CN102191043B - Zinc oxide luminescent material and preparation method thereof - Google Patents
Zinc oxide luminescent material and preparation method thereof Download PDFInfo
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- CN102191043B CN102191043B CN 201010119784 CN201010119784A CN102191043B CN 102191043 B CN102191043 B CN 102191043B CN 201010119784 CN201010119784 CN 201010119784 CN 201010119784 A CN201010119784 A CN 201010119784A CN 102191043 B CN102191043 B CN 102191043B
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Abstract
The invention discloses a zinc oxide luminescent material and a preparation method thereof. The zinc oxide luminescent material comprises of zinc oxide doped with M metal nano particles. A chemical formula is ZnO : yM, wherein M represents Ag, Au, Pt, Pd or Cu, and y is a molar ratio of the M metal nano particles to the zinc oxide and satisfies the relation: 0<y<=0.05. The preparation method includes the following steps: synthesizing a precursor consisting of zinc compound and metal nano particles by a liquid phase method; then calcining at 100-900 DEG C; and finally calcining in a reducing atmosphere at 500-1000 DEG C; cooling to obtain the zinc oxide luminescent material. The zinc oxide luminescent material of the present invention has a high luminous intensity and is characterized by good luminous efficiency, good stability, besides the preparation method has a simple process and low costs.
Description
Technical field
The present invention relates to the luminescent material technical field, relate in particular to a kind of zinc oxide luminescent material.
Background technology
Zinc oxide (ZnO) is a kind of broad stopband (Eg=3.4eV) direct band-gap semicondictor material, excellent properties with aspects such as piezoelectricity, electricity and optics has been used to prepare the function material components such as transparency electrode of gas sensor, ultrasonator, solar cell.ZnO also is widely used in fields such as photodiode, laser apparatus, cathodoluminescences as luminescent material, receives people's concern.But all the time, all there is the low problem of luminous efficiency in zinc oxide.
Existing many research at present changes or improves the luminescent properties of ZnO by doped metal ion.Pass through doping Ca as Chinese patent CN101104798A
2+Ion obtains launching the ZnO luminescent material of blue light; Chinese patent CN101104797A passes through doped with Mg
2+Ion obtains the ZnO luminescent material of transmitting white.US Patent No. 2408475 and the US4468589 oxide compound of the compound by adding Bi and W, Mo, V respectively improve the luminescent properties of ZnO.Japanese Patent JP08-245956 obtains the ZnO luminescent material by doping with rare-earth ions in ZnO.
But present ZnO luminescent material still exists the low problem of luminous efficiency, how to improve its luminous efficiency and is still a difficult problem needing solution badly.
Summary of the invention
The technical problem to be solved in the present invention is, for the defects of prior art, provides a kind of luminous efficiency high zinc oxide luminescent material.
The technical problem that the present invention further will solve is, a kind of preparation method of zinc oxide luminescent material is provided, and its technique is simple, with low cost, and the luminous luminous efficiency of the zinc oxide luminescent material of preparation is high.
In order to reach above-mentioned purpose, according to the present invention, a kind of zinc oxide luminescent material is provided, in zinc oxide doped with the M metal nanoparticle, chemical formula is ZnO:yM, and wherein, M is Ag, Au, Pt, Pd or Cu, y is the molar ratio of M metal nanoparticle and zinc oxide, and the span of y is 0＜y≤0.05.
In zinc oxide luminescent material of the present invention, the span of described y is preferably 0.0002≤y≤0.02.
In order to reach above-mentioned purpose, according to the present invention, also provide a kind of preparation method of zinc oxide luminescent material, comprise the following steps:
1. take zinc salt and M metal nanoparticle as raw material, with the synthetic compound of zinc and the presoma of M metal nanoparticle of containing of liquid phase method, wherein the molar ratio of M metal nanoparticle and zinc is y, and the span of y is 0＜y≤0.05, and M is Ag, Au, Pt, Pd or Cu;
2. the presoma that 1. step is obtained is calcined under 100～900 ℃, obtains the calcinates such as oxysalt doped with zinc oxide, zinc hydroxide or the zinc of M metal nanoparticle;
3. the calcinate that 2. step is obtained, namely the oxysalt doped with zinc oxide, zinc hydroxide or the zinc of M metal nanoparticle is placed in reducing atmosphere 500～1000 ℃ of calcinings, the cooling zinc oxide luminescent material that obtains.
In the preparation method of zinc oxide luminescent material of the present invention, preferably, described step 1. middle liquid phase method is the precipitator method, sol-gel method, hydrolysis method or hydrothermal method.
In the preparation method of zinc oxide luminescent material of the present invention, preferably, the compound of described zinc is oxide compound, oxyhydroxide or the salt of zinc.
In the preparation method of zinc oxide luminescent material of the present invention, preferably, described step 2. middle calcination time is 1～18h.
In the preparation method of zinc oxide luminescent material of the present invention, further preferably, described step 2. middle calcining temperature is 200～900 ℃, and calcination time is 3～10h.
In the preparation method of zinc oxide luminescent material of the present invention, preferably, described step 3. middle calcination time is 1～18h.
In the preparation method of zinc oxide luminescent material of the present invention, further preferably, described step 3. middle calcining temperature is 600～900 ℃, and calcination time is 2～10h.
In the preparation method of zinc oxide luminescent material of the present invention, preferably, described reducing atmosphere is that volume ratio is the nitrogen of 95: 5 and the atmosphere of hydrogen gas mixture, CO (carbon monoxide converter) gas or hydrogen formation.
Zinc oxide luminescent material of the present invention doped with Ag, Au, Pt, Pd or Cu metal nanoparticle, has higher luminous intensity in zinc oxide, luminous efficiency is high, and good stability can be used for illumination and demonstration field.
The preparation method of zinc oxide luminescent material of the present invention, technique is simple, with low cost, and the zinc oxide luminescent material of preparation has higher luminous efficiency.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in accompanying drawing:
Fig. 1 is the zinc oxide luminescent material and the luminescent spectrum comparison diagram that does not add the zinc oxide luminescent material of metal nanoparticle of the embodiment of the present invention 2,3,4 preparations.
Above-mentioned luminescent spectrum figure obtains under acceleration voltage is the cathode-ray exciting of 1.5kV.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is described in further detail.
In following specific embodiment, metal nanoparticle is that the mode with metal nanoparticle colloidal sol adds.The preparation of metal nanoparticle colloidal sol comprises the following steps:
1) take suitable metallic compound and be dissolved in solvent, be mixed with the solution that concentration is 0.001mol/L～0.1mol/L; Described metallic compound is Silver Nitrate, hydrochloro-auric acid, Platinic chloride, Palladous chloride, cupric nitrate; Described solvent is water and ethanol;
2) under the state of magnetic agitation, one or more auxiliary agent is dissolved into above-mentioned 1) in solution, and to make auxiliary agent can the content in the metal nanoparticle colloidal sol that finally obtains be 1.5 * 10
-4G/mL～2.1 * 10
-3G/mL; Described auxiliary agent is polyethylene arsenic pyrrolidone (PVP), Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate, sodium laurylsulfonate;
3) the reductive agent substance dissolves that takes respective quality is in solvent, and being mixed with concentration range is 1 * 10
-3Mol/L～1 * 10
-2The reductant solution of mol/L; Described reductive agent material is hydrazine hydrate, xitix, sodium borohydride; Described solvent is water and ethanol;
4) under the environment of magnetic agitation, it is the ratio of 1.2: 1～4.8: 1 in the ratio of reductive agent and the amount of substance of metal ion, toward above-mentioned 2) add above-mentioned 3 in resulting solution) reduced liquid that obtains, namely obtaining concentration after whole system reaction 10min～45min is 1 * 10
-3Mol/L～1 * 10
-2Mol/L metal nanoparticle colloidal sol;
5) measure certain volume above-mentioned 4) preparation metal nanoparticle colloidal sol, add surface treatment agent stir process 3h～12h, the add-on of surface treatment agent is 0.001g/mL～0.01g/mL; Described surface treatment agent is polyvinylpyrrolidone (PVP).
Metal nanoparticle colloidal sol in following examples is the use aforesaid method, uses the different metal compound to prepare different metal nanoparticle colloidal sol.
Embodiment 1 making ZnO: 0.0002Au zinc oxide luminescent material
Hydrothermal method is synthesized presoma: weighing 2.975g zinc nitrate hexahydrate is dissolved in 10mL water, and adding 2mL concentration is 10
-3The Au metal nanoparticle colloidal sol of mol/L continues to stir 5h, adds sodium hydroxide to regulate pH value to 8～10; Then sealing after solution being joined in the 50mL reactor 160 ℃ of insulations 24 hours, obtains comprising the presoma of Au metal nanoparticle.
The presoma that obtains is calcined 5h obtain the adulterating ZnO powder of Au metal nanoparticle under 500 ℃.
The ZnO powder of Au metal nanoparticle of adulterating at last is the N of 95: 5 in volume ratio
2And H
2In 800 ℃ of calcining 8h, be cooled to room temperature under the atmosphere that mixed gas forms, the ZnO:0.0002Au zinc oxide luminescent material of the Au metal nanoparticle that namely obtains adulterating.
Embodiment 2 making ZnOs: 0.0001Ag zinc oxide luminescent material
Sol-gel method synthesizes presoma: weighing 2.195g Zinc diacetate dihydrate is dissolved in 20mL ethanol, and adding 1mL concentration is 10
-3The Ag metal nanoparticle colloidal sol of mol/L continues to stir 10h, and then weighing 1.5g two oxalic acid hydrates and 0.5g citric acid are dissolved in the 30mL ethanolic soln.In 80 ℃ of water-baths, slowly oxalic acid solution is joined in zinc acetate solution under continuing to stir, continue stirring reaction 15h and form wet gel, will obtain comprising the presoma of Ag metal nanoparticle after the wet gel standing and drying.
The presoma that obtains is calcined 5h obtain the adulterating ZnC of Ag metal nanoparticle under 320 ℃
2O
4Powder.
The ZnC of Ag metal nanoparticle at last will adulterate
2O
4Powder is the N of 95: 5 in volume ratio
2And H
2In 700 ℃ of calcining 18h, be cooled to room temperature under the atmosphere that mixed gas forms, the ZnO:0.0001Ag zinc oxide luminescent material of the Ag metal nanoparticle that namely obtains adulterating.
Embodiment 3 making ZnOs: 0.001Ag zinc oxide luminescent material
According to method described in embodiment 2, using 1mL concentration is 10
-2The Ag metal nanoparticle colloidal sol of mol/L, the ZnO:0.001Ag zinc oxide luminescent material of preparation doping Ag metal nanoparticle.
Embodiment 4 making ZnOs: 0.01Ag zinc oxide luminescent material
According to method described in embodiment 2, using 10mL concentration is 10
-2The Ag metal nanoparticle colloidal sol of mol/L, the ZnO:0.01Ag zinc oxide luminescent material of preparation doping Ag metal nanoparticle.
Fig. 1 is the zinc oxide luminescent material and the luminescent spectrum comparison diagram that does not add the zinc oxide luminescent material of metal nanoparticle of the embodiment of the present invention 2,3,4 preparations.As shown in Figure 1, curve 1 is the luminescent spectrum that does not add the zinc oxide luminescent material of Ag metal nanoparticle, curve 2 is luminescent spectrums of the ZnO:0.0001Ag zinc oxide luminescent material of the embodiment of the present invention 2 preparations, curve 3 is luminescent spectrums of the ZnO:0.001Ag zinc oxide luminescent material of the embodiment of the present invention 3 preparations, and curve 4 is luminescent spectrums of the ZnO:0.001Ag zinc oxide luminescent material of the embodiment of the present invention 4 preparations.As can be seen from the figure, it is the emission peak place of 500nm left and right at wavelength, the zinc oxide luminescent material that the luminous intensity of the embodiment of the present invention 2,3 and 4 zinc oxide luminescent material does not add metal nanoparticle has had obvious enhancing, has that luminous efficiency is high, the characteristics of good stability.
Embodiment 5 making ZnOs: 0.001Pt zinc oxide luminescent material
The precipitator method are synthesized presoma: weighing 2.195g Zinc diacetate dihydrate, 0.75g thioacetamide, 10mL concentration are 10
-3The Pt metal nanoparticle colloidal sol of mol/L and 5mL 1mol/L nitric acid are dissolved in the 100mL ethanolic soln, then solution are placed in 60 ℃ of slow stirring reaction 4h, obtain comprising the presoma of Pt metal nanoparticle after the separating, washing drying.
The presoma that obtains is calcined 8h obtain the adulterating ZnO powder of Pt metal nanoparticle under 900 ℃.
The ZnO powder of Pt metal nanoparticle of adulterating at last is the N of 95: 5 in volume ratio
2And H
2In 600 ℃ of calcining 12h, be cooled to room temperature under the atmosphere that mixed gas forms, the ZnO:0.001Pt zinc oxide luminescent material of the Pt metal nanoparticle that namely obtains adulterating.
Embodiment 6 making ZnOs: 0.0025Pd zinc oxide luminescent material
The hydrolysis method presoma: weighing 2.195g Zinc diacetate dihydrate is dissolved in the 20mL deionized water, and adding 25mL concentration is 10
-3The Pd metal nanoparticle colloidal sol of mol/L is heated to boiling with solution, and circulation adds water to keep solution be the 20mL left and right, keeps boiling state reaction 5h, obtains comprising the presoma of Pd metal nanoparticle after filtration.
The presoma that obtains is calcined the Zn (OH) that 1h obtains the doping Pd metal nanoparticle under 100 ℃
2Powder.
At last with the Zn (OH) of doping Pd metal nanoparticle
2Powder is the N of 95: 5 in volume ratio
2And H
2In 500 ℃ of calcining 16h, be cooled to room temperature under the atmosphere that mixed gas forms, namely obtain the ZnO:0.0025Pd zinc oxide luminescent material of doping Pd metal nanoparticle.
Embodiment 7 making ZnOs: 0.01Cu zinc oxide luminescent material
Sol-gel method synthesizes presoma: weighing 2.195g Zinc diacetate dihydrate is dissolved in 20mL water, and it is 10 that solution is joined 100mL concentration
-3In the Cu metal nanoparticle colloidal sol of mol/L, continue to stir, and dropwise to add 20mL concentration be the triammonium citrate solution of 1mol/L, be heated to 80 ℃ of insulation 2h, obtain gelatinous precipitate, then dropwise add concentrated nitric acid, obtain colloidal sol, colloidal sol is heated to 120 ℃ of presomas that obtain comprising the Cu metal nanoparticle.
The presoma that obtains is calcined the ZnO powder that 1h obtains the doped with Cu metal nanoparticle under 500 ℃.
ZnO powder with the doped with Cu metal nanoparticle is the N of 95: 5 in volume ratio at last
2And H
2In 1000 ℃ of calcining 2h, be cooled to room temperature under the atmosphere that mixed gas forms, namely obtain the ZnO:0.01Cu zinc oxide luminescent material of doped with Cu metal nanoparticle.
Embodiment 8 making ZnOs: 0.02Au zinc oxide luminescent material
Hydrothermal method is synthesized presoma: weighing 3.0g zinc nitrate hexahydrate is dissolved in 10mL water, and it is 10 that solution is joined 200mL concentration
-3In the Au metal nanoparticle colloidal sol of mol/L, continue to stir 5h, add sodium hydroxide to regulate pH value to 8～10; Then sealing after solution being joined in the 50mL reactor 160 ℃ of insulations 24 hours, obtains comprising the presoma of Au metal nanoparticle.
The presoma that obtains is calcined 10h obtain the adulterating ZnO powder of Au metal nanoparticle under 200 ℃.
The ZnO powder of Au metal nanoparticle of adulterating at last is the N of 95: 5 in volume ratio
2And H
2In 600 ℃ of calcining 10h, be cooled to room temperature under the atmosphere that mixed gas forms, the ZnO:0.02Au zinc oxide luminescent material of the Au metal nanoparticle that namely obtains adulterating.
Embodiment 9 making ZnOs: 0.05Pt zinc oxide luminescent material
The precipitator method are synthesized presoma: weighing 2.195g Zinc diacetate dihydrate, 0.75g thioacetamide, 50mL concentration are 10
-2The Pt metal nanoparticle colloidal sol of mol/L and 5mL 1mol/L nitric acid are dissolved in the 100mL ethanolic soln, then solution are placed in 60 ℃ of slow stirring reaction 4h, obtain comprising the presoma of Pt metal nanoparticle after the separating, washing drying.
The presoma that obtains is calcined 3h obtain the adulterating ZnO powder of Pt metal nanoparticle under 700 ℃.
The ZnO powder of Pt metal nanoparticle of adulterating at last is the N of 95: 5 in volume ratio
2And H
2In 500 ℃ of calcining 18h, be cooled to room temperature under the atmosphere that mixed gas forms, the ZnO:0.05Pt zinc oxide luminescent material of the Pt metal nanoparticle that namely obtains adulterating.
Embodiment 10 making ZnOs: 0.0025Pd zinc oxide luminescent material
The hydrolysis method presoma: weighing 2.195g Zinc diacetate dihydrate is dissolved in the 20mL deionized water, and adding 25mL concentration is 10
-3The Pd metal nanoparticle colloidal sol of mol/L is heated to boiling with solution, and circulation adds water to keep solution be the 20mL left and right, keeps boiling state reaction 5h, obtains comprising the presoma of Pd metal nanoparticle after filtration.
The presoma that obtains is calcined the Zn (OH) that 18h obtains the doping Pd metal nanoparticle under 100 ℃
2Powder.
At last with the Zn (OH) of doping Pd metal nanoparticle
2Powder is the N of 95: 5 in volume ratio
2And H
2In 900 ℃ of calcining 2h, be cooled to room temperature under the atmosphere that mixed gas forms, namely obtain the ZnO:0.0025Pd zinc oxide luminescent material of doping Pd metal nanoparticle.
Embodiment 11 making ZnOs: 0.01Cu zinc oxide luminescent material
Sol-gel method synthesizes presoma: weighing 2.195g Zinc diacetate dihydrate is dissolved in 20mL water, and it is 10 that solution is joined 100mL concentration
-3In the Cu metal nanoparticle colloidal sol of mol/L, continue to stir, and dropwise to add 20mL concentration be the triammonium citrate solution of 1mol/L, be heated to 80 ℃ of insulation 2h, obtain gelatinous precipitate, then dropwise add concentrated nitric acid, obtain colloidal sol, colloidal sol is heated to 120 ℃ of presomas that obtain comprising the Cu metal nanoparticle.
The presoma that obtains is calcined the ZnO powder that 12h obtains the doped with Cu metal nanoparticle under 200 ℃.
ZnO powder with the doped with Cu metal nanoparticle is the N of 95: 5 in volume ratio at last
2And H
2In 1000 ℃ of calcining 1h, be cooled to room temperature under the atmosphere that mixed gas forms, namely obtain the ZnO:0.01Cu zinc oxide luminescent material of doped with Cu metal nanoparticle.
The above is only representative embodiment of the present invention, does not limit the present invention in any way, and all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces or improvement etc., within all should being included in protection scope of the present invention.
For example, reducing atmosphere is except being to be the N of 95: 5 by volume ratio
2And H
2Outside the atmosphere that mixed gas forms, can be also the atmosphere that CO (carbon monoxide converter) gas or hydrogen form.
Claims (8)
1. the preparation method of a zinc oxide luminescent material, is characterized in that, comprises the following steps:
1. the M metal nanoparticle colloidal sol of processing take zinc salt with through surface treatment agent is as raw material, with the synthetic compound of zinc and the presoma of M metal nanoparticle colloidal sol of containing of liquid phase method, wherein the molar ratio of M metal nanoparticle and zinc is y, the span of y is 0＜y≤0.05, and M is Au, Pt or Pd; In described M metal nanoparticle colloidal sol, add surface treatment agent stir process 3h～12h, the add-on of surface treatment agent is 0.001g/ml～0.01g/ml, described surface treatment agent is polyvinylpyrrolidone;
2. the presoma that 1. step is obtained is calcined under 100～900 ℃;
3. the calcinate that 2. step is obtained is placed in reducing atmosphere 500～1000 ℃ of calcinings, the cooling zinc oxide luminescent material that obtains.
2. the preparation method of zinc oxide luminescent material according to claim 1, is characterized in that, described step 1. middle liquid phase method is the precipitator method, sol-gel method, hydrolysis method or hydrothermal method.
3. the preparation method of zinc oxide luminescent material according to claim 1, is characterized in that, the compound of described zinc is oxide compound, oxyhydroxide or the salt of zinc.
4. the preparation method of zinc oxide luminescent material according to claim 1, is characterized in that, described step 2. middle calcination time is 1～18h.
5. the preparation method of zinc oxide luminescent material according to claim 4, is characterized in that, described step 2. middle calcining temperature is 200～900 ℃, and calcination time is 3～10h.
6. the preparation method of zinc oxide luminescent material according to claim 1, is characterized in that, described step 3. middle calcination time is 1～18h.
7. the preparation method of zinc oxide luminescent material according to claim 6, is characterized in that, described step 3. middle calcining temperature is 600～900 ℃, and calcination time is 2～10h.
8. the preparation method of zinc oxide luminescent material according to claim 1, is characterized in that, described step 3. middle reducing atmosphere is that volume ratio is the nitrogen of 95:5 and the atmosphere that hydrogen gas mixture, CO (carbon monoxide converter) gas or hydrogen form.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4586811A (en) * | 1982-04-23 | 1986-05-06 | Ricoh Company, Ltd. | Confidential document reproduction prevention method |
| CN1715191A (en) * | 2005-06-13 | 2006-01-04 | 中国科学院理化技术研究所 | Collosol and gel prepares the method for adulterated zinc oxide double crystal nano belt |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4586811A (en) * | 1982-04-23 | 1986-05-06 | Ricoh Company, Ltd. | Confidential document reproduction prevention method |
| CN1715191A (en) * | 2005-06-13 | 2006-01-04 | 中国科学院理化技术研究所 | Collosol and gel prepares the method for adulterated zinc oxide double crystal nano belt |
Non-Patent Citations (2)
| Title |
|---|
| Doping of ZnO by group-IB elements;Yanfa Yan, et al.,;《APPLIED PHYSICS LETTERS》;20061031;第89卷;181912 * |
| Yanfa Yan, et al.,.Doping of ZnO by group-IB elements.《APPLIED PHYSICS LETTERS》.2006,第89卷181912. |
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