CN102234512A - Modified luminescent material and preparation method thereof - Google Patents

Modified luminescent material and preparation method thereof Download PDF

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CN102234512A
CN102234512A CN2010101608482A CN201010160848A CN102234512A CN 102234512 A CN102234512 A CN 102234512A CN 2010101608482 A CN2010101608482 A CN 2010101608482A CN 201010160848 A CN201010160848 A CN 201010160848A CN 102234512 A CN102234512 A CN 102234512A
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colloid
luminescent material
mol
preparation
nano particle
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CN102234512B (en
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周明杰
马文波
吕婷
王烨文
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention discloses a modified luminescent material and a preparation method thereof. The modified luminescent material comprises fluorescent powder particles coated with aluminum-doped zinc oxide and elemental metal nanoparticles. The preparation method of the modified luminescent material comprises the following steps: firstly preparing a Zn1-xAlxO colloid and a metal nanoparticle colloid separately, and uniformly mixing the two colloids to obtain a mixed colloid; adding the fluorescent powder into the mixed colloid, and uniformly mixing and drying to obtain the coated fluorescent powder coated with the mixed colloid; and carrying out heat treatment on the coated fluorescent powder in an air atmosphere or a reducing atmosphere to obtain the modified luminescent material. According to the invention, the modified luminescent material has the advantages of high stability and high luminance; and the preparation method has the advantages of simple process, convenience in operation, low equipment requirement and short preparation period, and ensures that the prepared product is good in stability and high in luminance.

Description

Modification luminescent material and preparation method thereof
Technical field
The invention belongs to photoelectron and lighting technical field, relate to a kind of luminescent material and preparation method thereof, relate in particular to a kind of modification luminescent material and preparation method thereof, this modification luminescent material can be applied in the field emission light-emitting device.
Background technology
Field Emission Display (FED) is called as flat-panel monitor of future generation, it is to utilize a large amount of direct impact fluorescence material of micro cathode ejected electron bundle imaging on the field emission cathode array (FEA), compare with traditional cathode ray tube (CRT), FED does not need deflector coil, operating voltage low, can make very thin FED flat-panel monitor (FPD), and compare with other FPD, FED all has the potential advantage at aspects such as brightness, visual angle, time of response, operating temperature range, energy consumptions.One of key factor of the good FED of processability is a Preparation of Fluorescent Material.At present, form division from fluorescent material, can be divided into two big classes: sulfide series fluorescent material and oxide compound series fluorescent material, sulfide series fluorescent material has higher luminous efficiency, but its less stable, decompose generation sulphur easily under the low-voltage, high-current beam bombardment, make the performance degradation of material itself on the one hand, sulphur anticathode electron emission pin has serious " poisoning " effect on the other hand; Oxide compound series fluorescent material has advantages of higher stability, but under the denoted low voltage electron beam bombardment, luminous efficiency is not high enough, and oxide compound series fluorescent material is isolator, makes its use in the FED device be subjected to certain restriction.
Summary of the invention
The technical problem to be solved in the present invention is, at the above-mentioned defective of prior art, provides a kind of good stability, modification luminescent material that luminosity is high.
The technical problem that the present invention further will solve is, provides that a kind of preparation technology is simple, easy to operate, equipment requirements is low, preparation cycle is short and the preparation method of the modification luminescent material that preparing product good stability and luminosity thereof are high.
The technical solution adopted for the present invention to solve the technical problems is: a kind of modification luminescent material is to be coated with Al-Doped ZnO and the formation of metal simple-substance nanoparticle by the particle at fluorescent material.
In the modification luminescent material, described metal simple-substance nanoparticle is a kind of among Au, Pt, Ag or the Pd.
In the modification luminescent material, the Al-Doped ZnO that every 5g fluorescent material coats is 6 * 10 -5～4 * 10 -3Mol.
In the modification luminescent material, the metal simple-substance nanoparticle that every 5g fluorescent material coats is 1 * 10 -7～6.25 * 10 -5Mol.
The preparation method of modification luminescent material may further comprise the steps:
(1), prepares Zn respectively 1～xAl xO colloid, metal nanometer particle colloid, 0＜x≤0.05 wherein, Zn 1～xAl xO colloidal concentration is 0.05mol/L～0.70mol/L, and the concentration of metal nanometer particle colloid is 1 * 10 ～4～1 * 10 ～3Mol/L, and with Zn 1～xAl xO colloid and metal nanometer particle colloid are mixed and made into colloid mixture;
(2), fluorescent material is joined mixing in the colloid mixture in the step (1), 15～70 ℃ of reaction 2～10h down, dry then metal nanoparticle and Zn 1～xAl xThe coating fluorescent powder that the colloid mixture of O coats;
(3), at air atmosphere, reducing atmosphere or H 2Under the S atmosphere, the coating fluorescent powder that step (2) is made is in 400～1000 ℃ of anneal 0.5～6h, the modification luminescent material.
The preparation method of modification luminescent material, preferred in the described step (2): as after at first fluorescent material being carried out surface treatment, to join mixing in the colloid mixture in the step (1) again.
The preparation method of modification luminescent material, in the described step (1), Zn 1～xAl xThe preparation of O colloidal preferably includes following steps:
(1.11), press chemical formula Zn 1～xAl xThe molar ratio of each metal ion takes by weighing zinc salt and aluminium salt raw material among the O, and wherein the span of x is 0＜x≤0.05; In zinc salt and aluminium salt raw material, add stablizer and solvent, heat 40～70 ℃ and obtain precursor solution behind stirring 4～8h down;
(1.12), with the precursor solution of gained in 60 ℃ of following ageing 56～90h, obtain Zn 1～xAl xThe O colloid.
The preparation method of modification luminescent material, described step (1.11) is preferred: described zinc salt is zinc acetate, zinc nitrate, zinc chloride or zinc sulfate; Described aluminum nitrate, aluminum chloride or Tai-Ace S 150; Described stablizer is a kind of in monoethanolamine, diethanolamine, the trolamine, and solvent is ethylene glycol monomethyl ether or ethanolic soln.
The preparation method of modification luminescent material, in the described step (1), the preparation of metal nanometer particle colloid preferably includes following steps:
(1.21), taking by weighing feed metal salt is dissolved in ethanol or the deionized water and forms metal salt solution;
(1.22), stir down, in the metal salt solution of step (1.21), add auxiliary agent and make mixing solutions, wherein the content of auxiliary agent is 1.5 * 10 in the mixing solutions ～4G/mL～2.1 * 10 ～3G/mL;
(1.23), stir down, in the mixing solutions of step (1.22), be 1.2～4.8: 1 ratio in the mol ratio of reductant solution and metal-salt, adding concentration again is 1 * 10 ～3Mol/L～1 * 10 ～2The reductant solution of mol/L promptly obtains metal nanometer particle colloid behind reaction 10min～45min.
The preparation method of modification luminescent material, described step (1.22) is preferred: described metal salt solution is water-soluble or alcoholic acid Au salts solution, Pt salts solution, Ag salts solution or Pd salts solution; Auxiliary agent is at least a in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate, the sodium laurylsulfonate; In the described step (1.23), reductive agent is a kind of in hydrazine hydrate, xitix or the sodium borohydride.
The preparation method of modification luminescent material, it is to add dehydrated alcohol in the fluorescent material, at room temperature to stir 1～20h that described phosphor surface is handled, and filters to be placed on 50～200 ℃ of down dry 3～15h.
Modification luminescent material of the present invention is to be coated with Al-Doped ZnO and metal simple-substance nanoparticle at fluorescent material, because the metal simple-substance nanoparticle is coated on the fluorescent powder grain outside, formed surface plasma between metal simple-substance nanoparticle and the fluorescent material, because surface plasma (Surface Plasmon, SP) be a kind of ripple along metal and medium interface propagation, when at phosphor surface adhesiving metal simple substance nanoparticle, surface plasma excimer (Surface plasmon polaritons, character SPPs), dispersion relation, excitation mode, coupling effects etc. all will produce great variation.The electromagnetic field that SPPs causes, not only can limit light wave propagates in the sub-wavelength dimensions structure, and can produce and control electromagnetic radiation from the optical frequency to the microwave region, and realize the active that light is propagated is controlled, increase the optical state density of the fluorescent material that is coated and strengthen its spontaneous emission rate.And, utilize the coupling effect of surface plasma, can improve the internal quantum efficiency of fluorescent material greatly, thereby improve the luminous intensity of whole modification luminescent material.
The effect that Al-Doped ZnO plays adheres to phosphor surface by Al-Doped ZnO with the metal simple-substance nanoparticle exactly, thereby makes metal simple-substance nanoparticle and fluorescent material produce the SP effect, thereby strengthens the luminosity of fluorescent material.Simultaneously, the light transmission rate and the conductivity of Al-Doped ZnO are good, and therefore, the Al-Doped ZnO layer that forms at phosphor surface can guarantee that fluorescent material has higher brightness and stable preferably.
Among the preparation method of the present invention, utilize the colloid mixture of Al-Doped ZnO and metal nanoparticle, make that the metal ion in the metal nanometer particle colloid becomes the metal simple-substance particle after thermal treatment, and evenly stick on the fluorescent powder grain.Technology of the present invention is simple, equipment requirements is low, preparation cycle is short; The modification luminescent material that makes all improves a lot on stability and luminosity.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the preparation flow figure of the modification luminescent material of the embodiment of the invention;
Fig. 2 is the Y of embodiments of the invention 1 modification 2O 3: the Eu luminescent material and the Y of coating modification not 2O 3: the comparison diagram of Eu emmission spectrum;
Fig. 3 is the Y of embodiments of the invention 4 modifications 2O 3: the Eu luminescent material and the Y of coating modification not 2O 3: the comparison diagram of Eu emmission spectrum;
Fig. 4 is the Y of embodiments of the invention 5 modifications 2O 3: the Eu luminescent material and the Y of coating modification not 2O 3: the comparison diagram of Eu emmission spectrum;
Fig. 5 is the Y of embodiments of the invention 6 modifications 2O 3: the Eu luminescent material and the Y of coating modification not 2O 3: the comparison diagram of Eu emmission spectrum.
Cathodoluminescence spectrum is under the cathode-ray exciting of 5KV acceleration voltage, is that the detector analysis draws with Tianjin, island RF-5301PC spectrograph.
Embodiment
In the embodiments of the invention,
One, 1, fluorescent material is selected for use: blue colour fluorescent powder is selected ZnS:Ag:Cl, SrGa for use 2S 4: Ce, Y 2SiO 4: Ce, LaGaO 3: Tm, BaMgAl 10O 17: Eu, Zn 2SiO 4: Ti or YNbO 4: Bi;
Green emitting phosphor is selected SrGa for use 2S 4: Eu, ZnS:Cu, Au, Al, ZnGaO 4: Mn, Y 2SiO 4: Tb, Zn 2SiO 4: Mn or Zn 3Ta 2O 8: Mn;
Red fluorescence powder is selected Y for use 2O 2S:Eu, Y 2O 3: Eu or CaTiO 3: Pr.
2. prepare Zn 1～xAl xO colloidal raw material is selected for use:
Zinc salt is selected for use: analytical pure Zn (CH 3COO) 22H 2O (zinc acetate), Zn (NO 3) 26H 2O (zinc nitrate), ZnCl 22H 2O (zinc chloride), ZnSO 47H 2O (zinc sulfate);
Stablizer is selected for use: analytical pure monoethanolamine (C 2H 7NO), diethanolamine (C 4H 11NO 2) or trolamine (C 6H 15O 3N);
Solvent is selected for use: analytical pure ethylene glycol monomethyl ether (C 3H 8O 2), (ratio of ethanol and deionized water is 3～7 to ethanolic soln: 1);
Aluminium salt is selected for use: analyze Al (NO 3) 39H 2O (pure aluminum nitrate), AlCl 36H 2O (aluminum chloride), Al 2(SO 4) 3(Tai-Ace S 150).
3. the raw material of preparation metal nanoparticle is selected for use:
Metallic compound is selected analytical pure Silver Nitrate (AgNO for use 3), hydrochloro-auric acid (HAuCl 4), Platinic chloride (H 2PtCl 66H 2O), Palladous chloride (PdCl 2);
Selection of auxiliary analytical pure PVP (polyethylene arsenic pyrrolidone), C 6H 5Na 3O 7(Trisodium Citrate), C 16H 33(CH 3) 3NBr (cetyl trimethylammonium bromide), C 12H 25SO 4Na (sodium lauryl sulphate), CH 3(CH 2) 10CH 2SO 3Na (sodium laurylsulfonate);
Reductive agent is selected analytical pure hydrazine hydrate (N for use 2H 4H 2O), xitix (C 6H 8O 6) or sodium borohydride (NaBH 4);
Solvent is selected dehydrated alcohol (CH for use 3CH 2OH), deionized water (H 2O).
Two, as shown in Figure 1, be the preparation flow figure of modification luminescent material of the present invention.The preparation method of modification luminescent material may further comprise the steps:
1.Zn 1～xAl xThe preparation of O colloidal
Press chemical formula Zn 1～xAl xO, wherein the span of x is 0＜x≤0.05, the colloid concentration scope is: 0.05mol/L～0.70mol/L, take by weighing zinc salt and aluminium salt raw material respectively, add a kind of in stablizer monoethanolamine, diethanolamine, the trolamine, be dissolved in the container, behind 40～70 ℃ of stirring in water bath 4～8h, obtain uniform precursor solution with solvent ethylene glycol methyl ether or ethanolic soln, precursor solution ageing 56～90h in 60 ℃ of baking ovens with gained obtains light yellow Zn 1～xAl xThe O colloid.
2. metal nanoparticle colloidal preparation
1) takes by weighing an amount of Silver Nitrate, hydrochloro-auric acid, Platinic chloride, Palladous chloride and be dissolved in ethanol or the deionized water, be diluted to certain density solution;
2) under magnetic agitation, one or more auxiliary agent such as polyethylene arsenic pyrrolidone (PVP), Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate, sodium laurylsulfonate are dissolved into above-mentioned 1) in the solution, and to make auxiliary agent can be 1.5 * 10 at the content in the metal nanoparticle colloidal sol that finally obtains ～4G/mL～2.1 * 10 ～3G/mL;
3) hydrazine hydrate, xitix or the sodium borohydride that takes by weighing respective quality is dissolved in the solvent as reductive agent, and being mixed with concentration range is 1 * 10 ～3Mol/L～1 * 10 ～2The reductant solution of mol/L;
4) under magnetic agitation, it in the ratio of reductive agent and the amount of substance of metal ion 1.2: 1～4.8: 1 ratio, toward above-mentioned step 2) add above-mentioned steps 3 in the resulting solution) reduced liquid that obtains, promptly obtain metal nanoparticle colloidal sol behind whole system reaction 10min～45min;
3. metal nanoparticle colloid and Zn 1～xAl xThe O colloidal mixes
Get 1mL～15mL metal nanoparticle colloid and join 3mL～20mL Zn 1～xAl xMix in the O colloid, and under room temperature, stir 10min～1h, form even metal nano particle and Zn 1～xAl xThe colloid mixture of O.
4. the surface treatment of fluorescent material
In the commercial fluorescent material of 10g, add dehydrated alcohol 10～50mL, at room temperature stir 1～20h, filter and be placed on dry 3～15h in 50～200 ℃ of baking ovens.
5. metal nanoparticle and Zn 1～xAl xThe preparation of the colloid mixture coating fluorescent powder of O
Get the fluorescent material 1～10g after the surface treatment in the step 4, add the colloid 3～15mL in the step 3, magnetic agitation 2～10h is placed on dry 5～30h in 50～80 ℃ of baking ovens in 15～70 ℃ of water-baths, grinds, and obtains metal nanoparticle and Zn 1～xAl xThe fluorescent material that the colloid mixture of O coats.
6. metal nanoparticle and Zn 1～xAl xThe thermal treatment of the colloid mixture coating fluorescent powder of O
The product of step 5 is placed corundum crucible, and (reducing atmosphere is atmosphere or the H that carbon dust exists at air atmosphere or reducing atmosphere 2And N 2The atmosphere that exists of mixed gas) or H 2Behind 400～1000 ℃ of anneal 0.5～6h, grind and promptly get the finished product in the S atmosphere.
The Y of embodiment 1, modification 2O 3: Eu luminescent material: Y 2O 3: the Eu particle coats Al-Doped ZnO and nano platinum particle outward.
Under the room temperature, accurately take by weighing 2.1292g Zn (CH 3COO) 22H 2O, 0.1125g Al (NO 3) 39H 2O and 0.6mL C 2H 7NO places container, then adds ethylene glycol monomethyl ether to 50mL, after stirring 4h under 60 ℃ of water bath condition, obtains the Zn of clarifying 0.20mol/L 0.97Al 0.03The O precursor solution with resulting precursor solution ageing 70h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0052g Platinic chloride is dissolved in the ethanol of 17mL; After Platinic chloride dissolves fully, take by weighing 0.0080g Trisodium Citrate and 0.0012g sodium laurylsulfonate, under agitation be dissolved in the alcoholic solution of Platinic chloride; Take by weighing the 0.0004g sodium borohydride and be dissolved in the ethanol, preparation 10mL concentration is 1 * 10 ～3The sodium borohydride alcoholic solution of mol/L, cofabrication 10mL concentration is 1 * 10 ～2The alcoholic solution of the hydrazine hydrate of mol/L; Under the magnetic agitation, in chloroplatinic acid in alcohol, drip 0.4mL sodium borohydride alcoholic solution earlier, reaction 5min, and then in chloroplatinic acid in alcohol, drip 2.6mL 1 * 10 ～2The hydrazine hydrate solution of mol/L continues reaction 40min afterwards, and obtaining 20mL Pt content is 5 * 10 ～4The Pt nano particle colloidal sol of mol/L; Measure 15mL Pt nano particle colloidal sol, add 0.0150g PVP, stir 12h, Pt nano particle colloid that must be after surface treatment.
Get 15mL Pt nano particle colloid and join 10mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 10min, form uniform Pt nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 10mL dehydrated alcohol, at room temperature stir 1h, filter and place 40 ℃ of dry 15h of baking oven.At 5g Y 2O 3: add colloid mixture 5mL among the Eu, magnetic agitation 5h is placed on dry 7h in 100 ℃ of baking ovens in 15 ℃ of water-baths, and insulation annealing is handled 2h in 800 ℃ of retort furnaces then, obtains the modification luminescent material.
As shown in Figure 2, a is the Y of embodiment 1 preparation among the figure 2O 3: Eu modification luminescent material, b are unmodified Y 2O 3: Eu, as we can see from the figure, the luminous intensity of the modification luminescent material of present embodiment preparation is the Y for modification 2O 3: 1.44 times of Eu can make the luminous intensity of fluorescent material be improved significantly by this method.
The Y of embodiment 2, modification 2O 3: Eu luminescent material: Y 2O 3: the Eu particle coats Al-Doped ZnO and golden nanometer particle outward.
Under the room temperature, accurately take by weighing 2.4810g ZnCl 22H 2O, 0.1448g AlCl 36H 2O and 1.5mLC 4H 11NO 2Place container, the mixing solutions of second alcohol and water that then adds volume ratio and be 3: 1 after stirring 8h under 70 ℃ of water bath condition, obtains the Zn of uniform 0.30mol/L to 50mL 0.96Al 0.04The O precursor solution with resulting precursor solution ageing 70h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.96Al 0.04The O colloid.
Taking by weighing the 0.0041g hydrochloro-auric acid is dissolved in the ethanol of 8.4mL; After hydrochloro-auric acid dissolves fully, take by weighing 0.0140g Trisodium Citrate and 0.0060g cetyl trimethylammonium bromide, under agitation be dissolved in the alcoholic solution of hydrochloro-auric acid; Take by weighing the 0.0019g sodium borohydride and the 0.0176g xitix is dissolved into respectively in the 10mL ethanol, obtaining 10mL concentration is 5 * 10 ～3The sodium borohydride alcoholic solution of mol/L and 10mL concentration are 1 * 10 ～2The xitix alcoholic solution of mol/L; Under magnetic agitation, in the hydrochloro-auric acid alcoholic solution, add 0.04mL sodium borohydride alcoholic solution, in the hydrochloro-auric acid alcoholic solution, add 1.56mL1 * 10 again behind the stirring reaction 5min ～2The xitix alcoholic solution of mol/L continues reaction 30min, and promptly getting 10mL Au content is 1 * 10 ～3The Au nano particle colloidal sol of mol/L; Measure the Au nano particle colloidal sol that 6mL obtains, add 0.0010g PVP, stir 8h, Au nano particle colloid that must be after surface treatment.
Get 1mL Au nano particle colloid and join 5mL Zn 0.96Al 0.04Mix in the O colloid, and under room temperature, stir 20min, form uniform Au nano particle and Zn 0.96Al 0.04The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 30mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g Y 2O 3: add colloid mixture 3mL among the Eu, magnetic agitation 2h is placed on dry 5h in 90 ℃ of baking ovens in 40 ℃ of water-baths, and insulation annealing is handled 0.5h in 1000 ℃ of retort furnaces then, obtains the modification luminescent material.
The Y of embodiment 3, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 0.5460g Zn (CH 3COO) 22H 2O, 0.0047g Al (NO 3) 39H 2O and 0.4mL C 6H 15O 3N places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 4: 1 after stirring 5h under 40 ℃ of water bath condition, obtains the Zn of uniform 0.05mol/L to 50mL 0.995Al 0.005The O precursor solution with resulting precursor solution ageing 90h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.995Al 0.005The O colloid.
Taking by weighing the 0.0034g Silver Nitrate is dissolved in the ethanol of 18.4mL; After Silver Nitrate dissolves fully, take by weighing the 0.0420g Trisodium Citrate and under magnetic agitation, be dissolved in the Silver Nitrate alcoholic solution; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The sodium borohydride alcoholic solution of mol/L; Under magnetic agitation, disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 10min, and promptly getting the 20mL silver content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 15mL Ag nano particle colloidal sol, add 0.0400g PVP, stir 6h, Ag nano particle that must be after surface treatment.
Get 15mL Ag nano particle colloid and join 3mL Zn 0.995Al 0.005Mix in the O colloid, and under room temperature, stir 1h, form uniform Ag nano particle and Zn 0.995Al 0.005The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 50mL dehydrated alcohol, at room temperature stir 20h, filter and place 90 ℃ of dry 1h of baking oven.At 5g Y 2O 3: add colloid mixture 2mL among the Eu, magnetic agitation 20h is placed on dry 30h in 40 ℃ of baking ovens in 70 ℃ of water-baths, then in 400 ℃ of retort furnaces under the carbon reduction insulation annealing handle 6h, obtain the modification luminescent material.
The Y of embodiment 4, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and Pd nano particle outward.
Under the room temperature, accurately take by weighing 1.0865g Zn (CH 3COO) 22H 2O, 0.0188g Al (NO 3) 39H 2O and 0.4mL C 2H 7NO places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 5: 1 after stirring 6h under 50 ℃ of water bath condition, obtains the Zn of uniform 0.10mol/L to 50mL 0.99Al 0.01The O precursor solution with resulting precursor solution ageing 80h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.99Al 0.01The O colloid.
Taking by weighing the 0.0043g Palladous chloride is dissolved in the deionized water of 8.5mL; After Palladous chloride dissolves fully, take by weighing 0.0110g Trisodium Citrate and 0.0040g sodium lauryl sulphate, under magnetic agitation, be dissolved in the palladium chloride aqueous solution; It is molten in 10mL ethanol to take by weighing the 0.0038g sodium borohydride, and obtaining concentration is 1 * 10 ～2The sodium borohydride solution of mol/L; Under magnetic agitation, in palladium chloride aqueous solution, add 0.48mL 1 * 10 fast ～2The sodium borohydride alcoholic solution of mol/L continues reaction 20min, and promptly getting 10mL Pd content is 1 * 10 ～4The Pd nano particle colloidal sol of mol/L adds 0.0500g PVP afterwards in this 10mL Pd nano particle colloidal sol, stirs 4h, Pd nano particle colloid that must be after surface treatment.
Get 2mL Pd nano particle colloid and join 10mL Zn 0.99Al 0.01Mix in the O colloid, and under room temperature, stir 30min, form uniform Pd nano particle and Zn 0.99Al 0.01The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 14mL dehydrated alcohol, at room temperature stir 7h, filter and place 50 ℃ of dry 25h of baking oven.At 5g Y 2O 3: add colloid mixture 6mL among the Eu, magnetic agitation 16h is placed on dry 18h in 60 ℃ of baking ovens in 50 ℃ of water-baths, and insulation annealing is handled 3h in 700 ℃ of retort furnaces then, obtains the modification luminescent material.A is the Y of embodiment 4 preparations among Fig. 3 2O 3: Eu modification luminescent material, b are unmodified Y 2O 3: Eu, as we can see from the figure, the luminous intensity of the modification luminescent material of present embodiment preparation is the Y for modification 2O 3: 1.28 times of Eu.
The Y of embodiment 5, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 2.9452g Zn (NO 3) 26H 2O, 0.0241g AlCl 36H 2O and 0.6mLC 2H 7NO places container, then adds the solvent ethylene glycol methyl ether to 50mL, after stirring 7h under 60 ℃ of water bath condition, obtains the Zn of uniform 0.20mol/L 0.99Al 0.01The O precursor solution with resulting precursor solution ageing 56h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.99Al 0.01The O colloid.
Take by weighing the 0.0034g Silver Nitrate and be dissolved in the ethanol of 18.4mL, stirring is dissolved Silver Nitrate fully, takes by weighing 0.0355gPVP and under agitation is dissolved in the Silver Nitrate ethanolic soln; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The ethanol solution of sodium borohydride of mol/L; Stir down disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 15min afterwards, and promptly getting 20mLAg content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 10mL Ag nano particle colloidal sol afterwards, add 0.1000g PVP, stir 3h, obtain the Ag nano particle colloid after surface treatment.
Get 2mL Ag nano particle colloid and join 4mL Zn 0.99Al 0.01Mix in the O colloid, and under room temperature, stir 50min, form uniform Ag nano particle and Zn 0.99Al 0.01The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 25mL dehydrated alcohol, at room temperature stir 1h, filter and place 40 ℃ of dry 15h of baking oven.At 5g Y 2O 3: add colloid mixture 5mL among the Eu, magnetic agitation 5h is placed on dry 9h in 100 ℃ of baking ovens in 25 ℃ of water-baths, then in 800 ℃ of retort furnaces under the carbon reduction insulation annealing handle 2h, obtain the modification luminescent material.A is the Y of embodiment 5 preparations among Fig. 4 2O 3: Eu modification luminescent material, b are unmodified Y 2O 3: Eu, as we can see from the figure, the luminous intensity of the modification luminescent material of present embodiment preparation is the Y for modification 2O 3: 1.20 times of Eu.
The Y of embodiment 6, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and nano platinum particle outward.
Under the room temperature, accurately take by weighing 3.1937g Zn (CH 3COO) 22H 2O, 0.1688g Al (NO 3) 39H 2O and 0.9mL C 2H 7NO places container, then adds the solvent ethylene glycol methyl ether to 50mL, after stirring 8h under 60 ℃ of water bath condition, obtains the Zn of clarifying 0.30mol/L 0.97Al 0.03The O precursor solution, the precursor solution that will obtain ageing 65h in 60 ℃ of baking ovens obtains uniform light yellow Zn more again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0052g Platinic chloride is dissolved in the ethanol of 17mL; After Platinic chloride dissolves fully, take by weighing 0.0080g Trisodium Citrate and 0.0012g sodium laurylsulfonate, under agitation be dissolved in the alcoholic solution of Platinic chloride; Take by weighing the 0.0004g sodium borohydride and be dissolved in the ethanol, preparation 10mL concentration is 1 * 10 ～3The sodium borohydride alcoholic solution of mol/L, cofabrication 10mL concentration is 1 * 10 ～2The alcoholic solution of the hydrazine hydrate of mol/L; Under the magnetic agitation, in chloroplatinic acid in alcohol, drip 0.4mL sodium borohydride alcoholic solution earlier, reaction 5min, and then in chloroplatinic acid in alcohol, drip 2.6mL 1 * 10 ～2The hydrazine hydrate solution of mol/L continues reaction 40min afterwards, and obtaining 20mL Pt content is 5 * 10 ～4The Pt nano particle colloidal sol of mol/L; Measure 6mL Pt nano particle colloidal sol, add 0.0060g PVP, stir 12h, Pt nano particle that must be after surface treatment.
Get 1mL Pt nano particle colloid and join 10mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 10min, form uniform Pt nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 35mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g Y 2O 3: add colloid mixture 1.5mL among the Eu, magnetic agitation 2h is placed on dry 12h in 90 ℃ of baking ovens in 40 ℃ of water-baths, and insulation annealing is handled 1h in 900 ℃ of retort furnaces then, obtains the modification luminescent material.A is the Y of embodiment 6 preparations among Fig. 6 2O 3: Eu modification luminescent material, b are unmodified Y 2O 3: Eu, as we can see from the figure, the luminous intensity of the modification luminescent material of present embodiment preparation is the Y for modification 2O 3: 1.40 times of Eu.
The Y of embodiment 7, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and golden nanometer particle outward.
Under the room temperature, accurately take by weighing 4.2583g Zn (CH 3COO) 22H 2O, 0.2251g Al (NO 3) 39H 2O and 2mL C 4H 11NO 2Place container, then add the solvent ethylene glycol methyl ether, after stirring 4h under 60 ℃ of water bath condition, obtain the Zn of uniform 0.40mol/L to 50mL 0.97Al 0.03The O precursor solution with resulting precursor solution ageing 78h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0041g hydrochloro-auric acid is dissolved in the ethanol of 8.4mL; After hydrochloro-auric acid dissolves fully, take by weighing 0.0140g Trisodium Citrate and 0.0060g cetyl trimethylammonium bromide, under agitation be dissolved in the alcoholic solution of hydrochloro-auric acid; Take by weighing the 0.0019g sodium borohydride and the 0.0176g xitix is dissolved into respectively in the 10mL ethanol, obtaining 10mL concentration is 5 * 10 ～3The sodium borohydride alcoholic solution of mol/L and 10mL concentration are 1 * 10 ～2The xitix alcoholic solution of mol/L; Under magnetic agitation, in the hydrochloro-auric acid alcoholic solution, add 0.04mL sodium borohydride alcoholic solution, in the hydrochloro-auric acid alcoholic solution, add 1.56mL1 * 10 again behind the stirring reaction 5min ～2The xitix alcoholic solution of mol/L continues reaction 30min, and promptly getting 10mL Au content is 1 * 10 ～3The Au nano particle colloidal sol of mol/L; Measure the Au nano particle colloidal sol that 6mL obtains, add 0.0010g PVP, stir 8h, Au nano particle colloid that must be after surface treatment.
Get 2mL Au nano particle colloid and join 13mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 1h, form uniform Au nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 20mL dehydrated alcohol, at room temperature stir 20h, filter and place 90 ℃ of dry 1h of baking oven.At 5g Y 2O 3: add colloid mixture 4mL among the Eu, magnetic agitation 20h is placed on dry 30h in 40 ℃ of baking ovens in 70 ℃ of water-baths, and insulation annealing is handled 6h in 400 ℃ of retort furnaces then, obtains the modification luminescent material.
The Y of embodiment 8, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 7.2984g Zn (CH 3COO) 22H 2O, 0.6565g Al (NO 3) 39H 2O and 6mL C 2H 7NO places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 6: 1 after stirring 5h under 70 ℃ of water bath condition, obtains the Zn of uniform 0.70mol/L to 50mL 0.95Al 0.05The O precursor solution with resulting precursor solution ageing 85h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.95Al 0.05The O colloid.
Taking by weighing the 0.0034g Silver Nitrate is dissolved in the ethanol of 18.4mL; After Silver Nitrate dissolves fully, take by weighing the 0.0420g Trisodium Citrate and under magnetic agitation, be dissolved in the Silver Nitrate alcoholic solution; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The sodium borohydride alcoholic solution of mol/L; Under magnetic agitation, disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 10min, and promptly getting the 20mL silver content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 8mL Ag nano particle colloidal sol, add 0.0400g PVP, stir 6h, Ag nano particle colloid that must be after surface treatment.
Get 5mL Ag nano particle colloid and join 10mL Zn 0.95Al 0.05Mix in the O colloid, and under room temperature, stir 20min, form uniform Ag nano particle and Zn 0.95Al 0.05The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 40mL dehydrated alcohol, at room temperature stir 7h, filter and place 50 ℃ of dry 25h of baking oven.At 5g Y 2O 3: add colloid mixture 3mL among the Eu, magnetic agitation 16h is placed on dry 18h in 60 ℃ of baking ovens in 50 ℃ of water-baths, then in 700 ℃ of retort furnaces under the carbon reduction insulation annealing handle 3h, obtain the modification luminescent material.
The Y of embodiment 9, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and Pd nano particle outward.
Under the room temperature, accurately take by weighing 6.9733g ZnSO 47H 2O, 0.1283g Al 2(SO 4) 3And 1.5mLC 2H 7NO places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 7: 1 after stirring 5h under 60 ℃ of water bath condition, obtains the Zn of uniform 0.50mol/L to 50mL 0.97Al 0.03The O precursor solution with resulting precursor solution ageing 90h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0043g Palladous chloride is dissolved in the deionized water of 8.5mL; After Palladous chloride dissolves fully, take by weighing 0.0110g Trisodium Citrate and 0.0040g sodium lauryl sulphate, under magnetic agitation, be dissolved in the palladium chloride solution; It is molten in 10mL ethanol to take by weighing the 0.0038g sodium borohydride, and obtaining concentration is 1 * 10 ～2The sodium borohydride solution of mol/L; Under magnetic agitation, in palladium chloride solution, add 0.48mL1 * 10 fast ～2The sodium borohydride solution of mol/L continues reaction 20min, and promptly getting 10mL Pd content is 1 * 10 ～4The Pd nano particle colloidal sol of mol/L adds 0.0500g PVP afterwards in this 10mL Pd nano particle colloidal sol, stirs 4h, Pd nano particle colloid that must be after surface treatment.
Get 2mL Pd nano particle colloid and join 3mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 10min～1h, form uniform Pd nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 36mL dehydrated alcohol, at room temperature stir 1h, filter and place 40 ℃ of dry 15h of baking oven.At 5g Y 2O 3: add colloid mixture 5mL among the Eu, magnetic agitation 5h is placed on dry 7h in 100 ℃ of baking ovens in 15 ℃ of water-baths, and insulation annealing is handled 2h in 800 ℃ of retort furnaces then, obtains the modification luminescent material.
The Y of embodiment 10, modification 2O 3: Eu luminescent material: Y 2O 3: Eu coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 9.6620g ZnSO 47H 2O, 0.2395g Al 2(SO 4) 3And 4.7mLC 6H 15O 3N places container, then adds the solvent ethylene glycol methyl ether to 50mL, after stirring 5h under 60 ℃ of water bath condition, obtains the Zn of uniform 0.70mol/L 0.96Al 0.04The O precursor solution with resulting precursor solution ageing 60h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.96Al 0.04The O colloid.
Take by weighing the 0.0034g Silver Nitrate and be dissolved in the ethanol of 18.4mL, stirring is dissolved Silver Nitrate fully, takes by weighing 0.0355gPVP and under agitation is dissolved in the Silver Nitrate ethanolic soln; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The ethanol solution of sodium borohydride of mol/L; Stir down disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 15min afterwards, and promptly getting 20mLAg content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 10mL Ag nano particle colloidal sol afterwards, add 0.1000g PVP, stir 3h, obtain the Ag nano particle colloid after surface treatment.
Get 5mL Ag nano particle colloid and join 15mL Zn 0.96Al 0.04Mix in the O colloid, and under room temperature, stir 1h, form uniform Ag nano particle and Zn 0.96Al 0.04The colloid mixture of O.
Get 10g Y 2O 3: Eu fluorescent material, add the 13mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g Y 2O 3: add colloid mixture 1mL among the Eu, magnetic agitation 2h is placed on dry 5h in 90 ℃ of baking ovens in 40 ℃ of water-baths, then in 1000 ℃ of retort furnaces under the carbon reduction insulation annealing handle 2h, obtain the modification luminescent material.
The ZnS:Ag:Cl luminescent material of embodiment 11, modification: ZnS:Ag:Cl coats Al-Doped ZnO and nano platinum particle outward.
Under the room temperature, accurately take by weighing 2.1292g Zn (CH 3COO) 22H 2O, 0.1125g Al (NO 3) 39H 2O and 0.6mL C 2H 7NO places container, then adds ethylene glycol monomethyl ether to 50mL, after stirring 4h under 60 ℃ of water bath condition, obtains the Zn of clarifying 0.20mol/L 0.97Al 0.03The O precursor solution with resulting precursor solution ageing 70h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0052g Platinic chloride is dissolved in the ethanol of 17mL; After Platinic chloride dissolves fully, take by weighing 0.0080g Trisodium Citrate and 0.0012g sodium laurylsulfonate, under agitation be dissolved in the alcoholic solution of Platinic chloride; Take by weighing the 0.0004g sodium borohydride and be dissolved in the ethanol, preparation 10mL concentration is 1 * 10 ～3The sodium borohydride alcoholic solution of mol/L, cofabrication 10mL concentration is 1 * 10 ～2The alcoholic solution of the hydrazine hydrate of mol/L; Under the magnetic agitation, in chloroplatinic acid in alcohol, drip 0.4mL sodium borohydride alcoholic solution earlier, reaction 5min, and then in chloroplatinic acid in alcohol, drip 2.6mL 1 * 10 ～2The hydrazine hydrate solution of mol/L continues reaction 40min afterwards, and obtaining 20mL Pt content is 5 * 10 ～4The Pt nano particle colloidal sol of mol/L; Measure 6mL Pt nano particle colloidal sol, add 0.0060g PVP, stir 12h, Pt nano particle colloid that must be after surface treatment.
Get 4mL Pt nano particle colloid and join 21mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 20min, form uniform Pt nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g ZnS:Ag:Cl fluorescent material, add the 15mL dehydrated alcohol, at room temperature stir 1h, filter and place 40 ℃ of dry 15h of baking oven.Add colloid mixture 5mL in 5g ZnS:Ag:Cl, magnetic agitation 5h is placed on dry 7h in 100 ℃ of baking ovens in 15 ℃ of water-baths, then H in 800 ℃ of retort furnaces 2Insulation annealing is handled 2h in the S atmosphere, obtains the modification luminescent material.
The SrGa of embodiment 12, modification 2S 4: Ce luminescent material: SrGa 2S 4: Ce coats Al-Doped ZnO and golden nanometer particle outward.
Under the room temperature, accurately take by weighing 2.4810g ZnCl 22H 2O, 0.1448g AlCl 36H 2O and 1.5mLC 4H 11NO 2Place container, the mixing solutions of second alcohol and water that then adds volume ratio and be 3: 1 after stirring 8h under 70 ℃ of water bath condition, obtains the Zn of uniform 0.30mol/L to 50mL 0.96Al 0.04The O precursor solution with resulting precursor solution ageing 70h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.96Al 0.04The O colloid.
Taking by weighing the 0.0041g hydrochloro-auric acid is dissolved in the ethanol of 8.4mL; After hydrochloro-auric acid dissolves fully, take by weighing 0.0140g Trisodium Citrate and 0.0060g cetyl trimethylammonium bromide, under agitation be dissolved in the alcoholic solution of hydrochloro-auric acid; Take by weighing the 0.0019g sodium borohydride and the 0.0176g xitix is dissolved into respectively in the 10mL ethanol, obtaining 10mL concentration is 5 * 10 ～3The sodium borohydride alcoholic solution of mol/L and 10mL concentration are 1 * 10 ～2The xitix alcoholic solution of mol/L; Under magnetic agitation, in the hydrochloro-auric acid alcoholic solution, add 0.04mL sodium borohydride alcoholic solution, in the hydrochloro-auric acid alcoholic solution, add 1.56mL1 * 10 again behind the stirring reaction 5min ～2The xitix alcoholic solution of mol/L continues reaction 30min, and promptly getting 10mL Au content is 1 * 10 ～3The Au nano particle colloidal sol of mol/L; Measure the Au nano particle colloidal sol that 6mL obtains, add 0.0010g PVP, stir 8h, Au nano particle colloid that must be after surface treatment.
Get 2mL Au nano particle colloid and join 6mL Zn 0.96Al 0.04Mix in the O colloid, and under room temperature, stir 10min, form uniform Au nano particle and Zn 0.96Al 0.04The colloid mixture of O.
Get 10g SrGa 2S 4: Ce fluorescent material, add the 23mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g SrGa 2S 4: add colloid mixture 4mL among the Ce, magnetic agitation 2h is placed on dry 5h in 90 ℃ of baking ovens in 40 ℃ of water-baths, then in 1000 ℃ of retort furnaces under the carbon reducing agent insulation annealing handle 0.5h, obtain the modification luminescent material.
The Y of embodiment 13, modification 2SiO 4: Ce luminescent material: Y 2SiO 4: Ce coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 0.5460g Zn (CH 3COO) 22H 2O, 0.0047g Al (NO 3) 39H 2O and 0.4mL C 6H 15O 3N places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 4: 1 after stirring 5h under 40 ℃ of water bath condition, obtains the Zn of uniform 0.05mol/L to 50mL 0.995Al 0.005The O precursor solution with resulting precursor solution ageing 90h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.995Al 0.005The O colloid.
Taking by weighing the 0.0034g Silver Nitrate is dissolved in the ethanol of 18.4mL; After Silver Nitrate dissolves fully, take by weighing the 0.0420g Trisodium Citrate and under magnetic agitation, be dissolved in the Silver Nitrate alcoholic solution; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The sodium borohydride alcoholic solution of mol/L; Under magnetic agitation, disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 10min, and promptly getting the 20mL silver content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 8mL Ag nano particle colloidal sol, add 0.0400g PVP, stir 6h, Ag nano particle colloid that must be after surface treatment.
Get 5mL Ag nano particle colloid and join 15mL Zn 0.995Al 0.005Mix in the O colloid, and under room temperature, stir 1h, form uniform Ag nano particle and Zn 0.995Al 0.005The colloid mixture of O.
Get 10g Y 2SiO 4: Ce fluorescent material, add the 20mL dehydrated alcohol, at room temperature stir 20h, filter and place 90 ℃ of dry 1h of baking oven.At 5g Y 2SiO 4: add colloid mixture 0.8mL among the Ce, magnetic agitation 20h is placed on dry 30h in 40 ℃ of baking ovens in 70 ℃ of water-baths, then in 400 ℃ of retort furnaces under the carbon reducing agent insulation annealing handle 6h, obtain the modification luminescent material.
The LaGaO of embodiment 14, modification 3: Tm luminescent material: LaGaO 3: Tm coats Al-Doped ZnO and Pd nano particle outward.
Under the room temperature, accurately take by weighing 1.0865g Zn (CH 3COO) 22H 2O, 0.0188g Al (NO 3) 39H 2O and 0.4mL C 2H 7NO places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 5: 1 after stirring 6h under 50 ℃ of water bath condition, obtains the Zn of uniform 0.10mol/L to 50mL 0.99Al 0.01The O precursor solution with resulting precursor solution ageing 80h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.99Al 0.01The O colloid.
Taking by weighing the 0.0043g Palladous chloride is dissolved in the deionized water of 8.5mL; After Palladous chloride dissolves fully, take by weighing 0.0110g Trisodium Citrate and 0.0040g sodium lauryl sulphate, under magnetic agitation, be dissolved in the palladium chloride solution; It is molten in 10mL ethanol to take by weighing the 0.0038g sodium borohydride, and obtaining concentration is 1 * 10 ～2The sodium borohydride solution of mol/L; Under magnetic agitation, in palladium chloride solution, add 0.48mL1 * 10 fast ～2The sodium borohydride solution of mol/L continues reaction 20min, and promptly getting 10mL Pd content is 1 * 10 ～4The Pd nano particle colloidal sol of mol/L adds 0.0500g PVP afterwards in this 10mL Pd nano particle colloidal sol, stirs 4h, Pd nano particle colloid that must be after surface treatment.
Get 10mL Pd nano particle colloid and join 20mL Zn 0.99Al 0.01Mix in the O colloid, and under room temperature, stir 40min, form uniform Pd nano particle and Zn 0.99Al 0.01The colloid mixture of O.
Get 10g LaGaO 3: Tm fluorescent material, add the 20mL dehydrated alcohol, at room temperature stir 20h, filter and place 90 ℃ of dry 1h of baking oven.At 5g LaGaO 3: add colloid mixture 3mL among the Tm, magnetic agitation 20h is placed on dry 30h in 40 ℃ of baking ovens in 70 ℃ of water-baths, and insulation annealing is handled 6h in 400 ℃ of retort furnaces then, obtains the modification luminescent material.
The BaMgAl of embodiment 15, modification 10O 17: Eu luminescent material: BaMgAl 10O 17: Eu coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 2.9452g Zn (NO 3) 26H 2O, 0.0241g AlCl 36H 2O and 0.6mLC 2H 7NO places container, then adds the solvent ethylene glycol methyl ether to 50mL, after stirring 7h under 60 ℃ of water bath condition, obtains the Zn of uniform 0.20mol/L 0.99Al 0.01The O precursor solution with resulting precursor solution ageing 56h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.99Al 0.01The O colloid.
Take by weighing the 0.0034g Silver Nitrate and be dissolved in the ethanol of 18.4mL, stirring is dissolved Silver Nitrate fully, takes by weighing 0.0355gPVP and under agitation is dissolved in the Silver Nitrate ethanolic soln; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The ethanol solution of sodium borohydride of mol/L; Stir down disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 15min afterwards, and promptly getting 20mLAg content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 10mL Ag nano particle colloidal sol afterwards, add 0.1000g PVP, stir 3h, obtain the Ag nano particle colloid after surface treatment.
Get 8mL Ag nano particle colloid and join 12mL Zn 0.99Al 0.01Mix in the O colloid, and under room temperature, stir 1h, form uniform Ag nano particle and Zn 0.99Al 0.01The colloid mixture of O.
Get 10g BaMgAl 10O 17: Eu fluorescent material, add the 15mL dehydrated alcohol, at room temperature stir 1h, filter and place 40 ℃ of dry 15h of baking oven.At 5g BaMgAl 10O 17: add colloid mixture 5mL among the Eu, magnetic agitation 5h is placed on dry 9h in 100 ℃ of baking ovens in 25 ℃ of water-baths, then H in 1000 ℃ of tube furnaces 2And N 22h is handled in mixed gas reduction insulation annealing down, obtains the modification luminescent material.
The Zn of embodiment 16, modification 2SiO 4: Ti luminescent material: Zn 2SiO 4: Ti coats Al-Doped ZnO and nano platinum particle outward.
Under the room temperature, accurately take by weighing 3.1937g Zn (CH 3COO) 22H 2O, 0.1688g Al (NO 3) 39H 2O and 0.9mL C 2H 7NO places container, then adds the solvent ethylene glycol methyl ether to 50mL, after stirring 8h under 60 ℃ of water bath condition, obtains the Zn of clarifying 0.30mol/L 0.97Al 0.03The O precursor solution, the precursor solution that will obtain ageing 65h in 60 ℃ of baking ovens obtains uniform light yellow Zn more again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0052g Platinic chloride is dissolved in the ethanol of 17mL; After Platinic chloride dissolves fully, take by weighing 0.0080g Trisodium Citrate and 0.0012g sodium laurylsulfonate, under agitation be dissolved in the alcoholic solution of Platinic chloride; Take by weighing the 0.0004g sodium borohydride and be dissolved in the ethanol, preparation 10mL concentration is 1 * 10 ～3The sodium borohydride alcoholic solution of mol/L, cofabrication 10mL concentration is 1 * 10 ～2The alcoholic solution of the hydrazine hydrate of mol/L; Under the magnetic agitation, in chloroplatinic acid in alcohol, drip 0.4mL sodium borohydride alcoholic solution earlier, reaction 5min, and then in chloroplatinic acid in alcohol, drip 2.6mL 1 * 10 ～2The hydrazine hydrate solution of mol/L continues reaction 40min afterwards, and obtaining 20mL Pt content is 5 * 10 ～4The Pt nano particle colloidal sol of mol/L; Measure 6mL Pt nano particle colloidal sol, add 0.0060g PVP, stir 12h, Pt nano particle colloid that must be after surface treatment.
Get 1mL Pt nano particle colloid and join 9mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 50min, form uniform Pt nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g Zn 2SiO 4: Ti fluorescent material, add the 23mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g Zn 2SiO 4: add colloid mixture 3mL among the Ti, magnetic agitation 2h is placed on dry 12h in 90 ℃ of baking ovens in 40 ℃ of water-baths, and insulation annealing is handled 1h in 900 ℃ of retort furnaces then, obtains the modification luminescent material.
The YNbO of embodiment 17, modification 4: Bi luminescent material: YNbO 4: Bi coats Al-Doped ZnO and golden nanometer particle outward.
Under the room temperature, accurately take by weighing 4.2583g Zn (CH 3COO) 22H 2O, 0.2251g Al (NO 3) 39H 2O and 2mL C 4H 11NO 2Place container, then add the solvent ethylene glycol methyl ether, after stirring 4h under 60 ℃ of water bath condition, obtain the Zn of uniform 0.40mol/L to 50mL 0.97Al 0.03The O precursor solution with resulting precursor solution ageing 78h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0041g hydrochloro-auric acid is dissolved in the ethanol of 8.4mL; After hydrochloro-auric acid dissolves fully, take by weighing 0.0140g Trisodium Citrate and 0.0060g cetyl trimethylammonium bromide, under agitation be dissolved in the alcoholic solution of hydrochloro-auric acid; Take by weighing the 0.0019g sodium borohydride and the 0.0176g xitix is dissolved into respectively in the 10mL ethanol, obtaining 10mL concentration is 5 * 10 ～3The sodium borohydride alcoholic solution of mol/L and 10mL concentration are 1 * 10 ～2The xitix alcoholic solution of mol/L; Under magnetic agitation, in the hydrochloro-auric acid alcoholic solution, add 0.04mL sodium borohydride alcoholic solution, in the hydrochloro-auric acid alcoholic solution, add 1.56mL1 * 10 again behind the stirring reaction 5min ～2The xitix alcoholic solution of mol/L continues reaction 30min, and promptly getting 10mL Au content is 1 * 10 ～3The Au nano particle colloidal sol of mol/L; Measure the Au nano particle colloidal sol that 6mL obtains, add 0.0010g PVP, stir 8h, Au nano particle colloid that must be after surface treatment.
Get 4mL Au nano particle colloid and join 16mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 50min, form uniform Au nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g YNbO 4: Bi fluorescent material, add the 20mL dehydrated alcohol, at room temperature stir 20h, filter and place 90 ℃ of dry 1h of baking oven.At 5g YNbO 4: add colloid mixture 6mL among the Bi, magnetic agitation 20h is placed on dry 30h in 40 ℃ of baking ovens in 70 ℃ of water-baths, and insulation annealing is handled 6h in 400 ℃ of retort furnaces then, obtains the modification luminescent material.
The SrGa of embodiment 18, modification 2S 4: Eu luminescent material: SrGa 2S 4: Eu coats Al-Doped ZnO and Pd nano particle outward.
Under the room temperature, accurately take by weighing 7.2984g Zn (CH 3COO) 22H 2O, 0.6565g Al (NO 3) 39H 2O and 6mL C 2H 7NO places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 6: 1 after stirring 5h under 70 ℃ of water bath condition, obtains the Zn of uniform 0.70mol/L to 50mL 0.95Al 0.05The O precursor solution with resulting precursor solution ageing 85h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.95Al 0.05Colloid.
Taking by weighing the 0.0043g Palladous chloride is dissolved in the deionized water of 8.5mL; After Palladous chloride dissolves fully, take by weighing 0.0110g Trisodium Citrate and 0.0040g sodium lauryl sulphate, under magnetic agitation, be dissolved in the palladium chloride solution; It is molten in 10mL ethanol to take by weighing the 0.0038g sodium borohydride, and obtaining concentration is 1 * 10 ～2The sodium borohydride solution of mol/L; Under magnetic agitation, in palladium chloride solution, add 0.48mL1 * 10 fast ～2The sodium borohydride alcoholic solution of mol/L continues reaction 20min, and promptly getting 10mL Pd content is 1 * 10 ～4The Pd nano particle colloidal sol of mol/L adds 0.0500g PVP afterwards in this 10mL Pd nano particle colloidal sol, stirs 4h, Pd nano particle colloid that must be after surface treatment.
Get 5mL Pd nano particle colloid and join 15mL Zn 0.95Al 0.05Mix in the colloid, and under room temperature, stir 10min, form uniform Pd nano particle and Zn 0.95Al 0.05Colloid mixture.
Get 10.0g SrGa 2S 4: Eu fluorescent material, add the 14mL dehydrated alcohol, at room temperature stir 7h, filter and place 50 ℃ of dry 25h of baking oven.At 5g SrGa 2S 4: add colloid mixture 2.5mL among the Eu, magnetic agitation 16h is placed on dry 18h in 60 ℃ of baking ovens in 50 ℃ of water-baths, then at 700 ℃ of retort furnace H 2Insulation annealing is handled 3h in the S atmosphere, obtains the modification luminescent material.
The ZnS:Cu:Au:Al luminescent material of embodiment 19, modification: ZnS:Cu:Au:Al coats Al-Doped ZnO and Pd nano particle outward.
Under the room temperature, accurately take by weighing 6.9733g ZnSO 47H 2O, 0.1283g Al 2(SO 4) 3And 1.5mLC 2H 7NO places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 7: 1 after stirring 5h under 60 ℃ of water bath condition, obtains the Zn of uniform 0.50mol/L to 50mL 0.97Al 0.03The O precursor solution with resulting precursor solution ageing 90h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0043g Palladous chloride is dissolved in the deionized water of 8.5mL; After Palladous chloride dissolves fully, take by weighing 0.0110g Trisodium Citrate and 0.0040g sodium lauryl sulphate, under magnetic agitation, be dissolved in the palladium chloride solution; It is molten in 10mL ethanol to take by weighing the 0.0038g sodium borohydride, and obtaining concentration is 1 * 10 ～2The sodium borohydride solution of mol/L; Under magnetic agitation, in palladium chloride solution, add 0.48mL1 * 10 fast ～2The sodium borohydride alcoholic solution of mol/L continues reaction 20min, and promptly getting 10mL Pd content is 1 * 10 ～4The Pd nano particle colloidal sol of mol/L adds 0.0500g PVP afterwards in this 10mL Pd nano particle colloidal sol, stirs 4h, Pd nano particle colloid that must be after surface treatment.
Get 3mL Pd nano particle colloid and join 12mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 50min, form uniform Pd nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g ZnS:Cu:Au:Al fluorescent material, add the 15mL dehydrated alcohol, at room temperature stir 1h, filter and place 40 ℃ of dry 15h of baking oven.Add colloid mixture 5mL in 5g ZnS:Cu:Au:Al, magnetic agitation 5h is placed on dry 7h in 100 ℃ of baking ovens in 15 ℃ of water-baths, then at 800 ℃ of retort furnace H 2Insulation annealing is handled 2h in the S atmosphere, obtains the modification luminescent material.
The ZnGaO of embodiment 20, modification 4: Mn luminescent material: ZnGaO 4: Mn coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 9.6620g ZnSO 47H 2O, 0.2395g Al 2(SO 4) 3And 4.7mLC 6H 15O 3N places container, then adds the solvent ethylene glycol methyl ether to 50mL, after stirring 5h under 60 ℃ of water bath condition, obtains the Zn of uniform 0.70mol/L 0.96Al 0.04The O precursor solution with resulting precursor solution ageing 60h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.96Al 0.04The O colloid.
Take by weighing the 0.0034g Silver Nitrate and be dissolved in the ethanol of 18.4mL, stirring is dissolved Silver Nitrate fully, takes by weighing 0.0355gPVP and under agitation is dissolved in the Silver Nitrate ethanolic soln; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The ethanol solution of sodium borohydride of mol/L; Stir down disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 15min afterwards, and promptly getting 20mLAg content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 10mL Ag nano particle colloidal sol afterwards, add 0.1000g PVP, stir 3h, obtain the Ag nano particle colloid after surface treatment.
Get 7mL Ag nano particle colloid and join 13mL Zn 0.96Al 0.04Mix in the O colloid, and under room temperature, stir 10min, form uniform Ag nano particle and Zn 0.96Al 0.04The colloid mixture of O.
Get 10g ZnGaO 4: Mn fluorescent material, add the 13mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g ZnGaO 4: add colloid mixture 4mL among the Mn, magnetic agitation 2h is placed on dry 5h in 90 ℃ of baking ovens in 40 ℃ of water-baths, then in 1000 ℃ of retort furnaces under the carbon reducing agent insulation annealing handle 2h, obtain the modification luminescent material.
The Y of embodiment 21, modification 2SiO 5: Tb luminescent material: Y 2SiO 5: Tb coats Al-Doped ZnO and nano platinum particle outward.
Under the room temperature, accurately take by weighing 2.1292g Zn (CH 3COO) 22H 2O, 0.1125g Al (NO 3) 39H 2O and 0.6mL C 2H 7NO places container, then adds ethylene glycol monomethyl ether to 50mL, after stirring 4h under 60 ℃ of water bath condition, obtains the Zn of clarifying 0.20mol/L 0.97Al 0.03The O precursor solution with resulting precursor solution ageing 70h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.97Al 0.03The O colloid.
Taking by weighing the 0.0052g Platinic chloride is dissolved in the ethanol of 17mL; After Platinic chloride dissolves fully, take by weighing 0.0080g Trisodium Citrate and 0.0012g sodium laurylsulfonate, under agitation be dissolved in the alcoholic solution of Platinic chloride; Take by weighing the 0.0004g sodium borohydride and be dissolved in the ethanol, preparation 10mL concentration is 1 * 10 ～3The sodium borohydride alcoholic solution of mol/L, cofabrication 10mL concentration is 1 * 10 ～2The alcoholic solution of the hydrazine hydrate of mol/L; Under the magnetic agitation, in chloroplatinic acid in alcohol, drip 0.4mL sodium borohydride alcoholic solution earlier, reaction 5min, and then in chloroplatinic acid in alcohol, drip 2.6mL 1 * 10 ～2The hydrazine hydrate solution of mol/L continues reaction 40min afterwards, and obtaining 20mL Pt content is 5 * 10 -4The Pt nano particle colloidal sol of mol/L; Measure 6mL Pt nano particle colloidal sol, add 0.0060g PVP, stir 12h, Pt nano particle colloid that must be after surface treatment.
Get 1mL Pt nano particle colloid and join 4mL Zn 0.97Al 0.03Mix in the O colloid, and under room temperature, stir 30min, form uniform Pt nano particle and Zn 0.97Al 0.03The colloid mixture of O.
Get 10g Y 2SiO 5: Tb fluorescent material, add the 23mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g Y 2SiO 5: add colloid mixture 3mL among the Tb, magnetic agitation 2h is placed on dry 5h in 90 ℃ of baking ovens in 40 ℃ of water-baths, then in 1000 ℃ of retort furnaces under the carbon reducing agent insulation annealing handle 2h, obtain the modification luminescent material.
The Zn of embodiment 22, modification 2SiO 4: Mn luminescent material: Zn 2SiO 4: Mn coats Al-Doped ZnO and golden nanometer particle outward.
Under the room temperature, accurately take by weighing 2.4810g ZnCl 22H 2O, 0.1448g AlCl 36H 2O and 1.5mLC 4H 11NO 2Place container, the mixing solutions of second alcohol and water that then adds volume ratio and be 3: 1 after stirring 8h under 70 ℃ of water bath condition, obtains the Zn of uniform 0.30mol/L to 50mL 0.96Al 0.04The O precursor solution with resulting precursor solution ageing 70h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.96Al 0.04The O colloid.
Taking by weighing the 0.0041g hydrochloro-auric acid is dissolved in the ethanol of 8.4mL; After hydrochloro-auric acid dissolves fully, take by weighing 0.0140g Trisodium Citrate and 0.0060g cetyl trimethylammonium bromide, under agitation be dissolved in the alcoholic solution of hydrochloro-auric acid; Take by weighing the 0.0019g sodium borohydride and the 0.0176g xitix is dissolved into respectively in the 10mL ethanol, obtaining 10mL concentration is 5 * 10 ～3The sodium borohydride alcoholic solution of mol/L and 10mL concentration are 1 * 10 ～2The xitix alcoholic solution of mol/L; Under magnetic agitation, in the hydrochloro-auric acid alcoholic solution, add 0.04mL sodium borohydride alcoholic solution, in the hydrochloro-auric acid alcoholic solution, add 1.56mL1 * 10 again behind the stirring reaction 5min ～2The xitix alcoholic solution of mol/L continues reaction 30min, and promptly getting 10mL Au content is 1 * 10 ～3The Au nano particle colloidal sol of mol/L; Measure the Au nano particle colloidal sol that 6mL obtains, add 0.0010g PVP, stir 8h, Au nano particle colloid that must be after surface treatment.
Get 1mL Au nano particle colloid and join 9mL Zn 0.96Al 0.04Mix in the O colloid, and under room temperature, stir 10min, form uniform Au nano particle and Zn 0.96Al 0.04The colloid mixture of O.
Get 10g Zn 2SiO 4: Mn fluorescent material, add the 25mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g Zn 2SiO 4: add colloid mixture 1.5mL among the Mn, magnetic agitation 5h is placed on dry 5h in 90 ℃ of baking ovens in 40 ℃ of water-baths, then in 1000 ℃ of retort furnaces under the carbon reducing agent insulation annealing handle 2h, obtain the modification luminescent material.
The Zn of embodiment 23, modification 3Ta 2O 8: Mn luminescent material: Zn 3Ta 2O 8: Mn coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 0.5460g Zn (CH 3COO) 22H 2O, 0.0047g Al (NO 3) 39H 2O and 0.4mL C 6H 15O 3N places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 4: 1 after stirring 5h under 40 ℃ of water bath condition, obtains the Zn of uniform 0.05mol/L to 50mL 0.995Al 0.005The O precursor solution with resulting precursor solution ageing 90h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.995Al 0.005The O colloid.
Taking by weighing the 0.0034g Silver Nitrate is dissolved in the ethanol of 18.4mL; After Silver Nitrate dissolves fully, take by weighing the 0.0420g Trisodium Citrate and under magnetic agitation, be dissolved in the Silver Nitrate alcoholic solution; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The sodium borohydride alcoholic solution of mol/L; Under magnetic agitation, disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution -2The sodium borohydride alcoholic solution of mol/L continues reaction 10min, and promptly getting the 20mL silver content is 1 * 10 -3The Ag nano particle colloidal sol of mol/L; Measure 8mL Ag nano particle colloidal sol, add 0.0400g PVP, stir 6h, Ag nano particle colloid that must be after surface treatment.
Get 3mL Ag nano particle colloid and join 7mL Zn 0.995Al 0.005Mix in the O colloid, and under room temperature, stir 10min, form uniform Ag nano particle and Zn 0.995Al 0.005The colloid mixture of O.
Get 10g Zn 3Ta 2O 8: Mn fluorescent material, add the 18mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 15h of baking oven.At 5g Zn 3Ta 2O 8: add colloid mixture 3mL among the Mn, magnetic agitation 5h is placed on dry 5h in 80 ℃ of baking ovens in 40 ℃ of water-baths, then in 1000 ℃ of retort furnaces under the carbon reducing agent insulation annealing handle 2h, obtain the modification luminescent material.
The Y of embodiment 24, modification 2O 2S:Eu luminescent material: Y 2O 2S:Eu coats Al-Doped ZnO and Pd nano particle outward.
Under the room temperature, accurately take by weighing 1.0865g Zn (CH 3COO) 22H 2O, 0.0188g Al (NO 3) 39H 2O and 0.4mL C 2H 7NO places container, and the mixing solutions of second alcohol and water that then adds volume ratio and be 5: 1 after stirring 6h under 50 ℃ of water bath condition, obtains the Zn of uniform 0.10mol/L to 50mL 0.99Al 0.01The O precursor solution with resulting precursor solution ageing 80h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.99Al 0.01The O colloid.
Taking by weighing the 0.0043g Palladous chloride is dissolved in the deionized water of 8.5mL; After Palladous chloride dissolves fully, take by weighing 0.0110g Trisodium Citrate and 0.0040g sodium lauryl sulphate, under magnetic agitation, be dissolved in the palladium chloride solution; It is molten in 10mL ethanol to take by weighing the 0.0038g sodium borohydride, and obtaining concentration is 1 * 10 ～2The sodium borohydride solution of mol/L; Under magnetic agitation, in palladium chloride solution, add 0.48mL1 * 10 fast ～2The sodium borohydride alcoholic solution of mol/L continues reaction 20min, and promptly getting 10mL Pd content is 1 * 10 ～4The Pd nano particle colloidal sol of mol/L adds 0.0500g PVP afterwards in this 10mL Pd nano particle colloidal sol, stirs 4h, Pd nano particle colloid that must be after surface treatment.
Get 4mL Pd nano particle colloid and join 6mL Zn 0.99Al 0.01Mix in the O colloid, and under room temperature, stir 25min, form uniform Pd nano particle and Zn 0.99Al 0.01The colloid mixture of O.
Get 10g Y 2O 2S:Eu fluorescent material adds the 3mL dehydrated alcohol, at room temperature stirs 10h, filters and places 60 ℃ of dry 12h of baking oven.At Y 2O 2Add colloid mixture 3mL among the S:Eu, magnetic agitation 5h is placed on dry 5h in 80 ℃ of baking ovens in 60 ℃ of water-baths, then H in 1000 ℃ of retort furnaces 2Insulation annealing is handled 2h in the S atmosphere, obtains the modification luminescent material.
The CaTiO of embodiment 25, modification 3: Pr luminescent material: CaTiO 3: Pr coats Al-Doped ZnO and Nano silver grain outward.
Under the room temperature, accurately take by weighing 2.9452g Zn (NO 3) 26H 2O, 0.0241g AlCl 36H 2O and 0.6mLC 2H 7NO places container, then adds the solvent ethylene glycol methyl ether to 50mL, after stirring 7h under 60 ℃ of water bath condition, obtains the Zn of uniform 0.20mol/L 0.99Al 0.01The O precursor solution with resulting precursor solution ageing 56h in 60 ℃ of baking ovens, obtains uniform light yellow Zn again 0.99Al 0.01The O colloid.
Take by weighing the 0.0034g Silver Nitrate and be dissolved in the ethanol of 18.4mL, stirring is dissolved Silver Nitrate fully, takes by weighing 0.0355gPVP and under agitation is dissolved in the Silver Nitrate ethanolic soln; It is molten in 10mL ethanol to take by weighing the 0.0057g sodium borohydride, and obtaining 10mL concentration is 1.5 * 10 ～2The ethanol solution of sodium borohydride of mol/L; Stir down disposable adding 1.6mL 1.5 * 10 in the Silver Nitrate alcoholic solution ～2The sodium borohydride alcoholic solution of mol/L continues reaction 15min afterwards, and promptly getting 20mLAg content is 1 * 10 ～3The Ag nano particle colloidal sol of mol/L; Measure 10mL Ag nano particle colloidal sol afterwards, add 0.1000g PVP, stir 3h, obtain the Ag nano particle colloid after surface treatment.
Get 5mL Ag nano particle colloid and join 5mL Zn 0.99Al 0.01Mix in the O colloid, and under room temperature, stir 10min, form uniform Ag nano particle and Zn 0.99Al 0.01The colloid mixture of O.
Get 10g CaTiO 3: Pr fluorescent material, add the 15mL dehydrated alcohol, at room temperature stir 5h, filter and place 60 ℃ of dry 8h of baking oven.At 5g CaTiO 3: add colloid mixture 3mL among the Pr, magnetic agitation 5h is placed on dry 5h in 80 ℃ of baking ovens in 55 ℃ of water-baths, then in 1000 ℃ of retort furnaces in the carbon reducing agent atmosphere insulation annealing handle 2h, obtain the modification luminescent material.

Claims (11)

1. a modification luminescent material is characterized in that, is to be coated with Al-Doped ZnO and the formation of metal simple-substance nanoparticle by the particle at fluorescent material.
2. modification luminescent material according to claim 1 is characterized in that, described metal simple-substance nanoparticle is a kind of among Au, Pt, Ag or the Pd.
3. modification luminescent material according to claim 1 is characterized in that, the Al-Doped ZnO that every 5g fluorescent material coats is 6 * 10 -5～4 * 10 -3Mol.
4. modification luminescent material according to claim 1 is characterized in that, the metal simple-substance nanoparticle that every 5g fluorescent material coats is 1 * 10 -7～6.25 * 10 -5Mol.
5. the preparation method of modification luminescent material is characterized in that, may further comprise the steps:
(1), prepares Zn respectively 1～xAl xO colloid, metal nanometer particle colloid, 0＜x≤0.05 wherein, Zn 1～xAl xO colloidal concentration is 0.05mol/L～0.70mol/L, and the concentration of metal nanometer particle colloid is 1 * 10 -4～1 * 10 ～3Mol/L, and with Zn 1～xAl xO colloid and metal nanometer particle colloid are mixed and made into colloid mixture;
(2), fluorescent material is joined mixing in the colloid mixture in the step (1), 15～70 ℃ of reaction 2～10h down, dry then metal nanoparticle and Zn 1～xAl xThe coating fluorescent powder that the colloid mixture of O coats;
(3), at air atmosphere, reducing atmosphere or H 2Under the S atmosphere, the coating fluorescent powder that step (2) is made is in 400～1000 ℃ of anneal 0.5～6h, the modification luminescent material.
6. the preparation method of modification luminescent material according to claim 4 is characterized in that, in the described step (2), at first fluorescent material is carried out surface treatment after, join mixing in the colloid mixture in the step (1) again.
7. according to the preparation method of claim 4 or 5 described modification luminescent materials, it is characterized in that, in the described step (1), Zn 1～xAl xThe preparation of O colloidal may further comprise the steps:
(1.11), press chemical formula Zn 1～xAl xThe molar ratio of each metal ion takes by weighing zinc salt and aluminium salt raw material among the O, and wherein the span of x is 0＜x≤0.05; In zinc salt and aluminium salt raw material, add stablizer and solvent, heat 40～70 ℃ and obtain precursor solution behind stirring 4～8h down;
(1.12), with the precursor solution of gained in 60 ℃ of following ageing 56～90h, obtain Zn 1～xAl xThe O colloid.
8. the preparation method of modification luminescent material according to claim 6 is characterized in that, in the described step (1.11), described zinc salt is zinc acetate, zinc nitrate, zinc chloride or zinc sulfate; Described aluminum nitrate, aluminum chloride or Tai-Ace S 150; Described stablizer is a kind of in monoethanolamine, diethanolamine, the trolamine, and solvent is ethylene glycol monomethyl ether or ethanolic soln.
9. according to the preparation method of claim 4 or 5 described modification luminescent materials, it is characterized in that in the described step (1), the preparation of metal nanometer particle colloid may further comprise the steps:
(1.21), taking by weighing feed metal salt is dissolved in ethanol or the deionized water and forms metal salt solution;
(1.22), stir down, in the metal salt solution of step (1.21), add auxiliary agent and make mixing solutions, wherein the content of auxiliary agent is 1.5 * 10 in the mixing solutions ～4G/mL～2.1 * 10 ～3G/mL;
(1.23), stir down, in the mixing solutions of step (1.22), be 1.2～4.8: 1 ratio in the mol ratio of reductant solution and metal-salt, adding concentration again is 1 * 10 ～3Mol/L～1 * 10 ～2The reductant solution of mol/L promptly obtains metal nanometer particle colloid behind reaction 10min～45min.
10. the preparation method of modification luminescent material according to claim 8 is characterized in that, in the described step (1.22), described metal salt solution is water-soluble or alcoholic acid Au salts solution, Pt salts solution, Ag salts solution or Pd salts solution; Auxiliary agent is at least a in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate, the sodium laurylsulfonate; In the described step (1.23), reductive agent is a kind of in hydrazine hydrate, xitix or the sodium borohydride.
11. the preparation method of modification luminescent material according to claim 5 is characterized in that, it is to add dehydrated alcohol in the fluorescent material, at room temperature to stir 1～20h that described phosphor surface is handled, and filters to be placed on 50～200 ℃ of down dry 3～15h.
CN201010160848.2A 2010-04-30 2010-04-30 Preparation method of modified luminescent material Expired - Fee Related CN102234512B (en)

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WO2014019153A1 (en) * 2012-07-31 2014-02-06 海洋王照明科技股份有限公司 Zinc aluminate material and method for preparing same
CN104946254A (en) * 2015-06-02 2015-09-30 杭州萤鹤光电材料有限公司 Rare earth ion-activated multiphase fluorescent material
CN108796661A (en) * 2018-06-14 2018-11-13 中原工学院 A kind of electrostatic spinning preparation method of platinum doping fluorescent nanofiber

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014019153A1 (en) * 2012-07-31 2014-02-06 海洋王照明科技股份有限公司 Zinc aluminate material and method for preparing same
JP2015525816A (en) * 2012-07-31 2015-09-07 オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー Zinc aluminate fluorescent material and manufacturing method thereof
CN104946254A (en) * 2015-06-02 2015-09-30 杭州萤鹤光电材料有限公司 Rare earth ion-activated multiphase fluorescent material
CN104946254B (en) * 2015-06-02 2017-04-12 杭州萤鹤光电材料有限公司 Rare earth ion-activated multiphase fluorescent material
CN108796661A (en) * 2018-06-14 2018-11-13 中原工学院 A kind of electrostatic spinning preparation method of platinum doping fluorescent nanofiber
CN108796661B (en) * 2018-06-14 2020-06-12 中原工学院 Electrostatic spinning preparation method of platinum-doped fluorescent nanofiber

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