CN114883480A - Preparation method of bismuth titanate series ferroelectric film - Google Patents
Preparation method of bismuth titanate series ferroelectric film Download PDFInfo
- Publication number
- CN114883480A CN114883480A CN202210562469.9A CN202210562469A CN114883480A CN 114883480 A CN114883480 A CN 114883480A CN 202210562469 A CN202210562469 A CN 202210562469A CN 114883480 A CN114883480 A CN 114883480A
- Authority
- CN
- China
- Prior art keywords
- film
- bismuth titanate
- ferroelectric
- titanate series
- preparation
- 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.)
- Pending
Links
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 57
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 238000003980 solgel method Methods 0.000 claims abstract description 15
- 230000007547 defect Effects 0.000 claims abstract description 8
- 238000011282 treatment Methods 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 86
- 239000010409 thin film Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004544 sputter deposition Methods 0.000 description 19
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 14
- 239000010936 titanium Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 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
- 230000015654 memory Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8561—Bismuth-based oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Insulating Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method of a bismuth titanate series ferroelectric film, belonging to the field of ferroelectric film preparation. The invention firstly adopts a sol-gel method to prepare a bismuth titanate series film with defects, then carries out magnetron sputtering coating on the film layer, and then carries out annealing treatment, thus obtaining the film with larger grain size. The ferroelectric film prepared by the method has larger grain size, the longitudinal size can reach 2 mu m, and the ferroelectric film has good fatigue resistance and has potential application value in capacitors, piezoelectric elements and ferroelectric elements. The preparation method combines the sol-gel method and the magnetron sputtering, overcomes the defect that the film fails due to the defect caused by overhigh heat treatment temperature of the film, and is beneficial to preparing the high-quality ferroelectric film.
Description
Technical Field
The invention relates to a preparation method of a bismuth titanate series ferroelectric film, in particular to a method for preparing a large-grain bismuth titanate series ferroelectric film by a sol-gel method and a magnetron sputtering method in sequence, belonging to the field of preparation of ferroelectric films.
Background
The ferroelectric film material has the performances of dielectric, piezoelectric, ferroelectric and electrooptical effects and the like, and is an important functional film material. In recent years, with the development of microelectronic technology and internet technology and the advent of the era of big data and intelligent manufacturing, people have made higher demands on the functionalization, integration and miniaturization of electronic devices, and the development of ferroelectric thin films as capacitors, piezoelectric elements and ferroelectric elements has been actively carried out.
The bismuth titanate series ferroelectric film material comprises Bi4Ti3O12 and a material for carrying out metal element doping modification on Bi4Ti3O12, belongs to a bismuth-layer-shaped perovskite structure, has good ferroelectric property and higher Curie temperature, and has good application prospect in a ferroelectric random access memory. The common preparation methods of the bismuth titanate series film at present comprise a pulse laser deposition method, a sol-gel method and a magnetron sputtering method. The sol-gel method is one of wet chemical methods for preparing materials, and the technology is to solidify organic metal compounds or inorganic salts through solution, sol and gel, and obtain a film through heat treatment. When the sol-gel method is adopted to prepare the bismuth titanate series film, the final heat treatment temperature cannot be selected too high, otherwise the film can generate defects and be invalid. The higher the heat treatment temperature, the larger the crystal grain size, and therefore the crystal grains of the bismuth titanate-series ferroelectric thin film obtained by the sol-gel method are smaller. The process of preparing bismuth titanate series thin film by magnetron sputtering method is that charged ions are used for bombarding the surface of target material, so that target material particles are bombarded from the surface and deposited on the surface of a substrate to form a film, and then the bismuth titanate series thin film is obtained by heat treatment. The problem that the film is defective and ineffective due to overhigh heat treatment temperature also exists in the heat treatment process of the magnetron sputtering method, so that the grain size of the prepared bismuth titanate series film is limited. After the crystal grain size of the bismuth titanate series film is increased, the ferroelectric property of the film can be improved, and the service life reliability of a film device can be improved. Therefore, the large-grain bismuth titanate series ferroelectric film is suitable for integrating passive devices, ferroelectric memories and other applications.
Disclosure of Invention
The invention aims to solve the problem that the film is failed due to defects caused by excessive heat treatment temperature in the process of preparing a bismuth titanate series film by a sol-gel method or a magnetron sputtering method, and provides a preparation method of a bismuth titanate series ferroelectric film. The grain size of the film obtained by the preparation method can be obviously larger than that of the bismuth titanate series film prepared by a sol-gel method or a magnetron sputtering method.
Through repeated and intensive research, the inventor finds that a bismuth titanate series film with defects is prepared by a sol-gel method, then magnetron sputtering coating is carried out on the film layer, and then annealing treatment is carried out, so that the film with larger grain size can be obtained, and the fatigue resistance of the film is better due to higher quality and fewer defects of the film.
The purpose of the invention is realized by the following technical scheme.
A process for preparing bismuth titanate series ferroelectric film with chemical general formula A x Bi 4-x B y Ti 3-y O 12 Wherein A and B are both one or two of rare earth elements or/and transition metal elements, x is more than or equal to 0<Y is more than or equal to 1 and less than or equal to 0.1, and the preparation method is characterized by comprising the following steps:
the method comprises the following steps: according to the chemical formula of the bismuth titanate series ferroelectric film, soluble inorganic salt or organic alkoxide of metal elements is selected to be dissolved in an organic solvent, wherein the weight of the inorganic salt or the organic alkoxide of the Bi elements is 1-20 wt% more than the theoretical weight, and then precursor solution is obtained by heating and stirring;
step two: dripping the precursor solution on a substrate for spin coating to obtain a wet film;
step three: drying the wet film obtained in the step two, and performing pyrolysis treatment on the dried film at the temperature of 300-600 ℃ to remove organic matters;
step four: repeating the operation of the second step and the operation of the third step on the pyrolyzed film;
step five: heating the film processed in the fourth step at the temperature of 750-850 ℃;
step six: taking the film obtained in the fifth step as a substrate, taking bismuth titanate ceramic with excessive Bi element as a target material, and performing radio frequency magnetron sputtering film coating until the sputtered D film reaches the expected thickness; the bismuth titanate ceramic material is the same as the bismuth titanate series ferroelectric film;
step seven: and heating the film D obtained in the sixth step at the temperature of 750-850 ℃.
Further, the heat treatment temperature in the seventh step is the same as the heat treatment temperature in the fifth step.
Advantageous effects
The bismuth titanate series film with larger grain size and more uniform grain size can be manufactured by the preparation method of the invention, and the bismuth titanate series film has lower coercive field strength and better fatigue resistance, thereby manufacturing the bismuth titanate series film ferroelectric device with higher service life and reliability.
Drawings
FIG. 1 is an XRD pattern of a bismuth titanate series ferroelectric thin film prepared in example 1;
FIG. 2 is a SEM image of the surface of a bismuth titanate series ferroelectric thin film prepared in example 1;
fig. 3 is a graph showing the fatigue resistance test results of the bismuth titanate-series ferroelectric thin film prepared in example 1.
Detailed Description
Hereinafter, a mode for carrying out the present invention will be described, and a description of a known structure and technique will be omitted in the following description.
The bismuth titanate series ferroelectric film comprises a bismuth titanate ferroelectric film and a ferroelectric film which is doped with other elements on the basis of bismuth titanate and has a crystal structure of the bismuth titanate structure. The substrate for producing the bismuth titanate-based ferroelectric thin film is not particularly limited, and varies depending on the structure of the thin film device. For example, in the case of forming a thin film capacitor structure, a substrate with a lower electrode is used, and specifically, a substrate having a laminated structure of Pt/Ti/SiO2/Si, Pt/TiO2/SiO2/Si, or the like can be given. Next, a method for producing a bismuth titanate ferroelectric thin film according to the present embodiment will be described.
First, according to formula A of a bismuth titanate-based thin film x Bi 4-x B y Ti 3-y O 12 (0≤x<Y is more than or equal to 1 and less than or equal to 0.1), wherein the soluble inorganic salt or organic alkoxide of the metal element can freely select 2 or more than 3 of bismuth nitrate, bismuth acetate, titanium isopropoxide, tetrabutyl titanate, lanthanum carbonate, lanthanum nitrate, lanthanum acetylacetonate and the like. The organic solvent can be selected from 1 or more than 2 of ethylene glycol, ethylene glycol monomethyl ether, acetylacetone, glacial acetic acid, etc. After the solution is mixed, the solution is heated and stirred for a period of time to obtain a precursor solution, and further, the temperature is 20-60 ℃ in the stirring process.
After the precursor solution is prepared, a layer of film is obtained through the processes of glue homogenizing treatment, drying and pyrolysis, or the film is repeated for 1, 2 or 3 times to be thicker, and the film is too thick to prepare the device due to too many times of repetition. And crystallizing the pyrolyzed film, wherein the heat treatment temperature is 750-850 ℃. The film prepared by the sol-gel method is used as a substrate to carry out radio frequency magnetron sputtering, the sputtering parameters in the magnetron sputtering process are not particularly limited, and the final thickness is obtained according to the requirements of the size of a film device.
Example 1
A process for preparing bismuth titanate series ferroelectric film with chemical general formula of Bi 3.25 La 0.75 Ti 3 O 12 According to the chemical formula, the five water is selectedDissolving bismuth nitrate, lanthanum nitrate hexahydrate and tetrabutyl titanate in ethylene glycol monomethyl ether and acetylacetone solution, wherein the anhydrous bismuth nitrate is excessive by 3 wt%, and the specific weight is; bi (NO) 3 ) 3 ·5H 2 O＝8.1189g，La(NO 3 ) 3 ·6H 2 O＝1.6283，C 16 H 36 O 14 5.1048g of Ti, 30mL of ethylene glycol monomethyl ether and 5mL of acetylacetone were added. After the solutions were mixed, they were stirred at 30 ℃ for 30 min.
Then, a rubber head dropper is used for taking the solution and homogenizing the solution on a homogenizing machine, the rotating speed of the homogenizing machine is 3000 r/min, and the time is 5 min. The obtained wet film is dried in an oven and then is subjected to heat treatment at 400 ℃ for 30 min. And repeating the glue homogenizing and the heat treatment process twice after the heat treatment to obtain the three-layer film. Then the temperature is preserved for 30min at 800 ℃ in the air atmosphere in a tube furnace.
Using a film obtained by a sol-gel method as a substrate, and selecting Bi with 30 wt% of excessive Bi element 3.25 La 0.75 Ti 3 O 12 Performing radio frequency magnetron sputtering by using ceramic as a target material, wherein the sputtering parameters are as follows: the sputtering temperature is room temperature; the distance between the substrate and the target is 60mm, and the sputtering power is 50W; sputtering atmosphere Ar; sputtering pressure is 1.4 Pa; the sputtering time was 50 min.
Keeping the temperature of the sputtered film in a tube furnace at 800 ℃ for 30min in air atmosphere to obtain the bismuth titanate series ferroelectric film.
Fig. 1 is an XRD pattern of the bismuth titanate-based ferroelectric thin film prepared in example 1, and it can be seen from the XRD pattern that the thin film prepared has a bismuth titanate crystal structure, and the constituent thin film is a bismuth titanate-based thin film.
Fig. 2 is a SEM image of the surface of the bismuth titanate series ferroelectric thin film prepared in example 1, and it can be seen from the SEM image that the crystal grain size of the thin film is large and the longitudinal size of lamellar crystal grains reaches 2 μm, indicating that the crystal grain size of the bismuth titanate series thin film prepared by the preparation method is significantly increased.
FIG. 3 is a graph showing the fatigue resistance test results of the ferroelectric film of bismuth titanate series prepared in example 1, from which it can be seen that the film passes 10 10 After the secondary overturning, the remanent polarization strength is almost unchanged, which shows that the bismuth titanate series film has excellent fatigue resistance.
Example 2
A process for preparing bismuth titanate series ferroelectric film with chemical general formula of Bi 3.5 La 0.5 Ti 3 O 12 According to the chemical formula, bismuth nitrate pentahydrate, lanthanum nitrate hexahydrate and tetrabutyl titanate are selected to be dissolved in ethylene glycol monomethyl ether and acetylacetone solution, wherein the bismuth nitrate pentahydrate is excessive by 3 wt%, and the specific weight is as follows; bi (NO) 3 ) 3 ·5H2O＝8.7421g，La(NO 3 ) 3 ·6H2O＝1.0825，C 16 H 36 O 14 To 5.1048g of Ti, 30mL of ethylene glycol monomethyl ether and 5mL of acetylacetone were added. After the solutions were mixed, they were stirred at 30 ℃ for 30 min.
Then, a rubber head dropper is used for taking the solution and homogenizing the solution on a homogenizing machine, the rotating speed of the homogenizing machine is 3000 r/min, and the time is 5 min. The obtained wet film is dried in an oven and then is subjected to heat treatment at 400 ℃ for 30 min. And repeating the glue homogenizing and the heat treatment process twice after the heat treatment to obtain the three-layer film. Then preserving the heat for 30min at 800 ℃ in the air atmosphere in a tube furnace.
The film obtained by the sol-gel method is used as a substrate, and Bi with 30 wt% of excessive Bi element is selected 3.5 La 0.5 Ti 3 O 12 Performing radio frequency magnetron sputtering by using ceramic as a target material, wherein the sputtering parameters are as follows: the sputtering temperature is room temperature; the distance between the substrate and the target is 60mm, and the sputtering power is 50W; sputtering atmosphere Ar; sputtering air pressure is 1.4 Pa; the sputtering time was 50 min.
Keeping the temperature of the sputtered film in a tube furnace at 800 ℃ for 30min in air atmosphere to obtain the bismuth titanate series ferroelectric film.
Example 3
A process for preparing bismuth titanate series ferroelectric film with chemical general formula of Bi 3.1 La 0.9 Ti 3 O 12 According to the chemical formula, bismuth nitrate pentahydrate, lanthanum nitrate hexahydrate and tetrabutyl titanate are selected to be dissolved in ethylene glycol monomethyl ether and acetylacetone solution, wherein the excess of anhydrous bismuth nitrate is 3 wt%, and the specific weight is as follows; bi (NO) 3 ) 3 ·5H2O＝7.7430g，La(NO 3 ) 3 ·6H2O＝1.9485，C 16 H 36 O 14 Ti＝5.1048g, 30mL of ethylene glycol monomethyl ether and 5mL of acetylacetone were added. After the solutions were mixed, they were stirred at 30 ℃ for 30 min.
Then, a rubber head dropper is used for taking the solution and homogenizing the solution on a homogenizing machine, the rotating speed of the homogenizing machine is 3000 r/min, and the time is 5 min. The obtained wet film is dried in an oven and then is subjected to heat treatment at 400 ℃ for 30 min. And repeating the glue homogenizing and the heat treatment process twice after the heat treatment to obtain the three-layer film. Then the temperature is preserved for 30min at 800 ℃ in the air atmosphere in a tube furnace.
The film obtained by the sol-gel method is used as a substrate, and Bi with 30 wt% of excessive Bi element is selected 3.75 La 0.25 Ti 3 O 12 Performing radio frequency magnetron sputtering by using ceramic as a target material, wherein the sputtering parameters are as follows: the sputtering temperature is room temperature; the distance between the substrate and the target is 60mm, and the sputtering power is 50W; sputtering atmosphere Ar; sputtering pressure is 1.4 Pa; the sputtering time was 50 min.
Keeping the temperature of the sputtered film in a tube furnace at 800 ℃ for 30min in air atmosphere to obtain the bismuth titanate series ferroelectric film.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. A preparation method of a bismuth titanate series ferroelectric film is characterized by comprising the following steps: the chemical general formula of the bismuth titanate series ferroelectric film is A x Bi 4-x B y Ti 3-y O 12 Wherein A and B are both one or two combinations of rare earth elements or/and transition metal elements, x is more than or equal to 0<1，0≤y≤0.1；
The preparation method comprises the following steps: firstly, preparing a layer of defective bismuth titanate series film by adopting a sol-gel method; then carrying out magnetron sputtering coating on the thin film layer; finally, annealing treatment is carried out to obtain the film with large crystal size, high quality, less defects and good fatigue resistance.
2. The method for producing a bismuth titanate-based ferroelectric thin film according to claim 1, characterized in that: the method comprises the following specific steps:
the method comprises the following steps: according to the chemical formula of the bismuth titanate series ferroelectric film, soluble inorganic salt or organic alkoxide of metal elements is selected to be dissolved in an organic solvent, wherein the weight of the inorganic salt or the organic alkoxide of the Bi elements is 1-20 wt% more than the theoretical weight, and then precursor solution is obtained by heating and stirring;
step two: dripping the precursor solution obtained in the step one on a substrate for spin coating to obtain a wet film;
step three: drying the wet film obtained in the step two, and performing pyrolysis treatment on the dried film at the temperature of 300-600 ℃ to remove organic matters;
step four: repeating the operation of the second step and the operation of the third step on the pyrolyzed film;
step five: heating the film processed in the fourth step at the temperature of 750-850 ℃;
step six: taking the film obtained in the fifth step as a substrate, taking bismuth titanate ceramic with excessive Bi element as a target material, and performing radio frequency magnetron sputtering film coating until the sputtered D film reaches the expected thickness; the bismuth titanate ceramic material is the same as the bismuth titanate series ferroelectric film;
step seven: and heating the film D obtained in the sixth step at the temperature of 750-850 ℃.
3. The method for preparing a bismuth titanate-based ferroelectric thin film according to claim 1, characterized in that: the heat treatment temperature in the seventh step is the same as the heat treatment temperature in the fifth step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210562469.9A CN114883480A (en) | 2022-05-23 | 2022-05-23 | Preparation method of bismuth titanate series ferroelectric film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210562469.9A CN114883480A (en) | 2022-05-23 | 2022-05-23 | Preparation method of bismuth titanate series ferroelectric film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114883480A true CN114883480A (en) | 2022-08-09 |
Family
ID=82677170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210562469.9A Pending CN114883480A (en) | 2022-05-23 | 2022-05-23 | Preparation method of bismuth titanate series ferroelectric film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114883480A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116332641A (en) * | 2023-04-07 | 2023-06-27 | 广西华锡集团股份有限公司 | Yb-Sn co-doped bismuth titanate-based ferroelectric film and preparation method thereof |
-
2022
- 2022-05-23 CN CN202210562469.9A patent/CN114883480A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116332641A (en) * | 2023-04-07 | 2023-06-27 | 广西华锡集团股份有限公司 | Yb-Sn co-doped bismuth titanate-based ferroelectric film and preparation method thereof |
| CN116332641B (en) * | 2023-04-07 | 2024-04-12 | 广西华锡集团股份有限公司 | Yb-Sn co-doped bismuth titanate-based ferroelectric film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI613725B (en) | Method for producing ferroelectric thin film | |
| TWI549183B (en) | Method for producing ferroelectric thin film | |
| US7580241B2 (en) | Thin film capacitor element composition, high permittivity insulation film, thin film capacitor element, thin film multilayer capacitor, and method of production of thin film capacitor element | |
| CN1774776A (en) | Barium stronium titanate containing multilayer structures on metal foils | |
| KR100938073B1 (en) | Thin film dielectrics with co-fired electrodes for capacitors and methods of making thereof | |
| CN108395245B (en) | High-energy-storage-density sodium bismuth titanate-based dielectric film and preparation method and application thereof | |
| CN103708828A (en) | Preparation method of bismuth sodium titanate-barium titanate lead-free composite piezoelectric thick film | |
| EP1780305A2 (en) | Dielectric film and process for its fabrication | |
| CN114883480A (en) | Preparation method of bismuth titanate series ferroelectric film | |
| JP2012015505A (en) | Manufacturing method of thin film capacitor and thin film capacitor manufactured thereby | |
| JP4912081B2 (en) | Method for forming dielectric film having ABOx type perovskite crystal structure | |
| CN114671680B (en) | Bismuth scandium-barium titanate-based core-shell structure ferroelectric film and preparation method thereof | |
| CN109036878B (en) | Ferroelectric film material device and preparation method thereof | |
| CN110643948A (en) | Strontium titanate/ruthenate strontium ferroelectric superlattice thin film material and preparation method thereof | |
| CN101654779A (en) | Preparation method of Bi3.2Nd0.8Ti3O12 ferroelectric film | |
| CN112201478B (en) | Strontium bismuth titanate/bismuth ferrite heterogeneous dielectric film and preparation method and application thereof | |
| CN101872680A (en) | Dielectric film, film capacitor and manufacture method thereof | |
| CN107346802B (en) | Piezoelectric film and method for producing same | |
| CN114914087A (en) | Sodium bismuth titanate-barium zirconate titanate dielectric film with high energy storage characteristic and preparation method and application thereof | |
| JP2007277082A (en) | Method of forming ferroelectric film by sol-gel process and method of manufacturing capacitor | |
| JP2003160313A (en) | Compound for forming metal oxide thin film, method for producing metal oxide and metal oxide thin film | |
| Paik et al. | Ba titanate and barium/strontium titanate thin films from hydroxide precursors: Preparation and ferroelectric behavior | |
| JP3561123B2 (en) | Dielectric thin film and manufacturing method thereof | |
| CN100457292C (en) | (Ba,Zr)TiO3 ferroelectric film with optimized performance and its preparing method | |
| CN110698705A (en) | Preparation method of potassium tantalate niobate/P (VDF-TrFE-CTFE) based composite dielectric material |
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 |