JPWO2011092798A1 - Phosphor and light emitting device - Google Patents

Abstract

The phosphor has a general formula (M2x, M3y, M4z, M5k) mM1O3X (2 / n) (where M1 is at least one element including Si, M2 is at least one element including Ca, M3 Is at least one element containing at least Sr selected from the group consisting of Sr, Mg, Ca, Ra and Ba, X is at least one halogen element, and M4 is at least Eu2 + selected from the group consisting of rare earth elements. More than one element, M5 represents one or more elements selected from the group consisting of Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd, and Pb, and m is 1 ≦ m ≦ 4. / 3, n is in the range of 5 ≦ n ≦ 7, and x, y, z, and k are x + y + z + k = 1, 0 <x <0.985, 0 <y <0.985, 0.01 ≦ Satisfy z ≦ 0.3, 0.005 <k <0.3 Range is.) It is represented by.

Description

  The present invention relates to a phosphor that is efficiently excited and emits light by ultraviolet rays or short-wavelength visible light, and a light-emitting device using the same.

  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 (LED) 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.

  As a specific example of such a white light emitting device, a method of combining a plurality of LEDs that emit ultraviolet light or short wavelength visible light and phosphors that emit light of colors such as blue and yellow when excited by ultraviolet light or short wavelength visible light. Etc. are known (see Patent Document 1).

JP 2009-38348 A

  The phosphor in the above light emitting device has excellent properties in that it emits light with high efficiency. However, when the above-described light emitting device is to be applied to, for example, a thin display that requires vivid colors, there is room for further improvement from the viewpoint of color purity.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a phosphor that can be applied to a light-emitting device that requires light with high color purity.

In order to solve the above-described problem, the phosphor according to an aspect of the present invention has a general formula (M ² _x , M ³ _y , M ⁴ _z, M ⁵ _k ) _m M ¹ O ₃ X _{(2 / n)} (here M ¹ is one or more elements including at least Si selected from the group consisting of Si, Ge, Ti, Zr and Sn, and M ² is at least Ca selected from the group consisting of Ca, Mg, Sr, Ba and Ra. one or more elements including, ^{M 3} is Sr, Mg, Ca, one or more elements including at least Sr selected from the group consisting of Ra and Ba, X is at least one halogen element, ^{M 4} is a rare earth element One or more elements selected from the group consisting of at least Eu ²⁺ , M ⁵ is one or more elements selected from the group consisting of Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd and Pb In addition, m represents 1 ≦ m ≦ 4 / , N is in the range of 5 ≦ n ≦ 7, and x, y, z, and k are x + y + z + k = 1, 0 <x <0.985, 0 <y <0.985, 0.01 ≦ z ≦ 0.3 and 0.005 <k <0.3.).

  According to this aspect, it is possible to realize light emission having a relatively sharp spectrum.

Another embodiment of the present invention is a light-emitting device. This light-emitting device includes a light-emitting element that emits ultraviolet light or short-wavelength visible light, and a phosphor that emits visible light when excited by ultraviolet light or short-wavelength visible light. The phosphor has the general formula (M ² _x , M ³ _y , M ⁴ _z, M ⁵ _k ) _m M ¹ O ₃ X _{(2 / n)} (where M ¹ is Si, Ge, Ti, Zr and Sn) One or more elements including at least Si selected from the group consisting of: M ² is one or more elements including at least Ca selected from the group consisting of Ca, Mg, Sr, Ba and Ra; and M ³ is Sr, Mg , One or more elements containing at least Sr selected from the group consisting of Ca, Ra and Ba, X is at least one halogen element, and M ⁴ is one or more containing at least Eu ²⁺ selected from the group consisting of rare earth elements M ⁵ represents one or more elements selected from the group consisting of Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd and Pb, and m is 1 ≦ m ≦ 4 / 3 and n are in the range of 5 ≦ n ≦ 7, and x and y z and k are ranges satisfying x + y + z + k = 1, 0 <x <0.985, 0 <y <0.985, 0.01 ≦ z ≦ 0.3, and 0.005 <k <0.3. ).

Yet another embodiment of the present invention is a light emitting device. The light emitting device includes a light emitting element that emits ultraviolet light or short wavelength visible light, a first phosphor that emits visible light by being excited by ultraviolet light or short wavelength visible light, and is excited by ultraviolet light or short wavelength visible light. A second phosphor that emits visible light of a color different from that of the visible light emitted by the phosphor, and a light emitting device configured to obtain a mixed color by mixing light from each phosphor is there. The first phosphor has a general formula (M ² _x , M ³ _y , M ⁴ _z, M ⁵ _k ) _m M ¹ O ₃ X _{(2 / n)} (where M ¹ is Si, Ge, Ti, One or more elements including at least Si selected from the group consisting of Zr and Sn, M ² is one or more elements including at least Ca selected from the group consisting of Ca, Mg, Sr, Ba and Ra, M ³ is One or more elements containing at least Sr selected from the group consisting of Sr, Mg, Ca, Ra, and Ba, X is at least one halogen element, and M ⁴ includes at least Eu ²⁺ selected from the group consisting of rare earth elements One or more elements, M ⁵ represents one or more elements selected from the group consisting of Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd, and Pb, and m is 1 ≦ m. ≦ 4/3, n is in the range of 5 ≦ n ≦ 7, , Y, z, k are ranges satisfying x + y + z + k = 1, 0 <x <0.985, 0 <y <0.985, 0.01 ≦ z ≦ 0.3, 0.005 <k <0.3. It is expressed by.

  According to these aspects, a light emitting device suitable for an application requiring high color purity can be realized relatively easily.

  It should be noted that any combination of the above-described constituent elements and a representation obtained by converting the expression of the present invention between a method, an apparatus, a system, a vehicle lamp, and the like are also effective as an aspect of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the fluorescent substance applicable to the light-emitting device which emits light with high color purity can be provided.

It is a schematic sectional drawing of the light-emitting device concerning this Embodiment. 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 1-6 which concerns on a present Example and a comparative example. It is the figure which showed the emission spectrum of the fluorescent substance 1 and the fluorescent substance 6. It is the figure which showed the emission spectrum of the fluorescent substance 2 and the fluorescent substance 6. It is the figure which showed the emission spectrum of the fluorescent substance 3 and the fluorescent substance 6. It is the figure which showed the emission spectrum of the fluorescent substance 4 and the fluorescent substance 6. It is the figure which showed the emission spectrum of the fluorescent substance 5 and the fluorescent substance 6. It is the figure which showed the emission spectrum when the drive current of 350 mA was applied to the light-emitting device which concerns on Example 1 and a comparative example. It is the figure which showed the emission spectrum when a 350 mA drive current was applied to the light-emitting device which concerns on Example 2. FIG.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and repeated descriptions are omitted as appropriate.

  FIG. 1 is a schematic cross-sectional view of the light emitting device according to the present embodiment. In the light emitting device 10 shown in FIG. 1, a pair of electrodes 14 (anode) and an electrode 16 (cathode) are formed on a substrate 12. A semiconductor light emitting element 18 is fixed on the electrode 14 by a mount member 20. The semiconductor light emitting element 18 and the electrode 14 are electrically connected by a mount member 20, and the semiconductor light emitting element 18 and the electrode 16 are electrically connected by a wire 22. A dome-shaped fluorescent layer 24 is formed on the semiconductor light emitting element 18.

  The substrate 12 is preferably formed of a material having 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 14 and 16 are conductive layers formed of a metal material such as gold or copper.

  The semiconductor light-emitting element 18 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 20 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 18 is fixed to the electrode 14. The electrode 14 is electrically connected.

  The wire 22 is a conductive member such as a gold wire, and is joined to the upper surface side electrode and the electrode 16 of the semiconductor light emitting element 18 by, for example, ultrasonic thermocompression bonding, and electrically connects both.

  In the fluorescent layer 24, each phosphor described later is sealed in a hemispherical shape (dome shape) covering the upper surface of the substrate 12 including the semiconductor light emitting element 18 by a binder member. The phosphor layer 24 is prepared, for example, by preparing a phosphor paste in which a phosphor is mixed in a liquid or gel binder member, and then applying the phosphor paste to the upper surface of the semiconductor light emitting element 18 in a hemispherical form, and then phosphor. It is formed by curing the binder member of the paste. As the binder member, for example, a silicone resin or a fluorine resin can be used. Moreover, since the light-emitting device according to this embodiment 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 24 may be mixed with substances having various physical properties other than the phosphor. A substance having a higher refractive index than the binder member, such as a metal oxide, a fluorine compound, or a sulfide, is mixed in the fluorescent layer 24, whereby the refractive index of the fluorescent layer 24 can be increased. As a result, total reflection that occurs when light generated from the semiconductor light emitting element 18 enters the fluorescent layer 24 is reduced, and an effect of improving the efficiency of capturing excitation light into the fluorescent layer 24 is obtained. Furthermore, the refractive index can be increased without reducing the transparency of the fluorescent layer 24 by making the particle size of the substance to be mixed nanosize. In addition, white powder having an average particle size of about 0.3 to 3 μm, such as alumina, zirconia, or titanium oxide, can be mixed in the fluorescent layer 24 as a light scattering agent. Thereby, uneven brightness and chromaticity in the light emitting surface can be prevented.

  Next, each phosphor used in the light emitting device according to the present embodiment will be described in detail.

(First phosphor)
The first phosphor is a phosphor that emits visible light when excited by ultraviolet or short-wavelength visible light, and has a general formula (M ² _x , M ³ _y , M ⁴ _z, M ⁵ _k ) _m M ¹ O _3. X _{(2 / n)} (where M ¹ is one or more elements including at least Si selected from the group consisting of Si, Ge, Ti, Zr and Sn, and M ² is Ca, Mg, Sr, Ba and Ra) One or more elements including at least Ca selected from the group consisting of: M ³ is one or more elements including at least Sr selected from the group consisting of Sr, Mg, Ca, Ra and Ba; and X is at least one element halogen, ^{M 4} is a group consisting of at least one element including ^{Eu 2+, M 5} is Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd and Pb selected from the group consisting of rare earth elements One or more elements selected from Further, m is in the range of 1 ≦ m ≦ 4/3, n is in the range of 5 ≦ n ≦ 7, and x, y, z, and k are x + y + z + k = 1, 0 <x <0.985, 0 <. y <0.985, 0.01 ≦ z ≦ 0.3, and 0.005 <k <0.3.).

The first phosphor can be obtained, for example, as follows. For the first phosphor, compounds represented by the following composition formulas (1) to (5) can be used as raw materials.
(1) M ′ ¹ O ₂ (M ′ ¹ represents a tetravalent element such as Si, Ge, Ti, Zr, Sn, etc.)
(2) M ′ ² O (M ′ ² represents a divalent element such as Ca, Mg, Sr, Ba, Zn, Cd, Ra, Pb, or Co.)
(3) M ′ ³ X ₂ (M ′ ³ is a divalent element such as Sr, Mg, Ca, Ba, Zn, Cd, Ra, Pb, Co, and X is a halogen element.)
(4) M ′ ⁴ (M ′ ⁴ represents a rare earth element such as Eu ²⁺ )
(5) M ′ ⁵ (M ′ ⁵ represents an element such as Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd, and Pb.)

As a raw material of the composition formula (1), for example, SiO ₂ , GeO ₂ , TiO ₂ , ZrO ₂ , SnO _{2 and 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. Examples of the raw material of the composition formula (3) include 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. the _{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 or the like 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 and the} like can be used. As raw materials of the composition formula (5), for example, MnCO ₃ , MnO, Mn (OH) ₂ , MnCl ₂ .4H ₂ O, Mn (NO ₃ ) ₂ .6H ₂ O, ZnO, ZnCl ₂ , SnO, SnO ₂ , _{SnCl 2, SnCl 4, V 2} O 3, V 2 O 4, V 2 O 5, VOCl 3, Cr 2 O 3, CrO 3, CrCl 3, CoO, Co 3 O 4, CoCl 2, NiO, NiCl 2, Cu ₂ O, CuO, CuCl, CuCl ₂ , CdO, CdCl ₂ , CdCO ₃ , PbO, Pb ₃ O ₄ , PbO ₂ , PbCl ₂ , PbCO _3, or the like can be used.

As a raw material of the composition formula (1), M ′ ¹ preferably contains at least Si. Further, Si may be partially replaced with at least one element selected from the group consisting of Ge, Ti, Zr, and Sn. In this case, a compound in which the proportion of Si in M ′ ¹ is 80 mol% or more is preferable. As a raw material of the composition formula (2), it is preferable that M ′ ² contains at least Ca. Further, Ca may be partially replaced with at least one element selected from the group consisting of Mg, Sr, Ba, Cd, Co, Ra, Pb and Zn. In this case, a compound in which the proportion of Ca in M ′ ² is 60 mol% or more is preferable. As a raw material of the composition formula (3), it is preferable that M ′ ³ contains at least Sr. Further, Sr may be partially replaced with at least one element selected from the group consisting of Mg, Ca, Zn, Cd, Co, Ra, Ba, and Pb. In this case, the compound whose Sr is 30 mol% or more is preferable. Moreover, as a raw material of the composition formula (3), X preferably contains at least Cl. Further, Cl may be partially replaced with another halogen element. In this case, a compound having a Cl ratio of 50 mol% or more is preferable. As a raw material of the composition formula (4), it is preferable that M ′ ⁴ contains at least divalent Eu. Further, Eu may be partially replaced with another rare earth element. As a raw material of the composition formula (5), M ′ ⁵ preferably contains at least Mn. Further, Mn may be partially replaced with at least one element selected from the group consisting of Zn, Sn, V, Cr, Co, Ni, Cu, Cd, and Pb.

The molar ratio of the raw materials of the composition formulas (1) to (5) is (1) :( 2) = 1: 0.1 to 1.0, (2) :( 3) = 1: 0.2 to 12. 0, (2) :( 4) = 1: 0.05 to 4.0, (2) :( 5) = 1: 0.005 to 4.0, preferably (1) :( 2) = 1 : 0.25 to 1.0, (2): (3) = 1: 0.3 to 6.0, (2): (4) = 1: 0.05 to 3.0, (2): ( 5) = 1: 0.01-1.0, more preferably (1) :( 2) = 1: 0.25-1.0, (2) :( 3) = 1: 0.3-4. 0, (2) :( 4) = 1: 0.05 to 3.0, (2) :( 5) = 1: 0.05 to 0.5, and weighed each raw material into an alumina mortar The mixture is pulverized and mixed for about 30 minutes to obtain a raw material mixture. This raw material mixture is put in an alumina crucible and baked in a reducing atmosphere electric furnace at a predetermined atmosphere (H ₂ : N ₂ = 5: 95) at a temperature of 700 ° C. or higher and lower than 1100 ° C. for 3 to 40 hours to obtain a baked product . The first phosphor can be obtained by carefully washing the fired product with warm pure water and washing away excess chloride. The first phosphor is excited by ultraviolet light or short wavelength visible light and emits visible light.

  In addition, about the raw material (divalent metal halide) of a composition formula (3), it is preferable to weigh the excess amount beyond a stoichiometric ratio. This is because a part of the halogen element is vaporized and evaporated during firing, and is to prevent the occurrence of crystal defects in the phosphor due to the lack of the halogen element. Moreover, the raw material of the composition formula (3) added in excess is liquefied at the firing temperature and acts as a flux for the solid phase reaction, thereby promoting the solid phase reaction and improving the crystallinity.

  In addition, after baking the raw material mixture described above, the above-described excessively added raw material of the composition formula (3) is present as an impurity in the manufactured phosphor. Therefore, in order to obtain a phosphor having high purity and high emission intensity, these impurities may be washed away with warm pure water. The composition ratio shown in the general formula of the first phosphor of the present embodiment is the composition ratio after the impurities are washed away, and the raw material of the composition formula (3) that is added excessively and becomes impurities as described above. Is not taken into account in this composition ratio.

(Second phosphor)
The configuration of the second phosphor is not particularly limited, but a blue phosphor having a dominant wavelength of light emission in the range of 455 to 470 nm is preferable. In order to form a white color by additive mixing with the blue color, a first phosphor that emits light at a dominant wavelength of 577.5 nm or more is suitable. The second phosphor is not limited to a single compound, but may be a mixture of a plurality of compounds. Examples of the second phosphor include compounds represented by the following composition formula.
(Ca, M) ₅ (PO ₄ ) ₃ X: Eu (M is a divalent alkaline earth metal and X is a halogen element)
Sr ₅ (PO ₄ ) ₃ X: Eu (X is a halogen element)
BaMgAl ₁₀ O ₁₇ : Eu

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. The second phosphor emits visible light having a complementary color relationship with the visible light emitted from the first phosphor.

Note that the basis weight of CaCl ₂ in obtaining the aforementioned raw material mixture (molar ratio), with respect to the composition ratio of the second phosphor to be manufactured, an excess amount of more than 0.5mol than its stoichiometric ratio Is preferably weighed. Thereby, it is possible to prevent the occurrence of crystal defects of the second phosphor due to the lack of Cl.

<Identification of crystal structure of phosphor>
Next, determination of the crystal structure and the like of the phosphor according to the present embodiment will be described. Hereinafter, although a certain substance will be described as an example, the crystal structure of each phosphor described later can be determined by the same method.

First, a single crystal of a parent crystal described below was grown. This host crystal has a general formula of M ¹ O ₂ · a (M ² _1−Z · M ⁴ _Z ) O · bM ³ X ₂ , M ¹ = Si, M ² = Ca and Sr, M ³ = Sr, X = Cl, and M ⁴ is not contained.

<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, 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 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.

  The obtained parent crystal was subjected to elemental quantitative analysis by the following method to determine the composition ratio (values of a and b in the general formula).

(1) Quantitative analysis of Si After melting the base crystal with sodium carbonate in a platinum crucible, it was 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 element The base crystal was 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. With respect to this solution, the amount of metal element was measured using the above-mentioned ICP emission spectroscopic analyzer.
(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 thermally decomposed 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 element quantitative analysis, the approximate composition ratio of the obtained host crystal is as shown in the following formula (1).
SiO ₂ .1.05 (Ca _0.6 , Sr _0.4 ) O.0.15 SrCl ₂ Formula (1)

  Moreover, the specific gravity of the above-mentioned base 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).

  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. This 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 in the following formula (2).
SiO ₂ · 1.0 (Ca _0.55 , Sr _0.45 ) O · 0.17SrCl ₂ Formula (2)

In the above general formula of the phosphor, metal ions (divalent), tetravalent oxide ions, and halogen ions are rearranged to obtain new general formulas (M ² _x, M ³ _y, M ⁴ _z ) _m M ¹ O. _When expressed as ₃ X _{2 / n} , the following equation (3) is obtained.
(Ca _0.47 , Sr _0.53 ) _7/6 SiO ₃ Cl _2/6 Formula (3)

  As a result of the above analysis, it was found that the above-mentioned 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. Such an analysis method was also applied to each phosphor described later.

  The phosphors and light-emitting devices described above will be described more specifically with reference to the following examples. However, the description of the following materials and manufacturing methods of phosphors and light-emitting devices, the chemical composition of the phosphors, etc. The embodiment of the body and the light emitting device is not limited at all.

  First, the phosphor used in the light emitting device of this example will be described in detail.

<Phosphor 1>
The phosphor 1 is a phosphor represented by (Ca _0.52 , Sr _0.36 , Eu _0.11 , Mn _0.01 ) _7/6 SiO ₃ Cl _2/6 . The phosphor 1 has the general formula (M ² _x, M ³ _y, M ⁴ _z , M ⁵ _k ) _m M ¹ O ₃ X _{2 / n} , where M ¹ = Si, M ² = Ca, M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , M ⁵ = Mn, m = 7/6, n = 6, M ² , M ³ , M ⁴ , M ⁵ content x, y, z, k are Are respectively synthesized to be 0.52, 0.36, 0.11, 0.01. In addition, in the phosphor 1, a large amount of cristobalite is generated in the phosphor by adding SiO ₂ more excessively in the mixing ratio of the raw materials. First, the phosphor 1 is manufactured by using SiO ₂ , Ca (OH) ₂ , SrCl ₂ .6H ₂ O, Eu ₂ O ₃ , and MnCO ₃ with a molar ratio of SiO ₂ : Ca (OH) _2. : SrCl ₂ · 6H ₂ O: Eu ₂ O ₃ : MnCO ₃ = 1.0: 0.54: 0.50: 0.09: 0.01 Weighed each raw material 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 put into an alumina crucible and fired at a predetermined atmosphere (H ₂ : N ₂ = 5: 95) at a temperature of 1030 ° C. for 5 to 40 hours in a reducing atmosphere electric furnace to obtain a fired product. The obtained fired product was carefully washed with warm pure water to obtain phosphor 1.

<Phosphor 2>
The phosphor 2 is a phosphor represented by (Ca _0.50 , Sr _0.36 , Eu _0.11 , Mn _0.03 ) _7/6 SiO ₃ Cl _2/6 . Phosphor 2 has the general formula (M ² _x, M ³ _y, M ⁴ _z , M ⁵ _k ) _m M ¹ O ₃ X _{2 / n} , M ¹ = Si, M ² = Ca, M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , M ⁵ = Mn, m = 7/6, n = 6, M ² , M ³ , M ⁴ , M ⁵ contents x, y, z, k are respectively It is synthesized so as to be 0.50, 0.36, 0.11, and 0.03. Further, in the phosphor 2, a slight amount of cristobalite is generated in the phosphor by adding excessive SiO ₂ in 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, Eu ₂ O ₃ , and MnCO ₃ as raw materials with a molar ratio of SiO ₂ : Ca (OH) _2. : SrCl ₂ .6H ₂ O: Eu ₂ O ₃ : MnCO ₃ = 1.0: 0.52: 0.50: 0.09: 0.02 and then the same as phosphor 1 The phosphor 2 was obtained by this method.

<Phosphor 3>
The phosphor 3 is a phosphor represented by (Ca _0.46 , Sr _0.35 , Eu _0.11 , Mn _0.08 ) _7/6 SiO ₃ Cl _2/6 . The phosphor 3 has a general formula (M ² _x, M ³ _y, M ⁴ _z , M ⁵ _k ) _m M ¹ O ₃ X _{2 / n} , M ¹ = Si, M ² = Ca, M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , M ⁵ = Mn, m = 7/6, n = 6, M ² , M ³ , M ⁴ , M ⁵ contents x, y, z, k are respectively It is synthesized to be 0.46, 0.35, 0.11, 0.08. Further, in the phosphor 3, a slight amount of cristobalite is generated in the phosphor by adding excessive SiO ₂ at the mixing ratio of the raw materials. The phosphor 3 is manufactured by first using SiO ₂ , Ca (OH) ₂ , SrCl ₂ .6H ₂ O, Eu ₂ O _3, and MnCO ₃ with a molar ratio of SiO ₂ : Ca (OH) ₂ : SrCl ₂ .6H ₂ O: Eu ₂ O ₃ : MnCO ₃ = 1.0: 0.50: 0.50: 0.09: 0.05 Thus, phosphor 3 was obtained.

<Phosphor 4>
The phosphor 4 is a phosphor represented by (Ca _0.39 , Sr _0.36 , Eu _0.11 , Mn _0.14 ) _7/6 SiO ₃ Cl _2/6 . The phosphor 4 has the general formula (M ² _x, M ³ _y, M ⁴ _z , M ⁵ _k ) _m M ¹ O ₃ X _{2 / n} , M ¹ = Si, M ² = Ca, M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , M ⁵ = Mn, m = 7/6, n = 6, M ² , M ³ , M ⁴ , M ⁵ contents x, y, z, k are respectively It is synthesized to be 0.39, 0.36, 0.11, 0.14. Further, in the phosphor 4, a slight amount of cristobalite is generated in the phosphor by adding excessive SiO ₂ at the mixing ratio of the raw materials. First, the phosphor 4 is manufactured by using SiO ₂ , Ca (OH) ₂ , SrCl ₂ .6H ₂ O, Eu ₂ O ₃ , and MnCO ₃ with a molar ratio of SiO ₂ : Ca (OH) _2. : SrCl ₂ .6H ₂ O: Eu ₂ O ₃ : MnCO ₃ = 1.0: 0.45: 0.50: 0.09: 0.09 The phosphor 4 was obtained by this method.

<Phosphor 5>
The phosphor 5 is a phosphor represented by (Ca _0.33 , Sr _0.36 , Eu _0.11 , Mn _0.20 ) _7/6 SiO ₃ Cl _2/6 . The phosphor 5 has a general formula (M ² _x, M ³ _y, M ⁴ _z , M ⁵ _k ) _m M ¹ O ₃ X _{2 / n} , M ¹ = Si, M ² = Ca, M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , M ⁵ = Mn, m = 7/6, n = 6, M ² , M ³ , M ⁴ , M ⁵ contents x, y, z, k are respectively It is synthesized to be 0.33, 0.36, 0.11, 0.20. Further, in the phosphor 5, a slight amount of cristobalite is generated in the phosphor by adding excessive SiO ₂ at the mixing ratio of the raw materials. The phosphor 5 is manufactured by first using SiO ₂ , Ca (OH) ₂ , SrCl ₂ .6H ₂ O, BaCO ₃ , and Eu ₂ O ₃ in a molar ratio of SiO ₂ : Ca (OH) _2. : SrCl ₂ .6H ₂ O: Eu ₂ O ₃ : MnCO ₃ = 1.0: 0.41: 0.50: 0.09: 0.14, and then the same as phosphor 1 The phosphor 5 was obtained by this method.

(Comparative example)
<Phosphor 6>
The phosphor 6 is a phosphor represented by (Ca _0.53 , Sr _0.36 , Eu _0.11 , Mn _0.00 ) _7/6 SiO ₃ Cl _2/6 . The phosphor 6 has a general formula (M ² _x, M ³ _y, M ⁴ _z , M ⁵ _k ) _m M ¹ O ₃ X _{2 / n} , M ¹ = Si, M ² = Ca, M ³ = Sr, X = Cl, M ⁴ = Eu ²⁺ , M ⁵ = Mn, m = 7/6, n = 6, M ² , M ³ , M ⁴ , M ⁵ contents x, y, z, k are respectively It is synthesized to be 0.53, 0.36, 0.11, 0.00. Further, in the phosphor 6, a slight amount of cristobalite is generated in the phosphor by adding excessive SiO ₂ at the mixing ratio of the raw materials. The phosphor 6 is manufactured by first using SiO ₂ , Ca (OH) ₂ , SrCl ₂ .6H ₂ O, Eu ₂ O ₃ , and MnCO ₃ as raw materials with a molar ratio of SiO ₂ : Ca (OH) _2. : SrCl ₂ .6H ₂ O: Eu ₂ O ₃ : MnCO ₃ = 1: 0.54: 0.50: 0.09: 0.00 Weighed in the same manner as phosphor 1 after that. A phosphor 6 was obtained.

  Next, crystal X diffraction measurement was performed on each phosphor obtained by doping Eu, which is a luminescent center element, on the above-described host crystal. First, powder X-ray diffraction measurement was performed using a Kα characteristic X-ray of Cu with a powder X-ray diffractometer (manufactured by RIGAKU: RINT Ultimate III) (hereinafter referred to as measurement 2). The diffraction pattern observed in Measurement 2 is shown in FIG. FIG. 2 is a diagram showing measurement results of X-ray diffraction using Cu Kα characteristic X-rays for the phosphors 1 to 6 according to the present example and the comparative example. The diffraction pattern described at the bottom of FIG. 2 is a Cu Kα characteristic X-ray diffraction pattern calculated from the atomic coordinates of the single crystal of the initial structure model shown in Table 1. As shown in FIG. 2, the phosphors 1 to 6 have very good X-ray diffraction patterns and are found to be phosphors having the same crystal structure as the single crystal of the initial structure model.

The composition of the phosphor was determined by fluorescent X-ray measurement. Specifically, a crystal sample of each phosphor whose composition ratio was changed in advance was prepared, and the content of the element was quantified by ICP (Inductively Coupled Plasma) and ion chromatography. Then, the calibration curve of the fluorescent X-ray of this crystal was created by measuring the sample with the fluorescent X-ray measuring apparatus (RIXKU RIX1000). Using the calibration curve of the fluorescent X-ray, the component ratio of the phosphor 1 to 6 samples was determined by measurement. The results are shown in Table 2.

  Next, emission spectra were measured for phosphors 1-6. FIG. 3 is a diagram showing emission spectra of phosphor 1 and phosphor 6. FIG. 4 is a diagram showing emission spectra of the phosphor 2 and the phosphor 6. FIG. 5 is a diagram showing emission spectra of the phosphor 3 and the phosphor 6. FIG. 6 is a diagram showing emission spectra of the phosphors 4 and 6. FIG. 7 is a diagram showing emission spectra of the phosphor 5 and the phosphor 6. It can be seen that the phosphor according to this example is more excited by near-ultraviolet light and short-wavelength visible light, and emits yellow light on the longer wave side than the excitation light.

In addition, with respect to the phosphors 1 to 6, Table 3 shows the emission peak wavelength, emission peak intensity ratio (light flux ratio), half width, color purity, and k value.

The emission peak intensity ratio shown in Table 3 is a ratio when the emission intensity measured when the phosphor 6 is irradiated with excitation light having a peak wavelength of 400 nm is defined as 100. The color purity was calculated by the following formula (4).
Color purity [%] = (color difference between white chromaticity and emission chromaticity) / (color difference between white chromaticity and dominant chromaticity) × 100 (4)
The color coordinates (Cx, Cy) of white chromaticity are (0.33, 0.33), and Table 4 shows the emission chromaticity and dominant chromaticity of each phosphor.

  In summary, the phosphors 1 to 5 of the examples are yellow phosphors that emit light at a long wavelength of 577.5 nm or more. And with respect to the fluorescent substance 6, as for the emission spectrum in the fluorescent substance 1 to the fluorescent substance 5, as the content of Mn shown by k value increases, the half value width becomes narrow. Further, the phosphors 1 to 5 have a higher peak intensity than the phosphor 6 containing no Mn. As a result, the emission chromaticity approaches the spectrum locus curve, and the difference from the dominant chromaticity is reduced, indicating that the color purity is improved. That is, light emitted from the phosphor 1 from the phosphor 1 has higher color purity than the phosphor 6, and has a light emission spectrum with a narrow half-value width suitable for applications requiring color purity such as display applications.

  In addition, k value which shows the content rate of Mn and its similar element should just be larger than 0.005. If the k value is larger than 0.005, a phosphor having a sharp emission spectrum having a large emission peak intensity and a narrow half-value width as compared with the emission spectrum of the phosphor 6 can be obtained. More preferably, the k value is 0.05 or more. Within this range, a phosphor having an emission peak intensity of 20% or more, a half-value width of less than 100 nm, and a color purity of 95% or more is obtained as compared with the phosphor 6. When the k value was 0.30, a phosphor with good crystallinity could not be obtained. For this reason, the k value is preferably less than 0.30. More preferably, it is good in it being 0.20 or less.

  As described above, with respect to the phosphor 6 (comparative example), in the phosphor containing an appropriate amount of Mn and similar elements, the emission peak intensity of the emission spectrum of the phosphor is increased and the half width is also narrowed. Therefore, the phosphor according to the example can be applied to a light emitting device that requires high color purity.

  Next, the configuration of the light emitting device according to the example will be described in detail.

<Configuration of light emitting device>
The light-emitting device according to the example uses the following specific configuration in the light-emitting device shown in FIG. The configuration of the light emitting device described below is common in the examples and comparative examples except for the type of phosphor used.

First, an aluminum nitride substrate was used as the substrate 12, and an electrode 14 (anode) and an electrode 16 (cathode) were formed on the surface using gold. As the semiconductor light emitting element 18, a 1 mm square LED having a light emission peak at 405 nm (SemiLEDs, Inc .: MvpLED ^™ SL-V-U40AC) is used. Then, the lower surface of the LED is adhered onto the silver paste (Able Stick 84-1LMRIS4) dripped on the electrode 14 (anode) using a dispenser, and the silver paste is cured at 175 ° C. for 1 hour. I let you. Further, a Φ45 μm gold wire was used as the wire 22, and this gold wire was bonded to the upper surface side electrode of the LED and the electrode 16 (cathode) by ultrasonic thermocompression bonding. Further, various phosphors or a mixture of a plurality of phosphors were mixed in a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd .: JCR6126) as a binder member so as to be 1.4 vol% to prepare a phosphor paste. Then, after forming a hemispherical dome having a radius of 5 mm on the upper surface of the semiconductor light emitting element 18 with this phosphor paste, the dome-shaped phosphor layer 24 is fixed by curing for 1.5 hours in a 150 ° C. environment. Formed.

  Based on the structure of the phosphor and the light emitting device described above, the light emitting device according to the example was manufactured. In addition, as the second phosphor having a complementary color relationship with the first phosphor, the phosphor 7 adjusted as follows was used.

<Phosphor 7>
The phosphor 7 is a phosphor represented by (Ca _4.67 Mg _0.5 ) (PO ₄ ) ₃ Cl: Eu _0.08 . The phosphor 7 is an example of the second phosphor described above. The phosphor 7 is manufactured by first using the raw materials of CaCO ₃ , MgCO ₃ , CaCl ₂ , CaHPO ₄ , and Eu ₂ O ₃ with a molar ratio of CaCO ₃ : MgCO ₃ : CaCl ₂ : CaHPO ₄ : Eu _2. Weighed so that 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 7.

<Example 1>
In Example 1, the above-described phosphor 3 was used as the phosphor, and a light-emitting device was manufactured using the phosphor paste dispersed in the above-described silicone resin.

<Example 2>
Example 2 uses the above-described phosphor 3 as a first phosphor and the above-described phosphor 7 as a second phosphor, and a light-emitting device using a phosphor paste in which these are mixed Was made. In this embodiment, a mixed phosphor in which the phosphor 3 and the phosphor 7 are mixed at a weight ratio of 2: 1 is used.

<Comparative example>
In the comparative example, the above-described phosphor 6 was used as the phosphor, and a light-emitting device was manufactured using the phosphor paste dispersed in the above-described silicone resin.

  Each light emitting device was caused to emit light by applying a driving current of 350 mA in an integrating sphere, and an emission spectrum was measured with a spectroscope (manufactured by Instrument System: CAS140B-152).

  FIG. 8 is a diagram showing an emission spectrum when a driving current of 350 mA is applied to the light emitting devices according to Example 1 and the comparative example. Here, the thick line in FIG. 8 indicates Example 1, and the thin line indicates a comparative example.

  As shown in FIG. 8, it can be seen that the emission spectrum of Example 1 emits sharper light than the comparative example and has high color purity.

  FIG. 9 is a diagram showing an emission spectrum when a driving current of 350 mA is applied to the light emitting device according to Example 2. As shown in FIG. 9, it can be seen that a plurality of emission colors with good color purity can be emitted from one light emitting device.

  In the above, this invention was demonstrated based on embodiment and each Example. This embodiment is an exemplification, and it will be understood by those skilled in the art that various modifications can be made to combinations of the respective constituent elements and processing processes, and such modifications are also within the scope of the present invention. is there.

  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.

  DESCRIPTION OF SYMBOLS 10 Light-emitting device, 12 Substrate, 14,16 Electrode, 18 Semiconductor light emitting element, 20 Mount member, 22 Wire, 24 Fluorescent layer.

Claims (3)

Formula ^{_{(M 2 x, M 3 y}} , M 4 z, M 5 k) m M 1 O 3 X (2 / n)
(Wherein, ^{M 1} is Si, Ge, Ti, 1 or more elements including at least Si selected from the group consisting of Zr and Sn, ^{M 2} is selected from the group consisting of Ca, Mg, Sr, Ba and Ra One or more elements including at least Ca, M ³ is one or more elements including at least Sr selected from the group consisting of Sr, Mg, Ca, Ra and Ba, X is at least one halogen element, and M ⁴ is One or more elements selected from the group consisting of rare earth elements including at least Eu ²⁺ , M ⁵ is one or more selected from the group consisting of Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd and Pb In addition, m is in the range of 1 ≦ m ≦ 4/3 and n is in the range of 5 ≦ n ≦ 7, and x, y, z, and k are x + y + z + k = 1, 0 <x <0. .985, 0 <y <0.985, 0.01 ≦ ≦ 0.3,0.005 <k <a range satisfying 0.3.) Phosphor characterized by being represented by. A light emitting element emitting ultraviolet light or short wavelength visible light;
A phosphor that emits visible light when excited by the ultraviolet light or short-wavelength visible light;
A light emitting device comprising:
The phosphor has the general formula (M ² _x , M ³ _y , M ⁴ _z, M ⁵ _k ) _m M ¹ O ₃ X _{(2 / n)}
(Wherein, ^{M 1} is Si, Ge, Ti, 1 or more elements including at least Si selected from the group consisting of Zr and Sn, ^{M 2} is selected from the group consisting of Ca, Mg, Sr, Ba and Ra One or more elements including at least Ca, M ³ is one or more elements including at least Sr selected from the group consisting of Sr, Mg, Ca, Ra and Ba, X is at least one halogen element, and M ⁴ is One or more elements selected from the group consisting of rare earth elements including at least Eu ²⁺ , M ⁵ is one or more selected from the group consisting of Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd and Pb In addition, m is in the range of 1 ≦ m ≦ 4/3 and n is in the range of 5 ≦ n ≦ 7, and x, y, z, and k are x + y + z + k = 1, 0 <x <0. .985, 0 <y <0.985, 0.01 ≦ ≦ 0.3,0.005 <k <a range satisfying 0.3.) The light emitting device which is characterized by being represented by. A light emitting element emitting ultraviolet light or short wavelength visible light;
A first phosphor that emits visible light when excited by the ultraviolet or short wavelength visible light;
A second phosphor that emits visible light of a color different from the visible light that is excited by the ultraviolet light or short wavelength visible light and that the first phosphor emits;
A light-emitting device configured to obtain a mixed color by mixing light from each phosphor,
The first phosphor has the general formula (M ² _x , M ³ _y , M ⁴ _z, M ⁵ _k ) _m M ¹ O ₃ X _{(2 / n)}
(Wherein, ^{M 1} is Si, Ge, Ti, 1 or more elements including at least Si selected from the group consisting of Zr and Sn, ^{M 2} is selected from the group consisting of Ca, Mg, Sr, Ba and Ra One or more elements including at least Ca, M ³ is one or more elements including at least Sr selected from the group consisting of Sr, Mg, Ca, Ra and Ba, X is at least one halogen element, and M ⁴ is One or more elements selected from the group consisting of rare earth elements including at least Eu ²⁺ , M ⁵ is one or more selected from the group consisting of Mn, Zn, Sn, V, Cr, Co, Ni, Cu, Cd and Pb In addition, m is in the range of 1 ≦ m ≦ 4/3 and n is in the range of 5 ≦ n ≦ 7, and x, y, z, and k are x + y + z + k = 1, 0 <x <0. .985, 0 <y <0.985, 0.01 ≦ ≦ 0.3,0.005 <k <a range satisfying 0.3.) The light emitting device which is characterized by being represented by.

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