CN1103328C - Preparation of strontium-barium titanate film material - Google Patents

Preparation of strontium-barium titanate film material Download PDF

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CN1103328C
CN1103328C CN00115347A CN00115347A CN1103328C CN 1103328 C CN1103328 C CN 1103328C CN 00115347 A CN00115347 A CN 00115347A CN 00115347 A CN00115347 A CN 00115347A CN 1103328 C CN1103328 C CN 1103328C
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preparation
strontium
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CN1267653A (en
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程建功
褚君浩
唐军
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Shanghai Institute of Technical Physics of CAS
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Abstract

The present invention provides a preparation method for a strontium barium titanate film material. The preparation method comprises the following processes: barium acetate, strontium acetate, butyl titanate, acetic acid and acetylacetone are mixed according to a certain molar ratio for being prepared into a stable precursor solution; then, the precursor solution is uniformly interspersed on a Pt/Ti/SiO2/Si base sheet through a spin coater, and the heat processing of the precursor solution is carried out; in the process of heat processing, an auxiliary electric field is simultaneously applied to a film, and the process is repeated until ideal thickness is realized. In the method of the present invention, heterogeneous nucleation and isoepitaxial growth are realized through the control of the thickness of each gel film processed through the heat processing to 8 to 20 nanometers, and therefore, the large size film material with columnar grains is formed. The film material of the present invention is suitable for the aspects, such as a dynamic random access memory, a room temperature infrared focal plane array, etc., to use.

Description

The preparation method of barium strontium titanate film material
The present invention relates to the preparation method of barium strontium titanate film material, belong to function information material and devices field.
Strontium-barium titanate (Ba xSr 1-xTiO 3) specific inductivity very high, its Curie temperature can be regulated between 30～400K by changing component, its thin-film material is being with a wide range of applications aspect development dynamic RAM of future generation and the room temperature infrared focal plane array.Compare with numerous preparation methods, sol-gel method has plurality of advantages such as good uniformity, stoichiometric ratio are controlled easily, equipment is simple, has been widely used in the preparation of thin-film material.In recent years, existing much about adopting sol-gel method to prepare barium titanate (BaTiO 3), strontium-barium titanate (Ba xSr 1-xTiO 3) bibliographical information of thin-film material, as: " Preparation and Characterization ofBa xSr 1-xTiO 3Thin Films by a Sol-Gel Technique ", J.Am.Ceram.Soc.79,1593-98 (1996); " In-Situ Transmission Electron Microscopy Crystallization Studies of Sol-Gel-Derived Barium Titanate Thin Films ", J.Am.Ceram.Soc.80,2828-36 (1997); " Microstructure of Columnar-Grained SrTiO 3And BaTiO 3Thin Films Prepared byChemical Solution Deposition ", J.Mater.Res.13,2206-17 (1998); " Control ofMicrostructure and Orientation in Solution-Deposited BaTiO 3And SrTiO 3ThinFilms ", J.Am.Ceram.Soc.82,2359-67 (1999).From the result of these bibliographical informations, have only when X=0 be BaTiO 3With X=1 be SrTiO 3The time, grown have columnar grain, grain-size 100 nanometers to 200 nanometers thin-film material, but when 0＜x＜1, the Ba of growth xSr 1-xTiO 3Film still is made of spheric grain, and its grain-size is generally less than 70 nanometers, the Ba that is made of this crystal grain xSr 1-xTiO 3Film, its dielectric properties and ferroelectric properties are still relatively poor, can not satisfy the application requiring aspect development dynamic RAM of future generation and room temperature infrared focal plane array.
The object of the present invention is to provide a kind of stable precursor solution, prepare have columnar grain, grain-size is at the Ba of 100～200 nanometers xSr 1-xTiO 3(0＜x＜1) thin-film material satisfies at the application requiring of development aspect dynamic RAM of future generation, room temperature infrared detector and the room temperature infrared focal plane array it.
For achieving the above object, sol-gel processing is adopted in the preparation of thin-film material of the present invention, and its process is as follows:
1. stable precursor solution preparation:
According to X:(1-X), 0＜x＜1, mol ratio takes by weighing barium acetate ((CH 3COO) 2Ba), strontium acetate ((CH 3COO) 2Sr), put into acetic acid together, heating is also stirred, and dissolves fully until barium acetate, strontium acetate; Measure and ((CH 3COO) 2Ba+ (CH 3COO) 2Sr) methyl ethyl diketone of equimolar amount adds in the acetum of barium acetate, strontium acetate, stirs to make it to mix; Measure and ((CH 3COO) 2Ba+ (CH 3COO) 2Sr) the metatitanic acid fourth fat of equimolar amount joins in the mixing solutions for preparing above, stirs, and with concentration adjustment to 0.05～0.1 mol of acetic acid with solution, places 5～10 days then, makes it abundant chelating, promptly obtains stable precursor solution.
2. the preparation of thin-film material:
Adopt Pt/Ti/SiO 2/ Si makes substrate, film forming adopts the rotation lacquering technique, precursor solution is dripped on the substrate surface, with sol evenning machine solution is evenly thrown away again, whirl coating speed is 3000～7000 rev/mins, the gel-film that the even glue of spin coating is formed is put into annealing furnace with substrate and is heat-treated then, 250～300 ℃ of dryings, pyrolysis 5～30 minutes, then 600～750 ℃ of annealing 5～30 minutes down; In annealing process, simultaneously film is applied 2～4kv/cm auxiliary electric field, the gauge control after every layer of gel-film thermal treatment in 8～20 nanometers, is repeated above spin coating, heat treatment process, till ideal thickness, be generally 300～800 nanometers.
The present invention has added methyl ethyl diketone in the precursor solution process for preparation, make the precursor solution of preparation more stable.
The present invention passes through the gauge control after every layer of gel-film thermal treatment to realize Ba between 8～20 nanometers xSr 1-xTiO 3Heterogeneous nucleation, isoepitaxial growth, form columnar grain, reduce the crystallization temperature of film.
The present invention is at Ba xSr 1-xTiO 3Apply the auxiliary electric field of 2～4KV/cm in the annealing process, film forms the cubic phase perovskite structure of (001) preferred orientation easily in crystallization process like this.
The present invention has following beneficial effect:
1. thin-film material preparation method of the present invention, making equipment is simple, and cost of manufacture is lower, helps commercial applications.
2. thin-film material preparation method of the present invention has solved the gordian technique such as preparation, individual layer gel-film gauge control, thermal treatment, electric field auxiliary annealing of stable precursor solution, makes the Ba of preparation xSr 1-xTiO 3, characteristics such as (0＜x＜1) thin-film material has the large size column crystal grain of 100～200 nanometers, and physicals is good make it have boundless application prospect aspect development dynamic RAM, room temperature infrared detector and the room temperature infrared focal plane array.
Description of drawings of the present invention is as follows:
Fig. 1 is Ba 0.8Sr 0.2TiO 3The electron scanning micrograph of film (a) is surface topography, (b) is cross-section morphology.This film grain-size is between 100～200 nanometers, and grain shape is a column.
Fig. 2 is Ba 0.8Sr 0.2TiO 3The ferroelectric hysteresis loop of film.The residual polarization of film is 3.5 μ C/cm 2, coercive electric field is 53KV/cm, shows good ferroelectric.
Fig. 3 is Ba 0.8Sr 0.2TiO 3The pyroelectric coefficient of film is with the variation of temperature curve.Between 10～100 ℃, the pyroelectric coefficient of film is greater than 1.5 * 10 -4C/m 2K, this film is suitable for the application of pyroelectric detector and infrared focal plane array aspect.
Embodiment 1.
Ba xSr 1-xTiO 3(x=0.8) preparation of ferroelectric thin-flim materials:
At first used vessel are cleaned: the flask that will use, beaker, weighing bottle, still tube, transfer pipet, syringe soaked 24 hours with chloroazotic acid, used deionized water rinsing again 10 times, and cleaned vessel are standby after 5 hours in baking under 80 ℃ the condition.
1. precursor solution preparation:
Adopt analytically pure barium acetate ((CH 3COO) 2Ba), strontium acetate ((CH 3COO) 2Sr) and butyl (tetra) titanate ((C 4H 9) O 4Ti) make raw material, acetic acid is made solvent, methyl ethyl diketone (CH 3COCH 2COCH 3) used as stabilizers.
(a). weighing: take by weighing 0.008 mole of (2.0436 gram) barium acetate, 0.002 mole of (0.4294 gram) strontium acetate is put into 20 milliliters of acetic acid, is heated to 90 ℃, under this temperature, stir and dissolve fully until barium acetate, strontium acetate;
(b). measure 0.01 mole of methyl ethyl diketone (1 milliliter), inject the acetum of barium acetate, strontium acetate, stirred 30 minutes, make it to mix, being distilled to strength of solution then is 0.5 mol;
(c). measure 0.01 mole of butyl (tetra) titanate (3.5 milliliters), the solution that injection prepares above stirred 30 minutes;
(d). add an amount of acetic acid and be diluted to 0.1～0.05 mol, stirred 30～120 minutes, make it to mix;
(e). placed 5～10 days, and made it abundant chelating, promptly obtain stable precursor solution.
2. the preparation of thin-film material:
1). substrate is handled:
(a). use Pt/Ti/SiO 2/ Si makes substrate, cleans substrate surface repeatedly gently with the acetone cotton balls, to remove the organism on surface;
(b). the substrate that will clean is put into NH 4OH: H 2O 2: H 2O in 1: 4: 20 the mixing solutions, is heated to 60 ℃, cleans 5 minutes in ultrasonic cleaning tank, further removes organism;
(c). the substrate of top cleaning is put into HCl: H again 2O 2: H 2O in 1: 1: 20 the mixing solutions, is heated to 60 ℃, cleans 5 minutes deionizing, atomic impurity in ultrasonic cleaning tank;
(d). use a large amount of deionized water rinsings, till substrate surface is no longer hung the globule;
(e). infrared dry for standby.
2). the film spin coating:
Film forming adopts the even glue method of rotation whirl coating, and precursor solution is dripped on the substrate surface, with sol evenning machine it is evenly thrown away again, and whirl coating speed is 5000 rev/mins, 40 seconds time; Then gel-film and substrate being put into annealing furnace together heat-treats, 250 ℃ of dryings, pyrolysis 5 minutes, annealed 10 minutes down at 700 ℃ then, in annealing process, apply the auxiliary electric field of 4KV/cm, repeat above spin coating, heat treatment process till ideal thickness 300 nanometers; The film that with thickness is 300 nanometers is at last put into annealing furnace, anneals 5 minutes down at 750 ℃, has promptly made the ferroelectric thin-flim materials that can be used for room temperature infrared detector and room temperature infrared focal plane array.
3. material is identified:
1) structure and microstructure characterize:
(a) the .X diffraction analysis shows: the Ba of preparation xSr 1-xTiO 3(x=0.8) film is the polycrystal film of pure perovskite structure, is cubic phase under the room temperature.
(b). scanning electron microscope test shows: the Ba of preparation xSr 1-xTiO 3(x=0.8) the film grain-size between 100 to 200 nanometers, grain shape is column.See accompanying drawing 1.
2) electric property characterizes:
(a). the Ba of preparation xSr 1-xTiO 3(x=0.8) residual polarization that presents under the film room temperature is 3.5 μ C/cm 2, coercive electric field is 53KV/cm, shows good ferroelectric character.Ferroelectric hysteresis loop is seen accompanying drawing 2.
(b). the Ba of preparation xSr 1-xTiO 3(x=0.8) pyroelectric coefficient of film between 10～100 ℃ is greater than 1.5 * 10 -4C/m 2K.Pyroelectric coefficient is seen accompanying drawing 3 with the variation of temperature curve.
(c). the Ba of preparation xSr 1-xTiO 3(x=0.8) film is under the electric field of 100KV/cm, and the leakage current of film is less than 1 * 10 -7A/cm 2
The Ba of preparation xSr 1-xTiO 3(x=0.8) film is applicable to the application of room temperature infrared focus plane aspect.
Embodiment 2.
Ba xSr 1-xTiO 3(x=0.65) preparation of dielectric film material:
Preparation process is identical with embodiment 1, the Ba that makes xSr 1-xTiO 3(x=0.65) thin-film material relative permittivity ε after tested r＞600, under the electric field of 100kv/cm, film leakage current less than 1 * 10 -7A/cm 2, be applicable to the application of dynamic RAM aspect.

Claims (4)

1. strontium-barium titanate (Ba xSr 1-xTiO 3) preparation method of thin-film material, it is characterized in that this preparation method in turn includes the following steps:
(1). precursor solution preparation: according to X:(1-X), 0＜x＜1, mol ratio takes by weighing barium acetate ((CH 3COO) 2Ba), strontium acetate ((CH 3COO) 2Sr), put into acetic acid together, heating is also stirred, and dissolves fully until barium acetate, strontium acetate; Measure and ((CH 3COO) 2Ba+ (CH 3COO) 2Sr) methyl ethyl diketone of equimolar amount adds in the acetum of barium acetate, strontium acetate, stirs to make it to mix; Measure and ((CH 3COO) 2Ba+ (CH 3COO) 2Sr) the metatitanic acid fourth fat of equimolar amount joins in the mixing solutions for preparing above, stirs, and with concentration adjustment to 0.05～0.1 mol of acetic acid with solution, places 5～10 days then, makes it abundant chelating, promptly obtains stable precursor solution;
(2). the preparation of thin-film material: precursor solution is dropped on the substrate, with sol evenning machine solution is evenly thrown away, form gel-film, whirl coating speed is that per minute 3000 forwards 7000 commentaries on classics to, again substrate and gel-film being put into annealing furnace heat-treats, 250～300 ℃ of dryings, pyrolysis 5～30 minutes, annealed 5～30 minutes down at 600～750 ℃ then, in annealing process, apply the auxiliary electric field of 2～4kV/cm, gauge control after every layer of even glued membrane thermal treatment in 8～20 nanometers, is repeated above spin coating, heat treatment process is till film thickness is 300 to 800 nanometers.
2. strontium-barium titanate (Ba according to claim 1 xSr 1-xTiO 3) preparation method of thin-film material, it is characterized in that: described X span scope is 0.7＜x＜0.9, is applicable to the room temperature infrared focal plane array.
3. strontium-barium titanate (Ba according to claim 1 xSr 1-xTiO 3) preparation method of thin-film material, it is characterized in that: described X span scope is 0.5＜x≤0.7, is applicable to dynamic RAM.
4. strontium-barium titanate (Ba according to claim 1 xSr 1-xTiO 3) preparation method of thin-film material, it is characterized in that described substrate is Pt/Ti/SiO 2/ Si.
CN00115347A 2000-04-06 2000-04-06 Preparation of strontium-barium titanate film material Expired - Fee Related CN1103328C (en)

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CN100344575C (en) * 2004-08-13 2007-10-24 中国科学院上海硅酸盐研究所 Low temperature sitering and prparing method for lithium blended strontium-barium titanate ceramics
GB0423343D0 (en) * 2004-10-21 2004-11-24 Koninkl Philips Electronics Nv Metal-oxide-semiconductor device
CN100401109C (en) * 2005-03-18 2008-07-09 中国科学院上海技术物理研究所 Strontium-barium titanate reflective membrane and process for preparing same
CN1880253B (en) * 2005-06-16 2010-11-03 同济大学 Thick film material and its ferroelectric(Ba,Sr)TiO3 microcrystalline glass ceramic
CN100347131C (en) * 2005-09-07 2007-11-07 哈尔滨工业大学 Ferroelectric film alternating electric field heat treatment method
CN100385263C (en) * 2006-05-26 2008-04-30 中国科学院上海技术物理研究所 Strontium barium titanate Bragg mirror and its preparing method
CN101074491B (en) * 2007-03-29 2011-05-04 上海大学 Method for growing barium strontium titanate on metal titanium-based substrate
CN100456420C (en) * 2007-05-17 2009-01-28 上海交通大学 Manufacture method of (110) orientation ferroelectric thin film on Si baseplate
CN101168488B (en) * 2007-11-16 2010-06-02 华中科技大学 Method for preparing column-shape neodymium-doping bismuth titanate ferroelectric thin film used for ferroelectric memory
CN101307497B (en) * 2008-01-23 2010-10-06 同济大学 Composite ferro-electric thin film for microwave adjustable device and method for making same
CN108545771B (en) * 2018-07-03 2020-06-16 电子科技大学 Preparation method of barium strontium titanate aerogel
CN111554568A (en) * 2020-05-19 2020-08-18 湘潭大学 Preparation method of hafnium oxide based ferroelectric film

Citations (3)

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JPH01260870A (en) * 1988-04-12 1989-10-18 Toray Ind Inc Formation of thin film of modified lead zirconate titanate
US5001110A (en) * 1987-05-29 1991-03-19 Toray Industries, Inc. Organometallic solutions for forming oxide superconducting films
CN1194445A (en) * 1997-03-21 1998-09-30 中国科学院上海硅酸盐研究所 Process of preparing strontium-barium titanate film by using water as solvent for precursor solution

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5001110A (en) * 1987-05-29 1991-03-19 Toray Industries, Inc. Organometallic solutions for forming oxide superconducting films
JPH01260870A (en) * 1988-04-12 1989-10-18 Toray Ind Inc Formation of thin film of modified lead zirconate titanate
CN1194445A (en) * 1997-03-21 1998-09-30 中国科学院上海硅酸盐研究所 Process of preparing strontium-barium titanate film by using water as solvent for precursor solution

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