WO2011147088A1 - 含有金属粒子的稀土掺杂的卤氧化物发光材料及其制备方法 - Google Patents
含有金属粒子的稀土掺杂的卤氧化物发光材料及其制备方法 Download PDFInfo
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- WO2011147088A1 WO2011147088A1 PCT/CN2010/073290 CN2010073290W WO2011147088A1 WO 2011147088 A1 WO2011147088 A1 WO 2011147088A1 CN 2010073290 W CN2010073290 W CN 2010073290W WO 2011147088 A1 WO2011147088 A1 WO 2011147088A1
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- 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
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- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- 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
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Definitions
- Rare earth doped 13 ⁇ 4 oxide luminescent material containing metal particles and preparation method thereof Rare earth doped 13 ⁇ 4 oxide luminescent material containing metal particles and preparation method thereof
- the invention relates to a luminescent material and a preparation method thereof, in particular to a rare earth doped oxyhalide luminescent material containing metal nanoparticles and a preparation method thereof.
- field emission devices have attracted much attention due to their low operating voltage, low power consumption, no need for deflection coils, no X-ray radiation, anti-radiation and magnetic field interference.
- High-brightness can be obtained by field-emitting cathode ray excitation of luminescent materials.
- the high color rendering field emission source can be applied to professional lighting, display, various indications and general lighting. It can be seen that the preparation of high performance luminescent materials is of great significance for the development of excellent performance field emission devices.
- commercial field emission device luminescent materials are mainly derived from the sulfide series, oxide series and sulfur oxide series luminescent materials of conventional cathode ray tubes and projection television tubes.
- the sulfide has high luminance, but the stability is poor; the oxide has good stability, and the luminance and conductivity are not as good as sulfide. Therefore, researching a luminescent material with good stability and high luminescence intensity has become the focus of many researchers. The usual research direction is to modify these luminescent materials, or to develop new luminescent materials with superior performance for field use. On the launch device. technical problem
- the technical problem to be solved by the present invention is to provide a rare earth doped oxyhalide luminescent material with good stability, high internal quantum efficiency and high luminescence intensity and a preparation method thereof.
- a technical solution to solve the technical problem of the present invention is to provide a rare earth doped oxyhalide luminescent material containing metal particles, wherein: the chemical formula of the rare earth doped oxyhalide luminescent material containing metal particles is: Re x Re" x OX: yM, wherein Re' is the first rare earth element, Re" is the second rare earth element; X is F, Cl, or Br; M is a metal nanoparticle, x is 0.001 ⁇ 0.15, y is 5xl0 -5 ⁇ 2xl0 -3 .
- the first rare earth element 1 ⁇ ' is Y, La, or Sc
- the second rare earth element Re" is Tm, Tb, Eu, Sm, Gd, Dy, or Ce.
- the metal nanoparticles M are Ag, Au, Pt, or Pd metal nanoparticles.
- Step 1 preparing a metal nanoparticle colloid
- Step 2 adding a metal nanoparticle colloid to the polyvinylpyrrolidone solution to surface-treat the metal nano-particles;
- Step 3 Weighing rare earth oxide or rare earth oxalate and dissolving it with concentrated nitric acid, heating to evaporate excess nitric acid to obtain a rare earth salt;
- Step 4 Add the water and ethanol mixed solution with a volume ratio of 1:3 to 8 and the metal nanoparticles in the second step to the third step. After stirring, add citric acid monohydrate to make the molar ratio of citric acid to metal ions 1 ⁇ 5: 1 , sequentially adding polyethylene glycol and an excess of [3 ⁇ 4 ammonium, heating in a water bath, stirring to obtain a precursor sol;
- Step 5 Drying the precursor sol in step 4 to obtain a xerogel, then grinding the dry gel into a powder, preheating at a constant temperature, cooling, grinding, and then calcining in a reducing atmosphere or an air atmosphere, and then cooling A rare earth doped oxyhalide luminescent material containing metal particles.
- the step of preparing the metal nanoparticle colloid in the first step comprises the steps of: dissolving an appropriate amount of the metal salt solution into ethanol or water, diluting into a solution; and then sequentially adding and stabilizing and dispersing under magnetic stirring.
- the auxiliary agent and the reducing agent, the metal nanoparticle colloid is obtained after the reaction;
- the auxiliary agent is polyvinylpyrrolidone, sodium citrate, cetyltrimethylammonium bromide, dodecane Sodium sulphate or sodium dodecyl sulfonate, the reducing agent being hydrazine hydrate, ascorbic acid, sodium citrate or sodium borohydride.
- the concentration of the polyethylene glycol is the concentration of the polyethylene glycol
- the heating temperature of the water bath is 75°C ⁇ 90°C, and the stirring time is 2 ⁇ 8 hours; in the obtained precursor sol, the ammonium halide is added in an excess of 5%-50%.
- the element in the oxyhalide luminescent material is chlorine
- concentrated hydrochloric acid is used instead of concentrated nitric acid to dissolve the rare earth oxide or rare earth oxalate, and heating is performed to evaporate excess concentrated hydrochloric acid to obtain a rare earth chloride salt; Accordingly, in the fourth step, it is not necessary to add an excessive amount of ammonium chloride in the obtained precursor sol.
- the drying condition is drying in a blast drying oven at a temperature of 80 ° C to 120 ° C for 4 to 24 hours; the calcination temperature is 500 ° C to 800 ° C, and the calcination time is For 2 to 6 hours.
- the calcination temperature is 800-1000 ° C and the calcination time is 2 to 6 hours; the reducing atmosphere is a mixture of nitrogen and hydrogen or pure hydrogen or carbon monoxide.
- the present invention introduces metal particles into a rare earth doped oxide luminescent material, and the surface plasmon resonance effect generated by the metal surface improves the luminescence intensity of the oxide luminescent material;
- the luminescent material has good stability, uniformity and singleness, good luminescence performance, high purity and brightness of the light color emitted after excitation, and can be applied to field emission devices.
- the preparation method of the invention is simple in operation, non-polluting, easy to control, low in equipment requirements and advantageous for industrial production, and can be widely used in the field of preparation of luminescent materials.
- 1 is a flow chart of a method for preparing a rare earth doped oxyhalide luminescent material containing metal nanoparticles according to the present invention
- 2 is a comparison chart of luminescence spectra of a luminescent material prepared in Example 9 of the present invention under a cathode ray excitation at an acceleration voltage of 3.0 Kv, wherein a curve a is La. . 995 Tm. . . . . 5 OCl: lxl (the emission ray of the T 4 Ag luminescent material, curve b is the La of the 995 Tm without the addition of the metal nanoparticle Ag. 5 5 emission spectroscopy of the OCl luminescent material;
- FIG. 3 is a comparison chart of luminescence spectra of a luminescent material prepared in Example 10 of the present invention under a cathode ray excitation at an acceleration voltage of 3.0 Kv, wherein curve c is Lao. ⁇ Dyo. ⁇ OCl: 5xl (T 5 Ag luminescent material) Emission spectrum, curve d is the emission spectrum of La Q. 98 Dy aQ2 OCl luminescent material without metal nanoparticle Ag added.
- the invention provides a rare earth doped oxide luminescent material containing metal particles, the chemical formula of which is: ReV x Re" x OX: yM, wherein Re' is the first rare earth element and Re" is the second rare earth element Element; X is F, Cl, or Br; M is a metal nanoparticle, x is 0.001 ⁇ 0.15, and y is 5xl (T 5 ⁇ 2xl (T 3 ) .
- the first rare earth element 1 ⁇ ' is Y, La, or Sc
- the second rare earth element Re" is Tm, Tb, Eu, Sm, Gd, Dy, or Ce.
- the metal nanoparticles M are Ag, Au, Pt, or Pd metal nanoparticles.
- FIG. 1 shows the flow of the preparation method of the present invention, which comprises the following steps:
- Step S01 preparing a metal nanoparticle colloid
- Step S02 adding a metal nanoparticle colloid to a polyvinylpyrrolidone solution to surface-treat the metal nanoparticle;
- Step S03 Weighing rare earth oxide or rare earth oxalate and dissolving it with concentrated nitric acid, heating to evaporate excess nitric acid to obtain rare earth nitrate;
- Step S04 adding a water and ethanol mixed solution having a volume ratio of 1:3 to 8 and the metal nanoparticles in the step S02 to the step S03, and adding citric acid monohydrate after stirring, so that the molar ratio of the citric acid to the metal ion is 1 ⁇ 5: 1 , sequentially adding polyethylene glycol and an excess of [3 ⁇ 4 ammonium, heating in a water bath, stirring to obtain a precursor sol;
- Step S05 drying the precursor sol in step S04 to obtain a xerogel, and then grinding the xerogel into a powder, preheating at a constant temperature, cooling, grinding, and then calcining in a reducing atmosphere or an air atmosphere, and cooling is performed.
- the preparing the metal nanoparticle colloid in the step S01 comprises the following steps: dissolving an appropriate amount of the metal salt solution into ethanol or water, diluting into a solution; and then adding the auxiliary agent and the reducing agent in sequence under magnetic stirring. After the reaction, a metal nanoparticle colloid is obtained.
- the auxiliary agent is polyvinylpyrrolidone, sodium citrate, cetyltrimethylammonium bromide, sodium lauryl sulfate or sodium dodecyl sulfate, and the reducing agent is hydrazine hydrate. , ascorbic acid, sodium citrate or sodium borohydride.
- the concentration of the polyethylene glycol is 0.01 to 0.20 g/ml
- the heating temperature in the water bath is 75 ° C to 90 ° C
- the stirring time is 2 to 8 hours.
- An ammonium halide is added in an amount of 5% to 50% by weight in the obtained precursor sol.
- step S03 concentrated hydrochloric acid may be used instead of concentrated nitric acid to dissolve the rare earth oxide or rare earth oxalate, and heating to evaporate excess concentrated hydrochloric acid to obtain a rare earth chloride salt;
- step S04 it is not necessary to add an excessive amount of ammonium chloride in the obtained precursor sol.
- the drying condition is to dry in a blast drying oven at a temperature of 80 ° C to 120 ° C for 4 to 24 hours.
- the calcination temperature is 500 ° C to 800 ° C, the calcination time is 2 to 6 hours; the calcination temperature is 800 to 1000 ° C, and the calcination time is 2 to 6 hours; the reducing atmosphere is a mixture of nitrogen and hydrogen or Pure hydrogen or carbon monoxide.
- the invention introduces metal particles into the rare earth doped oxide luminescent material, and the surface plasmon resonance effect generated by the metal surface improves the luminescence intensity of the oxide luminescent material; the luminescent material prepared by the invention has good stability and has The appearance is hooked and single, the luminescence performance is good, and the excitation The color purity and brightness emitted after the hair is high, and can be applied to the field emission device.
- the preparation method of the invention has the advantages of simple operation, no pollution, easy control, low equipment requirements and favorable industrial production, and can be widely applied in the field of preparation of luminescent materials.
- Pt nanoparticle sol Weigh 5.18mg of chloroplatinic acid (H 2 PtCl 6 '6H 2 0 ) and dissolve it in 17mL of deionized water; 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 weighed and dissolved in 10 mL of deionized water to obtain 10 mL of boron having a concentration of lxl (T 3 mol/L).
- chloroplatinic acid H 2 PtCl 6 '6H 2 0
- Aqueous sodium hydride solution 10mL of hydrazine hydrate solution with a concentration of lxlO 2 mol / L; while magnetic stirring, first add 0.4mL aqueous sodium borohydride solution to the chloroplatinic acid aqueous solution, stir the reaction for 5min, then go to chlorine 2.6 mL of X 10 -2 mol/L hydrazine hydrate solution was added dropwise to the platinum acid aqueous solution, and then the reaction was continued for 40 min to obtain a Pt nanoparticle sol having a 20 mLPt content of 5 ⁇ 10 4 mol/L; then 3 mL of the obtained Pt nanometer was obtained.
- the granule sol, 3.0 mg of PVP was added to the Pt nanoparticle sol, and magnetically stirred for 12 hours (h) to obtain surface-treated Pt nanoparticles.
- the concentration of polyethylene glycol (PEG, molecular weight 10000) was 0.01 g/ml, and the mixture was stirred for 8 hours in a 75 ° C water bath to obtain uniformity.
- Transparent precursor sol The sol is dried in a blast oven at 80 ° C for 24 h, and the solvent is evaporated to obtain a dry gel; the obtained dry gel is ground into a powder and placed in a high temperature box furnace at 500 ° C. Preheated for 6 hours at a constant temperature, cooled and ground to obtain a precursor; the precursor was placed in a box-type high-temperature furnace, calcined at 1000 ° C for 2 h in an air atmosphere, and naturally cooled, and the desired luminescent material was obtained after taking out the grinding.
- Example 2 La was prepared by a sol-gel method. . 995 Sm. . . . . 5 OCl: l lO" 4 Au
- PEG polyethylene glycol
- Ag nanoparticle sol 3.40 mg of silver nitrate (AgN0 3 ) was weighed and dissolved in 18.4 mL of deionized water; when silver nitrate was completely dissolved, 22 mg of sodium citrate and 20 mg of PVP were weighed and dissolved under magnetic stirring.
- Lao. 985 Tbo.oiSmo.oo50Cl Preparation of 4x lO" 4 Ag: Accurately weigh 3.2092g La 2 0 3 , 0.0374g Tb 4 0 7 , 0.0349gSm 2 O 3 in a beaker, using concentrated hydrochloric acid (HC1) Dissolving, heating to evaporate excess HC1 to obtain a rare earth halide salt; adding a certain amount of a mixed solution of 10 ml of water and 50 ml of ethanol, wherein the volume ratio of water to ethanol is 1:5, and the above metal sol is fully stirred; 6.3042g citric acid monohydrate, the molar ratio of citric acid to metal ion in the raw material is 3:1, and then 10.2g of polyethylene glycol is added to make the concentration of polyethylene glycol (PEG, molecular weight 10000) 0.15g/ml.
- PEG polyethylene glycol
- Example 4 La was prepared by a sol-gel method. . 98 Eu. . . . 2 OCl: 1 10" 4 Pd
- Pd nanoparticle sol 0.43mg of palladium chloride (PdCl 2 '2H 2 0 ) was dissolved in 8.5mL of deionized water; when palladium chloride was completely dissolved, ll.Omg sodium citrate and 4.0mg were weighed. Sodium lauryl 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 a concentration of lxl (T 2 mol/L of sodium borohydride).
- the reducing solution under the magnetic stirring environment, rapidly add 0.48mL l xl (T 2 mol / L sodium borohydride aqueous solution) to the palladium chloride aqueous solution, and then continue the reaction for 20min, the lOmLPd content is I x l0_ 4 mol / L
- the Pd nanoparticle sol was then added to the lOmLPd nanoparticle sol to add ImgPVP and magnetically stirred for 4 hours to obtain surface treated Pd nanoparticles.
- Lao. 98 Eu. . 2 OCl Preparation of 1 10" 4 Pd: Accurately weigh 3.1929g La 2 0 3 and 0.0704g Eu 2 0 3 in a beaker, dissolve it with concentrated hydrochloric acid (HC1), and heat to evaporate excess concentrated hydrochloric acid.
- HC1 concentrated hydrochloric acid
- Obtaining a rare earth halide salt adding a certain amount of a mixed solution of 10 ml of water and 60 ml of ethanol, wherein water and ethanol are in a volume The ratio is 1:6, and the above metal particle sol is stirred well; 10.507 g of citric acid is added, the molar ratio of citric acid to the metal ion in the raw material is 5:1, and then 16 g of polyethylene glycol, polyethylene glycol (PEG) is added.
- PEG polyethylene glycol
- the molecular weight is 10000), the concentration is 0.20g/ml, and the mixture is stirred for 2 hours in a water bath at 85 ° C to obtain a transparent precursor sol; the sol is dried in a blast drying oven at 100 ° C for 12 h, and the solvent is evaporated. Dry gel; the obtained dry gel is ground into a powder, placed in a high temperature box furnace, preheated at 500 ° C for 2 h, cooled, and ground to obtain a precursor; the precursor is placed in a box type high temperature furnace, After calcination at 800 ° C for 5 h in an air atmosphere, it was naturally cooled, and the desired luminescent material was obtained after taking out the grinding.
- Preparation of Pt/Au nanoparticle sol Weigh 10.7mg of chloroauric acid ( AuCl 3 'HC14H 2 0 ) and 13.56mg of chloroplatinic acid ( H 2 PtCl 6 .6H 2 0 ) dissolved in 28mL of deionized water; After dissolving, 22 mg of sodium citrate and 20 mg of PVP were weighed and dissolved in the above mixed solution under magnetic stirring; the freshly 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 lO.
- the concentration was 0.10 g/ml, and stirred in a water bath at 80 ° C for 6 h to obtain a transparent precursor sol; the sol was dried in a blast oven at 110 ° C for 12 h, and the solvent was evaporated to obtain a dry gel; The dry gel is ground into a powder, placed in a high-temperature box furnace, preheated at 500 ° C for 5 h, cooled, and ground to obtain a precursor; the precursor is placed in a box-type high In the furnace, calcination was carried out in an air atmosphere at 900 ° C for 3 h, and it was naturally cooled, and the desired luminescent material was obtained after taking out the grinding.
- Example 6 Preparation by Sol-Gel Method. 97 8. . . . . 26 13 ⁇ 4. . . . . 4 ( ⁇ : 2 10 -3 into ⁇
- Ag nanoparticle sol 3.40 mg of silver nitrate (AgN0 3 ) was weighed and dissolved in 18.4 mL of deionized water; when silver nitrate was completely dissolved, 22 mg of sodium citrate and 20 mg of PVP were weighed and dissolved under magnetic stirring.
- the solvent obtained a dry gel was ground into a powder, placed in a high-temperature box furnace, preheated at 600 ° C for 3 hours, cooled, ground in a tube, at 900 ° C, reducing atmosphere (mixture of nitrogen and hydrogen, volume ratio of 95: 5) calcined for 4h, naturally cooled, taken out
- the desired luminescent material is obtained after grinding.
- Example 7 La was prepared by a sol-gel method. . 97 Ce. . . . 3 OBr: 2xlO" 4 Ag
- Ag nanoparticle sol 3.40 mg of silver nitrate (AgN0 3 ) was weighed and dissolved in 18.4 mL of deionized water; when silver nitrate was completely dissolved, 22 mg of sodium citrate and 20 mg of PVP were weighed and dissolved under magnetic stirring.
- Lao. 97 Ce 0 . 03 OBr Preparation of 2xlO -4 Ag: Accurately weigh 3.1604g La 2 0 3 , 0.1033g Ce0 2 in a beaker, dissolve it with concentrated nitric acid (HN0 3 ), heat to make excess Evaporation of HN0 3 to obtain rare earth nitrate; adding a certain amount of 10 ml of water and 46 ml of ethanol mixed solution, wherein the volume ratio of water to ethanol is 1:5, and the above metal particle sol is stirred well; adding 4.2028 g of hydrated citric acid, lemon The molar ratio of acid to metal ion in the raw material is 2:1, and 6 g of polyethylene glycol and 2.9383 g of NH 4 Br (molar fraction, excess 50%) are sequentially added, and the concentration of polyethylene glycol (PEG, molecular weight 10000) is 0.10 g.
- PEG polyethylene glycol
- Lao.ssGdo.iTbo.osOF Preparation of 5 lO" 4 Au: Accurately weigh 2.7694g La 2 O 3 , 0.3625g Gd 2 0 3 and 0.1869g Tb 4 0 7 in a beaker with concentrated nitric acid (HN0 3 Dissolving it, heating to evaporate excess HNO 3 to obtain rare earth nitrate; adding a certain amount of 10 ml of water and 50 ml of ethanol mixed solution and the above treated metal particle sol, stirring well; adding 8.5656 g of hydrated citric acid The molar ratio of citric acid to metal ion in the raw material is 4:1, and 6.6 g of polyethylene glycol and 0.9630 g of NH 4 F (molar fraction, excess 30%) are sequentially added, and the concentration of polyethylene glycol (PEG, molecular weight 10000) is 0.1g/ml, stirred in a water bath at 85 ° C for 4 h to obtain a uniform transparent
- Example 9 La was prepared by a sol-gel method. . 995 Tm. . . . . 5 OCl: 1 10" 4 Ag
- Ag nanoparticle sol 3.40 mg of silver nitrate (AgN0 3 ) was weighed and dissolved in 18.4 mL of deionized water; when silver nitrate was completely dissolved, 22 mg of sodium citrate and 20 mg of PVP were weighed and dissolved under magnetic stirring.
- Lao. 995 Tm. . . . . Preparation of 5 OCl: l lO" 4 Ag Accurately weigh 1.6209g La 2 0 3 and 0.0096g Tm 2 0 3 in a beaker, dissolve it with concentrated hydrochloric acid (HC1), and heat to evaporate excess HC1.
- HC1 hydrochloric acid
- a rare earth halide salt a mixed solution of 8 ml of water and 32 ethanol, wherein the volume ratio of water to ethanol is 1:5, and the above-mentioned treated metal particle sol is thoroughly stirred; 2.1014 g of hydrated citric acid, citric acid and raw materials are added.
- the molar ratio of metal ions is 2:1, and then 4g of polyethylene glycol is added.
- the concentration of polyethylene glycol (PEG, molecular weight is 10000) is 0.10g/ml, and stirred in a water bath of 80 ° C for 6 hours to obtain uniform transparency.
- Precursor sol the sol is dried in a blast oven at 110 ° C for 12 h, and the solvent is evaporated to obtain a dry gel; the obtained dry gel is ground into a powder, placed in a high temperature box furnace, 500 ° C, constant temperature After calcination for 5 h, cooling and grinding, the precursor is obtained; the precursor is placed in a box-type high-temperature furnace, calcined at 800 ° C for 4 h in an air atmosphere, and naturally cooled, and the desired luminescent material La is obtained after being taken out and ground. .
- La 0 . 995 Tm prepared in this example is 5 0C1: l lO" 4 Ag (curve a) and La 0 .995Tmo.oo 5 OCl (curve b) luminescent material at an accelerating voltage of 3.0Kv
- the comparison of the luminescence spectra under the excitation of the cathode ray shows that the emission peak at 461 nm can increase the luminescence intensity of the phosphor after coating the metal nanoparticles by 78% compared with the uncoated sample.
- Example 10 La was prepared by a sol-gel method. . 98 Dy. . . . 2 OCl: 5 10" 5 Ag
- Ag nanoparticle sol 3.40 mg of silver nitrate (AgN0 3 ) was weighed and dissolved in 18.4 mL of deionized water; when silver nitrate was completely dissolved, 22 mg of sodium citrate and 20 mg of PVP were weighed and dissolved under magnetic stirring.
- Lao. 98 Dy 0 . 02 OCl Preparation of 5 lO" 5 Ag: Accurately weigh 1.5965g La 2 0 3 and 0.0373g Dy 2 0 3 in a beaker, dissolve it with concentrated hydrochloric acid (HC1), heat to make Excess HC1 is evaporated to obtain a rare earth halide salt; a mixed solution of 8 ml of water and 32 ethanol is added, wherein the volume ratio of water to ethanol is 1:5, and the above treated metal particle sol is thoroughly stirred; 4.2028 g of hydrated citric acid is added.
- HC1 hydrochloric acid
- the molar ratio of citric acid to the metal ion in the raw material is 4:1, and then 4 g of polyethylene glycol is added, and the concentration of polyethylene glycol (PEG, molecular weight 10000) is 0.10 g/ml, in a water bath of 80 ° C, After stirring for 6 h, a uniform transparent precursor sol was obtained; the sol was dried in a blast oven at 100 ° C for 12 h, and the solvent was evaporated to obtain a dry gel; the obtained dry gel was ground into a powder and placed in a high temperature box furnace.
- PEG polyethylene glycol
- the precursor is obtained; the precursor is placed in a box-type high-temperature furnace, calcined in an air atmosphere at 800 ° C for 4 h, naturally cooled, and taken out after grinding to obtain the desired luminescent material La 0 . 98 Dy 0 . 02 OCl: 5xl (T 5 Ag. Meanwhile, under the same conditions, a luminescent material La. 98 Dy. 2 OCl was prepared without coating the metal particles.
- La 0 . 98 Dy 0 . 02 OCl: 5 l0" 5 Ag (curve c ) and La 0 .98Dy 0 .02OCl (curve d) luminescent material prepared in this example have an accelerating voltage of 3.0 Kv.
- the contrast of the illuminating light under the excitation of the cathode ray shows that the emission peak at 572 nm shows that the luminescent intensity of the phosphor after coating the metal nanoparticles is 79% higher than that of the uncoated sample.
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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EP10851960.4A EP2578660B1 (en) | 2010-05-27 | 2010-05-27 | Oxyhalide luminescent material doped with rare earth containing metal particle and production method thereof |
PCT/CN2010/073290 WO2011147088A1 (zh) | 2010-05-27 | 2010-05-27 | 含有金属粒子的稀土掺杂的卤氧化物发光材料及其制备方法 |
US13/699,951 US8834745B2 (en) | 2010-05-27 | 2010-05-27 | Oxyhalide luminescent material doped with rare earth containing metal particle and production method thereof |
JP2013511500A JP5649724B2 (ja) | 2010-05-27 | 2010-05-27 | 金属粒子を含有する、希土ドーピングされたハロゲン酸化物発光材料及びその調製方法 |
CN201080065459.XA CN102892858B (zh) | 2010-05-27 | 2010-05-27 | 含有金属粒子的稀土掺杂的卤氧化物发光材料及其制备方法 |
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EP (1) | EP2578660B1 (zh) |
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Cited By (6)
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CN104059667A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的钒酸钇发光材料及制备方法 |
CN104059659A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的钆酸钙绿光发光材料及制备方法 |
CN104059663A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的镓酸盐发光材料及制备方法 |
CN104059651A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的铌酸钇发光材料及制备方法 |
CN104059652A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的铌酸盐发光材料及制备方法 |
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DE19745647A1 (de) | 1997-10-15 | 1999-04-22 | Basf Ag | Wärmeisolationsbeschichtung |
EP2561038B1 (en) | 2010-04-20 | 2019-11-20 | Basf Se | Polymerized films with line texture or fingerprint texture |
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CN111936315A (zh) | 2018-04-25 | 2020-11-13 | 巴斯夫欧洲公司 | 在柔性基材上制备强粘附性液晶膜的方法 |
CN113800534A (zh) * | 2021-09-30 | 2021-12-17 | 畅的新材料科技(上海)有限公司 | 一种多稀土掺杂硼化物的制备方法 |
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CN104059659A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的钆酸钙绿光发光材料及制备方法 |
CN104059663A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的镓酸盐发光材料及制备方法 |
CN104059651A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的铌酸钇发光材料及制备方法 |
CN104059652A (zh) * | 2013-03-20 | 2014-09-24 | 海洋王照明科技股份有限公司 | 掺杂金属纳米粒子的铌酸盐发光材料及制备方法 |
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Publication number | Publication date |
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EP2578660A4 (en) | 2017-01-25 |
US20130069006A1 (en) | 2013-03-21 |
EP2578660A1 (en) | 2013-04-10 |
US8834745B2 (en) | 2014-09-16 |
JP5649724B2 (ja) | 2015-01-07 |
CN102892858A (zh) | 2013-01-23 |
EP2578660B1 (en) | 2019-06-05 |
CN102892858B (zh) | 2014-07-02 |
JP2013530269A (ja) | 2013-07-25 |
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