CN103421510B - Antimony terbium codoped alkaline earth halogen-phosphate luminescent material, preparation method and application thereof - Google Patents

Antimony terbium codoped alkaline earth halogen-phosphate luminescent material, preparation method and application thereof Download PDF

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CN103421510B
CN103421510B CN201210151221.XA CN201210151221A CN103421510B CN 103421510 B CN103421510 B CN 103421510B CN 201210151221 A CN201210151221 A CN 201210151221A CN 103421510 B CN103421510 B CN 103421510B
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alkaline earth
antimony
phosphate
earth halogen
ytb
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CN103421510A (en
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周明杰
王平
陈吉星
黄辉
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

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 the electroluminescent spectrum (EL) of the light-emitting film that this antimony terbium codoped alkaline earth halogen-phosphate luminescent material is made, there is very strong glow peak in 490nm and 580nm wavelength zone, can be applied in thin-film electroluminescent displays.The present invention also provides preparation method and the application thereof of this antimony terbium codoped alkaline earth halogen-phosphate luminescent material.

Description

Antimony terbium codoped alkaline earth halogen-phosphate luminescent material, preparation method and application thereof
[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 colour and extremely panchromatic TFELD, the material of exploitation multiband luminescence is 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 the 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, the membrane electro luminescent device using this antimony terbium codoped alkaline earth halogen-phosphate luminescent material and preparation method thereof that can be applicable to membrane electro luminescent device.
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 0.4, b be 0.4, c be 0.2, x be 0.02, y is 0.04.
A preparation method for 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
Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being Me at 900 DEG C ~ 1300 DEG C 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 0.4, b be 0.4, c be 0.2, x be 0.02, y is 0.04.
A preparation method for 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 to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, 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;
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 45mm ~ 95mm, and underlayer temperature is 250 DEG C ~ 750 DEG C, and the energy of laser is 80W ~ 300W, magnetron sputtering operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, is then 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 DEG C, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, and working gas is oxygen, and working gas flow is 20sccm.
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 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 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 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 the light-emitting 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 to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, 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;
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 45mm ~ 95mm, and underlayer temperature is 250 DEG C ~ 750 DEG C, and the energy of laser is 80W ~ 300W, magnetron sputtering operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, is then filmed, and obtaining chemical formula is Me 2(PO 4) F acl bbr c: xSb 3+, yTb 3+, described anode forms 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 light-emitting film made, have very strong glow peak in 490nm and 580nm 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 antimony terbium codoped alkaline earth halogen-phosphate light-emitting film prepared by embodiment 1;
Fig. 3 is the XRD figure of antimony terbium codoped alkaline earth halogen-phosphate light-emitting film prepared by embodiment 1;
Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and electric current and brightness relationship figure.
[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 illustrated further.
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 0.4, b be 0.4, c be 0.2, x be 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, there is very strong glow peak in 490nm and 580nm wavelength zone, 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, preferably, a is 0.4, b be 0.4, c be 0.2, x be 0.02, y is 0.04.
Step S12, by mixing equal powder sinter 0.5 hour ~ 5 hours can obtain chemical formula being Me at 900 DEG C ~ 1300 DEG C 2(PO 4) F acl bbr c: xSb 3+, yTb 3+antimony terbium codoped alkaline earth halogen-phosphate luminescent material.
In this step, preferably at 1250 DEG C, sinter 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 0.4, b be 0.4, c be 0.2, x be 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, by 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 to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, 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, preferably, a is 0.4, b be 0.4, c be 0.2, x be 0.02, y is 0.04, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.
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.
Step S23, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45mm ~ 95mm, underlayer temperature is 250 DEG C ~ 750 DEG C, 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 DEG C, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, and working gas is oxygen, and 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 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 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.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 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 obtained by following steps:
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 to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, 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, preferably, a is 0.4, b be 0.4, c be 0.2, x be 0.02, y is 0.04, and at 1250 DEG C, sinter 3 hours become diameter to be 50mm, thickness is the ceramic target of 2mm.
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, adjustment magnetron sputtering plating processing parameter is: base target spacing is 45mm ~ 95mm, underlayer temperature is 250 DEG C ~ 750 DEG C, the energy of laser is 80W ~ 300W, magnetron sputtering operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, is then 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, anode 2 is formed luminescent layer 3.
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 DEG C, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, and working gas is oxygen, and working gas flow is 20sccm.
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
By the P of the MgO of 1mol, 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 2with the Tb of 0.01mol 4o 7, after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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 working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, 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, then evaporation one deck Ag on light-emitting film, 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+, wherein Mg 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, there is very strong glow peak in 490nm and 580nm wavelength zone, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of antimony terbium codoped alkaline earth halogen-phosphate light-emitting film prepared by embodiment 1, test comparison standard P DF card.As can be seen from Figure 3, diffraction peak is all the peak crystallization that alkaline earth halogen-phosphate is relevant, does not occur the diffraction peak of doped element and other impurity.
Refer to Fig. 4, Fig. 4 is the voltage of membrane electro luminescent device prepared of embodiment 1 and electric current and brightness relationship figure, and curve 1 is voltage and current density relation curve in figure 4, can find out device luminescence from 6V, 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 P of the MgO of 1mol, 0.5mol 2o 5, the MgF of 0.4mol 2, the MgCl of 0.1mol 2, the SbO of 0.01mol 2with the Tb of 0.02mol 4o 7, after 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.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 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 3
By the P of the MgO of 1mol, 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 2with the Tb of 0.0025mol 4o 7, after 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.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 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 4
By the P of the CaO of 1mol, 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 2with the Tb of 0.01mol 4o 7, after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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 working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 5
By the P of the CaO of 1mol, 0.5mol 2o 5, the CaF of 0.4mol 2, the CaBr of 0.1mol 2, the SbO of 0.01mol 2with the Tb of 0.02mol 4o 7, after 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.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 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 6
By the P of the CaO of 1mol, 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 2with the Tb of 0.0025mol 4o 7, after 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.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 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 7
By the P of the SrO of 1mol, 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 2with the Tb of 0.01mol 4o 7, after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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 working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 8
By the P of the SrO of 1mol, 0.5mol 2o 5, the SrF of 0.4mol 2, the SrCl of 0.1mol 2, the SbO of 0.01mol 2with the Tb of 0.02mol 4o 7, after 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.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 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 9
By the P of the SrO of 1mol, 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 2with the Tb of 0.0025mol 4o 7, after 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.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 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 10
By the P of the BaO of 1mol, 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 2with the Tb of 0.01mol 4o 7, after Homogeneous phase mixing, at 1250 DEG C, sinter diameter into is 50mm, and thickness is the ceramic target of 2mm, and is loaded in vacuum cavity by target.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 working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 11
By the P of the BaO of 1mol, 0.5mol 2o 5, the BaF of 0.4mol 2, the BaCl of 0.1mol 2, the SbO of 0.01mol 2with the Tb of 0.02mol 4o 7, after 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.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 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, 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, then evaporation one deck Ag on light-emitting film, as negative electrode.
Embodiment 12
By the P of the BaO of 1mol, 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 2with the Tb of 0.0025mol 4o 7, after 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.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 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10 -5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, 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, 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 (10)

1. an antimony terbium codoped alkaline earth halogen-phosphate luminescent material, is characterized in that: its chemical formula is Me 2pO 4f acl bbr c: xSb 3+, yTb 3+, Me 2pO 4f 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, is characterized in that: a is 0.4, b be 0.4, c be 0.2, x be 0.02, y is 0.04.
3. a preparation method for antimony terbium codoped alkaline earth halogen-phosphate luminescent material, is characterized in that, comprise the following steps:
According to Me 2pO 4f 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
Namely the powder mixed sinter 0.5 hour ~ 5 hours to be obtained chemical formula being Me at 900 DEG C ~ 1300 DEG C 2pO 4f 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 2pO 4f acl bbr c: xSb 3+, yTb 3+, Me 2pO 4f 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, is characterized in that: a is 0.4, b be 0.4, c be 0.2, x be 0.02, y is 0.04.
6. a preparation method for antimony terbium codoped alkaline earth halogen-phosphate light-emitting film, is characterized in that, comprise the following steps:
According to Me 2pO 4f 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 to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, 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;
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 45mm ~ 95mm, and underlayer temperature is 250 DEG C ~ 750 DEG C, and the energy of laser is 80W ~ 300W, magnetron sputtering operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, is then filmed, and obtaining chemical formula is Me 2pO 4f 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, it 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 DEG C, and the energy of laser is 150W, magnetron sputtering operating pressure 3Pa, and working gas is oxygen, and working gas flow is 20sccm.
8. a membrane electro luminescent device, this membrane electro luminescent device comprises the substrate, anode layer, luminescent layer and the cathode layer that stack gradually, it is characterized in that, the material of described luminescent layer is 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 2pO 4f acl bbr c: xSb 3+, yTb 3+, Me 2pO 4f 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. 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 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 2pO 4f acl bbr c: xSb 3+, yTb 3+, Me 2pO 4f 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 the light-emitting 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 2pO 4f 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 to mix at 900 DEG C ~ 1300 DEG C sintering and makes target in 0.5 hour ~ 5 hours, 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;
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 45mm ~ 95mm, and underlayer temperature is 250 DEG C ~ 750 DEG C, and the energy of laser is 80W ~ 300W, magnetron sputtering operating pressure 0.5Pa ~ 5Pa, the flow of working gas is 10sccm ~ 40sccm, is then filmed, and obtaining chemical formula is Me 2pO 4f acl bbr c: xSb 3+, yTb 3+, described anode forms luminescent layer.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 Alkaline earth phosphate long afterglow luminous material and its preparing method

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TWI285671B (en) * 1998-10-13 2007-08-21 Orion 21 A D Pty Ltd Luminescent gel coats and moldable resins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 Alkaline earth phosphate long afterglow luminous material and its preparing method

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