WO2012118310A2 - Substance fluorescente et procédé pour la préparer - Google Patents

Substance fluorescente et procédé pour la préparer Download PDF

Info

Publication number
WO2012118310A2
WO2012118310A2 PCT/KR2012/001459 KR2012001459W WO2012118310A2 WO 2012118310 A2 WO2012118310 A2 WO 2012118310A2 KR 2012001459 W KR2012001459 W KR 2012001459W WO 2012118310 A2 WO2012118310 A2 WO 2012118310A2
Authority
WO
WIPO (PCT)
Prior art keywords
phosphor
compound
heat treatment
limited
nitride
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.)
Ceased
Application number
PCT/KR2012/001459
Other languages
English (en)
Korean (ko)
Other versions
WO2012118310A3 (fr
Inventor
윤대호
조덕수
김봉성
송영현
타카키마사키
정은준
송석현
강봉균
김명오
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sungkyunkwan University
Original Assignee
Sungkyunkwan University
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
Application filed by Sungkyunkwan University filed Critical Sungkyunkwan University
Publication of WO2012118310A2 publication Critical patent/WO2012118310A2/fr
Publication of WO2012118310A3 publication Critical patent/WO2012118310A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals

Definitions

  • the present application relates to an oxyhalide-based phosphor, a nitride-based or oxynitride-based phosphor, and a method for producing each thereof.
  • nitride-based or oxynitride-based phosphors have been produced by firing metal or oxide-based phosphors under a nitrogen atmosphere, but the high cost of the metals and the stability of the oxide-based phosphors have been a problem.
  • a method of nitriding carbonization by mixing carbon into an oxide-based phosphor by using a carbon thermal splitting method (CRN method; Cabothermal Reaction-Nitridation method) has been attempted, but the method is limited to materials having similar carbon and ion radius. It is pointed out that the problem can be applied and adversely affects the light emission of the phosphor, and improvement is needed.
  • the phosphor containing the rare earth metal has a feature that its emission and intensity vary depending on the valence of the rare earth metal.
  • Eu 3+ exhibits sharp light emission in a narrow region through the internal potential difference of 7 D 0 ⁇ 7 F energy potential difference
  • Eu 2+ exhibits light emission in a wide region due to the difference of 5d ⁇ 4f energy potential.
  • the valence of the rare earth metal can be adjusted through oxidation or reduction.
  • the method of calcination in an atmosphere in which oxygen is excluded and hydrogen is used, but the method has a low degree of reduction and thus the emission intensity of the phosphor obtained as a result is high. There was a problem that it is not uniform.
  • the obtained phosphors may be light emitting diodes (LEDs), plasma display panels (PDPs), or electric fields. It can be used in various fields such as field emission display (FED), and cold cathode fluorescent lamp (CCFL).
  • LEDs light emitting diodes
  • PDPs plasma display panels
  • FED field emission display
  • CCFL cold cathode fluorescent lamp
  • Korean Patent No. 10-1053884 discloses that a phosphor may be usefully used in a PDP.
  • a composition for forming a phosphor layer, a plasma display panel, and a method of manufacturing the plasma display panel are disclosed.
  • the present inventors have completed the present application by discovering that when the phosphor is produced according to the method of the present application, a phosphor having stable luminescence and a uniform luminescence intensity can be produced by an easy and economical method.
  • the present application is to provide an oxyhalide-based phosphor, a nitride or oxynitride-based phosphor, and their respective production methods.
  • a first aspect of the present application provides a solution comprising a first metal halide, a second metal halide, and an oxide precursor of a tricycle element selected from the group consisting of Al, Si, P, and combinations thereof. It provides a method for producing an oxyhalide-based phosphor, comprising the step of, and heat treatment after the addition of a reducing agent to the solution.
  • a second aspect of the present application is an oxyhalide-based phosphor prepared by the method according to the first aspect of the present application, wherein the oxyhalide-based phosphor has a composition of M 1 -M 2 -OX: M 3 , wherein M 1 is an alkali.
  • M 1 is an alkali.
  • M 2 is a tricyclic element selected from the group consisting of Al, Si, P, and combinations thereof,
  • X is a halogen element
  • M 3 is a rare earth metal
  • a third aspect of the present application provides a solution comprising a first metal halide, a second metal halide, and an oxide precursor of a tricycle element selected from the group consisting of Al, Si, P, and combinations thereof. It provides a method of producing a nitride-based or oxynitride-based phosphor, including the step, and the step of adding a reducing agent to the solution and heat treatment in a nitrogen-containing atmosphere.
  • a fourth aspect of the present application is a nitride-based or oxynitride-based phosphor prepared by the method according to the third aspect of the present application, wherein the nitride-based or oxynitride-based phosphor is M 1 -M 2 -NX: M 3 or M 1 -M 2 -ONX: has a composition of M 3 , wherein M 1 is an alkali metal, alkaline earth metal, or transition metal, and M 2 is 3 cycles selected from the group consisting of Al, Si, P, and combinations thereof Is an element, X is a halogen element, and M 3 is a rare earth metal, and provides a nitride or oxynitride-based phosphor.
  • a phosphor having stable luminescence and uniform luminescence intensity can be produced by an easy and economical method.
  • the oxyhalide-based phosphor when the oxyhalide-based phosphor is manufactured by using a liquid phase method rather than the conventional solid-phase method according to the present application, the oxyhalide-based phosphor is obtained in the form of a single phosphor uniformly distributed evenly without aggregation, and excellent light emission efficiency By having a round shape, it can be used for a variety of purposes such as white LED or CCFL.
  • the oxyhalide-based fluorescent substance is manufactured according to the present application, since it can be manufactured in a short time, there is an advantage that the productivity and economy are also excellent.
  • nitride or oxynitride-based fluorescent material when manufacturing a nitride or oxynitride-based fluorescent material according to the present application, by using a large ion size of the halogen atoms when firing the precursor in a nitrogen atmosphere, various metals such as alkali metal, alkaline earth metal, transition metal, rare earth metal Nitriding of ions can be easily implemented.
  • a reducing gas to remove residual oxygen and nitriding relatively difficult to form chloride-based phosphors such as SiO 2 (s) as a result, nitride-based or oxynitride-based phosphors can be easily and economically produced. .
  • the phosphor containing the rare earth metal is characterized in that the light emission and the intensity of the rare earth metal is different depending on the electron value, the treatment of the alkaline compound according to the present application by controlling the electron value of the rare earth metal, the light emission is It is possible to easily and economically produce a phosphor having stable and uniform luminous intensity.
  • FIG. 1 is a schematic diagram showing a process of forming an oxyhalide-based, or nitride-based or oxynitride-based phosphor according to the present application.
  • Example 2 is an SEM photograph of the phosphor powder prepared according to Example 1 of the present application.
  • Example 3 is an XRD analysis result of the phosphor powder prepared according to Example 1 of the present application.
  • Example 5 is a SEM-EDS analysis result of the phosphor powder prepared according to Example 1 of the present application.
  • 6A and 6B are PL analysis results of the phosphor powder prepared according to Example 1 of the present application.
  • Example 7 is a PL analysis result of the phosphor powder prepared according to Example 2 of the present application.
  • Example 8 is an X-ray pattern analysis result of the phosphor powder prepared according to Example 2 of the present application.
  • Example 10 is an X-ray pattern analysis result of the phosphor powder prepared according to Example 3 of the present application.
  • Example 11 is an X-ray pattern analysis of the phosphor powder prepared according to Example 4 of the present application.
  • 13A to 13D are FE-SEM photographs of phosphor powders prepared according to Example 4 of the present application.
  • Example 15 is a PL analysis result of the phosphor powder prepared according to Example 5 of the present application.
  • 16 is a schematic diagram of a nitriding process of the phosphor powder according to Example 6 of the present application.
  • 17 is a PL analysis result of the phosphor powder prepared according to Example 6 of the present application.
  • Example 19 is a PL analysis result of the phosphor powder prepared according to Example 8 of the present application.
  • Example 20 is an XRD analysis result of the phosphor powder prepared according to Example 8 of the present application.
  • 21A and 22B are SEM photographs of the phosphor powder prepared according to Example 9 of the present application.
  • Example 22 is a PL analysis result of the phosphor powder prepared according to Example 9 of the present application.
  • Example 23 is an XRD analysis result of the phosphor powder prepared according to Example 10 of the present application.
  • Example 24 is a PL analysis result of the phosphor powder prepared according to Example 10 of the present application.
  • Example 25 is an XRD analysis result of the phosphor powder prepared according to Example 11 of the present application.
  • 26 is a PL analysis result of the phosphor powder prepared according to Example 11 of the present application.
  • Example 30 is a PL analysis result of the phosphor powder prepared according to Example 13 of the present application.
  • the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.
  • a first aspect of the present application provides a solution comprising a first metal halide, a second metal halide, and an oxide precursor of a tricycle element selected from the group consisting of Al, Si, P, and combinations thereof. It provides a method for producing an oxyhalide-based phosphor, comprising the step of, and heat treatment after the addition of a reducing agent to the solution.
  • the oxyhalide-based phosphor is prepared by dissolving a first metal halide and a second metal halide in a solvent to form an aqueous solution, and adding a liquid silica precursor thereto to form a uniform mixed solution through liquid stirring. Obtained by impregnating the mixed solution into a polymeric material which is a reducing agent, to obtain an impregnated material, and heat treating the impregnated material to obtain an impurity-free phosphor powder, and pulverizing the phosphor powder to finally increase the surface area and uniformity. It may be prepared in the form of a phosphor having a composition, but is not limited thereto.
  • the oxyhalide-based fluorescent substance after adding SiO 2 sol as a liquid precursor to a solution containing a rare earth metal and metal chlorides to obtain a uniform mixed solution through liquid stirring, the mixed solution Impregnated to obtain an impregnated material by impregnating a polymer material such as cellulose, which is a reducing agent, and drying the impregnated product to obtain a form of xerogel or xerosol, and finally heat treating the xerogel or xerosol. It may be prepared in the form of a phosphor, but is not limited thereto.
  • the first metal halide includes a halide selected from the group consisting of alkali metal halides, alkaline earth metal halides, transition metal halides, and combinations thereof.
  • the second metal halide may include, but is not limited to, a rare earth metal halide.
  • a metal chloride having an ion radius of about 0.92 GPa to about 1.4 GPa may be used as the first metal halide to facilitate replacement with a rare earth metal material, but is not limited thereto.
  • the first metal halide has an ion radius of from about 0.92 kPa to about 1.0 kPa, from about 0.92 kPa to about 1.2 kPa, from about 0.92 kPa to about 1.4 kPa, from about 1.0 kPa to about 1.2 kPa, about 1.0 kPa About 1.4 kPa, or about 1.2 kPa to about 1.4 kPa, but is not limited thereto.
  • the alkali metal halide includes a chloride selected from the group consisting of LiCl, NaCl, KCl, and combinations thereof, and the alkaline earth metal halide is BeCl 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , and combinations thereof, may include chloride, but is not limited thereto.
  • the transition metal halide is ScCl 2 , TiCl 4 , VCl 4 , CrCl 3 , MnCl 3 , FeCl 3 , CoCl 2 , NiCl 2 , CuCl 2 , ZnCl 2 , YCl 3 , ZrCl 4 , NbCl 5 , MoCl 5 , and chlorides selected from the group consisting of combinations thereof, but is not limited thereto.
  • the rare earth metal halide is a chloride selected from the group consisting of LaCl 3 , CeCl 3 , NdCl 3 , EuCl 3 , GdCl 3 , TbCl 3 , DyCl 3 , ErCl 3 , YbCl 3 , and combinations thereof It may be to include, but is not limited thereto.
  • the oxide precursor of the tricycle element may include SiO 2 , Si (OH) 4 , SiH 4 , Si (OC 2 H 5 ) 4 , or a water-soluble silane, but is not limited thereto. It doesn't happen.
  • the oxide precursor of the tricycle element may include, but is not limited to, water soluble silicate (WSS) or SiO 2 sol having a particle size of about 5 nm to about 3000 nm. .
  • WSS water soluble silicate
  • SiO 2 sol having a particle size of about 5 nm to about 3000 nm.
  • the reducing agent is selected from the group consisting of corn starch, potato starch, cellulose powder, cellulose sheet, spherical cellulose, water soluble cellulose, pulp, crystallized cellulose, amorphous cellulose, rayon, and combinations thereof It may be to include a high molecular material, but is not limited thereto. For example, it may be desirable to use a high purity pulp having a purity of about 99.8% or more and having a fine matrix form, but is not limited thereto.
  • the heat treatment includes: a first heat treatment performed at about 150 ° C. to about 400 ° C., a second heat treatment performed at about 500 ° C. to about 1000 ° C., and about 700 ° C. to about 1400 ° C.
  • Tertiary heat treatment performed in may be to include that is performed sequentially, but is not limited thereto.
  • the step of heat treatment may include, but is not limited to, primary heat treatment at about 150 ° C to about 400 ° C.
  • the first heat treatment may be about 150 ° C. to about 200 ° C., about 150 ° C. to about 250 ° C., about 150 ° C. to about 300 ° C., about 150 ° C. to about 350 ° C., about 150 ° C.
  • to about 400 ° C. about 200 ° C to about 250 ° C, about 200 ° C to about 300 ° C, about 200 ° C to about 350 ° C, about 200 ° C to about 400 ° C, about 250 ° C to about 300 ° C, about 250 ° C to about 350 ° C, about 250 ° C To about 400 ° C, about 300 ° C to about 350 ° C, about 300 ° C to about 400 ° C, or about 350 ° C to about 400 ° C, but is not limited thereto.
  • the first heat treatment may decompose the polymer material used as a reducing agent such as cellulose, but is not limited thereto.
  • decomposition of the polymer material formed through the first heat treatment may include decomposition of a polymer ring, -OH group or -CH 2 O group in the polymer, and in addition to NO 3 of a metal halide.
  • the first heat treatment may be performed to decompose and remove the impurity ligand of, but is not limited thereto.
  • the primary heat treatment temperature is less than about 150 ° C., it may be difficult to decompose a polymer material used as a reducing agent such as cellulose, but is not limited thereto.
  • the primary heat treatment temperature is greater than about 400 ° C
  • the precursor of the phosphor is decomposed and oxidized to form an oxide such as an oxide silicate, which may affect the final resulting phosphor, but is not limited thereto.
  • the primary heat treatment may be performed without a separate grinding process, and when the grinding process is performed in parallel, it may be easy to obtain a uniform oxyhalide-based phosphor at a lower temperature, but is not limited thereto.
  • the heat treatment may include, but is not limited to, secondary heat treatment at about 500 ° C. to about 1000 ° C. after the first heat treatment.
  • the secondary heat treatment may be about 500 ° C. to about 600 ° C., about 500 ° C. to about 700 ° C., about 500 ° C. to about 800 ° C., about 500 ° C. to about 900 ° C., about 500 ° C.
  • the secondary heat treatment may be performed under an oxygen atmosphere to remove residual organic materials from the phosphor precursor powder in the solid state obtained through the first heat treatment and to crystallize the phosphor precursor powder, but is not limited thereto.
  • the temperature at which the second heat treatment is performed it is possible to easily remove the residual organic material and crystallize the phosphor precursor powder, but is not limited thereto.
  • the secondary heat treatment is performed at a temperature of less than about 500 ° C.
  • it is difficult to crystallize the amorphous precursor precursor powder and a long time heat treatment may be required, but is not limited thereto.
  • the secondary heat treatment is performed at a temperature of more than about 1000 ° C., some of the oxides may be oxidized according to the crystal stability of the phosphor precursor to form an oxide such as an oxidized silicate phosphor, but the present invention is not limited thereto.
  • LiCl, MgCl 2 , ScCl 3 , TiCl 4 , VCl 4 , CrCl 3 , MnCl 3 , FeCl 3 , CoCl as the first metal halide
  • a large ion between the metal ion and Cl ion of the first metal halide Due to the difference in radius ratio, it may be preferable to perform the secondary heat treatment for a long time of about 10 hours or more at a low temperature of about 500 ° C., but is not limited thereto.
  • the secondary heat treatment may be performed at a temperature of about 600 ° C. to about 800 ° C. for about 5 hours. It may be preferred, but is not limited thereto.
  • the heat treatment may include, but is not limited to, a third heat treatment at about 700 ° C. to about 1400 ° C. after the second heat treatment.
  • the third heat treatment may be about 700 ° C. to about 800 ° C., about 700 ° C. to about 900 ° C., about 700 ° C. to about 1000 ° C., about 700 ° C. to about 1100 ° C., about 700 ° C.
  • crystals of the phosphor precursor formed through the second heat treatment may be grown while reducing an activator such as a rare earth metal, but the present invention is not limited thereto.
  • an activator such as a rare earth metal
  • the present invention is not limited thereto.
  • the tertiary heat treatment is performed at a temperature of less than about 700 ° C., it is difficult to form a sufficient reducing atmosphere, and as a result, a decrease in luminance and emission intensity of the phosphor may be caused, but is not limited thereto.
  • the third heat treatment is performed at a temperature of more than about 1400 °C, as the phosphor powder becomes a sintered body may lose the properties of the powder, but is not limited thereto.
  • a light substance that is easy to dissolve and evaporates such as B
  • the organic material is removed by performing a long time at a low temperature of about 500 ° C. for about 10 hours or more, and the crystallization of SiO 2 is induced by performing the tertiary heat treatment for about 2 hours or more at about 700 ° C. in a reducing atmosphere without oxygen, Thereafter, a method of inducing growth of the phosphor crystal at about 900 ° C. may be selected, but is not limited thereto.
  • the second heat treatment is performed at a temperature of about 700 ° C. or more through a rapid temperature increase rate to crystallize SiO 2 . It is possible to take a method of obtaining a parent while inducing, but is not limited thereto.
  • an additional salt may be used in the method for preparing an oxyhalide-based phosphor according to the first aspect of the present application to easily control the amount of halogen in the phosphor, but is not limited thereto.
  • an additional salt may be used in the method for preparing an oxyhalide-based phosphor according to the first aspect of the present application to easily control the amount of halogen in the phosphor, but is not limited thereto.
  • different salts containing the same metal as the calcium chloride and containing oxygen for example
  • the addition of calcium nitrate salt can easily control the amount of chlorine in the phosphor produced, but is not limited thereto. Representing this example as a reaction scheme is as follows:
  • the reactants used in the reaction scheme 1 are all present in the liquid phase in the solvent, and a brief amount of the lubricant is omitted in order to simplify the reaction.
  • the calcium nitrate salt contains oxygen and thus can be easily oxidized, whereas the calcium chloride does not contain oxygen, so that the oxyhalide-based phosphor can be easily controlled through the reaction scheme, and the halogen in the phosphor The amount can be easily controlled, but is not limited thereto.
  • the method for preparing the oxyhalide-based phosphor may further include treating an alkaline compound to the oxyhalide-based phosphor prepared after the heat treatment, but is not limited thereto. .
  • the method of manufacturing the oxyhalide-based phosphor may further include treating an alkaline compound to the oxyhalide-based phosphor prepared for improving luminance of the phosphor after the heat treatment, but is not limited thereto. It is not.
  • the alkaline compound may include, but is not limited to, a compound including an -OH group or a -NH 2 group.
  • the alkaline compound is a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, NH 4 OH, H 2 O 2 , and combinations thereof, or propylamine (propylamine) ) -Based compound, butylamine-based compound, pentylamine-based compound, hexylamine-based compound, heptylamine-based compound, aminobenzene-based compound, metal amide compound, organic-based compound It may include, but is not limited to, a compound selected from the group consisting of alkaline compounds, and combinations thereof.
  • the metal amide compound may be a lithium amide compound, a sodium amide compound, a potassium amide compound, a cesium amide compound, and combinations thereof. It may be to include a compound selected from the group consisting of, but is not limited thereto.
  • the organic-based alkaline compound may include NH 4 OH, NH 2 NH 2 , C 6 H 5 NH 2 , or C 3 H 6 NH 2 , but is not limited thereto.
  • the alkaline compound may include a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, and combinations thereof, and a compound selected from the group consisting of combinations thereof.
  • the present invention is not limited thereto.
  • chlorine contained in the phosphor may be removed using a difference in reactivity through the ionic radius ratio between the chlorine contained in the phosphor and the alkaline compound, and the -OH group may be substituted in place of the place.
  • the electron value of the rare earth metal contained in the phosphor is increased, so that the function as an activator of the rare earth metal can be improved.
  • an alkaline compound containing Cs may be particularly preferable, because Cs is a soft metal and the chlorine and the ion radius ratio are similar, so that the reactivity with chlorine is good.
  • the reaction scheme of the oxidation reaction involving the alkaline compound is as follows:
  • the alkaline compound may be a propylamine compound, a butylamine compound, a pentylamine compound, a hexylamine compound, or a heptylamine compound.
  • Aminobenzene-based compound lithium amide-based compound, sodium amide-based compound, potassium amide-based compound, cesium amide-based compound, and combinations thereof It may be to include a compound selected from the group consisting of, but is not limited thereto.
  • the alkaline compound may be used in a strong reduction reaction to remove chlorine by reacting with a phosphor. As the carbon ring of the alkaline compound is more stable, the substitution reaction may occur more rapidly.
  • alkaline compounds an aminobenzene-based compound or a hydrazine-based compound may be preferable, but is not limited thereto.
  • alkaline compounds containing Li, Na, K, Rb, or Cs alkaline compounds containing Cs may be particularly preferred, since Cs is a soft metal and its chlorine and ion radius ratio are similar, which makes it highly reactive with chlorine.
  • the reaction schemes of the reduction reaction involving the alkaline compound are as follows:
  • the step of treating the alkaline compound may be performed at about -100 °C to about 1500 °C, but is not limited thereto.
  • the alkaline compound may be dissolved and reacted in a solvent, and the reaction may be performed at a melting point or higher of the alkaline compound itself, but is not limited thereto.
  • the treating of the alkaline compound may be performed at about -100 ° C to about 1500 ° C, but is not limited thereto.
  • treating the alkaline compound may comprise about -100 ° C to about 0 ° C, about -100 ° C to about 500 ° C, about -100 ° C to about 1000 ° C, about -100 ° C to about 1500 ° C, about 0 Is performed at from about 500 ° C. to about 500 ° C., from about 0 ° C. to about 1000 ° C., from about 0 ° C. to about 1500 ° C., from about 500 ° C. to about 1000 ° C., from about 500 ° C. to about 1500 ° C., or from about 1000 ° C. to about 1500 ° C. May be, but is not limited thereto.
  • the reaction may be difficult to perform due to its low reactivity, and at temperatures above about 1500 ° C., the alkaline compound may react with the matrix of the phosphor itself even after reacting with the chlorine of the phosphor.
  • the reaction may occur to synthesize a second phase, but is not limited thereto.
  • the phosphor obtained by treating the alkaline compound is washed with distilled water, alcohols, or nonpolar solvent to remove residual alkali metal chlorides, and then dried in a manner of drying at about 200 ° C. or lower. It may be, but is not limited thereto. For example, it may be preferable to remove the residual alkali metal chloride because it may react with the phosphor to affect the emission decrease, but is not limited thereto. Further, for example, the drying may be performed at a temperature of about 200 ° C. or less, about 180 ° C. or less, about 160 ° C. or less, about 140 ° C. or less, about 120 ° C. or less, or about 100 ° C.
  • the drying is performed at a temperature exceeding about 200 ° C.
  • the remaining alkali metal may react with the phosphor, causing a decrease in emission of the phosphor, but is not limited thereto.
  • the alkaline compound is used as a reducing agent, for drying the obtained phosphor, it may be preferable to use a vacuum oven or to dry using nitrogen or an inert gas, but is not limited thereto.
  • the amount of alkali metal chloride remaining may be adjusted or removed by adjusting the amount of the phosphor containing alkali metal and chloride, but is not limited thereto.
  • the phosphor as a precursor in the reduction schemes may be a material including an activator, but is not limited thereto.
  • all reactions in the reduction schemes may be performed under ultraviolet light, thereby improving reaction rate and reactivity, but are not limited thereto.
  • the reaction may be carried out in a very small amount on the surface of the phosphor particles, but may have a condition that can be reduced from Eu 3+ to Eu 2+ on the surface with respect to the amount of lubricant of the phosphor.
  • an alkaline solution material such as hydrazine may be synthesized by reducing the firing of the phosphor or reducing the phosphor, but the present invention is not limited thereto.
  • the side reaction product generated during the reaction may be removed or separated through centrifugation or gasification, but is not limited thereto.
  • the hydroxy group synthesis reaction may contribute to the improvement of the reaction, but is not limited thereto.
  • the time required for oxidation and reduction by further atomizing the phosphor powder and increasing the surface area It is possible to shorten or lower the synthesis temperature, but is not limited thereto.
  • a ball mill, a roller mill, a vibrating ball mill, an atorita mill, a planetary ball mill, a sand mill, a cutter mill Drying dispersers such as cutter mills, hammer mills, jet mills, ultrasonic dispersers, or grinding apparatuses such as high pressure homogenizers may be used, but are not limited thereto.
  • a second aspect of the present application is an oxyhalide-based phosphor prepared by the method according to the first aspect of the present application, wherein the oxyhalide-based phosphor has a composition of M 1 -M 2 -OX: M 3 , wherein M 1 is an alkali.
  • M 1 is an alkali.
  • M 2 is a tricyclic element selected from the group consisting of Al, Si, P, and combinations thereof,
  • X is a halogen element
  • M 3 is a rare earth metal
  • the composition of the oxyhalide-based phosphor according to the second aspect of the present application may also be represented by M 4 v ⁇ u Si w A x O y Cl z : M 5 u , wherein M 4 is an alkali metal or Chlorides of alkaline earth metals (eg, LiCl, NaCl, KCl, BeCl 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2, etc.), or chlorides of transition metals (eg, ScCl 3 , TiCl 4 , VCl 4) , CrCl 3 , MnCl 3 , FeCl 3 , CoCl 2 , NiCl 2 , CuCl 2 , ZnCl 2 , YCl 3 , ZrCl 4 , NbCl 5 , MoCl 5, etc .; A is B, Al, or P; M 5 is a chloride of a rare earth metal (eg
  • the basic composition of the oxyhalide-based phosphor according to the second aspect of the present application may also be represented as M-Si-AO-Cl (A: B, Al, or P), for example, M-Si-O -Cl, M-Si-BO-Cl, M-Si-Al-O-Cl, or M-Si-PO-Cl, wherein M may be a combination of at least two metals, but It is not limited.
  • M may be a combination of at least two metals selected from alkali metals, alkaline earth metals, transition metals, or rare earth metals, but is not limited thereto.
  • the oxyhalide-based phosphor may have ultra long afterglow phosphor characteristics, and may have a round particle shape and a particle size of about 50 nm to about 10 ⁇ m, but is not limited thereto.
  • the oxyhalide-based phosphor may be about 50 nm to about 100 nm, about 50 nm to about 500 nm, about 50 nm to about 1 ⁇ m, about 50 nm to about 10 ⁇ m, about 100 nm to about 500 nm , About 100 nm to about 1 ⁇ m, about 100 nm to about 10 ⁇ m, or about 1 ⁇ m to about 10 ⁇ m, but is not limited thereto.
  • the present application may include, for example, a display including the oxyhalide-based phosphor, but is not limited thereto.
  • the display may include a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), or a field emission display (FED), but is not limited thereto. It doesn't happen.
  • LED light emitting diode
  • PDP plasma display panel
  • FED field emission display
  • the present application may include, for example, a lamp including the oxyhalide-based phosphor, but is not limited thereto.
  • a third aspect of the present application provides a solution comprising a first metal halide, a second metal halide, and an oxide precursor of a tricycle element selected from the group consisting of Al, Si, P, and combinations thereof. It provides a method of producing a nitride-based or oxynitride-based phosphor, including the step, and the step of adding a reducing agent to the solution and heat treatment in a nitrogen-containing atmosphere.
  • the method for producing a nitride-based or oxynitride-based phosphor according to the third aspect of the present invention the step of heat treatment under a nitrogen-containing atmosphere in the middle of the method for producing an oxyhalide-based phosphor according to the first aspect of the present application, That is, by including the step of nitriding, by inducing a thermochemical reaction to replace the halogen element and nitrogen of the oxyhalide-based phosphor, the nitride-based or oxynitride-based phosphor may be easily and economically obtained, but is not limited thereto. no.
  • the nitride-based or oxynitride-based phosphor may be prepared by dissolving the first metal halide and the second metal halide in a solvent to form an aqueous solution, adding liquid silica precursor thereto, and then uniformly stirring the liquid.
  • a mixed solution is obtained, and the mixed solution is impregnated into a polymeric material which is a reducing agent to obtain an impregnation, and the impregnated phosphor powder is obtained by heat treatment of the impregnation, and finally the surface area increased by pulverizing the phosphor powder.
  • It may be prepared in the form of a phosphor having a uniform composition with, but is not limited thereto.
  • the nitride-based or oxynitride-based fluorescent material after adding SiO 2 sol as a liquid precursor to a solution containing a rare earth metal and metal chlorides to obtain a uniform mixed solution through liquid stirring,
  • the mixed solution is impregnated with a polymer material such as cellulose, which is a reducing agent, to obtain an impregnation.
  • the impregnation is dried to obtain a form of xerogel or xerosol, and finally, the heat treatment of the xerogel or xerosol is carried out.
  • It can be prepared in the form of a spherical phosphor, but is not limited thereto.
  • the first metal halide includes a halide selected from the group consisting of alkali metal halides, alkaline earth metal halides, transition metal halides, and combinations thereof.
  • the second metal halide may include, but is not limited to, a rare earth metal halide.
  • the metals contained in the first metal halide and the second metal halide are diversified. It is possible to facilitate the search for a new composition of the nitride-based or oxynitride-based fluorescent material prepared by, but is not limited thereto.
  • a metal chloride having an ion radius of about 0.92 GPa to about 1.4 GPa may be used as the first metal halide to facilitate replacement with a rare earth metal material, but is not limited thereto.
  • the first metal halide has an ion radius of from about 0.92 kPa to about 1.0 kPa, from about 0.92 kPa to about 1.2 kPa, from about 0.92 kPa to about 1.4 kPa, from about 1.0 kPa to about 1.2 kPa, about 1.0 kPa About 1.4 kPa, or about 1.2 kPa to about 1.4 kPa, but is not limited thereto.
  • the alkali metal halide includes a chloride selected from the group consisting of LiCl, NaCl, KCl, and combinations thereof, and the alkaline earth metal halide is BeCl 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , and combinations thereof, may include chloride, but is not limited thereto.
  • the transition metal halide is ScCl 2 , TiCl 4 , VCl 4 , CrCl 3 , MnCl 3 , FeCl 3 , CoCl 2 , NiCl 2 , CuCl 2 , ZnCl 2 , YCl 3 , ZrCl 4 , NbCl 5 , MoCl 5 , and chlorides selected from the group consisting of combinations thereof, but is not limited thereto.
  • the rare earth metal halide is a chloride selected from the group consisting of LaCl 3 , CeCl 3 , NdCl 3 , EuCl 3 , GdCl 3 , TbCl 3 , DyCl 3 , ErCl 3 , YbCl 3 , and combinations thereof It may be to include, but is not limited thereto.
  • the oxide precursor of the tricycle element may include SiO 2 , Si (OH) 4 , SiH 4 , Si (OC 2 H 5 ) 4 , or a water-soluble silane, but is not limited thereto. It doesn't happen.
  • the oxide precursor of the tricycle element may include, but is not limited to, water soluble silicate (WSS) or SiO 2 sol having a particle size of about 5 nm to about 3000 nm. .
  • WSS water soluble silicate
  • SiO 2 sol having a particle size of about 5 nm to about 3000 nm.
  • the reducing agent is selected from the group consisting of corn starch, potato starch, cellulose powder, cellulose sheet, spherical cellulose, water soluble cellulose, pulp, crystallized cellulose, amorphous cellulose, rayon, and combinations thereof It may be to include a high molecular material, but is not limited thereto. For example, it may be desirable to use a high purity pulp having a purity of about 99.8% or more and having a fine matrix form, but is not limited thereto.
  • the heat treatment includes: a first heat treatment performed at about 150 ° C. to about 400 ° C., a second heat treatment performed at about 500 ° C. to about 1000 ° C., and about 700 ° C. to about 1400 ° C.
  • Tertiary heat treatment performed in may be to include that is performed sequentially, but is not limited thereto.
  • the drying process may be performed at a temperature of about 50 ° C. to about 80 ° C. in a general drying oven or at a temperature of about 50 ° C. to about 150 ° C. in a vacuum oven, but is not limited thereto.
  • the secondary heat treatment may be omitted, and only the first heat treatment and the third heat treatment may be continuously performed, but the present invention is not limited thereto.
  • each of the primary, secondary, and tertiary heat treatments may be performed under a nitrogen atmosphere in which oxygen is excluded or under an inert gas atmosphere, but is not limited thereto.
  • the step of heat treatment may include, but is not limited to, primary heat treatment at about 150 ° C to about 400 ° C.
  • the first heat treatment may be about 150 ° C. to about 200 ° C., about 150 ° C. to about 250 ° C., about 150 ° C. to about 300 ° C., about 150 ° C. to about 350 ° C., about 150 ° C.
  • to about 400 ° C. about 200 ° C to about 250 ° C, about 200 ° C to about 300 ° C, about 200 ° C to about 350 ° C, about 200 ° C to about 400 ° C, about 250 ° C to about 300 ° C, about 250 ° C to about 350 ° C, about 250 ° C To about 400 ° C, about 300 ° C to about 350 ° C, about 300 ° C to about 400 ° C, or about 350 ° C to about 400 ° C, but is not limited thereto.
  • the first heat treatment may decompose the polymer material used as a reducing agent such as cellulose, but is not limited thereto.
  • the decomposition of the polymer material formed through the first heat treatment may include decomposition of the ring of the polymer, -OH group or -CH 2 O group in the polymer, in addition to NO 3 and the like of the metal halide
  • the first heat treatment may be performed to decompose and remove the impurity ligand of, but is not limited thereto.
  • the primary heat treatment temperature is less than about 150 ° C., it may be difficult to decompose a polymer material used as a reducing agent such as cellulose, but is not limited thereto.
  • the primary heat treatment temperature is greater than about 400 ° C
  • the precursor of the phosphor is decomposed and oxidized to form an oxide such as an oxide silicate, which may affect the final resulting phosphor, but is not limited thereto.
  • the primary heat treatment may be performed without a separate grinding process, and when the grinding process is performed in parallel, the surface area may be increased, so that it may be easy to obtain a uniform phosphor at a lower temperature, but is not limited thereto.
  • the heat treatment may include, but is not limited to, secondary heat treatment at about 500 ° C. to about 1000 ° C. after the first heat treatment.
  • the secondary heat treatment may be about 500 ° C. to about 600 ° C., about 500 ° C. to about 700 ° C., about 500 ° C. to about 800 ° C., about 500 ° C. to about 900 ° C., about 500 ° C.
  • the secondary heat treatment may be performed under an oxygen atmosphere to remove residual organic materials from the phosphor precursor powder in the solid state obtained through the first heat treatment and to crystallize the phosphor precursor powder, but is not limited thereto.
  • the temperature at which the second heat treatment is performed it is possible to easily remove the residual organic material and crystallize the phosphor precursor powder, but is not limited thereto.
  • the secondary heat treatment is performed at a temperature of less than about 500 ° C.
  • it is difficult to crystallize the amorphous precursor precursor powder and a long time heat treatment may be required, but is not limited thereto.
  • the secondary heat treatment is performed at a temperature of more than about 1000 ° C., some of the oxides may be oxidized according to the crystal stability of the phosphor precursor to form an oxide such as an oxidized silicate phosphor, but the present invention is not limited thereto.
  • the first metal halide LiCl, MgCl 2 , ScCl 3 , TiCl 4 , VCl 4 , CrCl 3 , MnCl 3 , FeCl
  • 3 , CoCl 2 , NiCl 2 , CuCl 2 , or ZnCl 2 and using the SiO 2 or SiO 2 + Al salt as the oxide precursor of the bicycle element between the metal and Cl ions of the first metal halide Due to the large difference in the ion radius ratio of, it may be preferable to perform the secondary heat treatment at a low temperature of about 500 ° C.
  • the secondary heat treatment may be performed at a temperature of about 600 ° C. to about 800 ° C. for about 5 hours. It may be preferred, but is not limited thereto.
  • the heat treatment may include, but is not limited to, a third heat treatment at about 700 ° C. to about 1400 ° C. after the second heat treatment.
  • the third heat treatment may be about 700 ° C. to about 800 ° C., about 700 ° C. to about 900 ° C., about 700 ° C. to about 1000 ° C., about 700 ° C. to about 1100 ° C., about 700 ° C.
  • crystals of the phosphor precursor formed through the second heat treatment may be grown while reducing an activator such as a rare earth metal, but the present invention is not limited thereto.
  • an activator such as a rare earth metal
  • the present invention is not limited thereto.
  • the tertiary heat treatment is performed at a temperature of less than about 700 ° C., it is difficult to form a sufficient reducing atmosphere, and as a result, a decrease in luminance and emission intensity of the phosphor may be caused, but is not limited thereto.
  • the third heat treatment is performed at a temperature of more than about 1400 °C, as the phosphor powder becomes a sintered body may lose the properties of the powder, but is not limited thereto.
  • the tertiary heat treatment may be performed in an atmosphere in which a nitrogen-containing gas flows at a speed of about 0.1 cm / s to about 10 cm / s, but is not limited thereto.
  • the tertiary heat treatment may comprise a nitrogen-containing gas from about 0.1 cm / s to about 1 cm / s, from about 0.1 cm / s to about 3 cm / s, from about 0.1 cm / s to about 5 cm / s, About 0.1 cm / s to about 7 cm / s, about 0.1 cm / s to about 10 cm / s, about 1 cm / s to about 3 cm / s, about 1 cm / s to about 5 cm / s, about 1 cm / s to about 7 cm / s, about 1 cm / s to about 10 cm / s, about 3 cm / s to about 5 cm / s, about 3 cm / s to about 5 cm / s,
  • the nitrogen-containing atmosphere may be formed by N 2 , NH 3 , or a combination thereof, but is not limited thereto.
  • the nitrogen-containing atmosphere may include one formed by N 2 , NH 3 , or a combination thereof, and may further include H 2 , or CH 3 , but is not limited thereto.
  • a light substance that is easy to dissolve and evaporates such as B
  • the secondary heat treatment is performed at a low temperature of about 500 ° C. for at least about 10 hours to remove organics
  • the third heat treatment is performed at about 700 ° C. for at least about 2 hours at a reduced atmosphere in which oxygen is excluded to crystallize SiO 2 .
  • Induction and may be selected to induce the growth of the phosphor crystal at about 900 °C, but is not limited thereto.
  • a nitride-based or oxynitride-based phosphor in the case of using a matrix of SiO 2 in combination with P as a parent of the phosphor, P having a high ionic bondability and high magnetism is Since Si is more likely to form MPO-Cl before forming a matrix with other metal salts, once the amorphous phase is obtained through primary heat treatment, the secondary heat treatment is carried out at a temperature of about 700 ° C. or higher through a rapid temperature increase rate to form SiO.
  • a method of obtaining a matrix while inducing crystallization of 2 may be selected, but is not limited thereto.
  • the part which is different from the manufacturing of the oxyhalide-based fluorescent material according to the first aspect of the present application may be referred to as a part for nitriding metal ions.
  • a part for nitriding metal ions For example, when chloride is used as the first metal halide and SiO 2 is used as the oxide precursor of the tricycle element, the difference in the ion radius ratio between Cl ( ⁇ 1.81 kV) and N (1.46 kV)
  • the nitriding can be achieved by inducing covalent bonds by substituting N for Cl instead of Cl, but the present invention is not limited thereto.
  • chloride As the first metal halide, but is not limited thereto.
  • nitriding may be induced by a relatively low temperature reaction, but is not limited thereto.
  • the ion radius size of the rare earth-based metal is about 0.92 kPa to It is preferable that the metal ion of the phosphor matrix also has a similar ion radius in that it is about 1.4 GHz, but is not limited thereto.
  • the method for producing a nitride or oxynitride-based phosphor according to the third aspect of the present application, the general carbon thermal decomposition method (CRN method; Cabothermal Reaction-Nitridation method) or gas reduction method (GRN method; Gas-Reduction-Nitridation )
  • CRN method General carbon thermal decomposition method
  • GNN method Gas reduction-Nitridation
  • high purity nitride-based phosphors are formed by mixing carbon with oxide-based phosphors and nitriding them through carbonization using the CRN method.
  • such a conventional method is applicable only to materials having similar carbon and ionic radii, such as SiO 2.
  • the present invention was intended to solve the above limitation.
  • Nitrile is advantageous in that it is easy to nitride due to the strong ionic bonding of chlorine, but on the other hand, oxidation may proceed before nitriding due to instability, and it is difficult to maintain chloride state due to the strong hydroxyl action during solution formation. There may be. In addition, there may also be a problem that the uniformity of the composition is lowered by being lost to the gas at a low or medium temperature of about 400 °C or less.
  • the CRN method or the GRN method is preferably combined with the method of the present application, and by inducing self oxidation using a nitrate-based material as a liquid material of the Al compound. It may be desirable to induce the solution of the problem, but is not limited thereto.
  • the rare earth metal which is a substance added in a small amount, is not shown for convenience of description.
  • a gas containing carbon such as methane gas
  • the efficiency of the reaction may be improved, but is not limited thereto.
  • Nitride-based or nitride-based phosphors may be prepared, and reaction schemes related thereto may be represented, for example, as follows, but are not limited thereto.
  • the reaction rate is lowered if the precursor materials are already crystallized before reacting with a gas containing a nitrogen atom, and thus the temperature at which crystallization becomes active is about 700 ° C. or less. It may be preferable to perform the second heat treatment at a temperature of, but is not limited thereto. In addition, since it is preferable to reach the third heat treatment temperature, which is a temperature at which the precursor crystallizes to the gas containing the nitrogen atom in a state where the crystallization is minimal, it may be advantageous to rapidly increase the temperature to the third heat treatment temperature. It is not.
  • the third heat treatment temperature is preferably about 1400 ° C. to about 1700 ° C. when the method of the present invention is combined with the CRN method, and about 1200 ° C. to about 1400 when the method of the present invention is combined with the GRN method. °C may be preferred, but is not limited thereto.
  • the flux of the gas containing a nitrogen atom in the above methods is a factor that must be considered for an efficient and safe nitriding reaction, when the method of the present invention and the CRN method in parallel, about 1 cm / s to about 2 cm / It is preferable to inject a gas containing the nitrogen atom at a flux of s, and when the method of the present application and the GRN method are used in combination, the nitrogen atom is removed at a flux of about 0.3 cm / s or less in consideration of the safety of NH 3 . It may be desirable to inject a gas containing, but is not limited thereto.
  • the method of manufacturing the nitride-based or oxynitride-based phosphor may further include treating an alkaline compound to the nitride-based or oxynitride-based phosphor prepared after the heat treatment.
  • the present invention is not limited thereto.
  • the method of manufacturing the nitride-based or oxynitride-based phosphor may further include treating an alkaline compound to the nitride-based or oxynitride-based phosphor prepared for improving the brightness of the phosphor after the heat treatment step.
  • an alkaline compound to the nitride-based or oxynitride-based phosphor prepared for improving the brightness of the phosphor after the heat treatment step.
  • the alkaline compound may include, but is not limited to, a compound including an -OH group or a -NH 2 group.
  • the alkaline compound is a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, NH 4 OH, H 2 O 2 , and combinations thereof, or propylamine (propylamine) ) -Based compound, butylamine-based compound, pentylamine-based compound, hexylamine-based compound, heptylamine-based compound, aminobenzene-based compound, metal amide compound, organic-based compound It may include, but is not limited to, a compound selected from the group consisting of alkaline compounds, and combinations thereof.
  • the metal amide compound may be a lithium amide compound, a sodium amide compound, a potassium amide compound, a cesium amide compound, and combinations thereof. It may be to include a compound selected from the group consisting of, but is not limited thereto.
  • the organic-based alkaline compound may include NH 4 OH, NH 2 NH 2 , C 6 H 5 NH 2 , or C 3 H 6 NH 2 , but is not limited thereto.
  • the alkaline compound may include a compound selected from the group consisting of LiOH, NaOH, KOH, RbOH, CsOH, and combinations thereof, and a compound selected from the group consisting of combinations thereof.
  • the present invention is not limited thereto.
  • chlorine contained in the phosphor may be removed using a difference in reactivity through the ionic radius ratio between the chlorine contained in the phosphor and the alkaline compound, and the -OH group may be substituted in place of the place.
  • the electron value of the rare earth metal contained in the phosphor is increased, so that the function as an activator of the rare earth metal can be improved.
  • an alkaline compound containing Cs may be particularly preferable, because Cs is a soft metal and the chlorine and the ion radius ratio are similar, so that the reactivity with chlorine is good.
  • the alkaline compound may be a propylamine compound, a butylamine compound, a pentylamine compound, a hexylamine compound, or a heptylamine compound.
  • Aminobenzene-based compound lithium amide-based compound, sodium amide-based compound, potassium amide-based compound, cesium amide-based compound, and combinations thereof It may be to include a compound selected from the group consisting of, but is not limited thereto.
  • the alkaline compound may be used in a strong reduction reaction to remove chlorine by reacting with a phosphor. As the carbon ring of the alkaline compound is more stable, the substitution reaction may occur more rapidly.
  • alkaline compounds an aminobenzene-based compound or a hydrazine-based compound may be preferable, but is not limited thereto.
  • alkaline compounds containing Li, Na, K, Rb, or Cs alkaline compounds containing Cs may be particularly preferred, since Cs is a soft metal and its chlorine and ion radius ratio are similar, which makes it highly reactive with chlorine. .
  • the step of treating the alkaline compound may be performed at about -100 °C to about 1500 °C, but is not limited thereto.
  • the alkaline compound may be dissolved and reacted in a solvent, and the reaction may be performed at a melting point or higher of the alkaline compound itself, but is not limited thereto.
  • the treating of the alkaline compound may be performed at about -100 ° C to about 1500 ° C, but is not limited thereto.
  • treating the alkaline compound may comprise about -100 ° C to about 0 ° C, about -100 ° C to about 500 ° C, about -100 ° C to about 1000 ° C, about -100 ° C to about 1500 ° C, about 0 Is performed at from about 500 ° C. to about 500 ° C., from about 0 ° C. to about 1000 ° C., from about 0 ° C. to about 1500 ° C., from about 500 ° C. to about 1000 ° C., from about 500 ° C. to about 1500 ° C., or from about 1000 ° C. to about 1500 ° C. May be, but is not limited thereto.
  • the reaction may be difficult to perform due to its low reactivity, and at temperatures above about 1500 ° C., the alkaline compound may react with the matrix of the phosphor itself even after reacting with the chlorine of the phosphor.
  • the reaction may occur to synthesize a second phase, but is not limited thereto.
  • the phosphor obtained by treating the alkaline compound is washed with distilled water, alcohols, or nonpolar solvent to remove residual alkali metal chlorides, and then dried in a manner of drying at about 200 ° C. or lower. It may be, but is not limited thereto. For example, it may be preferable to remove the residual alkali metal chloride because it may react with the phosphor to affect the emission decrease, but is not limited thereto. Further, for example, the drying may be performed at a temperature of about 200 ° C. or less, about 180 ° C. or less, about 160 ° C. or less, about 140 ° C. or less, about 120 ° C. or less, or about 100 ° C.
  • the drying is performed at a temperature exceeding about 200 ° C.
  • the remaining alkali metal may react with the phosphor, causing a decrease in emission of the phosphor, but is not limited thereto.
  • the alkaline compound is used as a reducing agent, for drying the obtained phosphor, it may be preferable to use a vacuum oven or to dry using nitrogen or an inert gas, but is not limited thereto.
  • the amount of alkali metal chloride remaining may be adjusted or removed by adjusting the amount of the phosphor containing alkali metal and chloride, but is not limited thereto.
  • the phosphor as a precursor in the reduction schemes may be a material including an activator, but is not limited thereto.
  • all reactions in the reduction schemes may be performed under ultraviolet light, thereby improving reaction rate and reactivity, but are not limited thereto.
  • the reaction may be carried out in a very small amount on the surface of the phosphor particles, but may have a condition that can be reduced from Eu 3+ to Eu 2+ on the surface with respect to the amount of lubricant of the phosphor.
  • an alkaline solution material such as hydrazine may be synthesized by reducing the firing of the phosphor or reducing the phosphor, but the present invention is not limited thereto.
  • the side reaction product generated during the reaction may be removed or separated through centrifugation or gasification, but is not limited thereto.
  • the hydroxy group synthesis reaction may contribute to the improvement of the reaction, but is not limited thereto.
  • the phosphor powder is further atomized and the surface area is increased to oxidize It may shorten the time required for reduction or lower the synthesis temperature, but is not limited thereto.
  • a ball mill, a roller mill, a vibrating ball mill, an atorita mill, a planetary ball mill, a sand mill, a cutter mill Drying dispersers such as cutter mills, hammer mills, jet mills, ultrasonic dispersers, or grinding apparatuses such as high pressure homogenizers may be used, but are not limited thereto.
  • a fourth aspect of the present application is a nitride-based or oxynitride-based phosphor prepared by the method according to the third aspect of the present application, wherein the nitride-based or oxynitride-based phosphor is M 1 -M 2 -NX: M 3 or M 1 -M 2 -ONX: has a composition of M 3 , wherein M 1 is an alkali metal, alkaline earth metal, or transition metal, and M 2 is 3 cycles selected from the group consisting of Al, Si, P, and combinations thereof Is an element, X is a halogen element, and M 3 is a rare earth metal, and provides a nitride or oxynitride-based phosphor.
  • the nitride-based or oxynitride-based phosphor may have ultra long afterglow phosphor characteristics, and may have a round particle shape and a particle size of about 50 nm to about 10 ⁇ m, but is not limited thereto.
  • the nitride-based or oxynitride-based phosphor may be about 50 nm to about 100 nm, about 50 nm to about 500 nm, about 50 nm to about 1 ⁇ m, about 50 nm to about 10 ⁇ m, about 100 nm to It may have a size of about 500 nm, about 100 nm to about 1 ⁇ m, about 100 nm to about 10 ⁇ m, or about 1 ⁇ m to about 10 ⁇ m, but is not limited thereto.
  • the present application may include, for example, a display including the nitride-based or oxynitride-based phosphor, but is not limited thereto.
  • the display may include a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), or a field emission display (FED), but is not limited thereto. It doesn't happen.
  • LED light emitting diode
  • PDP plasma display panel
  • FED field emission display
  • the present application may include, for example, a lamp including the nitride-based or oxynitride-based phosphor, but is not limited thereto.
  • Example 1 In Example 1, according to the method of the first aspect of the present application, 1.97 mol of CaCl 2 , 1 mol of Ca (NO 3 ) 2 , 1 mol of SiO 2 (Sol), and 0.03 mol of EuCl 3 , respectively, in deionized water After dissolution for about 10 to 20 minutes, a 20 wt% mixed solution was made through stirring. Ca 3 SiO 4 Cl 2 : Eu 2+ phosphor powder was weighed out to 5 g in the mixed solution. Thereafter, the cellulose powder was impregnated into the mixed solution with a ratio of 2: 1 of the mixed solution and cellulose powder. At this time, the mixture was stirred for 10 minutes using an ultrasonic apparatus for uniform stirring and impregnation. Thereafter, the impregnated precursor was placed in an 80 ° C. dryer, dried for 10 hours, and then calcined at 225 ° C. for 6 hours.
  • the calcined powder was pulverized into fine particles of FIG. 2 through a hand mill to increase the surface area, and the powder thus obtained was calcined at 700 ° C. for 2 hours in an atmosphere containing oxygen. Finally, the white powder thus obtained was calcined under a reducing atmosphere of N 2 / H 2 (95/5) in a tube furnace at 700 ° C. for 2 hours to obtain Ca 3 SiO 4 Cl 2 : Eu 2+ phosphor powder. It was.
  • the phosphor powders were analyzed by XRD, SEM, SEM-EDS, and PL, respectively, and are shown in FIGS. 3 to 6, respectively.
  • Example 2 according to the method of the first aspect of the present application, 1.97 mol of CaCl 2 , 1 mol of Ca (NO 3 ) 2 , 1 mol of WSS (Sol), and 0.03 mol of EuCl 3 , respectively, were dissolved in deionized water. After dissolving for 10 to 20 minutes, a 20 wt% mixed solution was made through stirring. Ca 3 SiO 4 Cl 2 : Eu 2+ phosphor powder was weighed out to 5 g in the mixed solution. Thereafter, the mixed solution was stirred at a ratio of 1: 3 with Starch (potato powder), and then stirred and impregnated for 10 minutes using an ultrasonic apparatus for uniform stirring. Thereafter, the impregnated precursor was placed in an 80 ° C. drier and then dried for 10 hours and calcined at 225 ° C. for 6 hours.
  • the impregnated precursor became bulky as it became xerogel during drying and primary calcination.
  • the powder obtained by heat treatment at 500 ° C. for 2 hours was increased to be easily oxidized through grinding, and further calcined in air at 700 ° C. for 1 hour. Thereafter, firing was performed at 700 ° C., 900 ° C., and 1000 ° C. for 3 hours for phosphor powder reduction.
  • the mixed solution was mixed with Starch (potato starch), dried at 100 ° C., calcined at 225 ° C., and then phosphors were obtained through oxidation at 700 ° C. and reduction at 700 ° C.
  • Starch potato starch
  • phosphors were obtained through oxidation at 700 ° C. and reduction at 700 ° C.
  • X-ray powder pattern analysis, PL analysis, and FE-SEM analysis results according to the Cl content of the obtained phosphor are shown in Figs. 11 to 13, respectively.
  • Example 6 was carried out in the same manner as in Scheme 5 in the present specification. Specifically, Ca 3 SiO 4 Cl 2 : 0.03Eu 2+ phosphor and NH 2 NH 2 solution was mixed in a molar ratio of 1: 4 and put in an aluminum crucible with a lid to achieve the same effect as FIG. 16. Thereafter, under a N 2 / H 2 (95/5) reducing atmosphere, reduction reaction was performed at 700 ° C. for 3 hours to obtain a phosphor powder, and the PL characteristics of the phosphor powder were analyzed and shown in FIG. 17.
  • Example 7 was carried out in the same manner as in Scheme 4 in the present specification. Specifically, NaNH 2 powder was added at a molar ratio of 1: 2 to Ca 3 SiO 4 Cl 2 : 0.03Eu 3+ phosphor and NH 2 NH 2 solution at high temperature, and then mixed evenly through a stirrer for 2 hours, followed by N 2 / H 2 (95/5) was reacted at a temperature of 400 ° C. under a reducing atmosphere. Thereafter, the obtained phosphor and the side reaction product were washed with H 2 O and dried. The result of PL analysis of the phosphor powder obtained by the above method is shown in FIG. 18.
  • Example 8 was carried out in the same manner as in Scheme 5 of the present specification. Specifically, the Ca 3 SiO 4 Cl 2 : 0.03Eu 3+ phosphor and the NH 2 NH 2 solution at high temperature were mixed in a molar ratio of 1: 4, and then placed in a glass vial and maintained for 5 hours while stirring the magnetic bar under ultraviolet light at 254 nm. I was. Subsequently, the phosphor powder was reduced into a vacuum oven at 100 ° C., and the PL characteristics and the XRD change of the phosphor powder were shown in FIGS. 19 and 20, respectively.
  • Example 9 was carried out in the same manner as in Scheme 5 in the present specification. Specifically, a nano-sized Na 1.49 Al 1.55 Si 0.45 O 4 : 0.06Eu 3+ phosphor containing 0.06 mol% and NH 2 NH 2 solution were mixed at a molar ratio of 1: 4, and then placed in an alumina crucible at a high temperature of 700 ° C. It was kept for 5 hours while heating to. SEM photographs and PL characterization results of the obtained phosphor powders are shown in FIGS. 21 and 22, respectively.
  • Example 10 was carried out in the same manner as in Scheme 15 of the present specification. Specifically, a mixed solution was obtained by dissolving 2.94 mol of CaCl 2 and 0.06 mol of EuCl 3 in deionized water, respectively, and stirring with 1 mol of SiO 2 (sol, 20 nm). Thereafter, the mixed solution was impregnated with 1 ⁇ m cellulose (C 6 H 10 O 5 ) in a ratio of 2: 1 and dried. The impregnated material was then heat treated at 225 ° C. and hand milled to increase the surface area. Thereafter, the obtained material was calcined in an oxidizing atmosphere at 700 ° C.
  • Example 11 was carried out in the same manner as in Scheme 14 in the present specification. Specifically, a mixed solution was obtained by dissolving 3 mol CaCl 2 and 0.06 mol EuCl 3 in deionized water, respectively, and stirring with 1 mol SiO 2 (sol, 20 nm). Thereafter, the mixed solution was impregnated with 1 ⁇ m cellulose (C 6 H 10 O 5 ) in a ratio of 2: 1 and dried. The impregnated material was then heat treated at 225 ° C. and hand milled to increase the surface area. Thereafter, the obtained material was calcined in an oxidizing atmosphere at 700 ° C.
  • Example 12 was carried out in the same manner as in Scheme 14 in the present specification. Specifically, a mixed solution was obtained by dissolving 2 mol of SrCl 2 and 0.06 mol of EuCl 3 in deionized water, respectively, and stirring with 1 mol of SiO 2 (sol, 20 nm). Thereafter, the mixed solution was impregnated with 1 ⁇ m cellulose (C 6 H 10 O 5 ) in a ratio of 2: 1 and dried. The impregnated material was then heat treated at 225 ° C. and hand milled to increase the surface area. Thereafter, the obtained material was calcined in an oxidizing atmosphere at 700 ° C.
  • Example 13 was carried out in the same manner as in Scheme 15 of the present specification. In particular, Example 13 was performed by preparing five kinds of mixed solutions having different compositions as follows: 1 0.92 mol CaCl 2 , 0.08 mol Eu (NO 3 ) 3 , and 1 mol Al (NO 3 ) 3 , respectively, in deionized water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une substance fluorescente à base d'oxyhalogénure, comprenant les étapes suivantes : obtention d'une solution contenant un premier halogénure de métal, un second halogénure de métal, et un précurseur d'oxyde d'un élément de la période 3 choisi dans le groupe comprenant Al, Si, P et leurs combinaisons ; et application d'un traitement à la chaleur après addition d'un agent réducteur à la solution.
PCT/KR2012/001459 2011-02-28 2012-02-27 Substance fluorescente et procédé pour la préparer Ceased WO2012118310A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20110017719 2011-02-28
KR20110017679 2011-02-28
KR10-2011-0017729 2011-02-28
KR10-2011-0017679 2011-02-28
KR20110017729 2011-02-28
KR10-2011-0017719 2011-02-28

Publications (2)

Publication Number Publication Date
WO2012118310A2 true WO2012118310A2 (fr) 2012-09-07
WO2012118310A3 WO2012118310A3 (fr) 2012-11-08

Family

ID=46758365

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/001459 Ceased WO2012118310A2 (fr) 2011-02-28 2012-02-27 Substance fluorescente et procédé pour la préparer

Country Status (1)

Country Link
WO (1) WO2012118310A2 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7713442B2 (en) * 2006-10-03 2010-05-11 Lightscape Materials, Inc. Metal silicate halide phosphors and LED lighting devices using the same
JPWO2009028657A1 (ja) * 2007-08-30 2010-12-02 日亜化学工業株式会社 発光装置
KR100979468B1 (ko) * 2007-10-10 2010-09-02 강준길 적색 형광체 및 이를 포함한 백색 발광 장치
JP2013500379A (ja) * 2009-07-28 2013-01-07 成均館大学校 産学協力団 酸窒化物系蛍光体粉末、窒化物系蛍光体粉末、及びこれらの製造方法
KR101098006B1 (ko) * 2009-09-29 2011-12-23 한국화학연구원 (할로)실리케이트계 형광체 및 이의 제조방법

Also Published As

Publication number Publication date
WO2012118310A3 (fr) 2012-11-08

Similar Documents

Publication Publication Date Title
WO2011014010A2 (fr) Poudre fluorescente d'oxynitrure, poudre fluorescente de nitrure et procédé de production associé
KR100984273B1 (ko) 질화물 형광체, 이의 제조방법 및 상기 형광체를 포함하는 발광 소자
WO2009048150A1 (fr) Phosphore de β-sialone pulvérulent et son procédé de production
CN102159665A (zh) 氮化物基荧光体的制备
Bernardo et al. Gehlenite: Eu3+ phosphors from a silicone resin and nano-sized fillers
CN102575158A (zh) β型赛隆荧光体的制造方法
WO2023282565A1 (fr) Procédé de réduction partielle de pentoxyde de vanadium à l'aide d'une solution ammoniacale, et poudre de dioxyde de vanadium ainsi préparée
TWI496873B (zh) Ｍ－ｃ－ｎ－ｏ系螢光體之製法
WO2012118310A2 (fr) Substance fluorescente et procédé pour la préparer
JP5502010B2 (ja) Ｂ−ｃ−ｎ−ｏ蛍光体の製造方法
WO2013058458A1 (fr) Procédé et appareil pour fabriquer une nanopoudre de verre à point de fusion bas
JP7693118B2 (ja) 熱伝導性フィラー、樹脂組成物、樹脂シートおよび六方晶窒化ホウ素粉末の製造方法
WO2012111929A2 (fr) Substance fluorescente et son procédé de fabrication
KR101052344B1 (ko) 염화마그네슘으로부터 고순도의 산화마그네슘 분말의 제조방법
CN101374929A (zh) 光致发光材料
KR101136744B1 (ko) 판상형 실리콘 산질화물계 형광체와 그의 제조방법
WO2024136621A1 (fr) Matériau émettant une lumière bleue ayant une structure de type pérovskite et présentant une excellente efficacité lumineuse, et son procédé de production
TW201819287A (zh) 氮化鋁製備方法
CN105969332A (zh) 一种氮化硼包覆M2Si5N8:Eu2+发光材料的合成方法
Petrykin et al. Synthesis of BaAl2S4: Eu phosphor using BaS: Eu precursor prepared by the polymerizable complex method
WO2012022041A1 (fr) Matériaux luminescents à base de borate, leurs procédés de préparation et leurs utilisations
CN121020995B (zh) 一种利用工业固体废弃物制备的无机纤维及其制备方法
WO2017052234A1 (fr) Phosphore rouge fluorure métallique et élément électroluminescent l'utilisant
CN113698927B (zh) 一种α型塞隆橙色荧光粉的制备方法
WO2024136378A1 (fr) Précurseur d'échange d'anions et procédé d'échange d'anions pour la préparation de nanoparticules de pérovskite

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12752131

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12752131

Country of ref document: EP

Kind code of ref document: A2