Metal particle doped indium salt-based phosphor and preparation method thereof

[0029] A preparation method of indium salt-based phosphor doped with metal particles, such as Figure 4 As shown, including the following steps:

[0030] S1, according to the general chemical formula Re' 1-x Re″InO 3 : The stoichiometric ratio of each element in yM, weighing the nanoparticles of M, the source compound of Re', the source compound of Re", and the source compound of indium; where Re' is one or two of Y, La, and Sc; Re" is one or two of Tm, Tb, Eu, Sm, Gd, Dy, Ce; M is one or two of Ag, Au, Pt, Pd; x is 0.001 to 0.2, y is 5 ×10 -5 ~1×10 -2;

[0031] S2. The weighed source compound of Re', the source compound of Re", and the source compound of In are dissolved in an aqueous alcohol solution to obtain a mixed solution;

[0032] S3. Adding the M nanoparticles to an aqueous solution containing a surface treatment agent to obtain surface-treated M nanoparticles;

[0033] S4. Add the surface-treated M nanoparticles to the mixed solution of step S2, stir, and then add citric acid monohydrate and polyethylene glycol in sequence, and then stir and react in a water bath to obtain Re' 1-x Re″InO 3 :yM precursor sol;

[0034] S5. Dry and grind the precursor sol, then go through a constant temperature pre-sintering treatment, cooling, and after grinding, place it in a reducing atmosphere or an air atmosphere for calcination, and cool it naturally. After grinding, the general chemical formula is Re' 1-x Re″InO 3 : yM indiumate-based phosphor.

[0035] In step S1, the M nanoparticles are prepared by a reduction method, and the preparation steps are as follows:

[0036] The salt solution of M, the auxiliary agent and the reducing agent are stirred and mixed and reacted to prepare a nanoparticle colloid of M; wherein the auxiliary agent is polyvinyl arsenide, sodium citrate, and cetyltrimethyl bromide At least one of ammonium chloride, sodium lauryl sulfate or sodium dodecyl sulfonate; the content of the adjuvant in the M nanoparticle colloid is 1×10 -4 g/mL~5×10 -2 g/mL; the reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate or sodium borohydride; the molar ratio of the added amount of the reducing agent to M is 3.6:1-18:1.

[0037] In step S1, in the source compound preparation step, the source compound of Re' is the nitrate of Re'; the source compound of Re" is the nitrate of Re"; the source compound of In is the nitrate of In or Chloride of In.

[0038] In step S2, the alcohol in the aqueous alcohol solution is ethanol; wherein the volume ratio of water to ethanol is 1:1 to 1:4.

[0039] In step S3, the concentration of the aqueous solution of the surface treatment agent is 0.005 g/mL to 0.1 g/mL; the surface treatment agent is polyvinylpyrrolidone (PVP, the same below).

[0040] In step S4, the complexing agent is citric acid monohydrate; the stabilizer is polyethylene glycol with a molecular weight of 10,000; the molar ratio of the added amount of citric acid monohydrate to M is 1:1 to 4: 1; The molecular weight of the polyethylene glycol is 10,000, and the concentration of the polyethylene glycol in the precursor sol is 0.01 to 0.10 g/ml; the temperature of the water bath is 75 to 95° C., the stirring The reaction time is 2-8h.

[0041] In step S5, the conditions of the drying treatment are 80-150°C blast drying for 4-24 hours; the temperature of the constant temperature pre-sintering treatment is 300-600°C, and the constant temperature time is 2-10 hours; the temperature of the calcination treatment 700~1000℃, the calcination time is 1~8h; the reducing atmosphere is one of a mixed reducing atmosphere of nitrogen and hydrogen, a carbon monoxide reducing atmosphere or a hydrogen reducing atmosphere; and in the mixed reducing atmosphere of nitrogen and hydrogen, nitrogen The volume ratio with hydrogen is 95:5 or 90:10.

[0043] Example 1

[0044] Preparation of Y by sol-gel method 0.999 Tm 0.001 InO 3 : 5×10 -4 Pt

[0045] Weigh 5.2 mg of chloroplatinic acid and dissolve it in 17 mL of ethanol. When it is completely dissolved, add 8 mg of sodium citrate and 1.2 mg of sodium lauryl sulfonate while stirring, and then slowly drop it into the solution with 0.4 mg of sodium borohydride. To 1×10 obtained in 10mL ethanol -3 mol/L sodium borohydride alcohol solution 0.4mL, after 5min reaction, add 1×10 -2 2.6 mL of mol/L hydrazine hydrate solution, after 40 minutes of reaction, 30 mL of Pt content is 5×10 -4 mol/L Pt nanoparticle sol. Weigh 0.15 g of PVP and add it to the Pt nanoparticle sol, and magnetically stir for 12 hours to obtain surface-treated Pt nanoparticles.

[0046] 0.01molY 0.999 Tm 0.001 InO 3 : 5×10 -4 Preparation of Pt: measure 10ml 1mol/L Y(NO 3 ) 3 , 1ml 0.01mol/L Tm(NO 3 ) 3 And 10ml 1mol/L In(NO 3 ) 3 Place the solution in a beaker, add 9ml of water and 30ml of ethanol mixed solution and 10ml of the above-mentioned treated metal particle sol, stir well; add 4.2028g of citric acid monohydrate, the molar ratio of citric acid to metal ions in the raw material is 1:1, and then Add 0.6g polyethylene glycol, the concentration of polyethylene glycol (PEG, molecular weight is 10000) is 0.01g/ml, and stir for 8h in a 75℃ water bath to obtain a uniform and transparent precursor sol; Dry in a blast drying oven for 24 hours to volatilize the solvent to obtain a xerogel; grind the obtained xerogel into powder, put it in a high-temperature box furnace, pre-fire at a constant temperature of 300°C for 10 hours, cool, and place it after grinding. In a box-type high-temperature furnace, calcinate in an air atmosphere at 1000°C for 1 hour, cool it naturally, and take out and grind to obtain the required phosphor.

[0047] Example 2

[0048] Preparation of La by sol-gel method 0.995 Sm 0.005 InO 3 :1×10 -3 Au

[0049] Weigh 7.6 mg of sodium borohydride and dissolve it in 10 mL of ethanol to obtain 10 mL of sodium borohydride alcohol solution with a concentration of 0.02 mol/L for use. Weigh 16.4mg of chloroauric acid and dissolve it in 7.5mL of ethanol. After it is completely dissolved, add 56mg of sodium citrate and 24mg of cetyltrimethylammonium bromide under stirring, and add to the mixed solution under magnetic stirring. Add 2.5mL of the sodium borohydride alcohol solution prepared above, and continue the reaction for 30 minutes to obtain a 10ml Au content of 4×10 -3 mol/L Au nanoparticle sol. Weigh 1g of PVP and add it to the Au nanoparticle sol, and magnetically stir for 8h to obtain the Au nanoparticle after surface treatment.

[0050] 0.01mlLa 0.995 Sm 0.005 InO 3 :1×10 -3 Preparation of Au: Measure 9.95ml 1mol/L LaCl 3 , 1ml0.05mol/L Sm(NO 3 ) 3 And 10ml 1mol/L In(NO 3 ) 3 Put the solution in a beaker, add 0.05ml of water and 30ml of ethanol mixed solution and 2.5ml of the above-mentioned treated metal particle sol, fully stir; add 8.4056g of citric acid monohydrate, so that the molar ratio of citric acid to metal ions in the raw material is 2: 1. Add 5.25g polyethylene glycol, and the concentration of polyethylene glycol (PEG, molecular weight is 10000) is 0.1g/ml. Stir in a water bath at 85℃ for 4 hours to obtain a uniform and transparent precursor sol; Dry in a blast drying oven at 100℃ for 8h, volatilize the solvent to obtain a dry gel; grind the obtained dry gel into powder, put it in a high-temperature box furnace, pre-fire at 600℃, constant temperature for 2h, cool and grind to obtain the precursor The precursor is placed in a tube furnace, calcined in an air atmosphere at 800 ℃ for 8 hours, natural cooling, and after taking out the grinding to obtain the required phosphor.