CN103788948A - Europium-terbium-codoped rare earth silicate luminescent material, and preparation method and application thereof - Google Patents
Europium-terbium-codoped rare earth silicate luminescent material, and preparation method and application thereof Download PDFInfo
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- CN103788948A CN103788948A CN201210427576.7A CN201210427576A CN103788948A CN 103788948 A CN103788948 A CN 103788948A CN 201210427576 A CN201210427576 A CN 201210427576A CN 103788948 A CN103788948 A CN 103788948A
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Abstract
The invention provides a europium-terbium-codoped rare earth silicate luminescent material with a chemical formula of LaaGdbLucSiO5: xEu2+, yTb3+, wherein LaaGdbLucSiO5 is a matrix, a europium ion and a terbium ion are active elements, x is in a range of 0.01 to 0.05, y is in a range of 0.005 to 0.03, a is in a range of 0 to 2, b is in a range of 0 to 2, c is in a range of 0 to 2, and a+b+c is equal to 2. In the electroluminescent spectrum (EL) of a luminescent film prepared from the europium-terbium-codoped rare earth silicate luminescent material, strong luminescent peaks appear at zones with wavelength of 480 nm and 580 nm, and the luminescent film is applicable to a thin-film electroluminescent display. The invention further provides a preparation method and application of the europium-terbium-codoped rare earth silicate luminescent material.
Description
Technical field
The present invention relates to a kind of europium terbium codoped rare earth silicate luminescent material, its preparation method, europium terbium codoped rare earth silicate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.
Background technology
Thin-film electroluminescent displays (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 luminous material of exploitation multiband, is the developing direction of this problem.But, can be applicable to the europium terbium codoped rare earth silicate luminescent material of thin-film electroluminescent displays, have not yet to see report.
Summary of the invention
Based on this, be necessary to provide a kind of europium terbium codoped rare earth silicate luminescent material, its preparation method, europium terbium codoped rare earth silicate light-emitting film, its preparation method that can be applicable to membrane electro luminescent device, use membrane electro luminescent device of this europium terbium codoped rare earth silicate luminescent material and preparation method thereof.
A kind of europium terbium codoped rare earth silicate luminescent material, its chemical formula is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
A preparation method for europium terbium codoped rare earth silicate luminescent material, comprises the following steps:
According to La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes, and wherein x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2; And
The powder mixing sintering at 900 ℃ ~ 1300 ℃ is obtained to chemical formula for 0.5 hour ~ 5 hours is La
agd
blu
csiO
5: xEu
2+, yTb
3+europium terbium codoped rare earth silicate luminescent material.
A kind of europium terbium codoped rare earth silicate light-emitting film, the chemical general formula of the material of this europium terbium codoped rare earth silicate light-emitting film is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
A preparation method for europium terbium codoped rare earth silicate light-emitting film, comprises the following steps:
According to La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes sintering at 900 ℃ ~ 1300 ℃ and within 0.5 hour ~ 5 hours, makes target, and wherein x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2;
Described target and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa; And
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, and the flow of working gas is 10sccm ~ 35sccm, and underlayer temperature is 250 ℃ ~ 750 ℃, is then filmed, and obtaining chemical formula is La
agd
blu
csiO
5: xEu
2+, yTb
3+europium terbium codoped rare earth silicate light-emitting film.
In a preferred embodiment, also comprise step: the vacuum annealing at 500 ℃ ~ 800 ℃ of described europium terbium codoped rare earth silicate light-emitting film is processed to 1h ~ 3h.
In a preferred embodiment, the vacuum tightness of described vacuum cavity is 5.0 × 10
-4pa, base target spacing is 60mm, and magnetron sputtering operating pressure is 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, underlayer temperature is 500 ℃.
A kind of membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is europium terbium codoped rare earth silicate luminescent material, and the chemical formula of this europium terbium codoped rare earth silicate luminescent material is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
A preparation method for membrane electro luminescent device, comprises the following steps:
The substrate with anode is provided;
On described anode, form luminescent layer, the material of described luminescent layer is europium terbium codoped rare earth silicate luminescent material, and the chemical formula of this europium terbium codoped rare earth silicate luminescent material is La
agd
blu
csiO
5: xEu
2+, yTb
3+, x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2;
On described luminescent layer, form negative electrode.
In a preferred embodiment, the preparation of described luminescent layer comprises the following steps:
According to La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes sintering at 900 ℃ ~ 1300 ℃ and makes target in 0.5 hour ~ 5 hours, and wherein, x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2;
Described target and described substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa;
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, the flow of working gas is 10sccm ~ 35sccm, underlayer temperature is 250 ℃ ~ 750 ℃, then be filmed, on described anode, form luminescent layer.
In a preferred embodiment, the preparation of described luminescent layer also comprises step: the vacuum annealing at 500 ℃ ~ 800 ℃ of described luminescent layer is processed to 1h ~ 3h.
Above-mentioned europium terbium codoped rare earth silicate luminescent material (La
agd
blu
csiO
5: xEu
2+, yTb
3+) in the electroluminescent spectrum (EL) of the light-emitting film made, there is very strong glow peak at 480nm and 580nm 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 the europium terbium codoped rare earth silicate light-emitting film prepared of embodiment 1;
Fig. 3 is the XRD figure of the europium terbium codoped rare earth silicate light-emitting film prepared of embodiment 1;
Fig. 4 is the graph of relation between voltage and current density and voltage and the brightness of the membrane electro luminescent device prepared of embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, europium terbium codoped rare earth silicate luminescent material, its preparation method, europium terbium codoped rare earth silicate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are further illustrated.
The europium terbium codoped rare earth silicate luminescent material of one embodiment, its chemical formula is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
Preferably, x is that 0.03, y is that 0.01, a is that 0.3, b is that 0.5, c is 1.2.
La in this europium terbium codoped rare earth silicate luminescent material
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements.In the electroluminescent spectrum (EL) of the light-emitting film that this europium terbium codoped rare earth silicate luminescent material is made, there is very strong glow peak at 480nm and 580nm wavelength zone, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned europium terbium codoped rare earth silicate luminescent material, comprises the following steps:
Step S11, according to La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder, wherein x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
In this step, preferred, x is that 0.03, y is that 0.01, a is that 0.3, b is that 0.5, c is 1.2.
Step S12, the powder mixing sintering at 900 ℃ ~ 1300 ℃ can be obtained to europium terbium codoped rare earth silicate luminescent material for 0.5 hour ~ 5 hours, its chemical formula is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
In this step, preferably sintering 3 hours at 1250 ℃.
The europium terbium codoped rare earth silicate light-emitting film of one embodiment, the chemical general formula of this europium terbium codoped rare earth silicate light-emitting film is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
Preferably, x is that 0.03, y is that 0.01, a is that 0.3, b is that 0.5, c is 1.2.
The preparation method of above-mentioned europium terbium codoped rare earth silicate light-emitting film, comprises the following steps:
Step S21, press La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes sintering at 900 ℃ ~ 1300 ℃ and within 0.5 hour ~ 5 hours, makes target, and wherein x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
In this step, preferred, x is that 0.03, y is that 0.01, a is that 0.3, b is that 0.5, c is 1.2, and at 1250 ℃, 3 hours one-tenth diameters of sintering are 50mm, the ceramic target that thickness is 2mm.
Step S22, the target obtaining in step S21 and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa.
In this step, preferred, vacuum tightness is 5 × 10
-4pa.
Step S23, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, and the flow of working gas is 10sccm ~ 35sccm, underlayer temperature is 250 ℃ ~ 750 ℃; Then be filmed, obtain europium terbium codoped rare earth silicate light-emitting film.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
Step S24, by europium terbium codoped rare earth silicate light-emitting film at 500 ℃ ~ 800 ℃ vacuum annealing process 1h ~ 3h.
In this step, preferred, 2h is processed in film sample vacuum annealing at 600 ℃.
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 europium terbium codoped rare earth silicate luminescent material, and the chemical formula of this europium terbium codoped rare earth silicate luminescent material is La
agd
blu
csiO
5: xEu
2+, yTb
3+, x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.The material of negative electrode 4 is silver (Ag).
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.The substrate 1 with anode 2 is successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning and use it is carried out to oxygen plasma treatment.
Step S32, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is europium terbium codoped rare earth silicate luminescent material, and the chemical formula of this europium terbium codoped rare earth silicate luminescent material is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
In present embodiment, luminescent layer 3 is made by following steps:
First, by La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes sintering at 900 ℃ ~ 1300 ℃ and within 0.5 hour ~ 5 hours, makes target, and wherein x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
In this step, preferred, x is that 0.03, y is that 0.01, a is that 0.3, b is that 0.5, c is 1.2, and at 1250 ℃, 3 hours one-tenth diameters of sintering are 50mm, the ceramic target that thickness is 2mm.
Secondly, target and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa.
In this step, preferred, vacuum tightness is 5 × 10
-4pa.
Then, adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, the flow of working gas is 10sccm ~ 35sccm, underlayer temperature is 250 ℃ ~ 750 ℃, is then filmed, and forms luminescent layer 3 on anode 2.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
Finally, luminescent layer 3 vacuum annealing at 500 ℃ ~ 800 ℃ is processed to 1h ~ 3h.
In this step, preferred, 2h is processed in film sample vacuum annealing at 600 ℃.
Step S33, on luminescent layer 3, form negative electrode 4.
In present embodiment, the material of negative electrode 4 is silver (Ag), is formed by evaporation.
Be specific embodiment below.
Embodiment 1
Selecting purity is 99.99% powder, by the La of 0.3mmol
2o
3, the Gd of 0.5mmol
2o
3, the Lu of 1.2mmol
2o
3, the SiO of 2mmol, the Eu of 0.03mol
2o
3with 0.005mmol Tb
4o
7powder, after even mixing, at 1250 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump
-4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 600 ℃, obtaining chemical formula is La
0.3gd
0.5lu
1.2siO
5: 0.03Eu
2+, 0.01Tb
3+light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the europium terbium codoped rare earth silicate light-emitting film obtaining in the present embodiment is La
0.3gd
0.5lu
1.2siO
5: 0.03Eu
2+, 0.01Tb
3+, wherein La
0.3gd
0.5lu
1.2siO
5be matrix, europium ion and terbium ion are active elements.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the europium terbium codoped rare earth silicate light-emitting film obtaining.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak at 480nm and 580nm wavelength zone, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of the europium terbium codoped rare earth silicate light-emitting film prepared of embodiment 1, test comparison standard P DF card.As can be seen from Figure 3 all diffraction peaks are the crystalline characteristics peaks that rare earth silicate is corresponding, do not occur doped element and the relevant diffraction peak of other impurity, and interpret sample has good crystalline structure.
Refer to Fig. 4, Fig. 4 is the graph of relation between voltage and current density and voltage and the brightness of the membrane electro luminescent device prepared of embodiment 1, curve 1 is voltage and current density relation curve, can find out that this device starts luminous from voltage 5.5V, curve 2 is voltage and brightness relationship curve, and the high-high brightness that can find out this device is 122cd/m
2, show that device has the good characteristics of luminescence.
Embodiment 2
Selecting purity is 99.99% powder, by the Gd of 1mmol
2o
3, the Lu of 1mmol
2o
3, the SiO of 2mmol, the Eu of 0.005mmol
2o
3with 0.0025mmol Tb
4o
7powder, after even mixing, at 900 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump
-3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 ℃.The sample the obtaining 1h that anneals in 0.01Pa vacuum oven, annealing temperature is 500 ℃.Obtaining chemical formula is GdLuSiO
5: 0.01Eu
2+, 0.005Tb
3+light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 3
Selecting purity is 99.99% powder, by the La of 0.4mmol
2o
3, the Lu of 1.6mmol
2o
3, the SiO of 2mmol, the Eu of 0.05mol
2o
3with 0.015mmol Tb
4o
7powder, after even mixing, at 1300 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump
-5pa, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃.The sample the obtaining 3h that anneals in 0.01Pa vacuum oven, annealing temperature is 800 ℃.Obtaining chemical formula is La
0.4lu
1.6siO
5: 0.05Eu
2+, 0.03Tb
3+light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 4
Selecting purity is 99.99% powder, by the La of 0.4mmol
2o
3, the Gd of 1mmol
2o
3, the Lu of 0.6mmol
2o
3, the SiO of 1mmol, the Eu of 0.03mol
2o
3with 0.04mmol Tb
4o
7powder, after even mixing, at 1250 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump
-4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 600 ℃.Obtaining chemical formula is La
0.4gdLu
0.6siO
5: 0.03Eu
2+, 0.04Tb
3+light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 5
Selecting purity is 99.99% powder, by the La of 1mmol
2o
3, the Gd of 0.8mmol
2o
3, the Lu of 0.2mmol
2o
3, the SiO of 1mmol, the Eu of 0.05mol
2o
3with 0.01mmol Tb
4o
7powder, after even mixing, at 900 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump
-3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 ℃.The sample the obtaining 1h that anneals in 0.01Pa vacuum oven, annealing temperature is 500 ℃.Obtaining chemical formula is LaGd
0.8lu
0.2siO
5: 0.05Eu
2+, 0.01Tb
3+light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 6
Selecting purity is 99.99% powder, by the La of 1.3mmol
2o
3, the Gd of 0.3mmol
2o
3, the Lu of 0.4mmol
2o
3, the SiO of 1mmol, the Eu of 0.01mol
2o
3with 0.04mmol Tb
4o
7powder, after even mixing, at 1300 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.The vacuum tightness of cavity is extracted into 1.0 × 10 with mechanical pump and molecular pump
-5pa, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃.The sample the obtaining 3h that anneals in 0.01Pa vacuum oven, annealing temperature is 800 ℃.Obtaining chemical formula is La
1.3gd
0.3lu
0.4siO
5: 0.01Eu
2+, 0.04Tb
3+light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 7
Selecting purity is 99.99% powder, by the La of 0.4mmol
2o
3, the Gd of 0.4mmol
2o
3, the Lu of 1.2mmol
2o
3, the SiO of 1mmol, the Eu of 0.02mol
2o
3with 0.03mmol Tb
4o
7powder, after even mixing, at 1250 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.The vacuum tightness of cavity is extracted into 5.0 × 10 with mechanical pump and molecular pump
-4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 600 ℃.Obtaining chemical general formula is La
0.4gd
0.4lu
1.2siO
5: 0.02Eu
2+, 0.03Tb
3+light-emitting film, then evaporation one deck Ag on light-emitting film, as negative electrode.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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 (10)
1. an europium terbium codoped rare earth silicate luminescent material, is characterized in that: its chemical formula is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
2. a preparation method for europium terbium codoped rare earth silicate luminescent material, is characterized in that, comprises the following steps:
According to La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes, and wherein x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2; And
The powder mixing sintering at 900 ℃ ~ 1300 ℃ is obtained to chemical formula for 0.5 hour ~ 5 hours is La
agd
blu
csiO
5: xEu
2+, yTb
3+europium terbium codoped rare earth silicate luminescent material.
3. an europium terbium codoped rare earth silicate light-emitting film, is characterized in that, the chemical general formula of the material of this europium terbium codoped rare earth silicate light-emitting film is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
4. a preparation method for europium terbium codoped rare earth silicate light-emitting film, is characterized in that, comprises the following steps:
According to La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes sintering at 900 ℃ ~ 1300 ℃ and makes target in 0.5 hour ~ 5 hours, and wherein, x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2;
Described target and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa; And
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, and the flow of working gas is 10sccm ~ 35sccm, and underlayer temperature is 250 ℃ ~ 750 ℃, is then filmed, and obtaining chemical formula is La
agd
blu
csiO
5: xEu
2+, yTb
3+europium terbium codoped rare earth silicate light-emitting film.
5. the preparation method of europium terbium codoped rare earth silicate light-emitting film according to claim 4, is characterized in that, also comprises step: the vacuum annealing at 500 ℃ ~ 800 ℃ of described europium terbium codoped rare earth silicate light-emitting film is processed to 1h ~ 3h.
6. the preparation method of europium terbium codoped rare earth silicate light-emitting film according to claim 4, is characterized in that, the vacuum tightness of described vacuum cavity is 5.0 × 10
-4pa, base target spacing is 60mm, and magnetron sputtering operating pressure is 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, underlayer temperature is 500 ℃.
7. a membrane electro luminescent device, this membrane electro luminescent device comprises 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 europium terbium codoped rare earth silicate luminescent material, and the chemical formula of this europium terbium codoped rare earth silicate luminescent material is La
agd
blu
csiO
5: xEu
2+, yTb
3+, wherein La
agd
blu
csiO
5be matrix, europium ion and terbium ion are active elements, and x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2.
8. a preparation method for membrane electro luminescent device, is characterized in that, comprises the following steps:
The substrate with anode is provided;
On described anode, form luminescent layer, the material of described luminescent layer is europium terbium codoped rare earth silicate luminescent material, and the chemical formula of this europium terbium codoped rare earth silicate luminescent material is La
agd
blu
csiO
5: xEu
2+, yTb
3+, x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2;
On described luminescent layer, form negative electrode.
9. the preparation method of membrane electro luminescent device according to claim 8, is characterized in that, the preparation of described luminescent layer comprises the following steps:
According to La
agd
blu
csiO
5: xEu
2+, yTb
3+the stoichiometric ratio of each element takes La
2o
3, Gd
2o
3, Lu
2o
3, SiO, Eu
2o
3and Tb
4o
7powder also mixes sintering at 900 ℃ ~ 1300 ℃ and within 0.5 hour ~ 5 hours, makes target, and wherein x is that 0.01 ~ 0.05, y is that 0.005 ~ 0.03, a is that 0 ~ 2, b is that 0 ~ 2, c is 0 ~ 2, and a+b+c=2;
Described target and described substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa;
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering operating pressure 0.2Pa ~ 4Pa, the flow of working gas is 10sccm ~ 35sccm, underlayer temperature is 250 ℃ ~ 750 ℃, then be filmed, on described anode, form luminescent layer.
10. the preparation method of membrane electro luminescent device according to claim 9, is characterized in that, the preparation of described luminescent layer also comprises step: the vacuum annealing at 500 ℃ ~ 800 ℃ of described luminescent layer is processed to 1h ~ 3h.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647525A (en) * | 2016-01-25 | 2016-06-08 | 深圳市聚飞光电股份有限公司 | Method for preparing MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder for LED |
| CN112011773A (en) * | 2020-08-14 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Yttrium silicate coating and preparation method and application thereof |
-
2012
- 2012-10-31 CN CN201210427576.7A patent/CN103788948A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647525A (en) * | 2016-01-25 | 2016-06-08 | 深圳市聚飞光电股份有限公司 | Method for preparing MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder for LED |
| CN112011773A (en) * | 2020-08-14 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Yttrium silicate coating and preparation method and application thereof |
| CN112011773B (en) * | 2020-08-14 | 2022-10-18 | 中国科学院宁波材料技术与工程研究所 | Yttrium silicate coating and preparation method and application thereof |
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Application publication date: 20140514 |