JP2016020424A - Phosphor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphor having a novel composition.SOLUTION: The phosphor is represented by general formula (M,M,M,M,M)MOX(where Mrepresents one or more elements including at least Si and selected from the group consisting of Si, Ge, Ti, Zr, and Sn; Mrepresents one or more elements including at least Ca and selected from the group consisting of Ca, Mg, Zn, Cd, Ni, Cu, Hg, Co, and Sn; Mrepresents one or more elements including at least Sr and selected from the group consisting of Sr, Ba, and Pb; X represents one or more halogen elements including at least Cl; Mrepresents at least one element selected from the group consisting of divalent rare earth elements and Mn; Mrepresents at least one element selected from the group consisting of trivalent rare earth elements; and Mrepresents at least one element selected from the group consisting of alkali metals).SELECTED DRAWING: Figure 2

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 Documents 1 to 3).

JP 2008-274240 A JP 2011-57663 A JP 2011-57664 A

  The present invention has been made in view of such circumstances, and an object thereof is to provide a phosphor having a new composition.

In order to solve the above-described problems, a phosphor of an embodiment of the present invention has a general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _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, M ² is Ca, Mg, Zn, Cd, Ni, Cu, Hg, Co and One or more elements including at least Ca selected from the group consisting of Sn, M ³ is one or more elements including at least Sr selected from the group consisting of Sr, Ba and Pb, and X is one or more elements including at least Cl M ⁴ is at least one element selected from the group consisting of a divalent rare earth element and Mn, M ⁵ is at least one element selected from the group consisting of a trivalent rare earth element, M ⁶ Is selected from the group consisting of alkali metals And at least one element selected from the group consisting of m ≦ 0.1 ≦ m ≦ 1.4, n ≦ 0.1 ≦ n ≦ 0.5, and x, y, z, v, w is a range satisfying x + y + z + v + w = 1, 0 <x <1, 0 <y <1, 0 ≦ z ≦ 0.5, 0 <v ≦ 0.5, and 0 ≦ w ≦ 0.5. expressed.

  According to this aspect, it is possible to realize a phosphor having a new composition that has not existed before.

M ⁵ described above may include at least one element selected from the group consisting of Ce, Sm, Dy, Ho, Er, Tm, Yb, Lu, Tb, and Pr.

M ⁶ described above may contain at least one element selected from the group consisting of Li, K, Na, Rb, and Cs.

  In the above general formula, v may be in the range of 0 <v <0.10.

  In the above general formula, w may be in a range of 0 ≦ w <0.10.

  It should be noted that any combination of the above-described constituent elements and a representation of the present invention converted between a method, an apparatus, a system, etc. are also effective as an aspect of the present invention.

  According to the present invention, a phosphor having a new composition can be provided.

It is a schematic sectional drawing of the light-emitting device concerning this Embodiment. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 1, fluorescent substance 2, fluorescent substance 1 ', and fluorescent substance 2'. It is a figure which shows the measurement result of the X-ray diffraction using the K alpha characteristic X-ray of Cu about fluorescent substance 1 ', fluorescent substance 1, fluorescent substance 2, and fluorescent substance 2'. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 3, the fluorescent substance 4, and the fluorescent substance 1 '. It is a figure which shows the measurement result of the X ray diffraction which used the K alpha characteristic X ray of Cu about fluorescent substance 1 ', fluorescent substance 3, and fluorescent substance 4. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 5, the fluorescent substance 6, and the fluorescent substance 1 '. It is a figure which shows the measurement result of the X-ray diffraction which used the K alpha characteristic X ray of Cu about fluorescent substance 1 ', fluorescent substance 5, and fluorescent substance 6. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 7, the fluorescent substance 8, and the fluorescent substance 1 '. It is a figure which shows the measurement result of the X-ray diffraction which used the K alpha characteristic X ray of Cu about fluorescent substance 1 ', fluorescent substance 7, and fluorescent substance 8. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 9, the fluorescent substance 10, and the fluorescent substance 1 '. It is a figure which shows the measurement result of the X-ray diffraction which used the K alpha characteristic X-ray of Cu about fluorescent substance 1 ', fluorescent substance 9, and fluorescent substance 10. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 11, the fluorescent substance 12, and the fluorescent substance 1 '. It is a figure which shows the measurement result of the X-ray diffraction using the K alpha characteristic X-ray of Cu about fluorescent substance 1 ', fluorescent substance 11, and fluorescent substance 12. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 13, the fluorescent substance 14, and the fluorescent substance 1 '. It is a figure which shows the measurement result of the X-ray diffraction using the K alpha characteristic X-ray of Cu about fluorescent substance 1 ', fluorescent substance 13, and fluorescent substance 14. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 15, the fluorescent substance 16, and the fluorescent substance 1 '. It is a figure which shows the measurement result of the X-ray diffraction using the K alpha characteristic X-ray of Cu about fluorescent substance 1 ', fluorescent substance 15, and fluorescent substance 16. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of fluorescent substance 17-19. It is a figure which shows the measurement result of the X-ray diffraction using the K alpha characteristic X-ray of Cu about fluorescent substance 1 ', fluorescent substances 17-19, and fluorescent substance 3'. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 18 and the fluorescent substance 20. It is a figure which shows the measurement result of the X ray diffraction which used the K alpha characteristic X ray of Cu about fluorescent substance 1 ', fluorescent substance 18, and fluorescent substance 20. It is a figure which shows the excitation spectrum (PLE) and emission spectrum (PL) of the fluorescent substance 18 and the fluorescent substance 21. It is a figure which shows the measurement result of the X-ray diffraction which used the K alpha characteristic X ray of Cu about fluorescent substance 1 ', fluorescent substance 18, and fluorescent substance 21.

  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 film-like 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, aluminum, A metal substrate such as copper can be used.

  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.

  The phosphor layer 24 is formed so that phosphors described later are dispersed and mixed in a binder member, and the light emitting surface 18a of the semiconductor light emitting element 18 is sealed by the binder member. The fluorescent layer 24 may be formed in a hemispherical shape (dome shape) that covers the upper surface of the substrate 12. 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, and thereafter binding the phosphor paste. It is formed by curing the member. 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 light or short-wavelength visible light, and the general formula is (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ). _m M ¹ O ₃ X _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, M ² is Ca, Mg, Zn, Cd, One or more elements containing at least Ca selected from the group consisting of Ni, Cu, Hg, Co and Sn, M ³ is one or more elements including at least Sr selected from the group consisting of Sr, Ba and Pb, X Is at least one halogen element containing at least Cl, M ⁴ is at least one element selected from the group consisting of divalent rare earth elements and Mn, and M ⁵ is at least selected from the group consisting of trivalent rare earth elements. one or more elements, ^{M 6} is It represents at least one element selected from the group consisting of rukari metals, m is in the range of 0.1 ≦ m ≦ 1.4, and n is in the range of 0.1 ≦ n ≦ 0.5. , Y, z, v, w are x + y + z + v + w = 1, 0 <x <1, 0 <y <1, 0 ≦ z ≦ 0.5, 0 <v ≦ 0.5, 0 ≦ w ≦ 0.5 It is the range to satisfy.)

The first phosphor can be obtained, for example, as follows. As the first phosphor, compounds represented by the following composition formulas (1) to (6) 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) A compound containing M ′ ² and O (M ′ ² represents a divalent element such as Mg, Ca, Sr, Ba, Cd, Co, Zn, etc.)
(3) M ′ ³ X ₂ or a compound containing M ′ ³ and O (M ′ ³ is a divalent element such as Mg, Ca, Pb, Sr, Ba, and Ra, and X is a halogen element.)
(4) M ^'4 compounds containing (M' ⁴ represents Eu, Yb, and a rare earth element and Mn of Sm and the like.)
(5) A compound containing M ′ ⁵ and O (M ′ ⁵ represents a trivalent rare earth element such as Ce, Sm, Dy, Ho, Er, Tm, Yb, Lu, Tb and Pr.)
(6) M ′ ⁶ X (M ′ ⁶ represents an alkali metal element such as Li, K, Na, Rb and Cs, and X represents a halogen element.)

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. _{, 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, Alternatively, carbonates, oxides, hydroxides, and the like of divalent metal ions can be used. As a raw material of the composition formula (4), for example, Eu ₂ O ₃ , Yb ₂ O ₃ , Sm 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. Examples of the raw material of the composition formula (5) include carbonates, oxides, hydroxides and the like of trivalent rare earth metal ions such as Ce, Sm, Dy, Ho, Er, Tm, Yb, Lu, Tb, and Pr. Can be used. As the raw material of the composition formula (6), for example, LiCl, NaCl, KCl, RbCl, CsCl, LiF, NaF, KF, RbF, CsF, LiBr, NaBr, KBr, RbBr, CsBr, LiI, NaI, KI, RbI, CsI Etc. 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, Zn, Cd, Co, and the like. 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, Ba, Ra, Pb, and the like. 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), M ′ ⁴ is preferably a divalent rare earth element or Mn ²⁺ . Trivalent rare earth elements such as Ce, Sm, Dy, Ho, Er, Tm, Yb, Lu, Tb, and Pr contained in the raw material of the composition formula (5) are used as an activator or a coactivator. In that case, when a divalent element in the basic structure of the crystal is replaced with a trivalent rare earth element, the charge becomes excessive. Therefore, in order to compensate for an excessive charge, it is preferable to add a monovalent alkali metal contained in the material of the composition formula (6) as a charge compensator.

The raw materials of the composition formulas (1) to (6) are weighed so that the molar ratio becomes a predetermined value, and each weighed 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 was put in an alumina crucible and fired in a reducing atmosphere electric furnace in a predetermined atmosphere (H ₂ : N ₂ = 5: 95 (vol%)) at a temperature of 700 ° C. or more and less than 1100 ° C. for 3 to 40 hours, A fired product is obtained. The first phosphor can be obtained by carefully washing the fired product with warm pure water and washing away excess metal, chloride, and the like. The first phosphor is excited by ultraviolet light or short wavelength visible light and emits visible light.

(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. 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, X is a halogen element)
Sr ₅ (PO ₄ ) ₃ X: Eu (X is a halogen element)
BaMgAl ₁₀ O ₁₇ : Eu

  The phosphor described above will be described more specifically with reference to the following examples. However, the following description of the phosphor raw material, the production method, the chemical composition of the phosphor, etc. limits the form of the phosphor of the present invention. Not what you want.

Example 1
The phosphor 1 according to Example 1 has a fluorescence represented by (Ca _0.26 , Sr _0.59 , Eu _0.14 , Sm _0.005 , K _0.005 ) _7/6 SiO ₃ Cl _2/6. Is the body. The phosphor 1 has the above general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , where M ¹ = Si, M ² = Ca, M ³ = Sr, M ⁴ = Eu, M ⁵ = Sm, M ⁶ = K, X = Cl, m = 7/6, n = 2/6, M ² , M ³ , M ⁴ , M ⁵ , M ⁶ The contents x, y, z, v, and w are synthesized to be 0.26, 0.59, 0.14, 0.005, and 0.005, respectively. The phosphor 1 is manufactured by first using CaCO ₃ , SrCO ₃ , Eu ₂ O ₃ , Sm ₂ O ₃ , KCl, and SiO ₂ with a molar ratio of CaCO ₃ : SrCO ₃ : Eu ₂ O ₃ : Sm. ₂ O ₃ : KCl: SiO ₂ = 0.30: 0.69: 0.082: 0.0029: 0.0058: 1.00 and weighed NH ₄ Cl as the above-mentioned raw material ( CaCO ₃ , SrCO ₃ , Eu ₂ O ₃ , Sm ₂ O ₃ , KCl and SiO ₂ ) are weighed at a weight ratio of 0.32, and each weighed raw material is placed in an alumina mortar and pulverized and mixed. A raw material mixture was obtained. This raw material mixture was put in an alumina crucible and baked for 10 hours at a predetermined atmosphere (H ₂ : N ₂ = 5: 95 (vol%)) and a temperature of 1000 ° C. in a reducing atmosphere electric furnace to obtain a baked product. The obtained fired product was washed four times with warm pure water and then dried at 150 ° C. for 1 hour to obtain phosphor 1. The composition of the phosphor was analyzed and confirmed using a fluorescent X-ray analyzer (Rigaku Corporation RIX1000).

表１における各元素は、Ｓｉ元素に対するモル比である。また、発光積分強度は、比較例１に対する相対値である。 The compositions of the phosphors according to Examples 1 to 16, Comparative Example 1 and Comparative Example 2 are shown in Table 1.

Each element in Table 1 is a molar ratio to Si element. Further, the integrated emission intensity is a relative value with respect to Comparative Example 1.

Table 2 shows the molar ratio and the weight ratio of each raw material used when the phosphors according to Examples 1 to 16, Comparative Example 1 and Comparative Example 2 are manufactured.

(Comparative Example 1)
The phosphor 1 ′ according to Comparative Example 1 is a phosphor represented by (Ca _0.26 , Sr _0.59 , Eu _0.15 ) _7/6 SiO ₃ Cl _2/6 . The phosphor 1 ′ has the general formula (M ² _x, M ³ _y, M ⁴ _z ) _m M ¹ O ₃ X _n , and M ¹ = Si, M ² = Ca, M ³ = Sr, X = Cl, M ⁴ = Eu, m = 7/6, n = 2/6, and the contents x, y, and z of M ² , M ³ , and M ⁴ are 0.26, 0.59, and 0.15, respectively. Has been synthesized. In addition, the phosphor 1 ′ is manufactured by first using CaCO ₃ , SrCO ₃ , Eu ₂ O ₃ and SiO ₂ raw materials with a molar ratio of CaCO ₃ : SrCO ₃ : Eu ₂ O ₃ : SiO ₂ = 0. It measured so that it might be set to 30: 0.69: 0.088: 1.00. Thereafter, phosphor 1 ′ was synthesized in the same manner as in Example 1.

  The phosphor 1 ′ contains neither a trivalent rare earth element as a coactivator nor a monovalent alkali metal as a charge compensator, but the phosphor 1 ′ is ultraviolet or short wavelength visible. It is one of yellow phosphors that are excited by light and emit light stably and efficiently. Therefore, the crystal phase in the phosphor 1 'is regarded as the reference crystal phase, and it is also determined whether or not other phosphors have the same crystal phase. The presence or absence of the reference crystal phase is shown in Table 1.

(Examples 2 to 16, Comparative Example 2)
The phosphors 2 to 16 according to Examples 2 to 16 and the phosphor 2 ′ according to Comparative Example 2 have the composition ratios shown in Table 1, respectively. Moreover, each raw material used when manufacturing fluorescent substance 2-16 which concerns on Examples 2-16 and fluorescent substance 2 'which concerns on the comparative example 2 is mixed by the molar ratio and weight ratio which are shown in Table 2, respectively. The production method is the same as in Example 1 except that the types and ratios of the raw materials to be mixed are different.

(When Sm is used as a coactivator)
FIG. 2 is a diagram showing excitation spectra (PLE) and emission spectra (PL) of phosphor 1, phosphor 2, phosphor 1 ′, and phosphor 2 ′. In the phosphor 1, the addition amount (v) of Sm is 0.005 mol with respect to 1 mol of Si. In the phosphor 2, the addition amount (v) of Sm is 0.020 mol with respect to 1 mol of Si. In the phosphor 2 ′, the addition amount (v) of Sm is 0.040 mol with respect to 1 mol of Si. In addition, the phosphor 1, the phosphor 2, and the phosphor 2 ′ contain the same amount of K as Sm.

  As shown in FIG. 2, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 1 has a value of Sm content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.17 times that of the reference phosphor 1 '. In addition, the phosphor 2 has an Sm content v value of 0.020 in the above-described general formula, and the integrated emission intensity is 1.04 times that of the reference phosphor 1 ′. On the other hand, in the phosphor 2 ', the value of the Sm content v in the above-described general formula was 0.040, and the integrated emission intensity was greatly reduced to 0.73 times that of the reference phosphor 1'.

  FIG. 3 is a diagram showing measurement results of X-ray diffraction using phosphor Kα characteristic X-rays for phosphor 1 ′, phosphor 1, phosphor 2, and phosphor 2 ′. The phosphor 1 'can obtain the same single-phase X-ray diffraction pattern as the phosphor disclosed in Japanese Patent Application Laid-Open No. 2008-274240 cited in the prior art document (reference crystal phase). As shown in FIG. 3, in phosphor 1, phosphor 2 and phosphor 2 ′, a characteristic strong peak exists in the same range of 28 ° to 31 ° as phosphor 1 ′ not containing Sm or K. A diffraction pattern is obtained. Therefore, it can be seen that phosphor 1, phosphor 2 and phosphor 2 'are composed of the same reference crystal phase as phosphor 1'. On the other hand, in the diffraction pattern of the phosphor 2 ′, there is a peak indicating another impurity phase in the range of 17 ° to 18 °, and the phosphor 2 ′ has an impurity phase different from those of the phosphor 1 and the phosphor 2. It can be seen that is included.

In other words, in the phosphors having an addition amount (v) of Sm of 0 mol (Comparative Example 1), 0.005 mol (Example 1), and 0.020 mol (Example 2), an impurity phase is hardly generated, and a desired amount is obtained. A reference crystal phase (single phase) is obtained. On the other hand, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol, an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , the Sm content v is preferably 0 <v <0.040. It is good to satisfy.

(When Dy is used as a coactivator)
FIG. 4 is a diagram showing excitation spectra (PLE) and emission spectra (PL) of phosphor 3, phosphor 4 and phosphor 1 ′. In the phosphor 3, the addition amount (v) of Dy is 0.005 mol with respect to 1 mol of Si. In the phosphor 4, the addition amount (v) of Dy is 0.020 mol with respect to 1 mol of Si. Further, the phosphor 3 and the phosphor 4 contain the same amount of K as Dy.

  As shown in FIG. 4, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 3 has a Dy content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.20 times that of the reference phosphor 1 '. Further, the phosphor 4 has a Dy content v value of 0.020 in the above-described general formula, and the integrated emission intensity is 1.05 times that of the reference phosphor 1 '.

  FIG. 5 is a diagram illustrating measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 3, and the phosphor 4. As shown in FIG. 5, in the phosphor 3 and the phosphor 4, a diffraction pattern having a characteristic strong peak in the same range of 28 ° to 31 ° as that of the phosphor 1 ′ not containing Dy or K is obtained. . Therefore, it can be seen that the phosphor 3 and the phosphor 4 are composed of the same reference crystal phase as the phosphor 1 ′.

That is, in the phosphors having the Dy addition amount (v) of 0 mol (Comparative Example 1), 0.005 mol (Example 3), and 0.020 mol (Example 4), almost no impurity phase is generated, A reference crystal phase (single phase) is obtained. On the other hand, as described above, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol (Comparative Example 2), an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, the same tendency is expected in Dy belonging to the same lanthanoid as Sm. Therefore, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , the Dy content v is preferably 0 <v <0.040. It is good to satisfy.

(When Ho is used as a coactivator)
FIG. 6 is a diagram showing the excitation spectrum (PLE) and emission spectrum (PL) of phosphor 5, phosphor 6 and phosphor 1 ′. In the phosphor 5, the addition amount (v) of Ho is 0.005 mol with respect to 1 mol of Si. In the phosphor 6, the addition amount (v) of Ho is 0.020 mol with respect to 1 mol of Si. Moreover, the fluorescent substance 5 and the fluorescent substance 6 contain K of the same amount as Ho.

  As shown in FIG. 6, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 5 has a Ho content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.14 times that of the reference phosphor 1 '. In addition, the phosphor 6 has a Ho content v value of 0.020 in the above-described general formula, and the integrated emission intensity is 1.06 times that of the reference phosphor 1 '.

  FIG. 7 is a diagram showing measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 5, and the phosphor 6. As shown in FIG. 7, in the phosphor 5 and the phosphor 6, a diffraction pattern in which a characteristic strong peak exists in the same range of 28 ° to 31 ° as the phosphor 1 ′ not containing Ho or K can be obtained. . Therefore, it can be seen that the phosphor 5 and the phosphor 6 are composed of the same reference crystal phase as the phosphor 1 ′.

That is, in the phosphors having the Ho addition amount (v) of 0 mol (Comparative Example 1), 0.005 mol (Example 5), and 0.020 mol (Example 6), an impurity phase is hardly generated, and a desired amount is obtained. A reference crystal phase (single phase) is obtained. On the other hand, as described above, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol (Comparative Example 2), an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, a similar tendency is expected even in Ho belonging to the same lanthanoid as Sm. Therefore, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , the Ho content v is preferably 0 <v <0.040. It is good to satisfy.

(When Er is used as a coactivator)
FIG. 8 is a diagram showing the excitation spectrum (PLE) and emission spectrum (PL) of phosphor 7, phosphor 8, and phosphor 1 ′. In the phosphor 7, the addition amount (v) of Er is 0.005 mol with respect to 1 mol of Si. The phosphor 8 has an Er addition amount (v) of 0.020 mol with respect to 1 mol of Si. Further, the phosphor 7 and the phosphor 8 contain the same amount of K as Er.

  As shown in FIG. 8, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 7 has an Er content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.22 times that of the reference phosphor 1 '. Further, the phosphor 8 has an Er content v of 0.020 in the above-described general formula, and the integrated emission intensity is 1.01 times that of the reference phosphor 1 '.

  FIG. 9 is a diagram illustrating measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 7, and the phosphor 8. As shown in FIG. 9, in the phosphor 7 and the phosphor 8, a diffraction pattern having a characteristic strong peak in the same range of 28 ° to 31 ° as the phosphor 1 ′ not containing Er or K is obtained. . Therefore, it can be seen that the phosphor 7 and the phosphor 8 are composed of the same reference crystal phase as the phosphor 1 ′.

That is, in the phosphors having an addition amount (v) of Er of 0 mol (Comparative Example 1), 0.005 mol (Example 7), and 0.020 mol (Example 8), an impurity phase is hardly generated, and the desired amount is obtained. A reference crystal phase (single phase) is obtained. On the other hand, as described above, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol (Comparative Example 2), an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, the same tendency is expected for Er belonging to the same lanthanoid as Sm. Accordingly, the general formula ^{_{(M 2 x, M 3 y}} , M 4 z, M 5 v, M 6 w) in m ^M 1 _O 3 _{X n,} preferably, the content v of Er is 0 <v <0.040 It is good to satisfy.

(When Tm is used as a coactivator)
FIG. 10 is a diagram showing excitation spectra (PLE) and emission spectra (PL) of phosphor 9, phosphor 10, and phosphor 1 ′. The phosphor 9 has a Tm addition amount (v) of 0.005 mol with respect to 1 mol of Si. The phosphor 10 has a Tm addition amount (v) of 0.020 mol with respect to 1 mol of Si. Moreover, the fluorescent substance 9 and the fluorescent substance 10 contain the same amount of K as Tm.

  As shown in FIG. 10, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 9 has a Tm content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.21 times that of the reference phosphor 1 ′. Further, the phosphor 10 has a Tm content v value of 0.020 in the above-described general formula, and the integrated emission intensity is 1.01 times that of the reference phosphor 1 '.

  FIG. 11 is a diagram illustrating measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 9, and the phosphor 10. As shown in FIG. 11, in the phosphor 9 and the phosphor 10, a diffraction pattern having a characteristic strong peak in the same range of 28 ° to 31 ° as the phosphor 1 ′ not containing Tm or K is obtained. . Therefore, it can be seen that the phosphor 9 and the phosphor 10 are composed of the same reference crystal phase as the phosphor 1 ′.

That is, in the phosphors having an addition amount (v) of Tm of 0 mol (Comparative Example 1), 0.005 mol (Example 9), and 0.020 mol (Example 10), an impurity phase is hardly generated, and a desired amount is obtained. A reference crystal phase (single phase) is obtained. On the other hand, as described above, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol (Comparative Example 2), an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, the same tendency is expected for Tm belonging to the same lanthanoid as Sm. Therefore, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , the Tm content v is preferably 0 <v <0.040. It is good to satisfy.

(When Yb is used as a coactivator)
FIG. 12 is a diagram showing the excitation spectrum (PLE) and emission spectrum (PL) of phosphor 11, phosphor 12, and phosphor 1 ′. In the phosphor 11, the addition amount (v) of Yb is 0.005 mol with respect to 1 mol of Si. In the phosphor 12, the addition amount (v) of Yb is 0.020 mol with respect to 1 mol of Si. Moreover, the phosphor 11 and the phosphor 12 contain the same amount of K as Yb.

  As shown in FIG. 12, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 11 has a Yb content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.22 times that of the reference phosphor 1 ′. Further, the phosphor 12 has a Yb content v value of 0.020 in the above-described general formula, and the integrated emission intensity is 1.03 times that of the reference phosphor 1 '.

  FIG. 13 is a diagram showing measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 11, and the phosphor 12. As shown in FIG. 11, in the phosphor 11 and the phosphor 12, a diffraction pattern in which a characteristic strong peak exists in the same range of 28 ° to 31 ° as the phosphor 1 ′ not containing Yb or K can be obtained. . Therefore, it can be seen that the phosphor 11 and the phosphor 12 are composed of the same reference crystal phase as the phosphor 1 ′.

That is, in the phosphors having the Yb addition amount (v) of 0 mol (Comparative Example 1), 0.005 mol (Example 11), and 0.020 mol (Example 12), almost no impurity phase is generated, A reference crystal phase (single phase) is obtained. On the other hand, as described above, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol (Comparative Example 2), an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, the same tendency is expected for Yb belonging to the same lanthanoid as Sm. Accordingly, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , the Yb content v is preferably 0 <v <0.040. It is good to satisfy.

(When Lu is used as a coactivator)
FIG. 14 is a diagram showing the excitation spectrum (PLE) and emission spectrum (PL) of phosphor 13, phosphor 14, and phosphor 1 ′. In the phosphor 13, the addition amount (v) of Lu is 0.005 mol with respect to 1 mol of Si. In the phosphor 14, the addition amount (v) of Lu is 0.020 mol with respect to 1 mol of Si. Further, the phosphor 13 and the phosphor 14 contain the same amount of K as Lu.

  As shown in FIG. 14, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 13 has a Lu content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.21 times that of the reference phosphor 1 '. In addition, the phosphor 14 has a Lu content v value of 0.020 in the above-described general formula, and the integrated emission intensity is 1.05 times that of the reference phosphor 1 '.

  FIG. 15 is a diagram showing measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 13, and the phosphor 14. As shown in FIG. 15, in the phosphor 13 and the phosphor 14, a diffraction pattern having a characteristic strong peak in the same range of 28 ° to 31 ° as that of the phosphor 1 ′ not containing Lu or K is obtained. . Therefore, it can be seen that the phosphor 13 and the phosphor 14 are composed of the same reference crystal phase as the phosphor 1 ′.

That is, in the phosphors with the addition amount (v) of Lu of 0 mol (Comparative Example 1), 0.005 mol (Example 13), and 0.020 mol (Example 14), almost no impurity phase is generated, and the desired amount is obtained. A reference crystal phase (single phase) is obtained. On the other hand, as described above, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol (Comparative Example 2), an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, the same tendency is expected in Lu belonging to the same lanthanoid as Sm. Therefore, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , the Lu content v is preferably 0 <v <0.040. It is good to satisfy.

(When Tb is used as a coactivator)
FIG. 16 is a diagram showing the excitation spectrum (PLE) and emission spectrum (PL) of phosphor 15, phosphor 16 and phosphor 1 ′. The phosphor 15 has an addition amount (v) of Tb of 0.005 mol with respect to 1 mol of Si. The phosphor 16 has an addition amount (v) of Tb of 0.020 mol with respect to 1 mol of Si. Moreover, the phosphor 15 and the phosphor 16 contain the same amount of K as Tb.

  As shown in FIG. 16, the excitation spectrum of each phosphor has a peak in the wavelength region of ultraviolet light or short-wavelength visible light. Each phosphor emits yellow light whose emission spectrum has a peak wavelength in the range of 570 to 580 nm. The phosphor 15 has a Tb content v of 0.005 in the above-described general formula, and the integrated emission intensity is 1.15 times that of the reference phosphor 1 '. Further, the phosphor 16 has a Tb content v value of 0.020 in the above-described general formula, and the integrated emission intensity is 1.01 times that of the reference phosphor 1 '.

  FIG. 17 is a diagram showing measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 15, and the phosphor 16. As shown in FIG. 17, in the phosphor 15 and the phosphor 16, a diffraction pattern having a characteristic strong peak in the same range of 28 ° to 31 ° as that of the phosphor 1 ′ not containing Tb or K is obtained. . Therefore, it can be seen that the phosphor 15 and the phosphor 16 are composed of the same reference crystal phase as the phosphor 1 ′.

That is, in the phosphors having the Tb addition amount (v) of 0 mol (Comparative Example 1), 0.005 mol (Example 15), and 0.020 mol (Example 16), an impurity phase is hardly generated, and the desired amount is obtained. A reference crystal phase (single phase) is obtained. On the other hand, as described above, in the phosphor 2 ′ having an Sm addition amount (v) of 0.040 mol (Comparative Example 2), an impurity phase is also generated in addition to the desired reference crystal phase. Therefore, the same tendency is expected for Tb belonging to the same lanthanoid as Sm. Therefore, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , the Tb content v is preferably 0 <v <0.040. It is good to satisfy.

In the phosphors represented by the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n as shown in Examples 1 to 16 above. When the content of at least one element M ⁵ selected from the group consisting of trivalent rare earth elements satisfies 0 <v <0.040, the emission integrated intensity can be improved. More preferably, the content of the element M ⁵ may satisfy 0 <v ≦ 0.020. Similarly, when the content of at least one element M ⁶ selected from the group consisting of alkali metals satisfies 0 <w <0.040, the emission integrated intensity can be improved. More preferably, the content of the element M ⁶ may satisfy 0 <v ≦ 0.020.

(Example 17)
The phosphor 17 according to Example 17 is a phosphor represented by (Ca _0.37 , Sr _0.59 , Ce _0.02 , K _0.02 ) _7/6 SiO ₃ Cl _2/6 . The phosphor 17 has the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , where M ¹ = Si, M ² = Ca, M ³ = Sr, M ⁴ = Eu, M ⁵ = Ce, M ⁶ = K, X = Cl, m = 7/6, n = 2/6, M ² , M ³ , M ⁴ , M ⁵ , M ⁶ The contents x, y, z, v, and w are synthesized so as to be 0.37, 0.59, 0.00, 0.02, and 0.02, respectively. First, the phosphor 17 is manufactured by using CaCO ₃ , SrCO ₃ , Ce ₂ O ₃ , KCl, and SiO ₂ as raw materials at a molar ratio of CaCO ₃ : SrCO ₃ : Ce ₂ O ₃ : KCl: SiO ₂ = 0. .43: 0.69: 0.012: 0.023: 1.00, and NH ₄ Cl as a flux is added to the above-mentioned raw materials (CaCO ₃ , SrCO ₃ , Ce ₂ O ₃ , KCl and SiO ₂ ) Weighed at a weight ratio of 0.09 to 0.34 with respect to the total weight, and weighed each raw material into an alumina mortar and pulverized and mixed to obtain a raw material mixture. This raw material mixture was put into an alumina crucible, fired at a temperature of 850 ° C. for 5 hours in a nitrogen atmosphere, and further reduced to a predetermined reducing atmosphere (H ₂ : N ₂ = 5: 95 (vol%)) in an electric furnace at a temperature of 1000 ° C. Baking was performed for a time to obtain a fired product. The obtained fired product was washed four times with warm pure water to remove excess metal and chlorine, and then dried at 150 ° C. for 1 hour to obtain phosphor 17. The composition of the phosphor was analyzed and confirmed using a fluorescent X-ray analyzer (Rigaku Corporation RIX1000) in the same manner as described above.

表３における各元素は、Ｓｉ元素に対するモル比である。また、発光強度（ピーク波長）は相対値である。 The compositions of the phosphors according to Examples 17 to 21 and Comparative Example 2 are shown in Table 3.

Each element in Table 3 is a molar ratio with respect to Si element. The emission intensity (peak wavelength) is a relative value.

In addition, Table 4 shows the molar ratio and the weight ratio of each raw material used when the phosphors according to Examples 17 to 21 and Comparative Example 3 are manufactured.

(Example 18)
The phosphor 18 according to Example 18 has the composition ratio shown in Table 3. Moreover, each raw material used when manufacturing the phosphor 18 is mixed at a molar ratio shown in Table 4. The type of raw materials to be mixed, the ratio is different, except that it uses a SrCl 2 · _6H 2 _O in the flux method is the same as in Example 17.

(Example 19)
The phosphor 19 according to Example 19 has the composition ratio shown in Table 3. Moreover, each raw material used when manufacturing the phosphor 19 is mixed in a molar ratio and a weight ratio shown in Table 4. The production method is the same as that of Example 17 except that the types and ratios of the raw materials to be mixed are different.

(Example 20)
The phosphor 20 according to Example 20 has the composition ratio shown in Table 3. Moreover, each raw material used when manufacturing the fluorescent substance 20 is mixed at a molar ratio and a weight ratio shown in Table 4. The phosphor 20 contains Na as an alkali metal represented by M ⁶ in the general formula, and NaCl is used as a charge compensator for introducing Na. The production method is the same as that of Example 17 except that the types and ratios of the raw materials to be mixed are different.

(Example 21)
The phosphor 21 according to Example 21 has the composition ratio shown in Table 3. Moreover, each raw material used when manufacturing the phosphor 21 is mixed at a molar ratio and a weight ratio shown in Table 4. Phosphor 21 does not contain the alkali metal represented by M ⁶ in the general formula, it is not used in the production of the charge compensation agent for introducing an alkali metal. The production method is the same as that of Example 17 except that the types and ratios of the raw materials to be mixed are different.

(Comparative Example 3)
The phosphor 3 ′ according to Comparative Example 3 has the composition ratio shown in Table 3. Moreover, each raw material used when manufacturing fluorescent substance 3 'is mixed by the molar ratio shown in Table 4, and weight ratio. The production method is the same as that of Example 17 except that the types and ratios of the raw materials to be mixed are different.

(Concentration dependence when Ce is used as an activator)
FIG. 18 is a diagram showing excitation spectra (PLE) and emission spectra (PL) of the phosphors 17 to 19. In the phosphor 17, the addition amount (v) of Ce is 0.02 mol with respect to 1 mol of Si. In the phosphor 18, the addition amount (v) of Ce is 0.03 mol with respect to 1 mol of Si. In the phosphor 19, the addition amount (v) of Ce is 0.07 mol with respect to 1 mol of Si. In phosphor 3 ′, the addition amount (v) of Ce is 0.10 mol with respect to 1 mol of Si. Further, the phosphors 17 to 19 and the phosphor 3 ′ contain the same amount of K as Ce.

  As shown in FIG. 18, the excitation spectra of the phosphors 17 to 19 have a peak in the ultraviolet wavelength region around 335 nm. Each phosphor emits short-wavelength visible light having an emission spectrum peak wavelength in the range of about 395 nm. The phosphor 17 has a Ce content v value of 0.02 in the aforementioned general formula, and an emission intensity at a peak wavelength (395 nm) of 0.73 (relative value). Further, the phosphor 18 has a Ce content v value of 0.03 in the above-described general formula, and an emission intensity at a peak wavelength (395 nm) of 2.2 (relative value). In addition, the phosphor 19 has a Ce content v value of 0.07 in the general formula described above, and an emission intensity at a peak wavelength (395 nm) of 1.84 (relative value). The phosphor 3 ′ did not emit light although the value of Ce content v in the above general formula was 0.10.

  FIG. 19 is a diagram showing measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphors 17 to 19, and the phosphor 3 ′. As shown in FIG. 19, in the phosphors 17 to 19, a diffraction pattern having a characteristic strong peak in the same range of 28 ° to 31 ° as that of the phosphor 1 'not containing Ce or K is obtained. Therefore, it can be seen that the phosphors 17 to 19 are composed of the same reference crystal phase as the phosphor 1 ′. On the other hand, in the diffraction pattern of phosphor 3 ′, there is no characteristic strong peak in the range of 28 ° to 31 °, and phosphor 3 ′ has a different crystal structure from phosphor 1 ′ and phosphors 17-19. It can be seen that it is.

That is, in the phosphors having an addition amount (v) of Ce of 0.02 mol (Example 17), 0.03 mol (Example 18), and 0.07 mol (Example 19), an impurity phase is hardly generated, The desired reference crystal phase (single phase) is obtained. On the other hand, in the phosphor 3 ′ having an addition amount (v) of Ce of 0.10 mol, a desired reference crystal phase is not generated and light is not emitted. Accordingly, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , preferably, the content v of M ⁵ = Ce is 0 <v < It is good to satisfy 0.10. More preferably, the Ce content v satisfies 0.02 ≦ v ≦ 0.07. Similarly, in the general formula (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _n , preferably, M ⁶ = alkali metal content w is 0 ≦ It is preferable to satisfy w <0.10. More preferably, the alkali metal content w satisfies 0.02 ≦ w ≦ 0.07.

(Effects of different charge compensators)
FIG. 20 is a diagram showing the excitation spectrum (PLE) and emission spectrum (PL) of the phosphor 18 and the phosphor 20. In the phosphor 18, the addition amount (w) of K is 0.03 mol with respect to 1 mol of Si. In the phosphor 20, the addition amount (w) of Na is 0.03 mol with respect to 1 mol of Si. In both phosphor 18 and phosphor 20, the addition amount (v) of Ce is 0.03 mol with respect to 1 mol of Si.

  As shown in FIG. 20, the excitation spectrum of the phosphor 20 has a peak in the wavelength region of ultraviolet rays around 335 nm. The phosphor 20 emits short-wavelength visible light having an emission spectrum peak wavelength in the range of about 395 nm. The phosphor 18 has a K (alkali metal) content w value of 0.03 in the above-described general formula, and an emission intensity at a peak wavelength (395 nm) of 2.2 (relative value). On the other hand, the phosphor 20 has a Na (alkali metal) content w value of 0.03 in the aforementioned general formula, and an emission intensity at a peak wavelength (395 nm) of 1.41 (relative value). Thus, the phosphor 20 contains the same amount of alkali metal as phosphor 18, but the emission intensity at the peak wavelength (395 nm) decreased by about 30% due to the change of element from K to Na. . That is, as the charge compensator, KCl is more preferable than NaCl.

  FIG. 21 is a diagram showing measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 18, and the phosphor 20. As shown in FIG. 21, in the phosphor 18 and the phosphor 20, a diffraction pattern having a characteristic strong peak in the same range of 28 ° to 31 ° as that of the phosphor 1 'is obtained. Therefore, it can be seen that the phosphor 18 and the phosphor 20 are composed of the same reference crystal phase as the phosphor 1 ′.

(Effect of presence or absence of charge compensator)
FIG. 22 is a diagram showing the excitation spectrum (PLE) and emission spectrum (PL) of the phosphor 18 and the phosphor 21. In both the phosphor 18 and the phosphor 21, the addition amount (v) of Ce is 0.03 mol with respect to 1 mol of Si. The phosphor 18 contains the same amount of K as Ce. On the other hand, in the phosphor 21, the addition amount (w) of K is 0 mol.

  As shown in FIG. 22, the excitation spectrum of the phosphor 21 has a peak in the wavelength region of ultraviolet rays around 335 nm. The phosphor 21 emits short-wavelength visible light having a peak wavelength of the emission spectrum in the range of about 395 nm. The phosphor 18 has a K content w value of 0.03 in the general formula described above, and an emission intensity at a peak wavelength (395 nm) of 2.2 (relative value). On the other hand, the phosphor 21 has a K content w of 0 in the general formula described above, and an emission intensity at a peak wavelength (395 nm) of 1.26 (relative value). Thus, since the phosphor 21 does not contain an alkali metal unlike the phosphor 18, the emission intensity at the peak wavelength (395 nm) is reduced by about 40%. That is, the luminous efficiency of an activator such as Ce can be improved by adding together a trivalent rare earth element such as Ce and a monovalent alkali metal as a charge compensator.

  FIG. 23 is a diagram showing measurement results of X-ray diffraction using the Kα characteristic X-ray of Cu for the phosphor 1 ′, the phosphor 18, and the phosphor 21. As shown in FIG. 23, in the phosphor 18 and the phosphor 21, a diffraction pattern having a characteristic strong peak in the range of 28 ° to 31 ° is obtained as in the phosphor 1 '. Therefore, it can be seen that the phosphor 1 ′, the phosphor 18, and the phosphor 21 include the same reference crystal phase.

  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 phosphor of the present invention can be used in various lamps such as 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 device, 18a Light-emitting surface, 20 Mount member, 22 Wire, 24 Fluorescent layer.

Claims (5)

The general formula is (M ² _x , M ³ _y , M ⁴ _z , M ⁵ _v , M ⁶ _w ) _m M ¹ O ₃ X _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, Zn, Cd, Ni, Cu, Hg, Co And at least one element containing Ca selected from the group consisting of Sn, M ³ is one or more elements containing at least Sr selected from the group consisting of Sr, Ba and Pb, and X is one kind containing at least Cl The above halogen element, M ⁴ is at least one element selected from the group consisting of a divalent rare earth element and Mn, M ⁵ is at least one element selected from the group consisting of a trivalent rare earth element, M ⁶ represents at least one element selected from the group consisting of alkali metals, m is in the range of 0.1 ≦ m ≦ 1.4, and n is in the range of 0.1 ≦ n ≦ 0.5. , X, y, z, v, w X + y + z + v + w = 1, 0 <x <1, 0 <y <1, 0 ≦ z ≦ 0.5, 0 <v ≦ 0.5, and 0 ≦ w ≦ 0.5. Phosphor. 2. The phosphor according to claim 1, wherein M ⁵ includes at least one element selected from the group consisting of Ce, Sm, Dy, Ho, Er, Tm, Yb, Lu, Tb, and Pr. . 3. The phosphor according to claim 1, wherein M ⁶ contains at least one element selected from the group consisting of Li, K, Na, Rb, and Cs as M ⁶ .   The phosphor according to any one of claims 1 to 3, wherein in the general formula, v is in a range of 0 <v <0.10.   5. The phosphor according to claim 1, wherein w is in a range of 0 ≦ w <0.10 in the general formula.

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