CN102838986B - Titanium manganese co-doped yttrium oxide luminescent film, preparation method thereof, and organic electroluminescent device - Google Patents
Titanium manganese co-doped yttrium oxide luminescent film, preparation method thereof, and organic electroluminescent device Download PDFInfo
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- CN102838986B CN102838986B CN201110169790.2A CN201110169790A CN102838986B CN 102838986 B CN102838986 B CN 102838986B CN 201110169790 A CN201110169790 A CN 201110169790A CN 102838986 B CN102838986 B CN 102838986B
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- yttrium oxide
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Abstract
The invention belongs to the field of luminescent materials, and discloses a titanium manganese co-doped yttrium oxide luminescent film, a preparation method thereof, and an organic electroluminescent device. The luminescent film has a chemical general formula of Y2O3:xTi<+4>, yMn<+4>, wherein Y2O3 is a substrate, Mn<+4> and Ti<+4> are doped elements, x ranges from 0.003 to 0.15, and y ranges from 0.0015 to 0.09. According to the invention, a magnetron sputtering equipment is adopted for preparing the titanium manganese co-doped yttrium oxide luminescent film. The film has strong luminescence peaks in a 505nm wavelength region and a 630nm wavelength region, and is a development material of electroluminescent devices.
Description
Technical field
The present invention relates to field of optoelectronic devices, relate in particular to manganese codoped yttrium oxide light-emitting film of a kind of titanium and preparation method thereof.The invention still further relates to a kind of manganese codoped yttrium oxide light-emitting film of this titanium that uses as the organic electroluminescence device of luminescent layer.
Background technology
Compare with the display screen that traditional luminescent powder is made, light-emitting film contrast gradient, resolving power, thermal conduction, homogeneity, and the aspect such as the tack of substrate, outgas speed all demonstrate stronger superiority.Therefore,, as functional materials, light-emitting film is having broad application prospects in showing the flat pannel display fields such as (ELDs) and Field Emission Display (FEDs) such as cathode tube (CRTs), electroluminescent.
In the research of LED fluorescent material, rear-earth-doped yttrium oxide fluorescent luminescent powder, the emmission spectrum that its excitation spectrum can mate existing near ultraviolet LED preferably can access good ruddiness exciting to blue light.But, with transient metal doped yttrium oxide class luminescent material, be prepared into the film of electroluminescent device, have not yet to see report.
Summary of the invention
It is a kind of with Y that the object of the invention is to provide
2o
3for matrix, Mn and the Ti element manganese codoped yttrium oxide light-emitting film of titanium that is main luminescence center.
The manganese codoped yttrium oxide light-emitting film of titanium of the present invention, the chemical general formula of film is Y
2o
3: xTi
+ 4, yMn
+ 4; Wherein, Y
2o
3for matrix, Mn
+ 4and Ti
+ 4for doped element; The span of x is that the span of 0.003～0.15, y is 0.0015～0.09; The value that preferably value of x is 0.04, y is 0.003.
Another goal of the invention of the present invention is to provide the preparation method of the manganese codoped yttrium oxide light-emitting film of above-mentioned titanium, and its preparation technology is as follows:
The preparation of step S1, ceramic target: according to chemical general formula Y
2o
3: xTi
+ 4, yMn
+ 4each element chemistry metering ratio, selects Y
2o
3, TiO
2and MnO
2powder, after even mixing, at 900～1300 ℃, (preferably sintering at 1250 ℃, obtains target; Wherein, the span that the span of x is 0.003～0.15, y is 0.0015～0.09; Preferably, the value that the value of x is 0.04, y is 0.003;
Step S2, the target in step S1 and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-3pa～1.0 * 10
-5pa, preferably vacuum tightness is 5.0 * 10
-4pa;
Step S3, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45～90mm, preferably 60mm; Underlayer temperature is 250 ℃～750 ℃, preferably 500 ℃; Gas flow 10～the 35sccm of argon gas working gas, preferably 25sccm; Magnetron sputtering operating pressure 0.2～4Pa, preferably 2.0Pa; After processing parameter has been adjusted, be then filmed, obtain film sample;
Step S4, the film sample that step S3 is obtained are placed in vacuum oven, (being 0.01Pa) anneal 1～3h under 500～800 ℃ (preferably 600 ℃), vacuum state (preferably 2h), and obtaining chemical general formula is Y
2o
3: xTi
+ 4, yMn
+ 4the manganese codoped yttrium oxide light-emitting film of titanium; Wherein, Y
2o
3for matrix, Mn
+ 4and Ti
+ 4for doped element.
The present invention also provides a kind of organic electroluminescence device, and this device is straticulate structure, and this straticulate structure is followed successively by substrate, anode layer, luminescent layer and cathode layer; Wherein, luminescent layer is that (chemical general formula of this film is Y to the manganese codoped yttrium oxide light-emitting film of titanium
2o
3: xTi
+ 4, yMn
+ 4; Wherein, Y
2o
3for matrix, Mn
+ 4and Ti
+ 4for doped element; The span of x is that the span of 0.003～0.15, y is 0.0015～0.09; Preferably, the value that the value of x is 0.04, y is 0.003), substrate is glass, and anode layer is ITO, and cathode layer is Ag layer, and Ag layer adopts evaporation process preparation at film surface.
The present invention adopts magnetron sputtering equipment, prepares the manganese codoped yttrium oxide light-emitting film of titanium, and obtaining, in the electroluminescent spectrum (EL) of film, has very strong glow peak at 505nm and 630nm wavelength zone, is the development material of electroluminescent device.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of the manganese codoped yttrium oxide light-emitting film of titanium of the present invention;
Fig. 2 is the structural representation of organic electroluminescence device of the present invention;
Fig. 3 is the electroluminescent spectrum that embodiment 4 obtains the manganese codoped yttrium oxide light-emitting film of titanium sample.
Embodiment
The present invention is in the manganese codoped yttrium oxide light-emitting film of a kind of titanium providing, and it is Y that the manganese codoped yttrium oxide light-emitting film of this titanium comprises film general formula
2o
3: xTi
+ 4, yMn
+ 4; Wherein, Y
2o
3for matrix, Mn
+ 4and Ti
+ 4for doped element; The span of x is that the span of 0.003～0.15, y is 0.0015～0.09; The value that preferably value of x is 0.04, y is 0.003.
The manganese codoped yttrium oxide light-emitting film of above-mentioned titanium provided by the invention preparation method, as shown in Figure 1, its preparation technology is as follows:
The preparation of step S1, ceramic target: according to chemical general formula Y
2o
3: xTi
+ 4, yMn
+ 4each element chemistry metering ratio, selects Y
2o
3, TiO
2and MnO
2powder, after even mixing, at 900～1300 ℃ (preferably 1250 ℃) lower sintering, naturally cooling, obtains target sample, and it is the target that 50mm, thickness are 2mm that target sample is cut into diameter; Wherein, the span that the span of x is 0.003～0.15, y is 0.0015～0.09; The value that preferably value of x is 0.04, y is 0.003;
Step S2, the target in step S1 and substrate are packed into the vacuum cavity of magnetic-controlled sputtering coating equipment, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-3pa～1.0 * 10
-5pa, preferably 5.0 * 10
-4pa;
Step S3, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45～90mm, preferably 60mm; Underlayer temperature is 250 ℃～750 ℃, preferably 500 ℃; Gas flow 10～the 35sccm of argon gas working gas, preferably 25sccm; Magnetron sputtering operating pressure 0.2～4Pa, preferably 2.0Pa; Processing parameter is then filmed after adjusting, and obtains film sample;
Step S4, the film sample that step S3 is obtained are placed in vacuum oven, (being 0.01Pa) anneal 1～3h under 500～800 ℃ (preferably 600 ℃), vacuum state (preferably 2h), and obtaining chemical general formula is Y
2o
3: xTi
+ 4, yMn
+ 4the manganese codoped yttrium oxide light-emitting film of described titanium; Wherein, Y
2o
3. be matrix, Mn
+ 4and Ti
+ 4for doped element.
In above-mentioned preparation method's step S1, according to chemical general formula Y
2o
3: xTi
+ 4, yMn
+ 4each element chemistry metering ratio, the actual Y that weighs
2o
3, MnO
2and TiO
2during powder, by mass percentage: MnO
2account for 0.1～5wt% of total amount, preferably 1.5wt%; TiO
2account for 0.05～3wt% of total amount, preferably 0.1wt%; Y
2o
3account for 95～99wt% of total amount, preferably 98.4wt%.
The present invention also provides a kind of organic electroluminescence device, and as shown in Figure 2, this device is straticulate structure, and this straticulate structure is followed successively by substrate 1, anode layer 2, luminescent layer 3 and cathode layer 4; Wherein, substrate 1 is glass, and anode layer is ITO layer, and ito glass, can buy acquisition; For the manganese codoped yttrium oxide light-emitting film of titanium layer, (chemical general formula of this film is Y to luminescent layer 3
2o
3: xTi
+ 4, yMn
+ 4; Wherein, Y
2o
3for matrix, Mn
+ 4and Ti
+ 4for doped element; The span of x is that the span of 0.003～0.15, y is 0.0015～0.09; Preferably, the value that the value of x is 0.04, y is 0.003); Cathode layer 4 is Ag layer, and Ag layer adopts evaporation process preparation at film surface.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
1, select purity to be respectively 99.99% Y
2o
3, MnO
2and TiO
2powder (wherein, Y
2o
3quality be 196.8g, MnO
2quality be 3g, TiO
2quality be 0.2g), after even mixing, sintering at 1250 ℃, naturally cooling, obtains target sample, it is the target that 50mm, thickness are 2mm that target sample is cut into diameter;
2, target is packed in the vacuum cavity of magnetic-controlled sputtering coating equipment;
3, successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass, and it is carried out to oxygen plasma treatment, put into the vacuum cavity of magnetic-controlled sputtering coating equipment after complete; Wherein, the base target spacing setting of target and glass is 60mm;
4, with mechanical pump and molecular pump, the vacuum tightness of the vacuum cavity of magnetic-controlled sputtering coating equipment is extracted into 5.0 * 10
-4pa;
5, adjust magnetron sputtering plating processing parameter: argon gas working gas flow is 25sccm; Magnetron sputtering operating pressure is 2.0Pa; Underlayer temperature is 500 ℃; Then be filmed the film sample obtaining;
6, film sample is annealed in 0.01Pa vacuum oven 2h, annealing temperature is 600 ℃, obtains the manganese codoped yttrium oxide light-emitting film of titanium, i.e. Y
2o
3: 0.04Ti
+ 4, 0.003Mn
+ 4.
Embodiment 2
1,, select purity to be respectively 99.99% Y
2o
3, MnO
2and TiO
2powder (wherein, Y
2o
3quality be 198g, MnO
2quality be 1g, TiO
2quality be 1g), after even mixing, sintering at 900 ℃, naturally cooling, obtains target sample, it is the target that 50mm, thickness are 2mm that target sample is cut into diameter;
2, target is packed in the vacuum cavity of magnetic-controlled sputtering coating equipment;
3, successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass, and it is carried out to oxygen plasma treatment, put into the vacuum cavity of magnetic-controlled sputtering coating equipment after complete; Wherein, the base target spacing setting of target and glass is 45mm;
4, with mechanical pump and molecular pump, the vacuum tightness of the vacuum cavity of magnetic-controlled sputtering coating equipment is extracted into 1.0 * 10
-3pa;
5, adjust magnetron sputtering plating processing parameter: argon gas working gas flow is 10sccm; Magnetron sputtering operating pressure is 4Pa; Underlayer temperature is 250 ℃; Then be filmed the film sample obtaining;
6, film sample is annealed in 0.01Pa vacuum oven 1h, annealing temperature is 500 ℃, obtains the manganese codoped yttrium oxide light-emitting film of titanium, i.e. Y
2o
3: 0.013Ti
+ 4, 0.015Mn
+ 4.
Embodiment 3
1, select purity to be respectively 99.99% Y
2o
3, MnO
2and TiO
2powder (wherein, Y
2o
3quality be 193.8g, MnO
2quality be 0.2g, TiO
2quality be 6g), after even mixing, sintering at 1300 ℃, naturally cooling, obtains target sample, it is the target that 50mm, thickness are 2mm that target sample is cut into diameter;
2, target is packed in the vacuum cavity of magnetic-controlled sputtering coating equipment;
3, successively by acetone, dehydrated alcohol and deionized water ultrasonic cleaning band glass substrate, and it is carried out to oxygen plasma treatment, put into the vacuum cavity of magnetic-controlled sputtering coating equipment after complete; Wherein, the base target spacing setting of target and glass is 90mm;
4, with mechanical pump and molecular pump, the vacuum tightness of the vacuum cavity of magnetic-controlled sputtering coating equipment is extracted into 1.0 * 10
-5pa;
5, adjust magnetron sputtering plating processing parameter: argon gas working gas flow is 35sccm; Magnetron sputtering operating pressure is 0.2Pa; Underlayer temperature is 750 ℃; Then be filmed the film sample obtaining;
6, film sample is annealed in 0.01Pa vacuum oven 3h, annealing temperature is 800 ℃, obtains the manganese codoped yttrium oxide light-emitting film of titanium, i.e. Y
2o
3: 0.003Ti
+ 4, 0.045Mn
+ 4.
In following embodiment 4, substrate is glass, and anode layer is ITO, plays electric action, and both are combined, and are called ito glass, can buy acquisition.
Embodiment 4
1, select purity to be respectively 99.99% Y
2o
3, MnO
2and TiO
2powder (wherein, Y
2o
3quality be 189.9g, MnO
2quality be 10g, TiO
2quality be 0.1g), after even mixing, sintering at 1250 ℃, naturally cooling, obtains target sample, it is the target that 50mm, thickness are 2mm that target sample is cut into diameter;
2, target is packed in the vacuum cavity of magnetic-controlled sputtering coating equipment;
3, successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ito glass, and it is carried out to oxygen plasma treatment, put into the vacuum cavity of magnetic-controlled sputtering coating equipment after complete; Wherein, the base target spacing setting of target and ito glass is 60mm;
4, with mechanical pump and molecular pump, the vacuum tightness of the vacuum cavity of magnetic-controlled sputtering coating equipment is extracted into 5.0 * 10
-4pa;
5, adjust magnetron sputtering plating processing parameter: argon gas working gas flow is 25sccm; Magnetron sputtering operating pressure is 2.0Pa; Underlayer temperature is 500 ℃; Then be filmed the film sample obtaining, i.e. Y
2o
3: 0.133Ti
+ 4, 0.0015Mn
+ 4;
6, film sample is annealed in 0.01Pa vacuum oven 2h, annealing temperature is 700 ℃, obtains the manganese codoped yttrium oxide light-emitting film of titanium;
7, adopt evaporation coating technique, the light-emitting film surface evaporation Ag layer in (6), as cathode layer, makes organic electroluminescence device.
Fig. 3 is electroluminescent spectrum (EL) figure that embodiment 4 obtains the manganese codoped yttrium oxide light-emitting film of titanium sample.As shown in Figure 3, obtaining, in the electroluminescent spectrum (EL) of film, at 505nm and 630nm wavelength zone, having very strong glow peak, is the development material of electroluminescent device.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (6)
1. a preparation method for the manganese codoped yttrium oxide light-emitting film of titanium, is characterized in that, comprises the steps:
Step S1, according to chemical general formula Y
2o
3: xTi
+ 4, yMn
+ 4each element chemistry metering ratio, takes Y
2o
3, TiO
2and MnO
2powder, after even mixing, sintering at 900～1300 ℃, makes target; Wherein, the span that the span of x is 0.003～0.15, y is 0.0015～0.09;
Step S2, packs the target obtaining in step S1 and substrate the vacuum cavity of magnetic-controlled sputtering coating equipment into, and the vacuum tightness of vacuum cavity is arranged on to 1.0 * 10
-3pa～1.0 * 10
-5between Pa;
Step S3, adjustment magnetron sputtering plating processing parameter is: base target spacing is 45～90mm, magnetron sputtering operating pressure 0.2～4Pa, the flow 10～35sccm of argon gas working gas, underlayer temperature is 250 ℃～750 ℃; Then be filmed, obtain film sample;
Step S4,1～3h is processed in the film sample that step S3 is obtained vacuum annealing at 500～800 ℃, and obtaining chemical general formula is Y
2o
3: xTi
+ 4, yMn
+ 4the manganese codoped yttrium oxide light-emitting film of described titanium; Wherein, Y
2o
3for matrix, Mn
+ 4and Ti
+ 4for doped element.
2. the preparation method of the manganese codoped yttrium oxide light-emitting film of titanium according to claim 1, is characterized in that, in described step S1, the value that the value of x is 0.04, y is 0.003.
3. the preparation method of the manganese codoped yttrium oxide light-emitting film of titanium according to claim 1 and 2, is characterized in that, in described step S1, the sintering temperature of described preparation of target materials is 1250 ℃.
4. the preparation method of the manganese codoped yttrium oxide light-emitting film of titanium according to claim 1, is characterized in that, in described step S2, the vacuum tightness of vacuum cavity is arranged on 5.0 * 10
-4pa.
5. the preparation method of the manganese codoped yttrium oxide light-emitting film of titanium according to claim 1, is characterized in that, in described step S3, described base target spacing is 60mm; Described magnetron sputtering operating pressure is 2.0Pa; The flow of described argon gas working gas is 25sccm; Described underlayer temperature is 500 ℃.
6. the preparation method of the manganese codoped yttrium oxide light-emitting film of titanium according to claim 1, is characterized in that, in described step S4, the annealing temperature in described anneal process is 600 ℃, and annealing time is 2h.
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| CN102838986B true CN102838986B (en) | 2014-04-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1403329A1 (en) * | 2002-09-27 | 2004-03-31 | Fuji Photo Film Co., Ltd. | Method for coating particles |
| CN1500367A (en) * | 2001-03-29 | 2004-05-26 | ��ʿ��Ƭ��ʽ���� | Electrolumine scence device |
| EP1570711B1 (en) * | 2002-12-11 | 2009-06-10 | LG Chem, Ltd. | Electroluminescent devices with low work function anode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4042895B2 (en) * | 2001-09-10 | 2008-02-06 | シンジーテック株式会社 | Oxide phosphor for PL, CL or EL, electroluminescence element, and method for producing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500367A (en) * | 2001-03-29 | 2004-05-26 | ��ʿ��Ƭ��ʽ���� | Electrolumine scence device |
| EP1403329A1 (en) * | 2002-09-27 | 2004-03-31 | Fuji Photo Film Co., Ltd. | Method for coating particles |
| EP1570711B1 (en) * | 2002-12-11 | 2009-06-10 | LG Chem, Ltd. | Electroluminescent devices with low work function anode |
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| Title |
|---|
| JP特开2003-155480A 2003.05.30 |
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