CN103289687A - Cerium-doped sulphoaluminate luminescent film, preparation method and application of same - Google Patents
Cerium-doped sulphoaluminate luminescent film, preparation method and application of same Download PDFInfo
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- CN103289687A CN103289687A CN2012100478705A CN201210047870A CN103289687A CN 103289687 A CN103289687 A CN 103289687A CN 2012100478705 A CN2012100478705 A CN 2012100478705A CN 201210047870 A CN201210047870 A CN 201210047870A CN 103289687 A CN103289687 A CN 103289687A
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Abstract
The invention discloses a cerium-doped sulphoaluminate luminescent film, which has a chemical expression of MeAl(2-x)S4: xCe<3+>, wherein MeAl(2-x)S4 is a matrix; the element Ce is an active element; x is not less than 0.01 and not greater than 0.08; Me is Mg or Ca or Sr or Ba. The cerium-doped sulphoaluminate luminescent film has very strong luminescent peaks in an area with a wave length of 540 nm in the electroluminescent spectra (EL) thereof, and can be applied to a film electroluminescent display. The invention further provides a preparation method for the cerium-doped sulphoaluminate luminescent film, and an application of the same.
Description
[technical field]
The present invention relates to a kind of cerium doping sulphoaluminate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof.
[background technology]
Thin-film electroluminescent displays (TFELD) since its active illuminating, total solidsization, shock-resistant, advantage such as reaction is fast, the visual angle is big, Applicable temperature is wide, operation is simple caused and paid close attention to widely, and development rapidly.At present, research is colored to be reached to panchromatic TFELD, and the luminous film of exploitation multiband is the developing direction of this problem.But, can be applicable to the cerium doping sulphoaluminate light-emitting film of thin-film electroluminescent displays, do not appear in the newspapers yet.
[summary of the invention]
Based on this, be necessary to provide a kind of cerium doping sulphoaluminate light-emitting film, its preparation method that can be applicable to membrane electro luminescent device, use electroluminescent device of this cerium doping sulphoaluminate light-emitting film and preparation method thereof.
A kind of cerium doping sulphoaluminate light-emitting film, the chemical general formula of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba;
The thickness of this cerium doping sulphoaluminate light-emitting film is 80nm～300nm.
A kind of preparation method of cerium doping sulphoaluminate light-emitting film may further comprise the steps:
With pack into the reaction chamber of chemical vapor depsotition equipment of substrate, 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 rev/mins～1000 rev/mins, under the carrier of argon stream, according to MeAl
2-xS
4: xCe
3+The stoichiometric ratio of each element is with (DPM)
2Me, trimethyl aluminium and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium feed in the reaction chamber; And
Feed hydrogen sulfide, carrying out chemical vapour deposition, to obtain chemical expression be MeAl
2-xS
4: xCe
3+Cerium doping sulphoaluminate light-emitting film, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba.。
In a preferred embodiment, (DPM)
2Me, the mol ratio of trimethyl aluminium and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 1: (0.92～0.99): (0.01～0.08).
In a preferred embodiment, described argon stream amount is 5～15sccm, and described stink damp flow is 10～200sccm.
In a preferred embodiment, described substrate is packed into behind the described reaction chamber described substrate 600 ℃～800 ℃ following thermal treatments 10 minutes～30 minutes.
A kind of membrane electro luminescent device, this membrane electro luminescent device comprises substrate, anode layer, luminescent layer and the cathode layer that stacks gradually, the material of described luminescent layer is cerium doping sulphoaluminate light-emitting film, and the chemical expression of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba.
A kind of preparation method of membrane electro luminescent device may further comprise the steps:
Substrate with anode is provided;
Form luminescent layer at described anode, the material of described luminescent layer is cerium doping sulphoaluminate light-emitting film, and the chemical expression of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba; And
Form negative electrode at described luminescent layer.
In a preferred embodiment, the preparation of described luminescent layer may further comprise the steps:
With pack into the reaction chamber of chemical vapor depsotition equipment of substrate, 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 rev/mins～1000 rev/mins, under the carrier of argon stream, according to MeAl
2-xS
4: xCe
3+The stoichiometric ratio of each element is with (DPM)
2Me, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) feed in the reaction chamber, the argon stream amount is 5～15sccm;
Feed hydrogen sulfide, the stink damp flow is 10～200sccm; Carry out chemical vapour deposition film and form luminescent layer at described anode.
Above-mentioned cerium doping sulphoaluminate light-emitting film (MeAl
2-xS
4: xCe
3+) electroluminescent spectrum (EL) in, at the 540nm wavelength zone very strong glow peak is arranged, can be applied in the thin-film electroluminescent displays.
[description of drawings]
Fig. 1 is the structural representation of the membrane electro luminescent device of an embodiment;
Fig. 2 is the electroluminescent spectrogram of the cerium doping sulphoaluminate light-emitting film of embodiment 1 preparation;
Fig. 3 is the XRD figure of the cerium doping sulphoaluminate light-emitting film of embodiment 1 preparation.
[embodiment]
Below in conjunction with the drawings and specific embodiments cerium doping sulphoaluminate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are further illustrated.
The cerium doping sulphoaluminate light-emitting film of one embodiment, the chemical expression of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba.
The thickness of this cerium doping sulphoaluminate light-emitting film is 80nm～300nm.
Preferably, x is 0.05, and thickness is 150nm.
The preparation method of above-mentioned cerium doping sulphoaluminate light-emitting film may further comprise the steps:
Step S11, with pack into the reaction chamber of chemical vapor depsotition equipment of substrate, 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 was successively used toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into reaction chamber after nitrogen is air-dry; Preferably, the vacuum tightness of reaction chamber is 4.0 * 10
-3Pa.
Step S12, with substrate 700 ℃ of following thermal treatments 10 minutes～30 minutes.
Step S13, adjusting substrate temperature are 250 ℃～650 ℃, and rotating speed is 50 rev/mins～1000 rev/mins, under the carrier of argon stream, according to MeAl
2-xS
4: xCe
3+The stoichiometric ratio of each element with the dipivaloylmethane hydrochlorate { (DPM)
2Me}, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) feed in the reaction chamber,
In this step, (DPM)
2Me, Pr (DpM)
3And titanium tetraisopropylate (TTIP) mol ratio is 1: (0.92～0.99): (0.01～0.08), argon stream amount are 5～15sccm,
Step S14, feed hydrogen sulfide then, carrying out chemical vapour deposition, to obtain its chemical expression of cerium doping sulphoaluminate light-emitting film be MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba.
In this step, preferred, the stink damp flow is 10～200sccm;
In this step, preferred, x is 0.05.
After finishing, step S15, cerium doping sulphoaluminate light-emitting film deposition stop to feed (DPM)
2Me, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) and helium, continue to feed hydrogen sulfide and make the temperature of cerium doping sulphoaluminate light-emitting film be down to 80 ℃～150 ℃.
Be understandable that step 1S2 and step S15 can omit.
See also Fig. 1, the membrane electro luminescent device 100 of an embodiment, this membrane electro luminescent device 100 comprise substrate 1, anode 2, luminescent layer 3 and the negative electrode 4 that stacks gradually.
Substrate 1 is glass substrate.Anode 2 is for being formed at the tin indium oxide (ITO) on the glass substrate.The material of luminescent layer 3 is cerium doping sulphoaluminate light-emitting film, and the chemical expression of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is the active element element, 0.01≤x≤0.08, and wherein, 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 may further comprise the steps:
Step S21, provide the substrate 1 with anode 2.
In the present embodiment, substrate 1 is glass substrate, and anode 2 is for being formed at the tin indium oxide (ITO) on the 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; Substrate was successively used toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into reaction chamber after nitrogen is air-dry; Preferably, the vacuum tightness of reaction chamber is 4.0 * 10
-3Pa.
Step S22, form luminescent layers 3 at anode 2, the material of luminescent layer 3 is cerium doping sulphoaluminate light-emitting film, and the chemical expression of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba.
In the present embodiment, luminescent layer 3 is made by following steps:
At first, with pack into the reaction chamber of chemical vapor depsotition equipment of substrate, and the vacuum tightness of reaction chamber is set to 1.0 * 10
-2Pa～1.0 * 10
-3Pa,
Secondly, with substrate 700 ℃ of following thermal treatments 10 minutes～30 minutes.Be appreciated that this step can omit.
Then, regulating substrate temperature is 250 ℃～650 ℃, and rotating speed is 50 rev/mins～1000 rev/mins, under the carrier of argon stream, according to MeAl
2-xS
4: xCe
3+The stoichiometric ratio of each element is with (DPM)
2Me, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) feed in the reaction chamber;
Preferably, (DPM)
2Me, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio is 1: (0.92～0.99): (0.01～0.08), described argon stream amount is 5～15sccm,
Then, feed hydrogen sulfide; Carry out chemical vapour deposition film and form luminescent layer at described anode.
Preferably, the stink damp flow is 10～200sccm for the stink damp flow;
At last, stop to feed (DPM) after cerium doping sulphoaluminate light-emitting film deposition finishes
2Me, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) and helium, continue to feed hydrogen sulfide and make the temperature of cerium doping sulphoaluminate light-emitting film be down to 80 ℃～150 ℃.This step can be omitted
Step S23, form negative electrodes 4 at luminescent layer 3.
In the 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, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 4.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 20 minutes, temperature is reduced to 500 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 300 rev/mins, feeds organic source (DPM)
2Mg, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 120sccm, the beginning depositing of thin film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample MgAl
1.95S
4: 0.05Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
The chemical general formula of the cerium doping sulphoaluminate light-emitting film that obtains in the present embodiment is MgAl
1.95S
4: 0.05Ce
3+, MgAl wherein
1.95S
4Be matrix, the Ce element is active element.
See also Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the cerium doping sulphoaluminate light-emitting film that obtains.As seen from Figure 2, in the electroluminescence spectrum, at the 540nm wavelength zone very strong glow peak is arranged, can be applied in the thin-film electroluminescent displays.
See also Fig. 3, Fig. 3 is the XRD curve of the cerium doping sulphoaluminate light-emitting film of embodiment 1 preparation, test reference standard PDF card.As can be seen from Figure 3 reference standard PDF card is the peak crystallization of sulphoaluminate, the diffraction peak of doped element and other impurity do not occur; Illustrate that the product that this preparation method obtains has good crystalline quality
Embodiment 2
Substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 10 minutes, temperature is reduced to 250 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 50 rev/mins, feeds organic source (DPM)
2Mg, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 10sccm, the beginning depositing of thin film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample MgAl
1.92S
4: 0.08Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 3
Substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-2Pa; Then substrate is carried out 700 ℃ of thermal treatments 30 minutes, temperature is reduced to 650 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 1000 rev/mins, feeds organic source (DPM)
2Mg, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 200sccm, the beginning depositing of thin film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample MgAl
1.99S
4: 0.01Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 4: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 4.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 20 minutes, temperature is reduced to 500 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 300 rev/mins, feeds organic source (DPM)
2Ca, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 120sccm, the beginning depositing of thin film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample CaAl
1.95S
4: 0.05Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 5: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 10 minutes, temperature is reduced to 250 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 50 rev/mins, feeds organic source (DPM)
2Ca, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 10sccm, the beginning depositing of thin film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample CaAl
1.92S
4: 0.08Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 6: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-2Pa; Then substrate is carried out 700 ℃ of thermal treatments 30 minutes, temperature is reduced to 650 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 1000 rev/mins, feeds organic source (DPM)
2Ca, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 200sccm, the beginning depositing of thin film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample CaAl
1.99S
4: 0.01Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 7: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 4.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 20 minutes, temperature is reduced to 500 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 300 rev/mins, feeds organic source (DPM)
2Sr, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 120sccm, the beginning depositing of thin film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample SrAl
1.95S
4: 0.05Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 8: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 10 minutes, temperature is reduced to 250 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 50 rev/mins, feeds organic source (DPM)
2Sr, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 10sccm, the beginning depositing of thin film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample SrAl
1.92S
4: 0.08Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 9: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-2Pa; Then substrate is carried out 700 ℃ of thermal treatments 30 minutes, temperature is reduced to 650 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 1000 rev/mins, feeds organic source (DPM)
2Sr, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 200sccm, the beginning depositing of thin film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample SrAl
1.99S
4: 0.01Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 10: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 4.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 20 minutes, temperature is reduced to 500 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 300 rev/mins, feeds organic source (DPM)
2Ba, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 120sccm, the beginning depositing of thin film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample BaAl
1.95S
4: 0.05Ce
3++Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 11: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-3Pa; Then substrate is carried out 700 ℃ of thermal treatments 10 minutes, temperature is reduced to 250 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 50 rev/mins, feeds organic source (DPM)
2Ba, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 10sccm, the beginning depositing of thin film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample BaAl
1.92S
4: 0.08Ce
3+Evaporation one deck Ag on light-emitting film at last is as negative electrode.
Embodiment 12: substrate is ito glass, successively uses toluene, acetone and ethanol ultrasonic cleaning 5 minutes, and is clean with distilled water flushing then, sends into equipment reaction chamber after nitrogen is air-dry.With mechanical pump and molecular pump the vacuum tightness of cavity is evacuated to 1.0 * 10
-2Pa; Then substrate is carried out 700 ℃ of thermal treatments 30 minutes, temperature is reduced to 650 ℃ then.Open rotating machine, the rotating speed of regulating substrate bracket is 1000 rev/mins, feeds organic source (DPM)
2Ba, trimethyl aluminium (TMAl) and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, the argon stream amount is 10sccm.Feed hydrogen sulfide, the stink damp flow is 200sccm, the beginning depositing of thin film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, continues logical hydrogen sulfide, and temperature drops to below 100 ℃, takes out sample BaAl
1.99S
4: 0.01Ce
3+Evaporation one deck Ag on light-emitting film at last is 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 claim of the present invention.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 cerium doping sulphoaluminate light-emitting film is characterized in that, the chemical general formula of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba.
2. cerium doping sulphoaluminate light-emitting film according to claim 1 is characterized in that, the thickness of described cerium doping sulphoaluminate light-emitting film is 80nm～300nm.
3. the preparation method of a cerium doping sulphoaluminate light-emitting film is characterized in that, may further comprise the steps:
With pack into the reaction chamber of chemical vapor depsotition equipment of substrate, 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 rev/mins～1000 rev/mins, under the carrier of argon stream, according to MeAl
2-xS
4: xCe
3+The stoichiometric ratio of each element is with (DPM)
2Me, trimethyl aluminium and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium feed in the reaction chamber; And
Feed hydrogen sulfide, carrying out chemical vapour deposition, to obtain chemical expression be MeAl
2-xS
4: xCe
3+Cerium doping sulphoaluminate light-emitting film, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba.
4. the preparation method of cerium doping sulphoaluminate light-emitting film according to claim 3 is characterized in that, described (DPM)
2Me, the mol ratio of trimethyl aluminium and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium is 1: (0.92～0.99): (0.01～0.08).
5. the preparation method of cerium doping sulphoaluminate light-emitting film according to claim 3 is characterized in that, described argon stream amount is 5～15sccm, and described stink damp flow is 10～200sccm.
6. the preparation method of cerium doping sulphoaluminate light-emitting film according to claim 3 is characterized in that, described substrate is packed into behind the described reaction chamber described substrate 600 ℃～800 ℃ following thermal treatments 10 minutes～30 minutes.
7. membrane electro luminescent device, this membrane electro luminescent device comprises substrate, anode layer, luminescent layer and the cathode layer that stacks gradually, it is characterized in that, the material of described luminescent layer is cerium doping sulphoaluminate light-emitting film, and the chemical expression of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba.
8. the preparation method of membrane electro luminescent device according to claim 7 is characterized in that, the thickness of described luminescent layer is 80nm～300nm.
9. the preparation method of a membrane electro luminescent device is characterized in that, may further comprise the steps:
Substrate with anode is provided;
Form luminescent layer at described anode, the material of described luminescent layer is cerium doping sulphoaluminate light-emitting film, and the chemical expression of this cerium doping sulphoaluminate light-emitting film is MeAl
2-xS
4: xCe
3+, MeAl wherein
2-xS
4Be matrix, the Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba; And
Form negative electrode at described luminescent layer.
10. the preparation method of membrane electro luminescent device according to claim 9 is characterized in that, the preparation of described luminescent layer may further comprise the steps:
With pack into the reaction chamber of chemical vapor depsotition equipment of substrate, 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 rev/mins～1000 rev/mins, under the carrier of argon stream, according to MeAl
2-xS
4: xCe
3+The stoichiometric ratio of each element is with (DPM)
2Me, trimethyl aluminium and four (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) cerium feeds in the reaction chamber, and the argon stream amount is 5～15sccm; And
Feed hydrogen sulfide, the stink damp flow is 10～200sccm, carries out chemical vapour deposition film and forms luminescent layer at described anode.
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