CN104178136A - Samarium-doped nitrogen-containing silicate light-emitting film and preparation method thereof and electroluminescent device - Google Patents
Samarium-doped nitrogen-containing silicate light-emitting film and preparation method thereof and electroluminescent device Download PDFInfo
- Publication number
- CN104178136A CN104178136A CN201310196837.3A CN201310196837A CN104178136A CN 104178136 A CN104178136 A CN 104178136A CN 201310196837 A CN201310196837 A CN 201310196837A CN 104178136 A CN104178136 A CN 104178136A
- Authority
- CN
- China
- Prior art keywords
- light
- emitting film
- preparation
- samarium
- silicon hydrochlorate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 24
- 239000000919 ceramic Substances 0.000 claims description 23
- 229910052772 Samarium Inorganic materials 0.000 claims description 20
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 238000001194 electroluminescence spectrum Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 47
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 150000002431 hydrogen Chemical class 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
- Electroluminescent Light Sources (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention belongs to the field of photoelectric materials, and discloses a samarium-doped nitrogen-containing silicate light-emitting film and a preparation method thereof and an electroluminescent device; the light-emitting film has a chemical formula of Me1-xSi2O2N2:xSm<3 +>; wherein Me1-xSi2O2N2 is a matrix, Sm<3 +> is activated light ions, and is light-emitting centers of the light-emitting film, Me is selected from the group consisting of Mg, Ca, Sr or Ba element, and the value range of x is 0.01-0.05. In the electroluminescence spectrum (EL) of the samarium-doped nitrogen-containing silicate light-emitting film, strong light-emitting peaks show at 620 nm position.
Description
Technical field
The present invention relates to field of photovoltaic materials, relate in particular to light-emitting film of a kind of samarium doping nitrogenated silicon hydrochlorate and preparation method thereof.The invention still further relates to a kind of this light-emitting film that uses as the electroluminescent device of luminescent layer.
Background technology
Compare with the display screen that traditional luminescent powder is made, light-emitting film contrast gradient, resolving power, thermal conduction, homogeneity, and the aspect such as the tack of substrate, outgas speed all demonstrate stronger superiority.Therefore,, as functional materials, light-emitting film is having broad application prospects in showing the flat pannel display fields such as (ELDs) and Field Emission Display (FEDs) such as cathode tube (CRTs), electroluminescent.
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.Monochromatic TFELD that the ZnS:Mn of take is luminescent layer is full-fledged and realized commercialization.At present, research colour and extremely panchromatic TFELD, the luminous material of exploitation multiband, is the developing direction of this problem.
In luminescence system material, rare earth ion doped silicates fluorescent material has obtained deep research, can access good ruddiness exciting to blue light.Meanwhile, owing to adding appropriate nitride can make its chemical stability and thermostability improve, and the excitation wavelength that can obtain changing in a big way, so nitrogenous silicate is as matrix Yu's of luminescent material hot topic.But, such material is made to light-emitting film, and has no report.
Summary of the invention
Based on the problems referred to above, the invention provides a kind of light-emitting film of samarium doping nitrogenated silicon hydrochlorate.
Technical scheme of the present invention is as follows:
The light-emitting film of samarium doping nitrogenated silicon hydrochlorate provided by the invention, its chemical general formula is: Me
1-xsi
2o
2n
2: xSm
3+; Wherein, Me
1-xsi
2o
2n
2matrix, Sm
3+be exciting light ion, in film, serve as main luminescence center, the value 0.01～0.05 of x, preferably 0.03, Me is selected from Mg, Ca, Sr or Ba element.Light-emitting film Me
1-xsi
2o
2n
2: xSm
3+in, x represents Sm
3+the mole number that replaces Me ion.
The present invention also provides the preparation method of the light-emitting film of above-mentioned samarium doping nitrogenated silicon hydrochlorate, and it utilizes magnetron sputtering equipment to prepare, and processing step is as follows:
(1), the preparation of ceramic target: take respectively MeO, SiO
2, Si
3n
4and Sm
2o
3powder, after evenly mixing, sintering at 900～1300 ℃, makes ceramic target, wherein, MeO, SiO
2, Si
3n
4and Sm
2o
3mol ratio be 1-x:0.5:0.5:x/2;
Preferably, ceramic target is cut, its specification is Φ 50 * 2mm; Preferably 1250 ℃ of sintering temperatures.
(2), the ceramic target making and ito glass substrate are packed in the cavity of filming equipment, after enclosed housing, cavity is vacuumized to processing, controlling cavity vacuum tightness is 1.0 * 10
-3pa～1.0 * 10
-5pa;
Preferably, ito glass substrate needs clean before putting into cavity: 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, and then put into vacuum cavity;
Vacuumizing to process adopts mechanical pump and molecular pump that cavity is carried out; Chamber vacuum degree is 5.0 * 10
-4pa.
(3), coating process parameter is set: it is 50～90mm that base target spacing is set, underlayer temperature is 350 ℃～750 ℃, argon gas and hydrogen hybrid working gas that the volume ratio that passes into flow in process and be 10～30sccm is 85～99:1～15, operating pressure is 0.2～4.5Pa; After processing parameter setting completes, carry out coating film treatment, obtain sample, subsequently sample is placed in to anneal 1～3h at 500～800 ℃ of 0.01Pa vacuum ovens; The light-emitting film that makes subsequently samarium doping nitrogenated silicon hydrochlorate on the ITO of ito glass substrate layer surface, its chemical general formula of this light-emitting film is: Me
1-xsi
2o
2n
2: xSm
3+; Wherein, Me
1-xsi
2o
2n
2matrix, Sm
3+being exciting light ion, is the luminescence center of light-emitting film, and Me is selected from Mg, Ca, and Sr or Ba element, the span of x is 0.01～0.05;
Preferably, coating process parameter is: base target spacing is 70mm, and underlayer temperature is 500 ℃, argon gas and hydrogen hybrid working gas that the volume ratio that passes into flow in process and be 20sccm is 95:5, and operating pressure is 1.0Pa, and annealing temperature is 600 ℃, and annealing time is 2h; And the value of x is 0.03.The process of deposit film passes into a certain amount of hydrogen, can make film produce hydrogen bonding, and some dangling bonds in film are combined, and are exactly the density that has reduced radiationless deathnium like this, finally reach the effect that increases luminous intensity.
The present invention also provides a kind of electroluminescent device, comprises glass substrate, ito anode, light-emitting film layer and cathode layer, and wherein, described light-emitting film is the light-emitting film of samarium doping nitrogenated silicon hydrochlorate, and its chemical general formula is: Me
1-xsi
2o
2n
2: xSm
3+; Wherein, Me
1-xsi
2o
2n
2matrix, Sm
3+being exciting light ion, is the luminescence center of light-emitting film, and Me is selected from Mg, Ca, and Sr or Ba element, the span of x is 0.01～0.05.
The preparation technology of electroluminescent device is as follows:
(1), the preparation of ceramic target: take respectively MeO, SiO
2, Si
3n
4and Sm
2o
3powder, after evenly mixing, sintering at 900～1300 ℃, makes ceramic target, wherein, MeO, SiO
2, Si
3n
4and Sm
2o
3mol ratio be 1-x:0.5:0.5:x/2;
(2), the ceramic target making and ito glass substrate are packed in the cavity of filming equipment, after enclosed housing, cavity is vacuumized to processing, controlling cavity vacuum tightness is 1.0 * 10
-3pa～1.0 * 10
-5pa;
(3), coating process parameter is set: it is 50～90mm that base target spacing is set, underlayer temperature is 350 ℃～750 ℃, argon gas and hydrogen hybrid working gas that the volume ratio that passes into flow in process and be 10～30sccm is 85～99:1～15, operating pressure is 0.2～4.5Pa; After processing parameter setting completes, carry out coating film treatment, obtain sample, subsequently sample is placed in to anneal 1～3h at 500～800 ℃ of 0.01Pa vacuum ovens; The light-emitting film that makes subsequently samarium doping nitrogenated silicon hydrochlorate on the ITO of ito glass substrate layer surface, its chemical general formula of this light-emitting film is: MeSi
2o
2n
2: xSm
3+; Wherein, Me
1-xsi
2o
2n
2matrix, Sm
3+being exciting light ion, is the luminescence center of light-emitting film, and Me is selected from Mg, Ca, and Sr or Ba element, the span of x is 0.01～0.05;
(4), step (3) makes containing the ito glass substrate of light-emitting film and Ag nanoparticle and moves in vacuum evaporation equipment, plays the Ag layer of cathodic process at light-emitting film surface evaporation one deck;
After above-mentioned steps completes, make electroluminescent device.
The present invention adopts magnetron sputtering equipment, prepares the samarium nitrogenous silicate light-emitting film that adulterates, and obtains, in the electroluminescence spectrum (EL) of film, in 620nm position, having very strong glow peak.
Accompanying drawing explanation
Fig. 1 is the EL spectrogram of the light-emitting film sample that makes of embodiment 3;
Fig. 2 is the EL device structure schematic diagram that embodiment 12 makes.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Select MgO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.97:0.5:0.5:0.015, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 20sccm, pressure 1.0Pa, hydrogen content 5%.Underlayer temperature is 500 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 600 ℃.Obtain Mg
0.97si
2o
2n
2: 0.03Sm
3+light-emitting film.
Embodiment 2
Select MgO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.99:0.5:0.5:0.005, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 25sccm, pressure 1.0Pa, hydrogen content 3%.Underlayer temperature is 550 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 650 ℃.Obtain Mg
0.99si
2o
2n
2: 0.01Sm
3+light-emitting film.
Embodiment 3
Select MgO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.95:0.5:0.5:0.025, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 23sccm, pressure 2.0Pa, hydrogen content 1%.Underlayer temperature is 400 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 500 ℃.Obtain Mg
0.95si
2o
2n
2: 0.05Sm
3+light-emitting film.
Fig. 1 is the EL spectrogram of the light-emitting film sample that makes of embodiment 3; As can be seen from Figure 1, in 620nm position, there is very strong glow peak.
Embodiment 4
Select CaO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.97:0.5:0.5:0.015, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 20sccm, pressure 1.0Pa, hydrogen content 5%.Underlayer temperature is 500 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 600 ℃.Obtain Ca
0.97si
2o
2n
2: 0.03Sm
3+light-emitting film.
Embodiment 5
Select CaO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.99:0.5:0.5:0.005, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 25sccm, pressure 1.0Pa, hydrogen content 3%.Underlayer temperature is 550 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 650 ℃.Obtain Ca
0.99si
2o
2n
2: 0.01Sm
3+light-emitting film.
Embodiment 6
Select CaO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.95:0.5:0.5:0.025, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 23sccm, pressure 2.0Pa, hydrogen content 1%.Underlayer temperature is 400 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 500 ℃.Obtain Ca
0.95si
2o
2n
2: 0.05Sm
3+light-emitting film.
Embodiment 7
Select SrO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.97:0.5:0.5:0.015, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 20sccm, pressure 1.0Pa, hydrogen content 5%.Underlayer temperature is 500 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 600 ℃.Obtain Sr
0.97si
2o
2n
2: 0.03Sm
3+light-emitting film.
Embodiment 8
Select SrO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.99:0.5:0.5:0.005, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 25sccm, pressure 1.0Pa, hydrogen content 3%.Underlayer temperature is 550 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 650 ℃.Obtain Sr
0.99si
2o
2n
2: 0.01Sm
3+light-emitting film.
Embodiment 9
Select SrO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.95:0.5:0.5:0.025, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 23sccm, pressure 2.0Pa, hydrogen content 1%.Underlayer temperature is 400 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 500 ℃.Obtain Sr
0.95si
2o
2n
2: 0.05Sm
3+light-emitting film.
Embodiment 10
Select BaO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.97:0.5:0.5:0.015, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 20sccm, pressure 1.0Pa, hydrogen content 5%.Underlayer temperature is 500 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 600 ℃.Obtain Ba
0.97si
2o
2n
2: 0.03Sm
3+light-emitting film.
Embodiment 11
Select BaO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.99:0.5:0.5:0.005, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 25sccm, pressure 1.0Pa, hydrogen content 3%.Underlayer temperature is 550 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 650 ℃.Obtain Ba
0.99si
2o
2n
2: 0.01Sm
3+light-emitting film.
Embodiment 12
Originally be embodied as electroluminescent device, as shown in Figure 2, wherein, 1 is glass substrate; 2 is ITO transparent conductive film, as anode; 3 is luminescent material thin-film layer; 4 is Ag layer, as negative electrode.
Select BaO, SiO
2, Si
3n
4and Sm
2o
3powder, its mol ratio is 0.95:0.5:0.5:0.025, after even mixing, sinters the ceramic target of Φ 50 * 2mm at 1200 ℃ into, 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 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4pa, hydrogen argon gas is as working gas, gas flow 23sccm, pressure 2.0Pa, hydrogen content 1%.Underlayer temperature is 400 ℃.The sample the obtaining 2h that anneals in 0.01Pa vacuum oven, annealing temperature is 500 ℃.Obtain Ba
0.95si
2o
2n
2: 0.05Sm
3+light-emitting film.Then light-emitting film is being moved in vacuum evaporation equipment, evaporation one deck Ag on light-emitting film, as negative electrode.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a light-emitting film for samarium doping nitrogenated silicon hydrochlorate, is characterized in that, its chemical general formula is: Me
1-xsi
2o
2n
2: xSm
3+; Wherein, Me
1-xsi
2o
2n
2matrix, Sm
3+being exciting light ion, is the luminescence center of light-emitting film, and Me is selected from Mg, Ca, and Sr or Ba element, the span of x is 0.01～0.05.
2. the light-emitting film of samarium doping nitrogenated silicon hydrochlorate according to claim 1, is characterized in that, the value of x is 0.03.
3. the light-emitting film of samarium doping nitrogenated silicon hydrochlorate according to claim 1, is characterized in that, comprises the light-emitting film of following chemical formula:
Mg
0.97Si
2O
2N
2:0.03Sm
3+；Mg
0.99Si
2O
2N
2:0.01Sm
3+；Mg
0.95Si
2O
2N
2:0.05Sm
3+；Ca
0.97Si
2O
2N
2:0.03Sm
3+；Ca
0.99Si
2O
2N
2:0.01Sm
3+；Ca
0.95Si
2O
2N
2:0.05Sm
3+；Sr
0.97Si
2O
2N
2:0.03Sm
3+；Sr
0.99Si
2O
2N
2:0.01Sm
3+；Sr
0.95Si
2O
2N
2:0.05Sm
3+；Ba
0.97Si
2O
2N
2:0.03Sm
3+；Ba
0.99Si
2O
2N
2:0.01Sm
3+；Ba
0.95Si
2O
2N
2:0.05Sm
3+。
4. a preparation method for the light-emitting film of samarium doping nitrogenated silicon hydrochlorate, is characterized in that, comprises the steps:
The preparation of ceramic target: take respectively MeO, SiO
2, Si
3n
4and Sm
2o
3powder, after evenly mixing, sintering at 900～1300 ℃, makes ceramic target, wherein, MeO, SiO
2, Si
3n
4and Sm
2o
3mol ratio be 1-x:0.5:0.5:x/2;
The ceramic target making and ito glass substrate are packed in the cavity of filming equipment, after enclosed housing, cavity is vacuumized to processing, controlling cavity vacuum tightness is 1.0 * 10
-3pa～1.0 * 10
-5pa;
Coating process parameter is set: it is 50～90mm that base target spacing is set, and underlayer temperature is 350 ℃～750 ℃, argon gas and hydrogen hybrid working gas that the volume ratio that passes into flow in process and be 10～30sccm is 85～99:1～15, operating pressure is 0.2～4.5Pa; After processing parameter setting completes, carry out coating film treatment, obtain sample, subsequently sample is placed in to anneal 1～3h at 500～800 ℃ of 0.01Pa vacuum ovens; The light-emitting film that makes subsequently samarium doping nitrogenated silicon hydrochlorate on the ITO of ito glass substrate layer surface, its chemical general formula of this light-emitting film is: Me
1-xsi
2o
2n
2: xSm
3+; Wherein, Me
1-xsi
2o
2n
2matrix, Sm
3+being exciting light ion, is the luminescence center of light-emitting film, and Me is selected from Mg, Ca, and Sr or Ba element, the span of x is 0.01～0.05.
5. the preparation method of the light-emitting film of samarium doping nitrogenated silicon hydrochlorate according to claim 4, is characterized in that, the sintering temperature in described ceramic target preparation process is 1250 ℃.
6. the preparation method of the light-emitting film of samarium according to claim 4 doping nitrogenated silicon hydrochlorate, is characterized in that, described in vacuumize to process and adopt mechanical pump and molecular pump that cavity is carried out.
7. the preparation method of the light-emitting film of samarium doping nitrogenated silicon hydrochlorate according to claim 4, is characterized in that, described chamber vacuum degree is 5.0 * 10
-4pa.
8. the preparation method of the light-emitting film of samarium according to claim 4 doping nitrogenated silicon hydrochlorate, it is characterized in that, described coating process parameter is: base target spacing is 70mm, underlayer temperature is 500 ℃, argon gas and hydrogen hybrid working gas that the volume ratio that passes into flow in process and be 20sccm is 95:5, operating pressure is 1.0Pa, and annealing temperature is 600 ℃, and annealing time is 2h.
9. the preparation method of the light-emitting film of samarium doping nitrogenated silicon hydrochlorate according to claim 4, is characterized in that, the value of x is 0.03.
10. an electroluminescent device, comprises glass substrate, ito anode, light-emitting film layer and Ag cathode layer, it is characterized in that, described light-emitting film is the light-emitting film of samarium doping nitrogenated silicon hydrochlorate, and its chemical general formula is: Me
1-xsi
2o
2n
2: xSm
3+; Wherein, Me
1-xsi
2o
2n
2matrix, Sm
3+being exciting light ion, is the luminescence center of light-emitting film, and Me is selected from Mg, Ca, and Sr or Ba element, the span of x is 0.01～0.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310196837.3A CN104178136A (en) | 2013-05-23 | 2013-05-23 | Samarium-doped nitrogen-containing silicate light-emitting film and preparation method thereof and electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310196837.3A CN104178136A (en) | 2013-05-23 | 2013-05-23 | Samarium-doped nitrogen-containing silicate light-emitting film and preparation method thereof and electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104178136A true CN104178136A (en) | 2014-12-03 |
Family
ID=51959490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310196837.3A Pending CN104178136A (en) | 2013-05-23 | 2013-05-23 | Samarium-doped nitrogen-containing silicate light-emitting film and preparation method thereof and electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104178136A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009012484A1 (en) * | 2007-07-19 | 2009-01-22 | University Of Cincinnati | Nearly index-matched luminescent glass-phosphor composites for photonic applications |
| CN102796517A (en) * | 2011-05-23 | 2012-11-28 | 海洋王照明科技股份有限公司 | Nitrogenous magnesium silicate film, and preparation method and application thereof |
-
2013
- 2013-05-23 CN CN201310196837.3A patent/CN104178136A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009012484A1 (en) * | 2007-07-19 | 2009-01-22 | University Of Cincinnati | Nearly index-matched luminescent glass-phosphor composites for photonic applications |
| CN102796517A (en) * | 2011-05-23 | 2012-11-28 | 海洋王照明科技股份有限公司 | Nitrogenous magnesium silicate film, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 逄茂林等: "发光薄膜的制备及应用", 《液晶与显示》, vol. 17, 30 October 2002 (2002-10-30), pages 372 - 380 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104745187A (en) | Manganese-doped cerium antimonate luminescent film and its preparation method and use | |
| CN102796517B (en) | Nitrogenous magnesium silicate film, and preparation method and application thereof | |
| CN102791052A (en) | Titanium cerium co-doped barium tungstate light-emitting film, preparation method thereof and organic light-emitting device | |
| CN103534333B (en) | Titanium-doped ternary silicate thin film and its preparation method and application | |
| CN102787293A (en) | Manganese-doped aluminosilicate oxynitride luminescent film, preparation method and organic electroluminescent devices thereof | |
| CN102952545B (en) | Europium-doped strontium vanadate luminescent film, preparation method and organic electroluminescent device | |
| CN104178137A (en) | Praseodymium-doped indium silicate luminescent film, preparing method thereof and electroluminescent device | |
| CN103451600A (en) | Cerium doped alkali metal scandate luminescent thin film, and preparation method and application thereof | |
| CN103820115A (en) | Chromium-manganese co-doped yttrium oxide light-emitting film and preparation method thereof, as well as and electroluminescent device | |
| CN104178139A (en) | Europium terbium co-doped gallium silicate light-emitting film and preparation method thereof and electroluminescent device | |
| CN104178136A (en) | Samarium-doped nitrogen-containing silicate light-emitting film and preparation method thereof and electroluminescent device | |
| CN102838991A (en) | Europium-doped yttrium oxide sulfide luminescent film, preparation method thereof, and organic electroluminescent device | |
| CN103534332B (en) | Cerium-doped barium magnesium tungstate luminescent thin film and its preparation method and application | |
| CN104178146A (en) | Manganese titanium co-doped nitrogen germanate light-emitting film and preparation method thereof and electroluminescent device | |
| CN102796984B (en) | Multielement-doped strontium phosphate luminescent film, and preparation method and applications thereof | |
| CN102796518A (en) | Luminescent thin film and preparation method and application thereof | |
| CN104178153A (en) | Europium terbium-doped hafnium oxide-based light-emitting film and preparation method thereof and electroluminescent device | |
| CN104178163A (en) | Cerium- terbium- co-doped rare earth boron gallate luminescent film, preparing method thereof and electroluminescent device | |
| CN102911666B (en) | Cerium-tin-codoped strontium chlorophosphate light-emitting film and preparation method thereof, and organic electroluminescent device | |
| CN102807859B (en) | Europium-doped chloride calcium magnesium silicate luminescent film, preparation method and applications thereof | |
| CN102786930B (en) | Titanium and cerium co-doped aluminosilicate oxynitride luminescent film, preparation method and organic electroluminescent devices thereof | |
| CN102838987B (en) | Europium and cerium co-doped yttrium oxide luminescent film, preparation method thereof, and organic electroluminescent device | |
| CN104178138A (en) | Europium-doped gallium silicate luminescent film, preparing method thereof and electroluminescent device | |
| CN104178145A (en) | Cerium terbium co-doped nitrogen germanate light-emitting film and preparation method thereof and electroluminescent device | |
| CN104178162A (en) | Cerium-doped rare earth boron aluminate luminescent film, preparing method thereof and electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141203 |