CN105870123B - A kind of preparation method of tungsten bismuth titanate ferro-electricity membrane - Google Patents
A kind of preparation method of tungsten bismuth titanate ferro-electricity membrane Download PDFInfo
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- CN105870123B CN105870123B CN201610177743.5A CN201610177743A CN105870123B CN 105870123 B CN105870123 B CN 105870123B CN 201610177743 A CN201610177743 A CN 201610177743A CN 105870123 B CN105870123 B CN 105870123B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 33
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000005621 ferroelectricity Effects 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title claims abstract description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002243 precursor Substances 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 14
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 12
- MGRORBOILBLUTP-UHFFFAOYSA-N propan-2-ol tungsten Chemical compound [W].C(C)(C)O MGRORBOILBLUTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000013557 residual solvent Substances 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
- 238000000224 chemical solution deposition Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 59
- 239000010409 thin film Substances 0.000 abstract description 26
- 230000010287 polarization Effects 0.000 abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000002929 anti-fatigue Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 1
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 37
- 230000002441 reversible effect Effects 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000005684 electric field Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910020294 Pb(Zr,Ti)O3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B53/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory capacitors
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02194—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing more than one metal element
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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Abstract
A kind of tungsten bismuth titanate ferro-electricity membrane, the chemical formula of the thin-film material is Bi4Ti3‑xWxO12, wherein 0 ＜ x≤0.5.The process route of preparation method is：It prepares precursor liquid → preparing precursor film → and prepares ferroelectric thin film；This method is using nitric hydrate bismuth, positive four butyl ester of metatitanic acid and isopropanol tungsten as predecessor, using the mixed solution of glacial acetic acid and diethanol methyl ether as solvent, prepare precursor liquid using acetylacetone,2,4-pentanedione as stabilizer, it is coated after high-temperature roasting be made it is smooth it is fine and close, thickness is uniform, the good tungsten bismuth titanate film of translucidus.This method has easily controllable material component, the advantages of being easy to implement large-scale production.The film has excellent ferroelectric properties, remanent polarization is high, anti-fatigue performance is good, compared with rare earth doped bismuth titanate ferro-electricity membrane, the membrane-film preparation process does not add any rare earth element, so as to reduce the production cost of film, have broad application prospects in Nonvolatile ferroelectric memory field.
Description
Technical field
The present invention relates to ferroelectricity storage and function film preparing technical fields, and in particular to a kind of system of tungsten bismuth titanate film
Preparation Method.
Background technology
Ferroelectric random read-write memory has non-volatile, low power consumption, high read or write speed, high density storage, anti-spoke
Feature is penetrated, is one of most potential memory, has in fields such as computer, aerospace and communication electronics and extensively should
Use prospect.It with ferroelectricity and thickness is nanometer to micron-sized film that ferroelectric thin film, which is, because its iron electric polarization inverts electricity
Force down, with semiconductor integrated circuit technique good compatibility the advantages that, become people's focus of attention.In ferroelectric thin film, zirconium metatitanic acid
Lead（Pb(Zr,Ti)O3）Film has larger ferroelectric remnant polarization value and relatively low reversal voltage, has obtained business at present
Change application, however its anti-fatigue performance is poor, and Pb containing harmful metal elements, therefore greatly limits it using model
It encloses.In order to invent unleaded, environmentally friendly ferroelectric thin film, the superior bismuth tantalate strontium of anti-fatigue performance（SrBi2Ta2O9）Successfully developed
Out, but the drawback is that ferroelectric remnant polarization value is low, and preparation temperature is high, is not easy and existing silicon integrated circuit（CMOS or GaAs
Circuit）It is compatible.《Nature》Magazine once reported a kind of La3+The bismuth titanates of doping（Bi4Ti3O12）Ferroelectric thin film not only has
Larger remanent polarization, and anti-fatigue performance is good, then has much about rare earth doped Ti acid bismuth ferroelectric thin film
Report, including Nd3+、Pr3+、Eu3+Wait the bismuth titanates of trivalent rare earth ions doping or these rare earth ions and other element codopes
Ferroelectric thin film, compared with undoped bismuth titanate ferro-electricity membrane, ferroelectric properties increases, and this film is considered a kind of
There is the ferroelectric thin film of application value very much.
Tungsten bismuth titanate film structure proposed by the present invention is bismuth stratiform calcium compared with rear-earth-doped metatitanic acid bismuth-based thin films
Perovskite like structure, but the advantages of it is most prominent is to make film preparation cost reduction, and its iron without rare earth element in thin film composition
Electrically it is better than rear-earth-doped bismuth titanate film.
Invention content
The present invention first is designed to provide a kind of ferroelectric thin film with excellent properties, and there is very high ferroelectricity to remain
Remaining polarization intensity and excellent anti-fatigue performance.
Second preparation method for being designed to provide this ferroelectric thin film of the invention.
The present invention is achieved by the following scheme above-mentioned purpose：
A kind of tungsten bismuth titanate ferro-electricity membrane, molecular formula Bi4Ti3-x W x O12, wherein 0 ＜x ≤ 0.5。
The preparation method of the tungsten bismuth titanate ferro-electricity membrane, this method are chemical solution deposition, specific preparation process
It is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti3-x W x O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid positive four
Butyl ester:Isopropanol tungsten=4:3-x: xEach raw material components are weighed, the five nitric hydrate bismuths that weighing is obtained add in mixed solvent
In, the mixed solvent is by glacial acetic acid and ethylene glycol monomethyl ether with VEthylene glycol monomethyl ether:VGlacial acetic acid=1~3:1 volume ratio is formulated, and is stirred
It mixes and is heated to 40~60 DEG C, after keeping the temperature 10~30 min, be down to room temperature；Then positive four fourth of metatitanic acid that above-mentioned weighing obtains is added in
Ester；Acetylacetone,2,4-pentanedione is added, acetylacetone,2,4-pentanedione addition is 1.5 ~ 2.5 times of the positive four butyl esters molal quantity of metatitanic acid；In most backward solution
The isopropanol tungsten that above-mentioned weighing obtains is added in, is stirred at room temperature to get to precursor liquid；
（2）By step（1）For the precursor liquid rotary coating of gained on substrate, rotary coating speed is 2000~4500 r/
Min, rotary coating time are 20~40 s, often coat 1 layer, toast 1~5 min, to remove residual solvent and decomposition unit in striping
Divide organic matter；It so repeats 5~15 times, until the precursor film of thickness needed for obtaining；
（3）By step（2）The precursor film of gained is heat-treated, and the heat treatment is in air by step（2）It prepares
Precursor film 550~720 DEG C, then 10~60 min of constant temperature be first warming up to the rate of 1~10 DEG C/min, cool to room with the furnace
Tungsten bismuth titanate film is made in temperature.
The step（2）In, substrate Pt/Ti/SiO2/Si (111)。
The step（1）In, five nitric hydrate bismuths are excessive 5~20% on the basis of nonstoichiometric molar ratio.
The step（1）In, by Bi4Ti3-x W x O12Molecular concentration calculate, a concentration of the 0.02~0.3 of precursor liquid
mol/L；The dosage of each raw material components and mixed solvent total amount and the precursor liquid ultimate density selected according to needed for preparing precursor liquid
It calculates.
The step（1）In, the time is stirred at room temperature at one hour or more.
Compared with prior art, it is of the invention to have the prominent advantages that：
The tungsten bismuth titanate ferro-electricity membrane of the present invention not only has very high ferroelectric remnant polarization intensity and good antifatigue
Property, and without lead element in film, also without rare earth element, be it is a kind of it is novel it is unleaded, without rare earth ferroelectric thin film.
The tungsten bismuth titanate film of the present invention is the oxide that high temperature sintering obtains, steady with excellent chemical stability and heat
It is qualitative.
Selecting tungsten bismuth titanate film prepared by chemical solution deposition has easily controllable material component, easy to operate, easy
In large-scale production the advantages of.
The tungsten bismuth titanate ferro-electricity membrane of preparation, have it is simple in structure, object is mutually pure, of low cost, be that one kind is had excellent performance
Ferroelectric thin film, nonvolatile memory field have potential application prospect.
Description of the drawings
Fig. 1 is in Pt/Ti/SiO using chemical solution deposition2Tungsten bismuth titanates ferroelectric thin is grown on/Si (111) substrate
The X-ray diffractogram of film.X-axis is surface sweeping angle（2θ）, unit is degree；Y-axis is diffracted intensity, no unit.This figure shows preparation
Tungsten bismuth titanate film crystalline condition it is good, all diffraction maximums correspond to the diffraction maximum of bismuth titanates phase, illustrate W6+It can be well
Into among bismuth titanates lattice, film object is mutually very pure, exists without dephasign.
Fig. 2 is the polarization intensity of metatitanic acid tungsten bismuth thin film（P）With electric field strength（E）Change curve.X-axis is electric-field strength
Degree, unit kV/cm；Y-axis is the polarization intensity of metatitanic acid tungsten bismuth thin film, and unit is μ C/cm2.A graceful iron is shown in figure
Electric loop line, loop line are ferroelectric remnant polarization intensity value with the distance between intersection point under Y-axis positive axis intersection point and negative semiaxis（2Pr）.
The film have very high ferroelectric remnant polarization intensity, 2PR is up to 78.2 μ C/cm2.The distance of loop line and X-axis intersection point to origin
For coercive field strength（Ec）, value is within 130 kV/cm.
Fig. 3 is for the reversible remanent polarization of tungsten bismuth titanate film with linear non-reversible remanent polarization with cycle-index
Change curve.X-axis is cycle-index, no unit；Y-axis is polarization intensity, and unit is μ C/cm2；In figure, Psw is just reversible surplus
Remaining polarization intensity ,-Psw are to bear reversible remanent polarization, and Pnsw is just non-reversible remanent polarization ,-Pnsw for it is negative it is non-can
Inverse remanent polarization.Display is with the increase of cycle-index in figure, the reversible remanent polarization of film and linear non-reversible
Remanent polarization value increases with cycle-index constantly to be reduced, but reduction amplitude is smaller, when cycle-index reaches 2,000,000 times,
Its reversible remanent polarization only reduces by 5.43%, and linear non-reversible remanent polarization only reduces by 2.79%；Work as cycle-index
When reaching 200,000,000 times, reversible remanent polarization only reduces by 12.80%, and linear non-reversible remanent polarization only reduces
11.09%, illustrate that tungsten bismuth titanate film has good anti-fatigue performance.
Specific embodiment
Technical scheme of the present invention is described further with reference to specific example, but specific example is not to the present invention
Do any restriction.
Embodiment 1
The present embodiment is with Bi4Ti2.99W0.01O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.99W0.01O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.99:0.01 weighs each raw material components, and the five nitric hydrate bismuths for claiming 3.881 g are added in mixing
In solvent, the mixed solvent is formulated by 15 ml glacial acetic acid and 15 ml ethylene glycol monomethyl ethers, is stirred and heated to 60 DEG C, is protected
After 20 min of temperature, it is down to room temperature；Then positive four butyl ester of 1.850 g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 1.109 ml；Finally
The isopropanol tungsten of 0.194 ml is added in into solution, 2 h are stirred at room temperature to get the tungsten metatitanic acid to molar concentration for 0.06 mol/L
Bismuth precursor liquid.
（2）Above-mentioned precursor liquid is spun and coated at Pt/Ti/SiO2On/Si (111) substrate, rotated and applied with 3000 r/min
30 s are covered, 1 layer is often coated, is placed on roasting glue platform and toasts 5 min, to remove residual solvent in striping and decompose partial organic substances；Such as
This is repeated 5 times, and obtains tungsten bismuth titanates precursor film；
（3）Above-mentioned precursor film is placed in resistance furnace, is heat-treated in air.To prevent film peeling, it is heat-treated
When with the heating speed of 5 DEG C/min be warming up to 600 DEG C, cool to room temperature with the furnace after keeping the temperature 30 min, be prepared
Bi4Ti2.99W0.01O12Ferroelectric thin film.
Embodiment 2
The present embodiment is with Bi4Ti2.97W0.03O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.97W0.03O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.97:0.03 weighs each raw material components, and the five nitric hydrate bismuths for claiming 3.881 g are added in mixing
In solvent, the mixed solvent is formulated by 10 ml glacial acetic acid and 20 ml ethylene glycol monomethyl ethers, is stirred and heated to 40 DEG C, is protected
After 40 min of temperature, it is down to room temperature；Then positive four butyl ester of 1.838 g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 1.101 ml；Finally
The isopropanol tungsten of 0.581 ml is added in into solution, 1.5 h are stirred at room temperature to get the tungsten titanium to molar concentration for 0.06 mol/L
Sour bismuth precursor liquid.
（2）This step and step in embodiment 1（2）It is identical.
（3）Above-mentioned precursor film is placed in resistance furnace, is heat-treated in air.To prevent film peeling, it is heat-treated
When with the heating speed of 3 DEG C/min be warming up to 700 DEG C, cool to room temperature with the furnace after keeping the temperature 40 min, be prepared
Bi4Ti2.97W0.03O12Ferroelectric thin film.
Embodiment 3
The present embodiment is with Bi4Ti2.94W0.06O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.94W0.06O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.94:0.06 weighs each raw material components, and the five nitric hydrate bismuths for claiming 3.881 g are added in mixing
In solvent, the mixed solvent is formulated by 10 ml glacial acetic acid and 20 ml ethylene glycol monomethyl ethers, is stirred and heated to 50 DEG C, is protected
After 20 min of temperature, it is down to room temperature；Then positive four butyl ester of 1.819 g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 1.090 ml；Finally
The isopropanol tungsten of 1.162 ml is added in into solution, 2 h are stirred at room temperature to get the tungsten metatitanic acid to molar concentration for 0.06 mol/L
Bismuth precursor liquid.
（2）This step and step in embodiment 1（2）It is identical.
（3）Above-mentioned precursor film is placed in resistance furnace, is heat-treated in air.To prevent film peeling, it is heat-treated
When with the heating speed of 1 DEG C/min be warming up to 700 DEG C, cool to room temperature with the furnace after keeping the temperature 30 min, be prepared
Bi4Ti2.94W0.06O12Ferroelectric thin film.
Embodiment 4
The present embodiment is with Bi4Ti2.9W0.1O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.9W0.1O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.9:0.1 weighs each raw material components, and it is molten that the five nitric hydrate bismuths for claiming 3.881 g are added in mixing
In agent, the mixed solvent is formulated by 8 ml glacial acetic acid and 22 ml ethylene glycol monomethyl ethers, is stirred and heated to 60 DEG C, heat preservation 5
After min, it is down to room temperature；Then positive four butyl ester of 1.794 g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 1.075 ml；It is most backward molten
The isopropanol tungsten of 1.937 ml is added in liquid, 1.5 h are stirred at room temperature to get the tungsten bismuth titanates to molar concentration for 0.06 mol/L
Precursor liquid.
（2）This step and step in embodiment 1（2）It is identical.
（3）Above-mentioned precursor film is placed in resistance furnace, is heat-treated in air.To prevent film peeling, it is heat-treated
When with the heating speed of 10 DEG C/min be warming up to 700 DEG C, cool to room temperature with the furnace after keeping the temperature 50 min, be prepared
Bi4Ti2.9W0.1O12Ferroelectric thin film.
Embodiment 5
The present embodiment is with Bi4Ti2.85W0.15O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.85W0.15O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.85:0.15 weighs each raw material components, and the five nitric hydrate bismuths for claiming 3.881 g are added in mixing
In solvent, the mixed solvent is formulated by 10 ml glacial acetic acid and 20 ml ethylene glycol monomethyl ethers, is stirred and heated to 60 DEG C, is protected
After 10 min of temperature, it is down to room temperature；Then positive four butyl ester of 1.763 g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 1.057 ml；Finally
The isopropanol tungsten of 2.905 ml is added in into solution, 2.5 h are stirred at room temperature to get the tungsten titanium to molar concentration for 0.06 mol/L
Sour bismuth precursor liquid.
（2）This step and step in embodiment 1（2）It is identical.
（3）Above-mentioned precursor film is placed in resistance furnace, is heat-treated in air.To prevent film peeling, it is heat-treated
When with the heating speed of 3 DEG C/min be warming up to 720 DEG C, cool to room temperature with the furnace after keeping the temperature 30 min, be prepared
Bi4Ti2.85W0.15O12Ferroelectric thin film.
Embodiment 6
The present embodiment is with Bi4Ti2.7W0.3O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.7W0.3O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.7:0.3 weighs each raw material components, and it is molten that the five nitric hydrate bismuths for claiming 3.881 g are added in mixing
In agent, the mixed solvent is formulated by 15 ml glacial acetic acid and 15 ml ethylene glycol monomethyl ethers, is stirred and heated to 60 DEG C, heat preservation
After 10 min, it is down to room temperature；Then positive four butyl ester of 1.671 g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 1.001 ml；It is most backward
The isopropanol tungsten of 5.81 ml is added in solution, 2 h are stirred at room temperature to get the tungsten bismuth titanates to molar concentration for 0.06 mol/L
Precursor liquid.
（2）This step and step in embodiment 1（2）It is identical.
（3）Above-mentioned precursor film is placed in resistance furnace, is heat-treated in air.To prevent film peeling, it is heat-treated
When with the heating speed of 2 DEG C/min be warming up to 700 DEG C, cool to room temperature with the furnace after keeping the temperature 10 min, be prepared
Bi4Ti2.7W0.3O12Ferroelectric thin film.
Embodiment 7
The present embodiment is to prepare the Bi of various concentration precursor liquid4Ti2.97W0.03O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.97W0.03O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.97:0.03 weighs each raw material components, and the five nitric hydrate bismuths for claiming 1.941 g are added in mixing
In solvent, the mixed solvent is formulated by 10 ml glacial acetic acid and 20 ml ethylene glycol monomethyl ethers, is stirred and heated to 60 DEG C, is protected
After 20 min of temperature, it is down to room temperature；Then positive four butyl ester of 0.919g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 0.551 ml；Finally
The isopropanol tungsten of 0.291 ml is added in into solution, 2 h are stirred at room temperature to get the tungsten metatitanic acid to molar concentration for 0.03 mol/L
Bismuth precursor liquid.
（2）Above-mentioned precursor liquid is spun and coated at Pt/Ti/SiO2On/Si (111) substrate, rotated and applied with 2000 r/min
20 s are covered, 1 layer is often applied, wet film is placed in thermal station and toasts 3 min, to remove residual solvent in striping and decompose partial organic substances；
It is so repeated 15 times, until the precursor film of thickness needed for obtaining.
（3）Above-mentioned precursor film is placed in electric furnace, is heat-treated in air.To prevent film peeling, during heat treatment
700 DEG C are warming up to the heating speed of 5 DEG C/min, room temperature is cooled to the furnace after keeping the temperature 30 min, is prepared
Bi4Ti2.97W0.03O12Ferroelectric thin film.
Embodiment 8
The present embodiment is to prepare the Bi of various concentration precursor liquid4Ti2.97W0.03O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.97W0.03O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.97:0.03 weighs each raw material components, and the five nitric hydrate bismuths for claiming 6.468 g are added in mixing
In solvent, the mixed solvent is formulated by 10 ml glacial acetic acid and 20 ml ethylene glycol monomethyl ethers, is stirred and heated to 60 DEG C, is protected
After 20 min of temperature, it is down to room temperature；Then positive four butyl ester of 3.063 g metatitanic acids is added in；Add the acetylacetone,2,4-pentanedione of 1.835 ml；Finally
The isopropanol tungsten of 0.968 ml is added in into solution, 2 h are stirred at room temperature to get the tungsten metatitanic acid to molar concentration for 0.1 mol/L
Bismuth precursor liquid.
（2）Above-mentioned precursor liquid is spun and coated at Pt/Ti/SiO2On/Si (111) substrate, rotated and applied with 4500 r/min
40 s are covered, 1 layer is often applied, wet film is placed in thermal station and toasts 1 min, to remove residual solvent in striping and decompose partial organic substances；
It is so repeated 10 times, until the precursor film of thickness needed for obtaining.
（3）Above-mentioned precursor film is placed in electric furnace, is heat-treated in air.To prevent film peeling, during heat treatment
550 DEG C are warming up to the heating speed of 3 DEG C/min, room temperature is cooled to the furnace after keeping the temperature 20 min, is prepared
Bi4Ti2.97W0.03O12Ferroelectric thin film.
Embodiment 9
The present embodiment is to prepare the long Bi of various concentration precursor liquid4Ti2.94W0.06O12For film, preparation process is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti2.94W0.06O12, it is in molar ratio five nitric hydrate bismuths:Metatitanic acid is just
Four butyl esters:Isopropanol tungsten=4:2.94:0.06 weighs each raw material components, and the five nitric hydrate bismuths for claiming 6.468 g are added in mixing
In solvent, the mixed solvent is formulated by 10 ml glacial acetic acid and 20 ml ethylene glycol monomethyl ethers, is stirred and heated to 50 DEG C, is protected
After 20 min of temperature, it is down to room temperature and then adds in positive four butyl ester of 3.032 g metatitanic acids；Add the acetylacetone,2,4-pentanedione of 1.817 ml；Finally
The isopropanol tungsten of 1.937 ml is added in into solution, 2 h are stirred at room temperature to get the tungsten metatitanic acid to molar concentration for 0.1 mol/L
Bismuth precursor liquid.
（2）This step and step in embodiment 7（2）It is identical.
（3）Above-mentioned precursor film is placed in electric furnace, is heat-treated in air.To prevent film peeling, during heat treatment
720 DEG C are warming up to the heating speed of 8 DEG C/min, room temperature is cooled to the furnace after keeping the temperature 60 min, is prepared
Bi4Ti2.94W0.06O12Ferroelectric thin film.
Claims (5)
1. a kind of preparation method of tungsten bismuth titanate ferro-electricity membrane, this method is chemical solution deposition, which is characterized in that specific system
Standby step is as follows：
（1）The preparation of precursor liquid：According to molecular formula Bi4Ti3-xWxO12, wherein 0 ＜ x≤0.5, is in molar ratio five hydration nitre
Sour bismuth:Positive four butyl ester of metatitanic acid:Isopropanol tungsten=4:3-x:X weighs each raw material components, the five nitric hydrate bismuths that weighing is obtained
In the mixed solvent is added in, the mixed solvent is by glacial acetic acid and ethylene glycol monomethyl ether with VEthylene glycol monomethyl ether:VGlacial acetic acid=1~3:1 volume ratio
It is formulated, is stirred and heated to 40~60 DEG C, after keeping the temperature 10~30 min, be down to room temperature；Then above-mentioned weighing is added in obtain
Positive four butyl ester of metatitanic acid；Acetylacetone,2,4-pentanedione is added, acetylacetone,2,4-pentanedione addition is 1.5 ~ 2.5 times of the positive four butyl esters molal quantity of metatitanic acid；
The isopropanol tungsten that above-mentioned weighing obtains finally is added in into solution again, is stirred at room temperature to get to precursor liquid；
（2）By step（1）For the precursor liquid rotary coating of gained on substrate, rotary coating speed is 2000~4500 r/min,
The rotary coating time is 20~40 s, often coats 1 layer, toasts 1~5 min, is had to remove in striping residual solvent and decompose part
Machine object；It so repeats 5~15 times, until the precursor film of thickness needed for obtaining；
（3）By step（2）The precursor film of gained is heat-treated, and the heat treatment is in air by step（2）Before preparing
It drives film and 550~720 DEG C, then 10~60 min of constant temperature is first warming up to the rate of 1~10 DEG C/min, cool to room temperature with the furnace, make
Obtain tungsten bismuth titanate film.
2. the preparation method of tungsten bismuth titanate ferro-electricity membrane according to claim 1, which is characterized in that the step（2）In,
Substrate is Pt/Ti/SiO2/Si (111)。
3. the preparation method of the tungsten bismuth titanate ferro-electricity membrane according to claim 1 or claim 2, which is characterized in that institute
State step（1）In, five nitric hydrate bismuths are excessive 5~20% on the basis of nonstoichiometric molar ratio.
4. the preparation method of tungsten bismuth titanate ferro-electricity membrane according to claim 1, which is characterized in that the step（1）In,
By Bi4Ti3-xWxO12Molecular concentration calculate, a concentration of 0.02~0.3 mol/L of precursor liquid；Each raw material components and mixing are molten
The dosage of agent total amount and the precursor liquid ultimate density selected according to needed for preparing precursor liquid calculate.
5. the preparation method of tungsten bismuth titanate ferro-electricity membrane according to claim 1, which is characterized in that the step（1）In,
The time is stirred at room temperature at one hour or more.
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| CN101717201A (en) * | 2009-11-13 | 2010-06-02 | 中山大学 | Rare earth doped bismuth titanate up-conversion luminescence ferroelectric film and preparation method thereof |
| CN104556240A (en) * | 2015-02-04 | 2015-04-29 | 西安工业大学 | Preparation method of bismuth titanate (BT) ferroelectric film |
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| CN101717201A (en) * | 2009-11-13 | 2010-06-02 | 中山大学 | Rare earth doped bismuth titanate up-conversion luminescence ferroelectric film and preparation method thereof |
| CN104556240A (en) * | 2015-02-04 | 2015-04-29 | 西安工业大学 | Preparation method of bismuth titanate (BT) ferroelectric film |
Non-Patent Citations (1)
| Title |
|---|
| Crystal Structure and Ferroelectric Property of Tungsten-substituted Bi4Ti3O12 Thin Films Prepared by Metal-Organic Chemical Vapor Deposition;Tomohiro SaKAI等;《Japanese Journal of Applied Phisics》;20030501;第42卷(第5A期);第2850页左栏第3段-第2852页右栏第1段及图1-7 * |
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