JP2007210831A - Nitridosilicate-based compound, method for producing the same, and nitridosilicate-based phosphor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for inexpensively producing a nitridosilicate-based compound being a mono-crystal phase and high in quality in good reproducibility, and to provide the nitridosilicate-based compound. <P>SOLUTION: This method for producing a nitridosilicate-based compound comprises reacting a raw material containing a compound oxide of gallium and an alkaline earth metal M1 (M1 denotes at least one element selected from among Mg, Ca, Sr and Ba), a silicon compound and carbon in a nitriding gas atmosphere. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a nitridosilicate compound (for example, nitridosilicate, oxonitridosilicate, nitridoaluminosilicate, oxonitridoaluminosilicate, alkaline earth metal sialon, etc.) that can be applied as a ceramic material or a phosphor material. , A compound containing at least an alkaline earth metal element, a silicon element, and a nitrogen element, a phosphor using the compound as a phosphor matrix, and a production method thereof.

  Conventionally, (1) alkaline earth metal element M (where M is at least one element selected from Mg, Ca, Sr, and Ba), (2) silicon, and (3) nitrogen are the main components. Nitridosilicate compounds containing at least elements are known.

Examples of the nitridosilicate compound include Sr ₂ Si ₅ N ₈ , Ba ₂ Si ₅ N ₈ (for example, see Patent Documents 1 to 3 and Non-Patent Document 1), BaSi ₇ N ₁₀ (for example, Patent Document). 1-3), SrSiAl ₂ O ₃ N ₂ , Sr ₂ Si ₄ AlON ₇ (see, for example, Patent Document 4), general formula M _{p / 2} Si _12-pq Al _{p + q} O _q N _16-q (However, M is Ca alone or combined with Sr, q is 0 ≦ q ≦ 2.5, and p is 1.5 ≦ p ≦ 3) (see, for example, Patent Document 5). ), (Ba, Eu) ₂ Si ₅ N ₈ (for example, see Non-Patent Document 2), Sr ₃ Ce ₁₀ Si ₁₈ Al ₁₂ O ₁₈ N ₃₆ (for example, see Non-Patent Document 3), CaSiN ₂ (for example, Non-Patent Document 4), CaAlSiN ₃ (see Non-Patent Document 5, for example), CaSi ₂ O ₂ N ₂ , SrSi ₂ O ₂ N ₂ (see, for example, Patent Document 7), (Ca, Sr, Ba) Al _2−x Si _x O _4−x N _x (where x represents 0 <x <2) For example, refer to Patent Document 8).

The nitridosilicate compound can be used not only as a ceramic material but also as a phosphor material. For example, it is known that a nitridosilicate compound containing Eu ²⁺ or Ce ³⁺ becomes a highly efficient phosphor (see, for example, Patent Documents 1 to 6).

  Further, the above-described highly efficient phosphor composed of the nitridosilicate compound is excited by near ultraviolet to blue light and emits blue, green, yellow, orange, or red visible light. It is also known that the LED is suitable for a light source (see, for example, Patent Documents 1 to 3 and Non-Patent Documents 4 and 5). In addition, use of a combination of a plurality of these phosphors in a light emitting device such as a white LED light source has been studied.

  As a method for producing such a nitridosilicate compound, a direct nitride reaction method using an alkaline earth metal nitride as the alkaline earth metal source and using silicon nitride as the silicon source is generally known. (For example, refer to Patent Document 1).

Further, an alkaline earth metal compound MO that can generate an alkaline earth metal oxide MO (wherein M is at least one element selected from Mg, Ca, Sr, and Ba) by heating, a silicon compound, and carbon. Also known is a carbothermal reduction nitriding method in which the reaction is performed in a nitriding gas atmosphere (for example, see Patent Document 9).
Special table 2003-515655 gazette Special table 2003-515665 gazette JP 2002-322474 A JP 2003-206481 A JP 2003-203504 A JP 2003-124527 A International Publication No. 04/030109 Pamphlet JP 2005-529229 A International Publication No. 05/049763 Pamphlet T. Schlieper et al., “Zeitschrift Fair Anorganische und Argemeine Hummy (Z. Anorg. Allg. Chem.)”, 1995, Vol. 621, p. 1380-1384 H.A Hope et al., “Journal of Physics and Chemistry of Solids”, 2000, Vol. 61, p. 2001-2006 W. Schnick, et al., “International Journal of Inoganic Material” (Int. J. Inorg. Mater.), 2001, Volume 3, p. 1267-1272 Yuta Ueda et al., “Proceedings of the 71st Annual Conference of the Electrochemical Society of Japan”, 2004, p. 75 Naoto Hirosaki et al., “National Institute for Materials Science Press Release”, August 31, 2004, No. 90

  However, according to the method for producing a nitridosilicate compound by the nitride direct reaction method, there is a problem that mass production is difficult because it is difficult to handle in the air and uses an expensive raw material. Another problem is that it is difficult to obtain a compound with high purity with good reproducibility because oxygen, which is an impurity, is likely to be mixed during production.

  On the other hand, according to the method for producing a nitridosilicate compound by the carbothermal reduction nitriding method, although it can be produced using a raw material that is inexpensive and easily available, to produce a single crystal phase nitridosilicate compound However, since mixing conditions of raw materials, temperature conditions, and the like must be strictly controlled, there is a problem that it is difficult to obtain a high-quality and high-performance compound with good reproducibility.

  The present invention relates to a method for producing a nitridosilicate compound that can produce a nitridosilicate compound having a single crystal phase and high quality at low cost and with good reproducibility, as well as a single crystal phase and high quality. Provided are a quality nitridosilicate compound and a nitridosilicate phosphor.

  The first method for producing a nitridosilicate compound of the present invention is a composite oxide of an alkaline earth metal M1 and gallium (provided that M1 contains at least one element selected from Mg, Ca, Sr and Ba). And a raw material containing a silicon compound and carbon is reacted in a nitriding gas atmosphere.

  The second method for producing a nitridosilicate compound of the present invention is represented by the chemical formula M2O by heating (wherein M2 represents at least one element selected from Mg, Ca, Sr and Ba). A raw material containing an alkaline earth metal compound capable of producing an alkaline earth metal oxide, a silicon compound, a gallium oxide, and carbon is reacted in a nitriding gas atmosphere.

  The first nitridosilicate compound of the present invention is a composite oxide of an alkaline earth metal M1 and gallium (wherein M1 represents at least one element selected from Mg, Ca, Sr and Ba). And a raw material containing a silicon compound and carbon is produced by reacting in a nitriding gas atmosphere.

  In addition, the second nitridosilicate compound of the present invention is heated to alkaline earth represented by the chemical formula M2O (wherein M2 represents at least one element selected from Mg, Ca, Sr and Ba). It is produced by reacting a raw material containing an alkaline earth metal compound capable of forming a metal oxide, a silicon compound, a gallium oxide, and carbon in a nitriding gas atmosphere.

The first nitride silicate phosphor of the present invention is a complex oxide of an alkaline earth metal M1 and gallium (wherein M1 represents at least one element selected from Mg, Ca, Sr and Ba). ), A silicon compound, and a carbon-containing raw material are reacted in a nitriding gas atmosphere, as a phosphor matrix, Ce ³⁺ , Pr ⁴⁺ , Eu ^{2 It} contains at least one ion selected from ⁺ , Tb ³⁺ and Mn ²⁺ as a luminescent center ion.

In addition, the second nitride silicate phosphor of the present invention is heated to an alkali represented by the chemical formula M2O (wherein M2 represents at least one element selected from Mg, Ca, Sr and Ba). Nitridosilicate compound produced by reacting a raw material containing an alkaline earth metal compound capable of producing an earth metal oxide, a silicon compound, a gallium oxide, and carbon in a nitriding gas atmosphere As a luminescent center ion, containing at least one ion selected from Ce ³⁺ , Pr ⁴⁺ , Eu ²⁺ , Tb ³⁺ and Mn ²⁺ .

  According to the method for producing a nitridosilicate compound of the present invention, a nitridosilicate compound having good crystallinity and high quality can be produced reasonably and with good reproducibility. Further, the manufacturing cost can be reduced.

  Further, the nitridosilicate compound and the nitridosilicate phosphor of the present invention have good crystallinity and high quality.

  Embodiments of the present invention will be described below.

(Embodiment 1)
An example of the manufacturing method of the 1st nitridosilicate type compound of this invention is a manufacturing method which belongs to the carbothermal reduction nitriding method, and is a complex oxide of alkaline-earth metal M1 and gallium, a silicon compound, and carbon. It is characterized in that a raw material containing is reacted in a nitriding gas atmosphere. However, the alkaline earth metal M1 represents at least one element selected from Mg, Ca, Sr and Ba.

  The method for producing a nitridosilicate compound according to the present embodiment includes reducing and nitriding a composite oxide of an alkaline earth metal and gallium by reaction with carbon in a nitriding gas atmosphere, and evaporating gallium. However, it is a production method of reacting at least with a silicon compound.

That is, the greatest feature of the method for producing a nitridosilicate compound of the present embodiment is that (1) an alkaline earth metal or an alkaline earth metal nitride is not substantially used as a raw material of the nitridosilicate compound. (2) Instead, a composite oxide of alkaline earth metal and gallium (alkaline earth metal gallium oxide) is used, and (3) part or all of the oxygen component contained in the composite oxide is Reduced by carbon, released and removed as carbon monoxide (CO) gas or carbon dioxide (CO ₂ ) gas, (4) At the same time, while removing the gallium component using natural phenomena such as heating and evaporation, (5) Further, while producing a nitride of an alkaline earth metal compound by reaction with a nitriding gas, (6) producing a nitridosilicate compound by reacting with a silicon compound or the like In the Rukoto.

  According to this method, the above-described conventional carbothermal reduction nitriding method (that is, a raw material containing an alkaline earth metal compound capable of forming an alkaline earth metal oxide, a silicon compound, and carbon is introduced into a nitriding gas atmosphere. It is easier to produce a nitridosilicate compound having a single crystal phase than in the production method in which a high-performance nitridosilicate phosphor is produced with good reproducibility.

  In the manufacturing method of the present embodiment, the complex oxide used as a supply source of the alkaline earth metal M1 constituting the nitridosilicate compound is a nitridation of an alkaline earth metal used in the conventional direct nitride reaction method described above. Unlike things, it can be handled in the atmosphere. In addition, materials other than the composite oxide, silicon compound, carbon, and nitriding gas used in the manufacturing method of the present embodiment are relatively easily available, easy to handle, and inexpensive.

  In addition, according to the manufacturing method of the present embodiment, the composite oxide and the silicon compound are actively reduced by carbon serving as a reducing agent, and oxygen components contained therein are converted into, for example, carbon monoxide gas, Since it can be removed as carbon dioxide gas or the like, the amount of oxygen that is an impurity contained in the nitridosilicate compound can be reduced. Therefore, the production method of the present embodiment can produce a highly pure nitridosilicate compound as in the conventional carbothermal reduction nitriding method described above, and as a result, various performances can be exhibited more highly.

Examples of the nitridosilicate compounds that can be produced according to the present invention include the following nitridosilicate compounds. For example, Ca ₂ Si ₅ N ₈ , Sr ₂ Si ₅ N ₈ , Ba ₂ Si ₅ N ₈ , BaSi ₇ N ₁₀ , CaAlSiN ₃ , CaSiN ₂ , BaSiN ₂ , Sr ₂ Si ₄ AlON ₇ , (1-x) Sr ₂ Si ₅ N ₈ · xSr ₂ Si ₄ AlON ₇ (where x represents a numerical value satisfying the formula 0 <x <1), CaSi ₆ AlON ₉ , Ca _1.5 Al ₃ Si ₉ N ₁₆ , (Ca, Sr _1.5 Al ₃ Si ₉ N ₁₆ , Ca _1.5 Al _3.5 Si _8.5 O _0.5 N _15.5 , Ca _1.5 (Al, Ga) ₃ Si ₉ N ₁₆ , Sr _1.5 Al ₃ Si ₉ N ₁₆ , CaAl ₂ Si ₁₀ N ₁₆ , Sr ₃ Ce ₁₀ Si ₁₈ Al ₁₂ O ₁₈ N ₃₆ , CaSi ₂ O ₂ N ₂ , SrSi ₂ O ₂ N ₂ , (Ca, Sr, Ba) Al _2-x Si _x O _4-x N _x (however, this x Represents a numerical value satisfying the formula 0 <x <2.) And the like.

  Here, the nitridosilicate compound is, for example, at least an alkaline earth metal element such as nitridosilicate, oxonitridosilicate, nitridoaluminosilicate, oxoaluminonitridosilicate, alkaline earth metal sialon, and silicon element. And a nitrogen-containing compound.

The effect of improving the performance of the nitridosilicate compound is, in particular, a highly nitrided nitridosilicate compound in which the number of oxygen atoms is less than the number of alkaline earth metal atoms per mole of the nitridosilicate compound. And is particularly remarkable in the production of nitridosilicate compounds substantially free of oxygen components. The highly nitrided nitride silicate compound is not particularly limited, but is preferably a compound represented by the chemical formula (1-x) M1 ₂ Si ₅ N ₈ .xM1 ₂ Si ₄ AlON ₇ , more preferably. Is a compound represented by the chemical formula M1AlSiN ₃ which does not substantially contain an oxygen component (wherein x represents a numerical value satisfying the formula 0 ≦ x ≦ 1). For example, for the purpose of obtaining a high-quality nitridosilicate compound that can be a phosphor matrix of a high-efficiency red phosphor, M1 is preferably mainly composed of at least one element selected from Ca and Sr. . Here, “mainly” means containing 50 atom% or more and 100 atom% or less, preferably 80 atom% or more and 100 atom% or less.

The complex oxide of the alkaline earth metal M1 and gallium is not particularly limited as long as it is a complex oxide containing at least the alkaline earth metal M1, gallium, and oxygen as constituent elements. For example, M1 ₃ Ga ₂ O ₆ , M1Ga ₂ O ₄ , M1 ₄ Ga ₂ O ₇ , M1 ₃ Ga ₄ O ₉ , M1Ga ₁₂ O ₁₉ , M1 ₅ Ga ₆ O ₁₄ , M1Ga ₄ O ₇ , M1 ₅ Ga ₂ O ₈ , at least one complex oxide selected from M1 ₇ Ga ₂ O ₁₀ and M1 ₇ Ga ₄ O ₁₃ .

In particular, for the purpose of reducing the amount of rare gallium and its compound used as much as possible, more preferable composite oxides are M1 ₃ Ga ₂ O ₆ and M1Ga ₂ O ₄ , which have a small amount of gallium with respect to the alkaline earth metal element M1. , M1 ₄ Ga ₂ O ₇ , M1 ₃ Ga ₄ O ₉ , M1 ₅ Ga ₆ O ₁₄ , M1 ₅ Ga ₂ O ₈ , M1 ₇ Ga ₂ O ₁₀ and M1 ₇ Ga ₄ O ₁₃ Further, for the purpose of facilitating production, a more preferable composite oxide is M1 ₃ Ga ₂ O ₆ . When these gallium-free complex oxides are used as alkaline earth metal sources, high-performance nitridosilicate compounds with good crystallinity and low impurity contamination can be reproduced at relatively low synthesis temperatures. It becomes possible to manufacture with good quality.

  The property of the composite oxide is not particularly limited, and may be appropriately selected from powder, lump, and the like. A preferred property for obtaining a powdered nitridosilicate compound is powder.

The silicon compound is not particularly limited in terms of the reaction principle as long as it is a silicon compound that can form a nitridosilicate compound, and may be appropriately selected from, for example, silicon oxide, silicon diimide, silicon nitride, and the like. Moreover, a silicon simple substance may be sufficient. In this case, after reacting with nitrogen or the like in a nitriding gas atmosphere to form a nitride compound of silicon, it may be reacted with an alkaline earth metal compound (including the above complex oxide). A preferred silicon compound is silicon nitride (Si ₃ N ₄ ) because a good quality nitridosilicate compound can be obtained with good reproducibility.

  The properties of the silicon compound are not particularly limited, and are appropriately selected from powders, lumps, and the like. Preferred properties for obtaining a powdered nitridosilicate compound are powders.

The carbon is not particularly limited in terms of the reaction principle as long as the composite oxide can be reduced. Examples thereof include solid carbon, amorphous carbon (coal, coke, charcoal, gas carbon, etc.), and carburizing gas. Natural gas, hydrocarbons such as methane (CH ₄ ), propane (C ₃ H ₈ ), butane (C ₄ H ₁₀ ), etc. may be appropriately selected. In particular, solid carbon powder is preferable because high-purity carbon can be easily obtained and handling is easy, and graphite (graphite) is more preferable among them.

  The carbon is not particularly limited in size and shape. For example, in the case of solid carbon, the preferred size and shape are powdery or granular having a size of 1 μm or more and 1 cm or less because they are easily available, but other solid carbon may be used. For example, solid carbon having various shapes such as powder, granule, lump, plate, and rod can be used. The purity of the solid carbon is not particularly limited. The purity of solid carbon preferable for the purpose of obtaining a high-quality nitridosilicate compound is 99% or higher, preferably 99.9% or higher.

  The carbon may be one that also serves as a heating element (such as a carbon heater) or one that also serves as a firing container (such as a carbon crucible). If the carbon can be used as a reducing agent, it may be used as a mixture with a raw material of a nitridosilicate compound or may simply be brought into contact.

  In principle, the amount of carbon used is sufficient to generate a nitridosilicate compound having a stoichiometric composition by a chemical reaction (reduction nitriding reaction). Since some carbon is consumed by the reaction, the amount is increased to 1 to 100% by weight, particularly 10 to 50% by weight of the amount used for the above-mentioned production for the purpose of replenishing the consumed amount. It is preferable.

  The nitriding gas is not particularly limited as long as it is a gaseous compound containing elemental nitrogen, but for reasons of availability of high-purity gas, ease of handling, price, etc., preferably It is at least one nitriding gas selected from nitrogen gas, nitrogen-hydrogen mixed gas and ammonia gas, more preferably nitrogen gas.

  The reaction in the production method of the present embodiment is started and maintained by adding energy to the raw material, for example, by heating. Therefore, a preferable temperature of the nitriding gas atmosphere is 1400 ° C. or more and 2000 ° C. or less, and a more preferable temperature is 1500 ° C. or more and 1800 ° C. When the temperature is within this range, a sufficiently reacted nitridosilicate compound can be obtained without decomposition or melting of the raw material or a fired product thereof.

  The reaction and reduction are insufficient at a temperature lower than the above temperature range, and it becomes difficult to obtain a high quality nitridosilicate compound, and at a temperature higher than this, the nitridosilicate compound is It becomes difficult to obtain a compound having a predetermined composition and shape (powder, molded body, etc.) by decomposing or melting. In addition, the manufacturing cost is high because it is necessary to use an expensive heating element or a heat-resistant heat-insulating material in the manufacturing facility, so it is difficult to provide the nitridosilicate compound at a low cost. .

  The above reaction may be carried out in several steps. If it does in this way, a metallic gallium or a highly volatile gallium compound will be produced | generated by the heat reaction of the said complex oxide and carbon, and it will be evaporated and discharge | released. Further, the alkaline earth metal or the alkali metal compound produced by the reduction and the release of gallium is partially nitrided or entirely nitrided with a nitriding gas to form an alkaline earth metal nitride. React with other raw materials. In this way, a nitridosilicate compound is produced.

  The preferable reaction conditions for the nitriding gas atmosphere are normal pressure atmospheres because simple equipment can be used, but any of a high pressure atmosphere, a pressurized atmosphere, a reduced pressure atmosphere, and a vacuum atmosphere may be used. A preferable reaction atmosphere for the purpose of producing a high-performance nitridosilicate compound is a high-pressure atmosphere, for example, 2 to 100 atm, and considering ease of handling, preferably 5 to 20 atm. Preferably, the atmosphere is mainly composed of nitrogen gas and having a pressure of 7 to 10 atmospheres. Such a high-pressure atmosphere can prevent or suppress the decomposition of compounds (nitrides, oxynitrides, etc.) that occur during high-temperature firing, so that the composition shift of the produced nitridosilicate compound can be suppressed. For the purpose of promoting decarburization of the reaction product (calcined product) after firing, a small amount or a trace amount of water vapor may be included in the atmosphere.

  Furthermore, a nitridosilicate compound can be produced by combining various reaction conditions. For example, after obtaining a nitride silicate compound having a predetermined composition by a desired reductive nitridation reaction in which reactants are reacted in a normal pressure atmosphere at a relatively low temperature of 1400 ° C. or higher and 1800 ° C. or lower, 1600 ° C. or higher By reacting in a high-pressure atmosphere at a relatively high temperature of 2000 ° C. or lower, it is possible to improve the quality, such as improving crystallinity, improving grain growth and grain boundaries.

In the method for producing a nitridosilicate compound of the present embodiment, a flux may be further added and reacted for the purpose of increasing the reactivity between the reactants. The flux is a compound other than a gallium compound (including the composite oxide), and is made of an alkali metal compound (for example, Na ₂ CO ₃ , NaCl, LiF, etc.) or a halogen compound (SrF ₂ , CaCl _2, etc.). These may be selected and used as necessary.

  In the method for producing a nitridosilicate compound of the present embodiment, an aluminum compound (for example, aluminum nitride, aluminum oxide, aluminum hydroxide, etc.) is preferably added, and aluminum nitride is more preferably added. This is because a nitridoaluminosilicate compound, an oxonitridoaluminosilicate compound, or the like can be produced by further adding and reacting such a compound.

  In the method for producing a nitridosilicate compound of the present embodiment, metal zinc or a zinc compound (for example, zinc oxide, zinc nitride, etc.), metal titanium or a titanium compound (for example, titanium oxide, titanium nitride, etc.), Metal zirconium or zirconium compound (eg, zirconium oxide, zirconium nitride, etc.), metal hafnium or hafnium compound (eg, hafnium oxide, hafnium nitride, etc.), metal tungsten or tungsten compound (eg, tungsten oxide, tungsten nitride, etc.), metal tin Alternatively, when a transition metal or a transition metal compound such as a tin compound (for example, tin oxide or tin nitride) is reacted, a nitridosilicate compound containing these transition metal elements can also be produced. Further, by producing phosphorus or a phosphorus compound (for example, phosphorus pentoxide, phosphorus pentanitride, phosphates, diammonium hydrogen phosphate, etc.), a nitride-containing compound containing phosphorus can be produced. Alternatively, when a boron compound (for example, boric acid, boron nitride, boric anhydride, etc.) is reacted, a nitridosilicate compound containing boron can also be manufactured.

(Embodiment 2)
An example of the second method for producing a nitridosilicate compound according to the present invention is a production method belonging to the carbothermal reduction nitriding method, which is capable of producing an alkaline earth metal oxide represented by the chemical formula M2O by heating. A raw material containing a metal compound, a silicon compound, gallium oxide functioning as a reaction accelerator, and carbon is reacted in a nitriding gas atmosphere. However, the alkaline earth metal M2 represents at least one element selected from Mg, Ca, Sr and Ba.

  The method for producing a nitridosilicate compound according to the present embodiment includes a compound oxide of an alkaline earth metal and gallium produced in the reaction process of an alkaline earth metal compound and gallium oxide with carbon in a nitriding gas atmosphere. This is a production method in which at least a silicon compound is reacted while reducing and nitriding by the above reaction and evaporating gallium.

That is, the greatest feature of the method for producing a nitridosilicate compound of the present embodiment is that (1) an alkaline earth metal or an alkaline earth metal nitride is not substantially used as a raw material of the nitridosilicate compound. (2) Instead, a combination of an alkaline earth metal compound capable of generating an alkaline earth metal oxide represented by the chemical formula M2O by heating and gallium oxide is used, and (3) an oxygen component contained in these compounds Part or all of this is reduced with carbon and released and removed as carbon monoxide (CO) gas or carbon dioxide (CO ₂ ) gas. (4) Simultaneously, natural phenomena such as heating and evaporation (5) Further, (6) react with a silicon compound or the like while generating a nitride of an alkaline earth metal compound by reaction with a nitriding gas. It is to produce a nitridosilicate-based compound by.

  According to this method, the same effect as that of the method for producing a nitridosilicate compound described in Embodiment 1 can be obtained, and a single crystal phase nitridosilicate compound can be easily produced. This is because a complex oxide of alkaline earth metal M2 and gallium is obtained by reacting gallium oxide with an alkaline earth metal compound capable of generating an alkaline earth metal oxide represented by the chemical formula M2O by heating. Because it can be manufactured.

  The nitridosilicate compound that can be produced in the present embodiment is the same as the nitridosilicate compound that can be produced by the production method described in Embodiment 1, and a compound having a single crystal phase and high purity can be obtained. As a result, this nitridosilicate compound can exhibit various performances higher.

  The alkaline earth metal compound is not particularly limited as long as it can react with the gallium oxide to produce the composite oxide. At least one compound selected from carbonates, oxalates and oxides of alkaline earth metals is preferable because the composite oxide can be generated relatively easily. Alkaline earths are preferred because they are easy to handle and obtain. Metal carbonates are more preferred.

The gallium oxide is not particularly limited as long as it acts as a reaction accelerator, and may be gallium oxide (III) (Ga ₂ O ₃ ) or gallium oxide (II) (GaO).

  The gallium oxide is preferably added in an amount of 0.03 mol or more and 3 mol or less, more preferably 0.1 mol or more and 1 mol or less in order to produce 1 mol of the nitridosilicate compound. . When the amount added is less than the above range, the effect as a reaction accelerator is diminished, and it becomes difficult to obtain a high-quality nitridosilicate compound. The amount increases and the performance of the nitridosilicate compound decreases.

In the method for producing a nitridosilicate compound of the present embodiment, the silicon compound, the carbon, and the nitriding gas described in the first embodiment are preferably used, and the same operational effects are achieved. The reaction conditions such as temperature and pressure for reacting these reactants are also the same as described in the first embodiment. The carbon needs 1 to 2 mol to reduce 1 mol of the alkaline earth metal oxide (M2O). Further, in order to reduce and remove oxygen contained in the gallium oxide, for example, The amount is preferably increased by 3 mol per mol of gallium oxide (Ga ₂ O ₃ ).

  In the method for producing a nitridosilicate compound of the present embodiment, at least one selected from the flux, aluminum compound, transition metal, transition metal compound, phosphorus, phosphorus compound, boron, and boron compound described in the first embodiment, It may be added.

The nitridosilicate compound produced by the production method of Embodiments 1 and 2 can be applied not only to ceramic members, but also as a nitridosilicate phosphor. For example, a nitridosilicate compound such as Sr ₂ Si ₅ N ₈ , Sr ₂ Si ₄ AlON ₇ , or CaAlSiN ₃ functions as a phosphor matrix of a high-efficiency phosphor, and thus the production of the nitridosilicate compound of the present invention. The method can be widely applied to a method for producing a nitridosilicate phosphor.

  In order to obtain a nitridosilicate phosphor by the method for producing a nitridosilicate compound of the present invention, an element L that can be a light emission center of the nitridosilicate phosphor may be contained in the raw material. However, the element L which can be the emission center is a transition metal (for example, lanthanide selected from atomic numbers 58 to 60 and 62 to 71, Mn, etc.), and particularly preferable elements L are Ce, Pr, Eu, Tb. And Mn.

(Embodiment 3)
Another example of the method for producing the first nitridosilicate compound of the present invention is the method for producing the nitridosilicate compound described in Embodiment 1, wherein the complex oxidation of the alkaline earth metal M1 and gallium is performed. As a material, a composite oxide to which the element L1 is added is used.

  The complex oxide to which the element L1 is added is the complex oxide to which the element L1 that can be a luminescent center ion is added. For example, at least one element selected from Ce, Pr, Eu, Tb, and Mn is previously contained. It is the added complex oxide.

The nitridosilicate compound that can be produced in the present embodiment is a compound containing at least an alkaline earth metal element, a silicon element, and a nitrogen element (for example, nitridosilicate, oxonitridosilicate, nitridoaluminosilicate, oxo Aluminonitridosilicate, alkaline earth metal sialon, etc.) as a phosphor matrix, and emission center ions (for example, Ce ³⁺ , Eu ²⁺ , Eu ³⁺ , Tb ^3+, etc.) in the crystal lattice of the phosphor matrix. It can be said that it is a nitridosilicate phosphor containing. Since this nitridosilicate phosphor can provide a compound having a single crystal phase and high purity, various performances can be exhibited more highly.

  In the manufacturing method of the present embodiment, the silicon compound, the carbon, and the nitriding gas described in the first embodiment are preferably used, and the same effects are achieved. The reaction conditions such as temperature and pressure for reacting these reactants are also the same as described in the first embodiment. The amount of carbon used is 1 to 100% by weight, particularly 10 to 50% of the amount required for the production of the nitridosilicate compound for the purpose of sufficiently reducing and removing oxygen contained in the composite oxide. It is even more preferable to set an amount obtained by increasing the weight%.

  In the manufacturing method of the present embodiment, at least one selected from the flux, aluminum compound, transition metal, transition metal compound, phosphorus, phosphorus compound, boron, and boron compound described in the first embodiment may be further added.

(Embodiment 4)
Another example of the method for producing the second nitridosilicate phosphor of the present invention is the method for producing the nitridosilicate compound described in Embodiment 2, wherein the raw material contains a metal containing element L2 or Further comprising a compound.

  The element L2 is an element that can be a light emission center, and is preferably a transition metal (for example, lanthanide or Mn selected from atomic numbers 58 to 60 and 62 to 71), particularly preferably Ce, Pr, Eu, Tb, and Mn. Is at least one element selected from Examples of the compound containing the element L2 include oxides, nitrides, hydroxides, carbonates, oxalates, nitrates, sulfates, halides, and phosphates of the transition metals.

  That is, the manufacturing method of this embodiment is at least one selected from transition metals and transition metal compounds (for example, at least one selected from metal lanthanides and lanthanide compounds excluding metal lanthanum, metal promethium, lanthanum compounds, and promethium compounds). It can also be said to be a method for producing a nitridosilicate phosphor that is produced by further reaction.

  The nitridosilicate compound that can be manufactured in the present embodiment is the same as the nitridosilicate compound that can be manufactured by the manufacturing method described in Embodiment 3, and can be said to be a nitridosilicate phosphor. Since this nitridosilicate phosphor can provide a compound having a single crystal phase and high purity, it can exhibit various performances.

In the manufacturing method of the present embodiment, the silicon compound, the carbon, and the nitriding gas described in the first embodiment are preferably used, and the same effects are achieved. The reaction conditions such as temperature and pressure for reacting these reactants are also the same as described in the first embodiment. For example, in the manufacture of a nitridosilicate phosphor activated with Eu ²⁺ ions, after reaction in a nitrogen-hydrogen mixed gas atmosphere at 1400 ° C. to 1800 ° C. and normal pressure, 1600 ° C. to 2000 ° C. It is also possible to obtain a high-performance phosphor having an internal quantum efficiency exceeding 80% by a production method in which the reaction is performed in a high-pressure nitrogen atmosphere of 2 to 10 atmospheres.

  In the manufacturing method of the present embodiment, at least one selected from the flux, aluminum compound, transition metal (including zinc), transition metal compound, phosphorus, phosphorus compound, boron, and boron compound described in the first embodiment is further added. May be.

Nitridosilicate phosphor such as Sr ₂ Si ₄ AlON ₇ : Eu ²⁺ red phosphor containing oxygen as a main component constituting the phosphor of stoichiometric composition by the production method of Embodiment 3 or 4 Can produce a high-quality nitridosilicate phosphor more easily and with good reproducibility, so that a large amount of a high-quality nitridosilicate phosphor can be provided.

In the case of producing a nitridosilicate phosphor containing a lanthanide ion such as Ce ³⁺ , Pr ³⁺ , Eu ²⁺ , Tb ³⁺ , or Mn ²⁺ as an emission center by the production method of Embodiment 3 or 4. In this case, the reaction atmosphere is preferably a reducing atmosphere, and a nitrogen-hydrogen mixed gas atmosphere is particularly preferable because a strong reducing power can be obtained relatively inexpensively and easily. In this way, ions that do not substantially function as the emission center of high-efficiency phosphors such as Ce ⁴⁺ , Pr ⁴⁺ , Eu ³⁺ , Tb ⁴⁺ , Mn ³⁺ , or a desired emission color were emitted. Transition metal ions (e.g., lanthanide ions, etc.) that can prevent generation of luminescent center ions and emit highly efficient luminescence such as Ce3 ⁺ , Pr3 ⁺ , Eu2 ⁺ , Tb3 ⁺ , Mn2 ⁺ , etc. ) Becomes high, it becomes possible to provide a highly efficient nitridosilicate phosphor. In a reducing atmosphere using hydrogen, it can be expected that the nitridosilicate phosphor is highly purified by the effect of decarburization with hydrogen gas. Furthermore, in a furnace having a carbon member in a heat insulating material, a heater and a structure, heating at a temperature of 1400 ° C. or more and 2000 ° C. or less in at least one atmosphere selected from nitrogen or an inert gas also achieves the above object. This is preferable. In this case, when firing at a temperature of about 1400 ° C. or higher using a furnace having a carbon member, even if 100% of nitrogen or an inert gas is used as the atmospheric gas, residual moisture in the atmosphere and carbon This is because some of the carbon monoxide is produced by the reaction with the above, and a reducing atmosphere is obtained.

According to the production method of Embodiment 3 or 4, a highly efficient nitridosilicate phosphor can be provided in a large amount at a relatively low synthesis temperature at low cost with high reproducibility. As typical nitridosilicate phosphors, (1-x) Sr ₂ Si ₅ N ₈ .xSr ₂ Si ₄ AlON ₇ : Eu ²⁺ (x is a numerical value satisfying 0 ≦ x ≦ 1). ), CaAlSiN ₃ : Eu ^{2+ and} other red light-emitting nitride phosphors, and (Ca, Sr, Ba) Al _2−x Si _x O _4−x N _x (where x is 0 <x ≦ 2) Nitridosilicate phosphors described above, such as a green light emitting nitride phosphor such as a satisfactory numerical value).

In particular, a nitridosilicate-based phosphor (for example, Sr ₂ Si ₄ AlON ₇ : Eu ²⁾ containing oxygen as a main component constituting the phosphor having a stoichiometric composition manufactured by the manufacturing method of Embodiment 3 or 4. ⁺ , Sr ₂ Si _4.25 Al _0.75 O _0.75 N _7.25 : Eu ^2+, etc.) are phosphor materials suitable for mass production based on the production method of the present invention. It can be provided in large quantities.

Such nitridosilicate phosphors are, for example, (1) a light source of an LED light source for illumination, (2) a white light source formed by combining an inorganic EL (electroluminescence) element and a phosphor as a wavelength conversion material. A combination of a light emitting layer, (3) a light emitting layer using Eu ²⁺ activated thioaluminate blue phosphor (for example, (Ba, Mg) Al ₂ S ₄ : Eu ²⁺ ), and a wavelength conversion layer The wavelength conversion layer of the multi-color display inorganic thin film EL panel can be used as a light emitting source of (4) a warm color (yellow to orange to red) light emitting component of a fluorescent lamp (discharge lamp). In addition, since the temperature characteristics are excellent and relatively high light emission performance is maintained even at high temperatures, the light emitting device with improved temperature characteristics can be provided at low cost.

The manufacturing method of Embodiment 3 or 4 is particularly nitrided for a white LED light source for illumination that emits high-efficiency red light that is excited by near-ultraviolet to blue light and has an emission peak in a wavelength region of 600 nm to 660 nm. Or oxynitride red phosphor (for example, (1-x) Sr ₂ Si ₅ N ₈ .xSr ₂ Si ₄ AlON ₇ : Eu ²⁺ (x is a numerical value satisfying 0 ≦ x ≦ 1), CaAlSiN ₃ : Eu ²⁺ , CaSiN ₂ : Eu ^2+, etc.).

  The nitridosilicate phosphor produced by the production method of Embodiment 3 or 4 is easy to obtain or produce, inexpensive, and easy to handle in the air. The composite oxide or the alkaline earth metal compound, Manufactured using carbon (especially solid carbon powder), silicon compound (especially silicon nitride), aluminum compound (especially aluminum nitride) and nitriding gas (especially nitrogen), etc., it is easy to produce, and these compounds are produced at low cost. become able to.

  Further, the nitridosilicate phosphor produced by the production method of Embodiment 3 or 4, particularly a highly nitrided nitridosilicate phosphor having a smaller number of oxygen atoms than the number of alkaline earth metal atoms, particularly Nitridosilicate phosphors substantially free of oxygen components actively reduce the calcined raw material by reaction with carbon as a reducing agent, and the oxygen component in the calcined raw material is converted to carbon monoxide or carbon dioxide. Since it is manufactured while removing it, the amount of oxygen which is an impurity is small, purity is high, and as a result, high material performance is exhibited.

  On the other hand, highly nitrided nitridosilicate phosphors containing oxygen as the main component of the stoichiometric compound are strictly compared to nitridosilicate phosphors substantially free of oxygen components. Therefore, high-quality phosphors can be provided in large quantities with high reproducibility, since the production conditions (for example, the control conditions for the purity of the compound raw material containing a nitriding gas) are not required.

  Therefore, it is possible to provide a low-cost and high-performance (high luminous flux, etc.) device (for example, a white LED light source) using a nitridosilicate phosphor manufactured using the manufacturing method of Embodiment 3 or 4. Become.

  Next, an apparatus using the nitridosilicate compound of the present invention will be described with reference to the drawings. FIG. 1 shows a cross-sectional view of an example of a light-emitting device using a nitride silicate phosphor produced by the manufacturing method of Embodiment 3 as a light-emitting source. The light emitting device shown in FIG. 1 is also a light source to which an LED is applied. FIG. 1 is also an example of a semiconductor light-emitting device that is frequently used for illumination or display devices.

  In FIG. 1, at least one light emitting element 1 is conductively mounted on a submount substrate 4, and at least a nitridosilicate phosphor 2 manufactured by the manufacturing method of Embodiment 3 is included, and the phosphor layer 3 is formed. 1 shows a semiconductor light emitting device having a structure in which a light emitting element 1 is sealed by a package of a base material (for example, resin, low melting point glass, etc.).

  In FIG. 1, a light-emitting element 1 is a photoelectric conversion element that converts electric energy into light, and specifically corresponds to an LED, a laser diode, a surface-emitting laser diode, an inorganic EL element, an organic EL element, and the like. In particular, from the viewpoint of increasing the output of the light source, an LED or an inorganic thin film EL element is preferable. The wavelength of light emitted from the light-emitting element 1 is basically not particularly limited and may be within a wavelength range (for example, 250 to 600 nm) that can excite the nitridosilicate phosphor. However, in order to be able to produce a light source having a high light emission performance that emits white light having a high demand when the nitridosilicate phosphor is excited with high efficiency, it is more than 360 nm and less than 500 nm, preferably more than 360 nm and less than 420 nm, or , 420 nm to 500 nm, preferably 380 nm to 410 nm, or 440 nm to 480 nm, that is, a light emitting element 1 having an emission peak in the near ultraviolet, purple, or blue wavelength region.

  Further, in FIG. 1, a phosphor layer 3 is a phosphor layer including at least a nitridosilicate phosphor 2, and for example, at least a nitrite is formed on a transparent base material such as a transparent resin (eg, a silicone resin) or low-melting glass. The dosilicate phosphor 2 is dispersed. For example, in the case of the transparent resin, the content of the nitridosilicate phosphor 2 in the transparent base material is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass. The nitride silicate phosphor 2 contained in the phosphor layer 3 absorbs part or all of the light emitted by the light emitting element 1 by driving, and has a wavelength longer than the peak wavelength of the light emitted by the light emitting element 1. Since it is a light conversion material that converts visible light (especially red light), the nitridosilicate phosphor 2 is excited by the light emitting element 1, and the semiconductor light emitting device includes at least a luminescent component emitted by the nitridosilicate phosphor 2. It comes to emit light.

Therefore, for example, when a light emitting device having the following combination structure is used and any one of the phosphors, particularly a red phosphor, is used as the nitridosilicate phosphor 2, the light emitted from the light emitting element 1 and the light emitted from the phosphor layer 3 are used. The white light can be obtained by the color mixture of the light source and the like, and it becomes a light source that emits white light with much demand.
(1) A combination of a light-emitting element that emits light (purple light) having a light emission peak in the near-ultraviolet light or purple wavelength region of more than 360 nm and 420 nm or less, a blue phosphor, a green phosphor, and a red phosphor Structure.
(2) A structure formed by combining a light emitting element that emits light selected from the near ultraviolet light or the violet light, a blue phosphor, a green phosphor, a yellow phosphor, and a red phosphor.
(3) A structure formed by combining the light emitting element that emits near-ultraviolet light, a blue phosphor, a yellow phosphor, and a red phosphor.
(4) A structure formed by combining a light emitting element that emits light (blue light) having a light emission peak in a blue wavelength range of more than 420 nm and 500 nm or less, a green phosphor, a yellow phosphor, and a red phosphor.
(5) A structure formed by combining the light emitting element that emits blue light, a yellow phosphor, and a red phosphor.
(6) A structure formed by combining the light emitting element that emits blue light, a green phosphor, and a red phosphor.
(7) A structure formed by combining a light-emitting element that emits light having a light emission peak in a blue-green wavelength region exceeding 485 nm and not more than 500 nm, and a red phosphor.

In addition, red light emission such as (1-x) Sr ₂ Si ₅ N ₈ .xSr ₂ Si ₄ AlON ₇ : Eu ²⁺ (x is a numerical value satisfying 0 ≦ x ≦ 1), CaAlSiN ₃ : Eu ²⁺ The nitridosilicate phosphor of the present invention that emits light is a phosphor exhibiting high internal quantum efficiency under the blue light excitation. Therefore, as an excitation source of such a nitridosilicate phosphor, a blue light emitting element having an emission peak in a blue wavelength region of more than 420 nm and less than 500 nm, preferably more than 440 nm and less than 480 nm, is used. The phosphor is excited by the blue light emitted from the blue light-emitting element, and emits at least the blue light component emitted from the blue light-emitting element and the light-emitting component emitted from the nitridosilicate phosphor as output light. When the light emitting device is configured, a high luminous flux light emitting device that emits warm light emission having a strong red light emitting component intensity can be configured, which is preferable.

  The nitridosilicate phosphor of the present invention can be any of blue, green, yellow, and red phosphors depending on the composition and type of luminescent center ion to be added. It can be used for at least one of a phosphor, a yellow phosphor, and a red phosphor.

In addition to the nitridosilicate phosphor of the present invention, the blue phosphor, the green phosphor, the yellow phosphor, and the red phosphor may be, for example, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu ^{2 +} Blue phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ blue phosphor, (Ba, Sr) ₂ SiO ₄ : Eu ²⁺ green phosphor, BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , Mn ²⁺ green phosphor, Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ green phosphor, Y ₃ Al ₅ O ₁₂ : Ce ³⁺ green phosphor, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce ³⁺ yellow phosphor, (Sr, Ba) ₂ SiO ₄ : Eu ²⁺ yellow phosphor, CaGa ₂ S ₄ : Eu ²⁺ yellow phosphor, CaS: Eu ²⁺ red phosphor, SrS: Eu ²⁺ red phosphor, La ₂ O ₂ S: Eu ³⁺ red phosphor and the like can be used.

The M constituting the nitridosilicate phosphor of the present invention is preferably composed mainly of at least one element selected from Ca and Sr. This is because the phosphor has good luminous efficiency. For example, in the case of a nitride silicate phosphor added with Eu ²⁺ ions as an activator, for example, Sr ₂ Si ₅ N ₈ : Eu ²⁺ , Sr ₂ Si ₄ AlON ₇ : Eu ²⁺ , 0.25Sr ₂ High-performance red phosphor such as Si ₅ N ₈ 0.75Sr ₂ Si ₄ AlON ₇ : Eu ²⁺ , CaAlSiN ₃ : Eu ^2+, or high-performance red phosphor such as SrSi ₂ O ₂ N ₂ : Eu ²⁺ It becomes a green phosphor, and a phosphor preferable for a light emitting device can be provided. In addition, a light emitting device using such a red phosphor or green phosphor emits light having a light color that is preferable in terms of color rendering.

  The present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.

Example 1
Hereinafter, as a method for producing a nitridosilicate compound according to the present invention, a method for producing a nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ (that is, Sr ₂ Si ₅ N ₈ : Eu ²⁺ phosphor). Will be explained.

  First, the following materials (a) to (c) were sufficiently mixed in the air using an automatic mortar to obtain a mixed powder A.

(A) Strontium carbonate powder (SrCO ₃ : purity 99.9 mol%) : 21.70 g
(B) Europium oxide powder (Eu ₂ O ₃ : purity 99.9 mol%): 0.53 g
(C) Gallium oxide powder (Ga ₂ O ₃ : purity 99.99 mol%): 9.37 g

This mixed powder A is charged into an alumina crucible and fired in an air atmosphere at 1100 ° C. for 2 hours using a box-type electric furnace, and europium element is added to strontium oxide which is a complex oxide of an alkaline earth metal and gallium. A powder of gallium (Sr _0.98 Eu _0.02 ) ₃ Ga ₂ O ₆₊ α (Material 1) was obtained.

  Next, the material (1), the material (2) that is a silicon compound, and the material (3) that is carbon were prepared as raw materials. The material (3) serves as a reducing agent (addition reducing agent) of the material (1).

(1) Strontium gallium oxide powder
((Sr _0.98 Eu _0.02 ) ₃ Ga ₂ O ₆₊ α): 20.09 g
(2) Silicon nitride powder (Si ₃ N ₄ : purity 99.9 mol%) : 14.03g
(3) Carbon (graphite) powder (purity 99.9 mol%): 3.17 g

  Subsequently, the materials (1) to (3) were sufficiently mixed in the air using an automatic mortar. This mixed powder B was charged into a carbon crucible and placed at a predetermined position in a tubular atmosphere electric furnace. In this tubular atmosphere electric furnace, a molybdenum disilicide heater was used as a heating element. The mixed powder B is first baked (temporary calcination) in a nitrogen gas atmosphere at 1400 ° C. for 1 hour, and further heated to a nitrogen-hydrogen mixed gas (nitrogen concentration 97 vol%, hydrogen concentration 3 vol%) at 1600 ° C. ) Heating (main baking) for 2 hours in an atmosphere. Then, it cooled, took out outside the furnace, and crushed lightly using the mortar and pestle, and the sample of the present Example was obtained. In addition, in order to simplify the process, post-treatment after the main firing such as full-scale crushing, classification, and washing was omitted.

When the crystal structure and composition of this sample were evaluated, it was confirmed that it was substantially a single crystal phase nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ . The body color of this sample was bright orange. The sample was confirmed to emit relatively bright red light (emission peak wavelength: 612 nm) under excitation of ultraviolet to near ultraviolet to purple to blue light at 254 nm, 365 nm, 405 nm, and 470 nm. I found out that An X-ray diffractometer (“MultiFlex” manufactured by Rigaku Corporation) was used for evaluation of the crystal structure (crystal constituent), and an X-ray microanalyzer (“JXA-” manufactured by JEOL Ltd.) was used for evaluation of the composition and the like. 8900 ") and an ICP emission spectroscopic analyzer (" ICPS-8000 "manufactured by Shimadzu Corporation).

(Example 2)
Hereinafter, as a method for producing a nitridosilicate compound according to the present invention, a method for producing a nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ (that is, Sr ₂ Si ₅ N ₈ : Eu ²⁺ phosphor). Will be explained.

First, using the following materials (a) to (c), a strontium gallium oxide (Sr _0.98 Eu _0.02 ) Ga ₂ O ₄₊ α powder (material 1) to which europium element was added was prepared in the same manner as in Example 1. Produced.

(A) Strontium carbonate powder (SrCO ₃ : purity 99.9 mol%) : 7.23g
(B) Europium oxide powder (Eu ₂ O ₃ : purity 99.9 mol%): 0.18 g
(C) Gallium oxide powder (Ga ₂ O ₃ : purity 99.99 mol%): 9.37 g

  Next, using the above material (1), the material (2) that is a silicon compound, and the material (3) that is carbon as raw materials, respectively, according to the same manufacturing method and manufacturing conditions as in Example 1, A sample of was prepared. The material (3) serves as a reducing agent (addition reducing agent) of the material (1).

(1) Strontium gallium oxide powder
((Sr _0.98 Eu _0.02 ) Ga ₂ O ₄₊ α): 11.69 g
(2) Silicon nitride powder (Si ₃ N ₄ : purity 99.9 mol%) : 4.68g
(3) Carbon (graphite) powder (purity 99.9 mol%): 2.11 g

When the crystal structure and composition of the sample of this example were evaluated in the same manner as in Example 1, it was substantially a single crystal phase nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N _8. It was confirmed. The body color of this sample was bright orange. In addition, this sample emits relatively bright red light (emission peak wavelength: 620 nm) under the excitation of ultraviolet light, near ultraviolet light, purple light, and blue light of 254 nm, 365 nm, 405 nm, and 470 nm, as in Example 1. It was confirmed that it was a red phosphor.

(Example 3)
Hereinafter, as a method for producing a nitridosilicate compound according to the present invention, an oxonitridoaluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ (that is, Sr ₂ Si ₄ AlON ₇ : Eu ²⁺ phosphor) is used. A manufacturing method will be described.

  A material (1) that is a complex oxide of an alkaline earth metal and gallium, a material (2) that is a silicon compound, a material (3) that is an aluminum compound, and a material (4) that is carbon are used as raw materials. The sample of this example was produced by using the same production method and production conditions as in Example 1, respectively. The material (1) was prepared in the same manner as the strontium gallium oxide added with the europium element prepared in Example 1.

(1) Strontium gallium oxide powder
((Sr _0.98 Eu _0.02 ) ₃ Ga ₂ O ₆₊ α): 20.09 g
(2) Silicon nitride powder (Si ₃ N ₄ : purity 99.9 mol%) : 11.22g
(3) Aluminum nitride powder (AlN: purity 99.9 mol%) : 2.46g
(4) Carbon (graphite) powder (purity 99.9 mol%) : 2.38g

When the crystal structure and composition of the sample of this example were evaluated in the same manner as in Example 1, the oxonidolide aluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ having a substantially single crystal phase was obtained. I confirmed that there was. The body color of this sample was bright orange. Further, as in Example 1, this sample emits relatively bright red light (emission peak wavelength: 625 nm) under excitation of ultraviolet light, near ultraviolet light, purple light, and blue light of 254 nm, 365 nm, 405 nm, and 470 nm. It was confirmed that it was a red phosphor.

Example 4
Hereinafter, as a method for producing a nitridosilicate compound according to the present invention, a method for producing a nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ (that is, Sr ₂ Si ₅ N ₈ : Eu ²⁺ phosphor). Will be explained.

  First, a material (1) which is an alkaline earth metal compound capable of generating an alkaline earth metal oxide by heating, a material (2) which is an oxide containing an element which becomes a light emission center, and a material which is a silicon compound (3), a material (4) that is gallium oxide, and a material (5) that is carbon were prepared as raw materials.

(1) Strontium carbonate powder
(SrCO ₃ : purity 99.98 mol%) : 14.47g
(2) Europium oxide powder (Eu ₂ O ₃ : purity 99.9 mol%): 0.35 g
(3) Silicon nitride powder (Si ₃ N ₄ : purity 99.9 mol%): 11.69 g
(4) Gallium oxide powder (Ga ₂ O ₃ : purity 99.99 mol%): 0.94 g
(However, 0.1 mol of Ga ₂ O _{3 with} respect to 2 mol of SrCO _3. )
(5) Carbon (graphite) powder (purity 99.9 mol%): 1.52 g

  Subsequently, the materials (1) to (5) were sufficiently mixed in the atmosphere using an automatic mortar to obtain a mixed powder. The mixed powder was charged into a carbon crucible, fired using a tubular atmosphere electric furnace, and then crushed to prepare a sample of this example. In addition, the manufacturing method and manufacturing conditions similar to Example 1 were used for these manufacturing processes. For simplification of the process, post-treatment after the main firing such as full-scale crushing, classification, and washing was omitted.

When the crystal structure and composition of the sample of this example were evaluated in the same manner as in Example 1, it was substantially a single crystal phase nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N _8. It was confirmed. The body color of this sample was bright orange. Further, as in Example 1, this sample emits relatively bright red light (emission peak wavelength: 623 nm) under excitation of ultraviolet light, near ultraviolet light, purple light, and blue light of 254 nm, 365 nm, 405 nm, and 470 nm. It was confirmed that it was a red phosphor.

(Examples 5 to 8)
Using the method for producing a nitridosilicate compound according to the present invention, a nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ was produced.

Examples 5 to 8 are the same as Example 4 except that the mass of the gallium oxide powder (Ga ₂ O ₃ ) of the material (4) of Example 4 and the mass of the carbon of the material (5) were changed. A sample of was prepared. Table 1 shows the addition amounts of the gallium oxide powder and the carbon powder of Examples 4 to 8. Incidentally, Ga ₂ O ₃ of Example 5-8, respectively 0.01 mol per SrCO ₃ 2 mol, 0.03 mol, 0.30 mol, 1.00 mol.

Example 9
Hereinafter, as a method for producing a nitridosilicate compound according to the present invention, an oxonitridoaluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ (that is, Sr ₂ Si ₄ AlON ₇ : Eu ²⁺ phosphor) is used. A manufacturing method will be described.

  A material (1) which is an alkaline earth metal compound capable of generating an alkaline earth metal oxide by heating, a material (2) which is an oxide containing an element serving as a light emission center, and a material (3) which is a silicon compound ), Gallium oxide material (4), aluminum compound material (5), and carbon material (6) as raw materials, respectively, A sample of this example was manufactured.

(1) Strontium carbonate powder
(SrCO ₃ : purity 99.98 mol%) : 14.47g
(2) Europium oxide powder (Eu ₂ O ₃ : purity 99.9 mol%): 0.35 g
(3) Silicon nitride powder (Si ₃ N ₄ : purity 99.9 mol%): 9.35 g
(4) Gallium oxide powder (Ga ₂ O ₃ : purity 99.99 mol%): 0.94 g
(However, 0.1 mol of Ga ₂ O _{3 with} respect to 2 mol of SrCO _3. )
(5) Aluminum nitride powder (AlN: purity 99.9 mol%) : 2.05g
(6) Carbon (graphite) powder (purity 99.9 mol%) : 0.86g

When the crystal structure and composition of the sample of this example were evaluated in the same manner as in Example 1, the oxonidolide aluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ having a substantially single crystal phase was obtained. I confirmed that there was. The body color of this sample was bright orange. Further, as in Example 1, this sample emits relatively bright red light (emission peak wavelength: 623 nm) under excitation of ultraviolet light, near ultraviolet light, purple light, and blue light of 254 nm, 365 nm, 405 nm, and 470 nm. It was confirmed that it was a red phosphor.

(Examples 10 to 13)
Using the method for producing a nitridosilicate compound according to the present invention, an oxonitridoaluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ was produced.

Examples 10 to 13 are the same as Example 9 except that the mass of the gallium oxide powder (Ga ₂ O ₃ ) of the material (4) of Example 9 and the mass of the carbon of the material (6) are changed. A sample of was prepared. Table 2 shows the addition amounts of the gallium oxide powder and the carbon powder of Examples 9 to 13. Incidentally, Ga ₂ O ₃ of Example 10 to 13 are each 0.01 moles relative SrCO ₃ 2 mol, 0.03 mol, 0.30 mol, 1.00 mol.

(Comparative Example 1)
As this comparative example, a nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ was produced by a production method using no complex oxide or gallium oxide, that is, a conventional carbothermal reduction nitriding method.

  First, a material (1) which is an alkaline earth metal compound capable of generating an alkaline earth metal oxide by heating, a material (2) which is an oxide containing an element which becomes a light emission center, and a material which is a silicon compound (3) and carbon material (4) were prepared as raw materials.

(1) Strontium carbonate powder
(SrCO ₃ : purity 99.9 mol%): 14.47 g
(2) Europium oxide powder (Eu ₂ O ₃ : purity 99.9 mol%) : 0.35g
(3) Silicon nitride powder (Si ₃ N ₄ : purity 99 mol%) : 11.69g
(4) Carbon (graphite) powder (purity 99.9 mol%) : 1.32g

  Subsequently, the materials (1) to (4) were sufficiently mixed in the air using an automatic mortar to obtain a mixed powder. The mixed powder was charged into a carbon crucible, fired using a gas atmosphere electric furnace, and then crushed to prepare a sample of this comparative example. In addition, the manufacturing method and manufacturing conditions similar to Example 1 were used for these manufacturing processes. For simplification of the process, post-treatment after the main firing such as full-scale crushing, classification, and washing was omitted.

When the crystal structure and composition of the sample of this comparative example were evaluated in the same manner as in Example 1, it was substantially a single crystal phase nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N _8. It was confirmed. The body color of this sample was bright orange. Further, as in Example 1, this sample emits relatively bright red light (emission peak wavelength 612 nm) under the excitation of ultraviolet light, near ultraviolet light, purple light, and blue light of 254 nm, 365 nm, 405 nm, and 470 nm. It was confirmed that it was a red phosphor.

(Comparative Example 2)
As this comparative example, an oxonitridoaluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ was produced by a production method using no complex oxide or gallium oxide, that is, a conventional carbothermal reduction nitridation method.

  A material (1) which is an alkaline earth metal compound capable of generating an alkaline earth metal oxide by heating, a material (2) which is an oxide containing an element serving as a light emission center, and a material (3) which is a silicon compound ), A material (4) which is an aluminum compound, and a material (5) which is carbon, respectively, were used as raw materials, and a sample of this comparative example was produced according to the same production method and production conditions as in Comparative Example 1.

(1) Strontium carbonate powder
(SrCO ₃ : purity 99.9 mol%): 14.47 g
(2) Europium oxide powder (Eu ₂ O ₃ : purity 99.9 mol%) : 0.35g
(3) Silicon nitride powder (Si ₃ N ₄ : purity 99 mol%) : 9.35g
(4) Aluminum nitride powder (AlN: purity 99.9 mol%) : 2.05g
(5) Carbon (graphite) powder (purity 99.9 mol%) : 0.66g

The sample of this comparative example was evaluated for the crystal structure and composition in the same manner as in Example 1. As a result, the oxonidolide aluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ having a substantially single crystal phase was obtained. I confirmed that there was. The body color of this sample was bright orange. In addition, this sample emits relatively bright red light (emission peak wavelength: 620 nm) under the excitation of ultraviolet light, near ultraviolet light, purple light, and blue light of 254 nm, 365 nm, 405 nm, and 470 nm, as in Example 1. It was confirmed that it was a red phosphor.

Hereinafter, characteristics of the samples of the nitridosilicate compounds (Sr ₂ Si ₅ N ₈ : Eu ²⁺ phosphor) of Examples 1, 2, and 4 and Comparative Example 1 obtained by the above production method will be described.

  First, the samples of Examples 1, 2, 4 and Comparative Example 1 are all bright orange in color, and these samples are ultraviolet to near ultraviolet to purple to blue of 254 nm, 360 nm, 405 nm and 470 nm. Under the excitation of light, it is confirmed that at least relatively bright red light is emitted, and it is found that the phosphor is a red phosphor.

  More specifically, FIG. 2 shows emission spectra of the samples of Examples 1, 2, 4 and Comparative Example 1 under ultraviolet excitation at 360 nm. Table 3 shows the relative value of the emission intensity at the emission peak of the emission spectrum of Examples 1, 2, and 4 shown in FIG. 2 (hereinafter referred to as relative emission intensity) and the color of the emission at the CIE chromaticity coordinates. The degrees (x, y) are summarized. Here, the relative light emission intensity is a value with the light emission peak height of the light emission spectrum of Comparative Example 1 as 100.

  2 and Table 3, each sample is a red phosphor having an emission peak in the vicinity of a wavelength of 620 nm, but the samples of Examples 1 and 4 have an emission peak of 136 to 198% with respect to the sample of Comparative Example 1. It can be seen that it has a height.

Next, about the sample of the said Example 1, 2, 4 and the comparative example 1, the crystal | crystallization structure was evaluated using the X ray diffraction method. FIGS. 3A, 3B, 3C and 3D show X-ray diffraction patterns of the samples of Example 1, Example 2, Example 4, and Comparative Example 1. FIG. FIG. 3E shows an X-ray diffraction pattern of Sr ₂ Si ₅ N ₈ obtained by simulation from the crystal structure using a Rietveld analysis program.

3A to 3D and FIG. 3E show similar X-ray diffraction patterns, the samples of Examples 1, 2, 4 and Comparative Example 1 are all nitrite. it can be seen that a de silicate compound Sr ₂ Si ₅ N _8. 3A to 3C and FIG. 3D, the samples of Examples 1, 2, and 4, particularly the samples of Examples 1 and 2, are the same as those of Comparative Example 1. It can be seen that the crystallinity is better than that of the sample, which is substantially a single crystal phase nitridosilicate compound Sr ₂ Si ₅ N ₈ .

The X-ray diffraction patterns of the samples of Examples 1, 2, and 4 were more reproducible than the X-ray diffraction pattern of the sample of Comparative Example 1. Therefore, the production method of the present invention is an effective production method for obtaining the nitrided silicate compound Sr ₂ Si ₅ N ₈ having better crystallinity with better reproducibility than the conventional carbothermal reduction nitriding method. Recognize.

  Next, when the constituent elements of the samples of Examples 1, 2, 4 and Comparative Example 1 were analyzed using an X-ray microanalyzer (“JXA-8900” manufactured by JEOL Ltd.), all the samples were Sr, Eu. , Si and N as main constituent elements. Moreover, the atomic ratio of the metal element which comprises the sample of Example 1, 2, 4 was about Sr: Eu: Si = 1.96: 0.04: 5.0.

From the above, it was confirmed that a phosphor having higher light emission performance than Comparative Example 1 was produced by the production method of the nitridosilicate compound Sr ₂ Si ₅ N ₈ of Examples 1, 2, and 4.

In Example 1, based on the following chemical reaction formula (1), a composite oxide (Sr _0.98 Eu _0.02 ) ₃ Ga ₂ O _{6 of} an alkaline earth metal doped with europium and gallium by carbon C is used. It is considered that a nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ was produced by reacting with nitrogen and silicon nitride while being reduced.

(Chemical formula 1)
2 (Sr _0.98 Eu _0.02 ) ₃ Ga ₂ O ₆ + 5Si ₃ N ₄ + 12C + 2N ₂ →
3 (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ + 12CO ↑ + 4Ga ↑ (1)

In Example 2, the compound oxide (Sr _0.98 Eu _0.02 ) Ga ₂ O ₄ to which europium was added was reduced by carbon C based on the following chemical reaction formula (2). It is considered that the reaction produced nitridosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ .

(Chemical formula 2)
6 (Sr _0.98 Eu _0.02 ) Ga ₂ O ₄ + 5Si ₃ N ₄ + 24C + 2N ₂ →
3 (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ + 24CO ↑ + 12Ga ↑ (2)

Further, in Example 4, based on the following chemical reaction formula (3), while the alkaline earth metal oxide, europium oxide, and gallium oxide are reduced by carbon C, it reacts with nitrogen and silicon nitride to produce nitride. It is considered that a silicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ was produced.

(Chemical formula 3)
5.88SrCO ₃ + 0.06Eu ₂ O ₃ + 0.3Ga ₂ O ₃ + 5Si ₃ N ₄ + 6.9C + 2N ₂ + 0.06H ₂ →
3 (Sr _0.98 Eu _0.02 ) ₂ Si ₅ N ₈ +5.88 CO ₂ ↑ + 6.9 CO ↑ + 0.6 Ga ↑ + 0.06 H ₂ O (3)

Hereinafter, characteristics of the samples of the oxonitridoaluminosilicate compounds (Sr ₂ Si ₄ AlON ₇ : Eu ²⁺ phosphor) of Examples 3 and 9 and Comparative Example 2 obtained by the above production method will be described.

  First, the samples of Examples 3 and 9 and Comparative Example 2 are bright orange in their body colors, and these samples are light of 254 nm, 360 nm, 405 nm, and 470 nm of ultraviolet to near ultraviolet to purple to blue light. It is confirmed that the phosphor is a red phosphor when it emits at least relatively bright red light under the excitation of.

  More specifically, FIG. 4 shows emission spectra of the samples of Examples 3 and 9 and Comparative Example 2 under excitation with ultraviolet light at 360 nm. Table 4 summarizes the relative light emission intensities of Examples 3 and 9 shown in FIG. 4 and the light emission chromaticity (x, y) in the CIE chromaticity coordinates. Here, the relative light emission intensity is a value with the light emission peak height of the light emission spectrum of Comparative Example 2 as 100.

  4 and Table 4, all the samples are red phosphors having an emission peak in the vicinity of a wavelength of 625 nm, but the sample of Example 9 has an emission peak height of 112% with respect to the sample of Comparative Example 2. I understand that.

Next, the crystal constituents of the samples of Examples 3 and 9 and Comparative Example 2 were evaluated using an X-ray diffraction method. 5A, 5B, and 5C show X-ray diffraction patterns of the samples of Example 3, Example 9, and Comparative Example 2, respectively. FIG. 5D shows an X-ray diffraction pattern of Sr ₂ Si ₅ N ₈ obtained by simulation from the crystal structure using a Rietveld analysis program.

5 (a) to 5 (c) and FIG. 5 (d) are similar X-ray diffraction patterns, the samples of Examples 3 and 9 and Comparative Example 2 are all oxontridoors. It can be seen that this is the luminosilicate compound Sr ₂ Si ₄ AlON ₇ . In addition, from the comparison between FIGS. 5A, 5B, and 5D and FIG. 5C, the samples of Examples 3 and 9 have better crystallinity than the sample of Comparative Example 2, and substantially In particular, it can be seen that it is a single crystal phase oxonitridoaluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ .

Note that the X-ray diffraction patterns of the samples of Examples 3 and 9 had better reproducibility than the X-ray diffraction pattern of the sample of Comparative Example 2. Therefore, the production method of the present invention is more effective for obtaining reproducible oxonitridoaluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ having better crystallinity than the conventional carbothermal reduction nitriding method. It can be seen that this is a simple manufacturing method.

  Next, the constituent elements of the samples of Examples 3 and 9 and Comparative Example 2 were analyzed using an X-ray microanalyzer. As a result, each sample contained Sr, Eu, Si, Al, O and N as main constituent elements. It was a compound. Further, the atomic ratio of the metal elements constituting the samples of Examples 3 and 9 was approximately Sr: Eu: Si: Al = 1.96: 0.04: 4.0: 1.0.

From the above, it was confirmed that the phosphor having higher light emission performance than that of Comparative Example 2 was produced by the production method of the oxonitridoaluminosilicate compound Sr ₂ Si ₄ AlON ₇ of Examples 3 and 9.

In Example 3, based on the following chemical reaction formula (4), nitrogen and nitridation were performed while the composite oxide (Sr _0.98 Eu _0.02 ) ₃ Ga ₂ O ₆ added with europium element was reduced by carbon C. It is considered that oxonitride aluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ was formed by reaction with silicon.

(Chemical formula 4)
2 (Sr _0.98 Eu _0.02 ) ₃ Ga ₂ O ₆ + 4Si ₃ N ₄ + 3AlN + 9C + N ₂ →
3 (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ + 9CO ↑ + 4Ga ↑ (4)

Further, in Example 9, on the basis of the following chemical reaction formula (5), while the alkaline earth metal oxide, europium oxide and gallium oxide are reduced by carbon C, they react with nitrogen and silicon nitride to produce oxontri It is thought that the doaluminosilicate compound (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ was formed.

(Chemical formula 5)
5.88SrCO ₃ + 0.06Eu ₂ O ₃ + 0.3Ga ₂ O ₃ + 4Si ₃ N ₄ + 3AlN + 3.9C + N ₂ + 0.06H ₂ →
3 (Sr _0.98 Eu _0.02 ) ₂ Si ₄ AlON ₇ +5.88 CO ₂ ↑ + 3.9 CO ↑ + 0.6 Ga ↑ + 0.06 H ₂ O (5)

Examples 4-8, the amount of gallium oxide powder used (Ga ₂ O ₃₎ are different. Therefore, for the samples of Examples 4 to 8, the wavelength of the emission peak under ultraviolet excitation of 254 nm, the relative emission intensity at this wavelength, and the chromaticity (x, y) of emission in the CIE chromaticity coordinates were measured, and gallium oxide was measured. The difference in light emission characteristics depending on the amount was examined. Table 5 shows the measurement results, the addition amount of Ga ₂ O ₃ was used to obtain 1 mol of nitridosilicate compound Sr ₂ Si ₅ N ₈ and (Ga ₂ O ₃ amount). FIG. 6 is a graph showing the difference in relative light emission intensity with respect to the added amount of Ga ₂ O ₃ . Here, the relative light emission intensity is a value with the light emission peak height (light emission intensity) of the light emission spectrum of Example 4 as 100.

From Table 5 and FIG. 6, the preferable addition amount of Ga ₂ O _{3 in} terms of emission intensity is 0.03 mol or more and 1 mol or less, and the more preferable addition amount of Ga ₂ O ₃ is 0.05 mol or more and 0.3 mol or less. It can be seen that it is.

Examples 9-13, the addition amount of the gallium oxide powder used (Ga ₂ O ₃₎ are different. Therefore, for the samples of Examples 9 to 13, the wavelength of the emission peak under ultraviolet excitation of 254 nm, the relative emission intensity at this wavelength, and the chromaticity (x, y) of emission in the CIE chromaticity coordinates were measured, and gallium oxide was measured. The difference in light emission characteristics depending on the amount was examined. Table 6 shows the measurement result, the amount of Ga ₂ O ₃ using oxonitridoaluminosilicate compound Sr ₂ Si ₄ AlON ₇ to obtain 1 mol (Ga ₂ O ₃ amount). FIG. 7 is a graph showing the difference in relative emission intensity with respect to the added amount of Ga ₂ O ₃ . Here, the relative light emission intensity is a value with the light emission peak height (light emission intensity) of the light emission spectrum of Example 9 as 100.

Table 6, the results of FIG. 7, considering the experimental accuracy and the like, in the same manner as in Example 4, the amount of preferred Ga ₂ O ₃ in terms of the emission intensity 0.03 mol 1 mol, more preferably Ga ₂ It can be seen that the amount of O ₃ added is 0.05 mol or more and 0.3 mol or less.

Further, FIG. 8 shows the results of analyzing the remaining amount of gallium with the emission spectroscopic analyzer (“Aurora” manufactured by Thermo Electron) for the samples of Examples 9 to 13 as a function of the added amount of Ga ₂ O _3. A summary graph is shown. FIG. 8 shows that even when the amount of Ga ₂ O ₃ added is 1 mol, the residual amount of gallium is 0.005% by weight or less, and the impurity gallium does not substantially remain. . Further, in order to obtain a compound having a low residual amount of gallium as an impurity and a high purity, the preferable addition amount of Ga ₂ O ₃ is 0.01 mol or more and 0.3 mol or less, and a more preferable addition amount of Ga ₂ O ₃ Is found to be 0.01 mol or more and 0.1 mol or less.

Although the data is omitted, as a result of analyzing the residual amount of gallium as an impurity in the samples of Examples 1 and 3 using Sr ₃ Ga ₂ O ₆ as a raw material for Sr, about 0. 0005% by weight. That is, it can be seen that it is the same level as the sample of Example 9 (the addition amount of Ga ₂ O ₃ is 0.1 mol). The addition amount of Ga ₂ O _{3 that} can produce a substantially single crystal phase compound with good reproducibility is 0.01 mol or more and 10 mol or less, preferably 0.03 mol or more and 1 mol or less, more preferably 0.8 mol. It was 05 mol or more and 0.3 mol or less.

In the above Examples 1 to 13, the case of a nitridosilicate compound containing Sr as a main constituent and alkaline earth metal and Eu ²⁺ as a luminescence center at 2 atom% based on Sr atoms has been described. Even if it is a nitridosilicate-based compound whose main constituent is an alkaline earth metal (for example, Ca or Ba) other than nitridosilicate, it contains a luminescent center ion (for example, Ce ³⁺ ) other than Eu ²⁺ Even if it is a system compound, even if it is a nitridosilicate system compound from which the addition amount of luminescent center ion differs, it can manufacture with the same manufacturing method. Further, a nitridosilicate compound in which a part of Sr that is an alkaline earth metal (for example, 50 atom% or less) is substituted with a metal such as Ba or Ca can also be produced by the same production method.

The manufacturing method of nitridosilicate-based compound of the present invention is not limited to the compositions of Examples 1 to 13, for example, formula _{(1-x) M 2 Si} 5 N 8 · xM 2 Si 4 AlON 7 Or a compound represented by any of the chemical formulas MAlSiN ₃ (wherein M is at least one alkaline earth metal element selected from Mg, Ca, Sr, and Ba, and x is a formula 0 ≦ x ≦ 1) The present invention is widely applicable to manufacturing methods such as

  As described above, the present invention provides a method for producing a nitridosilicate compound having good crystallinity and few impurities relatively easily and with good reproducibility. According to this production method, a method for producing a nitrided silicate compound having a substantially single crystal phase and high quality nitridosilicate in a rational and reproducible manner is provided. Moreover, since it is easy to handle and is manufactured using an inexpensive material, it can be applied to a method for industrial production of a nitridosilicate compound having good material performance.

  The present invention also provides a nitridosilicate compound having good crystallinity and few impurities. In particular, the present invention provides a nitridosilicate compound which is substantially in a single crystal phase and is high quality and inexpensive. Therefore, the nitridosilicate compound of the present invention has good material performance and requires an inexpensive nitridosilicate compound, for example, a nitridosilicate phosphor, an apparatus using the phosphor (for example, White LED light source) and various ceramic members.

It is sectional drawing which shows an example of the light-emitting device using the nitridosilicate type | system | group fluorescent substance. It is a figure which shows the emission spectrum under 360-nm ultraviolet excitation about the nitridosilicate compound of Example 1, 2, 4 and the comparative example 1. FIG. 1 is a diagram showing X-ray diffraction patterns of nitridosilicate compounds of Examples 1, 2, 4 and Comparative Example 1. FIG. It is a figure which shows the emission spectrum under 360-nm ultraviolet excitation about the oxonitrido aluminosilicate compound of Examples 3 and 9 and Comparative Example 2. FIG. 3 is a diagram showing X-ray diffraction patterns of oxonitridoaluminosilicate compounds of Examples 3 and 9 and Comparative Example 2. It is a figure which shows relative light emission intensity as a function of the addition amount of a gallium oxide about the nitridosilicate compound of Examples 4-8. It is a figure which shows relative light emission intensity as a function of the addition amount of a gallium oxide about the oxonitride aluminosilicate compound of Examples 9-13. It is a figure which shows the residual amount of a gallium as a function of the addition amount of a gallium oxide about the oxonitrido aluminosilicate compound of Examples 9-13.

Explanation of symbols

1 Light Emitting Element 2 Nitridosilicate Phosphor 3 Phosphor Layer 4 Submount Substrate

Claims (22)

  A composite oxide of an alkaline earth metal M1 and gallium (wherein M1 represents at least one element selected from Mg, Ca, Sr and Ba), a raw material containing a silicon compound and carbon, A method for producing a nitridosilicate compound, characterized by reacting in a nitriding gas atmosphere. The method for producing a nitridosilicate compound according to claim 1, wherein the composite oxide is a compound represented by a chemical formula M1 ₃ Ga ₂ O ₆ .   An alkaline earth metal compound capable of producing an alkaline earth metal oxide represented by the chemical formula M2O by heating (wherein M2 represents at least one element selected from Mg, Ca, Sr and Ba); A method for producing a nitride silicate compound, comprising reacting a raw material containing a silicon compound, a gallium oxide, and carbon in a nitriding gas atmosphere.   The method for producing a nitridosilicate compound according to claim 3, wherein the alkaline earth metal compound is at least one compound selected from carbonates, oxalates and oxides of alkaline earth metals.   The method for producing a nitridosilicate compound according to claim 3, wherein the amount of the gallium oxide is 0.03 mol or more and 3 mol or less with respect to 1 mol of the obtained nitridosilicate compound.   The method for producing a nitridosilicate compound according to claim 1 or 3, wherein the silicon compound is silicon nitride.   The method for producing a nitridosilicate compound according to claim 1 or 3, wherein the carbon is solid carbon powder.   The method for producing a nitridosilicate compound according to claim 1 or 3, wherein the nitriding gas is at least one gas selected from nitrogen gas, nitrogen-hydrogen mixed gas, and ammonia gas.   The method for producing a nitridosilicate compound according to claim 1 or 3, wherein the temperature of the nitriding gas atmosphere is 1400 ° C or higher and 2000 ° C or lower.   The said raw material is a manufacturing method of the nitridosilicate type compound of Claim 1 or 3 which further contains an aluminum compound.   The method for producing a nitridosilicate compound according to claim 10, wherein the aluminum compound is aluminum nitride. The nitridosilicate compound has a chemical formula (1-x) M ₂ Si ₅ N ₈ .xM ₂ Si ₄ AlON ₇ or a chemical formula MAlSiN ₃ (wherein M is at least one selected from Mg, Ca, Sr and Ba). 4. The method for producing a nitridosilicate compound according to claim 1, wherein x represents one element, and x represents a numerical value satisfying the formula 0 ≦ x ≦ 1.   The method for producing a nitridosilicate compound according to claim 12, wherein M is mainly composed of at least one element selected from Ca and Sr.   The said raw material further contains the element L (however, the said L shows at least 1 element chosen from Ce, Pr, Eu, Tb, and Mn) used as the light emission center of the said nitridosilicate type compound. Or the manufacturing method of the nitridosilicate type compound of 3.   2. The nitride according to claim 1, wherein the composite oxide is a compound to which an element L <b> 1 (wherein L <b> 1 represents at least one element selected from Ce, Pr, Eu, Tb, and Mn) is added. A method for producing a silicate compound.   4. The nitride according to claim 3, wherein the raw material further contains a metal or a compound containing an element L2 (wherein L2 represents at least one element selected from Ce, Pr, Eu, Tb, and Mn). A method for producing a silicate compound. The nitridosilicate compound has the chemical formula (1-x) (M, L) ₂ Si ₅ N ₈ .x (M, L) ₂ Si ₄ AlON ₇ or the chemical formula (M, L) AlSiN ₃ (wherein M Represents at least one element selected from Mg, Ca, Sr and Ba, L represents at least one element selected from Ce, Pr, Eu, Tb and Mn, and x represents the formula 0 ≦ x 15. The method for producing a nitridosilicate compound according to claim 14, which is a nitridosilicate phosphor represented by any one of ≦ 1.   The method for producing a nitridosilicate compound according to claim 17, wherein the emission center ion of the nitridosilicate compound is a europium ion.   A composite oxide of an alkaline earth metal M1 and gallium (wherein M1 represents at least one element selected from Mg, Ca, Sr and Ba), a raw material containing a silicon compound and carbon, A nitridosilicate compound produced by reacting in a nitriding gas atmosphere. A composite oxide of an alkaline earth metal M1 and gallium (wherein M1 represents at least one element selected from Mg, Ca, Sr and Ba), a raw material containing a silicon compound and carbon, A nitridosilicate compound produced by reacting in a nitriding gas atmosphere, as a phosphor matrix;
A nitridosilicate phosphor characterized in that it contains at least one ion selected from Ce ³⁺ , Pr ⁴⁺ , Eu ²⁺ , Tb ³⁺ and Mn ²⁺ as a luminescent center ion.   An alkaline earth metal compound capable of producing an alkaline earth metal oxide represented by the chemical formula M2O by heating (wherein M2 represents at least one element selected from Mg, Ca, Sr and Ba); A nitridosilicate compound produced by reacting a raw material containing a silicon compound, a gallium oxide, and carbon in a nitriding gas atmosphere. An alkaline earth metal compound capable of generating an alkaline earth metal oxide represented by the chemical formula M2O by heating (wherein M2 represents at least one element selected from Mg, Ca, Sr and Ba); A nitridosilicate compound produced by reacting a raw material containing a silicon compound, a gallium oxide, and carbon in a nitriding gas atmosphere includes a phosphor matrix,
A nitridosilicate phosphor characterized in that it contains at least one ion selected from Ce ³⁺ , Pr ⁴⁺ , Eu ²⁺ , Tb ³⁺ and Mn ²⁺ as a luminescent center ion.

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