl 2, MgF} 2, CaF 2, SrF 2, BaF 2, ZnF 2, MgBr 2, CaBr 2, SrBr 2, BaBr 2, ZnBr 2, MgI 2, CaI 2, SrI 2, BaI 2, ZnI ₂ etc. can be used.
As a raw material of the composition formula (4), for example, Eu ₂ O ₃ , Eu ₂ (CO ₃ ) ₃ , Eu (OH) ₃ , EuCl ₃ , MnO, Mn (OH) ₂ , MnCO ₃ , MnCl ₂ .4H ₂ O, Mn (NO ₃ ) ₂ · 6H ₂ O, or the like can be used.

As a raw material of the composition formula (1), M ¹ is at least Si, which is at least one element selected from the group consisting of Si, Ge, Ti, Zr and Sn, and the ratio of Si is 80 mol%. The compound which is the above is preferable.
As a raw material of the composition formula (2), M ² is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, at least Ca and / or Sr essential, and Ca and A compound having a ratio of / or Sr of 60 mol% or more is preferred.
As a raw material of the composition formula (3), M ³ is at least Sr essential, is at least one element selected from the group consisting of Mg, Ca, Sr, Mg, Ba and Zn, and Sr is 30 mol%. The above compounds are preferable, and the compound in which X is at least one halogen element in which at least Cl is essential and the proportion of Cl is 50 mol% or more is preferable.
As a raw material of the composition formula (4), M ⁴ is preferably a rare earth element in which divalent Eu is essential, and may contain a rare earth element other than Mn or Eu.

The molar ratio of the raw materials of the composition formulas (1) to (4) is (1) :( 2) = 1: 0.1 to 1.0, (2) :( 3) = 1: 0.2 to 12.0, (2) :( 4) = 1: 0.05-4.0, preferably (1) :( 2) = 1: 0.25-1.0, (2) :( 3) = 1: 0.3-6.0, (2) :( 4) = 1: 0.05-3.0, more preferably (1) :( 2) = 1: 0.25-1.0, (2): (3) = 1: 0.3-4.0, (2) :( 4) = 1: 0.05-3.0 Weighed and put each weighed raw material in an alumina mortar Grind and mix for 30 minutes to obtain a raw material mixture. This raw material mixture is put in an alumina crucible and fired in an electric furnace in a reducing atmosphere at (H ₂ / N ₂ ) in an atmosphere (5/95) at a temperature of 700 to 1100 ° C. for 3 to 40 hours to obtain a fired product. The phosphor of the present invention can be obtained by carefully washing the fired product with warm pure water and washing away excess chloride.

In particular, the raw material (divalent metal halide) having the composition formula (3) is preferably weighed in excess of the stoichiometric ratio. This is because it is considered that a part of the halogen element is vaporized and evaporated during firing, and this is to prevent the occurrence of crystal defects in the phosphor due to the lack of the halogen element. In addition, the excessively added (3) raw material is liquefied at the calcination temperature, works as a solid-phase reaction flux, promotes the solid-phase reaction, and improves the crystallinity.

In addition, after baking of the said raw material mixture, the raw material of the composition formula of said (3) added excessively exists as an impurity in the manufactured fluorescent substance. Therefore, in order to obtain a phosphor having high purity and high emission intensity, it is necessary to wash away these impurities with warm pure water.
The composition ratio shown in the general formula of the phosphor of the present invention is the composition ratio after the impurities are washed away, and the raw material of the composition formula (3), which is added excessively and becomes impurities as described above, is in this composition ratio. Not taken into account.

In order to obtain a phosphor with high luminous efficiency in the phosphor of the present invention, it is preferable to reduce the number of metal elements as impurities as much as possible. In particular, since transition metal elements such as Fe, Co, and Ni act as light emission inhibitors, use high-purity raw materials and mix impurities in the synthesis process so that the total of these elements is 500 ppm or less. It is preferable to prevent.

<Identification of crystal structure of first phosphor>
Determination of the crystal structure and the like of the first phosphor in the present invention was carried out based on the analysis results obtained by growing a single crystal of the host crystal described below.
This base crystal has M ¹ = Si, M ² = Ca and Sr, M ³ = Sr, X = Cl in the general formula M ¹ O ₂ · aM ² O · bM ³ X ₂ : M ⁴ , and M ⁴ Is a substance that does not contain.

<Generation and analysis of parent crystals>
The crystal growth of the single crystal of the base crystal was performed by the following procedure.
First, each raw material of SiO ₂ , CaO, and SrCl ₂ was weighed so that the molar ratio thereof was SiO ₂ : CaO: SrCl ₂ = 1: 0.71: 1.07, and each weighed raw material was placed in an alumina mortar. The mixture was pulverized and mixed for about 30 minutes to obtain a raw material mixture. This raw material mixture was packed in a tablet mold and uniaxially compression molded at 100 MPa to obtain a molded body. The molded body was put in an alumina crucible and covered, and then fired in air at 1030 ° C. for 36 hours to obtain a fired product. The obtained fired product was washed with warm pure water and ultrasonic waves to obtain a base crystal.
A single crystal having a diameter of 0.2 mm was obtained in the base crystal thus produced.

About the obtained base crystal, the element quantitative analysis was performed with the following method, and the composition ratio (value of a, b in the said general formula) was determined.
1. Quantitative analysis of Si The base crystal was melted with sodium carbonate in a platinum crucible, and then dissolved in diluted nitric acid to obtain a constant volume. About this solution, the amount of Si was measured using the ICP emission-spectral-analysis apparatus (SII nanotechnology Co., Ltd. product: SPS-4000).
2. Quantitative analysis of metal elements The base crystals were thermally decomposed with perchloric acid, nitric acid and hydrofluoric acid under an inert gas, and dissolved with dilute nitric acid to obtain a constant volume. About this solution, the amount of metal elements was measured using the ICP emission-spectral-analysis apparatus (SII nanotechnology Co., Ltd. product: SPS-4000).
3. Quantitative analysis of Cl The base crystal was burned in a tubular electric furnace, and the generated gas was adsorbed to the adsorbing liquid. The Cl amount of this solution was determined by ion chromatography using DX-500 manufactured by Dionex.
4). Quantitative analysis of O The base crystal was pyrolyzed in argon using a nitrogen oxygen analyzer TC-436 manufactured by LECO, and the generated oxygen was quantified by an infrared absorption method.

As a result of the above elemental quantitative analysis, the approximate composition ratio of the obtained host crystal is as follows.
SiO ₂ · 1.05 (Ca _0.6 , Sr _0.4 ) O · 0.15SrCl ₂
The specific gravity of the host crystal measured by a pycnometer was 3.4.

X-ray diffraction pattern using Mo Kα ray (wavelength λ = 0.71Å) was measured for the single crystal of the parent crystal by an imaging plate single crystal automatic X-ray structure analyzer (RIGAKU: R-AXIS RAPID). (Hereinafter referred to as measurement 1).
An example of an X-ray diffraction photograph obtained by this measurement 1 is shown in FIG.

From measurement 1, the following crystal structure analysis was performed using 5709 diffraction spots obtained in the range of 2θ <60 ° (d> 0.71 Å).

For the parent crystal, the crystal system, Brave lattice, space group, and lattice constant of the parent crystal were determined from the X-ray diffraction pattern obtained by Measurement 1 using data processing software (Rigaku: Rapid Auto) as follows.
Crystal system: Monoclinic Brave lattice: Bottom monoclinic lattice space group: C2 / m
Lattice constant:
a = 13.3030 (12) Å
b = 8.3067 (8) Å
c = 9.1567 (12) Å
α = γ = 90 °
β = 110.226 (5) °
V = 949.50 (18) ^{３ 3}

Thereafter, a rough structure was determined by a direct method using crystal structure analysis software (manufactured by RIGAKU: Crystal Structure), and then structural parameters (seat occupancy, atomic coordinates, temperature factor, etc.) were refined by a least square method.
Refinement was performed on | F | of independent 1160 points with | F |> 2σ _F , and as a result, a crystal structure model with a reliability factor R ₁ = 2.7% was obtained.
The crystal structure model is hereinafter referred to as “initial structure model”.

Table 1 shows the atomic coordinates and occupancy of the initial structure model obtained from the single crystal.

The composition ratio of the initial structure model obtained from the single crystal was calculated as follows.
SiO ₂ · 1.0 (Ca _0.6 , Sr _0.4 ) O · 0.17SrCl ₂

As a result of the above analysis, it was found that the base crystal is a crystal having a new structure that is not registered in ICDD (International Center for Diffraction Date) which is an X-ray diffraction database widely used for X-ray diffraction.

Next, the host crystal of the powder having the same form as the phosphor was prepared, and it was examined whether the crystal structure belonged to the initial structure model.

The powder base crystal was adjusted according to the following procedure. First, each raw material of SiO ₂ , CaO, SrO, and SrCl ₂ is weighed so that the molar ratio thereof is SiO ₂ : CaO: SrO: SrCl ₂ = 1.0: 0.7: 0.2: 1.0. Each raw material weighed was placed in an alumina mortar and ground and mixed for about 30 minutes to obtain a raw material mixture. This raw material mixture was packed in a tablet mold and uniaxially compression molded at 100 MPa to obtain a molded body. The molded body was placed in an alumina crucible and covered, and then fired at 1030 ° C. for 5 to 40 hours to obtain a fired product. The obtained fired product was washed with warm pure water and ultrasonic waves to obtain a powder base crystal.

Next, in order to obtain the detailed crystal structure of the powder base crystal, a powder X-ray diffraction measurement is performed using a Kα characteristic X-ray of Mo with a high-resolution powder X-ray diffractometer (manufactured by RIGAKU: custom-made) of Nagoya University. (Hereinafter referred to as measurement 2).
Rietveld analysis was performed on the result of measurement 2 to identify the crystal structure. In conducting the Rietveld analysis, the structural model was refined by the least-squares method using the lattice constant, atomic coordinates, and space group of the initial structural model as a model.

As a result, the diffraction pattern observed in measurement 2 and the calculated diffraction pattern fitted by Rietveld analysis are in good agreement, and the R factor for determining the coincidence scale is a very small value of R _WP = 2.84%. Indicated. From this, the single crystal base crystal and the powder base crystal were determined to be crystals having the same structure.

FIG. 5 shows a Rietveld analysis fitting diagram for measurement 2. FIG.
In the upper part of FIG. 5, the solid line is a powder X-ray diffraction pattern calculated by Rietveld analysis, and the cross plot shows the powder X diffraction pattern observed by measurement 2.
The middle stage in FIG. 5 shows the diffraction peak angle by the calculation obtained by Rietveld analysis.
The lower part in FIG. 5 is a plot of the difference between the calculated value and the observed value of the powder X-ray diffraction pattern shown in the upper part. There is almost no difference between the two, and it can be seen that they are in good agreement.

The lattice constant of the refined powder base crystal is shown below.
a = 13.2468 (4) Å, b = 8.3169 (2) Å, c = 9.1537 (3) Å
α = γ = 90 °, β = 110.251 (2) °
V = 946.1 (1) ^{３ 3}

Table 2 shows the atomic coordinates of the refined powder base crystal.

The theoretical composition ratio of the powder base crystal calculated by Rietveld analysis based on Measurement 2 is shown below.
<Theoretical composition ratio of powder base crystal>
SiO ₂ · 1.0 (Ca _0.6 , Sr _0.4 ) O · 0.17SrCl ₂

Elements that can form a solid solution in the host crystal are listed below.
Here, the solid solution is the same although the lattice constant is different from the parent crystal by changing the composition ratio of the elements constituting the parent crystal, or by substituting a part of the elements constituting the parent crystal with another element. It has a crystal structure of
<Elements that can be dissolved in the base crystal>
Si-substituted element of SiO ₂ : Ge, Ti, Zr, and Sn
Ca and / or Sr substitution elements of (Ca _0.6 , Sr _0.4 ) O: Mg, Ba, Zn, Mn and Sr substitution elements of rare earth element SrCl ₂ : Mg, Ca, Ba, and Zn
Cl substitution element of SrCl ₂ : F, Br, and I
In addition, a part of SiO ₂ composed of Group 4 element oxide can be replaced with 1/2 (B, P) O ₄ , 1/2 (Al, P) O ₄ .

<Identification of crystal structure of first phosphor>
Identification of the crystal structure of the solid solution can be determined by the identity of the diffraction results of X-ray diffraction or neutron diffraction, but a crystal in which a part of the constituent element is replaced with another element capable of solid solution from the original crystal Since the lattice constant changes, even if the crystal belongs to the same crystal structure as the original crystal, the diffraction results are not completely the same.
In crystals belonging to the same crystal structure, the diffraction angle shifts to the high angle side when the lattice constant decreases due to element replacement, and the diffraction angle shifts to the low angle side when the lattice constant increases.

Therefore, Eu ²⁺ (M ⁴ element in the general formula) in which the powder base crystal and a part of Ca and / or Sr (M ² element in the general formula) constituting the host crystal serve as the emission center of the phosphor. It was evaluated using the following determination method whether the first phosphor (phosphor 1 to be described later) replaced with 1 belongs to the same crystal structure.

As a determination method for identifying a crystal structure, Rietveld analysis is performed using the results of X-ray diffraction (or neutron diffraction) as a determination target, using the lattice constant, atomic coordinates, and space group of the initial crystal model as a model, and R factor It can be determined whether or not the same structure is obtained.
Specifically, if the Rietveld analysis to be determined converges to a low R factor at the same level as the Rietveld analysis of the powder base crystal, it can be determined that the crystals have the same structure.
In addition, by comparing lattice constants and atomic coordinates obtained by Rietveld analysis, it is possible to discuss fine structural differences.

In order to use this determination method, first, an X-ray diffraction pattern was measured for the phosphor of the present invention (phosphor 1 described later) under the same conditions as in measurement 2 (hereinafter referred to as measurement 3).
Based on the obtained X-ray diffraction pattern, Rietveld analysis was performed using the initial structure model as a model. As a result, the R factor R _wp value of the criterion was very small as 3.69%, and converged at the same level as the R _wp value of the powder base crystal.
FIG. 6 shows a Rietveld analysis fitting diagram for measurement 3. FIG.
In the upper part of FIG. 6, the solid line is the powder X-ray diffraction pattern calculated by Rietveld analysis, and the cross plot shows the powder X diffraction pattern observed by the measurement 3.
The middle stage in FIG. 6 shows the peak angle of diffraction by calculation obtained by Rietveld analysis.
The lower part in FIG. 6 is a plot of the difference between the calculated value and the observed value of the powder X-ray diffraction pattern shown in the upper part. There is almost no difference between the two, and it can be seen that they are in good agreement.
From the above, it is determined that the first phosphor has the same crystal structure as the host crystal.

The second phosphor can be obtained, for example, as follows.
The second phosphor uses CaCO ₃ , MgCO ₃ , CaCl ₂ , CaHPO ₄ , and Eu ₂ O ₃ as raw materials, and the molar ratio of these raw materials is CaCO ₃ : MgCO ₃ : CaCl ₂ : CaHPO ₄ : Eu _2. O ₃ = 0.05 to 0.35: 0.01 to 0.50: 0.17 to 0.50: 1.00: 0.005 to 0.050 Weighed at a predetermined ratio and weighed Each raw material is put in an alumina mortar and pulverized and mixed for about 30 minutes to obtain a raw material mixture. This raw material mixture is put in an alumina crucible and fired at a temperature of 800 ° C. or higher and lower than 1200 ° C. for 3 hours in an N ₂ atmosphere containing ₂ to 5% of H ₂ to obtain a fired product. The second phosphor can be obtained by carefully washing the fired product with warm pure water and washing away excess chloride.

Note that the for the second weighing CaCl ₂ in obtaining the raw material mixture (molar ratio), with respect to the composition ratio of the second phosphor to be manufactured, more than 0.5mol than its stoichiometric ratio It is preferable to weigh the excess amount. Thereby, it is possible to prevent the occurrence of crystal defects of the second phosphor due to the lack of Cl ₂ .

The light-emitting device configured as described above will be described in more detail with reference to the following examples. However, the following description of the light-emitting device, the manufacturing method, the chemical composition of the phosphor, and the like will be given below. The embodiment is not limited in any way.

First, the phosphor used in the light emitting device of this example will be described in detail.
<Phosphor 1>
A phosphor represented by SiO ₂ · 0.9 (Ca _0.5 , Sr _0.5 ) O · 0.17SrCl ₂ : Eu ²⁺ _0.1 .
The phosphor 1 is an example of the first phosphor. In the general formula M ¹ O ₂ .aM ² O.bM ³ X ₂ : M ⁴ , M ¹ = Si, M ² = Ca / Sr (mol) Ratio 50/50), M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , a = 0.9, b = 0.17, M ⁴ content c (molar ratio) is c / (a + c) = It is a phosphor synthesized so as to be 0.1.
The phosphor 1 is manufactured by first using SiO ₂ , Ca (OH) ₂ , SrCl ₂ .6H ₂ O, and Eu ₂ O ₃ with a molar ratio of SiO ₂ : Ca (OH) ₂ : SrCl. _{2 · 6H 2 O: Eu 2} O 3 = 1.0: 0.65: 1.0: 0.13 were weighed so, the raw materials were weighed and mixed placed about 30 minutes pulverized in an alumina mortar, raw A mixture was obtained. This raw material mixture was put into an alumina crucible and fired at 1030 ° C. for 5 to 95 hours (H ₂ / N ₂ ) in an atmosphere (5/95) in a reducing atmosphere electric furnace to obtain a fired product. The obtained fired product was carefully washed with warm pure water to obtain the present phosphor 1.

<Phosphor 2>
A phosphor represented by SiO ₂ · 0.9 (Ca _0.6 , Sr _0.4 ) O · 0.17SrCl ₂ : Eu ²⁺ _0.1 .
The phosphor 2 is an example of the first phosphor. In the general formula M ¹ O ₂ .aM ² O.bM ³ X ₂ : M ⁴ , M ¹ = Si, M ² = Ca / Sr (moles) Ratio 60/40), M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , a = 0.9, b = 0.17, M ⁴ content c (molar ratio) is c / (a + c) = It is a phosphor synthesized so as to be 0.1.
The phosphor 2 is a phosphor in which cristobalite is generated in the phosphor by adding excessive SiO ₂ at the mixing ratio of the raw materials.
The phosphor 2 is manufactured by first using SiO ₂ , Ca (OH) ₂ , SrCl ₂ .6H ₂ O, and Eu ₂ O ₃ with a molar ratio of SiO ₂ : Ca (OH) ₂ : SrCl. _{2 · 6H 2 O: Eu 2} O 3 = 1.1: 0.45: 1.0: 0.13 and were weighed so as to, after that obtaining phosphor 2 in the same manner as the phosphor 1 .

<Phosphor 3>
A phosphor represented by SiO ₂ · 0.86 (Ca _0.47 , Sr _0.52 , Ba _0.01 ) O · 0.17SrCl ₂ : Eu ²⁺ _0.14 .
The phosphor 3 is an example of the first phosphor. In the general formula M ¹ O ₂ .aM ² O.bM ³ X ₂ : M ⁴ , M ¹ = Si, M ² = Ca / Sr / Ba (Molar ratio 47/52/1), M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , a = 0.86, b = 0.17, index c defining the amount of M ⁴ content c This is a phosphor synthesized so that /(a+c)=0.14.
In addition, this phosphor 3 is a phosphor in which Ba is added in addition to Ca and Sr as M ² elements, and cristobalite is generated in the phosphor by adding excessive SiO ₂ at the mixing ratio of raw materials. Phosphor.
In the production of the phosphor 3, first, SiO ₂ , CaCO ₃ , BaCO ₃ , SrCl ₂ .6H ₂ O and Eu ₂ O ₃ are used in a molar ratio of SiO ₂ : CaCO ₃ : BaCO ₃ : SrCl _2. 6H ₂ O: Eu ₂ O ₃ = 1.68: 0.45: 0.02: 1.0: 0.13 Weighed so that the phosphor 3 was obtained in the same manner as the phosphor 1 after that. Got.

<Phosphor 4>
A phosphor represented by SiO ₂ · 0.86 (Ca _0.49 , Sr _0.50 , Mg _0.01 ) O · 0.17SrCl ₂ : Eu ²⁺ _0.14 .
The phosphor 4 is an example of the first phosphor. In the general formula M ¹ O ₂ .aM ² O.bM ³ X ₂ : M ⁴ , M ¹ = Si, M ² = Ca / Sr / Mg (Molar ratio 49/50/1), M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , a = 0.86, b = 0.17, index c defining the amount of M ⁴ content c This is a phosphor synthesized so that /(a+c)=0.14.
This phosphor 4 is a phosphor in which Mg is added in addition to Ca and Sr as M ² elements, and cristobalite is generated in the phosphor by adding excessive SiO ₂ at the mixing ratio of raw materials. Phosphor.
In the production of the phosphor 4, first, SiO ₂ , CaCO ₃ , MgCO ₃ , SrCl ₂ .6H ₂ O and Eu ₂ O ₃ are used in a molar ratio of SiO ₂ : CaCO ₃ : MgCO ₃ : SrCl _2. 6H ₂ O: Eu ₂ O ₃ = 1.68: 0.45: 0.02: 1.0: 0.13 Weighed so that the phosphor 4 was obtained in the same manner as the phosphor 1 after that. Got.

<Phosphor 5>
A phosphor represented by (Ca _4.67 Mg _0.5 ) (PO ₄ ) ₃ Cl: Eu _0.08 .
The phosphor 5 is an example of the second phosphor.
The phosphor 5 is manufactured by first using CaCO ₃ , MgCO ₃ , CaCl ₂ , CaHPO ₄ , and Eu ₂ O ₃ as raw materials, and the molar ratio thereof is CaCO ₃ : MgCO ₃ : CaCl ₂ : CaHPO ₄ : Eu. Weighed so that ₂ O ₃ = 0.42: 0.5: 3.0: 1.25: 0.04, and put each weighed raw material in an alumina mortar for about 30 minutes to obtain a raw material mixture. . This raw material mixture was put in an alumina crucible and fired at a temperature of 800 ° C. or more and less than 1200 ° C. for 3 hours in an N ₂ atmosphere containing ₂ to 5% of H ₂ to obtain a fired product. The obtained fired product was carefully washed with warm pure water to obtain the present phosphor 5.

<Comparative phosphor 1>
As a comparative phosphor 1, a phosphor represented by BaMgAl ₁₀ O ₁₇ : Eu, Mn (made by Kasei Optonics Co., Ltd.) was used.
This phosphor is known to have excellent light resistance among the near-ultraviolet-excited green-emitting phosphors listed in the national project “Development of high-efficiency electro-optic conversion compound semiconductor (21st Century Lighting Project)”. Yes.

<Comparative phosphor 2>
As the comparative phosphor 2, a phosphor represented by Sr ₅ (PO ₄ ) ₃ Cl: Eu (manufactured by Kasei Optonics Co., Ltd.) was used.
This phosphor is known as a blue phosphor for a three-wavelength fluorescent lamp.

The crystal structures of the phosphors 1 to 5 were confirmed to be the target crystal structure by using an X-ray diffractometer (manufactured by Rigaku Corporation: RINT-Ultima3, X-ray tube: Cu target enclosing tube). In particular, in the phosphors 1 to 4 as the first phosphor, two types of diffraction patterns represented by the following FIGS. 7 and 8 were confirmed.
FIG. 7 shows an X-ray diffraction pattern using Cu Kα characteristic X-rays measured for the phosphor 1.
FIG. 8 shows an X-ray diffraction pattern using Cu Kα characteristic X-rays measured for the phosphor 2.

7 and 8, in any X-ray diffraction pattern using the Kα characteristic X-ray of Cu, the diffraction peak 2θ having a diffraction angle 2θ in the range of 29.0 ° or more and 30.5 ° or less has the highest intensity. When the diffraction intensity is 100, a diffraction peak having a diffraction intensity of 50 or more exists in the range of the diffraction angle 2θ of 28.0 ° or more and 29.5 ° or less, and the diffraction angle 2θ is 19.0 ° or more and 22.0. There is a peak showing a diffraction intensity of 8 or more in the range of ° or less, a peak showing a diffraction intensity of 15 or more in a range of the diffraction angle 2θ of 25.0 ° or more and 28.0 ° or less, and a diffraction angle 2θ of 34. There is a peak showing a diffraction intensity of 15 or more in a range of 5 ° or more and 37.5 ° or less, a diffraction angle 2θ of 40.0 ° or more and 42.5 ° or less showing a diffraction intensity of 10 or more, and a diffraction angle 2θ of A peak exhibiting a diffraction intensity of 10 or more in a range of 13.0 ° to 15.0 °. There it can be seen to exist.
This suggests that the powder base crystal, phosphor 1 and phosphor 2 all belong to the same crystal structure.

Further, in FIG. 8, a diffraction peak that is not observed in the initial model is confirmed in the vicinity of 2θ = 21.7 °. As a result of qualitative analysis by X-ray diffraction, it was confirmed that this diffraction peak (arrow in the figure) was derived from cristobalite.
From this, it can be seen that the phosphor 2 contains impurities, but its crystal structure belongs to the same crystal structure as the host crystal or phosphor 1.
The composition ratios of phosphors 1 to 4 (values of a and b in the above general formula) are based on the above-described data relating to the crystal structure of the base crystal, and an electronic probe microanalyzer (manufactured by JEOL: JOEL JXA-8800R). Was used to measure and determine.

<Evaluation results of phosphors 1 to 4>
With respect to the phosphors 1 to 4 and the comparative phosphor 1, the integrated emission intensity under 400 nm excitation was measured. The measurement results are shown in Table 3 as relative values where the comparative phosphor 1 is 100.

From Table 3, the phosphors 1 to 4 show an integrated light emission intensity of at least 1.4 times that of the comparative phosphor 1. From this, it can be seen that the phosphors 1 to 4 can be efficiently excited in the wavelength region near 400 nm and emit visible light with high emission intensity.
In addition, it can be seen that phosphors 2 to 4 in which cristobalite is generated in the phosphor by adding SiO ₂ excessively in the mixing ratio of the raw materials show better light emission characteristics than phosphor 1. .

FIG. 9 shows the emission spectrum (solid line) of phosphor 1 under excitation of 400 nm and the emission spectrum (dotted line) of phosphor 1 for comparison.
FIG. 10 shows the emission spectrum (solid line) of phosphor 2 under excitation at 400 nm and the emission spectrum (dotted line) of phosphor 1 for comparison.
FIG. 11 shows the emission spectrum (solid line) of phosphor 3 under excitation at 400 nm and the emission spectrum (dotted line) of phosphor 1 for comparison.
FIG. 12 shows the emission spectrum (solid line) of phosphor 4 under excitation at 400 nm and the emission spectrum (dotted line) of phosphor 1 for comparison.
In addition, the vertical axis | shaft of the graph in FIGS. 9-12 shows the relative light emission intensity of fluorescent substance 1-4 and the fluorescent substance for a comparison.

9 to 12, it can be seen that phosphors 1 to 4 all have an emission spectrum peak in the wavelength range of 560 to 590 nm and a half width of 100 nm or more. From this, it can be seen that the phosphors 1 to 4 can emit broad visible light having high color rendering properties.

FIG. 13 shows an excitation spectrum of the phosphor 1.
From FIG. 13, it can be seen that phosphor 1 has an excitation spectrum peak in the wavelength range of 350 to 430 nm. From this, it can be seen that the phosphor 1 is efficiently excited in the wavelength region near 400 nm.
In addition, it can be seen from FIG. 13 that the phosphor 1 hardly absorbs light in the wavelength region of 450 to 480 nm. From this, when the phosphor 1 is used in combination with another phosphor that emits light in the wavelength range of 450 to 480 nm, for example, when a white light emitting device is configured by combining the phosphor 1 and the blue light emitting phosphor. Since the blue phosphor does not absorb the light emitted, a light emitting device with high luminous efficiency and little color shift can be constructed.

<Evaluation result of phosphor 5>
As a result of measuring the integrated luminescence intensity under the excitation of 400 nm for the phosphor 5 and the comparative phosphor 2, the integrated luminescence intensity of the phosphor 5 had a relative value of 141 with the comparative phosphor 2 being 100.

FIG. 14 shows the emission spectrum (solid line) of phosphor 4 under excitation at 400 nm and the emission spectrum (dotted line) of phosphor 2 for comparison.
From FIG. 14, it can be seen that the phosphor 4 has better emission intensity than the comparative phosphor 2. Moreover, since the half width of the emission spectrum of the phosphor 5 is as wide as 38 nm, it is expected that a white light emitting device having high color rendering properties will be configured using the phosphor 5. That is, in the white light emitting device using the above-described method of combining the LED emitting blue light and the phosphor emitting yellow light, the half width of the emission spectrum of the LED emitting blue light is about 20 nm. The white light emitting device using the present invention 4 as a blue light source can obtain a broader blue light and is expected to have a high color rendering property.

FIG. 15 shows an excitation spectrum of the phosphor 5.
FIG. 15 shows that the phosphor 5 is efficiently excited by light in the wavelength range of 380 to 430 nm.

Next, the structure of the light-emitting device of an Example is explained in full detail.
<Configuration of Light Emitting Device (Type 1)>
The light emitting devices of Examples 1a to 1c and 2a to 2d are those using the following specific configuration in the first embodiment.
In addition, the structure of the following light-emitting device is a structure common about Example 1a-1c, Example 2a-d2, Reference Example 1, and Comparative Example 1 except the kind of used fluorescent substance.
First, an aluminum nitride substrate was used as the substrate 2, and an electrode 3a (anode) and an electrode 3b (cathode) were formed using gold on the surface.
Further, as the semiconductor light emitting element 4, a 1 mm square LED having a light emission peak at 405 nm (SemiLEDs: MvpLED ^™ SL-V-U40AC) was used, and a silver paste dropped using a dispenser on the electrode 3a (anode). The lower surface of the LED was bonded onto (available from Able Stick, Inc .: 84-1LMISR4), and the silver paste was cured at 175 ° C. for 1 hour.
Also, a Φ45 μm gold wire was used as the wire 6, and this gold wire was bonded to the upper surface side electrode of the LED and the electrode 3b (cathode) by ultrasonic thermocompression bonding.
Moreover, using a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd .: JCR6140) as a binder member, a phosphor paste in which various phosphors or a mixture of plural phosphors is mixed so as to be 30 vol% is prepared. After applying this phosphor paste to the upper surface of the semiconductor light emitting device 4 to a thickness of 100 μm, the phosphor layer 7 is fixed by step curing for 40 minutes in an 80 ° C. environment and then for 60 minutes in a 150 ° C. environment. Formed.

The following Examples 1a to 1c, Examples 2a to 2d, Reference Example 1 and Comparative Example 1 were produced based on the above-described phosphor and the structure of the light emitting device (type 1).
<Examples 1a to 1d>
In Examples 1a to 1d, phosphors 1 to 4 are used as the first phosphor. As shown in Table 4, Example 1a is phosphor 1, Example 1b is phosphor 2, and In Example 1c, phosphor 3 was prepared using phosphor 3, and in Example 1d, phosphor 4 was prepared. Using these phosphor pastes, the light emitting devices of Examples 1a to 1d were prepared.
<Examples 2a to 2d>
This Example 2a-2d is an Example which used the fluorescent substance 2 as said 1st fluorescent substance, and used the fluorescent substance 5 as said 2nd fluorescent substance, Table 4 shows the fluorescent substance 2 and the fluorescent substance 5. The said phosphor paste was produced using the mixture mixed by the mixture ratio (weight ratio), and the light-emitting device of Example 2a-2d using these phosphor paste was produced.

<Reference Example 1>
As Reference Example 1, the phosphor paste was prepared using only the phosphor 5, and the light emitting device of Reference Example 1 using this phosphor paste was prepared.

<Comparative Example 1>
Phosphor BaMgAl ₁₀ O ₁₇ : Eu (blue), phosphor BaMgAl ₁₀ O ₁₇ : Eu, Mn (green) and phosphor La ₂ O ₂ S: Eu are blended (weight ratio) 3 (blue): 12 ( Green): The phosphor paste was prepared using a mixture of 85 (red), and the light emitting device of Comparative Example 1 using the phosphor paste was prepared.

<Evaluation of Examples 1a to 1d and Examples 2a to 2d>
Each light emitting device was caused to emit light by supplying a current of 10 mA in an integrating sphere, and the luminous flux ratio and the spectral spectrum were measured with a spectroscope (manufactured by Instrument System: CAS140B-152). The measurement results will be described in detail below.

Table 5 shows the luminous flux ratio, chromaticity coordinates (cx, cy), color temperature (K), and average color rendering coefficient (Ra) when a driving current of 10 mA is applied to each light emitting device.
The luminous flux ratio is shown as a relative value where the luminous flux is 100 when a driving current of 10 mA is applied to the light emitting device of Comparative Example 1.

From Table 5, it can be seen that the light emitting device of any of the examples is a light emitting device having a luminous flux that is six times higher than that of Comparative Example 1.
In addition, it can be seen that the color rendering properties of Comparative Example 1 are Ra 22.8, while all the examples have high color rendering properties of Ra 60 or more. In particular, it can be seen that Examples 2a to 2d using a mixture of phosphor 1 and phosphor 4 ensure a high color rendering property of Ra 70 or higher.

FIG. 16 shows chromaticity coordinates (cx, cy) of light emitted when a driving current of 10 mA is applied to each light emitting device on the chromaticity diagram.
In addition, the area | region shown as (alpha) in the figure is an area | region of the white prescription | regulation (JIS-D-5500) of a vehicle lamp.
From Table 5, the chromaticity coordinates of Example 1b using only the first phosphor (Phosphor 2) are located in the yellow region, and that of Reference Example 1 using only the second phosphor (Phosphor 5). It can be seen that the chromaticity coordinates are located in the blue region.
In addition, the chromaticity coordinates of Examples 2a to 2d using the mixture of the first phosphor (phosphor 2) and the second phosphor (phosphor 5) are implemented because the light of both phosphors is mixed. It can be seen that the chromaticity coordinates of Example 1b and the chromaticity coordinates of Reference Example 1 are positioned substantially linearly. In addition, the phosphor 2 and the phosphor 5 are in a complementary color relationship, and the chromaticity coordinates of Examples 2a to 2d are located in the white region, and the color temperature is in the warm white to daylight color region of 3000 to 4600K. .
From the above results, by adjusting the blend ratio of the first phosphor and the second phosphor of the present invention, light emission of a desired chromaticity coordinate on a straight line connecting the chromaticity coordinates of the emission colors of both phosphors A color light emitting device can be obtained.

FIG. 17 shows the emission spectrum (solid line) of Example 1b and the emission spectrum (dotted line) of Comparative Example 1 when a driving current of 10 mA is applied to the light emitting devices of Example 1b and Comparative Example 1.
In addition, the vertical axis | shaft of the graph in FIG. 17 shows the relative light emission intensity of Example 1b and the comparative example 1. FIG.
FIG. 17 shows that the light emitting device of Example 1b has a broad emission spectrum compared to Comparative Example 1, and has high color rendering properties.

FIG. 18 shows the emission spectrum (solid line) of Example 2a and the emission spectrum (dotted line) of Comparative Example 1 when a driving current of 10 mA is applied to the light emitting devices of Example 2a and Comparative Example 1.
FIG. 19 shows the emission spectrum (solid line) of Example 2b and the emission spectrum (dotted line) of Comparative Example 1 when a driving current of 10 mA is applied to the light-emitting devices of Example 2b and Comparative Example 1.
FIG. 20 shows the emission spectrum (solid line) of Example 2c and the emission spectrum (dotted line) of Comparative Example 1 when a driving current of 10 mA is applied to the light emitting devices of Example 2c and Comparative Example 1.
FIG. 21 shows the emission spectrum (solid line) of Example 2d and the emission spectrum (dotted line) of Comparative Example 1 when a driving current of 10 mA is applied to the light emitting devices of Example 2d and Comparative Example 1.
The vertical axis of the graphs in FIGS. 18 to 21 indicates the relative light emission intensity between Examples 2a to 2d and Comparative Example 1.
18 to 21 show that the light emitting devices of Examples 2a to 2d have a broad emission spectrum compared to Comparative Example 1, and have high color rendering properties.
Further, when the emission spectrum in the wavelength region of 450 to 480 nm in FIGS. 18 to 21 and the emission spectrum of the phosphor 4 shown in FIG. 14 are compared, the peak wavelength and the half-value width of both emission spectra are almost the same. From this, the light-emitting devices of Examples 2a to 2d emit light with the second phosphor (phosphor 5) being hardly absorbed by the first phosphor (phosphor 2). I understand.

<Structure of light emitting device (type 2)>
The light emitting devices 3a to 3g of the examples use the following specific configurations in the third embodiment.
In addition, the structure of the following light-emitting device is a structure common about Example 3a-3h and Comparative Examples 2a-2h except the kind of used fluorescent substance.
First, as the container 13, a cup-shaped molded product in which the copper electrode terminals 10a and 10b were integrated by insert molding using a polyphthalamide resin was produced.
Next, a 1 mm square LED (SemiLEDs: MvpLED ^™ SL-V-U40AC) having an emission peak at 405 nm is used as the semiconductor light emitting element 4, and the electrode terminal 10a disposed at the bottom of the cup-shaped molded product. Silver paste (manufactured by Able Stick: 84-1LMISR4) was dropped on the (anode), the lower surface of the LED was adhered on the silver paste, and the silver paste was cured at 175 ° C. for 1 hour.
Further, a Φ45 μm gold wire was used as the wire 6, and this gold wire was bonded to the upper surface side electrode of the LED and the electrode 10b (cathode) by ultrasonic thermocompression bonding.
Next, a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd .: JCR6140) is covered as the filling member, potted to a position that is flush with the upper surface of the container 13, and then for 40 minutes in an 80 ° C. environment. And fixed in a step curing for 60 minutes in an environment of 150 ° C.
Next, using a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd .: JCR6140) as a binder member, a phosphor paste was prepared by mixing various phosphors or a mixture of a plurality of phosphors to 30 vol%. .
This phosphor paste was applied to a glass substrate as a transparent plate 13 with an arbitrary film thickness using a spin coat, and then cured for 60 minutes in a 150 ° C. environment to form a phosphor layer 7.
Finally, the glass substrate was fixed to the upper surface of the cup-shaped molded product.

The following Examples 3a to 3h and Comparative Examples 2a to 2h were produced based on the structure of the phosphor and the light emitting device (type 2).
<Examples 3a to 3h>
Examples 3a to 3h are examples in which the phosphor 2 is used as the first phosphor and the phosphor 5 is used as the second phosphor. The phosphor 2 (yellow) and the phosphor 5 (blue) and a mixture ratio (weight ratio) of 37 (yellow): 63 (blue) were used to prepare the phosphor paste, and these phosphor pastes were formed in Table 6 using spin coating. The fluorescent layer 7 applied at the individual rotational speed and film thickness shown was formed, and light emitting devices of Examples 3a to 3h were manufactured.
<Comparative Examples 2a to 2h>
Phosphor (Sr, Ba, Ca) ₂ SiO ₄ : Eu ²⁺ (yellow) (hereinafter referred to as comparative phosphor 2) and phosphor 5 (blue) are blended (weight ratio) 27 (yellow): 73 (blue) The phosphor pastes are prepared using the mixture obtained in (1), and the phosphor layers 7 are formed by applying these phosphor pastes at individual rotational speeds and film thicknesses as shown in Table 6 using a spin coat. A light emitting device of 2a to 2h was manufactured.

<Evaluation of Examples 3a to 3h>
Each light-emitting device was made to emit light by supplying a current of 10 mA in an integrating sphere, and measured with an instantaneous multi-photometry system (manufactured by Otsuka Electronics Co., Ltd .: MCPD-1000) installed above the transparent plate 12. The measurement results will be described in detail below.

Table 6 shows the rotation speed (rpm) of the spin coat when the fluorescent layer 7 of each issuing device is formed, the film thickness (μm) of the fluorescent layer, and the chromaticity when a driving current of 10 mA is applied to each light emitting device. The coordinates (cx, cy) are shown.

FIG. 22 shows chromaticity coordinates (cx, cy) of light emitted when a driving current of 10 mA is applied to each light emitting device on the chromaticity diagram.

From Table 6 and FIG. 22, in both the example and the comparative example, the chromaticity is shifted in the yellow direction as the thickness of the fluorescent layer 7 is increased. This is because the yellow phosphor (phosphor 2, comparative phosphor 2) having a large Stokes shift mixed in the phosphor layer 7 absorbs the fluorescence of the blue phosphor (phosphor 5) and converts it into yellow light. This is a phenomenon that occurs because the amount of conversion increases as the fluorescent layer 7 becomes thicker.

Comparing the example and the comparative example with respect to the chromaticity shift amount due to the change in the film thickness, the film thickness difference between the examples 3a and 3h (205 μm) and the film thickness difference between the comparative examples 2a and 2h (202 μm) are almost the same. On the other hand, the chromaticity shift amount accompanying this is 0.07 in the example and 0.19 in the comparative example, and there is a difference of about 2.6 times between the two. This is because the yellow fluorescent material (phosphor 2) contained in the fluorescent layer 7 of the example is more excited in the blue region than the yellow fluorescent material (comparative phosphor 2) contained in the fluorescent layer 7 of the comparative example. Due to the low.

Therefore, with respect to the white defined region of the vehicular lamp shown as α in FIG. 22, the comparative example can be realized only within a limited film thickness range (about 30 μm) between 2b and 2d. An example can be realized in a wide film thickness range (about 190 μm) between 3a and 3g. As a result, if a white light emitting device is configured with the phosphor used in this embodiment, a light emitting device with stable chromaticity can be configured without precisely controlling the amount of phosphor applied, and it is inexpensive in terms of process management and yield. A light-emitting device can be manufactured.

As described above, the phosphor of the present invention has been described with reference to the examples. However, the present invention is not limited to these examples, and it is needless to say that various modifications, improvements, combinations, usage forms, and the like can be considered.

The light emitting device of the present invention can be used for various lamps, for example, lighting lamps, displays, vehicle lamps, traffic lights and the like.
In particular, the white light emitting device according to the present invention can be expected to be applied to a lamp that requires high output white light such as a vehicle headlamp.

It is a schematic sectional drawing which shows 1st embodiment of the light-emitting device of this invention. It is a schematic sectional drawing which shows 2nd embodiment of the light-emitting device of this invention. It is a schematic sectional drawing which shows 3rd embodiment of the light-emitting device of this invention. It is a figure which shows an example of the X-ray-diffraction photograph of a single crystal base crystal. It is a fitting figure about the X-ray diffraction (measurement 2) of a powder base crystal. It is a fitting figure about the X-ray diffraction (measurement 3) of the fluorescent substance 1 of the present invention. It is a figure which shows the measurement result of the X-ray diffraction using the K alpha characteristic X-ray of Cu about the fluorescent substance 1 of the present invention. It is a figure which shows the measurement result of the X-ray diffraction using the K alpha characteristic X-ray of Cu about the fluorescent substance 2 of the present invention. It is a figure which shows the emission spectrum (solid line) of the fluorescent substance 1, and the emission spectrum (dotted line) of the fluorescent substance 1 for a comparison. It is a figure which shows the emission spectrum (solid line) of the fluorescent substance of the fluorescent substance 2, and the emission spectrum (dotted line) of the fluorescent substance 1 for a comparison. It is a figure which shows the emission spectrum (solid line) of the fluorescent substance 3, and the emission spectrum (dotted line) of the fluorescent substance 1 for a comparison. It is a figure which shows the emission spectrum (solid line) of the fluorescent substance 4, and the emission spectrum (dotted line) of the fluorescent substance 1 for a comparison. It is a figure which shows the excitation spectrum of the fluorescent substance 1. It is a figure which shows the emission spectrum (solid line) of the fluorescent substance 5, and the emission spectrum (dotted line) of the fluorescent substance 2 for a comparison. It is a figure which shows the excitation spectrum of the fluorescent substance 5. It is a chromaticity diagram which shows the chromaticity coordinate of the light which the Example etc. light-emitted. The emission spectrum of Example 1b of the present invention (solid line) and the emission spectrum of Comparative Example 1 It is drawing which shows the emission spectrum (solid line) of Example 2a of this invention, and the emission spectrum (dotted line) of the comparative example 1. FIG. It is drawing which shows the emission spectrum (solid line) of Example 2b of this invention, and the emission spectrum (dotted line) of the comparative example 1. FIG. It is drawing which shows the emission spectrum (solid line) of Example 2c of this invention, and the emission spectrum (dotted line) of the comparative example 1. FIG. It is drawing which shows the emission spectrum (solid line) of Example 2d of this invention, and the emission spectrum (dotted line) of the comparative example 1. FIG. It is a chromaticity diagram which shows the chromaticity coordinate of the light which the Example etc. light-emitted.

Explanation of symbols

1: Light-emitting device 2: Substrate 3a: Electrode (anode)
3b: Electrode (cathode)
4: Semiconductor light emitting element 5: Mount member 6: Wire 7: Fluorescent layer 8: Can cap 9: Metal stem 10a: Electrode terminal (anode)
10b: Electrode terminal (cathode)
11: Opening 12: Transparent plate 13: Container 14: Filling member

Claims (22)

In a light emitting device including a light emitting element that emits ultraviolet light or short wavelength visible light, and at least one phosphor that emits visible light when excited by the ultraviolet light or short wavelength visible light,
As the phosphor, the general formula _{^{M 1 O 2 · aM 2 O}} · bM 3 X 2: M 4
(Where ^{M 1} is at least one element of Si, Ge, Ti, at least one element selected from the group consisting of Zr and Sn, ^{M 2} is selected from the group consisting of Mg, Ca, Sr, Ba and Zn , M ³ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba and Zn,
X represents at least one halogen element, and M ⁴ represents at least one element essential for Eu ²⁺ selected from the group consisting of rare earth elements and Mn. a is in the range of 0.1 ≦ a ≦ 1.3, b is in the range of 0.1 ≦ b ≦ 0.25)
A light-emitting device comprising the first phosphor represented by A light emitting element that emits ultraviolet light or short wavelength visible light, and at least two or more kinds of phosphors that are excited by the ultraviolet light or short wavelength visible light to emit visible light, and the visible light emitted by each phosphor has a complementary color relationship, In a light emitting device configured to add white light by adding light from these phosphors,
As the phosphor, the general formula _{^{M 1 O 2 · aM 2 O}} · bM 3 X 2: M 4
(Where ^{M 1} is at least one element of Si, Ge, Ti, at least one element selected from the group consisting of Zr and Sn, ^{M 2} is selected from the group consisting of Mg, Ca, Sr, Ba and Zn , M ³ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba and Zn,
X represents at least one halogen element, and M ⁴ represents at least one element essential for Eu ²⁺ selected from the group consisting of rare earth elements and Mn. a is a range of 0.1 ≦ a ≦ 1.3, b is a range of 0.1 ≦ b ≦ 0.25),
A light emitting device comprising: a second phosphor that emits visible light having a complementary color relationship with visible light emitted from the first phosphor. The light-emitting device according to claim 1, wherein 0.03 <c / (a + c) <0.8, where c (molar ratio) is the content of M ^{4 in} the general formula. The light emitting device according to any one of claims 1 to 3, wherein M ^{1 in the} general formula includes at least Si as an essential component, and a ratio of Si is 80 mol% or more. The light emitting device according to any one of claims 1 to 4, wherein M ^{2 in the} general formula includes at least Ca and / or Sr, and a ratio of Ca and / or Sr is 60 mol% or more. The light emitting device according to any one of claims 1 to 5, wherein M ^{3 in the} general formula includes at least Sr as essential, and Sr is 30 mol% or more. In the above general formula, a is in the range of 0.30 ≦ a ≦ 1.2, b is in the range of 0.1 ≦ b ≦ 0.2, and the content c of M ⁴ is 0.05 ≦ c / (a + c). The phosphor according to claim 1, wherein ≦ 0.5. The light emitting device according to any one of claims 1 to 7, wherein X in the general formula includes at least Cl as an essential component, and a ratio of Cl is 50 mol% or more. The light emitting device according to claim 1, wherein a strong excitation band of the first phosphor is in a wavelength range of 350 to 430 nm. 10. The light emitting device according to claim 1, wherein a peak of an emission spectrum of the first phosphor is in a wavelength range of 560 to 590 nm, and a half width is 100 nm or more. The light emitting device according to any one of claims 1 to 10, wherein at least a part of the crystal contained in the first phosphor is a crystal having a pyroxene type crystal structure. The at least part of the crystal contained in the first phosphor is a crystal belonging to crystal system: monoclinic crystal, Brave lattice: bottom-centered monoclinic lattice, space group: C2 / m. The light-emitting device in any one of 1-11. In the X-ray diffraction pattern using Cu Kα characteristic X-rays, at least a part of the crystals contained in the first phosphor is present in a diffraction angle 2θ of 29.0 ° or more and 30.5 ° or less. When the diffraction intensity of the diffraction peak with the highest intensity is 100, the diffraction angle 2θ ranges from 28.0 ° to 29.5 °, the diffraction angle 2θ ranges from 19.0 ° to 22.0 °, The diffraction angle 2θ is in the range of 25.0 ° to 28.0 °, the diffraction angle 2θ is in the range of 34.5 ° to 37.5 °, and the diffraction angle 2θ is in the range of 40.0 ° to 42.5 °. The light-emitting device according to claim 1, wherein there are peaks each having a diffraction intensity of 8 or more. In the X-ray diffraction pattern in which at least a part of the crystals contained in the first phosphor uses Cu Kα characteristic X-rays, the diffraction intensity 2θ is in the range of 28.0 ° to 29.5 °. There is a diffraction peak showing 50 or more, a peak showing a diffraction intensity of 8 or more exists in a range where the diffraction angle 2θ is 19.0 ° or more and 22.0 ° or less, and the diffraction angle 2θ is 25.0 ° or more and 28.0. There is a peak showing a diffraction intensity of 15 or more in the range of ≦ °, a peak showing a diffraction intensity of 15 or more in the range of the diffraction angle 2θ of 34.5 ° or more and 37.5 ° or less, and a diffraction angle 2θ of 40.degree. It has a diffraction intensity of 10 or more in a range of 0 ° or more and 42.5 ° or less, and a peak showing a diffraction intensity of 10 or more exists in a range of a diffraction angle 2θ of 13.0 ° or more and 15.0 ° or less. The light emitting device according to claim 1. In the diffraction pattern using Mo Kα characteristic X-rays, at least part of the crystals contained in the first phosphor is the most intense when the diffraction angle 2θ is in the range of 12.5 ° to 15.0 °. Assuming that the diffraction intensity of a high diffraction peak is 100, there is a diffraction peak having a diffraction intensity of 50 or more in a range where the diffraction angle 2θ is 12.0 ° or more and 14.5 ° or less, and the diffraction angle 2θ is 8.0. There is a peak showing a diffraction intensity of 8 or more in the range of from 1 ° to 10.5 °, and a peak showing a diffraction intensity of 15 or more in the range of the diffraction angle 2θ of from 11.0 ° to 13.0 °. There is a peak showing a diffraction intensity of 15 or more in a range where the bending angle 2θ is 15.5 ° or more and 17.0 ° or less, and a diffraction intensity 2θ is showing a diffraction intensity of 10 or more in a range where the diffraction angle 2θ is 17.5 ° or more and 19.5 ° or less. Diffraction intensity 2 in the range of diffraction angle 2θ of 5.0 ° to 8.0 °. The light emitting device according to any one of claims 1 to 14, characterized in that there are peaks indicating more. Said 1st fluorescent substance is comprised from the mixture of the crystal | crystallization which has the characteristics in any one of Claims 11-15, and another crystal phase or an amorphous phase, and the ratio of the said crystal | crystallization in a mixture is 20 weight% It is the above, The fluorescent substance in any one of Claims 1-15 characterized by the above-mentioned. The light emitting device according to claim 2, wherein the second phosphor is a blue light emitting phosphor. The light emitting device according to any one of claims 2 to 17, wherein a peak of an emission spectrum of the second phosphor is in a wavelength region of 440 to 470 nm and a half width is 30 to 60 nm. The second phosphor has the general formula _{Ca x-y-z Mg y} (PO 4) 3 Cl: Eu 2+ z
(However, x is 4.95 <x <5.50, y is 0 <y <1.50, z is in the range of 0.02 <z <0.20, and y + z is 0.02 ≦ y + z ≦ 1. .7)
The light-emitting device according to claim 2, wherein the light-emitting device is a phosphor represented by the formula: The light emitting device according to claim 1, wherein a peak of an emission spectrum of the light emitting element is in a wavelength region of 350 to 430 nm. The light-emitting device according to claim 1, wherein the light-emitting element is a semiconductor light-emitting element. The light-emitting device according to claim 21, wherein the semiconductor light-emitting element is an InGaN-based LED or LD.