CN110386624B - Preparation method of ultraviolet light-sensitive calcium-manganese oxygen sol and film micro-pattern thereof - Google Patents
Preparation method of ultraviolet light-sensitive calcium-manganese oxygen sol and film micro-pattern thereof Download PDFInfo
- Publication number
- CN110386624B CN110386624B CN201910763531.9A CN201910763531A CN110386624B CN 110386624 B CN110386624 B CN 110386624B CN 201910763531 A CN201910763531 A CN 201910763531A CN 110386624 B CN110386624 B CN 110386624B
- Authority
- CN
- China
- Prior art keywords
- solution
- camn
- ultraviolet
- sol
- sensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a method for preparing ultraviolet light-sensitive calcium-manganese oxygen sol and a film micro-pattern thereof. Ca (NO) is added to the calcium-containing material3)2·4H2O、Mn(CH3COO)2·4H2Respectively preparing O and 2, 2' -bipyridyl into methanol solutions, mixing in proportion, adding acrylic acid, fixing volume, and aging to obtain ultraviolet sensitive CaMn7O12Sol; reutilizing ultraviolet sensitive CaMn7O12Sol, preparing gel film on the substrate by dip-coating method, drying, exposing, dissolving and washing, and heat treating to obtain CaMn7O12And (3) fine patterning of the thin film. CaMn of the invention7O12Is a single-phase multiferroic material, has strong magnetoelectric coupling effect, has strong absorption peak at 298nm, and obtains ultraviolet-sensitive CaMn by dip-coating method7O12The gel film has the advantages of easily controlled thickness, large size, clear outline, regular structure, no pollution and stable performance.
Description
Technical Field
The invention belongs to the technical field of novel information storage and multifunctional electronic equipment preparation, and particularly relates to ultraviolet-sensitive calcium-manganese oxygen sol and a method for preparing a film micro-fine pattern by using the ultraviolet-sensitive calcium-manganese oxygen sol.
Background
Calcium manganese oxygen (CaMn) derived from perovskite family structural system7O12) Is a single-phase multiferroic material, and has ferroelectricity and ferromagnetism. Because of its high ferroelectric critical temperature (90K), large spontaneous ferroelectricPolarization intensity (2870 μ C/m)2) Strong intrinsic magnetoelectric coupling effect and special magnetoelectric physical mechanism, which makes it a hotspot of scientific research on materials. CaMn7O12As a single-phase multiferroic material with stronger magnetoelectric effect, the material has great potential in the aspects of developing novel information storage processing and magnetoelectric devices based on ferroelectric-magnetic integrated effect, and the like, and particularly has wide application prospect in the fields of information storage, microwaves, current measurement of high-voltage transmission lines, and multifunctional electronic equipment such as sensors, brakes, inductors, converters and the like.
The miniaturization of single equipment is a new requirement of modern novel functional devices on material science. The single-phase multiferroic material CaMn7O12The method is applied to the field of microelectronic devices, and the key is to carry out micro-processing on the microelectronic devices, and the methods for carrying out the micro-processing on functional devices comprise a photoresist-chemical etching method, a plasma etching method, a focused ion beam etching method, an electron beam direct writing method, a nano-imprinting method and the like.
The ultraviolet photosensitive sol-gel process for preparing fine film pattern is one promising technological process, and the technological process includes adding chemical modifier into precursor sol to coordinate with some metal ions to form chelate structure, which is disintegrated fast under the irradiation of ultraviolet ray to change the solubility in organic solvent. The method does not need photoresist, has small equipment investment and simple process, and the prepared film micro-fine pattern has clear outline and regular structure. At present, the preparation of CaMn by using a UV-sensitive sol-gel method is concerned7O12The literature and patent of the fine pattern of the thin film have not been reported.
Disclosure of Invention
The invention aims to provide a preparation method of ultraviolet sensitive calcium-manganese oxygen sol, which comprises the following steps:
step 1: mixing Ca (NO)3)2·4H2Adding of OAdding into anhydrous methanol, and stirring at room temperature to obtain solution A;
mixing Mn (CH)3COO)2·4H2Adding O into absolute methanol, and stirring at room temperature until the O is completely dissolved to obtain a solution B;
dissolving 2, 2' -bipyridine in anhydrous methanol to obtain a solution C;
step 2: according to Ca in the solution A, the solution B and the solution C2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 3.5-7, uniformly mixing the solution A, the solution B and the solution C, adding acrylic acid, stirring at room temperature for 30-40 min, adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.4-0.6 mol/L, and aging to obtain ultraviolet-sensitive CaMn7O12And (3) sol.
Wherein, the preparation method of the ultraviolet sensitive calcium manganese oxygen sol comprises the step 1 of adding Ca in the solution A2+The molar ratio of the methanol to the anhydrous methanol is 1: 10 to 20.
Wherein, the preparation method of the ultraviolet sensitive calcium manganese oxygen sol comprises the step 1, Mn in the solution B2+The molar ratio of the methanol to the anhydrous methanol is 1: 10 to 20.
Wherein, the preparation method of the ultraviolet sensitive calcium manganese oxygen sol comprises the steps of 1, 2' -bipyridyl in solution C and Mn (CH) in solution B3COO)2·4H2The molar ratio of O is 0.5-1: 1.
wherein, the preparation method of the ultraviolet sensitive calcium manganese oxygen sol comprises the step 2 of mixing acrylic acid and Mn (CH)3COO)2·4H2The molar ratio of O is 2: 1.
the preparation method of the ultraviolet light-sensitive calcium-manganese oxygen sol comprises the step 2, wherein the aging time is 24-36 hours.
The invention also aims to use the ultraviolet sensitive calcium-manganese oxygen sol prepared by the method for preparing a film fine pattern, and the method comprises the following steps:
step A: adopt above-mentioned ultraviolet sensitization CaMn7O12The sol is a precursor for preparing a fine pattern, and CaMn is prepared on a substrate by a dip-coating method7O12Gel film, drying to obtainDried CaMn7O12A gel film;
and B: c, adopting an ultraviolet mask plate method to carry out treatment on the CaMn obtained in the step A7O12Exposing the gel film to obtain exposed CaMn7O12A gel film;
and C: the exposed CaMn obtained in the step B7O12Dissolving and washing the gel film in a dissolving and washing agent, and then carrying out heat treatment to obtain CaMn7O12And (3) fine patterning of the thin film.
In the method for forming the film micro-patterns, in the step A, the substrate is a lanthanum aluminate substrate or a monocrystalline silicon substrate; the dipping and pulling speed is 0.05-0.20 cm/s; the drying temperature is 80-100 ℃, and the drying time is 5-10 min.
In the step B, the ultraviolet mask plate method adopts an ultraviolet lamp light source with the dominant wavelength of 365nm, and the exposure time is 3600s to 4800 s.
In the method for forming the fine pattern of the film, in the step C, the solvent-washing agent is a mixed solution of ethanol and n-butanol, wherein the volume ratio of the ethanol to the n-butanol is 1: 4-15; the time of the solution washing is 3 s-10 s; the heat treatment temperature is 700-800 ℃, and the time is 30-60 min.
The invention has the beneficial effects that:
CaMn of the invention7O12Is a single-phase multiferroic material, has strong magnetoelectric coupling effect, has strong absorption peak at 298nm, and obtains ultraviolet-sensitive CaMn by dip-coating method7O12The thickness of the gel film is easy to control, and a gel film with larger size can be obtained; the method takes ultraviolet sensitive calcium manganese oxygen sol as a precursor, adopts an ultraviolet mask method to directly carry out photoetching on a gel film, does not need other auxiliary processes, and can prepare large-area CaMn7O12Fine patterns; the CaMn thus obtained7O12The film has the advantages of fine pattern, clear outline, regular structure, no pollution, stable performance, and wide application in information storage, microwave, current measurement of high-voltage transmission line, and multifunctional electronic equipment such as sensor, brake, inductor, converter, etcAnd the application prospect is good.
Drawings
FIG. 1 shows CaMn prepared in example 1 of the present invention7O12Ultraviolet absorption spectrum of the gel film and a graph showing the change with the irradiation time of ultraviolet light.
FIG. 2 shows CaMn prepared in example 1 of the present invention7O12Laser confocal images of fine patterns of thin films.
Detailed Description
Specifically, the preparation method of the ultraviolet sensitive calcium-manganese oxygen sol comprises the following steps:
step 1: mixing Ca (NO)3)2·4H2Adding O into absolute methanol, and uniformly stirring at room temperature for 5-10 min to obtain a solution A;
mixing Mn (CH)3COO)2·4H2Adding O into absolute methanol, and stirring at room temperature until the O is completely dissolved for 30-40 min to obtain a solution B;
dissolving 2, 2' -bipyridine in anhydrous methanol to obtain a solution C;
step 2: according to Ca in the solution A, the solution B and the solution C2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 3.5-7, uniformly mixing the solution A, the solution B and the solution C, adding acrylic acid, stirring at room temperature for 30-40 min, adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.4-0.6 mol/L, and aging to obtain ultraviolet-sensitive CaMn7O12And (3) sol.
In the invention, bipyridine is used as a chemical modifier, and the solution A, the solution B and the solution C can generate precipitate after being mixed, so that Mn (CH) is added3COO)2·4H2Stirring acrylic acid with twice molar weight of O for 30-40 min to dissolve the precipitate, wherein the precipitate does not appear after dissolution, and the result shows that bipyridyl and manganese ions have good chelation; the adoption of other chemical modifiers, such as benzoylacetone, can generate a large amount of granular precipitates, and although acrylic acid is added to temporarily dissolve the precipitates, the chelation of the chemical modifiers and manganese ions is not stable enough, so that sol cannot be formed.
Sol-gel processes are generally carried out with inorganic substances or alkoxidesThese raw materials are mixed in a liquid phase as a precursor, and subjected to hydrolysis and condensation chemical reactions to form a stable transparent sol system in a solution. In the present invention, Ca is used2+And a network structure cannot be well formed between the sol and a sol system, so that the sol system is more stable in order to establish a stable three-dimensional network structure, and the sol needs to be aged for a long time (24-36 h) after constant volume.
According to the dissolving capacity of the calcium-manganese oxygen sol, the sol is favorable for preparing combined CaMn7O12The invention has the advantages that the film micro-pattern can meet different use requirements, the constant volume is preferably set to the total metal ion concentration of 0.4-0.6 mol/L, so that the film has no cracks and high quality, and the contour of the film micro-pattern obtained after the processes of masking, ultraviolet irradiation, solution washing and heat treatment is clear.
Preferably, the preparation method of the ultraviolet sensitive calcium-manganese oxygen sol comprises the following steps:
step 1: according to Ca2+The molar ratio of the methanol to the anhydrous methanol is 1: 10 to 20 parts by weight of Ca (NO)3)2·4H2Adding O into absolute methanol, and uniformly stirring at room temperature for 5-10 min to obtain a solution A;
according to Mn2+The molar ratio of the methanol to the anhydrous methanol is 1: 10 to 20, adding Mn (CH)3COO)2·4H2Adding O into absolute methanol, and stirring at room temperature until the O is completely dissolved for 30-40 min to obtain a solution B;
according to the formula, 2' -bipyridine and Mn (CH) in the solution B3COO)2·4H2The molar ratio of O is 0.5-1: 1, dissolving 2, 2' -bipyridine in absolute methanol to obtain a solution C;
step 2: according to Ca in the solution A, the solution B and the solution C2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 3.5-7, uniformly mixing the solution A, the solution B and the solution C, and then adding Mn (CH)3COO)2·4H2Stirring acrylic acid with twice molar weight of O at room temperature for 30-40 min, adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.4-0.6 mol/L, and aging for 24-36 h to obtain the ultraviolet-sensitive CaMn7O12And (3) sol.
The invention also uses the ultraviolet sensitive calcium manganese oxygen sol prepared by the method for preparing the film micro-fine pattern, and the method comprises the following steps:
step A: adopt above-mentioned ultraviolet sensitization CaMn7O12The sol is a precursor for preparing a fine pattern, and CaMn is prepared on a substrate by a dip-coating method7O12Gel film, drying to obtain dried CaMn7O12A gel film;
and B: c, adopting an ultraviolet mask plate method to carry out treatment on the CaMn obtained in the step A7O12Exposing the gel film to obtain exposed CaMn7O12A gel film;
and C: the exposed CaMn obtained in the step B7O12Dissolving and washing the gel film in a dissolving and washing agent, and then carrying out heat treatment to obtain CaMn7O12And (3) fine patterning of the thin film.
In the step A, the substrate is a lanthanum aluminate substrate or a monocrystalline silicon substrate; the dipping and pulling speed is 0.05-0.20 cm/s; the drying temperature is 80-100 ℃, and the drying time is 5-10 min.
In the step B, an ultraviolet lamp light source with the dominant wavelength of 365nm is adopted in the ultraviolet mask plate method, and the exposure time is 3600 s-4800 s.
In the step C, the solvent-washing agent is a mixed solution of ethanol and n-butanol, wherein the volume ratio of the ethanol to the n-butanol is 1: 4-15; the time of the solution washing is 3 s-10 s; the heat treatment temperature is 700-800 ℃, and the time is 30-60 min.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
Preparation of ultraviolet-sensitive CaMn7O12Sol:
step 1: mixing Ca (NO)3)2·4H2Adding O into anhydrous methanol to make Ca2+The molar ratio of the methanol to the anhydrous methanol is 1: stirring for 5min at room temperature for uniformly mixing to form solution A;
mixing Mn (CH)3COO)2·4H2Adding O into anhydrous methanol to obtain Mn2+The molar ratio of the methanol to the anhydrous methanol is 1: stirring for 35min at room temperature to completely dissolve the components to form a solution B;
adding 2,2 '-bipyridine as chemical modifier into anhydrous methanol in the amount of 2, 2' -bipyridine and Mn (CH)3COO)2·4H2The molar ratio of O is 1: 1, fully stirring to obtain a solution C;
step 2: mixing the solution A, the solution B and the solution C obtained in the step 1 according to Ca2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 7 mixing, adding proper amount of acrylic acid, acrylic acid and Mn2+In a molar ratio of 2: 1, stirring for 30min at room temperature, then adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.4mol/L, and aging for 24h to obtain the photosensitive CaMn7O12And (3) sol.
Preparing CaMn from the ultraviolet photosensitive sol7O12Fine patterning:
preparation of CaMn on lanthanum aluminate substrate by dip-pulling method7O12Pulling the gel film at 0.15cm/s, drying at 80 deg.C for 8min, and placing the mask plate with lattice in the dried CaMn7O12Exposing above the gel film for 3600s under an ultraviolet lamp light source with the dominant wavelength of 365nm, and then performing ultraviolet curing on the gel film in a volume ratio of 1: 4, dissolving and washing for 3s in a solvent composed of ethanol and n-butanol, taking out, drying residual organic matters on the surface of the graph by using high-purity nitrogen, leaving the needed graph, and carrying out heat treatment at the temperature of 730 ℃ for 40min to obtain the CaMn7O12And (5) fine patterning.
Photosensitive CaMn obtained in this example7O12The UV sensitivity of the sol can be characterized by UV-visible absorption spectroscopy, with CaMn in FIG. 17O12FIG. 1 shows the ultraviolet absorption spectrum of the gel film and the change with the time of ultraviolet irradiation, from which CaMn is shown7O12The main absorption peak of the gel film is at 298nm, and the intensity of the absorption peak is reduced along with the increase of the exposure time from 20min to 100min, which shows that CaMn7O12The sol has ultravioletPhotosensitivity. FIG. 2 shows a 50 μm lattice CaMn prepared in this example7O12Laser confocal pictures of fine patterns of thin films.
Example 2
Preparation of ultraviolet-sensitive CaMn7O12Sol:
step 1: mixing Ca (NO)3)2·4H2Adding O into anhydrous methanol to make Ca2+The molar ratio of the methanol to the anhydrous methanol is 1: stirring for 10min at room temperature to uniformly mix to form solution A;
mixing Mn (CH)3COO)2·4H2Adding O into anhydrous methanol to obtain Mn2+The molar ratio of the methanol to the anhydrous methanol is 1: stirring for 30min at room temperature for completely dissolving to form solution B;
adding 2,2 '-bipyridine as chemical modifier into anhydrous methanol in the amount of 2, 2' -bipyridine and Mn (CH)3COO)2·4H2The molar ratio of O is 0.75: 1, fully stirring to form a solution C;
step 2: mixing the solution A, the solution B and the solution C obtained in the step 1 according to Ca2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 5.25 mixing, adding a proper amount of acrylic acid, acrylic acid and Mn2+In a molar ratio of 2: 1, stirring at room temperature for 40min, then adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.6mol/L, and aging for 36h to obtain the photosensitive CaMn7O12And (3) sol.
Preparation of CaMn Using the above-described UV sensitive Sol7O12Fine patterning:
preparation of CaMn on lanthanum aluminate substrate by dip-pulling method7O12Pulling the gel film at 0.05cm/s, drying at 100 deg.C for 5min, and placing the mask plate with lattice in the dried CaMn7O12Above the gel film, after 4200s exposure to a uv light source having a dominant wavelength of 365nm, the resultant was irradiated with light at a volume ratio of 1: 10 dissolving and washing in solvent composed of ethanol and n-butanol for 6s, taking out, blowing with high purity nitrogen to dry residual organic matter on the surface of the pattern, leaving the required pattern, and heating at 700 deg.CAfter conditioning for 60min, CaMn is obtained7O12And (3) fine patterning of the thin film.
Example 3
Preparation of ultraviolet-sensitive CaMn7O12Sol:
step 1: mixing Ca (NO)3)2·4H2Adding O into anhydrous methanol to make Ca2+The molar ratio of the methanol to the anhydrous methanol is 1: stirring for 6min at room temperature to uniformly mix to form solution A;
taking Mn (CH)3COO)2·4H2Adding O into anhydrous methanol to obtain Mn2+The molar ratio of the methanol to the anhydrous methanol is 1: 13, stirring for 37min at room temperature to completely dissolve the mixture to form a solution B;
adding 2,2 '-bipyridine as chemical modifier into anhydrous methanol in the amount of 2, 2' -bipyridine and Mn (CH)3COO)2·4H2The molar ratio of O is 0.9: 1, fully stirring to form a solution C;
step 2: mixing the solution A, the solution B and the solution C obtained in the step 1 according to Ca2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 6.3 mixing, adding a proper amount of acrylic acid, acrylic acid and Mn2+In a molar ratio of 2: 1, stirring at room temperature for 35min, then adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.5mol/L, and aging for 30h to obtain the photosensitive CaMn7O12And (3) sol.
Preparation of CaMn using the prepared UV sensitive sol7O12Fine patterning:
preparation of CaMn on silicon substrate by dip-Czochralski method7O12Pulling the gel film at 0.1cm/s, drying at 90 deg.C for 7min, and placing the mask plate with lattice in dried CaMn7O12Exposing above the gel film for 4800s under an ultraviolet lamp light source with dominant wavelength of 365nm, and then treating the gel film in a volume ratio of 1: 15 dissolving and washing in a solvent composed of ethanol and n-butanol for 10s, taking out, blowing dry residual organic matter on the surface of the graph with high-purity nitrogen gas to leave the needed graph, and carrying out heat treatment at 750 ℃ for 50min to obtain the CaMn7O12Film(s)And (5) fine patterning.
Example 4
Preparation of ultraviolet-sensitive CaMn7O12Sol:
step 1: mixing Ca (NO)3)2·4H2Adding O into anhydrous methanol to make Ca2+And anhydrous methanol at a molar ratio of 1: stirring for 8min at room temperature to uniformly mix to form solution A;
mixing Mn (CH)3COO)2·4H2Adding O into anhydrous methanol to obtain Mn2+The molar ratio of the methanol to the anhydrous methanol is 1: stirring for 40min at room temperature to completely dissolve the mixture to form a solution B;
adding 2,2 '-bipyridine as chemical modifier into anhydrous methanol in the amount of 2, 2' -bipyridine and Mn (CH)3COO)2·4H2The molar ratio of O is 0.5: 1, fully stirring to form a solution C;
step 2: mixing the solution A, the solution B and the solution C obtained in the step 1 according to Ca2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 3.5 mixing, adding a proper amount of acrylic acid, acrylic acid and Mn2+In a molar ratio of 2: 1, stirring for 30min at room temperature, then adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.4mol/L, and aging for 24h to obtain the photosensitive CaMn7O12And (3) sol.
Preparation of CaMn using the prepared UV sensitive sol7O12Fine patterning:
preparation of CaMn on silicon substrate by dip-Czochralski method7O12Pulling the gel film at 0.20cm/s, drying at 85 deg.C for 10min, and placing the mask plate with lattice in the dried CaMn7O12Exposing above the gel film for 3600s under an ultraviolet lamp light source with the dominant wavelength of 365nm, and then performing ultraviolet curing on the gel film in a volume ratio of 1: 7 dissolving and washing for 5s in a solvent composed of ethanol and n-butanol, taking out, blowing the residual organic matter on the surface of the graph with high-purity nitrogen, leaving the needed graph, and performing heat treatment at 800 ℃ for 30min to obtain the CaMn7O12And (3) fine patterning of the thin film.
The invention provides CaMn7O12The method for preparing the film micro-fine pattern can conveniently and quickly prepare the CaMn7O12Fine pattern, thereby being applied to CaMn7O12A storage device that is a medium.
Claims (10)
1. The preparation method of the ultraviolet sensitive calcium manganese oxygen sol is characterized by comprising the following steps: the method comprises the following steps:
step 1: mixing Ca (NO)3)2·4H2Adding O into absolute methanol, and stirring uniformly at room temperature to obtain solution A;
mixing Mn (CH)3COO)2·4H2Adding O into absolute methanol, and stirring at room temperature until the O is completely dissolved to obtain a solution B;
dissolving 2, 2' -bipyridine in anhydrous methanol to obtain a solution C;
step 2: according to Ca in the solution A, the solution B and the solution C2+：Mn2+: the molar ratio of 2, 2' -bipyridine is 1: 7: 3.5-7, uniformly mixing the solution A, the solution B and the solution C, adding acrylic acid, stirring at room temperature for 30-40 min, adding a proper amount of anhydrous methanol to adjust the total metal ion concentration to be 0.4-0.6 mol/L, and aging to obtain ultraviolet-sensitive CaMn7O12And (3) sol.
2. The method for preparing the ultraviolet sensitive calcium-manganese oxygen sol according to claim 1, which is characterized in that: step 1, Ca in solution A2+The molar ratio of the methanol to the anhydrous methanol is 1: 10 to 20.
3. The method for preparing the ultraviolet sensitive calcium-manganese oxygen sol according to claim 1, which is characterized in that: step 1, Mn in the B solution2+The molar ratio of the methanol to the anhydrous methanol is 1: 10 to 20.
4. The method for preparing the ultraviolet sensitive calcium-manganese oxygen sol according to claim 1, which is characterized in that: step 1, 2' -bipyridine in solution C and Mn (CH) in solution B3COO)2·4H2The molar ratio of O is 0.5-1: 1.
5. the method for preparing the ultraviolet sensitive calcium-manganese oxygen sol according to claim 1, which is characterized in that: step 2, acrylic acid and Mn (CH)3COO)2·4H2The molar ratio of O is 2: 1.
6. the method for preparing the ultraviolet-sensitive calcium-manganese oxygen sol according to any one of claims 1 to 5, which is characterized in that: and 2, aging for 24-36 h.
7. The method for forming a fine pattern on a thin film is characterized in that: the method comprises the following steps:
step A: ultraviolet-sensitive CaMn prepared by adopting method of any one of claims 1-67O12The sol is a precursor for preparing a fine pattern, and CaMn is prepared on a substrate by a dip-coating method7O12Gel film, drying to obtain dried CaMn7O12A gel film;
and B: c, adopting an ultraviolet mask plate method to carry out treatment on the CaMn obtained in the step A7O12Exposing the gel film to obtain exposed CaMn7O12A gel film;
and C: the exposed CaMn obtained in the step B7O12Dissolving and washing the gel film in a dissolving and washing agent, and then carrying out heat treatment to obtain CaMn7O12And (3) fine patterning of the thin film.
8. The method of fine patterning a thin film according to claim 7, wherein: in the step A, the substrate is a lanthanum aluminate substrate or a monocrystalline silicon substrate; the dipping and pulling speed is 0.05-0.20 cm/s; the drying temperature is 80-100 ℃, and the drying time is 5-10 min.
9. The method of fine patterning a thin film according to claim 7, wherein: in the step B, an ultraviolet lamp light source with the dominant wavelength of 365nm is adopted in the ultraviolet mask plate method, and the exposure time is 3600 s-4800 s.
10. The method for patterning a thin film fine pattern according to any one of claims 7 to 9, wherein: in the step C, the solvent-washing agent is a mixed solution of ethanol and n-butanol, wherein the volume ratio of the ethanol to the n-butanol is 1: 4-15; the time of the solution washing is 3 s-10 s; the heat treatment temperature is 700-800 ℃, and the time is 30-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910763531.9A CN110386624B (en) | 2019-08-19 | 2019-08-19 | Preparation method of ultraviolet light-sensitive calcium-manganese oxygen sol and film micro-pattern thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910763531.9A CN110386624B (en) | 2019-08-19 | 2019-08-19 | Preparation method of ultraviolet light-sensitive calcium-manganese oxygen sol and film micro-pattern thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110386624A CN110386624A (en) | 2019-10-29 |
| CN110386624B true CN110386624B (en) | 2022-02-08 |
Family
ID=68288922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910763531.9A Active CN110386624B (en) | 2019-08-19 | 2019-08-19 | Preparation method of ultraviolet light-sensitive calcium-manganese oxygen sol and film micro-pattern thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110386624B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239389A (en) * | 2007-01-08 | 2008-08-13 | 雅富顿公司 | Methods for making metal-containing nanoparticles of controlled size and shape |
| CN104120416A (en) * | 2014-07-24 | 2014-10-29 | 西安理工大学 | Preparation method of ultraviolet photosensitive lanthanum-strontium-manganese oxygen sol and micro graphical film thereof |
| CN104266759A (en) * | 2014-10-22 | 2015-01-07 | 中国科学院新疆理化技术研究所 | Function of manganese aluminum acid lanthanum thin film material in intermediate infrared thermosensitive detection |
| CN107021525A (en) * | 2016-01-31 | 2017-08-08 | 湖南大学 | A kind of preparation method of high-purity birnessite type Mn oxide of efficient degradation of organic dye |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8974855B2 (en) * | 2005-08-05 | 2015-03-10 | The United States Department Of Energy | Manganite perovskite ceramics, their precursors and methods for forming |
| WO2009045177A1 (en) * | 2007-10-05 | 2009-04-09 | Agency For Science, Technology And Research | Methods of forming a nanocrystal |
-
2019
- 2019-08-19 CN CN201910763531.9A patent/CN110386624B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239389A (en) * | 2007-01-08 | 2008-08-13 | 雅富顿公司 | Methods for making metal-containing nanoparticles of controlled size and shape |
| CN104120416A (en) * | 2014-07-24 | 2014-10-29 | 西安理工大学 | Preparation method of ultraviolet photosensitive lanthanum-strontium-manganese oxygen sol and micro graphical film thereof |
| CN104266759A (en) * | 2014-10-22 | 2015-01-07 | 中国科学院新疆理化技术研究所 | Function of manganese aluminum acid lanthanum thin film material in intermediate infrared thermosensitive detection |
| CN107021525A (en) * | 2016-01-31 | 2017-08-08 | 湖南大学 | A kind of preparation method of high-purity birnessite type Mn oxide of efficient degradation of organic dye |
Non-Patent Citations (2)
| Title |
|---|
| "Preparation of epitaxial CaMn7O12 film via sol-gel method and its ferromagnetic properties";Wang, Yunwei et al.;《JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY》;20181103;第88卷(第3期);639-645 * |
| Wang, Yunwei et al.."Preparation of epitaxial CaMn7O12 film via sol-gel method and its ferromagnetic properties".《JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY》.2018,第88卷(第3期),639-645. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110386624A (en) | 2019-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Stehlin et al. | Room-temperature preparation of metal-oxide nanostructures by DUV lithography from metal-oxo clusters | |
| US8206892B2 (en) | Solution processed thin films and laminates, devices comprising such thin films and laminates, and method for their use and manufacture | |
| US8318407B2 (en) | Solution processed thin films and laminates, devices comprising such thin films and laminates, and method for their use and manufacture | |
| US20160159953A1 (en) | Reagent for enhancing generation of chemical species | |
| JP2011524627A (en) | SOLUTION TREATING THIN FILM AND LAMINATE, APPARATUS HAVING THIN FILM AND LAMINATE, ITS USE AND MANUFACTURING METHOD | |
| TW201512162A (en) | Reagent for enhancing generation of chemical species | |
| Zhao et al. | Preparation of photosensitive gel films and fine patterning of amorphous Al2O3–SiO2 thin films | |
| CN104120416B (en) | The preparation method of the photosensitive lanthanum strontium manganese oxygen colloidal sol of ultraviolet and minute graphic representation film thereof | |
| CN105152545A (en) | Preparation method for nanocrystal-doped tungsten oxide electrochromic film pattern | |
| TW495494B (en) | Photosensitive polysilazane composition and method of forming patterned polysilazane film | |
| CN110386624B (en) | Preparation method of ultraviolet light-sensitive calcium-manganese oxygen sol and film micro-pattern thereof | |
| CN108149228A (en) | A kind of CoFe2O4The preparation method and CoFe of photosensitive colloidal sol2O4The preparation method of Micropicture film | |
| Zhao et al. | Controllable planar electrodeposition of NaYF4: Yb3+, Er3+ thin films with efficient upconverting fluorescence | |
| CN108648878B (en) | Preparation method of bismuth strontium calcium copper oxygen high-temperature superconducting thin film micro-pattern | |
| Kim et al. | 14‐4L: Late‐News Paper: Self‐Pattern Process of InZnO Thin‐Film Transistors using Photosensitive Precursors | |
| KR20240090855A (en) | Compounds, patterning materials, semiconductor devices, terminals, and patterning methods | |
| CN108389801A (en) | The method that one step photoetching process prepares metal-oxide semiconductor (MOS) and dielectric film | |
| JPH01294506A (en) | Production of metallic oxide and thin film thereof with excimer laser | |
| WO2020066669A1 (en) | Method for processing semiconductor substrate | |
| Lei et al. | Micropatterning of LaCoO3 thin films through a novel photosensitive sol-gel lithography technique and their magnetic properties | |
| JPS63100448A (en) | Radiation sensitive material | |
| CN118393812B (en) | Patterning composition, patterning film, patterning substrate, semiconductor device, and method of manufacturing the same | |
| JP3007922B2 (en) | Manufacturing method of ceramic fine pattern | |
| Telecky | Photoresist and ion-exchange chemistry of HafSOx | |
| Gómez López | Flexible ferroelectric BiFeO3 perovskite thin films processed by photo-chemical solution deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |