CN103421510A - Antimony terbium co-doped alkaline earth halogen phosphate luminescent material and preparation method and application thereof - Google Patents
Antimony terbium co-doped alkaline earth halogen phosphate luminescent material and preparation method and application thereof Download PDFInfo
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- CN103421510A CN103421510A CN201210151221XA CN201210151221A CN103421510A CN 103421510 A CN103421510 A CN 103421510A CN 201210151221X A CN201210151221X A CN 201210151221XA CN 201210151221 A CN201210151221 A CN 201210151221A CN 103421510 A CN103421510 A CN 103421510A
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- alkaline earth
- antimony
- earth halogen
- phosphate
- ytb
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 62
- 239000010452 phosphate Substances 0.000 title claims abstract description 60
- FOYOVPODKSVTNZ-UHFFFAOYSA-N antimony terbium Chemical compound [Sb].[Tb] FOYOVPODKSVTNZ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052736 halogen Inorganic materials 0.000 title abstract 5
- -1 halogen phosphate Chemical class 0.000 title abstract 5
- 239000000126 substance Substances 0.000 claims abstract description 35
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 9
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 239000010409 thin film Substances 0.000 abstract description 7
- 238000001228 spectrum Methods 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract 2
- 229910052787 antimony Inorganic materials 0.000 abstract 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- 239000011521 glass Substances 0.000 description 16
- 239000000919 ceramic Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229960000935 dehydrated alcohol Drugs 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 238000009832 plasma treatment Methods 0.000 description 13
- 238000004506 ultrasonic cleaning Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 3
- 241001289141 Babr Species 0.000 description 2
- 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
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity 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
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
An antimony terbium co-doped alkaline earth halogen phosphate luminescent material has the following chemical general formula of Me2(PO4).F[a]Cl[b]Br[c]:xSb<3+>,yTb<3+>, wherein Me2(PO4).F[a]Cl[b]Br[c] is a matrix, element antimony and element terbium are active elements, Me is Mg, Ca, Ba or Sr, 0<= a <=0.8, 0<= b <= 0.8, 0<= c <=0.4, 0.01<= x <=0.05, 0.01<= y <=0.08 and a+b+c=1. In an electroluminescence (EL) spectrum of a luminescent thin film prepared by the antimony terbium co-doped alkaline earth halogen phosphate luminescent material, wavelength regions of 490 nm and 580 nm have very strong luminescence peaks, and the antimony terbium co-doped alkaline earth halogen phosphate luminescent material can be used in a thin-film electroluminescent display. The invention also provides a preparation method and application of the antimony terbium co-doped alkaline earth halogen phosphate luminescent material.
Description
[technical field]
The present invention relates to a kind of antimony terbium codoped alkaline earth halogen-phosphate luminescent material, its preparation method, antimony terbium codoped alkaline earth halogen-phosphate 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 is colored to be reached to panchromatic TFELD, and the luminous material of exploitation multiband, be the developing direction of this problem.But, can be applicable to the antimony terbium codoped alkaline earth halogen-phosphate 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 antimony terbium codoped alkaline earth halogen-phosphate luminescent material, its preparation method, antimony terbium codoped alkaline earth halogen-phosphate light-emitting film, its preparation method that can be applicable to membrane electro luminescent device, use membrane electro luminescent device of this antimony terbium codoped alkaline earth halogen-phosphate luminescent material and preparation method thereof.
A kind of antimony terbium codoped alkaline earth halogen-phosphate luminescent material, its chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
In a preferred embodiment, a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04.
A kind of preparation method of antimony terbium codoped alkaline earth halogen-phosphate luminescent material comprises the following steps:
According to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1; And
The powder mixed is obtained to chemical formula in 0.5 hour～5 hours at 900 ℃～1300 ℃ lower sintering is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+Antimony terbium codoped alkaline earth halogen-phosphate luminescent material.
A kind of antimony terbium codoped alkaline earth halogen-phosphate light-emitting film, the chemical general formula of the material of this antimony terbium codoped alkaline earth halogen-phosphate light-emitting film is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
In a preferred embodiment, a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04.
A kind of preparation method of antimony terbium codoped alkaline earth halogen-phosphate light-emitting film comprises the following steps:
According to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes at 900 ℃～1300 ℃ lower sintering and within 0.5 hour～5 hours, makes target, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1;
By pack into the vacuum cavity of magnetic-controlled sputtering coating equipment of described target and substrate, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3Pa～1.0 * 10
-5Pa; And
Adjusting the magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, and underlayer temperature is 250 ℃～750 ℃, and the energy of laser is 80W～300W, magnetron sputtering operating pressure 0.5Pa～5Pa, the flow of working gas is 10sccm～40sccm, then is filmed, and obtaining chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+Antimony terbium codoped alkaline earth halogen-phosphate light-emitting film.
In a preferred embodiment, the vacuum tightness of described vacuum cavity is 5.0 * 10
-4Pa, base target spacing is 60mm, and underlayer temperature is 500 ℃, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, working gas is oxygen, working gas flow is 20sccm.
A kind of membrane electro luminescent device, this membrane electro luminescent device comprises substrate, anode layer, luminescent layer and the cathode layer stacked gradually, the material of described luminescent layer is antimony terbium codoped alkaline earth halogen-phosphate luminescent material, and the chemical formula of this antimony terbium codoped alkaline earth halogen-phosphate luminescent material is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
A kind of preparation method of membrane electro luminescent device comprises the following steps:
Substrate with anode is provided;
Form luminescent layer on described anode, the material of described luminescent layer is antimony terbium codoped alkaline earth halogen-phosphate luminescent material, and the chemical formula of this antimony terbium codoped alkaline earth halogen-phosphate luminescent material is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1;
Form negative electrode on described luminescent layer.
In a preferred embodiment, the preparation of described luminescent layer comprises the following steps:
According to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes at 900 ℃～1300 ℃ lower sintering and within 0.5 hour～5 hours, makes target, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1;
By pack into the vacuum cavity of magnetic-controlled sputtering coating equipment of described target and described substrate, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3Pa～1.0 * 10
-5Pa;
Adjusting the magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, and underlayer temperature is 250 ℃～750 ℃, and the energy of laser is 80W～300W, magnetron sputtering operating pressure 0.5Pa～5Pa, the flow of working gas is 10sccm～40sccm, then is filmed, and obtaining chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, on described anode, form luminescent layer.
Above-mentioned antimony terbium codoped alkaline earth halogen-phosphate luminescent material (Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+) in the electroluminescent spectrum (EL) of the light-emitting film made, at 490nm and 580nm wavelength zone, very strong glow peak being arranged, can be applied in thin-film electroluminescent displays.
[accompanying drawing explanation]
The structural representation of the membrane electro luminescent device that Fig. 1 is an embodiment;
The electroluminescent spectrogram of the antimony terbium codoped alkaline earth halogen-phosphate light-emitting film that Fig. 2 is embodiment 1 preparation;
The XRD figure of the antimony terbium codoped alkaline earth halogen-phosphate light-emitting film that Fig. 3 is embodiment 1 preparation;
Voltage and electric current and the brightness relationship figure of the membrane electro luminescent device that Fig. 4 is embodiment 1 preparation.
[embodiment]
Below in conjunction with the drawings and specific embodiments, antimony terbium codoped alkaline earth halogen-phosphate luminescent material, its preparation method, antimony terbium codoped alkaline earth halogen-phosphate light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are further illustrated.
The antimony terbium codoped alkaline earth halogen-phosphate luminescent material of one embodiment, its chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
Preferably, a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04.
Me in this antimony terbium codoped alkaline earth halogen-phosphate luminescent material
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements.In the electroluminescent spectrum (EL) of the light-emitting film that this antimony terbium codoped alkaline earth halogen-phosphate luminescent material is made, at 490nm and 580nm wavelength zone, very strong glow peak is arranged, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned antimony terbium codoped alkaline earth halogen-phosphate luminescent material comprises the following steps:
Step S11, according to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
In this step, preferred, a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04.
Step S12, mixing equal powder, within 0.5 hour～5 hours, can to obtain chemical formula at 900 ℃～1300 ℃ lower sintering be Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+Antimony terbium codoped alkaline earth halogen-phosphate luminescent material.
In this step, preferably 1250 ℃ of lower sintering 3 hours.
The antimony terbium codoped alkaline earth halogen-phosphate light-emitting film of one embodiment, the chemical general formula of the material of this antimony terbium codoped alkaline earth halogen-phosphate light-emitting film is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
Preferably, a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04.
The preparation method of above-mentioned antimony terbium codoped alkaline earth halogen-phosphate light-emitting film comprises the following steps:
Step S21, press Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes at 900 ℃～1300 ℃ lower sintering and within 0.5 hour～5 hours, makes target, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
In this step, preferred, a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04, and within 3 hours, becoming diameter at 1250 ℃ of lower sintering is 50mm, the ceramic target that thickness is 2mm.
Step S22, by pack into the vacuum cavity of magnetic-controlled sputtering coating equipment of the target that obtains in step S21 and substrate, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3Pa～1.0 * 10
-5Pa.
In this step, preferred, vacuum tightness is 5 * 10
-4Pa.
Step S23, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45mm～95mm, underlayer temperature is 250 ℃～750 ℃, the energy of laser is 80W～300W, magnetron sputtering operating pressure 0.5Pa～5Pa, the flow of working gas is 10sccm～40sccm, then be filmed, obtaining chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+Antimony terbium codoped alkaline earth halogen-phosphate light-emitting film.
In this step, preferred base target spacing is 60mm, and underlayer temperature is 500 ℃, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, and working gas is oxygen, working gas flow is 20sccm.。
Refer to Fig. 1, the membrane electro luminescent device 100 of an embodiment, this membrane electro luminescent device 100 comprises substrate 1, anode 2, luminescent layer 3 and the negative electrode 4 stacked gradually.
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) on glass substrate.Substrate 1 with anode 2 is successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning and use it is carried out to oxygen plasma treatment.
Step S32, form luminescent layer 3 on anode 2, the material of luminescent layer 3 is antimony terbium codoped alkaline earth halogen-phosphate luminescent material, and the chemical formula of this antimony terbium codoped alkaline earth halogen-phosphate luminescent material is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
In present embodiment, luminescent layer 3 is made by following steps:
At first, according to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes at 900 ℃～1300 ℃ lower sintering and within 0.5 hour～5 hours, makes target, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
In this step, preferred, a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04, and within 3 hours, becoming diameter at 1250 ℃ of lower sintering is 50mm, the ceramic target that thickness is 2mm.
Secondly, by pack into the vacuum cavity of magnetic-controlled sputtering coating equipment of target and substrate, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3Pa～1.0 * 10
-5Pa.
In this step, preferred, vacuum tightness is 5 * 10
-4Pa.
Then, adjusting the magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, underlayer temperature is 250 ℃～750 ℃, the energy of laser is 80W～300W, magnetron sputtering operating pressure 0.5Pa～5Pa, the flow of working gas is 10sccm～40sccm, then is filmed, and obtaining chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+Antimony terbium codoped alkaline earth halogen-phosphate light-emitting film, form luminescent layer 3 on anode 2.
In this step, the vacuum tightness of preferred described vacuum cavity is 5.0 * 10
-4Pa, base target spacing is 60mm, and underlayer temperature is 500 ℃, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, working gas is oxygen, working gas flow is 20sccm.
Step S33, form negative electrode 4 on luminescent layer 3.
In present embodiment, the material of negative electrode 4 is silver (Ag), by evaporation, is formed.
It is below specific embodiment.
By the MgO of 1mol, the P of 0.5mol
2O
5, the MgF of 0.2mol
2, the MgCl of 0.2mol
2, the MgBr of 0.1mol
2, the SbO of 0.02mol
2Tb with 0.01mol
4O
7, after even mixing, sintering diameter under 1250 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 5.0 * 10
-4Pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 ℃, and laser energy is 150W.Obtaining chemical formula is Mg
2(PO
4) F
0.4Cl
0.4Br
0.2: 0.02Sb
3+, 0.04Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
The chemical general formula of the antimony terbium codoped alkaline earth halogen-phosphate light-emitting film obtained in the present embodiment is Mg
2(PO
4) F
0.4Cl
0.4Br
0.2: 0.02Sb
3+, 0.04Tb
3+, Mg wherein
2(PO
4) F
0.4Cl
0.4Br
0.2Be matrix, antimony element and terbium element are active elements.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the antimony terbium codoped alkaline earth halogen-phosphate light-emitting film obtained.As seen from Figure 2, in electroluminescence spectrum, at 490nm and 580nm wavelength zone, very strong glow peak is arranged, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, the XRD curve of the antimony terbium codoped alkaline earth halogen-phosphate light-emitting film that Fig. 3 is embodiment 1 preparation, test comparison standard P DF card.As can be seen from Figure 3, diffraction peak is all the peak crystallization that the alkaline earth halogen-phosphate is relevant, the diffraction peak of doped element and other impurity do not occur.
Refer to Fig. 4, voltage and electric current and the brightness relationship figure of the membrane electro luminescent device that Fig. 4 is embodiment 1 preparation, in accompanying drawing 4, curve 1 is voltage and current density relation curve, can find out that device starts from 6V luminous, curve 2 is voltage and brightness relationship curve, and high-high brightness is 78cd/m
2, show that device has the good characteristics of luminescence.
Embodiment 2
By the MgO of 1mol, the P of 0.5mol
2O
5, the MgF of 0.4mol
2, the MgCl of 0.1mol
2, the SbO of 0.01mol
2Tb with 0.02mol
4O
7, after even mixing, sintering diameter under 900 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-3Pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 ℃, and laser energy is 80W.Obtaining chemical formula is Mg
2(PO
4) F
0.8Cl
0.2: 0.01Sb
3+, 0.08Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 3
By the MgO of 1mol, the P of 0.5mol
2O
5, the MgF of 0.05mol
2, the MgCl of 0.8mol
2, the MgBr of 0.05mol
2, the SbO of 0.05mol
2Tb with 0.0025mol
4O
7, after even mixing, sintering diameter under 1300 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-5Pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 ℃, and laser energy is 300W.Obtaining chemical formula is Mg
2(PO
4) F
0.1Cl
0.8Br
0.1: 0.05Sb
3+, 0.01Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
By the CaO of 1mol, the P of 0.5mol
2O
5, the CaF of 0.2mol
2, the CaCl of 0.2mol
2, the CaBr of 0.1mol
2, the SbO of 0.02mol
2Tb with 0.01mol
4O
7, after even mixing, sintering diameter under 1250 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 5.0 * 10
-4Pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 ℃, and laser energy is 150W.Obtaining chemical formula is Ca
2(PO
4) F
0.4Cl
0.4Br
0.2: 0.02Sb
3+, 0.04Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
By the CaO of 1mol, the P of 0.5mol
2O
5, the CaF of 0.4mol
2, the CaBr of 0.1mol
2, the SbO of 0.01mol
2Tb with 0.02mol
4O
7, after even mixing, sintering diameter under 900 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-3Pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 ℃, and laser energy is 80W.Obtaining chemical formula is Ca
2(PO
4) F
0.8Br
0.2: 0.01Sb
3+, 0.08Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 6
By the CaO of 1mol, the P of 0.5mol
2O
5, the CaF of 0.05mol
2, the CaCl of 0.8mol
2, the CaBr of 0.05mol
2, the SbO of 0.05mol
2Tb with 0.0025mol
4O
7, after even mixing, sintering diameter under 1300 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-5Pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 ℃, and laser energy is 300W.Obtaining chemical formula is Ca
2(PO
4) F
0.1Cl
0.8Br
0.1: 0.05Sb
3+, 0.01Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
By the SrO of 1mol, the P of 0.5mol
2O
5, the SrF of 0.1mol
2, the SrCl of 0.2mol
2, the SrBr of 0.2mol
2, the SbO of 0.02mol
2Tb with 0.01mol
4O
7, after even mixing, sintering diameter under 1250 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 5.0 * 10
-4Pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 ℃, and laser energy is 150W.Obtaining chemical formula is Sr
2(PO
4) F
0.2Cl
0.4Br
0.4: 0.02Sb
3+, 0.04Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 8
By the SrO of 1mol, the P of 0.5mol
2O
5, the SrF of 0.4mol
2, the SrCl of 0.1mol
2, the SbO of 0.01mol
2Tb with 0.02mol
4O
7, after even mixing, sintering diameter under 900 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-3Pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 ℃, and laser energy is 80W.Obtaining chemical formula is Sr
2(PO
4) F
0.8Cl
0.2: 0.01Sb
3+, 0.08Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 9
By the SrO of 1mol, the P of 0.5mol
2O
5, the SrF of 0.05mol
2, the SrCl of 0.8mol
2, the SrBr of 0.05mol
2, the SbO of 0.05mol
2Tb with 0.0025mol
4O
7, after even mixing, sintering diameter under 1300 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-5Pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 ℃, and laser energy is 300W.Obtaining chemical formula is Sr
2(PO
4) F
0.1Cl
0.8Br
0.1: 0.05Sb
3+, 0.01Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
By the BaO of 1mol, the P of 0.5mol
2O
5, the BaF of 0.2mol
2, the BaCl of 0.2mol
2, the BaBr of 0.1mol
2, the SbO of 0.02mol
2Tb with 0.01mol
4O
7, after even mixing, sintering diameter under 1250 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 60mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 5.0 * 10
-4Pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 ℃, and laser energy is 150W.Obtaining chemical formula is Ba
2(PO
4) F
0.4Cl
0.4Br
0.2: 0.02Sb
3+, 0.04Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 11
By the BaO of 1mol, the P of 0.5mol
2O
5, the BaF of 0.4mol
2, the BaCl of 0.1mol
2, the SbO of 0.01mol
2Tb with 0.02mol
4O
7, after even mixing, sintering diameter under 900 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-3Pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 ℃, and laser energy is 80W.Obtaining chemical formula is Ba
2(PO
4) F
0.8Cl
0.2: 0.01Sb
3+, 0.08Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 12
By the BaO of 1mol, the P of 0.5mol
2O
5, the BaF of 0.05mol
2, the BaCl of 0.8mol
2, the BaBr of 0.05mol
2, the SbO of 0.05mol
2Tb with 0.0025mol
4O
7, after even mixing, sintering diameter under 1300 ℃ into is 50mm, the ceramic target that thickness is 2mm, and target is packed in vacuum cavity.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and use it is carried out to oxygen plasma treatment, put into vacuum cavity.The distance of target and substrate is set as to 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into to 1.0 * 10
-5Pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 ℃, and laser energy is 300W.Obtaining chemical formula is Ba
2(PO
4) F
0.1Cl
0.8Br
0.1: 0.05Sb
3+, 0.01Tb
3+Light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an antimony terbium codoped alkaline earth halogen-phosphate luminescent material, it is characterized in that: its chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
2. antimony terbium codoped alkaline earth halogen-phosphate luminescent material according to claim 1, it is characterized in that: a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04.
3. the preparation method of an antimony terbium codoped alkaline earth halogen-phosphate luminescent material, is characterized in that, comprises the following steps:
According to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1; And
The powder mixed is obtained to chemical formula in 0.5 hour～5 hours at 900 ℃～1300 ℃ lower sintering is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+Antimony terbium codoped alkaline earth halogen-phosphate luminescent material.
4. an antimony terbium codoped alkaline earth halogen-phosphate light-emitting film, is characterized in that, the chemical general formula of the material of this antimony terbium codoped alkaline earth halogen-phosphate light-emitting film is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
5. antimony terbium codoped alkaline earth halogen-phosphate light-emitting film according to claim 4, it is characterized in that: a is that 0.4, b is that 0.4, c is that 0.2, x is that 0.02, y is 0.04.
6. the preparation method of an antimony terbium codoped alkaline earth halogen-phosphate light-emitting film, is characterized in that, comprises the following steps:
According to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes at 900 ℃～1300 ℃ lower sintering and within 0.5 hour～5 hours, makes target, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1;
By pack into the vacuum cavity of magnetic-controlled sputtering coating equipment of described target and substrate, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3Pa～1.0 * 10
-5Pa; And
Adjusting the magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, and underlayer temperature is 250 ℃～750 ℃, and the energy of laser is 80W～300W, magnetron sputtering operating pressure 0.5Pa～5Pa, the flow of working gas is 10sccm～40sccm, then is filmed, and obtaining chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+Antimony terbium codoped alkaline earth halogen-phosphate light-emitting film.
7. the preparation method of antimony terbium codoped alkaline earth halogen-phosphate light-emitting film according to claim 6, is characterized in that, the vacuum tightness of described vacuum cavity is 5.0 * 10
-4Pa, base target spacing is 60mm, and underlayer temperature is 500 ℃, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, working gas is oxygen, working gas flow is 20sccm.
8. a membrane electro luminescent device, this membrane electro luminescent device comprises substrate, anode layer, luminescent layer and the cathode layer stacked gradually, it is characterized in that, the material of described luminescent layer is antimony terbium codoped alkaline earth halogen-phosphate luminescent material, and the chemical formula of this antimony terbium codoped alkaline earth halogen-phosphate luminescent material is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1.
9. the preparation method of a membrane electro luminescent device, is characterized in that, comprises the following steps:
Substrate with anode is provided;
Form luminescent layer on described anode, the material of described luminescent layer is antimony terbium codoped alkaline earth halogen-phosphate luminescent material, and the chemical formula of this antimony terbium codoped alkaline earth halogen-phosphate luminescent material is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, Me
2(PO
4) F
aCl
bBr
cBe matrix, antimony element and terbium element are active elements, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1;
Form negative electrode on 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 comprises the following steps:
According to Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+The stoichiometric ratio of each element takes MeO, P
2O
5, MeF
2, MeCl
2, MeBr
2, SbO
2And Tb
4O
7Powder also mixes at 900 ℃～1300 ℃ lower sintering and within 0.5 hour～5 hours, makes target, and wherein Me is Mg, Ca, Ba or Sr, 0≤a≤0.8,0≤b≤0.8,0≤c≤0.4,0.01≤x≤0.05,0.01≤y≤0.08 and a+b+c=1;
By pack into the vacuum cavity of magnetic-controlled sputtering coating equipment of described target and described substrate, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3Pa～1.0 * 10
-5Pa;
Adjusting the magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, and underlayer temperature is 250 ℃～750 ℃, and the energy of laser is 80W～300W, magnetron sputtering operating pressure 0.5Pa～5Pa, the flow of working gas is 10sccm～40sccm, then is filmed, and obtaining chemical formula is Me
2(PO
4) F
aCl
bBr
c: xSb
3+, yTb
3+, on described anode, form luminescent layer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010010367A1 (en) * | 1998-10-13 | 2001-08-02 | Peter Burnell-Jones | Luminescent gel coats and moldable resins |
| WO2004056940A1 (en) * | 2002-12-20 | 2004-07-08 | Toyoda Gosei Co., Ltd. | Phosphor and optical device using same |
| CN1775902A (en) * | 2005-12-16 | 2006-05-24 | 中国科学院长春应用化学研究所 | A kind of alkaline earth phosphate long afterglow luminescent material and its preparation method |
-
2012
- 2012-05-16 CN CN201210151221.XA patent/CN103421510B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010010367A1 (en) * | 1998-10-13 | 2001-08-02 | Peter Burnell-Jones | Luminescent gel coats and moldable resins |
| WO2004056940A1 (en) * | 2002-12-20 | 2004-07-08 | Toyoda Gosei Co., Ltd. | Phosphor and optical device using same |
| CN1775902A (en) * | 2005-12-16 | 2006-05-24 | 中国科学院长春应用化学研究所 | A kind of alkaline earth phosphate long afterglow luminescent material and its preparation method |
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