TW201229196A - Manganese-activated germanate fluorescent substance, production method therefor, and light-emitting element - Google Patents

Abstract

A manganese-activated germanate fluorescent substance that is excited by blue light and emits red light in a high emission intensity, and an industrially advantageous production method therefor, the manganese-activated germanate fluorescent substance being characterized by being represented by general formula (1): aMgO . bMgF2 . c {(Ge1-ySiy)O2}: xMn4+ (1). (In the formula, a is 0< a=4, b is 0.5=b=4, c is 0.8=c=1.2, x is 0.001=x=0.05, and y is 0< y=0.28.) In addition, the production method therefor is characterized by including a step for mixing magnesium fluoride, a magnesium compound other than magnesium fluoride, a germanium compound, a silicon compound, and a manganese compound, and sintering the resulting mixture.

Description

201229196 VI. Description of the Invention: [Technical Field] The present invention relates to a manganese activated acid sulfate phosphor useful as a red phosphor and a method for producing the same. Further, the present invention relates to a light-emitting element using the manganese-activated phthalate phosphor. [Prior Art] In recent years, it has been known that the blue dipole system has been put into practical use and the white light-emitting diode using the diode as a light-emitting source has been studied. The light-emitting diode system has the advantage of being so lightweight and not using mercury to have a long life. It is known to apply, for example, a blue light-emitting element to a white light-emitting diode of Y3Als〇i2: Ce. However, the light-emitting diode system is strictly white, and it is a mixture of blue-green white. Therefore, it is proposed to mix Y3Ah〇i2 to adjust the hue by emitting a red fluorescent red phosphor with and absorbing blue light. The report of the red phosphor which emits red fluorescent light by absorbing blue light is mostly about an organic material, but the inorganic material is less. On the other hand, as an ordinary red fluorescent system, inorganic materials such as oxide phosphors, oxysulfide phosphors, sulfide phosphors, and nitride phosphors are also proposed, and the following is also proposed. The manganese activated acid salt phosphor represented by the formula (A) (for example, refer to the following Patent Documents 1 to 2). a* MgO · b* MgF2 . cGe〇2 : x' Mn4+ ( A)

(In the formula, a + b' = 4, b' means 0.5Sb, S 1.0, and x means 〇.001gx, g〇〇i.) However, the manganese activated citrate fluorescent system is emitting light. Strength, problematic

201229196 The raw 'quantum yield rate is also low. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. The present invention provides a manganese-activated citrate phosphor which is excited by blue light to emit red light with high luminous intensity, and a manufacturing method advantageous for the same. [Means for Solving the Problem] The inventors of the present invention conducted this research in a thorough and thorough manner, and concluded that the manganese activated citrate phosphor represented by a specific formula is oxidized by oxidation. The ruthenium atom, in a specific amount, replaces a part of the ruthenium atom, but emits red light at a higher luminous intensity than conventionally, so as to complete the present invention. The present invention has been accomplished in accordance with the foregoing teachings and provides a vigorously activated phthalate phosphor characterized by the following formula (1), aMgO · bMgF2 · c { ( Ge Bu ySiy) 〇 2 } : xMn“ ( j ) (In the chemical formula, 'a indicates 〇 &lt;a$4, b indicates 〇.5sbs4, c indicates 0.8SCS1.2', and χ·〇0〇1$χ$〇〇5 The lanthanide series is represented by 0 &lt; y S 0. 28.). 'In addition to the acid salt camping body', the present invention is used to manufacture the aforementioned sparse

S 201229196 A method for producing a manganese activated phthalate phosphor, which is a suitable method,

[effect of the invention]

In the case of the method, the phosphor can be produced by the production of the present invention in an industrially advantageous manner. [Embodiment] The present invention will be described below based on its preferred embodiments. The manganese activated phthalate fluorescent system of the present invention is substantially excited by blue light to emit red light. Specifically, the light is emitted by excitation light of at least 27 Å to 550 nm, preferably 380 to 490 nm. Further, in the region of 600 to 750 nm, preferably 650 to 70 Å, there is a light-emitting band (i.e., having a red spectrum). The manganese activated phthalate fluorescent system of the present invention is represented by the following general formula (i). aMgO · bMgF2 · c { ( Ge ySiy) 〇 2 } : XMn4+ ^ j ^ a system 通式 in the formula (1) 〇 &lt; 4, preferably 1 &lt; a $3.4 ' b system 〇.5$b $4, preferably 0.6Sb each 3, c system is .8sc $1.2, preferably 〇.9gcsl.i, x is 0 〇〇1$χ$〇〇5, preferably 0. 005 $ 〇· 〇3 . Further, in the chemical gas showing the substitution rate of one of the ruthenium atoms of the ruthenium atom, the y series 0 &lt;y$0.28, preferably 0 &lt; yg 0.25, by which the substitution ratio of the 201222196 ruthenium atom becomes the aforementioned The treatment, the red light is strong and on the other hand, when the value of y exceeds 〇28, the quantum efficiency becomes unsatisfactory. _Zhe Shi lowered the interior of the manganese activated phthalate fluorescent system of the present invention and the helmet is 丨 Μ 遛 遛 遛 遛 遛 遛 遛 遛 遛The particle shape may be indefinite, in addition to the rr, ± 疋 column such as a spherical shape, a polyhedral spindle shape, or a needle shape. The manganese activated phthalate fluorescent system of the present invention has an average particle diameter of 5 Å/im, particularly preferably 5 to 45 #m. When the average particle size is not found in the ancient machine, when the A 1 work clothes are full of 1 # m, please wait for the valley to be scattered and reduce the absorption efficiency of the excitation light. When the number average particle diameter exceeds 5 Å, the surface area of the particles becomes small, and the absorption of the excitation light is still insufficient. Further, in the present invention, the average particle diameter of the secondary particles formed by the aggregation of the primary primary particles is formed. The flat gamma (four) median particle size. The average particle diameter (median diameter) of the secondary particles is as follows: a laser diffraction/scattering particle size distribution measuring device (model: LA-92〇) manufactured by Horiba, Ltd. Refractive = 181, as the refractive index (3) of the dispersion medium, by volume basis: the average particle size can be adjusted, for example, as follows. That is, 'the burnt body of the stimuli-activated acid-fluorescent body obtained by the firing process described later' is performed by an automatic mortar or a ball mill, etc.: the pulverization process is used as the state is used. The sieve of the opening of the target particle size is divided into stages to obtain a powder having a desired average particle diameter. The BET specific surface area of the manganese activated phthalate fluorescent system of the present invention is preferably ο.1~i〇〇&quot;g, especially 丨~-乂. Not enough BET specific surface area

S 6 201229196 0. At lm2/g, the absorption of excitation light is likely to be insufficient. When the specific surface area exceeds 10 〇 m 2 /g, the average particle diameter becomes small as the surface area becomes larger, and therefore, the excitation light is scattered and the absorption of the excitation light becomes insufficient. The BET specific surface area can be measured, for example, by using a single adsorption specific surface area measuring device (FlowS〇rb n23〇〇) manufactured by Shimadzu Corporation. The BET specific surface area can be adjusted, for example, as follows. In other words, the sintered body of the manganese-activated citrate phosphor obtained by the firing process described later can be subjected to pulverization treatment by an automatic mortar or a ball mill, etc., and the position is used with the state. The sieve having the opening of the target particle size is classified into 2 to obtain a powder having a desired BET specific surface area. Next, an ideal manufacturing method of the manganese activated phthalate phosphor of the present invention will be described. An ideal method for producing the manganese-activated citrate phosphor of the present invention comprises: "mixing magnesium compounds other than magnesium fluoride and magnesium fluoride (hereinafter, simply referred to as "b 5"). , a bismuth compound and a manganese compound, a process of firing a mixture of the servants. That is, the manufacturing method of the manganese activated bismuth silicate polishing agent of the present invention roughly comprises a (A) mixing process and a (B) firing process. a is prepared in a mixed process of (a) to uniformly mix a uniform compound of magnesium fluoride, magnesia, azide, zirconium compound and a compound. When β is easy to be mixed uniformly, it is preferable that the desired physical properties of the magnesium fluoride-based magnesium fluoride of the first raw material are an average particle diameter of 1. &quot; m below; t is good (7) ", especially 201229196 raw materials, the material of the money in addition to the oxidation town, condensed later, B) firing process, the use can be converted into magnesium oxide. As such The town can be used, for example, an oxide of a town, a bed of hydrochloric acid, a salt of a salt, or the like. These compounds can be used in the case of i or sputum, 'after firing, without leaving impurities. And: In terms of high sexuality, it is best to use magnesium hydroxide.

2 If the σ σ can be easily viewed, it is preferable that the ideal physical property of the magnesia A is an average entertainment ϋ ϋ 岣 也 也 也 也 也 也 也 5 5 5 5 5 5 5 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 5// The wrong compound of the description material is in addition to the oxidation error, and it can be converted into an oxidative error in the following. As the defect, it is possible to use, for example, an oxide of cerium, a cerium carbonate, cerium nitrate, _# ·»»' sulfur-antimony oxide, an organic acid salt or the like. This may be used in one type or in two or more types. Even in this one; *: The volatility of the sputum is low and it is not allowed to be dermatologically due to the oxidization of the escaping. The thirst is described by the following: θ people, therefore, by words, then the most It is good to use oxidation error. From the point of view of uniform mixing, it is the most variable. The ideal physical property of the best 疋锗 compound is 50 (four) or less, especially 1 to 3 (^m.) Particle size: 乍The chopped compound of the fourth raw material is a dioxic cut (b, which is described later as (b) calcined 〇« oxygen chopping. As this "compound" can be used = converted into diterpene, tantalum carbide, tantalum nitride,狮# such as - yttrium oxide, lanthanum boride, organic acid bismuth bismuth sulphate δ system can use 丨 荨. These kinds of more than two species. Even among these, 201229196 is also difficult to react due to dioxide Since water is not hydrolyzed, it is preferable to use cerium oxide from the viewpoint of easy adjustment of the composition by wet mixing described later. It is easy to mix by uniform = point of view 'It is best that the ideal physical property of the dioxic cut is from l〇#Hi below, the best county 〇~in 疋υ·υυΐ~10 to &quot;1, especially 0.001~1 #111. 5, the raw material of the compound can use, for example, hydrogen peroxide Compounds, carbonates, nitrates, sulfates, organic acid salts, etc. These compounds may be used alone or in combination of two or more. Even in these cases, since impurities are not retained after firing, and solid solution is easy. The aspect of the parent crystal is preferably manganese carbonate. From the viewpoint of being easily and uniformly mixed, the ideal physical property of the manganese compound is preferably an average particle diameter of 1 〇β m or less, particularly 1 to 9 # m. Regardless of the manufacturing history of the above-mentioned magnesium fluoride, magnesium compound, bismuth compound, bismuth compound and manganese compound, however, it is preferable to manufacture a high-purity manganese-activated citrate phosphor. In the present production method, the mixing ratio of the magnesium fluoride, the magnesium compound, the cerium compound, the cerium compound, and the manganese compound can be appropriately selected in accordance with the composition of the manganese activated citrate phosphor required for the above-mentioned requirements. Specifically, the mixing ratio of the magnesium fluoride, the magnesium compound, the cerium compound, the cerium compound, and the manganese compound is the amount of magnesium fluoride added to be fluorinated. The number of molecules is 0.5 to 4, preferably 0.5 to 4, based on the molar ratio (Ge + Si + Mn) of the total number of atoms of the ruthenium atom in the ruthenium compound, the ruthenium atom in the ruthenium compound, and the manganese atom in the ruthenium compound. It is 〇·6~3. Value (MgF2/ In addition, the amount of magnesium 201229196 added is the number of magnesium atoms in the magnesium compound relative to the ruthenium atom in the ruthenium compound, the ruthenium atom in the ruthenium compound, and the manganese in the manganese compound. The molar ratio of the atomic number of atoms (Mg/(Ge+Si + Mn)) is greater than 0, less than 4, and most preferably 1 to 3. 4. The amount of the compound added is the number of manganese atoms in the compound. The molar ratio (Mn/(Ge+Si + Mn)) of the total number of atoms relative to the ruthenium atom in the ruthenium compound, the ruthenium atom in the ruthenium compound, and the manganese atom in the manganese compound becomes 〇〇〇1 to 〇〇 5, preferably 0. 005~0. 03. Further, the addition amount of the ruthenium compound is such that the ratio of the number of ruthenium atoms in the ruthenium compound to the total number of atoms of the ruthenium atom of the ruthenium compound and the ruthenium atom of the ruthenium compound (Sl/Ge+Sl) becomes larger than 〇, less than °^28, preferably greater than 0, less than 〇. 2 5. The method of mixing the fluorinated town, the town compound, the wrong compound, the ruthenium compound, and the manganese compound of the first to fifth raw materials may be any of the wet method and the dry method. However, each raw material can be easily obtained. In the case of the average sentence, it is preferable to carry out the method by the wet method. It is possible to obtain a uniform mixture by using a media roll mill which is a machine capable of simultaneously pulverizing and mixing, and it is easier to obtain a homogeneous mixture, which is activated by a homogeneous mixture. In particular, the citrate fluorescent system has a high degree of hair growth. ^ This will be explained more in detail using a mixing process of a media mill. The mixing process in the media mill consists essentially of the process, and the resulting slurry is introduced into a media mill 2: Modulation/Processing Mixture 2012 20122196. In the polymerization process, magnesium fluoride, a magnesium compound, a deuterated human compound, and a stimulating compound are dispersed in a dispersion medium to form a slurry. = Even if it is any kind of water and non-aqueous dispersion medium = "," and it is easy to disperse the treatment, it is best to use: 2. The second is by the media. If you use water as a point, The concentration of the solid component (the total concentration of the fluorinated town, the magnesium compound, the cerium compound, and the manganese compound) is preferably from the viewpoint of the reduction in the weight of the oxime and the ease of handling. 5~(9) especially 10~30% by weight. The dispersant can be added to the polymer. The addition of the dispersant makes the magnesium fluoride, the eutrophic compound, the cerium compound, the cerium compound and the manganese compound more evenly dispersed. As a result, a homogeneous mixture of these raw materials can be obtained more easily. The dispersing agent to be used can be appropriately selected in accordance with the kind of the dispersing agent. In the state in which the dispersing agent is water, various types can be used as the dispersing agent. Interface activity (4), poly m (tetra) salt, etc. From the viewpoint of sufficient dispersion effect, it is preferred that the concentration of the dispersant in the slurry is 〇.01~10% by weight, especially .0.1~5 Then, the slurry obtained in the slurry preparation process is introduced into a media roll mill and mixed to obtain a homogenous mixture. As a medium emulsion mill, a particle mill, a ball mill, and a paint vibration can be used. , a plotter, a sander, etc. It is especially preferable to use a particle mill. In its state, the operating conditions or the type and size of the particles can match the size or amount of magnesium fluoride and magnesium compounds in the device. , the wrong compound, the ε 夕 compound, and the type of the object, etc., and the type of the object, etc., are appropriately selected. From the viewpoint of obtaining a more uniform mixture, the human form caused by the wet method is preferably ' &lt; The smuggling process is carried out to the diameter (the average of the secondary particles of the flat core / knife)

until. Pulling d becomes 1〇(4) or less, especially after U is blended and treated, the body is mixed with the body and the homogeneous mixture is recovered. Q=The mixture is preferably added to the firing process of (B) Tablets, dry and dry treatment. Drying treatment can be cited in the example ~100 hours. (:, carry out i

The force is followed by a mixture of the mixture obtained in the (A) mixing process, and the firing process of (B) is obtained to obtain the suspected activated acid sulfate phosphor. The firing conditions are preferably a firing temperature of 1 025 to 12 A 1 050 to 1 200. (:. In the π π 去 去 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the case of firing, there is a tendency that the sintering between the particles is excessively performed, and the powder tends to be easily obtained. The firing time is preferably 3 hours or longer, particularly 5 to 36 hours. The atmosphere is not particularly limited, and may be any one of an oxidizing atmosphere such as the atmosphere and an atmosphere of an inert gas. The firing system thus obtained may be accompanied by a firing process as needed. The chain-activated acid salt complex obtained after the formation needs to be 'crushed or pulverized, and the eight-stage activated phosphoric acid solution of the present invention can be modified due to the change of wetness 12 201229196' The surface of the particle is 'surface treated' by a metal oxide as needed. As the metal oxide system described above, it is composed of Be, Mg, M, Si, Ca, Sc, Ti, V, Cr, Mn, Fe. , c〇, M , Cu, zn, to, ^ '

Sr Y Zr , Nb , Mo , Cd , In ' Sn , Sb , Te , Ba , La , Hf , Τ λ pu n . _ , Bi, Ce, Pr, Nb, Pm, Sm, Eu, Gd, Tb, y Metal oxides of j or more than two metal elements selected from Ho Er, Tm, Yb, Lu, Th, Pa, U, and Pu. As a method of coating the surface of the particles of the manganese-activated phthalate phosphor by these metal oxides, a conventional method can be used, and if an example is shown, it is exemplified that the use of the aforementioned metal-containing substance is used. a metal alkoxide to which a metal alkoxide is added to a body or suspension containing the red phosphor to carry out a hydrolysis reaction of the metal alkoxide, and the particles of the red phosphor by the metal oxide described above The surface, the method of uniformly performing the surface treatment, and the like. The salt fluorescent system can be used in the excitation spectrum of 450 nm or so of a display element such as a device or an electroluminescence light, and is used for the manganese-activated tantalum-electrolytic radiation type display and the plasma display device thus obtained. Further, 'having close to this' can be applied to the use of a blue LED excitation phosphor. In particular, it is suitable for display elements that are electrically excited. In addition, the method of using the blue phosphor to excite the green phosphor, the method of using the blue “rib element and the blue excitation green phosphor, or the blue LED element and the blue excitation yellow fluorescent It is applied to a white LED by a method of using a light body or the like.

§ 13 201229196 EXAMPLES Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited to these Examples. The average particle diameter and the bet ratio of the examples and comparative examples below were measured as described below. Ιτ' average particle size: measured by laser diffraction/scattered particle size distribution manufactured by Horiba, Ltd.; t device (model: LA-92{)), and the refractive index of the sample becomes i. 8 is calculated as a refractive index of the dispersion medium. Fine volume by volume Specific surface area of the intestine: It was carried out using a monosorbed specific surface area measuring device of the βΕτ method manufactured by Shimadzu Corporation. &amp; device (7) (10) rbn2_) and [Example 1] (曱) uniform slurry preparation process: weighing chlorine oxidation town (average particle size 〇 57 / / m), gasification error (particle size 19.0M, oxidation error (average particle size 17 7^), diterpenes (average particle size 0. 016 m) and manganese carbonate (average molar ratio of 1:2 = 0.05. 0. (Π, loaded into the ball mill. In the ball ( Kao (stock) company system, mooring (a _, =: IS:: come from: liquid. Dispersing agent concentration is 2%, the Mohr number ratio shows not only the molar ratio of magnesium hydroxide. In the ball mill 'loading 2mm diameter cerium oxide ball into the method of mixing and crushing i 5 small a a wet... 5 hours. In the wrong way by the light scattering method measured in the mixed 14 201229196 comminuted solid state When the average particle size of the component is 〇·3", the mixture is filtered and recovered from the slurry at 12 Torr. The dried powder is dried for 15 hours to obtain a dry powder. The average particle size of the unorganized body is 0·5 m. (B) The firing process: Next, the 6-well body is allowed to stand still. 'In the electric furnace, the dry powder is placed in an hour, and the firing is performed. Under the atmosphere, 115 (Tc, when manganese activated strontium fluorite is obtained, the strontium ray diffraction is performed on the sensitized acid sulfate phosphor). 4 The manganese activated citrate fluorescent system "guGe5" is recognized. 〇". _, and into a composition of the early activation of the acid salt phosphoric acid. [Example 2] In addition to the uniform mixing process in the shell of Example 1 (A), the sample of magnesium hydroxide (Average particle size: .57&quot;), magnesium fluoride (average particle size 19 Å, oxygen domain (average particle size 17.7"), dioxotomy (average particle size 〇.〇i6am), and manganese carbonate (average particle size 5 2#m) and the Mohr number ratio of MgF2: : Ge : Si: Μη becomes i : 3 : 〇. 89 : 〇. i : 〇. 〇ι , is loaded into the ball mill, and the rest is the same as the embodiment A manganese-activated phthalate phosphor was obtained by hydrazine. When the Mn-ray diffraction was performed on the obtained manganese-activated phthalate phosphor, it was confirmed that it was composed of MguGesO24 and Mg ,, and it became a single composition of manganese activation. Hydrate phosphor. [Example 3] In addition to the uniform mixing slurry preparation process of Example 1 (A), the amount of magnesium hydroxide was weighed (average grain Square · 57 / z m), magnesium fluoride (average particle size of 19 square

15 201229196 V m), yttrium oxide (average particle size 17.7 // m), cerium oxide (average particle size 0. 016# m) and manganese carbonate (average particle size 5. 2 &quot; m) make MgF2: 〇, 〇 6.31: ^|11 Mohr number ratio, becomes 1:3: 〇.79: 〇.2: 〇. 〇 1, loaded into the ball mill, the rest is the same as in Example 1 to obtain manganese activation error Camp light body. When the X-ray diffraction measurement was carried out on the activated phosphoric acid phosphor, the manganese-activated citrate phosphor composed of Mgl4Ges〇24 and Mg〇 was confirmed to be a single composition. [Comparative Example 1] A mixed slurry preparation process, weighing magnesium fluoride (average particle diameter of 19.0 except for the uniform amount of magnesium hydroxide (average particle diameter 〇· 57 # m ), (d)) in Example 1 Cerium oxide (average particle size of 17.7//ffl) and manganese carbonate (average particle size of 5.2") such that the molar ratio of MgF2:Mg:Ge:Mn is 1:3: U9: 〇. Except for the ball mill, the rest are the same as the examples (the vibrating citrate phosphor is obtained. When the X-ray diffraction material is obtained by the activation of the citrate camping body, the scent is turned into a heart and _ And the manganese activated citrate phosphor which becomes a single composition. [Comparative Example 2] The uniform polymerization process of the (A) uniform mixture in Example 1 was carried out, and the average particle size D , gasification town (average particle size 19 〇# «〇, yttrium oxide (average grain, 〇filR, 17.7#, cerium oxide (average particle k 〇. 016 # m) and manganese carbonate (flat

Mg . Γρ . Q. _ ♦ 杬 5. m) and make ^^?2:

Mg · Ge · Si : Moir number ratio of Μη, into f person $ 抹 n 珉 is 1 · 3. 0. 69 : 〇. 3 : w, ^ 1 u outside 'the rest is the same as in embodiment 1 and ^ ^ Hydrate phosphor. In the case of the obtained m 彳 活化 活化 活化 活化 猛 猛 猛 猛 猛 猛 猛 猛 猛 猛 猛 猛 猛

S 16 201229196 At the time of the ray diffraction measurement, it was confirmed that it was composed of Mg0 and became a single composition of the stimuli-activated acid sulfate. &lt;Evaluation of physical properties of the activated citrate phosphor&gt; The manganese activated citrate phosphor obtained in the examples and the comparative examples was measured by the method described above to determine the average particle diameter and the bet ratio. The surface area, the results of which are shown in Table 2. [Table 1] Raw material loading amount (Mohr number ratio) Firing temperature firing time (h) MgF2 Mg atom Ge atom Si atom Μη atom (0〇 Example 1 1 3 0.94 0.05 0.01 1150 6 Example 2 1 3 0.89 0.1 0.01 1150 6 Example 3 1 3 0.79 0.2 0.01 1150 6 Comparative Example 1 1 3 0.99 - 0.01 1150 6 Comparative Example 2 1 3 0.69 0.3 0.01 1150 6 [Table 2] Composition average particle diameter (egg) BET specific surface area ( mVg) Example 1 3MgO»lMgF2· { (Ge0.94Si0.05) 〇2} : 〇. 〇1Μη4+ 9.2 16.2 Example 2 3MgO»lMgF2· { (Ge〇.89Si〇..) 〇2} : 0. 〇1Μη4+ 10.5 15.3 Example 3 3MgO«lMgF2· { (Ge〇.79Si〇.2) 〇2} : 0.01Mn4+ 12.1 14.7 Comparative Example 1 3MgO · lMgFa · Ge〇.99〇2 : 0. 01Mn4+ 7.9 20.3 Comparative Example 2 3MgO*lMgF2· { (Ge〇.69Si〇.3) O2} : 〇. 01Mn4+ 15.3 10.8 [Evaluation as Red Phosphor] Manganese-activated citrate phosphor obtained in the examples and comparative examples The internal quantum efficiency 17 201229196 and the relative luminous intensity at an excitation wavelength of 45 〇 nm were measured by the following methods. These results are shown in Table 3 below. [Internal quantum efficiency] Using a fluorescence spectrophotometer (F-7 〇〇〇) manufactured by 曰立科技有限公司 and the subsidiary product as a sphere, the excitation light is 45 〇 nm, and the scanning is performed from the beginning to the range of 700 nm. Conversion efficiency. In addition, in the sample for measuring the total scattered light, 'Oxide powder was used. The integrated value of the spectral intensity at 475 nm from the milk obtained by oxidizing the chain was used as the amount of excitation light to make the sample by the phosphor. The spectral intensity integral value from 435 to 475 nm was obtained as the amount of excitation light after absorption, and the spectral intensity integral value from 6 〇〇 to 70 〇 nm obtained by the phosphor sample was obtained as the amount of fluorescence. Next, the internal quantum efficiency is obtained by the following formula: Internal quantum efficiency (%) = 100 x fluorescence amount + (excitation amount - amount of excitation light after absorption) [Relative luminous intensity] Fluorescence spectrophotometry manufactured by Hitachi High-Technologies Corporation (F_ 7000 ) ' becomes 450 nm of excitation light, scans from 470 to 800 nm, and is applied to the fluorescence spectrum. From the obtained intensity value, the relative luminous intensity is obtained by taking the maximum luminous intensity as 100.[Table 3] Internal quantum efficiency __(%) Relative luminous intensity Example 1 __64. 0 100 Example 2 _65. 6 98. 6 Example 3 __67.3 92. 6

18 S 201229196 Comparative Example

Comparative Example 2 74. 9 61. 5 Further, it was judged by the results shown in Table 3 that the stimuli-activated acid salt phosphor of the first embodiment (the present invention) was compared with the manganese-activated hydrazine of Comparative Example 1. The acid salt phosphor further makes the luminous intensity in the red region become south. [Simplified illustration] No [Main component symbol description] None 19

Claims (1)

201229196 VII. Patent application scope: 1. A manganese activated citrate phosphor characterized by the following general formula (1): aMgO · bMgF2 · c { ( Ge Bu ySiy) 〇 2 } : xMn4+ ( 1) (In the chemical formula, a indicates 〇&lt;a$4, b indicates 〇.5SbS4, c indicates 0.8Sc$1.2, x indicates 0.001SxS0.05, and y indicates 〇<y$〇.28) Said. 2. The manganese-activated citrate phosphor according to the first aspect of the patent application, wherein the light is emitted by excitation light of 270 to 550 nm. 3. A manganese activated phthalate phosphor as claimed in claim 1 or 2, wherein the region has a light-emitting band in the region of 600 to 750 nm. 4. The manganese-activated bismuth sulphate mortar according to any one of claims 1 to 3, wherein the average particle diameter is 1 to 5 Å #m. 5. A method for producing a manganese-activated citrate phosphor, which comprises the manganese-activated citrate phosphor according to claim 1, characterized in that it comprises: a mixed magnesium fluoride or a magnesium fluoride A process in which a mixture of a magnesium compound, a cerium compound, a cerium compound, and a manganese compound is fired. 6. The method for producing a manganese activated citrate phosphor according to claim 5, wherein the firing temperature is 1 025 to 1 250. (: 7. The method for producing a manganese activated phthalate phosphor according to claim 5 or 6, wherein the bismuth compound is cerium oxide. 8. 70 kinds of luminescent materials, characterized in that the patent is used. The manganese activated phthalate phosphor of any one of the above items 1 to 4. S 20