CN103289687B - Cerium dopping sulphoaluminate light-emitting film, preparation method and application thereof - Google Patents
Cerium dopping sulphoaluminate light-emitting film, preparation method and application thereof Download PDFInfo
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- CN103289687B CN103289687B CN201210047870.5A CN201210047870A CN103289687B CN 103289687 B CN103289687 B CN 103289687B CN 201210047870 A CN201210047870 A CN 201210047870A CN 103289687 B CN103289687 B CN 103289687B
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Abstract
A kind of cerium dopping sulphoaluminate light-emitting film, its chemical expression is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, wherein 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba.In the electroluminescent spectrum (EL) of this cerium dopping sulphoaluminate light-emitting film, there is very strong glow peak in 540nm wavelength zone, can be applied in thin-film electroluminescent displays.The present invention also provides preparation method and the application thereof of this cerium dopping sulphoaluminate light-emitting film.
Description
[technical field]
The present invention relates to a kind of cerium dopping sulphoaluminate 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 film of exploitation multiband luminescence is the developing direction of this problem.But, can be applicable to the cerium dopping sulphoaluminate 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 the cerium dopping sulphoaluminate light-emitting film, its preparation method, the electroluminescent device using this cerium dopping sulphoaluminate light-emitting film and preparation method thereof that can be applicable to membrane electro luminescent device.
A kind of cerium dopping sulphoaluminate light-emitting film, the chemical general formula of this cerium dopping sulphoaluminate light-emitting film is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba;
The thickness of this cerium dopping sulphoaluminate light-emitting film is 80nm ~ 300nm.
A preparation method for cerium dopping sulphoaluminate light-emitting film, comprises the following steps:
Substrate is loaded 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;
Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to MeAl
2-xs
4: xCe
3+the stoichiometric ratio of each element is by (DPM)
2me, trimethyl aluminium and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium passes in reaction chamber; And
Pass into hydrogen sulfide, carrying out chemical vapour deposition, to obtain chemical expression be MeAl
2-xs
4: xCe
3+cerium dopping sulphoaluminate light-emitting film, wherein MeAl
2-xs
4be matrix, 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 (acid of 2,2,6,6-tetramethyl--3,5-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 loaded the thermal treatment 10 minutes ~ 30 minutes at 600 DEG C ~ 800 DEG C of described substrate after described reaction chamber.
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 cerium dopping sulphoaluminate light-emitting film, and the chemical expression of this cerium dopping sulphoaluminate light-emitting film is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba.
A preparation method for membrane electro luminescent device, comprises the following steps:
The substrate with anode is provided;
Described anode forms luminescent layer, and the material of described luminescent layer is cerium dopping sulphoaluminate light-emitting film, and the chemical expression of this cerium dopping sulphoaluminate light-emitting film is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba; And
Form negative electrode on the light-emitting layer.
In a preferred embodiment, the preparation of described luminescent layer comprises the following steps:
Substrate is loaded 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;
Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to MeAl
2-xs
4: xCe
3+the stoichiometric ratio of each element is by (DPM)
2me, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) pass in reaction chamber, argon stream amount is 5 ~ 15sccm;
Pass into hydrogen sulfide, stink damp flow is 10 ~ 200sccm; Carry out chemical vapour deposition film and form luminescent layer on described anode.
Above-mentioned cerium dopping sulphoaluminate light-emitting film (MeAl
2-xs
4: xCe
3+) electroluminescent spectrum (EL) in, have very strong glow peak in 540nm 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 cerium dopping sulphoaluminate light-emitting film prepared by embodiment 1;
Fig. 3 is the XRD figure of cerium dopping sulphoaluminate light-emitting film prepared by embodiment 1.
[embodiment]
Below in conjunction with the drawings and specific embodiments, cerium dopping sulphoaluminate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are illustrated further.
The cerium dopping sulphoaluminate light-emitting film of one embodiment, the chemical expression of this cerium dopping sulphoaluminate light-emitting film is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba.
The thickness of this cerium dopping sulphoaluminate light-emitting film is 80nm ~ 300nm.
Preferably, x is 0.05, and thickness is 150nm.
The preparation method of above-mentioned cerium dopping sulphoaluminate light-emitting film, comprises the following steps:
Step S11, substrate is loaded 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 present embodiment, substrate is indium tin oxide glass (ITO), be appreciated that in other embodiments, can be also fluorine doped tin oxide glass (FTO), mix the zinc oxide (AZO) of aluminium or mix the zinc oxide (IZO) of indium; Substrate priority toluene, acetone and EtOH Sonicate clean 5 minutes, then clean with distilled water flushing, the air-dry rear feeding reaction chamber of nitrogen; Preferably, the vacuum tightness of reaction chamber is 4.0 × 10
-3pa.
Step S12, by substrate thermal treatment 10 minutes ~ 30 minutes at 700 DEG C.
Step S13, adjustment substrate temperature are 250 DEG C ~ 650 DEG C, and rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to MeAl
2-xs
4: xCe
3+the stoichiometric ratio of each element is by dipivaloylmethane hydrochlorate { (DPM)
2me}, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) pass in reaction chamber,
In this step, (DPM)
2me, Pr (DpM)
3be 1 with titanium tetraisopropylate (TTIP) mol ratio: (0.92 ~ 0.99): (0.01 ~ 0.08), argon stream amount is 5 ~ 15sccm,
Step S14, then pass into hydrogen sulfide, carrying out chemical vapour deposition, to obtain its chemical expression of cerium dopping sulphoaluminate light-emitting film be MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba.
In this step, preferably, stink damp flow is 10 ~ 200sccm;
In this step, preferably, x is 0.05.
Stop passing into (DPM) after step S15, cerium dopping sulphoaluminate luminescent thin-film deposition
2me, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) and helium, continue to pass into hydrogen sulfide and make the temperature of cerium dopping sulphoaluminate light-emitting film be down to 80 DEG C ~ 150 DEG C.
Be understandable that, step 1S2 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 cerium dopping sulphoaluminate light-emitting film, and the chemical expression of this cerium dopping sulphoaluminate light-emitting film is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element element, and 0.01≤x≤0.08, 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, 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, can be also fluorine doped tin oxide glass (FTO), mix the zinc oxide (AZO) of aluminium or mix the zinc oxide (IZO) of indium; Substrate priority toluene, acetone and EtOH Sonicate clean 5 minutes, then clean with distilled water flushing, the air-dry rear feeding reaction chamber of nitrogen; Preferably, the vacuum tightness of reaction chamber is 4.0 × 10
-3pa.
Step S22, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is cerium dopping sulphoaluminate light-emitting film, and the chemical expression of this cerium dopping sulphoaluminate light-emitting film is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba.
In present embodiment, luminescent layer 3 is obtained by following steps:
First, substrate is loaded 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,
Secondly, by substrate thermal treatment 10 minutes ~ 30 minutes at 700 DEG C.Be appreciated that this step can be omitted.
Then, regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to MeAl
2-xs
4: xCe
3+the stoichiometric ratio of each element is by (DPM)
2me, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) pass in reaction chamber;
Preferably, (DPM)
2me, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-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, hydrogen sulfide is passed into; Carry out chemical vapour deposition film and form luminescent layer on described anode.
Preferably, stink damp flow is stink damp flow is 10 ~ 200sccm;
Finally, stop after cerium dopping sulphoaluminate luminescent thin-film deposition passing into (DPM)
2me, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) and helium, continue to pass into hydrogen sulfide and make the temperature of cerium dopping sulphoaluminate light-emitting film be down to 80 DEG C ~ 150 DEG C.This step can be omitted
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 cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 20 minutes, then temperature reduces to 500 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 300 revs/min, passes into organic source (DPM)
2mg, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample MgAl
1.95s
4: 0.05Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the cerium dopping sulphoaluminate light-emitting film obtained in the present embodiment is MgAl
1.95s
4: 0.05Ce
3+, wherein MgAl
1.95s
4be matrix, Ce element is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the cerium dopping sulphoaluminate light-emitting film obtained.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak in 540nm wavelength zone, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of cerium dopping sulphoaluminate light-emitting film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3 reference standard PDF card, is the peak crystallization of sulphoaluminate, does not occur the diffraction peak of doped element and other impurity; Illustrate that the product that this preparation method obtains has good crystalline quality
Embodiment 2
Substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 10 minutes, then temperature reduces to 250 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 50 revs/min, passes into organic source (DPM)
2mg, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample MgAl
1.92s
4: 0.08Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 3
Substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-2pa; Then substrate is carried out 700 DEG C of thermal treatments 30 minutes, then temperature reduces to 650 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 1000 revs/min, passes into organic source (DPM)
2mg, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample MgAl
1.99s
4: 0.01Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 4: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 20 minutes, then temperature reduces to 500 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 300 revs/min, passes into organic source (DPM)
2ca, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample CaAl
1.95s
4: 0.05Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 5: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 10 minutes, then temperature reduces to 250 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 50 revs/min, passes into organic source (DPM)
2ca, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample CaAl
1.92s
4: 0.08Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 6: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-2pa; Then substrate is carried out 700 DEG C of thermal treatments 30 minutes, then temperature reduces to 650 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 1000 revs/min, passes into organic source (DPM)
2ca, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample CaAl
1.99s
4: 0.01Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 7: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 20 minutes, then temperature reduces to 500 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 300 revs/min, passes into organic source (DPM)
2sr, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample SrAl
1.95s
4: 0.05Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 8: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 10 minutes, then temperature reduces to 250 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 50 revs/min, passes into organic source (DPM)
2sr, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample SrAl
1.92s
4: 0.08Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 9: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-2pa; Then substrate is carried out 700 DEG C of thermal treatments 30 minutes, then temperature reduces to 650 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 1000 revs/min, passes into organic source (DPM)
2sr, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample SrAl
1.99s
4: 0.01Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 10: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 4.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 20 minutes, then temperature reduces to 500 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 300 revs/min, passes into organic source (DPM)
2ba, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.95: 0.05, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 120sccm, starts the deposition of film.The thickness of film is deposited into 150nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample BaAl
1.95s
4: 0.05Ce
3++.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 11: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-3pa; Then substrate is carried out 700 DEG C of thermal treatments 10 minutes, then temperature reduces to 250 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 50 revs/min, passes into organic source (DPM)
2ba, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.92: 0.08, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 10sccm, starts the deposition of film.The thickness of film is deposited into 80nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample BaAl
1.92s
4: 0.08Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 12: substrate is ito glass, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate, then clean with distilled water flushing, the air-dry rear feeding equipment reaction chamber of nitrogen.With mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-2pa; Then substrate is carried out 700 DEG C of thermal treatments 30 minutes, then temperature reduces to 650 DEG C.Open rotating machine, the rotating speed regulating substrate bracket is 1000 revs/min, passes into organic source (DPM)
2ba, trimethyl aluminium (TMAl) and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium (Ce (TMHD)
4) mol ratio be 1: 0.99: 0.01, gas of carrier gas is argon gas, and argon stream amount is 10sccm.Pass into hydrogen sulfide, stink damp flow is 200sccm, starts the deposition of film.The thickness of film is deposited into 300nm, closes organic source and carrier gas, and continue logical hydrogen sulfide, temperature drops to less than 100 DEG C, takes out sample BaAl
1.99s
4: 0.01Ce
3+.Finally evaporation one deck Ag on light-emitting film, as negative electrode.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (4)
1. a preparation method for cerium dopping sulphoaluminate light-emitting film, is characterized in that, comprises the following steps:
Substrate is loaded 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;
Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to MeAl
2-xs
4: xCe
3+the stoichiometric ratio of each element is by (DPM)
2me, trimethyl aluminium and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium passes in reaction chamber, wherein, (DPM)
2me is dipivaloylmethane hydrochlorate; And
Pass into hydrogen sulfide, carrying out chemical vapour deposition, to obtain chemical expression be MeAl
2-xs
4: xCe
3+cerium dopping sulphoaluminate light-emitting film, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and Me is Mg, Ca, Sr or Ba;
Described argon stream amount is 5 ~ 15sccm, and described stink damp flow is 10 ~ 200sccm.
2. the preparation method of cerium dopping sulphoaluminate light-emitting film according to claim 1, is characterized in that, described (DPM)
2me, the mol ratio of trimethyl aluminium and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium is 1:(0.92 ~ 0.99): (0.01 ~ 0.08).
3. the preparation method of cerium dopping sulphoaluminate light-emitting film according to claim 1, is characterized in that, is loaded the thermal treatment 10 minutes ~ 30 minutes at 600 DEG C ~ 800 DEG C of described substrate by described substrate after described reaction chamber.
4. a preparation method for membrane electro luminescent device, is characterized in that, comprises the following steps:
The substrate with anode is provided;
Described anode forms luminescent layer, and the material of described luminescent layer is cerium dopping sulphoaluminate light-emitting film, and the chemical expression of this cerium dopping sulphoaluminate light-emitting film is MeAl
2-xs
4: xCe
3+, wherein MeAl
2-xs
4be matrix, Ce element is active element, 0.01≤x≤0.08, and wherein, Me is Mg, Ca, Sr or Ba; And
Form negative electrode on the light-emitting layer;
The preparation of described luminescent layer comprises the following steps:
Substrate is loaded 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;
Regulate substrate temperature to be 250 DEG C ~ 650 DEG C, rotating speed is 50 revs/min ~ 1000 revs/min, under the carrier of argon stream, according to MeAl
2-xs
4: xCe
3+the stoichiometric ratio of each element is by (DPM)
2me, trimethyl aluminium and four (acid of 2,2,6,6-tetramethyl--3,5-heptadione) cerium passes in reaction chamber, and argon stream amount is 5 ~ 15sccm, wherein, (DPM)
2me is dipivaloylmethane hydrochlorate; And
Pass into hydrogen sulfide, stink damp flow is 10 ~ 200sccm, carries out chemical vapour deposition film and form luminescent layer on described anode.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0740490A1 (en) * | 1994-11-14 | 1996-10-30 | Mitsui Mining & Smelting Co., Ltd. | Thin-film electroluminescent element |
CN1682570A (en) * | 2002-09-12 | 2005-10-12 | 伊菲雷技术公司 | Silicon oxynitride passivated rare earth activated thioaluminate phosphors for electroluminescent displays |
CN1926259A (en) * | 2004-03-04 | 2007-03-07 | 伊菲雷技术公司 | Reactive metal sources and deposition method for thioaluminate phosphors |
CN1989223A (en) * | 2004-07-22 | 2007-06-27 | 伊菲雷技术公司 | Aluminum oxide and aluminum oxynitride layers for use with phosphors for electroluminescent displays |
CN1993447A (en) * | 2004-08-06 | 2007-07-04 | 伊菲雷技术公司 | Barium thioaluminate phosphor materials with novel crystal structures |
CN101690400A (en) * | 2007-04-30 | 2010-03-31 | 伊菲雷知识产权公司 | Laminated thick film dielectric structure for thick film dielectric electroluminescent displays |
CN101872741A (en) * | 2009-04-24 | 2010-10-27 | 晶元光电股份有限公司 | Dominant wavelength distribution convergent light emitting element and manufacturing method thereof |
-
2012
- 2012-02-28 CN CN201210047870.5A patent/CN103289687B/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0740490A1 (en) * | 1994-11-14 | 1996-10-30 | Mitsui Mining & Smelting Co., Ltd. | Thin-film electroluminescent element |
CN1682570A (en) * | 2002-09-12 | 2005-10-12 | 伊菲雷技术公司 | Silicon oxynitride passivated rare earth activated thioaluminate phosphors for electroluminescent displays |
CN1926259A (en) * | 2004-03-04 | 2007-03-07 | 伊菲雷技术公司 | Reactive metal sources and deposition method for thioaluminate phosphors |
CN1989223A (en) * | 2004-07-22 | 2007-06-27 | 伊菲雷技术公司 | Aluminum oxide and aluminum oxynitride layers for use with phosphors for electroluminescent displays |
CN1993447A (en) * | 2004-08-06 | 2007-07-04 | 伊菲雷技术公司 | Barium thioaluminate phosphor materials with novel crystal structures |
CN101690400A (en) * | 2007-04-30 | 2010-03-31 | 伊菲雷知识产权公司 | Laminated thick film dielectric structure for thick film dielectric electroluminescent displays |
CN101872741A (en) * | 2009-04-24 | 2010-10-27 | 晶元光电股份有限公司 | Dominant wavelength distribution convergent light emitting element and manufacturing method thereof |
Non-Patent Citations (1)
Title |
---|
陈光华,等.绪论.《新型电子薄膜材料》.化学工业出版社,2002,6. * |
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