CN109081609A - A kind of ferroelectric thin film and preparation method thereof of strong polarization orientation - Google Patents

A kind of ferroelectric thin film and preparation method thereof of strong polarization orientation Download PDF

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CN109081609A
CN109081609A CN201810844049.3A CN201810844049A CN109081609A CN 109081609 A CN109081609 A CN 109081609A CN 201810844049 A CN201810844049 A CN 201810844049A CN 109081609 A CN109081609 A CN 109081609A
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thin film
iron titanate
polarization orientation
titanate bismuth
strong polarization
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李静波
王林
金海波
洪思明
桂萌琦
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation

Abstract

The present invention provides a kind of ferroelectric thin film and preparation method thereof of strong polarization orientation, the preparation method includes: to prepare iron titanate bismuth precursor solution；Obtain conductive substrates material；The iron titanate bismuth precursor solution is spin-coated on the conductive substrates material, iron titanate bismuth thin film is obtained；It is heat-treated the iron titanate bismuth thin film, obtains non-crystallized iron titanate bismuth thin film；In the environment of applying external electric field to the surface of the non-crystallized iron titanate bismuth thin film, it is heat-treated the non-crystallized iron titanate bismuth thin film under high temperature, obtains the ferroelectric thin film of strong polarization orientation.The embodiment of the present invention in the preparation process of ferroelectric thin film by applying external electric field, realize ferroelectric thin film strong polarization orientation growth so that ferroelectric thin film surfacing obtained and it is fine and close, crystallinity height, the polarization orientation of crystal grain is obvious, so that ferroelectric thin film obtained be made to have high optics catalytic performance.

Description

A kind of ferroelectric thin film and preparation method thereof of strong polarization orientation
Technical field
The present invention relates to ferroelectric material fields, ferroelectric thin film and its preparation side more particularly to a kind of strong polarization orientation Method.
Background technique
For a long time, ferroelectric material is because its distinctive spontaneous polarization is in capacitor, piezoelectric transducer, storage and micro- drive Dynamic device etc. is widely used, and Recent study person start to find application potential of the ferroelectric material in terms of photocatalysis. At present in photocatalysis technology, there is a series of problem there are also to be solved, wherein the compound of one hole pair of light induced electron is one non- Often important limitation.And recent years the study found that ferroelectric material inside spontaneous polarization can form built in field, to hinder Hinder the compound of photo-generate electron-hole, and then improves photocatalytic activity and incident photon-to-electron conversion efficiency.
The compound of derivative structure containing bismuth oxide-based layered perovskite is to be found by B.Aurivillius in 1949 and describe it Crystallographic features, therefore this eka-bismuth system laminated perovskite structure material is also referred to as Aurivillius profile material. The noticeable characteristic of Aurivillius compound first is that have preferable photocatalytic activity, this kind of lamellar compound due to Its unique layer structure is conducive to the separation of photo-generated carrier and the transmission in interlayer, reduces compound in catalytic inner Probability, to improve catalytic efficiency.
The compound of derivative structure containing bismuth oxide-based layered perovskite is expected to be applied in ferroelectric material, still, contains bismuth oxide-based layered perovskite There are anisotropy for derivative structure compound.The polarization orientation of ferroelectric material has strong influence to its performance, for current Semiconductor integrated technique and ferroelectricity for, the size of Integrated ferroelectrics device cell has evolved to nanoscale, takes at random It is not able to satisfy the performance needs of these devices to the crystal grain of growth.
Summary of the invention
In view of the above problems, it proposes the embodiment of the present invention and overcomes the above problem or at least partly in order to provide one kind A kind of ferroelectric thin film and preparation method thereof of the strong polarization orientation to solve the above problems.
To solve the above-mentioned problems, described the invention discloses a kind of preparation method of the ferroelectric thin film of strong polarization orientation Method includes:
Prepare iron titanate bismuth precursor solution；
Obtain conductive substrates material；
The iron titanate bismuth precursor solution is spin-coated on the conductive substrates material, iron titanate bismuth thin film is obtained；
It is heat-treated the iron titanate bismuth thin film, obtains non-crystallized iron titanate bismuth thin film；
In the environment of applying external electric field to the surface of the non-crystallized iron titanate bismuth thin film, heat treatment is described not under high temperature Crystallization iron titanate bismuth thin film, obtains the ferroelectric thin film of strong polarization orientation.
Preferably, the method also includes:
The ferroelectric thin film of the strong polarization orientation is placed in hydrochloric acid and is handled, the ferroelectricity THIN COMPOSITE of strong polarization orientation is obtained Film.
Preferably, described the step of preparing iron titanate bismuth precursor solution, includes:
Prepare Bi (NO3)3·5H2O、Fe(NO3)3·9H2And glacial acetic acid O,；
By Bi (NO3)3·5H2O、Fe(NO3)3·9H2O is added in glacial acetic acid, under 50~70 DEG C of water-baths, stirring 20~ 40min obtains the first mixed solution；
Acetylacetone,2,4-pentanedione is taken, is added in first mixed solution, under 50~70 DEG C of water-baths, 20~40min is stirred, obtains To the second mixed solution；
Butyl titanate is taken, is added in second mixed solution, under 50~70 DEG C of water-baths, stirs 20~40min Afterwards, it is cooled to room temperature and is aged, obtain iron titanate bismuth precursor solution.
Preferably, the Bi (NO3)3·5H2The O and Fe (NO3)3·9H2Molar ratio between O are as follows: Bi:Fe=5~ 5.3:1；
Bi (the NO3)3·5H2Molar ratio between O and the glacial acetic acid are as follows: glacial acetic acid: Bi=15~20:1；
Volume ratio between the acetylacetone,2,4-pentanedione and the glacial acetic acid are as follows: acetylacetone,2,4-pentanedione: glacial acetic acid=1:8~12；
The butyl titanate and the Fe (NO3)3·9H2Molar ratio between O are as follows: Ti:Fe=2.5~3.5:1.
Preferably, described the step of being heat-treated the iron titanate bismuth thin film, obtaining non-crystallized iron titanate bismuth thin film, includes:
Heat treatment step: it is heat-treated the iron titanate bismuth thin film；
Overcoating step: taking the iron titanate bismuth precursor solution, is spin-coated to the titanium handled through the heat treatment step On sour iron bismuth thin film；
Repeat the heat treatment step and overcoating step 5-10 times described；
The iron titanate bismuth thin film that the last time heat treatment step is obtained, as the non-crystallized iron titanate bismuth Film.
Preferably, the heat treatment step specifically includes:
It is heat-treated the iron titanate bismuth thin film, first rises to 100 DEG C from room temperature with the rate of 3~5 DEG C/min, heat preservation 10~ 30min；400~450 DEG C are risen to the rate of 3~5 DEG C/min again, keeps the temperature 20~40min；
The iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature.
Preferably, the conductive substrates material includes FTO glass, ito glass and Pt/Ti/SiO2/Si base material One of.
Preferably, described in the environment of applying external electric field to the surface of the non-crystallized iron titanate bismuth thin film, high warm The step of handling the non-crystallized iron titanate bismuth thin film, obtaining the ferroelectric thin film of strong polarization orientation include:
On the non-crystallized iron titanate bismuth thin film surface, by external wire, applying electric field strength is 10~30V/mm's External electric field；
Non-crystallized iron titanate bismuth thin film described in high-temperature heat treatment rises to 600~650 DEG C with the rate of 3~5 DEG C/min, protects 20~40min of temperature；
After naturally cool to the non-crystallized iron titanate bismuth thin film is taken out after room temperature, the ferroelectric thin of strong polarization orientation is obtained Film.
Preferably, the ferroelectric thin film of the strong polarization orientation is placed in hydrochloric acid and is handled, obtain the ferroelectricity of strong polarization orientation The step of laminated film includes:
The ferroelectric thin film of the strong polarization orientation is placed in 10~60min of processing in the hydrochloric acid of 0.5~2mol/L concentration, is obtained To the ferro-electricity compound film of strong polarization orientation.
The invention also discloses a kind of ferroelectric thin film of strong polarization orientation, use it is aforementioned it is any as described in preparation method It is made.
Compared with prior art, the present invention includes the following advantages:
The embodiment of the present invention realizes the strong pole of ferroelectric thin film by applying external electric field in the preparation process of ferroelectric thin film Change oriented growth so that ferroelectric thin film surfacing obtained and it is fine and close, crystallinity height, the polarization orientation of crystal grain is obvious, thus Make ferroelectric thin film obtained that there is high optics catalytic performance.The ferroelectricity of the strong polarization orientation obtained through HCl treatment 10min is compound Film, density of photocurrent increase~11 μ A/cm compared with without the ferroelectric thin film of polarization process and HCl treatment2。 Meanwhile the ferroelectric thin film preparation method difficulty of strong polarization orientation is lower, preparation cost is small.
Detailed description of the invention
Fig. 1 is the external electric field application direction schematic diagram of the embodiment of the present invention 1 and embodiment 2；
Fig. 2 is the XRD of the ferroelectric thin film of strong polarization orientation made from the embodiment of the present invention 1 and the unpolarized sample of comparison Figure；
Fig. 3 is strong pole made from the ferro-electricity compound film of strong polarization orientation made from the embodiment of the present invention 1 and embodiment 1 Change the XRD diagram of the ferroelectric thin film of orientation；
Fig. 4 is the ferroelectric thin film of strong polarization orientation made from the embodiment of the present invention 1 and the SEM Electronic Speculum for comparing unpolarized sample Figure；
Fig. 5 is the ferroelectric thin film of strong polarization orientation made from the embodiment of the present invention 1, strong polarization orientation made from embodiment 1 Ferro-electricity compound film and embodiment 3 made from strong polarization orientation ferro-electricity compound film SEM electron microscope；
Fig. 6 is strong polarization obtained by the ferroelectric thin film of strong polarization orientation, embodiment 2 obtained by the embodiment of the present invention 1 The ferroelectric thin film of orientation and the photoelectrochemical behaviour test chart of the unpolarized sample of comparison；
Fig. 7 is strong polarization obtained by the ferroelectric thin film of strong polarization orientation, embodiment 2 obtained by the embodiment of the present invention 2 The photoelectrochemical behaviour of the ferro-electricity compound film of strong polarization orientation obtained by the ferro-electricity compound film and embodiment 4 of orientation Test chart.
Fig. 8 is strong polarization obtained by the ferroelectric thin film of strong polarization orientation, embodiment 1 obtained by the embodiment of the present invention 1 The photoelectrochemical behaviour of the ferro-electricity compound film of strong polarization orientation obtained by the ferro-electricity compound film and embodiment 3 of orientation Test chart.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real Applying mode, the present invention is described in further detail.
In the embodiment of the present invention, when specifically preparing the ferroelectric thin film of strong polarization orientation, comprising the following steps:
Prepare iron titanate bismuth precursor solution；
Obtain conductive substrates material；
The iron titanate bismuth precursor solution is spin-coated on the conductive substrates material, iron titanate bismuth thin film is obtained；
It is heat-treated the iron titanate bismuth thin film, obtains non-crystallized iron titanate bismuth thin film；
It is unbrilliant described in high-temperature heat treatment in the environment of applying external electric field to the surface of the non-crystallized iron titanate bismuth thin film Change iron titanate bismuth thin film, obtains the ferroelectric thin film of strong polarization orientation.
In embodiments of the present invention, specifically, described the step of preparing iron titanate bismuth precursor solution may include:
Prepare Bi (NO3)3·5H2O、Fe(NO3)3·9H2O, and glacial acetic acid, by Bi (NO3)3·5H2O、Fe(NO3)3· 9H2O is added in glacial acetic acid, under 50~70 DEG C of water-baths, stirs 20~40min, obtains the first mixed solution
Acetylacetone,2,4-pentanedione is taken, is added in first mixed solution, under 50~70 DEG C of water-baths, 20~40min is stirred, obtains To the second mixed solution；
Butyl titanate is taken, is added in second mixed solution, under 50~70 DEG C of water-baths, stirs 20~40min Afterwards, it is cooled to room temperature and is aged, obtain iron titanate bismuth precursor solution.
Specifically, Bi (the NO3)3·5H2The O and Fe (NO3)3·9H2Molar ratio between O can be with are as follows: Bi:Fe =5~5.3:1；
Bi (the NO3)3·5H2Molar ratio between O and the glacial acetic acid can be with are as follows: glacial acetic acid: Bi=15~20:1；
Volume ratio between the acetylacetone,2,4-pentanedione and the glacial acetic acid can be with are as follows: acetylacetone,2,4-pentanedione: glacial acetic acid=1:8~12；
The butyl titanate and the Fe (NO3)3·9H2Molar ratio between O can be with are as follows: Ti:Fe=2.5~3.5: 1。
In embodiments of the present invention, specifically, the heat treatment iron titanate bismuth thin film, obtains non-crystallized iron titanate The step of bismuth thin film may include:
Heat treatment step: it is heat-treated the iron titanate bismuth thin film；
Overcoating step: taking the iron titanate bismuth precursor solution, is spin-coated to the titanium handled through the heat treatment step On sour iron bismuth thin film；
Repeat the heat treatment step and overcoating step 5-10 times described；
The iron titanate bismuth thin film that the last time heat treatment step is obtained, as the non-crystallized iron titanate bismuth Film.
Specifically, the heat treatment step step may include:
It is heat-treated the iron titanate bismuth thin film, first rises to 100 DEG C from room temperature with the rate of 3~5 DEG C/min, heat preservation 10~ 30min；400~450 DEG C are risen to the rate of 3~5 DEG C/min again, keeps the temperature 20~40min；
The iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature.
In embodiments of the present invention, specifically, the conductive substrates material may include FTO glass, ito glass, with And Pt/Ti/SiO2One of/Si base material can also be other base materials with conductive capability.
In embodiments of the present invention, specifically, it is described outside applying to the surface of the non-crystallized iron titanate bismuth thin film In the environment of electric field, non-crystallized iron titanate bismuth thin film described in high-temperature heat treatment, the step of obtaining the ferroelectric thin film of strong polarization orientation May include:
On the non-crystallized iron titanate bismuth thin film surface, by external wire, applying electric field strength is 10~30V/mm's External electric field；
Non-crystallized iron titanate bismuth thin film described in high-temperature heat treatment rises to 600~650 DEG C with the rate of 3~5 DEG C/min, protects 20~40min of temperature；
After naturally cool to the non-crystallized iron titanate bismuth thin film is taken out after room temperature, the ferroelectric thin of strong polarization orientation is obtained Film.
In embodiments of the present invention, when specifically preparing the ferroelectric thin film of strong polarization orientation, can with the following steps are included:
The ferroelectric thin film of the strong polarization orientation is placed in hydrochloric acid and is handled, the ferroelectricity THIN COMPOSITE of strong polarization orientation is obtained Film.
Specifically, the ferroelectric thin film by the strong polarization orientation is placed in hydrochloric acid and handles, strong polarization orientation is obtained Ferro-electricity compound film the step of may include:
The ferroelectric thin film of the strong polarization orientation is placed in 10~60min of processing in the hydrochloric acid of 0.5~2mol/L concentration, is obtained To the ferro-electricity compound film of strong polarization orientation.
The embodiment of the present invention also provides a kind of ferroelectric thin film of strong polarization orientation, and any of the above-described method is used to be made.
Specifically, the iron titanate bismuth on the surface of the ferroelectric thin film of the strong polarization orientation can be in laminated perovskite type, And to preferred orientation forward or backwards.
In order to enable those skilled in the art to better understand the present invention, illustrate this hair below by way of multiple specific embodiments The preparation method of the ferroelectric thin film of bright strong polarization orientation.
Embodiment 1
Weigh 5.145g Bi (NO3)3·5H2O and 0.816g Fe (NO3)3·9H2O, and 12ml glacial acetic acid is measured, it will claim Good Bi (NO3)3·5H2O and Fe (NO3)3·9H2O is added in glacial acetic acid, under 60 DEG C of water-baths, after stirring 30min, is obtained The first transparent mixed solution.
1.2ml acetylacetone,2,4-pentanedione is taken, acetylacetone,2,4-pentanedione is added in the first mixed solution, continues to stir under 60 DEG C of water-baths 30min obtains the second transparent mixed solution.
2.06ml butyl titanate is measured, the second mixed solution is dissolved in, it is cold after 30min is sufficiently stirred under 60 DEG C of water-baths But it arrives room temperature and is aged 2h, obtain iron titanate bismuth precursor solution.
FTO conductive substrates material is taken, is put into sol evenning machine after cleaning.
The iron titanate bismuth precursor solution is taken, is dropped on the FTO conductive substrates material, is rotated and is applied by sol evenning machine It is even, obtain iron titanate bismuth thin film, monolayer film thickness 330nm.
Heat treatment step: the iron titanate bismuth thin film is put into quartz tube furnace, first from room temperature with the rate of 5 DEG C/min 100 DEG C are risen to, 10min is kept the temperature；450 DEG C are risen to the rate of 5 DEG C/min again, 20min is kept the temperature, to furnace temperature cooled to room temperature After take out.
Overcoating step: the iron titanate bismuth thin film for the heat treatment step processing of learning from else's experience is placed again into sol evenning machine, takes The iron titanate bismuth precursor solution drops on the iron titanate bismuth thin film handled through the heat treatment step, passes through Sol evenning machine rotation smoothens, and monolayer film thickness is still 330nm.
After repeating the heat treatment step and the overcoating step 5 time, the heat treatment step is executed by the 6th time and is obtained The iron titanate bismuth thin film arrived, as the non-crystallized iron titanate bismuth thin film.
On the non-crystallized iron titanate bismuth thin film surface, by external wire, apply the dispatch from foreign news agency that electric field strength is 20V/mm , control current direction is anode.The current direction is shown as shown in figure 1 (a), wherein SnO2For FTO substrate surface conduction material Material, the i.e. base material of iron titanate bismuth thin film, Bi5Ti3FeO15For the iron titanate bismuth layer on iron titanate bismuth thin film surface, Ag is additional Silver electrode.
The non-crystallized iron titanate bismuth thin film is put into quartz tube furnace, 650 DEG C is risen to the rate of 5 DEG C/min, protects Warm 30min.
The non-crystallized iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature, obtains the ferroelectricity of strong polarization orientation Film.
The ferroelectric thin film of the strong polarization orientation is placed in the hydrochloric acid of 0.5mol/L concentration and handles 10min, is obtained strong The ferro-electricity compound film of polarization orientation.
Embodiment 2
Weigh 5.145g Bi (NO3)3·5H2O and 0.816g Fe (NO3)3·9H2O, and 12ml glacial acetic acid is measured, it will claim Good Bi (NO3)3·5H2O and Fe (NO3)3·9H2O is added in glacial acetic acid, under 60 DEG C of water-baths, after stirring 30min, is obtained The first transparent mixed solution.
1.2ml acetylacetone,2,4-pentanedione is taken, acetylacetone,2,4-pentanedione is added in the first mixed solution, continues to stir under 60 DEG C of water-baths 30min obtains the second transparent mixed solution.
2.06ml butyl titanate is measured, the second mixed solution is dissolved in, it is cold after 30min is sufficiently stirred under 60 DEG C of water-baths But it arrives room temperature and is aged 2h, obtain iron titanate bismuth precursor solution.
FTO conductive substrates material is taken, is put into sol evenning machine after cleaning.
The iron titanate bismuth precursor solution is taken, is dropped on the FTO conductive substrates material, is rotated and is applied by sol evenning machine It is even, obtain iron titanate bismuth thin film, monolayer film thickness 330nm.
Heat treatment step: the iron titanate bismuth thin film is put into quartz tube furnace, first from room temperature with the rate of 5 DEG C/min 100 DEG C are risen to, 10min is kept the temperature；450 DEG C are risen to the rate of 5 DEG C/min again, 20min is kept the temperature, to furnace temperature cooled to room temperature After take out.
Overcoating step: the iron titanate bismuth thin film for the heat treatment step processing of learning from else's experience is placed again into sol evenning machine, takes The iron titanate bismuth precursor solution drops on the iron titanate bismuth thin film of the heat treatment step processing of learning from else's experience, leads to It crosses sol evenning machine rotation to smoothen, monolayer film thickness is still 330nm.
After repeating the heat treatment step and the overcoating step 5 time, the heat treatment step is executed by the 6th time and is obtained The iron titanate bismuth thin film arrived, as the non-crystallized iron titanate bismuth thin film.
On the non-crystallized iron titanate bismuth thin film surface, by external wire, apply the dispatch from foreign news agency that electric field strength is 20V/mm , control current direction is cathode, and the current direction is shown as shown in figure 1 (b), wherein SnO2For FTO substrate surface conduction material Material, the i.e. base material of iron titanate bismuth thin film, Bi5Ti3FeO15For the iron titanate bismuth layer on iron titanate bismuth thin film surface, Ag is additional Silver electrode.
The non-crystallized iron titanate bismuth thin film is put into quartz tube furnace, 650 DEG C is risen to the rate of 5 DEG C/min, protects Warm 30min.
The non-crystallized iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature, obtains the ferroelectricity of strong polarization orientation Film.
The ferroelectric thin film of the strong polarization orientation is placed in the hydrochloric acid of 0.5mol/L concentration and handles 10min, is obtained strong The ferro-electricity compound film of polarization orientation.
Embodiment 3
Weigh 5.145g Bi (NO3)3·5H2O and 0.816g Fe (NO3)3·9H2O, and 12ml glacial acetic acid is measured, it will claim Good Bi (NO3)3·5H2O and Fe (NO3)3·9H2O is added in glacial acetic acid, under 60 DEG C of water-baths, after stirring 30min, is obtained The first transparent mixed solution.
1.2ml acetylacetone,2,4-pentanedione is taken, acetylacetone,2,4-pentanedione is added in the first mixed solution, continues to stir under 60 DEG C of water-baths 30min obtains the second transparent mixed solution.
2.06ml butyl titanate is measured, the second mixed solution is dissolved in, it is cold after 30min is sufficiently stirred under 60 DEG C of water-baths But it arrives room temperature and is aged 2h, obtain iron titanate bismuth precursor solution.
FTO conductive substrates material is taken, is put into sol evenning machine after cleaning.
The iron titanate bismuth precursor solution is taken, is dropped on the FTO conductive substrates material, is rotated and is applied by sol evenning machine It is even, obtain iron titanate bismuth thin film, monolayer film thickness 330nm.
Heat treatment step: the iron titanate bismuth thin film is put into quartz tube furnace, first from room temperature with the rate of 5 DEG C/min 100 DEG C are risen to, 10min is kept the temperature；450 DEG C are risen to the rate of 5 DEG C/min again, 20min is kept the temperature, to furnace temperature cooled to room temperature After take out.
Overcoating step: the iron titanate bismuth thin film for the heat treatment step processing of learning from else's experience is placed again into sol evenning machine, takes The iron titanate bismuth precursor solution drops on the iron titanate bismuth thin film handled through the heat treatment step, passes through Sol evenning machine rotation smoothens, and monolayer film thickness is still 330nm.
Repeat the overcoating and it is described dry step 5 time again after, will execute for the 6th time described in the heat treatment step obtains Iron titanate bismuth thin film, as the non-crystallized iron titanate bismuth thin film.
On the non-crystallized iron titanate bismuth thin film surface, by external wire, apply the dispatch from foreign news agency that electric field strength is 20V/mm , control current direction is anode.The current direction is shown as shown in figure 1 (a), wherein SnO2It is conductive for the substrate surface of FTO Material, the i.e. base material of iron titanate bismuth thin film, Bi5Ti3FeO15For the iron titanate bismuth layer on iron titanate bismuth thin film surface, Ag is outer The silver electrode added.
The non-crystallized iron titanate bismuth thin film is put into quartz tube furnace, 650 DEG C is risen to the rate of 5 DEG C/min, protects Warm 30min.
The non-crystallized iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature, obtains the ferroelectricity of strong polarization orientation Film.
The ferroelectric thin film of the strong polarization orientation is placed in the hydrochloric acid of 0.5mol/L concentration and handles 30min, is obtained strong The ferro-electricity compound film of polarization orientation.
Embodiment 4
Weigh 5.145g Bi (NO3)3·5H2O and 0.816g Fe (NO3)3·9H2O, and 12ml glacial acetic acid is measured, it will claim Good Bi (NO3)3·5H2O and Fe (NO3)3·9H2O is added in glacial acetic acid, under 60 DEG C of water-baths, after stirring 30min, is obtained The first transparent mixed solution.
1.2ml acetylacetone,2,4-pentanedione is taken, acetylacetone,2,4-pentanedione is added in the first mixed solution, continues to stir under 60 DEG C of water-baths 30min obtains the second transparent mixed solution.
2.06ml butyl titanate is measured, the second mixed solution is dissolved in, it is cold after 30min is sufficiently stirred under 60 DEG C of water-baths But it arrives room temperature and is aged 2h, obtain iron titanate bismuth precursor solution.
FTO conductive substrates material is taken, is put into sol evenning machine after cleaning.
The iron titanate bismuth precursor solution is taken, is dropped on the FTO conductive substrates material, is rotated and is applied by sol evenning machine It is even, obtain iron titanate bismuth thin film, monolayer film thickness 330nm.
Heat treatment step: the iron titanate bismuth thin film is put into quartz tube furnace, first from room temperature with the rate of 5 DEG C/min 100 DEG C are risen to, 10min is kept the temperature；450 DEG C are risen to the rate of 5 DEG C/min again, 20min is kept the temperature, to furnace temperature cooled to room temperature After take out.
Overcoating step: the iron titanate bismuth thin film for the heat treatment step processing of learning from else's experience is placed again into sol evenning machine, takes The iron titanate bismuth precursor solution drops on the iron titanate bismuth thin film handled through the heat treatment step, passes through Sol evenning machine rotation smoothens, and monolayer film thickness is still 330nm.
After repeating the heat treatment step and the overcoating step 5 time, the heat treatment step is executed by the 6th time and is obtained The iron titanate bismuth thin film arrived, as the non-crystallized iron titanate bismuth thin film.
On the non-crystallized iron titanate bismuth thin film surface, by external wire, apply the dispatch from foreign news agency that electric field strength is 20V/mm , control current direction is cathode, and the current direction is shown as shown in figure 1 (b), wherein SnO2It is conductive for the substrate surface of FTO Material, the i.e. base material of iron titanate bismuth thin film, Bi5Ti3FeO15For the iron titanate bismuth layer on iron titanate bismuth thin film surface, Ag is outer The silver electrode added.
The non-crystallized iron titanate bismuth thin film is put into quartz tube furnace, 650 DEG C is risen to the rate of 5 DEG C/min, protects Warm 30min.
The non-crystallized iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature, obtains the ferroelectricity of strong polarization orientation Film.
The ferroelectric thin film of the strong polarization orientation is placed in the hydrochloric acid of 0.5mol/L concentration and handles 30min, is obtained strong The ferro-electricity compound film of polarization orientation.
Embodiment 5
Weigh 4.8507g Bi (NO3)3·5H2O and 0.816g Fe (NO3)3·9H2O, and 8.59ml glacial acetic acid is measured, it will Bi (the NO weighed up3)3·5H2O and Fe (NO3)3·9H2O is added in glacial acetic acid, under 50 DEG C of water-baths, after stirring 40min, is obtained To the first transparent mixed solution.
0.72ml acetylacetone,2,4-pentanedione is taken, acetylacetone,2,4-pentanedione is added in the first mixed solution, continues to stir under 50 DEG C of water-baths 40min obtains the second transparent mixed solution.
1.70ml butyl titanate is measured, the second mixed solution is dissolved in, it is cold after 40min is sufficiently stirred under 50 DEG C of water-baths But it arrives room temperature and is aged 2h, obtain iron titanate bismuth precursor solution.
ITO conductive substrates material is taken, is put into sol evenning machine after cleaning.
The iron titanate bismuth precursor solution is taken, is dropped on the ITO conductive substrates material, is rotated and is applied by sol evenning machine It is even, obtain iron titanate bismuth thin film.
Heat treatment step: the iron titanate bismuth thin film is put into quartz tube furnace, first from room temperature with the rate of 3 DEG C/min 100 DEG C are risen to, 20min is kept the temperature；400 DEG C are risen to the rate of 3 DEG C/min again, 30min is kept the temperature, to furnace temperature cooled to room temperature After take out, obtain toasted iron titanate bismuth thin film.
Overcoating step:: the iron titanate bismuth thin film for the heat treatment step processing of learning from else's experience is placed again into sol evenning machine, The iron titanate bismuth precursor solution is taken, is dropped on the iron titanate bismuth thin film handled through the heat treatment step, is led to Sol evenning machine rotation is crossed to smoothen.
After repeating the heat treatment step and the overcoating step 9 time, the heat treatment step is executed by the 10th time The obtained iron titanate bismuth thin film, as the non-crystallized iron titanate bismuth thin film.
On the non-crystallized iron titanate bismuth thin film surface, by external wire, apply the dispatch from foreign news agency that electric field strength is 10V/mm , control current direction is anode.
The non-crystallized iron titanate bismuth thin film is put into quartz tube furnace, 600 DEG C is risen to the rate of 3 DEG C/min, protects Warm 40min.
The non-crystallized iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature, obtains the ferroelectricity of strong polarization orientation Film.
The ferroelectric thin film of the strong polarization orientation is placed in the hydrochloric acid of 2mol/L concentration and handles 30min, obtains strong pole Change the ferro-electricity compound film of orientation.
Embodiment 6
Weigh 4.9477g Bi (NO3)3·5H2O and 0.816g Fe (NO3)3·9H2O, and 10.51ml glacial acetic acid is measured, Bi (the NO that will be weighed up3)3·5H2O and Fe (NO3)3·9H2O is added in glacial acetic acid, under 70 DEG C of water-baths, after stirring 20min, Obtain the first transparent mixed solution.
1.31ml acetylacetone,2,4-pentanedione is taken, acetylacetone,2,4-pentanedione is added in the first mixed solution, continues to stir under 70 DEG C of water-baths 20min obtains the second transparent mixed solution.
2.38ml butyl titanate is measured, the second mixed solution is dissolved in, it is cold after 20min is sufficiently stirred under 70 DEG C of water-baths But it arrives room temperature and is aged 2h, obtain iron titanate bismuth precursor solution.
Take Pt/Ti/SiO2/ Si conductive substrates material is put into sol evenning machine after cleaning.
The iron titanate bismuth precursor solution is taken, the Pt/Ti/SiO is dropped to2On/Si conductive substrates material, pass through spin coating Machine rotation smoothens, and obtains iron titanate bismuth thin film.
Heat treatment step: the iron titanate bismuth thin film is put into quartz tube furnace, first from room temperature with the rate of 4 DEG C/min 100 DEG C are risen to, 30min is kept the temperature；430 DEG C are risen to the rate of 4 DEG C/min again, 40min is kept the temperature, to furnace temperature cooled to room temperature After take out, obtain toasted iron titanate bismuth thin film.
Overcoating step: the iron titanate bismuth thin film for the heat treatment step processing of learning from else's experience is placed again into sol evenning machine, takes The iron titanate bismuth precursor solution drops on the iron titanate bismuth thin film handled through the heat treatment step, passes through Sol evenning machine rotation smoothens.
After repeating the heat treatment step and the overcoating step 7 time, the heat treatment step is executed by the 8th time and is obtained The iron titanate bismuth thin film arrived, as the non-crystallized iron titanate bismuth thin film.
On the non-crystallized iron titanate bismuth thin film surface, by external wire, apply the dispatch from foreign news agency that electric field strength is 30V/mm , control current direction is cathode.
The non-crystallized iron titanate bismuth thin film is put into quartz tube furnace, 630 DEG C is risen to the rate of 4 DEG C/min, protects Warm 20min.
The non-crystallized iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature, obtains the ferroelectricity of strong polarization orientation Film.
The ferroelectric thin film of the strong polarization orientation is placed in the hydrochloric acid of 1mol/L concentration and handles 60min, obtains strong pole Change the ferro-electricity compound film of orientation.
Iron titanate bismuth is a kind of Aurivillius laminated perovskite derivative structure compound, (Bi2O2)2+Layer and four layers of calcium Perovskite like structure unit (Bi3Ti3FeO13)2-It is alternately arranged along c-axis, 749 DEG C of ferroelectricity transition temperature.The forbidden bandwidth of iron titanate bismuth is 2.08eV, therefore there is certain visible light absorption capacity.BiOCl is also a kind of Nb steel compound, is by double Cl- Sheath and (B2O2)2+It is alternately arranged to be formed along c-axis direction.Although BiOCl is not ferroelectric, its negative ions layer structure Inherent polarization field is formed, equally plays the role of promoting carrier separation, makes it have excellent photocatalytic activity.The present invention is real Example is applied by the way that iron titanate bismuth and bismuth oxychloride are compounded to form semiconductor heterostructure, and is applied in the preparation process of ferroelectric thin film Add external electric field, realizes the strong polarization orientation growth of ferroelectric thin film, the visible-light photocatalysis material being had excellent performance.This hair Ferroelectric thin film surfacing made from bright embodiment and it is fine and close, crystallinity is high, and the polarization orientation of crystal grain is obvious, ferroelectric thin obtained Film has high optics catalytic performance.Illustrate below by way of specific experimental data the embodiment of the present invention compared with the prior art Certain advantages.
Compare the preparation of unpolarized sample:
Weigh 5.145g Bi (NO3)3·5H2O and 0.816g Fe (NO3)3·9H2O, and 12ml glacial acetic acid is measured, it will claim Good Bi (NO3)3·5H2O and Fe (NO3)3·9H2O is added in glacial acetic acid, under 60 DEG C of water-baths, after stirring 30min, is obtained The first transparent mixed solution.
1.2ml acetylacetone,2,4-pentanedione is taken, acetylacetone,2,4-pentanedione is added in the first mixed solution, continues to stir under 60 DEG C of water-baths 30min obtains the second transparent mixed solution.
2.06ml butyl titanate is measured, the second mixed solution is dissolved in, it is cold after 30min is sufficiently stirred under 60 DEG C of water-baths But it arrives room temperature and is aged 2h, obtain iron titanate bismuth precursor solution.
FTO conductive substrates material is taken, is put into sol evenning machine after cleaning.
The iron titanate bismuth precursor solution is taken, is dropped on the FTO conductive substrates material, is rotated and is applied by sol evenning machine It is even, obtain iron titanate bismuth thin film, monolayer film thickness 330nm.
Processing step: the iron titanate bismuth thin film is put into quartz tube furnace, first from room temperature with the rate liter of 5 DEG C/min To 100 DEG C, 10min is kept the temperature；450 DEG C are risen to the rate of 5 DEG C/min again, 20min is kept the temperature, after furnace temperature cooled to room temperature It takes out.
Overcoating step: the iron titanate bismuth thin film for the heat treatment step processing of learning from else's experience is placed again into sol evenning machine, takes The iron titanate bismuth precursor solution drops on the iron titanate bismuth thin film of the heat treatment step processing of learning from else's experience, leads to It crosses sol evenning machine rotation to smoothen, monolayer film thickness is still 330nm.
After repeating the heat treatment step and the overcoating step 5 time, the heat treatment step is executed by the 6th time and is obtained The iron titanate bismuth thin film arrived, as the non-crystallized iron titanate bismuth thin film.
The non-crystallized iron titanate bismuth thin film is put into quartz tube furnace, 650 DEG C is risen to the rate of 5 DEG C/min, protects Warm 30min.
The non-crystallized iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature, obtains comparing unpolarized sample.
One, X-ray diffraction analysis (XRD)
It is compound to the ferroelectricity of strong polarization orientation made from the ferroelectric thin film of strong polarization orientation made from embodiment 1, embodiment 3 Film and the unpolarized sample of comparison, carry out X-ray diffraction analysis.
Method particularly includes: it is carried out using the Rigaku-D/max-2550pc type x-ray powder diffraction instrument of Hitachi, Japan Test, uses Cu-k α as radiation source, wavelength isUsing Ni filter plate, Guan Liuwei 40mA, pipe pressure is 40KV, is swept Retouching range is 10 °~90 °, and scanning speed is 8 °/min, and step-length is 0.02 °.By the ferroelectricity of strong polarization orientation made from embodiment 1 The ferro-electricity compound film of strong polarization orientation made from film, embodiment 1 and the unpolarized sample insertion instrument experiment slot of comparison are just In, it is tested；The identification of object phase and crystal structure information are analyzed by JADE5.0 software.
The XRD diagram of the ferroelectric thin film of strong polarization orientation made from embodiment 1 and the unpolarized sample of comparison as shown in Fig. 2, This it appears that being removed in the XRD spectral line of the ferroelectric thin film (polarization) of strong polarization orientation made from embodiment 1 SnO2Outside the diffraction maximum of (FTO conductive substrates), the position of remaining diffraction maximum all with Bi5Ti3FeO15(PDF#38-1257,Pnn2, ) consistent, the presence of obvious impurity phase diffraction maximum is not observed, it was demonstrated that The ferroelectric thin film of the strong polarization orientation of synthesis is more pure, the generation of non-oxidation bismuth or other impurities phase.It is unpolarized with comparing Sample (unpolarization) is compared, it is found that the iron titanate bismuth of polarization process 8.4 ° of low angle (004) and 12.8 ° of (006) diffraction maximum occurs, and the diffraction peak intensity of (008) and (0010) is remarkably reinforced, and shows the ferroelectricity of strong polarization orientation Film sample has certain { 00l } preferred orientation.The halfwidth at the peak XRD of the ferroelectric thin film of strong polarization orientation relatively compares non-pole The half-peak breadth for changing sample narrows, and the intensity (under the conditions of same test) of diffraction maximum is remarkably reinforced, and shows strong polarization orientation Ferroelectric thin film sample has better crystallinity.
The ferroelectricity of strong polarization orientation made from the ferro-electricity compound film of strong polarization orientation made from embodiment 3 and embodiment 1 The XRD diagram of film is fig. 3, it is shown that the ferro-electricity compound film (HCl 30min) of strong polarization orientation deducts FTO conduction Substrate SnO2Outside the diffraction maximum of iron titanate bismuth, there is new diffraction maximum on 12 °, 25.8 °, 40.9 ° and 58.8 ° positions, with Standard PDF card comparison discovery respectively correspond BiOCl (PDF 06-0249, P4/nmm,) crystal (001), (101), (112) and (212) crystal face diffraction maximum.Card Part iron titanate bismuth is successfully passed through ion exchange after 0.5mol/L salt acid soak 30min by the ferroelectric thin film of bright strong polarization orientation Reaction is converted into bismuth oxychloride, is successfully prepared polarization iron titanate bismuth-bismuth oxychloride composite heterogenous junction film, i.e., strong polarization orientation Ferro-electricity compound film.
Two, microstructure is tested
To the ferroelectric thin film of strong polarization orientation made from embodiment 1 and the unpolarized sample of comparison, using Hitachi S-4800 High-resolution Flied emission scanning electron microscope (SEM) carries out microstructure test to film, as a result as shown in figure 4, wherein Fig. 4 (a) is The SEM electron microscope of unpolarized sample is compared, Fig. 4 (b) is the SEM Electronic Speculum of the ferroelectric thin film of strong polarization orientation made from embodiment 1 Figure, Fig. 4 (c) are the section SEM electron microscope of the ferroelectric thin film of strong polarization orientation made from embodiment 1.
From fig. 4, it can be seen that using iron obtained by the preparation method of embodiment 1 and the preparation method of the unpolarized sample of comparison Conductive film is more smooth and fine and close, even grain size distribution.Wherein, the crystallite dimension 70nm for comparing unpolarized sample is left The right side, and the crystal grain of the ferroelectric thin film of strong polarization orientation made from embodiment 1 also shows apparent strip-like features, size is about 110nm (face) 20nm (thickness).The variation of film crystallite dimension and pattern further illustrates, handles by extra electric field The ferroelectric thin film of strong polarization orientation has better crystallinity, this result and above-mentioned X-ray compared with comparing unpolarized sample Diffraction analysis matches.The section SEM electron microscope of the ferroelectric thin film of strong polarization orientation made from the embodiment 1, i.e. Fig. 4 (c) can To find out, the film thickness of preparation is~2 μm, and side view reflects that film thickness is uniform, surface is regular indirectly.
It is compound to the ferroelectricity of strong polarization orientation made from the ferroelectric thin film of strong polarization orientation made from embodiment 1, embodiment 1 The ferro-electricity compound film of strong polarization orientation, is swept using Hitachi S-4800 high-resolution Flied emission made from film and embodiment 3 It retouches Electronic Speculum (SEM) and microstructure test is carried out to film, as a result as shown in figure 5, wherein Fig. 5 (a) is strong pole made from embodiment 1 Change the SEM electron microscope of the ferroelectric thin film of orientation, Fig. 5 (b) is the ferro-electricity compound film of strong polarization orientation made from embodiment 1 SEM electron microscope, Fig. 5 (c) are the SEM electron microscope of the ferro-electricity compound film of strong polarization orientation made from embodiment 3.
As seen from Figure 5, the crystallite dimension of the ferroelectric thin film of strong polarization orientation made from embodiment 1 be 110nm, Fig. 5 (b) with Fig. 5 (a) is compared, and the sheet crystal that particle size is about 200nm occurs, and film surface is fine and close.In X-ray diffraction analysis In have shown sheet crystal be ion exchange reaction generate stratiform bismuth oxychloride.As shown in Fig. 5 (c), when salt acid soak Between when increasing to 30min, the bismuth oxychloride structure of laminated structure further increases, and crystallite dimension is also further enlarged as 300nm Left and right, the arrangement of surface patch layered crystal are more loose.
Three, photoelectrochemical behaviour is tested
Photoelectrochemical behaviour test method particularly includes: with epoxy resin that film is sealed around, there are straight for middle section The blank area of diameter 6mm circle is as working electrode, using three electrode test systems, using saturated calomel electrode as reference electrode, and platinum electricity Extremely to electrode, 1mol/LNa2SO4As electrolyte.Electrochemical workstation uses Shanghai Chen Hua chi660e, and light source uses xenon light Lamp, in a standard sunlight intensity (100mW/cm2) under testing film surface photocurrent variations.
To the ferroelectricity of strong polarization orientation obtained by the ferroelectric thin film of strong polarization orientation, embodiment 2 obtained by embodiment 1 Film and the unpolarized sample of comparison carry out photoelectrochemical behaviour test, as a result as shown in Figure 6.
By Fig. 6 a as it can be seen that under identical applied voltage, the ferroelectric thin film of strong polarization orientation obtained by embodiment 1 (+ Polarization) and the photoelectric current of the ferroelectric thin film (- polarization) of strong polarization orientation obtained by embodiment 2 is close Degree, which is all greater than, compares unpolarized sample (unpolarization), this is because polarized sample has preferable crystallinity and interior It builds electric field and promotes the effect of electrode surface carrier separation, illustrate the ferroelectric thin film of positive polarized ferroelectric thin film and reverse polarization Photocatalytic activity be all better than without external electric field handle the unpolarized sample of comparison.By Fig. 6 b as it can be seen that in fixed outer power-up It presses under (vs SCE 1.2V), the ferroelectric thin film of strong polarization orientation obtained by embodiment 1, i.e., positive polarized ferroelectric thin film, Density of photocurrent (~6 μ A/cm2) it is greater than ferroelectric thin film (~4 μ A/cm of strong polarization orientation obtained by embodiment 22), i.e., reversely Polarized ferroelectric thin film illustrates that the photocatalytic activity of positive polarized ferroelectric thin film is better than the ferroelectricity of the ferroelectric thin film of reverse polarization Film.
To the ferroelectricity of strong polarization orientation obtained by the ferroelectric thin film of strong polarization orientation, embodiment 2 obtained by embodiment 2 The ferro-electricity compound film of strong polarization orientation obtained by laminated film and embodiment 4 carries out photoelectrochemical behaviour test, as a result As shown in Figure 7.
As Fig. 7 (a) as it can be seen that the ferroelectric thin film of strong polarization orientation obtained by embodiment 2 is in the light after HCl immersion treatment Current density preceding is highly improved compared to untreated.As Fig. 7 (b) as it can be seen that strong polarization orientation obtained by embodiment 2 Ferroelectric thin film, i.e., it is 3.9 μ A/cm that the density of photocurrent of the reverse polarization ferroelectric thin film without HCl processing is minimum2；Embodiment The ferro-electricity compound film of strong polarization orientation obtained by 2, i.e. immersion 10min HCl treated reverse polarization ferro-electricity compound film Density of photocurrent difference before and after illumination is~8 μ A/cm2；The ferro-electricity compound film of strong polarization orientation obtained by embodiment 4, Before and after impregnating 30min HCl treated reverse polarization ferro-electricity compound film illumination, density of photocurrent difference is~9 μ A/ cm2.Illustrate by impregnating 10min HCl treated reverse polarization ferro-electricity compound film than the reversed pole that handles without HCl Change ferroelectric thin film, photocatalysis performance has been significantly improved, and impregnates 30min HCl treated that reverse polarization ferroelectricity is compound Film and 10min HCl treated reverse polarization ferro-electricity compound film is impregnated, photocatalysis performance is but still obvious without being obviously improved Better than the reverse polarization ferroelectric thin film handled without HCl.
To the ferroelectricity of strong polarization orientation obtained by the ferroelectric thin film of strong polarization orientation, embodiment 1 obtained by embodiment 1 The ferro-electricity compound film of strong polarization orientation obtained by laminated film and embodiment 3 carries out photoelectrochemical behaviour test, as a result As shown in Figure 8.
As Fig. 8 (a) as it can be seen that the ferro-electricity compound film of strong polarization orientation obtained by embodiment 1, i.e. immersion 10min HCl Treated, and sample density of photocurrent is highest in all samples.The ferroelectricity of strong polarization orientation obtained by embodiment 3 is multiple Close film, i.e. ferroelectricity of immersion 30min HCl treated the sample density of photocurrent than strong polarization orientation obtained by embodiment 1 Laminated film is slightly smaller.
From the point of view of photoelectric current in Fig. 8 (b) changes with time trend (vs SCE 1.2V), strong pole obtained by embodiment 1 Change the ferroelectric thin film of orientation, i.e., it is 6.32 μ A/cm that the density of photocurrent of the sample without HCl processing is minimum2；Embodiment 1 is made Strong polarization orientation ferro-electricity compound film, i.e. photoelectric current difference before and after immersion 10min HCl treated sample illumination For~10 μ A/cm2；The ferro-electricity compound film of strong polarization orientation obtained by embodiment 3, i.e., treated by immersion 30min HCl Sample photoelectric current difference before and after illumination is up to~11 μ A/cm2。
The positive polarized ferro-electric laminated film that illustrates that treated by impregnating 10min HCl without HCl than handling just To polarized ferro-electric film, photocatalysis performance is had been significantly improved, and impregnates 30min HCl treated positive polarized ferro-electric Laminated film and impregnate 10min HCl treated positive polarized ferro-electric laminated film, photocatalysis performance without being obviously improved, but still It is substantially better than the positive polarized ferro-electric film handled without HCl.
The ferro-electricity compound film of either positive polarized strong polarization orientation or reverse polarization as can be seen from the above The ferro-electricity compound film of strong polarization orientation, photoelectrochemical behaviour is all obviously improved after area load bismuth oxychloride.
Detailed Jie has been carried out to a kind of ferroelectric thin film of strong polarization orientation provided by the present invention and preparation method thereof above It continues, used herein a specific example illustrates the principle and implementation of the invention, and the explanation of above embodiments is only It is to be used to help understand method and its core concept of the invention；At the same time, for those skilled in the art, according to this hair Bright thought, there will be changes in the specific implementation manner and application range, in conclusion the content of the present specification should not manage Solution is limitation of the present invention.

Claims (10)

1. a kind of preparation method of the ferroelectric thin film of strong polarization orientation characterized by comprising
Prepare iron titanate bismuth precursor solution；
Obtain conductive substrates material；
The iron titanate bismuth precursor solution is spin-coated on the conductive substrates material, iron titanate bismuth thin film is obtained；
It is heat-treated the iron titanate bismuth thin film, obtains non-crystallized iron titanate bismuth thin film；
In the environment of applying external electric field to the surface of the non-crystallized iron titanate bismuth thin film, it is heat-treated under high temperature described non-crystallized Iron titanate bismuth thin film obtains the ferroelectric thin film of strong polarization orientation.
2. the preparation method of the ferroelectric thin film of strong polarization orientation as described in claim 1, which is characterized in that the method is also wrapped It includes:
The ferroelectric thin film of the strong polarization orientation is placed in hydrochloric acid and is handled, the ferro-electricity compound film of strong polarization orientation is obtained.
3. the preparation method of the ferroelectric thin film of strong polarization orientation as described in claim 1, which is characterized in that described to prepare metatitanic acid The step of iron bismuth precursor solution includes:
Prepare Bi (NO3)3·5H2O、Fe(NO3)3·9H2And glacial acetic acid O,；
By Bi (NO3)3·5H2O、Fe(NO3)3·9H2O is added in glacial acetic acid, under 50~70 DEG C of water-baths, stirs 20~40min, Obtain the first mixed solution；
Acetylacetone,2,4-pentanedione is taken, is added in first mixed solution, under 50~70 DEG C of water-baths, 20~40min is stirred, obtains the Two mixed solutions；
Butyl titanate is taken, is added in second mixed solution, it is cold after stirring 20~40min under 50~70 DEG C of water-baths But it to room temperature and is aged, obtains iron titanate bismuth precursor solution.
4. the preparation method of the ferroelectric thin film of strong polarization orientation as claimed in claim 3, which is characterized in that the Bi (NO3)3·5H2The O and Fe (NO3)3·9H2Molar ratio between O are as follows: Bi:Fe=5~5.3:1；
Bi (the NO3)3·5H2Molar ratio between O and the glacial acetic acid are as follows: glacial acetic acid: Bi=15~20:1；
Volume ratio between the acetylacetone,2,4-pentanedione and the glacial acetic acid are as follows: acetylacetone,2,4-pentanedione: glacial acetic acid=1:8~12；
The butyl titanate and the Fe (NO3)3·9H2Molar ratio between O are as follows: Ti:Fe=2.5~3.5:1.
5. the preparation method of the ferroelectric thin film of strong polarization orientation as described in claim 1, which is characterized in that the heat treatment institute The step of stating iron titanate bismuth thin film, obtaining non-crystallized iron titanate bismuth thin film include:
Heat treatment step: it is heat-treated the iron titanate bismuth thin film；
Overcoating step: taking the iron titanate bismuth precursor solution, is spin-coated to the iron titanate handled through the heat treatment step On bismuth thin film；
Repeat the heat treatment step and overcoating step 5-10 times described；
The iron titanate bismuth thin film that the last time heat treatment step is obtained is thin as the non-crystallized iron titanate bismuth Film.
6. the preparation method of the ferroelectric thin film of strong polarization orientation as claimed in claim 5, which is characterized in that the heat treatment step Suddenly it specifically includes:
It is heat-treated the iron titanate bismuth thin film, first 100 DEG C is risen to from room temperature with the rate of 3~5 DEG C/min, keeps the temperature 10~30min； 400~450 DEG C are risen to the rate of 3~5 DEG C/min again, keeps the temperature 20~40min；
The iron titanate bismuth thin film is taken out after furnace temperature cooled to room temperature.
7. the preparation method of the ferroelectric thin film of strong polarization orientation as claimed in claim 5, which is characterized in that the conductive substrates Material includes FTO glass, ito glass and Pt/Ti/SiO2One of/Si base material.
8. the preparation method of the ferroelectric thin film of polarization orientation as described in claim 1 strong, which is characterized in that described to described In the environment of the surface of non-crystallized iron titanate bismuth thin film applies external electric field, non-crystallized iron titanate bismuth thin film described in high-temperature heat treatment, The step of obtaining the ferroelectric thin film of strong polarization orientation include:
On the non-crystallized iron titanate bismuth thin film surface, by external wire, apply the dispatch from foreign news agency that electric field strength is 10~30V/mm ?；
Non-crystallized iron titanate bismuth thin film described in high-temperature heat treatment rises to 600~650 DEG C with the rate of 3~5 DEG C/min, heat preservation 20 ~40min；
After naturally cool to the non-crystallized iron titanate bismuth thin film is taken out after room temperature, the ferroelectric thin film of strong polarization orientation is obtained.
9. the preparation method of the ferroelectric thin film of strong polarization orientation as claimed in claim 2, which is characterized in that by the strong polarization The ferroelectric thin film of orientation is placed in hydrochloric acid, and the step of handling, obtaining the ferro-electricity compound film of strong polarization orientation, includes:
The ferroelectric thin film of the strong polarization orientation is placed in 10~60min of processing in the hydrochloric acid of 0.5~2mol/L concentration, is obtained strong The ferro-electricity compound film of polarization orientation.
10. a kind of ferroelectric thin film of strong polarization orientation uses preparation method as described in any one of claims 1 to 9 to be made.
CN201810844049.3A 2018-07-27 2018-07-27 A kind of ferroelectric thin film and preparation method thereof of strong polarization orientation Pending CN109081609A (en)

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CN1288981A (en) * 2000-09-18 2001-03-28 南京大学 Low-electric field inducting control method to orient film prepared through a wet chemical process
CN104511293A (en) * 2014-10-31 2015-04-15 北京理工大学 Bismuth oxychloride-iron bismuth titanate composite photocatalyst and preparation method thereof
CN104952628A (en) * 2015-07-22 2015-09-30 齐齐哈尔大学 High-performance electrochemical capacitor plate material and preparation method thereof
KR20170085852A (en) * 2016-01-15 2017-07-25 가천대학교 산학협력단 Method for forming photo electrode of dye sensitized solar cell, method for manufacturing dye-sensitized solar cell using the method and dye sensitized solar cell manufactured by the method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1288981A (en) * 2000-09-18 2001-03-28 南京大学 Low-electric field inducting control method to orient film prepared through a wet chemical process
CN104511293A (en) * 2014-10-31 2015-04-15 北京理工大学 Bismuth oxychloride-iron bismuth titanate composite photocatalyst and preparation method thereof
CN104952628A (en) * 2015-07-22 2015-09-30 齐齐哈尔大学 High-performance electrochemical capacitor plate material and preparation method thereof
KR20170085852A (en) * 2016-01-15 2017-07-25 가천대학교 산학협력단 Method for forming photo electrode of dye sensitized solar cell, method for manufacturing dye-sensitized solar cell using the method and dye sensitized solar cell manufactured by the method

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