CN102229265B - Barium strontium titanate multilayered film, and preparation method thereof - Google Patents
Barium strontium titanate multilayered film, and preparation method thereof Download PDFInfo
- Publication number
- CN102229265B CN102229265B CN 201110109667 CN201110109667A CN102229265B CN 102229265 B CN102229265 B CN 102229265B CN 201110109667 CN201110109667 CN 201110109667 CN 201110109667 A CN201110109667 A CN 201110109667A CN 102229265 B CN102229265 B CN 102229265B
- Authority
- CN
- China
- Prior art keywords
- tio
- acetate
- barium
- substrate
- strontium
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Inorganic Insulating Materials (AREA)
- Semiconductor Memories (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a barium strontium titanate multilayered film, and a preparation method thereof. According to the invention, barium acetate, strontium acetate and tetrabutyl titanate with certain molar ratios are dissolved into an acetic acid solution, an ethylene glycol methyl ether solution and an acetylacetone solution, such that stable precursory sols with different barium-strontium ratios are prepared. Sol distribution processes and heat treatment processes are alternatively carried out upon substrates such as silicon-based platinum, until a required thickness is reached. According to the invention, the barium strontium titanate multilayered structure is prepared with a chemical solution deposition method. With the method, a film material with high tuning rate and low dielectric loss can be obtained. The film can be used in microwave tuning devices.
Description
Technical field
The present invention relates to a kind of barium strontium titanate plural layers and preparation method thereof, belong to function information material field.
Background technology
Barium strontium titanate (Ba
xSr
1-xTiO
3, BST) thin-film material is with a wide range of applications at aspects such as dynamic RAM of future generation, microwave-tuned devices owing to its superior dielectric properties.Plurality of advantages such as compare with numerous preparation methods, chemical method has good uniformity, stoichiometric proportion is controlled easily, and equipment is simple, the present preparation that has been widely used in thin-film material.In recent years, the existing report that much prepares barium strontium titanate film material about the employing chemical method, as: " Synthesis and dielectric characteristic of Ba
1-xSr
xTiO
3Thin films-based strontium-barium alkoxides derivatives ", MaterialsChemistry and Physics.69,166; " Chemical mechanical polishing ofBa
0.6Sr
0.4TiO
3Film prepared by sol-gel method ", MicroelectronicEngineering 75,149; " Chemical solution deposition of＜100 〉-orientedSrTiO
3Buffer layers on Ni substrates, Journal of Materials Research 17,1678.From the result of these bibliographical informations, majority is the barium strontium titanate (Ba that preparation has one-component
xSr
1-xTiO
3) film, because the one-component barium strontium titanate can not have low dielectric loss again usually when possessing the high tuning rate, can not satisfy application requirements.
Summary of the invention
The objective of the invention is to by a kind of barium strontium titanate multilayer film (Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2Preparation, under the situation that does not increase dielectric loss, make its dielectric constant and tuning rate owing to the Maxwell-Wagner effect improves, thereby obtain high tuning rate and low-loss bst thin film material.
The present invention adopts following technical scheme to achieve these goals:
The barium strontium titanate plural layers is characterized in that: the barium strontium titanate plural layers are at substrate Pt/Ti/SiO
2/ Si is last with Ba
0.5Sr
0.5TiO
3And Ba
0.7Sr
0.3TiO
3Sequencing prepare two cycles, constitute (Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2The multi-layer film structure of/substrate form.
The preparation method of described barium strontium titanate plural layers is characterized in that may further comprise the steps:
(1) preparation of forerunner's colloid:
A:Ba
0.5Sr
0.5TiO
3The preparation of forerunner's colloid
Adopt analytically pure barium acetate, strontium acetate and metatitanic acid fourth fat as solute, EGME and acetylacetone,2,4-pentanedione are as solvent;
Weighing: the molar ratio according to Ba: Sr is 5: 5, takes by weighing the adding of barium acetate and strontium acetate and fills in the beaker of acetic acid, dissolves fully up to barium acetate and strontium acetate 40-80 ℃ of stirring;
Measure the butyl titanate with barium acetate and strontium acetate sum equimolar amounts, add and fill in the beaker of acetylacetone,2,4-pentanedione, 40-80 ℃ was stirred 10-20 minute;
Above two kinds of solution are mixed, and 40-80 ℃ of stirring at room temperature stirred 5.5-6.5 hour after 20-40 minute again, and the spent glycol methyl ether is adjusted to the 0.1-0.5 mol with the solute concentration in the solution then, obtains stable Ba after the filtration
0.5Sr
0.5TiO
3Forerunner's colloid.
B:Ba
0.7Sr
0.3TiO
3The preparation of forerunner's colloid
Adopt analytically pure barium acetate, strontium acetate and metatitanic acid fourth fat as solute, EGME and acetylacetone,2,4-pentanedione are as solvent;
Weighing: the molar ratio according to Ba: Sr is 7: 3, takes by weighing the adding of barium acetate and strontium acetate and fills in the beaker of acetic acid, dissolves fully up to barium acetate and strontium acetate 40-80 ℃ of stirring;
Measure the butyl titanate with barium acetate and strontium acetate sum equimolar amounts, add and fill in the beaker of acetylacetone,2,4-pentanedione, 40-80 ℃ was stirred 10-20 minute;
Above two kinds of solution are mixed, and 40-80 ℃ of stirring at room temperature stirred 5.5-6.5 hour after 20-40 minute again, and the spent glycol methyl ether is adjusted to the 0.1-0.5 mol with the solute concentration in the solution then, obtains stable Ba after the filtration
0.7Sr
0.3TiO
3Forerunner's colloid.
(2) whirl coating and pyrolytic process: with Ba
0.5Sr
0.5TiO
3Forerunner's colloid drips on the substrate, with sol evenning machine solution is evenly thrown away, form gel at substrate, whirl coating speed is changeed for per minute 3000-6000, the whirl coating time is 20-60 second, and then substrate and gel mould are put into annealing furnace carry out pyrolysis processing, 200 ℃-400 ℃ of pyrolysis temperatures, time 10-40 minute;
(3) heat treatment crystallization process: the film of above-mentioned pyrolysis is inserted in the tubular type annealing furnace, be warmed up to 650 ℃-900 ℃, annealed 30-120 minute, in annealing process, the aerating oxygen atmosphere obtains the Ba of crystallization at last
0.5Sr
0.5TiO
3/ substrate membrane;
(4) multilayer film forms: with the Ba of above-mentioned crystallization
0.5Sr
0.5TiO
3Film drips Ba on its surface
0.7Sr
0.3TiO
3Forerunner's colloid repeats above-mentioned whirl coating and Technology for Heating Processing, obtains Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3/ substrate the bilayer film, (Ba that alternately repeats to obtain two cycles like this again
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2/ substrate multilayer film.
The preparation method of barium strontium titanate plural layers, the consumption that it is characterized in that described acetic acid, acetylacetone,2,4-pentanedione is indefinite, only need solute wherein dissolves fully and gets final product.Substrate is Pt/Ti/SiO
2/ Si substrate.
Beneficial effect of the present invention:
1, multilayer film preparation method of the present invention, making apparatus and technology are simple, and cost of manufacture is low, is applicable to the preparation of large tracts of land film, is conducive to commercial the application.
2, multilayer film preparation method of the present invention has obtained the good barium strontium titanate of dielectric properties, with Ba
0.5Sr
0.5TiO
3And Ba
0.7Sr
0.3TiO
3The one pack system film is compared, dielectric constant and the tuning rate of multilayer film are bigger, and the dielectric loss of multilayer film is lower than monofilm, thereby multilayer film has more superior performance, is adapted at the application of aspects such as microwave-tuned device, dynamic RAM of future generation.
Description of drawings:
Fig. 1 is the x-ray diffraction pattern of barium strontium titanate, (a) is Ba
0.5Sr
0.5TiO
3, (b) be Ba
0.7Sr
0.3TiO
3, (c) be (Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2Multilayer film.As can be seen from the figure, multilayer film and monofilm have all formed perovskite structure, and do not have dephasign to generate.
Fig. 2 is field emission scanning electron microscope (FE-SEM) photo of barium strontium titanate, (a) is Ba
0.5Sr
0.5TiO
3, (b) be Ba
0.7Sr
0.3TiO
3, (c) be (Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2Multilayer film.As can be seen from the figure multi-layer film surface is very fine and close, does not have hole.
Fig. 3 (a) is the dielectric constant of three kinds of films and the relation of frequency, BST0.5 wherein, and BST0.7 and BST0.7/0.5 represent Ba respectively
0.5Sr
0.5TiO
3, Ba
0.7Sr
0.3TiO
3(Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2Thin-film material, (b) be the dielectric loss of three kinds of films with the variation relation of frequency, be that the dielectric constant of three kinds of films is with the relation of applying bias (c).As can be seen from the figure, multilayer film has bigger dielectric constant and tuning rate and lower dielectric loss than monofilm.
The specific embodiment
Barium strontium titanate (Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2The chemical solution deposition preparation of multilayer film:
At first used vessel are cleaned, the beaker that will use, dropper, syringe, measuring cup, glass bar were with rare nitric acid dousing of 15% 24 hours, wash with running water again, deionized water rinsing repeatedly, use alcohol wash then, cleaned vessel are standby after 2 hours in baking under 50 ℃ the condition.
1.Ba
0.5Sr
0.5TiO
3The preparation of forerunner's colloid
Adopt analytically pure barium acetate, strontium acetate and butyl titanate as solute, EGME and acetylacetone,2,4-pentanedione are as solvent;
(1) strontium acetate of the barium acetate of 0.0015 mole of weighing and 0.0015 mole adds in the beaker of the acetic acid that fills 5 milliliters, dissolves fully up to barium acetate and strontium acetate 70 ℃ of stirrings;
(2) the weighing butyl titanate is 0.003 mole, adds to fill in the beaker of 5 milliliters of acetylacetone,2,4-pentanediones, and 70 ℃ were stirred 15 minutes;
(3) above two kinds of solution are mixed, 70 ℃ are stirred after 30 minutes and at room temperature stirred 6 hours again, and spent glycol methyl ether volumetric soiutions to 10 milliliter obtains stable Ba after the filtration
0.5Sr
0.5TiO
3Forerunner's colloid.
2.Ba
0.7Sr
0.3TiO
3The preparation of forerunner's colloid
(1) strontium acetate of the barium acetate of 0.0021 mole of weighing and 0.0009 mole adds in the beaker of the acetic acid that fills 5 milliliters, dissolves fully up to barium acetate and strontium acetate 70 ℃ of stirrings;
(2) the weighing butyl titanate is 0.003 mole, adds to fill in the beaker of 5 milliliters of acetylacetone,2,4-pentanediones, and 70 ℃ were stirred 15 minutes;
(3) above two kinds of solution are mixed, 70 ℃ are stirred after 30 minutes and at room temperature stirred 6 hours again, and spent glycol methyl ether volumetric soiutions to 10 milliliter obtains stable Ba after the filtration
0.7Sr
0.3TiO
3Colloid.
3. (Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2The preparation of multilayer film:
With the Ba for preparing
0.5Sr
0.5TiO
3Colloid drips to substrate Pt/Ti/SiO
2On/the Si, with sol evenning machine it is evenly thrown away, whirl coating speed is 4000 rev/mins again, and the time is 30 seconds; Again substrate and gel mould are put into annealing furnace and heat-treat, 400 ℃ of dryings, pyrolysis 30 minutes, be warmed up to 700 ℃ of annealing 60 minutes down then, in annealing process, atmosphere is oxygen.Drip Ba at this film afterwards
0.7Sr
0.3TiO
3Colloid with same whirl coating and Technology for Heating Processing, has so just obtained the duplicature of one-period.And then prepare Ba in the above successively
0.5Sr
0.5TiO
3And Ba
0.7Sr
0.3TiO
3Film can obtain to have (the Ba in two cycles
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2Multilayer film.
4. material is identified:
(1) X-ray diffractometer the analysis showed that: barium strontium titanate multilayer film and monofilm all have complete perovskite structure, do not have second to exist mutually.
(2) scanning electron microscope test shows: multi-layer film surface is fine and close, does not have hole.
(3) to thin-film dielectric performance test shows: the dielectric constant of multilayer film and tuning rate all are higher than monofilm, and the dielectric loss of multilayer film is lower.
(the Ba of method for preparing
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2Multilayer film has superior dielectric properties, thereby can be applied in microwave-tuned device.In addition, the preparation method of above-mentioned barium strontium titanate multilayer film not only is used for Pt/Ti/SiO
2/ Si substrate can be used for other various substrates, as substrates such as single crystalline Si, sapphires.
Claims (2)
1. barium strontium titanate plural layers, it is characterized in that: the barium strontium titanate plural layers are at substrate Pt/Ti/SiO
2/ Si is last with Ba
0.5Sr
0.5TiO
3And Ba
0.7Sr
0.3TiO
3Sequencing prepare two cycles, constitute (Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2The multi-layer film structure of/substrate form;
The preparation method of described barium strontium titanate plural layers may further comprise the steps:
(1) preparation of forerunner's colloid:
A:Ba
0.5Sr
0.5TiO
3The preparation of forerunner's colloid
Adopt analytically pure barium acetate, strontium acetate and metatitanic acid fourth fat as solute, EGME and acetylacetone,2,4-pentanedione are as solvent;
Weighing: the molar ratio according to Ba:Sr is 5:5, takes by weighing the adding of barium acetate and strontium acetate and fills in the beaker of acetic acid, dissolves fully up to barium acetate and strontium acetate 40-80 ℃ of stirring;
Measure the butyl titanate with barium acetate and strontium acetate sum equimolar amounts, add and fill in the beaker of acetylacetone,2,4-pentanedione, 40-80 ℃ was stirred 10-20 minute;
Above two kinds of solution are mixed, and 40-80 ℃ of stirring at room temperature stirred 5.5-6.5 hour after 20-40 minute again, and the spent glycol methyl ether is adjusted to 0.1-0.5 mol with the solute concentration in the solution then, obtains stable Ba after the filtration
0.5Sr
0.5TiO
3Forerunner's colloid;
B:Ba
0.7Sr
0.3TiO
3The preparation of forerunner's colloid
Adopt analytically pure barium acetate, strontium acetate and metatitanic acid fourth fat as solute, EGME and acetylacetone,2,4-pentanedione are as solvent;
Weighing: the molar ratio according to Ba:Sr is 7:3, takes by weighing the adding of barium acetate and strontium acetate and fills in the beaker of acetic acid, dissolves fully up to barium acetate and strontium acetate 40-80 ℃ of stirring;
Measure the butyl titanate with barium acetate and strontium acetate sum equimolar amounts, add and fill in the beaker of acetylacetone,2,4-pentanedione, 40-80 ℃ was stirred 10-20 minute;
Above two kinds of solution are mixed, and 40-80 ℃ of stirring at room temperature stirred 5.5-6.5 hour after 20-40 minute again, and the spent glycol methyl ether is adjusted to 0.1-0.5 mol with the solute concentration in the solution then, obtains stable Ba after the filtration
0.7Sr
0.3TiO
3Forerunner's colloid;
(2) whirl coating and pyrolytic process: with Ba
0.5Sr
0.5TiO
3Forerunner's colloid drips on the substrate, with sol evenning machine solution is evenly thrown away, form gel at substrate, whirl coating speed is that per minute 3000-6000 changes, the whirl coating time is 20-60 second, and then substrate and gel mould are put into annealing furnace carry out pyrolysis processing, 200 ℃-400 ℃ of pyrolysis temperatures, time 10-40 minute;
(3) heat treatment crystallization process: the film of above-mentioned pyrolysis is inserted in the tubular type annealing furnace, be warmed up to 650 ℃-900 ℃, annealed 30-120 minutes, in annealing process, atmosphere is oxygen, obtains the Ba of crystallization at last
0.5Sr
0.5TiO
3/ substrate membrane;
(4) multilayer film forms: with the Ba of above-mentioned crystallization
0.5Sr
0.5TiO
3Film drips Ba on its surface
0.7Sr
0.3TiO
3Forerunner's colloid repeats above-mentioned whirl coating and Technology for Heating Processing, obtains Ba
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3/ substrate the bilayer film, (Ba that alternately repeats to obtain two cycles like this again
0.7Sr
0.3TiO
3/ Ba
0.5Sr
0.5TiO
3)
2/ substrate multilayer film.
2. barium strontium titanate plural layers according to claim 1, the consumption that it is characterized in that described acetic acid, acetylacetone,2,4-pentanedione is indefinite, only needs wherein a solute to dissolve fully and gets final product, substrate is Pt/Ti/SiO
2/ Si substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110109667 CN102229265B (en) | 2011-04-29 | 2011-04-29 | Barium strontium titanate multilayered film, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110109667 CN102229265B (en) | 2011-04-29 | 2011-04-29 | Barium strontium titanate multilayered film, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102229265A CN102229265A (en) | 2011-11-02 |
| CN102229265B true CN102229265B (en) | 2013-09-25 |
Family
ID=44841890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110109667 Expired - Fee Related CN102229265B (en) | 2011-04-29 | 2011-04-29 | Barium strontium titanate multilayered film, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102229265B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104029432B (en) * | 2014-06-26 | 2016-02-24 | 天津大学 | The preparation method of BST/BMN/BST multi-layer compound film |
| CN112259374A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | BST-based multilayer dielectric enhanced film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6660414B1 (en) * | 1999-04-26 | 2003-12-09 | U.S. Department Of Energy | Tungsten-doped thin film materials |
| CN1718561A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院合肥物质科学研究院 | Barium strontium titanate film material and preparation method |
| CN101060231A (en) * | 2007-03-29 | 2007-10-24 | 中国科学院上海技术物理研究所 | BST Fabry-Perot micro-cavity and manufacture method |
| CN101074491A (en) * | 2007-03-29 | 2007-11-21 | 上海大学 | Method for growing barium strontium titanate on metal titanium-based substrate |
| CN101863154A (en) * | 2010-06-17 | 2010-10-20 | 天津大学 | Multilayer gradient Ba1-xSrxTiO3 (BST) dielectric ceramic material and preparation method |
-
2011
- 2011-04-29 CN CN 201110109667 patent/CN102229265B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6660414B1 (en) * | 1999-04-26 | 2003-12-09 | U.S. Department Of Energy | Tungsten-doped thin film materials |
| CN1718561A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院合肥物质科学研究院 | Barium strontium titanate film material and preparation method |
| CN101060231A (en) * | 2007-03-29 | 2007-10-24 | 中国科学院上海技术物理研究所 | BST Fabry-Perot micro-cavity and manufacture method |
| CN101074491A (en) * | 2007-03-29 | 2007-11-21 | 上海大学 | Method for growing barium strontium titanate on metal titanium-based substrate |
| CN101863154A (en) * | 2010-06-17 | 2010-10-20 | 天津大学 | Multilayer gradient Ba1-xSrxTiO3 (BST) dielectric ceramic material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102229265A (en) | 2011-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103360062B (en) | Ferroelectric thin film forms the forming method with sol-gel liquid and ferroelectric thin film | |
| CN101885606A (en) | Method for preparing piezoelectric-ferroelectric thin film | |
| CN101333107B (en) | Process for preparing niobium-doped strontium titanate film | |
| JP6887770B2 (en) | Method of forming PZT ferroelectric film | |
| JP5208758B2 (en) | Coating film manufacturing process based on oxide ceramics adapted to the shape of the substrate with relief characteristics | |
| JP5896586B2 (en) | Method for manufacturing a piezoelectric material | |
| CN103360107A (en) | Gold-lanthanum nickelate composite conductive thin-film material and preparation method for same | |
| CN102229265B (en) | Barium strontium titanate multilayered film, and preparation method thereof | |
| CN103979617B (en) | LaNiO3Film-forming composition and the LaNiO using said composition3The forming method of film | |
| CN102320670A (en) | Method for prepararing lanthanum nickelate conductive metal oxide film material | |
| CN103695872A (en) | Preparation method of low dielectric-loss CaCu3Ti4O12 film | |
| JP4603254B2 (en) | Method for producing metal oxide sol liquid, crystalline metal double oxide sol and metal oxide film | |
| CN106191821A (en) | The preparation method of lanthanum-strontium-cobalt-oxygen conductive film material | |
| CN102515763B (en) | Preparation method for perovskite structural ceramic sol | |
| CN1196807C (en) | Wet chemical prepn process of leadless functional barium titanate ceramic film | |
| KR100408517B1 (en) | Manufacturing method for ferroelectric thin film using sol-gel process | |
| CN101388434B (en) | Preparation of silicium/strontium lanthanum cobaltocyanate/lead zirconate titanate three layer construction ferroelectric material | |
| JP2001026421A (en) | Formation of crystalline thin film by sol/gel method | |
| Liu et al. | Thick layer deposition of lead perovskites using diol-based chemical solution approach | |
| CN107540402A (en) | A kind of preparation method of porous calcium copper titanate film | |
| CN104030680B (en) | The preparation method of barium strontium titanate medium film | |
| CN102061460B (en) | Nanometer Ag particle-(Ba0.65, Sr0.35)TiO3 seepage-type composite ceramic film and preparation method thereof | |
| CN112201478A (en) | High-energy-storage-density strontium bismuth titanate/bismuth ferrite heterogeneous dielectric film and preparation method and application thereof | |
| CN100457292C (en) | (Ba,Zr)TiO3 ferroelectric film with optimized performance and its preparing method | |
| CN1693281A (en) | Process for preparing quantum para electric EuTiO3 film by sol-gel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130925 Termination date: 20150429 |
|
| EXPY | Termination of patent right or utility model |