CN103571476A - Cerium-doped Group-III molybdate light-emitting film, preparation method and application thereof - Google Patents
Cerium-doped Group-III molybdate light-emitting film, preparation method and application thereof Download PDFInfo
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- CN103571476A CN103571476A CN201210268340.3A CN201210268340A CN103571476A CN 103571476 A CN103571476 A CN 103571476A CN 201210268340 A CN201210268340 A CN 201210268340A CN 103571476 A CN103571476 A CN 103571476A
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Abstract
A cerium-doped Group-III molybdate light-emitting film has a chemical formula of Re2 (MoO4) 3:xCe<3+>, wherein 0.01<=x<= 0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion, Re2 (MoO4) 3 is a matrix, and cerium element is an active element. In the electroluminescent spectra (EL) of the cerium-doped three-family molybdate light-emitting film, strong light-emitting peaks at a 620nm wavelength region exist, so that the light-emitting film can be used in a thin film electroluminescent display. The invention also provides a preparation method and application of the cerium-doped Group-III molybdate light-emitting film.
Description
Technical field
The present invention relates to light-emitting film, its preparation method, membrane electro luminescent device of a kind of cerium doping three races molybdate 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 light-emitting film of the cerium doping three races molybdate 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 and can be applicable to the light-emitting film of the cerium doping three races molybdate of membrane electro luminescent device, light-emitting film electroluminescent device of this cerium doping three races molybdate of its preparation method and preparation method thereof.
A light-emitting film for cerium doping three races molybdate, its chemical formula is Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion, Re
2(MoO
4)
3be matrix, Ce elements is active element.
In a preferred embodiment, the thickness of the light-emitting film of cerium doping three races molybdate is 80nm ~ 300nm.
A preparation method for the light-emitting film of doping three races molybdate, 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 Re
2(MoO
4)
3: xCe
3+the stoichiometric ratio general of each element (tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium pass in reaction chamber, and
Then pass into oxygen, carrying out its chemical formula of light-emitting film that chemical vapour deposition obtains cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion.
Tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium mol ratio are (1.95 ~ 1.99) in a preferred embodiment: 3:(0.01 ~ 0.05);
In preferred embodiment, tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium mol ratio are 1.97:3:0.03;
In a preferred embodiment, argon stream amount is 5 ~ 15sccm, and oxygen flow amount is 10sccm ~ 200sccm.
A kind of membrane electro luminescent device, this membrane electro luminescent device comprises substrate, anode layer, luminescent layer and the cathode layer stacking gradually, the material of described luminescent layer is the light-emitting film of cerium doping three races molybdate, and the chemical formula of the light-emitting film of this cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion.
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 the light-emitting film of cerium doping three races molybdate, and the chemical formula of the light-emitting film of this cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion;
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 Re
2(MoO
4)
3: xCe
3+the stoichiometric ratio of each element passes into tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium 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 Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion.
The above-mentioned cerium doping molybdate light-emitting film (Re of three races
2(MoO
4)
3: xCe
3+) electroluminescent spectrum (EL) in, in 620nm wavelength zone, have very strong glow peak, can be applied in thin-film electroluminescent displays.
Accompanying drawing explanation
Fig. 1 is the structural representation of the membrane electro luminescent device of an embodiment;
Fig. 2 is the electroluminescent spectrogram of light-emitting film of the cerium doping three races molybdate of embodiment 1 preparation;
Fig. 3 is the XRD figure of light-emitting film of the cerium doping three races molybdate of embodiment 1 preparation;
Fig. 4 is voltage and electric current and the brightness relationship figure of the membrane electro luminescent device of embodiment 1 preparation.
Embodiment
Below in conjunction with the drawings and specific embodiments, light-emitting film, its preparation method and membrane electro luminescent device of cerium doping three races molybdate and preparation method thereof are further illustrated.
The light-emitting film of the cerium doping three races molybdate of one embodiment, its chemical formula is Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion, Re
2(MoO
4)
3be matrix, Ce elements is active element.
Preferably, the thickness of the light-emitting film of cerium doping three races molybdate is 80nm ~ 300nm, and x is 0.03.
Re in the light-emitting film of this cerium doping three races molybdate
2(MoO
4)
3be matrix, Ce elements is active element, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion.In the electroluminescent spectrum (EL) of the light-emitting film of this cerium doping three races molybdate, in 620nm wavelength zone, there is very strong glow peak, can be applied in thin-film electroluminescent displays.
The preparation method of the light-emitting film of above-mentioned cerium doping three races molybdate, 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), is 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 used 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 Re
2(MoO
4)
3: xCe
3+the stoichiometric ratio of each element passes into tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium in reaction chamber;
In a preferred embodiment, tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium mol ratio are (1.95 ~ 1.99): 3:(0.01 ~ 0.05);
In preferred embodiment, tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium mol ratio are 1.97:3:0.03,
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 its chemical formula of light-emitting film that chemical vapour deposition obtains cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, wherein, Re
2(MoO
4)
3be matrix, Ce elements is active element, and wherein, Re is aluminum ion, gallium ion, indium ion or thallium ion, 0.01≤x≤0.05.
In a preferred embodiment, oxygen flow amount is 10 ~ 200sccm, and x is 0.03.
In more preferred embodiment, oxygen flow amount is 120sccm.
After step S15, deposition, stop passing into tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium and argon gas, continue to pass into oxygen and make the temperature of the light-emitting film of cerium doping three races molybdate be down to 80 ℃ ~ 150 ℃.
In present embodiment, preferred, make the temperature of the light-emitting film of cerium doping three races molybdate 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 substrate 1, anode 2, luminescent layer 3 and the negative electrode 4 stacking 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 the light-emitting film of cerium doping three races molybdate, and the chemical formula of the light-emitting film of this cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, wherein, Re
2(MoO
4)
3be matrix, Ce elements is active element, and wherein, Re is aluminum ion, gallium ion, indium ion or thallium ion, 0.01≤x≤0.05.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 the light-emitting film of cerium doping three races molybdate, and the chemical formula of the light-emitting film of this cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, wherein, Re
2(MoO
4)
3be matrix, Ce elements is active element, and wherein, Re is aluminum ion, gallium ion, indium ion or thallium ion, 0.01≤x≤0.05.
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 Re
2(MoO
4)
3: xCe
3+the stoichiometric ratio of each element passes into tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium in reaction chamber;
In a preferred embodiment, tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium mol ratio are (1.95 ~ 1.99): 3:(0.01 ~ 0.05)
In preferred embodiment, tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium mol ratio are 1.97:3:0.03
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 tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium and argon gas, continue to pass into oxygen and make the temperature of the light-emitting film of cerium doping three races molybdate be down to 80 ℃ ~ 150 ℃.
In present embodiment, preferred, make the temperature of the light-emitting film of cerium doping three races molybdate 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), by evaporation, is formed.
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 * 10
-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 tetramethyl-pimelic acid aluminium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.03 with four, and gas of carrier gas is argon gas, and 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 Al
2(MoO
4)
3: 0.03Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the light-emitting film of the cerium doping three races molybdate obtaining in the present embodiment is Al
2(MoO
4)
3: 0.03Ce
3+, Al wherein
2(MoO
4)
3be matrix, Ce elements is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the light-emitting film of the cerium doping three races molybdate obtaining.As seen from Figure 2, in electroluminescence spectrum, in 620nm wavelength zone, there is very strong glow peak to be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of light-emitting film of the cerium doping three races molybdate of embodiment 1 preparation, test comparison standard P DF card.As can be seen from Figure 3 all diffraction peaks can find out that all diffraction peaks are the crystalline characteristics peaks that three races's molybdate is corresponding, do not occur doped element and the relevant diffraction peak of other impurity, and interpret sample has good crystalline structure.
Refer to Fig. 4, Fig. 4 is voltage and electric current and the brightness relationship figure of the membrane electro luminescent device of embodiment 1 preparation, and in accompanying drawing 4, curve 1 is voltage and current density relation curve, can find out that device starts from 5.0V luminous, curve 2 is voltage and brightness relationship curve, and high-high brightness is 118cd/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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid aluminium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.06 with four, and gas of carrier gas is argon gas, and 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 Al
2(MoO
4)
3: 0.06Ce
3+.Last 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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid aluminium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.01 with four, and gas of carrier gas is argon gas, and 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 Al
2(MoO
4)
3: 0.01Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid gallium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.03 with four, and gas of carrier gas is argon gas, and 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 Ga
2(MoO
4)
3: 0.03Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid gallium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.06 with four, and gas of carrier gas is argon gas, and 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 Ga
2(MoO
4)
3: 0.06Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 * 10
-3pa; 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 tetramethyl-pimelic acid gallium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.01 with four, and gas of carrier gas is argon gas, and 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 Ga
2(MoO
4)
3: 0.01Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 7
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid indium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.03 with four, and gas of carrier gas is argon gas, and 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 In
2(MoO
4)
3: 0.03Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid indium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.06 with four, and gas of carrier gas is argon gas, and 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 In
2(MoO
4)
3: 0.06Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 9
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid indium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.01 with four, and gas of carrier gas is argon gas, and 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 In
2(MoO
4)
3: 0.01Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 10
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 * 10
-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 tetramethyl-pimelic acid thallium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.03 with four, and gas of carrier gas is argon gas, and 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 Tl
2(MoO
4)
3: 0.03Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 11
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid thallium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.06 with four, and gas of carrier gas is argon gas, and 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 Tl
2(MoO
4)
3: 0.06Ce
3+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 12
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.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-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 tetramethyl-pimelic acid thallium, hexacarbonylmolybdenum Mo (CO)
6the mol ratio of (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 2:3:0.01 with four, and gas of carrier gas is argon gas, and 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 Tl
2(MoO
4)
3: 0.01Ce
3+.Last 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 light-emitting film for cerium doping three races molybdate, is characterized in that, its chemical formula is Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion, Re
2(MoO
4)
3be matrix, Ce elements is active element.
2. the light-emitting film of cerium according to claim 1 doping three races molybdate, is characterized in that, the thickness of the light-emitting film of described cerium doping three races molybdate is 80nm ~ 300nm.
3. a preparation method for the light-emitting film of cerium doping three races molybdate, 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 Re
2(MoO
4)
3: xCe
3+the stoichiometric ratio of each element passes into tetramethyl-pimelic acid three-group metal salt, molybdenum carbonyl and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium in reaction chamber; And
Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical formula be Re
2(MoO
4)
3: xCe
3+the light-emitting film of cerium doping three races molybdate, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion.
4. the preparation method of the light-emitting film of cerium according to claim 3 doping three races molybdate, it is characterized in that, described tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3,5-heptadione acid) cerium mol ratio is (1.95 ~ 1.99): 3:(0.01 ~ 0.05).
5. the preparation method of the light-emitting film of cerium according to claim 3 doping three races molybdate, is characterized in that, described argon stream amount is 5 ~ 15sccm, and described oxygen flow amount is 10 ~ 200sccm.
6. the preparation method of the light-emitting film of cerium according to claim 3 doping three races molybdate, 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 substrate, anode layer, luminescent layer and the cathode layer stacking gradually, it is characterized in that, the material of described luminescent layer is the light-emitting film of cerium doping three races molybdate, and the chemical formula of the light-emitting film of this cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion.
8. the preparation method of 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 the light-emitting film of cerium doping three races molybdate, and the chemical formula of the light-emitting film of this cerium doping three races molybdate is Re
2(MoO
4)
3: xCe
3+, wherein, 0.01≤x≤0.05, Re is aluminum ion, gallium ion, indium ion or thallium ion;
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:
The reaction chamber that described substrate is packed into 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 Re
2(MoO
4)
3: xCe
3+the stoichiometric ratio of each element passes into tetramethyl-pimelic acid three-group metal salt, hexacarbonylmolybdenum and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333731A (en) * | 2023-04-07 | 2023-06-27 | 上海理工大学 | Near ultraviolet/blue light excited aluminum boron/molybdate near infrared fluorescent powder and preparation method thereof |
-
2012
- 2012-07-31 CN CN201210268340.3A patent/CN103571476A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333731A (en) * | 2023-04-07 | 2023-06-27 | 上海理工大学 | Near ultraviolet/blue light excited aluminum boron/molybdate near infrared fluorescent powder and preparation method thereof |
| CN116333731B (en) * | 2023-04-07 | 2024-05-14 | 上海理工大学 | Near ultraviolet/blue light excited aluminum boron/molybdate near infrared fluorescent powder and preparation method thereof |
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