WO2011134173A1 - 一种硼酸盐基红色发光材料及其制备方法 - Google Patents

一种硼酸盐基红色发光材料及其制备方法 Download PDF

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WO2011134173A1
WO2011134173A1 PCT/CN2010/072391 CN2010072391W WO2011134173A1 WO 2011134173 A1 WO2011134173 A1 WO 2011134173A1 CN 2010072391 W CN2010072391 W CN 2010072391W WO 2011134173 A1 WO2011134173 A1 WO 2011134173A1
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borate
salt
luminescent material
based red
metal nanoparticle
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PCT/CN2010/072391
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English (en)
French (fr)
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周明杰
刘军
马文波
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海洋王照明科技股份有限公司
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Priority to US13/643,902 priority Critical patent/US20130099162A1/en
Priority to EP10850506.6A priority patent/EP2565254B1/en
Priority to JP2013506443A priority patent/JP5655135B2/ja
Priority to CN2010800649869A priority patent/CN102869749B/zh
Priority to PCT/CN2010/072391 priority patent/WO2011134173A1/zh
Publication of WO2011134173A1 publication Critical patent/WO2011134173A1/zh

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    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7797—Borates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention belongs to the technical field of luminescent materials, and in particular relates to a borate-based red luminescent material and a preparation method thereof.
  • the conventional high-temperature solid phase preparation (Y, Gd) BO 3 :Eu 3+ has a simple process and is advantageous for industrial production, but the reaction time is long, the mixing is uneven, and a ball milling is required for a certain period of time, not only the luminescent center is in the matrix.
  • the dispersion is uneven, affecting its luminous efficiency, and the prepared luminescent powder has a large particle size and a poor morphology.
  • impurities are easily introduced during the ball milling process and cause lattice defects.
  • the physical and chemical changes of the powder caused by the ball milling often lead to a decrease in the brightness of the phosphor, which is not conducive to its application.
  • a borate-based red light-emitting material having uniform particle size distribution, stable structure, high luminous intensity, and high luminous efficiency is provided.
  • the invention provides a preparation method of a borate-based red luminescent material which is simple in preparation process, equipment requirement, low pollution-free, reaction and material morphology, and easy to control particle size, and is suitable for industrial production.
  • a borate-based red luminescent material comprising a core and a shell encasing the core, the core being a metal nanoparticle, the outer shell being chemically represented as (Y 1-xy Eu x Gd y )BO 3
  • the value of x is 0 ⁇ x ⁇ 0.3
  • the value of y is 0 ⁇ y ⁇ 0.7.
  • a method for preparing a borate-based red luminescent material comprising the steps of:
  • the metal nanoparticle sol is added to the polyvinylpyrrolidone surface treatment agent for mixing and mixing for 8 to 24 hours, thereby preparing a metal nanoparticle mixed sol;
  • Y salt, Eu salt, Gd salt, and boric acid or/and borate in an excess of 1% to 50% by stoichiometric ratio according to the stoichiometric ratio of the corresponding element in the formula (Y 1-xy Eu x Gd y ) BO 3
  • the metal nanoparticle mixed sol is added, and the mixture is heated and stirred at 75 to 90 ° C to form a wet gel, and then dried to obtain a precursor; or according to the formula (Y 1-xy Eu x Gd y ) BO
  • the stoichiometric ratio of the corresponding element in 3 is mixed with Y salt, Eu salt, Gd salt, and boric acid in an excess of 1% to 50% of the stoichiometric ratio, and dissolved in the alcohol solution, and then the metal nanoparticle mixed sol and the combustion agent are added. And stirring, boiling and dehydrating, and then igniting and burning to obtain a precursor; wherein x is 0 ⁇ x ⁇ 0.3, and
  • the precursor is pre-fired, calcined, cooled and ground to obtain the borate-based red luminescent material.
  • the borate-based red luminescent material adopts metal nanoparticles as a core, and (Y 1-xy Eu x Gd y ) BO 3 as a shell to form a spherical or spherical shape.
  • the fluorescent material of the fine particles has Eu 3+ as the illuminating center, so that the luminescent material has high luminescence intensity, and the fluorescent material has uniform particle size distribution, stable structure and high luminous efficiency;
  • the borate-based red luminescent material adopts wet chemical method or It is prepared by the combustion coating method, which not only reduces the temperature of the synthesis reaction, but also improves the microstructure and macroscopic properties of the borate-based red luminescent material, and the obtained borate-based red luminescent material has uniform particle size distribution and effectively improves the particle size distribution.
  • the luminescence property of the material can also flexibly adjust the particle size of the borate-based red luminescent material by controlling the particle size of the metal nanoparticles and the thickness of the phosphor, and without introducing other impurities, the product quality is high, and at the same time, the boric acid
  • the preparation method of the salt-based red luminescent material can obtain the product only by temperature control and adding the reactants in an appropriate ratio. Therefore, the preparation method is simple. Single, low equipment requirements, no pollution, easy to control, suitable for industrial production.
  • Embodiments of the present invention provide a borate-based red luminescent material including a core and a shell covering the core, the core being a metal nanoparticle, and the outer shell is represented by a chemical formula (Y 1-xy Eu x Gd y ) BO 3 phosphor, x has a value of 0 ⁇ x ⁇ 0.3, and y has a value of 0 ⁇ y ⁇ 0.7.
  • the above borate-based red luminescent material structural formula can be expressed as: (Y 1-xy Eu x Gd y ) BO 3 @zM, where @ represents M as a core and (Y 1-xy Eu x Gd y ) BO 3 For the outer casing, (Y 1-xy Eu x Gd y ) BO 3 wraps M therein.
  • x is 0 ⁇ x ⁇ 0.3, x is preferably 0.005 ⁇ x ⁇ 0.20; y is 0 ⁇ y ⁇ 0.7, and y is preferably 0.01 ⁇ y ⁇ 0.5; z is M The molar ratio of (Y 1-xy Eu x Gd y )BO 3 , z is 0 ⁇ z ⁇ 1 ⁇ 10 -2 , and the value of z is preferably 1 ⁇ 10 -4 ⁇ y ⁇ 2 ⁇ 10 -3 ; M is a metal nanoparticle, and is preferably at least one of Ag, Au, Pt, and Pd nanoparticles.
  • the outer casing is coated on the surface of the core in a layered form, and the borate-based red luminescent material is a spherical or spheroidal particle structure.
  • the borate-based red luminescent material adopts a fluorescent material in which a metal nanoparticle is a core and (Y 1-xy Eu x Gd y ) BO 3 is a shell to form a spherical or spherical-like fine particle, so that the particle size distribution of the fluorescent material is uniform and the structure is Stable, luminous intensity and luminous efficiency are high.
  • the material has Eu 3+ as the illuminating center, which makes the luminescent material have high luminescence intensity, especially under the excitation of ultraviolet light with wavelengths of 147 and 172 nm, and has strong luminescence performance, which matches 147 nm or 172 nm generated by Xe gas radiation discharge. Suitable for use in plasma display panels and mercury-free fluorescent lamps.
  • an embodiment of the present invention provides a method for preparing the above borate-based red luminescent material, comprising the following steps:
  • the metal nanoparticle sol is added to the polyvinylpyrrolidone surface treatment agent for mixing and mixing for 8 to 24 hours, thereby preparing a metal nanoparticle mixed sol;
  • Y salt, Eu salt, Gd salt, and boric acid or/and borate in an excess of 1% to 50% by stoichiometric ratio according to the stoichiometric ratio of the corresponding element in the formula (Y 1-xy Eu x Gd y ) BO 3
  • the metal nanoparticle mixed sol is added, and the mixture is heated and stirred at 75 to 90 ° C to form a wet gel, followed by drying to obtain a precursor; or according to the formula (Y 1-xy Eu x Gd y )
  • the stoichiometric ratio of the corresponding element in BO 3 is mixed with Y salt, Eu salt, Gd salt, and boric acid in an excess of 1% to 50% of the stoichiometric ratio, and dissolved in the alcohol solution, and then the metal nanoparticle mixed sol is added and burned.
  • the agent is stirred, boiled and dehydrated, and then ignited and burned to obtain a precursor; wherein x is 0 ⁇ x ⁇ 0.3, and
  • the precursor is pre-fired, calcined, cooled and ground to obtain the borate-based red luminescent material.
  • the above metal nanoparticle sol preparation method is preferably:
  • the metal compound corresponding to the metal nanoparticle dissolved in a solvent to prepare a metal salt solution
  • the metal compound is preferably at least one of silver nitrate, chloroauric acid, chloroplatinic acid, and palladium chloride
  • the solvent is preferably, but not limited to, water and/or ethanol, because the solvent functions only to dissolve the metal compound corresponding to the metal nanoparticles, and therefore, any solvent capable of achieving the object can be used;
  • the auxiliary agent is preferably polyvinylpyrrolidone (PVP), sodium citrate, cetyltrimethylammonium bromide, sodium lauryl sulfate, twelve At least one of sodium alkyl sulfonates, the auxiliary agent acts to disperse, so that 1) the solution forms a uniform dispersion, preventing the final metal nanoparticle sol from agglomerating;
  • PVP polyvinylpyrrolidone
  • the auxiliary agent acts to disperse, so that 1) the solution forms a uniform dispersion, preventing the final metal nanoparticle sol from agglomerating;
  • reducing agent substance preferably hydrazine hydrate, At least one of ascorbic acid and sodium borohydride;
  • the solvent is preferably water and/or ethanol;
  • the molar ratio of the reducing agent to the metal ion is 1.2 to 4.8:1, and the obtained reducing agent solution is added to the solution obtained in the above 2), and the reaction of the whole system is 10 minutes to 45 minutes. A metal nanoparticle sol was obtained.
  • the method for preparing the metal nanoparticle mixed sol is preferably a method in which a metal nanoparticle sol is added to a polyvinylpyrrolidone (PVP) but not limited to a surface treatment agent solution of PVP, and the metal nanoparticles are surface-treated and stirred to obtain a metal-containing nanoparticle.
  • Metal nanoparticle hybrid sol is preferably 0.001 in the metal nanoparticle mixed sol.
  • the treatment time is preferably 8 ⁇ 24h
  • the surface treatment agent is added to improve the adsorption and deposition properties of metal nanoparticles
  • the purpose of the stirring reaction is In order to roughen the surface of the metal nanoparticles, it is advantageous for the adsorption and deposition of the metal nanoparticles.
  • the above precursor preparation method may employ a sol-gel coating method: that is, it is preferable to use a stoichiometric ratio of the corresponding element in the formula (Y 1-x Ce x ) 3 (Al 1-y Ga y ) 5 O 12 to Eu salt, Gd salt, and boric acid or/and borate in an excess of 1% to 50% of stoichiometric ratio are uniformly mixed under magnetic stirring, dissolved in an alcohol solution, and then mixed with a metal nanoparticle mixed sol at 75-90. The mixture is heated and stirred at ° C to form a wet gel, and then preliminarily dried in a blast drying oven at 50 to 80 ° C or lower, and then dried at 90 to 150 ° C or lower to prepare a precursor.
  • a sol-gel coating method that is, it is preferable to use a stoichiometric ratio of the corresponding element in the formula (Y 1-x Ce x ) 3 (Al 1-y Ga y ) 5 O 12 to Eu salt
  • the value of x is 0 ⁇ x ⁇ 0.3, and the value of y is 0 ⁇ y ⁇ 0.7;
  • the Y salt is preferably at least one of Y(NO 3 ) 3 and YCl 3
  • the Eu salt is preferably Eu (NO) 3 ) 3 , at least one of EuCl 3
  • the Gd salt is preferably at least one of Gd (NO 3 ) 3 and GdCl 3
  • the borate is preferably, but not limited to, tributyl borate
  • the alcohol solution is in the technical field.
  • a commonly used alcohol solution preferably an ethanol solution
  • the temperature control in this step is preferably controlled by heating with a water bath; the pre-drying may also be dried by other means such as natural drying, drying, or the like.
  • the preferred preparation method for preparing the precursor by the sol-gel coating method is as follows: the Y salt, the Eu salt, the Gd salt, the excess stoichiometric ratio according to the stoichiometric ratio of the corresponding element in the formula (Y 1-xy Eu x Gd y ) BO 3 1% to 50% of boric acid and a total rare earth ion molar ratio of 1 to 3:1 of citric acid monohydrate mixed, so that it is complexed with metal particles, added to the ethanol solution to dissolve, and then added metal nanoparticle mixed sol,
  • the wet gel is formed by heating and stirring at 75 to 90 ° C, and then preferably pre-dried in a blast drying oven at 60 ° C and then dried at 100 ° C to obtain a precursor.
  • the above precursor preparation method may employ a combustion coating method: that is, the Y salt, the Eu salt, the Gd salt, and the excess stoichiometric ratio according to the stoichiometric ratio of the corresponding element in the formula (Y 1-xy Eu x Gd y ) BO 3 1% to 50% of boric acid is mixed, dissolved in an alcohol solution, and then a metal nanoparticle mixed sol and a combustion agent are added, stirred, boiled and dehydrated, and then ignited and burned to obtain a precursor; wherein x is 0 ⁇ x ⁇ 0.3, the value of y is 0 ⁇ y ⁇ 0.7; the combustion agent is at least one of citric acid, urea, and glycine monohydrate.
  • a combustion coating method that is, the Y salt, the Eu salt, the Gd salt, and the excess stoichiometric ratio according to the stoichiometric ratio of the corresponding element in the formula (Y 1-xy Eu x Gd y
  • the preferred method for preparing the precursor by the above combustion coating method is to use a stoichiometric ratio of the corresponding element in the formula (Y 1-xy Eu x Gd y ) BO 3 to form a Y salt, an Eu salt, a Gd salt, and an excess in stoichiometric ratio 1 Mixing % to 50% of boric acid, adding to the ethanol solution, adding the metal nanoparticle mixed sol and the combustion agent with a molar ratio of total rare earth ions of 1 to 4:1, stirring, boiling and dehydrating, and then preferably 300-600 Ignition and combustion at °C to obtain a precursor.
  • the pre-firing is performed by placing the precursor in a high-temperature furnace at a temperature of 500 ° C to 1000 ° C for 3 to 8 hours; for calcination, the pre-fired precursor is preferably placed in a box type high temperature furnace or a tube furnace at 800 After heat treatment at ⁇ 1300 °C for 2 ⁇ 5h, the pre-fired precursor can be ground first and then placed in a high-temperature furnace or a tube furnace for calcination, which helps to fully remove the organic matter in the precursor, after calcination The precursor is cooled and then ground to obtain the borate-based red luminescent material.
  • the borate-based red luminescent material is prepared by a wet chemical method, which not only reduces the temperature of the synthesis reaction, but also improves the microstructure and macroscopic properties of the borate-based red luminescent material, and obtains a borate-based red luminescence.
  • the particle size distribution is uniform, which effectively improves the luminescence properties of the material.
  • the particle size of the boride-based red luminescent material can be flexibly adjusted by controlling the particle size of the metal nanoparticles and the thickness of the phosphor, and no other impurities are introduced to obtain high product quality.
  • the preparation method of the borate-based red luminescent material can obtain the product only by temperature control and adding the reactants in an appropriate ratio.
  • the preparation method has the advantages of simple process, low equipment requirement, no pollution, and easy control. Suitable for industrial production.
  • the borate-based red luminescent material is prepared by the combustion coating method, all the raw materials are mixed at the atomic level in the liquid phase, and uniform doping of ions is achieved, and the size of the particles can be controlled and reacted. The speed is fast, and the obtained phosphor does not need to be ball milled, which is beneficial to the application of the product.
  • compositions of the borate-based red luminescent materials and their preparation methods, as well as their properties and the like, are exemplified below by various embodiments.
  • Au nanoparticle sol Weigh 20.6mg of chloroauric acid (AuCl 3 •HCl•4H 2 O) and dissolve it into 16.8mL of deionized water. When chloroauric acid is completely dissolved, weigh 14mg sodium citrate and 6mg ten. Hexyltrimethylammonium bromide and dissolved in aqueous chloroauric acid solution under magnetic stirring; 1.9 mg of sodium borohydride and 17.6 mg of ascorbic acid were dissolved in 10 mL of deionized water to obtain 10 mL of 5 ⁇ concentration.
  • chloroauric acid AlCl 3 •HCl•4H 2 O
  • Preparation of Ag nanoparticle sol Weigh 3.40 mg of silver nitrate (AgNO 3 ) and dissolve it into 18.4 mL of deionized water. When the silver nitrate is completely dissolved, weigh 42 mg of sodium citrate and dissolve it into a silver nitrate aqueous solution under magnetic stirring. Dissolve 5.7 mg of sodium borohydride in 10 mL of deionized water to obtain 10 mL of a sodium borohydride aqueous solution with a concentration of 1.5 ⁇ 10 -2 mol/L; in a magnetic stirring environment, add 1.6 to the silver nitrate aqueous solution at one time.
  • AgNO 3 silver nitrate
  • the precursor is placed in a high-temperature furnace, pre-fired at 700 ° C for 4 h, cooled to room temperature, and then placed in a box-type high-temperature furnace after grinding, calcined at 1200 for 2 h, naturally cooled, and then obtained after removal.
  • a luminescent material (Y 0.98 Eu 0.02 ) BO 3 which was not coated with metal particles was prepared under the same conditions.
  • FIG. 1 is a comparison chart of emission spectra of an illuminating material prepared by an embodiment of the present invention (excitation wavelength is 172 nm), wherein curve 1 is an emission spectrum of a luminescent material of (Y 0.98 Eu 0.02 ) BO 3 @Ag; curve 2 is (Y The emission spectrum of the 0.98 Eu 0.02 )BO 3 luminescent material.
  • the luminescent intensity of the luminescent material after coating the metal nanoparticles was 27% higher than that of the uncoated sample. It is shown that the borate-based red luminescent material of the embodiment of the invention has high luminous intensity and luminous efficiency.
  • Pt nanoparticle sol Weigh 5.18mg of chloroplatinic acid (H 2 PtCl 6 •6H 2 O) and dissolve it into 17mL of ethanol solution; when chloroplatinic acid is completely dissolved, weigh 8.0mg of sodium citrate and 12.0mg Sodium dodecyl sulfonate is dissolved in chloroplatinic acid aqueous solution under magnetic stirring; 0.38 mg of sodium borohydride is dissolved and dissolved in 10 mL of deionized water to obtain 10 mL of a concentration of 1 ⁇ 10 -3 mol/L.
  • chloroplatinic acid H 2 PtCl 6 •6H 2 O
  • Sodium borohydride aqueous solution was prepared simultaneously with 10 mL of hydrazine hydrate solution with a concentration of 1 ⁇ 10 -2 mol/L; under magnetic stirring, 0.4 mL of sodium borohydride aqueous solution was added dropwise to the chloroplatinic acid aqueous solution, and the reaction was stirred for 5 min, then Then add 2.6mL of 1 ⁇ 10 -2 mol/L hydrazine hydrate solution to the chloroplatinic acid aqueous solution, and then continue the reaction for 40 minutes to obtain Pt nanoparticle sol with 20mLPt content of 5 ⁇ 10 -4 mol/L; 5 ⁇ 10 -4 mol/L Pt nanoparticle sol was placed in a beaker, and 32 mg of PVP was added and magnetically stirred for 12 h to obtain surface-treated Pt nanoparticles.
  • Pd nanoparticle sol 0.43 mg of palladium chloride (PdCl 2 • 2H 2 O) was weighed and dissolved in 8.5 mL of deionized water; when palladium chloride was completely dissolved, 11.0 mg of sodium citrate and 4.0 mg of ten were weighed.
  • Sodium dialkyl sulfate was dissolved in an aqueous solution of palladium chloride under magnetic stirring; 3.8 mg of sodium borohydride was dissolved in 10 mL of deionized water to obtain sodium borohydride at a concentration of 1 ⁇ 10 -2 mol/L.
  • the reducing solution under the magnetic stirring environment, rapidly add 0.48mL of 1 ⁇ 10 -2 mol/L sodium borohydride aqueous solution to the palladium chloride aqueous solution, and then continue the reaction for 20 minutes to obtain 10mL Pd content of 1 ⁇ 10 -4 mol. /L Pd nanoparticle sol; 6 mL of 1 ⁇ 10 -4 mol/L Pd nanoparticle sol was weighed into a beaker and 60 mg of PVP was added, and magnetically stirred for 8 h to obtain surface-treated Pd nanoparticles.
  • the precursor is obtained; the precursor is placed in a high-temperature furnace, pre-fired at 500 ° C for 7 h, cooled to room temperature, and then placed in a box-type high-temperature furnace after grinding, calcined at 900 for 5 h, naturally cooled, and taken out.
  • the desired luminescent material (Y 0.25 Eu 0.05 Gd 0.7 ) BO 3 @Pd is obtained.
  • Ag nanoparticle sol 3.40 mg of silver nitrate (AgNO 3 ) was weighed and dissolved in 18.4 mL of methanol solution; when silver nitrate was completely dissolved, 42 mg of sodium citrate was weighed and dissolved in a silver nitrate aqueous solution under magnetic stirring. Dissolve 5.7 mg of sodium borohydride in 10 mL of deionized water to obtain 10 mL of a sodium borohydride aqueous solution with a concentration of 1.5 ⁇ 10 -2 mol/L; in a magnetic stirring environment, add 1.6 to the silver nitrate aqueous solution at one time.
  • AgNO 3 silver nitrate
  • Au nanoparticle sol Weigh 20.6 mg of chloroauric acid (AuCl 3 •HCl•4H 2 O) and dissolve it into 16.8 mL of deionized water; when chloroauric acid is completely dissolved, weigh 14 mg of sodium citrate and 6 mg of ten Hexyltrimethylammonium bromide and dissolved in aqueous chloroauric acid solution under magnetic stirring; 1.9 mg of sodium borohydride and 17.6 mg of ascorbic acid were dissolved in 10 mL of deionized water to obtain 10 mL of 5 ⁇ concentration.
  • chloroauric acid AlCl 3 •HCl•4H 2 O
  • Preparation of Ag nanoparticle sol Weigh 3.40 mg of silver nitrate (AgNO 3 ) and dissolve it into 18.4 mL of deionized water. When the silver nitrate is completely dissolved, weigh 42 mg of sodium citrate and dissolve it into a silver nitrate aqueous solution under magnetic stirring. Dissolve 5.7 mg of sodium borohydride in 10 mL of deionized water to obtain 10 mL of a sodium borohydride aqueous solution with a concentration of 1.5 ⁇ 10 -2 mol/L; in a magnetic stirring environment, add 1.6 to the silver nitrate aqueous solution at one time.
  • AgNO 3 silver nitrate
  • a viscous solution is formed, and then immediately placed in a preheated muffle furnace (500 ° C) to ignite, burning in a few seconds to obtain a fluffy white precursor; the precursor is placed in a high temperature furnace, Preheated at 1000 °C for 2 h, cooled to room temperature, ground in a tube furnace, calcined at 1300 °C for 2 h, naturally cooled, and the desired luminescent material (Y 0.7 Eu 0.1 Gd 0.2 ) BO was obtained after removal. 3 @ Ag.
  • Preparation of Pt nanoparticle sol Weigh 5.18mg of chloroplatinic acid (H 2 PtCl 6 •6H 2 O) and dissolve it into 17mL of propanol solution; when chloroplatinic acid is completely dissolved, weigh 8.0mg of sodium citrate and 12.0 Mg sodium dodecyl sulfate, dissolved in chloroplatinic acid aqueous solution under magnetic stirring; weigh 0.38mg sodium borohydride dissolved in 10mL deionized water to obtain 10mL concentration of 1 ⁇ 10 -3 mol / L
  • the aqueous sodium borohydride solution was prepared simultaneously with 10 mL of a hydrazine hydrate solution having a concentration of 1 ⁇ 10 -2 mol/L; under a magnetic stirring environment, 0.4 mL of an aqueous solution of sodium borohydride was added dropwise to the aqueous solution of chloroplatinic acid, and the reaction was stirred for 5 minutes.
  • Preparation of Pt/Au nanoparticle sol Weigh 6.2 mg of chloroauric acid (AuCl 3 •HCl•4H 2 O) and 7.8 mg of chloroplatinic acid (H 2 PtCl 6 •6H 2 O) into 28 mL of deionized water; When completely dissolved, 22 mg of sodium citrate and 20 mg of PVP were weighed and dissolved in the above mixed solution under magnetic stirring; the newly prepared 5.7 mg of sodium borohydride was dissolved in 10 mL of deionized water to obtain a concentration of 10 mL of 1.5 mL.

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Description

一种硼酸盐基红色发光材料及其制备方法 技术领域
本发明属于发光材料技术领域，具体涉及一种硼酸盐基红色发光材料及其制备方法。
背景技术
近年来，随着PDP显示技术的发展以及无汞光源的深入研究，研发高效、稳定、强吸收172nm光的红、绿、蓝发光材料具有广阔的应用前景。目前，商用发光材料主要有红色发光材料Y2O3: Eu3+，(Y, Gd)BO3:Eu3+，绿色发光材料Zn2SiO4: Mn2+，BaAl12O19:Mn2+和蓝色发光材料Y2SiO5：Ce3+，LaPO4：Tm3+，BaMgAl10O17:Eu2+。其中，由于(Y, Gd)BO3:Eu3+红色发光材料在真空紫外（VUV）激发下具有很高的发光效率，因此，目前它是真空紫外光激发中所用到的最常见的红色组成发光材料。另外，研究表明，VUV射线激发可以穿透发光材料的厚度大约是100~200nm，表面和有效的激发空间在光发射中起到重要的作用，这就要求VUV激发的发光材料具有形貌较好，如球形，类球形以及颗粒均匀，小尺寸（平均粒度1~2μm）等优点。然而，荧光粉的发光性能与其制备方法也有密切的关系。例如，常规的高温固相法的制备(Y, Gd)BO3:Eu3+，工艺简单，有利于工业化生产，但反应时间长，混合不均匀，需要一定时间的球磨，不但发光中心在基质中分散不均匀，影响其发光效率，而且制备的发光粉的颗粒尺寸较大，形貌不佳。另外，在球磨过程中易引入杂质并引起晶格缺陷，由球磨引起的粉体物理和化学上变化往往导致荧光粉亮度降低，不利于其应用。
技术问题
有鉴于此，提供一种粒度分布均匀、结构稳定、发光强度和发光效率高的硼酸盐基红色发光材料。
以及，提供一种制备工艺简单、设备要求、低无污染、反应和材料形貌及粒度大小易于控制，适于工业化生产的硼酸盐基红色发光材料制备方法。
 技术解决方案
本发明解决上述技术问题所采用的技术方案是：
一种硼酸盐基红色发光材料，其包括核、以及包覆所述核的外壳，所述核为金属纳米粒子，所述外壳是化学式表示为(Y1-x-yEuxGdy)BO3的荧光粉，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7。
以及，提供一种硼酸盐基红色发光材料制备方法，包括如下步骤：
将与金属纳米粒子相应的金属化合物溶解，再依次与助剂、还原剂混合，制得金属纳米粒子溶胶；
将金属纳米粒子溶胶加入聚乙烯吡咯烷酮表面处理剂中进行搅拌混合处理8h～24h后，制得金属纳米粒子混合溶胶；
按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸或/和硼酸盐混合，加入醇溶液溶解后，再加入所述金属纳米粒子混合溶胶，在75～90℃下加热搅拌形成湿凝胶，然后干燥得到前驱体；或按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸混合，加入醇溶液溶解后，再加入所述金属纳米粒子混合溶胶和燃烧剂，并搅拌、煮沸脱水，然后点火燃烧，得到前驱体；其中，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7；
将前驱体先预烧，再煅烧，冷却后研磨，得到所述的硼酸盐基红色发光材料。
 有益效果
在上述硼酸盐基红色发光材料及其制备方法中，该硼酸盐基红色发光材料采用金属纳米粒子为核、(Y1-x-yEuxGdy)BO3为壳构成球形或类似球形的微小颗粒的荧光材料，以Eu3+为发光中心，使得该发光材料发光强度高，且该荧光材料粒度分布均匀、结构稳定、发光效率高；该硼酸盐基红色发光材料采用湿化学法或燃烧包覆法制备而成，不仅降低了合成反应的温度，而且改善了该硼酸盐基红色发光材料的微观结构和宏观性质，获得的硼酸盐基红色发光材料粒度分布均匀，有效提高了材料的发光性能，还可以通过控制金属纳米粒子粒径和荧光粉的厚度而灵活调整硼酸盐基红色发光材料颗粒大小，且不引入其他杂质，获得产品质量高，与此同时，该硼酸盐基红色发光材料制备方法只需控温以及按合适比例添加各反应物即能得到产物，因此，该制备方法工艺简单、设备要求低、无污染、易于控制，适于工业化生产。
附图说明
下面将结合附图及实施例对本发明作进一步说明，附图中：
图1是本发明实施例2制备的硼酸盐基红色发光材料与(Y0.98Eu0.02)BO3在激发波长为172nm下发射光谱对比图，其中，曲线1是(Y0.98Eu0.02)BO3@Ag的发光材料的发射光谱；曲线2是(Y0.98Eu0.02)BO3发光材料的发射光谱。
 本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供一种硼酸盐基红色发光材料，其包括核、以及包覆所述核的外壳，所述核为金属纳米粒子，所述外壳是化学式表示为(Y1-x-yEuxGdy)BO3的荧光粉，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7。
上述硼酸盐基红色发光材料结构式可表达为：(Y1-x-yEuxGdy)BO3@zM，其中，@表示以M为核，以(Y1-x-yEuxGdy)BO3为外壳，(Y1-x-yEuxGdy)BO3将M包裹其中。式中，x的取值为0＜x≤0.3，x取值优选为0.005≤x≤0.20；y的取值为0≤y≤0.7，y取值优选为0.01≤y≤0.5；z为M与(Y1-x-yEuxGdy)BO3的摩尔比，z取值为0＜z≤1×10-2，z取值优选为1×10-4≤y≤2×10-3；M为金属纳米粒子，优选为Ag、Au、Pt、Pd纳米粒子中的至少一种。
上述外壳以层状形式包覆于所述核表面，所述硼酸盐基红色发光材料是球形或者类球形颗粒结构。
上述硼酸盐基红色发光材料采用金属纳米粒子为核、(Y1-x-yEuxGdy)BO3为壳构成球形或类似球形的微小颗粒的荧光材料，使得该荧光材料粒度分布均匀、结构稳定、发光强度和发光效率高。该材料以Eu3+为发光中心，使得该发光材料发光强度高，特别是在波长为147和172nm的紫外光激发下有较强的发光性能，与Xe气辐射放电产生的147nm或172nm相匹配，适合用于等离子显示平板和无汞荧光灯中。
进一步的，本发明实施例提供上述硼酸盐基红色发光材料制备方法，包括如下步骤：
将与金属纳米粒子相应的金属化合物溶解，再依次与助剂、还原剂混合，制得金属纳米粒子溶胶；
将金属纳米粒子溶胶加入聚乙烯吡咯烷酮表面处理剂中进行搅拌混合处理8h～24h后，制得金属纳米粒子混合溶胶；
按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸或/和硼酸盐混合，加入醇溶液溶解后，再加入所述金属纳米粒子混合溶胶，在75～90℃下加热搅拌形成湿凝胶，然后干燥，得到前驱体；或按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸混合，加入醇溶液溶解后，再加入所述金属纳米粒子混合溶胶和燃烧剂，并搅拌、煮沸脱水，然后点火燃烧，得到前驱体；其中，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7；
将前驱体先预烧，再煅烧，冷却后研磨，得到所述的硼酸盐基红色发光材料。
上述金属纳米粒子溶胶制备方法优选为：
1）称取与金属纳米粒子相应的金属化合物溶于溶剂中，配制成金属盐溶液，所述的金属化合物优选为硝酸银、氯金酸、氯铂酸、氯化钯中的至少一种；所述的溶剂优选但不仅仅限于水和/或乙醇，因为，溶剂的作用只是将与金属纳米粒子相应的金属化合物溶解，因此，只要能实现该目的的溶剂均可使用；
2）在磁力搅拌的状态下，将一种或一种以上的助剂溶解到上述1）溶液中，并使助剂能在最终得到的金属纳米粒子溶胶中的含量优选为1.5×10-4g/mL～2.1×10-3g/mL，所述助剂优选为聚乙烯吡咯烷酮（PVP）、柠檬酸钠、十六烷基三甲基溴化铵、十二烷基硫酸钠、十二烷基磺酸钠中的至少一种，该助剂起分散作用，使得1）溶液形成均匀的分散液，防止最终的金属纳米粒子溶胶发生团聚；
3）称取还原剂物质溶解到溶剂中，配制成浓度范围优选为1×10-3mol/L～1×10-2mol/L的还原剂溶液；所述的还原剂优选为水合肼、抗坏血酸、硼氢化钠中的至少一种；所述的溶剂优选为水和/或乙醇；
4）在磁力搅拌的环境下，按还原剂与金属离子的摩尔比为1.2～4.8:1将3）所得还原剂溶液加入上述2）所得到的溶液中，待整个体系反应10min～45min后即得到金属纳米粒子溶胶。
上述金属纳米粒子混合溶胶制备方法优选为将金属纳米粒子溶胶加入聚乙烯吡咯烷酮（PVP）但不限于PVP的表面处理剂溶液中，对金属纳米粒子进行表面处理，搅拌反应制得含金属纳米粒子的金属纳米粒子混合溶胶。其中，PVP的添加量在金属纳米粒子混合溶胶中含量优选为0.001 g/mL~0.01g/mL，其作用是对金属纳米粒子进行表面处理，处理的时间优选为8～24h，加入表面处理剂是为了改善金属纳米粒子的吸附和沉积性能，搅拌反应的目的是为了使金属纳米粒子的表面粗糙，利于金属纳米粒子吸附和沉积。
上述前驱体制备方法可以选用溶胶-凝胶包覆法：即是优选按分子式(Y1-xCex)3(Al1-yGay)5O12中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸或/和硼酸盐在磁力搅拌下混合均匀，加入醇溶液溶解后，再加入金属纳米粒子混合溶胶，在75～90℃下加热搅拌形成湿凝胶，然后先优选在50～80℃以下鼓风干燥箱中预干，再在90～150℃以下烘干，制得前驱体。其中，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7；Y盐优选为Y (NO3)3、YCl3中的至少一种，Eu盐优选为Eu (NO3)3、EuCl3中的至少一种，Gd盐优选为Gd (NO3)3、GdCl3中的至少一种，硼酸盐优选但不仅仅限于硼酸三丁酯；醇溶液是本技术领域常用的醇类溶液，优选乙醇溶液；该步骤中的温度控制优选用水浴加热控制；预干也可采用自然晾干、晒干等其他方式干燥。
上述溶胶-凝胶包覆法制备前驱体优选方案是：按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、过量于化学计量比1%～50%的硼酸以及与总稀土离子摩尔比为1～3:1的一水合柠檬酸混合，使之与金属粒子进行络合，加入乙醇溶液溶解后，再加入金属纳米粒子混合溶胶，在75～90℃下加热搅拌形成湿凝胶，然后优选先在60℃下鼓风干燥箱中预干，再在100℃下烘干，制得前驱体。
上述前驱体制备方法可以选用燃烧包覆法：即是按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸混合，加入醇溶液溶解后，再加入金属纳米粒子混合溶胶和燃烧剂，并搅拌、煮沸脱水，然后点火燃烧，得到前驱体；其中，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7；燃烧剂为一水合柠檬酸、尿素、甘氨酸中的至少一种。
上述燃烧包覆法法制备前驱体优选方案是：按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸混合，加入乙醇溶液溶解后，再加入金属纳米粒子混合溶胶和与总稀土离子摩尔比为1～4:1的燃烧剂，并搅拌、煮沸脱水，然后优选在300～600℃下点火燃烧，得到前驱体。
上述的预烧优选将前驱体置于高温炉中在500℃~1000℃下热处理3~8h；煅烧优选将进行预烧处理后的前驱体置于箱式高温炉中或管式炉中于800~1300℃下热处理2~5h，预烧后的前驱体可先进行研磨后再将其置于高温炉中或管式炉中进行煅烧，这样有助于充分除去前驱体中的有机物，煅烧后的前驱体经冷却，再进行研磨得到所述的硼酸盐基红色发光材料。
该硼酸盐基红色发光材料采用湿化学法制备而成，不仅降低了合成反应的温度，而且改善了该硼酸盐基红色发光材料的微观结构和宏观性质，获得的硼酸盐基红色发光材料粒度分布均匀，有效提高了材料的发光性能，还可以通过控制金属纳米粒子粒径和荧光粉的厚度而灵活调整硼酸盐基红色发光材料颗粒大小，且不引入其他杂质，获得产品质量高，与此同时，该硼酸盐基红色发光材料制备方法只需控温以及按合适比例添加各反应物即能得到产物，因此，该制备方法工艺简单、设备要求低、无污染、易于控制，适于工业化生产。当该硼酸盐基红色发光材料采用燃烧包覆法制备而成时，使所有的原料在液相中到达原子级别的混合，实现了离子的均匀掺杂，同时颗粒的尺寸可得到控制，反应速度快，所得的荧光粉不需要再进行球磨，有利于产物的应用。
以下通过多个实施例来举例说明硼酸盐基红色发光材料的不同组成及其制备方法，以及其性能等方面。
实施例1
溶胶-凝胶包覆法制备结构式为(Y0.495Eu0.005Gd0.5)BO3@Au的硼酸盐基红色发光材料的制备：
Au纳米颗粒溶胶的制备：称取20.6mg氯金酸（AuCl3•HCl•4H2O）溶解到16.8mL的去离子水中，当氯金酸完全溶解后，称取14mg柠檬酸钠和6mg十六烷基三甲基溴化铵，并在磁力搅拌的环境下溶解到氯金酸水溶液中；称取1.9mg硼氢化钠和17.6mg抗坏血酸分别溶解到10mL去离子水中，得到10mL浓度为5×10-3mol/L的硼氢化钠水溶液和10mL浓度为1×10-2mol/L的抗坏血酸水溶液；在磁力搅拌的环境下，先往氯金酸水溶液中加入0.08mL硼氢化钠水溶液，搅拌反应5min后再往氯金酸水溶液中加入3.12mL1×10-2mol/L的抗坏血酸水溶液，之后继续反应30min，即得20mLAu含量为5×10-3mol/L的Au纳米颗粒溶胶；量取8mL浓度为5×10-3mol/L的Au纳米颗粒溶胶，往该8mL 的Au纳米颗粒溶胶中加入8mg的PVP，磁力搅拌8h，得经表面处理后的Au纳米颗粒。
(Y0.495Eu0.005Gd0.5)BO3@Au的制备：取9.9ml 0.2 mol/L的Y(NO3)3、0.4ml 0.05 mol/L的Eu(NO3)3、10ml 0.2 mol/L的Gd(NO3)3溶液以及0.2498g H3BO3于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后滴加上述经表面处理后的金属纳米颗粒溶胶形成混合液；将0.8406g一水合柠檬酸（金属离子物质的量的1倍）溶于乙醇中，再加入到上述混合液中，然后置于75℃的水浴中加热搅拌直至形成湿凝胶；将该湿凝胶在60℃的鼓风干燥箱中干燥12小时，再在110℃干燥完全，得到前躯体；将前驱体置于高温炉中，在500℃下预烧2h，冷却至室温，研磨后再将其置于箱式高温炉中，在800下煅烧5h，自然冷却，取出后即得所需发光材料(Y0.495Eu0.005Gd0.5)BO3@Au。
实施例2
溶胶-凝胶包覆法制备结构式为(Y0.98Eu0.02)BO3@Ag的硼酸盐基红色发光材料的制备：
Ag纳米颗粒溶胶的制备：称取3.40mg硝酸银（AgNO3）溶解到18.4mL的去离子水中；当硝酸银完全溶解后，称取42mg柠檬酸钠在磁力搅拌的环境下溶解到硝酸银水溶液中；称取5.7mg硼氢化钠溶到10mL去离子水中，得到10mL浓度为1.5×10-2mol/L的硼氢化钠水溶液；在磁力搅拌的环境下，往硝酸银水溶液中一次性加入1.6mL1.5×10-2mol/L的硼氢化钠水溶液，之后继续反应10min，即得20mL银含量为1×10-3mol/L的Ag纳米颗粒溶胶；量取2mL 1×10-3mol/L的Ag纳米颗粒溶胶于烧杯中，再加入4mg的PVP，并磁力搅拌12h，得经表面处理后的Ag纳米颗粒。
(Y0.98Eu0.02)BO3@ Ag的制备：取19.6ml 0.2 mol/L的Y(NO3)3、1.6ml 0.05 mol/L的Eu(NO3)3溶液以及0.3710g H3BO3（过量50mol%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后滴加上述经处理过的金属纳米颗粒溶胶；将1.6811g一水合柠檬酸（金属离子物质的量的2倍）溶于乙醇中，再加入到上述形成混合液中，然后置于90℃的水浴中加热搅拌直至形成湿凝胶；60℃的鼓风干燥箱中干燥15小时，再在110℃干燥完全，得到前躯体；将前驱体置于高温炉中，在700℃下预烧4h，冷却至室温，研磨后再将其置于箱式高温炉中，在1200下煅烧2h，自然冷却，取出后即得所需发光材料(Y0.98Eu0.02)BO3@ Ag。同时，用同样的条件，制备出未包覆金属颗粒的发光材料(Y0.98Eu0.02)BO3。
如图1是本发明实施例制备的发光材料发射光谱对比图（激发波长为172nm），其中，曲线1是(Y0.98Eu0.02)BO3@Ag的发光材料的发射光谱；曲线2是(Y0.98Eu0.02)BO3发光材料的发射光谱。包覆金属纳米粒子后发光材料的发光强度较未包覆的样品提高了27%。表明本发明实施例硼酸盐基红色发光材料发光强度和发光效率高。
实施例3
溶胶-凝胶包覆法制备结构式为(Y0.5Eu0.3Gd0.2)BO3@Pt的硼酸盐基红色发光材料的制备：
Pt纳米颗粒溶胶的制备：称取5.18mg氯铂酸（H2PtCl6•6H2O）溶解到17mL的乙醇溶液中；当氯铂酸完全溶解后，称取8.0mg柠檬酸钠和12.0mg十二烷基磺酸钠，并在磁力搅拌的环境下溶解到氯铂酸水溶液中；称取0.38mg硼氢化钠溶解到10mL去离子水中，得到10mL浓度为1×10-3mol/L的硼氢化钠水溶液，同时配制10mL浓度为1×10-2mol/L的水合肼溶液；磁力搅拌的环境下，先往氯铂酸水溶液中滴加0.4mL硼氢化钠水溶液，搅拌反应5min，然后再往氯铂酸水溶液中滴加2.6mL1×10-2mol/L的水合肼溶液，之后继续反应40min，即得20mLPt含量为5×10-4mol/L的Pt纳米颗粒溶胶；量取16mL 5×10-4mol/L的Pt纳米颗粒溶胶于烧杯中，并加入32mg PVP，磁力搅拌12h，得经表面处理后的Pt纳米颗粒。
(Y0.5Eu0.3Gd0.2)BO3@ Pt的制备：取10ml 0.2 mol/L的Y(NO3)3、24ml 0.05 mol/L的Eu(NO3)3、4ml 0.2 mol/L的Gd(NO3)3溶液以及0.2968g H3BO3（过量20mol%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后滴加上述经处理过的金属纳米颗粒溶胶形成混合液；将2.5217g一水合柠檬酸（金属离子物质的量的3倍）溶于乙醇中，再加入到上述混合液中，然后置于80℃的水浴中加热搅拌直至形成湿凝胶；60℃的鼓风干燥箱中干燥10小时，再在110℃干燥完全，得到前躯体；将前驱体置于高温炉中，在1000℃下预烧2h，冷却至室温，研磨后再将其置于管式炉中，在1300下煅烧2h，自然冷却，取出后即得所需发光材料(Y0.5Eu0.3Gd0.2)BO3@ Pt。
实施例4
溶胶-凝胶包覆法制备结构式为(Y0.25Eu0.05Gd0.7)BO3@Pd的硼酸盐基红色发光材料的制备：
Pd纳米颗粒溶胶的制备：称取0.43mg氯化钯（PdCl2•2H2O）溶解到8.5mL的去离子水中；当氯化钯完全溶解后，称取11.0mg柠檬酸钠和4.0mg十二烷基硫酸钠，并在磁力搅拌的环境下溶解到氯化钯水溶液中；称取3.8mg硼氢化钠溶到10mL去离子水中，得到浓度为1×10-2mol/L的硼氢化钠还原液；在磁力搅拌的环境下，往氯化钯水溶液中快速加入0.48mL1×10-2mol/L的硼氢化钠水溶液，之后继续反应20min，即得10mL Pd含量为1×10-4mol/L的Pd纳米颗粒溶胶；量取6mL 1×10-4mol/L的Pd纳米颗粒溶胶于烧杯中并加入60mg PVP，并磁力搅拌8h，得经表面处理后的Pd纳米颗粒。
(Y0.25Eu0.05Gd0.7)BO3@ Pd的制备：(Y0.5Eu0.3Gd0.2)BO3@ Pt的制备：取5ml 0.2 mol/L的Y(NO3)3、4ml 0.05 mol/L的Eu(NO3)3、14ml 0.2 mol/L的Gd(NO3)3溶液以及0.9752g 硼酸三丁酯（C12H27BO3，过量20mol%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后滴加上述经处理过的金属纳米颗粒溶胶，再置于85℃的水浴中加热搅拌直至形成湿凝胶；50℃的鼓风干燥箱中干燥12小时，再在150℃干燥完全，得到前躯体；将前驱体置于高温炉中，在500℃下预烧7h，冷却至室温，研磨后再将其置于箱式高温炉中，在900下煅烧5h，自然冷却，取出后即得所需发光材料(Y0.25Eu0.05Gd0.7)BO3@Pd。
实施例5
燃烧包覆法制备结构式为(Y0.79Eu0.20Gd0.01)BO3@Ag的硼酸盐基红色发光材料的制备：
Ag纳米颗粒溶胶的制备：称取3.40mg硝酸银（AgNO3）溶解到18.4mL的甲醇溶液中；当硝酸银完全溶解后，称取42mg柠檬酸钠在磁力搅拌的环境下溶解到硝酸银水溶液中；称取5.7mg硼氢化钠溶到10mL去离子水中，得到10mL浓度为1.5×10-2mol/L的硼氢化钠水溶液；在磁力搅拌的环境下，往硝酸银水溶液中一次性加入1.6mL1.5×10-2mol/L的硼氢化钠水溶液，之后继续反应10min，即得20mL银含量为1×10-3mol/L的Ag纳米颗粒溶胶；量取5mL 1×10-3mol/L的Ag纳米颗粒溶胶于烧杯中，再加入30mgPVP，并磁力搅拌24h，得经表面处理后的Ag纳米颗粒。
(Y0.79Eu0.20Gd0.01)BO3@ Ag的制备：取15.8ml 0.2 mol/L的Y(NO3)3、16ml 0.05 mol/L的Eu(NO3)3、0.2ml 0.2 mol/L的Gd(NO3)3以及0.2721g硼酸（按化学计量比过量10%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后加入上述经处理过的金属纳米颗粒溶胶形成混合液；将0.8406g一水合柠檬酸（一水合柠檬酸物质的量与总稀土离子物质的量的比为1）溶于乙醇中，再加入到上述混合液中，充分搅拌后，再置于刚玉坩埚中，在电阻炉上加热，煮沸脱水，直至形成粘稠状溶液，然后立即将其放入到预先加热的马弗炉中（300℃）点火，数秒燃烧完全，得到蓬松的白色前驱物；将前驱体置于高温炉中，在500℃下预烧7h，冷却至室温，再将其置于箱式高温炉中，在800℃下煅烧2h，自然冷却，取出研磨后即得所需发光材料(Y0.79Eu0.20Gd0.01)BO3@ Ag。
实施例6
燃烧包覆法制备结构式为(Y0.9Eu0.05Gd0.05)BO3@Au的硼酸盐基红色发光材料的制备：
Au纳米颗粒溶胶的制备：称取20.6mg氯金酸（AuCl3•HCl•4H2O）溶解到16.8mL的去离子水中；当氯金酸完全溶解后，称取14mg柠檬酸钠和6mg十六烷基三甲基溴化铵，并在磁力搅拌的环境下溶解到氯金酸水溶液中；称取1.9mg硼氢化钠和17.6mg抗坏血酸分别溶解到10mL去离子水中，得到10mL浓度为5×10-3mol/L的硼氢化钠水溶液和10mL浓度为1×10-2mol/L的抗坏血酸水溶液；在磁力搅拌的环境下，先往氯金酸水溶液中加入0.08mL硼氢化钠水溶液，搅拌反应5min后再往氯金酸水溶液中加入3.12mL1×10-2mol/L的抗坏血酸水溶液，之后继续反应30min，即得20mLAu含量为5×10-3mol/L的Au纳米颗粒溶胶；量取1mL为5×10-3mol/L的Au纳米颗粒溶胶，往Au纳米颗粒溶胶中于烧杯中并加入3mgPVP，磁力搅拌8h，得经表面处理后的Au纳米颗粒。
(Y0.9Eu0.05Gd0.05)BO3@ Au的制备：量取18ml 0.2 mol/L的Y(NO3)3、4ml 0.05 mol/L的Eu(NO3)3、1ml 0.2 mol/L的Gd(NO3)3以及0.3710g硼酸（按化学计量比过量50%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后加入经处理过的金属纳米颗粒溶胶形成混合液；将0.7219g尿素（CO(NH2)2，尿素物质的量与总稀土离子物质的量的比为3）加入到上述混合液中，充分搅拌后，再置于刚玉坩埚中，在电阻炉上加热，煮沸脱水，直至形成粘稠状溶液，然后，立即将其放入到预先加热的马弗炉中600℃点火，数秒燃烧完全，得到蓬松的白色前驱物；将前驱体置于高温炉中，在600℃预烧7h，冷却至室温，研磨后再将其置于管式炉中，在1300℃下煅烧2h，自然冷却，取出后即得所需发光材料(Y0.9Eu0.05Gd0.05)BO3@ Au。
实施例7
燃烧包覆法制备结构式为(Y0.7Eu0.1Gd0.2)BO3@Ag的硼酸盐基红色发光材料的制备：
Ag纳米颗粒溶胶的制备：称取3.40mg硝酸银（AgNO3）溶解到18.4mL的去离子水中；当硝酸银完全溶解后，称取42mg柠檬酸钠在磁力搅拌的环境下溶解到硝酸银水溶液中；称取5.7mg硼氢化钠溶到10mL去离子水中，得到10mL浓度为1.5×10-2mol/L的硼氢化钠水溶液；在磁力搅拌的环境下，往硝酸银水溶液中一次性加入1.6mL1.5×10-2mol/L的硼氢化钠水溶液，之后继续反应10min，即得20mL银含量为1×10-3mol/L的Ag纳米颗粒溶胶；量取1mL 1×10-3mol/L的Ag纳米颗粒溶胶于烧杯中，再加入2mgPVP，并磁力搅拌12h，得经表面处理后的Ag纳米颗粒。
(Y0.7Eu0.1Gd0.2)BO3@ Ag的制备：量取14ml 0.2 mol/L的Y(NO3)3、8ml 0.05 mol/L的Eu(NO3)3、4ml 0.2 mol/L的Gd(NO3)3以及0.2498g硼酸（按化学计量比过量1%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后加入上述经处理过的金属纳米颗粒溶胶形成混合液；将1.2012甘氨酸（C2H5NO2，甘氨酸物质的量与总稀土离子物质的量的比为4）加入到上述混合液中，充分搅拌后，再置于刚玉坩埚中，在电阻炉上加热，煮沸脱水，直至形成粘稠状溶液，然后，立即将其放入到预先加热的马弗炉中（500℃）点火，数秒燃烧完全，得到蓬松的白色前驱物；将前驱体置于高温炉中，在1000℃下预烧2h，冷却至室温，研磨后再将其置于管式炉中，在1300 ℃下煅烧2h，自然冷却，取出后即得所需发光材料(Y0.7Eu0.1Gd0.2)BO3@ Ag。
实施例8
燃烧包覆法制备结构式为(Y0.9Eu0.02Gd0.08)BO3@Pt的硼酸盐基红色发光材料的制备：
Pt纳米颗粒溶胶的制备：称取5.18mg氯铂酸（H2PtCl6•6H2O）溶解到17mL的丙醇溶液中；当氯铂酸完全溶解后，称取8.0mg柠檬酸钠和12.0mg十二烷基磺酸钠，并在磁力搅拌的环境下溶解到氯铂酸水溶液中；称取0.38mg硼氢化钠溶解到10mL去离子水中，得到10mL浓度为1×10-3mol/L的硼氢化钠水溶液，同时配制10mL浓度为1×10-2mol/L的水合肼溶液；磁力搅拌的环境下，先往氯铂酸水溶液中滴加0.4mL硼氢化钠水溶液，搅拌反应5min，然后再往氯铂酸水溶液中滴加2.6mL1×10-2mol/L的水合肼溶液，之后继续反应40min，即得20mLPt含量为5×10-4mol/L的Pt纳米颗粒溶胶；量取4mL 5×10-4mol/L的Pt纳米颗粒溶胶于烧杯中，并加入16.0mg PVP，磁力搅拌12h，得经表面处理后的Pt纳米颗粒。
(Y0.9Eu0.02Gd0.08)BO3@ Pt的制备：量取18ml 0.2 mol/L的Y(NO3)3、1.6ml 0.05 mol/L的Eu(NO3)3、1.6ml 0.2 mol/L的Gd(NO3)3以及0.2844g硼酸（按化学计量比过量15%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后加入上述经处理过的金属纳米颗粒溶胶形成混合液；将0.9610尿素（尿素物质的量与总稀土离子物质的量的比为4）加入到上述混合液中，充分搅拌后，再置于刚玉坩埚中，在电阻炉上加热，煮沸脱水，直至形成粘稠状溶液，然后立即将其放入到预先加热的马弗炉中（400℃）点火，数秒燃烧完全，得到蓬松的白色前驱物；将前驱体置于高温炉中，在700℃下预烧5h，冷却至室温，研磨后再将其置于箱式高温炉中，在900 ℃下煅烧5h，自然冷却，取出后即得所需发光材料。
实施例9
溶胶-凝胶包覆法制备结构式为(Y0.5Eu0.3Gd0.2)BO3@ Pt/Au的硼酸盐基红色发光材料的制备：
Pt/Au纳米颗粒溶胶的制备：称取6.2mg氯金酸（AuCl3•HCl•4H2O）和7.8mg氯铂酸（H2PtCl6•6H2O）溶解到28mL的去离子水中；当完全溶解后，称取22mg柠檬酸钠和20mgPVP，并在磁力搅拌的环境下溶解到上述混合溶液中；称取新制备的5.7mg硼氢化钠溶到10mL去离子水中，得到10mL浓度为1.5×10-2mol/L的硼氢化钠水溶液；在磁力搅拌的环境下，往上述混合溶液中一次性加入2mL的1.5×10-2mol/L的硼氢化钠水溶液，之后继续反应20min，即得30mL 总金属浓度为1×10-3mol/L的 Pt/Au纳米颗粒溶胶；之后量取5mL得到的Pt/Au纳米颗粒溶胶，往Pt/Au纳米颗粒溶胶中加入20mg的PVP，并磁力搅拌6h，得经表面处理后的Pt/Au纳米颗粒。
(Y0.5Eu0.3Gd0.2)BO3@ Pt/Au的制备：取10ml 0.2 mol/L的YCl3、24ml 0.05 mol/L的EuCl3、4ml 0.2 mol/L的GdCl3溶液以及0.2968g H3BO3（过量20mol%）于烧杯中，搅拌并滴加乙醇溶液至完全溶解，然后滴加上述经处理过的金属纳米颗粒溶胶形成混合液；将2.5217g一水合柠檬酸（金属离子物质的量的3倍）溶于乙醇中，然后加入到上述混合液中，然后置于80℃的水浴中加热搅拌直至形成湿凝胶；80℃的鼓风干燥箱中干燥10小时，再在90℃干燥完全，得到前躯体；将前驱体置于高温炉中，在1000℃下预烧2h，冷却至室温，研磨后再将其置于管式炉中，在1300下煅烧2h，自然冷却，取出后即得所需发光材料(Y0.5Eu0.3Gd0.2)BO3@ Pt/Au。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种硼酸盐基红色发光材料，其包括核、以及包覆所述核的外壳，所述核为金属纳米粒子，所述外壳是化学式表示为(Y1-x-yEuxGdy)BO3的荧光粉，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7。
  2. 如权利要求1所述的硼酸盐基红色发光材料，其特征在于：
    所述核与外壳的摩尔比大于0、小于或等于1×10-2；
    所述金属纳米粒子为Ag、Au、Pt、Pd中的至少一种。
  3. 如权利要求1所述的硼酸盐基红色发光材料，其特征在于，所述外壳以层状形式包覆于所述核表面，所述硼酸盐基红色发光材料是球形或者类球形颗粒结构；
    所述核与外壳的摩尔比1×10-4～2×10-3；
    所述x取值为0.005≤x≤0.20；
    所述y取值为0.01≤y≤0.5。
  4. 一种硼酸盐基红色发光材料制备方法，包括如下步骤：
    将与金属纳米粒子相应的金属化合物溶解，再依次与助剂、还原剂混合，制得金属纳米粒子溶胶；
    将金属纳米粒子溶胶加入聚乙烯吡咯烷酮中进行搅拌混合处理8h～24h后，制得金属纳米粒子混合溶胶；
    按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于所述化学计量比1%～50%的硼酸或/和硼酸盐混合，加入醇溶液溶解后，再加入所述金属纳米粒子混合溶胶，在75～90℃下加热搅拌形成湿凝胶，然后干燥，得到前驱体；或按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸混合，加入醇溶液溶解后，再加入所述金属纳米粒子混合溶胶和燃烧剂，并搅拌、煮沸脱水，然后点火燃烧，得到前驱体；其中，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7；
    将前驱体先预烧，再煅烧，冷却后研磨，得到所述的硼酸盐基红色发光材料。
  5. 如权利要求4所述的硼酸盐基红色发光材料制备方法，其特征在于：所述金属纳米粒子溶胶制备步骤中，与金属纳米粒子相应的金属化合物为硝酸银、氯金酸、氯铂酸、氯化钯中的至少一种；
    所述助剂为聚乙烯吡咯烷酮、柠檬酸钠、十六烷基三甲基溴化铵、十二烷基硫酸钠、十二烷基磺酸钠中的至少一种，其在金属纳米粒子溶胶中的浓度为1.5×10-4 g/mL～2.1×10-3 g/mL；
    所述还原剂为水合肼、抗坏血酸、硼氢化钠中的至少一种，其用量与金属纳米粒子溶胶中金属离子的摩尔比为1.2～4.8:1。
  6. 如权利要求4所述的硼酸盐基红色发光材料制备方法，其特征在于：所述金属纳米粒子混合溶胶制备步骤中的聚乙烯吡咯烷酮在所述的金属纳米粒子混合溶胶中浓度为0.001 g/mL～0.01g/mL。
  7. 如权利要求4所述的硼酸盐基红色发光材料制备方法，其特征在于：所述前驱体的制备是按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、过量于化学计量比1%～50%的硼酸以及与总稀土离子摩尔比为1～3:1的一水合柠檬酸混合，加入醇溶液溶解后，再加入金属纳米粒子混合溶胶，在75～90℃下加热搅拌形成湿凝胶，然后干燥得到前驱体；或按分子式(Y1-x-yEuxGdy)BO3中相应元素化学计量比将Y盐、Eu盐、Gd盐、以及过量于化学计量比1%～50%的硼酸混合，加入醇溶液溶解后，再加入金属纳米粒子混合溶胶和与总稀土离子摩尔比为1～4:1的燃烧剂，并搅拌、煮沸脱水，然后在300～600℃下点火燃烧，得到前驱体；其中，x的取值为0＜x≤0.3，y的取值为0≤y≤0.7。
  8. 如权利要求4或7所述的硼酸盐基红色发光材料制备方法，其特征在于：所述前驱体制备步骤中的Y盐为Y (NO3)3、YCl3中的至少一种；
    所述Eu盐为Eu (NO3)3、EuCl3中的至少一种；
    所述Gd盐为Gd (NO3)3、GdCl3中的至少一种；
    所述硼酸盐为硼酸三丁酯。
  9. 如权利要求4或7所述的硼酸盐基红色发光材料制备方法，其特征在于：所述前驱体的制备步骤中所述燃烧剂为一水合柠檬酸、尿素、甘氨酸中的至少一种。
  10. 如权利要求4所述的硼酸盐基红色发光材料制备方法，其特征在于：
    所述的预烧是在500℃~1000℃下热处理3~8h；
    所述的煅烧是在800~1300℃下热处理2~5h。
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