CN115557789A - Preparation method and application of flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film - Google Patents
Preparation method and application of flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film Download PDFInfo
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- PIRUAZLFEUQMTG-UHFFFAOYSA-N lanthanum;oxomanganese;strontium Chemical compound [Sr].[La].[Mn]=O PIRUAZLFEUQMTG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 15
- 230000005307 ferromagnetism Effects 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 230000005294 ferromagnetic effect Effects 0.000 claims abstract description 57
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 50
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims description 96
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 claims description 61
- 238000000498 ball milling Methods 0.000 claims description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000002002 slurry Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 40
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 claims description 9
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 9
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical group CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 9
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 9
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 9
- 229940117972 triolein Drugs 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- -1 oxygen ions Chemical class 0.000 abstract description 11
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 abstract description 10
- 239000003302 ferromagnetic material Substances 0.000 abstract description 7
- 230000005684 electric field Effects 0.000 abstract description 3
- 230000005291 magnetic effect Effects 0.000 abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 14
- 238000010345 tape casting Methods 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910002578 La0.2Sr0.8MnO3 Inorganic materials 0.000 description 7
- 229910003367 La0.5Sr0.5MnO3 Inorganic materials 0.000 description 7
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 7
- 229910002113 barium titanate Inorganic materials 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 150000005690 diesters Chemical class 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention relates to the technical field of ferromagnetic materials, in particular to a flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetic thick film, a preparation method and application thereof. The LSMO thick film is also a perovskite type oxide, oxygen ions and transition metal ions interact, so that the electronic behavior of the LSMO thick film has a plurality of characteristics, particularly good conductivity, a new idea can be provided for potential application of a metal oxide electrode, and the LSMO thick film has more possibilities for application due to influences of an electric field, a magnetic field, an interface and the like.
Description
Technical Field
The invention relates to the technical field of ferromagnetic materials, in particular to a flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetic thick film, a preparation method and application thereof.
Background
In this increasingly developing society, computers are rapidly developed, the information transmission speed is faster, the transmission range is wider, and human beings enter the information age, so that the development of the age is further required to be kept up with our devices. Since their advent, semiconductor transistors have been found in a wide variety of industrial products due to their unique characteristics. Televisions, automobiles, air conditioners, and the like, which are commonly used in daily life, particularly, semiconductor devices in memories, are widely used. The conventional large-scale information industry has not met the requirements of the current era, and microelectronic devices have gradually been developed towards miniaturization and integration. However, the semiconductor technology is slowly developed nowadays, so that a new material or a new process is required to meet the requirements of people of the present generation. Transition metal oxides are considered to be a novel material capable of substituting for next-generation semiconductor devices of silicon due to their excellent properties.
The transition metal oxide is a perovskite type oxide, and due to interaction between oxygen ions and transition metal ions, charges, spins, orbitals and lattices are mutually coupled, so that ferromagnetism is induced. In which the spin of an electron has two orientations, up and down, respectively, which can serve as a medium for information storage and processing in ferromagnetic materials. Ferromagnetic materials are also widely concerned due to unique physical properties, so that a new research direction is brought to magnetoelectric coupling and electric field regulation and control magnetization dynamics, and the ferromagnetic materials have important significance in both basic research and practical application.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
The invention aims to solve the problem of how to obtain a ferromagnetic material with good ferromagnetism and conductivity and excellent performance, and provides a flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film, a preparation method and application thereof.
In order to achieve the purpose, the invention discloses a flexible transition metal oxide lanthanum strontium manganese oxygen ironThe magnetic thick film is characterized in that the chemical general formula of the flexible transition ferromagnetic metal oxide lanthanum strontium manganese oxygen ferromagnetic thick film is La 0.7 Sr 0.3 MnO 3 。
The thickness of the flexible transition ferromagnetic metal oxide lanthanum strontium manganese oxygen ferromagnetic thick film is 10-20 μm.
The invention also discloses a preparation method of the flexible transition ferromagnetic metal oxide lanthanum strontium manganese oxygen ferromagnetic thick film, which comprises the following steps:
s1, lanthanum oxide, strontium carbonate and manganese oxide are mixed according to the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Weighing a chemical formula of the thick film, mixing the mixed powder, a ball milling medium and alcohol, and performing ball milling;
s2, drying the ball-milled powder obtained in the step S1, pre-sintering and preserving heat on the dried powder, grinding the powder, and drying to obtain a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Powder;
s3, mixing the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 The powder and the organic solvent are fully mixed to obtain the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 A thick film paste;
s4, removing bubbles from the slurry obtained in the step S3, then casting the slurry into a film, and drying to obtain the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 And (3) thick film.
The ball milling medium in the step S1 is agate balls, and the diameters of the agate balls are 2-10 mm.
During ball milling in the step S1, the mass ratio of the mixed powder to the ball milling medium to the alcohol is 1.5.
In the step S2, the drying temperature is 60-100 ℃, and the drying time is 6-12 h.
In the step S2, the pre-sintering temperature is 650-1050 ℃, the heat preservation time is 2-8 h, the ball milling time is 24h, and the drying time is 6-12 h.
In the step S3, firstly, the flexible ferromagnetic metal oxide L is put intoa 0.7 Sr 0.3 MnO 3 Mixing the powder with an organic solvent, a dispersing agent and zirconia balls, uniformly mixing for 200-300 min to obtain a primary slurry, mixing with a binder and a homogenizing agent, and uniformly mixing for 200-300 min to obtain a final slurry, wherein the organic solvent is toluene-ethanol, the dispersing agent is triolein, the binder is polyethylene glycol, and the homogenizing agent is butyl phthalate.
And in the step S4, defoaming is carried out through a vacuum defoaming machine, wherein the defoaming time is 25-60 min.
The invention also discloses the application of the flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film in a semiconductor device.
Compared with the prior art, the invention has the beneficial effects that: the LSMO thick film prepared by the tape casting method has the advantages of compactness, good ductility and stronger plasticity. The preparation process is simple, and the prepared thick film has good ferromagnetism, a colossal magnetoresistance effect, conductivity and the like due to mutual coupling among spin, charge, a track and crystal lattices in the LSMO, so that the prepared device has the advantages of low energy consumption, high reading speed and long service life. The prepared thick film has good ferromagnetism, a colossal magnetoresistance effect, conductivity and the like due to mutual coupling among spin, charge, tracks and lattices in the LSMO. The flexible ferromagnetic metal oxide LSMO thick film prepared by the invention is also a perovskite type oxide, and the electronic behavior of the flexible ferromagnetic metal oxide LSMO thick film has a plurality of characteristics due to the interaction of oxygen ions and transition metal ions. Particularly, the conductive film has good conductivity, a new idea can be provided for potential application of the metal oxide electrode, and the film can be applied more possibly due to the influence of an electric field, a magnetic field, an interface and the like.
Drawings
FIG. 1 shows a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 XRD patterns of the thick film at different pre-sintering temperatures;
FIG. 2 shows a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 SEM images of thick films at different prefiring temperatures and comparative example 3;
FIG. 3 shows flexibilityFerromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 The thick film is subjected to energy spectrum charts of the comparative example 3 at different pre-sintering temperatures;
FIG. 4 shows a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick film and comparative examples 1,2,3 hysteresis curves at 10K;
FIG. 5 shows a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 M-T curves for thick films and comparative examples 1, 2.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
The present embodiment provides a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick film of, in which, a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 The preparation method of the thick film comprises the following steps:
s1: preparation of La 0.7 Sr 0.3 MnO 3 And (3) powder.
S2: preparation of La 0.7 Sr 0.3 MnO 3 And (4) thick film.
According to one example of the present invention, the specific operation of S1 is as follows:
s101: according to the chemical general formula, lanthanum oxide (99.99%), strontium carbonate (99%), manganese dioxide (99.8%), barium titanate (99%), titanium dioxide powder (100%) are weighed, and after weighing, the powder is weighed as follows: ball milling media (agate balls): alcohol =1:1.5:1 in a ball milling tank, setting the rotating speed of the planetary ball mill to 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S102: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃.
S103: pre-sintering the dried mixed powder, putting the powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, introducing oxygen, setting the temperature to be between room temperature and 650 ℃, keeping the temperature for 4 hours, and cooling the powder to the room temperature along with the furnace when the temperature is reduced to 500 ℃, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min.
S104: pre-burning the La 0.7 Sr 0.3 MnO 3 The powder was taken out and triturated with an agate mortar, following the powder: ball milling media (agate balls): alcohol =1:1.5:1 in a ball mill jar. The rotation speed of the planetary ball mill is set to be 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the used agate balls is 2-10mm, and the agate balls have different sizes.
S105: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃. Drying to obtain dried La 0.7 Sr 0.3 MnO 3 And (3) powder.
According to an example of the present invention, the specific operation of S2 is as follows:
s201: mixing the dried powder with an organic solvent toluene-ethanol and a dispersant triolein, adding zirconia balls, and putting into a three-dimensional powder mixer for mixing, wherein the mass of the powder is as follows: the mass of the zirconia balls is as follows: and (3) the mass of the solvent: dispersant mass =18:27:25:2. mixing for 240min to obtain primary slurry
S202: adding polyethylene glycol, phthalic diester and polyvinyl butyl acetal into the primary slurry, wherein the mass ratio of the original powder: polyethylene glycol: phthalic acid diester: polyvinyl butyl acetal =18:10:3:5. then mixing the powder for 360min to obtain the final slurry.
S203: removing bubbles from the slurry by using a vacuum bubble removing machine for 40min, casting the bubble-removed slurry into a film by using a casting machine, adjusting the cutter to be 200 at a casting speed of 20cm/min, and drying at room temperature for 4h to obtain the La 0.7 Sr 0.3 MnO 3 And (3) thick film.
Example 2
The present embodiment provides a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick film of, in which, a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 The thick film was prepared as follows:
s1: preparation of La 0.7 Sr 0.3 MnO 3 And (3) powder.
S2: preparation of La 0.7 Sr 0.3 MnO 3 And (4) thick film.
According to one example of the present invention, the specific operation of S1 is as follows:
s101: according to the chemical general formula, lanthanum oxide (99.99%), strontium carbonate (99%), manganese dioxide (99.8%), barium titanate (99%), titanium dioxide powder (100%) are weighed, and then the weight percentages are as follows: ball milling media (agate balls): alcohol =1:1.5:1 in a ball milling tank, setting the rotating speed of the planetary ball mill to 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S102: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃.
S103: pre-sintering the dried mixed powder, putting the powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, introducing oxygen, setting the temperature to be between room temperature and 750 ℃, keeping the temperature for 4 hours, and cooling the powder to the room temperature along with the furnace when the temperature is reduced to 500 ℃, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min.
S104: pre-burning the La 0.7 Sr 0.3 MnO 3 The powder was taken out and triturated with an agate mortar, following the powder: ball milling media (agate balls): alcohol =1:1.5:1 in a ball mill jar. The rotation speed of the planetary ball mill is set to be 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S105: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃. Drying to obtain dried La 0.7 Sr 0.3 MnO 3 And (3) powder.
According to an example of the present invention, the specific operation of S2 is as follows:
s201: mixing the dried powder with an organic solvent toluene-ethanol and a dispersant triolein, adding zirconia balls, and putting into a three-dimensional powder mixer for mixing, wherein the powder mass is as follows: the mass of the zirconia balls is as follows: and (3) the mass of the solvent: dispersant mass =18:27:25:2. mixing for 240min to obtain primary slurry
S202: adding polyethylene glycol, diester phthalate and polyvinyl butyl acetal into the primary slurry, wherein the mass ratio of the original powder: polyethylene glycol: phthalic acid diester: polyvinyl butyl acetal =18:10:3:5. then mixing the powder for 360min to obtain the final slurry.
S203: carrying out defoaming treatment on the slurry by using a vacuum defoaming machine for 40min, carrying out tape casting on the defoamed slurry to form a film by using a tape casting machine, adjusting the tape casting speed to be 200, and drying at room temperature for 4h to obtain the La 0.7 Sr 0.3 MnO 3 And (3) thick film.
Example 3
The present embodiment provides a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick film of, in which, a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 The thick film was prepared as follows:
s1: preparation of La 0.7 Sr 0.3 MnO 3 And (3) powder.
S2: preparation of La 0.7 Sr 0.3 MnO 3 And (3) thick film.
According to an example of the present invention, the specific operation of S1 is as follows:
s101: according to the chemical general formula, lanthanum oxide (99.99%), strontium carbonate (99%), manganese dioxide (99.8%), barium titanate (99%), titanium dioxide powder (100%) are weighed, and then the weight percentages are as follows: ball milling media (agate balls): alcohol =1:1.5:1 in a ball milling tank, setting the rotating speed of a planetary ball mill to 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S102: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃.
S103: pre-burning the dried mixed powder, putting the mixed powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, introducing oxygen, setting the temperature to be between room temperature and 850 ℃, keeping the temperature for 4 hours, and cooling the mixed powder to the room temperature along with the furnace when the temperature is reduced to 500 ℃, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min.
S104: pre-burning the La 0.7 Sr 0.3 MnO 3 The powder was taken out and triturated with an agate mortar, following the powder: ball milling media (agate balls): alcohol =1:1.5:1 in a ball mill jar. The rotation speed of the planetary ball mill is set to be 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the used agate balls is 2-10mm, and the agate balls have different sizes.
S105: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃. Drying to obtain dried La 0.7 Sr 0.3 MnO 3 And (3) powder.
According to an example of the present invention, the specific operation of S2 is as follows:
s201: mixing the dried powder with an organic solvent toluene-ethanol and a dispersant triolein, adding zirconia balls, and putting into a three-dimensional powder mixer for mixing, wherein the mass of the powder is as follows: the mass of the zirconia balls is as follows: and (3) the mass of the solvent: dispersant mass =18:27:25:2. mixing for 240min to obtain primary slurry
S202: adding polyethylene glycol, phthalic diester and polyvinyl butyl acetal into the primary slurry, wherein the mass ratio of the original powder: polyethylene glycol: phthalic acid diester: polyvinyl butyl acetal =18:10:3:5. then mixing the powder for 360min to obtain the final slurry.
S203: carrying out defoaming treatment on the slurry by using a vacuum defoaming machine for 40min, carrying out tape casting on the defoamed slurry to form a film by using a tape casting machine, adjusting the tape casting speed to be 200, and drying at room temperature for 4h to obtain the La 0.7 Sr 0.3 MnO 3 And (4) thick film.
Example 4
The present embodiment provides a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick film of, in which, a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 The preparation method of the thick film comprises the following steps:
s1: preparation of La 0.7 Sr 0.3 MnO 3 And (3) powder.
S2: preparation of La 0.7 Sr 0.3 MnO 3 And (3) thick film.
According to one example of the present invention, the specific operation of S1 is as follows:
s101: according to the chemical general formula, lanthanum oxide (99.99%), strontium carbonate (99%), manganese dioxide (99.8%), barium titanate (99%), titanium dioxide powder (100%) are weighed, and after weighing, the powder is weighed as follows: ball milling media (agate balls): alcohol =1:1.5:1 in a ball milling tank, setting the rotating speed of the planetary ball mill to 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S102: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃.
S103: pre-burning the dried mixed powder, putting the mixed powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, introducing oxygen, setting the temperature to be between room temperature and 950 ℃, keeping the temperature for 4 hours, and cooling the mixed powder to the room temperature along with the furnace when the temperature is reduced to 500 ℃, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min.
S104: pre-burning the La 0.7 Sr 0.3 MnO 3 The powder was taken out and triturated with an agate mortar, following the powder: ball milling media (agate balls): alcohol =1:1.5:1 in a ball mill jar. The rotation speed of the planetary ball mill is set to be 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S105: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃. Drying to obtain dried La 0.7 Sr 0.3 MnO 3 And (3) powder.
According to an example of the present invention, the specific operation of S2 is as follows:
s201: mixing the dried powder with an organic solvent toluene-ethanol and a dispersant triolein, adding zirconia balls, and putting into a three-dimensional powder mixer for mixing, wherein the mass of the powder is as follows: the mass of the zirconia ball is as follows: and (3) the mass of the solvent: dispersant mass =18:27:25:2. mixing for 240min to obtain primary slurry
S202: adding polyethylene glycol, phthalic diester and polyvinyl butyl acetal into the primary slurry, wherein the mass ratio of the original powder: polyethylene glycol: phthalic acid diester: polyvinyl butyl acetal =18:10:3:5. then mixing the powder for 360min to obtain the final slurry.
S203: removing bubbles from the slurry by using a vacuum bubble removing machine for 40min, casting the bubble-removed slurry into a film by using a casting machine, adjusting the cutter to be 200 at a casting speed of 20cm/min, and drying at room temperature for 4h to obtain the La 0.7 Sr 0.3 MnO 3 And (3) thick film.
Example 5
The present embodiment provides a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick film of, in which, a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 The thick film was prepared as follows:
s1: preparation of La 0.7 Sr 0.3 MnO 3 And (3) powder.
S2: preparation of La 0.7 Sr 0.3 MnO 3 And (4) thick film.
According to an example of the present invention, the specific operation of S1 is as follows:
s101: according to the chemical general formula, lanthanum oxide (99.99%), strontium carbonate (99%), manganese dioxide (99.8%), barium titanate (99%), titanium dioxide powder (100%) are weighed, and after weighing, the powder is weighed as follows: ball milling media (agate balls): alcohol =1:1.5:1 in a ball milling tank, setting the rotating speed of the planetary ball mill to 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S102: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃.
S103: and pre-sintering the dried mixed powder, putting the powder into an alumina crucible, putting the alumina crucible into a tubular furnace, introducing oxygen, setting the temperature to be between room temperature and 1050 ℃, keeping the temperature for 4 hours, and cooling the powder to the room temperature along with the furnace when the temperature is reduced to 500 ℃, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min.
S104: pre-burning the La 0.7 Sr 0.3 MnO 3 The powder was taken out and triturated with an agate mortar, following the powder: ball milling media (agate balls): alcohol =1:1.5:1 in a ball mill jar. The rotation speed of the planetary ball mill is set to be 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S105: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃. Drying to obtain dried La 0.7 Sr 0.3 MnO 3 And (3) powder.
According to an example of the present invention, the specific operation of S2 is as follows:
s201: mixing the dried powder with an organic solvent toluene-ethanol and a dispersant triolein, adding zirconia balls, and putting into a three-dimensional powder mixer for mixing, wherein the powder mass is as follows: the mass of the zirconia ball is as follows: and (3) the mass of the solvent: dispersant mass =18:27:25:2. mixing for 240min to obtain primary slurry
S202: adding polyethylene glycol, phthalic diester and polyvinyl butyl acetal into the primary slurry, wherein the mass ratio of the original powder: polyethylene glycol: phthalic acid diester: polyvinyl butyl acetal =18:10:3:5. then mixing the powder for 360min to obtain the final slurry.
S203: carrying out defoaming treatment on the slurry by using a vacuum defoaming machine for 40min, carrying out tape casting on the defoamed slurry to form a film by using a tape casting machine, adjusting the tape casting speed to be 200, and drying at room temperature for 4h to obtain the La 0.7 Sr 0.3 MnO 3 And (4) thick film.
Comparative example 1
The present embodiment provides a ferromagnetic metal oxide La 0.5 Sr 0.5 MnO 3 Thick film of ferromagnetic metal oxide La 0.5 Sr 0.5 MnO 3 Preparation of thick filmsThe preparation method comprises the following steps:
s1: preparation of La 0.5 Sr 0.5 MnO 3 And (3) powder.
S2: preparation of La 0.5 Sr 0.5 MnO 3 And (4) thick film.
According to an example of the present invention, the specific operation of S1 is as follows:
s101: according to the chemical general formula, lanthanum oxide (99.99%), strontium carbonate (99%), manganese dioxide (99.8%), barium titanate (99%), titanium dioxide powder (100%) are weighed, and then the weight percentages are as follows: ball milling media (agate balls): alcohol =1:1.5:1 in a ball milling tank, setting the rotating speed of the planetary ball mill to 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S102: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃.
S103: pre-sintering the dried mixed powder, putting the powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, introducing oxygen, setting the temperature to be between room temperature and 850 ℃, keeping the temperature for 4 hours, and cooling the powder to the room temperature along with the furnace when the temperature is reduced to 500 ℃, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min.
S104: pre-burning the La 0.5 Sr 0.5 MnO 3 The powder was taken out and triturated with an agate mortar, following the powder: ball milling media (agate balls): alcohol =1:1.5:1 in a ball mill jar. The rotation speed of the planetary ball mill is set to be 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the used agate balls is 2-10mm, and the agate balls have different sizes.
S105: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃. Drying to obtain dried La 0.5 Sr 0.5 MnO 3 And (3) powder.
According to an example of the present invention, the specific operation of S2 is as follows:
s201: mixing the dried powder with an organic solvent toluene-ethanol and a dispersant triolein, adding zirconia balls, and putting into a three-dimensional powder mixer for mixing, wherein the powder mass is as follows: the mass of the zirconia balls is as follows: and (3) the mass of the solvent: dispersant mass =18:27:25:2. mixing for 240min to obtain primary slurry
S202: adding polyethylene glycol, phthalic diester and polyvinyl butyl acetal into the primary slurry, wherein the mass ratio of the original powder: polyethylene glycol: phthalic acid diester: polyvinyl butyl acetal =18:10:3:5. then mixing the powder for 360min to obtain the final slurry.
S203: removing bubbles from the slurry by using a vacuum bubble removing machine for 40min, casting the bubble-removed slurry into a film by using a casting machine, adjusting the cutter to be 200 at a casting speed of 20cm/min, and drying for 4h to obtain the La 0.5 Sr 0.5 MnO 3 And (3) thick film.
Comparative example 2
The present embodiment provides a flexible ferromagnetic metal oxide La 0.2 Sr 0.8 MnO 3 Thick film of ferromagnetic metal oxide La 0.2 Sr 0.8 MnO 3 The preparation method of the thick film comprises the following steps:
s1: preparation of La 0.2 Sr 0.8 MnO 3 And (3) powder.
S2: preparation of La 0.2 Sr 0.8 MnO 3 And (3) thick film.
According to one example of the present invention, the specific operation of S1 is as follows:
s101: according to the chemical general formula, lanthanum oxide (99.99%), strontium carbonate (99%), manganese dioxide (99.8%), barium titanate (99%), titanium dioxide powder (100%) are weighed, and after weighing, the powder is weighed as follows: ball milling media (agate balls): alcohol =1:1.5:1 in a ball milling tank, setting the rotating speed of a planetary ball mill to 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S102: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃.
S103: pre-sintering the dried mixed powder, putting the powder into an alumina crucible, then putting the alumina crucible into a tubular furnace, introducing oxygen, setting the temperature to be between room temperature and 850 ℃, keeping the temperature for 4 hours, and cooling the powder to the room temperature along with the furnace when the temperature is reduced to 500 ℃, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min.
S104: pre-burning the La 0.2 Sr 0.8 MnO 3 The powder was taken out and triturated with an agate mortar, following the powder: ball milling media (agate balls): alcohol =1:1.5:1 in a ball mill jar. The rotation speed of the planetary ball mill is set to be 400rpm, wherein the ball milling time is 24h. Wherein the diameter of the agate balls is 2-10mm, and the agate balls have different sizes.
S105: after ball milling, the mixture is taken out and placed in an oven to be dried for 9 hours, and the drying temperature is 80 ℃. Drying to obtain dried La 0.2 Sr 0.8 MnO 3 And (3) powder.
According to an example of the present invention, the specific operation of S2 is as follows:
s201: mixing the dried powder with an organic solvent toluene-ethanol and a dispersant triolein, adding zirconia balls, and putting into a three-dimensional powder mixer for mixing, wherein the powder mass is as follows: the mass of the zirconia balls is as follows: and (3) the mass of the solvent: dispersant mass =18:27:25:2. mixing for 240min to obtain primary slurry
S202: adding polyethylene glycol, phthalic diester and polyvinyl butyl acetal into the primary slurry, wherein the mass ratio of the original powder: polyethylene glycol: phthalic acid diester: polyvinyl butyl acetal =18:10:3:5. then mixing the powder for 360min to obtain the final slurry.
S203: carrying out defoaming treatment on the slurry by using a vacuum defoaming machine for 40min, carrying out tape casting on the defoamed slurry to form a film by using a tape casting machine, adjusting the cutter to be 200, carrying out tape casting at the tape casting speed of 20cm/min, and drying for 12h to obtain La 0.2 Sr 0.8 MnO 3 And (4) thick film.
Comparative example 3
This comparative example provides a ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Ceramic, wherein the ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Ceramic materialThe preparation method comprises the following steps:
s1: la prepared in the above example 1 0.7 Sr 0.3 MnO 3 The thick film is cut into 5 x 5mm in size, and the method is characterized in that the substrate is a zirconia plate, and the film can be pressed on the substrate in a hot pressing mode, wherein the pressure is 80MPa, the time is 40min, and the temperature is 65 ℃.
S2: and (3) putting the pressed film in a tube furnace, introducing oxygen, and keeping the temperature at 600 ℃ for 300min at a heating rate of 3 ℃/min and a cooling rate of 5 ℃/min.
S3: and (3) sintering the film after the glue is discharged in a tube furnace under the condition of introducing oxygen, setting the temperature to be from room temperature to 1200 ℃, setting the temperature rising speed to be 3 ℃/min, the heat preservation time to be 500min, setting the temperature reduction speed to be 5 ℃/min, and cooling to the room temperature along with the furnace when the temperature is reduced to 500 ℃. Obtaining the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 And (6) ceramic plates.
FIG. 1 shows a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 XRD patterns of the thick film at different pre-sintering temperatures are shown in figure 1, and the flexible ferromagnetic metal oxide La prepared by the method is 0.7 Sr 0.3 MnO 3 The thick film is a perovskite type oxide and no significant impurity is generated.
FIG. 2 shows a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick film and comparative La at different pre-firing temperatures 0.7 Sr 0.3 MnO 3 SEM image of the ceramic wafer, as can be seen from FIG. 2, the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 When the pre-sintering temperature of the thick film is continuously increased, the particles are more closely arranged, and the compactness is good. The morphology was best at 850 ℃, after which the sample appeared porous and less dense with increasing temperature. And La 0.7 Sr 0.3 MnO 3 The SEM of the ceramic is formed by thick film sintering at 850 deg.C. The ceramic sheet has good compactness, thereby showing that the flexible ferromagnetic metal oxide La prepared by the invention 0.7 Sr 0.3 MnO 3 The thick film has good processability, and good moldability.
FIG. 3 (a) - (e)Is a flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Thick films at different prefiring temperatures and FIG. 3 (f) comparative example La 0.7 Sr 0.3 MnO 3 The energy spectrum diagram of the ceramic chip is undistorted, and the data is reliable.
As shown in FIG. 4 and FIG. 5, the flexible thick film of ferromagnetic metal oxide LSMO prepared by the present invention has good ferromagnetism and good stability in a wide temperature range. It can also be seen that it exhibits a significant hysteresis curve at ambient temperature. Comparative examples 1,2 thick films of different compositions of LSMO, it is evident that the thick films prepared in example 3 exhibit better ferromagnetic properties in comparison to the hysteresis curves of comparative examples 1,2, while the ceramics prepared in example 3 also exhibit good ferromagnetic properties. From another aspect, the ferromagnetic metal oxide La prepared by the present invention is also embodied 0.7 Sr 0.3 MnO 3 The thick film has strong processability and certain flexibility. As can be seen from FIG. 5, example 3 has a higher Curie temperature, illustrating the flexible ferromagnetic metal oxide La prepared in accordance with the present invention 0.7 Sr 0.3 MnO 3 The thick film has better ferromagnetism, and simultaneously embodies the flexible ferromagnetic metal oxide La prepared by the invention 0.7 Sr 0.3 MnO 3 The thick film has good research prospect, and provides a new idea for the preparation and research of ferromagnetic materials.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film is characterized in that the chemical general formula of the flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film is La 0.7 Sr 0.3 MnO 3 。
2. The flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetic thick film of claim 1, wherein the thickness of the flexible transition ferromagnetic thick film is 10-20 μ ι η.
3. A method for preparing a flexible thick film of transition metal oxide lanthanum strontium manganese oxygen ferromagnetism as claimed in claim 1 or 2, characterized by comprising the following steps:
s1, lanthanum oxide, strontium carbonate and manganese oxide are mixed according to the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Weighing a chemical formula of the thick film, mixing the mixed powder, a ball milling medium and alcohol, and performing ball milling;
s2, drying the ball-milled powder obtained in the step S1, pre-burning and preserving heat the dried powder, grinding the powder, and drying to obtain the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Powder;
s3, mixing the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 Fully and uniformly mixing the powder with an organic solvent to obtain the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 A thick film paste;
s4, removing bubbles from the slurry obtained in the step S3, then casting the slurry into a film, and drying to obtain the flexible ferromagnetic metal oxide La 0.7 Sr 0.3 MnO 3 And (4) thick film.
4. The method according to claim 3, wherein the ball-milling medium in step S1 is agate balls, and the diameter of the agate balls is 2-10 mm.
5. The method for preparing a flexible thick film of transition metal oxide lanthanum strontium manganese oxygen ferromagnetism according to claim 3, wherein during ball milling in the step S1, the mass ratio of the mixed powder, the ball milling medium and the alcohol is 1.5.
6. The method according to claim 3, wherein the drying temperature in step S2 is 60-100 ℃ and the drying time is 6-12 h.
7. The method according to claim 3, wherein the pre-sintering temperature in step S2 is 650-1050 ℃, the holding time is 2-8 h, the ball milling time is 24h, and the drying time is 6-12 h.
8. The method according to claim 3, wherein in step S3, the flexible thick film of lanthanum strontium manganese oxygen ferromagnetic is first prepared by 0.7 Sr 0.3 MnO 3 Mixing the powder with an organic solvent, a dispersing agent and zirconia balls, uniformly mixing for 200-300 min to obtain a primary slurry, then mixing with a binder and a homogenizing agent, and uniformly mixing for 200-300 min to obtain a final slurry, wherein the organic solvent is toluene-ethanol, the dispersing agent is triolein, the binder is polyethylene glycol, and the homogenizing agent is butyl phthalate.
9. The method according to claim 3, wherein the defoaming in step S4 is performed by a vacuum defoaming machine for 25-60 min.
10. Use of a flexible thick film of transition metal oxide lanthanum strontium manganese oxygen ferromagnetism as defined in claim 1 or 2 in a semiconductor device.
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