CN102796517B - Nitrogenous magnesium silicate film, and preparation method and application thereof - Google Patents
Nitrogenous magnesium silicate film, and preparation method and application thereof Download PDFInfo
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- CN102796517B CN102796517B CN201110134003.0A CN201110134003A CN102796517B CN 102796517 B CN102796517 B CN 102796517B CN 201110134003 A CN201110134003 A CN 201110134003A CN 102796517 B CN102796517 B CN 102796517B
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000391 magnesium silicate Substances 0.000 title abstract description 9
- 229910052919 magnesium silicate Inorganic materials 0.000 title abstract description 9
- 235000019792 magnesium silicate Nutrition 0.000 title abstract description 9
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 53
- 238000004544 sputter deposition Methods 0.000 claims abstract description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 6
- UHXWLHYMUGRLKG-UHFFFAOYSA-N [Mg].O[Si](O)(O)O Chemical compound [Mg].O[Si](O)(O)O UHXWLHYMUGRLKG-UHFFFAOYSA-N 0.000 claims description 68
- 239000007789 gas Substances 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 71
- 239000000758 substrate Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 9
- -1 rare earth ion Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000009832 plasma treatment Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- SVFOMDDAWOLOME-UHFFFAOYSA-N [N].[Mg] Chemical compound [N].[Mg] SVFOMDDAWOLOME-UHFFFAOYSA-N 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 238000005406 washing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Physical Vapour Deposition (AREA)
Abstract
The invention relates to the field of preparation of semiconductor materials, and provides a nitrogenous magnesium silicate film which is a titanium-doped nitrogenous magnesium silicate film of which the general formula is Mg1-XSi2O2N2:XTi4+, wherein X-0.01-0.15. The invention also provides a preparation method of the nitrogenous magnesium silicate film, which comprises the following steps: mixing MgO powder, SiO2 powder, Si3N4 powder and TiO2 powder, and sintering to obtain a target; and filling the target into a magnetron sputtering chamber, vacuumizing, setting working parameters, and sputtering to obtain the nitrogenous magnesium silicate film. The invention also provides application of the nitrogenous magnesium silicate film in electroluminescent devices.
Description
Technical field
The invention belongs to photoelectric semiconductor material field, be specifically related to a kind of nitrogenous silicic acid magnesium film and its preparation method and application.
Background technology
Compared with the display screen made with traditional luminescent powder, light-emitting film contrast gradient, resolving power, thermal conduction, homogeneity, with the tack, outgas speed etc. of substrate in all demonstrate stronger superiority.Therefore, as functional materials, light-emitting film has broad application prospects in the flat display field such as such as cathode tube (CRTs), electroluminance display (ELDs) and Field Emission Display (FEDs).
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.Be that the monochromatic TFELD of luminescent layer is full-fledged and realize commercialization with ZnS:Mn.Research colour and extremely panchromatic TFELD, the material of exploitation multiband luminescence is extremely urgent task.In luminescence system material, rare earth ion doped silicates fluorescent material has obtained deep research, can obtain good ruddiness exciting to blue light.Meanwhile, its chemical stability and thermostability can be made to improve owing to adding appropriate nitride, and the excitation wavelength that can be changed in a big way, therefore, nitrogenous silicate is the substrate material of great potential as luminescent material.But, this type of material powder morphology often of report at present, and rare earth price is more expensive, scarcity of resources, and make application difficult in actual production, cost is higher.
Summary of the invention
Technical problem to be solved by this invention is the defect overcoming prior art, provides a kind of nitrogenous silicic acid magnesium film and its preparation method and application.
The embodiment of the present invention is achieved in that first aspect provides a kind of nitrogenous silicic acid magnesium film, and described film is titanium doped nitrogenous silicic acid magnesium film, and the chemical general formula of described titanium doped nitrogenous silicic acid magnesium film is Mg
1-Xsi
2o
2n
2:
xti
4+, wherein, the span of X is 0.01 ~ 0.15.
Another object of the embodiment of the present invention is the preparation method providing above-mentioned nitrogenous silicic acid magnesium film, and it comprises the steps:
By MgO powder, SiO
2powder, Si
3n
4powder and TiO
2powder is according to mol ratio (1-X): 0.5: 0.5: X mixing, and sinter as target, wherein, the span of described X is 0.01 ~ 0.15;
Described target is loaded in magnetron sputtering cavity, vacuumize, arranging operating pressure is 0.2Pa ~ 4.5Pa, pass into the mixed gas of rare gas element and hydrogen, mixed gas flow is 15sccm ~ 30sccm, underlayer temperature is 350 DEG C ~ 750 DEG C, and sputtering power is 30W ~ 150W, sputters to obtain nitrogenous silicic acid magnesium film.
Another object of the embodiment of the present invention is to provide above-mentioned nitrogenous silicic acid magnesium film in the application in feds, cathode tube and/or electroluminescent device.
The embodiment of the present invention provides a kind of nitrogenous silicic acid magnesium film, to be adulterated nitrogenous Magnesium Silicate q-agent by Ti, obtains cost low, thermostability and the high electroluminescent film of luminous intensity stability.Preparation method adopts magnetron sputtering method, and it has, and sedimentation rate is high, film tack is good, easy to control and can realize the advantages such as extensive deposition.Further, this film shows the advantage that stability is high, the life-span is long in the application of electroluminescent device.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the nitrogenous silicic acid magnesium film of the embodiment of the present invention;
Fig. 2 is using the nitrogenous silicic acid magnesium film of the embodiment of the present invention as the structural representation of electroluminescent device making luminescent layer;
Fig. 3 is nitrogenous silicic acid magnesium film electroluminescent spectrum figure prepared by the embodiment of the present invention 1;
Fig. 4 is after the nitrogenous silicic acid magnesium film of the embodiment of the present invention 1 preparation uses at 300 DEG C, the graph of a relation of luminous intensity and time;
Fig. 5 is the X-ray diffractogram of nitrogenous silicic acid magnesium film prepared by the embodiment of the present invention 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention is achieved in that first aspect provides a kind of nitrogenous silicic acid magnesium film, and described film is titanium doped nitrogenous silicic acid magnesium film, and the chemical general formula of described titanium doped nitrogenous silicic acid magnesium film is Mg
1-Xsi
2o
2n
2:
xti
4+, wherein, the span of X is 0.01 ~ 0.15.
Substrate material Mg
1-Xsi
2o
2n
2there is chemical stability and the high advantage of thermostability, appropriate Ti
4+doping can obtain the good titanium doped nitrogenous Magnesium Silicate q-agent of luminous intensity, and preferably, the span of X is 0.02 ~ 0.08, now can ensure to obtain good thin-film light emitting intensity and crystalline quality.
Another object of the embodiment of the present invention is the preparation method of the nitrogenous silicic acid magnesium film providing the embodiment of the present invention, and refer to Fig. 1, it comprises the steps:
S01: by MgO powder, SiO
2powder, Si
3n
4powder and TiO
2powder is according to mol ratio (1-X): 0.5: 0.5: X mixing, and sinter as target, wherein, the span of described X is 0.01 ~ 0.15;
S02: described target is loaded in magnetron sputtering cavity, vacuumize, arranging operating pressure is 0.2Pa ~ 4.5Pa, pass into the mixed gas of rare gas element and hydrogen, mixed gas flow is 15sccm ~ 30sccm, underlayer temperature is 350 DEG C ~ 750 DEG C, and sputtering power is 30W ~ 150W, sputters to obtain nitrogenous silicic acid magnesium film.
In step S01, by MgO powder, SiO
2powder, Si
3n
4powder and TiO
2powder is according to mol ratio (1-X): 0.5: 0.5: X mixes, high temperature sintering, such as, sinter at 900 DEG C ~ 1300 DEG C temperature, obtain target.Preferably, sintering temperature is 1200 DEG C.The purity of above-mentioned powder is preferably greater than 99.99%.The quality taken is respectively: MgO 6.8g ~ 7.92g, SiO
26g, Si
3n
414g and TiO
20.16g ~ 2.4g, make the mol ratio of four kinds of powders for (1-X): 0.5: 0.5: X, now X value is 0.01 ~ 0.15; Preferably X value is 0.06 ~ 0.1, TiO
2quality be 0.9g ~ 1.6g, more preferably X value is 0.08, TiO
2quality be 1.28g.The content of matrix composition and doped element is the important factor affecting film performance and structure.Its chemical stability and thermostability can be made to improve owing to adding appropriate nitride in substrate material, and the excitation wavelength that can be changed in a big way, and the content of Ti can affect luminous intensity.But doped metal ion has impact to material structure, exogenous metal ions enters lattice, crystalline structure generating portion is distorted, and therefore, doping is excessive, lattice distortion can be caused excessive, upset the ion ordering in lattice or cause generating dephasign in material, material property severe weakness can be made.
In step S02, substrate is the hard substrates such as sapphire, silica glass, silicon chip.Use front acetone, dehydrated alcohol and deionized water supersound washing.Also substrate can be selected, as ito glass substrate according to applying further.The distance of target and substrate is preferably 50mm ~ 90mm.More preferably, the distance of target and substrate is 70mm.Target loads after in sputtering cavity, with mechanical pump or molecular pump, the vacuum tightness of cavity is evacuated to 1.0 × 10
-3pa ~ 1.0 × 10
-5more than Pa, is preferably 6.0 × 10
-4pa.Obtain the nitrogenous silicic acid magnesium film of excellent performance, processing condition arrange extremely important.Working gas in sputtering chamber is the mixed gas of rare gas element and hydrogen, and wherein, the volume percent of hydrogen is 1% ~ 15%, is preferably 3% ~ 8%.Preferably, mixed gas flow is 20sccm ~ 25sccm, and operating pressure is 0.8Pa ~ 2.5Pa, and underlayer temperature is 400 DEG C ~ 600 DEG C, and sputtering power is 80W ~ 120W.Further, anneal is carried out to obtained nitrogenous silicic acid magnesium film, the performance of film can be improved.Carry out anneal to nitrogenous silicic acid magnesium film obtained under above-mentioned specific process conditions, anneal comprises nitrogenous silicic acid magnesium film is warming up to annealing temperature and the process of insulation.Annealing temperature is 500 DEG C ~ 800 DEG C.Anneal environment can be rare gas element gas, as nitrogen, and argon gas etc., or vacuum annealing.In a preferred embodiment of the invention, anneal is annealed in the vacuum oven of 0.01Pa.Annealing temperature is preferably 550 DEG C ~ 650 DEG C.Annealing heats up not easily too fast or excessively slow, and temperature rise rate is 1 DEG C/min ~ 10 DEG C/min, and preferably, temperature rise rate is 5 DEG C/min ~ 8 DEG C/min.After being warming up to annealing temperature, keep 1h ~ 3h, preferably, keep 2h.Annealing improves the crystalline quality of film, improves the luminous efficiency of film.
The embodiment of the present invention also provides the application of above-mentioned nitrogenous silicic acid magnesium film in feds, cathode tube and/or electroluminescent device.For electroluminescent device, refer to Fig. 2, the organic electroluminescence device adopting nitrogenous silicic acid magnesium film material in above-described embodiment is shown, it comprises the glass-base 21, anode 22, luminescent layer 23 and the negative electrode 24 that are cascading.Anode 22 can adopt tin indium oxide (referred to as ITO), and luminescent layer 23 comprises the nitrogenous silicic acid magnesium film in the embodiment of the present invention; Negative electrode 24 can be but be not limited to metal A g.Thus, in a specific embodiment, membrane electro luminescent device representation is: the nitrogenous silicic acid magnesium film/Ag of glass/ITO/.Each layer can adopt existing method to be formed, and as adopted the glass substrate with ITO layer, adopts the above-mentioned nitrogenous silicic acid magnesium film of magnetically controlled sputter method sputtering, then evaporation Ag layer.
The embodiment of the present invention provides a kind of nitrogenous silicic acid magnesium film, by regulating the composition of each composition, obtains luminous intensity high, the nitrogenous silicic acid magnesium film that degree of crystallinity is high.The preparation method of this nitrogenous silicic acid magnesium film, adopts magnetron sputtering method, achieves thin-film light emitting intensity high, stable performance, keep good work-ing life simultaneously.And, adopt the gallium-doped zinc oxide film of the mixed gas of rare gas element and hydrogen to sputtering gained to carry out anneal, the luminous efficiency of film can be improved, the titanium doped film that just can obtain excellent performance of small amount.
Be described in detail specific implementation of the present invention below in conjunction with specific embodiment, for convenience of practical application, the parameter of each powder will describe with mass percent:
Embodiment 1:
Select purity be 99.99% 7.36g MgO powder, 6g SiO
2powder, 14g Si
3n
4powder and 1.28g TiO
2powder, after being mixed, 1200 DEG C of high temperature sinterings become the ceramic target of Φ 50 × 2mm, and are loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and oxygen plasma treatment is carried out to it, put into vacuum cavity.The distance of target and substrate is set as 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 7.0 × 10
-4pa, the argon gas passed into vacuum cavity and the mixed gas of hydrogen, wherein, hydrogen content is 5% (volume ratio), and gas flow is 20sccm, and pressure is adjusted to 1.0Pa, underlayer temperature is set as 500 DEG C, and sputtering power is adjusted to 100W, and sputtering obtains nitrogenous silicic acid magnesium film.Annealed in the vacuum oven of 0.01Pa by nitrogenous for gained silicic acid magnesium film, wherein, annealing temperature is 600 DEG C, and temperature rise rate is 6 DEG C/min, and soaking time is 2h again.Obtain nitrogenous silicic acid magnesium film, its molecular formula is: Mg
0.92si
2o
2n
2:
0.08ti
4+.
Embodiment 2:
Select purity be 99.99% 6.8g MgO powder, 6g SiO
2powder, 14g Si
3n
4powder and 2.4g TiO
2powder, after being mixed, 900 DEG C of high temperature sinterings become the ceramic target of Φ 50 × 2mm, and are loaded in vacuum cavity by target.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning quartz substrate, and dry up with high pure nitrogen, put into vacuum cavity.The distance of target and substrate is set as 50mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10
-3pa, the argon gas passed into vacuum cavity and the mixed gas of hydrogen, wherein, hydrogen content is 1% (volume ratio), and gas flow is 20sccm, and pressure is adjusted to 0.2Pa, underlayer temperature is set as 350 DEG C, and sputtering power is adjusted to 100W, and sputtering obtains nitrogenous silicic acid magnesium film.Annealed in the vacuum oven of 0.01Pa by nitrogenous for gained silicic acid magnesium film, wherein, annealing temperature is 500 DEG C, and temperature rise rate is 5 DEG C/min, and soaking time is 1h again.Obtain nitrogenous silicic acid magnesium film, its molecular formula is: Mg
0.85si
2o
2n
2:
0.15ti
4+.
Embodiment 3:
Select purity be 99.99% 7.92g MgO powder, 6g SiO
2powder, 14g Si
3n
4powder and 0.16g TiO
2powder, after being mixed, 1000 DEG C of high temperature sinterings become the ceramic target of Φ 50 × 2mm, and are loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and oxygen plasma treatment is carried out 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 6.0 × 10
-4pa, the argon gas passed into vacuum cavity and the mixed gas of hydrogen, wherein, hydrogen content is 2% (volume ratio), and gas flow is 23sccm, and pressure is adjusted to 0.5Pa, underlayer temperature is set as 400 DEG C, and sputtering power is adjusted to 100W, and sputtering obtains nitrogenous silicic acid magnesium film.Annealed in the vacuum oven of 0.01Pa by nitrogenous for gained silicic acid magnesium film, wherein, annealing temperature is 600 DEG C, and temperature rise rate is 5 DEG C/min, and soaking time is 1.5h again.Obtain nitrogenous silicic acid magnesium film, its molecular formula is: Mg
0.99si
2o
2n
2:
0.01ti
4+.
Embodiment 4:
Select purity be 99.99% 7.84g MgO powder, 6g SiO
2powder, 14g Si
3n
4powder and 0.32g TiO
2powder, after being mixed, 1100 DEG C of high temperature sinterings become the ceramic target of Φ 50 × 2mm, and are loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and oxygen plasma treatment is carried out to it, put into vacuum cavity.The distance of target and substrate is set as 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 8.0 × 10
-4pa, the argon gas passed into vacuum cavity and the mixed gas of hydrogen, wherein, hydrogen content is 15% (volume ratio), and gas flow is 30sccm, and pressure is adjusted to 1.0Pa, underlayer temperature is set as 520 DEG C, and sputtering power is adjusted to 30W, and sputtering obtains nitrogenous silicic acid magnesium film.Annealed in the vacuum oven of 0.01Pa by nitrogenous for gained silicic acid magnesium film, wherein, annealing temperature is 650 DEG C, and temperature rise rate is 1 DEG C/min, and soaking time is 2h again.Obtain nitrogenous silicic acid magnesium film, its molecular formula is: Mg
0.98si
2o
2n
2:
0.02ti
4+.
Embodiment 5:
Select purity be 99.99% 7.64g MgO powder, 6g SiO
2powder, 14g Si
3n
4powder and 0.72g TiO
2powder, after being mixed, 1200 DEG C of high temperature sinterings become the ceramic target of Φ 50 × 2mm, and are loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and oxygen plasma treatment is carried out to it, put into vacuum cavity.The distance of target and substrate is set as 70mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 × 10
-4pa, the argon gas passed into vacuum cavity and the mixed gas of hydrogen, wherein, hydrogen content is 3.5% (volume ratio), and gas flow is 23sccm, and pressure is adjusted to 0.5Pa, underlayer temperature is set as 500 DEG C, and sputtering power is adjusted to 150W, and sputtering obtains nitrogenous silicic acid magnesium film.Again by nitrogenous for gained silicic acid magnesium film in AN, wherein, annealing temperature is 600 DEG C, and temperature rise rate is 1 DEG C/min, and soaking time is 2h.Obtain nitrogenous silicic acid magnesium film, its molecular formula is: Mg
0.955si
2o
2n
2:
0.045ti
4+.
Embodiment 6:
Select purity be 99.99% 7.48g MgO powder, 6g SiO
2powder, 14g Si
3n
4powder and 1.04g TiO
2powder, after being mixed, 1300 DEG C of high temperature sinterings become the ceramic target of Φ 50 × 2mm, and are loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and oxygen plasma treatment is carried out to it, put into vacuum cavity.The distance of target and substrate is set as 90mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10
-5pa, the argon gas passed into vacuum cavity and the mixed gas of hydrogen, wherein, hydrogen content is 15% (volume ratio), and gas flow is 30sccm, and pressure is adjusted to 4.5Pa, underlayer temperature is set as 550 DEG C, and sputtering power is adjusted to 100W, and sputtering obtains nitrogenous silicic acid magnesium film.Annealed in the vacuum oven of 0.01Pa by nitrogenous for gained silicic acid magnesium film, wherein, annealing temperature is 800 DEG C, and temperature rise rate is 10 DEG C/min, and soaking time is 3h again.Obtain nitrogenous silicic acid magnesium film, its molecular formula is: Mg
0.935si
2o
2n
2:
0.065ti
4+.
Embodiment 7:
Select purity be 99.99% 7.2g MgO powder, 6g SiO
2powder, 14g Si
3n
4powder and 1.6g TiO
2powder, after being mixed, 1300 DEG C of high temperature sinterings become the ceramic target of Φ 50 × 2mm, and are loaded in vacuum cavity by target.Then, successively use the glass substrate of acetone, dehydrated alcohol and deionized water ultrasonic cleaning band ITO, and oxygen plasma treatment is carried out to it, put into vacuum cavity.The distance of target and substrate is set as 90mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 × 10
-5pa, the argon gas passed into vacuum cavity and the mixed gas of hydrogen, wherein, hydrogen content is 8% (volume ratio), and gas flow is 15sccm, and pressure is adjusted to 0.2Pa, underlayer temperature is set as 550 DEG C, and sputtering power is adjusted to 120W, and sputtering obtains nitrogenous silicic acid magnesium film.Annealed in the vacuum oven of 0.01Pa by nitrogenous for gained silicic acid magnesium film, wherein, annealing temperature is 800 DEG C, and temperature rise rate is 10 DEG C/min, and soaking time is 3h again.Obtain nitrogenous silicic acid magnesium film, its molecular formula is: Mg
0.9si
2o
2n
2:
0.1ti
4+.
Fig. 3 is the electroluminescent spectrum figure of nitrogenous silicic acid magnesium film prepared by the embodiment of the present invention 1, and it has the transmitting of the last one at 500nm place.
Fig. 4 be the embodiment of the present invention 1 prepare nitrogenous silicic acid magnesium film at 300 DEG C, use the luminous intensity variations figure after 0 day, 2 days, 4 days, 6 days, 8 days, 10 days, 12 days, 14 days.As can be seen from the figure film uses one week under 300 DEG C of high temperature, still keeps the luminous intensity of original 90%.
Fig. 5 is the X-ray diffractogram of nitrogenous silicic acid magnesium film prepared by the embodiment of the present invention 1.Reference standard PDF card in figure, corresponding diffraction peak is nitrogen-oxygen-silicon magnesium crystallization phases, does not occur the peak crystallization that titanium is relevant illustrating that titanium is the lattice entering matrix.Can find out that titanium ion is doped to in the nitrogen Magnesium Silicate q-agent crystal that is matrix, not destroy crystalline structure
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a nitrogenous silicic acid magnesium film, is characterized in that, described film is titanium doped nitrogenous silicic acid magnesium film, and the chemical general formula of described titanium doped nitrogenous silicic acid magnesium film is Mg
1-Xsi
2o
2n
2:
xti
4+, wherein, the span of described X is 0.02 ~ 0.08.
2. a preparation method for nitrogenous silicic acid magnesium film as claimed in claim 1, it is characterized in that, described method comprises the steps:
By MgO powder, SiO
2powder, Si
3n
4powder and TiO
2powder mixes according to mol ratio (1-X): 0.5:0.5:X, sinters as target, and wherein, the span of described X is 0.02 ~ 0.08;
Described target is loaded in magnetron sputtering cavity, vacuumize, arranging operating pressure is 0.2Pa ~ 4.5Pa, pass into the mixed gas of rare gas element and hydrogen, mixed gas flow is 15sccm ~ 30sccm, underlayer temperature is 350 DEG C ~ 750 DEG C, and sputtering power is 30W ~ 150W, sputters to obtain nitrogenous silicic acid magnesium film.
3. the preparation method of nitrogenous silicic acid magnesium film as claimed in claim 2, is characterized in that, carries out anneal further to obtained nitrogenous silicic acid magnesium film.
4. the preparation method of nitrogenous silicic acid magnesium film as claimed in claim 3, is characterized in that, the annealing temperature of described anneal is 500 DEG C ~ 800 DEG C, and the soaking time of described annealing is 1h ~ 3h.
5. the preparation method of nitrogenous silicic acid magnesium film as claimed in claim 2, is characterized in that, in described mixed gas, the volumn concentration of hydrogen is 1% ~ 15%.
6. the preparation method of nitrogenous silicic acid magnesium film as claimed in claim 2, is characterized in that, in described mixed gas, the volumn concentration of hydrogen is 3% ~ 8%.
7. the preparation method of the nitrogenous silicic acid magnesium film as described in any one of claim 2 to 6, is characterized in that, the operating pressure of described cavity is 0.8Pa ~ 2.5Pa, and described underlayer temperature is 400 DEG C ~ 600 DEG C, and described sputtering power is 80W ~ 120W.
8. the application of nitrogenous silicic acid magnesium film as claimed in claim 1 in feds, cathode tube and/or electroluminescent device.
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| CN104178145A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Cerium terbium co-doped nitrogen germanate light-emitting film and preparation method thereof and electroluminescent device |
| CN104178146A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Manganese titanium co-doped nitrogen germanate light-emitting film and preparation method thereof and electroluminescent device |
| CN104178136A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Samarium-doped nitrogen-containing silicate light-emitting film and preparation method thereof and electroluminescent device |
| CN104232087A (en) * | 2014-08-11 | 2014-12-24 | 北京大学工学院包头研究院 | Fluorescent material and preparation method and application thereof |
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