CN104673282A - Manganese-chromium/codoped alkaline-earth zincate luminescent material, and preparation method and application thereof - Google Patents
Manganese-chromium/codoped alkaline-earth zincate luminescent material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN104673282A CN104673282A CN201310634783.4A CN201310634783A CN104673282A CN 104673282 A CN104673282 A CN 104673282A CN 201310634783 A CN201310634783 A CN 201310634783A CN 104673282 A CN104673282 A CN 104673282A
- Authority
- CN
- China
- Prior art keywords
- zincate
- zno
- alkaline earth
- manganese chromium
- ycr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Luminescent Compositions (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a manganese/chromium-codoped alkaline-earth zincate luminescent material of which the chemical formula is Me[1-x-y]ZnO2:xMn<4+>,yCr<3+>, wherein x is 0.01-0.05, y is 0.01-0.08, and Me is selected from at least one of calcium, strontium and barium. The luminescent film prepared from the manganese/chromium-codoped alkaline-earth zincate luminescent material has strong luminescence peaks at the wavelength of 607nm and 629nm in the electroluminescent spectrum (EL), and thus, is applicable to film electroluminescent display devices. The invention also provides a preparation method and application of the manganese/chromium-codoped alkaline-earth zincate luminescent material.
Description
[technical field]
The present invention relates to a kind of manganese chromium codoped alkaline earth zincate luminescent material, its preparation method, manganese chromium codoped alkaline earth zincate 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 material of exploitation multiband luminescence is the developing direction of this problem.But, can be applicable to the manganese chromium codoped alkaline earth zincate 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 manganese chromium codoped alkaline earth zincate luminescent material, its preparation method, manganese chromium codoped alkaline earth zincate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.
A kind of manganese chromium codoped alkaline earth zincate luminescent material, its chemical formula is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
A preparation method for manganese chromium codoped alkaline earth zincate luminescent material, comprises the following steps:
According to Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also mixes, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, MeO is selected from calcium oxide, at least one in strontium oxide and barium oxide; And
Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being Me at 900 DEG C ~ 1300 DEG C
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate luminescent material, Me is selected from calcium constituent, at least one in strontium element and barium element.
A kind of manganese chromium codoped alkaline earth zincate light-emitting film, the chemical general formula of the material of this manganese chromium codoped alkaline earth zincate light-emitting film is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
A preparation method for manganese chromium codoped alkaline earth zincate light-emitting film, comprises the following steps:
According to Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element;
Described target and substrate are loaded 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
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering 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 Me
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate light-emitting film, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
The vacuum tightness of described vacuum cavity is 5.0 × 10
-4pa, base target spacing is 60mm, and magnetron sputtering operating pressure is 2.0Pa, 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, 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 manganese chromium codoped alkaline earth zincate luminescent material, and the chemical formula of this manganese chromium codoped alkaline earth zincate luminescent material is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
Comprise the following steps:
The substrate with anode is provided;
Described anode forms luminescent layer, and the material of described luminescent layer is manganese chromium codoped alkaline earth zincate luminescent material, and the chemical formula of this manganese chromium codoped alkaline earth zincate luminescent material is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element;
Form negative electrode on the light-emitting layer.
The preparation of described luminescent layer comprises the following steps:
According to Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element;
Described target and described substrate are loaded 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;
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering 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 Me
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate light-emitting film, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, and at least one in strontium element and barium element, described anode forms luminescent layer.
Described x is 0.03, y is 0.04.
Above-mentioned manganese chromium codoped alkaline earth zincate luminescent material (Me
1-x-yznO
2: xMn
4+, yCr
3+) in the electroluminescent spectrum (EL) of light-emitting film made, have very strong glow peak in 607nm and 629nm 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 manganese chromium codoped alkaline earth zincate light-emitting film prepared by embodiment 1;
Fig. 3 is the XRD figure of manganese chromium codoped alkaline earth zincate 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, manganese chromium codoped alkaline earth zincate luminescent material, its preparation method, manganese chromium codoped alkaline earth zincate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are illustrated further.
The manganese chromium codoped alkaline earth zincate luminescent material of one embodiment, its chemical formula is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
Preferably, x is 0.03, y is 0.04.
Me in this manganese chromium codoped alkaline earth zincate luminescent material
1-x-yznO
2matrix, Mn
4+ion and Cr
3+ion is active element.In the electroluminescent spectrum (EL) of the light-emitting film that this manganese chromium codoped alkaline earth zincate luminescent material is made, there is very strong glow peak in 607nm and 629nm wavelength zone, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned manganese chromium codoped alkaline earth zincate luminescent material, comprises the following steps:
Step S11, according to Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also mixes, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, MeO is selected from calcium oxide, at least one in strontium oxide and barium oxide.
Step S12, the equal powder of mixing is sintered 0.5 hour ~ 5 hours and can obtain manganese chromium codoped alkaline earth zincate luminescent material at 900 DEG C ~ 1300 DEG C, its chemical formula is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
In this step, preferably at 1250 DEG C, sinter 3 hours.
The manganese chromium codoped alkaline earth zincate light-emitting film of one embodiment, the chemical general formula Me of the material of this manganese chromium codoped alkaline earth zincate light-emitting film
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate luminescent material, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
Preferably, x is 0.03, y is 0.04.
The preparation method of above-mentioned manganese chromium codoped alkaline earth zincate light-emitting film, comprises the following steps:
Step S21, by Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
In this step, preferably, x is 0.03, y is 0.04, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.
Step S22, the target that obtains in step S21 and substrate are loaded 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, preferably, 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 0.5Pa ~ 5Pa, and the flow of working gas is 10sccm ~ 40sccm, and underlayer temperature is 250 DEG C ~ 750 DEG C; Laser energy is 80mJ ~ 300mJ, is then filmed, and obtaining chemical formula is Me
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate light-emitting film, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2.0Pa, 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.
Refer to Fig. 1, the membrane electro luminescent device of an embodiment, this membrane electro luminescent device 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 manganese chromium codoped alkaline earth zincate luminescent material, and the chemical formula of this manganese chromium codoped alkaline earth zincate luminescent material is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.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.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 manganese chromium codoped alkaline earth zincate luminescent material, and the chemical formula of this manganese chromium codoped alkaline earth zincate luminescent material is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
In present embodiment, luminescent layer 3 is obtained by following steps:
First, by Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
In this step, preferably, x is 0.03, y is 0.04, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.
Secondly, target and substrate are loaded 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, preferably, vacuum tightness is 5 × 10
-4pa.
Then, adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering 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 anode 2 is formed luminescent layer 3.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2.0Pa, 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 formed by evaporation.
Be specific embodiment below.
Embodiment 1
Select purity be 99.99% powder, by CaO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.93mmol, 1mmol, 0.03mmol and 0.02mmol after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The sample chemical formula obtained is Ca
0.93znO
2: 0.03Mn
4+, 0.04Cr
3+light-emitting film, thickness is 180nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the manganese chromium codoped alkaline earth zincate light-emitting film obtained in the present embodiment is Ca
0.93znO
2: 0.03Mn
4+, 0.04Cr
3+, wherein Ca
0.93znO
2matrix, Mn
4+and Cr
3+ion is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the manganese chromium codoped alkaline earth zincate light-emitting film obtained.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak in 650nm and 670nm wavelength zone, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of manganese chromium codoped alkaline earth zincate light-emitting film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3, in figure, diffraction peak is the peak crystallization of alkaline earth zincate, does not occur the diffraction peak of doped element and other impurity; Illustrate that the product that this preparation method obtains has good crystalline quality.
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, the luminescence from voltage 5.5V of this device can be found out, curve 2 is voltage and brightness relationship curve, can find out that the high-high brightness of this device is 188cd/m
2, show that device has the good characteristics of luminescence.
Embodiment 2
Select purity be 99.99% powder, by CaO, ZnO, MnO
2and Cr
2o
3powder is 0.98mmol, 1mmol, 0.01mmol and 0.005mmol according to mole number, and after Homogeneous phase mixing, at 900 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Ca
0.98znO
2: 0.01Mn
4+, 0.01Cr
3+light-emitting film, thickness is 300nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 3
Select purity be 99.99% powder, by CaO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.87mmol, 1mmol, 0.05mmol and 0.08mmol after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Ca
0.87znO
2: 0.05Mn
4+, 0.08Cr
3+light-emitting film, thickness is 70nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 4
Select purity be 99.99% powder, by SrO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.93mmol, 1mmol, 0.03mmol and 0.02mmol after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Sr
0.93znO
2: 0.03Mn
4+, 0.04Cr
3+light-emitting film, thickness is 180nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 5
Select purity be 99.99% powder, by SrO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.98mmol, 1mmol, 0.01mmol and 0.005mmol after Homogeneous phase mixing, at 900 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Sr
0.98znO
2: 0.01Mn
4+, 0.01Cr
3+light-emitting film, thickness is 300nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 6
Select purity be 99.99% powder, by SrO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.87mmol, 1mmol, 0.05mmol and 0.08mmol after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Sr
0.87znO
2: 0.05Mn
4+, 0.08Cr
3+light-emitting film, thickness is 70nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 7
Select purity be 99.99% powder, by BaO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.93mmol, 1mmol, 0.03mmol and 0.02mmol after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Ba
0.93znO
2: 0.03Mn
4+, 0.04Cr
3+light-emitting film, thickness is 180nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 8
Select purity be 99.99% powder, by BaO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.98mmol, 1mmol, 0.01mmol and 0.005mmol after Homogeneous phase mixing, at 900 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Ba
0.98znO
2: 0.01Mn
4+, 0.01Cr
3+light-emitting film, thickness is 300nm, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 9
Select purity be 99.99% powder, by BaO, ZnO, MnO
2and Cr
2o
3powder according to mole number be 0.87mmol, 1mmol, 0.05mmol and 0.08mmol after Homogeneous phase mixing, at 1300 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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.The chemical formula of the sample obtained is Ba
0.87znO
2: 0.05Mn
4+, 0.08Cr
3+light-emitting film, thickness is 70nm, then evaporation one deck Ag on light-emitting film, 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 manganese chromium codoped alkaline earth zincate luminescent material, is characterized in that: its chemical formula is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
2. a preparation method for manganese chromium codoped alkaline earth zincate luminescent material, is characterized in that, comprise the following steps:
According to Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also mixes, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, MeO is selected from calcium oxide, at least one in strontium oxide and barium oxide; And
Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being Me at 900 DEG C ~ 1300 DEG C
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate luminescent material, Me is selected from calcium constituent, at least one in strontium element and barium element.
3. a manganese chromium codoped alkaline earth zincate light-emitting film, is characterized in that, the chemical general formula of the material of this manganese chromium codoped alkaline earth zincate light-emitting film is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
4. a preparation method for manganese chromium codoped alkaline earth zincate light-emitting film, is characterized in that, comprise the following steps:
According to Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element;
Described target and substrate are loaded 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
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering 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 Me
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate light-emitting film, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
5. the preparation method of manganese chromium codoped alkaline earth zincate light-emitting film according to claim 4, it 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 2.0Pa, 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.
6. 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 manganese chromium codoped alkaline earth zincate luminescent material, and the chemical formula of this manganese chromium codoped alkaline earth zincate luminescent material is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element.
7. a preparation method for membrane electro luminescent device, is characterized in that, comprises the following steps:
The substrate with anode is provided;
Described anode forms luminescent layer, and the material of described luminescent layer is manganese chromium codoped alkaline earth zincate luminescent material, and the chemical formula of this manganese chromium codoped alkaline earth zincate luminescent material is Me
1-x-yznO
2: xMn
4+, yCr
3+, wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element;
Form negative electrode on the light-emitting layer.
8. the preparation method of membrane electro luminescent device according to claim 7, is characterized in that, the preparation of described luminescent layer comprises the following steps:
According to Me
1-x-yznO
2: xMn
4+, yCr
3+the stoichiometric ratio of each element takes MeO, ZnO, MnO
2and Cr
2o
3powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, and wherein, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, at least one in strontium element and barium element;
Described target and described substrate are loaded 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;
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, magnetron sputtering 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 Me
1-x-yznO
2: xMn
4+, yCr
3+manganese chromium codoped alkaline earth zincate light-emitting film, x is 0.01 ~ 0.05, y is that 0.01 ~ 0.08, Me is selected from calcium constituent, and at least one in strontium element and barium element, described anode forms luminescent layer.
9. the preparation method of membrane electro luminescent device according to claim 8, is characterized in that, described x is 0.03, y is 0.04.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310634783.4A CN104673282A (en) | 2013-11-30 | 2013-11-30 | Manganese-chromium/codoped alkaline-earth zincate luminescent material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310634783.4A CN104673282A (en) | 2013-11-30 | 2013-11-30 | Manganese-chromium/codoped alkaline-earth zincate luminescent material, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104673282A true CN104673282A (en) | 2015-06-03 |
Family
ID=53308887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310634783.4A Pending CN104673282A (en) | 2013-11-30 | 2013-11-30 | Manganese-chromium/codoped alkaline-earth zincate luminescent material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104673282A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285965A (en) * | 2023-03-31 | 2023-06-23 | 江西理工大学 | Novel Mn 4+ 、Cr 3+ Co-doped fluoride near infrared fluorescent powder and preparation method thereof |
-
2013
- 2013-11-30 CN CN201310634783.4A patent/CN104673282A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285965A (en) * | 2023-03-31 | 2023-06-23 | 江西理工大学 | Novel Mn 4+ 、Cr 3+ Co-doped fluoride near infrared fluorescent powder and preparation method thereof |
| CN116285965B (en) * | 2023-03-31 | 2023-12-15 | 江西理工大学 | Near infrared fluorescent powder of manganese-chromium co-doped fluoride and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104673298A (en) | Samarium-doped alkaline-earth niobium zincate luminescent material, and preparation method and application thereof | |
| CN102863957B (en) | Manganese-chromium-doped zinc tungstate luminescent material and preparation method and application thereof | |
| CN104449685A (en) | Cerium-doped alkaline earth gallate luminescent material as well as preparation method and application thereof | |
| CN104673297A (en) | Cerium/europium-codoped alkaline-earth niobium zincate luminescent material, and preparation method and application thereof | |
| CN104178148A (en) | Antimony and terbium co-doped alkali niobate luminescent material, and preparation method and application thereof | |
| CN104673282A (en) | Manganese-chromium/codoped alkaline-earth zincate luminescent material, and preparation method and application thereof | |
| CN104449684A (en) | Europium-doped alkaline earth indate light-emitting material, and preparation method and application thereof | |
| CN104342158A (en) | Europium-erbium double-doped zinc selenide luminescent material, and preparation method and application thereof | |
| CN104449680A (en) | Fluorine/copper-codoped alkaline earth sulfide light-emitting material, and preparation method and application thereof | |
| CN104178160A (en) | Cerium terbium double-doped nitrogen silicon lanthanum luminescent material and preparation method and application thereof | |
| CN104342142A (en) | Cerium-doped alkaline earth arsenate luminescent material, and preparation method and application thereof | |
| CN102863956B (en) | Praseodymium-doped barium titanate luminescent material and preparation method and application thereof | |
| CN104650869A (en) | Europium- terbium- co-doped aluminium niobate luminescent materials, and preparing method and applications thereof | |
| CN104119906A (en) | Antimony terbium co-doped silicon nitride luminescent material and preparation method and application thereof | |
| CN104140812A (en) | III-group scandium silicate luminescent material co-doped with titanium and manganese, preparing method thereof and applications of the material | |
| CN104673280A (en) | Titanium-doped alkaline-earth zincate luminescent material, and preparation method and application thereof | |
| CN104650890A (en) | Samarium-doped gallium antimonate luminescent material, preparation method and application thereof | |
| CN103571475A (en) | Titanium manganese-codoped group-III molybdate luminescent material, preparation method and application thereof | |
| CN103421510B (en) | Antimony terbium codoped alkaline earth halogen-phosphate luminescent material, preparation method and application thereof | |
| CN104140810A (en) | Manganese-doped barium nitrosilicate luminescence material, and preparation method and application thereof | |
| CN103571477A (en) | Europium bismuth co-doped Group-III molybdate light-emitting material, preparation method and application thereof | |
| CN103571468A (en) | Antimony terbium co-doped silicon aluminum nitrogen oxide light-emitting material and preparation method and application thereof | |
| CN103805189A (en) | Manganese-chromium-codoped alkaline earth titanium phosphate light-emitting thin film as well as preparation method and application thereof | |
| CN104650918A (en) | Europium- bismuth- co-doped IIIA-group yttrium fluoride luminescent materials, and preparing method and applications thereof | |
| CN104650916A (en) | Manganese/titanium-codoped alkaline earth fluoscandate luminescent material, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150603 |