JP2005307035A - Halophosphate salt fluorophor, and light-emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a halophosphate salt fluorophor capable of improving emission efficiency in the visible light wavelength region, and to provide a light-emitting device using the fluorophor. <P>SOLUTION: The fluorophor is represented by the compositional formula: (M<SB>1-u-v</SB>Eu<SB>u</SB>Mn<SB>v</SB>)-mX<SB>2</SB>-n(PO<SB>4</SB>)<SB>6</SB>[ wherein, 0<u/v<100; 1>(u+v); 0<m<10; 0<n<10; 1>10n; M is at least one alkaline earth metal element selected from Mg, Ca, Sr and Ba; and X is one or more halogen elements including at least F, selected from F, Cl, Br and I ]. The light-emitting device is such as to be furnished with this fluorophor in a fluorophor region subject to incidence of light emitted from a light-emitting diode. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a halophosphate phosphor and a light emitting device using the same, and more particularly to a halophosphate phosphor suitable for improving the light emission efficiency in the visible light wavelength region and a light emitting device using the same.

  Brightness is often required especially for white light emitting applications such as white light emitting diodes. As one configuration example of the white light emitting diode, there is a configuration in which the light emission of near ultraviolet to blue violet light emitting diodes is used as excitation light, and the phosphors of the respective colors that are excited to emit light and the light emitting diodes are combined. As phosphors, for example, halophosphate containing Eu (europium) as an activating (activating) ion for blue, silicate containing Eu as an activating ion for yellow, for example, Eu and Sm (samarium) for red Can be used as an activating ion.

On the other hand, the halophosphate phosphor can be used not only for blue as described above but also for red due to light emission derived from Mn by making the activation ion a co-activation of Eu and Mn (manganese). It is also known. An example of such a phosphor is described in US Pat. No. 6,616,862. The phosphor described in this document has a composition in which the ratio of metal atoms to phosphorus atoms is 3 phosphorus atoms to 4.5 to 5.0 metal atoms.
US Pat. No. 6,616,862

  In the case of the oxysulfide phosphor described above, the emission spectrum of red is also present in the long wavelength region (near 700 nm) with low visibility, and the luminous efficiency in the visible light wavelength region is poor accordingly. In addition, the emission intensity is highly dependent on the wavelength of near-ultraviolet or blue-violet, which is excitation light, and it is difficult to emit light with a stable intensity. Therefore, there is a disadvantage that color variation occurs when used for a white light-emitting diode.

In the case of a red halophosphate phosphor containing Eu and Mn as activation ions, the inventors have clarified that there is room for improvement in terms of emission intensity in the composition shown in the above document. . Furthermore, according to the inventors, in a halophosphate phosphor whose composition formula is specified as (Cal _-u-v Eu _u Mn _v ) · mCl ₂ · (PO ₄ ) ₆ , red light emission derived from Mn Is known to not be effective.

  The present invention has been made in consideration of the above-described circumstances. In a halophosphate phosphor and a light-emitting device using the halophosphate phosphor, the halophosphate phosphor capable of improving the luminous efficiency in the visible light wavelength region and the use thereof are used. An object of the present invention is to provide a light emitting element.

In order to solve the above-described problem, the halophosphate phosphor according to one embodiment of the present invention has a composition formula represented by (M ₁ -u _−v Eu _u Mn _v ) · mX ₂ · n (PO ₄ ) _6. (However, 0 <u / v <100, l> u + v, 0 <m <10, 0 <n <10, l> 10n), Mg (magnesium), Ca (calcium), Sr (as the metal element M) Strontium) and one or more alkaline earth metal elements selected from the group consisting of Ba (barium) and the halogen element X as F (fluorine), Cl (chlorine), Br (bromine), and I ( And at least one element containing at least F selected from the group consisting of iodine).

In addition, the halophosphate phosphor according to another aspect of the present invention has a compositional formula represented by (M ₁ -u _-v Eu _u Mn _v ) · mX ₂ · n (PO ₄ ) ₆ (where 0 < u / v <100, l> u + v, 0 <m <10, 0 <n <10, l> 10n), Mg (magnesium), Ca (calcium), Sr (strontium), and Ba as metal elements M Two or more alkaline earth metal elements including at least Ca and Mg selected from the group consisting of (barium), F (fluorine), Cl (chlorine), Br (bromine) as the halogen element X, and And one or more elements selected from the group consisting of I (iodine).

  The light-emitting element according to one embodiment of the present invention includes a light-emitting diode that emits near-ultraviolet to blue-violet light, and a phosphor region into which the emitted light is incident, and the halophosphate as described above And a phosphor region having a phosphor.

  According to the halophosphate phosphor and the light emitting device according to the present invention, red light emission derived from Mn is efficiently performed by co-activation of Eu and Mn, and an improvement in light emission efficiency in the visible light wavelength region is achieved.

  The halophosphate phosphor according to one aspect of the present invention has at least F as a halogen element. In addition, the ratio of the ratio of metal atom l to the ratio of phosphorus atom 6n has a magnitude relationship of l> 10n (that is, the metal atom is more than 10/6 times the phosphorus atom). By having such a composition, the excitation of Mn accompanying the excitation of Eu becomes active as a result, and red light having a wavelength near 600 nm derived from Mn is efficiently output. Visibility characteristics are good in the vicinity of the wavelength of 600 nm, and therefore, the emission efficiency in the visible light wavelength region is improved. Although the detailed mechanism by which F is excited as a halogen element and the metal atom is more than 10/6 times the phosphorus atom and Mn excitation is activated is not yet clear, the energy transfer to Mn ions becomes smooth. Certainly.

Here, as an embodiment, the alkaline earth metal element, and includes at least Ca free of at least Mg, and the ratio m of the halogen element _{X 2} is 0.5 <m <2.5, phosphoric acid The ratio n of the group (PO ₄ ) ₆ is n = 1, and the ratio of the alkaline earth metal elements (l−v−v) is (l−v−v)> (10−uv). can do. A realistic and practical ratio is defined as the composition of the phosphor.

Further, more specifically, the alkaline earth metal is only Ca, and the ratio (l-uv) of this Ca is approximately (10.4-uv), and the halogen element X ₂ The ratio m may be 0.5 <m <2.0. A more realistic and practical ratio is defined as the composition of the phosphor.

  The halophosphate phosphor according to another aspect of the present invention has at least Ca and Mg as the alkaline earth metal elements. In addition, the ratio of the ratio of metal atom l to the ratio of phosphorus atom 6n has a magnitude relationship of l> 10n (that is, the metal atom is more than 10/6 times the phosphorus atom). By having such a composition, the excitation of Mn accompanying the excitation of Eu becomes active as a result, and red light having a wavelength near 600 nm derived from Mn is efficiently output. Visibility characteristics are good in the vicinity of the wavelength of 600 nm, and therefore, the emission efficiency in the visible light wavelength region is improved. Although the detailed mechanism by which Mn excitation is activated by having at least Ca and Mg as the alkaline earth metal elements and the metal atoms being more than 10/6 times the phosphorus atoms is not yet clear, the energy for Mn ions is not yet clear. There is no doubt that the communication is smooth. In addition, if both the conditions as the alkaline earth metal and the conditions as the halogen element of the above embodiment are provided, light emission in the visible wavelength region can be achieved with higher efficiency.

Here, as an embodiment, the ratio m of the halogen element X ₂ is 0.5 <m <2.5, the ratio n of the phosphate group (PO ₄ ) ₆ is n = 1, and the alkaline earth metal element The ratio (l−u−v) of (l−u−v)> (10−u−v) may be satisfied. A realistic and practical ratio is defined as the composition of the phosphor.

Further, further limited, the alkaline earth metal is only Ca and Mg, and the combined ratio (l-uv) of Ca and Mg is approximately (10.4-uv). There may be a ratio m of the halogen element _{X 2} is 0.5 <m <2.0, that. A more realistic and practical ratio is defined as the composition of the phosphor.

  In addition, the light-emitting element according to one embodiment of the present invention includes a light-emitting diode that emits near-ultraviolet to blue-violet light, and the light emitted from the light-emitting diode is incident on the phosphor region including each phosphor as described above. . Thereby, red light emission derived from Mn is efficiently performed by the co-activation of Eu and Mn, so that the emission efficiency in the visible light wavelength region is improved.

  Here, as an embodiment, the phosphor region may further include a blue phosphor and a phosphor that emits green to yellow light. Thereby, a white light emitting element is easily obtained. Here, white means, for example, the chromaticity point coordinates (Cx, Cy) in the CIE (International Commission on Illumination) color system are 0.12 ≦ Cx ≦ 0.48, 0.19 ≦ Cy ≦ 0.45. It can be said that it is the range.

Based on the above, embodiments of the present invention will be described below with reference to the drawings. First, oxysulfide (La ₂ O ₂ S: Eu, Sm) will be described as an example of the red phosphor of the comparative reference example. This phosphor has a composition in which a small amount of Eu and Sm are added as activation ions in La ₂ O ₂ S. FIG. 6 shows an example in which the spectrum of the visible light region of the fluorescence output is measured using the output light of a light emitting diode having a central wavelength of 395 nm as excitation light.

  As shown in FIG. 6, the fluorescence output has light emission in the vicinity of a wavelength of 700 nm as well as light emission in the vicinity of a wavelength of 620 nm. In the visible light region, as is well known, the visibility is greatly reduced at a wavelength of approximately 650 nm or more. Therefore, the output light in this band hardly contributes to the light emission output as brightness, and the light emission in the vicinity of the wavelength of about 620 nm defines the luminous intensity. Therefore, it cannot be said that the luminous efficiency is good. The output near the wavelength of 395 nm is observed when the excitation light is reflected by the phosphor without being absorbed.

As another comparative reference phosphor, a halophosphate phosphor (Ca ₁ -u _-v Eu _u Mn _v ) · mCl ₂ · (PO ₄ ) ₆ will be described. This phosphor has a composition in which Eu and Mn are added in small amounts (u and v, respectively) as activation ions in Cal _-u-v · mCl ₂ (PO ₄ ) ₆ . FIG. 7 shows an example in which the spectrum of the fluorescence output in the visible light region is measured using the output light of the light emitting diode having the central wavelength of 395 nm as the excitation light in the same manner as described above.

  This phosphor is intended to emit light derived from Mn by having Mn as an activating ion in addition to Eu. The light emission derived from Mn becomes red light emission in view of the energy transition amount in which the electrons return from the excited state to the ground state. However, as shown in FIG. 7, light emission derived from Mn is almost only emitted at a wavelength of about 560 nm, compared with light emission derived from Eu at a wavelength of about 460 nm (blue). I can't say that. This phosphor is therefore difficult to use as a red phosphor.

Therefore, although the white light emitting diode using the phosphor has a problem in efficiency, the above red oxysulfide has been often used for the oxysulfide. For example, a combination of a light emitting diode having a wavelength of 395 nm, a blue phosphor, a green phosphor, and a red phosphor of oxysulfide. Here, a halophosphate phosphor having a composition of ((Sr, Ca) ₅ (PO ₄ ) ₆ Cl: Eu) is used as a blue phosphor, and (BaMgAl ₁₆ O ₂₇ : Eu, Mn) is used as a green phosphor. The spectrum of white light emission when each of the aluminate phosphors having the composition is used is as shown in FIG. (Indicates that all elements separated by “,” in the composition formula are included.)

  In the white light emission shown in FIG. 8, although the stability of the blue and green output intensities is relatively good with respect to the change in the central wavelength of the excitation light of 395 nm, the intensity change in the red output of the oxysulfide is relatively large. know. That is, since the intensity of red changes greatly with respect to the change in the emission wavelength of the near-ultraviolet or blue-violet light emitting diode that emits the excitation light, a color change as white light emission is likely to occur. This is a disadvantage as a white light emitting element.

Next, a red phosphor according to an embodiment of the present invention will be described. This red phosphor is obtained by changing the composition of the halophosphate phosphor described in the comparative reference example. Specifically, the composition _{formula, (Ca l-u-v} Eu u Mn v) · mCl 2 · (PO 4) 6 of a part of the Cl composition replaced with _{F (Ca l-u-v} Eu _{u Mn v) · m (Cl} , F) 2 · (PO 4) has become _6.

Such a halophosphate phosphor will be described from the production process. First, CaHPO ₄ (calcium hydrogen phosphate), CaCO ₃ (calcium carbonate), NH ₄ Cl (ammonium chloride), MnF ₂ (manganese fluoride), Eu _A predetermined amount of ₂ O ₃ (europium oxide) is prepared. The predetermined amount is a molecular ratio, for example, a ratio of CaHPO ₄ : CaCO ₃ : NH ₄ Cl: MnF ₂ : Eu ₂ O ₃ = 6.00: 3.65: 2.40: 0.50: 0.125. Here, MnCO ₃ (manganese carbonate) may be used instead of MnF ₂ , and 2EuF ₃ (europium fluoride) may be used instead of Eu ₂ O ₃ .

After weighing, the above raw materials are sufficiently mixed by a ball mill, packed in an alumina crucible, and fired at 900 ° C. for 3 hours in the atmosphere. Next, the fired product obtained after cooling is pulverized, ball milled, packed in an alumina crucible, and then fired in an H ₂ / N ₂ forming gas atmosphere, for example, at 900 ° C. for 2 hours. Further, the fired product obtained after cooling is pulverized and sieved. _Thus, it is possible to obtain the _{(Ca l-u-v Eu} u Mn v) · m (Cl, F) 2 · (PO 4) ₆ composition of halophosphate phosphor. More specifically, l: m is about 10.4: 1.7 here. Moreover, it is about l: u: v = 10.40: 0.25: 0.50.

  FIG. 1 shows the result of obtaining the fluorescence output after dishing out the obtained halophosphate phosphor and exciting it with the output light of the light emitting diode having a central wavelength of 395 nm. FIG. 1 is a spectrum diagram showing a spectrum of fluorescence obtained by exciting a halophosphate phosphor according to an embodiment of the present invention with output light of a light emitting diode having a central wavelength of 395 nm. In FIG. 1, the comparative reference example shown in FIG. 7 is indicated by a broken line for comparison.

  As shown in FIG. 1, in the halophosphate phosphor of this embodiment, light emission derived from Mn is remarkably observed centering around the wavelength of 590 nm. Compared with the comparative reference example (FIG. 7), the height of the peak is about 9 to 10 times. Therefore, it can be used as a red (or orange) phosphor. Further, the red light emission has a small intensity dependency from the wavelength change of the excitation light, and can be used as a red phosphor of a white light emitting element to obtain an element with small color variation.

  It is not clearly known how the composition of the halophosphate phosphor in which a part of Cl is replaced with F causes an increase in red fluorescence. It is clear that at least the energy transfer to Mn ions is smoothed with the excitation of Eu, and the Mn excitation becomes active as a result.

The effect of this embodiment is obtained by using a composition in which part of Cl is replaced with F as the composition of the halophosphate phosphor. Practically, the ratio u / v between co-activated ions Eu and Mn is 0 <u / v <100, and the ratio of (Cl, F) ₂ : (PO ₄ ) ₆ is more than 0 and less than 10: It can be considered in the range of more than 0 and less than 10. More practically, the ratio of (Ca, Eu, Mn) :( Cl, F) ₂ : (PO ₄ ) ₆ can be more than 10: more than 0.5: less than 2.5: 1. Furthermore, practically, the ratio of (Ca, Eu, Mn) :( Cl, F) ₂ : (PO ₄ ) ₆ can be 10.4: more than 0.5 and less than 2: 1.

Further, when considered as a more general composition formula, (M _1−u−v Eu _u Mn _v ) · mX ₂ · n (PO ₄ ) ₆ , the metal element M is selected from Mg, Ca, Sr, and Ba. One or more can be selected to be part of the composition as the halophosphate phosphor. Halogen element X ₂ may be at least F to include F, Cl, Br, and part of the composition of the halophosphate phosphor select one or more from among I.

Next, a red phosphor according to another embodiment of the present invention will be described. This red phosphor specifically identifies the metal element M as a composition composed of Ca and Mg in the red phosphor in the above embodiment. Specifically, composition formula _{((Ca, Mg) l-} u-v Eu u Mn v) · m (Cl, F) becomes 2 · _{(PO 4) 6.}

In order to describe the manufacturing process of such a halophosphate phosphor, a predetermined amount of MgCO ₃ (magnesium carbonate) is prepared in addition to the same raw materials as described in the above embodiment. The predetermined amount is a molecular ratio, for example, CaHPO ₄ : CaCO ₃ : MgCO ₃ : NH ₄ Cl: MnF ₂ : Eu ₂ O ₃ = 6.00: 2.45: 1.20: 2.40: 0.50: 0 .125 ratio. Then, two firings similar to those in the above embodiment are performed. Further, the fired product obtained after cooling is pulverized and sieved. As a result, a halophosphate phosphor having a composition of ((Ca, Mg) ₁ -u _-v Eu _u Mn _v ) .m (Cl, F) _2. (PO ₄ ) ₆ can be obtained. More specifically, l: m is about 10.4: 1.7. Moreover, it is about l: u: v = 10.40: 0.25: 0.50. This is the same as the above embodiment.

  FIG. 2 shows the result of obtaining the fluorescence output after dishing out the obtained halophosphate phosphor and exciting it with the output light of the light emitting diode having a central wavelength of 395 nm. FIG. 2 is a spectrum diagram showing a spectrum of fluorescence obtained by exciting a halophosphate phosphor according to another embodiment of the present invention with output light of a light emitting diode having a central wavelength of 395 nm. In FIG. 2, the comparative reference example shown in FIG. 7 is indicated by a broken line for comparison.

  As shown in FIG. 2, in the halophosphate phosphor of this embodiment, light emission derived from Mn is more remarkably observed centering around a wavelength of 600 nm. Compared with the comparative reference example (FIG. 7), the height of the peak is about 27 to 30 times (9 to 10 times, further 3 times). Therefore, the light emission is more preferable as a red (or orange) phosphor. Further, the red light emission has a small intensity dependency from the wavelength change of the excitation light, and can be used as a red phosphor of a white light emitting element to obtain an element with small color variation. This is the same as in the above embodiment.

  In this embodiment as well, it is not clearly known how red fluoresce is increased by having Mg as part of the alkaline earth metal M as the composition of the halophosphate phosphor. It is clear that at least the energy transfer to Mn ions is smoothed with the excitation of Eu, and the Mn excitation becomes active as a result.

The effect of this embodiment is obtained by having Ca and Mg in the alkaline earth metal M as the composition of the halophosphate phosphor. Practically, the ratio u / v between co-activated ions Eu and Mn is 0 <u / v <100, and the ratio of (Cl, F) ₂ : (PO ₄ ) ₆ is more than 0 and less than 10: It can be considered in the range of more than 0 and less than 10. More practically, the ratio of (Ca, Mg, Eu, Mn) :( Cl, F) ₂ : (PO ₄ ) ₆ may be more than 10: more than 0.5: less than 2.5: 1. it can. More practically, the ratio of (Ca, Mg, Eu, Mn) :( Cl, F) ₂ : (PO ₄ ) ₆ can be 10.4: more than 0.5 and less than 2: 1. . The same as the above embodiment except that Mg is added.

Further, when considered as a more general composition formula, (M _1−u−v Eu _u Mn _v ) · mX ₂ · n (PO ₄ ) ₆ , the metal element M is selected from Mg, Ca, Sr, and Ba. Two or more kinds including at least Ca and Mg can be selected to be a part of the composition as the halophosphate phosphor. Halogen element X ₂ may be at least F to include F, Cl, Br, and part of the composition of the halophosphate phosphor select one or more from among I. This embodiment is based on the condition that the halogen element X ₂ contains at least F, but at least Mn is derived from the comparative reference example shown in FIG. Luminescence seems to be active. Eu effect transfer of energy becomes smooth to Mn ions with the excitation of, when it and a halogen element X ₂ in which the Ca and Mg is used in the alkaline-earth metal M is a synergistic effect of including at least F It is possible.

  FIG. 3 is measurement data obtained by examining how the emission intensity changes in the phosphor sample in which the ratio of the metal element is changed in the composition of the embodiment described with reference to FIG. A sample was used in which only Ca was changed as the metal element, and the remaining Mg, Eu, and Mn were unchanged at ratios of 1.2, 0.25, and 0.50, respectively.

As shown in FIG. 3, when the ratio l of the metal element M is around 10 (that is, 5/3 times the phosphorus element P), the emission intensity is in a transition range, and when l is about 10.1 or more, the characteristic is saturated. I understood it. Therefore, the ratio l of the metal element M is preferably set so as to exceed at least 5/3 times the phosphorus element P. This means that l> 10n in a more general composition formula (M _{1 -u−v} Eu _u Mn _v ) · mX ₂ · n (PO ₄ ) ₆ . The above embodiment in which n = 1 and the ratio l of the metal element M is 10.4 is set with a margin in this sense.

  Next, a light emitting device according to an embodiment of the present invention will be described with reference to FIGS. FIG. 4 is a cross-sectional view showing the structure of a light emitting device (more specifically, a white light emitting device) according to an embodiment of the present invention, and FIG. 5 is a diagram showing the light emission spectrum thereof.

  As shown in FIG. 4, in this light emitting element, a recess 2 is provided in a resin stem 6, and the light emitting diode chip 1 is fixed to the bottom surface thereof. The light emitting diode chip 1 has the center of the light emission spectrum in the near ultraviolet to blue-violet range (for example, wavelength 350 nm to 430 nm). The light emitting diode chip 1 is electrically connected to two leads 5 penetrating the resin stem 6 via bonding wires 4. A phosphor region 3 containing a phosphor is formed in the recess 2 of the resin stem 6 so as to cover the light emitting diode chip 1.

The phosphor region 3 is a red phosphor ((Ca, Mg) _{1 -u-v} Eu _u Mn _v ) .m (Cl, F) _2. In addition to PO ₄ ) ₆ , it contains a blue phosphor ((Sr, Ca) ₅ (PO ₄ ) ₆ Cl: Eu) and a green phosphor (BaMgAl ₁₆ O ₂₇ : Eu, Mn), and further visible light as a binder. Including transparent resin.

  The light-emitting diode chip 1 emits near-ultraviolet to blue-violet light by passing a current between the two leads 5. The three phosphors absorb this light emission, and emit red, blue, and green fluorescence, respectively. FIG. 5 shows an example of a light emission spectrum due to these mixed colors. As shown in FIG. 5, the white light emission of such a spectrum is mainly light emission in a wavelength region where the visibility is large, and the light emission efficiency is good. Compared to the comparative reference example shown in FIG. 8, an improvement in luminous efficiency of 10% to 15% is achieved. Further, the emission intensity of each color with respect to the change in the emission wavelength of the light-emitting diode chip 1 is stable, and the color variation as white is small as compared with the comparative reference example shown in FIG.

  In this embodiment, the phosphor region 3 may be obtained by sintering, forming, and hardening each phosphor. It is also useful to improve the light extraction efficiency by providing fine irregularities on the light emission side surface of the phosphor region 3. Further, the light-emitting diode chip 1 can be fixed to the resin stem 6 by using a flip chip connection. In this case, the light emitting diode chip 1 and the lead 5 are electrically connected without using the bonding wire 4. Further, as the red phosphor, those described in “One Embodiment” can be used.

The spectrum figure which shows the spectrum of the fluorescence obtained by exciting the halophosphate fluorescent substance which concerns on one Embodiment of this invention with the output light of the light emitting diode of central wavelength 395nm. The spectrum figure which shows the spectrum of the fluorescence obtained by exciting the halophosphate fluorescent substance which concerns on another embodiment of this invention with the output light of the light emitting diode of central wavelength 395nm. The graph of the measurement data which investigated how light emission intensity changed with the fluorescent substance sample which changed the ratio of the metal element in the composition of embodiment described using FIG. 1 is a cross-sectional view illustrating a structure of a light-emitting element according to an embodiment of the present invention. The figure which shows the light emission spectrum of the light emitting element which concerns on one Embodiment of this invention. The spectrum figure which shows the spectrum of the fluorescence obtained by exciting the red phosphor (oxysulfide (La ₂ O ₂ S: Eu, Sm)) as a comparative reference example with the output light of a light emitting diode having a central wavelength of 395 nm. As another comparative reference example, a red phosphor (halophosphate phosphor (Cal _-u-v Eu _u Mn _v ) · mCl ₂ · (PO ₄ ) ₆ ) is used as an output light of a light emitting diode having a central wavelength of 395 nm The spectrum figure which shows the spectrum of the fluorescence obtained by exciting. The figure which shows the light emission spectrum of the light emitting element as a comparative reference example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Light emitting diode chip, 2 ... Recessed part, 3 ... Phosphor area | region, 4 ... Bonding wire, 5 ... Lead, 6 ... Resin stem.

Claims (9)

The compositional formula is represented by (M _{1 -u−v} Eu _u Mn _v ) · mX ₂ · n (PO ₄ ) ₆ (where 0 <u / v <100, l> u + v, 0 <m <10, 0 <N <10, l> 10n),
As the metal element M, one or more alkaline earth metal elements selected from the group consisting of Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium);
One or more elements including at least F selected from the group consisting of F (fluorine), Cl (chlorine), Br (bromine), and I (iodine) as the halogen element X Halophosphate phosphor.   The halophosphate phosphor according to claim 1, wherein the alkaline earth metal element contains at least Ca and Mg. The compositional formula is represented by (M _{1 -u−v} Eu _u Mn _v ) · mX ₂ · n (PO ₄ ) ₆ (where 0 <u / v <100, l> u + v, 0 <m <10, 0 <N <10, l> 10n),
Two or more alkaline earth metal elements containing at least Ca and Mg selected from the group consisting of Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium) as the metal element M ,
Halogen phosphate fluorescence having one or more elements selected from the group consisting of F (fluorine), Cl (chlorine), Br (bromine), and I (iodine) as the halogen element X body. The alkaline earth metal element includes at least Ca and does not include at least Mg;
The halophosphate phosphor according to claim 1, wherein 0.5 <m <2.5, n = 1, and l> 10.   4. The halophosphate phosphor according to claim 2, wherein 0.5 <m <2.5, n = 1, and l> 10. The alkaline earth metal is only Ca,
And l is approximately 10.4,
The halophosphate phosphor according to claim 4, wherein 0.5 <m <2.0. The alkaline earth metal is only Ca and Mg,
And l is approximately 10.4,
The halophosphate phosphor according to claim 5, wherein 0.5 <m <2.0. A light emitting diode that emits near ultraviolet or blue-violet light;
A light emitting device comprising: a phosphor region into which the emitted light is incident, the phosphor region having a halophosphate phosphor according to any one of claims 1 to 7.   The light emitting device according to claim 8, wherein the phosphor region further includes a blue phosphor and a phosphor emitting green or yellow.

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