CN104119894A - Titanium-doped alkaline earth borophosphate luminescent thin film and preparation method and application thereof - Google Patents
Titanium-doped alkaline earth borophosphate luminescent thin film and preparation method and application thereof Download PDFInfo
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- CN104119894A CN104119894A CN201310149446.6A CN201310149446A CN104119894A CN 104119894 A CN104119894 A CN 104119894A CN 201310149446 A CN201310149446 A CN 201310149446A CN 104119894 A CN104119894 A CN 104119894A
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Abstract
A titanium doped alkaline earth borophosphate luminescent thin film has a chemical formula of Me(PO4)x(BO3) 1-x:yTi<4+>, wherein x is greater than or equal to 0.1 and is less than or equal to 0.4, y is greater than or equal to 0.01 and is less than or equal to 0.06, Me(PO4)x(BO3) 1-x is a matrix, titanium element is an activation element, and Me is Mg, Ca, Sr or Ba. In an electroluminescence (EL) spectrum of the titanium doped alkaline earth borophosphate luminescent thin film, a wavelength region of 410 nm has very strong luminescence peaks, and the titanium doped alkaline earth borophosphate luminescent thin film can be used in a thin-film electroluminescent display. The invention also provides a preparation method and application of the titanium doped alkaline earth borophosphate luminescent thin film.
Description
[technical field]
The present invention relates to a kind of titanium doped alkaline-earth borophosphate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.
[background technology]
Thin-film electroluminescent displays (TFELD), due to its active illuminating, total solids, the advantage such as shock-resistant, reaction is fast, visual angle is large, Applicable temperature is wide, operation is simple, has caused and paid close attention to widely, and development rapidly.At present, research colour and extremely panchromatic TFELD, the luminous film of exploitation multiband, is the developing direction of this problem.But, can be applicable to the titanium doped alkaline-earth borophosphate 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 titanium doped alkaline-earth borophosphate light-emitting film that can be applicable to membrane electro luminescent device, this titanium doped alkaline-earth borophosphate light-emitting film electroluminescent device of its preparation method and preparation method thereof.
A titanium doped alkaline-earth borophosphate light-emitting film, its chemical formula is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
The thickness of titanium doped alkaline-earth borophosphate light-emitting film is 80nm～300nm.
A preparation method for titanium doped alkaline-earth borophosphate 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 (PO
4)
x(BO
3)
1-x: yTi
4+the stoichiometric ratio of each element passes into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate in reaction chamber, and
Then pass into oxygen, carrying out chemical vapour deposition, to obtain titanium doped its chemical formula of alkaline-earth borophosphate light-emitting film be Me (PO
4)
x(BO
3)
1-x: yTi
4+titanium doped alkaline-earth borophosphate light-emitting film, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
Dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate mol ratio are 1:(0.1～0.4): (0.7～0.9): (0.01～0.06);
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 substrate, anode layer, luminescent layer and the cathode layer stacking gradually, the material of described luminescent layer is titanium doped alkaline-earth borophosphate light-emitting film, and the chemical formula of this titanium doped alkaline-earth borophosphate light-emitting film is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
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 titanium doped alkaline-earth borophosphate light-emitting film, and the chemical formula of this titanium doped alkaline-earth borophosphate light-emitting film is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba;
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 (PO
4)
x(BO
3)
1-x: yTi
4+the stoichiometric ratio of each element passes into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate 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 (PO
4)
x(BO
3)
1-x: yTi
4+titanium doped alkaline-earth borophosphate light-emitting film, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
Above-mentioned titanium doped alkaline-earth borophosphate light-emitting film (Me (PO
4)
x(BO
3)
1-x: yTi
4+) electroluminescent spectrum (EL) in, in 410nm 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 the titanium doped alkaline-earth borophosphate light-emitting film of embodiment 1 preparation;
Fig. 3 is the Raman spectrum of the titanium doped alkaline-earth borophosphate light-emitting film 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, titanium doped alkaline-earth borophosphate light-emitting film, its preparation method and membrane electro luminescent device and preparation method thereof are further illustrated.
The titanium doped alkaline-earth borophosphate light-emitting film of one embodiment, its chemical formula is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
Preferably, the thickness of titanium doped alkaline-earth borophosphate light-emitting film is 80nm～300nm, and x is that 0.3, y is 0.03.
Me (PO in this titanium doped alkaline-earth borophosphate light-emitting film
4)
x(BO
3)
1-xbe matrix, titanium elements is active element.In the electroluminescent spectrum of this titanium doped alkaline-earth borophosphate light-emitting film (EL), in 410nm wavelength zone, there is very strong glow peak, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned titanium doped alkaline-earth borophosphate 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), 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 Me (PO
4)
x(BO
3)
1-x: yTi
4+the stoichiometric ratio of each element passes into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate in reaction chamber;
In a preferred embodiment, dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate mol ratio are 1:(0.1～0.4): (0.7～0.9): (0.01～0.06).
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 titanium doped its chemical formula of alkaline-earth borophosphate light-emitting film be Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
In a preferred embodiment, oxygen flow amount is 10～200sccm, and x is that 0.3, y is 0.03.
In more preferred embodiment, oxygen flow amount is 120sccm.
After step S15, deposition, stop passing into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate and helium, continue to pass into the temperature that oxygen makes titanium doped alkaline-earth borophosphate light-emitting film and be down to 80 ℃～150 ℃.
In present embodiment, preferred, make the temperature of titanium doped alkaline-earth borophosphate 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 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 titanium doped alkaline-earth borophosphate light-emitting film, and the chemical formula of this titanium doped alkaline-earth borophosphate light-emitting film is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.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 titanium doped alkaline-earth borophosphate light-emitting film, and the chemical formula of this titanium doped alkaline-earth borophosphate light-emitting film is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
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 (PO
4)
x(BO
3)
1-x: yTi
4+the stoichiometric ratio of each element passes into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate in reaction chamber;
In a preferred embodiment, dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate mol ratio are 1:(0.1～0.4): (0.7～0.9): (0.01～0.06);
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, stop passing into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate and helium after deposition, continue to pass into the temperature that oxygen makes titanium doped alkaline-earth borophosphate light-emitting film and be down to 80 ℃～150 ℃.
In present embodiment, preferred, make the temperature of titanium doped alkaline-earth borophosphate 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), 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 dicyclopentadiene magnesium (Mg (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and titanium tetraisopropylate (Ti{OCH (CH
3)
2}
4) mol ratio be 1:0.3:0.7:0.03, 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 (PO
4)
0.3(BO
3)
0.7: 0.03Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the titanium doped alkaline-earth borophosphate light-emitting film obtaining in the present embodiment is Mg (PO
4)
0.3(BO
3)
0.7: 0.03Ti
4+, Mg (PO wherein
4)
0.3(BO
3)
0.7be matrix, titanium elements is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the titanium doped alkaline-earth borophosphate light-emitting film that embodiment 1 obtains.The electroluminescent spectral curve of the titanium doped alkaline-earth borophosphate light-emitting film that as seen from Figure 2, embodiment 1 obtains has very strong glow peak to be applied in thin-film electroluminescent displays in 410nm wavelength zone.
Refer to Fig. 3, Fig. 3 is the Raman spectrum of the titanium doped alkaline-earth borophosphate light-emitting film of embodiment 1 preparation, Raman peaks in figure is depicted as alkaline-earth borophosphate characteristic peak, does not occur the peak of doped element and other impurity, illustrates that doped element and substrate material have formed good bonding.
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 curve 1 is voltage-to-current density, can find out that device starts from 5.5V luminous, and curve 2 is voltage-brightness, and high-high brightness is 89cd/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 machine source dicyclopentadiene magnesium (Mg (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and titanium tetraisopropylate (Ti{OCH (CH
3)
2}
4) mol ratio be 1:0.2:0.8:0.06, 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 (PO
4)
0.2(BO
3)
0.8: 0.06Ti
4+.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 dicyclopentadiene magnesium (Mg (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.1:0.9:0.01, 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 (PO
4)
0.1(BO
3)
0.9: 0.01Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 4: substrate is ito glass, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, then clean with distilled water flushing, after nitrogen is air-dry, send 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 dicyclopentadiene calcium (Ca (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and titanium tetraisopropylate (Ti{OCH (CH
3)
2}
4) mol ratio be 1:0.3:0.7:0.03, 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 (PO
4)
0.3(BO
3)
0.7: 0.03Ti
4+last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 5: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 machine source dicyclopentadiene calcium (Ca (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and titanium tetraisopropylate (Ti{OCH (CH
3)
2}
4) mol ratio be 1:0.2:0.8:0.06, 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 (PO
4)
0.2(BO
3)
0.8: 0.06Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 6: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 dicyclopentadiene calcium (Ca (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.1:0.9:0.01, 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 (PO
4)
0.1(BO
3)
0.9: 0.01Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 7: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 dicyclopentadiene strontium (Sr (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.3:0.7:0.03, 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 (PO
4)
0.3(BO
3)
0.7: 0.03Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 8: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 dicyclopentadiene strontium (Sr (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.2:0.8:0.06, 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 (PO
4)
0.2(BO
3)
0.8: 0.06Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 9: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 machine source dicyclopentadiene strontium (Sr (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.1:0.9:0.01, 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 (PO
4)
0.1(BO
3)
0.9: 0.01Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 10: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 machine source dicyclopentadiene barium (Ba (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.3:0.7:0.03, 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 (PO
4)
0.3(BO
3)
0.7: 0.03Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 11: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 machine source dicyclopentadiene barium (Ba (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.2:0.8:0.06, 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 (PO
4)
0.2(BO
3)
0.8: 0.06Ti
4+.Last evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 12: the ito glass that substrate Wei Nan glass company buys, successively use toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and then clean with distilled water flushing, after nitrogen is air-dry, send 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 machine source dicyclopentadiene barium (Ba (C
5h
5)
2), borine (BH
3), phosphine (PH
3) and the mol ratio of titanium tetraisopropylate (Ti{OCH (CH3) 2}4) be 1:0.1:0.9:0.01, 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 Ba (PO
4)
0.1(BO
3)
0.9: 0.01Ti
4+.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 titanium doped alkaline-earth borophosphate light-emitting film, is characterized in that, its chemical formula is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
2. titanium doped alkaline-earth borophosphate light-emitting film according to claim 1, is characterized in that, the thickness of described titanium doped alkaline-earth borophosphate light-emitting film is 80nm～300nm.
3. a preparation method for titanium doped alkaline-earth borophosphate 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 (PO
4)
x(BO
3)
1-x: yTi
4+the stoichiometric ratio of each element passes into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate in reaction chamber; And
Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical formula be Me (PO
4)
x(BO
3)
1-x: yTi
4+titanium doped alkaline-earth borophosphate light-emitting film, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
4. the preparation method of titanium doped alkaline-earth borophosphate light-emitting film according to claim 3, it is characterized in that, described dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate mol ratio are 1:(0.1～0.4): (0.7～0.9): (0.01～0.06).
5. the preparation method of titanium doped alkaline-earth borophosphate 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 titanium doped alkaline-earth borophosphate 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 substrate, anode layer, luminescent layer and the cathode layer stacking gradually, it is characterized in that, the material of described luminescent layer is titanium doped alkaline-earth borophosphate light-emitting film, and the chemical formula of this titanium doped alkaline-earth borophosphate light-emitting film is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba.
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 titanium doped alkaline-earth borophosphate light-emitting film, and the chemical formula of this titanium doped alkaline-earth borophosphate light-emitting film is Me (PO
4)
x(BO
3)
1-x: yTi
4+, wherein, 0.1≤x≤0.4,0.01≤y≤0.06, Me (PO
4)
x(BO
3)
1-xbe matrix, titanium elements is active element, and Me is Mg, Ca, Sr or Ba;
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 Me (PO
4)
x(BO
3)
1-x: yTi
4+the stoichiometric ratio of each element passes into dicyclopentadiene alkaline earth metal source, borine, phosphine and titanium tetraisopropylate 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753363A (en) * | 2016-11-29 | 2017-05-31 | 河北大学 | A kind of fluorescent material for warm white LED and preparation method thereof |
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|---|---|---|---|---|
| CN1338501A (en) * | 2001-09-27 | 2002-03-06 | 中国科学院长春应用化学研究所 | Process for preparing luminous rare-earth material |
| CN102134486A (en) * | 2010-01-26 | 2011-07-27 | 海洋王照明科技股份有限公司 | Vacuum ultraviolet induced green emitting phosphor and preparation method thereof |
| WO2012055729A1 (en) * | 2010-10-26 | 2012-05-03 | Leuchtstoffwerk Breitungen Gmbh | Borophosphate phosphor and light source |
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2013
- 2013-04-26 CN CN201310149446.6A patent/CN104119894A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1338501A (en) * | 2001-09-27 | 2002-03-06 | 中国科学院长春应用化学研究所 | Process for preparing luminous rare-earth material |
| CN102134486A (en) * | 2010-01-26 | 2011-07-27 | 海洋王照明科技股份有限公司 | Vacuum ultraviolet induced green emitting phosphor and preparation method thereof |
| WO2012055729A1 (en) * | 2010-10-26 | 2012-05-03 | Leuchtstoffwerk Breitungen Gmbh | Borophosphate phosphor and light source |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106753363A (en) * | 2016-11-29 | 2017-05-31 | 河北大学 | A kind of fluorescent material for warm white LED and preparation method thereof |
| CN106753363B (en) * | 2016-11-29 | 2019-05-07 | 河北大学 | A kind of fluorescent powder and preparation method thereof for warm white LED |
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