CN102275976B - Luminescence film material and its preparation method - Google Patents
Luminescence film material and its preparation method Download PDFInfo
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- CN102275976B CN102275976B CN 201010198917 CN201010198917A CN102275976B CN 102275976 B CN102275976 B CN 102275976B CN 201010198917 CN201010198917 CN 201010198917 CN 201010198917 A CN201010198917 A CN 201010198917A CN 102275976 B CN102275976 B CN 102275976B
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Abstract
A luminescence film material contains rare-earth zinc oxide and metal nanoparticles doped in the rare-earth zinc oxide. The general formula of the luminescence film material is Zn1-xRexO:M, wherein x is larger than 0 and less than or equal to 0.05; Re contains at least one element selected from europium (Eu), terbium (Tb), erbium (Er) and dysprosium (Dy); and M contains at least one element selected from aurum (Au), argentums (Ag), platinum (Pt) and palladium (Pd). The mol ratio of the rare-earth zinc oxide to the metal nanoparticles is 1: (2*10-5-1*10-2). The luminescence film material has high luminescent efficiency. The invention also provides a preparation method of the above luminescence film material.
Description
[technical field]
The present invention relates to a kind of light-emitting film material, relate in particular to a kind of light-emitting film material that contains zinc oxide and preparation method thereof.
[background technology]
Zinc oxide (ZnO) is a kind of important II-VI family broad stopband, direct band-gap semicondictor material, its energy gap under room temperature is 3.20eV, exciton bind energy is 60meV, be considered to another the novel photoelectric material after ZnSe, GaN, be with a wide range of applications in high-tech areas such as information storage and demonstration, optical communication, semi-conductor white-light illuminating, medical science and biologies.People can use methods such as molecular beam epitaxy (MBE), metal organic chemical vapor deposition (MOCVD) and magnetron sputtering to prepare quality ZnO film preferably at present, make the window material of solar cell, photo-sensor and flat-panel display device to replace traditional tin indium oxide (ITO) conductive film, can also be applied on the device of cathode-ray exciting.
Yet, the characteristics such as high refractive index that the defective of ZnO own and semiconductor material are total, make that the zno-based luminescent device be about to move towards market is the same with the luminescent device of other commercialization, face the not high problem of luminous efficiency, the luminous efficiency that therefore improves ZnO film is the essential step in the complete practicability of zno-based luminescent device, the high efficiency.
[summary of the invention]
Based on this, be necessary to provide higher light-emitting film material of a kind of luminous efficiency and preparation method thereof.
A kind of light-emitting film material, it comprises rare-earth oxidation zinc and is entrained in the interior metal nanoparticle of this rare-earth oxidation zinc that it forms general formula is Zn
1～xRe
xO:M, wherein: 0＜x≤0.05; Re is at least a in europium (Eu), terbium (Tb), erbium (Er), the dysprosium (Dy); M is at least a in gold (Au), silver (Ag), platinum (Pt), the palladium (Pd); The mol ratio of this rare-earth oxidation zinc and this metal nanoparticle is 1: (2 * 10
-5～1 * 10
-2).
Wherein, the thickness of this light-emitting film material is 100 nanometers～2 micron.
A kind of preparation method of light-emitting film material, comprise the steps: that material dissolution with M is in first solvent, be mixed with the M solion of 0.001mol/L～0.01mol/L, wherein, M is at least a in gold (Au), silver (Ag), platinum (Pt), the palladium (Pd); In Zn: Re=(1-x): the ratio of x takes by weighing the raw material of zinc and the raw material of rare earth, adds successively in stablizer and this M solion to the second solvent, and being mixed with zine ion and rare earth ion total concn is the precursor solution of 0.05mol/L～0.70mol/L; Wherein, Re is at least a in europium (Eu), terbium (Tb), erbium (Er), the dysprosium (Dy); 0＜x≤0.05; The mol ratio of this zine ion and this M ion is 1: (2 * 10
-5～1 * 10
-2); Dry this precursor solution is doped with the rare-earth oxidation zinc colloid of this M ion with formation; After on the substrate this colloid being carried out coating film treatment, under reducing atmosphere, carry out calcination processing is doped with metal nanoparticle with formation rare-earth oxidation zinc light-emitting film material again.
Wherein, in this M solion configuration step, the raw material of this M is hydrochloro-auric acid (HAuCl
44H
2O), Platinic chloride (H
2PtCl
66H
2O), Silver Nitrate (AgNO
3) or Palladous chloride (PdCl
2) at least a; This first solvent is ethanol or deionized water.
Wherein, in this rare-earth oxidation zinc colloid configuration step, the raw material of this zinc is zinc acetate (Zn (CH
3COO)
22H
2O), zinc nitrate (Zn (NO
3)
26H
2O), zinc chloride (ZnCl
22H
2O), zinc sulfate (ZnSO
47H
2O) at least a in; The raw material of this rare earth is europium nitrate (Eu (NO
3)
36H
2O), Europium trichloride (EuCl
36H
2O), Terbium trinitrate (Tb (NO
3)
36H
2O), terbium chloride (TbCl
36H
2O), Erbium trinitrate (Er (NO
3)
36H
2O), Dysprosium trinitrate (Dy (NO
3)
3), Dysprosium trichloride (DyCl
3H
2O) at least a in; This stablizer is at least a in monoethanolamine, diethanolamine or the trolamine, and the mol ratio of this stablizer and this M ion is (1～3): 1; This second solvent is ethylene glycol monomethyl ether or ethanolic soln; The volume ratio of ethanol and deionized water is 3～7: 1 in this ethanolic soln.
Wherein, the step of preparation precursor solution is included under 40～70 ℃ of conditions and stirred 4～8 hours, to form uniform dissolved colloidal state presoma.
Wherein, the step that forms colloid be with the ageing 50～95 hours under 60 ℃ of conditions of dissolved colloidal state presoma, with the formation colloid.
Wherein, this reducing atmosphere is N
2With H
2Mix reducing atmosphere, carbon reducing agent atmosphere, CO reducing atmosphere, pure H
2At least a in the reducing atmosphere.
Wherein, the plated film step places 100～150 ℃ of conditions to dry 5～30 minutes film for using spin coated instrument coating 3～10 times after having applied at every turn.
Wherein, the calcination processing process is the rare-earth oxidation zinc film after the coating film treatment to be placed to be heated under 700～1200 ℃ the environment with 1～5 ℃/minute heat-up rate be incubated 1～3 hour.
In the above-mentioned light-emitting film material, the effective codoped of rare earth element and metal ion enters the lattice of zinc oxide, has produced surface phasmon (surface plasmon, SP) effect, zinc oxide interband radiative recombination speed is accelerated, to reach the effect that strengthens luminous efficiency.The performance test results shows that above-mentioned light-emitting film material has higher light emission intensity at the range of wavelengths of 610～620 nanometers.Advantages such as in addition, the preparation method of above-mentioned light-emitting film material has that technology is simple, equipment requirements is low and preparation cycle is short.
[description of drawings]
Fig. 1 is the light-emitting film material (a) of embodiment 1 and the fluorescence spectrum figure of traditional zinc oxide luminescent material (b).
[embodiment]
Below in conjunction with drawings and the embodiments light-emitting film material and preparation method thereof is described in detail.
The light-emitting film material of present embodiment comprises rare-earth oxidation zinc and is entrained in the interior metal nanoparticle of rare-earth oxidation zinc that it forms general formula is Zn
1～xRe
xO:M.Wherein, 0＜x≤0.05; Re is at least a in europium (Eu), terbium (Tb), erbium (Er), the dysprosium (Dy); M is at least a in gold (Au), silver (Ag), platinum (Pt), the palladium (Pd); The mol ratio of rare-earth oxidation zinc and metal nanoparticle is 1: (2 * 10
-5～1 * 10
-2).The thickness of above-mentioned light-emitting film material is preferably 100 nanometers～2 micron.
In the above-mentioned light-emitting film material, the effective codoped of rare earth element and metal nanoparticle enters the lattice of zinc oxide, has produced surface phasmon (surface plasmon, SP) effect, zinc oxide interband radiative recombination speed is accelerated, to reach the effect that strengthens luminous efficiency.
The preparation method of above-mentioned light-emitting film material can be sol-gel method, and it comprises the steps:
(1) preparation M solion.To contain the material dissolution of M in first solvent, be mixed with the M solion of 0.001mol/L～0.01mol/L.Wherein the raw material of M can be the salt of this M, is preferably hydrochloro-auric acid (HAuCl
44H
2O), Platinic chloride (H
2PtCl
66H
2O), Silver Nitrate (AgNO
3) or Palladous chloride (PdCl
2) at least a.First solvent is preferably dehydrated alcohol or deionized water.
(2) preparation precursor solution.Can be in Zn: Re=(1-x): the ratio of x takes by weighing the raw material of zinc and the raw material of rare earth, adds stablizer and aforementioned M solion, and is mixed with zine ion and the rare earth ion total concn is the precursor solution of 0.05mol/L～0.70mol/L with second solvent.Wherein the raw material of zinc can be zinc salt, is preferably zinc acetate (Zn (CH
3COO)
22H
2O), zinc nitrate (Zn (NO
3)
26H
2O), zinc chloride (ZnCl
22H
2O), zinc sulfate (ZnSO
47H
2O) at least a in; The salt that contains rare earth is europium nitrate (Eu (NO
3)
36H
2O), Europium trichloride (EuCl
36H
2O), Terbium trinitrate (Tb (NO
3)
36H
2O), terbium chloride (TbCl
36H
2O), Erbium trinitrate (Er (NO
3)
36H
2O), Dysprosium trinitrate (Dy (NO
3)
3), Dysprosium trichloride (DyCl
3H
2O) at least a in; 0＜x≤0.05; The mol ratio of zine ion and M ion is 1: (2 * 10
-51 * 10
-2).Function of stabilizer is to promote in many ways the formation of colloid, and it is preferably at least a in monoethanolamine, diethanolamine or the trolamine; The mol ratio of stablizer and metal ion is (1～3): 1.Second solvent is preferably ethylene glycol monomethyl ether or ethanol.
(3) aforementioned precursor solution was stirred under 40～70 ℃ water bath condition 4～8 hours, to form uniform dissolved colloidal state presoma.
(4) aforementioned dissolved colloidal state presoma is placed 60 ℃ baking oven is dry, ageing 50～95 hours, be doped with the rare-earth oxidation zinc colloid of metal ion with formation.
(5) use this colloid to carry out plated film.Can use multiple film coating method during plated film, be preferably and use spin coated instrument coating 3～10 times, place 100～150 ℃ conditions dry 5～30 minute film after having applied at every turn.
(6) under reducing atmosphere, carry out calcination processing.Rare-earth oxidation zinc film after the coating film treatment is placed the temperature programming stove, and under reducing atmosphere, be heated under 700～1200 ℃ the environment with 1～5 ℃/minute heat-up rate, be incubated 1～3 hour, be doped with the rare-earth oxidation zinc thin-film material of metal nanoparticle with formation.The effect of reducing atmosphere is the nano particle that the M ion is reduced to M simple substance, is preferably N
2With H
2Mix reducing atmosphere, carbon reducing agent atmosphere, CO reducing atmosphere, pure H
2At least a in the reducing atmosphere.
Preparation method to above-mentioned light-emitting film material is described further below by various embodiments.Following all reagent are analytical pure.
Embodiment 1
Take by weighing Silver Nitrate 0.8494g, being made into concentration is the aqueous solution 1000mL of 0.005mol/L; Press chemical formula Zn
0.99Eu
0.01The mol ratio of each element among the O takes by weighing zinc chloride 1.3494g respectively, and europium nitrate 0.0446g and thanomin 1.26mL add silver nitrate solution 12mL then, and is the ethanolic soln 50mL of 0.2mol/L with ethanol preparation zine ion and europium ion total mol concentration; Behind 65 ℃ of stirring in water bath 4h, obtain uniform Zn subsequently
0.99Eu
0.01The O precursor solution; At last with the Zn of gained
0.99Eu
0.01The O precursor solution places 60 ℃ of baking oven ageing 60h, obtains being doped with the Zn of silver ions
0.99Eu
0.01The O colloid.
Zn with the adding silver ions that obtains
0.99Eu
0.01The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 8 times, places 120 ℃ of baking ovens to dry 15 minutes film after having applied at every turn; At last the film of spin coating moulding is placed the temperature programming stove to adopt carbon reducing agent atmosphere, sinter to 1200 ℃ and be incubated 1 hour with 3 ℃/minute heat-up rates, the thickness that obtains being doped with silver ions is 1.5 microns Zn
0.99Eu
0.01The O light-emitting film.
Embodiment 2
Take by weighing Silver Nitrate 1.6987g, being made into concentration is the ethanolic soln 1000mL of 0.01mol/L; Press chemical formula Zn
0.96Tb
0.04The mol ratio of each element among the O takes by weighing zinc nitrate 1.4280g respectively, and terbium chloride 0.0747g and thanomin 0.63mL add silver nitrate solution 2.5mL then, and is the ethanolic soln 50mL of 0.1mol/L with ethanol preparation zine ion and terbium ion total mol concentration; Behind 50 ℃ of stirring in water bath 8h, obtain uniform Zn subsequently
0.96Tb
0.04The O precursor solution is at last with the Zn of gained
0.96Tb
0.04The O precursor solution places 55 ℃ of baking oven ageing 88h, obtains being doped with the Zn of silver ions
0.96Tb
0.04The O colloid.
Zn with the adding silver ions that obtains
0.96Tb
0.04The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 10 times, places 120 ℃ of baking ovens to dry 15 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove to adopt at 95%N at last
2Add 5%H
2Reducing atmosphere, sinter to 1000 ℃ and be incubated 2 hours with 5 ℃/minute heat-up rates, the thickness that obtains being doped with silver ions is 2 microns Zn
0.96Tb
0.04The O light-emitting film.
Embodiment 3
Take by weighing Platinic chloride 2.5896g, being made into concentration is the aqueous solution 1000mL of 0.005mol/L; Press chemical formula Zn
0.98Dy
0.02The mol ratio of each element among the O takes by weighing zinc acetate 4.2144g respectively, and Dysprosium trichloride 0.1147g and thanomin 1.20mL add platinum acid chloride solution 3.2mL then, and is the ethanolic soln 50mL of 0.4mol/L with ethanol preparation zine ion and dysprosium ion total mol concentration; Behind 55 ℃ of stirring in water bath 7h, obtain uniform Zn subsequently
0.98Dy
0.02The O precursor solution; At last, with the Zn of gained
0.98Dy
0.02The O precursor solution places 65 ℃ of baking oven ageing 85h, obtains being doped with the Zn of platinum ion
0.98Dy
0.02The O colloid.
Zn with the adding platinum ion that obtains
0.98Dy
0.02The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 6 times, places 100 ℃ of baking ovens to dry 20 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove to adopt at 95%N at last
2Add 5%H
2Reducing atmosphere, sinter to 1000 ℃ and be incubated 2 hours with 3 ℃/minute heat-up rates, the thickness that obtains being doped with platinum ion is 1 micron Zn
0.98Dy
0.02The O light-emitting film.
Embodiment 4
Take by weighing Palladous chloride 0.8866g, being made into concentration is the aqueous solution 1000mL of 0.005mol/L; Press chemical formula Zn
0.96Dy
0.04The mol ratio of each element among the O, take by weighing zinc sulfate 4.1409g respectively, Dysprosium trinitrate 0.2091g and trolamine 2.00mL add palladium chloride solution 0.3mL then, and the spent glycol methyl ether is prepared zine ion and the dysprosium ion total mol concentration is the ethylene glycol monomethyl ether solution 50mL of 0.3mol/L; Behind 65 ℃ of stirring in water bath 7h, obtain uniform Zn subsequently
0.96Dy
0.04The O precursor solution; At last with the Zn of gained
0.96Dy
0.04The O precursor solution places 75 ℃ of baking oven ageing 70h, obtains being doped with the Zn of palladium ion
0.96Dy
0.04The O colloid.
Zn with the adding palladium ion that obtains
0.96Dy
0.04The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 10 times, places 120 ℃ of baking ovens to dry 15 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove to adopt at 95%N at last
2Add 5%H
2Reducing atmosphere, sinter to 1200 ℃ and be incubated 1 hour with 4 ℃/minute heat-up rates, the thickness that obtains being doped with palladium ion is 2 microns Zn
0.96Dy
0.04The O light-emitting film.
Embodiment 5
Take by weighing Platinic chloride 5.1792g, being made into concentration is the ethanolic soln 1000mL of 0.01mol/L; Press chemical formula Zn
0.999Tb
0.001The mol ratio of each element among the O takes by weighing zinc acetate 7.6748g respectively, and Terbium trinitrate 0.0159g and thanomin 4.20mL add platinum acid chloride solution 2.1mL then, and is the ethanolic soln 50mL of 0.7mol/L with ethanol preparation zine ion and terbium ion total mol concentration; Behind 60 ℃ of stirring in water bath 5h, obtain uniform Zn subsequently
0.999Tb
0.001The O precursor solution is at last with the Zn of gained
0.999Tb
0.001The O precursor solution places 65 ℃ of baking oven ageing 80h, obtains being doped with the Zn of platinum ion
0.999Tb
0.001The O colloid.
Zn with the adding platinum ion that obtains
0.999Tb
0.001The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 8 times, places 120 ℃ of baking ovens to dry 20 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove to adopt at 95%N at last
2Add 5%H
2Reducing atmosphere, sinter to 1000 ℃ and be incubated 2 hours with 5 ℃/minute heat-up rates, the thickness that obtains being doped with platinum ion is 1.5 microns Zn
0.999Tb
0.001The O light-emitting film.
Embodiment 6
Take by weighing Platinic chloride 0.5179g, being made into concentration is the aqueous solution 100mL of 0.01mol/L; Press chemical formula Zn
0.96Tb
0.04The mol ratio of each element among the O, take by weighing zinc nitrate 1.4280g respectively, Terbium trinitrate 0.0906g and diethanolamine 0.96mL add platinum acid chloride solution 2.5mL then, and the spent glycol methyl ether is prepared zine ion and the terbium ion total mol concentration is the ethylene glycol monomethyl ether solution 50mL of 0.1mol/L; Behind 70 ℃ of stirring in water bath 4h, obtain uniform Zn subsequently
0.96Tb
0.04The O precursor solution is with the Zn of gained
0.96Tb
0.04The O precursor solution places 50 ℃ of baking oven ageing 95h, obtains being doped with the Zn of platinum ion
0.96Tb
0.04The O colloid.
Zn with the adding platinum ion that obtains
0.96Tb
0.04The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 6 times, places 100 ℃ of baking ovens to dry 30 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove to adopt at 95%N at last
2Add 5%H
2Reducing atmosphere, sinter to 1200 ℃ and be incubated 2 hours with 5 ℃/minute heat-up rates, the thickness that obtains being doped with platinum ion is 1 micron Zn
0.96Tb
0.04The O light-emitting film.
Embodiment 7
Take by weighing Palladous chloride 1.7731g, being made into concentration is the ethanolic soln 1000mL of 0.01mol/L; Press chemical formula Zn
0.97Eu
0.03The mol ratio of each element among the O, take by weighing zinc acetate 5.3228g respectively, europium nitrate 0.3345g and trolamine 3.30mL, add palladium chloride solution 5mL then, and be the ethanolic soln 50mL of 0.5mol/L with ethanol preparation zine ion and europium ion total mol concentration, behind 60 ℃ of stirring in water bath 5h, obtain uniform Zn subsequently
0.97Eu
0.03The O precursor solution is with the Zn of gained
0.97Eu
0.03The O precursor solution places 60 ℃ of baking oven ageing 70h, obtains being doped with the Zn of palladium ion
0.97Eu
0.03The O colloid.
Zn with the adding palladium ion that obtains
0.97Eu
0.03The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 4 times, places 120 ℃ of baking ovens to dry 15 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove under the CO reducing atmosphere at last, sinters to 1000 ℃ and be incubated 3 hours with 4 ℃/minute heat-up rates, and the thickness that obtains being doped with palladium ion is the Zn of 800 nanometers
0.97Eu
0.03The O light-emitting film.
Embodiment 8
Take by weighing Silver Nitrate 1.6987g, being made into concentration is the aqueous solution 1000mL of 0.001mol/L.Press chemical formula Zn
0.99Er
0.01The mol ratio of each element among the O, take by weighing zinc chloride 1.3494g respectively, Erbium trinitrate 0.0461g and trolamine 3.96mL add silver nitrate solution 0.2mL then, and the spent glycol methyl ether is prepared zine ion and the erbium ion total mol concentration is the ethylene glycol monomethyl ether solution 50mL of 0.2mol/L; Behind 40 ℃ of stirring in water bath 8h, obtain uniform Zn subsequently
0.99Er
0.01The O precursor solution is at last with the Zn of gained
0.99Er
0.01The O precursor solution places 70 ℃ of baking oven ageing 50h, obtains being doped with the Zn of silver ions
0.99Er
0.01The O colloid.
Zn with the adding silver ions that obtains
0.99Er
0.01The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 3 times, places 150 ℃ of baking ovens to dry 5 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove at pure H at last
2Sinter to 700 ℃ and be incubated 3 hours with 1 ℃/minute heat-up rate under the reducing atmosphere, the thickness that obtains being doped with silver ions is the Zn of 100 nanometers
0.99Er
0.01The O light-emitting film.
Embodiment 9
Take by weighing hydrochloro-auric acid 0.3398g, being made into concentration is the aqueous solution 1L of 0.001mol/L.Press chemical formula Zn
0.90Eu
0.10The mol ratio of each element among the O, take by weighing zinc acetate 0.4939g respectively, europium nitrate 0.1115g and monoethanolamine 0.16mL, add chlorauric acid solution 2.5mL then, and the spent glycol methyl ether is prepared zine ion and the europium ion total mol concentration is the ethylene glycol monomethyl ether solution 50mL of 0.05mol/L, obtains uniform Zn subsequently behind 50 ℃ of stirring in water bath 6h
0.90Eu
0.10The O precursor solution; At last with the Zn of gained
0.90Eu
0.10The O precursor solution places 60 ℃ of baking oven ageing 75h, obtains being doped with the Zn of gold ion
0.90Eu
0.10The O colloid.
Zn with the adding gold ion that obtains
0.90Eu
0.10The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 6 times, places 120 ℃ of baking ovens to dry 15 minutes film after having applied at every turn; At last the film of spin coating moulding is placed the temperature programming stove under carbon dust and the common reducing atmosphere of building of CO, sinter to 1000 ℃ and be incubated 3 hours with 3 ℃/minute heat-up rates, the thickness that obtains being doped with gold ion is 1 micron Zn
0.90Eu
0.10The O light-emitting film.
Embodiment 10
Take by weighing Platinic chloride 0.5179g, being made into concentration is the ethanolic soln 1000mL of 0.001mol/L; Press chemical formula Zn
0.90Eu
0.10The mol ratio of each element among the O takes by weighing zinc acetate 0.4939g respectively, and Europium trichloride 0.0916g and diethanolamine 0.72mL add platinum acid chloride solution 10mL then, and is the ethanolic soln 50mL of 0.05mol/L with ethanol preparation zine ion and europium ion total mol concentration; Behind 60 ℃ of stirring in water bath 7h, obtain uniform Zn subsequently
0.90Eu
0.10The O precursor solution is with the Zn of gained
0.90Eu
0.10The O precursor solution places 55 ℃ of baking oven ageing 60h, obtains being doped with the Zn of platinum ion
0.90Eu
0.10The O colloid.
Zn with the adding platinum ion that obtains
0.90Eu
0.10The O colloid is coated on the substrate, applies to adopt spin coated, and number of times is 6 times, places 120 ℃ of baking ovens to dry 15 minutes film after having applied at every turn; Film with the spin coating moulding places the temperature programming stove to adopt at 95%N at last
2Add 5%H
2Reducing atmosphere, sinter to 1000 ℃ and be incubated 3 hours with 3 ℃/minute heat-up rates, the thickness that obtains being doped with platinum ion is 1 micron Zn
0.90Eu
0.10The O light-emitting film.
Fig. 1 is the fluorescence spectrum figure of embodiment 1 (a) and traditional zinc oxide luminescent material (b).As can be seen from Figure 1, compare with traditional zinc oxide luminescent material, the light-emitting film material of embodiment 1 has higher light emission intensity in the wavelength region may of 610～620 nanometers.
In addition, those skilled in the art can also do other variation in spirit of the present invention, and certainly, these are included within the scope of protection of present invention according to the variation that spirit of the present invention is done.
Claims (6)
1. the preparation method of a light-emitting film material, this light-emitting film material comprises rare-earth oxidation zinc and is entrained in metal nanoparticle in this rare-earth oxidation zinc that it forms general formula is Zn
1～xRe
xO:M, wherein:
0<x≤0.05；
Re is at least a in europium, terbium, erbium, the dysprosium;
M is at least a in gold and silver, platinum, the palladium;
The mol ratio of this rare-earth oxidation zinc and this metal nanoparticle is 1:(2 * 10
-5～1 * 10
-2);
This preparation method comprises the steps:
The material dissolution of M in first solvent, is mixed with the M solion of 0.001mol/L～0.01mol/L, and wherein, M is at least a in gold and silver, platinum, the palladium;
In Zn:Re=(1-x): the ratio of x takes by weighing the raw material of zinc and the raw material of rare earth, adds successively in stablizer and this M solion to the second solvent, and being mixed with zine ion and rare earth ion total concn is the precursor solution of 0.05mol/L～0.70mol/L; Wherein, Re is at least a in europium, terbium, erbium, the dysprosium; 0＜x≤0.05; The mol ratio of this zine ion and this M ion is 1:(2 * 10
-5～1 * 10
-2);
Dry this precursor solution is doped with the rare-earth oxidation zinc colloid of this M ion with formation;
After on the substrate this colloid being carried out coating film treatment, under reducing atmosphere, carry out calcination processing is doped with metal nanoparticle with formation rare-earth oxidation zinc light-emitting film material again;
In this M solion preparation steps,
The raw material of this M is hydrochloro-auric acid, Platinic chloride, at least a in Silver Nitrate or the Palladous chloride;
This first solvent is ethanol or deionized water;
In this rare-earth oxidation zinc colloid preparation steps,
The raw material of this zinc is at least a in zinc acetate, zinc nitrate, zinc chloride, the zinc sulfate;
The raw material of this rare earth is europium nitrate, Europium trichloride, Terbium trinitrate, terbium chloride, Erbium trinitrate, Dysprosium trinitrate, at least a in the Dysprosium trichloride;
This stablizer is at least a in monoethanolamine, diethanolamine or the trolamine, and the mol ratio of this stablizer and this M ion is (1～3): 1;
This second solvent is ethylene glycol monomethyl ether or ethanolic soln; The volume ratio of ethanol and deionized water is 3～7:1 in this ethanolic soln.
2. the preparation method of light-emitting film material as claimed in claim 1, it is characterized in that: the step of this preparation precursor solution is included under 40～70 ℃ of conditions and stirred 4～8 hours, to form uniform dissolved colloidal state presoma.
3. the preparation method of light-emitting film material as claimed in claim 2 is characterized in that: the step of this formation colloid is for the ageing 50～95 hours under 60 ℃ of conditions of this dissolved colloidal state presoma, to form colloid.
4. the preparation method of light-emitting film material as claimed in claim 1, it is characterized in that: this reducing atmosphere is N
2With H
2Mix reducing atmosphere, carbon reducing agent atmosphere, CO reducing atmosphere, pure H
2At least a in the reducing atmosphere.
5. the preparation method of light-emitting film material as claimed in claim 1 is characterized in that: this coating film treatment step places 100～150 ℃ of conditions to dry 5～30 minutes film for using spin coated instrument coating 3～10 times after having applied at every turn.
6. the preparation method of light-emitting film material as claimed in claim 1 is characterized in that: the calcination processing process is the rare-earth oxidation zinc film after the coating film treatment to be placed to be heated under 700～1200 ℃ the environment with 1～5 ℃/minute heat-up rate be incubated 1～3 hour.
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| CN1442883A (en) * | 2003-02-28 | 2003-09-17 | 浙江大学 | Method of preparing high effect silicon base luminuous film on silicon sheet |
| CN1772375A (en) * | 2005-10-27 | 2006-05-17 | 南京大学 | Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria |
| CN101660120A (en) * | 2009-09-15 | 2010-03-03 | 中国科学院上海硅酸盐研究所 | Multi-element doping n-type zinc-oxide-base transparent conducting film and preparation method thereof |
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| JP4952956B2 (en) * | 2008-12-24 | 2012-06-13 | 独立行政法人産業技術総合研究所 | Phosphor with crystallized metal oxide thin film |
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| CN1442883A (en) * | 2003-02-28 | 2003-09-17 | 浙江大学 | Method of preparing high effect silicon base luminuous film on silicon sheet |
| CN1772375A (en) * | 2005-10-27 | 2006-05-17 | 南京大学 | Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria |
| CN101660120A (en) * | 2009-09-15 | 2010-03-03 | 中国科学院上海硅酸盐研究所 | Multi-element doping n-type zinc-oxide-base transparent conducting film and preparation method thereof |
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