CN104120416B - The preparation method of the photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet and minute graphic representation film thereof - Google Patents
The preparation method of the photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet and minute graphic representation film thereof Download PDFInfo
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Abstract
The present invention discloses the preparation method of the photosensitive lanthanum strontium manganese oxygen colloidal sol of a kind of ultraviolet, by La (NO3)3��6H2O��Sr(CH3COO)2��0.5H2O��Mn(CH3COO)2��4H2O, bipy 2,2' bipyridyl are 0.67:0.33:1:(0.665��1.33 according to mol ratio) make; The method preparing miniaturization film is: prepare photosensitivity La by this colloidal sol through dip-coating method0.67Sr0.33MnO3Gel film; Then expose through ultraviolet mask method or double light beam laser interferometric method, dissolve and wash away the La obtaining minute graphic representation with thermal treatment successively0.67Sr0.33MnO3Film. Preparation technology of the present invention is simple, preparation cost is low, environmental pollution is little; Prepared La0.67Sr0.33MnO3The Micropicture compound with regular structure of film, dimension can be as small as micron order; Preparation process is easy to control, is applicable to suitability for industrialized production.
Description
Technical field
The invention belongs to microelectronics and technical field of magnetic materials, the present invention relates to the preparation method of the photosensitive lanthanum strontium manganese oxygen colloidal sol of a kind of ultraviolet, the present invention also relates to the method using this colloidal sol to prepare minute graphic representation film.
Background technology
There is the lanthanum-strontium-manganese oxide (La of perovskite crystal structurexSr1-xMnO3, it is abbreviated as LSMO) and it is a kind of rare earth manganese oxide, the discovery of giant magnetoresistance effect becomes the focus of Materials science research. In the multiple magneto-resistance effect devices such as magnetic head, random access memory, transverter and sensor that LSMO has been widely used in hard disc of computer as typical magnetic resistance material; In magnetic cooling field, LSMO can be used as room temperature magnetic refrigeration material, and thus in health care, space flight and automobile and other industries have broad application prospects; In addition, the Curie temperature (T of LSMOc=370K) higher than room temperature, and only there is the 3d state conduction band of complete polarization at Fermi surface place, there is not s state, Nature comparison is stablized, in atmosphere can not be oxidized, thus still a kind of desirable ferromagnetic electrode material.
Micrometer-Nanometer Processing Technology is that function ceramics film is carried out patterned main method, is support one of gordian technique that electronics and photoelectron element constantly improve. Existing Micrometer-Nanometer Processing Technology, such as selective wet chemical etching technology, deep UV exposure technique, electron beam lithography, ion beam etching technology, plasma etching technology, nano-imprint method and soft lithography etc., in microelectronics develops, play keying action, establish the basis of microtronics. All must first prepare function ceramics film due to these technology and just can carry out corresponding microfabrication subsequently, so the usual complicated operation of class technology, operating environment are harsh, costly, and work material is only limitted to semiconductor material and partial polymer material. LSMO ceramic membrane solidity to corrosion is strong, extremely difficult corrosion. So, the Micropicture of its high quality, big area is difficult to prepare by traditional method. Secondly, if above-mentioned technology is directly used in the microfabrication of LSMO film, often cause its physical and chemical performance to change, and then limit its application in micro element neighborhood.
The function ceramics film that the sol-gel method of employing chemically modified and ultraviolet mask/laser interferance method combine and Micropicture technology of preparing (being called for short " photosensitive sol-gel method ") are a kind of novel methods preparing minute graphic representation function ceramics film that development in recent years is got up. It is characterized in without the need to photoresist material, corrosive fluid and other high precise equipment, and ceramic membrane preparation can be realized and synchronously carry out with what minute graphic representation was processed. Photosensitive 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 preparation high-density, integrated functionality ceramic film most future. But, owing to the consistency of the chemical modifiers such as methyl ethyl diketone/benzoyl acetone that " the photosensitive sol-gel method " of routine uses in LSMO colloidal sol is very poor, causes and still do not adopt photosensitive sol-gel method to prepare pertinent literature and the patent report of minute graphic representation LSMO film at present.
Summary of the invention
It is an object of the invention to provide the preparation method of the photosensitive lanthanum strontium manganese oxygen colloidal sol of a kind of ultraviolet.
It is a further object to provide and use the photosensitive lanthanum strontium manganese oxygen colloidal sol of this ultraviolet to prepare the method for minute graphic representation film, 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 the photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet is by La (NO3)3��6H2O��Sr(CH3COO)2��0.5H2O��Mn(CH3COO)2��4H2O, bipy 2,2' bipyridyl are 0.67:0.33:1:(0.665��1.33 according to mol ratio) La that makes0.67Sr0.33MnO3Photosensitive colloidal sol, specifically comprises the following steps:
Step 1: by Sr (CH3COO)2��0.5H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, continues stirring 20��30min, forms solution A;
By Mn (CH3COO)2��4H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, continues stirring 20��30min, forms solution B;
By La (NO3)3��6H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, forms solution C after stirred at ambient temperature;
Step 2: solution A, solution B and solution C step 1 obtained is La by lanthanum, strontium, manganese three metal ion species mol ratio3+:Sr2+:Mn4+=0.67:0.33:1 mixes, and obtains chemical group and becomes La0.67Sr0.33MnO3Photosensitive colloidal sol, adding proper amount of methanol, to be settled to metal ion total concn be 0.1��0.5mol/L.
The feature of the present invention is also,
Sr (CH in step 13COO)2��0.5H2O:2,2 '-dipyridyl: mol ratio=1:(0.5��1.0 of anhydrous methanol): 20; Mn (CH3COO)2��4H2O:2,2 '-dipyridyl: mol ratio=1:(0.5��1.0 of anhydrous methanol): 20; La (NO3)3��6H2O: the mol ratio of anhydrous methanol is 1:20.
2nd kind of technical scheme of the present invention is: use the photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet to prepare the method for minute graphic representation film, with La0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet by dip-coating method on substrate0.67Sr0.33MnO3Gel film, subsequently drying, expose, dissolve and wash away and thermal treatment, obtain having the La of minute graphic representation structure0.67Sr0.33MnO3Film.
The feature of the present invention is also,
Comprise the following steps:
Step 1: with the photosensitive La of ultraviolet0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet by dip-coating method on substrate0.67Sr0.33MnO3Gel film, is then dried, and obtains dry La0.67Sr0.33MnO3Gel film;
Step 2: the La of the drying that step 1 is obtained by employing ultraviolet mask method or double light beam laser interferometric method0.67Sr0.33MnO3Gel film exposes, the La after being exposed0.67Sr0.33MnO3Gel film;
Step 3: the La after the exposure that step 2 is obtained0.67Sr0.33MnO3Gel film dissolves and washes away in mixed solvent, then heat-treats, and obtains having the La of minute graphic representation0.67Sr0.33MnO3Film.
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 80��100 DEG C, the time be 5��10min.
In step 2, ultraviolet mask method employing predominant wavelength is the ultraviolet lamp of 365nm is exposure light source, and double light beam laser interferometric method take output wavelength as the krypton ion laser of 350.7nm is light source.
In step 2, the time of exposure is 20��40min.
In step 3, mixed solvent is that the ethanol of 1:5��20 and Virahol form by volume ratio, and the time of dissolveing and washing away is 4��10s.
In step 3 heat treated temperature be 750��800 DEG C, the time be 30��40min.
The invention has the beneficial effects as follows: the present invention adopts ultraviolet mask method or double light beam laser interferometric method directly at La0.67Sr0.33MnO3Film is prepared Micropicture, it is achieved that La0.67Sr0.33MnO3What film preparation and minute graphic representation were processed synchronously carries out, its preparation process is without the need to expensive equipment, without the need to corrosive medium, technical process is simple, has the advantage being 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, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is La prepared by the embodiment of the present invention 10.67Sr0.33MnO3The ultra-violet absorption spectrum of gel film and the variation diagram with the UV-irradiation time;
Fig. 2 is the La with miniaturization figure prepared by the embodiment of the present invention 10.67Sr0.33MnO3The X-ray diffracting spectrum of film;
Fig. 3 is the La with cylindrical bump Micropicture prepared by the embodiment of the present invention 10.67Sr0.33MnO3The 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 and prepares on a silicon substrate0.67Sr0.33MnO3The 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 the photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet of the present invention is by La (NO3)3��6H2O��Sr(CH3COO)2��0.5H2O��Mn(CH3COO)2��4H2O, bipy 2,2' bipyridyl are 0.67:0.33:1:(0.665��1.33 according to mol ratio) La that makes0.67Sr0.33MnO3Photosensitive colloidal sol, specifically comprises the following steps:
Step 1: by Sr (CH3COO)2��0.5H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Sr (CH3COO)2��0.5H2O:2,2 '-dipyridyl: mol ratio=1:(0.5��1.0 of anhydrous methanol): 20, continue stirring 20��30min, form solution A;
By Mn (CH3COO)2��4H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Mn (CH3COO)2��4H2O:2,2 '-dipyridyl: mol ratio=1:(0.5��1.0 of anhydrous methanol): 20, continue stirring 20��30min, form solution B;
By La (NO3)3��6H2O adds in anhydrous methanol, La (NO3)3��6H2O: the mol ratio of anhydrous methanol is 1:20, and stirred at ambient temperature makes it dissolve completely, forms solution C after stirred at ambient temperature;
Step 2: solution A, solution B and solution C step 1 obtained is La by lanthanum, strontium, manganese three metal ion species mol ratio3+:Sr2+:Mn4+=0.67:0.33:1 mixes, and obtains chemical group and becomes La0.67Sr0.33MnO3Photosensitive colloidal sol, adding proper amount of methanol, to be settled to metal ion total concn be 0.1��0.5mol/L.
Use the photosensitive lanthanum strontium manganese oxygen colloidal sol preparation of above-mentioned ultraviolet to have the method for minute graphic representation film, comprise the following steps:
Step 1: with the photosensitive La of ultraviolet0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet by dip-coating method on glass, silicon or lanthanuma luminate single crystal substrate0.67Sr0.33MnO3Gel film, pull rate is 0.05��0.25cm/s, and then dry 5��10min at the temperature of 80��100 DEG C, obtains dry La0.67Sr0.33MnO3Gel film;
Step 2: the La that the mask plate with figure is positioned over the drying that step 1 obtains0.67Sr0.33MnO3On gel film, the ultraviolet lamp taking predominant wavelength as 365nm is for exposure light source employing ultraviolet mask method is to La0.67Sr0.33MnO3Gel film carries out exposing or is that the krypton ion laser of 350.7nm uses double light beam laser interferometric method directly to La for light source taking output wavelength0.67Sr0.33MnO3Gel film exposes, and the time shutter is 20��40min, the La after being exposed0.67Sr0.33MnO3Gel film;
Step 3: the La after the exposure that step 2 is obtained0.67Sr0.33MnO3Gel film is being dissolve and wash away 4��10s in the mixed solvent that forms of the ethanol of 1:5��20 and Virahol by volume ratio, then heat-treat, heat treated temperature is 750��800 DEG C, the time be 30��40min, make the organism in film fully volatilize and decompose, obtain having the La of minute graphic representation0.67Sr0.33MnO3Film.
The present invention has following useful effect:
1) La that prepared by the present invention0.67Sr0.33MnO3Film has that good uniformity, roughness be little, non-microcracked and the feature such as stable performance;
2)La0.67Sr0.33MnO3The thickness of film can be controlled by adjustment collosol concentration, pull rate;
3) adopt ultraviolet mask method or double light beam laser interferometric method directly at La0.67Sr0.33MnO3Film is prepared Micropicture, it is achieved that La0.67Sr0.33MnO3What film preparation and minute graphic representation were processed synchronously carries out, and its preparation technology has without the need to expensive equipment, it is not necessary to corrosive medium, and technical process is simple, is easy to make the advantage of big area Micropicture.
Embodiment 1
The preparation photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet:
Step 1: by Sr (CH3COO)2��0.5H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Sr (CH3COO)2��0.5H2O:2,2 '-dipyridyl: the mol ratio=1:0.5:20 of anhydrous methanol, continues to stir 30min, forms solution A;
By Mn (CH3COO)2��4H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Mn (CH3COO)2��4H2O:2,2 '-dipyridyl: the mol ratio=1:0.5:20 of anhydrous methanol, continues to stir 30min, forms solution B;
By La (NO3)3��6H2O adds in anhydrous methanol, La (NO3)3��6H2O: the mol ratio of anhydrous methanol is 1:20, and stirred at ambient temperature makes it dissolve completely, forms solution C after stirred at ambient temperature;
Step 2: solution A, solution B and solution C step 1 obtained is La by lanthanum, strontium, manganese three metal ion species mol ratio3+:Sr2+:Mn4+=0.67:0.33:1 mixes, and obtains total metal ion and sensitizer bipy 2,2' bipyridyl mol ratio is the photosensitive La of ultraviolet of 2:0.6650.67Sr0.33MnO3Colloidal sol, adding proper amount of methanol, to be settled to metal ion total concn be 0.1mol/L.
The photosensitive lanthanum strontium manganese oxygen colloidal sol preparation of above-mentioned ultraviolet is used to have minute graphic representation film:
Step 1: with the photosensitive La of ultraviolet0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet on the glass substrate by dip-coating method0.67Sr0.33MnO3Gel film, pull rate is 0.05cm/s, and then dry 10min at the temperature of 80 DEG C, obtains dry La0.67Sr0.33MnO3Gel film;
Step 2: the La that the mask plate with circular dot pattern is positioned over the drying that step 1 obtains0.67Sr0.33MnO3On gel film, the ultraviolet lamp taking predominant wavelength as 365nm is for exposure light source is to La0.67Sr0.33MnO3Gel film exposes, and the time shutter is 40min, the La after being exposed0.67Sr0.33MnO3Gel film;
Step 3: the La after the exposure that step 3 is obtained0.67Sr0.33MnO3Gel film is being dissolve and wash away 10s in the mixed solvent that forms of the ethanol of 1:20 and Virahol by volume ratio, raffinate is blown away with elevated pressure nitrogen air-flow after taking-up, then heat-treat, heat treated temperature is 750 DEG C, the time be 40min, make the organism in film fully volatilize and decompose, obtain having the La of cylindrical bump Micropicture0.67Sr0.33MnO3Film.
This La0.67Sr0.33MnO3The photosensitivity of colloidal sol can be characterized with ultra-violet absorption spectrum, La under the test different UV-irradiation time0.67Sr0.33MnO3The ultra-violet absorption spectrum of gel film, can disclose this La0.67Sr0.33MnO3The photobehavior of gel film. As shown in Figure 1, without the La of UV-irradiation0.67Sr0.33MnO3The maximum absorption band of gel film appears at 298nm, and after the UV-irradiation of more than 20min, maximum absorption band red shift is to 300nm, and peak intensity weakens gradually with the UV-irradiation time.
As shown in Figure 2, X-ray diffracting spectrum analysis shows prepared La0.67Sr0.33MnO3Film is without assorted phase, good crystallinity; Fig. 3 is the La of the Micropicture prepared by this example0.67Sr0.33MnO3The laser co-focusing Photomicrograph of film, wherein the height of cylindrical bump is about 13nm.
Embodiment 2
The preparation photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet:
Step 1: by Sr (CH3COO)2��0.5H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Sr (CH3COO)2��0.5H2O:2,2 '-dipyridyl: the mol ratio=1:0.75:20 of anhydrous methanol, continues to stir 20min, forms solution A;
By Mn (CH3COO)2��4H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Mn (CH3COO)2��4H2O:2,2 '-dipyridyl: the mol ratio=1:0.75:20 of anhydrous methanol, continues to stir 20min, forms solution B;
By La (NO3)3��6H2O adds in anhydrous methanol, La (NO3)3��6H2O: the mol ratio of anhydrous methanol is 1:20, and stirred at ambient temperature makes it dissolve completely, forms solution C after stirred at ambient temperature;
Step 2: solution A, solution B and solution C step 1 obtained is La by lanthanum, strontium, manganese three metal ion species mol ratio3+:Sr2+:Mn4+=0.67:0.33:1 mixes, and obtains total metal ion and sensitizer bipy 2,2' bipyridyl mol ratio is the photosensitive La of ultraviolet of 1:0.50.67Sr0.33MnO3Colloidal sol, adding proper amount of methanol, to be settled to metal ion total concn be 0.25mol/L.
The photosensitive lanthanum strontium manganese oxygen colloidal sol preparation of above-mentioned ultraviolet is used to have minute graphic representation film:
Step 1: with the photosensitive La of ultraviolet0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet by dip-coating method on lanthanuma luminate single crystal substrate0.67Sr0.33MnO3Gel film, pull rate is 0.15cm/s, and then dry 7.5min at the temperature of 90 DEG C, obtains dry La0.67Sr0.33MnO3Gel film;
Step 2: the La that the mask plate with circular dot pattern is positioned over the drying that step 1 obtains0.67Sr0.33MnO3On gel film, the ultraviolet lamp taking predominant wavelength as 365nm is for exposure light source is to La0.67Sr0.33MnO3Gel film exposes, and the time shutter is 30min, the La after being exposed0.67Sr0.33MnO3Gel film;
Step 3: the La after the exposure that step 3 is obtained0.67Sr0.33MnO3Gel film is being dissolve and wash away 7s in the mixed solvent that forms of the ethanol of 1:10 and Virahol by volume ratio, raffinate is blown away with elevated pressure nitrogen air-flow after taking-up, then heat-treat, heat treated temperature is 775 DEG C, the time be 35min, make the organism in film fully volatilize and decompose, obtain having the La of cylindrical bump Micropicture0.67Sr0.33MnO3Film, the height of cylindrical bump is about 20nm.
Embodiment 3
The preparation photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet:
Step 1: by Sr (CH3COO)2��0.5H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Sr (CH3COO)2��0.5H2O:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continues to stir 25min, forms solution A;
By Mn (CH3COO)2��4H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Mn (CH3COO)2��4H2O:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continues to stir 25min, forms solution B;
By La (NO3)3��6H2O adds in anhydrous methanol, La (NO3)3��6H2O: the mol ratio of anhydrous methanol is 1:20, and stirred at ambient temperature makes it dissolve completely, forms solution C after stirred at ambient temperature;
Step 2: solution A, solution B and solution C step 1 obtained is La by lanthanum, strontium, manganese three metal ion species mol ratio3+:Sr2+:Mn4+=0.67:0.33:1 mixes, and obtains total metal ion and sensitizer bipy 2,2' bipyridyl mol ratio is the photosensitive La of ultraviolet of 1:0.6650.67Sr0.33MnO3Colloidal sol, adding proper amount of methanol, to be settled to metal ion total concn be 0.5mol/L.
The photosensitive lanthanum strontium manganese oxygen colloidal sol preparation of above-mentioned ultraviolet is used to have minute graphic representation film:
Step 1: with the photosensitive La of ultraviolet0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet on a silicon substrate by dip-coating method0.67Sr0.33MnO3Gel film, pull rate is 0.25cm/s, and then dry 5min at the temperature of 100 DEG C, obtains dry La0.67Sr0.33MnO3Gel film;
Step 2: the La that the mask plate with circular dot pattern is positioned over the drying that step 1 obtains0.67Sr0.33MnO3On gel film, the ultraviolet lamp taking predominant wavelength as 365nm is for exposure light source is to La0.67Sr0.33MnO3Gel film exposes, and the time shutter is 20min, the La after being exposed0.67Sr0.33MnO3Gel film;
Step 3: the La after the exposure that step 3 is obtained0.67Sr0.33MnO3Gel film is being dissolve and wash away 4s in the mixed solvent that forms of the ethanol of 1:5 and Virahol by volume ratio, raffinate is blown away with elevated pressure nitrogen air-flow after taking-up, then heat-treat, heat treated temperature is 800 DEG C, the time be 30min, make the organism in film fully volatilize and decompose, obtain having the La of cylindrical bump Micropicture0.67Sr0.33MnO3Film, the height of cylindrical bump is about 36nm.
Embodiment 4
The preparation photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet:
Step 1: by Sr (CH3COO)2��0.5H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Sr (CH3COO)2��0.5H2O:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continues to stir 30min, forms solution A;
By Mn (CH3COO)2��4H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, Mn (CH3COO)2��4H2O:2,2 '-dipyridyl: the mol ratio=1:1:20 of anhydrous methanol, continues to stir 30min, forms solution B;
By La (NO3)3��6H2O adds in anhydrous methanol, La (NO3)3��6H2O: the mol ratio of anhydrous methanol is 1:20, and stirred at ambient temperature makes it dissolve completely, forms solution C after stirred at ambient temperature;
Step 2: solution A, solution B and solution C step 1 obtained is La by lanthanum, strontium, manganese three metal ion species mol ratio3+:Sr2+:Mn4+=0.67:0.33:1 mixes, and obtains total metal ion and sensitizer bipy 2,2' bipyridyl mol ratio is the photosensitive La of ultraviolet of 1:0.6650.67Sr0.33MnO3Colloidal sol, adding proper amount of methanol, to be settled to metal ion total concn be 0.5mol/L.
The photosensitive lanthanum strontium manganese oxygen colloidal sol preparation of above-mentioned ultraviolet is used to have minute graphic representation film:
Step 1: with the photosensitive La of ultraviolet0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet on a silicon substrate by dip-coating method0.67Sr0.33MnO3Gel film, pull rate is 0.25cm/s, and then dry 5min at the temperature of 100 DEG C, obtains dry La0.67Sr0.33MnO3Gel film;
Step 2: take output wavelength as the La of drying that the krypton ion laser of 350.7nm uses double light beam laser interferometric method directly step 2 to be obtained for light source0.67Sr0.33MnO3Gel film exposes, and the time shutter is 40min, the La after being exposed0.67Sr0.33MnO3Gel film;
Step 3: the La after the exposure that step 3 is obtained0.67Sr0.33MnO3Gel film is being dissolve and wash away 4s in the mixed solvent that forms of the ethanol of 1:5 and Virahol by volume ratio, raffinate is blown away with elevated pressure nitrogen air-flow after taking-up, then heat-treat, heat treated temperature is 800 DEG C, the time be 30min, make the organism in film fully volatilize and decompose, obtain the La with channel form Micropicture as shown in Figure 40.67Sr0.33MnO3Film.
Claims (9)
1. the preparation method of the photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet, it is characterised in that, it is by La (NO3)3��6H2O��Sr(CH3COO)2��0.5H2O��Mn(CH3COO)2��4H2O, bipy 2,2' bipyridyl are 0.67:0.33:1:(0.665��1.33 according to mol ratio) La that makes0.67Sr0.33MnO3Photosensitive colloidal sol, specifically comprises the following steps:
Step 1: by Sr (CH3COO)2��0.5H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, continues stirring 20��30min, forms solution A, Sr (CH3COO)2��0.5H2O:2,2 '-dipyridyl: mol ratio=1:(0.5��1.0 of anhydrous methanol): 20;
By Mn (CH3COO)2��4H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, then adds bipy 2,2' bipyridyl, continues stirring 20��30min, forms solution B, Mn (CH3COO)2��4H2O:2,2 '-dipyridyl: mol ratio=1:(0.5��1.0 of anhydrous methanol): 20;
By La (NO3)3��6H2O adds in anhydrous methanol, and stirred at ambient temperature makes it dissolve completely, forms solution C after stirred at ambient temperature, La (NO3)3��6H2O: the mol ratio of anhydrous methanol is 1:20;
Step 2: solution A, solution B and the solution C described step 1 obtained is La by lanthanum, strontium, manganese three metal ion species mol ratio3+:Sr2+:Mn4+=0.67:0.33:1 mixes, and obtains chemical group and becomes La0.67Sr0.33MnO3Photosensitive colloidal sol, adding proper amount of methanol, to be settled to metal ion total concn be 0.1��0.5mol/L.
2. one kind has the preparation method of miniaturization graphic films, it is characterised in that: adopt the photosensitive lanthanum strontium manganese oxygen colloidal sol preparation method of ultraviolet as claimed in claim 1 to prepare the lanthanum strontium manganese oxygen colloidal sol, with La0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet by dip-coating method on substrate0.67Sr0.33MnO3Gel film, subsequently drying, expose, dissolve and wash away and thermal treatment, obtain having the La of minute graphic representation structure0.67Sr0.33MnO3Film.
3. a kind of preparation method with miniaturization graphic films according to claim 2, it is characterised in that, comprise the following steps:
Step 1: with the photosensitive La of ultraviolet0.67Sr0.33MnO3Colloidal sol is masking precursor, prepares the photosensitive La of ultraviolet by dip-coating method on substrate0.67Sr0.33MnO3Gel film, is then dried, and obtains dry La0.67Sr0.33MnO3Gel film;
Step 2: adopt ultraviolet mask method or double light beam laser interferometric method to the La of the drying that described step 1 obtains0.67Sr0.33MnO3Gel film exposes, the La after being exposed0.67Sr0.33MnO3Gel film;
Step 3: the La after the exposure that described step 2 is obtained0.67Sr0.33MnO3Gel film dissolves and washes away in mixed solvent, then heat-treats, and obtains having the La of minute graphic representation0.67Sr0.33MnO3Film.
4. a kind of preparation method with miniaturization graphic films according to claim 3, it is characterised in that, in described step 1, substrate is glass, silicon or lanthanuma luminate single crystal.
5. a kind of preparation method with miniaturization graphic films according to claim 3, it is characterised in that, in described step 1, the pull rate of dip-coating method is 0.05��0.25cm/s; The temperature of described drying is 80��100 DEG C, the time be 5��10min.
6. a kind of preparation method with miniaturization graphic films according to claim 3, it is characterized in that, in described step 2, ultraviolet mask method employing predominant wavelength is the ultraviolet lamp of 365nm is exposure light source, and double light beam laser interferometric method take output wavelength as the krypton ion laser of 350.7nm is light source.
7. a kind of preparation method with miniaturization graphic films according to claim 3, it is characterised in that, in described step 2, the time of exposure is 20��40min.
8. a kind of preparation method with miniaturization graphic films according to claim 3, it is characterised in that, in described step 3, mixed solvent is that the ethanol of 1:5��20 and Virahol form by volume ratio, and the time of dissolveing and washing away is 4��10s.
9. a kind of preparation method with miniaturization graphic films according to claim 3, it is characterised in that, in described step 3 heat treated temperature be 750��800 DEG C, the time be 30��40min.
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