TW201215664A - β-SiAlON fluorescent body, manufacturing method thereof, and usage thereof - Google Patents

Abstract

The object of the present invention is to provide an Eu activating β -SIALON fluorescent body with high fluorescent luminous efficiency and short wavelength at its fluorescent peak to enable light emission within narrow band. The solution to the present invention is to provide a β -SIALON fluorescent body comprising of β -SIALON with general formula of Si6-zAlzOzN8-z as matrix material and solid-soluted Eu2+ as light emitting center. The lattice constant ''a'' of β -SIALON crystal is 0.7605 to 0.7610 nm, the lattice constant ''c'' of β -SIALON crystal is 0.2906 to 0.2911 nm; the amount of Eu of β -SIALON crystal is 0.4 to 2 mass %; and the amount of the first transition metal of β -SIALON crystal is less than 5ppm.

Description

201215664 VI. Description of the Invention: [Technical Field] The present invention relates to a method capable of utilizing a blue light emitting diode (Light Emitting Diode) or an ultraviolet light emitting diode (UV LED) A white light-emitting diode (white LED) or the like is a phosphor of various types of light-emitting devices, and a light-emitting device using the same. [Prior Art] Patent Document 1 discloses a white LED which combines a semiconductor light-emitting element and a glare which emit a short wavelength of blue to purple, and causes the light-emitting of the semiconductor light-emitting element to be emitted by the phosphor. The wavelength-converted light is mixed to obtain white light. T is known that the fluorescent system converts transition metal or rare earth gold into a luminescent center by using a body material of a metal salt, a phosphate, a salt, and a sulfide. With the high output power of the white LED, the heat resistance and long-term requirements of the phosphor are getting higher and higher. However, the use of the above-mentioned light s' will result in the following ugliness: as the degree of abundance is lowered, the smattering of the smuggling occurs when it is exposed to the shackles and occurs as a white one. Nitride or oxynitride with high valence bond =: Luminescent body's phosphor with excellent durability as temperature rises and brightness decreases. A representative of a phosphor of a dinitrogen, an oxynitride as a riding material, is a celestial emulsified cerium solid solution. There are two crystal systems of type 0C and type β with nitrogen. For example, Sailong ^ as the center of illumination, - 押 有 有 . 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化 活化A phosphor of yellow light of 550 to 600 nm (Patent Document 2). In addition, it is found in the β-type sialon, and the luminescent center is expressed by adding Mn, Ce, and Eu (Patent Document 3). The β-type Sialon is a solid solution of β-type tantalum nitride, which is the Si position of A1 crystallized in the β-type fossilized day, and the solid solution is replaced by the niobium at the niobium position. Since there are two types of atoms in the unit cell (unit lattice), the general formula is "Si6-ZA1Z0ZN8-Z". Here, the composition z is 0 to 4.2, and the solid solution range is extremely wide. In addition, the molar ratio of (Si, Al) / (N, 0) must be maintained at 3/4. In general, the β-sialon can be obtained by heating cerium oxide and aluminum nitride or by adding aluminum oxide and aluminum nitride to a tantalum nitride. When Eu2+ is contained in the crystal of the β-Sialon, it is excited by ultraviolet to blue light, and is a phosphor that emits green light of 520 to 550 nm, and can be used as a green light-emitting component of a light-emitting device such as a white LED. This Eu2+-activated β-Sialon has a sharp fluorescence spectrum even in the phosphor activated by Eu2+, and is particularly suitable for liquid crystal display panel backlights that require illumination in narrow-band regions of blue, green, and red. A phosphor of a green light-emitting component of a light source. It has also been revealed that the β-Sialon phosphor synthesized by sintering at a high temperature can reduce crystal defects and remarkably improve fluorescence characteristics by post-treatment of a combination of heat treatment and acid treatment under specified conditions (Patent Document 4). . However, at this time, as the luminous efficiency is increased, the wavelength of the fluorescent peak is increased or the width is increased. Patent Document 5 discloses that a narrow-frequency region of fluorescence emission is reduced by reducing the amount of oxygen solid solution in the β-sialon crystal, and as a method of synthesizing a β-sialon having a low oxygen solid solution amount, nitriding is exemplified. The method of forming the element gold 5/25 201215664 is a powder; or the method of heating the nitride and the oxide raw material in a reducing nitriding environment. However, in this case, the β-sialon phosphor has extremely low luminous efficiency and is difficult to provide practical use. Patent Document 1: Japanese Patent No. 2927279 Patent Document 2: Japanese Patent No. 3668770 Patent Document 3: Japanese Patent Publication No. 2005-255895 Patent Document 4: International Publication No. 2008/062781 Patent Document 5: International SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The conventionally activated Eu-activated β-Sialon fluorescent system has a trade-off relationship with the spectral width. Therefore, when the white LED using the Eli-activated β-Sialon phosphor is narrowed in the region, sufficient brightness cannot be obtained. On the other hand, after the luminous efficiency is improved, the color reproduction range is narrowed, especially for the backlight of the liquid crystal display. It is difficult to provide practical use for sources and the like. The present invention has been made in view of the above problems, and provides an Eu-activated β-Sialon phosphor having high fluorescence emission efficiency and a short peak wavelength of a fluorescent wave, thereby enabling light emission in a narrow-frequency region. Means for Solving the Problem The fluorescent system of the present invention has a β-sialon represented by the general formula Si6-ZA1Z0ZN8-Z as a parent crystal, and a light-emitting center is used to solidify Eu2+, as shown in Patent Document 5, The amount of oxygen solid solution in the β-Sialon crystal is reduced, that is, the enthalpy of the above formula is lowered to achieve narrow-band regionalized luminescence. The present inventors have continuously studied the enthalpy value, crystal structure, composition, and fluorescence characteristics of the β-type Sialon, and found that the crystal size of the β-type Sialon 6/25 201215664 inch can not only estimate the Z value, but also speculate that it is within the crystal. Eu2 + solid solution amount. As a result, it was found that when the ζ value of the β-Sialon fluorescent system produced by the conventional method is lowered, the amount of Eu 2+ which is actually dissolved in the β-Sialon crystal is reduced, and the luminous efficiency is lowered. Further, the present invention has been achieved by optimizing the crystal system or impurities of the tantalum nitride powder of the main raw material of the β-Sialon, and subjecting the synthesized phosphor to the specified conditions. After the treatment, even at a low enthalpy value, the Eu2+ solid solution amount is increased, and high luminous efficiency is maintained, and narrow-frequency regionalized luminescence can be realized. That is, the present invention provides a β-Sialon phosphor which is a β-type sialon represented by the general formula Si6-ZA1Z0ZN8-Z as a matrix material, and has a Eu2 + solid solution in the luminescent center, and the β-Sialon crystal The lattice constant a is 0.7605 to 0.7610 nm, the lattice constant c is 0.2906 to 0.2911 nm, the Eu content is 0.4 to 2% by mass, and the first transition metal content is 5 ppm or less. The β-Sialon fluorescent system has an emission peak wavelength in a wavelength range of 520 to 540 nm by irradiating an excitation source, and its chroma is 〇.28Sxg〇.33, 0.62^y<0.67 in a CIExy chromaticity coordinate. . In the P-type Sialon phosphor, the integral volume fraction in the particle size distribution measured by the laser diffraction scattering method is 90% in diameter (D90), preferably 10 to 50 μm, and 10% in diameter (D10). ) is preferably 2 μηι or more. In addition, the present invention provides a method for producing a β-Sialon phosphor, which is a β-type sialon represented by the general formula Si6—ζΑ1ζΟζΝ8-ζ, and a β-type Sialon having a luminescent center which has solid solution of Eu2+. A method for producing a phosphor comprising the steps of: sintering a sintering powder comprising a tantalum nitride powder containing cerium 1 and an inorganic compound containing Eu in a temperature range of 1850 to 2050 ° C in a nitrogen atmosphere; In the rare gas 7/25 201215664 body environment, 1300~boo fc·/ s; and 0.5 hour or more, the main heat treatment step aa θ yv ^ . . / 呗An acid treatment step in a mixed acid of hydrofluoric acid and nitric acid at 60 ° C or higher. In this manufacturing method, the yttrium-transition synthesized by the nitrogen-based metal: nitridation method: content: two: : and contains (U 2 to 2% by mass of Ai. In addition, in the nitriding powder) Preferably, the β rate is 5 G% or more, and the gold (4) content is i〇% or less. ', again, 'The present invention provides a "germ" element having a maximum intensity of the emission wavelength of 24 〇 to 48 〇. The LED of nm and the above-mentioned β-sialon phosphor laminated on the light-emitting surface of the LED; and also provides a light-emitting device that has the light-emitting element and a power source that supplies electricity to the light-emitting element. According to the present invention, there is provided an Eu-activated β-Sialon phosphor having high fluorescence emission efficiency and a short emission wavelength, which enables light emission in a narrow-band region. ' [Achievement method] β.β-sialon phosphor The Eu2+ of the luminescent center of the fluorescent system of the present invention has been dissolved in the parent crystal of the β-Sialon represented by the general formula & 6-ζΑ1ζΟζΝ8-ζ. The β-type sialon is mixed with the nitrogen of the type. The raw material powder of the compound or oxide is synthesized by sintering at a high temperature. However, the obtained β-Sialon is not completely single-phase 'inevitably, the Si-Al-Ο-Ν glass phase is indirectly generated, and depending on the case, a hetero phase such as αιΝ polytypoid or α-Sialon is generated. By means of raw material rubbing 8/25 201215664 . t into the composition analysis of the powder and grasping the correct Z value is the area where the Z value is low for the purpose of frequency modulation, and the feed group 组成 or composition analysis value The dissociation from the actual solid solution composition is very significant. Since the β-type Sailong system is solid-dissolved in the N-position in the P-type nitride rock, it is dissolved in the N-position, and the solid solution amount increases. The length of the a-axis (==b-axis) and the length of the e-axis will increase as the day of the day, the day, and the day of the mouth. According to the investigation of the amount of Euh solid solution and the number of crystals of the P-type Sialon crystal, the inventors reviewed The results show that the Z value is a certain 凊 shape, and when the right Eu2+ is dissolved in the β-Sialon crystal, only the a-axis length will increase and the 'c-axis length will be almost constant. It is presumed that this system is due to Eu2+ intrusion and solidification. In the β-Sialon crystal, the c-axis direction is large in the gap. Therefore, the lattice constant of the β-Sialon crystal becomes sensitive, reverse, and E The parameter of the ir+ solid solution amount. In the phosphor of the present invention, the lattice constant c of the ^-type Sialon crystal is preferably within the dry circumference of 〇~MWlnm. If the lattice constant c is smaller than 〇.2906mn, Eu2+ The solid solution limit will be low and sufficient fluorescence intensity will not be obtained. On the other hand, if the lattice constant c exceeds 29.2911 nm, the fluorescence spectrum will be broadened as the true Z value of the p-type Sialon crystal increases. Therefore, for the β type, the amount of Ειτ+ ϋ solubility of the crystallization of the crystallization is as good as possible, but since the solid solution limit depends on the value of 2, the lattice constant a is higher in the luminaire of the present invention.佳成〇.76〇5~〇761〇_ Now this lattice constant, the Eu content of the fluorescent shot is preferably set to m mass%. From the viewpoint of fluorescence emission, it is desirable that the phosphor contains a β-sialon crystal phase with high purity and a large amount, and is composed of a single phase of P-type Sialon crystals as much as possible 9/25 201215664, and the characteristics are not lowered. The range includes a mixture of an amorphous phase inevitably and an amount of other crystalline phases. In particular, the phosphor of the present invention having a low z value, although the reason is not clear, for Fe, Ni,

The first transition metal impurity such as Co is very sensitive, and it is preferred to set the content to 5 ppm or less. The fluorescent system of the present invention emits green light having a peak wavelength in a wavelength range of 520 to 540 nm by irradiating an excitation source. The fluorescence spectrum of the β-Sialon phosphor that activates Eu2+ has a feature that even if the enthalpy is increased, the wavelength of the rising edge of the spectrum hardly changes, and the fluorescent component on the long wavelength side increases. That is, when the enthalpy is increased, the peak wavelength will slowly shift toward the long wavelength side, and the half value width of the spectrum will also increase. As a result, the χ value on the CIE chromaticity coordinates will increase and the y value will decrease. In addition to the devaluation factor, the factor affecting the shape of the camping spectrum can be exemplified by the crystallinity of the β-Sialon. Even if the enthalpy is low, the crystallinity of the β-Sialon is low, and the half-value width of the spectrum will be Increase. The β-type Sialon crystal has a low enthalpy value and a high crystallinity, and the half value width is narrow in the phosphor of the present invention, and the CIE chromaticity coordinates are used (χ, phantom value is 0·28Α<0.33, 〇·62 slitting) Value of .67. For the form of the phosphor of the present invention, in the case of use as a powder, 90% of the cumulative fraction of the volume basis in the particle size distribution measured by the laser diffraction scattering method The diameter (D90) is preferably from 1 〇 to 5 〇 μιη. The fluorescent system of the present invention is adjusted to 5 () μηη or less, because it is easy to mix the resin of the resin of =LED, and at the same time It is preferable to reduce the chromaticity deviation or the color unevenness of the illuminating surface. Further, 'the diameter of the luminaire of the present invention is preferably one. The crystallinity of the particles smaller than S is low. Not only the luminous intensity of the fluorescent body itself 10/25 201215664 is low, but also close to the wavelength of visible light. By making D10 2μΓη or more, it is possible to use such a small amount of phosphor with a small particle content to assemble the LED, and to suppress the light from containing fluorescence. Strong scattering occurs in the layer of the body, which can improve the luminous efficiency of the LED (light extraction effect) 2. Method for Producing β-Sialon Phosphor Next, a method for producing a phosphor of the present invention will be described. In the method for producing a β-Sialon phosphor of the present invention, it is preferably used. The tantalum nitride powder of Α1 corresponds to the ζ value of the β-sialon crystal synthesized by the metal ruthenium nitridation method. The tantalum nitride powder of the present invention preferably minimizes impurities other than Si and yttrium. The element, in particular, makes the content of the first transition metal to be less than 10 ppm. In the β-sialon of low-ruthenium composition, since excess oxygen promotes the formation of a heterogeneous phase, it is necessary to reduce the oxygen content of the tantalum nitride raw material. The tantalum nitride raw material powder obtained by directly nitriding the tantalum powder having high purity and low oxygen content is preferably synthesized. The tantalum nitride powder obtained by the direct nitridation method is synthesized by a conventional method. For example, In a nitrogen-containing gas atmosphere, the niobium powder is heated at a temperature of 1200 ° C or higher to be nitrided, and then subjected to a powdering step of dissolving, pulverizing, classifying, or acid-treating the obtained nitride. Producing nitrogen a cerium oxide powder. Since the cerium nitride powder obtained by the conventional direct nitriding method is mostly used for sintering, it is a fine powder having an average particle diameter of from submicron to several micrometers, but in the use of the phosphor of the present invention, It is not necessary to use a fine powder, and the average particle diameter may be about 5 to 1 (8) μηι, and it is important to suppress the incorporation of impurities in the powdering step due to excessive pulverization or the like as much as possible. Further, since the β-type in the phosphor of the present invention The solid solution amount of the sialon system is 11/25 5 201215664 >, white' Therefore, by the gasification stage of the cut powder, the specified amount is included in advance = A Bu in the final sintering step, a small amount of ~ will be uniformly dissolved, namely: It is a solid solution with a uniform composition. The method of adding A1 or the method of adding K= at the end of gasification (4) and Oxidation powder, or the method of using the alloy of the wheel to form the raw material of the alloy. About the phosphor;

The dispersion can also be made into a non-solid solution of nitriding: = The A-type Sialon lattice constant of the nitrogen-cut powder towel of the present invention is preferably in the range of 2 to 2% by mass. In the range of 5 to 2% by mass, if the unreacted dream is 1% by mass or less, when the synthetic camp is smashed by 1 ()% by mass, that is, the Shi Xi system absorbs UV ~ visible '^ f Shi Xi It will also survive. In the middle, the brightness will be greatly reduced: the light in the wide wavelength region, if present in the glory body, the high-diazetanium powder, by the extraction rate (β rate = β amount / (α# + β, ° ^ P The ratio of the β phase content can make Eu2+ to the right))) so that it is preferably 50% or more when the β-sialon is synthesized. ☆In the Ρ 赛 结晶 结晶 ' 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The light body synthesis step is carried out, and the composition of the β-type Sialon which is carried out by the complex main phase is a trace amount of oxidation present in the raw material. 12/25 201215664 Qiao Wangwen is now knife-&lt;single; jp cut skirt L±Boselon's grain grows. Compared with β phase, the α phase of tantalum nitride, .. (Ding 'the dissolution rate of this liquid phase is significantly larger, the grain growth rate is faster. Eu2+ is difficult &amp; a ^ ^ chicken to solid> valley In the β-Sialon crystal, the right grain grows too fast, and it will not be able to charge n 4, is -a- 〇口〉谷. Therefore, the mouth is the ratio of fine = coffee, reducing the growth rate of the grain, and promoting Eu2 + t solid Dissolved. = The β-Sialon fluorescent system of Ming is formed by the addition of «=: nitrogen-cut powder and the compound containing 185 in the I gas atmosphere. For the heating temperature, it is preferably in the range of = 〇 = g5QC. If the heating temperature is more than or equal to t, it is possible to make μ butterfly enter the =Sialon crystal, and it is possible to obtain a camping light with sufficient brightness = another/b> heating temperature is 2Q5 generation or less, and no significant nitrogen pressure is applied to suppress β. The type of Sialon is necessary for decomposition, so it is industrially more abbreviated for the necessity of a hot special device. When the β-Sylon camp light body is manufactured, its V-form becomes a disintegration, pulverization and/or classification operation. The composition becomes a powder of 疋 size. In order to be suitable for use as a phosphor for LED, as described above, it is necessary Specific examples of the treatments include a method of performing a sieve classification process of 20 to 45 μm of a sieve of a composition to obtain a powder which passes through a sieve, or a ball mill, a vibration mill, a jet mill, or the like. - The method of pulverizing the particle size by the pulverizer. In the latter method, the excessive material not only produces the particles which are easy to scatter light, but also produces the peak name aa glutinous soil on the surface of the particle, and the daily defects are According to the investigation by the inventors of the present invention, the pulverization treatment is not carried out, and the treatment by only the sieve classification and the disintegration treatment by the jet pulverizer are used, and the powder of the (four) is the most 13/25. 201215664 • , the luminous efficiency of the luminescence. The phosphor obtained by the method of the method of the luminescence of the luminaire is treated with the following acid mixed acid: the ammonia smear is reduced in one step. The gentleman π 4 knives become the nitrogen of the elements that are more unstable. The ambiguous phase is formed by the broad absence of the phosphor. The reason for removing the phase is to increase the scent.隹为譲= ^ AlWr is low, and the 'day and day part can be unstable. (3) The decomposition of the 'Qin Sina type Sialon. The unsettled t is enough to use the dissolution and removal by acid or test. In the pot, in the pot, the mixture of hydrofluoric acid and nitric acid is more than 6 ,, and the dissolution treatment of the second or more 'preferably 0.5 hours or more is effective. 3. Light-emitting element and illuminating device A light-emitting device composed of a body, in particular, irradiated with ultraviolet light or visible light having a wavelength of 24 〇 to 480 nm as an excitation source, and performs green-narrowed light-emitting illuminating by illuminating an ultraviolet LED or a blue LED In the case of a surface, if necessary, a red phosphor and/or a blue phosphor are combined to form a light-emitting element, and white light is easily obtained. In addition, since the brightness reduction of the β-Sialon phosphor at a high temperature is small, the luminance of the light-emitting device using the same is small and the chromaticity deviation is small, and even if 14/25 201215664 is exposed to high temperature, it will not deteriorate. It has superior thermal properties and excellent long-term stability in an oxidizing gas environment and a water vapor environment. Therefore, it has high brightness and long life. In the fluorescent device, at least one of the illuminating light source and the phosphor of the present invention (the type 3 sialon is used as a main component), for example, the Japanese Patent Application Laid-Open No. Hei 5-152609, No. Hei 7-99345 An LED is manufactured by the conventional method disclosed in Japanese Patent No. 2927279. In this case, the illuminating light source is preferably an ultraviolet LED or a blue LED emitting light of a wavelength of 240 to 480 nm, and particularly preferably emitting light of a wavelength of 440 to 470 nm. As the light-emitting element of the blue LED, a nitride semiconductor such as GaN or InGaN can be used as a light-emitting source that emits light of a predetermined wavelength by adjusting the composition. In addition to the phosphor of the invention, it can also be used in combination with a phosphor having other light-emitting characteristics to form a light-emitting device that emits a desired color. In particular, the green narrow-band illumination system of the present invention uses a blue LED as a blue LED. The excitation source is suitable for images with superior color reproducibility by combining a red camping body with a peak wavelength of 600~7 〇〇 nm, such as CaAlSiN'Eu. A white LED for backlighting of a display device is used. The embodiment will be described in detail with reference to a comparative example, using a table and a diagram. The first embodiment shows the β-type Sialon in the first to third embodiments and the second comparative example. The phosphor spectrum of the phosphor obtained by external excitation light at a wavelength of 455 nm. [Example 1] <Reduction and evaluation of luu field containing A1> 15/25 201215664 ^V-type mixer "S_3" manufactured by the Chemical and Chemical Equipment Co., Ltd.) is a mixed powder of purity powder (purity of 99.999% or more, _75, μΓη) 98.81% by mass and a toluene powder manufactured by Tokuy Co., Ltd. (E et al. % ' Further all through the sieve 25 squeaking screen to remove the spin-poly, poetry to the raw material mixed powder. The raw material mixed powder is filled in a cylindrical nitriding container with a cover of 6 mm in diameter and 3 高度 in height ( Electrochemical m system, "then" grade) The 'electric furnace using the after-heater' is heated in c' for 8 hours in a pressurized nitrogen atmosphere of a5 MPa. The heating rate at the time of heat treatment is changed to · To, dish ~ Uooc is 20 ° C / min, 1200 ~ 1500 ° C is 0.5 T: / min. The resulting product is in the form of a block, which is pulverized by a high-speed mashing mill (manufactured by Nippon Scientific Co., Ltd., ANS-143PL, honing and hammering). The pulverized powder was classified by a sieve having a mesh size of 45 μm, and the following powder was used as a tantalum nitride powder for phosphor synthesis. Further, the sieve throughput of the sieve of 45 μm was about 40%. The bismuth powder was subjected to powder X-ray diffraction measurement (xrd) using a rifling diffraction device (ULTIMA IV, manufactured by Rigaku Co., Ltd.). The crystal phase present is a phase of β-type nitride, an α-type nitride, and a metal-phase. The result of Rietvdd analysis of the obtained powder X-ray diffraction pattern by the analytical program jADE manufactured by Rigaku Co., Ltd., (3 ratio (representing the ratio of the β phase in the nitride crystal) is 90.2% by mass, metal stone In the evening, it is 0.8% by mass. Next, the content of Α1 is in accordance with the alkali melting method; the content of impurities is dissolved in the powder according to the pressurized oxygen decomposition method, and then the ICP emission spectroscopic analyzer (Rigaku Co., Ltd., CIR〇S_120) 16/25 201215664 and analyzed. The content of A] of this powder is 〇46% by mass, and the content of transition metal is 2ppm. &lt;Synthesis and Evaluation of Type 0 Sialon Phosphors> Dry by Oxidation Mixing the above-mentioned A1-containing nitriding powder, East 98.03 milifan and Shin-Etsu Chemical Co., Ltd. yttrium oxide powder (Ru grade) 】.97 quality summer%' further all through the sieve hole is called the claw sieve, and the p-type blasting is obtained. The raw material mixed powder is filled in a cylindrical nitriding butterfly container with a lid of 30 mm in height and having a height of 30 mm (manufactured by Electric Chemical Industry Co., Ltd., "(6)" grade) Inside, use carbon to cry

The electric furnace, in the 8 MPa plus Wei gas environment, at 200 (TC, heat treatment at M. The resulting _ scales (10) slowly agglomerated blocks can be easily decomposed by the hands of clean rubber gloves After the slight disintegration in this way, the meshing rate of 45 μm is 45°. The sieve passing rate of the mesh 45 μm in this state is about 9〇%. The above powder is filled in the straight (four) coffee, and the height is 3Qmm. In the cylindrical nitriding filling container of the pen (Wei Chemical Weiye Co., Ltd. (4), "Ν" grade), the fine carbon is added to the surface, in the field-pressure argon atmosphere, in the "two 〇〇 ^ The heat treatment was carried out for 8 hours, and the color of the obtained powder was changed from green to dark green in the treatment. The obtained powder was completely free from the pouring and the like, and all passed through a sieve of 45 mesh. % hydrogen _ with the nitric acid, 1 mixed acid, the powder obtained in this way, the suppression of the twisting treatment. At the right, from dark green to scale _ green. ',, travel / care ' , washing with water and drying to obtain a phosphor powder. 〇. For the result of the measurement of the phosphor, the knot Crystal phase Early phase. The lattice constant of β-Sialon is h〇.7606nm, c = 〇.2908 surface. μ and 17/25 according to ICP emission spectrometry. 201215664

The Eu content was 0.49 and 0.77% by mass, respectively, and the first transition metal content was less than 5 ppm. Then, using a particle size distribution measuring apparatus (manufactured by Beckman Coulter Co., Ltd., LS-230 type), the particle size distribution was measured by a laser diffraction/scattering method, and as a result, 10% of the cumulative fraction of the volume basis (D10) ) is 6·7 μηι, 90% diameter (D90) is 38.4 μιη. The adjustment of the sample for measuring the particle size distribution was carried out in accordance with the conditions of the cerium nitride measurement of the attached Table 1 in accordance with the principle JIS R 1629-1997. The luminescent properties of the phosphors were evaluated as follows. The phosphor powder is filled in such a manner that the surface of the concave member is smooth, and an integrating sphere is mounted. Monochrome light that has been split into a predetermined wavelength from an illuminating light source (Xe lamp) is introduced into the integrating sphere using an optical fiber. The monochromatic light was used as an excitation source to illuminate the phosphor sample, and a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., MCPD-7000) was used to measure the fluorescence of the sample and the reflected light. In the present embodiment, the monochromatic light system uses near-ultraviolet light having a wavelength of 405 nm and blue light having a wavelength of 455 nm. In the obtained fluorescence spectrum, the data of the wavelength range of 415 to 780 nm and 465 to 780 nm from the excitation wavelengths of 4〇5 nm and 455 nm', respectively, are calculated in accordance with JIS Z 8724, as defined in JIS Z 8701. The chromaticity coordinates ciEx and CIEy in the XYZ color system. The chromaticities ciEx and CIEy of the excitation wavelength of 405 nm were 0.312 and 0.655, respectively, and the chromaticities CIEx and CIEy of the excitation wavelength of 455 nm were 〇318 and 〇65, respectively, and the luminous efficiency was obtained as follows. First, a standard reflection plate (SPECTRALON manufactured by Labsphere Co., Ltd.) having a reflectance was placed in a sample portion, and the spectrum of the excitation light was measured. The excitation wavelength was 4 〇 5 nm, and the wavelength range from the 415 nm to the excitation wavelength was 455 nm. ~ 18/25 201215664 465 The spectrum of the wavelength range of the brain is calculated by the number of excitation photons. The glory is set in Jane, and the number of spectral sources ((10)) and the number of fluorescent photons (Qem) are set. In addition, the excitation = photon photon excitation lacks the _ wave record, and the fluorescence photon is calculated in the following range f: the excitation wavelength is 4 〇 5 nm in the wavelength range of 2; the excitation light is 455 nm. ~ 800nm range. From the three kinds of _ (=Qem/Qexx100)i_(=(Qex-Qref)xi〇〇)^, the efficiency is Qem/(Qex__ χ _. Near wavelength of 4〇5·, external light In the case of bursting, the absorption rate, internal quantum efficiency, and external quantum efficiency were 83.2%, 59.2%, and 49 3%, respectively, and the blue light excited by the wavelength pole surface was 73.1%, 56.6%, and 41.3%, respectively. [Comparative Example 1] The Si: AM Eu ratio was changed in the same manner as the phosphor of Example i, and the α-type nitride powder (SN-E10 grade) manufactured by Ube Industries, Ltd., and the nitrided product manufactured by Tokuyama Co., Ltd. were replaced. Powder (Grade F) and Shin-Etsu Chemical Co., Ltd. made a powder (Nan), and synthesized β-Sialon by the same method as in Example 1. The obtained product was a green hard agglomerate formed on the surface thereof. There is a reddish-brown precipitate. This product is as difficult to accomplish powdering by mild disintegration as in the case of Example 1. Thus, it is pulverized by oxidizing the mortar until it passes through the sieve 15 Before sieving, the sieve was further sieved with a sieve of 45 μm. The method was the same as in Example 1. Heat treatment and acid treatment of the powder passing through the sieve were carried out to obtain a p-type Sialon phosphor. As a result of XRD measurement of the phosphor, the crystal phase was a p-type Sialon single phase. 19/25 201215664 a = 0.7604 nm The lattice constant of c = β-Sialon is 0.2909nm. The 'A1 and Ευ content of the '- 光 光 46.46, 〇.22% by mass, the transition metal content Below PP: a comparison of the application of Example 1, especially the EU content is also reduced. Into the heart, the results of the particle size distribution of the workforce, volume basis: 1% of the two 'knife rate diameter ( D10) is '4, m; 90% diameter (D90) is 43 3μηι. ^ K for J: 鸯 体 body wavelength 4〇5Μ near ultraviolet light excitation (4CK “partial efficiency, external quantum efficiency QEX and CIEy are M pi * 9 5%, 39 2%, 〇·304, 〇.655, respectively; the cases excited by blue with a wavelength of 455 nm are 45.1%, 68.4%, 3_, 〇314, respectively. Compared with the examples! -Comparison's solid solution (4) Sialon has a small amount and low absorption rate, so the external quantum efficiency becomes low. [Examples 2 to 4, comparison 2 to 4] In addition to the mixing ratio of the niobium powder and the aluminum nitride powder, and the ', the degree of twist, and the temperature of the nitrile, the synthesis temperature of the niobium powder is displayed in the form of "exhibition", For example, the synthesis of nitriding, the sintering of p-type Sialon, and the post-treatment (heat treatment and acid treatment) are carried out to obtain a β-Sialon phosphor. Also, in Example 3 and Comparative Example 2, Alumina powder is also added to adjust the amount of oxygen in the β-Sialon crystal. In "Table 1", the β ratio calculated from XRD of the nitride powder, the amount of metal ruthenium, and the A1 content determined by ICP and the first transition metal έ i are shown. In "Table 2", the lattice constant, composition, impurity content, and particle size distribution of the obtained ?-sialon phosphor are shown; and in "Table 3", the light-emitting characteristics are shown. 20/25 201215664 [Table 1]

Si purity (%) Mixing ratio (% by mass) fllation temperature (°C) XRD after IU 1CP analysis Si AIN ΑΙ: 0? P rate Si amount A1 amount (mass f %) First transition metal content (ppm) Example i 99.999 98.81 U9 0 1500 90.2 0.8 0.46 2 Example 2 99.999 99.03 0.97 0 1500 91.3 0.7 0.36 6 Example 3 99.999 97.4 1.61 1 1500 88.7 1.2 0.96 4 Example 4 99.999 98.81 1.19 0 1450 88.3 1.3 0.45 6 Comparative Example 2 99.999 94.66 2.38 2.96 1500 89.5 1.4 1.93 4 Comparative Example 3 99.9 98.81 1,19 0 1500 89 2.5 0.48 260 Comparative Example 4 99.999 98.81 1.19 0 1350 70.5 20.5 0.49 4 [Table 2] Lattice constant (nm) ICP analysis particle size distribution (μηι) ac A1 amount (% by mass) Eu amount (% by mass) First transition metal content (ppm) DIO D90 Example 1 0.7606 0.2908 0.49 0.77 &lt; 5 ppm 6.7 38.4 Example 2 0.7605 0.2907 0.39 0.67 &lt; 5 ppm 6.5 32.1 Example 3 0.7607 0.2909 0.86 0.68 &lt; 5 ppm 7.9 37.3 Example 4 0.7606 0.2908 0.46 0.71 &lt; 5 ppm 5.9 28.9 Comparative Example 1 0.7604 0.2909 0.46 22 &lt; 5 ppm 4.3 43.3 Comparative Example 2 0,7608 0.2911 1.7 0.72 &lt; 5 ppm 6.3 33.3Comparative Example 3 0.7604 0.2908 0.37 0.55 18 ppm 8.7 42.1 Comparative Example 4 0.7605 0.2909 0.42 0.63 &lt; 5 ppm 8.7 45.5 21/25 201215664 [Table 3]

肱Each P ~ -LJ~~0.323 Ο.ι Shixi raw materials mn~3 and Comparative Example 2 -Compared, as the number of nitriding numbers c increases, the lattice of p-type Sialon phosphors often The chromaticity shifts to the red side. Yu Youyou.曰Expanding the raw material two&quot;, using the first-transition metal miscellaneous mass, 'the situation of the uncle's uncle' or the information of the tantalum nitride raw material...± j using the metal bismuth treatment, the first-per-second acid The high purity of the treatment or the like is left in the phosphor or the metal stone is also somewhat dissipated to reduce the light-emitting characteristics of the article. [Example 2] The amount = the knot of the broad measurement * 'In addition to the crystal of the comparative light body The phase difference is only the metal/detected, and the obtained fluorescein 1 difference is the β-type Sialon phase. Industrial use possibility 22/25 201215664 Since the β-Sialon fluorescent system of the present invention is scraped from ultraviolet to blue Excited by the wide wavelength of the chromatic light, the display of high-brightness and green luminescence can be adapted to make the blue or material light a self-color LED phosphor, especially 'can be suitable for use in image display devices. Since the brightness of the fluorescing precursor of the present invention is less than that of the high temperature enthalpy, the other field: energy can be used for the above-mentioned image display, and the brightness and illuminating color of the change of the brightness and the luminescent color of the above-mentioned image are changed. Ming's method of manufacturing phosphors (4) Stable provisioning Material =, the more often the above is used. Fig. 1 is the surface of the phosphor _ by the external excitation light of 455 nm in the surface of the β-type Sialon of Examples 1 to 3 and Comparative Example 2 Fluorescent [Main I-' with graphics. Wide-formed with sharp words] No 0 23/25

Claims (1)

201215664 VII. Patent application scope: 1. A β-Sialon phosphor, which is a β-type sialon represented by the general formula Si6-ZA1Z0ZN8-Z, and has Eu2+, β-Sialon in the luminescent center. The lattice constant a of the crystal is 0.7605 to 0.7610 nm, the lattice constant c is 0.2906 to 0.2911 nm, the Eu content is 0.4 to 2% by mass, and the first transition metal content is 5 ppm or less. 2. The β-type Sialon phosphor according to the scope of the patent application, wherein the illuminating peak wavelength is in the CIExy chromaticity coordinate at a wavelength of 520 to 540 nm by illuminating the excitation source, and the chromaticity is 0.28. SXS0.33, 0.62 office 0.67. 3. For example, the β-type Sialon phosphor of claim 1 or 2, wherein the cumulative volume fraction in the particle size distribution measured by the laser diffraction scattering method is 90%, and the diameter (D90) is 1. 〇~5〇μηι, and 10% diameter (D10) is 2 μmη or more. 4. A method for producing a β-Sialon phosphor, which is a β-Sialon phosphor having a β-sialon represented by the formula si6-ZA1Z0ZNS-Z as a matrix material and having Eu-2+ dissolved in the center of the luminescence A manufacturing method comprising the steps of: 1850~2050 in a nitrogen atmosphere. (in the temperature range, sintering step of sintering a raw material mixed powder containing a tantalum nitride powder containing A1 and an inorganic compound containing Eu; and a heat treatment step of maintaining a 丨~ moving hour at 1300 to 1500 t in a rare gas atmosphere; An acid treatment step in a mixed acid of hydrofluoric acid and nitric acid which is immersed at a temperature above 6 ° C for more than 0.5 hours. 24/25 201215664 5. Method for producing β-type Sialon phosphor according to item 4 of the patent application scope The tantalum nitride powder is a tantalum nitride powder having a first transition metal content of 10 ppm or less and containing 0.1 to 2% by mass of ruthenium 1 according to the metal ruthenium nitridation method. A method for producing a β-type sialon phosphor according to the fifth aspect, wherein the cerium nitride powder has a β ratio of 50% or more and a metal cerium content of 1 〇 mass% or less. 7. A light-emitting element having an emission wavelength An LED having a maximum intensity of 240 to 480 nm and a β-sialon phosphor as disclosed in any one of claims 1 to 3 of the LED light-emitting surface. 8. A light-emitting device having For example, the scope of patent application is 7 The light-emitting element, and the electric power supplied to the light emitting element. 3 25/25