CN104449707A - Ce-doped zirconium niobate light-emitting film as well as preparation method and application thereof - Google Patents

Ce-doped zirconium niobate light-emitting film as well as preparation method and application thereof Download PDF

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CN104449707A
CN104449707A CN201310461172.4A CN201310461172A CN104449707A CN 104449707 A CN104449707 A CN 104449707A CN 201310461172 A CN201310461172 A CN 201310461172A CN 104449707 A CN104449707 A CN 104449707A
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ion
emitting film
light
zirconium niobate
cerium dopping
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周明杰
陈吉星
王平
钟铁涛
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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 Ce-doped zirconium niobate light-emitting film having a chemical formula of MeZr[4-x]Nb6O24:xCe<3+>, wherein x is between 0.01 and 0.05, and Me is magnesium ion, calcium ion, strontium ion or barium ion. In the electroluminescence (EL) spectrum of the Ce-doped zirconium niobate light-emitting film, a strong light emission peak appears in a 535nm wavelength region, and therefore, the Ce-doped zirconium niobate light-emitting film can be applied to a thin film electroluminescent device. The invention provides a preparation method and application of the Ce-doped zirconium niobate light-emitting film.

Description

Cerium dopping zirconium niobate light-emitting film, preparation method and application thereof
[technical field]
The present invention relates to a kind of cerium dopping zirconium niobate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.
[background technology]
Membrane electro luminescent device (TFELD), due to its active illuminating, total solids, the advantage such as shock-resistant, reaction is fast, visual angle is large, Applicable temperature is wide, operation is simple, has caused and paid close attention to widely, and development rapidly.At present, research colour and extremely panchromatic TFELD, the film of exploitation multiband luminescence is the developing direction of this problem.But, can be applicable to the cerium dopping zirconium niobate light-emitting film of membrane electro luminescent device, have not yet to see report.
[summary of the invention]
Based on this, be necessary to provide a kind of the cerium dopping zirconium niobate light-emitting film, its preparation method, the membrane electro luminescent device using this cerium dopping zirconium niobate light-emitting film and preparation method thereof that can be applicable to membrane electro luminescent device.
A kind of cerium dopping zirconium niobate light-emitting film, the chemical general formula of described cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
Ce 3+ion is the luminescence center of material, 4f 1→ 5d 1transition radiation between energy level goes out the ruddiness of 610nm.
Preferably, described x is 0.02.
A preparation method for cerium dopping zirconium niobate light-emitting film, comprises the following steps:
By MeO, ZrO 2, Nb 2o 5and CeO 2powder is 1:(4-x in molar ratio): the ratio of 3:x mixes and obtains mixed powder, described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
Described target and substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 -5pa ~ 1.0 × 10 -3pa; And
Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, operating pressure 0.5Pa ~ 5Pa, and the flow of working gas is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80 ~ 300MJ, is then filmed, and obtaining chemical formula is MeZr 4-xnb 6o 24: xCe 3+cerium dopping zirconium niobate light-emitting film, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
Preferably, the vacuum tightness of described vacuum cavity is 5.0 × 10 -4pa, base target spacing is 60mm, and operating pressure is 3Pa, and working gas is oxygen, and the flow of working gas is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150mJ.
A kind of membrane electro luminescent device, comprise the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is cerium dopping zirconium niobate light-emitting film, and the chemical formula of described cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
Preferably, described x is 0.02.
Preferably, the thickness of described luminescent layer is 60nm ~ 350nm.
A preparation method for membrane electro luminescent device, comprises the following steps:
The substrate with anode is provided;
By MeO, ZrO 2, Nb 2o 5and CeO 2powder is 1:(4-x in molar ratio): the ratio of 3:x mixes and obtains mixed powder, namely described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
By described target and described in there is anode substrate load the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 -5pa ~ 1.0 × 10 -3pa; And
Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80 ~ 300mJ, is then filmed, and described anode prepares luminescent layer, the material of described luminescent layer is cerium dopping zirconium niobate light-emitting film, and the chemical formula of described cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
Prepare negative electrode on the light-emitting layer, obtain described membrane electro luminescent device.
Preferably, the vacuum tightness of described vacuum cavity is 5.0 × 10 -4pa, base target spacing is 60mm, and operating pressure is 3Pa, and working gas is oxygen, and the flow of working gas is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150mJ.
Cerium dopping zirconium niobate light-emitting film of the present invention, matrix zirconium niobate MeZr 4-xnb 6o 24there is higher calorifics and mechanical stability, also there is good optical transparence, lower phonon energy, for light emitting ionic provides excellent crystal field, thus produce less radiationless transition in the process of photovoltaic energy conversion, there is higher luminous efficiency.For dopant ion, Ce 3+be that in rare earth element, content is the highest be also the most cheap, relative to other rare earth ions, its level structure is the simplest, at ground state 4f 1with excited state 5d 1between there is no intermediate level, therefore produce radiationless relaxation probability low, in different matrix, have wider radioluminescence wavelength region.
Above-mentioned cerium dopping zirconium niobate light-emitting film (MeZr 4-xnb 6o 24: xCe 3+) electroluminescent spectrum (EL) in, have very strong glow peak in 535nm wavelength zone, can be applied in thin-film electroluminescent displays.
[accompanying drawing explanation]
Fig. 1 is the structural representation of the membrane electro luminescent device of an embodiment;
Fig. 2 is the electroluminescent spectrogram of cerium dopping zirconium niobate light-emitting film prepared by embodiment 1;
Fig. 3 is the XRD figure of cerium dopping zirconium niobate light-emitting film prepared by embodiment 1;
Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and current density and the graph of relation between voltage and brightness.
[embodiment]
Below in conjunction with the drawings and specific embodiments, cerium dopping zirconium niobate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are illustrated further.
The cerium dopping zirconium niobate light-emitting film of one embodiment, the chemical formula of this cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, MeZr 4-xnb 6o 24for matrix, Ce 3+for active element, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
Preferably, x is 0.02.
The preparation method of above-mentioned cerium dopping zirconium niobate light-emitting film, comprises the following steps:
Step S21, by MeO, ZrO 2, Nb 2o 5and CeO 2powder is 1:(4-x in molar ratio): the ratio of 3:x mixes and obtains mixed powder, and described mixed powder is made target for 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
In this step, preferably, x is 0.02, and within 1.5 hours, become diameter to be 50mm at 1250 DEG C of sintering, thickness is the ceramic target of 2mm.
Step S22, described target and substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 -5pa ~ 1.0 × 10 -3pa;
In this step, preferably, vacuum tightness is 5 × 10 -4pa.
Step S23, adjustment pulsed laser deposition coating process parameter are: base target spacing is 45mm ~ 95mm, operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80 ~ 300mJ, then be filmed, obtaining chemical formula is MeZr 4-xnb 6o 24: xCe 3+cerium dopping zirconium niobate light-emitting film, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
In this step, preferred base target spacing is 60mm, operating pressure 3Pa, and working gas is oxygen, and the flow of working gas is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150mJ.
Preferably, the thickness of cerium dopping zirconium niobate light-emitting film is 60nm ~ 350nm, and more preferably, the thickness of cerium dopping zirconium niobate light-emitting film is 130nm.
Refer to Fig. 1, the membrane electro luminescent device 100 of an embodiment, this membrane electro luminescent device 100 comprises the substrate 1, anode 2, luminescent layer 3 and the negative electrode 4 that stack gradually.
Substrate 1 is glass substrate.Anode 2 is for being formed at the tin indium oxide (ITO) in glass substrate.The material of luminescent layer 3 is cerium dopping zirconium niobate light-emitting film, and the chemical formula of this cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.The material of negative electrode 4 is silver (Ag).
Preferably, the thickness of luminescent layer 3 is 60nm ~ 350nm, and more preferably, the thickness of luminescent layer 3 is 130nm.
The preparation method of above-mentioned membrane electro luminescent device, comprises the following steps:
Step S31, provide the substrate 1 with anode 2.
In present embodiment, substrate 1 is glass substrate, and anode 2 is for being formed at the tin indium oxide (ITO) in glass substrate.There is the substrate 1 priority acetone of anode 2, dehydrated alcohol and deionized water ultrasonic cleaning and carry out oxygen plasma treatment with to it.
Step S32, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is cerium dopping zirconium niobate light-emitting film, and the chemical formula of this cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
In present embodiment, luminescent layer 3 is obtained by following steps:
First, by MeO, ZrO 2, Nb 2o 5and CeO 2powder is 1:(4-x in molar ratio): the ratio of 3:x mixes and obtains mixed powder, described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
In this step, preferably, x is 0.02, and within 1.5 hours, become diameter to be 50mm at 1250 DEG C of sintering, thickness is the ceramic target of 2mm.
Secondly, described target and substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 -5pa ~ 1.0 × 10 -3pa;
In this step, preferably, described substrate is glass or sapphire.
In this step, preferably, vacuum tightness is 5 × 10 -4pa.
Then, adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80 ~ 300MJ, is then filmed, and obtaining chemical formula is MeZr 4-xnb 6o 24: xCe 3+cerium dopping zirconium niobate light-emitting film, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
In this step, preferred base target spacing is 60mm, operating pressure 3Pa, and working gas is oxygen, and the flow of working gas is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150mJ.
Step S33, on luminescent layer 3, form negative electrode 4.
In present embodiment, the material of negative electrode 4 is silver (Ag), is prepared by the method for evaporation.
Cerium dopping zirconium niobate light-emitting film of the present invention, matrix zirconium niobate MeZr 4-xnb 6o 24: xCe 3+there is higher calorifics and mechanical stability, also there is good optical transparence, lower phonon energy, for light emitting ionic provides excellent crystal field, thus produce less radiationless transition in the process of photovoltaic energy conversion, there is higher luminous efficiency.For dopant ion, Ce 3+be that in rare earth element, content is the highest be also the most cheap, relative to other rare earth ions, its level structure is the simplest, at ground state 4f 1with excited state 5d 1between there is no intermediate level, therefore produce radiationless relaxation probability low, in different matrix, have wider radioluminescence wavelength region.
Above-mentioned cerium dopping zirconium niobate light-emitting film (MeZr 4-xnb 6o 24: xCe 3+) electroluminescent spectrum (EL) in, have very strong glow peak in 535nm wavelength zone, can be applied in thin-film electroluminescent displays.
Be specific embodiment below.
Embodiment 1
Select purity be 99.99% powder, by MgO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.98:3:0.02 mixes and obtains mixed powder according to mol ratio, and it is 50mm that mixed powder is formed diameters at 1250 DEG C of sintering 1.5h, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 -4pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, and laser energy is 150mJ, obtains the luminescent layer that thickness is 130nm, and the material of luminescent layer is chemical formula is MgZr 3.98nb 6o 24: 0.02Ce 3+light-emitting film, then at luminous aspect evaporation one deck Ag, as negative electrode.
The chemical formula of the cerium dopping zirconium niobate light-emitting film obtained in the present embodiment is MgZr 3.98nb 6o 24: 0.02Ce 3+, wherein MgZr 3.98nb 6o 24matrix, Ce 3+it is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the cerium dopping zirconium niobate light-emitting film obtained.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak in 535nm wavelength zone, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of cerium dopping zirconium niobate light-emitting film prepared by embodiment 1, test comparison standard P DF card.The characteristic peak of what in figure, X-ray diffraction peak was corresponding is zirconium niobate, do not occur doped element and the relevant peak of impurity, illustrate that cerium dopping ion enters the lattice of zirconium niobate, sample has good crystallographic property.
Refer to Fig. 4, Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and current density and the graph of relation between voltage and brightness.Curve 1 is voltage and current density relation curve, can find out that device can find out device luminescence from 6.0V, and curve 2 is voltage and brightness relationship curve, and high-high brightness is 170cd/m 2, show that device has the good characteristics of luminescence.
Embodiment 2
Select purity be 99.99% powder, by MgO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.99:3:0.01 mixes and obtains mixed powder according to mol ratio, and it is 50mm that mixed powder is formed diameters at 900 DEG C of sintering 0.5h, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, and laser energy is 80mJ, and to obtain thickness be 60nm is luminescent layer, and the material of luminescent layer is chemical formula is MgZr 3.99nb 6o 24: 0.01Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 3
Select purity be 99.99% powder, by MgO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.95:3:0.05 mixes and obtains mixed powder according to mol ratio, and it is 50mm that mixed powder is formed diameters at 1300 DEG C of sintering 3h, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, laser energy 300mJ, and to obtain thickness be 350nm is luminescent layer, and the material of luminescent layer is chemical formula is MgZr 3.95nb 6o 24: 0.05Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 4
Select purity be 99.99% powder, by CaO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.98:3:0.02 mixes and obtains mixed powder according to mol ratio, and it is 50mm that mixed powder is formed diameters at 1250 DEG C of sintering 2h, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 -4pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, laser energy 150mJ, and to obtain thickness be 200nm is luminescent layer, and the material of luminescent layer is chemical formula is CaZr 3.98nb 6o 24: 0.02Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 5
Select purity be 99.99% powder, by CaO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.99:3:0.01 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 900 DEG C of sintering 1h, formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, laser energy 80mJ, and to obtain thickness be 100nm is luminescent layer, and the material of luminescent layer is chemical formula is CaZr 3.99nb 6o 24: 0.01Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 6
Select purity be 99.99% powder, by CaO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.95:3:0.05 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 1300 DEG C of sintering 1.5h, formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, laser energy 300mJ, and to obtain thickness be 150nm is luminescent layer, and the material of luminescent layer is chemical formula is CaZr 3.95nb 6o 24: 0.05Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 7
Select purity be 99.99% powder, by SrO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.98:3:0.02 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 1250 DEG C of sintering 3h, formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 -4pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, and laser energy is 150mJ, and to obtain thickness be 350nm is luminescent layer, and the material of luminescent layer is chemical formula is SrZr 3.98nb 6o 24: 0.02Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 8
Select purity be 99.99% powder, by SrO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.99:3:0.01 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 900 DEG C of sintering 0.5h, formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, and laser energy is 80mJ, and to obtain thickness be 60nm is luminescent layer, and the material of luminescent layer is chemical formula is SrZr 3.99nb 6o 24: 0.01Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 9
Select purity be 99.99% powder, by SrO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.95:3:0.05 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 1300 DEG C of sintering 2h, formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, and laser energy is 300mJ, and to obtain thickness be 200nm is luminescent layer, and the material of luminescent layer is chemical formula is SrZr 3.95nb 6o 24: 0.05Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 10
Select purity be 99.99% powder, by BaO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.98:3:0.02 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 1250 DEG C of sintering 1h, formation diameter is 60mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10 -4pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, and laser energy is 150mJ, and to obtain thickness be 100nm is luminescent layer, and the material of luminescent layer is chemical formula is BaZr 3.98nb 6o 24: 0.02Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 11
Select purity be 99.99% powder, by BaO, ZrO 2, Nb 2o 5, CeO 2powder is that 1:3.99:3:0.01 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 900 DEG C of sintering 2.5h, formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, and laser energy is 80mJ, and to obtain thickness be 150nm is luminescent layer, and the material of luminescent layer is chemical formula is BaZr 3.99nb 6o 24: 0.01Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
Embodiment 12
Select purity be 99.99% powder, by BaO, ZrO 2, Nb 2o 5and CeO 2powder is that 1:3.95:3:0.05 mixes and obtains mixed powder according to mol ratio, and by mixed powder at 1300 DEG C of sintering 2h, formation diameter is 50mm, and thickness is the ceramic target of 2mm, and is loaded by target in the vacuum cavity of pulsed laser deposition filming equipment.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, and laser energy is 300mJ, and to obtain thickness be 150nm is luminescent layer, and the material of luminescent layer is chemical formula is BaZr 3.95nb 6o 24: 0.05Ce 3+light-emitting film, then evaporation one deck Ag on luminescent layer, as negative electrode.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (9)

1. a cerium dopping zirconium niobate light-emitting film, is characterized in that, the chemical formula of described cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
2. cerium dopping zirconium niobate light-emitting film according to claim 1, it is characterized in that, described x is 0.02.
3. a preparation method for cerium dopping zirconium niobate light-emitting film, is characterized in that, comprise the following steps:
By MeO, ZrO 2, Nb 2o 5and CeO 2powder is 1:(4-x in molar ratio): the ratio of 3:x mixes and obtains mixed powder, described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
Described target and substrate are loaded the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 -5pa ~ 1.0 × 10 -3pa; And
Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, operating pressure 0.5Pa ~ 5Pa, and the flow of working gas is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80mJ ~ 300mJ, is then filmed, and obtaining chemical formula is MeZr 4-xnb 6o 24: xCe 3+cerium dopping zirconium niobate light-emitting film, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
4. the preparation method of cerium dopping zirconium niobate light-emitting film according to claim 3, is characterized in that, the vacuum tightness of described vacuum cavity is 5.0 × 10 -4pa, base target spacing is 60mm, and operating pressure is 3Pa, and working gas is oxygen, and the flow of working gas is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150mJ.
5. a membrane electro luminescent device, comprise the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, it is characterized in that, the material of described luminescent layer is cerium dopping zirconium niobate light-emitting film, and the chemical formula of described cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion.
6. membrane electro luminescent device according to claim 5, is characterized in that, the thickness of described luminescent layer is 60nm ~ 350nm.
7. membrane electro luminescent device according to claim 5, described x is 0.02.
8. a preparation method for membrane electro luminescent device, is characterized in that, comprises the following steps:
The substrate with anode is provided;
By MeO, ZrO 2, Nb 2o 5and CeO 2powder is 1:(4-x in molar ratio): the ratio of 3:x mixes and obtains mixed powder, namely described mixed powder is made target in 0.5 hour ~ 3 hours at 900 DEG C ~ 1300 DEG C sintering, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
By described target and described in there is anode substrate load the vacuum cavity of pulsed laser deposition filming equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10 -5pa ~ 1.0 × 10 -3pa; And
Adjustment pulsed laser deposition coating process parameter is: base target spacing is 45mm ~ 95mm, operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, underlayer temperature is 250 DEG C ~ 750 DEG C, laser energy is 80mJ ~ 300mJ, is then filmed, and described anode prepares luminescent layer, the material of described luminescent layer is cerium dopping zirconium niobate light-emitting film, and the chemical formula of described cerium dopping zirconium niobate light-emitting film is MeZr 4-xnb 6o 24: xCe 3+, wherein, x is 0.01 ~ 0.05, Me is magnesium ion, calcium ion, strontium ion or barium ion;
Prepare negative electrode on the light-emitting layer, obtain described membrane electro luminescent device.
9. the preparation method of membrane electro luminescent device according to claim 8, is characterized in that, the vacuum tightness of described vacuum cavity is 5.0 × 10 -4pa, base target spacing is 60mm, and operating pressure is 3Pa, and working gas is oxygen, and the flow of working gas is 20sccm, and underlayer temperature is 500 DEG C, and laser energy is 150mJ.
CN201310461172.4A 2013-09-25 2013-09-25 Ce-doped zirconium niobate light-emitting film as well as preparation method and application thereof Pending CN104449707A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111505005A (en) * 2020-04-25 2020-08-07 中南大学 Mineral exploration method for rapidly judging mineral potential of vein-like mineral deposit by using zircon

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111505005A (en) * 2020-04-25 2020-08-07 中南大学 Mineral exploration method for rapidly judging mineral potential of vein-like mineral deposit by using zircon

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