WO2011129331A1 - ケイ酸塩系蛍光体及びケイ酸塩系蛍光体の製造方法 - Google Patents
ケイ酸塩系蛍光体及びケイ酸塩系蛍光体の製造方法 Download PDFInfo
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- the present invention relates to a silicate phosphor and a method for producing the silicate phosphor, and more specifically, utilizing a gas phase reaction of SiO x (0.5 ⁇ x ⁇ 1.9).
- a silicate phosphor and a method for producing a silicate phosphor are described in detail below.
- White LEDs are broadly classified into two types from the viewpoint of a white realization method.
- two-wavelength white LEDs which are the mainstream, are GaInN blue LEDs and yellow phosphors YAG: Ce 3+ (Y 3 Al 5 O 12). : Ce 3+ ), a pseudo white color is obtained.
- Ce 3+ yellow phosphors YAG: Ce 3+ (Y 3 Al 5 O 12). : Ce 3+ )
- a pseudo white color is obtained.
- the color rendering is not so good, white color close to natural light cannot be emitted (see Non-Patent Document 1).
- an object of the present invention is to provide a silicate phosphor excellent in emission intensity and a method for producing the silicate phosphor.
- Non-Patent Document 2 A technique for obtaining a phosphor by firing is widely adopted (see Non-Patent Document 2). Since this synthesis method is based on a reaction between solid phases, it is generally called a solid phase method.
- the present inventors synthesize phosphors using SiO x in a gas phase, which is not normally used in the phosphor manufacturing field (reacting volatilized SiO x with other solid phase raw materials to phosphor And the phosphor obtained by using the vapor-solid method is better than the phosphor obtained by the conventional solid-phase method.
- the present inventors have found that it exhibits luminescent characteristics and have completed the present invention.
- the present invention has the following configuration / features.
- a raw material powder containing a compound containing at least one luminescent ion of Eu, Ce, Mn, and Tb is placed in a container, and SiO x in a gas phase state (0.5 ⁇ x ⁇ 1. 9) The raw material powder is fired while supplying the silicate phosphor.
- the silicate phosphor is M 2 SiO 4 : Eu 2+ (where M is one or more selected from the group consisting of Ca, Sr and Ba) [2] ]
- [4] The production of a silicate phosphor according to any one of [1] to [3], wherein the range of x of the SiO x is 0.8 ⁇ x ⁇ 1.2. Method.
- the SiO x is supplied to the raw material powder in a gas atmosphere at a temperature of 1200 to 1700 ° C., and the raw material powder is subjected to a gas phase-solid phase reaction at a temperature of 700 to 1700 ° C.
- vapor phase synthesis is used in a part of the phosphor manufacturing process, it is possible to provide a phosphor having better light emission characteristics than a phosphor obtained by a conventional solid phase method.
- a phosphor obtained by a conventional solid phase method.
- it is about 2.6 times when excited at each optimum excitation wavelength, and a practical myopia LED (405 nm).
- the emission intensity was much higher than that of the phosphor produced by the conventional method.
- FIG. 3 is a graph showing the results of X-ray diffraction (XRD) measurement of Ba 2 SiO 4 : Eu 2+ manufactured according to Example 1. It is a flowchart of the manufacturing method (conventional solid-phase method) of the comparative example 1. It is the figure which compared the fluorescence characteristic (excitation spectrum and emission spectrum) of the fluorescent substance of Example 1, and the fluorescent characteristic of the fluorescent substance of the comparative example 1.
- XRD X-ray diffraction
- FIG. 6 is a diagram showing the result of X-ray diffraction (XRD) measurement of the phosphor of Example 2.
- FIG. 6 is a diagram showing the fluorescence characteristics of the phosphor of Example 2.
- FIG. 6 is a diagram showing the results of X-ray diffraction (XRD) measurement of the phosphor of Example 3.
- FIG. 6 is a diagram showing the fluorescence characteristics of the phosphor of Example 3.
- a raw material powder having a compound containing at least one luminescent ion of Eu, Ce, Mn, and Tb is contained in a container, and is in a gas phase state.
- the raw material powder is fired while supplying SiO x (0.5 ⁇ x ⁇ 1.9).
- the raw material powder is preferably a mixture further containing at least one of an alkali metal compound, an alkaline earth metal compound, a magnesium compound, and a rare earth compound.
- the compound containing the luminescent ion is not particularly limited, but Eu 2 O 3 , Eu 2 (CO 3 ) 3 .2H 2 O, Eu (NO 3 ) 3 .6H 2 O, Eu Compounds containing Eu such as 2 (C 2 O 4 ) 3 ⁇ 10H 2 O, Ce 2 O 3 , Ce 2 (CO 3 ) 3 ⁇ 5H 2 O, Ce (NO 3 ) 3 ⁇ 5H 2 O, Ce 2 (C 2 O 4) 3 ⁇ 9H 2 O, Ce 2 (C 2 O 4) 3 ⁇ 10H 2 O containing Ce, such as a compound, MnO, MnCO 3, Mn ( NO 3) 2 ⁇ 6H 2 O, Mn (C 2 O 4 ), Mn (C 2 O 4 ) 3 ⁇ 2H 2 O and other compounds containing Mn, Tb 2 O 3 , Tb 2 (CO 3 ) ⁇ nH 2 O, Tb (NO 3 ) 3 Compounds containing Tb such as 6H 2 O,
- the alkali metal compound is not particularly limited, but Li 2 O, Li 2 CO 3 , LiNO 3 , Li 2 C 2 O 4 , Na 2 O, Na 2 CO 3 , NaNO 3 , Na 2 C 2 O 4, K 2 O , K 2 CO 3, KNO 3, Rb 2 O, Rb 2 CO 3, RbNO 3, Cs 2 O, Cs 2 CO 3, CsNO 3, Cs 2 C 2 O 4 , and their Combinations are used, and those that can be decomposed and oxidized at high temperatures to form oxides are preferably used.
- the alkaline earth metal compound is not particularly limited, but CaO, CaCO 3 , Ca (NO 3 ) 2 , Ca (NO 3 ) 2 .4H 2 O, SrO, SrCO 3 , Sr (NO 3 ) 2 , Sr (NO 3 ) 2 .4H 2 O, BaO, BaCO 3 , Ba (NO 3 ) 2 , BaC 2 O 4 , and combinations thereof are used, and preferably decompose and oxidize at high temperature. Those that can be converted into oxides are used.
- a magnesium compound containing the same divalent Mg as the alkaline earth metal compound can also be used instead of the alkaline earth metal compound.
- the rare earth compound is not particularly limited, but Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , and combinations thereof are used.
- the rare earth compound is decomposed and oxidized at high temperature to be oxidized. What can be used is used.
- a raw material mixture suitably containing at least one of the above-mentioned alkali metal compound, alkaline earth metal compound, magnesium compound, and rare earth compound is used, for example, at a temperature range of 700 ° C. to 1700 ° C. It is fired by holding for 100 hours, and SiO x which is in a gas phase in a gas atmosphere at a temperature of 1200 ° C. to 1700 ° C. is further supplied to cause a gas phase-solid phase reaction of the raw material mixture, thereby obtaining light emission characteristics. A very good phosphor can be obtained.
- the metal compound mentioned above contains a substance that can be decomposed and / or oxidized at high temperature such as hydrate, hydroxide, carbonate, nitrate, oxalate, etc., before firing
- the raw material mixture is calcined while being held at a temperature lower than the firing temperature, whereby it can be converted into an oxide or a precursor of a phosphor by removing crystal water.
- it can also grind
- FIG. 1 shows a flowchart of a preferred production method among the production methods of the silicate phosphor of the present invention.
- Prepare raw materials for starting a solid phase reaction raw materials for solid phase reaction
- raw materials for starting a gas phase reaction raw materials for gas phase reaction
- a desired silicate phosphor is manufactured through mixing and heating of the solid phase reaction raw material and heating of the gas phase reaction raw material.
- the heating temperature (firing temperature) range of the solid phase reaction raw material is preferably 700 ° C. to 1700 ° C.
- the heating temperature range of the gas phase reaction raw material for supplying SiO x is 1200 ° C. to 1700 ° C. Is preferred.
- the firing temperature is more preferably set to 1400 ° C. to 1600 ° C.
- raw material powder solid-phase reaction raw material
- gas-phase SiO x 0.5 ⁇ x ⁇ 1.9
- a part of the gas phase (raw material for gas phase reaction) is heated to cause a gas phase reaction, and this gas phase reactant is fired while reacting with a solid phase reactant, in other words, a gas phase-solid phase reaction.
- This is greatly different from general solid phase synthesis (that is, solid phase synthesis of all starting materials) used in the conventional phosphor manufacturing method.
- the conventional gas phase synthesis is a synthesis method applied to a process for producing nanoparticles of about 1 to 100 nm.
- the above-mentioned solid-phase method has become a suitable and proven method for many years. Therefore, the idea of adopting vapor phase synthesis suitable for the production of nano-order particles in the production of phosphors is usually inexplicable and difficult to conceive for researchers in the field of phosphor production.
- the gas phase raw material by the conventional gas phase method is usually an expensive material such as an organometallic compound and is not handled in the reducing atmosphere gas at the time of manufacturing the phosphor, it is important to manufacture the phosphor.
- the production method of the present invention is characterized by gas phase-solid phase synthesis in which gas phase SiO x reacts with other raw materials in the solid phase.
- SiO x (0.5 ⁇ x ⁇ 1.9), which is a raw material for synthesis in the gas phase state in the production method of the present invention, is a material that is inexpensive and safe to handle.
- a general method for producing SiO x is to heat a mixture of silicon dioxide-based oxide powder and a substance that reduces it, such as metal silicon, in a temperature range of 1100 to 1600 ° C. in an inert gas atmosphere or under reduced pressure. Then, the generated SiO x gas is collected by cooling.
- SiO x may exist as impurities such as unreacted substances (Si, SiO 2 ) or SiO 2 due to oxidation of SiO.
- the SiO x since the SiO x the state close to SiO acts more favorably, it is preferable that the range of x in SiO x is 0.8 ⁇ x ⁇ 1.2, further Preferably 0.95 ⁇ x ⁇ 1.1.
- Such suitable high purity SiO is commercially available from, for example, Osaka Titanium Technologies Co., Ltd. or Sanyo Trading Co., Ltd.
- Solid SiO x is volatilized by heating to 1200 to 1700 ° C., preferably 1400 to 1700 ° C. in a gas atmosphere, and can be in a gas phase.
- the gas phase SiO x is supplied to the raw material mixture, and the raw material mixture is heated at a desired temperature within a temperature range of 700 ° C. to 1700 ° C. to cause a gas phase-solid phase reaction.
- the gas atmosphere includes (1) an inert gas atmosphere composed of nitrogen, argon, etc., (2) an oxidizing gas atmosphere composed of air, oxygen, oxygen-containing nitrogen, oxygen-containing argon, and (3) 0.1 hydrogen.
- Reducing gas atmospheres such as hydrogen containing nitrogen containing ⁇ 10% by volume, hydrogen containing argon containing 0.1 ⁇ 10% by volume of hydrogen and the like can be mentioned.
- the carrier gas for supplying SiO x and the atmosphere during firing include hydrogen-containing nitrogen containing 0.1 to 10% by volume of hydrogen, A reducing atmosphere such as hydrogen-containing argon containing 0.1 to 10% by volume of hydrogen is particularly preferable.
- the silicate phosphor of the present invention produced as described above is not particularly limited as long as it is synthesized by the production method described above, but M 2 SiO 4 : Eu 2+ , Li 2 MSiO 4 : Eu 2+ , M 3 SiO 5 : Eu 2+ , M 2 (Mg, Zn) Si 2 O 7 : Eu 2+ , M 3 Si 2 O 7 : Eu 2+ , M 3 MgSi 2 O 8 : Eu 2+ , MAl 2 Si 2 O 8 : Eu 2+ , M 3 Sc 2 Si 3 O 12 : Ce 3+ , M 9 Sc 2 Si 6 O 24 : Eu 2+ and combinations thereof are suitable.
- M is one or more selected from the group consisting of Ca, Sr and Ba.
- M 2 SiO 4 : Eu 2+ is preferable as the silicate phosphor of the present invention, and (Ba 1-y Sr y ) 2 More preferred is SiO 4 : Eu 2+ (0 ⁇ y ⁇ 1).
- the starting material for producing (Ba 1-y Sr y ) 2 SiO 4 : Eu 2+ (0 ⁇ y ⁇ 1) and the material to be subjected to solid phase reaction starting material excluding SiO x , such as BaCO 3
- starting material excluding SiO x such as BaCO 3
- the preferred temperature range for the gas phase synthesis of SiO x (1200 ⁇ 1700 ° C.)
- the volatilization of SiO x It is possible to effectively perform solid phase synthesis (that is, firing) simultaneously.
- FIG. 2 shows some examples of the phosphor manufacturing apparatus 1 that realizes the method for manufacturing a silicate phosphor according to the present invention.
- the manufacturing apparatus 1 shown in FIG. 2A is a gas-permeable (for example, porous) first material on which a raw material powder 3 (that is, a solid-phase reaction raw material) containing a compound containing a luminescent ion is placed. Is provided in the container 2, a second dish 6 on which the SiO x powder 4 (that is, a raw material for gas phase reaction) is placed is provided below the first dish 5, and a carrier gas is supplied.
- the gas supply port 7a and the gas discharge port 7b are provided on the side surface and the upper surface of the container 2 (referred to as a vertical manufacturing apparatus for comparison with FIG.
- the solid-phase reaction raw material 3 is baked, but the gas phase SiO x (volatilized from the SiO x powder 4 in a gas atmosphere (preferably in a reducing gas atmosphere).
- the calcination reaction proceeds while passing through the first dish 5 and entering the raw material powder 3 (indicated by reference numeral 8 in the figure).
- the material of the first disc 5 for accommodating the solid reciprocal application raw material powder for example, boron nitride (BN), alumina (Al 2 O 3), although silicon carbide (SiC) and the like, during firing Boron nitride (BN), which hardly causes unintended reaction with the raw material powder, is preferable.
- the second dish 6 is housed in a separate container, and a vertical type is formed so as to supply SiO x in a gas phase together with the carrier gas from the gas supply port 7 a to the solid-phase reaction raw material powder 3.
- You may comprise a manufacturing apparatus.
- the first dish 5 on which the raw material powder 3 is placed and the second dish 6 on which the SiO x powder 4 is placed are placed on the same horizontal surface 2 a in the container 2.
- the manufacturing apparatus 1 may be used.
- SiO x moves from the upper space of the second plate 6 to the upper space of the first plate 5 along the flow of the carrier gas, so that the inside of the first plate 5 In order to pour onto the raw material powder 3, the first dish 5 does not necessarily need to be made of a gas permeable material.
- the silicate phosphor of Example 1 Ba 2 SiO 4 : Eu 2+
- the silicate phosphor of Example 1 was produced by the gas phase-solid phase synthesis method of the present invention.
- the flowchart of the manufacturing method of Example 1 is shown in FIG.
- the starting materials BaCO 3 (Kanto Chemical Co., Ltd., 3N), Sc 2 O 3 (Shin-Etsu Chemical Co., Ltd., 4N), Al 2 O 3 (High Purity Chemical Laboratory, 4N) ), Eu 2 O 3 (Shin-Etsu Chemical Co., Ltd., 4N) was used.
- Each raw material was weighed according to the stoichiometric ratio, and acetone wet mixing was performed in an agate mortar.
- Example identification A powder X-ray diffractometer (manufactured by Mac Science Co., Ltd., MX-Labo) was used for identification of the sample after firing.
- FIG. 4 shows the results of X-ray diffraction (XRD) measurement of the sample manufactured according to Example 1.
- the results of the lowermost stage and the upper stage show the XRD patterns on the inside and the surface of the sample (Example 1), respectively.
- the results at the top and the bottom are respectively obtained from an inorganic crystal structure database (ICSD) provided by the Japan Society for Chemical Information (JACI) (Ba 0.99 Eu 0.01 ) 7 Sc 6 It shows the XRD pattern of the a l2 O 19 and Ba 2 SiO 4.
- ISD inorganic crystal structure database
- Comparative Example 1 Conventional method of synthesis of Ba 2 SiO 4 : Eu 2+
- Ba 2 SiO 4 : Eu 2+ was synthesized by a conventional solid phase reaction.
- the flowchart of the manufacturing method of the comparative example 1 is shown in FIG. Using BaCO 3 , SiO 2 , and Eu 2 O 3 as starting materials, each raw material was weighed in a stoichiometric amount, mixed with acetone in an agate mortar, and then in a reducing gas atmosphere with a weak H 2 —Ar. Firing was performed at 1300 ° C. for 12 hours. When the firing temperature was set to 1500 ° C., the raw material powder melted and the target phosphor could not be obtained. In Comparative Example 1, 1300 ° C. was set as the firing temperature.
- the phosphors of Example 1 and Comparative Example 1 both exhibit very wide excitation spectra in the range of 300 to 450 nm.
- the phosphor of Example 1 is strongly excited at a wavelength near 380 nm, and the phosphor of Comparative Example 1 is strongly excited at a wavelength near 360 nm.
- the wavelength emitted by the near-ultraviolet LED is generally 350 to 400 nm, and it can be seen that the phosphors of Example 1 and Comparative Example 1 are excited efficiently as phosphors for near-ultraviolet LED.
- Example 1 The reason why the peak of the excitation spectrum was different between Example 1 and Comparative Example 1 was that the method of Example 1 was able to synthesize a phosphor having a higher concentration of Eu 2+ , which is a luminescent ion. It is believed that there is.
- Example 1 and Comparative Example 1 showed an emission spectrum having a peak near 500 nm as shown in FIG. 6, and emitted green light.
- the emission intensity of Example 1 was excited by a practical myopic LED (405 nm) about 2.6 times when excited at the respective optimum excitation wavelength compared to the emission intensity of Comparative Example 1. In some cases, it was about 3.5 times, indicating a very high value.
- the use of the production method of the present invention provides a silicate-based phosphor having an excellent emission intensity.
- the phosphor of Example 1 can be used as a green phosphor of a three-wavelength white LED having a near-ultraviolet LED.
- the internal quantum efficiency means the emission rate with respect to the absorbed energy.
- the external quantum efficiency means the emission efficiency with respect to the irradiated energy, and is calculated by multiplying the internal quantum efficiency by the sample absorption rate.
- Example 1 the external quantum efficiency of Example 1 is improved by about 20% compared to the case of Comparative Example 1.
- the difference in the sample absorption rate substantially affects the improvement of the external quantum efficiency of Example 1.
- the reason why the sample absorptance of Example 1 is improved may be that the activation amount of the luminescent ions Eu 2+ is increased and the crystallinity of the phosphor particles is improved.
- FIG. 7 shows the results of observing the phosphor surface of Example 1 and the phosphor surface of Comparative Example 1 at the same magnification using a scanning electron microscope (JSM-5600, manufactured by JEOL Ltd.).
- the phosphor of Example 1 is uniformly composed of large particles having a particle size of about 15 to 20 ⁇ m, whereas the phosphor of Comparative Example 1 is shown in FIG. ), It is understood that the particles are composed of small particles having a non-uniform particle diameter of less than 5 ⁇ m.
- the method of the present invention employs gas phase synthesis, it is considered that the crystal growth of the particles and the uniformization of the particle size are easily promoted in the phosphor synthesis process. It has been reported in the past that the larger the particle, the higher the emission intensity. For the above reasons, it is considered that the emission intensity of the phosphor synthesized by the method of the present invention is improved.
- Example 1 Ba 2 SiO 4 : Eu 2 was produced as a silicate-based phosphor, and the emission characteristics thereof were described in detail.
- SrCO 3 or the like was added to the starting material (Ba 1 ⁇ y Sr y) 2 SiO 4: Eu 2+ (0 ⁇ y ⁇ 1) may be produced.
- Example 1 first, produce a solid phase reaction by (Ba 0.99 Eu 0.01) 7 Sc 6 A l2 O 19 to the main phase solid phase reaction of the starting material between the process of synthesizing the phosphor
- a method of generating a phosphor on the surface of the reaction product is adopted, the method is not necessarily limited to this.
- Various solid phase reactants may be produced by a combination of starting materials. Further, as in the method described with reference to FIG. 1, it is possible to synthesize only a silicate phosphor by a gas phase-solid phase reaction without generating such a solid phase reactant.
- FIG. 8 is a diagram showing the influence of the firing temperature on the fluorescence characteristics of the phosphor of Example 1. It can be seen that the excitation spectrum and the emission spectrum show excitation and emission peaks at almost the same wavelength regardless of the firing temperature of 1400 ° C., 1500 ° C., or 1600 ° C. Further, it can be seen that the excitation intensity and the emission intensity are improved in the order of the firing temperatures of 1600 ° C., 1400 ° C., and 1500 ° C., that is, the best fluorescence characteristics are exhibited when the firing temperature is 1500 ° C.
- FIG. 9 is a diagram comparing the light emission intensity of the sample obtained by the solid phase method as shown in Comparative Example 1 and the light emission intensity of the sample manufactured under each firing temperature condition of Example 1.
- the abscissa in the figure shows each firing temperature in Example 1, and the ordinate shows the percentage value of the value obtained by dividing the emission intensity of the sample of Example 1 under each baking temperature by the emission intensity of the sample by the solid phase method ( %) (Also referred to as “emission intensity ratio”).
- the emission intensity ratio of the sample fired at 1400 ° C. was 170%, and it was confirmed that the emission characteristics were improved.
- the emission intensity ratio of the sample fired at 1500 ° C. was 265%, and the emission characteristics were most improved.
- the light emission intensity ratio of the sample fired at 1600 ° C. was about 100%, and the expected improvement in light emission characteristics could not be confirmed. This is considered as one of the causes that particles constituting the fired sample were excessively grown. However, it was confirmed that even at a temperature condition of 1600 ° C., at least light emission characteristics equivalent to those of the solid-phase method sample were obtained.
- Example 1 a simple silicate-based (Ba—Si—O-based) phosphor containing only the Ba component was used.
- Example 2 or Example 3 described later whether or not a silicate-based phosphor containing an Sc component and an Al component in addition to the Ba component can be produced by the gas phase-solid phase method of the present invention, and the product It was decided to investigate whether or not shows an appropriate light emission characteristic.
- the dishes were accommodated in a container placed in an inert gas atmosphere consisting only of argon, and baked at 1600 ° C. for 12 hours to perform a gas phase-solid phase reaction.
- the second dish on which the SiO is placed is the first dish on which the solid-phase reaction sample is placed so that the vaporized SiO in the vapor phase is appropriately supplied toward the solid-phase reaction sample. It was arrange
- Example identification In the same manner as in Example 1, the baked sample was identified using a powder X-ray diffractometer (manufactured by Mac Science Co., Ltd., MX-Labo).
- FIG. 10 shows the X-ray diffraction (XRD) measurement results of the sample manufactured according to Example 2.
- the lower results show the XRD patterns of the sample (Example 2), respectively.
- the results of the upper stage and the middle stage are respectively XRDs of SiO 2 and Ba 9 Sc 2 Si 6 O 24 obtained from the inorganic crystal structure database (ICSD) provided by the Japan Chemical Information Association (JACI). Indicates a pattern.
- ISD inorganic crystal structure database
- JACI Japan Chemical Information Association
- the XRD pattern in the lower part of FIG. 10 almost matches and corresponds to the sample XRD pattern in the middle part, and the target product, Ba 9 Sc 2 Si 6 O 24 : Eu 2+, is generated. It was supported. Further, the lower XRD pattern also has a peak corresponding to the upper XRD pattern, and it can be seen that SiO 2 is mixed somewhat as an impurity in addition to the target. This is presumably because SiO supplied in the gas phase was oxidized. Note that SiO 2 does not affect the light emission characteristics of the phosphor.
- FIG. 11 is a diagram showing the fluorescence characteristics of Ba 9 Sc 2 Si 6 O 24 : Eu 2+ manufactured according to Example 2.
- the phosphor of Example 2 showed a wide excitation spectrum with a peak near 300 nm, an emission spectrum with a peak near 460 nm, and emitted blue light.
- the fluorescence characteristics shown in FIG. 11 were confirmed to be in good agreement with the known fluorescence characteristics (not shown) of Ba 9 Sc 2 Si 6 O 24 : Eu 2+ obtained by the conventional solid phase method.
- the phosphor obtained by the conventional solid phase method may emit blue light or green light depending on manufacturing conditions.
- FIG. 12 shows the X-ray diffraction (XRD) measurement results of the sample manufactured according to Example 3.
- the lower results show the XRD patterns of the sample (Example 3), respectively.
- the results in the upper and middle stages are XRD patterns of SiO 2 and BaAl 2 Si 2 O 8 obtained from the inorganic crystal structure database (ICSD) provided by the Japan Chemical Information Association (JACI), respectively. Show.
- the XRD pattern in the lower part of FIG. 12 almost matches and corresponds to the XRD pattern in the middle part as a sample, which confirms that the target product, BaAl 2 Si 2 O 8 : Eu 2+, has been generated. It was. Note that, similarly to the XRD result of Example 2, the lower XRD pattern also has a peak corresponding to the upper XRD pattern, and it can be seen that SiO 2 is somewhat mixed as an impurity in addition to the target product.
- FIG. 13 is a diagram showing the fluorescence characteristics of BaAl 2 Si 2 O 8 : Eu 2+ manufactured according to Example 3.
- the phosphor of Example 3 showed a wide excitation spectrum with a peak near 310 nm, an emission spectrum with a peak near 510 nm, and emitted green light.
- Example 3 it was found that the target product, BaAl 2 Si 2 O 8 : Eu 2+, was synthesized by the gas phase-solid phase method of the present invention, and this was allowed to emit light.
- the phosphors produced by the present invention are not necessarily limited to these phosphors without departing from the spirit of the invention in the above-described novel synthesis method.
- the silicate phosphor produced according to the present invention can be used as a phosphor of a three-wavelength white LED, for example, to provide a white LED that is closer to natural light and has dramatically improved luminance.
- the silicate phosphor produced according to the present invention is not limited to white LEDs, but can be applied to a wide range of uses such as display panel display devices such as CRT, PDP, and FED, and illumination devices such as fluorescent lamps.
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Abstract
Description
[1] Eu、Ce、Mn、及びTbのうちの少なくとも一つの発光イオンを含んだ化合物を有した原料粉末を容器内に収容し、気相状態のSiOx(0.5≦x≦1.9)を供給しながら前記原料粉末を焼成することを特徴とするケイ酸塩系蛍光体の製造方法。
[2] 前記原料粉末は、アルカリ金属化合物、アルカリ土類金属化合物、マグネシウム化合物、及び、希土類化合物の少なくとも一つをさらに含んだ混合物であることを特徴とする[1]に記載のケイ酸塩系蛍光体の製造方法。
[3] 前記ケイ酸塩系蛍光体がM2SiO4:Eu2+(ただし、MはCa、SrおよびBaからなる群より選ばれる1種以上である。)であることを特徴とする[2]に記載のケイ酸塩系蛍光体の製造方法。
[4] 前記SiOxのxの範囲が0.8≦x≦1.2であることを特徴とする[1]~[3]のいずれか1項に記載のケイ酸塩系蛍光体の製造方法。
[5] 前記焼成は、1200~1700℃の温度のガス雰囲気下で前記SiOxを前記原料粉末に供給し、かつ、700~1700℃の温度で前記原料粉末を気相-固相反応させることを特徴とする[1]~[4]のいずれか1項に記載のケイ酸塩系蛍光体の製造方法。
[6] 前記ガス雰囲気が還元性ガス雰囲気であることを特徴とする[5]に記載のケイ酸塩系蛍光体の製造方法。
[7] [1]~[6]のいずれか1項に記載のケイ酸塩系蛍光体の製造方法により製造されたケイ酸塩系蛍光体。
実施例1のケイ酸塩系蛍光体は、本発明の気相-固相合成手法により製造した。なお、実施例1の製造方法のフローチャートを図3に示す。出発原料のうち固相反応用原料として、BaCO3(関東化学(株),3N)、Sc2O3(信越化学工業(株),4N)、Al2O3(高純度化学研究所,4N)、Eu2O3(信越化学工業(株),4N)を用いた。各原料を化学量論比に従って秤量し、メノウ乳鉢でアセトン湿式混合を行なった。混合後、ペレット状に加圧成形し、ついで乾燥した試料を容器内の第1の皿(アルミナ製ボート)に載置し、水素ガスを5vol.%含有させたアルゴンガスからなる還元性ガス雰囲気下で、SiOx(0.95≦x≦1.1)を1500℃に加熱・揮発させて供給し、12時間蛍光体原料を焼成して気相-固相反応を行った。
焼成後の試料の同定には粉末X線回折装置((株)マックサイエンス製,MX-Labo)を使用した。図4は、実施例1により製造された試料のX線回折(XRD)測定結果を示す。ここで、最下段及びその上段の結果は、それぞれ、試料(実施例1)の内部及び表面におけるXRDパターンを示す。一方、最上段およびその下段の結果は、それぞれ、社団法人化学情報協会(JAICI)が提供している無機結晶構造データベース(ICSD)から取得された(Ba0.99Eu0.01)7Sc6Al2O19とBa2SiO4とのXRDパターンを示す。
比較例1として従来の固相反応によってBa2SiO4:Eu2+を合成した。なお、比較例1の製造方法のフローチャートを図5に示す。出発原料としてBaCO3,SiO2,及びEu2O3を用い、各原料を化学量論量で秤量して、メノウ乳鉢でアセトン湿式混合の後、H2-Arの弱い還元性ガス雰囲気において、1300℃、12時間焼成した。なお、焼成温度を1500℃に設定すると、原料粉末が溶融してしまい目的の蛍光体が得られなかったため、比較例1では1300℃を焼成温度に設定した。
図6は、本発明の製造方法(実施例1)により製造したBa2SiO4:Eu2+の励起発光スペクトルと従来の固相法(比較例1)により製造したBa2SiO4:Eu2+の励起発光スペクトルとを比較した図である。ここで、図6中、破線は、実施例1又は比較例1の励起スペクトルを示し、実線はそれぞれの最適励起波長で励起した場合の発光スペクトルを示す。励起・発光スペクトルの測定には、分光蛍光光度計(日本分光(株),FP-6500)を使用した。なお、後述する実施例2及び実施例3の蛍光体に関する蛍光特性を示した図においても、図6と同様に表示する。
実施例1の蛍光体と比較例1の蛍光体とで発光強度に大きな違いが生じた理由を検討するために、それぞれの蛍光体の量子効率を分光蛍光光度計(日本分光(株),FP-6500)用いて測定した。これらの測定結果を以下の表1に示す。
次に、実施例1のケイ酸塩系蛍光体を製造する上での焼成温度の条件について検討する。1500℃での上記温度条件に加え、1400℃及び1600℃の温度条件でもケイ酸塩系蛍光体を製造し、同様に蛍光特性を評価した。なお、1400℃及び1600℃の焼成温度の場合は、焼成温度以外の製造条件については、1500℃の場合と同様である。
出発原料のうち固相反応用原料として、BaCO3(関東化学(株),3N)、Sc2O3(信越化学工業(株),4N)、Eu2O3(信越化学工業(株),4N)を用いた。各原料を化学量論比に従って秤量し、メノウ乳鉢でアセトン湿式混合を行い、乾燥させた。この混合及び乾燥させた固相反応用試料を第1の皿(ボロンナイトライド(BN)製の収容皿)に載置するとともに、気相反応用原料であるSiOを第2の皿に載置した。これらの皿はアルゴンのみからなる不活性ガス雰囲気下に置かれた容器内に収容され、1600℃にて12時間、焼成して気相-固相反応を行った。なお、揮発した気相状態のSiOが固相反応用試料に向かって適切に供給されるように、SiOを載置した第2の皿は、固相反応用試料を載置した第1の皿よりも不活性ガスの流れ方向上流側に配置した。
実施例1と同様に、粉末X線回折装置((株)マックサイエンス製,MX-Labo)を使用して焼成後の試料の同定を行った。図10は、実施例2により製造された試料のX線回折(XRD)測定結果を示す。ここで、下段の結果は、それぞれ、試料(実施例2)のXRDパターンを示す。一方、上段およびその中段の結果は、それぞれ、社団法人化学情報協会(JAICI)が提供している無機結晶構造データベース(ICSD)から取得されたSiO2とBa9Sc2Si6O24とのXRDパターンを示す。
図11は、実施例2により製造したBa9Sc2Si6O24:Eu2+の蛍光特性を示した図である。実施例2の蛍光体は、300nm付近をピークとした幅広い励起スペクトルを示し、460nm近くにピークを持った発光スペクトルを示し、青色に発光した。図11に示す蛍光特性は、従来の固相法で得られるBa9Sc2Si6O24:Eu2+の既知の蛍光特性(図示せず)と良く一致することを確認した。なお、従来の固相法で得られる上記蛍光体は、製造条件等により青色に発光する場合と緑色に発光する場合とがある。
出発原料のうち固相反応用原料として、BaCO3(関東化学(株),3N)、Al2O3(高純度化学研究所,4N)、Eu2O3(信越化学工業(株),4N)を用いた。混合方法及び焼成方法等の条件は、実施例2の場合と同様であり、ここでは説明を省略する。
図12は、実施例3により製造された試料のX線回折(XRD)測定結果を示す。ここで、下段の結果は、それぞれ、試料(実施例3)のXRDパターンを示す。一方、上段およびその中段の結果は、それぞれ、社団法人化学情報協会(JAICI)が提供している無機結晶構造データベース(ICSD)から取得されたSiO2とBaAl2Si2O8とのXRDパターンを示す。
図13は、実施例3により製造したBaAl2Si2O8:Eu2+の蛍光特性を示した図である。実施例3の蛍光体は、310nm付近をピークとした幅広い励起スペクトルを示し、510nm近くにピークを持った発光スペクトルを示し、緑色に発光した。
2 容器
2a 容器内の水平面
3 発光イオンを含んだ化合物を含んだ原料粉末(固相反応用原料)
4 固体状のSiOx(気相反応用原料)
5 第1の皿
6 第2の皿
7a ガス供給口
7b ガス排出口
8 気相状態のSiOx
Claims (7)
- Eu、Ce、Mn、及びTbのうちの少なくとも一つの発光イオンを含んだ化合物を有した原料粉末を容器内に収容し、気相状態のSiOx(0.5≦x≦1.9)を供給しながら前記原料粉末を焼成することを特徴とするケイ酸塩系蛍光体の製造方法。
- 前記原料粉末は、アルカリ金属化合物、アルカリ土類金属化合物、マグネシウム化合物、及び、希土類化合物の少なくとも一つをさらに含んだ混合物であることを特徴とする請求項1に記載のケイ酸塩系蛍光体の製造方法。
- 前記ケイ酸塩系蛍光体がM2SiO4:Eu2+(ただし、MはCa、SrおよびBaからなる群より選ばれる1種以上である。)であることを特徴とする請求項2に記載のケイ酸塩系蛍光体の製造方法。
- 前記SiOxのxの範囲が0.8≦x≦1.2であることを特徴とする請求項1~3のいずれか1項に記載のケイ酸塩系蛍光体の製造方法。
- 前記焼成は、1200~1700℃の温度のガス雰囲気下で前記SiOxを前記原料粉末に供給し、かつ、700~1700℃の温度で前記原料粉末を気相-固相反応させることを特徴とする請求項1~4のいずれか1項に記載のケイ酸塩系蛍光体の製造方法。
- 前記ガス雰囲気が還元性ガス雰囲気であることを特徴とする請求項5に記載のケイ酸塩系蛍光体の製造方法。
- 請求項1~6のいずれか1項に記載のケイ酸塩系蛍光体の製造方法により製造されたケイ酸塩系蛍光体。
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CN105647525A (zh) * | 2016-01-25 | 2016-06-08 | 深圳市聚飞光电股份有限公司 | 一种LED用MAlSiO4:Tb3+,Eu2+黄光荧光粉的制备方法 |
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