CN104449710A - Light-emitting thin film, preparation method thereof and electroluminescent device - Google Patents

Light-emitting thin film, preparation method thereof and electroluminescent device Download PDF

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CN104449710A
CN104449710A CN201310443197.1A CN201310443197A CN104449710A CN 104449710 A CN104449710 A CN 104449710A CN 201310443197 A CN201310443197 A CN 201310443197A CN 104449710 A CN104449710 A CN 104449710A
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light
substrate
emitting film
film
preparation
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周明杰
陈吉星
王平
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention provides a light-emitting thin film with the chemical general formula as follows: Me3(VF8)2: xEu<3+>, yTb<3+>, wherein Me3(VF8)2 is used as a substrate, Me is Mg, Ca, Sr or Ba, Eu<3+> and Tb<3+> are used as doped ions, x ranges from 0.01-0.05, and y ranges from 0.01-0.04. The light-emitting thin film has very strong light-emitting peaks at the positions with the wavelengths of 490nm and 510nm in an electroluminescent spectrum, and can be used as a material for manufacturing an electroluminescent device. In addition, the invention provides a preparation method of the light-emitting thin film and the electroluminescent device.

Description

Light-emitting film and preparation method thereof and electroluminescent device
Technical field
The present invention relates to photoelectric semiconductor material technical field, particularly a kind of light-emitting film and preparation method thereof, and use the electroluminescent device of this light-emitting film.
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.
The green powder of arsenate system, because its synthesis temperature is moderate, luminosity is high, the more greatly and extremely investigator's favor of chromaticity coordinates X value, is the popular research material of LED fluorescent powder.But because the preparation of this material is all at high temperature reacted, have arsenic oxide arsenoxide evaporation like this, cause the ratio of arsenate and rare earth element uncontrollable, thus add preparation difficulty, and therefore, research colour and extremely panchromatic TFELD, the material of exploitation multiband luminescence is the developing direction of present stage.
Summary of the invention
Given this, be necessary that providing a kind of as light-emitting film of the material of electroluminescent device and preparation method thereof, and can use the electroluminescent device of this light-emitting film.
A kind of light-emitting film, the chemical general formula of described light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+; Wherein, Me 3(VF 8) 2for matrix, Me is Mg, Ca, Sr or Ba, Eu 3+and Tb 3+for dopant ion, x is 0.01 ~ 0.05, y is 0.01 ~ 0.04.
Wherein in an embodiment, described x is 0.03, and described y is 0.02.
A preparation method for light-emitting film, comprises the steps:
According to chemical general formula Me 3(VF 8) 2: xEu 3+, yTb 3+in the stoichiometric ratio of each element, take MeF 2, VF 5, EuF 3and TbF 3powder, after mixing, sinter at 900 DEG C ~ 1300 DEG C, make target, wherein, Me is Mg, Ca, Sr or Ba, and x is 0.01 ~ 0.05, y is 0.01 ~ 0.04;
Described target and substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, is evacuated to 1.0 × 10 -3pa ~ 1.0 × 10 -5pa;
The processing parameter of adjustment magnetron sputtering plating, film sample is prepared at described substrate surface, wherein, the processing parameter of described magnetron sputtering plating is base target spacing is 45 millimeters ~ 95 millimeters, substrate temperature is 250 DEG C ~ 750 DEG C, flow 10sccm ~ the 35sccm of argon working gas, pressure 0.2Pa ~ 4Pa; And
By described film sample 500 DEG C ~ 800 DEG C vacuum annealing process 1 hour ~ 3 hours, obtain light-emitting film, the chemical general formula of described light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+; Wherein, Me 3(VF 8) 2for matrix, Mn 4+and Ti 4+for dopant ion.
Wherein in an embodiment, described x is 0.03, and described y is 0.02.
Wherein in an embodiment, before described substrate being loaded the cavity of described magnetic-controlled sputtering coating equipment, also comprise and acetone, dehydrated alcohol and deionized water ultrasonic cleaning are used successively to described substrate, then carry out the step of plasma treatment.
Wherein in an embodiment, described substrate is the glass that one side is formed with transparent conductive film, and described film sample magnetron sputtering is formed on described transparent conductive film; Described cavity is evacuated to 5.0 × 10 -4pa.
Wherein in an embodiment, described base target spacing is 60 millimeters; Described substrate temperature is 500 DEG C; The flow 25sccm of described argon working gas; Described pressure 2.0Pa.
Wherein in an embodiment, the vacuum tightness of described anneal is 0.01Pa, and temperature is 600 DEG C, and the time is 2 hours.
A kind of electroluminescent device, comprise stack gradually substrate, anode layer, luminescent layer and cathode layer, the material of described luminescent layer is light-emitting film, and the chemical general formula of described light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+; Wherein, Me 3(VF 8) 2for matrix, Me is Mg, Ca, Sr or Ba, Eu 3+and Tb 3+for dopant ion, x is 0.01 ~ 0.05, y is 0.01 ~ 0.04.
Wherein in an embodiment, described x is 0.03, and described y is 0.02.
The electroluminescent spectrum (EL) of above-mentioned light-emitting film has very strong glow peak in the position that wavelength is 490nm and 510nm, can as the material of electroluminescent device.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the light-emitting film of an embodiment;
Fig. 2 is the structural representation of the electroluminescent device of an embodiment;
Fig. 3 is the electroluminescent spectrum (EL) of light-emitting film prepared by embodiment 1;
Fig. 4 is the X ray diffracting spectrum (XRD) of light-emitting film prepared by embodiment 1.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments light-emitting film and preparation method thereof and electroluminescent device are described in further detail below.
The chemical general formula of the light-emitting film of one embodiment is Me 3(VF 8) 2: xEu 3+, yTb 3+; Wherein, Me 3(VF 8) 2for matrix, Me is Mg, Ca, Sr or Ba, Eu 3+and Tb 3+for dopant ion, x is 0.01 ~ 0.05, y is 0.01 ~ 0.04.
Wherein, Eu 3+inspire the glow peak of 610nm position, and Tb 3+inspire the glow peak of 510nm position.
Preferably, x is 0.03, y is 0.02.Dopant ion is as the luminescence center of material, and the increase of content can improve luminous efficiency, but excessive concentration, can affect the crystal field that matrix is stable, there will be the phenomenon of concentration quenching, luminous efficiency can decline on the contrary.The optimum concentration value of x is 0.03, y to be 0.02 be dopant ion in this system, can reach maximum luminous efficiency.
The electroluminescent spectrum (EL) of above-mentioned light-emitting film has very strong glow peak in the position that wavelength is 490nm and 510nm, can as the material of electroluminescent device.
As shown in Figure 1, the preparation method of the light-emitting film of an embodiment, comprises the steps:
Step S110: according to chemical general formula Me 3(VF 8) 2: xEu 3+, yTb 3+in the stoichiometric ratio of each element, take MeF 2, VF 5(vanadium pentafluoride), EuF 3and TbF 3powder, after mixing, sinters, makes target at 900 DEG C ~ 1300 DEG C.Wherein, Me is Mg, Ca, Sr or Ba, and x is 0.01 ~ 0.05, y is 0.01 ~ 0.04.Me is similar second main group alkali earth metal Mg, Ca, Sr or the Ba of character, its fluorochemical MeF 2and VF 5(vanadium pentafluoride) combines the Me formed 3(VF 8) 2be the excellent substrate material of a kind of photoelectric property, can be the crystal field that light emitting ionic provides suitable, there is very high luminous efficiency.
Preferably, x is 0.03, y is 0.02.
Preferably, sintering temperature is 1250 DEG C.
Step S120: target and substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, is evacuated to 1.0 × 10 -3pa ~ 1.0 × 10 -5pa.Magnetron sputtering method is a kind of application film coating method widely, and the material in the present invention is electron opaque material, scleroid, evaporation or plating all very difficult; And sputter rule and be easy to preparation, and the film thickness obtained is even, and well-crystallized, is conducive to realizing high efficiency light-emitting.
Preferably, before substrate being loaded the cavity of magnetic-controlled sputtering coating equipment, also comprise and acetone, dehydrated alcohol and deionized water ultrasonic cleaning are used successively to substrate, then carry out the step of plasma treatment.
Preferably, substrate is the glass that one side is formed with transparent conductive film.Cavity is evacuated to 5.0 × 10 -4pa.Wherein, mechanical pump and molecular pump is used to vacuumize cavity.
Step S130: the processing parameter of adjustment magnetron sputtering plating, prepares film sample at substrate surface.Wherein, the processing parameter of magnetron sputtering plating is base target spacing is 45 millimeters ~ 95 millimeters, and substrate temperature is 250 DEG C ~ 750 DEG C, the flow 10sccm ~ 35sccm of argon working gas, pressure 0.2Pa ~ 4Pa.Magnetic-controlled sputtering coating equipment can obtain preferably beneficial effect under adopting these coating process parameters, and the value that goes beyond the scope just does not reach beneficial effect.
Preferably, base target spacing is 60 millimeters.This parameter value can reach best beneficial effect.
Preferably, substrate temperature is 500 DEG C, and wherein, film sample magnetron sputtering is formed on transparent conductive film.The transparent material with conductivity that transparent conductive film can be commonly used for this area, is preferably the one in indium tin oxide transparent conductive film (ITO), aluminium zinc oxide transparent conductive film (AZO) and indium-zinc oxide transparent conductive film (IZO).
Preferably, the flow 25sccm of argon working gas.Pressure 2.0Pa in magnetic-controlled sputtering coating equipment cavity.
Step S140: by film sample 500 DEG C ~ 800 DEG C vacuum annealing process 1 hour ~ 3 hours, obtain light-emitting film, the chemical general formula of light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+.Wherein, Me 3(VF 8) 2for matrix, Mn 4+and Ti 4+for dopant ion.
Preferably, the vacuum tightness of anneal is 0.01Pa; Temperature is 600 DEG C; Time is 2 hours.This parameter value can reach best beneficial effect.
Light-emitting film prepared by the preparation method of above-mentioned light-emitting film, there is very strong glow peak the position that its electroluminescent spectrum (EL) is 490nm and 510nm at wavelength, can as the material of electroluminescent device.
As shown in Figure 2, the electroluminescent device 200 of an embodiment, comprise stack gradually substrate 210, anode layer 220, luminescent layer 230 and cathode layer 240.
The transparent substrates that substrate 210 can be commonly used for this area, is preferably glass.
Anode layer 220 is laminated in substrate 210.The transparent material with conductivity that the material of anode layer 220 can be commonly used for this area, is preferably the one in indium tin oxide transparent conductive film (ITO), aluminium zinc oxide transparent conductive film (AZO) and indium-zinc oxide transparent conductive film (IZO).Wherein, anode layer 220 can adopt the mode of sputter to form transparent conductive film on a glass substrate.
Luminescent layer 230 is laminated on anode layer 220.The material of luminescent layer 230 is light-emitting film, and the chemical general formula of light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+.Wherein, Me 3(VF 8) 2for matrix, Mn 4+and Ti 4+for dopant ion, x is 0.01 ~ 0.05, y is 0.01 ~ 0.04.Preferably, x is 0.03, y is 0.02.
Cathode layer 240 is laminated on luminescent layer 230.The material of cathode layer 240 can be the conventional cathode material in this area, and such as, silver (Ag), aluminium (Al) or gold (Au), be preferably silver (Ag).Wherein, cathode layer 240 can adopt the mode of evaporation to be formed.
The material of the luminescent layer 230 of above-mentioned electroluminescent device 200 is light-emitting film, and the electroluminescent spectrum of this light-emitting film (EL) has very strong glow peak in the position that wavelength is 490nm and 510nm.
Be below specific embodiment part:
Embodiment 1
The structure of the present embodiment is glass/ITO/Mg 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Mg 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the preparation of light-emitting film: the MgF taking 3mmol, 2mmol, 0.03mmol and 0.02mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1250 DEG C; The glass substrate being formed with ITO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with ITO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 5.0 × 10 with mechanical pump and molecular pump -4pa; The distance of target and substrate is set as 60 millimeters, and the working gas flow regulating argon gas is 25sccm, pressure 2.0Pa, and substrate temperature is 500 DEG C, prepares film sample at substrate surface; By this film sample 600 DEG C of anneal 2 hours in the vacuum oven of 0.01Pa, obtain Mg 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of ITO transparent conductive film is substrate, and ITO transparent conductive film is anode layer.
(2) at above-mentioned Mg 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/ITO/Mg 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the electroluminescent device of/Ag.
The electroluminescent spectrum (EL) of what Fig. 3 represented is light-emitting film prepared by the present embodiment, as can be seen from the figure, light-emitting film prepared by the present embodiment has very strong glow peak in the position that wavelength is 490nm and 510nm.
The X ray diffracting spectrum (XRD) of what Fig. 4 represented is light-emitting film prepared by the present embodiment, according to reference standard PDF card, the diffraction peak in figure is Me 3(VF 8) 2, there is not the peak of doped element in the peak crystallization of matrix, illustrates that doped element enters the lattice of matrix, have good crystalline quality.
Embodiment 2
The structure of the present embodiment is glass/AZO/Mg 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Mg 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+the preparation of light-emitting film: the MgF taking 3mmol, 2mmol, 0.01mmol and 0.01mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 900 DEG C; The glass substrate being formed with AZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with AZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -3pa; The distance of target and substrate is set as 45 millimeters, and the working gas flow regulating argon gas is 10sccm, pressure 0.2Pa, and substrate temperature is 250 DEG C, prepares film sample at substrate surface; By this film sample 500 DEG C of anneal 1 hour in the vacuum oven of 0.01Pa, obtain Mg 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of AZO transparent conductive film is substrate, and AZO transparent conductive film is anode layer.
(2) at above-mentioned Mg 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/AZO/Mg 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+the electroluminescent device of/Ag.
Embodiment 3
The structure of the present embodiment is glass/IZO/Mg 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Mg 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the preparation of light-emitting film: the MgF taking 3mmol, 2mmol, 0.05mmol and 0.04mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1300 DEG C; The glass substrate being formed with IZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with IZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -5pa; The distance of target and substrate is set as 95 millimeters, and the working gas flow regulating argon gas is 35sccm, pressure 4.0Pa, and substrate temperature is 750 DEG C, prepares film sample at substrate surface; By this film sample 800 DEG C of anneal 3 hours in the vacuum oven of 0.01Pa, obtain Mg 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of IZO transparent conductive film is substrate, and IZO transparent conductive film is anode layer.
(2) at above-mentioned Mg 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/IZO/Mg 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the electroluminescent device of/Ag.
Embodiment 4
The structure of the present embodiment is glass/ITO/Ca 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Ca 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the preparation of light-emitting film: the CaF taking 3mmol, 2mmol, 0.03mmol and 0.02mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1250 DEG C; The glass substrate being formed with ITO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with ITO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 5.0 × 10 with mechanical pump and molecular pump -4pa; The distance of target and substrate is set as 60 millimeters, and the working gas flow regulating argon gas is 25sccm, pressure 2.0Pa, and substrate temperature is 500 DEG C, prepares film sample at substrate surface; By this film sample 600 DEG C of anneal 2 hours in the vacuum oven of 0.01Pa, obtain Ca 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+, 0.04Ti 4+light-emitting film.Wherein, being formed with glass in the glass substrate of ITO transparent conductive film is substrate, and ITO transparent conductive film is anode layer.
(2) at above-mentioned Ca 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/ITO/Ca 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the electroluminescent device of/Ag.
Embodiment 5
The present embodiment there is glass/AZO/Ca 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+being prepared as follows of the electroluminescent device of/Ag light-emitting film:
(1) Ca 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+the preparation of light-emitting film: the CaF taking 3mmol, 2mmol, 0.01mmol and 0.01mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 900 DEG C; The glass substrate being formed with AZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with AZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -3pa; The distance of target and substrate is set as 45 millimeters, and the working gas flow regulating argon gas is 10sccm, pressure 0.2Pa, and substrate temperature is 250 DEG C, prepares film sample at substrate surface; By this film sample 500 DEG C of anneal 1 hour in the vacuum oven of 0.01Pa, obtain Ca 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of AZO transparent conductive film is substrate, and AZO transparent conductive film is anode layer.
(2) at above-mentioned Ca 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/AZO/Ca 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+the electroluminescent device of/Ag.
Embodiment 6
The structure of the present embodiment is glass/IZO/Ca 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Ca 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the preparation of light-emitting film: the CaF taking 3mmol, 2mmol, 0.05mmol and 0.04mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1300 DEG C; The glass substrate being formed with IZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with IZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -5pa; The distance of target and substrate is set as 45 millimeters, and the working gas flow regulating argon gas is 35sccm, pressure 4.0Pa, and substrate temperature is 750 DEG C, prepares film sample at substrate surface; By this film sample 800 DEG C of anneal 3 hours in the vacuum oven of 0.01Pa, obtain Ca 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of IZO transparent conductive film is substrate, and IZO transparent conductive film is anode layer.
(2) at above-mentioned Ca 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/IZO/Ca 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the electroluminescent device of/Ag.
Embodiment 7
The structure of the present embodiment is glass/IZO/Sr 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Sr 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the preparation of light-emitting film: the SrF taking 3mmol, 2mmol, 0.03mmol and 0.02mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1250 DEG C; The glass substrate being formed with ITO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with ITO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 5.0 × 10 with mechanical pump and molecular pump -4pa; The distance of target and substrate is set as 60 millimeters, and the working gas flow regulating argon gas is 25sccm, pressure 2.0Pa, and substrate temperature is 500 DEG C, prepares film sample at substrate surface; By this film sample 600 DEG C of anneal 2 hours in the vacuum oven of 0.01Pa, obtain Sr 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of ITO transparent conductive film is substrate, and ITO transparent conductive film is anode layer.
(2) at above-mentioned Sr 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/IZO/Sr 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the electroluminescent device of/Ag.
Embodiment 8
The present embodiment there is glass/AZO/Sr 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+being prepared as follows of the electroluminescent device of/Ag light-emitting film:
(1) Sr 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+the preparation of light-emitting film: the SrF taking 3mmol, 2mmol, 0.01mmol and 0.01mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 900 DEG C; The glass substrate being formed with AZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with AZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -3pa; The distance of target and substrate is set as 45 millimeters, and the working gas flow regulating argon gas is 10sccm, pressure 0.2Pa, and substrate temperature is 250 DEG C, prepares film sample at substrate surface; By this film sample 500 DEG C of anneal 1 hour in the vacuum oven of 0.01Pa, obtain Sr 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of AZO transparent conductive film is substrate, and AZO transparent conductive film is anode layer.
(2) at above-mentioned Sr 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/AZO/Sr 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3+the electroluminescent device of/Ag.
Embodiment 9
The structure of the present embodiment is glass/IZO/Sr 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Sr 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the preparation of light-emitting film: the CaF taking 3mmol, 2mmol, 0.05mmol and 0.04mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1300 DEG C; The glass substrate being formed with IZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with IZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -5pa; The distance of target and substrate is set as 45 millimeters, and the working gas flow regulating argon gas is 35sccm, pressure 4.0Pa, and substrate temperature is 750 DEG C, prepares film sample at substrate surface; By this film sample 800 DEG C of anneal 3 hours in the vacuum oven of 0.01Pa, obtain Sr 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of IZO transparent conductive film is substrate, and IZO transparent conductive film is anode layer.
(2) at above-mentioned Sr 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/IZO/Sr 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the electroluminescent device of/Ag.
Embodiment 10
The structure of the present embodiment is glass/IZO/Ba 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Ba 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the preparation of light-emitting film: the BaF taking 3mmol, 2mmol, 0.03mmol and 0.02mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1250 DEG C; The glass substrate being formed with ITO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with ITO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 5.0 × 10 with mechanical pump and molecular pump -4pa; The distance of target and substrate is set as 60 millimeters, and the working gas flow regulating argon gas is 25sccm, pressure 2.0Pa, and substrate temperature is 500 DEG C, prepares film sample at substrate surface; By this film sample 600 DEG C of anneal 2 hours in the vacuum oven of 0.01Pa, obtain Ba 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of ITO transparent conductive film is substrate, and ITO transparent conductive film is anode layer.
(2) at above-mentioned Ba 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/IZO/Ba 3(VF 8) 2: 0.03Eu 3+, 0.02Tb 3+the electroluminescent device of/Ag.
Embodiment 11
The present embodiment there is glass/AZO/Ba 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3being prepared as follows of the electroluminescent device of/Ag light-emitting film:
(1) Ba 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3the preparation of light-emitting film: the SrF taking 3mmol, 2mmol, 0.01mmol and 0.01mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 900 DEG C; The glass substrate being formed with AZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with AZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -3pa; The distance of target and substrate is set as 45 millimeters, and the working gas flow regulating argon gas is 10sccm, pressure 0.2Pa, and substrate temperature is 250 DEG C, prepares film sample at substrate surface; By this film sample 500 DEG C of anneal 1 hour in the vacuum oven of 0.01Pa, obtain Ba 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3light-emitting film.Wherein, being formed with glass in the glass substrate of AZO transparent conductive film is substrate, and AZO transparent conductive film is anode layer.
(2) at above-mentioned Ba 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/AZO/Ba 3(VF 8) 2: 0.01Eu 3+, 0.01Tb 3the electroluminescent device of/Ag.
Embodiment 12
The structure of the present embodiment is glass/IZO/Ba 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+being prepared as follows of the electroluminescent device of/Ag:
(1) Ba 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the preparation of light-emitting film: the BaF taking 3mmol, 2mmol, 0.05mmol and 0.04mmol respectively 2, VF 5, EuF 3and TbF 3powder, after Homogeneous phase mixing, sinters the target that diameter is 50 × 2mm at 1300 DEG C; The glass substrate being formed with IZO transparent conductive film is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning successively, and plasma treatment is carried out to the glass substrate that this is formed with IZO transparent conductive film; Then this target and above-mentioned substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, be evacuated to 1.0 × 10 with mechanical pump and molecular pump -5pa; The distance of target and substrate is set as 45 millimeters, and the working gas flow regulating argon gas is 35sccm, pressure 4.0Pa, and substrate temperature is 750 DEG C, prepares film sample at substrate surface; By this film sample 800 DEG C of anneal 3 hours in the vacuum oven of 0.01Pa, obtain Ba 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+light-emitting film.Wherein, being formed with glass in the glass substrate of IZO transparent conductive film is substrate, and IZO transparent conductive film is anode layer.
(2) at above-mentioned Ba 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+evaporation silver (Ag) on light-emitting film, form cathode layer, the structure obtaining the present embodiment is glass/IZO/Ba 3(VF 8) 2: 0.05Eu 3+, 0.04Tb 3+the electroluminescent device of/Ag.
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 (10)

1. a light-emitting film, is characterized in that, the chemical general formula of described light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+; Wherein, Me 3(VF 8) 2for matrix, Me is Mg, Ca, Sr or Ba, Eu 3+and Tb 3+for dopant ion, x is 0.01 ~ 0.05, y is 0.01 ~ 0.04.
2. light-emitting film according to claim 1, is characterized in that, described x is 0.03, and described y is 0.02.
3. a preparation method for light-emitting film, is characterized in that, comprises the steps:
According to chemical general formula Me 3(VF 8) 2: xEu 3+, yTb 3+in the stoichiometric ratio of each element, take MeF 2, VF 5, EuF 3and TbF 3powder, after mixing, sinter at 900 DEG C ~ 1300 DEG C, make target, wherein, Me is Mg, Ca, Sr or Ba, and x is 0.01 ~ 0.05, y is 0.01 ~ 0.04;
Described target and substrate are loaded in the cavity of magnetic-controlled sputtering coating equipment, is evacuated to 1.0 × 10 -3pa ~ 1.0 × 10 -5pa;
The processing parameter of adjustment magnetron sputtering plating, film sample is prepared at described substrate surface, wherein, the processing parameter of described magnetron sputtering plating is base target spacing is 45 millimeters ~ 95 millimeters, substrate temperature is 250 DEG C ~ 750 DEG C, flow 10sccm ~ the 35sccm of argon working gas, pressure 0.2Pa ~ 4Pa; And
By described film sample 500 DEG C ~ 800 DEG C vacuum annealing process 1 hour ~ 3 hours, obtain light-emitting film, the chemical general formula of described light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+; Wherein, Me 3(VF 8) 2for matrix, Mn 4+and Ti 4+for dopant ion.
4. the preparation method of light-emitting film according to claim 3, is characterized in that, described x is 0.03, and described y is 0.02.
5. the preparation method of light-emitting film according to claim 3, it is characterized in that, before described substrate being loaded the cavity of described magnetic-controlled sputtering coating equipment, also comprise and acetone, dehydrated alcohol and deionized water ultrasonic cleaning are used successively to described substrate, then carry out the step of plasma treatment.
6. the preparation method of the light-emitting film according to claim 3 or 5, is characterized in that, described substrate is the glass that one side is formed with transparent conductive film, and described film sample magnetron sputtering is formed on described transparent conductive film; Described cavity is evacuated to 5.0 × 10 -4pa.
7. the preparation method of light-emitting film according to claim 3, is characterized in that, described base target spacing is 60 millimeters; Described substrate temperature is 500 DEG C; The flow 25sccm of described argon working gas; Described pressure 2.0Pa.
8. the preparation method of light-emitting film according to claim 3, is characterized in that, the vacuum tightness of described anneal is 0.01Pa, and temperature is 600 DEG C, and the time is 2 hours.
9. an electroluminescent device, comprise stack gradually substrate, anode layer, luminescent layer and cathode layer, it is characterized in that, the material of described luminescent layer is light-emitting film, and the chemical general formula of described light-emitting film is Me 3(VF 8) 2: xEu 3+, yTb 3+; Wherein, Me 3(VF 8) 2for matrix, Me is Mg, Ca, Sr or Ba, Eu 3+and Tb 3+for dopant ion, x is 0.01 ~ 0.05, y is 0.01 ~ 0.04.
10. electroluminescent device according to claim 9, is characterized in that, described x is 0.03, and described y is 0.02.
CN201310443197.1A 2013-09-25 2013-09-25 Light-emitting thin film, preparation method thereof and electroluminescent device Pending CN104449710A (en)

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Application publication date: 20150325