CN103805186A - Copper-iridium co-doped vanadate light-emitting film, and preparation method and application thereof - Google Patents
Copper-iridium co-doped vanadate light-emitting film, and preparation method and application thereof Download PDFInfo
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- CN103805186A CN103805186A CN201210456902.7A CN201210456902A CN103805186A CN 103805186 A CN103805186 A CN 103805186A CN 201210456902 A CN201210456902 A CN 201210456902A CN 103805186 A CN103805186 A CN 103805186A
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Abstract
The invention provides a copper-iridium co-doped vanadate light-emitting film. The chemical formula of the copper-iridium co-doped vanadate light-emitting film is Me3(VO4)2: xCu<2+>, yIr<3+>, wherein x is greater than or equal to 0.01 and less than or equal to 0.08, y is greater than or equal to 0.01 and less than or equal to 0.1, Me3(VO4)2 is a matrix, the copper element and the iridium element are active elements, and Me is Mg, Ca, Sr or Ba. According to the electroluminescent spectra (EL) of the copper-iridium co-doped vanadate light-emitting film, strong light emitting peaks appear within the region of the wavelength of 611nm, and therefore, the copper-iridium co-doped vanadate light-emitting film can be applied to a thin-film electroluminescent display. The invention also provides a preparation method and an application of the copper-iridium co-doped vanadate light-emitting film.
Description
[technical field]
The present invention relates to a kind of copper iridium codoped vanadate light-emitting film and preparation method thereof and membrane electro luminescent device and preparation method thereof.
[background technology]
Thin-film electroluminescent displays (TFELD), due to its active illuminating, total solids, the advantage such as shock-resistant, reaction is fast, visual angle is large, Applicable temperature is wide, operation is simple, has caused and paid close attention to widely, and development rapidly.At present, research colour and extremely panchromatic TFELD, the luminous film of exploitation multiband, is the developing direction of this problem.But, can be applicable to the copper iridium codoped vanadate light-emitting film 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 copper iridium codoped vanadate light-emitting film that can be applicable to membrane electro luminescent device and preparation method thereof and membrane electro luminescent device and preparation method thereof.
A kind of copper iridium codoped vanadate light-emitting film, its chemical formula is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
In a preferred embodiment, the thickness of copper iridium codoped vanadate light-emitting film is 80nm～300nm.
A preparation method for copper iridium codoped vanadate light-emitting film, comprises the following steps:
Substrate is packed in the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10
-2pa～1.0 × 10
-3pa;
Regulating substrate temperature is 250 ℃～650 ℃, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to Me
3(VO
4)
2: xCu
2+, yIr
3+the stoichiometric ratio of each element is by (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and pass in reaction chamber, and
Then pass into oxygen, carrying out chemical vapour deposition, to obtain its chemical formula of copper iridium codoped vanadate light-emitting film be Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein, Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
In a preferred embodiment, described (C
5h
5)
2it is 3: 2 that Me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium mol ratio: (0.01～0.08): (0.01～0.1).In preferred embodiment, (C
5h
5)
2it is 3: 2: 0.04 that Me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium mol ratio: 0.05.
In a preferred embodiment, argon stream amount is 5～15sccm, and oxygen flow amount is 10～200sccm.
A kind of membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is copper iridium codoped vanadate light-emitting film, and the chemical formula of this copper iridium codoped vanadate light-emitting film is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
In a preferred embodiment, the thickness of luminescent layer is 80nm～300nm.
A preparation method for membrane electro luminescent device, comprises the following steps:
The substrate with anode is provided;
On described anode, form luminescent layer, the material of described luminescent layer is copper iridium codoped vanadate light-emitting film, and the chemical formula of this copper iridium codoped vanadate light-emitting film is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1;
On described luminescent layer, form negative electrode.
In a preferred embodiment, the preparation of described luminescent layer comprises the following steps:
Substrate is packed in the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10
-2pa～1.0 × 10
-3pa;
Regulating substrate temperature is 250 ℃～650 ℃, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to Me
3(VO
4)
2: xCu
2+, yIr
3+the stoichiometric ratio of each element is by (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and pass in reaction chamber, and wherein, argon stream amount is 5～15sccm, and
Then pass into oxygen, flow is 10～200sccm; Carrying out chemical vapour deposition, to obtain luminescent layer chemical formula be Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
Above-mentioned copper iridium codoped vanadate light-emitting film (Me
3(VO
4)
2: xCu
2+, yIr
3+) electroluminescent spectrum (EL) in, have very strong glow peak in 611nm 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 that the copper iridium codoped vanadate light-emitting film prepared of embodiment 1 and comparative example compare;
Fig. 3 is the XRD figure of the copper iridium codoped vanadate light-emitting film prepared of embodiment 1;
Fig. 4 is voltage and electric current and the brightness relationship figure of the membrane electro luminescent device prepared of embodiment 1.
[embodiment]
Below in conjunction with the drawings and specific embodiments, copper iridium codoped vanadate light-emitting film, its preparation method and membrane electro luminescent device and preparation method thereof are further illustrated.
The copper iridium codoped vanadate light-emitting film of one embodiment, its chemical formula is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
Preferably, the thickness of copper iridium codoped vanadate light-emitting film is 80nm～300nm, and x is that 0.05, y is 0.06.
Me in this copper iridium codoped vanadate light-emitting film
3(VO
4)
2be matrix, copper and iridium are active elements.In the electroluminescent spectrum (EL) of this copper iridium codoped vanadate light-emitting film, there is very strong glow peak in 611nm wavelength zone, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned copper iridium codoped vanadate light-emitting film, comprises the following steps:
Step S11, substrate is packed in the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10
-2pa～1.0 × 10
-3pa.
In the present embodiment, substrate is indium tin oxide glass (ITO), be appreciated that in other embodiments, also can be for fluorine doped tin oxide glass (FTO), mix the zinc oxide (AZO) of aluminium or mix the zinc oxide (IZO) of indium; Substrate is successively with toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into reaction chamber;
Preferably, the vacuum tightness of reaction chamber is 4.0 × 10
-3pa.
Step S12, by substrate thermal treatment 10 minutes～30 minutes at 600 ℃～800 ℃.
Step S13, adjusting substrate temperature are 250 ℃～650 ℃, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to Me
3(VO
4)
2: xCu
2+, yIr
3+the stoichiometric ratio of each element is by (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and pass in reaction chamber;
In a preferred embodiment, (C
5h
5)
2it is 3: 2 that Me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium mol ratio: (0.01～0.08): (0.01～0.1).
In preferred embodiment, ((C
5h
5)
2it is 3: 2 that Me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium mol ratio: (0.01～0.08): (0.01～0.1).
In a preferred embodiment, substrate temperature is preferably 500 ℃, and the rotating speed of substrate is preferably 300 revs/min, and argon stream amount is 5～15sccm.
In more preferred embodiment, argon stream amount is 10sccm.
Step S14, then pass into oxygen, carrying out chemical vapour deposition, to obtain its chemical formula of copper iridium codoped vanadate light-emitting film be Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
In a preferred embodiment, oxygen flow amount is 10～200sccm, and x is that 0.05, y is 0.06.
In more preferred embodiment, oxygen flow amount is 120sccm.
After step S15, deposition, stop passing into (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and argon gas, continue to pass into oxygen and make the temperature of copper iridium codoped vanadate light-emitting film be down to 80 ℃～150 ℃.
In present embodiment, preferred, make the temperature of copper iridium codoped vanadate light-emitting film be down to 100 ℃.
Be appreciated that step S12 and step S15 can omit.
Refer to Fig. 1, the membrane electro luminescent device 100 of an embodiment, this membrane electro luminescent device 100 comprises the substrate 1, anode 2, luminescent layer 3 and the negative electrode 4 that stack gradually.
Substrate 1 is glass substrate.Anode 2 is for being formed at the tin indium oxide (ITO) in glass substrate.The material of luminescent layer 3 is copper iridium codoped vanadate light-emitting film, and the chemical formula of this copper iridium codoped vanadate light-emitting film is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.The material of negative electrode 4 is silver (Ag).
The preparation method of above-mentioned membrane electro luminescent device, comprises the following steps:
Step S21, 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.Be appreciated that in other embodiments, also can be for fluorine doped tin oxide glass (FTO), mix the zinc oxide (AZO) of aluminium or mix the zinc oxide (IZO) of indium; The substrate 1 with anode 2 is successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning and use it is carried out to oxygen plasma treatment.
Step S22, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is copper iridium codoped vanadate light-emitting film, and the chemical formula of this copper iridium codoped vanadate light-emitting film is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
In present embodiment, luminescent layer 3 is made by following steps:
First, substrate is packed in the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10
-2pa～1.0 × 10
-3pa,
Moreover, by substrate thermal treatment 10 minutes～30 minutes at 600 ℃～800 ℃.Also can be without this step.
Secondly, regulating substrate temperature is 250 ℃～650 ℃, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to Me
3(VO
4)
2: xCu
2+, yIr
3+the stoichiometric ratio of each element is by (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and pass in reaction chamber;
In a preferred embodiment, (C
5h
5)
2it is 3: 2 that Me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium mol ratio: (0.01～0.08): (0.01～0.1).
In preferred embodiment, (C
5h
5)
2it is 3: 2 that Me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium mol ratio: (0.01～0.08): (0.01～0.1).
In a preferred embodiment, substrate temperature is preferably 500 ℃, and the rotating speed of substrate is preferably 300 revs/min, and argon stream amount is 5～15sccm.
In more preferred embodiment, argon stream amount is 10sccm.
Then pass into oxygen, carry out chemical vapour deposition film and form luminescent layer on described anode.
In preferred embodiment, the flow of oxygen is preferably 10～200sccm.
In more preferred embodiment, oxygen flow amount is 120sccm.
Finally, after deposition, stop passing into (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and argon gas, continue to pass into oxygen and make the temperature of copper iridium codoped vanadate light-emitting film be down to 80 ℃～150 ℃.
In present embodiment, preferred, make the temperature of copper iridium codoped vanadate light-emitting film be down to 100 ℃.Can be without this step.
Step S23, 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
Substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 4.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 20 minutes, then temperature is reduced to 500 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into organic source dicyclopentadiene magnesium ((C
5h
5)
2mg), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.04: 0.06, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Mg
3(VO
4)
2: 0.05Cu
2+, 0.06Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the copper iridium codoped vanadate light-emitting film obtaining in the present embodiment is Mg
3(VO
4)
2: 0.05Cu
2+, 0.06Ir
3+, wherein Mg
3(VO
4)
2be matrix, copper and iridium are active elements.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) that copper iridium codoped vanadate light-emitting film that embodiment 1 obtains and comparative example compare.As seen from Figure 2, curve 1 is the electroluminescent spectral curve of the copper iridium codoped vanadate light-emitting film that obtains of embodiment 1, can find out in 611nm wavelength zone have very strong glow peak can be applied in thin-film electroluminescent displays by curve 1, curve 2 is electroluminescent spectral curves of the iridium adulterated vanadate light-emitting film that obtains of comparative example, article two, curve comparison can be found out, the film that has added copper iridium codoped has better luminous efficiency than the sample that only has iridium doping.
Refer to Fig. 3, Fig. 3 is the XRD curve of the copper iridium codoped vanadate light-emitting film prepared of embodiment 1, test comparison standard P DF card.From Fig. 3, reference standard PDF card, the diffraction peak in figure is the peak crystallization of vanadate, does not occur the diffraction peak of doped element and other impurity, illustrates that the product that this preparation method obtains has good crystalline quality.
Refer to Fig. 4, Fig. 4 is voltage and electric current and the brightness relationship figure of the membrane electro luminescent device prepared of embodiment 1, and in accompanying drawing 4, curve 1 is voltage and current density relation curve, can find out that device starts from 5.5V luminous, curve 2 is voltage and brightness relationship curve, and high-high brightness is 70cd/m
2, show that device has the good characteristics of luminescence.
Embodiment 2
Substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 10 minutes, then temperature is reduced to 250 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into organic source dicyclopentadiene magnesium ((C
5h
5)
2mg), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.01: 0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Mg
3(VO
4)
2: 0.01Cu
2+, 0.01Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 3
Substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-2pa; Then substrate is carried out to 700 ℃ of thermal treatments 30 minutes, then temperature is reduced to 650 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into organic source dicyclopentadiene magnesium ((C
5h
5)
2mg), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.08: 0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Mg
3(VO
4)
2: 0.08Cu
2+, 0.1Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 4: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 4.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 20 minutes, then temperature is reduced to 500 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into organic source dicyclopentadiene calcium ((C
5h
5)
2ca), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.05: 0.06, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Ca
3(VO
4)
2: 0.05Cu
2+, 0.06Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 5: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 10 minutes, then temperature is reduced to 250 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into organic source dicyclopentadiene calcium ((C
5h
5)
2ca), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.01: 0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Ca
3(VO
4)
2: 0.01Cu
2+, 0.01Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 6: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-2pa; Then substrate is carried out to 700 ℃ of thermal treatments 30 minutes, then temperature is reduced to 650 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into organic source dicyclopentadiene calcium ((C
5h
5)
2ca), oxidation diacetyl acetone closes vanadium (VO (acac)
2) acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.08: 0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Ca
3(VO
4)
2: 0.08Cu
2+, 0.1Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 7: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 4.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 20 minutes, then temperature is reduced to 500 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into organic source dicyclopentadiene strontium ((C
5h
5)
2sr), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium Ir (acac)
3mol ratio be 3: 2: 0.05: 0.06, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Sr
3(VO
4)
2: 0.05Cu
2+, 0.06Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 8: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 10 minutes, then temperature is reduced to 250 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into organic source dicyclopentadiene strontium ((C
5h
5)
2sr), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.01: 0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Sr
3(VO
4)
2: 0.01Cu
2+, 0.01Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 9: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-2pa; Then substrate is carried out to 700 ℃ of thermal treatments 30 minutes, then temperature is reduced to 650 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into organic source dicyclopentadiene strontium ((C
5h
5)
2sr), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.08: 0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Sr
3(VO
4)
2: 0.08Cu
2+, 0.1Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 10: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 4.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 20 minutes, then temperature is reduced to 500 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into organic source dicyclopentadiene barium ((C
5h
5)
2ba), oxidation diacetyl acetone closes vanadium (VO (acac)
2), acetylacetone copper (Cu (acac)
2) and methyl ethyl diketone iridium (Ir (acac)
3) mol ratio be 3: 2: 0.02: 0.06, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Ba
3(VO
4)
2: 0.02Cu
2+, 0.06Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 11: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-3pa; Then substrate is carried out to 700 ℃ of thermal treatments 10 minutes, then temperature is reduced to 250 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into organic source dicyclopentadiene barium ((C
5h
5)
2ba), oxidation diacetyl acetone closes vanadium (VO (acac)
2) and acetylacetone copper (Cu (acac)
2), methyl ethyl diketone iridium Ir (acac)
3mol ratio be 3: 2: 0.05: 0.07, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Ba
3(VO
4)
2: 0.05Cu
2+, 0.07Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 12: substrate is the ito glass that Nan Bo company buys, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, sends into equipment reaction chamber.The vacuum tightness of cavity is evacuated to 1.0 × 10 with mechanical pump and molecular pump
-2pa; Then substrate is carried out to 700 ℃ of thermal treatments 30 minutes, then temperature is reduced to 650 ℃.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into organic source dicyclopentadiene barium ((C
5h
5)
2ba), oxidation diacetyl acetone closes vanadium (VO (acac)
2) and acetylacetone copper (Cu (acac)
2), methyl ethyl diketone iridium Ir (acac)
3mol ratio be 3: 2: 0.03: 0.06, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into oxygen, oxygen flow amount is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical oxygen, and temperature drops to below 100 ℃, takes out sample Ba
3(VO
4)
2: 0.03Cu
2+, 0.06Ir
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a copper iridium codoped vanadate light-emitting film, is characterized in that, its chemical formula is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
2. copper iridium codoped vanadate light-emitting film according to claim 1, is characterized in that, the thickness of described copper iridium codoped vanadate light-emitting film is 80nm～300nm.
3. a preparation method for copper iridium codoped vanadate light-emitting film, is characterized in that, comprises the following steps:
Substrate is packed in the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10
-2pa～1.0 × 10
-3pa;
Regulating substrate temperature is 250 ℃～650 ℃, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to Me
3(VO
4)
2: xCu
2+, yIr
3+the stoichiometric ratio of each element is by (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and pass in reaction chamber; And
Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical formula be Me
3(VO
4)
2: xCu
2+, yIr
3+copper iridium codoped vanadate light-emitting film, wherein, Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
4. the preparation method of copper iridium codoped vanadate light-emitting film according to claim 3, is characterized in that described (C
5h
5)
2it is 3: 2 that Me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium mol ratio: (0.01～0.08): (0.01～0.1).
5. the preparation method of copper iridium codoped vanadate light-emitting film according to claim 3, is characterized in that, described argon stream amount is 5～15sccm, and described oxygen flow amount is 10～200sccm.
6. the preparation method of copper iridium codoped vanadate light-emitting film according to claim 3, is characterized in that, described substrate is packed into after described reaction chamber the thermal treatment 10 minutes～30 minutes at 600 ℃～800 ℃ of described substrate.
7. a membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, it is characterized in that, the material of described luminescent layer is copper iridium codoped vanadate light-emitting film, and the chemical formula of this copper iridium codoped vanadate light-emitting film is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1.
8. membrane electro luminescent device according to claim 7, is characterized in that, the thickness of described luminescent layer is 80nm～300nm.
9. a preparation method for membrane electro luminescent device, is characterized in that, comprises the following steps:
The substrate with anode is provided;
On described anode, form luminescent layer, the film of described luminescent layer is copper iridium codoped vanadate light-emitting film, and the chemical formula of this copper iridium codoped vanadate light-emitting film is Me
3(VO
4)
2: xCu
2+, yIr
3+, wherein Me
3(VO
4)
2be matrix, copper and iridium are active elements, and Me is Mg, Ca, Sr or Ba, 0.01≤x≤0.08,0.01≤y≤0.1;
On described luminescent layer, form negative electrode.
10. the preparation method of membrane electro luminescent device according to claim 9, is characterized in that, the preparation of described luminescent layer comprises the following steps:
Described substrate is packed into the reaction chamber of chemical vapor depsotition equipment, and the vacuum tightness of reaction chamber is set to 1.0 × 10
-2pa～1.0 × 10
-3pa;
Regulating substrate temperature is 250 ℃～650 ℃, and rotating speed is 50 revs/min～1000 revs/min, adopts argon stream as carrier, according to Me
3(VO
4)
2: xCu
2+, yIr
3+the stoichiometric ratio of each element is by (C
5h
5)
2me, oxidation diacetyl acetone close vanadium, acetylacetone copper and methyl ethyl diketone iridium and pass in reaction chamber, and wherein, argon stream amount is 5～15sccm,
Then pass into oxygen, oxygen flow amount is 10～200sccm; Deposit film forms luminescent layer on described anode.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449659A (en) * | 2014-12-12 | 2015-03-25 | 武汉纺织大学 | Method for rapidly preparing large-area multi-chromic composite film and multi-chromic composite film |
| CN111807410A (en) * | 2020-06-08 | 2020-10-23 | 中国地质大学（武汉） | Copper-doped vanadate electrode material and preparation method and application thereof |
-
2012
- 2012-11-14 CN CN201210456902.7A patent/CN103805186A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449659A (en) * | 2014-12-12 | 2015-03-25 | 武汉纺织大学 | Method for rapidly preparing large-area multi-chromic composite film and multi-chromic composite film |
| CN111807410A (en) * | 2020-06-08 | 2020-10-23 | 中国地质大学（武汉） | Copper-doped vanadate electrode material and preparation method and application thereof |
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Application publication date: 20140521 |