CN105977374A - Barium calcium zirconate titanate film with seed crystal layer and preparation method and application thereof - Google Patents
Barium calcium zirconate titanate film with seed crystal layer and preparation method and application thereof Download PDFInfo
- Publication number
- CN105977374A CN105977374A CN201610293378.4A CN201610293378A CN105977374A CN 105977374 A CN105977374 A CN 105977374A CN 201610293378 A CN201610293378 A CN 201610293378A CN 105977374 A CN105977374 A CN 105977374A
- Authority
- CN
- China
- Prior art keywords
- zirconate titanate
- crystal layer
- calcium zirconate
- substrate
- thin film
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 67
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 60
- 239000010409 thin film Substances 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 5
- 238000000137 annealing Methods 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
- 230000005621 ferroelectricity Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 62
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 49
- 239000010936 titanium Substances 0.000 description 16
- 230000008859 change Effects 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 7
- 230000005684 electric field Effects 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 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
- 229910052791 calcium Inorganic materials 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
- 230000005611 electricity Effects 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- RQIHICWHMWNVSA-UHFFFAOYSA-N propan-1-ol;zirconium Chemical compound [Zr].CCCO RQIHICWHMWNVSA-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- LMCBEWMQFKWHGU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O LMCBEWMQFKWHGU-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- YIMPFANPVKETMG-UHFFFAOYSA-N barium zirconium Chemical compound [Zr].[Ba] YIMPFANPVKETMG-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 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
- 235000009566 rice Nutrition 0.000 description 2
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 230000036626 alertness Effects 0.000 description 1
- 230000009286 beneficial effect 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
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 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
- 230000006872 improvement Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 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 the field of function material and devices, and specifically relates to a barium calcium zirconate titanate film with a seed crystal layer and the preparation method and application thereof. The barium calcium zirconate titanate film comprises a substrate layer, the seed crystal layer and a thin film layer, wherein the seed crystal layer is arranged between the substrate layer and the thin film layer, and the general chemical formula of the seed crystal layer and the thin film layer is Ba<(1 x)>Ca<x>Ti<(1 y)>Zr<y>O<3>, with x=0.01-0.16,y=0.02-0.12. The preparation method includes that a low-density precursor solution is used to prepare the seed crystal layer, and a high-density precursor solution is then used to prepare the barium calcium zirconate titanate film. The problem of cracking during preparing the barium calcium zirconate titanate film can be solved, the piezo-electricity and dielectricity of lead-free film are improved, and the cost is low and controllable. The barium calcium zirconate titanate film has the advantages of high flatness, good uniformity, no cracks and high quality, and can be actually applied in micro-electro-mechanical systems, ferroelectric storage systems or multifunctional integrated components.
Description
Technical field
The invention belongs to functional material and devices field, be specifically related to a kind of barium calcium zirconate titanate thin film with inculating crystal layer and system thereof
Preparation Method and application.
Background technology
Piezoelectricity ferro material information detection, change, process, show and the aspect such as storage has a wide range of applications, be weight
The high-tech functional material wanted, but the lead content that remains accounting for piezoelectric leading position at present is up to the lead base piezoresistive material of 70%
Material lead zirconate titanate (PZT).Ecological environment and human health are caused serious danger in preparation, use and waste procedures by plumbum-based material
Evil, therefore, develops leadless piezoelectric ferroelectric material, is one of urgent task being related to China's electronic technology sustainable development.
In the nineties in last century, along with development and people's demand to precision micro-displacement device of micro-processing technology, electric adjustable alertness should
Become material and become a focus of microelectric technique investigation of materials.In recent years, the demand day to piezoelectric film material Yu device
Benefit increases, and lead-free piezoelectric thin film research is particularly important.Barium zirconium phthalate calcium material is since two thousand nine due to its relatively low rectifying
Stupid field and high piezoelectric property and receive much concern, the structure of its block materials of people's numerous studies and performance.But, zirconium
The research of barium titanate calcium thin-film material really rarely has information, its main cause be between this system thin film and substrate due to thermal mismatching and
Lattice mismatch and there is bigger internal stress, so that thin film occurs cracking phenomena in preparation process, it is difficult to preparation structure
Excellent thin-film material.
The preparation method of thin film and technical process have highly important impact to its structure and performance, by selecting suitably system
The technical process of Preparation Method and optimization obtain component uniformly, crystallization completely, fine and close and low roughness aimed thin film be thin all the time
One main contents of membrane material research.But, owing to the selection of method for manufacturing thin film and technical process is again by film forming matter
Restriction, therefore, although the preparation method of thin film is the most ripe, has multiple method available, but by lead base material
Expect the impact of the factors such as volatile and toxicity, currently mainly have three kinds of methods to be in the news for preparing piezoelectric membrane, respectively:
Sol-gel process (Sol-Gel), sputtering method (sputtering) and pulsed laser deposition (PLD), wherein sol-gel process is to utilize
There is hydrolysis in a solvent in solute, forms colloid, be coated in substrate surface the most again, processes lower film forming through uniform temperature,
The advantage of the method is: (1) can realize the accurate control of film chemical component, it is easy to carries out ion doping；(2) it is prone to big
Area film forming；(3) equipment is simple, with low cost；(4) good with semiconductor technology compatibility.But this method also has it
Itself be difficult to the shortcoming overcome, as poor repeatability, easy to crack, be not suitable for preparing the thickness thin film more than 1 μm.But due to this
Cost and accurate component that the method for kind is cheap control, and are the preparation methoies that current thin film is conventional, are used to synthesize different component
Piezoelectric membrane, and obtained the most flawless aimed thin film by choosing suitable technical process.For barium calcium zirconate titanate
For the thin film of system, how to prepare high-quality piezoelectric membrane by improvement sol-gel technology, improve piezoelectric property and have
Very important social value and economic implications.
Summary of the invention
It is an object of the invention to overcome deficiency of the prior art, it is provided that a kind of barium calcium zirconate titanate thin film with inculating crystal layer and
Preparation method and application, described preparation method solves the problem of cracking in barium calcium zirconate titanate membrane-film preparation process, improves unleaded
The piezoelectricity of thin film and dielectricity, and low cost and controlled, the barium calcium zirconate titanate thin film flatness with inculating crystal layer prepared is high,
Uniformity is good, flawless, and quality is high so that it is obtain actual application in multifunctional unit device.
For achieving the above object and other relevant purposes, first aspect present invention provides a kind of barium calcium zirconate titanate thin film, described zirconium
Barium titanate calcium thin film includes substrate layer, inculating crystal layer and thin layer, described inculating crystal layer between described substrate layer and thin layer, institute
The chemical general formula stating inculating crystal layer and thin layer is 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, described substrate layer is Pt/Ti/SiO2/ Si substrate, single crystal Si substrate, monocrystalline SrTiO3Substrate or single crystal La AlO3
Substrate.
Preferably, the thickness of described inculating crystal layer is 8～40nm, such as 8～20nm, 20～30nm or 30～40nm, described
The thickness of thin layer is 150～600nm, such as 150～360nm or 360～600nm.
Second aspect present invention provides the preparation method of a kind of above-mentioned barium calcium zirconate titanate thin film, comprises the steps:
A) raw material is weighed by the stoichiometric proportion of element in above-mentioned chemical general formula: containing Ba compound, containing Ca compound, containing Ti
Compound and the compound Han Zr, be dissolved in acetic acid and ethylene glycol or acetic acid and ethylene glycol monomethyl ether by raw material, with acetylacetone,2,4-pentanedione is
Chelating agent preparation precursor solution one and precursor solution two, the concentration of described precursor solution one is 0.05～0.15M, as
0.05～0.1M or 0.1～0.15M, the concentration of described precursor solution two is 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, then carries out heat treatment；
C) select to repeat the number of times of step b) according to the thickness of inculating crystal layer, obtain the substrate of inculating crystal layer；
D) substrate obtained by step c) precursor solution two described in rotary coating on inculating crystal layer, then carries out heat treatment；
E) select to repeat the number of times of step d) according to the thickness of thin layer, then anneal, obtain described barium calcium zirconate titanate thin film.
Described precursor solution one and precursor solution two concentration refer to chemical general formula Ba(1-x)CaxTi(1-y)ZryO3Meter
Molar concentration.
Described is Barium acetate or barium nitrate containing Ba compound.
Described is calcium acetate or calcium nitrate containing Ca compound.
Described is isopropyl titanate or butyl titanate containing Ti compound.
Described is propanol zirconium or zirconium iso-propoxide containing Zr compound.
Preferably, the mole of acetylacetone,2,4-pentanedione is 1:1～1:2 with the ratio of the mole of chemical general formula, such as 1:1～1:
1.5 or 1:1.5～1:2.
Preferably, ethylene glycol accounts for the 30～40% of precursor solution volume, such as 30～35% or 35～40%.Ethylene glycol
What ether accounted for precursor solution volume 30～40% refers to: ethylene glycol accounts for the 30～40% of precursor solution one volume, second
Glycol ether accounts for the 30～40% of precursor solution two volume.
Preferably, acetic acid accounts for the 50～60% of precursor solution volume, such as 50～55% or 55～60%.Acetic acid accounts for presoma
The 50 of liquor capacity～60% refer to: acetic acid accounts for the 50～60% of precursor solution one volume, and acetic acid accounts for precursor solution disome
Long-pending 50～60%.
The concentration of precursor solution one and precursor solution two can control the thickness of inculating crystal layer and thin film, such as 0.05M respectively
Precursor solution two monolayer of precursor solution one monolayer 10nm, 0.2M of precursor solution one monolayer 8nm, 0.1M
The precursor solution two monolayer 60nm of 30nm, 0.3M, according to the number of plies of the THICKNESS CONTROL rejection film of required inculating crystal layer and thin film,
The i.e. number of times of rotary coating.
Preferably, in step b), the condition of rotary coating: rotating speed is 2000～3000 revolutions per seconds, as 2000～2500 turns/
Second or 2500～3000 revolutions per seconds, the time was 20～30 seconds, such as 20～25 seconds or 25～30 seconds.
Preferably, in step b), the condition of heat treatment: 100～200 DEG C process 2～3 minutes, such as 100～150 DEG C successively
Or 150～200 DEG C, 300～400 DEG C process 2～5 minutes, such as 300～350 DEG C or 350～400 DEG C；2～3 minutes or 3～
5 minutes, 600～700 DEG C processed 5～10 minutes, such as 600～650 DEG C or 650～700 DEG C, and 5～8 minutes or 8～10 points
Clock.Described Technology for Heating Processing can all be carried out in tube furnace, decreases operating procedure and instrument cost.
Preferably, in step b), on substrate before rotary coating, first described substrate is carried out pretreatment.
It is furthermore preferred that the condition of described pretreatment: 600～700 DEG C of pretreatment 10～20 minutes, 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: rotating speed is 2000～3000 revolutions per seconds, as 2000～2500 turns/
Second or 2500～3000 revolutions per seconds, the time was 20～30 seconds, such as 20～25 seconds or 25～30 seconds.
Preferably, in step d), the condition of heat treatment: process 2～5 minutes at 100～200 DEG C successively, such as 100～150 DEG C
Or 150～200 DEG C；2～3 minutes or 3～5 minutes, 400～500 DEG C process 5～10 minutes, as 400～450 DEG C or 450～
500℃.Described heat treatment can be carried out in tube furnace.
Preferably, in step e), the condition of annealing: 700～750 DEG C anneal 20～50 minutes, 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 the application of a kind of above-mentioned barium calcium zirconate titanate thin film, is applied to MEMS, and ferroelectricity stores
System or multifunctional unit device, such as: micrometric displacement device, sonic transducer, ferroelectric memory etc..
Beneficial effects of the present invention: use sol-gel process, by using low concentration (0.05～0.15M) precursor solution system
The inculating crystal layer of standby 8～40 nano thickness, prepares 150～600nm thickness with high concentration (0.2～0.4) precursor solution the most again
Barium calcium zirconate titanate thin film, thin film and cushion homogeneity, isomorphism, thin film uniformly, fine and close, do not ftracture, strain reaches 0.45nm,
Piezoelectric constant, up to 64pm/V, significantly reduces low-frequency dielectric and is lost, and minimum 0.023.Described preparation method solves zirconium
The problem of cracking in barium titanate calcium membrane-film preparation process, improves without the piezoelectricity of thin film lead and dielectricity, and low cost and controlled,
The barium calcium zirconate titanate thin film flatness with inculating crystal layer prepared is high, and uniformity is good, flawless, and quality is high so that it is at microcomputer
Electricity system, obtains actual application in ferroelectricity storage system and multifunctional unit device.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the barium calcium zirconate titanate piezoelectric thin film of embodiment 1 to 4 gained difference inculating crystal layer thickness.
Fig. 2 is that the barium calcium zirconate titanate piezoelectric thin film electric field induced strain of embodiment 1 to 4 gained difference inculating crystal layer thickness is with extra electric field
Change curve.
Fig. 3 is barium calcium zirconate titanate piezoelectric thin-film dielectric constant and the dielectric loss of embodiment 1 to 4 gained difference inculating crystal layer thickness
With frequency variation curve figure.
Detailed description of the invention
The present invention is expanded on further, it should be appreciated that these embodiments are merely to illustrate the present invention and need not below in conjunction with specific embodiment
In limiting the scope of the invention.
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by disclosed by this specification
Content understand other advantages and effect of the present invention easily.The present invention can also be added by the most different detailed description of the invention
To implement or application, the every details in this specification can also be based on different viewpoints and application, in the essence without departing from the present invention
Various modification or change is carried out under god.
It should be clear that the conventional equipment in the not concrete process equipment indicated or device all use this area in the following example or device；
All force value and scope are all referring to relative pressure, and the raw material of use is also the conventional use of raw material in this area.
Also may be used before and after described combination step in addition, it is to be understood that the one or more method steps mentioned in the present invention do not repel
There is additive method step or additive method step can also be inserted, unless otherwise saying between these steps specifically mentioned
Bright；Should also be understood that the combination annexation between the one or more equipment/devices mentioned in the present invention is not repelled described
Other equipment/devices can also be there are before and after unit equipment/device or also may be used between these two equipment/devices specifically mentioned
To insert other equipment/devices, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only and differentiates
The convenient tool of various method steps, rather than for limiting the ordering of various method steps or limiting the enforceable scope of the present invention,
Being altered or modified of its relativeness, in the case of without essence change technology contents, when being also considered as the enforceable model of the present invention
Farmland.
Embodiment 1:
At Pt/Ti/SiO2After preparing 8 nanometer inculating crystal layers on/Si substrate, prepare barium calcium zirconate titanate piezoelectric thin film.
A) Ba is pressed0.92Ca0.08Ti0.95Zr0.05O3The stoichiometric proportion of middle element weighs raw material: Barium acetate, calcium acetate, isopropanol
Titanium and propanol zirconium, be dissolved in acetic acid and ethylene glycol by raw material, is chelating agent preparation precursor solution one and front with acetylacetone,2,4-pentanedione
Driving liquid solution two, the concentration of described precursor solution one is 0.05M, and the concentration of described precursor solution two is 0.2M, acetic acid
Accounting for the 60% of precursor solution volume, ethylene glycol accounts for the 30% of precursor solution volume, Ba0.92Ca0.08Ti0.95Zr0.05O3
It is 1:1 with the mol ratio of acetylacetone,2,4-pentanedione；After standing 24 hours, it is used for preparing barium calcium zirconate titanate inculating crystal layer and thin layer；
B) by Pt/Ti/SiO2Precursor solution one rotary coating of 0.05M, 600 DEG C of pretreatment 10 minutes, is existed by/Si substrate
Pt/Ti/SiO2On/Si substrate, rotating speed is 2000 revolutions per seconds, and the time is 30 seconds；By coated gel successively in tube furnace
200 DEG C process 2 minutes, and 300 DEG C process 2 minutes, and 600 DEG C process 10 minutes, it is thus achieved that the inculating crystal layer of 8 nanometer thickness；
C) precursor solution two of rotary coating 0.2M on inculating crystal layer, rotating speed is 2000 revolutions per seconds, and the time is 30 seconds；To be coated with
The gel covered successively in tube furnace 200 DEG C process 3 minutes, 400 DEG C process 10 minutes；
D) repeat step c) i.e. coat and Technology for Heating Processing 4 times, finally 700 DEG C of annealing 20 minutes, finally obtain 150 and receive
The thin layer that rice is thick.
The method using d.c. sputtering sputters gold electrode at film surface, and a diameter of 0.5 millimeter, thickness is 80 nanometers, test
Electrical property.
In Fig. 1, (a) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric thin film on 8 nanometer inculating crystal layers, and crystal grain is about 100
Nanometer, size uniform, there is no crackle, in Fig. 2, (a) gives the strain of barium calcium zirconate titanate piezoelectric thin film on 8 nanometer inculating crystal layers
With voltage change curve, electric field induction deformation quantity reaches 0.4 nanometer, and piezoelectric constant reaches 39pm/V.Fig. 3 (a) gives 8 and receives
On rice inculating crystal layer, dielectric constant and the dielectric loss of barium calcium zirconate titanate piezoelectric thin film change with frequency, and low-frequency dielectric loss is 0.112.
Embodiment 2:
After single crystal Si substrate is prepared 20 nanometer inculating crystal layers, prepare barium calcium zirconate titanate piezoelectric thin film.
A) Ba is pressed0.99Ca0.01Ti0.98Zr0.02O3The stoichiometric proportion of middle element weighs raw material: barium nitrate, calcium nitrate, metatitanic acid four
Butyl ester and zirconium iso-propoxide, be dissolved in acetic acid and ethylene glycol by raw material, is that precursor solution one prepared by chelating agent with acetylacetone,2,4-pentanedione
With precursor solution two, the concentration of described precursor solution one is 0.1M, and the concentration of described precursor solution two is 0.3M, second
Acid accounts for the 55% of precursor solution volume, and ethylene glycol accounts for the 40% of precursor solution volume, Ba0.99Ca0.01Ti0.98Zr0.02O3
It is 1:1.5 with the mol ratio of acetylacetone,2,4-pentanedione；After standing 24 hours, it is used for preparing barium calcium zirconate titanate inculating crystal layer and thin layer；
B) by single crystal Si substrate 650 DEG C of pretreatment 15 minutes, by precursor solution one rotary coating of 0.1M at monocrystalline
On Si substrate, rotating speed is 2500 revolutions per seconds, and the time is 25 seconds；150 DEG C of process 2 in tube furnace successively by coated gel
Minute, 350 DEG C process 3 minutes, and 650 DEG C process 5 minutes；
C) step b) is repeated once, it is thus achieved that the inculating crystal layer of 20 nanometer thickness；
D) precursor solution two of rotary coating 0.3M on inculating crystal layer, rotating speed is 2500 revolutions per seconds, and the time is 20 seconds, will
Coated gel successively in tube furnace 150 DEG C process 5 minutes, 450 DEG C process 5 minutes；
E) repeat step d) i.e. coat and Technology for Heating Processing five times；Finally anneal 30 minutes at 720 DEG C, it is thus achieved that 360 nanometer thickness
Thin layer.
The method using d.c. sputtering is millimeter at film surface sputtering electrode, diameter 0.2, and thickness is 80 nanometers, test electricity
Performance.
In Fig. 1, (b) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric thin film on 20 nanometer inculating crystal layers, and crystal grain is about 100
Nanometer, size uniform, there is no crackle, in Fig. 2, (b) gives the strain of barium calcium zirconate titanate piezoelectric thin film on 20 nanometer inculating crystal layers
With voltage change curve, electric field induction deformation quantity reaches 0.45 nanometer, and piezoelectric constant reaches 64pm/V.Fig. 3 (b) gives 20
On nanometer inculating crystal layer, dielectric constant and the dielectric loss of barium calcium zirconate titanate piezoelectric thin film change with frequency, and low-frequency dielectric loss is
0.052。
Embodiment 3:
At monocrystalline SrTiO3After preparing 30 nanometer inculating crystal layers on substrate, prepare barium calcium zirconate titanate piezoelectric thin film.
A) Ba is pressed0.84Ca0.16Ti0.90Zr0.10O3The stoichiometric proportion of middle element weighs raw material: Barium acetate, calcium acetate, isopropanol
Titanium and propanol zirconium, be dissolved in acetic acid and ethylene glycol monomethyl ether by raw material, is chelating agent preparation precursor solution one and front with acetylacetone,2,4-pentanedione
Driving liquid solution two, the concentration of described precursor solution one is 0.15M, and the concentration of described precursor solution two is 0.3M, acetic acid
Accounting for the 60% of precursor solution volume, ethylene glycol monomethyl ether accounts for the 35% of precursor solution volume, Ba0.84Ca0.16Ti0.90Zr0.10O3
It is 1:2 with the mol ratio of acetylacetone,2,4-pentanedione；After standing 24 hours, it is used for preparing barium calcium zirconate titanate inculating crystal layer and thin layer；
B) by monocrystalline SrTiO3Substrate was 700 DEG C of pretreatment 20 minutes, by the precursor solution rotary coating of 0.15M at monocrystalline
SrTiO3On substrate, rotating speed is 3000 revolutions per seconds, and the time is 20 seconds；By coated gel in tube furnace 200 DEG C successively
Processing 2 minutes, 400 DEG C process 5 minutes, and 700 DEG C process 8 minutes.
C) step b) 1 time is repeated, it is thus achieved that the inculating crystal layer of 30 nanometer thickness；
D) precursor solution of rotary coating 0.3M on inculating crystal layer, rotating speed is 3000 revolutions per seconds, and the time is 20 seconds.To be coated with
The gel covered successively in tube furnace 100 DEG C process 3 minutes, 400 DEG C process 10 minutes.
E) repeat step d) i.e. coat and Technology for Heating Processing five times, finally 700 DEG C of annealing 40 minutes, it is thus achieved that 360 nanometer thickness
The thin layer of degree.
The method using d.c. sputtering is millimeter at film surface sputtering electrode, diameter 0.2, and thickness is 80 nanometers, test electricity
Performance.
In Fig. 1, (c) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric thin film on 30 nanometer inculating crystal layers, and crystal grain is about 100
Nanometer, size uniform, there is no crackle, in Fig. 2, (c) gives the strain of barium calcium zirconate titanate piezoelectric thin film on 30 nanometer inculating crystal layers
With voltage change curve, electric field induction deformation quantity reaches 0.42 nanometer, and piezoelectric constant reaches 61pm/V.Fig. 3 (c) gives 30
On nanometer inculating crystal layer, dielectric constant and the dielectric loss of barium calcium zirconate titanate piezoelectric thin film change with frequency, and low-frequency dielectric loss is
0.030。
Embodiment 4:
At single crystal La AlO3After preparing 40 nanometer inculating crystal layers on substrate, prepare barium calcium zirconate titanate piezoelectric thin film.
A) Ba is pressed0.90Ca0.10Ti0.88Zr0.12O3The stoichiometric proportion of middle element weighs raw material: Barium acetate, calcium acetate, isopropanol
Titanium and propanol zirconium, be dissolved in acetic acid and ethylene glycol monomethyl ether by raw material, is chelating agent preparation precursor solution one and front with acetylacetone,2,4-pentanedione
Driving liquid solution two, the concentration of described precursor solution one is 0.05M, and the concentration of described precursor solution two is 0.4M, acetic acid
Accounting for the 50% of precursor solution volume, ethylene glycol monomethyl ether accounts for the 30% of precursor solution volume, Ba0.90Ca0.10Ti0.88Zr0.12O3
It is 1:2 with the mol ratio of acetylacetone,2,4-pentanedione；After standing 24 hours, it is used for preparing barium calcium zirconate titanate inculating crystal layer and thin layer；
B) by single crystal La AlO3Substrate was 700 DEG C of pretreatment 10 minutes.By precursor solution one rotary coating of 0.05M at list
Brilliant LaAlO3On substrate, rotating speed is 3000 revolutions per seconds, and the time is 20 seconds.By coated gel successively in tube furnace 100
DEG C process 3 minutes, 300 DEG C process 3 minutes, 700 DEG C process 10 minutes.
C) step b) 4 times are repeated, it is thus achieved that the inculating crystal layer of 40 nanometer thickness.
D) precursor solution two of rotary coating 0.4M on inculating crystal layer, rotating speed is 3000 revolutions per seconds, and the time is 20 seconds.To be coated with
The gel covered successively in tube furnace 200 DEG C process 2 minutes, 500 DEG C process 10 minutes.
E) repeat step d) i.e. coat and Technology for Heating Processing five times, finally 750 DEG C of annealing 50 minutes, it is thus achieved that 600 nanometer thickness
The thin layer of degree.
The method using d.c. sputtering is millimeter at film surface sputtering electrode, diameter 0.2, and thickness is 80 nanometers, test electricity
Performance.
In Fig. 1, (d) gives the scanning electron microscope image of barium calcium zirconate titanate piezoelectric thin film on 40 nanometer inculating crystal layers, and crystal grain is about 100
Nanometer, size uniform, there is no crackle, in Fig. 2, (d) gives the strain of barium calcium zirconate titanate piezoelectric thin film on 40 nanometer inculating crystal layers
With voltage change curve, electric field induction deformation quantity reaches 0.4 nanometer, and piezoelectric constant reaches 44pm/V.Fig. 3 (d) gives 40
On nanometer inculating crystal layer, dielectric constant and the dielectric loss of barium calcium zirconate titanate piezoelectric thin film change with frequency, and low-frequency dielectric loss is
0.023。
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any it is familiar with this
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage of technology.Therefore,
Art has what usually intellectual was completed under without departing from disclosed spirit and technological thought such as
All equivalences are modified or change, and must be contained by the claim of the present invention.
Claims (12)
1. a barium calcium zirconate titanate thin film, it is characterised in that described barium calcium zirconate titanate thin film includes substrate layer, inculating crystal layer and thin layer,
Described inculating crystal layer is between described substrate layer and thin layer, and the chemical general formula of described inculating crystal layer and thin layer is
Ba(1-x)CaxTi(1-y)ZryO3, wherein x=0.01～0.16, y=0.02～0.12.
2. barium calcium zirconate titanate thin film as claimed in claim 1, it is characterised in that described substrate layer is Pt/Ti/SiO2/ Si substrate,
Single crystal Si substrate, monocrystalline SrTiO3Substrate or single crystal La AlO3Substrate.
3. barium calcium zirconate titanate thin film as claimed in claim 1, it is characterised in that the thickness of described inculating crystal layer is 8～40nm, institute
The thickness stating thin layer is 150～600nm.
4. the preparation method of a barium calcium zirconate titanate thin film as claimed in claim 1, it is characterised in that comprise the steps:
A) in the chemical general formula as described in claim 1, the stoichiometric proportion of element weighs raw material: containing Ba compound, containing Ca
Compound, containing Ti compound and the compound Han Zr, raw material is dissolved in acetic acid and ethylene glycol or acetic acid and ethylene glycol monomethyl ether,
Being chelating agent preparation precursor solution one and precursor solution two with acetylacetone,2,4-pentanedione, the concentration of described precursor solution one is
0.05～0.15M, the concentration of described precursor solution two is 0.2～0.4M；
B) precursor solution one described in rotary coating on substrate, then carries out heat treatment；
C) select to repeat the number of times of step b) according to the thickness of inculating crystal layer, obtain the substrate of inculating crystal layer；
D) substrate obtained by step c) precursor solution two described in rotary coating on inculating crystal layer, then carries out heat treatment；
E) select to repeat the number of times of step d) according to the thickness of thin layer, then anneal, obtain described barium calcium zirconate titanate thin film.
Preparation method the most according to claim 4, it is characterised in that in step b), the condition of rotary coating: rotating speed be 2000～
3000 revolutions per seconds, the time is 20～30 seconds.
Preparation method the most according to claim 4, it is characterised in that in step b), the condition of heat treatment: successively 100～
200 DEG C process 2～3 minutes, and 300～400 DEG C process 2～5 minutes, and 600～700 DEG C process 5～10 minutes.
Preparation method the most according to claim 4, it is characterised in that in step b), on substrate before rotary coating, first
Described substrate is carried out pretreatment.
Preparation method the most according to claim 7, it is characterised in that the condition of described pretreatment: 600～700 DEG C of pretreatment
10～20 minutes.
Preparation method the most according to claim 4, it is characterised in that in step d), the condition of rotary coating: rotating speed be 2000～
3000 revolutions per seconds, the time is 20～30 seconds.
Preparation method the most according to claim 4, it is characterised in that in step d), the condition of heat treatment: successively 100～
200 DEG C process 2～5 minutes, and 400～500 DEG C process 5～10 minutes.
11. preparation methoies according to claim 4, it is characterised in that in step e), the condition of annealing: 700～750 DEG C are moved back
Fire 20～50 minutes.
12. 1 kinds of barium calcium zirconate titanate thin film as described in any one of claims 1 to 3 are applied to MEMS, ferroelectricity storage system
Or multifunctional unit devices field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610293378.4A CN105977374B (en) | 2016-05-05 | 2016-05-05 | A kind of barium calcium zirconate titanate film and its preparation method and application with seed layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610293378.4A CN105977374B (en) | 2016-05-05 | 2016-05-05 | A kind of barium calcium zirconate titanate film and its preparation method and application with seed layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105977374A true CN105977374A (en) | 2016-09-28 |
| CN105977374B CN105977374B (en) | 2019-03-01 |
Family
ID=56992636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610293378.4A Expired - Fee Related CN105977374B (en) | 2016-05-05 | 2016-05-05 | A kind of barium calcium zirconate titanate film and its preparation method and application with seed layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105977374B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-05-05 CN CN201610293378.4A patent/CN105977374B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| YEMEI HAN等: "Piezoelectric properties of bilayer ferroelectric thin films based on (1-x)[Ba(Zr0.2Ti0.8)O3] –x(Ba0.7Ca0.3TiO3", 《MATERIALS LETTERS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105977374B (en) | 2019-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sanchez et al. | Optimization of PbTiO3 seed layers and Pt metallization for PZT-based piezoMEMS actuators | |
| JP5808262B2 (en) | Piezoelectric element and piezoelectric device | |
| CN100587910C (en) | Preparation for ferroelectric material with quartz/lanthanum nickelate/bismuth ferrite-lead titanate three-layer structure | |
| CN104609856B (en) | The highly preparation method of preferred orientation bismuth titanate sodium titanate-barium lead-free piezoelectric thin film | |
| Abou Dargham et al. | Synthesis and electrical properties of lead-free piezoelectric Bi0. 5Na0. 5TiO3 thin films prepared by Sol-Gel method | |
| Shakeri et al. | Synthesis and characterization of thick PZT films via sol–gel dip coating method | |
| Ohno et al. | Understanding of the development of in-plane residual stress in sol-gel-derived metal oxide thin films | |
| CN105732022A (en) | Preparation method of piezoelectric ceramic with high Curie temperature and film thereof | |
| EP2998988A1 (en) | Silicon substrate having ferroelectric film attached thereto | |
| Corkovic et al. | Development of residual stress in sol-gel derived Pb (Zr, Ti) O3 films: An experimental study | |
| Chen et al. | Low temperature growth of (100)-oriented Ba (Zr0. 2Ti0. 8) O3-0.5 (Ba0. 7Ca0. 3) TiO3 thin films using a LaNiO3 seed layer | |
| CN102731107A (en) | Method for preparing Mn-doped bismuth sodium titanate-barium titanate film | |
| JP5461951B2 (en) | Manufacturing method of ceramic film | |
| Peters et al. | Thermal stress accommodation in dip cast lead zirconate‐titanate ferroelectric films on flexible substrates | |
| Chi et al. | Low temperature preparation and electric properties of highly (100)-oriented Pb 0.8 La 0.1 Ca 0.1 Ti 0.975 O 3 thin films prepared by a sol–gel route | |
| WO2014136463A1 (en) | Oxide layer and production method for oxide layer, as well as capacitor, semiconductor device, and microelectromechanical system provided with oxide layer | |
| CN105977374A (en) | Barium calcium zirconate titanate film with seed crystal layer and preparation method and application thereof | |
| JP2005503311A (en) | Method for preparing a stable sol for lead zirconate titanate and a method for producing a film from such sol | |
| CN107346802B (en) | Piezoelectric film and method for producing same | |
| van der Veer et al. | Piezoelectric properties of PZT by an ethylene glycol-based chemical solution synthesis | |
| Yang et al. | Structural and ferroelectric properties of textured KNN thick films prepared by sol-gel methods | |
| Yu et al. | Preparation, structure, and properties of 0.3 Pb (Zn1/3Nb2/3) O3-0.7 PbTiO3 thin films on LaNiO3/YSZ/Si substrates | |
| CN104072131B (en) | The manufacturing method and application thereof of ferroelectric thin film formation composition | |
| Ohno et al. | Stress engineering for the design of morphotropic phase boundary in piezoelectric material | |
| Chou et al. | Preparation and dielectric properties of highly preferred-(100) orientation (Pb, La)(Zr, Ti) O 3 antiferroelectric thick films by sol–gel processing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190301 |