CN104140816A - Samarium-doped rare-earth silicon nitride luminescent material and preparation method and application thereof - Google Patents
Samarium-doped rare-earth silicon nitride luminescent material and preparation method and application thereof Download PDFInfo
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- CN104140816A CN104140816A CN201310168124.6A CN201310168124A CN104140816A CN 104140816 A CN104140816 A CN 104140816A CN 201310168124 A CN201310168124 A CN 201310168124A CN 104140816 A CN104140816 A CN 104140816A
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- -1 rare-earth silicon nitride Chemical class 0.000 title claims abstract description 110
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 59
- 229910052761 rare earth metal Inorganic materials 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 32
- 239000000126 substance Substances 0.000 claims abstract description 34
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 25
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 25
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 claims abstract description 25
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical group [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims description 46
- 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 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000203 mixture Substances 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
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 239000010409 thin film Substances 0.000 abstract description 8
- 238000001194 electroluminescence spectrum Methods 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 44
- 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
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
A samarium-doped rare-earth silicon nitride luminescent material is disclosed. Chemical formula of the material is Me2Si6N10:xSm3<+>, wherein x is 0.01-0.05; Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion. In the electroluminescence spectra (EL) of a luminescent thin-film prepared from the samarium-doped rare-earth silicon nitride luminescent material, there is strong luminescence peak at wavelengths of 638nm and 727nm, and the luminescent thin-film can be applied in a thin-film electroluminescent display. The invention also provides a preparation method of the samarium-doped rare-earth silicon nitride luminescent material and its application.
Description
[technical field]
The present invention relates to a kind of samarium-doped rare earth silicon nitride luminescent material, its preparation method, samarium-doped rare earth silicon nitride 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 luminous material of exploitation multiband, is the developing direction of this problem.But, can be applicable to the samarium-doped rare earth silicon nitride 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 samarium-doped rare earth silicon nitride luminescent material, its preparation method, samarium-doped rare earth silicon nitride light-emitting film, its preparation method that can be applicable to membrane electro luminescent device, use membrane electro luminescent device of this samarium-doped rare earth silicon nitride luminescent material and preparation method thereof.
A samarium-doped rare earth silicon nitride luminescent material, its chemical formula is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
A preparation method for samarium-doped rare earth silicon nitride luminescent material, comprises the following steps:
According to Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder and mix, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion; And
The powder mixing sintering at 900 ℃～1300 ℃ is obtained to chemical formula for 0.5 hour～5 hours is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride luminescent material.
A samarium-doped rare earth silicon nitride light-emitting film, the chemical general formula of the material of this samarium-doped rare earth silicon nitride light-emitting film is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
A preparation method for samarium-doped rare earth silicon nitride light-emitting film, comprises the following steps:
According to Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder and mix sintering at 900 ℃～1300 ℃ and make target in 0.5 hour～5 hours, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion;
The vacuum cavity that described target and substrate is packed into magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3pa～1.0 * 10
-5pa; And
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃, laser energy is 80W～300W, is then filmed, and obtaining chemical formula is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride light-emitting film, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
The vacuum tightness of described vacuum cavity is 5.0 * 10
-4pa, base target spacing is 60mm, and magnetron sputtering operating pressure is 2Pa, and working gas is oxygen, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃, and laser energy is 150W.
A kind of membrane electro luminescent device, this membrane electro luminescent device comprises substrate, anode layer, luminescent layer and the cathode layer stacking gradually, the material of described luminescent layer is samarium-doped rare earth silicon nitride luminescent material, and the chemical formula of this samarium-doped rare earth silicon nitride luminescent material is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
A preparation method for membrane electro luminescent device, comprises the following steps:
The substrate with anode is provided;
On described anode, form luminescent layer, the material of described luminescent layer is samarium-doped rare earth silicon nitride luminescent material, and the chemical formula of this samarium-doped rare earth silicon nitride luminescent material is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion;
On described luminescent layer, form negative electrode.
The preparation of described luminescent layer comprises the following steps:
According to Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder powder and mix sintering at 900 ℃～1300 ℃ and make target in 0.5 hour～5 hours, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion;
The vacuum cavity that described target and described substrate is packed into magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3pa～1.0 * 10
-5pa;
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃, laser energy is 80W～300W, is then filmed, and obtaining chemical formula is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride light-emitting film, on described anode, form luminescent layer.
Above-mentioned samarium-doped rare earth silicon nitride luminescent material (Me
2si
6n
10: xSm
3+) in the electroluminescent spectrum (EL) of the light-emitting film made, at 638nm and 727nm wavelength zone, there is very strong glow peak, 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 the samarium-doped rare earth silicon nitride light-emitting film of embodiment 1 preparation;
Fig. 3 is the XRD figure of the samarium-doped rare earth silicon nitride light-emitting film of embodiment 1 preparation;
Fig. 4 is the voltage of membrane electro luminescent device of embodiment 1 preparation and the graph of relation between current density and voltage and brightness.
[embodiment]
Below in conjunction with the drawings and specific embodiments, samarium-doped rare earth silicon nitride luminescent material, its preparation method, samarium-doped rare earth silicon nitride light-emitting film, its preparation method, membrane electro luminescent device and preparation method thereof are further illustrated.
The samarium-doped rare earth silicon nitride luminescent material of one embodiment, its chemical formula is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
Preferably, x is 0.03.
Me in this samarium-doped rare earth silicon nitride luminescent material
2si
6n
10be matrix, samarium ion is active element.In the electroluminescent spectrum (EL) of the light-emitting film that this samarium-doped rare earth silicon nitride luminescent material is made, at 638nm and 727nm wavelength zone, there is very strong glow peak, can be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned samarium-doped rare earth silicon nitride luminescent material, comprises the following steps:
Step S11, according to Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
In this step, preferred, x is 0.03.
Step S12, by mixing equal powder sintering at 900 ℃～1300 ℃, within 0.5 hour～5 hours, can obtain samarium-doped rare earth silicon nitride luminescent material, its chemical formula is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
In this step, preferred sintering 3 hours at 1250 ℃.
The samarium-doped rare earth silicon nitride light-emitting film of one embodiment, the chemical general formula of the material of this samarium-doped rare earth silicon nitride light-emitting film is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride luminescent material, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
Preferably, x is 0.03.
The preparation method of above-mentioned samarium-doped rare earth silicon nitride light-emitting film, comprises the following steps:
Step S21, press Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder and mix sintering at 900 ℃～1300 ℃ and make target in 0.5 hour～5 hours, wherein, x is 0.01～0.05.
In this step, preferred, x is 0.03, and at 1250 ℃, 3 hours one-tenth diameters of sintering are 50mm, the ceramic target that thickness is 2mm.
Step S22, the target obtaining in step S21 and substrate are packed into 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, preferred, vacuum tightness is 5 * 10
-4pa.
Step S23, adjustment magnetron sputtering plating processing parameter are: base target spacing is 45mm～95mm, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃; Laser energy is 80W～300W, is then filmed, and obtaining chemical formula is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride light-emitting film, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is oxygen, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃, and laser energy is 150W.
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 stacking 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 samarium-doped rare earth silicon nitride luminescent material, and the chemical formula of this samarium-doped rare earth silicon nitride luminescent material is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride light-emitting film, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.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.The 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, on anode 2, form luminescent layer 3, the material of luminescent layer 3 is samarium-doped rare earth silicon nitride luminescent material, and the chemical formula of this samarium-doped rare earth silicon nitride luminescent material is Me
2si
6n
10: xSm
3+, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
In present embodiment, luminescent layer 3 is made by following steps:
First, by Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder and mix sintering at 900 ℃～1300 ℃ and make target in 0.5 hour～5 hours, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
In this step, preferred, x is 0.03, and at 1250 ℃, 3 hours one-tenth diameters of sintering are 50mm, the ceramic target that thickness is 2mm.
Secondly, target and substrate are packed into 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, preferred, vacuum tightness is 5 * 10
-4pa.
Then, adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, magnetron sputtering operating pressure 0.2Pa～4Pa, the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃, laser energy is 80W～300W, is then filmed, and forms luminescent layer 3 on anode 2.
In this step, preferred base target spacing is 60mm, magnetron sputtering operating pressure 2Pa, and working gas is oxygen, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃, and laser energy is 150W.
Step S33, on luminescent layer 3, form negative electrode 4.
In present embodiment, the material of negative electrode 4 is silver (Ag), by evaporation, is formed.
Be specific embodiment below.
Embodiment 1
Selecting purity is 99.99% powder, by LaN, and Si
3n
4with SmN powder according to mole number, be 1.97mmol, 2mmol and 0.03mmol are after even mixing, at 1250 ℃, sintering diameter 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 5.0 * 10
-4pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 ℃, laser energy 150W.The sample chemical formula obtaining is La
2si
6n
10: 0.03Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
The chemical general formula of the samarium-doped rare earth silicon nitride light-emitting film obtaining in the present embodiment is La
2si
6n
10: 0.03Sm
3+, La wherein
2si
6n
10matrix, Sm
3+it is active element.
Refer to Fig. 2, Figure 2 shows that the electroluminescence spectrum (EL) of the samarium-doped rare earth silicon nitride light-emitting film obtaining.As seen from Figure 2, in electroluminescence spectrum, at 638nm and 727nm wavelength zone, there is very strong glow peak, can be applied in thin-film electroluminescent displays.
Refer to Fig. 3, Fig. 3 is the XRD curve of the samarium-doped rare earth silicon nitride light-emitting film of embodiment 1 preparation, test comparison standard P DF card.As can be seen from Figure 3, the diffraction peak in figure is the peak crystallization of three races's aluminosilicate, does not occur the diffraction peak of doped element and other impurity; Illustrate that the product that this preparation method obtains has good crystalline quality.
Refer to Fig. 4, Fig. 4 is the voltage of membrane electro luminescent device of embodiment 1 preparation and the graph of relation between current density and voltage and brightness, curve 1 is voltage and current density relation curve, can find out that this device starts luminous from voltage 6.0V, curve 2 is voltage and brightness relationship curve, and the high-high brightness that can find out this device is 76cd/m
2, show that device has the good characteristics of luminescence.
Embodiment 2
Selecting purity is 99.99% powder, by LaN, and Si
3n
4with SmN powder according to mole number, be 1.99mmol, 2mmol and 0.01mmol are after even mixing, at 900 ℃, sintering diameter 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 1.0 * 10
-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 ℃, laser energy 80W.The chemical formula of the sample obtaining is La
2si
6n
10: 0.01Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 3
Selecting purity is 99.99% powder, by LaN, and Si
3n
4with SmN powder according to mole number, be 1.95mmol, 2mmol and 0.05mmol are after even mixing, at 1300 ℃, sintering diameter 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 1.0 * 10
-5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃, laser energy 300W.The chemical formula of the sample obtaining is La
2si
6n
10: 0.05Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 4
Selecting purity is 99.99% powder, by GdN, and Si
3n
4with SmN powder according to mole number, be 1.97mmol, 2mmol and 0.03mmol powder, after even mixing, at 1250 ℃, sintering diameter 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 5.0 * 10
-4pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃, laser energy 300W.The chemical formula of the sample obtaining is Gd
2si
6n
10: 0.03Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 5
Selecting purity is 99.99% powder, by GdN, and Si
3n
4with SmN powder according to mole number, be 1.99mmol, 2mmol and 0.01mmol powder, after even mixing, at 900 ℃, sintering diameter 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 1.0 * 10
-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 ℃, laser energy 500W.The chemical formula of the sample obtaining is Gd
2si
6n
10: 0.01Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 6
Selecting purity is 99.99% powder, by GdN, and Si
3n
4with SmN powder according to mole number, be 1.95mmol, 2mmol and 0.05mmol powder, after even mixing, at 1300 ℃, sintering diameter 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 1.0 * 10
-5pa, the working gas flow of oxygen is 40sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃, laser energy 50W.The chemical formula of the sample obtaining is Gd
2si
6n
10: 0.05Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 7
Selecting purity is 99.99% powder, by YbN, and Si
3n
4with SmN powder according to mole number, be 1.97mmol, 2mmol and 0.03mmol powder, after even mixing, at 1250 ℃, sintering diameter 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 5.0 * 10
-4pa, the working gas flow of oxygen is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 ℃, laser energy 150W.The chemical general formula of the sample obtaining is Yb
2si
6n
10: 0.03Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 8
Selecting purity is 99.99% powder, by YbN, and Si
3n
4with SmN powder according to mole number, be 1.99mmol, 2mmol and 0.01mmol powder, after even mixing, at 900 ℃, sintering diameter 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 1.0 * 10
-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 ℃, laser energy 80W.The chemical formula of the sample obtaining is Yb
2si
6n
10: 0.01Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 9
Selecting purity is 99.99% powder, by YbN, and Si
3n
4with SmN powder according to mole number, be 1.95mmol, 2mmol and 0.05mmol powder, after even mixing, at 1300 ℃, sintering diameter 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 1.0 * 10
-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃, laser energy 300W.The chemical formula of the sample obtaining is Yb
2si
6n
10: 0.05Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 10
Selecting purity is 99.99% powder, by LuN, and Si
3n
4with SmN powder according to mole number, be 1.97mmol, 2mmol and 0.03mmol powder, after even mixing, at 1250 ℃, sintering diameter 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 5.0 * 10
-4pa, the working gas flow of oxygen is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃, laser energy 150W.The chemical formula of the sample obtaining is Lu
2si
6n
10: 0.03Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 11
Selecting purity is 99.99% powder, by LuN, and Si
3n
4with SmN powder according to mole number, be 1.99mmol, 2mmol and 0.01mmol powder, after even mixing, at 900 ℃, sintering diameter 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 1.0 * 10
-3pa, the working gas flow of oxygen is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 ℃, laser energy 500W.The chemical formula of the sample obtaining is Lu
2si
6n
10: 0.01Sm
3+light-emitting film, evaporation one deck Ag on light-emitting film then, as negative electrode.
Embodiment 12
Selecting purity is 99.99% powder, by LuN, and Si
3n
4with SmN powder according to mole number, be 1.95mmol, 2mmol and 0.05mmol powder, after even mixing, at 1300 ℃, sintering diameter 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 1.0 * 10
-5pa, the working gas flow of oxygen is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃, laser energy 300W.The chemical formula of the sample obtaining is Lu
2si
6n
10: 0.05Sm
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 (9)
1. a samarium-doped rare earth silicon nitride luminescent material, is characterized in that: its chemical formula is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
2. a preparation method for samarium-doped rare earth silicon nitride luminescent material, is characterized in that, comprises the following steps:
According to Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder and mix, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion; And
The powder mixing sintering at 900 ℃～1300 ℃ is obtained to chemical formula for 0.5 hour～5 hours is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride luminescent material.
3. a samarium-doped rare earth silicon nitride light-emitting film, is characterized in that, the chemical general formula of the material of this samarium-doped rare earth silicon nitride light-emitting film is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
4. a preparation method for samarium-doped rare earth silicon nitride light-emitting film, is characterized in that, comprises the following steps:
According to Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder and mix sintering at 900 ℃～1300 ℃ and make target in 0.5 hour～5 hours, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion;
The vacuum cavity that described target and substrate is packed into magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3pa～1.0 * 10
-5pa; And
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃, laser energy is 80W～300W, is then filmed, and obtaining chemical formula is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride light-emitting film, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
5. the preparation method of samarium-doped rare earth silicon nitride light-emitting film according to claim 4, 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 2Pa, and working gas is oxygen, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃, and laser energy is 150W.
6. a membrane electro luminescent device, this membrane electro luminescent device comprises substrate, anode layer, luminescent layer and the cathode layer stacking gradually, it is characterized in that, the material of described luminescent layer is samarium-doped rare earth silicon nitride luminescent material, and the chemical formula of this samarium-doped rare earth silicon nitride luminescent material is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion.
7. a preparation method for membrane electro luminescent device, is characterized in that, comprises the following steps:
The substrate with anode is provided;
On described anode, form luminescent layer, the material of described luminescent layer is samarium-doped rare earth silicon nitride luminescent material, and the chemical formula of this samarium-doped rare earth silicon nitride luminescent material is Me
2si
6n
10: xSm
3+, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion;
On described luminescent layer, form negative electrode.
8. the preparation method of membrane electro luminescent device according to claim 7, is characterized in that, the preparation of described luminescent layer comprises the following steps:
According to Me
2si
6n
10: xSm
3+the stoichiometric ratio of each element takes MeN, Si
3n
4with SmN powder and mix sintering at 900 ℃～1300 ℃ and make target in 0.5 hour～5 hours, wherein, x is that 0.01～0.05, Me is lanthanum ion, gadolinium ion, ytterbium ion or lutetium ion;
The vacuum cavity that described target and described substrate is packed into magnetic-controlled sputtering coating equipment, and the vacuum tightness of vacuum cavity is set to 1.0 * 10
-3pa～1.0 * 10
-5pa;
Adjusting magnetron sputtering plating processing parameter is: base target spacing is 45mm～95mm, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃, laser energy is 80W～300W, is then filmed, and obtaining chemical formula is Me
2si
6n
10: xSm
3+samarium-doped rare earth silicon nitride light-emitting film, on described anode, form luminescent layer.
9. the preparation method of membrane electro luminescent device according to claim 8, is characterized in that, described x is 0.03.
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2013
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| JP2003096446A (en) * | 2001-09-21 | 2003-04-03 | National Institute For Materials Science | Lanthanum silicon nitride phosphor activated with cerium ions |
| EP1296376A2 (en) * | 2001-09-25 | 2003-03-26 | Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH | Illumination device with at least one LED as the light source |
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