JP2006176546A - Phosphor and light source using phosphor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a phosphor for producing a light source hardly causing degradation of optical properties such as reduction of luminous efficiency, change of emission wavelength, etc., by passage of time in use and the light source using the phosphor. <P>SOLUTION: The phosphor has ≤10% weight change as the result of measurement with a thermobalance in the air from a room temperature to 1,000°C and is represented by composition formula MmBbOoNn:Z (M is a divalent element; B is a tetravalent element; Z is an activator). The light source is produced by combining the phosphor with the luminescence part of an LED, etc., emitting an ultraviolet light to a visible light. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a phosphor used in a display device such as a CRT, PDP, FED, or EL, or a lighting device such as a fluorescent display tube or a fluorescent lamp, and further, an LED or a light source using the phosphor. And a lighting unit.

  At present, discharge fluorescent lamps and incandescent lamps used as lighting devices have various problems such as containing harmful substances such as mercury and short life. However, in recent years, LEDs that emit blue and ultraviolet light have been developed one after another, and a combination of ultraviolet to blue light generated from the LED and light emission of a phosphor having an excitation band in the ultraviolet to blue wavelength range is combined with white light. Research and development has been actively conducted to prepare light and use the white light as next-generation lighting. Since this white LED illumination is composed of a semiconductor element and a phosphor with less heat generation, it does not break like conventional incandescent bulbs, and no harmful substances such as mercury are required. It is an ideal lighting device.

  Here, in order to obtain white light by combining the LED and the phosphor described above, two methods are generally considered. One is a combination of an LED that emits blue light and a phosphor that receives the blue light emission and is excited to emit yellow light, and obtains white light emission by combining the blue light emission and the yellow light emission.

The other is an LED that emits near ultraviolet / ultraviolet light, a phosphor that emits red (R) light when excited by the near ultraviolet / ultraviolet light emission, a phosphor that emits green (G) light, and a fluorescent light that emits blue (B) light. The body and the other are combined to obtain white light emission by the other light of RGB. This method of obtaining white light emission by RGB other light can obtain any light emission color other than white light depending on the combination and mixing ratio of RGB other phosphors, and has an application range as a lighting device. wide. Then, as the phosphors used in the applications such _{(Y, Gd) 3 (Al} , Ga) 5 O 12: Ce, YAG: Ce, Tb 3 Al 5 O 12: Ce, Ca 3 Sc 2 Si 3 O ₁₂ : Ce, (Ca, Ba, Sr) ₂ SiO ₄ : Eu, BAM: Eu, BAM: Mn, Eu, SrAl ₂ O ₄ : Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (Sr, Ca , Mg, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu and other oxide-based phosphors, ZnS: Cu, Al, CaGa ₂ S ₄ : Eu, SrGa ₂ S ₄ : Eu, BaGa ₂ S ₄ : Eu, Ca (Al, Ga, In) ₂ S ₄ : Eu, Sr (Al, Ga, In) ₂ S ₄ : Eu, Ba (Al, Ga, In) ₂ S ₄ : Eu, Y ₂ O ₂ S: Eu, La ₂ O ₂ S: Sulfides such as Eu, acid sulfide Fluoride phosphor, CaSi ₂ O ₂ N ₂ : Eu, SrSi ₂ O ₂ N ₂ : Eu, BaSi ₂ O ₂ N ₂ : Eu, (Ca, Sr) Si ₂ O ₂ N ₂ : Eu, (Sr, Ba) There are nitride-based and oxynitride-based phosphors such as Si ₂ O ₂ N ₂ : Eu and (Ca, Ba) Si ₂ O ₂ N ₂ : Eu. Then, by combining these RGB and other phosphors with a light emitting part such as an LED that emits near ultraviolet light or ultraviolet light, it is attempted to obtain a light source or an illuminating device such as a white or desired LED. ing.

However, white LED illumination using a combination of a blue LED and a yellow phosphor (YAG: Ce) results in insufficient light emission on the long wavelength side in the visible light region, resulting in light emission that is slightly bluish white. Can not get a slightly reddish white light like a light bulb.
In addition, in white LED illumination using a combination of near-ultraviolet / ultraviolet LEDs and RGB and other phosphors, the red phosphor of the three color phosphors has lower excitation efficiency on the longer wavelength side than other phosphors, and the luminous efficiency Therefore, it is necessary to increase the mixing ratio of only the red phosphor, and the phosphor for improving the luminance is insufficient, so that a high luminance white color cannot be obtained. Furthermore, since the emission spectrum of the phosphor is sharp, there is a problem that the color rendering property of the obtained light is poor.
Therefore, recently, an oxynitride glass phosphor that has good excitation on the long wavelength side and a broad emission half-width emission peak (see, for example, Patent Document 1), and a phosphor based on sialon (for example, a patent) References 2 and 3) and phosphors containing nitrogen such as silicon nitride (for example, see Patent References 4 and 5) have been reported. The phosphor containing nitrogen has a characteristic of having a good excitation band even in light having a wavelength of 400 nm or more because the ratio of the covalent bond is larger than that of the oxide phosphor and the like. Has attracted attention as a body.

Japanese Patent Laid-Open No. 2001-214162 JP2003-336059 Japanese Patent Laid-Open No. 2003-124527 Special table 2003-515655 JP 2003-277746 A

However, although the light source that combines the light emitting unit including the white LED and the phosphor has a longer life than the incandescent bulb described above, the light emission efficiency decreases and the light emission wavelength changes with the passage of time of use. Cause deterioration of optical characteristics.
An object of this invention is to provide the fluorescent substance which does not raise | generate such an optical characteristic deterioration easily, and the light source using the said fluorescent substance.

The inventors of the present invention have described the deterioration of the optical characteristics in the light source that combines the light emitting unit that emits the irradiation light and the phosphor, and the phosphor used has a large energy from the light emitting unit. It has been conceived that the main factors are that the structure is deteriorated by receiving, and that chemical changes such as oxidation are caused by continuing to receive heat generated from the light emitting portion. In particular, white LEDs as light sources continue to be required to have higher brightness in the future, and this problem is even more important because the heat generated from the light emitting part increases due to an increase in the current flowing through the light emitting part. Is increasing.
Based on the elucidated results, the present inventors combined a light emitting part with a phosphor that exhibits durability against oxidation at high temperatures, etc. It has been conceived that a light source such as an LED which hardly causes deterioration of optical characteristics such as changes can be obtained.

That is, the first configuration for solving the above-described problem is:
Composition formula MmBbOoNn: Z (where M element is one or more elements having a valence of II, B element is one or more elements having a valence of IV, O is oxygen, N is nitrogen and Z element is an activator.)
In the thermobalance measurement from room temperature to 1000 ° C. in the atmosphere, the phosphor has a change in weight of 10% or less.

The second configuration is
M element is one or more elements selected from Mg, Ca, Sr, Ba, Zn,
The B element is one or more elements selected from Si and Ge,
The Z element is the phosphor according to the first configuration, which is one or more elements selected from Eu, Mn, and Ce.

The third configuration is
In the composition formula MmBbOoNn: Z of the phosphor, when m = a + p, b = 3, o = a + q, n = 4 + r, the range of a is 0 <a ≦ 10, and the range of p is −a / In the first or second configuration, 2 <p <a / 2, the range of q is −a / 2 <q <2a, and the range of r is −2 <r <2. It is a fluorescent substance of description.

The fourth configuration is
The phosphor according to any one of the first to third aspects, wherein the M element is Sr, the B element is Si, and the Z element is Eu.

The fifth configuration is
The phosphor according to any one of the first to fourth configurations and a light emitting unit that emits light in the ultraviolet to visible region, and using a part of the light in the ultraviolet to visible region as an excitation source, A light source characterized in that the phosphor emits light.

The sixth configuration is
The light source according to the fifth aspect, wherein the light emitting unit is a light emitting diode.

  The phosphor according to any one of the first to fourth configurations is resistant to light and heat with a large amount of energy, and even when receiving such light and heat, optical characteristics are hardly deteriorated.

  The light source according to the fifth or sixth configuration is a long-life light source that hardly deteriorates optical characteristics even when used for a long time.

  The embodiment of the present invention will be described using the phosphors according to Examples 1 and 2 of the present invention and the known phosphor according to Comparative Example 1 as examples.

(Example 1)
As an example of the phosphor according to the present invention, composition formula MmBbOoNn: Z (where M element is one or more elements having a valence of II, and B element is one or more of elements having an valence of IV) A phosphor represented by the following formula: element, O is oxygen, N is nitrogen, and Z element is an activator. The phosphor according to Example 1 will be described. In this example, Sr is used as the M element, Si is used as the B element, Eu is used as the Z element, and 2.75SrO.Si ₃ N ₄ : Eu is used. A phosphor having a chemical formula.

First, referring to FIGS. 1 and 2, a thermobalance measurement of a phosphor according to Example 1 (hereinafter sometimes referred to as TG measurement) and the results will be described. FIG. 1 shows temperature and weight change rate on the vertical axis, time on the horizontal axis, and the temperature (° C.) of the sample for each hour (minute) in the atmosphere as an atmosphere in a dash-dot line. It is the graph which plotted the change rate (%) of the weight of the sample for every minute) with a solid line. On the other hand, FIG. 2 is a graph when TG measurement is performed under the same conditions as those described in FIG. 1 except that the atmosphere is nitrogen gas.
As shown in FIG. 1, the sample temperature was raised from room temperature to 1000 ° C. over 100 minutes and maintained at 1000 ° C. for 60 minutes. When the sample temperature was raised and maintained as described above, the weight change rate of the sample in the atmosphere hardly changed until 600 ° C., and then gradually increased to + 5% when reaching 1000 ° C. for 60 minutes. It was found that the weight change rate of the sample was + 6% or less after holding and + 6% or less. On the other hand, as shown in FIG. 2, it was found that the phosphor that received the same temperature rise and hold as in FIG. 1 in a nitrogen gas atmosphere had a weight change rate of 1% or less both during the temperature rise and hold. did. From the above, it is shown that the phosphor according to Example 1 has a strong resistance to oxidation although it is slightly oxidized at 800 ° C. or higher. Further, it is considered that nitriding hardly occurs up to 1000 ° C.

From the above, it has been found that the phosphor having the chemical formula of 2.75SrO.Si ₃ N ₄ : Eu according to Example 1 has durability against changes in the chemical structure due to oxidation under heating. From this, in the white light source other than the white LED in which the phosphor is installed, the phosphor does not change its chemical structure while receiving heat simultaneously while receiving light such as ultraviolet light from the light emitting part, Since it continues to emit predetermined fluorescence, it was possible to obtain a light source such as a white LED that hardly deteriorates optical characteristics.

(Example 2)
As in Example 1, a phosphor having a chemical formula of 1.25CaO.Si ₃ N ₄ : Eu was prepared as a phosphor represented by the composition formula MmBbOoNn: Z.

First, the TG measurement result of the phosphor according to Example 2 will be described with reference to FIGS. The vertical and horizontal axes in FIG. 3 are the same graphs as in FIG. 1, and the vertical and horizontal axes in FIG. 4 are the same graphs as in FIG.
The sample temperature is the same as in Example 1. When the sample temperature was raised and maintained as described above, the weight change rate of the sample in the atmosphere hardly changed up to 800 ° C, and then gradually increased to + 2% when reaching 1000 ° C for 60 minutes. It was found that the weight change rate of the sample was 6% or less and + 6% or less after holding. On the other hand, as shown in FIG. 4, a phosphor that has been heated and held in the same manner as in FIG. 3 in a nitrogen gas atmosphere has a weight change rate of 1% or less both when heated to 1000 ° C. and held. It turned out to be. From the above, it is shown that the phosphor according to Example 2 has a strong resistance to oxidation although it is slightly oxidized at 800 ° C. or higher. Moreover, it is considered that nitriding hardly occurs.

From the above, it has been found that the phosphor having the chemical formula of 1.25CaO.Si ₃ N ₄ : Eu according to Example 2 has durability against changes in chemical structure due to oxidation under heating. From this, in the white light source other than the white LED in which the phosphor is installed, the phosphor does not change its chemical structure while receiving heat simultaneously while receiving light such as ultraviolet light from the light emitting part, Since it continues to emit predetermined fluorescence, it was possible to obtain a light source such as a white LED that hardly deteriorates optical characteristics.

(Comparative Example 1)
A known phosphor represented by the chemical formula Ca ₂ Si ₅ N ₈ : Eu according to Comparative Example 1 will be described.

First, the TG measurement result of the phosphor according to Comparative Example 1 will be described with reference to FIGS. The vertical and horizontal axes in FIG. 5 are the same graphs as in FIG. 1, and the vertical and horizontal axes in FIG. 6 are the same graphs as in FIG.
As shown in FIG. 5, when the temperature of the sample was raised in the same manner as in Example 1, the weight change rate of the sample in the atmosphere hardly changed up to 800 ° C., but then increased greatly to 1000 ° C. It was found that the weight change rate of the sample was 12%, + 5% at the time of arrival and + 12% after holding for 60 minutes. On the other hand, as shown in FIG. 6, it was found that the phosphor that received the same temperature rise and hold as in FIG. 5 in the nitrogen gas atmosphere had a weight change rate of about 2% both during the temperature rise and hold. did. From the above, it has been found that the phosphor according to Comparative Example 1 has no resistance to oxidation and is oxidized at 800 to 1000 ° C. or higher. On the other hand, it was also found that nitriding occurred slightly.

From the above, it was found that the phosphor having the chemical formula of Ca ₂ Si ₅ N ₈ : Eu according to Comparative Example 1 undergoes a chemical structure change due to oxidation under heating. From this, in the white LED and other light sources where the phosphor is installed, the phosphor undergoes a change in chemical structure by receiving heat simultaneously while receiving light such as ultraviolet light from the light emitting part, It is difficult to continue to emit fluorescence, and it is considered that the light source is likely to cause deterioration of optical characteristics.

(Examination of durability of the phosphor according to the present invention against oxidation under heating and chemical structure of the phosphor)
In the phosphors according to Examples 1 and 2 of the present invention, the change in weight was 10% or less in the TG measurement from room temperature to 1000 ° C., whereas the known phosphor Ca ₂ Si according to Comparative Example 1 ₅ N ₈ : Eu showed a change in weight of 10% or more in the TG measurement from room temperature to 1000 ° C.
This is because the phosphors according to Examples 1 and 2 of the present invention have a composition formula MmBbOoNn: Z (where M element is one or more elements having a valence of II, and B element is a valence of IV. 1 or more elements that take a number, O is oxygen, N is nitrogen, and Z element is an activator), and already has oxygen in the matrix structure Therefore, it is considered that it exhibits durability against further oxidation.
On the other hand, it is considered that the phosphor according to Comparative Example 1 does not have oxygen in the host structure and is inferior in durability against oxidation.

(Structure of phosphor according to the present invention)
Here, the structure of the phosphor according to the present invention will be further described.
As described above, the phosphor according to the present invention is a phosphor having a host structure represented by the general formula MmBbOoNn: Z. The M element having a valence of II in the phosphor is one or more elements selected from Mg, Ca, Sr, Ba, and Zn, and the B element having a valence of IV is It is one or more elements selected from Si and Ge. When m = a + p, b = 3, o = a + q, n = 4 + r, a is in the range of 0 <a ≦ 10, more preferably 0 <a ≦ When p is −a / 2 <p <a / 2, q is −a / 2 <q <2a, and r is −2 <r <2, It became the fluorescent substance which has.
Further, when the Z element serving as the activator is at least one element selected from Eu, Mn, and Ce, the luminous efficiency of the phosphor is further increased, which is a more preferable configuration.
Furthermore, when the M element is Sr, the B element is Si, and the Z element is Eu, an orange-based phosphor for a white light emitting unit having a very high emission efficiency can be obtained as well as obtaining a raw material is easy. This is a preferred configuration.

  In the phosphor according to the present invention, the addition amount of the Z element is preferably in the range of 0.0001 mol or more and 0.5 mol or less with respect to 1 mol of the corresponding M element. When the addition amount of the Z element is in the range, it is possible to avoid a decrease in light emission efficiency due to concentration quenching due to an excessive content of the activator, and on the other hand, due to an excessive content of the activator. It is also possible to avoid a decrease in light emission efficiency due to the excessive emission contributing atoms. Depending on the kind of the activation element Z to be added, the optimum amount of addition of the Z element is slightly different, but more preferably high luminous efficiency is obtained when it is in the range of 0.0005 mol or more and 0.1 mol or less.

  Since the phosphor according to the present invention emits light in a wide range of wavelengths of 300 to 550 nm, it can be combined with a light emitting unit that emits light in the ultraviolet to green, so that a highly efficient light source of visible light or white can be obtained. Can be manufactured.

(Method for producing phosphor according to the present invention)
The phosphor manufacturing method according to the present invention will be described with reference to an example of manufacturing a phosphor in which the M element is Sr, the B element is Si, and the Z element is Eu.
As a raw material for Sr, which is an element M, an oxide, carbonate, hydroxide, nitride, or the like of Sr can be used. As the Si raw material, Si ₃ N ₄ or SiO ₂ can be preferably used. As the nitrogen source, Si ₃ N ₄ or a nitride of M element (for example, a nitride of Sr) can be preferably used. Eu ₂ O ₃ can be used favorably as a raw material for Eu, which is a Z element. Each raw material may be a commercially available raw material, but since a higher purity is preferable, 2N or more, more preferably 3N or more is prepared.

As a raw material of the element _{M, SrO [3N], SrCO 3} [3N], may be prepared compounds such as _{Sr (OH) 2 [3N]} . The element Z _may be prepared Eu ₂ O 3 [3N]. As Si and N material _Si 3 _N 4 may be prepared [3N].
In these raw material blends, in Example 1, each raw material is weighed so that the molar ratio is SrCO ₃ : Si ₃ N ₄ : Eu ₂ O ₃ = 2.77085: 1: 0.020625.

The mixing of the weighed raw materials may be a normal mixing method using a mortar or the like. The mixing may be performed in the air, but when SrO or Sr (OH) ₂ is used as a raw material, it may react with moisture or carbon dioxide in the air to cause a shape change. Since Si ₃ N ₄ may be oxidized by oxygen in the atmosphere, it is preferable to carry out in an inert atmosphere from which moisture has been removed. For example, operation in a glove box under an inert atmosphere is convenient.

The mixed raw material is heated to 1400 ° C. at a rate of 15 ° C./min in an inert atmosphere such as nitrogen, held and fired at 1400 ° C. for 1 hour, and then further heated to 1600 ° C. at 15 ° C. / The temperature is increased at a temperature increase rate of min, and held and fired at 1600 ° C. for 2 hours. After the firing is completed, it is cooled from 1600 ° C. to 200 ° C. in 1 hour, and further cooled to room temperature. After the cooling is completed, the fired product is pulverized to a predetermined (preferably 0.1 μm to 20 μm) average particle size using a pulverizing means such as a mortar and a ball mill, and the phosphor whose M element is Sr Got. As a result of conducting composition analysis about the manufactured phosphor, in Example 1, it was Sr _2.70 Si ₃ O _4.15 N ₃ : Eu _0.04 .

The values of a, p, q, and r are the amounts of oxygen and nitrogen contained in oxides, carbonates, hydroxides and nitrides of M, which are raw materials of element M, and Si ₃ N, which is the raw material of Si. _4. Since it can be controlled by the amount of oxygen and nitrogen contained in SiO ₂ , a phosphor having a predetermined matrix structure can be obtained by examining the blending of each raw material while keeping in mind the matrix structure of the phosphor, which is the production purpose. Can be manufactured.

  As described above, the manufactured phosphor is used in combination with an appropriate light emitting unit such as an LED. Therefore, the phosphor is preferably in the form of a powder that can be easily applied or filled. Here, since the phosphor according to Example 1 does not contain aluminum that is easily oxidized in the constituent parts that are the skeleton of the host structure and contains oxygen, it has excellent oxidation resistance. It can be easily pulverized to a predetermined particle size in the air without controlling to an inert atmosphere. Here, from the viewpoint of luminous efficiency, the phosphor preferably has an average particle diameter of 20 μm or less, and can be easily pulverized by a known pulverization method if the average particle diameter is 0.1 μm or more.

(Method of applying phosphor according to the present invention to a light source)
By using the phosphor according to the present invention in a powder form, it is possible to manufacture a light source such as an LED that emits various kinds of light including white light having excellent color rendering properties.
Here, as the light emitting portion of the light source, for example, an LED light emitting element that emits blue light made of a material containing Ga, a discharge lamp that emits blue light, or the like can be applied. And when the fluorescent substance based on this invention is combined with the said LED light emitting element, various illumination units and a display apparatus can be manufactured. In addition, when the phosphor according to the present invention is combined with the discharge lamp, various fluorescent lamps, illumination units, and display devices can be manufactured.

The method of combining the phosphor and the light emitting unit according to the present invention may be performed by a known method, but in the case of a light emitting device using an LED for the light emitting unit, the light emitting device is manufactured as follows. be able to.
Hereinafter, a light-emitting device using an LED light-emitting element that emits blue light that is made of a material containing Ga in a light-emitting portion will be described with reference to the drawings.
7A to 7C are schematic cross-sectional views of the bullet-type LED light-emitting device, and FIGS. 8A to 8E are schematic cross-sectional views of the reflective LED light-emitting device. In addition, in each drawing, the same code | symbol is attached | subjected about the corresponding part and description may be abbreviate | omitted.

First, with reference to FIG. 7A, an example of a light-emitting device that uses an LED for a light-emitting portion and is combined with a phosphor according to the present invention will be described.
In the bullet-type LED light emitting device, the LED light emitting element 2 is installed in a cup-shaped container 5 provided at the tip of the lead frame 3. In this embodiment, the phosphor according to the present invention or a mixture in which the phosphor is dispersed in a light-transmitting resin such as silicon or epoxy (hereinafter referred to as phosphor 1) is used as a cup-shaped container. The LED 1 is filled with the LED light emitting element 2 and the phosphor 1 is molded together with a part of the lead frame 3 and the cup-shaped container 5 with a translucent resin 4.

Next, an example of a different light-emitting device will be described with reference to FIG.
In this embodiment, a mixture in which the phosphor 1 is dispersed in a translucent resin such as silicon or epoxy is applied on the cup-shaped container 5 and the upper surface of the LED light emitting element 2.

Next, another example of a light-emitting device will be described with reference to FIG.
In this embodiment, the phosphor 1 is installed on the LED light emitting element 2.

  As described above, in the bullet-type LED light emitting device described with reference to FIGS. 7A to 7C, light is emitted upward from the LED light emitting element 2, but the same method is used even when the light emission direction is downward. It is possible to create a light emitting device. For example, a reflection type LED light emitting device is provided that includes a reflecting surface and a reflecting plate in the light emitting direction of an LED light emitting element, and reflects light emitted from the element to the reflecting surface to emit light to the outside. Accordingly, an example of a light emitting device in which the phosphor according to the present invention is applied to a reflective LED light emitting device will be described with reference to FIGS.

First, with reference to FIG. 8A, an example of a light-emitting device using an LED as a light-emitting portion and combined with a phosphor according to the present invention will be described.
In the reflective LED light-emitting device, the LED light-emitting element 2 is installed at the tip of one lead frame 3, and light emitted from the LED light-emitting element is reflected downward by the reflecting plate 8 and emitted from above. In this embodiment, the phosphor 1 is applied on the reflecting surface 8. The concave portion formed by the reflecting plate 8 may be filled with a transparent mold material 9 to protect the LED light emitting element 2.

Next, an example of a different light-emitting device will be described with reference to FIG.
In this embodiment, the phosphor 1 is installed below the LED light emitting element 2.

Next, an example of a different light-emitting device will be described with reference to FIG.
In this embodiment, the phosphor 1 is filled in a recess formed by the reflector 8.

Next, an example of a different light-emitting device is described with reference to FIG.
In this embodiment, the phosphor 1 is applied on the transparent mold material 9 for protecting the LED light emitting element 2.
Next, an example of a different light-emitting device will be described with reference to FIG.
In this embodiment, the phosphor 1 is applied to the surface of the LED light emitting element 2.

  The bullet-type LED light-emitting device and the reflection-type LED light-emitting device may be properly used depending on the application, but the reflection-type LED light-emitting device can be made thin, the light emission area can be increased, and the light utilization efficiency can be increased. There are merits such as.

6 is a graph showing a TG measurement result of the phosphor according to Example 1 in the atmosphere. 4 is a graph showing a TG measurement result of a phosphor according to Example 1 in a nitrogen atmosphere. It is a graph which shows the TG measurement result in the air | atmosphere of the fluorescent substance which concerns on Example 2. FIG. It is a graph which shows the TG measurement result in the nitrogen atmosphere of the fluorescent substance concerning Example 2. It is a graph which shows the TG measurement result in the air | atmosphere of the fluorescent substance which concerns on the comparative example 1. It is a graph which shows the TG measurement result in the nitrogen atmosphere of the fluorescent substance concerning the comparative example 1. It is sectional drawing which shows the bullet-type LED light-emitting device based on this invention. It is sectional drawing which shows the reflection type LED light-emitting device based on this invention.

Explanation of symbols

1. 1. Phosphor mixture 2. LED light emitting element 3. Lead frame Resin 5. 7. Cup-shaped container Reflector 9. Transparent mold material

Claims (6)

Composition formula MmBbOoNn: Z (where M element is one or more elements having a valence of II, B element is one or more elements having a valence of IV, O is oxygen, N is nitrogen and Z element is an activator.)
A phosphor having a change in weight of 10% or less in thermobalance measurement from room temperature to 1000 ° C. in the air. M element is one or more elements selected from Mg, Ca, Sr, Ba, Zn,
The B element is one or more elements selected from Si and Ge,
The phosphor according to claim 1, wherein the Z element is one or more elements selected from Eu, Mn, and Ce.   In the composition formula MmBbOoNn: Z of the phosphor, when m = a + p, b = 3, o = a + q, n = 4 + r, the range of a is 0 <a ≦ 10, and the range of p is −a / The range of q is 2 <p <a / 2, the range of q is −a / 2 <q <2a, and the range of r is −2 <r <2. Phosphor.   The phosphor according to any one of claims 1 to 3, wherein the M element is Sr, the B element is Si, and the Z element is Eu.   5. The phosphor according to claim 1, and a light emitting unit that emits light in any of the ultraviolet to visible regions, wherein the fluorescence is generated using a part of the light in the ultraviolet to visible region as an excitation source. A light source characterized by causing the body to emit light.   The light source according to claim 5, wherein the light emitting unit is a light emitting diode.

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