CN105977374B - A kind of barium calcium zirconate titanate film and its preparation method and application with seed layer - Google Patents
A kind of barium calcium zirconate titanate film and its preparation method and application with seed layer Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010408 film Substances 0.000 claims abstract description 86
- 239000002243 precursor Substances 0.000 claims abstract description 67
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000011575 calcium Substances 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 230000005621 ferroelectricity Effects 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 44
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 63
- 238000000034 method Methods 0.000 description 33
- 239000010936 titanium Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 230000008859 change Effects 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 230000005684 electric field Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 208000037656 Respiratory Sounds Diseases 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BNUACWDJFAPHCF-UHFFFAOYSA-F [Ca+2].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Zr+4].[Ba+2].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-] Chemical compound [Ca+2].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Zr+4].[Ba+2].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-] BNUACWDJFAPHCF-UHFFFAOYSA-F 0.000 description 1
- 230000036626 alertness Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- YIMPFANPVKETMG-UHFFFAOYSA-N barium zirconium Chemical compound [Zr].[Ba] YIMPFANPVKETMG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 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 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- H10N30/8536—Alkaline earth metal based oxides, e.g. barium titanates
-
- 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
- H10N30/097—Forming inorganic materials by sintering
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Formation Of Insulating Films (AREA)
Abstract
The invention belongs to functional materials and devices field, and in particular to a kind of barium calcium zirconate titanate film and preparation method thereof with seed layer.The barium calcium zirconate titanate film includes substrate layer, seed layer and film layer, and for the seed layer between the substrate layer and film layer, the chemical general formula of the seed layer and film layer is Ba(1‑x)CaxTi(1‑y)ZryO3, wherein x=0.01~0.16, y=0.02~0.12.The preparation method prepares seed layer using low concentration precursor solution, then barium calcium zirconate titanate film is prepared with high concentration precursor solution again, it solves the problems, such as to crack in barium calcium zirconate titanate membrane-film preparation process, improve piezoelectricity and dielectricity without thin film lead, and low cost and controllable, the barium calcium zirconate titanate film flatness height obtained with seed layer, uniformity is good, flawless, quality is high, it is made to obtain practical application in MEMS, ferroelectricity storage system or multifunctional unit device.
Description
Technical field
The invention belongs to functional materials and devices field, and in particular to a kind of barium calcium zirconate titanate film with seed layer and
Preparation method and application.
Background technique
Piezoelectricity ferro material the detection of information, conversion, processing, display and in terms of have a wide range of applications, be
Important high-tech functional material, but account for piezoelectric material leading position at present is still lead base piezoelectricity that lead content is up to 70%
Material lead zirconate titanate (PZT).Plumbum-based material causes seriously ecological environment and human health in preparation, use and waste procedures
Therefore harm develops leadless piezoelectric ferroelectric material, is one of the urgent task for being related to China's electronic technology sustainable development.
In the nineties in last century, demand with the development and people of micro-processing technology to precision micro-displacement device, electricity is adjustable, and alertness is answered
Becoming material becomes a hot spot of microelectric technique investigation of materials.In recent years, to the demand day of piezoelectric film material and device
Benefit increases, and lead-free piezoelectric thin film research is particularly important.Barium zirconium phthalate calcium material is rectified since its is lower since two thousand nine
Stupid field and high piezoelectric property and be concerned, people's numerous studies structure and performance of its block materials.But zirconium titanium
The research of sour barium calcium thin-film material really rarely has information, the main reason is that due to thermal mismatching and crystalline substance between the system film and substrate
Lattice mismatch and there are biggish internal stress so that cracking phenomena occurs during the preparation process for film, it is difficult to which preparation structure is excellent
Good thin-film material.
The preparation method and technical process of film have highly important influence to its structure and performance, suitable by selecting
Preparation method and optimization technical process obtain component uniformly, crystallization completely, fine and close and low roughness aimed thin film always
It is a main contents of thin-film material research.However, since the selection of method for manufacturing thin film and technical process is formed a film again
The restriction of substance, therefore, although the preparation method of film have been relatively mature, there are many method it is available, by lead base
Material is volatile and the influence of the factors such as toxicity, and there are mainly three types of methods to be reported for preparing piezoelectric membrane at present, is respectively:
Sol-gel method (Sol-Gel), sputtering method (sputtering) and pulsed laser deposition (PLD), wherein sol-gel method
It is that hydrolysis occurs in a solvent using solute, forms colloid, is then coated in substrate surface again, is handled down through certain temperature
Film forming, the advantages of this method is: (1) being able to achieve the accurate control of film chemical component, be easy to carry out ion doping；(2) it is easy to
Large area film forming；(3) equipment is simple, low in cost；(4) good with semiconductor technology compatibility.But this method also has it
Body is difficult to the shortcomings that overcoming, as poor repeatability, it is easy to crack, be not suitable for preparing the film that thickness is greater than 1 μm.But due to this method
Cheap cost and the control of accurate component, are the common preparation methods of current film, are used to the piezoelectricity of synthesis different component
Film, and the aimed thin film of basic flawless has been obtained by choosing technical process appropriate.For barium calcium zirconate titanate system
For film, the piezoelectric membrane of high quality how is prepared by improving sol-gel technology, improves piezoelectric property with very heavy
The social value and economic significance wanted.
Summary of the invention
The purpose of the present invention is overcoming deficiency in the prior art, a kind of barium calcium zirconate titanate film with seed layer is provided
And its preparation method and application, the preparation method solves the problems, such as to crack in barium calcium zirconate titanate membrane-film preparation process, improves
Piezoelectricity and dielectricity without thin film lead, and low cost, with controllably, the barium calcium zirconate titanate film obtained with seed layer is smooth
Degree is high, and uniformity is good, flawless, and quality is high, it is made to obtain practical application in multifunctional unit device.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of barium calcium zirconate titanate film, institute
Stating barium calcium zirconate titanate film includes substrate layer, seed layer and film layer, the seed layer between the substrate layer and film layer,
The seed layer and the chemical general formula of film layer are Ba(1-x)CaxTi(1-y)ZryO3, wherein x=0.01~0.16, such as 0.01~
0.08,0.08~0.10 or 0.10~0.16, y=0.02~0.12, such as 0.02~0.05,0.05~0.10 or 0.10~
0.12。
Preferably, the substrate layer is Pt/Ti/SiO2/ Si substrate, single crystal Si substrate, monocrystalline SrTiO3Substrate or monocrystalline
LaAlO3Substrate.
Preferably, the seed layer with a thickness of 8~40nm, such as 8~20nm, 20~30nm or 30~40nm are described thin
Film layer with a thickness of 150~600nm, such as 150~360nm or 360~600nm.
Second aspect of the present invention provides a kind of preparation method of above-mentioned barium calcium zirconate titanate film, includes the following steps:
A) weigh raw material by the stoichiometric ratio of element in above-mentioned chemical general formula: compound containing Ba, contains Ti at compound containing Ca
Raw material is dissolved in acetic acid and ethylene glycol ethyl ether or acetic acid and ethylene glycol monomethyl ether, is with acetylacetone,2,4-pentanedione by compound and compound containing Zr
Complexing agent prepares precursor solution one and precursor solution two, and the concentration of the precursor solution one is 0.05~0.15M, such as
0.05~0.1M or 0.1~0.15M, the concentration of the precursor solution two are 0.2~0.4M, such as 0.2~0.3M or 0.3~
0.4M；
B) precursor solution one described in rotary coating on substrate, is then heat-treated；
C) number that step b) is repeated according to the thickness selection of seed layer, obtains the substrate of seed layer；
D) substrate for obtaining step c) precursor solution two described in rotary coating on seed layer, then carries out hot place
Reason；
E) number that step d) is repeated according to the thickness selection of film layer, then anneals, obtains the barium zirconium phthalate
Calcium film.
The concentration of the precursor solution one and precursor solution two refers to chemical general formula Ba(1-x)CaxTi(1-y)
ZryO3The molar concentration of meter.
The compound containing Ba is barium acetate or barium nitrate.
The compound containing Ca is calcium acetate or calcium nitrate.
The compound containing Ti is isopropyl titanate or butyl titanate.
The compound containing Zr is propyl alcohol zirconium or zirconium iso-propoxide.
Preferably, the ratio of the mole of the mole and chemical general formula of acetylacetone,2,4-pentanedione is 1:1~1:2, such as 1:1~1:
1.5 or 1:1.5~1:2.
Preferably, ethylene glycol ethyl ether accounts for the 30~40% of precursor solution volume, and such as 30~35% or 35~40%.Second two
What alcohol ether accounted for precursor solution volume 30~40% refers to: ethylene glycol ethyl ether accounts for the 30~40% of one volume of precursor solution,
Ethylene glycol ethyl ether accounts for the 30~40% of two volume of precursor solution.
Preferably, acetic acid accounts for the 50~60% of precursor solution volume, and such as 50~55% or 55~60%.Acetic acid accounts for forerunner
The 50~60% of liquid solution volume refer to: acetic acid accounts for the 50~60% of one volume of precursor solution, and acetic acid accounts for precursor solution two
The 50~60% of volume.
The concentration of precursor solution one and precursor solution two can be controlled separately the thickness of seed layer and film, such as
Two single layer of precursor solution of precursor solution one the single layer 10nm, 0.2M of precursor solution one the single layer 8nm, 0.1M of 0.05M
The two single layer 60nm of precursor solution of 30nm, 0.3M are revolved according to the number of plies of the thickness control rejection film of required seed layer and film
Turn the number of coating.
Preferably, in step b), the condition of rotary coating: revolving speed is 2000~3000 revolutions per seconds, such as 2000~2500 turns/
Second or 2500~3000 revolutions per seconds, the time be 20~30 seconds, such as 20~25 seconds or 25~30 seconds.
Preferably, in step b), the condition of heat treatment: successively being handled 2~3 minutes for 100~200 DEG C, and such as 100~150 DEG C
Or 150~200 DEG C, 300~400 DEG C are handled 2~5 minutes, and such as 300~350 DEG C or 350~400 DEG C；2~3 minutes or 3~5 points
Clock, 600~700 DEG C are handled 5~10 minutes, and such as 600~650 DEG C or 650~700 DEG C, 5~8 minutes or 8~10 minutes.It is described
Heat treatment process can be carried out all in tube furnace, reduce operating procedure and instrument cost.
Preferably, in step b), on substrate before rotary coating, first the substrate is pre-processed.
It is furthermore preferred that the pretreated condition: 600~700 DEG C pre-process 10~20 minutes, such as 600~650 DEG C or
650~700 DEG C, 10~15 minutes or 15~20 minutes.
Preferably, in step d), the condition of rotary coating: revolving speed is 2000~3000 revolutions per seconds, such as 2000~2500 turns/
Second or 2500~3000 revolutions per seconds, the time be 20~30 seconds, such as 20~25 seconds or 25~30 seconds.
Preferably, in step d), the condition of heat treatment: successively being handled 2~5 minutes at 100~200 DEG C, and such as 100~150
DEG C or 150~200 DEG C；2~3 minutes or 3~5 minutes, 400~500 DEG C were handled 5~10 minutes, such as 400~450 DEG C or 450~
500℃.The heat treatment can carry out in tube furnace.
Preferably, in step e), the condition of annealing: 700~750 DEG C are annealed 20~50 minutes, such as 700~720 DEG C or 720
~750 DEG C, 20~30 minutes, 30~40 minutes or 40~50 minutes.
Third aspect present invention provides a kind of application of above-mentioned barium calcium zirconate titanate film, is applied to MEMS, ferroelectricity
Storage system or multifunctional unit device, such as: micro-displacement device, sonic transducer, ferroelectric memory etc..
Beneficial effects of the present invention: using sol-gel method, molten by using low concentration (0.05~0.15M) presoma
Liquid prepares the seed layer of 8~40 nano thickness, then prepares 150~600nm with high concentration (0.2~0.4) precursor solution again
The barium calcium zirconate titanate film of thickness, film and buffer layer homogeneity, isomorphism, film is uniform, densification, does not crack, and strain reaches 0.45nm,
Piezoelectric constant significantly reduces low-frequency dielectric and is lost up to 64pm/V, and minimum 0.023.The preparation method solves zirconium titanium
The problem of cracking in sour barium calcium membrane-film preparation process improves piezoelectricity and dielectricity without thin film lead, and low cost and controllable, system
The barium calcium zirconate titanate film flatness with seed layer obtained is high, and uniformity is good, flawless, and quality is high, makes it in micro-electro-mechanical systems
It unites, obtains practical application in ferroelectricity storage system and multifunctional unit device.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the barium calcium zirconate titanate piezoelectric film of the different seed layer thickness of 1 to 4 gained of embodiment.
Fig. 2 is the barium calcium zirconate titanate piezoelectric film electric field induced strain of the different seed layer thickness of 1 to 4 gained of embodiment with outer power-up
Field change curve.
Fig. 3 is the barium calcium zirconate titanate piezoelectric thin-film dielectric constant and dielectric damage of the different seed layer thickness of 1 to 4 gained of embodiment
Consumption is with frequency variation curve figure.
Specific embodiment
The present invention is further explained combined with specific embodiments below, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device；All pressure values and range all refer to relative pressure, and the raw material used is also conventional use of raw material in the art.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relationship between one or more equipment/device mentioned in the present invention is not repelled
The two equipment/devices specifically mentioned before and after the unit equipment/device there may also be other equipment/device or at these it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Identify the convenient tool of various method steps, rather than for the arrangement order of limitation various method steps or limits the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
Embodiment 1:
In Pt/Ti/SiO2After preparing 8 nanometers of seed layers on/Si substrate, barium calcium zirconate titanate piezoelectric film is prepared.
A) Ba is pressed0.92Ca0.08Ti0.95Zr0.05O3The stoichiometric ratio of middle element weighs raw material: barium acetate, calcium acetate, isopropyl
Alcohol titanium and propyl alcohol zirconium, are dissolved in acetic acid and ethylene glycol ethyl ether for raw material, are that complexing agent prepares one He of precursor solution with acetylacetone,2,4-pentanedione
Precursor solution two, the concentration of the precursor solution one are 0.05M, and the concentration of the precursor solution two is 0.2M, acetic acid
The 60% of precursor solution volume is accounted for, ethylene glycol ethyl ether accounts for 30%, Ba of precursor solution volume0.92Ca0.08Ti0.95Zr0.05O3
Molar ratio with acetylacetone,2,4-pentanedione is 1:1；After standing 24 hours, for preparing barium calcium zirconate titanate seed layer and film layer；
B) by Pt/Ti/SiO2/ Si substrate pre-processes 10 minutes at 600 DEG C, and the precursor solution one of 0.05M is rotated and is applied
Overlay on Pt/Ti/SiO2On/Si substrate, revolving speed is 2000 revolutions per seconds, and the time is 30 seconds；By coated gel successively in tube furnace
In 200 DEG C handle 2 minutes, 300 DEG C handle 2 minutes, 600 DEG C handle 10 minutes, obtain 8 nanometer thickness seed layer；
C) on seed layer rotary coating 0.2M precursor solution two, revolving speed be 2000 revolutions per seconds, the time be 30 seconds；It will
Coated gel successively in tube furnace 200 DEG C handle 3 minutes, 400 DEG C handle 10 minutes；
D) step c) i.e. coating and heat treatment process 4 times are repeated, is finally annealed 20 minutes at 700 DEG C, is finally obtained 150 and receive
The thick film layer of rice.
Gold electrode is sputtered in film surface using the method for d.c. sputtering, diameter is 0.5 millimeter, with a thickness of 80 nanometers, is surveyed
Try electrical property.
(a) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric film on 8 nanometers of seed layers in Fig. 1, and crystal grain is about
100 nanometers, of uniform size, without crackle, (a) gives the strain of barium calcium zirconate titanate piezoelectric film on 8 nanometers of seed layers in Fig. 2
With voltage change curve, electric field induces deformation quantity up to 0.4 nanometer, and piezoelectric constant reaches 39pm/V.Fig. 3 (a) gives 8 nanometers of seed crystals
The dielectric constant of barium calcium zirconate titanate piezoelectric film and dielectric loss change with frequency on layer, and low-frequency dielectric loss is 0.112.Implement
Example 2:
After preparing 20 nanometers of seed layers on single crystal Si substrate, barium calcium zirconate titanate piezoelectric film is prepared.
A) Ba is pressed0.99Ca0.01Ti0.98Zr0.02O3The stoichiometric ratio of middle element weighs raw material: barium nitrate, calcium nitrate, metatitanic acid
Raw material is dissolved in acetic acid and ethylene glycol ethyl ether by four butyl esters and zirconium iso-propoxide, is that complexing agent prepares precursor solution with acetylacetone,2,4-pentanedione
One and precursor solution two, the concentration of the precursor solution one is 0.1M, and the concentration of the precursor solution two is 0.3M, second
Acid accounts for the 55% of precursor solution volume, and ethylene glycol ethyl ether accounts for the 40% of precursor solution volume,
Ba0.99Ca0.01Ti0.98Zr0.02O3Molar ratio with acetylacetone,2,4-pentanedione is 1:1.5；After standing 24 hours, for preparing barium calcium zirconate titanate
Seed layer and film layer；
B) single crystal Si substrate is pre-processed 15 minutes at 650 DEG C, by one rotary coating of precursor solution of 0.1M in monocrystalline
On Si substrate, revolving speed is 2500 revolutions per seconds, and the time is 25 seconds；Successively 150 DEG C of 2 points of processing in tube furnace by coated gel
Clock, 350 DEG C are handled 3 minutes, and 650 DEG C are handled 5 minutes；
C) it repeats step b) once, obtains the seed layer of 20 nanometer thickness；
D) on seed layer rotary coating 0.3M precursor solution two, revolving speed be 2500 revolutions per seconds, the time be 20 seconds, will
Coated gel successively in tube furnace 150 DEG C handle 5 minutes, 450 DEG C handle 5 minutes；
E) step d) is repeated to coat and heat treatment process five times；It finally anneals 30 minutes at 720 DEG C, obtains 360 nanometers
Thick film layer.
Using the method for d.c. sputtering in film surface sputtering electrode, diameter 0.2 is millimeter, with a thickness of 80 nanometers, test
Electrical property.
(b) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric film on 20 nanometers of seed layers in Fig. 1, and crystal grain is about
100 nanometers, of uniform size, without crackle, (b) gives answering for barium calcium zirconate titanate piezoelectric film on 20 nanometers of seed layers in Fig. 2
Become with voltage change curve, electric field induces deformation quantity up to 0.45 nanometer, and piezoelectric constant reaches 64pm/V.Fig. 3 (b) gives 20 nanometers
The dielectric constant of barium calcium zirconate titanate piezoelectric film and dielectric loss change with frequency on seed layer, and low-frequency dielectric loss is 0.052.
Embodiment 3:
In monocrystalline SrTiO3After preparing 30 nanometers of seed layers on substrate, barium calcium zirconate titanate piezoelectric film is prepared.
A) Ba is pressed0.84Ca0.16Ti0.90Zr0.10O3The stoichiometric ratio of middle element weighs raw material: barium acetate, calcium acetate, isopropyl
Alcohol titanium and propyl alcohol zirconium, are dissolved in acetic acid and ethylene glycol monomethyl ether for raw material, are that complexing agent prepares one He of precursor solution with acetylacetone,2,4-pentanedione
Precursor solution two, the concentration of the precursor solution one are 0.15M, and the concentration of the precursor solution two is 0.3M, acetic acid
The 60% of precursor solution volume is accounted for, ethylene glycol monomethyl ether accounts for 35%, Ba of precursor solution volume0.84Ca0.16Ti0.90Zr0.10O3
Molar ratio with acetylacetone,2,4-pentanedione is 1:2；After standing 24 hours, for preparing barium calcium zirconate titanate seed layer and film layer；
B) by monocrystalline SrTiO3Substrate pre-processes 20 minutes at 700 DEG C, by the precursor solution rotary coating of 0.15M in list
Brilliant SrTiO3On substrate, revolving speed is 3000 revolutions per seconds, and the time is 20 seconds；By coated gel successively in tube furnace at 200 DEG C
Reason 2 minutes, 400 DEG C are handled 5 minutes, and 700 DEG C are handled 8 minutes.
C) it repeats step b) 1 time, obtains the seed layer of 30 nanometer thickness；
D) on seed layer rotary coating 0.3M precursor solution, revolving speed be 3000 revolutions per seconds, the time be 20 seconds.It will apply
The gel covered successively in tube furnace 100 DEG C handle 3 minutes, 400 DEG C handle 10 minutes.
E) step d) i.e. coating and heat treatment process five times are repeated, are finally annealed 40 minutes at 700 DEG C, obtain 360 nanometers
The film layer of thickness.
Using the method for d.c. sputtering in film surface sputtering electrode, diameter 0.2 is millimeter, with a thickness of 80 nanometers, test
Electrical property.
(c) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric film on 30 nanometers of seed layers in Fig. 1, and crystal grain is about
100 nanometers, of uniform size, without crackle, (c) gives answering for barium calcium zirconate titanate piezoelectric film on 30 nanometers of seed layers in Fig. 2
Become with voltage change curve, electric field induces deformation quantity up to 0.42 nanometer, and piezoelectric constant reaches 61pm/V.Fig. 3 (c) gives 30 nanometers
The dielectric constant of barium calcium zirconate titanate piezoelectric film and dielectric loss change with frequency on seed layer, and low-frequency dielectric loss is 0.030.
Embodiment 4:
In single crystal La AlO3After preparing 40 nanometers of seed layers on substrate, barium calcium zirconate titanate piezoelectric film is prepared.
A) Ba is pressed0.90Ca0.10Ti0.88Zr0.12O3The stoichiometric ratio of middle element weighs raw material: barium acetate, calcium acetate, isopropyl
Alcohol titanium and propyl alcohol zirconium, are dissolved in acetic acid and ethylene glycol monomethyl ether for raw material, are that complexing agent prepares one He of precursor solution with acetylacetone,2,4-pentanedione
Precursor solution two, the concentration of the precursor solution one are 0.05M, and the concentration of the precursor solution two is 0.4M, acetic acid
The 50% of precursor solution volume is accounted for, ethylene glycol monomethyl ether accounts for 30%, Ba of precursor solution volume0.90Ca0.10Ti0.88Zr0.12O3
Molar ratio with acetylacetone,2,4-pentanedione is 1:2；After standing 24 hours, for preparing barium calcium zirconate titanate seed layer and film layer；
B) by single crystal La AlO3Substrate pre-processes 10 minutes at 700 DEG C.One rotary coating of precursor solution of 0.05M is existed
Single crystal La AlO3On substrate, revolving speed is 3000 revolutions per seconds, and the time is 20 seconds.By coated gel successively 100 DEG C in tube furnace
Processing 3 minutes, 300 DEG C are handled 3 minutes, and 700 DEG C are handled 10 minutes.
C) it repeats step b) 4 times, obtains the seed layer of 40 nanometer thickness.
D) on seed layer rotary coating 0.4M precursor solution two, revolving speed be 3000 revolutions per seconds, the time be 20 seconds.It will
Coated gel successively in tube furnace 200 DEG C handle 2 minutes, 500 DEG C handle 10 minutes.
E) step d) i.e. coating and heat treatment process five times are repeated, are finally annealed 50 minutes at 750 DEG C, obtain 600 nanometers
The film layer of thickness.
Using the method for d.c. sputtering in film surface sputtering electrode, diameter 0.2 is millimeter, with a thickness of 80 nanometers, test
Electrical property.
(d) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric film on 40 nanometers of seed layers in Fig. 1, and crystal grain is about
100 nanometers, of uniform size, without crackle, (d) gives answering for barium calcium zirconate titanate piezoelectric film on 40 nanometers of seed layers in Fig. 2
Become with voltage change curve, electric field induces deformation quantity up to 0.4 nanometer, and piezoelectric constant reaches 44pm/V.Fig. 3 (d) gives 40 nanometers
The dielectric constant of barium calcium zirconate titanate piezoelectric film and dielectric loss change with frequency on seed layer, and low-frequency dielectric loss is 0.023.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (8)
1. a kind of barium calcium zirconate titanate film, which is characterized in that the barium calcium zirconate titanate film includes substrate layer, seed layer and film
Layer, for the seed layer between the substrate layer and film layer, the chemical general formula of the seed layer and film layer is Ba(1-x)
CaxTi(1-y)ZryO3, wherein x=0.01~0.16, y=0.02~0.12, the seed layer with a thickness of 8~40nm, it is described thin
Film layer with a thickness of 150~600nm, the barium calcium zirconate titanate film passes through the preparation method included the following steps and obtains:
A) weigh raw material by the stoichiometric ratio of element in chemical general formula: compound containing Ba, compound containing Ca, compound containing Ti and
Raw material is dissolved in acetic acid and ethylene glycol ethyl ether or acetic acid and ethylene glycol monomethyl ether by compound containing Zr, is that complexing agent is matched with acetylacetone,2,4-pentanedione
Precursor solution one and precursor solution two processed, the concentration of the precursor solution one are 0.05~0.15M, the presoma
The concentration of solution two is 0.2~0.4M；
B) precursor solution one described in rotary coating on substrate, is then heat-treated；
C) number that step b) is repeated according to the thickness selection of seed layer, obtains the substrate of seed layer；
D) substrate for obtaining step c) precursor solution two described in rotary coating on seed layer, is then heat-treated；
E) number that step d) is repeated according to the thickness selection of film layer, then anneals, it is thin to obtain the barium calcium zirconate titanate
Film；
In step b), the condition of heat treatment: successively being handled 2~3 minutes for 100~200 DEG C, and 300~400 DEG C are handled 2~5 minutes,
600~700 DEG C are handled 5~10 minutes；
In step d), the condition of heat treatment: successively handled at 100~200 DEG C 2~5 minutes, 400~500 DEG C handle 5~10 points
Clock；
In step e), the condition of annealing: 700~750 DEG C are annealed 20~50 minutes.
2. barium calcium zirconate titanate film as described in claim 1, which is characterized in that the substrate layer is Pt/Ti/SiO2/ Si lining
Bottom, single crystal Si substrate, monocrystalline SrTiO3Substrate or single crystal La AlO3Substrate.
3. a kind of preparation method of barium calcium zirconate titanate film as claimed in claim 1 or 2, which is characterized in that including walking as follows
It is rapid:
A) stoichiometric ratio of element weighs raw material in chemical general formula according to claim 1: compound containing Ba, chemical combination containing Ca
Raw material is dissolved in acetic acid and ethylene glycol ethyl ether or acetic acid and ethylene glycol monomethyl ether, uses acetyl by object, compound containing Ti and compound containing Zr
Acetone is that complexing agent prepares precursor solution one and precursor solution two, the concentration of the precursor solution one is 0.05~
0.15M, the concentration of the precursor solution two are 0.2~0.4M；
B) precursor solution one described in rotary coating on substrate, is then heat-treated；
C) number that step b) is repeated according to the thickness selection of seed layer, obtains the substrate of seed layer；
D) substrate for obtaining step c) precursor solution two described in rotary coating on seed layer, is then heat-treated；
E) number that step d) is repeated according to the thickness selection of film layer, then anneals, it is thin to obtain the barium calcium zirconate titanate
Film；
In step b), the condition of heat treatment: successively being handled 2~3 minutes for 100~200 DEG C, and 300~400 DEG C are handled 2~5 minutes,
600~700 DEG C are handled 5~10 minutes；
In step d), the condition of heat treatment: successively handled at 100~200 DEG C 2~5 minutes, 400~500 DEG C handle 5~10 points
Clock；
In step e), the condition of annealing: 700~750 DEG C are annealed 20~50 minutes.
4. preparation method according to claim 3, which is characterized in that in step b), the condition of rotary coating: revolving speed is
2000~3000 revolutions per seconds, the time is 20~30 seconds.
5. preparation method according to claim 3, which is characterized in that in step b), on substrate before rotary coating, first
The substrate is pre-processed.
6. preparation method according to claim 5, which is characterized in that the pretreated condition: 600~700 DEG C of pre- places
Reason 10~20 minutes.
7. preparation method according to claim 3, which is characterized in that in step d), the condition of rotary coating: revolving speed is
2000~3000 revolutions per seconds, the time is 20~30 seconds.
8. a kind of as the described in any item barium calcium zirconate titanate films of claim 1 to 2 are applied to MEMS, ferroelectricity storage system
System or multifunctional unit devices field.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102503409A (en) * | 2011-11-02 | 2012-06-20 | 聊城大学 | Tin calcium barium titanate lead-free piezoelectric ceramic and preparation technology thereof |
| CN103145413A (en) * | 2013-03-21 | 2013-06-12 | 聊城大学 | Tin barium titanate calcium leadless piezoelectric ceramic and preparation technology thereof |
| CN103922735A (en) * | 2014-04-17 | 2014-07-16 | 哈尔滨理工大学 | Preparation method of low-temperature crystalized BZT-BCT piezoelectric film |
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| CN102503409A (en) * | 2011-11-02 | 2012-06-20 | 聊城大学 | Tin calcium barium titanate lead-free piezoelectric ceramic and preparation technology thereof |
| CN103145413A (en) * | 2013-03-21 | 2013-06-12 | 聊城大学 | Tin barium titanate calcium leadless piezoelectric ceramic and preparation technology thereof |
| CN103922735A (en) * | 2014-04-17 | 2014-07-16 | 哈尔滨理工大学 | Preparation method of low-temperature crystalized BZT-BCT piezoelectric film |
Non-Patent Citations (1)
| Title |
|---|
| Piezoelectric properties of bilayer ferroelectric thin films based on (1-x)[Ba(Zr0.2Ti0.8)O3] –x(Ba0.7Ca0.3TiO3;Yemei Han等;《Materials Letters》;20160422;第177卷(第15期);ABSTRACT，2 Experimental procedure部分 |
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