CN103289682B - Fluorine copper codoped sulfurated lime luminescent material, preparation method and application thereof - Google Patents
Fluorine copper codoped sulfurated lime luminescent material, preparation method and application thereof Download PDFInfo
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- CN103289682B CN103289682B CN201210047862.0A CN201210047862A CN103289682B CN 103289682 B CN103289682 B CN 103289682B CN 201210047862 A CN201210047862 A CN 201210047862A CN 103289682 B CN103289682 B CN 103289682B
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- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 title claims abstract description 55
- 229940051851 sulfurated lime Drugs 0.000 title claims abstract description 55
- MVOSNYGTDFGKIB-UHFFFAOYSA-N [F].[Cu] Chemical compound [F].[Cu] MVOSNYGTDFGKIB-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 23
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 239000010408 film Substances 0.000 abstract description 33
- 239000010409 thin film Substances 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000009832 plasma treatment Methods 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Physical Vapour Deposition (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
A kind of fluorine copper codoped sulfurated lime luminescent material, its chemical formula is CaS:xCu
2+, yF
-, wherein 0.005≤x≤0.05,0.001≤y≤0.03.In the electroluminescent spectrum (EL) of the light-emitting film that this fluorine copper codoped sulfurated lime luminescent material is made, there is very strong glow peak in 437nm wavelength zone, can be applied in thin-film electroluminescent displays.The present invention also provides preparation method and the application thereof of this fluorine copper codoped sulfurated lime luminescent material.
Description
[technical field]
The present invention relates to a kind of fluorine copper codoped sulfurated lime luminescent material, its preparation method, fluorine copper codoped sulfurated lime 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 material of exploitation multiband luminescence is the developing direction of this problem.But, can be applicable to the fluorine copper codoped sulfurated lime luminescent material 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 fluorine copper codoped sulfurated lime luminescent material, its preparation method, fluorine copper codoped sulfurated lime light-emitting film, its preparation method, the membrane electro luminescent device using this fluorine copper codoped sulfurated lime luminescent material and preparation method thereof that can be applicable to membrane electro luminescent device.
A kind of fluorine copper codoped sulfurated lime luminescent material, its chemical formula is CaS:xCu
2+, yF
-, wherein CaS is matrix, and Cu element is active element, 0.005≤x≤0.05,0.001≤y≤0.03.
A preparation method for fluorine copper codoped sulfurated lime luminescent material, comprises the following steps:
According to CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2powder also mixes, wherein 0.005≤x≤0.05,0.001≤y≤0.03; And
Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being CaS:xCu at 900 DEG C ~ 1300 DEG C
2+, yF
-fluorine copper codoped sulfurated lime luminescent material.
A kind of fluorine copper codoped sulfurated lime light-emitting film, the chemical general formula of the material of this fluorine copper codoped sulfurated lime light-emitting film is CaS:xCu
2+, yF
-, wherein, CaS is matrix, and Cu element is active element, 0.005≤x≤0.05,0.001≤y≤0.03.
A preparation method for fluorine copper codoped sulfurated lime light-emitting film, comprises the following steps:
According to CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target, wherein 0.005≤x≤0.05,0.001≤y≤0.03 in 0.5 hour ~ 5 hours;
Described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa; And
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 50mm ~ 90mm, magnetron sputtering operating pressure 0.2Pa ~ 1.5Pa, the flow of working gas is 15sccm ~ 20sccm, and underlayer temperature is 200 DEG C ~ 500 DEG C, then be filmed, obtaining chemical formula is CaS:xCu
2+, yF
-fluorine copper codoped sulfurated lime light-emitting film.
In a preferred embodiment, also step is comprised: by described fluorine copper codoped sulfurated lime light-emitting film vacuum annealing process 0.5h ~ 3h at 500 DEG C ~ 800 DEG C.
In a preferred embodiment, the vacuum tightness of described vacuum cavity is 5.0 × 10
-4pa, base target spacing is 60mm, and magnetron sputtering operating pressure is 1Pa, and working gas is argon gas, and the flow of working gas is 20sccm, and underlayer temperature is 450 DEG C.
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 fluorine copper codoped sulfurated lime luminescent material, and the chemical formula of this fluorine copper codoped sulfurated lime luminescent material is CaS:xCu
2+, yF
-, wherein 0.005≤x≤0.05,0.001≤y≤0.03.
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 fluorine copper codoped sulfurated lime luminescent material, and the chemical formula of this fluorine copper codoped sulfurated lime luminescent material is CaS:xCu
2+, yF
-, wherein 0.005≤x≤0.05,0.001≤y≤0.03;
Form negative electrode on the light-emitting layer.
In a preferred embodiment, the preparation of described luminescent layer comprises the following steps:
According to CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target, wherein 0.005≤x≤0.05,0.001≤y≤0.03 in 0.5 hour ~ 5 hours;
Described target and described substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa;
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 50mm ~ 90mm, magnetron sputtering operating pressure 0.2Pa ~ 1.5Pa, the flow of working gas is 15sccm ~ 20sccm, and underlayer temperature is 200 DEG C ~ 500 DEG C, then be filmed, described anode forms luminescent layer.
In a preferred embodiment, the preparation of described luminescent layer also comprises step: by described luminescent layer vacuum annealing process 0.5h ~ 3h at 500 DEG C ~ 800 DEG C.
Above-mentioned fluorine copper codoped sulfurated lime luminescent material (CaS:xCu
2+, yF
-) in, CaS is matrix, Cu element is active element, main luminescence center is served as in luminescent material, the doping of F ion can make luminescent material produce a large amount of holes, plays a part to strengthen luminous speed, in the electroluminescent spectrum (EL) of the light-emitting film that fluorine copper codoped sulfurated lime luminescent material is made, there is very strong blue light emitting peak in 437nm 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 fluorine copper codoped sulfurated lime light-emitting film prepared by embodiment 1;
Fig. 3 is the XRD figure of fluorine copper codoped sulfurated lime light-emitting film prepared by embodiment 1.
[embodiment]
Below in conjunction with the drawings and specific embodiments, fluorine copper codoped sulfurated lime luminescent material, its preparation method, fluorine copper codoped sulfurated lime light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are illustrated further.
The fluorine copper codoped sulfurated lime luminescent material of one embodiment, its chemical formula is CaS:xCu
2+, yF
-, wherein, CaS is matrix, and Cu element is active element, 0.005≤x≤0.05,0.001≤y≤0.03.
Preferably, x is 0.025, y is 0.01.
In this fluorine copper codoped sulfurated lime luminescent material, CaS is matrix, and Cu element is that active element serves as main luminescence center in luminescent material, and the doping of F ion can make luminescent material produce a large amount of holes, plays a part to strengthen luminous speed.In the electroluminescent spectrum (EL) of the light-emitting film that this fluorine copper codoped sulfurated lime luminescent material is made, there is very strong glow peak in 437nm wavelength zone, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned fluorine copper codoped sulfurated lime luminescent material, comprises the following steps:
Step S11, according to CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2powder, wherein 0.005≤x≤0.05,0.001≤y≤0.03.
In this step, preferably, x is 0.025, y is 0.01.
Be appreciated that in this step and also can take CaS, CuS and CaF
2powder also mixes, and wherein the molar content of CuS is 0.5% ~ 5%, CaF
2molar content be 0.05% ~ 1.5%, surplus is CaS.Preferably, the molar content of CuS is 2.5%, CaF
2molar content be 0.5%.
Step S12, by mixing equal powder sinter 0.5 hour ~ 5 hours can obtain chemical formula being CaS:xCu at 900 DEG C ~ 1300 DEG C
2+, yF
-fluorine copper codoped sulfurated lime luminescent material.
In this step, preferably at 1200 DEG C, sinter 3 hours.
The fluorine copper codoped sulfurated lime light-emitting film of one embodiment, the chemical general formula of the material of this fluorine copper codoped sulfurated lime light-emitting film is CaS:xCu
2+, yF
-, wherein, CaS is matrix, and Cu element is active element, 0.005≤x≤0.05,0.001≤y≤0.03.
Preferably, x is 0.025, y is 0.01.
The preparation method of above-mentioned fluorine copper codoped sulfurated lime light-emitting film, comprises the following steps:
Step S21, by CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target, wherein 0.005≤x≤0.05,0.001≤y≤0.03 in 0.5 hour ~ 5 hours.
In this step, preferably, x is 0.025, y is 0.01, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.
Be appreciated that in this step and also can take CaS, CuS and CaF
2powder also mixes, and wherein the molar content of CuS is 0.5% ~ 5%, CaF
2molar content be 0.05% ~ 1.5%, surplus is CaS.Preferably, the molar content of CuS is 2.5%, CaF
2molar content be 0.5%.
Step S22, the target that obtains in step S21 and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa.
In this step, preferably, vacuum tightness is 5 × 10
-4pa.Substrate is indium tin oxide glass (ITO), is appreciated that in other embodiments, can be also fluorine doped tin oxide glass (FTO), mixes the zinc oxide (AZO) of aluminium or mix the zinc oxide (IZO) of indium.
Step S23, adjustment magnetron sputtering plating processing parameter are: base target spacing is 50mm ~ 90mm, magnetron sputtering operating pressure 0.2Pa ~ 1.5Pa, and the flow of working gas is 15sccm ~ 20sccm, and underlayer temperature is 200 DEG C ~ 500 DEG C; Then be filmed, obtaining chemical formula is CaS:xCu
2+, yF
-fluorine copper codoped sulfurated lime light-emitting film.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 1Pa, and working gas is argon gas, and the flow of working gas is 20sccm, and underlayer temperature is 450 DEG C.
Step S24, by fluorine copper codoped sulfurated lime light-emitting film vacuum annealing process 0.5h ~ 3h at 500 DEG C ~ 800 DEG C.
In this step, preferably, film sample vacuum annealing process 1h at 650 DEG C.
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 fluorine copper codoped sulfurated lime luminescent material, and the chemical formula of this fluorine copper codoped sulfurated lime luminescent material is CaS:xCu
2+, yF
-, wherein 0.005≤x≤0.05,0.001≤y≤0.03.The material of negative electrode 4 is silver (Ag).
The preparation method of above-mentioned membrane electro luminescent device, comprises the following steps:
Step S31, 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.There is the substrate 1 priority acetone of anode 2, dehydrated alcohol and deionized water ultrasonic cleaning and carry out oxygen plasma treatment with to it.
Step S32, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is fluorine copper codoped sulfurated lime luminescent material, and the chemical formula of this fluorine copper codoped sulfurated lime luminescent material is CaS:xCu
2+, yF
-, wherein 0.005≤x≤0.05,0.001≤y≤0.03.
In present embodiment, luminescent layer 3 is obtained by following steps:
First, according to CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target, wherein 0.005≤x≤0.05,0.001≤y≤0.03 in 0.5 hour ~ 5 hours.
In this step, preferably, x is 0.025, y is 0.01, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.
Be appreciated that in this step and also can take CaS, CuS and CaF
2powder also mixes, and wherein the molar content of CuS is 0.5% ~ 5%, CaF
2molar content be 0.05% ~ 1.5%, surplus is CaS.Preferably, the molar content of CuS is 2.5%, CaF
2molar content be 0.5%.
Secondly, target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa.
In this step, preferably, vacuum tightness is 5 × 10
-4pa.
Then, adjusting magnetron sputtering plating processing parameter is: base target spacing is 50mm ~ 90mm, magnetron sputtering operating pressure 0.2Pa ~ 1.5Pa, the flow of working gas is 15sccm ~ 20sccm, underlayer temperature is 200 DEG C ~ 500 DEG C, is then filmed, and anode 2 is formed luminescent layer 3.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 1Pa, and working gas is argon gas, and the flow of working gas is 20sccm, and underlayer temperature is 450 DEG C.
Finally, by luminescent layer 3 vacuum annealing process 0.5h ~ 3h at 500 DEG C ~ 800 DEG C.
In this step, preferably, film sample vacuum annealing process 1h at 650 DEG C.
Step S33, 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
Select purity be 99.99% powder, by CaS, CuS and CaF
2after mol ratio 97: 2.5: 0.5 Homogeneous phase mixing, at 1200 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.And target is loaded in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 × 10
-4pa, the airshed of argon working gas is 20sccm, and pressure is adjusted to 1.0Pa, and underlayer temperature is 450 DEG C.The sample obtained is annealed 1h in 0.01Pa vacuum oven, and annealing temperature is 650 DEG C, and obtaining chemical formula is CaS:0.025Cu
2+, 0.01F
-light-emitting film.Then evaporation one deck Ag on light-emitting film, as negative electrode.
The chemical general formula of the fluorine copper codoped sulfurated lime light-emitting film obtained in the present embodiment is CaS:0.025Cu
2+, 0.01F
-, wherein CaS is matrix, and Cu element is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the fluorine copper codoped sulfurated lime light-emitting film obtained.As seen from Figure 2, in electroluminescence spectrum, there is very strong glow peak in 437nm wavelength zone, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of fluorine copper codoped sulfurated lime light-emitting film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3, all diffraction peaks are all the characteristic peaks that sulfurated lime is relevant, do not occur the diffraction peak of doped element and other impurity, prove that doped element is the lattice entering sulfurated lime.
Embodiment 2
Select purity be 99.99% powder, by CaS, CuS and CaF
2after mol ratio 99.45: 0.5: 0.05 Homogeneous phase mixing, at 900 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.And target is loaded in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 50mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10
-5pa, the airshed of argon working gas is 25sccm, and pressure is adjusted to 1.5Pa, and underlayer temperature is 500 DEG C.The sample obtained is annealed 1h in 0.01Pa vacuum oven, and annealing temperature is 800 DEG C, and obtaining chemical formula is CaS:0.005Cu
2+, 0.001F
-light-emitting film.Then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 3
Select purity be 99.99% powder, by CaS, CuS and CaF
2after mol ratio 93.5: 5: 1.5 Homogeneous phase mixing, at 1300 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.And target is loaded in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 90mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10
-3pa, the airshed of argon working gas is 15sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C.The sample obtained is annealed 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C, and obtaining chemical formula is CaS:0.05Cu
2+, 0.03F
-light-emitting film.Then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 4
Select purity be 99.99% powder, by CaS, CuS and CaF
2after mol ratio 97: 2: 1 Homogeneous phase mixing, at 1300 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.And target is loaded in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 90mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10
-3pa, the airshed of argon working gas is 15sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C.The sample obtained is annealed 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C, and obtaining chemical formula is CaS:0.02Cu
2+, 0.02F
-light-emitting film.Then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 5
Select purity be 99.99% powder, by CaS, CuS and CaF
2after mol ratio 98: 1.5: 0.5 Homogeneous phase mixing, at 1300 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.And target is loaded in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and carry out oxygen plasma treatment with to it, put into vacuum cavity.The distance of target and substrate is set as 90mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10
-3pa, the airshed of argon working gas is 15sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 DEG C.The sample obtained is annealed 1h in 0.01Pa vacuum oven, and annealing temperature is 500 DEG C, and obtaining chemical formula is CaS:0.015Cu
2+, 0.01F
-light-emitting film.Then 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 (5)
1. a preparation method for fluorine copper codoped sulfurated lime light-emitting film, is characterized in that, comprise the following steps:
According to CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2and to mix at 900 DEG C ~ 1300 DEG C sintering and make target, wherein x=0.025, y=0.01 in 0.5 hour ~ 5 hours;
Described target and substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa; And
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 50mm ~ 90mm, magnetron sputtering operating pressure 0.2Pa ~ 1.5Pa, the flow of working gas is 15sccm ~ 20sccm, and underlayer temperature is 200 DEG C ~ 500 DEG C, then be filmed, obtaining chemical formula is CaS:xCu
2+, yF
-fluorine copper codoped sulfurated lime light-emitting film.
2. the preparation method of fluorine copper codoped sulfurated lime light-emitting film according to claim 1, is characterized in that, also comprise step: by described fluorine copper codoped sulfurated lime light-emitting film vacuum annealing process 0.5h ~ 3h at 500 DEG C ~ 800 DEG C.
3. the preparation method of fluorine copper codoped sulfurated lime light-emitting film according to claim 1, it is characterized in that, the vacuum tightness of described vacuum cavity is 5.0 × 10
-4pa, base target spacing is 60mm, and magnetron sputtering operating pressure is 1Pa, and working gas is argon gas, and the flow of working gas is 20sccm, and underlayer temperature is 450 DEG C.
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 fluorine copper codoped sulfurated lime luminescent material, and the chemical formula of this fluorine copper codoped sulfurated lime luminescent material is CaS:xCu
2+, yF
-, wherein x=0.025, y=0.01;
Form negative electrode on the light-emitting layer,
The preparation of described luminescent layer comprises the following steps:
According to CaS:xCu
2+, yF
-the stoichiometric ratio of each element takes CaS, CuS and CaF
2powder also to mix at 900 DEG C ~ 1300 DEG C sintering and makes target, wherein x=0.025, y=0.01 in 0.5 hour ~ 5 hours;
Described target and described substrate are loaded the vacuum cavity of magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 × 10
-3pa ~ 1.0 × 10
-5pa;
Adjustment magnetron sputtering plating processing parameter is: base target spacing is 50mm ~ 90mm, magnetron sputtering operating pressure 0.2Pa ~ 1.5Pa, the flow of working gas is 15sccm ~ 20sccm, and underlayer temperature is 200 DEG C ~ 500 DEG C, then be filmed, described anode forms luminescent layer.
5. the preparation method of membrane electro luminescent device according to claim 4, is characterized in that, the preparation of described luminescent layer also comprises step: by described luminescent layer vacuum annealing process 0.5h ~ 3h at 500 DEG C ~ 800 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0030853A1 (en) * | 1979-12-12 | 1981-06-24 | Hitachi, Ltd. | Phosphor and method of manufacturing the phosphor |
| WO2004007636A1 (en) * | 2002-07-16 | 2004-01-22 | Futaba Corporation | Composite nanoparticle and process for producing the same |
| CN1536684A (en) * | 2003-04-03 | 2004-10-13 | 诠兴开发科技股份有限公司 | Long afterglow LED |
| CN101516146A (en) * | 2008-02-22 | 2009-08-26 | 株式会社半导体能源研究所 | Method for producing inorganic EL blue light-emitting body |
| CN101768728A (en) * | 2010-01-15 | 2010-07-07 | 深圳大学 | Method for preparing doped ZnO-based film through magnetron sputtering |
-
2012
- 2012-02-28 CN CN201210047862.0A patent/CN103289682B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0030853A1 (en) * | 1979-12-12 | 1981-06-24 | Hitachi, Ltd. | Phosphor and method of manufacturing the phosphor |
| WO2004007636A1 (en) * | 2002-07-16 | 2004-01-22 | Futaba Corporation | Composite nanoparticle and process for producing the same |
| CN1536684A (en) * | 2003-04-03 | 2004-10-13 | 诠兴开发科技股份有限公司 | Long afterglow LED |
| CN101516146A (en) * | 2008-02-22 | 2009-08-26 | 株式会社半导体能源研究所 | Method for producing inorganic EL blue light-emitting body |
| CN101768728A (en) * | 2010-01-15 | 2010-07-07 | 深圳大学 | Method for preparing doped ZnO-based film through magnetron sputtering |
Non-Patent Citations (1)
| Title |
|---|
| "Luminescent Properties of CaS Phosphors Activated by Copper and Fluorine";Nakanishi Y. 等;《Journal of Crystal Growth》;19900401;第101卷(第1-4 期);第462-465页 * |
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