TW200944577A - Phosphor composition and method for producing the same, and light-emitting device using the same - Google Patents

Abstract

A light-emitting device is produced using a phosphor composition containing a phosphor host having as a main component a composition represented by a composition formula: aM3N2.bAlN.cSi3N4, where "M" is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and "a", "b", and "c" are numerical values satisfying 0.2 ≤ a/(a+b) ≤ 0.95, 0.05 ≤ b/(b+c) ≤ 0.8, and 0.4 ≤ c/(c+a) ≤ 0.95. This enables a light-emitting device emitting white light and satisfying both a high color rendering property and a high luminous flux to be provided.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphor composition, a method of manufacturing the same, and a light-emitting device using the same; the phosphor composition can be applied For example, various light-emitting devices such as white light-emitting diodes (hereinafter referred to as white LEDs), and the present invention relates in particular to a phosphor composition which is excited by near-ultraviolet, purple or blue light to emit orange or red. The warm color is light. [Prior Art] A nitride-based phosphor is known as follows. Such a nitride phosphor can be excited by ultraviolet light to near-ultraviolet light to purple-blue light, and emits warm-colored visible light having a light-emitting peak in a wavelength region of 580 nm or more and less than 660 nm, and thus is known to be applicable to, for example, white light. A light source such as an LED light source. (1) M2Si5N8: Eu2+ (refer to Japanese Patent Publication No. 2〇〇3 515665) (2) MSi7N1(): Eu (Refer to 曰本特表2〇〇3 515665) (3) M2Si5Ns: Ce3 + (Ref. Japanese Patent Laid-Open Publication No. 2 222 324474) (^CauAUSbNu.Ce (Refer to JP-A-2-2〇〇35〇4) (5) Ca! 5Al3Si9Ni6:Eu2+ (Chun Zhao η ▲ recognizes 1 hand photo Japanese Unexamined Patent Publication No. 2003-124527 (6) CaAl2Si10Ni6:Eu2+ (J. Sho., JP-A-2003-124527) (7) Sr 丨.5Al3Si9Ni6: Eu2+ (refer to Japanese, W Bent Japanese Patent Publication No. 2003-124527 (Embodiment) No. 2003-44527 (8) MSi3N5: Eu2+ (refer to Japanese Patent Laid-Open Publication No. 2003-206481) (9) M2Si4N7: Eu2+ (refer to Japanese Unexamined Patent Publication No. 2003-206481) (10) CaSi6A10N9: Eu2+ (Refer to JP-A-2003-206481) (11) Sr2Si4A10N7: Eu2+ (Refer to JP-A-2-2-3-481) (12) CaSiN2_Eu (Refer to SS Lee, S. Lim, SS Sun and JF Wager, Proceedings of SPIE-the International Society for ❹ Optical Engineering, Vol. 3241 (1997), p 75·83). At least one of the earth metal elements (Mg, ^, Sr, Ba) or zinc (Zn). The nitride phosphor is mainly a nitride or a metal of the element, and a nitride of the stone And/or the nitride of the glory is produced as a raw material of the glomanium precursor and is reacted with a compound containing an element forming the luminescent center ion in a nitriding gas atmosphere. Further, the conventional illuminating device uses the nitride. However, since the requirements for the above-mentioned light-emitting device are diversified year by year, it is expected that there is a novel phosphor different from the above-described conventional nitride phosphor. In particular, the light emission to the above-mentioned warm color system The composition, in which a light-emitting device having a large amount of red light-emitting components is in great demand, and there is a strong expectation for its development, but the phosphor material which can be applied to it is rare, so it is expected to have a new firefly. Development of a novel light-emitting device and a novel light-emitting device having a large amount of warm-colored light-emitting components. Moreover, in the conventional method for producing a nitride phosphor, the high-purity material 200944577 is difficult to obtain and manufacture, and It is difficult to mass produce high-purity phosphors and produce a decrease in yield by making nitrides of soil-based metals or soils such as soils that are difficult to operate in the atmosphere with chemical instability and operating in the atmosphere. The rise in the price of phosphors is a problem. Furthermore, since the conventional light-emitting device has a small variety of applicable labor materials, the material selectivity is small, and the supplier limited to a certain number of phosphors can cause the price of the light-emitting device to be high. Further, the warm color-based luminescent component (especially red) has a strong illuminating intensity, and the number of inexpensive illuminating devices having a large special color evaluation number R9 is small, which is also a problem. The present invention has been made to solve the above problems, and an object thereof is to provide a completely novel luminous body composition which can emit warm color light, in particular, a glare body composition which emits red light. The object of the present invention is also to provide - A method for producing a phosphor composition, which is suitable for mass production of the nitrided (four) phosphor assembly wire of the present invention, and which is manufactured at low cost. Further, the present invention also provides an inexpensive light-emitting device. The warm color luminescent component (especially red) of the device has a strong illuminating intensity and a special color rendering number R9 is large. Further, 'the technical aspect of measuring the internal quantum efficiency and the external quantum efficiency of the phosphor of the present invention' has established a technique capable of performing high-precision chirp, and the phosphor for the fluorescent lamp is irradiated with light of a specific excitation wavelength. (Excitation of 4 nm ultraviolet light), the absolute values of internal quantum efficiency and external quantum efficiency are known (for example, refer to Okubo and Akira, "Lighting Society", Heisei 11 (Vol. 83, No. 2, p87) β [Abstract] 200944577 The present invention is a phosphor composition, which is a composition represented by the structural formula of alV^N2 · bAIN · cSisN4 as a main body of a fluorescent fluorene matrix, characterized in that: M in the above structural formula, In order to use at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a and ^ c respectively satisfy 0.2$a/(a+b)$〇.95, 〇.〇5 $b/(b+c)S〇.8, 0.4$c/(c + a)$0.95. Further, the present invention is a light-emitting device characterized by using the above-described phosphor composition as a light-emitting source. Further, the present invention provides a method for producing a phosphor composition, which comprises producing the above phosphor composition, characterized in that it is contained in at least a group selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. The compound formed by heating the oxide of the element, the ruthenium compound, the aluminum compound, the compound containing the element forming the luminescent center ion, and the carbon-containing raw material are reacted in a nitriding gas atmosphere. Further, the present invention provides a light-emitting device comprising a phosphor layer containing a nitride phosphor and a light-emitting element, wherein the light-emitting element has an emission peak in a wavelength region of 36 〇ηη or more and not more than 5 〇〇 nm. The phosphor is excited by the light emitted from the light-emitting element, and at least the light-emitting component emitted by the nitride horn is used as the output light of the light-emitting device. The light-emitting device is characterized by: the nitride phosphor a phosphor which is activated by Eu2+ and represented by a structural formula (MhxEudAlSiNs, the oxime is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and the aforementioned X satisfies 〇.005 $χ^〇3. The present invention provides a light-emitting device comprising a phosphor layer containing a nitride phosphor and a light-emitting element, wherein the light-emitting element has an emission peak in a wavelength region of 360 nm or more and 7 200944577 less than 500 nm, and the nitride phosphor is The light emitted from the light-emitting element is excited to emit light, and at least the light-emitting component emitted by the nitride phosphor is used as an output light of the light-emitting device. The light-emitting device is characterized by: the nitrogen The phosphor includes a nitride phosphor or an oxynitride colloid which is activated by Eu2+ and has an emission peak in a wavelength region of 600 or more and less than 660 nm, and is activated by Eu2+ and is not more than 5 Å. The internal quantum efficiency of the phosphor is 80% or more under excitation of light emitted from the light-emitting element in a region having a wavelength of 600 nm and having a luminescence of a soil-reactive metal-based phosphoric acid phosphor. Embodiments of the present invention are described below. (Embodiment 1) First, an embodiment of a phosphor composition of the present invention will be described. An example of the phosphor composition of the present invention contains a phosphor precursor and a luminescent center ion. 'A composition containing a structural formula represented by aM^2 · bAIN · cShN4 as a main component of a fluorescent fluorene matrix, wherein hydrazine is at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. The elements a, b, and c satisfy the values of 〇.2Sa/(a+b)$0.95, 0.05^b/(b+c)^0.8 > 〇-4Sc/(c+a)s〇.95, respectively. When such a composition is used as a phosphor precursor, when Eu2 + ions are added as a luminescent center, The bulk composition is excited by ultraviolet, near-ultraviolet, violet, or blue light to become a phosphor that emits a warm orange or red color. Here, as a host, it means that the content is more than 50% by weight, and the content is More preferably, it is 75 wt% or more, and more preferably 85 wt% or more. 200944577 From the viewpoint of luminous efficiency or luminescent color tone, it is preferable that the above a, b, and c satisfy 〇.2Sa/(a+b)S0, respectively. 6, 0.3$b / (b + c) S0.8, 0.4 $ c / (c + a) S0.8 value 'better to meet 0.2sa / (a + b) $ 0.3, 0.6 Sb / (b + c) The value of S0.8, 0.4^c/(c+a)S0.6. The above-mentioned phosphor precursor ' can be a composition represented by the structural formula of MAlSiN3. Further, the phosphor precursor of the present invention is further selected from the group consisting of M2Si5N8 > MSi7N, 〇^ M1.5Al3Si9N16^MAl2Si10N16 > MSi3N5 'M2Si4N7, MSi6A10N9, M2Si4A10N7, MSiN2, which is selected from the soil test. The nitride of the metal-like nitride and the nitride of the compound, the oxidized lock, the vaporized stone, the nitride of the Ming, and the molar ratio of 2 (1-x): 3x: 2:6 (4) The composition of the mixed raw materials mixed in a ratio of 16 GGC nitrogen gas mixture gas was burned for 2 hours. In order to select white from the viewpoint of luminous efficiency or luminescent color tone, it is preferred that the above element Μ is at least one selected from the group consisting of Ca and Sr t, and the red color of the cerium is 70 y, and can be obtained as a good pure For the purpose of the phosphor of the colored light, & or Sr is also preferred from the case where the main component of the bismuth elbow is Ca. The element Μ can be composed of a conjugate of the aforementioned element group. The mixture of the above-mentioned species of bismuth is preferably the main component of 元/Μ, which means that the element "half is preferably 80 atom% or more.) For the manufacturer, the county ^) is ^ or Sr. Further, the raw material management or species, such as - sound, and the composition of the elements are all one of the aforementioned element groups: such as ... all composed of as. In the above, it is preferable that the composition of the above-mentioned MAlSiN3 structural formula is preferably a compound represented by the above chemical formula MAlSiNs, and the above compound is preferred. The phosphor compound of the present embodiment preferably contains no impurities 'but' may contain a metal impurity element or a vaporized impurity equivalent to less than 1 atom% of at least one of the elements M, A1' Si or n. At least one element. Further, if the above composition is represented by the chemical formula MAlSiN3, as long as it is in the range of not more than 10 atom%, even if Al, Si or N of the above chemical formula MAiSiN3 is excessive or insufficient, the phosphor parent is a compound represented by the chemical formula MA1SiN3. For the subject. That is to say, in order to improve the luminescence properties of the work, a small amount or a small amount of impurities may be added, which is slightly deviated from the chemical composition. For example, in order to slightly improve the luminescent properties of the phosphor composition of the present embodiment, one part of Si may be substituted with at least one of elements which may be tetravalent, such as Ge or Ti, and a part of A1 may be substituted for 3 At least one of the elements of the valence, such as B, Ga, In, Sc, Y, Fe, Cr, Ti, Zr Hf 'V, Nb, Ta, and the like. Here, the above part means, for example, that the number of atoms of ? or A1 is less than 30 atom%. The substantial composition range of the above composition is ❹ MAllt〇3Si 1±/) 31^3(40.3)0 (^0 3 ' is preferably a composition range represented by the structural formula MA11±_0. Further, the above composition is especially SrAlSiNs Or the structural formula or chemical formula of CaAlSiN3 is preferred. For example, it may be (Sr Ca) A1SiN3, (&

A composition having a plurality of alkaline earth metal elements such as Mg)AlSiN3, (Ca, Mg)AlSiN3, (Sr, Ca, Ba)AlSiN3. Further, the ruthenium (oxygen) in the above structural formula is an impurity element which is mixed when the phosphor composition is produced. 10 200944577 In the crystal lattice of the compound constituting the above-mentioned phosphor precursor, at least one ion (luminescence center ion) which can serve as an illuminating center is added to constitute a phosphor composition. If a luminescent center is added to the phosphor precursor The ions form a fluorescent body that emits fluorescence. The luminescent center ion may be appropriately selected from metal ions selected from various rare earth ions or transition metal ions. Specific examples of the luminescent center ion include a valence of a trivalent rare earth metal ion such as Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, and Yb3+, Sm2+, © Eu2+, and Yb2+. a rare earth metal ion, a divalent transition metal ion such as Mn2+, a trivalent transition metal ion such as Cr3 + or Fe3+, or a tetravalent transition metal ion such as Mn4+.

In the phosphor composition of the present embodiment, it is preferable that the luminescent center ion is an ion selected from at least one of Ce3 + and Eu 2+ from the viewpoint of luminous efficiency, and if it is a phosphor containing the ion, It can be a better phosphor for white LEDs. When Eu2 + is used as the luminescent center ion, a phosphor that emits warm light can be obtained, and it can be used as a luminescent device, particularly for a illuminating device. If Ce3+ is used as the luminescent center ion, a phosphor emitting blue-green light can be obtained, which is suitable for a high color rendering light-emitting device, especially a phosphor for illumination devices. The phosphor composition of the present embodiment is preferably an ion selected from at least one of Ce3+, Eu2+, Eu3+, and Tb3+ as a light-emitting medium from the viewpoint of luminescent color. If Ce3+ is used as the luminescent center ion, a high-efficiency phosphor emitting at least blue-green light can be obtained. If Eu2+ is used as the luminescent center ion, Bay J can obtain a high-efficiency phosphor that emits orange to red light. For example, 3 + is the first central ion of 200944577, and the target sentence is * a: 丨 w • A high-efficiency phosphor that emits red light. If Μ is used as the illuminating body in the illuminating light, then the half-receiving body that emits green light is obtained. Any one of the decontamination roads +^j, the fluorescent body emits red or green or blue as the light color of the three primary colors of light, or the orange light that is large in the fly, so it is suitable as a light-emitting device. The phosphor used.较佳 The preferred addition amount of the luminescent center ion depends on the type of luminescent center ion: it is different 'for example, 卩 2+ 2+ or . When 3 + is used as the luminescent center ion, the amount of the luminescent center ion added to the element M' is preferably 〇" atom% to 3 〇 atom% t is preferably G. 5 atom% to 1 G atom%. If the amount added is less than this or more than this, it cannot be a phosphor which combines both good luminescent color and high brightness. Further, basically, it is preferable to add the luminescent center ion in such a manner as to replace a part of the lattice position of the element M, but it is also possible to replace the lattice position of one part of A1 or Si. The phosphor composition of the present embodiment may be a phosphor in which a plurality of luminescent center ions are co-activated. Examples of the fluorescent conjugates in which the luminescent center ions are co-activated include a phosphor that is co-activated with Ce3 ions and Eu2+ ions, a phosphor that is coactivated with Eu2+ ions and Dy3+ ions, and a phosphor that is coactivated with Eu2+ ions and Nd3+ ions. A phosphor, a phosphor that co-activates Ce3+ ions and Mn2+ ions, a phosphor that is co-activated with eu2+ ions and Mn2+ ions, and the like. In this way, the energy transfer phenomenon from one of the luminescent center ions to the other ion can be utilized to obtain a phosphor whose shape of the excitation spectrum or the luminescence spectrum is controlled, or to use the excitation phenomenon due to heat to obtain afterglow ( Afterglow) Long long afterglow phosphor. Preferred phosphors for use in the light-emitting device of the present invention are as follows. Such a phosphor can be obtained by changing the value of the above a, b, c or the element ratio of the element 或 or the amount of the illuminating 12 200944577 center or the amount added. (1) A warm color system having a luminescence peak, particularly red, in a wavelength region of 580 nm or more and less than 660 nm (from the viewpoint of color purity and visibility required for a light-emitting device, preferably 610 or more and less than 65 〇 nm) The glory of the shade of light. (2) A phosphor which can be excited by irradiation of ultraviolet light or ultraviolet light of 350 nm or more and less than 420 nm (from the viewpoint of the excitation characteristics required for the light-emitting device, preferably 38 Onm or more and less than 41 Onm). (3) A phosphor that can be excited by blue light of 420 nm or more and less than 500 nm (from the viewpoint of the excitation characteristics required for the light-emitting device, preferably 440 nm or more and less than 480 nm). (4) A phosphor that can be excited by irradiation with green light of 550 nm or more and less than 560 nm. Further, the properties of the phosphor composition of the present embodiment are not particularly limited, and may be a single crystal block, a ceramic molded body, a film having a thickness of several nm to several m/m, and a thickness of 10 #m to several 1 〇. Thick film, powder, etc., but when applied as a light-emitting device, it is preferably a powder, and a powder having a center particle diameter (D5G) of 0.1 to 30 #m is more preferable, and more preferably a center particle diameter ( D5Q) is a powder of 〇5~2〇A m. Further, the shape of the particles of the phosphor composition itself is not particularly limited, and may be any of a spherical shape, a plate shape, and a rod shape. The phosphor composition of the present embodiment obtained as described above can be excited by at least 250 to 600 nm of ultraviolet to near ultraviolet to blue to green to yellow to orange light 'at least to emit blue-green, orange or red light. Fluorescent body. Also, i obtains a red-lighted fluorescent light having a luminescence peak in a wavelength region of 610 to 650 nm. Further, the excitation spectrum and the luminescence spectrum shape of the above-mentioned red-emitting phosphor having Eu2+ ions as an illuminating center are a conventional Eu2+ activated phosphor using Si^SieNg nitride citrate as a mother material. Its excitation spectrum is similar to the shape of the luminescence spectrum. Hereinafter, a method of producing the phosphor composition of the present embodiment will be described. <Manufacturing Method 1 of the Present Invention> The phosphor composition of the present embodiment can be produced, for example, by the production method described below. First, prepare a nitride of a soil-like metal bismuth (Μ Ν Ν 2) or a zinc nitride (Ζη3Ν2), tantalum nitride (Si3N4), or aluminum nitride (Α1Ν) as a raw material for forming a phosphor precursor. Among them, the nitride of an alkaline earth metal or the vapor of zinc is not commonly used as a ceramic raw material, and is not only difficult to obtain and expensive, and is easily deteriorated by reaction with water vapor in the atmosphere, and is difficult to handle in the atmosphere. Further, various rare earth metals or transition metals or such humans are used as a raw material for adding luminescent center ions. The element is, for example, a network element or a transition metal having an atomic number of 58 to 60 or 62 to 71, particularly Ce, Pl*, Eu, Tb, Μη. The compound containing such an element may be an oxide, a nitride, a hydroxide, a carbonate, an oxalate, a nitrate, a sulfate, a tooth, a phosphate or the like of the above-described lanthanide or transition metal. Specifically, for example, there are cesium carbonate, cerium oxide, cerium nitride, metal cerium, manganese carbonate, and the like. Next, the phosphor raw materials are weighed so that the atomic ratio of each atom is a(Mi-xLcx)3N2 · bAIN · cSi3N4 ' and mixed to obtain a mixed raw material. Wherein, Μ is selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and one element is less than 200944577, and a, b, and c satisfy 0.2Sa/(a+b)$〇.95, 0.05$b. /(b+c)S0.8, 0.4 The value of each c/(c + a)$〇.95' Lc represents an element as a luminescent center ion, and x represents 〇&lt;x&lt;〇.3, preferably O.OOlSx each, 2 'better is the value of χ5$χ^〇ι. For example, the atomic ratio can be set to MhLqAlSi%. Then, the mixed raw material is fired in an atmosphere of a vacuum atmosphere, a neutral atmosphere (inert gas or nitrogen), or a reducing atmosphere (CO, nitrogen-hydrogen mixed gas, etc.).

Further, in the above-mentioned ambient atmosphere, it is preferable to use a simple equipment, and it is preferably an atmospheric atmosphere, but it may be any of a high-pressure atmosphere, a pressurized atmosphere, a reduced-pressure atmosphere, and a vacuum atmosphere. In order to improve the performance of the phosphor, the reaction atmosphere is preferably a high-pressure atmosphere, for example, 2 to atmospheric pressure, and if considering the viewpoint of the operation of the ambient atmosphere, it is preferably an atmospheric atmosphere composed of nitrogen gas as a main component. . According to this high-pressure atmosphere, it is possible to prevent or suppress decomposition of the nitride phosphor composition during high-temperature firing, and to suppress the phosphor composition deviation, thereby producing a high-performance phosphor composition. Further, as the luminescent center ion, in order to generate a large amount of ions such as ce3+, Eu2+, Tb3+, and Μπ2+, a preferred ambient atmosphere is a reducing atmosphere. The firing temperature is, for example, 1300 to 200 (TC), and in order to improve the performance of the phosphor, it is preferably 1600 to 200 (rc, more preferably 17 to 19 〇 (rc.) if mass production is required, More preferably, it is preferably 16 〇〇 to 17 〇〇 β (:. For example, the firing interval is 30 minutes to 1 GM, and when the productivity is considered, the comparison time is 2 to 8 hours. The firing is possible. In the case of a different ambient atmosphere or the same ambient atmosphere 15 in 200944577, the fired product obtained by the firing is a phosphor composition. The phosphor composition of the present embodiment is not limited to the above. The production method can be produced not only by the solid phase reaction described above, but also by, for example, a gas phase reaction or a liquid phase reaction. Further, nitrides such as ShN4 or A1N are not as difficult as nitrides of alkaline earth metals. Obtained, but it is difficult to obtain high-purity. In most cases of the above-mentioned or ain nitrides, most of them will be oxidized to become Si〇2 or ΑΙΑ3, and the purity will be slightly lowered. For the above reasons, Benedict The phosphor composition of the embodiment is as long as the substance The above-mentioned atomic ratio composition may be included, and in the above structural formula MA1SiNs, a part of ΜΑ# or A1N may be oxidized and deteriorated to Si〇2 or ai2〇3. <Production Method 2 of the Present Invention> This embodiment The phosphor composition can be produced, for example, according to the production method described below. In the production method 2 of the present invention, a composition in which the composition represented by the aCMhLcAN2 · bAIN · cShN4 structural formula is a fluorescent-derived precursor is produced. The composition is an oxide obtained by heating at least one element M selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and a compound, an IS compound, a compound containing an element forming a luminescent center ion, and carbon. The raw material is reacted in an atmosphere of a nitriding gas atmosphere. An example of the manufacturing method 2 of the present invention is to form a metal oxide MO (wherein 'PCT is Mg, Ca, 仏, 仏 and zn) by heating. The earth metal oxide or the compound (preferably a metal compound which can be heated to form CaO or SrO 16 200944577 7) is reduced and nitrided by reacting with carbon in a nitriding atmosphere. The alkaline earth metal compound or the compound is reacted with a nitride, an aluminide, or a compound containing an element forming a luminescent center ion. The production method 2 of the present invention may be referred to as a reduction nitridation method, and the above-mentioned ?·bA1N · _Ν4 (especially M! xLCxA丨3) A method for producing a phosphor, in particular, a method for industrially producing a powdered glomerium composition. n. The manufacturing method 2 of the present invention will be described in detail below. The compound, telluride, and aluminide of the above-mentioned element lanthanum oxide are used as a raw material for forming a fluorescent ruthenium precursor. A compound (described later) which forms an oxide of the above element cerium by heating is preferably used as a ceramic material. This raw material is not only easy to obtain but also inexpensive, and is stable in the atmosphere and easy to handle in the atmosphere. Further, various rare earth metals or transition metals or the like are prepared as a raw material to be added to the luminescent center ions. Also, quasi-prepared carbon is used as a reducing agent. Next, the phosphor raw materials and the reducing agent are weighed so that the atomic ratio of each atom is, for example, a(Ml_xLCx)3N2 · bA1N · cSi3N4, and a carbon monoxide gas (c〇) is formed by reacting with the carbon of the reducing agent. The ratio of oxygen in the phosphor raw material is completely removed and mixed to obtain a mixed raw material. Wherein, Lc represents a metal element which becomes a luminescent center ion, and X represents a value satisfying 〇&lt;x&lt;3., preferably 0.001 SxS0.2, more preferably 〇5$χ$〇1. Next, the above mixed raw materials are fired in a nitriding gas atmosphere at a temperature of 17 200944577 to cause a reaction. body. Here, the nitriding gas system means that the gas generated by the gasification reaction can be used as the luminescent center ion, and in order to generate a large amount of ions such as Ce3+, Eu2+, Tb3+, Mnh, the preferred ambient atmosphere is the reducing ring 1 atmosphere. For example, nitrogen and hydrogen are mixed in an ambient atmosphere. The firing temperature is, for example, 1300 to 2000 ° C, and in order to improve the performance of the phosphor, it is preferably 16 〇〇 to 2 〇〇〇.

°C, more preferably 1700~1900. (: If it is to be mass-produced, it is preferably 14 〇 0 to 180 (TC, more preferably 1600 to 1700 t. The firing time is, for example, "minutes to 100 hours", and if productivity is considered, the firing time is preferred. It is 2 to 8 hours. The firing can be carried out in several different ambient atmospheres or in the same ambient atmosphere. The burnt money obtained by the firing is a composition of labor (4). The above-mentioned oxidation of the above elements can be generated by heating. The compound of the product is not particularly limited. From the viewpoints of easiness of obtaining a high-purity compound or easy to obtain in the atmosphere, the price is preferably selected from a metal or zinc carbonate or oxalate. , nitrate, acetate, oxide, peroxidation: or at least one of the soil-recovering metal compounds or the compound of the hydroxide, more preferably an alkali earth metal carbonate, an oxalate or an oxide The metal-based carbonate is more preferably selected from the group consisting of a powdery form, a preferred form of the above-mentioned alkaline earth metal block, and the like. It is also a powder. The properties are not particularly limited, 'for obtaining a powdery phosphor lens As long as it can be The composition of the fluorescene body of the present embodiment is formed by the above reaction, and is particularly limited to the phosphor of each of the properties based on the reason of the above-mentioned alkaline earth metal. For the reason, the preferred telluride 18 200944577 is tantalum nitride (ShN4) or bismuth imide (Si(NH) 2 ), more preferably tantalum nitride. The properties of the dream compound are not particularly limited and may be from powder form, Further, in order to obtain a powdery phosphor, a preferred property is a powder. In the production method 2 of the present invention, the supply source of the crucible may be a germanium monomer. The monomer reacts with nitrogen or the like of the nitriding atmosphere atmosphere to form a niobium nitride (such as tantalum nitride), and then reacts with the alkaline earth metal nitride or aluminide or the like. Therefore, the production method of the present invention 2 also includes the above-mentioned dream compound for Shi Xi single.

The aluminide may be formed by the above-described reaction to form the phosphor composition of the present embodiment, and is preferably limited to aluminum nitride (A1N) for the same reason as the above (four) compound. The properties of the above-mentioned inscription are not particularly limited, and X' may be selected from a powdery or blocky form to obtain a powdery phosphor, and a preferred property is a powder. In the production method 2 of the present invention, the supply source of the invention may be a metal monomer. In this case, the metal can be reacted with nitrogen or the like in the atmosphere of the nitriding gas to form a sulphur compound (nitriding, etc.), and then reacted with the above-mentioned soil-based metal nitride or lithium compound. . Therefore, the manufacturing method 2 of the present invention also includes the case where the aluminide is aluminum metal. The properties of the carbon are not particularly limited, and solid carbon is preferred, and carbon black, southern purity carbon powder, carbon block or the like can be used, and among them, graphite is particularly preferable. However, amorphous carbon (coal, coke, charcoal, gaseous carbon, etc.) can also be used. Further, a carburizing gas such as natural gas, smoldering (CH4), propyl sulphide, or butyl sulphide (C4H1 fluorene) may be used as the carbon source. In addition, in a vacuum atmosphere or a neutral atmosphere in an inert atmosphere, a carbonaceous burn 200944577 is used. When the vaporized carbon is used as a container or a heating element, some of the carbon may be used as a reducing agent. . The above-mentioned solid Zhao carbon has the size and shape of the makeup, and there is no special limitation on the shape. From the point of view of ease of use, the preferred solid carbon size and shape are the longest straight (four) and the longest side is micronized powder of l〇nm~lcm. Powder or particles, also other solid carbon. Solid carbon of various shapes such as powder, granules, lumps, lumps, and rods can be used. The purity of solid carbon is not particularly limited.

The phosphor of the material "the purity of the solid carbon is preferably as high as possible", for example, a purity of 99% or more, preferably a high purity carbon having an alcohol degree of 99.9% or more. The amount of the solid carbon to be added is a reaction ratio required to remove the stoichiometric amount of the milk contained in the abrasive material, but it is preferably excessive in order to completely remove the oxygen. If specified by specific values, the excess amount of solid carbon added is preferably not more than 0/〇 of the atom required for the above stoichiometry. Further, the solid carbon to be reacted may also serve as a heating element (carbon heater) or as a firing container (carbon crucible or the like). The above-mentioned carbon as a reducing agent may be used in combination with a phosphor raw material, or may be simply contacted. In addition, the nitriding gas is not particularly limited as long as it is nitriding the above-mentioned alkaline earth metal or zinc compound which is reduced by the carbon, and it is easy to take in high-purity fluorine, ease of handling, price, etc. The viewpoint is preferably at least one selected from the group consisting of nitrogen and ammonia, and more preferably nitrogen. Further, in order to increase the reducing power of the firing atmosphere, to improve the performance of the fluorescent iridium or to obtain a high-performance phosphor, a nitrogen-hydrogen mixed gas may be used. The reaction atmosphere containing a nitriding gas is considered to be a reason for using the apparatus 20 200944577, and is preferably a normal-pressure atmosphere, but may be a high-pressure atmosphere, a pressurized atmosphere, a reduced-pressure atmosphere, or a vacuum environment. Any of the atmosphere. In order to improve the performance of the phosphor, the reaction atmosphere is preferably a high-pressure atmosphere, for example, 2 to 1 Torr atmosphere, and if considering the operation of the ambient atmosphere, it is preferably 5 to 20 atm with nitrogen gas as the main component. The atmosphere of the environment. According to this high-pressure atmosphere, it is possible to prevent or suppress decomposition of the nitride phosphor composition during high-temperature firing, and it is possible to suppress the phosphor composition deviation and to manufacture a high-performance phosphor composition. Further, in order to promote the decarburization of the ® reactant (calcined product), a small amount or a slightly 3C water vapor may be contained in the above reaction atmosphere ♦. In order to increase the reactivity of the above-mentioned compound raw materials, a flux reaction may be added. The flux can be appropriately selected from an alkali metal compound (Na2C〇3, Naa, uf) or a halide (SrFa, CaCl2) or the like. The most important feature of the production method 2 of the present invention is that: (1) the raw material of the phosphor composition of the present embodiment does not substantially use an alkaline earth metal or a nitride, an alkaline earth metal or a zinc metal; (2) instead, Using a compound which can form a metal oxide (the above M〇) by heating; (3) reacting the oxygen component contained in the compound with carbon (preferably solid carbon); (4) by further reacting with nitrogen The alkaline gas metal compound is nitrided by a chemical gas reaction, and (5) is reacted with a telluride and an aluminide to produce a phosphor composition of the present embodiment. In the above-described production method 2 of the present invention, the reaction temperature is preferably i 3 〇〇 2 2 〇〇〇 C, and in order to improve the performance of the phosphor, it is preferably ι 6 〇〇 2 2, more preferably 1700. If it is a large amount of production, it is preferably 14 〇〇 18 〇〇 &lt; t, more preferably 1600 〜 1700 ° C. . Also, the reaction can be carried out in fractions. In this way, 21 200944577 by heating, the metal oxide compound can be formed into a metal oxide M〇, and further reacted with carbon, and the metal oxide is reduced by generating carbon monoxide or carbon dioxide, and then the reduced metal is oxidized. The substance is nitrided by a nitriding gas to form a nitride, and is simultaneously reacted with other compounds such as the above-mentioned telluride or aluminide or a gas or the like. Thereby, the nitride phosphor composition of the present embodiment can be produced. If the reaction is carried out at a temperature lower than the above temperature range, the above reaction or reduction may be incomplete, and it is difficult to obtain a high-quality nitride phosphor composition, and if it is reacted at a temperature higher than the above temperature range, nitrogen is required. The phosphor composition is decomposed or melted, and it is difficult to obtain a fluorescent composition having a desired composition or shape (powder, shape, and the like). Further, when the reaction is carried out at a temperature higher than the above temperature range, the manufacturing equipment must use a high-priced heat generating body or a high heat-resistant heat insulating material, and the equipment cost is increased, so that it is difficult to provide an inexpensive phosphor composition. According to the production method 2 of the present invention, it is not necessary to use a high-purity material to obtain an alkaline earth metal or zinc nitride which is difficult to handle in the atmosphere, and it is used as a main raw material of the fluorescent ruthenium. The production method 2 of the present invention is characterized in that a compound containing a compound capable of forming an oxide of the element M by heating with a telluride, an aluminide, a raw material for breaking, and a compound containing an element forming an emission center ion is used for nitriding property. The reaction is carried out in a gaseous atmosphere. Since these raw materials are relatively inexpensive and easy to handle, and are easy to handle in the atmosphere, they are suitable for mass production, and the phosphor of the present embodiment can be produced at low cost. Meanwhile, if the fluorescent iridium composition manufactured by the manufacturing method 2 of the present invention is used, the illuminating device can be made more inexpensive, and an inexpensive illuminating device can be provided. 22 200944577 Further, the above-described manufacturing method 2 of the present invention can be applied to the above-described manufacturing method 1 of the present invention. For example, if at least one of the alkaline earth metal nitride (M3N2) and the zinc nitride (ZnsN2) used for forming the glomanium parent material is formed and added to tantalum nitride (Si3N4) and aluminum nitride (A1N). When the carbon (Carbon) as a reducing agent is fired, the impurity oxygen in the firing can be removed as carbon monoxide (CO), and the oxygen in the phosphor can be prevented or suppressed, so that it can be produced high. Purity nitride phosphor composition. That is, in the method of producing a nitride crab composition in which at least one nitride selected from the group consisting of a nitride of a soil-based metal and a tantalum nitride of zinc is used as at least one kind of phosphor raw material A method for producing a phosphor composition obtained by adding carbon to a raw material and firing the same may be used as a method for producing a phosphor composition of the above other embodiment. In addition, the nitride phosphor composition means a phosphor composition containing nitrogen as a gas element constituting a phosphor precursor, such as a nitride phosphor composition or an oxynitride phosphor composition, in particular, A phosphor composition containing nitrogen as a main gas component element. In addition, the composition of the composition of the above-mentioned MAlSiN3 is used as a raw material of the phosphor composition of the main body of the phosphor precursor, and even if a nitride compound such as Si3N4, M^SisNg, MSiN2, or MSi7Ni〇 is mixed and fired, A phosphor composition similar to the luminescent properties of the above-described phosphor composition can also be obtained. Therefore, the phosphor composition of the present embodiment may be a phosphor in which the nitride represented by any one of MAlSiN3 · aSi3N4, MAlSiN3 · aM2Si5N8, MAlSiN3 · aMSiN2, MAlSiN3 · aMSi7N10 is a phosphor precursor. Composition. Wherein M is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and 23 200944577 a is a value satisfying 0SaS2, preferably osagi. Such a phosphor composition is, for example, 2MAlSiN3 · Si3N4, 4MAlSiN3 · 3Si3N4, MAIS1N3 · S13N4 ' MAIS1N3 * 2Si3N4 ' 2MAlSiN3 · M2Si5N8 ' MAIS1N3 · M2Si5N8 , MAlSiN3 · 2M2Si5N8 , 2MAlSiN3 · MSiN2, MAlSiN3 · MSiN2, MAlSiN3 · 2MSiN2 ' A phosphor composition in which a luminescent center ion is added to a composition represented by 2MAlSiN3, MSi7N10, MAlSiN3, MSi7N10, MAlSiN3, 2MSi7N10 or the like. (Embodiment 2) Hereinafter, an embodiment of a light-emitting device of the present invention will be described. In the example of the light-emitting device of the present invention, the phosphor composition of the above embodiment may be used as the light-emitting source, and the form thereof is not particularly limited. For example, an electromagnetic wave of at least one selected from the group consisting of X-ray, electron beam, ultraviolet ray, near-ultraviolet light, visible light (purple, blue, green light, etc.), near infrared ray, infrared ray, or the like can be used as the excitation source of the work beam. An electric field may be applied to the phosphor of the first embodiment, or an electron or the like may be injected to excite and emit light to serve as a light-emitting source. The light-emitting device of the present embodiment is, for example, a device of the following name. ο (1) Fluorescent lamps, (2) plasma displays, (3) inorganic electroluminescent panels, (4) field emission displays, (5) electron tubes, and (6) white led light sources. More specifically, the light-emitting device of the present embodiment includes various types of display devices including white LEDs and white LEDs (for example, LED information display terminals, LED traffic signals, and LED lights for automobiles (lights, lights, front lights) Various lighting devices (lighting inside and outside LEDs, in-vehicle LED lights, LED emergency lights, LED light sources, led 24 200944577 decorative lights) using white LEDs, various display devices without using white LED lights (electron tubes) For example, an inorganic electroluminescence panel, a plasma display panel, or the like, and various illumination devices (fluorescent lamps, etc.) of a white LED are not used. From another viewpoint, the light-emitting device of the present embodiment is, for example, ultraviolet or blue. A color light-injecting electroluminescent device (a light-emitting diode, a semiconductor laser, an organic electroluminescence device, or the like) is combined with at least the phosphor composition of the first embodiment to form a white light-emitting element, various light sources, an illumination device, and a display device. Or a light-emitting device comprising: a display device and a lighting device using at least one of the above-mentioned white light-emitting elements The light-emitting device of the present embodiment is preferably a warm-colored light having a light-emitting peak in a wavelength region of 580 to 660 nm, and more preferably a red-based light-emitting nitride having a light-emitting peak in a wavelength region of 610 to 65 nm. A light-emitting device comprising a light-emitting device as a light-emitting source, wherein the light-emitting body composition of the first embodiment is used as the nitride phosphor composition. Further, the light-emitting device of the embodiment is, for example, a combination of 36. a light-emitting device having an emission source of primary light of 〇nm or more and less than 560 nm, and a phosphor composition of visible light that is longer than a wavelength of the primary light, and a primary light that absorbs the primary light of the emission source, wherein the fluorescent device The phosphor composition is the phosphor composition of the first embodiment, and more preferably a phosphor composition that emits warm color light. More specifically, the emitted light is 36 〇 nm or more and less than 420 nm. An emission source having a luminescence peak in a wavelength region of 420 nm or more, less than 500 nm, 5 〇〇 nm or more, and less than 560 nm, and absorbing the primary light of the emission source and converting to the above-mentioned one time A light-emitting device in which a phosphor composition having a long wavelength of visible light is combined, wherein the phosphor 25 200944577 body composition uses the fluorescent composition of the first embodiment, and the light-emitting device of the embodiment is The above-mentioned emission source can use an injection type electroluminescence element. The 'injection type electroluminescence element means a photoelectric conversion element which can convert electric energy into light energy to emit light by injecting electric power to inject electrons into the fluorescent substance. The specific example is as described above. The light-emitting device of the present embodiment uses a completely novel phosphor that can increase the selectivity of the phosphor material as a light-emitting source, so that it is not necessary to use a rare and expensive conventional phosphor. A light-emitting device can be constructed to produce an inexpensive light-emitting device. Further, since a phosphor that emits warm light, in particular, red light, is used as the light source, the intensity of the light-emitting component of the warm color is strong, and the light-emitting device having a high number of special color evaluation numbers R9 can be obtained. Hereinafter, the light-emitting device of the present embodiment will be described with reference to the drawings. The light-emitting device of the present embodiment is not particularly limited as long as it is configured by using the phosphor composition of the above embodiment as a light-emitting source. In a preferred embodiment, in addition to using the phosphor composition of the first embodiment, a light-emitting element is used as a light-emitting source, and the phosphor composition and the light-emitting element are provided so that the phosphor composition covers the light-emitting element. Combined composition. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1, Fig. 2, and Fig. 3 are cross-sectional views showing a semiconductor light-emitting device of a representative embodiment of a light-emitting device in which a phosphor composition of an embodiment is combined with a light-emitting device. 1 shows a semiconductor light-emitting device in which at least one light-emitting element 1 is mounted on a submount element 4, and at least contains the phosphor composition of Embodiment 1 and also serves as a fluorescent light. The light-emitting element 1 is sealed by encapsulation of a base material of the bulk layer 3 (for example, a transparent resin or a low (four) glass or the like). Figure 26 200944577 2 shows a semiconductor light-emitting device in which at least one light-emitting element 封装 is packaged in a cup 6 disposed in a carrier wire of the conductive frame 5, and is disposed in the cup body 6 to contain at least the firefly of the embodiment i The base material of the photo composition 2 forms the phosphor layer 3, and the whole is encapsulated by a sealing material such as a resin. Fig. 3 is a view showing a wafer type semiconductor light-emitting device in which at least '1 light-emitting elements 1' are disposed in a housing 8 and at least a mother body containing a phosphor composition 2 of an embodiment is provided in the housing 8. The glory layer 3 formed by the material. In FIGS. 1 to 3, the light-emitting element i is a photoelectric conversion element that converts electrical energy into light energy, and specifically, for example, a light-emitting diode, a laser diode, and a surface-emitting laser diode Electroluminescent elements, organic electroluminescent elements, and the like. In particular, from the viewpoint of increasing the output of the +conductor illuminant composition, a light-emitting diode or a surface-emitting diode is preferable. The wavelength of light emitted by the light-emitting element 基本上 is basically not particularly limited as long as it can excite the wavelength range of the fluorescent iridium composition of the embodiment 1 (for example, 250 to 550 nm). However, in order to excite the phosphor composition of the first embodiment with high efficiency, and to produce a high-luminance semiconductor light-emitting device having a white light-emitting system, the light-emitting element 1 preferably exceeds 340 and 500 nm, and more preferably More than 350, 420 nm or less, more preferably more than 42 〇, 5 〇〇 nm or less, more preferably more than 360, 41 〇 nm or less, and even more preferably more than 44 〇, 48 〇 nm or less, also That is, the wavelength region near the ultraviolet, purple or blue has a luminescence peak. Further, in the 'Fig. 1 to Fig. 3', the refractory layer 3 contains at least the phosphor composition 2 of the embodiment, and for example, the phosphor composition of the embodiment can be dispersed in a transparent resin (epoxy resin or tantalum resin). Etc.) or low-melting glass, etc. 27 200944577 Ming base material. The content of the phosphor composition 2 in the transparent base material, for example, in the above transparent resin, is preferably 5 to 8 % by weight, more preferably 1 to 6 % by weight. The phosphor composition 2 included in the embodiment of the phosphor layer 3 is a light conversion material, and absorbs part or all of the light emitted by the light-emitting element 1 and converts it into yellow to deep red light. The phosphor composition 2 is excited by the light-emitting element 1 to cause the semiconductor light-emitting device to emit a light-emitting component emitted from at least the phosphor composition 2. Therefore, if the light-emitting device of the combination structure is manufactured as described above, the light emitted from the light-emitting element 1 is mixed with the light emitted from the phosphor layer, and the white light is obtained, so that the demand is large. A light-emitting semiconductor light-emitting element. U) emits near-ultraviolet light (wavelength of 300 or more, less than 380 nm, from the viewpoint of output, preferably 350 or more, less than 38 Onm) or violet light (wavelength of 380 or more and less than 420 nm, from the viewpoint of output, preferably A structure in which a light-emitting element of any of 395 or more and less than 41 5 nm is combined with a blue phosphor, a green phosphor, and a red phosphor composition of the first embodiment. (2) A combination of a light emitting element that emits light of either near-ultraviolet light or violet light, and a blue phosphor, a green phosphor, a yellow phosphor, and a red phosphor composition of the first embodiment structure. (3) A structure in which a light-emitting element of either near-ultraviolet light or violet light is combined with a blue phosphor, a yellow phosphor, and a red phosphor composition of the first embodiment. (4) A light-emitting element that emits blue light (having a wavelength of 420 or more and less than 480 nm, which is preferably 450 or more and less than 480 nm from the viewpoint of output), green light 28 200944577 light body, yellow phosphor, and embodiment 1 The structure of the combination of the red fluorescent 艎 composition. (5) A structure in which a blue light emitting element is combined with a blue phosphor, a yellow illuminant, and a red phosphor composition of the first embodiment. (6) A structure in which a blue light emitting element is combined with a green phosphor and a red phosphor composition of the embodiment. (7) A structure in which a light-emitting element of blue-green light (wavelength: 480 nm or more and less than 510 nm) is combined with the red phosphor composition of the first embodiment. © The phosphor composition of Embodiment 1 which emits red light may be excited by green light having a wavelength of 5 1 Onm or less, green light of less than 560 nm, or yellow light of 560 nm or more and less than 590 nm. The light-emitting element of either the green light or the yellow light is combined with the red phosphor composition of the first embodiment to fabricate a semiconductor light-emitting device. Further, since the phosphor composition of the first embodiment can emit yellow light, the yellow phosphor can also be used as the yellow phosphor composition of the first embodiment. Further, in this case, the red phosphor composition may be used as the red phosphor other than the phosphor composition of the embodiment 1. Further, white light can be obtained by combining the light-emitting element emitting blue light with the yellow phosphor composition of the first embodiment. Further, the blue phosphor, the green phosphor, the yellow phosphor, and the red phosphor other than the phosphor composition of the first embodiment may be used in the Eu2+ activated aluminate phosphor. Ειι2+ activated halophosphate-based phosphor, Eu2+-activated phosphate-based phosphor, Eu2+-activated citrate-based phosphor, Ce3+-activated garnet-based fluorescent iridium (especially, yaG (钇•aluminium•pomegranate 29 200944577) Stone): ce-based phosphor), Tb3 + activated citrate-based phosphor, Eu2+-activated thiosilicate, Eu2+ activated nitride-based phosphor (especially SiAi〇N (Sialon) fluorescence鳢), Eu2+ activated soil-based metal sulfide-based phosphors, Eu3 + activated acid sulfide-based phosphors, and the like are widely selected, and more specifically, for example, '(Ba,Sr)MgAl10O17:Eu2+ blue can be used. Color phosphor, (Sr, Ca, Ba, Mg) i〇 (P04) 6Cl2: Eu2+ blue phosphor, (Ba, Sr) 2Si04: Eu2+ green phosphor, BaMgAl10O17: Eu2+, Mn2+ green phosphor , Y3Al5012: Ce3 + green phosphor, BaY2SiAl4012: Ce3+ green phosphor, Ca3Sc2Si3012: Ce3 + green phosphor, Y2Si05: Ce3 + , Tb3+ green phosphor, BaSiN2: Eu2+ green phosphor, SrGa2S4: Eu2+ green phosphor, (Y, Gd) 3Al5012: Ce3 + yellow phosphor, Y3Al5012: Ce3 +, Pr3 + yellow phosphor, (Sr, Ba) 2Si04: Eu2 + yellow phosphor, CaGa2S4: Eu2+ yellow phosphor, 〇.75CaO · 2.25A1N · 3.25Si3N4: Eu2+ yellow phosphor, CaS: Eu2+ red phosphor, SrS: Eu2+ red phosphor , La202S: Eu3 + red fluorescent 逋, Y202S: Eu3 + red fluorescent body. Further, conventionally, a blue LED has been known as an excitation source for a phosphor, and the phosphor layer contains, for example, a Sr2Si5N8:Eu2+ nitride-based red phosphor, and the YAG:Ce-based yellow phosphor. Or a strong green light beam and a high-color white LED, and since the phosphor composition of Embodiment 1 and the above-mentioned Sr2Si5N8:Eu2+ nitride red phosphor can exhibit similar light-emitting characteristics, The color LED is used as an excitation source of the phosphor, and the light-emitting device in which the red phosphor composition of the first embodiment and the YAG:Ce-based yellow phosphor are combined can also be emitted in the same manner as the conventional light-emitting device. A strong light beam and a high-color white light white LED. 200944577 The semiconductor light-emitting device of the present embodiment can be excited by near-ultraviolet to blue light, is easy to manufacture, has high luminous intensity, and is chemically stable, and is composed of the phosphor composition of the first embodiment having a large red light-emitting component. It can be a light-emitting device which is stronger than the red light-emitting component of the conventional light-emitting device, has high luminous intensity, is excellent in reliability, and can be manufactured at low cost. (Embodiment 3) Figs. 4 and 5 are schematic diagrams showing the configuration of an illumination and display device as an example of a light-emitting device of the present invention. Fig. 4 shows an illumination and display device comprising at least one semi-conductive light-emitting device 9 which combines the phosphor composition of the first embodiment described above with a light-emitting element. An example of a light-emitting device. Fig. 5 shows an illumination and display device in which at least one light-emitting element 1 is combined with a phosphor layer 3 containing at least the phosphor composition 2 of the first embodiment. The light-emitting element 1 and the phosphor layer 3 can be the same as those of the semiconductor light-emitting device of the second embodiment described above. The operation and effect of the illumination and display device of this configuration are also the same as those of the semiconductor light-emitting device of the second embodiment. Further, in Fig. 4 and Fig. 5, 10 is © output light. Fig. 6 to Fig. 12 show a specific example of an illumination device which is combined with the illumination and display device of the embodiment schematically shown in Figs. 4 and 5 described above. Fig. 6 shows a perspective view of the illumination module 12 having the integrated light-emitting portion 11. Fig. 7 shows a perspective view of the illumination module 12 having the plurality of light-emitting portions 11. Fig. 8 is a perspective view showing a table type illumination device having a light-emitting portion 11 and capable of controlling 〇n_〇ff or a controllable light amount with a switch 13. Fig. 9 is a perspective view showing the illumination of a light source using a lighting module having a screw-in base 14, a reflector 15, and a plurality of light-emitting portions U. 10 is a bottom view of the lighting device of FIG. 9. Fig. 11 is a perspective view of a flat-panel image display device having a light-emitting portion 11. Figure 12 is a perspective view of a line segment type digital display device having a light emitting portion. The illumination and display device of the present embodiment are easy to manufacture, have high luminous intensity, and are chemically stable, and the phosphor composition or the red luminescent component of the first embodiment in which the red luminescent component is used has high luminous intensity and good reliability. Since the semiconductor light-emitting device of the second embodiment can be manufactured at a low cost, it can be a light-emitting intensity of a red light-emitting component of a conventional illumination display device, and the reliability is good, and the illumination display device can be manufactured at low cost. (Fourth Embodiment) Fig. 13 is a partial perspective view showing an end portion of a fluorescent lamp using an example of a light-emitting device of the fluorescent boat composition of the first embodiment. In Fig. π, the glass tube 16 is sealed at both ends by the electron tube 17, and the inside is sealed with a rare gas such as helium, argon or neon, and mercury. The phosphor composition 18 of the embodiment i is applied to the inner surface of the glass tube 16. The electron tube 17 is provided with the filament electrode 2〇 by two wires 19. Both ends of the glass tube 16 are followed by a cap 22 having an electrode terminal 21, and the electrode terminal 21 ❹ is connected to the lead wire 19. The shape, size, wattage of the fluorescent lamp of the present embodiment and the light emitted by the fluorescent lamp Light color, color rendering, and the like are not particularly limited. The shape is not limited to the straight tube of the present embodiment, and may be, for example, a circular shape, a double ring shape, a double subtype, a small shape, a U shape, a light bulb shape, or the like, and a thin tube for liquid crystal backlight. The size is, for example, a shape of 4 to 11 等. The wattage is, for example, several watts to several hundreds of watts, which can be appropriately determined depending on the application. Light colors such as painted light, painted white, white, warm white 32 200944577 and so on. The fluorescent lamp of the present embodiment is formed of a phosphor composition which is easy to manufacture, has high luminous intensity, is chemically stable, and can use a red light-emitting component. Therefore, it is compatible with a conventional fluorescent lamp. Compared with the red luminescent component, the illuminating intensity is stronger, and the fluorescent lamp can be manufactured at low cost. (Fifth Embodiment) Fig. 14 is a cross-sectional view showing a double-insulation structure thin film electroluminescent panel which is an example of a light-emitting device using a phosphor composition of an embodiment. In Fig. 14, the back surface substrate 23 is a substrate for holding a thin film EL panel, and is made of metal, glass, ceramics or the like. The lower electrode 24 is an electrode for applying an alternating voltage of about 1 〇〇 to 3 〇〇 v to the laminated structure of the thick film dielectric 25 / the thin phosphor 26 / the thin film dielectric 27, for example, by printing. A metal electrode or an In-Sn-O transparent electrode formed by a method such as a technique. In addition to the film formation substrate of the thin film phosphor 26, the thick film dielectric body 25 is also used to limit the amount of charge flowing through the thin film phosphor 26 when the AC voltage is applied. For example, the thickness may be 1 〇 (four) to several (10) (4) is called the formation of ceramic materials. Further, the thin film phosphor % is composed of an electroluminescent material which can emit a high-brightness glory by a charge flowing through the working layer, for example, a film formed by a thin film technique such as an electron beam evaporation method or a ruthenium plating method. A thioaluminate phosphor (blue-emitting blue light (Ba, Mg) Al2S4: Eu2+, etc.) or a thiodecanoate light-emitting body (blue light-emitting caGa2s4: ce3+, etc.). In addition to limiting the amount of charge flowing through the film working body 26, the thin film dielectric body 27 can prevent the film colloidal body from reacting with water vapor in the atmosphere to deteriorate, for example, U ^ , 1 ^ by chemical vapor deposition Or a light-transmissive dielectric such as Oxide Oxide or Oxide, which is formed by a thin film technique such as a sputtering method. Further, 33 200944577 The electrode 28 and the lower electrode 24 are paired, and an alternating current voltage of about 1 〇〇 3 〇〇 v is applied to the laminated structure of the thick film dielectric body 25 / the film varnish 26 / the thin film dielectric ZH 27 . The electrode 'for example, a transparent electrode made of In_Sn_〇 or the like is formed on the film dielectric body 27 by a film forming technique such as a vacuum vapor forging method or a bond-killing method. The light wavelength conversion layer 29 converts light emitted from the thin film phosphor 26 and transmitted through the thin film dielectric body 27 and the upper electrode 28 (for example, blue light) into wavelengths such as green light or yellow light or red light. Further, the optical wavelength conversion layer 29 may be provided in a plurality of types, and the surface glass 3 is used for protecting the double insulating structural film EL panel having the above configuration.施加 If a voltage of about 100 to 300 V is applied between the lower electrode 24 and the upper electrode 28 of the thin film EL panel, the laminated structure of the thick film dielectric 25 / the thin film phosphor 26 / the thin film dielectric 27 An alternating voltage of about 1 〇〇 to about 30,000 volts is applied to cause a charge to flow through the thin film phosphor 26 and emit light. This light is transmitted through the light transmissive thin film dielectric body 27 and the upper electrode 28, and the optical wavelength conversion layer 29 is excited to become wavelength-converted light. The wavelength converted light is emitted through the surface glass 30 toward the outside of the panel and can be viewed from outside the panel. In the embodiment of the light-emitting device using the phosphor composition of the first embodiment, at least one of the light-wavelength conversion layers 29 is a phosphor composition of the first embodiment, in particular, a red-light-emitting phosphor composition. Composition. Further, in a preferred embodiment, a blue-light thin film blue phosphor is used as the thin film working body 26, and the optical wavelength conversion layer 29 is excited by a blue-emitting green light-emitting material (for example, 'SrGa2S4: Eu2+ phosphor). The wavelength conversion layer 31 of the green light and the wavelength conversion layer 32 of the phosphor composition of the first embodiment which emits red light as a red light wavelength conversion layer are formed, and further, as shown in FIG. 14 34 200944577 A portion of the blue light emitted by the thin neon blue phosphor shown does not excite the light wavelength conversion layer 29 and is emitted toward the outside of the panel. Further, the electrode structure is formed in a lattice shape which can be driven by a matrix. As shown above, 'if the light-emitting device emits the blue light 33 emitted from the thin film phosphor 26, the wavelength is converted into the green light 34 by the light wavelength conversion layer 29 (31), and the wavelength is converted by the wavelength conversion layer 29 (32). When it is red light 35, the light-emitting device can emit three primary colors of light such as blue, green, and red. Furthermore, since the lighting of each pixel emitting blue, green, and red light can be separately controlled, a display device capable of full color display can be provided. According to a preferred embodiment of the phosphor composition of the first embodiment, the red phosphor composition of the first embodiment is used (it is easy to manufacture, chemically stable, and can be excited by blue light to emit red with good color purity) The light) constitutes a part of the light wavelength conversion layer 29, so that the above-described light-emitting device having high red light-emitting characteristics and high reliability can be provided. As described above, the present invention can provide a phosphor composition containing a composition represented by the above structural formula of aM#2 · bAIN · cShlSU as a main body of a phosphor precursor, which can emit a completely novel warm color system. Light (especially red). Further, the present invention provides a method for producing a nitride phosphor composition which is suitable for mass production, and which can inexpensively produce the nitride phosphor composition of the present invention. Further, by using a highly efficient novel nitride chrome composition, it is possible to provide a light-emitting device which is excellent in luminous intensity of a warm-colored luminescent component (especially red) and which is inexpensive and uses a novel material. Hereinafter, the present invention will be specifically described based on examples. (Example 1) 200944577 As a nitride phosphor composition of the present invention, a phosphor composition having a substantial composition of Sr0 98Eu0.02AlSiN3 was produced by the following method. The phosphor composition in this example was the following compound. . (1) Cerium nitride powder (Sr3N2: purity 99.5%): 25. 〇〇g (2) cerium oxide powder (Eu203: purity 99.9%): 0.93 g (3) cerium nitride powder (Si3N4: purity 99%) : 13.00 g (4) Aluminum nitride powder (A1N: purity: 99.9%): 10.78 g Using a glove box, the phosphor raw materials were weighed in a nitrogen atmosphere, and then thoroughly mixed in a mortar. Thereafter, the mixed powder was placed in an aluminum crucible field and placed in a predetermined position in an ambient atmosphere furnace, and heated in a nitrogen atmosphere of 1600 ° C (97% nitrogen 3% hydrogen) for 2 hours. For simplification, post-processing such as pulverization, classification, and cleaning is omitted. Hereinafter, the properties of the fired product (SrAlSiN3: Eu2+ phosphor composition) obtained by the above production method will be described. The above phosphor composition is bright orange. Fig. 15 is a view showing the luminescence spectrum (254 η η excitation) 37 and the excitation spectrum 36 of the phosphor composition of the present embodiment obtained by the above production method. Fig. 15 is a view showing the above-mentioned fired material having a broad wavelength range of 220 to 600 nm in a red phosphor having a peak of luminescence at a wavelength of 63 5 nm, that is, 'in the ultraviolet to near ultraviolet to violet ~ cyan to green to yellow to yellow. ~ Orange light is excited. Further, the chromaticity (x, y) of the luminescence in the CIE chromaticity coordinates is χ = 〇 612, y = 379 379. As a result of semi-quantitative analysis of the constituent metal elements of the fired product by the fluorescent X-ray analysis method, the fired product is a compound mainly composed of Sr, EU, A1, and Si. These results show that the composition represented by 36 200944577 (SrQ.98EuG_〇2)AlSiN3 can be manufactured by the manufacturing method of the present embodiment, and can be manufactured.

SrAlSiN3: Eu2+ phosphor. . For ease of reference, Fig. 16 shows an X-ray diffraction pattern of the phosphor composition of this embodiment. As shown in FIG. 16, the phosphor composition of the present embodiment is in the diffraction evaluation by X-ray diffraction method using at least Cu-Ko: line at normal temperature and normal pressure, at the diffraction angle (20). In the vicinity of 28 to 370, unlike the phosphorous raw material such as an alkaline earth metal oxide or a tantalum nitride or aluminum nitride, or a diffraction peak of a conventional Sr2Si5N8 compound, it is a crystalline fluorescent fluorene having a plurality of strong diffraction peaks. body. Further, in the present embodiment, it is considered that a compound represented by a chemical formula (SrQ.MEuo.GjAlSiN3 or a structural formula represented by (Sro^Euo.UAlSiN3) or a similar structural formula is formed according to the following chemical reaction formula. Reaction formula 1) 1.96Sr3N2+0.06Eu2O3+2Si3N4+6AlN+0.04N2+0.l8H2 + 6Sr0.98Eu0.02AlSiN3+〇18H2〇The use of the production method of the present example, even if chemical instability is used in the atmosphere In the case where the operation is difficult and the price is small, the SrAlSiN3:Eu2+ phosphor can be produced. In addition, this embodiment describes the case of a nitride phosphor composition containing Eu2+ ions as the luminescent center ion, but also A phosphor composition containing a luminescent center ion other than Eu ions (for example, Ce3 + ion) can be produced in the same manner. (Example 2) 37 200944577 As a nitride phosphor composition of the present invention, the following In the production method of Example 1, a phosphor composition having a substantial composition of Sr〇98Eu〇〇2AlSiN3 was produced. In the present example, the following compounds were used as a phosphor raw material. (1) Barium carbonate powder (Sr3C03: purity 99.9%): 2.894g (2) Cerium oxide powder (Eu203: purity 99.9%): 0.070g (3) Cerium nitride powder (Si3N4: purity 99%): 〇.988g (4) Aluminum nitride powder (A1N: Purity: 99.9%): 0.820 g Further, the following solid carbon was used as the above-mentioned cerium carbonate and the above-mentioned reducing agent of cerium oxide (adding a reducing agent). (5) Carbon (graphite) powder (C: purity: 99.9%): 0.240 g First The phosphor raw materials and the added reducing agent are thoroughly mixed in an automatic mortar. Thereafter, the mixed powder is placed in an aluminum crucible, and placed in a predetermined position in an ambient atmosphere furnace at 16 Torr. The mixed gas (97% nitrogen and 3% hydrogen) was heated in an atmosphere for 2 hours. For the sake of simplification, the post-treatment such as pulverization and classification 'cleaning is omitted. Hereinafter, the fired product obtained by the above production method (STAlSiN3: Eu2+ phosphor composition) will be described. The phosphor composition is orange. Fig. 17 shows the luminescence spectrum (254ηπ1 excitation) 37 and the excitation spectrum 36 of the phosphor composition of the present embodiment obtained by the above production method. The red phosphor having a luminescent peak near the wavelength of 640 nm can be 220 600nm wide wavelength range of light, that is, excited by ultraviolet ~ near ultraviolet ~ purple ~ cyan ~ green ~ yellow ~ orange light. Also 'fluorescence X-ray analysis of the above-mentioned burnt composition of the metal element 200944577 As a result of the semi-quantitative analysis evaluation, the fired product was a compound mainly composed of a heart, A1', and Si. These results show that the composition represented by (Sro^Euo.JAlSiN3) can be manufactured by the manufacturing method of the present embodiment, and the SrAlSiN3:Eu2+ phosphor can be manufactured. For convenience of reference, FIG. 18 shows the fluorescence of this embodiment. The X-ray diffraction pattern of the bulk composition. As shown in Fig. 18, the phosphor composition of the present embodiment is diffracted by a calender diffraction method using at least a Cu-Κα line at normal temperature and pressure. In the evaluation, in the vicinity of the diffraction angle (2 illusion in the vicinity of 30 to 37 ,, different from the diffraction peak of the phosphorous material such as the metal oxide or the tantalum nitride or the aluminum nitride or the conventional compound, In addition, in the present embodiment, it is considered that the alkaline earth metal oxide Sr0 and the lanthanide oxide Eu 〇 are substantially reduced by carbon c according to the following chemical reaction formula. And a reaction of cerium nitride to form a compound represented by a chemical formula (Sr 〇 98 EU ( ) ^ octagonal oxime, or a composition represented by a structural formula of Sro.wEuo.oJAlSiN3 or a similar structural formula. Reaction formula 2) 0.98SrCO3 + 0.01Eu2O3 + (l/3) Si3N4+AlN+C + (l/3)N2+0.0 lH2^Sr〇.9 8Eu〇.〇2AlSiN3+〇.98C〇2 t+CO t+0.01H2O t Thus, using the manufacturing method of the present embodiment, it is possible to completely eliminate the use of Sr metal or Sr3N2 which is difficult to operate in the atmosphere and which is difficult to operate in the atmosphere. The SrAlSiN3:Eu2+ phosphor is produced by using cesium carbonate which is easy and inexpensive to operate as a supply source of an alkaline earth metal. Hereinafter, the description of the SrAlSiN3:Eu2+ phosphor composition 39 200944577 of the second embodiment will be changed. The substitution ratio (Eu substitution amount: Eu / (Sr + Eu) x 100 (atomic %)). Fig. 19 is an emission spectrum of a different Eu substitution amount of SrAlSiN3:Eu2+ phosphor under ultraviolet light excitation of 254 nm. As can be understood from Fig. 19, the luminescence peak wavelength is gradually shifted from about 615 nm (Eu substitution amount: 100 atom%) to about 750 nm on the long wavelength side (Eu substitution amount: 100 atom%) as the Eu substitution amount increases. In addition, as the Eu substitution amount increases, the luminescence peak intensity gradually becomes stronger, and the Eu substitution amount is 1 to 3 atom%, and the maximum value is gradually decreased. Further, even in the ultraviolet range to the near ultraviolet range of 250 to 550 nm. ~ purple ~ blue ~ green light excitation, hair The peak position of the optical spectrum is also hardly changed. Fig. 20 is a graph showing the relationship between the Eu substitution amount of the SrAlSiN3:Eu2 + phosphor composition to the alkaline earth metal element (Sr) and the luminescence peak wavelength. The luminescence peak wavelength is 610 to 660 nm, preferably 620 to 650 nm. From the above, it can be understood from the figure that the preferred Eu substitution amount of the red phosphor used as the light-emitting device is 〇·丨 or more, less than 7 atom%. Further, Fig. 21 is a graph showing the relationship between the amount of Eu substitution of the alkaline earth metal element (Sr) and the height of the luminescence peak (luminescence intensity) of the composition of the SrAlSiN3:Eu2+ phosphor. Further, even if the peak wavelength of the excitation light source changes between the wavelength range of 250 to 500 nm, the same tendency is exhibited. As can be seen from Fig. 21, in terms of luminescent color, the Eu substitution amount is preferably 0.3 atom% or more, less than 6 atom%, more preferably t atom% or more, and less than 4 atom 〇/〇. In other words, as can be seen from FIG. 20 and FIG. 21, the preferred Eu substitution amount of the red phosphor used as the light-emitting device is 〇丨 or more, and less than 7 atoms 200944577 ° / 〇 ' is preferably 1 atom% or more. , less than 4 atoms 〇 / 0. Further, the present embodiment describes a case of a nitride phosphor composition containing Eu2+ ions as an emission center ion, but a phosphor composition containing an emission center ion other than Eu2+ ions may be produced in the same manner. (Example 3) As the nitride phosphor composition of the present invention, a phosphor composition having a substantial composition of Sr〇.98Ce〇.2AlSiN3 was produced by the following method. The following compounds were used as the phosphor raw material in this example. &amp; (1) Barium carbonate powder (Sr3C03: purity 99.9%): 2.894 g (2) Yttrium oxide powder (ce〇2: purity: 99.99%): 〇.〇69g (3) Nitriding dream powder (Si3N4: purity 99%) 〇.988g (4) Aluminum nitride powder (A1N: purity: 99.9%): 0.820 g Further, the following solid carbon was used as the reducing agent for the above-mentioned cerium oxide. (5) Carbon (graphite) powder (c: purity: 99.9%): 0.240 g A phosphor composition was produced in the same manner as in Example 2 using these phosphor materials. The following describes the characteristics of the fired product (SrAlSiN3: Ce3 + phosphor composition) obtained by the above production method. The above phosphor composition is white with a blue-green color. Fig. 22 is a view showing an emission spectrum (254 nm excitation) 37 and an excitation spectrum 36 of the phosphor composition of the present embodiment obtained by the above-described production method. Fig. 22 is a blue-green phosphor having an emission peak at a wavelength of 504 nm in the above-mentioned fired product. It can be excited by a wide wavelength range of light, that is, ultraviolet ~ near ultraviolet ~ violet ~ blue light. 200944577 These results show that the manufacturing method of the present embodiment can produce a composition represented by SrAlSiN3:Ce3 + . In the present embodiment, it is considered that the same chemical reaction formula as in Example 2 substantially reduces the alkaline earth metal oxide SrO and the lanthanide oxide Ce〇2 by carbon C, and reacts with nitrogen and tantalum nitride. A composition represented by a structural formula close to the chemical formula (SrQ.98Ce〇.()2) AlSiN3 was produced. As described above, by using the production method of the present embodiment, it is possible to use a commercially inexpensive and inexpensive strontium carbonate as a supply source of an alkaline earth metal without using a Sr metal or Sr3N2 which is chemically unstable and which is difficult to operate in the atmosphere and expensive. A SrAlSiN3:Ce3+ phosphor composition was produced. (Example 4) As a nitride fluorescent iridium composition of the present invention, a mortar composition having a substantial composition of Ca〇.98Eu〇.〇2AlSiN3 was produced by the following method. In the present embodiment, a phosphor composition was produced by the same production method and firing conditions as in Example 2 except that the following materials were used as the phosphor raw material and the addition of the reducing agent (carbon powder). (1) Calcium carbonate powder (CaC03: purity: 99.9%): 1.962 g (2) Cerium oxide powder (Eu203: purity: 99.9%): 0.070 g (3) Barium nitride powder (Si3N4: purity: 99%): 〇.988g (4) Aluminum nitride powder (A1N: purity: 99.9%): 0.820 g (5) Carbon (graphite) powder (C: purity: 99.9%): 240240 g or less, the calcined product obtained by the above production method (CaAlSiN3) : Characteristics of Eu2+ phosphor composition). The above phosphor composition is orange. Fig. 23 shows the above-mentioned production method 200944577. The luminescence spectrum (254 nm excitation) 37 and the excitation spectrum 36 of the phosphor composition of this example were obtained. Fig. 23 shows that the above-mentioned fired product is a red-orange phosphor having a luminescence peak at a wavelength of about 6 〇〇 nm, and can be light of a wide wavelength range of 22 〇 to 55 〇 nm, that is, ultraviolet to near ultraviolet to purple to blue. ~ Green light is inspired. Also, the illuminance chromaticity (乂, 7) in the CIE chromaticity coordinates is χ = 〇 496, y = 471 471. Moreover, as a result of semi-quantitative analysis and evaluation of the constituent metal elements of the fired product by the fluorescent X-ray analysis method, the fired product is a compound β composed mainly of Ca, Eu, A1, and Si. As a result, it was revealed that the manufacturing method of the present embodiment can produce a composition represented by (CaQ, 98EuQ, G2)AlSiN3, and a CaAlSiN3:Eu2+ phosphor can be produced. Further, in the present embodiment, it is considered that the alkaline earth metal oxide Ca〇 and the lanthanide oxide Eu〇 are substantially reduced by carbon C in the following chemical reaction formula, and reacted with nitrogen and tantalum nitride to generate a near chemical formula ( CaG.98Ce().()2) A composition represented by the structural formula of AlSiN3, or a composition represented by a structural formula of (CaQ 98CeQ Q2) AlsiN3. (Chemical reaction formula 3) 〇.98CaC03+0.01Eu2〇3+(l/3)Si3N4+AlN+C+(l/3)N2+〇.〇lH2~&gt;Ca〇, 98Eu〇〇2AlSiN3 + 0.98C02 t+ CO t+0.01H20 t Thus, by using the production method of the present embodiment, it is possible to use calcium carbonate or Ca3N2 which is difficult to operate in the atmosphere and which is difficult to operate in the atmosphere, and to use an easy-to-use and inexpensive calcium carbonate as an alkaline earth metal. The source is supplied to produce a CaAlSiN3:Eu2+ phosphor. In the present embodiment, the case of the 43 200944577 nitride phosphor composition containing the Eu2+ ion as the luminescent center ion is described. However, the fluorescence of the luminescent center ion (for example, ce3+) other than the Eu2 ion can be produced in the same manner. Body composition. Further, this embodiment describes the use of carbon powder as a method of producing a reducing agent, but a phosphor material such as a nitride (Ca3N2), a tantalum nitride (Si3N4), or an aluminum nitride (AIN) using an alkaline earth metal element (calcium). A CaAlSiN3:Eu2+ phosphor can also be produced in the same manner as in Example 1 using an Eu raw material (Eu2〇3) or lanthanum nitride (EuN) or a metal Eu, without using a reducing agent. 'By appropriate selection of Eu2+ addition amount or manufacturing conditions,

The CaAlSiN3:Eu2+ phosphor has red light having an emission peak in a wavelength region of 61 〇 nm or more and less than 650 nm, and the CaAlSiN3:Eu2+ phosphor may also be a red phosphor. (Examples 5 to 8) As the phosphor composition of Examples 5 to 8 of the present invention, a nitride having a structural formula of SrAlSiNs · a and a structural formula of SisN4 as a phosphor precursor was produced by the following method. Body composition. In the following 'as an example, the phosphor composition of a_5, 〇.75, 1-2, for each a', is composed of 2SrAlSiN3 · Si3N4, 4SrAlSiN3 · 3Si3N4, SrAlSiN3 · Si3N4, SrAlSiN3 · 2Si3N4 The production method and characteristics of the phosphor composition which is a phosphor precursor and in which 2 atom% of Sr is substituted with Eu will be described. These are used at the time of manufacture to use the same phosphor raw materials and addition reducing agents as described in Example 2. A phosphor composition was produced and evaluated in the same manner and under the same conditions as in Example 2 except that the mixing ratio was set to the weight ratio of 200944577 shown in Table 1. Table 1 Structural formula SrC03 EU2O3 S13N4 AIN C Example 5 2 (Sr〇.98Eu〇.〇2) AlSiN3 · Si3N4 5.787g 0.141g 4.942g 1.639g 0.480g Example 6 4(Sr〇.98Eu〇.〇2) AlSiN3 · 3S13N4 11.574g 0.282g 12.849g 3.279g 0.961g Example 7 (Sr〇.98Eu〇.〇2) AlSiN3 · S13N4 2.894g 0.070g 3.953g 0.820g 0.240g Example 8 (Sr〇, 98Eu〇, 〇 2) AlSiN3 · 2S13N4 2.894g 0.070g 6.919g 0.820g 0.240g _ The characteristics of the obtained phosphor composition are demonstrated below. The above phosphor compositions are all orange. Figs. 24 to 27 are representative examples showing the luminescence spectrum (254 nm excitation) 37 and the excitation spectrum 36 of the phosphor compositions of Examples 5 to 8 obtained by the above production method. 24 to 27 show that the above-mentioned fired materials are red phosphors having an emission peak near a wavelength of 640 nm, and can be light of a wide wavelength range of 220 to 600 nm, that is, ultraviolet to near ultraviolet to violet to blue to green to yellow to yellow. ~ Orange light is excited. Further, the detailed data is omitted. As described in the fifth to eighth embodiments, not only the phosphor composition in which the Eu2+ ion is added to the composition of Si3N4 is excessively added to the SrAlSiN3Q, but the composition of Sr2Si5N8, SrSiN2, and SrSi7N10 is excessively added to the SrAlSiN3. A composition in which Eu2+ ions are added, that is, a composition represented by a structural formula such as SrAlSiN3 · a'Sr2Si5N8 or SrAlSiN3. a'SrSiN2 is used as a main body of the phosphor precursor, and Eu2+ ions are added as an illuminating center. The nitride-based phosphor composition also has the same light-emitting characteristics as the phosphor composition in which Eu2 + ions are added to the composition in which Si3N4 is excessively added. Here, the above a' may be a value satisfying 0Sa'S2, preferably OSa'Sl, specifically, a value of 0, 0.25, 0.33, 0.5, 0.67, 0.75, 45 200944577 1, 1.15, 2, and the like. Further, the above a' may be a value satisfying 0.25 Sa'S2, preferably 0.25 Sa'Sl. Excess Si3N4, Sr2Si5N8, and SrSi7N1() are present in the phosphor composition to coexist with the above-mentioned SrAlSiN3, or to form a novel compound, for example, Sr2Al2Si5N10, Sr4Al4Si13N24, SrAlSi4N7, SrAlSi7Nn'Sr4Al2Si7N14, Sr3AlSi6Nn, Sr5AlSinN19, Sr3Al2Si3N8, Sr2AlSi2N5, Sr3AlSi3N7 Sr3Al2Si9N16, Sr2AlSi8N13, Sr3AlSi15N23, etc., whether or not the novel compound has a function as a phosphor precursor has not been confirmed, and it is necessary to carry out careful inspection by various crystal structure analysis methods in the future, but both have great possibilities. (Examples 9 to 25) As a phosphor composition of Examples 9 to 25 of the present invention, a composition represented by a structural formula having a substantial composition of aSr3N2 · bAIN · cSi3N4 was produced as a phosphor precursor by the following method. Body composition. Hereinafter, as an example, the values of a, b, and c are each shown in Table 2.

The phosphor composition in which 2 atom% of Sr is substituted with Eu is shown in Table 2, Table 3, and Table 6, and the production method and characteristics thereof will be described. The fluorescent ® body compositions of Tables 2, 3, and 6 have slightly different expression methods, but represent phosphor compositions of the same composition ratio. Table 2 abc Phosphor composition Example 9 2 3 2 2 (Sr〇.98Eu〇.〇2) 3N2 · 3A1N · 2S13N4 Example 10 1 1 1 (Sr〇.98Eu〇.〇2) 3N2 · AIN · SI3N4 Example 11 4 3 4 4 (Sr〇.98Eu〇.〇2) 3N2 · 3A1N · 4Si3N4 Example 12 1 2 1 (Sr〇.9gEu〇.〇2) 3N2 · 2A1N · S13N4 Example 13 1 1 2 (Sr〇.98Eu〇.〇2) 3N2 · AIN · 2S "N4 Example 14 5 3 11 5(Sr〇.98En〇.〇2) 3N2 · 3AIN * IIS13N4 Example 15 7 3 16 7(Sr0.98Eu 〇.02)3N2 · 3A1N · 16Si3N4 46 200944577 Example 16 4 6 7 4(Sr〇.98Eu〇.〇2)3N2 · 6A1N · 7Si〗N4 Example 17 2 3 8 2 (Sr〇, 98Eu〇,〇 2) 3N2 · 3A1N · 8S13N4 Example 18 1 1 5 (Sr〇.98Eu〇.〇2) 3N2 * AIN · 5SI3N4 Example 19 4 3 22 4(Sr0.98Eu〇.02)3N2 · 3A1N · 22Si3N4 Example 20 1 2 3 (Sr〇.9gEu〇.〇2) 3N2 · 2AIN · 3S13N4 Example 21 1 3 10 (Sr〇.98Eu〇.〇2) 3N2 · 3A1N · 10Si3N4 Example 22 1 2 3 (Sr〇. 98Eu〇.〇2)3N2 · 2AIN · 3S13N4 Example 23 5 6 14 5(Sr〇.98Eu〇.〇2)3N2 · 6AIN · I4S13N4 Example 24 7 6 19 7(Sr〇.98Eu〇. 2) 3N2 · 6A1N · I9S13N4 Example 25 9 6 24 9 (Sr〇.98Eu〇.〇2) 3N2 · 6A1N · 24S13N4 Table 3 Phosphor composition Example 9 (Sr〇.98Eu〇.〇2) 3AlSiN3 (Sr〇_9sEu〇.〇2) SiN2 Example 10 (Sr〇.98Eu〇,〇2)3AlSiN3 · 2(Sr〇.98Eu〇,〇2)SiN2 Example 11 (Sr〇, 98Eu〇.〇 2) 3AlSiN3 · 3 (Sr〇.98Eu〇.〇2) SiN2 Example 12 2 (Sr〇.98Eu〇,〇2)3AlSiN3 · (Sr〇.98Eu〇.〇2)SiN2 Example 13 (Sr〇. 98Eu〇.〇2)3AlSiN3 · (Sra98Eu〇,〇2)2Si5N8 Example 14 (Sr〇.98Eu〇.〇2)3AlSiN3 · 2(Sr〇.98Eu〇.〇2) 2Si5N8 Example 15 (Sr〇. 9sEu〇.〇2)3AlSiN3 · 3(Sr〇.98Eu〇.〇2) 2Si5N8 Example 16 2(Sr〇.98Eu〇_〇2)3AlSiN3 · (Sr〇.98Eu〇.〇2) 2Si5N8 Example 17 (Sr〇.98Eu〇.〇2)3AlSiN3 · (Sr〇.98Eu〇.〇2) 2Si7Ni〇Example 18 (Sr〇_98Eu〇.〇2)3AlSiN3 · 2(Sr〇.98Eu〇_〇2) 2Si7Ni〇Example 19 (Sr〇.98Eu〇.〇2) 3AlSiN3 · 3(Sra98Eu〇.〇2) 2Si7Ni〇Example 20 2(Sr〇.98Eu〇.〇2)3AlSiN3 · (Sr〇.98Eu〇. 〇 2) 2Si7Ni〇 Example 21 (Sr〇.98Eu , 〇 2) AlSiN3 · 3S13N4 Example 22 (Sr〇.9gEu〇.〇2)Al2 · SI9N16 Example 23 (Sr〇.98Eu〇.〇2)Al2 · SI14N24 Example 24 (Sr〇.98Eu〇,〇 2) Al2 · S119N32 Example 25 (Sr〇.9sEu〇.〇2) Al2 · SI249N40 Further, as Comparative Examples 1 to 5, the values of a, b, and c are the values shown in Table 4, and 2 in Sr. The phosphor composition in which the atomic % was replaced with Eu is shown in Table 4, Table 5, and Table 6, and was produced and evaluated in the same manner as described above. The phosphor compositions of Tables 4, 5 and 6 are slightly different, but each represents a phosphor composition of the same composition ratio. 47 200944577 Table 4 abc Phosphor composition comparison example 1 1 6 1 (Sr〇.98Eu〇.〇2)N2 * 6A1N · S13N4 Comparative example 2 1 9 1 (Sr〇.98Eu〇.〇2)N2 · 9A1N · S13N4 Comparative Example 3 2 9 2 2 (Sr〇, 98Eu〇.〇2) N2 · 9A1N · 2S13N4 Comparative Example 4 1 6 4 (Sr〇.98Eu〇.〇2)N2 · 6A1N · 4S13N4 Comparative Example 5 2 0 5 2(Sr〇.98Eu〇.〇2)N2 · 5SI3N4 Table 5 abc Phosphor composition Comparative Example 1 1 6 1 (Sr〇.98Eu〇.〇2)AlSiN3 · AIN Comparative Example 2 1 9 1 (Sr 〇.98Eu〇_〇2)AlSiN3 _ 2A1N Comparative Example 3 2 9 2 2(Sr〇.98Eu〇.〇2)AlSiN3 · AIN Comparative Example 4 1 6 4 (Sr〇.98Eu〇.〇2)Al2Si4N8 Comparative Example 5 2 0 5 (Sr〇.98Ell〇_〇2) 2Si5N8 In the production of these, the same phosphor raw materials and addition reducing agents as described in Example 2 were used. The phosphor composition was produced and evaluated in the same manner and under the same conditions as in Example 2 except that the mixing weight ratio was changed to the weight ratio shown in Table 6. Table 6 Structural formula SrC〇3 Eu2〇3 S13N4 AIN C Example 9 (Sr〇.98Eu〇.〇2)3AlSi2N5 5.787g 0.141g 1.977g 0.820g 0.480g Example l〇(Sr〇.98Eu〇.〇2) 3AlSi3N7 8.681g 0.211g 2.965g 0.820g 0.721g Example 11 (Sr〇.98Eu〇.〇2)3AlSi4N9 11.574g 0.282g 3.953g 0.820g 0.96 lg Example 12 (Sr〇'98Eu〇.〇2)3Al2Si3N8 8.681 g 0.21 lg 2.965g 1.639g 0.721g Example 13 (Sr〇, 98Eu〇.〇2) 3AlSi6Ni 1 8.681g 0.21 lg 5.930g 0.820g 0.721g Example 14 (Sr〇.98Eu〇.〇2)5AlSillNi9 14.468g 0.352g 10.873⁄4 0.820g 1.201g Example 15 (Sr〇.9gEu〇.〇2)7AlSii6N27 20.255g 0.493g 15.814g 0.820g 1.682g Example 16 (Sr〇.9sEu〇.〇2)4Al2Si7Ni4 11.574g 0.282g 6.919 g 1.639 g 0.961 g Example 17 (Sr〇.9gEu〇.〇2) 2AlSi8Ni3 5.787g 0.141g 7.907g 0.820g 0.480g Example 18 (Sr〇.98Eu〇.〇2)3AlSii5N23 8.681g 0.21 lg 14.825g 0.820 g 0.72 lg 48 200944577 Example 19 (Sr〇.98Eu〇.〇2) 4AlSi22N33 11.574g 0.282g 21.744g 0.820g 0.961g Example 20 (Sr〇.98Eu〇.〇2)3Al2Sl9Ni6 8.681g 0.21 lg 8.895g 1.639g 721.721g Example 21 (Sr〇.98Eu〇.〇2) AlSii〇Ni5 2.894g 0.070g 9.884g 0.820g 0.240g Example 22 (Sr〇.98Eu〇.〇2)3Al2Si9Ni6 8.681g 0.21 lg 8.895g 1.639 g 0.72 lg Example 23 (Sr〇, 9sEu〇.〇2)5Al2Sii4N24 14.468g 0.352g 13.837g 1.639g 1.201g Example 24 (Sr〇.9sEu〇.〇2)7Al2Sii9N32 20.255g 0.493g 18.779g 1.639g 1.682 g Example 25 (Sr〇.98Eu〇.〇2) 9Al2Si24N4〇26.042g 0.663g 23.721g l_639g 2.162g Comparative Example 1 (Sr〇.9sEu〇.〇2)Al2SiN4 2.894g 0.070g 0.988g 1.639g 0.240g Comparison Example 2 (Sr〇.98Eu〇, 〇2) Al2SiN5 2.894g 0.070g 0.988g 2.459g 0.240g Comparative Example 3 (Sr〇.98Eu〇.〇2) 2Al3Si2N7 5.787g 0.141g 1.977g 2.459g 0.480g Comparative Example 4 (Sr〇.9gEu〇.〇2)Al2Si4N8 2.894g 0.070g 3.953g 1.639g 0.240g Comparative Example 5 (Sr〇.98Eu〇.〇2) 2Si5N8 14.468g 0.352g 12.355g 〇g 1.2〇lg 〇 Below, simple The characteristics of the resulting phosphor composition are illustrated. The phosphor compositions of the above examples were all orange. The luminescence spectrum and the excitation spectrum were omitted, but any of the phosphor compositions of Examples 9 to 25 was the same as the phosphor of Example 1 or Example 2 shown in Fig. 15 or Fig. 17 at a wavelength of 620 〜 A red phosphor having a luminescent peak near 640 nm can be excited by a wide wavelength range of light of 220 to 600 nm, that is, ultraviolet ~ near ultraviolet ~ violet ~ cyan ~ green ~ yellow ~ orange light. For the sake of reference, the relative values of the luminescence peak wavelength and the luminescence peak height of the phosphor compositions of Examples 9 to 25 and Comparative Examples 1 to 5 are summarized in Table 7. Table 7 Luminescence peak wavelength (nm) Relative luminescence peak height (arbitrary unit) Example 9 639 39 Example 10 626 38 Example 11 629 38 Example 12 639 40 Example 13 625 97 Example 14 630 100 Example 15 628 86 Example 16 628 92 49 200944577 Example 17 631 73 Example 18 628 67 Example 19 628 66 Example 20 626 54 Example 21 638 55 Example 22 625 60 Example 23 630 67 Example 24 625 82 Example 25 628 92 Comparative Example 1 490 69 Comparative Example 2 484 79 Comparative Example 3 487 99 Comparative Example 4 594 12 Comparative Example 5 621 104

Further, Fig. 28 is a ternary composition diagram showing the composition range of the phosphor composition of the present invention. In the luminescent color of the phosphor compositions of Examples 1, 2, 5, and 5 to 25 and the phosphor compositions of Comparative Examples 1 to 5 in Fig. 28, red is indicated by ?, and colors other than red are indicated by Δ. . In Fig. 28, a conventional red light-emitting Sr2Si5N8:Eu2+ nitride tellurite phosphor is shown. Further, Fig. 28 shows a Si*3A12N5:Eu2+ glaze composition in which the chemical properties are not stabilized in the atmosphere and the luminescent properties are not evaluated. Further, when the production conditions of the second embodiment are used, the composition having a high ratio of SqN2 in the composition diagram of Fig. 28 will be dazzled to make the production difficult, and there is a tendency for chemical instability in the atmosphere. From Fig. 28 and Table 7, it can be understood that the present invention is a phosphor composition different from a conventional nitride bismuth silicate phosphor (e.g., SnALNyEu2), and the phosphor composition of the present invention is aSrsN2. · The structure represented by bAIN · cShN4 is the main body of the phosphor precursor, and Eu2+ ions are used as the activator', and a, b, and c respectively satisfy 0.2$a/(a+b)S0.95, 50 200944577 0.05Sb / (b + c) S0.8, 0.4 $ c / (c + a) S0.95 value, and become a red phosphor. Further, in comparison with the conventional nitride phthalate phosphor, the composition of the phosphor represented by the composition is such that a, b, and c satisfy 0.2Sa/(a+b)S0.6, 0.3, respectively. The value of $b/(b+c)S0.8, 0.4$c/(c+a)g〇.8 is 'especially' for a, b, and c respectively satisfying 0.2Sa/〇+b:)S0. 3. A value of 0.6Sb/(b+c)S0.8, 0.4gc/(c+a)S0.6, and a phosphor composition composition represented by the SrA1SiN3 structural formula containing Eu2+ as an activator.

Further, in the examples 9 to 25, the case where the phosphor composition is produced in the same manner as the production method of the second embodiment will be described. However, the same production method as in the first embodiment in which the raw material of the compound is directly reacted with each other can be obtained. the result of. Further, 'Examples 9 to 25 show the case where the element Μ is Sr, but the same result can be obtained when M is Ca' or Ca or Sr is the main body of ruthenium, and a part of the above M is substituted with Ba, Mg or Zn. . The following describes other embodiments of the present invention. The characteristics of the phosphors activated by Eu2+ were examined in detail, and it was found that the phosphors shown in the following (丨) to (3) were excited not only by the violet light-emitting elements having a luminescence peak in the near-ultraviolet to violet region of wavelengths of 360 nm or more and less than 420 nm. The quantum efficiency is good at a wavelength of 420 nm or more and less than 500 nm. In particular, a blue light-emitting element having a light-emitting peak in a blue region having a wavelength of 440 nm or more and less than 500 nm has a high internal quantum efficiency and is excellent, and the internal quantum efficiency thereof is 90~1〇〇〇/0. 51 200944577 (1) Alkaline earth metal orthosilicate type, thiophthalate type, aluminate type and nitride type (nitride 活化 activated by Eu2+ and having a luminescence peak in a wavelength range of 500 nm to less than 560 nm A green phosphor such as an acid salt or a sialon system, for example, a phosphor such as (Ba, Sr) 2Si04: Eu2+, SrGa2S4: Eu2+ &gt; SrAl204: Eu2+, BaSiN2: Eu2+, SruAhSisN^Ei^. (2) Alkaline earth metal orthosilicates, thiosilicates, and nitrides (nitride tellurite or sialon) having an emission peak in a wavelength region of 560 nm to less than 600 nm activated by Eu2+ a yellow phosphor such as (Sr, Ba)2Si04:Eu2+, CaGa2S4:Eu2+, 〇〇.75(Ca〇.9Eu〇.i)0 · 2.25A1N · 3.25Si3N4:Eu2+ ,

Ca15Al3Si9N16: Eu2+, (Sr, Ca) 2Si04: Eu2+, CaSiAl203N2: Eu2+,

CaSi6A10N9: phosphor such as Eu2+. (3) A red phosphor which is activated by Eu2+ and has a luminescence peak (nitride bismuth hydride or nitride amide citrate) in a wavelength range of from 600 nm to less than 660 nm, for example, Sr2Si5N8 : Eu2+, SrSiN2: Eu2+, SrAlSiN3: Eu2+, CaAlSiN3: Eu2+, Sr2Si4A10N7: Eu2+ and the like. The excitation spectrum of the phosphors is in a region shorter than the wavelength of the light emitted by the blue light-emitting element, and the ultraviolet-violet-purple region having a wavelength of 360 nm or more and less than 420 nm has an excitation spectrum. The external quantum efficiency under excitation of the illuminating element is not necessarily high. The internal quantum efficiency is unexpectedly higher than the excitation spectrum, which is 70% or more, and particularly good is 90 to 100%. As an example, Fig. 29 shows the internal quantum efficiency 40, the external quantum efficiency, and the excitation spectrum 42 of the SrSiN2:Eu2+ red phosphor. Further, for ease of reference, 52 200944577 also shows the luminescence spectrum 43 of the glare. In Fig. 3〇 to Fig. 35, SrAisiN3:Eu2+ red phosphor (Fig. 3〇), Sr2lSi5N8: Eu2+ red phosphor (Fig. 3i) (Ba

Sr) 2Si〇4: heart green phosphor (Fig. 32), (Sr, Ba) 2si〇4: Eu2+ yellow fluorescent iridium (Fig. 33), (Sr, Ca) 2Si 〇 4: Eu2+ yellow glory (Fig. 、, 〇.75(Ca〇9EuG·^ 2·25Α1Ν · u5Si3N4: Eu2+ yellow camping body (Fig. 35)+, which is represented in the same manner as Fig. 29. For example, as shown in Fig. 33,

Eu2+ activated soil test type full shield function metal orthosilicate phosphoric acid (Sr, ❹ ❹

Ba) 2Si〇4: The external quantum efficiency of the Eu1 color laborer is about 75% under the excitation of the blue light-emitting π element with a fine wavelength, about 67% at the wavelength "On" and about 6 at the wavelength 470nm.内部%. The internal quantum efficiency is in the blue region of the wavelength Young (4) M and less than 5 mm, which is 85% or more from the excitation spectrum, and is particularly good, about 94%. In addition to the phosphor, the mortar which is activated by Eu2+ or Ce3+ has the same characteristics. As an example, Fig. 36 to Fig. ", /, (Y, Gd) 3Al5012: Ce3 + yellow Laoguang 艎 (Fig. 36), BaMgAiiQ〇”Eu2+ blue phosphor (Fig. 37), Sr4Al14〇25: Eu2 + blue-green phosphor (Fig. %), (Sr, Ba) 10 (P〇4) 6Cl2: Eu2+ blue glory The body (Fig. 39) is also expressed in the same way as Fig. μ. From Fig. 29~®36, it can be seen that the dependence of the external quantum efficiency of each glory on the excitation wavelength is similar to that of the excitation optical error. The peak is a long-wavelength photoexcited 胄'example>, and under the excitation of the blue light-emitting element, the external quantum efficiency is not high, but the internal quantum efficiency is The blue light-emitting element exhibits a high value under excitation. Further, it can be seen from FIGS. 29 to 35 and FIGS. 37 to 39 that each of the phosphors is excited by the ultraviolet light-emitting element, 53 200944577, and the internal quantum efficiency is high, and the good is good. As a result of further investigation, it was found that the phosphors other than the above (1) to (3) have the internal quantum efficiency high under the excitation of the above-mentioned purple light-emitting elements (4) and (5). a cyan or green phosphor that is activated by Eu or Ce and has a luminescence peak in the wavelength range of 49 〇 nm to 550 nm (nitride sulphate system, sialon system, etc.), for example, Sr2Si5N8: Ce3+ , SrSiAl203N2: Eu2+,

A phosphor such as Ca丨.5Al3Si9N16: Ce3+. (5) An alkaline earth metal orthosilicate type having a luminescence peak in a wavelength region of 420 nm or more and less than 500 nm, a blue-green or blue phosphor of a halophosphate type, for example, Ba3Mgsi2〇 8: a phosphor such as Eu2+, (Sr, Ca)10(PO4)6Cl2: Eu2+. Since the excitation spectrum of the luminescent elements has an excitation peak in a near-ultraviolet to purple region having a wavelength of 360 nm or more and less than 420 nm, the external quantum efficiency is not high when the purple light-emitting element is excited. As an example, FIG. 40 shows an internal quantum efficiency 4 〇, an external quantum efficiency 41, and an excitation spectrum 42 of a La 2 〇 2 s:Eu 3 + red phosphor commonly used in combination with the above-described purple light-emitting element, for convenience of reference. The fluorescence spectrum of the phosphor is also shown together. As can be seen from FIG. 40, the internal quantum efficiency and external quantum efficiency of the above-mentioned La2〇2s:Eu3+ red phosphor are obtained in the ultraviolet region of the excitation spectrum of 380 nm or more, the ultraviolet region of less than 420 nm, and the excitation wavelength of about 360 to 380 nm. It decreases rapidly as the excitation wavelength increases. For example, in a purple region having an excitation wavelength of 380 nm or more and less than 420 nm, when the excitation wavelength is sequentially increased, the internal quantum efficiency is about 80% (380 nm), about 62% (400 nm), and about 25% (420 nm). Drastically lower. 54 200944577 'Also omitted, Y2〇2S: internal quantum efficiency, external quantum efficiency and excitation spectrum of Eu3 + red phosphor, and internal quantum efficiency and external quantum efficiency of the above La2〇2s:Eu3 + red phosphor And the excitation characteristic 'is shifted by 1 〇 to 5 〇 nm toward the short wavelength side. That is to say, La2〇2s:Eu3+ red phosphor and Y2〇2S:Eu3 + red phosphor, which are commonly used in combination with the above-mentioned purple light-emitting elements, can have the same conversion efficiency at a wavelength of 360 nm or more and less than The near-ultraviolet to purple region of 42〇nm (especially the purple region with a wavelength of 380 nm or more and less than 420 nm) is converted into a red light wavelength by light emitted from a light-emitting element having a light-emitting peak, but is fluorescently difficult to handle in terms of material properties. body. 'The above La2〇2S:Eu3 + red phosphor and Y2〇2S:Eu3 + red phosphor, the reason for the excitation wavelength dependence of the above internal quantum efficiency is 'When Eu3+ is in charge transfer state (CTS:charge) When the transfer sute) is in the excited state, when the excitation energy is relaxed and illuminates through the energy level of C 4, the 4f energy level of CTS will emit light with high efficiency, and if the light is directly excited by Eu3 + without CTS, it cannot be High efficiency illumination. The above CTS is a state in which i electric rafts are moved from the surrounding anions (〇 or S) to Eu3 + . Therefore, due to the above mechanism, the above-mentioned acid sulfide-based red phosphor and the light-emitting element, particularly the ultraviolet light-emitting element, are difficult to obtain a light-emitting device of a strong light beam. Further, when a plurality of phosphors are excited by a purple light-emitting element to constitute a white light-emitting device, in order to consider the hue balance, the intensity of the output light is correlated with the internal quantum efficiency of the phosphor having the lowest internal quantum efficiency. In other words, if there is one phosphor having a low internal quantum efficiency in the phosphor constituting the light-emitting device, the intensity of the output light is also lowered, and the white light of the strong light beam 55 200944577 cannot be obtained. Here, the internal quantum efficiency refers to the ratio of the quantum number of light emitted from the phosphor to the quantum number of the excitation light absorbed by the phosphor, and the external quantum efficiency is the excitation of the quantum number of the light emitted by the phosphor to the phosphor. The quantum number of light. That is to say, the high quantum efficiency indicates that the excitation light is efficiently subjected to optical conversion. The measurement method of the quantum efficiency has been established, and is described in detail in the aforementioned illumination society. The light emitted by the light-emitting element absorbed by the phosphor having a high internal quantum efficiency is efficiently emitted after light conversion. On the other hand, light emitted from a light-emitting element that is not absorbed by the phosphor is directly discharged. Therefore, a light-emitting device including a light-emitting peak in the above-mentioned wavelength region, and a light-emitting device having a phosphor having a high internal quantum efficiency excited by the light-emitting element can effectively use light energy. Therefore, by combining at least the above-described phosphor and the above-mentioned light-emitting element, a strong light beam and a high-color light-emitting device can be obtained. On the other hand, a light-emitting device having a light-emitting element having a light-emitting peak in the wavelength region and a phosphor having a low internal quantum efficiency when excited by the light emitted from the light-emitting element is not effective in order to make the light emitted from the light-emitting element The ground is changed, and a low beam illumination device is used. Further, a light-emitting device having a light-emitting peak having a light-emitting peak in a near-ultraviolet to purple region of 360 nm to less than 420 nm, and a light-emitting device having a low quantum efficiency of excitation by light emitted from the light-emitting element are emitted Light with a low visibility and a near-ultraviolet to purple region that is almost independent of the enhanced beam, so if the thickness of the phosphor layer is not increased, the concentration of the phosphor in the phosphor layer is increased, so that the light emitted by the above-mentioned light-emitting element is When the phosphor absorbs a large amount, it becomes a low-beam light-emitting device. Hereinafter, other embodiments of the light-emitting device of the present invention will be described. (Embodiment 6) An example of a light-emitting device of the present invention includes a phosphor layer containing a nitride phosphor and a light-emitting element. In the light-emitting device, the light-emitting element has light emission ♦ in a wavelength region of 360 nm or more and less than 500 nm, and the nitride phosphor is excited by light emitted from the light-emitting element to emit light, and the nitride phosphor emits light. The components are used as output light. Further, the nitride fluorescent system is activated by Eu2+ and is a phosphor represented by a structural formula (M1-xEux)AlSiN3, wherein the lanthanum is an element selected from at least one of Mg, Ca, Sr, Ba, and Zn, x is a value satisfying 0.005 S x S 0.3. The light-emitting element is a photoelectric conversion element that converts electric energy into light, and may be emitted at 360 nm or more, less than 420 nm or 420 nm or more, less than 500 nm, more preferably 380 nm or more, less than 420 nm or 440 nm or more, and less than 500 nm. The light source having a light-emitting peak in one wavelength region is not particularly limited, and for example, a light-emitting diode (LED), a laser diode (LD), a surface light-emitting LD, an inorganic electroluminescence (EL) element, or an organic EL element can be used. Wait. When an LED or LD having a GaN-based compound as a light-emitting layer is used for a light-emitting element, it is preferable to emit purple light having a light-emitting peak at 380 nm or more, less than 420 nm, and more preferably 395 nm to 415 nm from the viewpoint of obtaining a high output. The element, or, preferably, is a blue-emitting 57 200944577 optical element having a light-emitting peak in a wavelength region of 440 nm or more, less than 500 nm, and more preferably 450 to 480 nm. Preferably, the circulated light includes a luminescent component that emits light by the illuminating element. In particular, when the illuminating element has an illuminating peak in the blue region, the illuminating component emitted by the output phosphor includes the nitride phosphor. And the output light' can get white light with higher color rendering. The nitride phosphor is a warm-colored light having an emission peak in a wavelength region of 6 〇〇 nm or more and less than 660 nm, and preferably emits red light having a luminescence peak in a wavelength region of 610 nm to 65 Onm, and has the above structure. The formula (MhEuJAlSiN3, the above-mentioned nitride phosphor having high internal quantum efficiency under excitation light of a wavelength region of 360 nm or more and less than 5,000 nm, for example, SrAlSiN3: Eu2+ red phosphor or CaAlSiN3 shown in FIG. : Eu2+ red fluorescent iridium, etc. A phosphor layer having at least a nitride phosphor having a high internal quantum efficiency and a light-emitting device having the above-described light-emitting element can efficiently output light energy. A device with a strong luminescent component and a high color R9 value. These can be compared to the conventional illuminating device using La202S:Eu3+luminescence' or a combination of Si*2Si5N8:Eu2+ phosphor and ❹YAG. Ming·Shi Quanshi): The well-known illuminating device of the Ce glory body has a strong light beam and high color rendering. The light-emitting device of the present embodiment is not particularly limited as long as it has at least a phosphor layer containing the nitride phosphor and the light-emitting element.

It can be used with a semi-lighting device, a white LED, a display device using a white lED, and a lighting device using a white LED. More specifically, a display device using a white LED includes, for example, an LED information display terminal, an LED 58 200944577 traffic signal lamp, an LED lamp for an automobile, and the like, and a lighting device using a white LED, for example, an LED indoor and outdoor lighting lamp, a car interior lamp , which emergency lights, led decorative lights, etc. Ο

In particular, the above LEDs are preferred. In general, the conventional LED is a light-emitting element that emits a monochromatic light source of a specific wavelength. That is, it is conventionally impossible to obtain a light-emitting element that emits white light. In contrast to the white light of the present embodiment, white fluorescent light can be obtained by, for example, a combination of a conventional LED and a phosphor. In the present embodiment, in the nitride working body, when the main component of the element m is Sr or Ca, a good color tone and a strong light-emitting intensity can be obtained, which is preferable. Further, the main component is &amp; or Ca, meaning that the % atomic % of the element Μ is U or Sn, more preferably the element Μ &lt; 8 〇 atomic % or more is &amp; or ^, and all the atoms of the element 为 are Sr or Ca Better. Further, it is preferable that the light-emitting element can emit strong output light by using the above-mentioned injection type electroluminescent element. If it is used for an LED or LED having a GaN-based semiconductor in its active layer, a strong and stable output light can be obtained, which is more preferable. (Embodiment 7) In another embodiment of the light-emitting device of the present invention, the phosphor layer of the above-described Embodiment 6 may further include a wavelength region activated by Eu2%tCe3+ and having a wavelength of M5〇〇nm or more and less than 56〇nm. Green phosphor of the luminescence peak. The phosphor may be excited by light emitted from the light-emitting element described in the sixth embodiment, and may be emitted in a wavelength region of 550 nm or more and less than 56 〇 nm (preferably, a wavelength region of 51 〇 nm to 550 nm). More preferably, it is a wavelength region of 525 to 55 〇 nm) 59 200944577 A phosphor having an illuminating peak is not particularly limited. For example, when a blue light-emitting element is used, the excitation peak at the longest wavelength side of the excitation spectrum is not a green phosphor in a wavelength region of 420 nm or more and less than 500 nm, that is, it may be the longest wavelength side of the excitation spectrum. The excitation peak is a green fluorescent ray that is below the 420 nm wavelength region. The green phosphor is a phosphor having a high internal quantum efficiency at excitation light having a wavelength of 360 nm or more and less than 5 nm, and is, for example, '(Ba,Sr)2Si〇4:Eu2+ shown in FIG. Green fluorescent hip. It is preferable that at least the light-emitting device including the phosphor layer containing the phosphor and the light-emitting device can efficiently emit light energy. In the light-emitting device, the green light intensity of the output light is increased, and the color rendering property is improved. Moreover, the green light has a good visibility and a strong beam. In particular, by combining with the phosphor contained in the phosphor layer, it is possible to obtain an output light having a high color rendering property with an average color rendering number (Ra) of 90 or more. If the green phosphor is an oxide phosphor or oxynitride colloid activated by Eu2+, such as BaSiN2:Eu2+, sri 5Al3Si9N16:Eu2+, cai.5Al3Si9N16; Eu2+% CaSiAl2〇3N2:Eu2+'SrSiAl203N2:Eu2+ ' CaSl2〇2N2: Eu2+, SrSi2〇2N2: Eu2+, BaSi202N2: Eu2+, etc.; Eu-active 丄+alumina-based metal orthosilicate phosphor, for example (Ba: ST) 2S1〇4'Eu2+, (Ba , Ca) 2Si04: Eu2+, etc.; Eu-activated thiodecanoic acid·salt rong ^ t t difficult 'for example 'SrGa2S4: Eu 2+, etc.; Eu-activated aluminate lacquer» » J, SrAl2 〇 4: Eu2+, etc.; a citrate phosphor that is co-activated with Eu2+ and Mn2+/. For example, BaMgAl10O17:Eu2+, Mn2+, etc.; a gas activated by Ce3+ and an oxynitride phosphor or oxynitride phosphor , for example, 200944577

Sr2Si5N8: Ce3+, CauAhSbNwCe3, Ca2Si5N8: Ce3 +, etc.;

Ce3+ activated garnet-structured phosphor, such as Y3(Al,Ga)5〇i2:Ce3+, Y3Al5〇12:Ce3+, BaY2SiAl4〇12:Ce3+, CagSc^S^ObCe3—etc. Under excitation, the internal quantum efficiency will increase, which is better. As described above, the light-emitting device of the present embodiment includes the phosphor layer including at least the nitride phosphor of the sixth embodiment and the green phosphor, and the light-emitting element of the sixth embodiment, and the output light contains the nitride. The red component emitted by the light body and the green light component emitted by the green phosphor. (Embodiment 8) Another example of the light-emitting device of the present invention may be that the phosphor layer of the above-described Embodiment 6 or Embodiment 7 may be activated by, for example, 2+ or Ce3 + and may be 560 nm or more and less than 600 nm. A yellow phosphor having a luminescence peak in the wavelength region. The yellow phosphor may be excited by light emitted from the light-emitting element described in the sixth embodiment, and may be emitted in a wavelength region of 56 〇 nm or more and less than 600 nm, preferably 565 nm to 580 nm. More preferably, it is a fluorescent body having a light-emitting peak in a wavelength region of 525 to 550 nm, and is not particularly limited. For example, when a blue light-emitting element is used, a yellow light-emitting body in which the excitation peak on the longest wavelength side of the excitation spectrum is not in a wavelength region of 42 〇 nm or more and less than 5 〇〇 nm may be an excitation spectrum. The excitation peak on the longest wavelength side is a yellow phosphor having a wavelength region of less than 42 〇 nm. The above-mentioned 53⁄4 color glory Zhao is a phosphor having a high internal quantum efficiency under the excitation light of the above-mentioned 36 〇 nm or more and less than 500 nm of the wavelength of 200944577, for example, (Sr, Ba) 2Si04: Eu 2+ yellow fluorite shown in FIG. Light body, Ca) 2Si〇4: Eu2+ yellow phosphor shown in Fig. 34, 0.75CaO · 2.25A1N · 3.25Si3N4: Eu2+ yellow phosphor shown in Fig. 35, etc. = 420 nm or more, less than 50'0 nm wavelength A phosphor having high internal quantum efficiency under the excitation light of the region, for example, (γ, Gd) 3A15〇12: Ce3 + yellow phosphor shown in Fig. 36. It is preferable that the light-emitting device including the phosphor layer containing the phosphor and the S-light element can efficiently output light energy. In the light-emitting device, the yellow light-emitting intensity of the output light is increased, and the color rendering property is improved, and in particular, a light-emitting device that emits a warm color system or a warm color light can be provided. Moreover, the yellow light has a high visibility and the light beam is strong. In particular, by designing the material of the phosphor material, it is possible to obtain an output light having a color rendering property of Ra of 90 or more. If the yellow phosphor is a nitride phosphor or an oxynitride phosphor activated with Eu2+, for example, 0.75CaO · 2.25A1N · 3.25Si3N4:Eu2+, Cai.5Al3Si9N16:Eu2+,

CaSiAl203N2: Eu2+, CaSi6A10N9: Eu2+, etc.; alkaline earth activated by Eu2+ © metal orthosilicate phosphor, for example, (Sr, Ba) 2Si04: Eu2+, CSr, Ca) 2Si〇4: Eu2+, etc.; activated with Eu2+ a thiophthalate phosphor, such as CaGaaSvEu2, etc.; and a garnet-structured phosphor activated by Ce3+, such as (Y, Gd)3Al5〇12:Ce3+, etc., excited by the above-mentioned light-emitting element The internal quantum efficiency will increase, which is better. As described above, the light-emitting device of the present embodiment includes the phosphor layer including at least the nitride phosphor of the sixth embodiment and the yellow phosphor, and the light-emitting elements of 62 200944577 and the sixth embodiment, and the output light contains The red component emitted by the nitride phosphor and the yellow luminescent component emitted by the yellow phosphor (Embodiment 9) Another example of the illuminating device of the present invention may be any of the above embodiments 6-8 One of the phosphor layers further contains a blue phosphor which is activated by Eu2+ and has a light-emitting peak in a wavelength region of 42 nm or more and less than 500 nm. The blue phosphor can be excited by the light emitted from the light-emitting element described in the sixth embodiment, and is in a wavelength region of 420 nm or more and less than 500 nm (preferably from 440 to 480 nm from the viewpoints of color rendering and output). The wavelength region is a fluorescent fluorene having a luminescence peak, and is not particularly limited. In this case, the light-emitting element is not particularly limited as long as it is a light-emitting element described in the embodiment, and it is preferable to use a purple light-emitting element because the selectivity of the phosphor material can be increased, and not only the design light can be made. The light color emitted by the device is easy, and even if the wavelength position emitted by the light-emitting element fluctuates due to driving conditions such as the input power of the light-emitting element, the influence on the output light is not large. The blue light-emitting body is a phosphor having a high internal quantum efficiency in excitation light in a wavelength region of 36 〇 nm or more and less than 5 〇〇 nm (preferably 360 nm or more and less than 420 nm), for example, The BaMgAl10〇17:Eu2+ blue fluorescent enamel shown in Fig. 37 and the four phantom 14 〇25 shown in Fig. 38: 2+ blue phosphor, (Sr, Ba) 1 〇 shown in Fig. 39 ( P〇4) 6Ci2: Eu2_^ color phosphor, etc. It is preferable that the light-emitting device including the phosphor layer containing the phosphor and the light-emitting element can efficiently output light energy. In the illuminating device, the illuminating intensity of the blue light contained in the output light is increased, and the color rendering property 63 200944577 and the β high beam are lifted. In particular, by designing the material of the phosphor material, it is possible to obtain an output of high color rendering of Ra4 90 or higher*, and all the special color evaluation numbers of ri to ri5 are 8. In the above, the preferred case is 85 or more. More preferably, a white output light of 9 G or more close to sunlight can be obtained. For example, 'by using BaMgAllG〇17: Eu2+, (Sr, Ba)iG(p〇4)6Ci2:Eu2+,

Ba3MgSi2〇8: Eu2+, SrMgAl1() 017: EU2+, (Sr,

Ca)10(P〇4)Cl2:Eu2+ . Ba5Si〇4Cl6:Eu2+ ^ BaAl8〇1,:Eu- /

Sr10(P〇4)Cl2: Eu, a yellow mortar, 彳 to obtain an output light having the above-described high color rendering property and special color rendering number. Further, the blue phosphor is a nitride phosphor or an oxynitride phosphor activated by Eu2+, for example, SrSiAl2〇3N2:Eu2+ or the like; and an alkaline earth metal protoporate fired by 2+ Light body, for example

Ba3MgSi208: Eu2+, Sr3MgSi2〇8: Eu2+, etc.; Eu2+ activated aluminate phosphor, such as BaMgAl1Q〇17: Eu2+, BaAl8013: EU2+,

Sr4AlM〇25: Eu2+, etc.; and a tooth phosphoric acid phosphor activated with Eu2+, for example,

Sr 丨0(PO4)6C12:Eu2+, (Sr,Ca)10(PO4)6Cl2:Eu2+, (Ba,Ca,Mg)1()(P04)6Cl2:Eu2+, etc., under the excitation of the above-mentioned light-emitting element, internal The quantum efficiency will increase, so it is better. In the sixth to ninth embodiments, in order to obtain a strong light beam, it is preferable that the phosphor contained in the phosphor layer does not substantially contain a phosphor other than the phosphor activated by the 2+ or Ce3 + , and substantially It is preferred that the inorganic fluorescent ray other than the nitride phosphor or the oxynitride phosphor is contained. The phosphor is substantially free of fluorescent fluorophores other than the phosphor activated by Eu2+ or Ce3+, and 90% by weight or more, preferably 95% by weight or more, more preferably %, of the phosphor contained in the phosphor layer. 200944577 Above weight% is a phosphor activated with Eu2+ or Ce3+. The inorganic phosphor other than the nitride phosphor or the oxynitride phosphor is substantially 90% by weight or more, preferably 95% by weight or more, and more preferably 98% or more of the phosphor contained in the glare layer. The weight % or more is a nitride phosphor or an oxynitride phosphor. The nitride phosphor and the oxynitride phosphor can maintain a high internal quantum efficiency and a wavelength peak of the luminescence spectrum even at an operating temperature of 1 〇〇 to 15 〇〇C and at an ambient temperature. It is shifted to the short-wavelength side like the alkaline earth metal orthosilicate phosphor or the phosphor having a garnet structure. Therefore, in the fluorescent device having the above configuration, even if the input power is increased and the intensity of the excitation light is increased, or the use is performed in a high-temperature atmosphere, the fluctuation of the luminescent color is small, and stable output light can be obtained. Further, in order to obtain a light-emitting device that emits a strong light beam, the internal quantum efficiency (absolute value) of the phosphor having the lowest internal quantum efficiency excited by the light emitted from the light-emitting element among the phosphors substantially contained in the phosphor layer is 8〇% or more, preferably 85% or more, more preferably 9〇% or more. (Embodiment 10) An example of a light-emitting device of the invention includes a phosphor layer containing a fluorescent ray and a light-emitting element, wherein the light-emitting element has an emission peak in a wavelength region not larger than 36 Å or more, and the luminescence The light is excited by the light emitted by the light-emitting element, and the output light contains at least the light-emitting component emitted by the glare. Further, the phosphor includes a nitride phosphor or an oxygen oxide light-emitting body which is activated by Eu2+ and has a light-emitting peak in a wavelength region of less than 66 Å, and is activated by 2+ and above 5 (10) nm. The alkaline earth metal orthosilicate phosphorescent light having a luminescence peak in a wavelength region of less than 600 nm is excited by the light emitted from the light-emitting element, and the internal quantum efficiency of the phosphor is 80% or more. The light-emitting element described above can be used in the same manner as the light-emitting element described in the sixth embodiment. Preferably, the output light is included in the light emitted by the light-emitting element. In particular, when the light-emitting element has a light-emitting peak in a blue-wavelength region, the output light contains the light-emitting component emitted by the phosphor and the light-emitting component

It is more preferable that the luminescent component emitted from the component can obtain white light having a higher color rendering property. The above-mentioned Eu2+-activated nitride phosphor or oxynitride phosphor is a warm-colored light having an emission peak in a wavelength region of 600 nm or more and less than 660 nm, preferably having a wavelength region of 61 Å to 650 nm. The phosphor having a red light of the luminescence peak is a phosphor having a high internal quantum efficiency under excitation light in a wavelength region of 36 〇 nm or more and less than 5 〇〇 nm 上述. More specifically, it is a nitride aluminosilicate phosphor represented by the structural formula (M^xEuJAlSiN3, for example, SrAiSiN3_Eu2+ red phosphor or CaAlSiN3: Eu2+ red mortar shown in FIG. 30; structural formula (Mi xEux) a nitride silicate phosphor represented by SiN2, for example, SrSiN2.Eu2+ red phosphor or CaSiNyEuh red phosphor shown in Fig. 29; nitride citrate represented by structural formula (Mi xEux) si5Ns A phosphor, for example, a red mortar as shown in FIG. 31 or 2 with 5^: such as 2+ red phosphor or 卟 如 2, color phosphor, etc.; structural formula (Μι 为)丨〇 N7 represents an oxonitride sulphate phosphor, for example, a Sr2Si4Ai〇N7:Eu2 + red phosphor, wherein the enthalpy of the above structural formula is selected from the group consisting of Mg c; a, sr, 66 200944577

At least one of Ba and Zn is doped; the 7^ prime of ^ ^ is again a value satisfying 0.005S xS 0.3. The above-mentioned soil-based metal orthophosphate phosphor is a phosphor which is activated by Eu2+ and has a luminescence peak at a wavelength of 500 nm or more and less than 6 Å, preferably 525 nm or more, and (9) a wavelength region such as a claw. More specifically, in the wavelength region of 525 or more and less than 56 〇 nm, a green phosphor having a light-emitting peak in a wavelength region of 53 〇 nm to 55 〇 nm is preferable, for example, as shown in FIG. 32 (Ba, Sr) 2Si 〇 4: Eu 2+ green phosphor; or a yellow glory having an illuminating peak in a wavelength region of 56 〇 nm or more and less than 〇〇 6 〇〇 nm, for example, (Sr'Ba) 2Si04: Eii 2+ yellow as shown in FIG. The phosphor is shown in Fig. 34 (Sr, Cahsi〇4: Eu2+ yellow phosphor, etc., and the internal quantum efficiency is high under the excitation light of the wavelength region of 36 〇 nm or more and less than 5 〇〇 nm. The phosphor has an internal quantum efficiency of 80% or more, preferably 85% or more, more preferably 9% or more, excited by the light emitted from the light-emitting element. At least a phosphor having a high internal quantum efficiency as described above The phosphor layer and the light-emitting device of the above-described light-emitting element can efficiently output light energy. The light-emitting device comprising the above-described nitride phosphor or oxynitride phosphor has a strong intensity of a warm-colored light-emitting component, and has a large number of special color evaluation numbers R9. Further, the light-emitting device having the above configuration does not have reliability. The problem is a sulfide-based phosphor, and only a red phosphor using a high-priced nitride phosphor or an oxynitride phosphor is used, so that a white light source with a strong beam and a high color can be provided, and the white color can be lowered. The cost of the light-emitting device such as a light source. The light-emitting device of the present embodiment includes at least the above-described nitride phosphor or oxynitride phosphor containing red light activated by Eu2+ 67 200944577, and

In the oxynitride phosphor, if the pre-Sr or Ca is a nitride phosphor represented by the structural formula or if the main component of the element 为 is Sr or Ca,

All of the elements are all Sr or Ca. f

Sr or axe. Further, if the light-emitting element uses the injection-type electroluminescent element, it is possible to emit strong output light, which is more preferable. The alkaline earth metal orthosilicate phosphor is preferably activated by EU 2+ and is in a wavelength region of 500 nm or more and less than 56 〇 11111, preferably 525 or more and less than 560 nm, more preferably 53 Å. A green phosphor having a luminescence peak in a wavelength region of less than 55 〇 nm, for example, (Ba, s〇2Si〇4: Eu2+, (Ba,

Ca) 2Si〇4: Eu2+. In the light-emitting device using a green phosphor, the output light contains a green light having a high luminous intensity and a high color rendering property. Moreover, the green light is visible. The degree of light is higher and the beam is stronger. In particular, the combination of phosphors in different phosphor layers can produce high color rendering output light with Ra of 90 or more. And especially the above-mentioned soil-based metal ortho-alkaline mortar is preferably activated by eu2+ and has a luminescence peak in a wavelength region of 560 nm or more and less than 600 nm, preferably 565 to 580 nm. For the light body, for example, (Sr, Ba) 2Si〇4: Eu2+ can be used. By using the yellow phosphor light-emitting device, the yellow light intensity of the output light is enhanced, and the color rendering property is improved. 68 200944577 It is a light-emitting device that emits a warm color or a warm color. Moreover, the yellow light has a higher visibility and the light beam also becomes stronger. In particular, according to the design of the phosphor $ material, it is possible to obtain a high color rendering output light with Ra of 90 or more. Further, it is preferable to use (Sr, Ca) 2Si04: Eu2+ yellow phosphor which emits a glory close to the above-mentioned yellow glory. In the present embodiment, it is preferable that the phosphor other than the red refractory contained in the phosphor layer substantially does not contain a nitride phosphor or an oxynitride phosphor. By using the nitride working agent or the oxynitride phosphor used in the light-emitting device to minimize the manufacturing cost of the light-emitting device, the manufacturing cost of the light-emitting device can be reduced by 0.2% of the red phosphor contained in the phosphor layer. Preferably, the phosphor is substantially free of sulfide fluorescene. Thereby, the reliability of the light-emitting device can be improved, and for example, a light-emitting device having little change with time such as deterioration can be provided. Further, in the tenth embodiment, the phosphor contained in the phosphor layer is a strong light beam, and is preferably a phosphor other than the phosphor which is substantially not activated by Eu2+ or Ce3+. Further, in the phosphor contained in the phosphor layer, it is preferable that the internal quantum efficiency of the glory having the lowest internal quantum efficiency is 80% or more under the excitation of the light emitted from the light-emitting element. Fig. 12 illustrates a light-emitting device of Embodiment 6 to 1A. Fig. 2 and Fig. 3 are cross-sectional views showing a conductor light-emitting device which is an example of a light-emitting device of the present invention. A semiconductor light-emitting device is shown which is attached to the base member 4 to a structure in which a light-emitting body is 70 pieces of light and sealed with a base material containing the phosphor group 2 and also serving as the layer 3. 2, a semiconductor light-emitting device 69 200944577 is disposed in the cup body 6 provided on the carrier wire of the lead frame 5, to constitute a light-emitting element, and is disposed in the cup body 6. The phosphor layer 3 of the photobody composition 2 has a structure in which the sealing material 7 such as a resin is sealed as a whole. Fig. 3 shows a wafer type semiconductor light-emitting device in which at least one light-emitting element 1 is mounted in a housing 8, and a phosphor layer 3 containing a phosphor composition is provided. In FIGS. 1 to 3, the light-emitting element i is a photoelectric conversion element capable of converting electric energy into light energy, and is preferably 36 〇 nm or more, less than 5 〇〇 nm, preferably 38 〇 nm or more, and less than 42 〇. N, or 44 〇 nm or more, less than 5 〇, such as melon, more preferably 395 to 415 im or 450 to 480 nm, the wavelength region has a luminescence peak light, and is not particularly limited, and for example, LED, ld, surface-emitting LED can be used. Inorganic EL elements, organic EL elements, and the like. In particular, in order to increase the output of the semiconductor light-emitting element, it is preferable to use an LED or a surface-emitting LED. In Fig. 3, the phosphor composition 2 in the phosphor layer 3 is a nitride emitter represented by the formula %), which is obtained by dispersing a labyrinth. Μ is selected from...'. An element of at least one of ~, such as and ~ is 满足 to satisfy the value of 0.005$χ$0.3. The material used for the base material of the f-light layer 3 is not particularly limited, and generally: a transparent resin such as an epoxy resin or a phase resin or a low melting point == may be used. In order to provide a luminescent inorganic base material having a decrease in luminous intensity with a decrease in Fa1 during operation, it is preferably a transparent inorganic material such as a ketone resin or a (four) point glass, and more preferably the above-mentioned light-transmitting property is not sufficient. For example, if the amount of the transparent material is the same as that of the L material, the content of the vaporizer is 5 to 8 % by weight, more preferably 1 to 6 % by weight. The nitride phosphor contained in the working layer 3 200944577 can absorb a part or all of the light emitted by the light-emitting element to be converted into red light. Therefore, the output light of the semiconductor light-emitting device at least contains the nitride fluorescent body. Luminous composition. Further, in the case where the phosphor composition 2 contains at least the nitride phosphor of the structural formula, the phosphor layer 3 may further contain a phosphor other than the above-described nitride phosphor, or may not be contained. For example, if the above-mentioned high-internal bismuth metal orthosilicate phosphor, nitride fluorite having high internal quantum efficiency, for example, activated by Eu2+ or Ce3+ and excited in a wavelength region of 360 nm or more and less than 500 nm is used. Light body, oxynitride mortar, chromic acid phosphor, _phosphate phosphor, thioxanthate, etc., according to the combination of (1) to (6) shown below, the light-emitting element (1) A purple light-emitting element having a light-emitting peak in a wavelength region of 36 〇 nm or more and less than 420 nm is formed, and light emitted from the light-emitting element 1 can efficiently excite the phosphor and emit light by the plurality of phosphors. The color mixture is, for example, a semiconductor light-emitting element that emits white light. ' (1) A working layer comprising: a blue luminous body, which emits light having a luminescence peak in a wavelength region of 420 nm or more and less than 500 nm, preferably 440 nm or more and less than 5 〇〇 nm; a green phosphor emits Preferably, the light having a luminescence peak is in a wavelength region of 5 〇〇 nm or more, less than 56 〇 nm, preferably 51 〇 nm to 55 〇 nm 2 ; and the yellow light-emitting body is emitted at 560 nm or more and less than 6 〇〇 nm, preferably The wavelength region of 565 nm to 580 nm has light of a luminescence peak; and the above nitrided phosphor. (7) - a phosphor layer comprising: a blue phosphor, emitted at 42 〇 or more, less than 50 〇 nm, preferably 44 〇 nm or more, and less than 5 〇〇 nm wave 71 200944577 long area has luminescence The light of the peak; the green phosphor emits light having a luminescence peak in a wavelength region of 500 nm or more, less than 560 nm, preferably 510 nm to 550 nm; and the vapor phosphor. (3) a phosphor layer comprising: a blue phosphor which emits light having a luminescence peak in a wavelength region of 420 nm or more and less than 500 nm, preferably 440 nm or more and less than 500 nm; a yellow phosphor emitted from Light having a luminescence peak in a wavelength region of 560 nm or more, less than 600 nm, preferably 565 nm to 580 nm; and the above-described nitride phosphor. (4) A phosphor layer comprising: a green phosphor which emits light having a luminescence peak in a wavelength region of 500 nm or more and less than 560 nm, preferably 5 1 Onm to 550 nm; and a yellow phosphor which emits at 5 60 nm The light having a luminescence peak in a wavelength region of less than 600 nm, preferably 565 nm to 580 nm; and the above-described nitride phosphor. (5) A phosphor layer comprising the yellow phosphor and the nitride phosphor. 〇 (6) A phosphor layer comprising the above green phosphor and the above nitride phosphor. Further, when the phosphor combinations of (7) to (9) are used as follows, the light-emitting element 1 is formed into a blue light-emitting element having a light-emitting peak in a wavelength region of 420 nm to less than 500 nm, and the light-emitting element 1 is emitted. When the light is mixed with the light emitted by the phosphor, it can be a semiconductor light-emitting device that emits white light. (7) A phosphor layer comprising: a green phosphor which emits light having a luminescence peak in a wavelength region of 500 nm or more and less than 560 nm, preferably 525 nm or more and less than 560 nm; a yellow phosphor is emitted from 560 nm or more, 72 200944577 less than 600 nm, preferably 565 nm to 580 nm, having a luminescence peak in a wavelength region; and the above nitride phosphor. (8) A phosphor layer comprising the yellow phosphor and the nitride phosphor. (9) A phosphor layer 'containing the green phosphor and the nitride phosphor. When the light-emitting element is a blue light-emitting element, the green phosphor and the yellow phosphor are in addition to Eu2+-activated alkaline earth metal orthofluoride phosphor, Eu2+-activated nitride phosphor or oxygen-nitrogen In addition to the phosphor, a phosphor having a Ce3 + activated garnet structure (particularly, YAG: Ce-based phosphor), a thiosilicate phosphor activated with Eu2+, or the like can be used. More specifically, for example, SrGa2S4:Eu2+ green phosphor, γ3(Α1, Ga)5〇12:Ce3+green fluorescent vessel, Y3Al5〇i2:ce3+green phosphor, 丫281 181140: 〇63 can be used. + green phosphor, 〇 &amp; 38 (; 2313012: € 63 + green phosphor, (Y, Gd) 3Al5 〇 12: Ce3 + yellow phosphor, Y3Al5 〇 i2: Ce3 + pr3 + yellow phosphor, CaGa2S4: Eu2+ yellow phosphor, etc. or 'The phosphor composition 2 of the phosphor layer 3 in FIGS. 1 to 3 may be a red photonitride fluorescein or oxynitride which is activated by at least Eu2+. The phosphor is formed by dispersing an alkaline earth metal orthosilicate phosphor having an emission peak in any wavelength region of 500 nm or more, less than 560 nm or more than 560 nm, and less than 6 nm in activation with Eu2+. The base material 3 can use the base material of the phosphor layer 3. Further, the phosphor composition 2 contained in the luminescent layer 3 can absorb a part or all of the light emitted by the light-emitting element 并 and convert it into light, so the semiconductor light-emitting device 73 200944577 The output light will contain at least the luminescent component and alkali emitted by the nitride phosphor or oxynitride phosphor. a luminescent component emitted by a metal-like orthophosphate phosphor. Further, the phosphor composition 2 contains a red-emitting photo-nitride phosphor or oxynitride phosphor activated by Eu2+, and is activated by Eu2+. And at 500nm

The above-mentioned nitride phosphor 3 or oxynitride may be contained in the phosphor layer 3 having a luminescent peak in the wavelength range of less than 560 nm or more than 560 nm or less than 600 nm. Phosphors other than phosphors and alkaline earth metal orthosilicate phosphors, but they are not included. In order to reduce the amount of use of the nitride phosphor or the oxynitride phosphor or the sulfide-based phosphor, it is preferred to contain the nitride fluorescent or oxynitride phosphor or sulfide other than the above. A fluorescent body. For example, 'the above-mentioned (1) to (6) are the above-mentioned (1) to (6) activated by Eu2+ or Ce3+ and excited by a wavelength region of 36 〇 nm or more and less than 5,000 nm. When the phosphors are combined, the light emitted from the light-emitting element 1 can efficiently excite the phosphor, and the color light emitted by the plurality of phosphors becomes a semiconductor light-emitting device that emits white light. Further, when the phosphors shown in the above (7) to (9) are combined, the light emitted from the light-emitting element 1 is mixed with the light emitted from the plaster to become a semiconductor light-emitting device that emits white light. In the semiconductor light-emitting device of the present embodiment, since the external quantum efficiency is not high when excited by the above-described three-color light-emitting element, but the internal quantum 5 = Laoguang Zhao, for example, the blue light-emitting element is intended to be used first. When the light emitted by the body is mixed to obtain the desired white light, a fluorescent body of more than 74,044,577 is required. Therefore, in order to obtain desired white light, it is necessary to increase the thickness of the phosphor layer, and if the thickness of the phosphor layer is increased, it becomes a light-emitting device having less white color light spots, which is an advantage. When the phosphor layer 3 has a complex or multilayer structure and a part of the layer is a phosphor layer containing the nitride phosphor or the oxynitride phosphor, the luminescent color spot of the semiconductor light-emitting device of the embodiment can be suppressed. Or it is better to output spots. 'Because the nitride phosphor or yttrium nitride phosphor with Eu2+ as the luminescent center ion can absorb blue, green, and yellow visible light and convert it into red light, so if the above contains a nitride phosphor or oxygen nitrogen The phosphor layer of the phosphor is a mixture of a phosphor of a blue phosphor, a green phosphor, and a yellow phosphor, and the above-described nitride phosphor or oxynitride phosphor. The light emission of the blue, green, and yellow phosphors is also absorbed, so that the nitride phosphor or the oxynitride phosphor emits red light. Therefore, the illuminating color control of the illuminating device becomes difficult due to the process of the phosphor layer. In order to prevent this problem, it is preferable that the phosphor layer 3 has a multi-layer or multi-layer structure, and the layer closest to the main light output surface of the light-emitting element 1 is a red-emitting nitride phosphor or oxynitride. The phosphor is not easily excited by the luminescence of the blue, green, and yellow labor bodies described above. In addition, since the yellow phosphor activated by Eu2+ or Ce3+ is excited by blue light or green light, and the green phosphor activated by Eu2+ or Ce3+ is excited by blue light, When a plurality of kinds of phosphors having different luminescent colors are mixed to form the phosphor layer 3, the same problem as described above occurs. In order to solve this problem, in the semiconductor light-emitting device of the present embodiment, the phosphor layer 3 is preferably a multi-layer or multi-layer 75, 2009, 577, 577 layer structure, and the layer away from the main light output surface of the illuminating element is a fluorite emitting short-wavelength light. The layer of light. The semiconductor light-emitting device of the present embodiment includes the above-described light-emitting element and a nitride phosphor or oxynitride phosphor which has high internal quantum efficiency and can efficiently convert excitation light into red light under excitation of the light-emitting element. a phosphor layer of the body, so that the output light of the light-emitting device contains at least the red-based luminescent component emitted by the nitride phosphor or the oxynitride phosphor, and has both a strong light beam and a color rendering property, especially It emits white light in warm colors. Further, when the light-emitting element is a blue light-emitting element, the output light further includes a light-emitting component emitted by the light-emitting element.囫4 and Fig. 5 are schematic diagrams showing the structure of the 〇-J and the display device. Figure 4 shows at least one semiconductor hair

An illumination display device comprising the device 9 (combining the glare layer 3 of the above-described phosphor composition &amp; 2 and the hairpin 1) and its output light 1 。. Figure 5 shows at least i illuminating elements! The illuminating display device composed of the luminescent body layer 3 of the above-described working body composition 2 and the phosphor layer 3' of the illuminating light emitting device 1 can be used in the same manner as the semiconductor light-emitting device described above. Further, the operation and effect of the illumination display device of this configuration are the same as those of the semiconductor light-emitting device described.圃¢) to Fig. 12 is an example of the illumination display device of the embodiment of the hair-emitting device of the present invention shown in the above-mentioned Fig. 4 and Fig. 5, and the 艚 尤 八 八 八. Fig. 6 is a perspective view showing the steps of the legs m and 4 of the illumination module 12 of the body shaping light-emitting portion 11. Fig. 7 shows that the lighting module 12 of the plurality of light-emitting portions 11 does not have a Zhao map. Fig. 8 shows a solid circle having a right-hand light-emitting portion 11 and which can be controlled by the switch 11 to be turned on and off, and has a light-off or a predetermined amount of the table illumination device of the type 76 200944577. Fig. 9 shows a side view of a lighting device comprising a lighting module 12 having a screw-in base 14, a reflector 15 and a plurality of light-emitting portions 11. Further, Fig. 10 is a bottom view of the lighting device of Fig. 9. Figure t i is a perspective view of a flat-panel image display device having a light-emitting portion 11. Figure 12 is a perspective view of a segmented digital display device having a light emitting portion 11. In the illumination and display device of the present embodiment, a phosphor having a high internal quantum efficiency under excitation by the above-described light-emitting element is used, and in particular, a semiconductor light-emitting device having a strong red light-emitting component and excellent color rendering properties is used. Therefore, it has better characteristics than the conventional illumination display device, and has high color rendering properties of strong light beams and particularly red-based light-emitting components. As described above, according to the present invention, a light-emitting device having both a strong light beam and high color rendering property can be obtained by combining at least the nitride phosphor shown by the above structural formula (MNxEUx) AlSiN3 and the above-mentioned light-emitting element, in particular, a warm color is obtained. A white light emitting device. Further, according to the present invention, at least the above-mentioned nitride or oxynitride phosphor having an emission peak in a wavelength region of 6 〇〇 nm or more and 〇 less than 66 〇 nm is combined, and the above is 500 nm or more and less than 6 An alkaline earth metal orthosilicate phosphor having an emission peak in a wavelength region of 〇〇nm, and the above-mentioned light-emitting element, can provide a light-emitting device having both a strong light beam and high color rendering, and in particular, a light-emitting device that emits white light of warm color . The illuminating device of the present invention will be described in more detail by way of examples. (Embodiment 26) In this embodiment, a light source of a card type lighting module shown in Fig. 41 was produced, and the light-emitting characteristics were evaluated. Figure 42 is a partial cross-sectional view of Figure 41. First, a method of manufacturing the semiconductor light-emitting device 44 will be described. The pair of n-electrode 46 and p-electrode 47 of the Si diode element (base element) 45 formed on the n-type Si wafer in an array form are passed through a microbump (microbump; A blue LED wafer 49 having a light-emitting peak at about 470 nm is emitted from the light-emitting layer.

Further, the blue LED chips 49 are mounted on the respective Si diode elements 45 formed in a matrix shape. Therefore, the blue LED chips 49 are also arranged in a matrix. Next, the n electrode 46 and the p electrode 47 are connected to the n electrode and the P electrode of each of the blue LED chips 49, and then a phosphor layer 3 containing a phosphor composition is formed on the peripheral portion of the blue LEE wafer 49 by a printing technique. . The upper surface of the above-mentioned phosphor I 3 was ground and flattened, and then cut into semiconductor light-emitting devices 44 by using a diamond knife.

Next, a first insulator thick film 51 (thickness 75#m), a copper electrode 52 (thickness about Mem, a width of 55 mm), and a second insulator thickness are sequentially laminated on an aluminum metal substrate 5 (size: 3 cm x 3 cm, thickness: 1 mm). The film 53 (thickness electrode pads 54a and 54b (having a thickness of about 1 〇//m, a total of 64 pairs) is formed to form the heat dissipation multilayer substrate 55. The first insulator thickness 51 and the second insulator thick film 53' are thermocompression bonded. The formed oxide electrode is composed of an epoxy resin, and the copper electrode 52 is formed into a round shape by the technique of (4), and the electrodes 塾 and 5 are formed by a etching technique to form a negative electrode and a positive electrode for power supply. A portion of the film thickness film 53 is provided with a contact hole, so that the electrode pads and (10) can be supplied with power through the copper electrode 52. 78 200944577 Next, the semiconductor light-emitting device 44 is placed on the heat-dissipating multilayer substrate 55 at a predetermined position. At this time, the inner electrode (n electrode) 56 of the Si diode element 45 is fixedly connected to the electrode pad 54a by using an Ag paste, and the bonding pad portion 58 on the p electrode 47 is connected to the bonding pad 58 by using the Au wire 57. The electrode pad 54b enables power supply to the semiconductor light-emitting device. The aluminum metal reflector 59 having an inverted conical cylindrical grinding hole is adhered to the heat dissipation multilayer substrate 55. At this time, the semiconductor light emitting device 44 on the heat dissipation multilayer substrate 55 may be wrapped in an aluminum metal reverse sputtering plate. The inside of the polishing hole portion of 59. Then, the semiconductor light-emitting device 44 and the entire polishing hole portion were sealed with an epoxy resin to form a dome-shaped crucible, thereby obtaining the light-emitting device of Example 26. Fig. 41 is a light-emitting device of Example 26. In the embodiment 26, a card-type illumination module light source ' is fabricated using 64 semiconductor light-emitting devices 44 and its light-emitting characteristics are evaluated. In the embodiment 26, 32 copper electrodes 52 are connected in series by two. The semiconductor light-emitting device group 'flows a total of 80 mA left-right current of about 4 mA, respectively, to drive the semiconductor light-emitting device 44 to obtain output light. The output light is the light emitted by the blue LED chip 49, and Light-exciting the mixed color light of the light emitted by the phosphor contained in the phosphor layer 3. The output light can be obtained by appropriately selecting the type and amount of the LED chip and the phosphor. The phosphor layer 3 will be described in detail below. The phosphor layer 3' is formed by drying and solidifying an epoxy resin to which a phosphor is added. In the embodiment 26, two kinds of phosphors are used, one of which has a wavelength of 625 nm and a frequency of 79,2009,577. SrA1SiN3:Eu2+ red phosphor of luminescence peak (center particle size: 2 2 //m' maximum internal quantum efficiency: 6G%) 'Another species is near the wavelength of milk (10)" has S peak (Ba Sr) 2Si () 4: Eu2+ green phosphor (center particle size: 12.7 core 'maximum internal quantum efficiency · 91%), epoxy resin using two-liquid mixed epoxy resin, the main agent is bisphenol A liquid resin as the main component The epoxy resin 'hardener is an epoxy resin mainly composed of an alicyclic acid field. SrA1SlN3: Eu2+ red phosphor and (Ba,Sr)2Si〇4:Eu2' green phosphor 11: H tt example about $i:. The weight ratio of the mixed phosphor to the epoxy resin was about 1:3 (phosphor concentration = 25% by weight). (Comparative Example 6) Two types of phosphors were used, one of which was an Sr2Si5N8:Eu2+ red phosphor having a luminescence peak at a wavelength of 625 nm (central particle diameter: 1.8 _, maximum internal quantum efficiency: 62%) 'The other is 56 A YsAlsOaCeK yellow phosphor having a luminescence peak near the 〇nm wavelength (central particle diameter: 17 6 a-claw, maximum internal quantum efficiency: 98 / 〇) was fabricated in the same manner as in Example 26 to produce a card-type illumination module light source. In the phosphor layer 3, the mixing ratio of the 'Sr2Si5Ns:Eu2+ red phosphor to the YsAlsOaCeh yellow phosphor is about 1:6, and the mixing ratio of the mixed phosphor to the epoxy resin is about 1:14 (fluorescent body). Concentration = 67% by weight). Then, as in the embodiment, the output light was obtained by flowing a current through the semiconductor light emission, and the light-emitting characteristics were evaluated. Regarding the thickness of the phosphor layer 3, in order to obtain white light of a homochromatic color (correlation color temperature of about 3800 K, duv, chromaticity), the thickness in Example 26 is about 5 〇〇 β m, and the thickness of Comparative Example 6 is about 100 m from m. . Further, the luminescent characteristics of the SrAlSiN3:Eu2+ red phosphor of Example 26 and the Sr2Si5N8:Eu2+ red 200944577 glory of Comparative Example 6 were similar. Therefore, in order to increase the comparison accuracy as much as possible, the fluorescent system of Example 26 was selected as much as possible from the green phosphor of Comparative Example 6. The atomic ratio of the (仏,Sr)2Si〇4:Eu2+ green luminescent agent of Example 26 to the heart of [Ba,Sr)2Si〇4:Eu2+ green luminescent agent shown in Fig. 32 is different from that of β&amp; However, the excitation wavelength dependence on internal quantum efficiency and external quantum efficiency is similar. Hereinafter, the light-emitting characteristics of the light-emitting devices of Example 26 and Comparative Example 6 will be described. Fig. 43 and Fig. 44 show the luminescence spectra of Example 26 and Comparative Example, respectively. As can be seen from FIG. 43 and FIG. 44, the light-emitting devices of Example 26 and Comparative Example 6 have very similar luminescence spectra, and all emit white light having a luminescence peak near 47 〇 nm and around 600 nm, that is, blue light is emitted. White light mixed with yellow light. Table 8 shows the characteristics of the light-emitting devices of Example 26 and Comparative Example 6. Table 8 Example 26 Comparative Example 6 Correlated color temperature (K) 3800 3797 duv 0 -0.02 Chromaticity (x, y) (0.3897, 0.3823) (0.3898, 0.3823) Ra 83 83 R9 31 33 Relative beam 98.7 100 Table 8 duv An index that shows the deviation of white light from the black body emission trajectory. Ra is the average color rendering number 'R9 is the special color evaluation number of red, and the color seen by the reference light is 100, which indicates the degree of reproduction of the test light to the test color faithful 81 200944577. Implemented under the same light color (correlated color temperature, duv and chromaticity)

In Example 26, although 发光\S〇2Si〇4:Eu2+ green phosphor having a low light-emitting intensity under irradiation of 47 〇nm light was used, Ra, R9 and a light beam which were substantially equivalent to those of Comparative Example 6 were also exhibited. Example 26 has the same luminescent performance as the conventional light-emitting device having both high color rendering and strong light beam. The reason is presumed to be the fluorescence used in Example 26 under the illumination of blue led light. The quantum efficiency inside the body is high, so that the blue color absorbed by the phosphor [ED

The emitted light can be efficiently wavelength-converted and illuminated, and the light emitted by the unabsorbed blue LED is efficiently output. Moreover, the correlated color temperature of the illuminating device can be arbitrarily adjusted by changing the above-mentioned fluorescence concentration or the thickness of the phosphor layer, and at least a phosphor having a predetermined spectral distribution and a predetermined internal quantum efficiency, and a transmittance are used. a base material of 1% by mass (for example, a resin) constitutes a phosphor layer, and a fixed output light-emitting element having a predetermined spectral distribution is used to constitute a light-emitting device, and

The number of color evaluations and the light-emitting characteristics such as the light beam when the correlated color temperature of the output light is changed are evaluated by simulation. Among them, the color evaluation number may not require an internal quantum efficiency value, and may be simulated only from the spectral distribution of the phosphor and the light-emitting element. Therefore, in order to examine the light color of the light-emitting device which has both high color rendering properties and strong light beams, the duv of the white light emitted by the light-emitting devices of Example 26 and Comparative Example 6 is used as the 〇 and the correlated color temperature is changed to simulate Ra Evaluate with the behavior of the relative beam. Fig. 45' shows the white light emitted from the light-emitting devices of Example 26 and Comparative Example 6 to simulate the influence of the relative light beam when the correlation color temperature was changed. It can be seen from FIG. 82 200944577 45 that 'Example 26 and Comparative Example 6 show the same fluctuation. When the color temperature of the white light is 3,000 to 6000 K, preferably 3500 to 5000 K, when the correlated color temperature is 3797 K, the implementation is performed. Example 26 is 95 to 100% of the light beam of Comparative Example 6, which is a strong beam. Further, the light beam when the correlated color temperature of Comparative Example 6 is controlled to 3797 K is indicated by a solid line in FIG. 45. FIG. 46 is a white light emitted from the light-emitting devices of Example 26 and Comparative Example 6 to change the correlated color temperature by analog evaluation. The impact on Ra. When the color temperature of the white light ray is ～5000 K, preferably 2500 to 4000 K, the Ra of Example 26 and Comparative Example 6 is a higher value of 80 or more. As can be seen from FIG. 45 and FIG. 46, when the color temperature of the white light is 3,000 to 5,000 K, preferably 3,000 to 4,500 K', more preferably 3,500 to 4,000 K, the embodiment 26 and the comparative example 6 can be obtained. A light-emitting device with a strong beam and high Ra. (Example 27) The (Ba,Sr)2Si〇4:Eu2 + green phosphor of Example 26 was changed from a phosphor having an emission peak near a wavelength 555 555 ηπι to a phosphor having an emission peak at a wavelength of 535 nm. A light-emitting device in which a duv is made into a crucible to change the correlated color temperature. Fig. 47 shows the results of evaluation of the white light emitted in Example 27 by simulation. As can be seen from Fig. 47, when the light-emitting device with a lower color Ra and a white light having a correlated color temperature of 2000 to 5000 K is produced, Ra is 80 or more, and when the correlated color temperature is 30 〇〇 κ or less, Ra is 9 〇 or more. . Fig. 48 shows the results of evaluation of R9 of the white light emitted in Example 27 in a simulation of 83 200944577. As can be seen from Fig. 48, when a light-emitting device having a white light having a color temperature of 2000 to 8000 K is produced, R9 is a high value of 40 or more, and when the correlated color temperature is 2500 to 6500 K, Ra is as high as about 80 or more. Fig. 49 is a graph showing the results of evaluation of the relative light beams when the correlated color temperature of the white light emitted in Example 27 was changed. In Fig. 49, when the color temperature of the white light of Example 27 is 2500~8000K, preferably 3000~5000K, more preferably 3500~4500K, Example 27 is shown as related in Comparative Example 6. The color temperature is a strong light beam of 82 to 85% of the beam at 3797K. Further, the light beam when the correlated color temperature of Comparative Example 6 is 3797 is shown by the solid line in Fig. 49. In Figs. 47 to 49, when the color temperature of the light-emitting device of Example 27 is 3000 to 5000 K, Ra and R9 are 80 or more, and a strong light beam is obtained and high color rendering output light is emitted. When the correlated color temperature is 3500 to 4500K, Ra and R9 are 82 or more, and a strong light beam is obtained and a higher color rendering output light is emitted. In particular, when the correlated color temperature is about 4000K, Ra and R9 are above 85, and a stronger beam is obtained and a higher color rendering output light is emitted. Fig. 50 is a view showing simulation data of the luminescence spectrum of the illuminating device of Example 27 which emits a particularly warm color-based white light having a correlated color temperature of 4000 K (duv = 0). In the luminescence spectrum, the chromaticity (X, y) was (0.3805, 0.3768), Ra was 86, and R9 was 95. The shape of the luminescence spectrum is emitted from 520 to 550 nm of the green phosphor of Example 27 emitted from the blue LED by the luminescence peak of the wavelength region of 460 to 480 nm and by the 5d-4f electron transfer of the rare earth ion. The luminescence peak, the intensity of the luminescence peak of 610 to 640 nm emitted by the red phosphor of Example 27 which is emitted by the 5d-4f electron transfer of the rare earth ion, is 460 to 480 nm: 520 to 55 〇 nm: 6 l 〇~64〇nm is 24~28, 12~15:16~20. One of the preferred embodiments of the present invention is a light-emitting device characterized in that the light-emitting peak has a warm-light white light having an H 匕 rate of an emission spectrum. Further, the phosphor which emits light by the transfer of the rare earth ions 5 (1_bake electrons) exhibits a rare earth ion such as 2+ or Ce3 + as a light-emitting center ion. When the wavelength of the luminescence peak is the same, a similar luminescence spectrum shape is formed regardless of the type of the phosphor precursor. Further, if the green phosphor of Example 26 is changed to have a luminescence peak in the wavelength range of 520 to 550 nm (BaSr) 2Si〇4: Eu2+ green phosphor, and added to a (Sr, Ba)Si〇4:Eu2+ yellow phosphor having an emission peak in the wavelength range of 560 to 580 nm, a high color rendering light-emitting device can be obtained from the simulation. For example, in the output light with a relative color temperature of 380 〇K, duv=〇, and chromaticity (0.3897, 0.3823), 1^ is 88, 119 is 72, and the relative beam is 93%. The phosphor of Example 26 is changed. For shorter, for example, (Ba, Sr)2Si〇4:Eu2+ green phosphors with a luminescence peak in the 52〇nm long region, the color temperature is compared with Ra, R9 and relative in the simulation of duv=〇 light color conditions. The relationship between the beams, and the result is that the shorter the wavelength of the luminescence peak of the green phosphor The lower the number of Ra, R9 and relative light beams, the lower the performance of the illumination device. For example, when used for a green phosphor having a luminescence peak at a wavelength of 520 nm, when the correlated color temperature is 3800 K, duv = 0, In the case of chromaticity (〇.3897, 0.3823), it is assumed that 80 and ruler 9 are 71, and the relative light beam is 85%. From the above, it is understood that 'green 85 200944577 color phosphor having a wavelength of 525 nm or more is preferably used. The SrAlSiN3:Eu2+ red phosphor used in the embodiment 26 and the embodiment 27 is a red phosphor represented by the structural formula (MhxEuJAlSiN3, and the lanthanum is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, Further, X satisfies 0.005 SXS 0.3, which is not particularly limited. For example, CaAlSiN3:Eu2+ red phosphor can also obtain the same effect. Further, in place of SrAlSiN3:Eu2 + red phosphor, for example, a well-known nitrogen exhibiting similar luminescence characteristics can be obtained. a phosphor or an oxynitride phosphor, for example, a nitrogen oxide silicate phosphor represented by a structural formula (Mi-xEux)SiN2 or a structural formula or an oxo represented by a structural formula (M^EUxhSiAm?) When a nitride aluminosilicate phosphor The same effect can be obtained, wherein Μ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and X satisfies 0.005 S 0.3. Further, the 'green phosphor and the yellow phosphor are not limited to The user of the above embodiment can be used as long as it is a light-emitting body having a light-emitting peak in a wavelength region of 525 nm or more and less than 600 nm. For example, it can be used on the longest wavelength side of an excitation spectrum for a wavelength region of less than 42 〇 nm. The phosphor of the excitation peak. © In addition, YAG:Ce-based phosphors such as 'Y3 (A1, Ga) 5〇12: Ce3+ green phosphor, Y3Al5〇i2: Ce3 + green fluorescent light are known as fluorescent materials in white LEDs. The same effect can be obtained when the body, (Y, GdhAlsOaCe^ yellow phosphor, YsAlsOeCe'Pi^ yellow phosphor, or the like) is used as the green phosphor or the yellow phosphor. (Example 28) This example The card type lighting module light source 86 200944577 shown in FIGS. 41 and 42 is produced and evaluated for its light-emitting characteristics. The blue LED chip 49 described in the embodiment 26 or the embodiment 27 is modified to have a (four) heart illumination. The layer also emits a purple coffee wafer having a luminescence peak near the stencil. The output light of the embodiment can be excited by the light emitted by the purple LED chip to emit light, which is emitted by the phosphor contained in the trowel layer 3. The light is the main color mixed light, and the output light can be made into arbitrary white light by appropriately selecting the type and amount of the phosphor. Hereinafter, the phosphor layer 3 of the present embodiment will be described in detail. The phosphor layer 3' will be The epoxy resin to which the phosphor is added is dried and solidified to form. This embodiment The phosphor used in the three types of phosphors: SrA1SiN3:Eu2+ red glomerium with a luminescence peak near the wavelength of 625 (central particle size · 2 2 maximum internal quantum efficiency: 6〇%, internal quantum under the excitation of (10) Efficiency. About 60%), with a luminescence peak near the wavelength of 535 nm, S〇2Si〇4: Eu2+ green phosphor (central particle size: i 5 2 maximum internal quantum efficiency (4), internal quantum efficiency at 405 nm excitation About 97 〇 pepper has a luminescence peak near the wavelength of 4 〇 5 coffee BaMgAlu) 〇i7: Eu2+ blue phosphor (center particle size: 8.5 &quot; m, maximum internal quantum efficiency: about 1%, at 4 〇 fine The internal quantum efficiency under excitation: about %), while the epoxy resin is a two-liquid mixed epoxy resin, and the epoxy resin is mainly used as a main component of the A-type liquid epoxy resin, and The epoxy resin containing the alicyclic anhydride as the main component is a hardener. Further, the above-mentioned SrA1SiN3:Eu2+ red glory is not optimized as the production conditions are satisfied, so the internal quantum efficiency is low, but in the future, it can be improved by optimizing the manufacturing conditions. Internal quantum efficiency is more than h5 times. SrAisiN3: Eu2+ red Color phosphor, (Ba, Sr) 2Si〇4: Eu2+ green phosphor and 87 200944577

BaMgAl1G〇17: EU2+ blue fluorescent 鳢 weight mixing ratio is about 6: 丨丨: 3 〇, the mixing ratio of the mixed phosphor to the epoxy resin is about 丨: 3 (phosphor concentration = 25% by weight) ). (Comparative Example 7) A card type illumination module light source was produced in the same manner as in Example 28 using three kinds of phosphors: LhOAEf red phosphor having a luminescence peak near a wavelength of 626 nm (central particle) Diameter: 93 (4) Maximum internal quantum efficiency: 84%, internal quantum efficiency at 402 nm excitation: about 50%) 'Yu wave| (BaSr)2Si〇4: Eu2+ 〇 green phosphor (central particle size) near 535 nm : 15.2 "m, maximum internal quantum efficiency: 97%, internal quantum efficiency at 405 nm excitation: about 97%), and BaMgAlwOKEu2 - blue phosphor with luminescence peak at a wavelength of 4 〇 5 nm (center particle diameter: 8.5 //111, maximum internal quantum efficiency: about 1〇〇%, internal quantum efficiency at 4〇511111 excitation: about 1〇〇%ρ phosphor layer 3, which is La2〇2S:Eu3 + red phosphor, (Ba, Sr) 2Si〇4: Eu2+ green phosphor and BaMgAhOaEi^ blue phosphor, mixed in a weight mixing ratio of about 155:20:33, the mixing ratio of the mixed phosphor to the weight of the epoxy resin〇 It is about 1:3 (phosphor concentration = 25% by weight), and as in Embodiment 28, by flowing a current through half The body light-emitting device obtains the light emitted from the wheel and evaluates the light-emitting characteristics of the output light. The thickness of the white light 'phosphor layer 3 to the homogenous light color (correlation color temperature of about 3800 K, duv, chromaticity) is compared with Example 28 and Each of Examples 7 was formed to have a thickness of about 500 m. The following description of the light-emitting device of Example 28 and Comparative Example 7 was carried out. The light-emitting spectrum of Example 28 and Comparative Example 7 is shown in FIG. As can be seen from FIG. 51 and FIG. 52, the light-emitting devices of Example 28 and Comparative Example 7 emit white light having a luminescence peak near 405 nm, around 450 nm, around 535 nm, and around 625 nm, that is, purple light is emitted. White light mixed with blue light, green light and red light. Further, the illuminating sound near 405 nm is the light leakage of the purple light-emitting element, and the illuminating peak near 45 Onm, around 535 nm, and near 625 nm is fluorescent. The light is converted into light of the above-mentioned purple light wavelength. Table 9 shows the light-emitting characteristics of the light-emitting devices of Example 28 and Comparative Example 7.

Table 9 Example 28 Comparative Example 7 Correlated color temperature (K) 3800 3792 duv 0 0.03 Chromaticity (x, y) (0.3897, 0.3823) (0.3901, 0.3826) Relative beam (%) 117 100 Ra 96 78 R1 98 71 R2 97 93 R3 92 82 R4 93 67 R5 98 77 R6 98 85 R7 96 85 R8 95 66 R9 83 34 R10 92 91 R11 90 62 R12 92 90 R13 99 77 R14 94 86 R15 97 71 89 200944577 The duv of Table 9 is white light The index of deviation from the blackbody emission trajectory. Ra is the average color rendering number, and R1 to R15 are the special color evaluation numbers, and it is not necessary to set the color of the reference light to 1 〇〇, and the test light faithfully reproduces the degree of the test color. In particular, R9 is a special color evaluation number of red. Although a red phosphor having a production condition of a phosphor that has not been optimized, a maximum internal quantum efficiency of 60%, and low performance is used, Example 28 is under the condition of approximately equivalent light color (correlated color temperature, duv, and chromaticity). It is possible to emit white light which is 17% higher than the relative light beam of Comparative Example 7. In Comparative Example 7, the maximum internal quantum efficiency of the red phosphor was 83%, and the output efficiency of the light-emitting device was improved by about 20%. However, the maximum internal quantum efficiency of the red phosphor used in Example 28 was 6. 〇% can improve the white output of the illuminating device by more than 60%. That is to say, in theory, the material of the light-emitting device of Embodiment 28 constitutes a white light which can emit a strong light beam. Further, in the light-emitting device of the twenty-eighth embodiment, when white light having a correlated color temperature of 3800 K is emitted in combination with at least the above-described phosphor, Ra can be larger than that of Comparative Example 7. Further, not only the number of special color renderings of all of R9' R1 to R15, but also a number I which is larger than that of Comparative Example 7, it is shown that Example 28 can emit white light having excellent color rendering properties. Further, in the light-emitting device of the twenty-seventh embodiment, it is possible to emit a high color rendering white light having a special color plaque of R1 to R15 of 80 or more, which is displayed to emit light close to sunlight. The illuminating device is particularly suitable for medical use, for example, it can be provided as an LED light source that can be applied to an endoscope or the like, and can be used in an excellent endoscope system that is diagnosed under the sunlight of the sun. Hereinafter, in order to examine the light color of the light-emitting device having both high color rendering property and strong light beam, the duv of the white light emitted by the light-emitting devices of Example 28 and Comparative Example 7 is 〇, and the Ra and the relative beam influence are changed when the correlated color temperature is changed. , evaluate by simulation, and explain the results. Fig. 53 is a view showing the relative light beams obtained by changing the correlated color temperatures of the white light emitted from the light-emitting devices of Example 28 and Comparative Example 7, and the evaluation results were carried out using simulation. As is apparent from Fig. 53, the light-emitting device of Example 28 can emit white light of about 10 to 20% higher than that of Comparative Example 7 in the wide range of correlated color temperatures of 〜 2000 to 12000K. Further, when the light-emitting device of the embodiment 28 is configured to output light having a correlated color temperature of 2500 to 12000 K, preferably 3500 to 7000, it is about 110 to 115% of the light beam of Comparative Example 7 at a correlated color temperature of 37921^. Strong beam. Further, the solid line in Fig. 53 indicates the light beam when the correlated color temperature of Comparative Example 7 is 3792K. Hereinafter, it is assumed that the production conditions of the respective phosphors used in Example 28 and Comparative Example 7 have been optimized, and a Dengguang® body having a maximum internal quantum efficiency of 1% is obtained, and the beam is simulated with the ideal phosphor. The result of the evaluation. This simulation was evaluated by the internal internal quantum efficiency of Figs. 30, 32, 37, and 40 as estimated by excitation of each of the phosphors in the following Table 10 at 405 nm. Fluorescent 髅 Internal quantum efficiency (%) SrAlSiN3: EuiT red fluorescent light 100 La202S: Eu3+ red fluorescent body 60 (Ba, Sr) 2Si 〇 4: Eu' green fluorescent 艎 100 BaMgAl1 () 〇 n: Eua blue Phosphor 100 91 200944577 In Fig. 54, the effect of changing the influence of the correlated color temperature of the white light emitted from the light-emitting device of Example 28 and Comparative Example 7 on the relative light beam was simulated by using an ideal phosphor. As can be seen from Fig. 54, in the light-emitting device of Example 28, when an ideal phosphor is used, a wide range of correlated color temperatures of 2000 to 12000 K can be used to emit white light of about 45 to 65% higher than that of Comparative Example 7. . Further, when a light-emitting device having a white light-related color temperature of 25 00 to 1200 0K, preferably 3500 to 6000K is produced, it is a light beam of 150 to 160% or more of the light beam at a correlated color temperature of 3 792 K in Comparative Example 7. . Further, the light beam when the correlated color temperature of Comparative Example 7 is 3792 , is indicated by the solid line in Fig. 54. In other words, it is presumed that in the future, the SrAlSiN3:Eu2+ red phosphor can be obtained by a high-performance device, and a light-emitting device having a light beam height of about 45 to 65% higher than that of the comparative example 7 can be obtained under the same correlated color temperature evaluation. Further, Fig. 55 shows the results of the evaluation of the influence on the average color rendering number (Ra) when the color temperature of the white light emitted from the light-emitting devices of Example 28 and Comparative Example 7 was changed. The illuminating device of the illuminating device of the illuminating device of the illuminating device has a color temperature range of 2000 to 12000 K and exhibits a range of 90 or more. To Ra', and preferably a luminescent device of 3000 to 12000 K, a very high Ra of 95 or more is exhibited. . Fig. 56 is a graph showing the results of evaluation by simulation when the correlation color temperature of red (R9) was changed when the correlated color temperature of white light emitted by the light-emitting devices of Example 28 and Comparative Example 7 was changed. The R9 of the light-emitting device of Example 28 having a correlated color temperature of 2500 to 12000 K was larger than Comparative Example 7. Further, the color temperature of the light-emitting device of Example 28 is "(10) ~ 丨 2 〇〇〇 之 广泛 92 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 120001^ is 80 or more, and 50005~120001^ is 90 or more high R9, which is a preferred light-emitting device for emitting white light with a high red color appearance evaluation number. Further, the R9 maximum value can be obtained in a correlated color temperature range of 6000 to 8000K. (96 to 98) It can be seen from Figs. 53 to 55 that the light-emitting device of the embodiment 28 can emit a white light of a strong light beam and a high Ra ratio in Comparative Example 7 over a wide range of correlated color temperatures of 2000 to 12000 K. When the light-related color temperature is 0 2500 to 12000 K, preferably 3500 to 7000 K, and more preferably 4000 to 5000 K, the light beam can have both a strong beam and a high Ra. As can be seen from FIGS. 56 to 58, the light-emitting device of Embodiment 28 The wide range of correlated color temperatures of 2500 to 12000K can emit white light of Comparative Example 7 and high R9, and the correlated color temperature for producing white light is 3000~12000K, preferably 3500~12000K, more preferably 5000~12000K. , especially good for 6000~8000k At the time of setting, it can combine both a strong beam and a high R9». Fig. 57 shows the luminescence spectrum of the illuminating device of the illuminating device of Example 28 which emits a light beam and a Ra to a correlated color temperature of 4500K (duv = 0) Ο. Medium, chromaticity (again, 乂) is (〇.3608, 0.3635), 1^ is 96, R1 is 96, R2 and R6~R8 are 97, R3, R10 and R11 are 91, R4 and R14 are 94, R5 R13 and R15 are 99, and R9 and R12 are 88. From the above, it is known that a light-emitting device can be provided which can emit white light having good color rendering properties of R1 to R15 of 85 or more. The shape of the light-emitting spectrum It is an RGB phosphor that emits light having a luminescence peak in a wavelength range of 400 to 410 nm from an ultraviolet color LED and emits light by electron transfer from a rare earth ion of 5 &lt;i-4f. The RGB phosphor of Example 28 200944577 is at 440 to 460 nm, 520. The luminescence peaks in the wavelength range of ~540nm and 610~640nm have an intensity ratio of 400 to 410 nm: 440 to 460 nm: 520 to 540 nm: 610 to 640 nm are 8 to 10: 12 to 14: 15 to 17: 16 to 18. One of the forms is a light-emitting device 'characterized to emit a light-emitting peak having the above ratio Warm color white light spectrum shape. Further, the rare earth ions 5d-4f electron mobility of the light-emitting phosphor, a phosphor mainly containing means to Eu2 + or Ce3 + rare earth ions such as luminescent center ion. When the wavelength of the luminescence peak is the same, the luminescence spectrum shape of the phosphor is similar regardless of the type of the phosphor precursor. Fig. 58 is a view showing the luminescence spectrum simulation data of the illuminating device of Example 28, which emits a light beam and a white light having a correlated color temperature of 5500 K (duv = 0). In the luminescence spectrum, the chromaticity (x, y) is (0.3324, 0.3410), Ra is 96, R1 and R13 are 98, R2 and R8 and R15 are 97, R3 and R12 are 90, R4 is 92, and R5 is 99. 'R6 is 96, R7 is 95, R9 and R14 are 94' R10 and R11 is 91. That is, according to the present invention, it is possible to provide a light-emitting device which emits white light of almost all of the special color evaluation numbers of R1 to R15 suitable for medical use and which is close to sunlight. Further, regarding the shape of the luminescence spectrum, the RGB phosphor of Example 28 in which the ultraviolet color LED emits light having a luminescence peak in a wavelength range of 400 to 410 nm and emits light by 5 d-4f electron transfer from the rare earth ion is 440. The intensity ratio of the luminescence peaks in the wavelength regions of 460 nm, 520 to 540 nm, and 610 to 640 nm is 400 to 410 nm: 440 to 460 nm: 520 to 540 nm: 610 to 640 nm is 4 to 6: 9 to 11: 8 to 10: 7 to 9. One of the preferred embodiments of the light of the present invention is a luminescent ray 94 200944577 which is characterized by being capable of emitting white light having an illuminating spectral shape having a ratio of the above-mentioned ratio. Example 28 illustrates the combination of three kinds of phosphors of purple LED and red green blue (rgb), and SrA1SiN3:Eu2+ as red light. When at least the above-mentioned purple one or the like (the combination of phosphors represented by the structural formula of MhEudMSiN3) When the composition of the phosphor is four kinds of red yellow green blue (RYGB) or red yellow blue (ryb), the same action and effect can be obtained. 实施 Example 28 shows the use of SrAlSiNyEi^ as red fluorescent light. In the case of a body, the phosphor is represented by the structural formula (Mi x EUx) A1SiN3, and the element is at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and x is 0.005 S. The value of 0.3 is not particularly limited, and the green phosphor is not limited to the green phosphor used in the above embodiment, and is a green fluorescent light having a light-emitting peak in a wavelength region of 560 nm or more and less than 600 nm. The green phosphor may be replaced by a yellow ruthenium body having a luminescence peak of 560 nm or more and less than 600 nm. The light output of the green or yellow phosphor is preferably Eu2+ or Ce3+ activated phosphor. Due to SrAlS The characteristics of the iN3:Eu2+ red phosphor are similar to those of the conventional red phosphor 'for example, a nitride phosphor or an oxynitride phosphor such as SrSm2: Eu2+, Sr2Si5N8: Eu2+, Sr2Si4A10N7: Eu2+, and thus Example 27 And the same effect can be obtained by substituting the SrAlSiN3:Eu2+ red phosphor with the above-described conventional nitride glomer or oxynitride phosphor. In the following, SrAlSiN3: Eu2+, Sr2Si5N8 in the above phosphor will be described. : 95 200944577

Eu2+, SrSiN2: Eu2+, (Ba, Sr)2Si04: Eu2+ (luminescence peak: 555 nm), (Ba, Sr) 2Si04: Eu2+ (luminescence peak: 535 nm), (Ba, Sr) 2Si04: Eu2+ (luminescence peak: 520 nm) A method for producing (Sr, Ba)2Si〇4: Eu2+ (luminescence peak: 570 nm) is for reference. Further, a commercially available product was used for the Y3Al5012:Ce3+ yellow phosphor, the La202S:Eu3+red phosphor, and the BaMgAl10O17:Eu2+ blue fluorescent system. Tables 11 and 12 show the mass of the raw material compound used in the production of each phosphor. Table 11 Phosphor phosphor raw material (g) Sr3N2 Si3N4 AIN Eu2〇3 SrAlSiNj: Eu2+ 10.000 4.291 4.314 0.370 Sr2Si5N8: Eu2+ 10.000 12.303 0 0.370 SrSiN2: Eu2+ 10.000 4.291 0 0.370 Table 12 Fluorescent phosphor raw material (g BaC03 SrC03 Si02 Eu2〇3 (Ba,Sr)2Si〇4: Eu2+ (peak: 520 nm) 386.457 183.348 100.000 11.480 (Ba,Sr)2Si04: Eu2+ (peak: 535 nm) 257.638 279.847 100.000 11.480 (Ba,Sr)2Si04: Eu2+ (peak: 555 nm) 128.819 376.345 100.000 11.480 (Ba, Sr) 2Si04: Eu2+ (peak: 570mn) 32.205 448.719 100.000 11.480

The method for producing the three red phosphors shown in Table 11 will be described below. First, a predetermined compound shown in Table 11 was mixed in a dry nitrogen atmosphere using a handle box and a mortar to obtain a mixed powder. At this time, no reaction accelerator (flux) is used. Next, the mixed powder is placed in an aluminum crucible, and temporarily calcined in a nitrogen atmosphere at a temperature of 800 to 1400 ° C for 2 to 4 hours, and then at a temperature of 1600 to 1800 ° C in a nitrogen atmosphere of 97%, a hydrogen atmosphere of 3%. The firing was carried out for 2 hours to synthesize a red phosphor. The phosphor powder after the firing is 96 200944577. After the firing, a predetermined post-treatment such as pulverization, classification, washing, and drying is applied to obtain a red phosphor.

Next, a description will be given of a method of manufacturing four kinds of green phosphors and yellow phosphors shown in Fig. 12 . First, a predetermined compound shown in Table 12 was mixed in the atmosphere using a mortar to obtain a mixed powder. Next, the mixed powder is placed in an aluminum crucible and temporarily calcined in an atmosphere at a temperature of 950 to 1000 t for 2 to 4 hours until the powder is temporarily calcined. Calcined calcium (CaCD powder 3.62 〇g as a fluxing agent was added to the temporarily calcined powder at a temperature of 1200 to 1300. (: Nitrogen 97%, © hydrogen atmosphere 3% ambient atmosphere for 4 hours, this was baked. Synthetic green illuminant and yellow phosphor. After the firing, the phosphor powder is green to yellow. After the firing, the granules are pulverized, classified, washed, dried, and the like, and the green phosphor is described. The present invention can be carried out in other forms than those described above. The embodiments disclosed in the present application are merely examples, and are not limited thereto. All the changes within the scope of the above-mentioned specification are included in the scope of the patent application. The composition of the present invention is represented by the structure shown in the figure b·BN1N. The composition is a main body of the phosphor precursor. In the above structural formula, Μ is an element selected from at least one of Mg, Ca, Sr, Ba, and Ζη, and a, b, and e satisfy 0.2Sa/(a+b). 〇.95, 0.05gb/(b+c) 〇8, 〇4gc/ (c+a) S 0.95 ; in particular, the structural formula of the α MA leg 3 is the main body of the labyrinth precursor, which can be excited by ultraviolet to near ultraviolet ~ violet ~ blue ~ green ~ yellow ~ orange light In particular, a novel phosphor which emits a red color of a warm color is used. 97 200944577 Further, the method for producing a phosphor composition of the present invention is a compound containing a compound which generates an oxide of the above element due to heating, and a ruthenium compound. , a compound containing a compound containing an element forming a luminescent center ion, and a raw material of carbon 'reacted in a nitriding gas atmosphere to produce a phosphor composition, which does not require chemical instability and is difficult to operate in the atmosphere. A high-priced alkaline earth metal nitride or an alkaline earth metal is used, and an easy-to-operate and inexpensive raw material is used to produce the phosphor group of the present invention. Therefore, it is possible to inexpensively industrially produce a novel nitride phosphor having good material properties. Further, the illuminating device of the present invention is made of the above-described phosphor composition of the present invention which emits warm color light, especially novel, high performance and low cost. Therefore, it is possible to provide a light-emitting device (led light source, etc.) having a strong red light-emitting component, high performance, low cost, and novel material composition. Furthermore, according to the present invention, it is possible to provide both high color rendering and strong light beam. Further, a light-emitting device that emits white light, in particular, can provide a light-emitting device such as an LED light source that emits warm white light and has a strong red light-emitting component. [FIG. 1] FIG. 1 is a semiconductor light-emitting device according to an embodiment of the present invention. Fig. 2 is a cross-sectional view of a semiconductor light emitting device according to an embodiment of the present invention. Fig. 3 is a cross-sectional view showing a semiconductor light emitting device according to an embodiment of the present invention. Fig. 4 is a schematic view showing the configuration of an illumination and display device according to an embodiment of the present invention. . Fig. 5 is a schematic view showing the configuration of an illumination and display device according to an embodiment of the present invention. 98 200944577 Fig. 6 is a perspective view of a lighting module in accordance with an embodiment of the present invention. Fig. 7 is a perspective view of a lighting module in accordance with an embodiment of the present invention. Fig. 8 is a perspective view of the lighting device in the embodiment of the present invention. Fig. 9 is a side view of the lighting device in the embodiment of the present invention. Figure 10 is a bottom plan view of the lighting device of Figure 9. Figure 11 is a perspective view of a video display device in accordance with an embodiment of the present invention. Figure 12 is a perspective view of a digital display device in accordance with an embodiment of the present invention. Figure 13 is a partial perspective view of the end portion of the fluorescent lamp in the embodiment of the present invention. Figure 14 is a cross-sectional view showing an EL panel in an embodiment of the present invention. Fig. 15 is a view showing the luminescence spectrum and excitation spectrum of the phosphor composition in the first embodiment of the present invention. Fig. 16 is a view showing a calender diffraction pattern of the phosphor composition in the first embodiment of the present invention. Fig. 17 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 2 of the present invention. © Fig. 18 shows an X-ray diffraction pattern of the glare composition in the second embodiment of the present invention. Fig. 19 is a view showing the luminescence spectrum of the phosphor composition according to Example 2 of the present invention. Fig. 20 is a graph showing the relationship between the Eu substitution amount and the luminescence peak wavelength of the phosphor composition according to Example 2 of the present invention. Fig. 21 is a graph showing the relationship between the Eu substitution amount and the luminescence intensity of the phosphor composition according to Example 2 of the present invention. 99 200944577 Fig. 22 shows an emission spectrum and an excitation spectrum of a fluorescent iridium composition in Example 3 of the present invention. Fig. 23 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 4 of the present invention. Fig. 24 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 5 of the present invention. Fig. 25 is a view showing an emission spectrum and an excitation spectrum of a phosphor composition in Example 6 of the present invention. Fig. 26 is a view showing the luminescence spectrum © and the excitation spectrum of the phosphor composition in Example 7 of the present invention. Fig. 27 is a view showing the luminescence spectrum and excitation spectrum of the varnish composition in the eighth embodiment of the present invention. Fig. 28 is a three-element diagram showing the composition range of the phosphor composition of the present invention. Fig. 29 is a graph showing the luminescence characteristics of a SrSiN2:Eu2+ red phosphor. Fig. 30 is a graph showing the luminescence characteristics of a SrAlSiN3:Eu2+ red phosphor. Fig. 31 is a graph showing the luminescence characteristics of a Si2Si5Ns:Eu2+ red phosphor. ® Figure 32 shows the luminescence characteristics of the (Ba,Sr)2Si〇4:Eu2+ green phosphor. Fig. 33 is a graph showing the luminescence characteristics of (Sr, Ba) 2Si 〇 4: Eu 2+ yellow phosphor. Fig. 34 is a view showing the illuminance of (Sr,Ca)2Si〇4:Eu2+ yellow phosphor. Fig. 35 is a graph showing the luminescence characteristics of a 0.75CaO2.25AlN3.25Si3N4:Eu2+ yellow phosphor. Fig. 36 is a graph showing the luminescence characteristics of (Y, Gd)3Al5〇i2:Ce3 + yellow phosphor. 100 200944577 Figure 37 shows the luminescence characteristics of BaMgAl10O17:Eu2+ blue phosphor. Fig. 38 is a graph showing the luminescence characteristics of a Si^AImOkEu2·&quot; blue-green phosphor. Fig. 39 is a view showing the light-emitting characteristics of (Sr, Ba)10(PO4)6Cl2:Eu2+ blue phosphor. Fig. 40 is a view showing the luminescence characteristics of the La202S:Eu3 + red phosphor. Figure 41 is a perspective view of a light-emitting device of Embodiment 26 of the present invention. Figure 42 is a partial cross-sectional view of a light-emitting device of Example 26 of the present invention. Figure 43 is a graph showing the luminescence spectrum of a light-emitting device of Example 26 of the present invention. Fig. 44 is a chart showing the luminescence spectrum of the light-emitting device of Comparative Example 6 of the present invention. Fig. 45 is a graph showing the results of simulating the relationship between the correlated color temperature and the relative light beam in Example 26 and Comparative Example 6 of the present invention. Fig. 46 is a graph showing the results of simulating the relationship between the correlated color temperature and Ra in Example 26 and Comparative Example 6 of the present invention. Fig. 47 is a graph showing the results of simulating the relationship between the correlated color temperature and Ra in the twenty-seventh embodiment of the present invention. Fig. 48 is a view showing the result of simulating the relationship between the correlated color temperature and R9 in the twenty-seventh embodiment of the present invention. Fig. 49 is a view showing the result of simulating the relationship between the correlated color temperature and the relative light beam in the twenty-seventh embodiment of the present invention. Figure 50 is a graph showing the luminescence spectrum of a light-emitting device in Example 27 of the present invention. Figure 51 is a graph showing the luminescence spectrum of a light-emitting device in Example 28 of the present invention. Figure 52 is a graph showing the luminescence spectrum of a light-emitting device of Comparative Example 7 of the present invention. Figure 53 is a graph showing the results of simulation of the relationship between the correlated color temperature 101 200944577 and the relative light beam in Example 28 and Comparative Example 7 of the present invention. Figure 54 shows the use of 1 in Example 28 and Comparative Example 7 of the present invention.

A simulation result plot of the relationship between the correlated color temperature and the relative beam of a luminescent device of a phosphor. Fig. 55 is a graph showing the results of simulation of the relationship between the correlated color temperature and Ra in Example 28 and Comparative Example 7 of the present invention. Fig. 56 is a graph showing the results of simulation of the relationship between the correlated color temperature and R9 in Example 28 and Comparative Example 7 of the present invention. Fig. 57 is a view showing the simulation results of the luminescence spectrum of the light-emitting device of the warm-light white light of the light-emission-related color temperature ◎ 4500K (duv = 0) in the twenty-eighthth embodiment of the present invention. Fig. 58 is a view showing the simulation results of the luminescence spectrum of the illuminating device of the warm-color white light having an emission-related color temperature of 5,500 K (duv = 0) in Example 28 of the present invention. [Description of main component symbols] 1 Light-emitting element 2 Phosphor composition 〇3 Phosphor layer 4 Base element 5 Lead frame 6 Cup body 7 Sealing material 8 Frame 9 Semiconductor light-emitting device 102 200944577 ίο 11 12 13 14 15 16 17 ❹ 18 19 20 21 22 23 24 25 Ο 26 27 28 29 30 31 32 Output light illuminating part lighting module switch lamp reflector glass tube tube fluorescent body composition wire filament electrode electrode terminal lamp back substrate lower electrode thick film dielectric Bulk film phosphor film dielectric upper electrode light wavelength conversion layer surface glass wavelength conversion layer wavelength conversion layer blue light 33 200944577 34 green light 35 red light 36 excitation spectrum of phosphor composition 37 glow of phosphor composition Spectral 40 Internal quantum efficiency of the phosphor 41 External quantum efficiency of the phosphor 42 Internal quantum efficiency of the phosphor 43 External quantum efficiency of the phosphor 44 Semiconductor light-emitting device 45 Si diode 46 η electrode 47 ρ electrode 48 micro Bump 49 Blue LED chip 50 Aluminum metal substrate 51 1st source thick film 52 Copper electrode 53 2nd insulator thick film 54a, 54b Electrode pad 5 5 Heat-dissipating multi-layer substrate 56 Inner electrode 57 Au wire 58 Bonding pad 59 Aluminum metal reflector 104 200944577 稜鏡 60

105

Claims (1)

200944577 VII. Patent application scope: 1. A phosphor composition containing nitrogen represented by any one of MAlSiN3 · a, Si3N4, MAlSiN3 · a'M2Si5N8, MAlSiN3 · a, MSiN2, gas MAlSiN3 · a MSi7N1Q The compound is a main body of the phosphor precursor and contains a metal ion selected from the group consisting of a rare earth ion and a transition metal ion as a light-emitting center ion, wherein the structure is selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. At least one element of the group formed, a' is a value of 〇.25Sa, $2. 2. The phosphor composition according to claim 1, wherein the illuminating light mother system is a composition represented by the structural formula of mais "n7." a composition in which one of the elements A1 is partially substituted with an element which is trivalent, and the amount of substitution is less than 30 atom% with respect to the element A1. 4. The phosphor composition according to claim 1 of the patent application, a metal element having an amount equivalent to less than 1 atomic % of at least one of the elements Μ, A1, or si. 5. The phosphor composition of claim i, which contains equivalent to the element 6. The amount of oxygen of less than 1 atomic % of N. 6. The phosphor composition of claim 1, which contains at least one atom corresponding to at least one of the element Μ, Ab or si. % of the metal element 'and contains an amount of oxygen corresponding to less than 1 atomic % of the element N. 7. The phosphor composition of claim 1, wherein the luminescent center ion is selected from the group consisting of C An ion of at least one of ^ + and Eu2+. 8. A phosphor group as in claim 7 The amount of the light center ion added to the element 106, which is 0.5 atom% or more and 10 atomic % or less with respect to the element Μ. 9. The phosphor composition of the first aspect of the patent application, wherein The main component of the element is selected from the group consisting of at least one element of Ca and Sr. 10. The phosphor composition of claim </ RTI> wherein the main component of the element is Sr. The phosphor composition of the seventh aspect, wherein the luminescent center ion is Eu 2+ , and the phosphor composition has an illuminating peak in a wavelength region of 58 〇 nm or more and lower than 66 〇 nm. The device is characterized in that it comprises a phosphor composition of claim 1 as a light-emitting source. 13. The light-emitting device according to claim 12, further comprising a light emitting device of 360 nm or more and less than 56 nm. a primary light emitting source that absorbs the primary light emitted by the emitting source to emit a secondary light having a wavelength greater than the primary light. 14. For example, in the illumination device of claim 13 (4), wherein , the emission source The light-emitting device of the invention of claim 14 is a white light-emitting device. The light-emitting device of claim 14, which is a display device comprising a white light-emitting element, comprising A light source of a white light-emitting element or an illumination device containing a white light-emitting element.