CN104120416A - Preparation method of ultraviolet photosensitive lanthanum-strontium-manganese oxygen sol and micro graphical film thereof - Google Patents
Preparation method of ultraviolet photosensitive lanthanum-strontium-manganese oxygen sol and micro graphical film thereof Download PDFInfo
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- CN104120416A CN104120416A CN201410356077.2A CN201410356077A CN104120416A CN 104120416 A CN104120416 A CN 104120416A CN 201410356077 A CN201410356077 A CN 201410356077A CN 104120416 A CN104120416 A CN 104120416A
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- PIRUAZLFEUQMTG-UHFFFAOYSA-N lanthanum;oxomanganese;strontium Chemical compound [Sr].[La].[Mn]=O PIRUAZLFEUQMTG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910003369 La0.67Sr0.33MnO3 Inorganic materials 0.000 claims abstract description 34
- 239000011572 manganese Substances 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 147
- 206010070834 Sensitisation Diseases 0.000 claims description 50
- 230000008313 sensitization Effects 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 42
- 229910021645 metal ion Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 238000003618 dip coating Methods 0.000 claims description 11
- 230000000873 masking effect Effects 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- -1 krypton ion Chemical class 0.000 claims description 5
- MYZAXBZLEILEBR-RVFOSREFSA-N (2S)-1-[(2S,3R)-2-[[(2R)-2-[[2-[[(2S)-2-[(2-aminoacetyl)amino]-5-(diaminomethylideneamino)pentanoyl]amino]acetyl]amino]-3-sulfopropanoyl]amino]-3-hydroxybutanoyl]pyrrolidine-2-carboxylic acid Chemical compound C[C@@H](O)[C@H](NC(=O)[C@H](CS(O)(=O)=O)NC(=O)CNC(=O)[C@H](CCCN=C(N)N)NC(=O)CN)C(=O)N1CCC[C@H]1C(O)=O MYZAXBZLEILEBR-RVFOSREFSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052743 krypton Inorganic materials 0.000 claims description 4
- 108700002400 risuteganib Proteins 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 108010025899 gelatin film Proteins 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002689 soil Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- 230000005291 magnetic effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YMVZSICZWDQCMV-UHFFFAOYSA-N [O-2].[Mn+2].[Sr+2].[La+3] Chemical compound [O-2].[Mn+2].[Sr+2].[La+3] YMVZSICZWDQCMV-UHFFFAOYSA-N 0.000 description 1
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical compound [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007687 exposure technique Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002174 soft lithography Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a preparation method of ultraviolet photosensitive lanthanum-strontium-manganese oxygen soil. The ultraviolet photosensitive lanthanum-strontium-manganese oxygen sol is prepared by La(NO3)3.6H2O, Sr(CH3COO)2.0.5H2O, Mn(CH3COO)2.4H2O, 2,2'-dipyridyl according to the mol ratio of 0.67: 0.33: 1: (0.665-1.33). The method for preparing the micro film comprises the following steps: a photosensitive La0.67Sr0.33MnO3 gel film is prepared by the sol through a dipping extraction method; and then, the exposure, the soluble washing and the heat treatment are performed in sequence by an ultraviolet mask method or a double-beam laser interference method to obtain a micro graphical La0.67Sr0.33MnO3 film. The preparation method has the advantages of simple process, low preparation cost and little environmental pollution; the micro graphical structure of the prepared La0.67Sr0.33MnO3 film is tidy; the linearty can be decreased to the micron stage; the preparation process is easily controlled; and the preparation method is suitable for industrial production.
Description
Technical field
The invention belongs to microelectronics and technical field of magnetic materials, the present invention relates to a kind of preparation method of ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol, the invention still further relates to the method that uses this colloidal sol to prepare minute graphic representation film.
Background technology
There is the lanthanum-strontium-manganese oxide (La of perovskite crystal structure
xsr
1-xmnO
3, be abbreviated as LSMO) and be a kind of rare earth manganese oxide, the discovery of giant magnetoresistance effect becomes the focus of Materials science research.LSMO has been widely used in the multiple magneto-resistance effect device of magnetic head, random access memory, transverter and sensor in hard disc of computer as typical magnetic resistance material; In magnetic cooling field, LSMO can be used as room temperature magnetic refrigeration material, thereby in health care, space flight and automobile and other industries have broad application prospects; In addition Curie temperature (the T of LSMO,
c=370K) higher than room temperature, and only there is the 3d state conduction band of complete polarization at Fermi surface place, and there is not s state, character is more stable, can not be oxidized in air, thereby or a kind of desirable ferromagnetic electrode material.
Micrometer-Nanometer Processing Technology is that function ceramics film is carried out to patterned main method, is to support one of electronics and the continuous progressive gordian technique of photoelectron element.Existing Micrometer-Nanometer Processing Technology, as wet chemical lithographic technique, deep UV exposure technique, electron beam lithography, ion beam etching technology, plasma etching technology, nano impression method and soft lithography etc., in microelectronics development, bring into play keying action, established microelectronic basis.Because these technology all must first be prepared function ceramics film and just can carry out subsequently corresponding microfabrication, so the common complicated operation of class technology, operating environment harshness, expense are high, and work material only limits to semiconductor material and partial polymer material.LSMO ceramic membrane solidity to corrosion is strong, extremely difficult corrosion.So its high quality, large-area Micropicture are to be difficult to prepare by traditional method.Secondly, if above-mentioned technology is directly used in the microfabrication of LSMO film, tend to cause its physical and chemical performance to change, and then limited its application in micro element neighborhood.
The sol-gel method of employing chemically modified and the function ceramics film that ultraviolet mask/laser interferance method combines and Micropicture technology of preparing (being called for short " sensitization sol-gel method ") are a kind of novel methods of preparing minute graphic representation function ceramics film that development in recent years is got up.Be characterized in without photoresist material, corrosive fluid and other high precise equipment, and can realize synchronously carrying out of ceramic membrane preparation and minute graphic representation processing.Sensitization sol-gel method has been applied to the preparation of the minute graphic representation function films such as silicon oxide, titanium oxide, zirconium white, Pb-based lanthanumdoped zirconate titanates and yttrium barium copper oxide, and becomes one of technique of the tool future of preparation high-density, integrated functionality ceramic film.But, because the consistency of the chemical modifiers such as methyl ethyl diketone/BA in LSMO colloidal sol that " the sensitization sol-gel method " of routine used is very poor, cause and still do not adopt sensitization sol-gel method to prepare pertinent literature and the patent report of minute graphic representation LSMO film at present.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol.
Another object of the present invention is to provide and uses this ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol to prepare the method for minute graphic representation film, and film surface Micropicture compound with regular structure, the technique of preparation is simple, be easy to control.
The first technical scheme of the present invention is: the preparation method of ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol is by La (NO
3)
36H
2o, Sr (CH
3cOO)
20.5H
2o, Mn (CH
3cOO)
24H
2o, 2,2 '-dipyridyl is 0.67:0.33:1:(0.665～1.33 according to mol ratio) La that makes
0.67sr
0.33mnO
3sensitization colloidal sol, specifically comprises the following steps:
Step 1: by Sr (CH
3cOO)
20.5H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, continues to stir 20～30min, forms solution A;
By Mn (CH
3cOO)
24H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, continues to stir 20～30min, forms solution B;
By La (NO
3)
36H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, after stirring under room temperature, forms solution C;
Step 2: solution A, solution B and the solution C that step 1 is obtained is La by lanthanum, strontium, manganese three metal ion species mol ratios
3+: Sr
2+: Mn
4+=0.67:0.33:1 mixes, and obtaining chemical constitution is La
0.67sr
0.33mnO
3sensitization colloidal sol, adding appropriate methanol constant volume to metal ion total concn is 0.1～0.5mol/L.
Feature of the present invention is also,
Sr (CH in step 1
3cOO)
20.5H
2o:2,2 '-dipyridyl: mol ratio=1:(0.5～1.0 of anhydrous methanol): 20; Mn (CH
3cOO)
24H
2o:2,2 '-dipyridyl: mol ratio=1:(0.5～1.0 of anhydrous methanol): 20; La (NO
3)
36H
2o: the mol ratio of anhydrous methanol is 1:20.
The second technical scheme of the present invention is: use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol to prepare the method for minute graphic representation film, with La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on substrate
0.67sr
0.33mnO
3gel film, subsequently drying, expose, dissolve and wash away and thermal treatment, obtain having the La of minute graphic representation structure
0.67sr
0.33mnO
3film.
Feature of the present invention is also,
Comprise the following steps:
Step 1: with ultraviolet sensitization La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on substrate
0.67sr
0.33mnO
3gel film, is then dried, and obtains dry La
0.67sr
0.33mnO
3gel film;
Step 2: the dry La that adopts ultraviolet mask means or double light beam laser interferometric method to obtain step 1
0.67sr
0.33mnO
3gel film exposes, and obtains the La after exposure
0.67sr
0.33mnO
3gel film;
Step 3: the La after the exposure that step 2 is obtained
0.67sr
0.33mnO
3gel film dissolves and washes away in mixed solvent, then heat-treats, and obtains having the La of minute graphic representation
0.67sr
0.33mnO
3film.
In step 1, substrate is glass, silicon or lanthanuma luminate single crystal.
In step 1, the pull rate of dip-coating method is 0.05～0.25cm/s; Dry temperature is that 80～100 DEG C, time are 5～10min.
It is exposure light source that step 2 medium ultraviolet mask means adopts the ultraviolet lamp that predominant wavelength is 365nm, and the krypton ion laser of double light beam laser interferometric method taking output wavelength as 350.7nm is light source.
In step 2, the time of exposure is 20～40min.
Ethanol and Virahol that in step 3, mixed solvent is 1:5～20 by volume ratio form, and the time of dissolveing and washing away is 4～10s.
In step 3, heat treated temperature is that 750～800 DEG C, time are 30～40min.
The invention has the beneficial effects as follows: the present invention adopts ultraviolet mask means or double light beam laser interferometric method directly at La
0.67sr
0.33mnO
3on film, prepare Micropicture, realized La
0.67sr
0.33mnO
3synchronously carrying out of film preparation and minute graphic representation processing, its preparation process is without expensive equipment, without corrosive medium, technical process is simple, has advantages of and is easy to make big area Micropicture, and preparation cost is low, environmental pollution is little, the compound with regular structure of prepared Micropicture, dimension can be as small as micron order, and preparation process is easy to control, and is applicable to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is La prepared by the embodiment of the present invention 1
0.67sr
0.33mnO
3the ultra-violet absorption spectrum of gel film and with the variation diagram of UV-irradiation time;
Fig. 2 is the La with miniaturization figure prepared by the embodiment of the present invention 1
0.67sr
0.33mnO
3the X-ray diffracting spectrum of film;
Fig. 3 is the La with cylindrical bump Micropicture prepared by the embodiment of the present invention 1
0.67sr
0.33mnO
3the laser co-focusing Photomicrograph of film;
Fig. 4 is the La that the embodiment of the present invention 4 utilizes double light beam laser interferometric method to prepare on silicon substrate
0.67sr
0.33mnO
3the light micrograph of minute groove.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The preparation method of ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol of the present invention is by La (NO
3)
36H
2o, Sr (CH
3cOO)
20.5H
2o, Mn (CH
3cOO)
24H
2o, 2,2 '-dipyridyl is 0.67:0.33:1:(0.665～1.33 according to mol ratio) La that makes
0.67sr
0.33mnO
3sensitization colloidal sol, specifically comprises the following steps:
Step 1: by Sr (CH
3cOO)
20.5H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Sr (CH
3cOO)
20.5H
2o:2,2 '-dipyridyl: mol ratio=1:(0.5～1.0 of anhydrous methanol): 20, continue to stir 20～30min, form solution A;
By Mn (CH
3cOO)
24H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Mn (CH
3cOO)
24H
2o:2,2 '-dipyridyl: mol ratio=1:(0.5～1.0 of anhydrous methanol): 20, continue to stir 20～30min, form solution B;
By La (NO
3)
36H
2o adds in anhydrous methanol, La (NO
3)
36H
2o: the mol ratio of anhydrous methanol is 1:20, stirs it is dissolved completely under room temperature, after stirring under room temperature, forms solution C;
Step 2: solution A, solution B and the solution C that step 1 is obtained is La by lanthanum, strontium, manganese three metal ion species mol ratios
3+: Sr
2+: Mn
4+=0.67:0.33:1 mixes, and obtaining chemical constitution is La
0.67sr
0.33mnO
3sensitization colloidal sol, adding appropriate methanol constant volume to metal ion total concn is 0.1～0.5mol/L.
Use above-mentioned ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation to there is the method for minute graphic representation film, comprise the following steps:
Step 1: with ultraviolet sensitization La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on glass, silicon or lanthanuma luminate single crystal substrate
0.67sr
0.33mnO
3gel film, pull rate is 0.05～0.25cm/s, then dry 5～10min at the temperature of 80～100 DEG C, obtains dry La
0.67sr
0.33mnO
3gel film;
Step 2: the mask plate with figure is positioned over to the dry La that step 1 obtains
0.67sr
0.33mnO
3on gel film, the ultraviolet lamp taking predominant wavelength as 365nm is as exposure light source employing ultraviolet mask means is to La
0.67sr
0.33mnO
3gel film exposes or krypton ion laser taking output wavelength as 350.7nm uses double light beam laser interferometric method directly to La as light source
0.67sr
0.33mnO
3gel film exposes, and the time shutter is 20～40min, obtains the La after exposure
0.67sr
0.33mnO
3gel film;
Step 3: the La after the exposure that step 2 is obtained
0.67sr
0.33mnO
3gel film dissolves and washes away 4～10s in the mixed solvent that the ethanol that is 1:5～20 by volume ratio and Virahol form, then heat-treat, heat treated temperature is that 750～800 DEG C, time are 30～40min, makes the organism in film fully volatilize and decompose, and obtains having the La of minute graphic representation
0.67sr
0.33mnO
3film.
The present invention has following beneficial effect:
1) La that prepared by the present invention
0.67sr
0.33mnO
3film has the features such as little, the non-microcracked and stable performance of good uniformity, roughness;
2) La
0.67sr
0.33mnO
3the thickness of film can be controlled by adjustment collosol concentration, pull rate;
3) adopt ultraviolet mask means or double light beam laser interferometric method directly at La
0.67sr
0.33mnO
3on film, prepare Micropicture, realized La
0.67sr
0.33mnO
3synchronously carrying out of film preparation and minute graphic representation processing, its preparation technology has without expensive equipment, and without corrosive medium, technical process is simple, is easy to make the advantage of big area Micropicture.
Embodiment 1
Preparation ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol:
Step 1: by Sr (CH
3cOO)
20.5H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Sr (CH
3cOO)
20.5H
2o:2,2 '-dipyridyl: the mol ratio=1:0.5:20 of anhydrous methanol, continue to stir 30min, form solution A;
By Mn (CH
3cOO)
24H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Mn (CH
3cOO)
24H
2o:2,2 '-dipyridyl: the mol ratio=1:0.5:20 of anhydrous methanol, continue to stir 30min, form solution B;
By La (NO
3)
36H
2o adds in anhydrous methanol, La (NO
3)
36H
2o: the mol ratio of anhydrous methanol is 1:20, stirs it is dissolved completely under room temperature, after stirring under room temperature, forms solution C;
Step 2: solution A, solution B and the solution C that step 1 is obtained is La by lanthanum, strontium, manganese three metal ion species mol ratios
3+: Sr
2+: Mn
4+=0.67:0.33:1 mixes, and obtains the ultraviolet sensitization La that total metal ion and sensitizer 2,2 '-dipyridyl mol ratio is 2:0.665
0.67sr
0.33mnO
3colloidal sol, adding appropriate methanol constant volume to metal ion total concn is 0.1mol/L.
Use above-mentioned ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation to there is minute graphic representation film:
Step 1: with ultraviolet sensitization La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on glass substrate
0.67sr
0.33mnO
3gel film, pull rate is 0.05cm/s, then dry 10min at the temperature of 80 DEG C, obtains dry La
0.67sr
0.33mnO
3gel film;
Step 2: the mask plate with circular dot pattern is positioned over to the dry La that step 1 obtains
0.67sr
0.33mnO
3on gel film, the ultraviolet lamp taking predominant wavelength as 365nm is as exposure light source is to La
0.67sr
0.33mnO
3gel film exposes, and the time shutter is 40min, obtains the La after exposure
0.67sr
0.33mnO
3gel film;
Step 3: the La after the exposure that step 3 is obtained
0.67sr
0.33mnO
3gel film dissolves and washes away 10s in the mixed solvent that the ethanol that is 1:20 by volume ratio and Virahol form, after taking out, blow away raffinate with elevated pressure nitrogen air-flow, then heat-treat, heat treated temperature is that 750 DEG C, time are 40min, make the organism in film fully volatilize and decompose, obtain having the La of cylindrical bump Micropicture
0.67sr
0.33mnO
3film.
This La
0.67sr
0.33mnO
3the photosensitivity of colloidal sol can be characterized with ultra-violet absorption spectrum, tests La under the different UV-irradiation time
0.67sr
0.33mnO
3the ultra-violet absorption spectrum of gel film, can disclose this La
0.67sr
0.33mnO
3the photobehavior of gel film.As shown in Figure 1, without the La of UV-irradiation
0.67sr
0.33mnO
3the maximum absorption band of gel film appears at 298nm, and after UV-irradiation more than 20min, maximum absorption band red shift is to 300nm, and peak intensity weakened gradually with the UV-irradiation time.
As shown in Figure 2, X-ray diffracting spectrum analysis shows prepared La
0.67sr
0.33mnO
3film is without dephasign, good crystallinity; Fig. 3 is the La of the prepared Micropicture of this example
0.67sr
0.33mnO
3the laser co-focusing Photomicrograph of film, wherein the height of cylindrical bump is about 13nm.
Embodiment 2
Preparation ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol:
Step 1: by Sr (CH
3cOO)
20.5H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Sr (CH
3cOO)
20.5H
2o:2,2 '-dipyridyl: the mol ratio=1:0.75:20 of anhydrous methanol, continue to stir 20min, form solution A;
By Mn (CH
3cOO)
24H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Mn (CH
3cOO)
24H
2o:2,2 '-dipyridyl: the mol ratio=1:0.75:20 of anhydrous methanol, continue to stir 20min, form solution B;
By La (NO
3)
36H
2o adds in anhydrous methanol, La (NO
3)
36H
2o: the mol ratio of anhydrous methanol is 1:20, stirs it is dissolved completely under room temperature, after stirring under room temperature, forms solution C;
Step 2: solution A, solution B and the solution C that step 1 is obtained is La by lanthanum, strontium, manganese three metal ion species mol ratios
3+: Sr
2+: Mn
4+=0.67:0.33:1 mixes, and obtains the ultraviolet sensitization La that total metal ion and sensitizer 2,2 '-dipyridyl mol ratio is 1:0.5
0.67sr
0.33mnO
3colloidal sol, adding appropriate methanol constant volume to metal ion total concn is 0.25mol/L.
Use above-mentioned ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation to there is minute graphic representation film:
Step 1: with ultraviolet sensitization La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on lanthanuma luminate single crystal substrate
0.67sr
0.33mnO
3gel film, pull rate is 0.15cm/s, then dry 7.5min at the temperature of 90 DEG C, obtains dry La
0.67sr
0.33mnO
3gel film;
Step 2: the mask plate with circular dot pattern is positioned over to the dry La that step 1 obtains
0.67sr
0.33mnO
3on gel film, the ultraviolet lamp taking predominant wavelength as 365nm is as exposure light source is to La
0.67sr
0.33mnO
3gel film exposes, and the time shutter is 30min, obtains the La after exposure
0.67sr
0.33mnO
3gel film;
Step 3: the La after the exposure that step 3 is obtained
0.67sr
0.33mnO
3gel film dissolves and washes away 7s in the mixed solvent that the ethanol that is 1:10 by volume ratio and Virahol form, after taking out, blow away raffinate with elevated pressure nitrogen air-flow, then heat-treat, heat treated temperature is that 775 DEG C, time are 35min, make the organism in film fully volatilize and decompose, obtain having the La of cylindrical bump Micropicture
0.67sr
0.33mnO
3film, the height of cylindrical bump is about 20nm.
Embodiment 3
Preparation ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol:
Step 1: by Sr (CH
3cOO)
20.5H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Sr (CH
3cOO)
20.5H
2o:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continue to stir 25min, form solution A;
By Mn (CH
3cOO)
24H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Mn (CH
3cOO)
24H
2o:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continue to stir 25min, form solution B;
By La (NO
3)
36H
2o adds in anhydrous methanol, La (NO
3)
36H
2o: the mol ratio of anhydrous methanol is 1:20, stirs it is dissolved completely under room temperature, after stirring under room temperature, forms solution C;
Step 2: solution A, solution B and the solution C that step 1 is obtained is La by lanthanum, strontium, manganese three metal ion species mol ratios
3+: Sr
2+: Mn
4+=0.67:0.33:1 mixes, and obtains the ultraviolet sensitization La that total metal ion and sensitizer 2,2 '-dipyridyl mol ratio is 1:0.665
0.67sr
0.33mnO
3colloidal sol, adding appropriate methanol constant volume to metal ion total concn is 0.5mol/L.
Use above-mentioned ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation to there is minute graphic representation film:
Step 1: with ultraviolet sensitization La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on silicon substrate
0.67sr
0.33mnO
3gel film, pull rate is 0.25cm/s, then dry 5min at the temperature of 100 DEG C, obtains dry La
0.67sr
0.33mnO
3gel film;
Step 2: the mask plate with circular dot pattern is positioned over to the dry La that step 1 obtains
0.67sr
0.33mnO
3on gel film, the ultraviolet lamp taking predominant wavelength as 365nm is as exposure light source is to La
0.67sr
0.33mnO
3gel film exposes, and the time shutter is 20min, obtains the La after exposure
0.67sr
0.33mnO
3gel film;
Step 3: the La after the exposure that step 3 is obtained
0.67sr
0.33mnO
3gel film dissolves and washes away 4s in the mixed solvent that the ethanol that is 1:5 by volume ratio and Virahol form, after taking out, blow away raffinate with elevated pressure nitrogen air-flow, then heat-treat, heat treated temperature is that 800 DEG C, time are 30min, make the organism in film fully volatilize and decompose, obtain having the La of cylindrical bump Micropicture
0.67sr
0.33mnO
3film, the height of cylindrical bump is about 36nm.
Embodiment 4
Preparation ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol:
Step 1: by Sr (CH
3cOO)
20.5H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Sr (CH
3cOO)
20.5H
2o:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continue to stir 30min, form solution A;
By Mn (CH
3cOO)
24H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, Mn (CH
3cOO)
24H
2o:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continue to stir 30min, form solution B;
By La (NO
3)
36H
2o adds in anhydrous methanol, La (NO
3)
36H
2o: the mol ratio of anhydrous methanol is 1:20, stirs it is dissolved completely under room temperature, after stirring under room temperature, forms solution C;
Step 2: solution A, solution B and the solution C that step 1 is obtained is La by lanthanum, strontium, manganese three metal ion species mol ratios
3+: Sr
2+: Mn
4+=0.67:0.33:1 mixes, and obtains the ultraviolet sensitization La that total metal ion and sensitizer 2,2 '-dipyridyl mol ratio is 1:0.665
0.67sr
0.33mnO
3colloidal sol, adding appropriate methanol constant volume to metal ion total concn is 0.5mol/L.
Use above-mentioned ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation to there is minute graphic representation film:
Step 1: with ultraviolet sensitization La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on silicon substrate
0.67sr
0.33mnO
3gel film, pull rate is 0.25cm/s, then dry 5min at the temperature of 100 DEG C, obtains dry La
0.67sr
0.33mnO
3gel film;
Step 2: the dry La that the krypton ion laser taking output wavelength as 350.7nm uses double light beam laser interferometric method directly step 2 to be obtained as light source
0.67sr
0.33mnO
3gel film exposes, and the time shutter is 40min, obtains the La after exposure
0.67sr
0.33mnO
3gel film;
Step 3: the La after the exposure that step 3 is obtained
0.67sr
0.33mnO
3gel film dissolves and washes away 4s in the mixed solvent that the ethanol that is 1:5 by volume ratio and Virahol form, after taking out, blow away raffinate with elevated pressure nitrogen air-flow, then heat-treat, heat treated temperature is that 800 DEG C, time are 30min, make the organism in film fully volatilize and decompose, obtain the La with channel form Micropicture as shown in Figure 4
0.67sr
0.33mnO
3film.
Claims (10)
1. the preparation method of ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol, is characterized in that, is by La (NO
3)
36H
2o, Sr (CH
3cOO)
20.5H
2o, Mn (CH
3cOO)
24H
2o, 2,2 '-dipyridyl is 0.67:0.33:1:(0.665～1.33 according to mol ratio) La that makes
0.67sr
0.33mnO
3sensitization colloidal sol, specifically comprises the following steps:
Step 1: by Sr (CH
3cOO)
20.5H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, continues to stir 20～30min, forms solution A;
By Mn (CH
3cOO)
24H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, then adds 2,2 '-dipyridyl, continues to stir 20～30min, forms solution B;
By La (NO
3)
36H
2o adds in anhydrous methanol, under room temperature, stirs it is dissolved completely, after stirring under room temperature, forms solution C;
Step 2: solution A, solution B and the solution C that described step 1 is obtained is La by lanthanum, strontium, manganese three metal ion species mol ratios
3+: Sr
2+: Mn
4+=0.67:0.33:1 mixes, and obtaining chemical constitution is La
0.67sr
0.33mnO
3sensitization colloidal sol, adding appropriate methanol constant volume to metal ion total concn is 0.1～0.5mol/L.
2. the preparation method of ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol as claimed in claim 1, is characterized in that, Sr (CH in described step 1
3cOO)
20.5H
2o:2,2 '-dipyridyl: mol ratio=1:(0.5～1.0 of anhydrous methanol): 20; Mn (CH
3cOO)
24H
2o:2,2 '-dipyridyl: mol ratio=1:(0.5～1.0 of anhydrous methanol): 20; La (NO
3)
36H
2o: the mol ratio of anhydrous methanol is 1:20.
3. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation as claimed in claim 1 to there is the method for minute graphic representation film, it is characterized in that, with La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on substrate
0.67sr
0.33mnO
3gel film, subsequently drying, expose, dissolve and wash away and thermal treatment, obtain having the La of minute graphic representation structure
0.67sr
0.33mnO
3film.
4. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation as claimed in claim 3 has the method for minute graphic representation film, it is characterized in that, comprises the following steps:
Step 1: with ultraviolet sensitization La
0.67sr
0.33mnO
3colloidal sol is masking precursor, prepares ultraviolet sensitization La by dip-coating method on substrate
0.67sr
0.33mnO
3gel film, is then dried, and obtains dry La
0.67sr
0.33mnO
3gel film;
Step 2: the dry La that adopts ultraviolet mask means or double light beam laser interferometric method to obtain described step 1
0.67sr
0.33mnO
3gel film exposes, and obtains the La after exposure
0.67sr
0.33mnO
3gel film;
Step 3: the La after the exposure that described step 2 is obtained
0.67sr
0.33mnO
3gel film dissolves and washes away in mixed solvent, then heat-treats, and obtains having the La of minute graphic representation
0.67sr
0.33mnO
3film.
5. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation as claimed in claim 4 has the method for minute graphic representation film, it is characterized in that, in described step 1, substrate is glass, silicon or lanthanuma luminate single crystal.
6. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation as claimed in claim 4 has the method for minute graphic representation film, it is characterized in that, in described step 1, the pull rate of dip-coating method is 0.05～0.25cm/s; Described dry temperature is that 80～100 DEG C, time are 5～10min.
7. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation as claimed in claim 4 has the method for minute graphic representation film, it is characterized in that, it is exposure light source that described step 2 medium ultraviolet mask means adopts the ultraviolet lamp that predominant wavelength is 365nm, and the krypton ion laser of double light beam laser interferometric method taking output wavelength as 350.7nm is light source.
8. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation as claimed in claim 4 has the method for minute graphic representation film, it is characterized in that, in described step 2, the time of exposure is 20～40min.
9. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol preparation as claimed in claim 4 has the method for minute graphic representation film, it is characterized in that, ethanol and Virahol that in described step 3, mixed solvent is 1:5～20 by volume ratio form, and the time of dissolveing and washing away is 4～10s.
10. use ultraviolet sensitization lanthanum strontium manganese oxygen colloidal sol as claimed in claim 4 preparation has the method for minute graphic representation film, it is characterized in that, in described step 3, heat treated temperature is that 750～800 DEG C, time are 30～40min.
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| CN106565242A (en) * | 2016-11-15 | 2017-04-19 | 昆明理工大学 | Method for improving electrical performance of lanthanum-calcium-manganese-oxygen (LCMO) ceramic material |
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| CN110386624A (en) * | 2019-08-19 | 2019-10-29 | 西安理工大学 | The preparation method of ultraviolet photosensitive calcium manganese oxygen colloidal sol and its film fine-pattern |
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