JP5545665B2 - Method for manufacturing phosphor - Google Patents

Method for manufacturing phosphor Download PDF

Info

Publication number
JP5545665B2
JP5545665B2 JP2010505622A JP2010505622A JP5545665B2 JP 5545665 B2 JP5545665 B2 JP 5545665B2 JP 2010505622 A JP2010505622 A JP 2010505622A JP 2010505622 A JP2010505622 A JP 2010505622A JP 5545665 B2 JP5545665 B2 JP 5545665B2
Authority
JP
Japan
Prior art keywords
phosphor
mn
crystal
example
sif
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2010505622A
Other languages
Japanese (ja)
Other versions
JPWO2009119486A1 (en
Inventor
定雄 安達
亨 高橋
Original Assignee
国立大学法人群馬大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2008076929 priority Critical
Priority to JP2008076929 priority
Priority to JP2008267596 priority
Priority to JP2008267596 priority
Application filed by 国立大学法人群馬大学 filed Critical 国立大学法人群馬大学
Priority to PCT/JP2009/055622 priority patent/WO2009119486A1/en
Priority to JP2010505622A priority patent/JP5545665B2/en
Publication of JPWO2009119486A1 publication Critical patent/JPWO2009119486A1/en
Application granted granted Critical
Publication of JP5545665B2 publication Critical patent/JP5545665B2/en
Application status is Active legal-status Critical
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/615Halogenides
    • C09K11/616Halogenides with alkali or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C09K11/626Halogenides
    • C09K11/628Halogenides with alkali or alkaline earth metals
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664Halogenides
    • C09K11/665Halogenides with alkali or alkaline earth metals
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18Luminescent screens
    • H01J29/20Luminescent screens characterised by the luminescent material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00Gas- or vapour-discharge lamps
    • H01J61/02Details
    • H01J61/38Devices for influencing the colour or wavelength of the light
    • H01J61/42Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • H01J61/44Devices characterised by the luminescent material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20Constructional details
    • H01J2211/34Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/42Fluorescent layers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00Electron emission display panels, e.g. field emission display panels
    • H01J2329/18Luminescent screens
    • H01J2329/20Luminescent screens characterised by the luminescent material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies
    • Y02B20/16Gas discharge lamps, e.g. fluorescent lamps, high intensity discharge lamps [HID] or molecular radiators
    • Y02B20/18Low pressure and fluorescent lamps
    • Y02B20/181Fluorescent powders

Description

The present invention relates to how to manufacture easily a novel phosphor obtained by substituting transition metals the portion of the host crystal.

The phosphor is an indispensable substance for a fluorescent display tube, a high color rendering lamp, an X-ray / radiation dose meter (scintillator), a PDP (Plasma Display Panel), an inorganic EL (Electroluminescence) panel, a solid laser material, and the like. For example, the first discovery of a solid-state laser is a ruby laser (Al 2 O 3 : Cr) in which a portion of a ruby crystal is substituted with a small amount of Cr (chromium) transition metal impurity at the emission center, and light that exhibits a red color of 694 nm Has been observed. As described above, phosphors are used in various applications, and due to their importance, research on phosphors in which an emission center is substituted in an insulator base crystal is still actively conducted.

Major examples of phosphor materials in which a small amount of transition metal impurities serving as emission centers are substituted on an insulator base crystal are introduced. For example, Al 2 O 3 (sapphire), CaAl 12 O 19 , CaYAlO 4 , GaN, GdAlO 3 , Gd 3 Ga 5 O can be used as a base crystal when the transition metal that is an activator and serves as the emission center is Mn (manganese). 12 (GGG: Gadolinium Gallium Garnet) , Gd 2 MgTiO 6, Li 2 Ge 7 O 15, MgGa 2 O 4, MgO, ScPO 4, SrAl 12 O 19, SrTiO 3, Y 3 Al 5 O 12, YAlO 3 (YAP ), YAl 3 (BO 3 ) 4 , ZnGa 2 O 4 , 2MgO × GeO 2 , 2MgO × GeO 2 × MgF 2 and the like are known. A common feature of these host crystal materials is that they all have a very high melting point. For example, Gd 3 Ga 5 O 12 , famous as GGG, has a melting point of 1825 ° C. (2098 K), and YAlO 3 and SrTiO 3 , which are actively studied, have melting points of 1870 ° C. and 2353 ° C., respectively. Is much higher than the softening temperature (about 1500 ° C.). Furthermore, the melting point of the famous Al 2 O 3 (sapphire) is 2325 ° C., which is about 500 ° C. higher than the aforementioned GGG.

When synthesizing an insulator phosphor in which a part of the crystal is substituted with a desired transition metal, when a base insulator material having a high melting point is used, the growth of the crystal becomes complicated and complicated, and an expensive apparatus is required. Therefore, the manufacturing cost tends to increase. For example, a method for producing a YAlO 3 : Mn phosphor according to Non-Patent Document 1 will be introduced. The method used in the manufacturing method of Non-Patent Document 1 is a famous crystal growth method called Czochralski method as shown in FIG. First, a YAlO 3 raw material is put in a crucible 1 made of iridium (Ir), which is a rare metal, and this crucible 1 is placed in a chamber (not shown), and the melting point of the raw material in a nitrogen (95%) / oxygen (5%) atmosphere ( 1870 ° C.) or higher. Mn impurities are put in the crucible 1 in the form of MnO 2 . When the MnO 2 contained in the crucible 1 is sufficiently mixed in the molten YAlO 3 , the YAlO 3 seed crystal 4 held by the seed crystal holding part 3 located at the lower part of the pulling rod 2 is converted into a crystal in the crucible 1. By dipping in the melted part 6 and slowly pulling it up, the crystal growing part 5 grows under the seed crystal 4 so as to follow the crystal orientation of the seed crystal. Thereby, a phosphor composed of a YAlO 3 crystal in which a part of the crystal is substituted with Mn is obtained. Further, as a method of pulling up a crystal from a similar crucible, there is a Kyropoulos method, and an example in which, for example, a SrTiO 3 : Mn phosphor is produced is known. Since the melting point of the base material used in this example is as high as 2353 ° C. as described above, it is necessary to use not only a crucible but also an electric furnace apparatus that is complicated and expensive.

In addition to the crystal growth method by the pulling method, there is a flux method. For example, in the production of the CaAl 12 O 19 : Mn phosphor disclosed in Non-Patent Document 2, as shown in FIG. 56, CaO and Al 2 O 3 are used as the base crystal material, CaF 2 and MgF 2 are used as the flux material, and Mn is used. MnCO 3 as an impurity source is filled in an expensive platinum crucible, which is placed in an electric furnace, heated to 1650 ° C. and melted, and supersaturated crystals are grown at the bottom of the flux as shown in FIG. 56, reference numeral 11 denotes an electric furnace protective wall, reference numeral 12 denotes a seal for closing the crucible opening, reference numeral 13 denotes a flux melting part melted by heating, reference numeral 14 denotes a crystal growth part, and reference numeral 15 denotes a thermocouple. . In this document, the crystal thus produced is ground into a fine powder phosphor by grinding with an alumina mortar.

As another example of the conventional phosphor manufacturing method, production of MgGa 2 O 4 phosphor in which a part of the crystal is substituted with a transition metal (Mn) by a method called floating zone melting crystal growth (Floating zone) method A method is also introduced (see, for example, Patent Document 1). In the method disclosed in Patent Document 1, first, Ga 2 O 3 powder and MgO powder are mixed in a stoichiometric composition, and a very small amount of Mn powder that becomes an impurity is added. Subsequently, these mixed powders are packed into a predetermined shape, and a raw material rod is produced by applying a hydrostatic pressure of 300 MPa. Next, after the produced raw material rod is put into an electric furnace and fired at about 1000 ° C. in the atmosphere, the fired raw material rod 24 is placed in the quartz tube 22 of the floating zone molten crystal growth apparatus 21 as shown in FIG. The tip of the seed rod 23 of MgGa 2 O 4 and the tip of the raw material rod 24 are installed so as to face each other. Then, while rotating the seed rod 23 and the raw material rod 24 with the shaft 25, both ends of the seed rod 23 and the raw material rod 24 are heated and melted by the spheroid mirror 26 and the infrared condensing heating source 27 and then brought into contact with each other. 28 is formed, and the melting zone is moved to the raw material rod 24 side, thereby producing a MgGa 2 O 4 : Mn crystal. Note that the temperature of the floating zone during crystal growth is as extremely high as about 2100 ° C.

As is clear from the above, in the conventionally known method for synthesizing an insulator phosphor in which a part of a crystal is substituted with a transition metal, an expensive material such as rare earth (iridium) or noble metal (platinum) is used. A crucible material must be used, and an extremely high-temperature electric furnace apparatus capable of precise temperature control is required. The higher the heating temperature, the more expensive the electric furnace apparatus and the higher the operation and maintenance costs. In addition, as described above, most of the host crystals of the phosphor are materials that use rare, expensive metals such as Y, Gd, Ga, Ti, Li, Sc, and Sr as constituent elements. Sapphire (Al 2 O 3 ) contains only inexpensive Al and O (oxygen) as constituent elements. However, since the melting point is extremely high (2325 ° C.), the production cost is high. In fact, sapphire is well known as a jewelery.

Here, FIG. 58 shows a typical emission spectrum of a conventionally known insulator phosphor in which a part of the crystal is substituted with a transition metal. The spectrum shown in FIG. 58 is a photoexcitation emission spectrum from Gd 3 Ga 5 O 12 : Mn prepared by the Czochralski method disclosed in Non-Patent Document 3. Specific emission due to Mn 4+ ions in the insulator crystal is observed in the wavelength region near 670 nm. Although the fine structure peculiar to 3d electrons is clearly observed in a low temperature environment of T = 5K, it gradually becomes a broad spectrum as the temperature increases, and in a room temperature environment of T = 290K, it is observed as a considerably broad spectrum due to thermal influence. ing.

  Next, white light emitting diodes that are currently mainstream will be described. In white light-emitting diodes, true white light is produced by exciting phosphors of the three primary colors (red, green, and blue) with ultraviolet light-emitting diodes, or exciting green and red phosphors with blue light-emitting diodes. Is known to be obtained. However, as shown in FIG. 59, the white light-emitting diodes that are currently mainstream are composed of a combination of a blue light-emitting diode 29 and a yellow phosphor 30 encapsulated in a resin. A method is used in which white light 31 is obtained by emitting a yellow phosphor by photoexcitation. The light emission of a white light emitting diode using such a complementary color relationship is a pseudo white light that humans recognize a combination of yellow light and blue light between green and red as white, and is the primary color of light. The red color component of red, green and blue is largely lacking, so that the problem of poor color rendering is left. The reason why neutral yellow phosphors are currently used instead of the combination of green and red phosphors is that blue excitation light emits light with high luminous efficiency and high intensity even at high temperatures. This is because a red phosphor has not been developed. For example, in the case of an automobile headlight, the operating temperature of the white light emitting diode is usually as high as 100 ° C. or higher.

A well-known red phosphor for white light emitting diodes is a sulfide phosphor (Ca, Sr) S: Eu. Since this phosphor absorbs moisture in the air and generates hydrogen sulfide for decomposition, it is important to reduce moisture in the atmosphere as much as possible when it is incorporated into a blue light emitting diode. Moreover, in order to improve the durability of the white light emitting diode, it is necessary to devise a package such as using a sealant that shields moisture.
JP 2007-31668 A (paragraphs [0012] to [0013] in the specification) RR Rakhimov et al., Journal of Applied Physics, Vol. 95, No. 10, p. 5653 (2004) T. Murata et al., Journal of Luminescence, Vol. 114, p. 207 (2005) A. Brenier et al., Physical Review B, Vol. 46, No. 6, p. 3219 (1992)

  The above-described conventional phosphors have a problem in that the emission intensity varies depending on the temperature at which the light is emitted, and stable light emission cannot be obtained.

  Moreover, since the excitation wavelength that maximizes the emission intensity is not the wavelength that is required for the red light emission characteristics of the white light emitting diode, its use is limited.

  Further, in the production, as described above, since it is necessary to heat to a high temperature, there is a problem that the production cost is increased.

  Furthermore, the currently known red phosphors for white light emitting diodes have a problem that the light emission efficiency with blue excitation light is small and the light emission intensity is significantly reduced at high temperatures. Furthermore, when incorporating it into a blue light emitting diode, it was necessary to devise the atmosphere and package.

The purpose of the present invention, the emission intensity is strong, not easily affected by temperature changes, such as a novel phosphor having an excellent effect, very low temperatures as compared with the manufacturing method of the phosphor conventionally known An object of the present invention is to provide a production method that can be easily produced in an environment.

The first aspect of the present invention is that a B-containing material (where B is Si, B) is added to a mixed solution prepared by adding AMnO 4 (where A is K, Na, Rb or Cs) as an oxidizing agent to an HF aqueous solution. A 2 BF 6 (where A is K, Na, Rb or Cs, B is Si, Ge) by immersing Ge, Sn, Ti, or Zr, excluding oxide material. , Sn, Ti, or Zr), a phosphor comprising a crystal having a structure in which Mn is substituted as an activator is generated in a part of a base crystal represented by (Sn, Ti, or Zr). .

The second aspect of the present invention is an invention based on the first aspect , wherein the material of the B-containing material immersed in the mixed solution is crystalline or amorphous, and the shape thereof is plate-like or rod-like. It is characterized by being porous or powdery.

A third aspect of the present invention is the invention based on the first aspect, characterized in that the concentration of AMnO 4 in the mixed liquid to be further prepared is in the range of 0.01 to 1 mol with respect to the HF aqueous solution. And

The fourth aspect of the present invention is that a B-containing oxide material (provided that B is a compound) prepared by adding AMnO 4 (where A is K, Na, Rb or Cs) as an oxidizing agent to an aqueous HF solution. By immersing Si, Ge, Sn, Ti, or Zr), the mixed solution and the B-containing oxide material are reacted, and A 2 BF 6 (where A is K, Na, Rb or Cs, B is Si, A phosphor comprising a crystal having a structure in which Mn is substituted as an activator on a part of a base crystal represented by Ge, Sn, Ti, or Zr). is there.

A fifth aspect of the present invention is an invention based on the fourth aspect , wherein the material of the B-containing oxide material immersed in the mixed solution is crystalline or amorphous, and the shape thereof is plate-like. It is characterized by having a rod shape, a porous shape or a powder shape.

A sixth aspect of the present invention is the invention based on the fourth aspect, characterized in that the concentration of AMnO 4 in the mixed liquid to be further prepared is in the range of 0.01 to 2 mol with respect to the HF aqueous solution. And

A seventh aspect of the present invention, after generating the phosphor by a method based on the aspect of the first through sixth, organic solvent phosphor powder was produced, an acidic solution or a mixture with an acidic solution and the organic solvent It is a method for purifying a phosphor characterized in that it is purified by dipping in a glass.

According to the method for manufacturing a phosphor according to the present invention, a phosphor having excellent effects such as strong emission intensity and being hardly affected by temperature change is compared with a conventionally known phosphor manufacturing method. It can be easily produced in an extremely low temperature environment.

K 2 SiF 6 of the present invention using the substrate-shaped Si material: illustrates a method for producing Mn phosphor. K of the present invention using a rod-shaped Si material 2 SiF 6: shows a method for manufacturing a Mn phosphor. K 2 SiF 6 of the present invention using a Si material particulate form: illustrates a method for manufacturing a Mn phosphor. K 2 SiF 6 of the present invention: shows another embodiment of the production method of the Mn phosphor. The figure which shows the manufacturing method of the fluorescent substance of this invention using a powdery oxide material. The figure which shows the manufacturing method of the fluorescent substance of this invention using a rod-shaped oxide material. Example 1 K 2 SiF was produced in the resulting Si substrate 6: diagram showing the surface optical photograph of Mn phosphor. Obtained in Example 1 K 2 SiF 6: shows an X-ray diffraction curve of Mn phosphor powder crystals. SiF K 2 obtained in Example 1 6: Mn phosphor powder diagram showing an X-ray photoelectron spectroscopy measurements of the crystal. Obtained in Example 1 K 2 SiF 6: Mn phosphor and body, shows a photoluminescence spectrum of porous Si at room temperature produced by the conventional stain etching. Example 1 K obtained in 2 SiF 6: shows measured temperature dependence of the photoluminescence spectrum by Mn phosphor. K 2 SiF 6 obtained in Example 1: Figure showing the temperature dependence of photoluminescence peak wavelength due Mn phosphor. Example 1 K obtained in 2 SiF 6: diagram showing the temperature dependence of photoluminescence peak half width due Mn phosphor. Example 1 K obtained in 2 SiF 6: shows the dependence of the red light emission intensity to the excitation wavelength at room temperature Mn phosphor. Obtained in Example 1 K 2 SiF 6: Mn phosphor and body, shows a light absorption spectrum at room temperature of the phosphor matrix which Mn is not at all replaced (K 2 SiF 6). GeF K 2 obtained in Example 2 6: Mn shows a photoluminescence spectrum at room temperature from the phosphor. Obtained in Example 3 Na 2 SiF 6: shows an electron micrograph of Mn phosphor. Obtained in Example 3 Na 2 SiF 6: it shows the results of analysis by Mn phosphor electron probe micro analyzer. Obtained in Example 3 Na 2 SiF 6: it shows an X-ray diffraction curve of Mn phosphor powder crystals. Obtained in Example 3 Na 2 SiF 6: it shows a light absorption spectrum of the Mn phosphor. Example 3 Na obtained in 2 SiF 6: shows measured temperature dependence of the photoluminescence spectrum by Mn phosphor. Obtained in Example 3 Na 2 SiF 6: it shows the dependence of the red light emission intensity to the excitation wavelength at room temperature Mn phosphor. Obtained in Example 3 Na 2 SiF 6: diagram showing the temperature dependence of the red emission integrated intensity of Mn phosphor. GeF Na 2 obtained in Example 4 6: shows an electron micrograph of Mn phosphor. GeF Na 2 obtained in Example 4 6: Mn phosphor shows an analysis result by the electron probe micro-analyzer. GeF Na 2 obtained in Example 4 6: shows an X-ray diffraction curve of Mn phosphor powder crystals. GeF Na 2 obtained in Example 4 6: shows measured temperature dependence of the photoluminescence spectrum by Mn phosphor. GeF Na 2 obtained in Example 4 6: diagram showing the temperature dependence of the red emission integrated intensity of Mn phosphor. Example K 2 obtained in 5 ZrF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example Na 2 obtained in 6 SnF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example 7 obtained in Na 2 TiF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Obtained in Example 8 were Cs 2 SiF 6: it shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example 5 Na 2 unpurified obtained GeF 6: Mn phosphor powder Na 2 the emission spectrum purified in Example 9 of GeF 6: shows a comparison of the emission spectra of Mn phosphor powder. Obtained in Example 1 K 2 SiF 6: Mn phosphor is dispersed in an epoxy resin, shows an optical photograph of the sample excited by was red emission with ultraviolet laser after 1 month FIG. Example 11 K 2 SiF 6 obtained in: Mn phosphor, shows an optical photograph that red emission by ultraviolet excitation. Example 11 obtained in K 2 SiF 6: shows an electron micrograph of Mn phosphor. Example 11 K 2 SiF 6 obtained in: shows the dependence of the red light emission intensity to the emission spectrum and the excitation wavelength of Mn phosphor. Obtained in Example 12 was K 2 SiF 6: shows an electron micrograph of Mn phosphor. Obtained in Example 12 was K 2 SiF 6: it shows an X-ray diffraction curve of Mn phosphor powder crystals. Obtained in Example 12 was K 2 SiF 6: it shows the dependence of the red light emission intensity to the emission spectrum and the excitation wavelength of Mn phosphor. Obtained in Example 12 was K 2 SiF 6: diagram showing the temperature dependence of the red emission integrated intensity of Mn phosphor. Example 13 obtained in K 2 SiF 6: shows an electron micrograph of Mn phosphor. Example 13 obtained in K 2 SiF 6: shows the dependence of the red light emission intensity to the emission spectrum and the excitation wavelength of Mn phosphor. Example 14 obtained in K 2 SiF 6: shows an electron micrograph of Mn phosphor. Example 14 obtained in K 2 SiF 6: shows an X-ray diffraction curve of Mn phosphor powder crystals. Example 14 K 2 SiF 6 obtained in: shows the dependence of the red light emission intensity to the emission spectrum and the excitation wavelength of Mn phosphor. Example 14 obtained in K 2 SiF 6: diagram showing the temperature dependence of the red emission integrated intensity of Mn phosphor. Example 15 obtained in Na 2 SiF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example 16 obtained in Na 2 GeF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example 17 obtained in K 2 SnF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example 18 obtained in K 2 TiF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example 19 obtained in Cs 2 TiF 6: shows a photoluminescence spectrum at room temperature of the Mn phosphor. Example 15 Na 2 SiF obtained unpurified 6: Mn phosphor Na 2 SiF the emission spectrum purified in Example 20 of the powder 6: shows a comparison of the emission spectra of Mn phosphor powder. Example 11 obtained in K 2 SiF 6: Mn phosphor is dispersed in an epoxy resin, shows an optical photograph of the sample excited by was red emission with ultraviolet laser after 1 month FIG. YAlO the conventional Czochralski method 3: diagram showing a method for producing a Mn phosphor. CaAl the conventional flux method 12 O 19: illustrates a method for manufacturing a Mn phosphor. MgGa the conventional floating zone melting crystal growth method 2 O 4: illustrates a method for manufacturing a Mn phosphor. Conventional Cho Gd prepared in class Le ski Method 3 Ga 5 O 12: shows a typical emission spectrum from Mn phosphor. The figure which shows the structure of the conventional pseudo white light emitting diode.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

In the first production method of the phosphor of the present invention, an oxidant, AMnO 4 (where A is K, Na, Rb or Cs) is added to an aqueous HF solution at 0 to 80 ° C., and the mixed solution is dissolved. As shown in FIG. 1 (a), the B-containing material (where B is Si, Ge, Sn, Ti or Zr, excluding the oxide material) is added to the mixed solution at 0 to 80 ° C. 1), the surface layer of the material is A 2 BF 6 (where A is K, Na, Rb or Cs, B is Si, Ge, Sn, Ti or Zr) as shown in FIG. A phosphor composed of a crystal having a structure in which Mn is substituted as an activator is generated in a part of the base crystal represented by the formula.

  In addition, the activator as used in the field of this invention means what exists in a base crystal and becomes an excitation source for light emission.

It is made of a crystal having a structure of A 2 BF 6 : Mn on the surface layer of the immersed material by a very simple technique such as immersing the B-containing material in a mixed solution in which the oxidant AMnO 4 is dissolved in an HF aqueous solution. A phosphor can be produced. The obtained crystal is formed into a film on the surface layer of the material, and most of the film-like crystal is naturally peeled off from the material. Further, by applying a physical force that is lightly rubbed, it can be easily peeled off from the surface layer of the material, so that separation of the crystal from the material and recovery of the crystal are very easy.

In preparing the mixed solution, it is preferable to dissolve AMnO 4 with pure water and mix this AMnO 4 aqueous solution with HF aqueous solution in order to uniformly dissolve AMnO 4 in the HF aqueous solution. However, in particular, when the oxidizing agent is NaMnO 4 (A = Na), it may be preferable to dissolve it directly in the HF aqueous solution without dissolving it in pure water.

  The mixed solution is preferably maintained at a constant temperature in order to immerse the B-containing material and form a crystal uniformly in the surface layer. For example, the prepared mixed liquid is allowed to stand for a certain period of time in a room temperature environment, and the liquid temperature is made uniform, whereby a simple and high-quality phosphor can be produced.

The produced crystal is rate-determined by the B element (Si, Ge, Sn, Ti or Zr) constituting the B-containing material, or the fluorine and A element (K, Na, Rb or Cs) in the mixed solution. Therefore, even if a large amount of fluorine or element A is present in the mixed solution, the amount of crystals produced is determined if the amount of the B-containing material to be immersed is small. The amount of Mn substituted in the crystal is slightly different depending on the amount of AMnO 4 , HF, H 2 O used in preparing the mixed solution and the amount of the B-containing material immersed in the mixed solution. .

  In the first method for producing the phosphor of the present invention, as is apparent from FIG. 1, since it is not necessary to heat to a high temperature, a large apparatus such as an electric furnace is not required at all. Only a chemical solution tank for storing the liquid mixture and an appropriate chemical solution for preparing the liquid mixture are necessary. When manufacturing phosphors at room temperature, a heater for heating the chemical solution tank is not required. is there.

  In the above embodiment, a plate-like material is used as a starting material, but the shape of the material can be changed according to the use of the phosphor to be produced. For example, a rod-like crystal as shown in FIG. 2 may be used as a starting material. By using a material having such a shape, it is possible to improve the production efficiency of the phosphor. Further, the shape is not limited to a rod shape, and a powdery material or a porous material as shown in FIG. 3 may be used. Since the powdery material has a large surface area, the crystal formation rate is high, and the production efficiency of the phosphor can be further improved.

  Moreover, crystalline or amorphous is mentioned as a material of the B containing material immersed in a liquid mixture. Further, even in an alloy semiconductor material such as SiGe, crystals can be generated.

  When a B-containing material such as a Si material or a Ge material is immersed in a mixed solution, pretreatment such as degreasing the surface or removing the surface oxide film generates a high-quality crystal. Therefore, it is suitable.

Furthermore, the crystal obtained by the first production method of the present invention has low solubility in not only water but also HF aqueous solution. Utilizing such a technical advantage, for example, as shown in FIG. 4A, a Si material is immersed in a reaction tank in which a KMnO 4 / HF mixed solution is stored, and shown in FIG. 4B. In this way, the phosphor film formed on the surface layer is physically peeled off using an acid-resistant brush such as Teflon (registered trademark) material on the Si substrate on which the phosphor composed of the crystal is generated on the surface layer. To do. Thereby, since Si is exposed on the surface layer of the Si substrate, a phosphor made of a crystalline material is generated again on the surface layer, and as a result, the phosphor can be continuously produced. In addition, although the exfoliation material of the phosphor physically exfoliated from the Si substrate remains deposited in the lower part of the reaction vessel, it does not disappear after being dissolved in the mixed solution. Since it is exposed to Mn ions in the mixed solution for a long time, the substitution of Mn to the base crystal proceeds, and the emission intensity of the obtained phosphor increases. Actually, in the experiment in which the phosphor was produced while peeling the crystal formed on the surface of the Si substrate with a brush in the process as shown in FIGS. 4A and 4B, the peeled material was in the mixed solution. The phosphor obtained by being exposed to Mn ions for a long time, and then filtered and extracted, emits light in comparison with the phosphor produced by the steps shown in FIGS. 1 (a) and (b). It has also been confirmed that the intensity increases nearly 10 times.

Here, a chemical reaction mechanism of K 2 SiF 6 crystal when Si material is used as the B-containing material and KMnO 4 is used as the oxidizing agent will be described. The chemical reaction of Si in an HF aqueous solution to which KMnO 4 as an oxidizing agent is added proceeds as shown in the following formula (1).

Si (s) + 6HF (aq ) 2- + xh + → SiF 6 (aq) + (6-2y) H + (aq) + yH 2 (g) + ze - ...... (1)

Here, (s) is solid, (aq) is aqueous, (g) is gas, and h + and e are holes and electrons, respectively. Further, there is a relationship of x + 2y + z = 4. SiF 6 2− in the above formula (1) reacts with K + ions in the KMnO 4 / HF mixed solution as shown in the following formula (2) to generate K 2 SiF 6 .

2K + + SiF 6 2- → K 2 SiF 6 (2)

K 2 SiF 6 is formed by the chemical reaction of the above formulas (1) and (2).
Even when NaMnO 4 , RbMnO 4 or CsMnO 4 is used as the oxidizing agent, it is explained by replacing K in the above formula (2) with Na, Rb or Cs. Further, regarding the B-containing material which is a base material, even when Ge, Sn, Ti or Zr is used instead of Si, it is explained by replacing Si with Ge, Sn, Ti or Zr.

Next, Mn is discussed effect of replacing the K 2 SiF 6 crystals as a host crystal. In the KMnO 4 / HF mixed solution, not only K ions but also Mn ions exist as metal ions. The effective radii of each valence of Mn are 0.83Å (Mn 2+ ), 0.65Å (Mn 3+ ), and 0.54Mn (Mn 4+ ), respectively. On the other hand, the effective radius of Si 4+ ions, which are elements constituting the K 2 SiF 6 crystal, is 0.41 Å. Moreover, the charge neutralization conditions of the constituent atoms of the K 2 SiF 6 crystal are as shown in the following formula (3).

2K + + Si 4+ = 6F - ...... (3)
Therefore, even if the Mn atom is substituted in the +4 valence state at the Si site of the K 2 SiF 6 crystal as the base crystal, there is no wonder. Fortunately, the effective ionic radius of Si 4+ is 0.41A, and the effective ionic radius of Mn 4+ is 0.53 Å, because it has a radius of about both radii said to substantially equal, Mn 4+ ions, It is considered that the K 2 SiF 6 chemical reaction production process proceeding in the above formulas (1) and (2) has been replaced with Si sites without difficulty. Although the ionic radius of Sn 4+ with a relatively large atomic number is as large as 0.69 cm, red emission related to Mn 4+ is clearly observed, so that the Mn 4+ ion is also substituted for the Sn site. become.

The liquid mixture used in the first method for producing a phosphor in the present invention is prepared by adding AMnO 4 (where A is K, Na, Rb or Cs), which is an oxidizing agent, to an HF aqueous solution. If this oxidant is not added, that is, in the HF aqueous solution (HF + H 2 O), the natural oxide film on the Si surface is only etched away as expected.

However, by adding KMnO 4 to the HF aqueous solution, the Si surface is etched by the chemical reaction formula of the formula (1) due to the influence of the redox potential on the Si in the solution. When the concentration of KMnO 4 is low, the Si surface is only etched into a porous or mirror-like shape simply due to the influence of the redox potential. However, when the KMnO 4 concentration is higher than a certain level, the chemical reaction of the formula (2) follows the formula (1), and the K 2 SiF 6 phosphor doped with Mn is deposited. The concentration of KMnO 4 in the mixed solution for precipitating the K 2 SiF 6 phosphor is preferably in the range of 0.01 to 1 mol with respect to the HF aqueous solution. If the concentration is less than the lower limit, the crystal formation rate is extremely slow, which is not practical, and even if the concentration exceeds the upper limit, the crystal can be generated, but the formation rate does not change. The concentration of the HF aqueous solution used is preferably 1 to 50%. If the amount is less than the lower limit, the crystal formation rate is extremely slow and impractical, and even if the upper limit is exceeded, the crystal can be produced, but the production rate does not change. The 50% HF aqueous solution concentration is generally a commercially available HF aqueous solution, and it is particularly preferable to use an about 25% HF aqueous solution obtained by diluting this with the same amount of pure water.

  The temperature of the mixed solution is the same as a normal chemical reaction, and the higher the temperature of the solution, the more severe the reaction occurs. Conversely, the lower the solution temperature, the milder the reaction occurs. Therefore, the temperature of the mixed liquid for generating crystals may be selected at an optimum temperature during production, such as 20 ° C. or 80 ° C., and a temperature according to the purpose. As described in the background art above, these temperatures are extremely low temperatures, such as near room temperature, unlike high temperatures of 1000 ° C. or higher as in the method of manufacturing phosphors based on crystal growth. It can be easily manufactured.

In addition, as a device, if a chemical reaction tank or a simpler method is used, for example, if there is only a Teflon (registered trademark) beaker, it is possible to produce a crystal, which is a high-temperature electric furnace or temperature control. This is clearly different from the conventional manufacturing method that requires an apparatus or the like. Si and Ti are very abundant elements on the ground, and are easily available. KMnO 4 and NaMnO 4 are industrially very inexpensive chemical materials generally used as oxidizing agents.

  In this way, by simply immersing an easily available and inexpensive material in a chemical reaction tank storing a mixed solution, the chemical reaction proceeds spontaneously, and the end point of this reaction is the end of the phosphor synthesis, which is a crystalline substance. Therefore, there is no need for complicated control of the liquid temperature during the reaction. For this reason, the work of the phosphor manufacturer is as simple as putting the material into the chemical reaction tank.

In the second method for producing the phosphor of the present invention, AMnO 4 (where A is K, Na, Rb or Cs) is added to an aqueous HF solution at 0 to 80 ° C., and the mixture is dissolved. Prepared and mixed by immersing a B-containing oxide material (where B is Si, Ge, Sn, Ti, or Zr) in the mixed solution at 0 to 80 ° C. as shown in FIG. As shown in FIG. 5B, A 2 BF 6 (where A is K, Na, Rb or Cs, B is Si, Ge, Sn, Ti or Zr, as shown in FIG. 5B). ), A phosphor composed of a crystal having a structure in which Mn is substituted as an activator is generated in a part of the base crystal represented by (2).

  In addition, the activator as used in the field of this invention means what exists in a base crystal and becomes an excitation source for light emission similarly to the 1st manufacturing method mentioned above.

A crystal in which the soaked material has a structure of A 2 BF 6 : Mn by a chemical reaction by a very simple technique of immersing the B-containing oxide material in a mixed solution obtained by dissolving the oxidizing agent AMnO 4 in an HF aqueous solution. It changes into phosphor particles consisting of the body. The obtained phosphor particles composed of the crystal are precipitated in the solution, and thus are very easy to recover.

In preparing the mixed solution, it is preferable to dissolve AMnO 4 with pure water and mix this AMnO 4 aqueous solution with HF aqueous solution in order to uniformly dissolve AMnO 4 in the HF aqueous solution.

  The mixed solution is preferably maintained at a constant temperature. For example, the prepared mixed liquid is allowed to stand for a certain period of time in a room temperature environment, and the liquid temperature is made uniform, whereby a simple and high-quality phosphor can be produced.

The produced crystal is B element (Si, Ge, Sn, Ti or Zr) constituting the B-containing oxide material immersed in the mixed solution, or fluorine, A element (K, Na, Rb or Cs). Therefore, even if a large amount of fluorine or A element is present in the mixed solution, the amount of crystals produced is determined if the amount of the B-containing oxide material to be immersed is small. The amount of Mn substituted in the crystal was slightly different depending on the amount of AMnO 4 , HF, H 2 O used in preparing the mixed solution and the amount of the B-containing oxide material immersed in this mixed solution. Result.

  In the second method for producing the phosphor of the present invention, as is apparent from FIG. 5, a large-sized device such as an electric furnace is not required at all. Only a chemical solution tank for storing the liquid mixture and an appropriate chemical solution for preparing the liquid mixture are necessary. When manufacturing phosphors at room temperature, a heater for heating the chemical solution tank is not required. is there.

  In the above embodiment, a powdered oxide is used as a starting material, but the shape of the material can be changed according to the use of the phosphor to be manufactured. For example, a rod-shaped oxide as shown in FIG. 6 may be used as a starting material. In this case, phosphor particles are generated from the rod-like oxide. A porous or plate-like oxide material may be used.

As the B-containing oxide material immersed in the mixed solution, a material containing Si, Ge, Sn, Ti, or Zr is used. As the oxide material containing Si, include quartz (SiO 2) it is. Further, not only a simple oxide such as quartz but also a mixture of oxides such as borosilicate glass and soda glass may be used. An example of the oxide containing Ge is Ge 2 O 3 . Moreover, SnO is mentioned as an oxide containing Sn. Furthermore, examples of the oxide containing Ti include TiO 2 and Ti 2 O 3 .

  Moreover, crystalline or amorphous is mentioned as a material of the oxide material immersed in a liquid mixture.

Here, the formation chemical reaction mechanism of the Na 2 SiF 6 crystal when quartz (SiO 2 ), which is an oxide material containing Si, is used as the B-containing oxide material, and NaMnO 4 is used as the oxidant will be described. . The chemical reaction of Si in an HF aqueous solution to which NaMnO 4 as an oxidizing agent is added proceeds as shown in the following formula (4).

SiO 2 (s) + 6HF (aq) + xh +
SiF 6 2- (aq) + ( 6-2y) H + (aq) + yH 2 (g) + ze - + O 2 (g) ...... (4)

Here, (s) is solid, (aq) is aqueous, (g) is gas, and h + and e are holes and electrons, respectively. Further, there is a relationship of x + 2y + z = 4. SiF 6 2- in the above formula (4) reacts with K + ions in the NaMnO 4 / HF mixed solution as shown in the following formula (5), whereby Na 2 SiF 6 is generated.

2Na + + SiF 6 2- → Na 2 SiF 6 (5)

Na 2 SiF 6 is formed by the chemical reaction of the above formulas (4) and (5).
Even when KMnO 4 , RbMnO 4 or CsMnO 4 is used as the oxidizing agent, it is explained by replacing Na in the above formula (5) with K, Rb or Cs. Further, regarding the B-containing oxide material that is a base material, for example, when TiO 2 that is an oxide containing Ti is used, SiO 2 is replaced with TiO 2 . Moreover, when an oxide material is SnO, it demonstrates with the following formula | equation (4 ') and Formula (5').

SnO (s) + 6HF (aq) + xh +
SnF 6 2- (aq) + ( 6-2y) H + (aq) + yH 2 (g) + ze - + 1 / 2O 2 (g) ...... (4 ')

2Na + + SnF 6 2- → Na 2 SnF 6 (5 ')

Next, Mn is considered acting to replace the Na 2 SiF 6 crystals as a host crystal. In the NaMnO 4 / HF mixed solution, not only Na ions but also Mn ions exist as metal ions. The effective radii of each valence of Mn are 0.83Å (Mn 2+ ), 0.65Å (Mn 3+ ), and 0.54Mn (Mn 4+ ), respectively. On the other hand, the effective radius of Si 4+ ions, which are elements constituting the Na 2 SiF 6 crystal, is 0.41 Å. The charge neutralization conditions for the constituent atoms of the Na 2 SiF 6 crystal are as shown in the following formula (6).

2Na + + Si 4+ = 6F - ...... (6)
Therefore, even if the Mn atom is substituted in the +4 valence state at the Si site of the Na 2 SiF 6 crystal as the base crystal, there is no wonder. Fortunately, the effective ionic radius of Si 4+ is 0.41A, and the effective ionic radius of Mn 4+ is 0.53 Å, because it has a radius of about both radii said to substantially equal, Mn 4+ ions, It is thought that the Si site was replaced with Si sites without difficulty in the Na 2 SiF 6 chemical reaction generation process proceeding in the above formulas (4) and (5).

The liquid mixture used in the second method for producing a phosphor in the present invention is prepared by adding NaMnO 4 as an oxidizing agent to an HF aqueous solution. If this oxidizing agent is not added, that is, an HF aqueous solution ( In HF + H 2 O), as everyone expects, the oxide is simply dissolved in the etchant.

However, when NaMnO 4 is added to the HF aqueous solution, an etching reaction occurs in the oxide according to the chemical reaction formula (4) due to the influence of the oxidation-reduction potential on the oxide in the solution. When the concentration of NaMnO 4 is small, the oxide is mainly etched only by the influence of the redox potential. However, when the NaMnO 4 concentration is higher than a certain level, the chemical reaction of the formula (5) becomes remarkable following the formula (4), and the Na 2 SiF 6 phosphor doped with Mn is deposited. The concentration of NaMnO 4 in the mixed solution for depositing the Na 2 SiF 6 phosphor is preferably in the range of 0.01 to 2 mol relative to the HF aqueous solution. If the concentration is less than the lower limit, the crystal formation rate is extremely slow, which is not practical, and even if the concentration exceeds the upper limit, the crystal can be generated, but the formation rate does not change. The concentration of the HF aqueous solution used is preferably 1 to 50%. If the amount is less than the lower limit, the crystal formation rate is extremely slow and impractical, and even if the upper limit is exceeded, the crystal can be produced, but the production rate does not change. A 50% HF aqueous solution concentration is generally a commercially available HF aqueous solution.

  The temperature of the mixed solution is the same as a normal chemical reaction, and the higher the temperature of the solution, the more severe the reaction occurs. Conversely, the lower the solution temperature, the milder the reaction occurs. Therefore, the temperature of the mixed solution for generating crystals is preferably 20 to 40 ° C. Of these, for example, an optimum temperature in production such as 20 ° C. or 80 ° C., and a temperature according to the purpose may be selected. As described in the background art above, these temperatures are extremely low, such as around room temperature, unlike a high temperature of 1000 ° C. or higher as in the case of a conventionally known phosphor manufacturing method based on crystal growth. Temperature, and therefore can be easily manufactured.

In addition, as a device, if a chemical reaction tank or a simpler method is used, for example, if there is only a Teflon (registered trademark) beaker, it is possible to produce a crystal, which is a high-temperature electric furnace or temperature control. This is clearly different from the conventional manufacturing method that requires an apparatus or the like. For example, SiO 2 , which is an oxide containing Si, is a very abundant element on the ground, and is also referred to as quartzite. It is easily available, and KMnO 4 and NaMnO 4 are also generally oxidized industrially. It is an inexpensive chemical material used as an agent.

In this way, a phosphor that is easily available and inexpensive, and the chemical reaction proceeds spontaneously simply by immersing it in a chemical reaction tank in the atmosphere where the liquid mixture is stored, and the end point of this reaction is a crystalline substance. Since it is the end of the synthesis, there is no need for complicated control of the liquid temperature during the reaction. For this reason, the work of the phosphor manufacturer is as simple as putting the material into the chemical reaction tank.
In addition, although it changes also with various conditions, such as the density | concentration and temperature of a liquid mixture, and the surface area and magnitude | size of an oxide material, 1 to 48 hours are preferable for the time which immerses an oxide material in a liquid mixture.

The phosphor of the present invention is obtained by the first manufacturing method or the second manufacturing method described above, and A 2 BF 6 (where A is K, Na, Rb or Cs, B is Si, Ge, A crystal having a structure in which a transition metal is substituted as an activator in a part of a base crystal represented by Sn, Ti, or Zr, excluding a combination of K and Si, K and Ge, and K and Ti. It consists of a body. A 2 BF 6 of the parent crystal (where A is K, Na, Rb or Cs, B is Si, Ge, Sn, Ti or Zr, excluding the combination of K and Si, K and Ge, K and Ti) .) Has a cubic or trigonal (hexagonal) crystal structure. Mn is mentioned as a transition metal used as an activator. That is, K 2 SnF 6 : Mn, K 2 ZrF 6 : Mn, Na 2 SiF 6 : Mn, Na 2 GeF 6 : Mn, Na 2 SnF 6 : Mn, Na 2 TiF 6 : Mn, Na 2 ZrF 6 : Mn Rb 2 SiF 6 : Mn, Rb 2 GeF 6 : Mn, Rb 2 SnF 6 : Mn, Rb 2 TiF 6 : Mn, Rb 2 ZrF 6 : Mn, Cs 2 SiF 6 : Mn, Cs 2 GeF 6 : Mn, Cs 2 SnF 6 : Mn, Cs 2 TiF 6 : Mn, Cs 2 ZrF 6 : Mn.

  The phosphor of the present invention emits light based on excitation of electrons in the phosphor. Specifically, the phosphor emits light having a peak in the wavelength region exhibiting red by exciting the electrons in the phosphor. Specifically, it has the strongest light emission in the vicinity of 630 nm.

When the transition metal serving as the activator is Mn, the phosphor of the present invention has a structure in which a part of B in the A 2 BF 6 crystal that is the base crystal is substituted with Mn. Its valence exists in a tetravalent state.

In this phosphor, the optimum amount of Mn substitution in the A 2 BF 6 base crystal is 0.05 mol% to 90 mol%. The reason why the optimum amount of Mn substitution is within the above range is that the substitution amount less than the lower limit is considered to be because light emission is slightly weak and impractical. Exceeding the upper limit causes problems such as time-consuming manufacture and failure to obtain light emission.

The site shown in B of A 2 BF 6 host crystal Mn, like BF 6 2-ions of atoms represented by B, the periphery of F - stable at MnF 6 2-state by coupling with ions Existing. Therefore, strictly speaking, Mn in A 2 BF 6 can also be expressed as a solid solution represented by the following formula (7).

A 2 (BF 6 ) x (MnF 6 ) (1-x) (7)
Here, the phosphor of the present invention is in the range of 0.1 ≦ x ≦ 0.9995. This range corresponds to the aforementioned optimum amount of Mn substitution of 0.05 mol% to 90 mol%.

Although it is outside the range of the phosphor of the present invention, when x = 0 in the above formula (7), it corresponds to 100% Mn substitution and is represented by A 2 MnF 6 . Further, when x = 1 in the above formula (7), it corresponds to the Mn substitution amount of 0% and is represented by A 2 BF 6 .

  The novel phosphor of the present invention has excellent effects such as high emission intensity and being hardly affected by temperature changes.

The phosphor powder produced by the first production method or the second production method of the present invention looks slightly dark. This can be easily understood from the following reaction formula (8) using K 2 SiF 6 as an example in the first production method.

Si + 4KMnO 4 + 12HF → K 2 SiF 6 + K 2 MnF 6 + 3MnO 2 + 6H 2 O + 2O 2 ...... (8)
That is, by immersing silicon (Si) in a mixed solution of hydrofluoric acid (HF) and oxidizing agent (KMnO 4 ), not only K 2 SiF 6 and K 2 MnF 6 that become red phosphors but also water (H 2 It is presumed that manganese oxide (MnO 2 ), which causes the phosphor to darken, is formed as a by-product in addition to O) and oxygen gas (O 2 ). Since MnO 2 absorbs red light emission, the light emission intensity is weakened and the half width of the spectrum is widened. For this reason, if MnO 2 is present in the phosphor, the performance of the phosphor deteriorates as a result.

Further, the second production method can be easily understood from the following reaction formula (9) using Na 2 SiF 6 as an example.

SiO 2 + 4NaMnO 4 + 12HF →
Na 2 SiF 6 + Na 2 MnF 6 + 3MnO 2 + 6H 2 O + 3O 2 ...... (9)
That is, by immersing quartz glass (SiO 2 ) in a mixed solution of hydrofluoric acid (HF) and oxidizing agent (NaMnO 4 ), not only Na 2 SiF 6 and Na 2 MnF 6 that become red phosphors but also water ( In addition to H 2 O) and oxygen gas (O 2 ), it is presumed that manganese oxide (MnO 2 ) that causes the phosphor to darken is formed as a by-product. Since MnO 2 absorbs red light emission, the light emission intensity is weakened and the half width of the spectrum is widened. For this reason, if MnO 2 is present in the phosphor, the performance of the phosphor deteriorates as a result.

  Therefore, in the purification method of the present invention, after the phosphor is produced by the first production method or the second production method, the produced phosphor powder is mixed with an organic solvent, an acidic solution or an acidic solution and an organic solvent. It is characterized by being purified by dipping in a mixed solution of

Specifically, by immersing the produced phosphor powder in an organic solvent, an acidic solution, or a mixed solution of an acidic solution and an organic solvent, MnO 2 present as a by-product in the phosphor powder is gradually Dissolved and removed. By performing the immersion treatment, the dark phosphor becomes a beautiful light yellow. By applying this purification method, the performance of the phosphor is enhanced. The immersion treatment may be repeated a plurality of times. Further, the immersion treatment may be performed a plurality of times by combining the organic solvent, the acidic solution, or the mixed solution of the acidic solution and the organic solvent, such as the immersion treatment again after the immersion treatment with the acidic solution. Examples of the organic solvent used include methyl alcohol, ethyl alcohol, and acetone. Examples of the acidic solution include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid and the like.

The purification effect due to the difference in chemicals used for purification varies slightly depending on the type of host crystal of the phosphor. For example, in the case of potassium (K) -based phosphors such as K 2 SiF 6 and K 2 GeF 6 , It has been confirmed that hydrochloric acid gives better results in phosphors based on sodium (Na) such as Na 2 SiF 6 and Na 2 GeF 6 , although it does not depend much on the type. In addition, when purifying Na-based phosphors with nitric acid, nitric acid has a defect that not only MnO 2 but also the host crystal of the phosphor is dissolved. Appropriate combination needs to be examined in advance.

It has also been confirmed that the organic solvent has a high solubility in MnO 2 , and conversely, the solubility of the phosphor in the base crystal is low, so that the purification efficiency is high. In particular, it is preferable to use methyl alcohol for potassium-based phosphors such as K 2 SiF 6 : Mn and acetone for sodium-based phosphors such as Na 2 SiF 6 : Mn.

When the A 2 BF 6 : Mn phosphor according to the present invention is formed on the surface of a substrate such as Si, the phosphor on the substrate can be applied as a phosphor as it is or to a scintillator or the like. Moreover, it can be used as a solid laser material by crystallizing the phosphor powder or making the phosphor into large crystals. Of particular note, the strongest emission wavelength of this phosphor is in the range of 610 to 640 nm, which is almost the same as the oscillation wavelength (632.8 nm) of the He—Ne laser, which is the most used gas laser in the industry. We can expect to realize an ultra-compact red-emitting solid-state laser that can replace this gas laser.

  Furthermore, since the phosphor of the present invention has an excellent effect that the emission intensity is strong and is not easily affected by temperature change, the green phosphor and the red phosphor are respectively converted by blue light excitation from the blue light emitting diode. By using it as a red phosphor of the white light emitting diode of the principle of emitting light, it has high luminous efficiency with blue excitation light and can be operated stably even at high temperatures, and is composed of the current mainstream blue light emitting diode and yellow phosphor It can be expected to realize a new three-wavelength type true white light emitting diode instead of the pseudo white light emitting diode.

  Next, embodiments of the present invention will be described in detail.

<Example 1>
An n-type Si single crystal substrate was prepared as a Si material, and this substrate was subjected to pretreatment cleaning. Specifically, degreasing cleaning was performed in which trichlorethylene cleaning was first performed for 10 minutes, then acetone cleaning was performed for 10 minutes, and then methanol cleaning was performed for 10 minutes while applying ultrasonic waves. After this degreasing and cleaning, the natural oxide film formed on the Si substrate surface was removed using 5% HF aqueous solution.

On the other hand, KMnO 4 was dissolved in pure water at 20 ° C., this aqueous KMnO 4 solution was mixed with an aqueous HF solution at 20 ° C., and then the mixed liquid was allowed to stand at room temperature to prepare a mixed solution. The composition of the prepared mixed solution is 50% HF: H 2 O: KMnO 4 = 100 cc: 100 cc: 6 g.

  Next, as shown to Fig.1 (a), Si substrate was immersed for 10 minutes in the liquid mixture prepared in room temperature environment. In the surface layer of the Si substrate immersed in the liquid, a crystal as shown in FIG. 1B was generated.

  FIG. 7 shows a surface optical photograph of the Si substrate in which a crystal is formed on the surface layer. In the surface optical photograph shown in FIG. 7, it can be confirmed that a yellow crystal is generated on the Si crystal surface layer. This crystal was hardly soluble in water and could be easily peeled off. Thereby, it was confirmed that a powdery phosphor can be easily obtained. The size of these powders was on the order of tens of microns.

Next, X-ray diffraction measurement was performed on the crystal formed on the surface layer of the Si substrate. The result is shown in FIG. As is clear from FIG. 8, the peak of X-ray diffraction ((a) in FIG. 8) agrees well with the theoretical prediction peak of cubic K 2 SiF 6 ((b) in FIG. 8). From this, it can be concluded that the chemical reaction product shows a crystal structure of K 2 SiF 6 . K 2 SiF 6 has a cubic crystal structure and a lattice constant of about 8.14 Å. Further, as apparent from the X-ray diffraction peak shown in FIG. 8, it can be seen that the crystal is a high-quality crystal that does not contain an impurity crystal such as (NH 4 ) 2 SiF 6 or an amorphous impurity. .

Next, X-ray photoelectron spectroscopy measurement was performed on the crystal formed on the surface layer of the Si substrate. The result is shown in FIG. As is clear from FIG. 9, not only K, Si and F, which are atoms constituting the K 2 SiF 6 crystal, but also a peak of Mn is clearly observed. The other observed peaks are peaks caused by air adsorbed molecules such as C (carbon) and O (oxygen). Incidentally, the amount of Mn substitution predicted from the X-ray photoelectron spectroscopic measurement is about 0.5 mol%, which indicates that Mn is very efficiently substituted at a high rate. Conventionally, it has been known that an insulator phosphor doped with a transition metal has a high luminous efficiency. For example, the Mn content in the GGG crystal in FIG. 58 is about 0.5 mol%.

From the above measurement results, it was confirmed that the crystal obtained in Example 1 was K 2 SiF 6 : Mn.

  In Example 1, an n-type Si single crystal substrate was used as a starting material. However, when a phosphor having the same properties was obtained, an additional experiment was conducted. It was confirmed that Further, when an additional experiment was performed using polycrystalline Si having a different material as a starting material, it was confirmed that a phosphor having the same effect was obtained.

<Evaluation 1-1>
Example 1 K obtained in 2 SiF 6: For Mn, measured photoluminescence spectrum at room temperature was evaluated for its emission characteristics. A He—Cd laser having an oscillation wavelength of 325 nm was used as the light excitation light source. FIG. 10 shows the photoexcitation emission spectrum of K 2 SiF 6 : Mn. For reference, FIG. 10 shows 50 times the photoexcitation emission spectrum from porous Si prepared with a typical stain etchant of 50% HF: HNO 3 : H 2 O = 1: 5: 10. The enlarged spectrum is also included for comparison. The reason why the emission spectrum from the porous Si is expanded to 50 times is that the emission intensity from the K 2 SiF 6 : Mn phosphor is very weak. Porous Si as a comparison is a light-emitting technology that has attracted attention in recent years. This is considered to be light emission by electrons confined in porous Si fine particles produced by stain etching, unlike light emission from a phosphor. As is clear from FIG. 10, the intensity of the emission intensity from the K 2 SiF 6 : Mn phosphor is evident from the comparison with the emission intensity from the porous Si.

The essential difference between the chemical composition of the mixed solution used to produce K 2 SiF 6 : Mn of Example 1 and a typical stain etching solution for producing porous Si is that the former is KMnO 4 and the latter Is the only difference in the so-called oxidant of HNO 3 . However, the former oxidizing agent contains Mn as a constituent element, which is compatible with the chemical reaction process as shown in the above formulas (1) and (2), and the ionic radius between Mn and Si is almost equal. It is presumed that Mn was easily substituted as a luminescent center in the K 2 SiF 6 base crystal.

Incidentally, an experiment was conducted in the same manner as in Example 1 except that a mixed solution (50% HF: K 2 Cr 2 O 7 : H 2 O) using an oxidizing agent K 2 Cr 2 O 7 containing Cr was used. The emission spectrum on the surface layer of the Si substrate was measured, and no emission spectrum peculiar to transition metals in the phosphor such as K 2 SiF 6 : Mn in Example 1 shown in FIG. Only an emission spectrum similar to the emission spectrum was observed.

<Evaluation 1-2>
Subsequent to the evaluation 1-1, the K 2 SiF 6 : Mn obtained in Example 1 was measured for temperature dependence of the emission spectrum in order to investigate the emission characteristics of the phosphor in more detail. Measurements were performed between 20 and 300 K (−253 to 27 ° C.). FIG. 11 shows the measurement results at three temperatures (20K, 200K, and 300K).

Compared with the spectrum from the GGG: Mn phosphor shown in FIG. 58 and disclosed in Non-Patent Document 3, the result becomes clearer, but the emission intensity from the K 2 SiF 6 : Mn phosphor shown in FIG. The results are stronger at higher temperatures than at lower temperatures. Also, the microstructure light emission line peculiar to 3d electrons of Mn is clearly observed at room temperature (300K) as well as the low temperature, and it emits light without being affected by the temperature of the host crystal. I understand. Such a stable emission spectral characteristic with respect to temperature is a very important property in the application of phosphors. In addition, the tendency to increase the emission intensity as the temperature rises is a very useful property when used as a red light emitter of a white light source at a high temperature, for example, an automobile headlight used as a red light source of a white light emitting diode. It is.

<Evaluation 1-3>
Among the main emission peak wavelengths observed in the emission spectrum shown in FIG. 11 in the evaluation 1-2, three emission peaks of 614 nm, 631 nm, and 648 nm observed at room temperature are about −250 to 27 ° C. FIG. 12 shows the result of investigating the influence of the emission peak wavelength on the temperature in more detail within the range.

  As is clear from FIG. 12, the emission peak wavelength hardly changed in the temperature range of −250 to 27 ° C., and it was found that light was emitted at a wavelength extremely stable with respect to the temperature.

<Evaluation 1-4>
Among the main emission peak wavelengths found in the emission spectrum shown in FIG. 11 in the evaluation 1-2, the half widths of 614 nm, 631 nm and 648 nm are measured in the range of −250 to 27 ° C. FIG. 13 shows the result plotted. The half width of each emission peak was determined by fitting each emission peak with a Gaussian function.

  As is clear from FIG. 13, it was confirmed that the half-value width of the emission peak wavelength was slightly wider as the temperature increased, and was within an extremely narrow range of ± 1 nm between −250 to 27 ° C.

For example, as shown in FIG. 58, in the case of light emission from a Gd 3 Ga 5 O 12 (GGG): Mn phosphor produced by the conventional Czochralski method, a peak drawn at an extremely low temperature of 5K (−268 ° C.) is observed separately. However, at 290 K (17 ° C.) at room temperature, the light emission changes to a very wide range.

From these results, it can be seen that the half-value width of the emission peak from the K 2 SiF 6 : Mn phosphor is hardly influenced by the temperature.

<Evaluation 1-5>
For the application of phosphors, it is very important to know the excitation light wavelength for causing the strongest emission. Therefore, the relationship of the emission intensity with respect to the excitation wavelength was determined for the K 2 SiF 6 : Mn phosphor. The result is shown in FIG. Note that the broken line in FIG. 14 represents the emission intensity with respect to the excitation wavelength, and the thick solid line represents the emission spectrum.

  As is clear from FIG. 14, the red light emission indicated by the thick solid line has the maximum light emission intensity at an excitation wavelength of about 450 nm.

  The characteristics confirmed from FIG. 14 are the red light emission required for realizing a three-wavelength type true white light-emitting diode instead of the pseudo white light-emitting diode composed of the current blue light-emitting diode and yellow phosphor. It is a very favorable characteristic that perfectly matches the body characteristics.

<Evaluation 1-6>
FIG. 15 shows a comparison of light absorption spectra of the phosphor K 2 SiF 6 : Mn according to the present invention in which Mn is substituted in the base crystal and a simple K 2 SiF 6 crystal in which Mn is not substituted in the crystal. Show.

  As can be seen from FIG. 15, absorption band peaks are clearly observed in blue (about 450 nm) and ultraviolet region (<400 nm) due to substitution of Mn in the base crystal, which contributes to red light emission. It is understood that

<Example 2>
In order to confirm that the phosphor manufacturing method according to the present invention is useful not only for a Si material but also for a Ge material, a Ge material ( The experiment was performed in the same manner as in Example 1 except that Ge fine powder was used.

<Evaluation 2>
Subsequently, the crystal produced in Example 2 was subjected to X-ray diffraction measurement in the same manner as in Example 1. Although not shown, it was confirmed that the crystal obtained in Example 2 had a K 2 GeF 6 crystal structure. Further, X-ray photoelectron spectroscopic measurement was performed on the crystal produced in Example 2 in the same manner as in Example 1. Although not shown in the figure, not only K, Ge and F, which are elements constituting the K 2 GeF 6 crystal, but also Mn peaks were clearly observed in the crystal obtained in Example 2.

From the above measurement results, it was confirmed that the crystal obtained in Example 2 was K 2 GeF 6 : Mn.

For K 2 GeF 6 : Mn obtained in Example 2, the photoexcitation emission spectrum at room temperature was measured in the same manner as in Evaluation 1 of Example 1 above, and the emission characteristics were evaluated. The photoexcitation emission spectrum is shown in FIG.

As is clear from FIG. 16, a peak similar to the emission spectrum of K 2 SiF 6 : Mn shown in FIG. 10 was observed, and strong red light emission was confirmed.

<Example 3>
NaMnO 4 was used instead of KMnO 4 in order to confirm that not only KMnO 4 but also other oxidizing agents are useful as the oxidizing agent in the method for producing the phosphor according to the present invention. Otherwise, the experiment was performed in the same manner as in Example 1. However, the solution used in this example was a solution in which 12 g of NaMnO 4 was added to a 100 cc 50% HF solution.

<Evaluation 3>
FIG. 17 shows an electron micrograph of the red phosphor produced by the method of Example 3. From this photograph, it can be seen that the red phosphor produced in the present invention is on the order of several tens of microns.

  FIG. 18 shows the results of composition analysis using an electron probe microanalyzer. From the result of this composition analysis, it is concluded that the phosphor is a compound mainly composed of Na, Si, F and Mn.

Next, X-ray diffraction measurement of this phosphor crystal was performed. The result is shown in FIG. As can be seen from FIG. 19, the X-ray diffraction peak coincides with the calculated peak of trigonal Na 2 SiF 6 . Therefore, it is concluded that the phosphor crystal obtained in Example 3 is a trigonal crystal Na 2 SiF 6 containing Mn. The lattice constants of the trigonal Na 2 SiF 6 crystal are a = about 8.859Å and c = about 5.038Å.

FIG. 20 shows a light absorption spectrum of the phosphor Na 2 SiF 6 : Mn according to the present invention. As is clear from this figure, absorption band peaks are clearly observed in blue (about 460 nm) and ultraviolet (about 350 nm), and it is understood that these contribute to red emission as excitation levels. The

For the Na 2 SiF 6 : Mn obtained in Example 3, the temperature dependence of the emission spectrum was measured in order to investigate the emission characteristics of the phosphor in more detail. Measurements were performed between 20 and 300 K (−253 to 27 ° C.). FIG. 21 shows the measurement results at three temperatures (20K, 200K, and 300K). Since the half-value width of the emission spectrum is insensitive to temperature, it can be seen that the phosphor emits light without being affected by the temperature of the host crystal. Such a phosphor that emits light stably over a wide temperature range is a very important property for its application.

Since it is very important to know the wavelength of the excitation light for causing the strongest light emission in the application of the phosphor, the Na 2 SiF 6 : Mn fluorescence is the same as the case of the K 2 SiF 6 : Mn phosphor in FIG. For the body, the relationship of the emission intensity to the excitation wavelength was determined. The result is shown in FIG. In addition, the broken line in FIG. 22 represents the emission intensity with respect to the excitation wavelength, and the thick solid line represents the emission spectrum. As is clear from this figure, the red light emission indicated by the thick solid line has the maximum light emission intensity at an excitation wavelength of about 460 nm. It can be seen that it is optimal as a red phosphor for blue (about 460 nm) excited white light emitting diodes.

FIG. 23 is a plot of the integrated emission intensity of the red phosphor Na 2 SiF 6 : Mn against temperature. As the temperature increases, the red light emission intensity gradually increases. Most luminescent materials usually have a luminescence intensity that decreases with increasing temperature, which is one of the unique features of the phosphor of the present invention.

<Example 4>
An experiment was performed in the same manner as in Example 1 except that the same oxidizing agent NaMnO 4 as in Example 3 was used and Ge grain crystals were used as immersion crystals. However, as the solution, a solution obtained by adding 24 g of NaMnO 4 to a 100 cc 50% HF solution was used.

<Evaluation 4>
FIG. 24 shows an electron micrograph of the red phosphor produced in Example 4. It can be seen that the red phosphor produced in this example has a particle size of 20 microns or less.

  FIG. 25 shows the results of composition analysis using an electron probe microanalyzer. From the result of the composition analysis, it is concluded that the phosphor is a compound containing Na, Ge, F and Mn as main components.

Next, X-ray diffraction measurement of this phosphor crystal was performed. The result is shown in FIG. As is apparent from this figure, the peak of X-ray diffraction coincides with the calculated peak of trigonal Na 2 GeF 6 . Therefore, it is concluded that the phosphor crystal obtained in Example 4 is a trigonal crystal Na 2 GeF 6 containing Mn. The lattice constants of the trigonal Na 2 GeF 6 crystal are a = about 9.058 Å and c = about 5.109 Å, which are slightly larger than the lattice constant of the trigonal Na 2 SiF 6 crystal phosphor of Example 3.

The temperature dependence of the Na 2 GeF 6 : Mn phosphor obtained in Example 4 was measured. FIG. 27 shows the measurement results at three temperatures of 20K, 200K, and 300K. Similar to K 2 SiF 6 in Example 1 and Na 2 SiF 6 in Example 3, the half-value width of the optical spectrum is insensitive to temperature, so that this phosphor is affected by the temperature of the host crystal. It can be seen that there is no light emission.

FIG. 28 is a plot of the integrated emission intensity of the red phosphor Na 2 GeF 6 : Mn against temperature. As the temperature increases, the red light emission intensity gradually increases. This is one of the unique features of the phosphor according to the present invention.

<Example 5>
A phosphor was produced in the same manner as in Example 1 except that Zr was used as the immersion crystal. The phosphor produced by this method was confirmed to be K 2 ZrF 6 doped with Mn by X-ray diffraction measurement.

<Evaluation 5>
FIG. 29 is an emission spectrum at room temperature of the K 2 ZrF 6 : Mn phosphor. Red light emission having a peak in the vicinity of 630 nm of the wavelength is observed.

<Example 6>
A phosphor was produced in the same manner as in Example 3 except that Sn was used as the immersion crystal. However, as the solution, a solution having a composition ratio of 50% HF solution 100 cc: H 2 O 100 cc: NaMnO 4 10 g was used. The phosphor produced by this method was confirmed to be K 2 SnF 6 doped with Mn by X-ray diffraction measurement.

<Evaluation 6>
FIG. 30 is an emission spectrum at room temperature of the Na 2 SnF 6 : Mn phosphor. Red light emission having a peak in the vicinity of 630 nm of the wavelength is observed.

<Example 7>
A phosphor was produced in the same manner as in Example 3 except that Ti was used as the immersion crystal. The phosphor produced by this method was confirmed to be Na 2 TiF 6 doped with Mn by X-ray diffraction measurement.

<Evaluation 7>
FIG. 31 is an emission spectrum at room temperature of the Na 2 TiF 6 : Mn phosphor. Red light emission having a peak in the vicinity of 630 nm of the wavelength is observed.

<Example 8>
CsMnO 4 was used instead of KMnO 4 or NaMnO 4 in order to confirm that not only KMnO 4 and NaMnO 4 but also other oxidizing agents are useful as the oxidizing agent in the method for producing a phosphor according to the present invention. Otherwise, the experiment was performed in the same manner as in Example 1. However, the solution used here is a mixing ratio of 50% HF solution 100 cc: H 2 O 100 cc: CsMnO 4 2 g.

<Evaluation 8>
FIG. 32 is an emission spectrum at room temperature of the phosphor prepared in Example 8. Red light emission having a peak in the vicinity of 630 nm of the wavelength is observed.

<Example 9>
First, the phosphor powder obtained in Example 1 was prepared, and this phosphor powder was immersed in nitric acid and lightly stirred. Next, the phosphor powder was taken out from nitric acid, subsequently immersed in methanol, taken out and dried. By going through the above treatment, the phosphor powder which was darkened became a beautiful light yellow.

This is presumably because MnO 2 existing as a by-product in the phosphor powder was dissolved and removed in nitric acid and ethanol by immersing the produced phosphor powder in nitric acid and ethanol, respectively.

<Evaluation 9>
FIG. 33 is a diagram comparing the emission spectrum of the phosphor powder purified in Example 9 and the emission spectrum of the unpurified phosphor powder of Example 5.

  As is apparent from FIG. 33, it can be seen that the emission intensity of the phosphor is greatly increased and the spectrum is sharpened by purification using nitric acid and ethanol.

  In Example 9, nitric acid was used as the type of acid, but hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and the like were tested in addition to nitric acid, and similar effects were obtained. In addition to these acids, the same effect can be obtained by washing with an organic solvent such as methanol, ethanol or acetone. Furthermore, the effectiveness of purification has been confirmed even when a mixed solution of an acid and an organic solvent is used.

<Example 10>
When the phosphor is sealed in a resin material, for example, a sulfide phosphor such as (Ca, Sr) S: Eu, which is currently well known as a red phosphor for white light emitting diodes, decomposes in the air. The phosphor may be deteriorated only by generating toxic hydrogen sulfide or dispersing it in the resin.

Therefore, a sample was prepared by dispersing and sealing the K 2 SiF 6 : Mn phosphor obtained in Example 1 in an epoxy resin, and the sample was allowed to stand for one month, and the change with time was examined.

  FIG. 34 is an optical photograph of a sample after one month that has been excited by an ultraviolet laser to emit red light. As is clear from FIG. 34, the ultraviolet laser irradiated portion is shown in white in the photograph, but it is actually red. Further, since the phosphor sealed with the resin emits red light, not only the entire sealed sample but also the surroundings were illuminated in red. It has been confirmed that the intensity of light emission is as large as that immediately after sealing even after one month of sealing to the resin.

<Example 11>
A so-called quartz glass powder having 100% SiO 2 was prepared as an oxide material, and this material was pretreated and washed. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes.

On the other hand, KMnO 4 was dissolved in pure water at 20 ° C., this aqueous KMnO 4 solution was mixed with an aqueous HF solution at 20 ° C., and then the mixed liquid was allowed to stand at room temperature to prepare a mixed solution. The composition of the prepared mixed solution is 50% HF: H 2 O: KMnO 4 = 100 cc: 100 cc: 6 g.

  Next, as shown in FIG. 5A, the quartz glass powder was immersed for 48 hours in a mixed solution prepared in a room temperature environment. By soaking for the above time, a crystalline powder was obtained from the quartz glass powder soaked in the liquid as shown in FIG.

  In this example, the powder material was used as the oxide material, but it was confirmed that a crystalline powder was obtained in the same manner even when a rod-shaped material as shown in FIG. 6 was used. In addition, the rod shape is particularly suitable when a glassy (amorphous) oxide material is used. When a crystalline oxide material such as quartz crystal is used, it is more realistic to use a powder shape. there were.

  FIG. 35 shows an optical photograph of the produced crystal powder. The reason why the crystalline powder is shown in red in the optical photograph shown in FIG. 35 is that the phosphor was irradiated with ultraviolet light to emit red light, and it was confirmed that the phosphor acted as a phosphor.

FIG. 36 shows an electron micrograph of the produced crystal powder. As shown in FIG. 36, it can be seen that the particle size of the crystalline powder is on the order of about ten microns. From the analysis by an electron probe / microanalyzer, it was confirmed that the crystalline powder was K 2 SiF 6 : Mn doped with Mn.

<Evaluation 10>
FIG. 37 (a) is an emission spectrum of K 2 SiF 6 : Mn obtained in Example 11 at room temperature. As is clear from FIG. 37A, red light emission having a peak in the vicinity of a wavelength of 630 nm is observed.

  For the application of phosphors, it is very important to know the excitation light wavelength, the so-called excitation spectrum, for causing the strongest emission. FIG. 37 (b) shows the excitation spectrum of this red phosphor. As is apparent from FIG. 37 (b), it can be seen that red is emitted most strongly by excitation of blue light having a wavelength of about 460 nm.

  The characteristics confirmed from FIG. 37 (b) are required for the realization of a three-wavelength type true white light-emitting diode that replaces the pseudo white light-emitting diode composed of the current blue light-emitting diode and yellow phosphor. This is a very favorable characteristic that is completely consistent with the characteristics of the red phosphor.

<Example 12>
Borosilicate glass powder was prepared as an oxide material, and this material was pretreated and washed. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes. Borosilicate glass is generally called hard glass, and is a glass mainly composed of SiO 2 and B 2 O 3 and containing a small amount of Al 2 O 3 and the like. In this example, a borosilicate glass powder obtained by pulverizing a cover glass for chemical experiments in a mortar was used.

On the other hand, KMnO 4 was dissolved in pure water at 20 ° C., this aqueous KMnO 4 solution was mixed with an aqueous HF solution at 20 ° C., and then the mixed liquid was allowed to stand at room temperature to prepare a mixed solution. The composition of the prepared mixed solution is 50% HF: H 2 O: KMnO 4 = 100 cc: 100 cc: 6 g.

  Next, as shown to Fig.5 (a), the borosilicate glass powder was immersed in the liquid mixture prepared in room temperature environment for 48 hours. By soaking for the above time, a crystalline powder was obtained from the borosilicate glass powder soaked in the liquid as shown in FIG.

FIG. 38 shows an electron micrograph of the produced crystal powder. As shown in FIG. 38, it can be seen that the particle size of the crystalline powder is on the order of about ten microns. Moreover, it was confirmed from the analysis by an electron probe microanalyzer that this crystalline powder is K 2 SiF 6 : Mn.

Further, it was examined by X-ray diffraction measurement that the produced crystal powder was K 2 SiF 6 : Mn. FIG. 39 shows the result. As is clear from FIG. 39, the peak of X-ray diffraction are in good agreement with theoretical data cubic K 2 SiF 6, a chemical reaction generating material is concluded that K 2 SiF 6. This K 2 SiF 6 has a cubic crystal structure and a lattice constant of about 8.14 Å.

<Evaluation 11>
FIG. 40A is an emission spectrum of K 2 SiF 6 : Mn obtained in Example 12 at room temperature. As is apparent from FIG. 40A, red light emission having a peak in the vicinity of a wavelength of 630 nm is observed.

  FIG. 40B is an excitation spectrum of this red phosphor. As is apparent from FIG. 40 (b), as in the case of the phosphor using the quartz glass of Example 11 shown in FIG. 37 (b) as a material, red light is excited by excitation of blue light having a wavelength of about 460 nm. It can be seen that the light is emitted most intensely.

FIG. 41 is a plot of the integrated emission intensity of this red phosphor with respect to temperature. In FIG. 41, I PL (T) is the emission intensity at the absolute temperature T, and I PL (0) is the emission intensity at the temperature of 0K. As is apparent from FIG. 41, it can be seen that the red light emission intensity gradually increases as the temperature increases.

In addition to borosilicate glass as an oxide material, an oxide mixture mainly composed of barium borosilicate glass, SiO 2 , BaO, and B 2 O, is the same as the case where borosilicate glass is used. I'm getting results.

<Example 13>
Soda glass powder was prepared as an oxide material, and this material was pretreated and washed. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes. The soda glass is a commonly used glass such as a slide glass and a window glass, and main raw materials are SiO 2 , soda ash (Na 2 O 3 ), and calcium carbonate (CaCO 3 ). In this example, a soda glass powder obtained by grinding a slide glass with a mortar was used.

On the other hand, KMnO 4 was dissolved in pure water at 20 ° C., this aqueous KMnO 4 solution was mixed with an aqueous HF solution at 20 ° C., and then the mixed liquid was allowed to stand at room temperature to prepare a mixed solution. The composition of the prepared mixed solution is 50% HF: H 2 O: KMnO 4 = 100 cc: 100 cc: 6 g.

  Next, as shown in FIG. 5 (a), soda glass powder was immersed in a mixed solution prepared in a room temperature environment for 48 hours. By soaking for the above-mentioned time, as shown in FIG. 5B, a powder of a crystal was obtained from the soda glass powder immersed in the liquid.

FIG. 42 shows an electron micrograph of the produced crystal powder. As shown in FIG. 42, it can be seen that the particle size of the crystalline powder is on the order of 10 microns. From the analysis by an electron probe / microanalyzer, it was confirmed that the crystalline powder was K 2 SiF 6 : Mn doped with Mn.

<Evaluation 12>
FIG. 43A is an emission spectrum of K 2 SiF 6 : Mn obtained in Example 13 at room temperature. As is clear from FIG. 43A, red light emission having a peak in the vicinity of a wavelength of 630 nm is observed.

  FIG. 43B is an excitation spectrum of this red phosphor. As is clear from FIG. 43 (b), the phosphor using the quartz glass of Example 11 shown in FIG. 37 (b) as the material and the borosilicate glass of Example 12 shown in FIG. 40 (b) as the material. As in the case of the used phosphor, it can be seen that red is emitted most strongly by excitation of blue light having a wavelength of about 460 nm.

<Example 14>
Silica stone (silica sand) was prepared as an oxide material. Silica is a rock that has silicic acid (SiO 2 ) as its main component and is also called quartz schist, and is rolling everywhere on the ground.

On the other hand, KMnO 4 was dissolved in pure water at 20 ° C., this aqueous KMnO 4 solution was mixed with an aqueous HF solution at 20 ° C., and then the mixed liquid was allowed to stand at room temperature to prepare a mixed solution. The composition of the prepared mixed solution is 50% HF: H 2 O: KMnO 4 = 100 cc: 100 cc: 6 g.

  Next, as shown in FIG. 5 (a), silica sand was immersed in a mixed solution prepared in a room temperature environment for 48 hours. By soaking for the above time, a crystalline powder was obtained from the silica sand soaked in the liquid as shown in FIG.

FIG. 44 shows an electron micrograph of the produced crystal powder. As shown in FIG. 44, it can be seen that the average particle size of the crystalline powder is 10 microns or less. Moreover, it was confirmed from analysis by an electron probe / microanalyzer that the main component of the crystal powder is K 2 SiF 6 : Mn.

Further, it was examined by X-ray diffraction measurement that the produced crystal powder was K 2 SiF 6 : Mn. FIG. 45 shows the result. As is clear from FIG. 45, the peak of the X-ray diffraction agrees well with the theoretical data of cubic K 2 SiF 6 , and in the same manner as the phosphor using the borosilicate glass as the material in Example 12 described above, It was concluded that the chemical reaction product was K 2 SiF 6 .

<Evaluation 13>
FIG. 46A shows an emission spectrum of K 2 SiF 6 : Mn obtained in Example 14 at room temperature. As is clear from FIG. 46A, red light emission having a peak in the vicinity of a wavelength of 630 nm is observed.

  FIG. 46B shows an excitation spectrum of this red phosphor. As is apparent from FIG. 46 (b), a phosphor using the quartz glass of Example 11 shown in FIG. 37 (b) as a material and a borosilicate glass of Example 12 shown in FIG. 40 (b) as a material. In the case of the phosphor used, as in the case of the phosphor using the soda glass of Example 13 shown in FIG. 43 (b) as a material, red light is emitted most strongly by excitation of blue light having a wavelength of about 460 nm. I know that.

FIG. 47 is a plot of the integrated emission intensity of this red phosphor with respect to temperature. In FIG. 47, I PL (T) is the emission intensity at the absolute temperature T, and I PL (0) is the emission intensity at the temperature of 0K. As is apparent from FIG. 47, it can be seen that the red light emission intensity gradually increases as the temperature increases.

<Example 15>
A soda glass powder was prepared as an oxide material in the same manner as in Example 13, and this material was pretreated and washed. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes.

On the other hand, NaMnO 4 was used instead of KMnO 4 used as the oxidizing agent in Examples 11 to 14, NaMnO 4 was dissolved in 20 ° C. pure water, and this NaMnO 4 aqueous solution was mixed with 20 ° C. HF aqueous solution. The mixed liquid was prepared by leaving the liquid mixed for about 1 hour at room temperature. The composition of the prepared mixed solution is 50% HF: H 2 O: NaMnO 4 = 100 cc: 100 cc: 6 g.

  Next, as shown in FIG. 5 (a), soda glass powder was immersed in a mixed solution prepared in a room temperature environment for 48 hours. By soaking for the above-mentioned time, as shown in FIG. 5B, a powder of a crystal was obtained from the soda glass powder immersed in the liquid.

<Evaluation 14>
FIG. 48 is an emission spectrum at room temperature of the crystal powder obtained in Example 15. As is clear from FIG. 48, red light emission having a peak in the vicinity of a wavelength of 630 nm is observed as in the case of the red phosphor produced using KMnO 4 as the oxidizing agent. From the X-ray diffraction measurement, it was found that the chemical reaction product here was Na 2 SiF 6 : Mn.

<Example 16>
GeO 2 powder was prepared as an oxide material, and this material was subjected to pretreatment cleaning. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes.

On the other hand, in the same manner as in Example 15, using NaMnO 4 as oxidizing agent, and dissolved in pure water NaMnO 4 to 20 ° C., mixing the NaMnO 4 aqueous HF solution of 20 ° C., followed by mixing for about 1 hour A liquid mixture was prepared by allowing the liquid to stand at room temperature. The composition of the prepared mixed solution is 50% HF: H 2 O: NaMnO 4 = 100 cc: 100 cc: 6 g.

Next, as shown in FIG. 5 (a), GeO 2 powder was immersed in a mixed solution prepared in a room temperature environment for 48 hours. By soaking for the above time, a crystalline powder was obtained from the GeO 2 powder soaked in the liquid as shown in FIG.

<Evaluation 15>
FIG. 49 is an emission spectrum at room temperature of the crystal powder obtained in Example 16. As is apparent from FIG. 49, light emission specific to the red phosphor having a peak in the vicinity of a wavelength of 630 nm is observed. From the X-ray diffraction measurement, the chemical reaction product was found to be Na 2 GeF 6 : Mn.

<Example 17>
SnO powder was prepared as an oxide material, and this material was pretreated and washed. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes.

On the other hand, KMnO 4 was dissolved in pure water at 20 ° C., this aqueous KMnO 4 solution was mixed with an aqueous HF solution at 20 ° C., and then the mixed liquid was allowed to stand at room temperature to prepare a mixed solution. The composition of the prepared mixed solution is 50% HF: H 2 O: KMnO 4 = 100 cc: 100 cc: 6 g.

  Next, as shown to Fig.5 (a), SnO powder was immersed in the liquid mixture prepared in room temperature environment for 48 hours. By soaking for the above time, a crystalline powder was obtained from the SnO powder soaked in the solution as shown in FIG.

<Evaluation 16>
FIG. 50 is an emission spectrum of the crystalline powder obtained in Example 17 at room temperature. As is clear from FIG. 50, emission specific to the red phosphor having a peak in the vicinity of a wavelength of 630 nm is observed. From the X-ray diffraction measurement, the chemical reaction product was found to be K 2 SnF 6 : Mn.

<Example 18>
TiO 2 powder was prepared as an oxide material, and this material was pretreated and washed. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes.

On the other hand, KMnO 4 was dissolved in pure water at 20 ° C., this aqueous KMnO 4 solution was mixed with an aqueous HF solution at 20 ° C., and then the mixed liquid was allowed to stand at room temperature to prepare a mixed solution. The composition of the prepared mixed solution is 50% HF: H 2 O: KMnO 4 = 100 cc: 100 cc: 6 g.

Next, as shown in FIG. 5A, TiO 2 powder was immersed in a mixed solution prepared under a room temperature environment for 48 hours. By soaking for the above time, a crystalline powder was obtained from the TiO 2 powder soaked in the liquid as shown in FIG.

<Evaluation 17>
FIG. 51 is an emission spectrum of the crystalline powder obtained in Example 18 at room temperature. As is clear from FIG. 51, light emission specific to the red phosphor having a peak in the vicinity of a wavelength of 630 nm is observed. From the X-ray diffraction measurement, the chemical reaction product was found to be K 2 TiF 6 : Mn.

<Example 19>
TiO 2 powder was prepared as an oxide material in the same manner as in Example 18, and this material was subjected to pretreatment cleaning. Specifically, degreasing was performed in which trichlorethylene was first washed for 10 minutes, then acetone was washed for 10 minutes, and then methanol was washed for 10 minutes.

On the other hand, CsMnO 4 was used instead of KMnO 4 used as the oxidizing agent in Examples 11 to 14, CsMnO 4 was dissolved in pure water at 20 ° C., this CsMnO 4 aqueous solution was mixed with 20 ° C. HF aqueous solution, and then The mixed liquid was prepared by leaving the liquid mixed for about 1 hour at room temperature. The composition of the prepared mixed solution is 50% HF: H 2 O: CsMnO 4 = 100 cc: 100 cc: 4 g.

Next, as shown in FIG. 5A, TiO 2 powder was immersed in a mixed solution prepared under a room temperature environment for 48 hours. By soaking for the above time, a crystalline powder was obtained from the TiO 2 powder soaked in the liquid as shown in FIG.

<Evaluation 18>
FIG. 52 is an emission spectrum of the crystalline powder obtained in Example 19 at room temperature. As is clear from FIG. 52, light emission specific to the red phosphor having a peak in the vicinity of a wavelength of 630 nm is observed. From the X-ray diffraction measurement, the chemical reaction product was found to be Cs 2 TiF 6 : Mn.

<Example 20>
First, the phosphor powder obtained in Example 15 was prepared, and this phosphor powder was immersed in hydrochloric acid and lightly stirred. Next, the phosphor powder was taken out from hydrochloric acid, subsequently immersed in acetone, taken out and dried. By going through the above treatment, the phosphor powder which was darkened became a beautiful light yellow.

This is presumably because MnO 2 present as a by-product in the phosphor powder was dissolved and removed in hydrochloric acid and acetone by immersing the produced phosphor powder in hydrochloric acid and acetone, respectively.

<Evaluation 19>
53 is a diagram comparing the emission spectrum of the phosphor powder purified in Example 20 and the emission spectrum of the unpurified phosphor powder of Example 15. FIG.

  As is apparent from FIG. 53, it can be seen that the emission intensity of the phosphor is greatly increased and the spectrum is sharpened by purification using hydrochloric acid and acetone.

<Example 21>
When the phosphor is sealed in a resin material, for example, a sulfide phosphor such as (Ca, Sr) S: Eu, which is currently well known as a red phosphor for white light emitting diodes, decomposes in the air. The phosphor may be deteriorated only by generating toxic hydrogen sulfide or dispersing it in the resin.

Therefore, a sample was prepared by dispersing and sealing the K 2 SiF 6 : Mn phosphor obtained in Example 11 in an epoxy resin, and the sample was allowed to stand for one month, and its change with time was examined.

  FIG. 54 is an optical photograph of a sample one month after the red light was emitted by excitation with an ultraviolet laser. As is clear from FIG. 54, the ultraviolet laser irradiated portion appears white in the photograph, but actually shines red. Further, since the phosphor sealed with the resin emits red light, not only the entire sealed sample but also the surroundings were illuminated in red. It has been confirmed that the intensity of light emission is as large as that immediately after sealing even after one month of sealing to the resin.

Phosphor obtained by the method of the present onset bright as applications other than three band type white light emitting diode, fluorescent display tube and a high color rendering lamp, X-rays, dosimeters (scintillator), PDP, backlight fluorescent LCD It can be applied to a wide range of applications such as body, inorganic EL panel, solid laser material.

Claims (7)

  1. A mixed solution prepared by adding oxidant AMnO 4 (where A is K, Na, Rb or Cs) to an aqueous HF solution was added to a B-containing material (where B was Si, Ge, Sn, Ti, or Zr). A 2 BF 6 (where A is K, Na, Rb or Cs, and B is Si, Ge, Sn, Ti, or Zr) on the surface layer of the material. A method for producing a phosphor, comprising: producing a phosphor comprising a crystal having a structure in which Mn is substituted as an activator on a part of a host crystal represented.
  2. The material of the B-containing material is immersed in the mixed solution, a crystalline or amorphous, their shape is plate-like, rod-like, the manufacturing method of the porous or powdery in which claim 1 phosphor according.
  3. Manufacturing method of the phosphor according to claim 1, wherein the concentration of AMNO 4 in the mixed solution is in the range of 0.01 to 1 mole relative to HF aqueous solution to prepare.
  4. To a mixed solution prepared by adding an oxidizing agent AMnO 4 (where A is K, Na, Rb or Cs) to an HF aqueous solution, B is an oxide material (where B is Si, Ge, Sn, Ti or Zr). ) Is reacted with the B-containing oxide material, and A 2 BF 6 (where A is K, Na, Rb or Cs, B is Si, Ge, Sn, Ti or Zr) A phosphor comprising a crystal having a structure in which Mn is substituted as an activator on a part of a host crystal represented by (2) is generated.
  5. 5. The phosphor according to claim 4 , wherein the material of the B-containing oxide material immersed in the mixed solution is crystalline or amorphous, and the shape thereof is plate, rod, porous, or powder. Method.
  6. Manufacturing method of the phosphor according to claim 4 wherein the concentration of AMNO 4 in the mixed solution is in the range of 0.01 to 2 mol with respect to HF aqueous solution to prepare.
  7. A phosphor is produced by the method according to any one of claims 1 to 6 , and then the produced phosphor powder is purified by immersing it in an organic solvent, an acidic solution or a mixed solution of an acidic solution and an organic solvent. phosphor purification method, characterized in that to.
JP2010505622A 2008-03-25 2009-03-23 Method for manufacturing phosphor Active JP5545665B2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2008076929 2008-03-25
JP2008076929 2008-03-25
JP2008267596 2008-10-16
JP2008267596 2008-10-16
JP2010505622A JP5545665B2 (en) 2008-03-25 2009-03-23 Method for manufacturing phosphor
PCT/JP2009/055622 WO2009119486A1 (en) 2008-03-25 2009-03-23 Fluorescent material, process for producing the same, and white-light-emitting diode employing the fluorescent material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010505622A JP5545665B2 (en) 2008-03-25 2009-03-23 Method for manufacturing phosphor

Publications (2)

Publication Number Publication Date
JPWO2009119486A1 JPWO2009119486A1 (en) 2011-07-21
JP5545665B2 true JP5545665B2 (en) 2014-07-09

Family

ID=41113679

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2010505622A Active JP5545665B2 (en) 2008-03-25 2009-03-23 Method for manufacturing phosphor

Country Status (2)

Country Link
JP (1) JP5545665B2 (en)
WO (1) WO2009119486A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016053178A (en) * 2011-03-23 2016-04-14 ゼネラル・エレクトリック・カンパニイ Color stable manganese-doped phosphors
US10000695B2 (en) 2014-12-26 2018-06-19 Samsung Electronics Co., Ltd. Method of manufacturing fluoride phosphor, white light emitting apparatus, display apparatus, and lighting device
US10301541B2 (en) 2015-07-06 2019-05-28 Samsung Electronics Co., Ltd. Fluoride phosphor, method of manufacturing the same, and light emitting device

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101559603B1 (en) 2008-02-07 2015-10-12 미쓰비시 가가꾸 가부시키가이샤 Semiconductor light emitting device, backlighting device, color image display device and phosphor used for those devices
JP5682104B2 (en) * 2008-09-05 2015-03-11 三菱化学株式会社 Phosphor and method for producing the same, phosphor-containing composition and light emitting device using the phosphor, and image display device and lighting device using the light emitting device
JP5446432B2 (en) * 2009-04-28 2014-03-19 三菱化学株式会社 Phosphor, phosphor-containing composition and light emitting device using the phosphor, and image display device and illumination device using the light emitting device
US20120161170A1 (en) * 2010-12-27 2012-06-28 GE Lighting Solutions, LLC Generation of radiation conducive to plant growth using a combination of leds and phosphors
MY167700A (en) 2011-04-08 2018-09-21 Shinetsu Chemical Co Preparation of complex fluoride and complex fluoride phosphor
EP2663611B1 (en) * 2011-12-16 2014-07-23 Koninklijke Philips N.V. Mn-activated hexafluorosilicates for led applications
JP2014177511A (en) * 2013-03-13 2014-09-25 Toshiba Corp Fluophor, its manufacturing method, and light emitting device using the fluophor
US9698314B2 (en) 2013-03-15 2017-07-04 General Electric Company Color stable red-emitting phosphors
US9580648B2 (en) 2013-03-15 2017-02-28 General Electric Company Color stable red-emitting phosphors
JP2014177586A (en) * 2013-03-15 2014-09-25 Toshiba Corp Fluorescent substance, method of producing the same and light-emitting device using the same
US10230022B2 (en) 2014-03-13 2019-03-12 General Electric Company Lighting apparatus including color stable red emitting phosphors and quantum dots
US9399732B2 (en) 2013-08-22 2016-07-26 General Electric Company Processes for preparing color stable manganese-doped phosphors
US10208943B2 (en) * 2013-10-28 2019-02-19 GE Lighting Solutions, LLC Lamps for enhanced optical brightening and color preference
JP2015074684A (en) * 2013-10-07 2015-04-20 株式会社東海理化電機製作所 Method of manufacturing fluorescent thin film
CN103540314B (en) * 2013-10-10 2015-01-14 上海师范大学 Low-temperature synthesized fluorosilicate nanorod red fluorescent powder and preparation method thereof
JP6287311B2 (en) * 2013-12-06 2018-03-07 日亜化学工業株式会社 Fluoride phosphor and method for producing the same
JP6342146B2 (en) * 2013-12-09 2018-06-13 株式会社東芝 Phosphor, method for producing the same, and light emitting device using the phosphor
TWI633171B (en) 2013-12-13 2018-08-21 奇異電器公司 Processes for preparing color stable manganese-doped complex fluoride phosphors
WO2015093430A1 (en) * 2013-12-17 2015-06-25 電気化学工業株式会社 Method for producing fluorescent substance
JP6327125B2 (en) * 2014-01-30 2018-05-23 信越化学工業株式会社 Hexafluoromanganese (IV) acid salt and double fluoride phosphor and method for producing them
US9546318B2 (en) * 2014-05-01 2017-01-17 General Electric Company Process for preparing red-emitting phosphors
US9512356B2 (en) * 2014-05-01 2016-12-06 General Electric Company Process for preparing red-emitting phosphors
US9376615B2 (en) 2014-06-12 2016-06-28 General Electric Company Color stable red-emitting phosphors
US9567516B2 (en) 2014-06-12 2017-02-14 General Electric Company Red-emitting phosphors and associated devices
US9371481B2 (en) * 2014-06-12 2016-06-21 General Electric Company Color stable red-emitting phosphors
US9385282B2 (en) 2014-06-12 2016-07-05 General Electric Company Color stable red-emitting phosphors
US9929319B2 (en) 2014-06-13 2018-03-27 General Electric Company LED package with red-emitting phosphors
US10047286B2 (en) 2014-10-27 2018-08-14 General Electric Company Color stable red-emitting phosphors
US9982190B2 (en) 2015-02-20 2018-05-29 General Electric Company Color stable red-emitting phosphors
KR20180063132A (en) 2015-09-30 2018-06-11 덴카 주식회사 Fluoride fluorescent substance, light emitting device and method for producing fluoride fluorescent substance
JP2017095677A (en) * 2015-11-17 2017-06-01 株式会社東芝 Fluophor, manufacturing method therefor, light emitting device using the fluophor
WO2017104406A1 (en) 2015-12-18 2017-06-22 三菱化学株式会社 Fluorescent body, light emitting device, illuminating apparatus, and image displaying apparatus
TWI575058B (en) 2016-01-06 2017-03-21 隆達電子股份有限公司 Phosphors, fabricating method thereof, method of regulating the crystal phase thereof and method of producing phase transition thereof
JP6486990B2 (en) * 2017-05-19 2019-03-20 株式会社東芝 Phosphor, method for producing the same, and light emitting device using the phosphor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576756A (en) * 1968-06-12 1971-04-27 Mallinckrodt Chemical Works Fluocomplexes of titanium, silicon, tin and germanium, activated by tetravalent manganese
WO2007100824A2 (en) * 2006-02-28 2007-09-07 Lumination, Llc Red line emitting phosphors for use in led applications

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576756A (en) * 1968-06-12 1971-04-27 Mallinckrodt Chemical Works Fluocomplexes of titanium, silicon, tin and germanium, activated by tetravalent manganese
WO2007100824A2 (en) * 2006-02-28 2007-09-07 Lumination, Llc Red line emitting phosphors for use in led applications

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JPN6009029209; J.Electrochem.Soc.;SOLID-STATE SCIENCE AND TECHNOLOGY 120(7), 942-947 *
JPN6009029210; J.Electrochem.Soc. 155(12), 20081013, E183-E188 *
JPN6009029211; JOURNAL OF APPLIED PHYSICS 104, 20080718, 023512-1〜023512-3 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016053178A (en) * 2011-03-23 2016-04-14 ゼネラル・エレクトリック・カンパニイ Color stable manganese-doped phosphors
US10000695B2 (en) 2014-12-26 2018-06-19 Samsung Electronics Co., Ltd. Method of manufacturing fluoride phosphor, white light emitting apparatus, display apparatus, and lighting device
US10301541B2 (en) 2015-07-06 2019-05-28 Samsung Electronics Co., Ltd. Fluoride phosphor, method of manufacturing the same, and light emitting device

Also Published As

Publication number Publication date
JPWO2009119486A1 (en) 2011-07-21
WO2009119486A1 (en) 2009-10-01

Similar Documents

Publication Publication Date Title
Zhu et al. Highly efficient non-rare-earth red emitting phosphor for warm white light-emitting diodes
Du et al. Near-ultraviolet light induced visible emissions in Er3+-activated La2MoO6 nanoparticles for solid-state lighting and non-contact thermometry
Singh et al. Role of Li+ ion in the luminescence enhancement of lanthanide ions: favorable modifications in host matrices
Khanna et al. Narrow spectral emission CaMoO4: Eu3+, Dy3+, Tb3+ phosphor crystals for white light emitting diodes
Zhang et al. Recent progress in quantum cutting phosphors
JP2014148677A (en) NANO-YAG:Ce PHOSPHOR COMPOSITIONS AND METHODS OF PREPARATION THEREOF
Saha et al. Charge compensation assisted enhanced photoluminescence derived from Li-codoped MgAl 2 O 4: Eu 3+ nanophosphors for solid state lighting applications
JP5549001B2 (en) Phosphor and production method thereof
Su et al. Synthesis and optimum luminescence of CaWO4-based red phosphors with codoping of Eu3+ and Na+
Peng et al. Synthesis of SrAl2O4: Eu, Dy phosphor nanometer powders by sol–gel processes and its optical properties
Qiu et al. Combustion synthesis of long-persistent luminescent MAl2O4: Eu2+, R3+ (M= Sr, Ba, Ca, R= Dy, Nd and La) nanoparticles and luminescence mechanism research
Singh et al. Luminescence study on Eu3+ doped Y2O3 nanoparticles: particle size, concentration and core–shell formation effects
Parchur et al. Luminescence properties of Tb 3+-doped CaMoO 4 nanoparticles: annealing effect, polar medium dispersible, polymer film and core–shell formation
JP5503288B2 (en) Aluminum silicate orange-red phosphor mixed with divalent and trivalent cations
Gao et al. Fabrication and luminescence properties of Dy3+ doped CaMoO4 powders
Gao et al. Enhanced photoluminescence from mixed-valence Eu-doped nanocrystalline silicate glass ceramics
Lou et al. Cathodoluminescence of CaWO4 and SrWO4 thin films prepared by spray pyrolysis
Shi et al. Solution combustion synthesis, photoluminescence and X-ray luminescence of Eu-doped nanoceria CeO 2: Eu
Zhang et al. Tunable photoluminescence and energy transfer of YBO 3: Tb 3+, Eu 3+ for white light emitting diodes
KR101037616B1 (en) Phosphor, process for producing the same, lighting fixture and image display unit
US6096243A (en) Method for producing a divalent europium-activated phosphor
Wang et al. Phase transition, size control and color tuning of NaREF 4: Yb 3+, Er 3+(RE= Y, Lu) nanocrystals
Han et al. New full-color-emitting phosphor, Eu 2+-doped Na 2− x Al 2− x Si x O 4 (0≤ x≤ 1), obtained using phase transitions for solid-state white lighting
Luo et al. Synthesis of high efficient Ca2SiO4: Eu2+ green emitting phosphor by a liquid phase precursor method
EP0871900B1 (en) Glass matrix doped with activated luminescent nanocrystalline particles

Legal Events

Date Code Title Description
A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20120319

A621 Written request for application examination

Effective date: 20120319

Free format text: JAPANESE INTERMEDIATE CODE: A621

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20131210

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20140204

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20140415

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20140507

R150 Certificate of patent or registration of utility model

Ref document number: 5545665

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250