CN104178142A - Manganese-doped alkaline-earth nitrogen-aluminium-silicon-salt luminescent film, preparation method and application thereof - Google Patents
Manganese-doped alkaline-earth nitrogen-aluminium-silicon-salt luminescent film, preparation method and application thereof Download PDFInfo
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- CN104178142A CN104178142A CN201310191471.0A CN201310191471A CN104178142A CN 104178142 A CN104178142 A CN 104178142A CN 201310191471 A CN201310191471 A CN 201310191471A CN 104178142 A CN104178142 A CN 104178142A
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Abstract
A manganese-doped alkaline-earth nitrogen-aluminium-silicon-salt luminescent film is disclosed. A chemical formula of the luminescent film is MeAlSiN3:xMn4<+>, wherein x is less than or equal to 0.08 and greater than or equal to 0.01; MeAlSiN3 is a matrix; the manganese element is an active element; and Me is one element selected from zinc element, magnesium element, calcium element, strontium element and barium element. In the electroluminescent spectra (EL) of the manganese-doped alkaline-earth nitrogen-aluminium-silicon-salt luminescent film, there are intense luminescence peaks at the wavelength of 655nm. The luminescent film can be applied to a thin-film electroluminescent display. The invention also provides a preparation method of the manganese-doped alkaline-earth nitrogen-aluminium-silicon-salt luminescent film and its application.
Description
[technical field]
The present invention relates to a kind of manganese doping alkaline earth nitrogen aluminium silicon salt 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 manganese doping alkaline earth nitrogen aluminium silicon salt 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 manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film that can be applicable to membrane electro luminescent device, this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film electroluminescent device of its preparation method and preparation method thereof.
A kind of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, its chemical formula is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
The thickness of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is 80nm～300nm.
A preparation method for manganese doping alkaline earth nitrogen aluminium silicon salt 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 DEG C～650 DEG C, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to MeAlSiN
3: xMn
4+the stoichiometric ratio of each element is by (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two pass in reaction chamber, and
Then pass into ammonia, carrying out chemical vapour deposition, to obtain its chemical formula of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film be MeAlSiN
3: xMn
4+manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, Ce elements is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
(C
5h
5)
2me, (CH
3)
3the luxuriant manganese mol ratio of Al, silane and methyl two is 1:(0.92～0.99): 1:(0.01～0.08);
Argon stream amount is 5～15sccm, and ammonia airshed is 10～200sccm.
A kind of membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, and the chemical formula of this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
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 manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, and the chemical formula of this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element;
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 DEG C～650 DEG C, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to MeAlSiN
3: xMn
4+the stoichiometric ratio of each element is by (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two pass in reaction chamber, and wherein, argon stream amount is 5～15sccm, and
Then pass into ammonia, flow is 10～200sccm; Carrying out chemical vapour deposition, to obtain luminescent layer chemical formula be MeAlSiN
3: xMn
4+manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, wherein, 0.01≤x≤0.08, MeAlSiN
3: xMn
4+be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
Above-mentioned manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film (MeAlSiN
3: xMn
4+) electroluminescent spectrum (EL) in, have very strong glow peak in 655nm wavelength zone, can be applied in thin-film electroluminescent displays.
[brief description of the drawings]
Fig. 1 is the structural representation of the membrane electro luminescent device of an embodiment;
Fig. 2 is the electroluminescent spectrogram of the manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film prepared of embodiment 1;
Fig. 3 is the XRD figure of the manganese doping alkaline earth nitrogen aluminium silicon salt 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, manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, its preparation method and membrane electro luminescent device and preparation method thereof are further illustrated.
The manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film of one embodiment, its chemical formula is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
Preferably, the thickness of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is 80nm～300nm, and x is 0.05.
MeAlSiN in this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film
3be matrix, manganese element is active element.In the electroluminescent spectrum (EL) of this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, there is very strong glow peak in 655nm wavelength zone, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned manganese doping alkaline earth nitrogen aluminium silicon salt 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 amide glass (ITO), is appreciated that in other embodiments, also can be for mixing fluorine ammonification tin glass (FTO), mix the ammonification zinc (AZO) of aluminium or mix the ammonification zinc (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 DEG C～800 DEG C.
Step S13, adjusting substrate temperature are 250 DEG C～650 DEG C, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to MeAlSiN
3: xMn
4+the stoichiometric ratio of each element is by (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two pass in reaction chamber;
Described (C
5h
5)
2me, (CH
3)
3the luxuriant manganese mol ratio of Al, silane and methyl two is 1:(0.92～0.99): 1:(0.01～0.08);
Described substrate temperature is preferably 500 DEG C, and the rotating speed of substrate is preferably 300 revs/min, and argon stream amount is 5～15sccm;
Described argon stream amount is 10sccm;
Step S14, then pass into ammonia, carrying out chemical vapour deposition, to obtain its chemical formula of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film be MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
Described ammonia airshed is 10～200sccm, and x is 0.05.
More preferably ammonia airshed is 120sccm.
After step S15, deposition, stop passing into (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two and helium, continue to pass into ammonia and make the temperature of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film be down to 80 DEG C～150 DEG C.
In present embodiment, preferred, make the temperature of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film be down to 100 DEG C.
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 ammonification indium tin (ITO) in glass substrate.The material of luminescent layer 3 is manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, and the chemical formula of this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.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 ammonification indium tin (ITO) in glass substrate.Be appreciated that in other embodiments, also can be for mixing fluorine ammonification tin glass (FTO), mix the ammonification zinc (AZO) of aluminium or mix the ammonification zinc (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 ammonia plasma processing.
Step S22, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, and the chemical formula of this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
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 DEG C～800 DEG C.Also can be without this step.
Secondly, regulating substrate temperature is 250 DEG C～650 DEG C, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to MeAlSiN
3: xMn
4+the stoichiometric ratio of each element is by (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two pass in reaction chamber;
In a preferred embodiment, (C
5h
5)
2me, (CH
3)
3the luxuriant manganese mol ratio of Al, silane and methyl two is 1:(0.92～0.99): 1:(0.01～0.08);
In a preferred embodiment, substrate temperature is preferably 500 DEG C, 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 ammonia, carry out chemical vapour deposition film and form luminescent layer on described anode.
In preferred embodiment, the flow of ammonia is preferably 10～200sccm;
In more preferred embodiment, ammonia airshed is 120sccm.
Finally, after deposition, stop passing into (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two and helium, continue to pass into ammonia and make the temperature of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film be down to 80 DEG C～150 DEG C.
In present embodiment, preferred, make the temperature of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film be down to 100 DEG C.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 DEG C of thermal treatments 20 minutes, then temperature is reduced to 500 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into organic source (C
5h
5)
2zn, (CH
3)
3al, silane (SiH
4) and the mol ratio of methyl two luxuriant manganese be 1:0.95:1:0.035, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample ZnAlSiN
3: 0.05Mn
4+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film obtaining in the present embodiment is ZnAlSiN
3: 0.05Mn
4+, wherein ZnAlSiN
3be matrix, manganese element is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film that embodiment 1 obtains.The electroluminescent spectral curve of the manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film that as seen from Figure 2, embodiment 1 obtains has very strong glow peak can be applied in thin-film electroluminescent displays in 655nm wavelength zone.
Refer to Fig. 3, Fig. 3 is the XRD curve of the manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film prepared of embodiment 1, test comparison standard P DF card.As can be seen from Figure 3, reference standard PDF card, in figure, major part is the diffraction peak of alkaline earth nitrogen aluminium silicon salt, does not occur the diffraction peak of doped element and other impurity, proves that doped element is the lattice that has entered alkaline earth nitrogen aluminium silicon salt, does not occur phase-splitting.
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 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 80cd/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 DEG C of thermal treatments 10 minutes, then temperature is reduced to 250 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into machine source (C
5h
5)
2zn, (CH
3)
3al, silane (SiH
4) and the mol ratio of methyl two luxuriant manganese be 1:0.99:1:0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample ZnAlSiN
3: 0.01Mn
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 DEG C of thermal treatments 30 minutes, then temperature is reduced to 650 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into organic source (C
5h
5)
2zn, (CH
3)
3al, silane (SiH
4) and the mol ratio of methyl two luxuriant manganese be 1:0.92:1:0.08, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample ZnAlSiN
3: 0.08Mn
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 DEG C of thermal treatments 20 minutes, then temperature is reduced to 500 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into organic source (C
5h
5)
2mg, (CH
3)
3al, silane (SiH
4) and the mol ratio of methyl two luxuriant manganese be 1:0.95:1:0.05, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample MgAlSiN
3: 0.05Mn
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 DEG C of thermal treatments 10 minutes, then temperature is reduced to 250 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into machine source (C
5h
5)
2mg, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.99:1:0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample MgAlSiN
3: 0.01Mn
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 DEG C of thermal treatments 30 minutes, then temperature is reduced to 650 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into organic source (C
5h
5)
2mg, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.92:1:0.08, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample MgAlSiN
3: 0.08Mn
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 DEG C of thermal treatments 20 minutes, then temperature is reduced to 500 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into organic source (C
5h
5)
2ca, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.95:1:0.05, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample CaAlSiN
3: 0.05Mn
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 DEG C of thermal treatments 10 minutes, then temperature is reduced to 250 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into organic source (C
5h
5)
2ca, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.99:1:0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample CaAlSiN
3: 0.01Mn
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 DEG C of thermal treatments 30 minutes, then temperature is reduced to 650 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into machine source (C
5h
5)
2ca, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.92:1:0.08, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample CaAlSiN
3: 0.08Mn
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 DEG C of thermal treatments 20 minutes, then temperature is reduced to 500 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into machine source (C
5h
5)
2sr, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.95:1:0.05, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample SrAlSiN
3: 0.05Mn
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 DEG C of thermal treatments 10 minutes, then temperature is reduced to 250 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into machine source (C
5h
5)
2sr, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.99:1:0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample SrAlSiN
3: 0.01Mn
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 DEG C of thermal treatments 30 minutes, then temperature is reduced to 650 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into machine source (C
5h
5)
2sr, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.92:1:0.08, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample SrAlSiN
3: 0.08Mn
4+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 13: 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 DEG C of thermal treatments 20 minutes, then temperature is reduced to 500 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 300 revs/min, passes into machine source (C
5h
5)
2ba, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.95:1:0.05, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample BaAlSiN
3: 0.05Mn
4+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 14: 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 DEG C of thermal treatments 10 minutes, then temperature is reduced to 250 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 50 revs/min, passes into machine source (C
5h
5)
2ba, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.99:1:0.01, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample BaAlSiN
3: 0.01Mn
4+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 15: 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 DEG C of thermal treatments 30 minutes, then temperature is reduced to 650 DEG C.Open rotating machine, regulating the rotating speed of substrate bracket is 1000 revs/min, passes into machine source (C
5h
5)
2ba, (CH
3)
3al, SiH
4with the mol ratio of methyl two luxuriant manganese be 1:0.92:1:0.08, gas of carrier gas is argon gas, argon stream amount is 10sccm.Pass into ammonia, ammonia airshed is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical ammonia, and temperature drops to below 100 DEG C, takes out sample BaAlSiN
3: 0.08Mn
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 manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, is characterized in that, its chemical formula is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
2. manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film according to claim 1, is characterized in that, the thickness of described manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is 80nm～300nm.
3. a preparation method for manganese doping alkaline earth nitrogen aluminium silicon salt 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 DEG C～650 DEG C, and rotating speed is 50 revs/min～1000 revs/min, adopts the carrier of argon stream, according to MeAlSiN
3: xMn
4+the stoichiometric ratio of each element is by (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two pass in reaction chamber; And
Pass into ammonia, carrying out chemical vapour deposition, to obtain chemical formula be MeAlSiN
3: xMn
4+manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, wherein, 0.01≤x≤0.08, MeAlSiN
3: xMn
4+be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
4. the preparation method of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film according to claim 3, is characterized in that described (C
5h
5)
2me, (CH
3)
3the luxuriant manganese mol ratio of Al, silane and methyl two is 1:(0.92～0.99): 1:(0.01～0.08).
5. the preparation method of manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film according to claim 3, is characterized in that, described argon stream amount is 5～15sccm, and described ammonia airshed is 10～200sccm.
6. the preparation method of manganese according to claim 3 doping alkaline earth nitrogen aluminium silicon salt light-emitting film, is characterized in that, described substrate is packed into after described reaction chamber the thermal treatment 10 minutes～30 minutes at 600 DEG C～800 DEG C 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 manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, and the chemical formula of this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element.
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 manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film, and the chemical formula of this manganese doping alkaline earth nitrogen aluminium silicon salt light-emitting film is MeAlSiN
3: xMn
4+, wherein, 0.01≤x≤0.08, MeAlSiN
3be matrix, manganese element is active element, and Me is zinc element, magnesium elements, calcium constituent, the one in strontium element and barium element;
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 DEG C～650 DEG C, and rotating speed is 50 revs/min～1000 revs/min, adopts argon stream as carrier, according to MeAlSiN
3: xMn
4+the stoichiometric ratio of each element is by (C
5h
5)
2me, (CH
3)
3al, silane and the luxuriant manganese of methyl two pass in reaction chamber, and wherein, argon stream amount is 5～15sccm,
Then pass into ammonia, ammonia airshed is 10～200sccm; Deposit film forms luminescent layer on described anode.
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|---|---|---|---|---|
| CN1918262A (en) * | 2003-11-26 | 2007-02-21 | 独立行政法人物质·材料研究机构 | Phosphor and light emission appliance using phosphor |
| CN102994079A (en) * | 2012-12-21 | 2013-03-27 | 北京有色金属研究总院 | Nitrogen-oxide orange-red fluorescent material comprising light-emitting film or light-emitting piece and light-emitting device |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1918262A (en) * | 2003-11-26 | 2007-02-21 | 独立行政法人物质·材料研究机构 | Phosphor and light emission appliance using phosphor |
| CN102994079A (en) * | 2012-12-21 | 2013-03-27 | 北京有色金属研究总院 | Nitrogen-oxide orange-red fluorescent material comprising light-emitting film or light-emitting piece and light-emitting device |
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| ZHIJUN ZHANG等: "Photoluminescence Properties of Red-Emitting Mn2+-Activated CaAlSiN3 Phosphor for White-LEDs", 《ECS JOURNAL OF SOLID STATE SCIENCE AND TECHNOLOGY》 * |
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Application publication date: 20141203 |