CN102583568A - Method for preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment - Google Patents

Method for preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment Download PDF

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CN102583568A
CN102583568A CN2012100338521A CN201210033852A CN102583568A CN 102583568 A CN102583568 A CN 102583568A CN 2012100338521 A CN2012100338521 A CN 2012100338521A CN 201210033852 A CN201210033852 A CN 201210033852A CN 102583568 A CN102583568 A CN 102583568A
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ultraviolet light
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CN102583568B (en
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谈国强
尹君
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Shaanxi University of Science and Technology
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Abstract

The invention provides a method for preparing a bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment. The method comprises the following steps of: dissolving Bi(NO3)3.5H2O and Fe(NO3)3.9H2O which serve as raw materials into distilled water, and regulating the pH value of the solution by using glacial acetic acid; preparing a film by using citric acid as a complexing agent, using a functionalized self-assembly single-layer film as a template and suspending the functionalized template on the surface of the solution through reverse adsorption; and drying at room temperature, treating in short wave ultraviolet (lambda is 184.9 nanometers), preserving the heat at the temperature of 550 DEG C and annealing, and thus obtaining the crystallized bismuth ferrite functional film. The amorphous bismuth ferrite functional film is treated in ultraviolet by combining a liquid-phase self-assembly and reverse adsorption technology, and the organic substance chain is oxidized through ozone generated by short wave ultraviolet irradiation air to remove organic substances. Because the organic substances are removed at the room temperature, the film is shrunk slightly, and cracks produced due to over high shrinkage of the film when the organic substances are decomposed at a high temperature are prevented.

Description

The pre-treatment of a kind of short wave ultraviolet light irradiation prepares the method for ferrous acid bismuth function film
Technical field
The invention belongs to field of functional materials, relate to the method that the pre-treatment of a kind of short wave ultraviolet light irradiation prepares ferrous acid bismuth function film.
Background technology
In recent years, a kind of novel ferromagnetic electric material BiFeO 3,, caused the great interest of people as one of single-phase ferromagnetic electric material that has ferroelectricity and magnetic under the minority room temperature simultaneously.BiFeO 3The high Tc (T of calcium titanium ore structure with tripartite distortion C=810 ℃) and Neel temperature (T N=380 ℃), EM coupling acts on information storage, spin electric device aspect, and all there is extremely important application prospect Magnetic Sensor and electric capacity-aspects such as inductor integrated device.
At present for BiFeO 3The preparation method of film mainly contains pulsed laser deposition, magnetron sputtering method etc.Its advantage of pulsed laser deposition is to reduce base reservoir temperature, can keep better chemical metering ratio, and film quality good (density is high), adhesion property are strong, the film of the complicated component that is suitable for growing, and need tackle the major problem is how to obtain large area uniform film.Sputtering method can the big area film forming, and film quality is high, but the speed of growth is slow, and the microstructure and the composition homogeneity of film are held improvement.More than these preparation technology's equipment comparatively complicated, need strict vacuum environment and process system, cost expensive, and the small amount of impurities that often contains is difficult to remove and can not get pure phase, like Bi 2Fe 4O 9And Bi 25FeO 40The chemical liquid deposition method is a kind of wet chemical method, and it does not need expensive device, is suitable for the large-area preparation film, is widely used in synthetic various functional materialss, and has obtained great success.
Self-assembled monolayer (self-assembled monolayers) technology (being called for short the SAMs technology) is the core technology of bionical synthesis technique; It is through producing chemisorption between an activity base of tensio-active agent and the substrate, the orderly molecule assembled layers of spontaneous formation on the interface.Prepare bismuth ferrite thin film for self-assembling technique; Because SAMs is that organic molecule (perhaps organic molecule steam) in solution is spontaneous and is adsorbed on formed ultra-thin organic membrane on the solid substrate securely through chemical bond, so it has the spontaneous formation of original position, becomes characteristics such as the key high-sequential is arranged, defective is few, bonding force is strong.But also because SAMs is an organic membrane, organic removal is a difficult problem in the process of preparation film simultaneously.Prepare bismuth ferrite thin film for self-assembly method at present, what all adopt is the pyrolytic decomposition organism and since under the high temperature during decomposing organic matter film shrink excessively, make prepared film to crack.
The present invention is a template with self-assembly octadecyl trichlorosilane (OTS) unitary film; (λ=184.9nm) radiation instrument carries out surface-treated to OTS-SAMs to the radiothermy UV-light; In conjunction with liquid phase deposition; Utilize reverse adsorption technology to prepare bismuth ferrite thin film, and (λ=184.9nm) handle, make organism: the macromole of octadecyl trichlorosilane (OTS) unitary film, Glacial acetic acid min. 99.5, Hydrocerol A is converted into CH before film annealing, under room temperature, to carry out short wave ultraviolet light 3-waiting small molecules, annealing prepares the crystalline state bismuth ferrite thin film then.This technology that not only this novel liquid phase self-assembling method is prepared bismuth ferrite thin film is a kind of breakthrough progress; And because short wave ultraviolet light (λ=184.9nm) handles and removes organism is at room temperature to carry out; Film shrinks very little; Make that (λ=184.9nm) the employing liquid phase self-assembly method of processing prepares bismuth ferrite thin film surfacing densification and do not have crackle, and this also has directive significance to studying its dielectricity and many iron property through short wave ultraviolet light.
Summary of the invention
Technical problem to be solved by this invention provides the method that the pre-treatment of a kind of short wave ultraviolet light irradiation prepares ferrous acid bismuth function film, and (λ=184.9nm) handles that to prepare by annealing surfacing finer and close and do not have a ferrous acid bismuth function film of crackle to utilize short wave ultraviolet light before liquid phase self-assembled monolayer membrane technique combines annealing.
For realizing above-mentioned purpose, the invention provides the method that the pre-treatment of a kind of short wave ultraviolet light irradiation prepares ferrous acid bismuth function film, with Bi (NO 3) 35H 2O, Fe (NO 3) 39H 2O is a raw material, is dissolved in the zero(ppm) water together with Glacial acetic acid min. 99.5, adds the complexing agent Hydrocerol A then, obtains precursor liquid; Wherein, in precursor liquid, bismuth ion concentration is 0.01mol/L; Iron concentration is 0.01～0.045mol/L, and the volume(tric)fraction of Glacial acetic acid min. 99.5 is 2%, and citric acid concentration is 0.02mol/L; With the functionalization self-assembled monolayer is template; Under 60～90 ℃, template is suspended in the reverse absorption preparation in precursor liquid surface film; Then, film is at room temperature carried out UV-irradiation perhaps at 300 ℃ of annealing 30min, to remove the film surface residual organic after the drying; At last, get final product at 550 ℃ of insulation annealings.
As the preferred embodiments of the present invention, the preparation method of said functionalization self-assembled monolayer is: at first with the substrate washes clean, under UV-light, shine 20min then; Then, in the OTS-toluene solution, soak 30min and get final product, wherein; In the OTS-toluene solution; The volume(tric)fraction of OTS is 1%, and is last, under UV-light, shining 40min after 120 ℃ of dryings again;
As the preferred embodiments of the present invention, the depositing time that said template is suspended in the precursor liquid surface is 6～30h;
As the preferred embodiments of the present invention, said ferrous acid bismuth function film thickness is 40nm;
As the preferred embodiments of the present invention, said film is at room temperature carried out UV-irradiation after the drying when removing the film surface residual organic, said ultraviolet light wavelength is 184.9nm.
The method that the pre-treatment of a kind of short wave ultraviolet light irradiation of the present invention prepares ferrous acid bismuth function film has the following advantages at least: the present invention combines the reverse adsorption technology of liquid phase self-assembly; Carry out treatment with ultraviolet light non-crystalline state ferrous acid bismuth thin film; (ozone that the irradiation of λ=184.9nm) air produces is with the oxidation of organism chain, to reach rapid temperature and to remove organic purpose through short wave ultraviolet light.And owing to be to remove organism in room temperature, the contraction of film is very little, and film shrinks excessive and cracks when having prevented at high temperature decomposing organic matter.(the film surface densification after λ=184.9nm) handles is smooth, does not have crackle through short wave ultraviolet light.In addition, technology of the present invention is simple, and requirement for experiment condition is low, and the bismuth ferrite thin film even compact that obtains, crystal grain connect perforation and do not have crackle.
Description of drawings
Fig. 1 is through short wave ultraviolet light (the SEM figure of the bismuth ferrite thin film after λ=184.9nm) handles;
Fig. 2 is that (λ=184.9nm) handles, the SEM figure of the bismuth ferrite thin film of decomposing organic matter at high temperature without short wave ultraviolet light;
Fig. 3 is through short wave ultraviolet light (the section SEM figure of the bismuth ferrite thin film after λ=184.9nm) handles.
Embodiment
Do below in conjunction with specific embodiment and the accompanying drawing method that pre-treatment prepares ferrous acid bismuth function film to short wave ultraviolet light irradiation of the present invention and to describe in further detail:
Embodiment 1
Step 1: the configuration of precursor liquid.Take by weighing Bi (NO 3) 35H 2O, Fe (NO 3) 39H 2O is measured Glacial acetic acid min. 99.5, is dissolved in the solution that zero(ppm) water is configured to 200ml.Stirring at room adds Hydrocerol A to clarification fully, continues stirring at room and clarifies until solution; Promptly get precursor liquid, in this precursor liquid, said bismuth ion concentration is 0.01mol/L; Iron concentration is 0.045mol/L, and citric acid concentration is 0.02mol/L, and the volume parts of Glacial acetic acid min. 99.5 is 2%.
Step 2: the functionalization of substrate.Substrate is placed deionized water, acetone, absolute ethyl alcohol supersound washing 10min respectively., in OTS (1vol%)-toluene solution, soak 30min and prepare the OTS unitary film down behind the irradiation 20min in UV-light, in 120 ℃ of dry 5min to remove organism.Shine 40min down in UV-light at last, obtain the substrate of functionalization.
Step 3: depositing of thin film.With the precursor liquid surface that one of functional substrateization faces down and is suspended in the step 1 preparation, prepare noncrystalline membrane at 60 ℃～90 ℃ deposition 6h～30h.
Step 4: treatment with ultraviolet light.Prepared noncrystalline membrane is carried out treatment with ultraviolet light 20min～60min after drying at room temperature, when being positioned over UV-irradiation, the ozone oxidation organism chain that is produced through the UV-irradiation air is to remove organism.
Step 5: the crystallization of film.Step 4 is handled film later obtains crystallization in 550 ℃ of insulation annealing 10min～120min film.
Step 6: the sign of film.Characterize the surface and the cross-section morphology of film with SEM.
Embodiment 2
Step 1: the configuration of precursor liquid.Take by weighing Bi (NO 3) 35H 2O, Fe (NO 3) 39H 2O is measured Glacial acetic acid min. 99.5, is dissolved in the solution that zero(ppm) water is configured to 200ml.Stirring at room adds Hydrocerol A to clarification fully, continues stirring at room and clarifies until solution; Promptly get precursor liquid, in this precursor liquid, said bismuth ion concentration is 0.01mol/L; Iron concentration is 0.01mol/L, and citric acid concentration is 0.02mol/L, and the volume parts of Glacial acetic acid min. 99.5 is 2%.
Step 2: the functionalization of substrate.Substrate is placed deionized water, acetone, absolute ethyl alcohol supersound washing 10min respectively., in OTS (1vol%)-toluene solution, soak 30min and prepare the OTS unitary film down behind the irradiation 20min in UV-light, in 120 ℃ of dry 5min to remove organism.Shine 40min down in UV-light at last, obtain the substrate of functionalization.
Step 3: depositing of thin film.One of functional substrateization faced down is suspended in solution surface, prepares noncrystalline membrane at 60 ℃～90 ℃ deposition 6h～30h.
Step 4: pyrolytic decomposition organism.Prepared noncrystalline membrane is incubated 30min to remove organism in 300 ℃ after drying at room temperature.
Step 5: the crystallization of film.To obtain the film of crystallization through the organic film of pyrolytic decomposition in 550 ℃ of insulation annealing 10min～120min.
Step 6: the sign of film.Characterize the surface topography of film with SEM.
With the surface and the cross-section morphology of SEM mensuration film, its result is as shown in figs. 1 and 3.Can know that therefrom (it is even that the irradiation pre-treatment of λ=184.9nm) prepares the film even compact that the method for ferrous acid bismuth function film obtains, and do not have crackle, and grain-size is about 100～300nm with short wave ultraviolet light.
The above is merely one embodiment of the present invention; It or not whole or unique embodiment; The conversion of any equivalence that those of ordinary skills take technical scheme of the present invention through reading specification sheets of the present invention is claim of the present invention and contains.

Claims (6)

1. short wave ultraviolet light irradiation pre-treatment prepares the method for ferrous acid bismuth function film, it is characterized in that: with Bi (NO 3) 35H 2O, Fe (NO 3) 39H 2O is a raw material, is dissolved in the zero(ppm) water together with Glacial acetic acid min. 99.5, adds the complexing agent Hydrocerol A then, obtains precursor liquid; Wherein, in precursor liquid, bismuth ion concentration is 0.01mol/L; Iron concentration is 0.01～0.045mol/L, and the volume(tric)fraction of Glacial acetic acid min. 99.5 is 2%, and citric acid concentration is 0.02mol/L; With the functionalization self-assembled monolayer is template; Under 60～90 ℃, template is suspended in the reverse absorption preparation in precursor liquid surface film; Then, film is at room temperature carried out UV-irradiation perhaps at 300 ℃ of annealing 30min, to remove the film surface residual organic after the drying; At last, get final product at 550 ℃ of insulation annealings.
2. a kind of short wave ultraviolet light irradiation as claimed in claim 1 pre-treatment prepares the method for ferrous acid bismuth function film, it is characterized in that: the preparation method of said functionalization self-assembled monolayer is: at first with the substrate washes clean, under UV-light, shine 20min then; Then, in the OTS-toluene solution, soak 30min and get final product, wherein; In the OTS-toluene solution; The volume(tric)fraction of OTS is 1%, and is last, under UV-light, shining 40min after 120 ℃ of dryings again.
3. according to claim 1 or claim 2 a kind of short wave ultraviolet light irradiation pre-treatment prepares the method for ferrous acid bismuth function film, it is characterized in that: the depositing time that said template is suspended in the precursor liquid surface is 6～30h.
4. according to claim 1 or claim 2 a kind of short wave ultraviolet light irradiation pre-treatment prepares the method for ferrous acid bismuth function film, and it is characterized in that: said ferrous acid bismuth function film thickness is 40nm.
5. a kind of short wave ultraviolet light irradiation as claimed in claim 1 pre-treatment prepares the method for ferrous acid bismuth function film; It is characterized in that: said film is at room temperature carried out UV-irradiation after the drying when removing the film surface residual organic, and said ultraviolet light wavelength is 184.9nm.
6. short wave ultraviolet light irradiation pre-treatment prepares the method for ferrous acid bismuth function film, it is characterized in that: may further comprise the steps:
Step 1: the configuration of precursor liquid: take by weighing Bi (NO 3) 35H 2O, Fe (NO 3) 39H 2O is measured Glacial acetic acid min. 99.5, is dissolved in the solution that zero(ppm) water is configured to 200ml; Stirring at room adds Hydrocerol A to clarification fully, continues stirring at room and clarifies until solution; Promptly get precursor liquid, in this precursor liquid, said bismuth ion concentration is 0.01mol/L; Iron concentration is 0.01～0.045mol/L, and citric acid concentration is 0.02mol/L, and the volume(tric)fraction of Glacial acetic acid min. 99.5 is 2%;
Step 2: the functionalization of substrate: substrate is placed deionized water, acetone, absolute ethyl alcohol supersound washing 10min respectively, after UV-light shines 20min down, in the OTS-toluene solution, soak 30min and prepare the OTS unitary film; Then in 120 ℃ of dry 5min to remove organism; Shine 40min down in UV-light at last, obtain the substrate of functionalization, wherein; In the OTS-toluene solution, the volume(tric)fraction of OTS is 1%;
Step 3: depositing of thin film: one of functional substrateization faced down is suspended in the precursor liquid surface, prepares noncrystalline membrane at 60 ℃～90 ℃ deposition 6h～30h;
Step 4: with prepared noncrystalline membrane after drying at room temperature, carry out treatment with ultraviolet light 20min～60min or in 300 ℃ the insulation 30min, wherein, the ultraviolet light wavelength is 184.9nm;
Step 5: the crystallization of film: the film that treatment with ultraviolet light film is later obtained crystallization in 550 ℃ of insulation annealing 10min～120min.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104773959A (en) * 2015-03-31 2015-07-15 陕西科技大学 Method for preparing BiVO4 film through biomimetic method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101654218A (en) * 2009-09-17 2010-02-24 陕西科技大学 Method for preparing BiFeO3 film pattern on surface of self-assembly single layer film
CN101659520A (en) * 2009-09-17 2010-03-03 陕西科技大学 Method for preparing bismuth iron functional film on glass substrate by utilizing liquid-phase self-assembly method
CN102163487A (en) * 2010-12-30 2011-08-24 陕西科技大学 Method of preparing patterned BiFeO3 film on surface of functional Si substrate
CN102163486A (en) * 2010-12-30 2011-08-24 陕西科技大学 Photoethcing self assembly preparation method of patterned BiFeO3 film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101654218A (en) * 2009-09-17 2010-02-24 陕西科技大学 Method for preparing BiFeO3 film pattern on surface of self-assembly single layer film
CN101659520A (en) * 2009-09-17 2010-03-03 陕西科技大学 Method for preparing bismuth iron functional film on glass substrate by utilizing liquid-phase self-assembly method
CN102163487A (en) * 2010-12-30 2011-08-24 陕西科技大学 Method of preparing patterned BiFeO3 film on surface of functional Si substrate
CN102163486A (en) * 2010-12-30 2011-08-24 陕西科技大学 Photoethcing self assembly preparation method of patterned BiFeO3 film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
谈国强等: "自组装单层膜表面制备BiFeO3图案化薄膜的研究", 《无机化学学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104773959A (en) * 2015-03-31 2015-07-15 陕西科技大学 Method for preparing BiVO4 film through biomimetic method

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