CN103805177A - Titanium-doped borate luminescent film, preparation method and application thereof - Google Patents

Titanium-doped borate luminescent film, preparation method and application thereof Download PDF

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CN103805177A
CN103805177A CN201210456811.3A CN201210456811A CN103805177A CN 103805177 A CN103805177 A CN 103805177A CN 201210456811 A CN201210456811 A CN 201210456811A CN 103805177 A CN103805177 A CN 103805177A
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titanium
emitting film
substrate
meb
doped borate
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周明杰
王平
陈吉星
黄辉
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention provides a titanium-doped borate luminescent film. The chemical formula of the film is MeB4O7:xTi<4+>, wherein, x is more than or equal to 0.01 and less than or equal to 0.05, MeB4O7 is matrix, titanium is an active element, x is more than or equal to 0.01 and less than or equal to 0.05, and Me is Mg, Ca, Sr or Ba. In the electroluminescent (EL) spectra of the titanium-doped borate luminescent film, very strong luminescent peaks are present at the wavelength area of 430nm, so the luminescent film can be applied to thin-film electroluminescent displays. The invention also provides a preparation method and an application of the titanium-doped borate luminescent film.

Description

Titanium doped borate light-emitting film, preparation method and application thereof
[technical field]
The present invention relates to a kind of titanium doped borate 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 titanium doped borate 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 borate 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 titanium doped borate light-emitting film, its chemical formula is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
A preparation method for titanium doped borate 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 MeB 4o 7: xTi 4+the stoichiometric ratio of each element is by Me (C 5h 5) 2, BH 3pass in reaction chamber with titanium tetraisopropylate, and
Then pass into oxygen, carrying out chemical vapour deposition, to obtain titanium doped its chemical formula of borate light-emitting film be MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
In a preferred embodiment, Me (C 5h 5) 2, BH 3with titanium tetraisopropylate mol ratio be 1:4:(0.01 ~ 0.05).
In preferred embodiment, Me (C 5h 5) 2, BH 3with titanium tetraisopropylate mol ratio be 1:4:0.02.
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, and the material of described luminescent layer is titanium doped borate light-emitting film, and the chemical formula of this titanium doped borate light-emitting film is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
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 titanium doped borate light-emitting film, and the chemical formula of this titanium doped borate light-emitting film is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, 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 MeB 4o 7: xTi 4+the stoichiometric ratio of each element is by Me (C 5h 5) 2, BH 3pass in reaction chamber with titanium tetraisopropylate, 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 MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, Ti element is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
Above-mentioned titanium doped borate light-emitting film (MeB 4o 7: xTi 4+) electroluminescent spectrum (EL) in, have very strong glow peak in 430nm 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 of the titanium doped borate light-emitting film prepared of embodiment 1;
Fig. 3 is the XRD figure of the titanium doped borate 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, titanium doped borate light-emitting film, its preparation method and membrane electro luminescent device and preparation method thereof are further illustrated.
The titanium doped borate light-emitting film of one embodiment, its chemical formula is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
Preferably, the thickness of titanium doped borate light-emitting film is 80nm ~ 300nm, and x is 0.04.
MeB in this titanium doped borate light-emitting film 4o 7be matrix, titanium elements is active element.In the electroluminescent spectrum (EL) of this titanium doped borate light-emitting film, there is very strong glow peak in 430nm wavelength zone, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned titanium doped borate 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 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 MeB 4o 7: xTi 4+the stoichiometric ratio of each element is by Me (C 5h 5) 2, BH 3pass in reaction chamber with titanium tetraisopropylate.
In a preferred embodiment, (Me (C 5h 5) 2, BH 3with titanium tetraisopropylate mol ratio be 1:4:(0.01 ~ 0.05).
In preferred embodiment, (Me (C 5h 5) 2, BH 3with titanium tetraisopropylate mol ratio be 1:4:0.02.
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 borate light-emitting film be MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
In a preferred embodiment, oxygen flow amount is 10 ~ 200sccm, and x is 0.02.
In more preferred embodiment, oxygen flow amount is 120sccm.
After step S15, deposition, stop passing into Me (C 5h 5) 2, BH 3with titanium tetraisopropylate and argon gas, continue to pass into the temperature that oxygen makes titanium doped borate light-emitting film and be down to 80 ℃ ~ 150 ℃.
In present embodiment, preferred, make the temperature of titanium doped borate 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 titanium doped borate light-emitting film, and the chemical formula of this titanium doped borate light-emitting film is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, 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 borate light-emitting film, and the chemical formula of this titanium doped borate light-emitting film is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, 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 B 4o 7: xTi 4+the stoichiometric ratio of each element is by Me (C 5h 5) 2, BH3 and titanium tetraisopropylate pass in reaction chamber.
In a preferred embodiment, Me (C 5h 5) 2, BH 3with titanium tetraisopropylate mol ratio be 1:4:(0.01 ~ 0.05).
In preferred embodiment, Me (C 5h 5) 2, BH 3with titanium tetraisopropylate mol ratio be 1:4:0.02.
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 Me (C 5h 5) 2, BH 3with titanium tetraisopropylate and argon gas, continue to pass into the temperature that oxygen makes titanium doped borate light-emitting film and be down to 80 ℃ ~ 150 ℃.
In present embodiment, preferred, make the temperature of titanium doped borate 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 two (pentamethyl-cyclopentadiene) magnesium (Mg (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.02, 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 MgB 4o 7: 0.02Ti 4+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the titanium doped borate light-emitting film obtaining in the present embodiment is MgB 4o 7: 0.02Ti 4+, wherein MgB 4o 7be matrix, Ti element is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the titanium doped borate light-emitting film obtaining.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak can be applied in thin-film electroluminescent displays in 430nm wavelength zone.
Refer to Fig. 3, Fig. 3 is the XRD curve of the titanium doped borate light-emitting film prepared of embodiment 1, test comparison standard P DF card.As can be seen from Figure 3, reference standard PDF card, the diffraction peak in figure is boratory peak crystallization, 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 6.0V luminous, curve 2 is voltage and brightness relationship curve, and high-high brightness is 88cd/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 two (pentamethyl-cyclopentadiene) magnesium (Mg (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.05, 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 MgB 4o 7: 0.05Ti 4+.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 two (pentamethyl-cyclopentadiene) magnesium (Mg (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.01, 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 MgB 4o 7: 0.01Ti 4+.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 two (pentamethyl-cyclopentadiene) calcium (Ca (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.02, 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 CaB 4o 7: 0.02Ti 4+.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 two (pentamethyl-cyclopentadiene) calcium (Ca (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.05, 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 CaB 4o 7: 0.05Ti 4+.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 two (pentamethyl-cyclopentadiene) calcium (Ca (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.01, 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 CaB 4o 7: 0.01Ti 4+.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 two (pentamethyl-cyclopentadiene) strontium (Sr (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.02, 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 SrB 4o 7: 0.02Ti 4+.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 two (pentamethyl-cyclopentadiene) strontium (Sr (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.05, 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 SrB 4o 7: 0.05Ti 4+.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 two (pentamethyl-cyclopentadiene) strontium (Sr (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.01, 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 SrB 4o 7: 0.01Ti 4+.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 two (pentamethyl-cyclopentadiene) barium (Ba (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.02, 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 BaB 4o 7: 0.02Ti 4+.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 two (pentamethyl-cyclopentadiene) barium (Ba (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.05, 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 BaB 4o 7: 0.05Ti 4+.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 two (pentamethyl-cyclopentadiene) barium (Ba (C in organic source 5h 5) 2), borine (BH 3) and the mol ratio of titanium tetraisopropylate (TTIP) be 1:4:0.01, 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 BaB 4o 7: 0.01Ti 4+.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 titanium doped borate light-emitting film, is characterized in that, its chemical formula is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
2. titanium doped borate light-emitting film according to claim 1, is characterized in that, the thickness of described titanium doped borate light-emitting film is 80nm ~ 300nm.
3. a preparation method for titanium doped borate 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 MeB 4o 7: xTi 4+the stoichiometric ratio of each element is by Me (C 5h 5) 2, BH 3pass in reaction chamber with titanium tetraisopropylate; And
Pass into oxygen, carrying out chemical vapour deposition, to obtain chemical formula be Me B 4o 7: xTi 4+titanium doped borate light-emitting film, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, and Me is Mg, Ca, Sr or Ba.
4. the preparation method of titanium doped borate light-emitting film according to claim 3, is characterized in that, described Me (C 5h 5) 2, BH 3with titanium tetraisopropylate mol ratio be 1:4:(0.01 ~ 0.05).
5. the preparation method of titanium doped borate 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 borate 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 titanium doped borate light-emitting film, and the chemical formula of this titanium doped borate light-emitting film is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, Ti element is active element, 0.01≤x≤0.05, 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 borate light-emitting film, and the chemical formula of this titanium doped borate light-emitting film is MeB 4o 7: xTi 4+, wherein MeB 4o 7be matrix, titanium elements is active element, 0.01≤x≤0.05, 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:
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 MeB 4o 7: xTi 4+the stoichiometric ratio of each element is by Me (C 5h 5) 2, BH 3pass in reaction chamber with titanium tetraisopropylate, 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.
CN201210456811.3A 2012-11-14 2012-11-14 Titanium-doped borate luminescent film, preparation method and application thereof Pending CN103805177A (en)

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