CN107540402B - Preparation method of porous copper calcium titanate film - Google Patents
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- CN107540402B CN107540402B CN201710896396.6A CN201710896396A CN107540402B CN 107540402 B CN107540402 B CN 107540402B CN 201710896396 A CN201710896396 A CN 201710896396A CN 107540402 B CN107540402 B CN 107540402B
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- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012456 homogeneous solution Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 241000877463 Lanio Species 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims 1
- 238000009501 film coating Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000000919 ceramic Substances 0.000 abstract description 8
- 238000004146 energy storage Methods 0.000 abstract description 4
- 229910002966 CaCu3Ti4O12 Inorganic materials 0.000 abstract description 2
- 229910002340 LaNiO3 Inorganic materials 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses porous calcium copper titanate CaCu3Ti4O12A CCTO film is prepared from LaNiO3The (LNO for short) is used as a buffer layer, and a CCTO wet film is coated on a substrate covered by the LNO by adopting a solution chemical method; and (4) obtaining the CCTO film with a porous structure through heat treatment. The invention does not need a template, can prepare the CCTO film material with the surface appearance presenting a porous structure under the process condition of lower cost, and has wide application prospect in the fields of porous ceramics, high-density energy storage and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic non-metallic materials, and particularly relates to a preparation method of a calcium copper titanate film material, which is a method for preparing porous calcium copper titanate films on various substrates by a solution chemical method.
Technical Field
The development of porous ceramics began in the seventies of the nineteenth century and was used only in the early days as a material for bacterial filtration and uranium purification. With the continuous improvement of the preparation level of materials and the diversification of the process, various new materials and high-performance porous ceramic materials continuously appear, and the application field and the application range of the porous ceramic materials are continuously expanded and developed. Due to the bonding of the covalent bond and the complex ionic bond of the porous ceramic and the complex crystal structure, the porous ceramic has the characteristics of high temperature resistance, corrosion resistance and good thermal stability. Moreover, when fluid flows through the pores, various physicochemical effects (such as capillary siphon effect) are generated on the inner and outer surfaces of the porous ceramic material. Porous ceramics have attracted high attention from the world material world because of their many excellent properties such as low density, high permeability, large specific surface area, corrosion resistance, low thermal conductivity, and high temperature resistance. The material is widely applied to catalyst carriers, industrial sewage treatment, molten metal filtration, automobile exhaust treatment, heat and sound insulation materials and other aspects. With the development of science and technology, the application of porous ceramics is expanded to the fields of electronics, environmental protection, biochemistry, medical materials, aviation, and the like.
With the rapid development of information technology industry and electronics and power related industry, electronic ceramic materials with high dielectric constant and low dielectric loss become hot points of industrial attention. The material is mainly applied to the production of high-power capacitors, so that the material is required to have the characteristics of light weight, high energy storage density and strong stability, and the material is required to have the characteristics of small density and large dielectric constant. In about 2000, scientists discovered CaCu3Ti4O12CCTO materials have a very high dielectric constant, low loss and high thermal stability, and have attracted much attention. The good comprehensive performance of the material makes the material hopeful to be applied to electronic ceramic components such as high-density energy storage, high-dielectric capacitors and the like. The CCTO ceramic material reported in the literature at present is mostly prepared by a solid-phase reaction method, the sintering temperature is from 850 ℃ to over 1000 ℃, and the constant temperature time is from several hours to dozens of hours. The solid-phase reaction method has larger energy waste and does not accord with the strategic trend of national sustainable development. The preparation of the CCTO film mainly comprises a physical method (pulse laser deposition, magnetron sputtering and the like) and a chemical method (sol-gel method and the like). The chemical method has low cost, low annealing temperature (750 ℃), simple process steps and easy operation, and is a convenient and efficient method for preparing the CCTO film.
Although CCTO has high dielectric constant and can meet the requirement of high-density energy storage, the CCTO materials prepared by the method are all compact polycrystalline ceramics, have no obvious special structure on the surface appearance and cannot meet the requirements of light weight and low density of devices/equipment. However, in the preparation of the porous film at present, a method of filling the porous film with a template or organic polymer beads is mostly adopted, and the template and fillers need to be removed by adopting technological links such as corrosion or sintering, so that the complexity of the process is increased.
Disclosure of Invention
The invention aims to provide a method for preparing a copper calcium titanate film material with a porous surface without a template or a filler, aiming at the problems in the prior art.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
a. covering a layer of LaNiO on the substrate by a physical or chemical method3A buffer layer having a thickness of 10 to 30 nm;
b. preparation of calcium copper titanate precursor solution
Taking copper nitrate Cu (NO)3)2Ca (NO), Ca nitrate3)2Dissolving the solid into ethylene glycol monomethyl ether according to the molar ratio of 3:1, heating and stirring in a water bath at the temperature of 30-80 ℃ for 1-6 hours to form a homogeneous solution; weighing butyl titanate and acetylacetone with the same mole number according to the molar ratio of Ca to Ti atoms of 1:4, adding the butyl titanate and the acetylacetone into the solution, stirring and heating the solution in a water bath at the temperature of 30-80 ℃ for 1-8 hours to form a homogeneous solution, and finally preparing a calcium copper titanate precursor solution with the concentration of 0.01-0.1 mol/L;
c. preparation of porous copper calcium titanate film
Coating a calcium copper titanate precursor solution on a substrate with a lanthanum nickelate buffer layer by adopting modes of rotary coating, lifting coating and the like to obtain a wet calcium copper titanate film; carrying out three-stage heat treatment in a rapid annealing furnace: in the first stage, the temperature is 140-200 ℃ and the time is 180-360 seconds; in the second stage, the temperature is 360-420 ℃ and the time is 180-360 seconds; in the third stage, the temperature is 650-850 ℃ for 180-600 seconds to obtain a layer of porous calcium copper titanate film, and the coating-heat treatment process is repeated to obtain a plurality of layers of porous calcium copper titanate films; the pore diameter is in the range of 40-200 nm.
Compared with the prior art, the invention is characterized in that: (1) the obtained copper calcium titanate film is of a porous structure; (2) no template or filler is needed in the growth process of the copper calcium titanate film; (3) the aperture of the porous calcium copper titanate film can be regulated.
Drawings
FIG. 1 is an AFM image of the surface of a lanthanum nickelate buffer of example 1;
FIG. 2 is an AFM image of the porous calcium copper titanate film of example 1;
FIG. 3 is a high level scale view of the AFM of FIG. 1;
FIG. 4 is a cross-sectional view of the porous calcium copper titanate film of example 1.
Detailed Description
Example 1
a. Substrate selection and cleaning
Adopting a <100> heavily doped silicon substrate, carrying out ultrasonic treatment on the substrate for 20 minutes by using ethanol and deionized water, and then putting the substrate into a rapid thermal treatment device for secondary annealing: in the first stage, the temperature is 200 ℃ and the time is 200 s; in the second stage, the temperature is 400 ℃ and the time is 200 s.
b. Preparation of lanthanum nickelate buffer layer
Weighing lanthanum nitrate La (NO)3)3·6H23.2 g of O solid, and nickel acetate C is weighed according to the molar ratio of La to Ni atoms of 1:14H6O4Ni·4H2And adding an ethanol solvent into the O solid, and stirring and heating the O solid in a water bath at the temperature of 40 ℃ for about 3 hours to obtain a lanthanum nickelate homogeneous solution with the concentration of 0.1 mol/L. Standing for a period of time, and using without precipitation.
Putting the cleaned silicon substrate in a spin coater, setting the rotation speed to be 4000 rpm, and coating a layer of lanthanum nickelate wet film on the silicon substrate by adopting the lanthanum nickelate solution; putting the mixture into a rapid heat treatment device for three-stage heat treatment: a first stage, wherein the temperature is 180 ℃ for 240 seconds; in the second stage, the temperature is 380 ℃ and the duration is 240 seconds; and thirdly, growing a lanthanum nickelate buffer layer with the thickness of about 10 nanometers at the temperature of 700 ℃ for 300 seconds. As can be seen from the attached figure 1, the lanthanum nickelate has a smooth surface and does not have obvious holes.
c. Preparation of calcium copper titanate precursor solution
Copper nitrate Cu (NO) was weighed separately3)2And calcium nitrate Ca (NO)3)20.3542 g and 1.0872 g of solid are dissolved in ethylene glycol methyl ether solvent and heated and stirred in a water bath at 40 ℃ for about 1 hour to form a homogeneous solution. Then measuring 0.9 ml of each of butyl titanate and acetylacetone, adding the solution into a water bath at 40 DEG CStirring and heating for about 2 hours to form a homogeneous solution, and finally preparing the copper calcium titanate solution with the concentration of 0.05 mol/L.
d. Preparation of porous copper calcium titanate film
And (3) placing the silicon wafer with the lanthanum nickelate buffer layer on a spin coater, setting the rotation speed to be 4000r/min and the time to be 20 seconds, and coating a calcium copper titanate solution to obtain a wet calcium copper titanate film. Carrying out three-stage heat treatment in a rapid annealing furnace: a first stage, wherein the temperature is 180 ℃ for 240 seconds; in the second stage, the temperature is 380 ℃ and the duration is 240 seconds; and thirdly, obtaining a layer of calcium copper titanate porous film at the temperature of 700 ℃ for 300 seconds, and repeating the coating-heat treatment process to obtain two layers of calcium copper titanate porous films (shown in figure 2), wherein the thickness of the two layers of calcium copper titanate porous films is about 40 nanometers, and the maximum pore diameter of the two layers of calcium copper titanate porous films is about 120 nanometers (shown in figure 4).
Example 2
a. Substrate selection and cleaning
Quartz glass is used as the substrate. The substrate was sonicated with ethanol and deionized water for 20 minutes and blown dry with high purity nitrogen.
b. Preparation of lanthanum nickelate buffer layer
And fixing the cleaned quartz glass substrate on a sample tray of a pulse laser deposition system. The deposition chamber is evacuated to 10 deg.C-5Pa below; introducing oxygen with the purity not lower than 99.999 percent, and maintaining the air pressure of the cavity at 5 Pa; the sample tray was heated to 700 deg.foC; pulse laser ablates the lanthanum nickelate target material, and the laser frequency is 5 Hz; and after the laser is closed, the oxygen pressure of the cavity is raised to 100Pa, and the temperature is kept for 30 minutes to obtain the lanthanum nickelate buffer layer with the thickness of about 10 nanometers.
c. Preparation of calcium copper titanate precursor solution
Calcium nitrate Ca (NO)3)2Copper nitrate Cu (NO)3)2Dissolving the mixture into ethylene glycol monomethyl ether according to the molar ratio of Ca to Cu of 1:3, and heating and stirring the mixture to form a homogeneous solution. And then measuring butyl titanate and acetylacetone with the same quantity according to the molar ratio of Ca to Ti atoms of 1:4, adding the solution into the solution, stirring and heating the solution in a water bath at 40 ℃ for about 2 hours to form a homogeneous solution, and finally preparing the copper calcium titanate precursor solution with the concentration of 0.05 mol/L.
d. Preparation of porous copper calcium titanate film
And (3) placing the substrate with the lanthanum nickelate buffer layer on a spin coater, setting the rotating speed of 6000r/min and the spin coater time to be 20 seconds, and coating a calcium copper titanate solution to obtain the wet calcium copper titanate film. Carrying out three-stage heat treatment in a rapid annealing furnace: a first stage, wherein the temperature is 180 ℃ for 240 seconds; in the second stage, the temperature is 380 ℃ and the duration is 240 seconds; and in the third stage, the temperature is 750 ℃ for 300 seconds to obtain a layer of copper calcium titanate porous film, and the coating-heat treatment process is repeated to obtain a plurality of layers of copper calcium titanate porous films.
Claims (1)
1. The preparation method of the porous calcium copper titanate film is characterized by comprising the following specific steps of:
a. covering a layer of LaNiO on the substrate by a physical or chemical method3A buffer layer having a thickness of 10 to 30 nm;
b. preparation of calcium copper titanate precursor solution
Taking copper nitrate Cu (NO)3)2Ca (NO), Ca nitrate3)2Dissolving the solid into ethylene glycol monomethyl ether according to the mol ratio of 3:1, heating and stirring in a water bath at the temperature of 30-80 ℃ for 1-6 hours to form a homogeneous solution; weighing butyl titanate and acetylacetone with the same mole number into the solution according to the molar ratio of Ca to Ti atoms of 1 to 4, stirring and heating the solution in a water bath at the temperature of 30-80 ℃ for 1-8 hours to form a homogeneous solution, and finally preparing a calcium copper titanate precursor solution with the concentration of 0.01-0.1 mol/L;
c. preparation of porous copper calcium titanate film
Coating a calcium copper titanate precursor solution on a substrate with a lanthanum nickelate buffer layer by adopting a rotary coating or pulling coating mode to obtain a wet calcium copper titanate film; carrying out three-stage heat treatment in a rapid annealing furnace: in the first stage, the temperature is 140-200 ℃ and the time is 180-360 seconds; in the second stage, the temperature is 360-420 ℃ and the time is 180-360 seconds; in the third stage, the temperature is 650-850 ℃ for 180-600 seconds to obtain a layer of porous calcium copper titanate film, and the coating-heat treatment process is repeated to obtain a plurality of layers of porous calcium copper titanate films; the pore diameter is in the range of 40-200 nm.
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| CN109748580A (en) * | 2019-03-15 | 2019-05-14 | 上海朗研光电科技有限公司 | A method of efficiently synthesizing huge dielectric constant material |
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Non-Patent Citations (1)
| Title |
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| Preparation and properties of CaCu3Ti4O12 thin film grown on LaNiO3-coated silicon by sol-gel process;Y.W. Li等;《Journal of Crystal Growth》;20071113;第310卷;第378-381页 * |
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