CN102583568B - 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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CN102583568B
CN102583568B CN201210033852.1A CN201210033852A CN102583568B CN 102583568 B CN102583568 B CN 102583568B CN 201210033852 A CN201210033852 A CN 201210033852A CN 102583568 B CN102583568 B CN 102583568B
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bismuth ferrite
wave ultraviolet
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CN102583568A (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

A kind of method of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment
Technical field
The invention belongs to field of functional materials, relate to a kind of method of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment.
Background technology
In recent years, a kind of novel ferromagnetic electric material BiFeO 3, as there is one of single-phase ferromagnetic electric material of ferroelectricity and magnetic under minority room temperature simultaneously, caused the great interest of people.BiFeO 3there is the high Curie temperature (T of perovskite structure of tripartite's distortion c=810 DEG C) and Neel temperature (T n=380 DEG C), electromagnetic coupled acts on information storage, spin electric device aspect, and 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 good stoichiometric ratio, 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 big area film forming, and film quality is high, but the speed of growth is slow, and microstructure and the composition homogeneity of film are held improvement.Above these preparation technology's equipment comparatively complicated, need strict vacuum environment and process system, cost costliness, and a small amount of impurity often containing is difficult to remove and can not get pure phase, as Bi 2fe 4o 9and Bi 25feO 40.Chemical liquid deposition method is a kind of wet chemical method, and it does not need expensive device, is suitable for big area and prepares film, is widely used in synthetic various functional materialss, and has obtained huge success.
Self-assembled monolayer (self-assembled monolayers) technology (being called for short SAMs technology) is the core technology of bionical synthesis technique, it is by producing chemisorption between an activity base of tensio-active agent and substrate, the orderly molecule assembled layers of spontaneous formation on interface.Prepare bismuth ferrite thin film for self-assembling technique, because SAMs is the spontaneous ultra-thin organic membrane forming in solid substrate that is adsorbed on securely by chemical bond of organic molecule in solution (or organic molecule steam), therefore it has the spontaneous formation of original position, becomes the features such as key high-sequential is arranged, defect is few, bonding force is strong.But simultaneously also because SAMs is organic membrane, organic removal is a difficult problem in the process of preparing film.Prepare bismuth ferrite thin film for self-assembly method at present, what all adopt is pyrolytic decomposition organism, due under high temperature when decomposing organic matter film shrink excessively, prepared film can be cracked.
The present invention is taking self-assembly octadecyl trichlorosilane alkane (OTS) unitary film as template, radiothermy UV-light (λ=184.9nm) radiation instrument carries out surface modification to OTS-SAMs, in conjunction with liquid phase deposition, utilize reverse adsorption technology to prepare bismuth ferrite thin film, and before Thin-film anneal, under room temperature, carry out short wave ultraviolet light (λ=184.9nm) and process, make organism: the macromole of octadecyl trichlorosilane alkane (OTS) unitary film, Glacial acetic acid, citric acid is converted into CH 3-wait small molecules, then crystalline state bismuth ferrite thin film is prepared in annealing.This technology of not only this novel liquid phase self-assembling method being prepared to bismuth ferrite thin film is a kind of breakthrough progress, and because short wave ultraviolet light (λ=184.9nm) processing removal organism is at room temperature to carry out, film shrinks very little, make the employing liquid phase self-assembly method of processing by short wave ultraviolet light (λ=184.9nm) prepare bismuth ferrite thin film surfacing densification and there is no crackle, this also has directive significance to studying its dielectricity and multiferroic.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment, utilizes liquid phase self-assembled monolayer membrane technique to process the bismuth ferrite function film for preparing by annealing surfacing densification again and there is no crackle in conjunction with the short wave ultraviolet light (λ=184.9nm) before annealing.
For achieving the above object, the invention provides a kind of method of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment, with Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o is raw material, is dissolved in distilled water together with Glacial acetic acid, then adds complexing agent citric acid, 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 fraction of Glacial acetic acid is 2%, and citric acid concentration is 0.02mol/L; Taking functionalization self-assembled monolayer as template, template is suspended in to precursor liquid surface reverse adsorption at 60～90 DEG C and prepares film, then, after being at room temperature dried, film carries out UV-irradiation, to remove the residual organism of film surface, last, at 550 DEG C of insulation annealings; The preparation method of described functionalization self-assembled monolayer is: first by substrate washes clean, then under UV-light, irradiate 20min, then, in OTS-toluene solution, soak 30min, wherein, in OTS-toluene solution, the volume fraction of OTS is 1%, finally, under UV-light, irradiate 40min at 120 DEG C again after dry.
As the preferred embodiments of the present invention, the depositing time that described template is suspended in precursor liquid surface is 6～30h;
As the preferred embodiments of the present invention, described bismuth ferrite function film thickness is 40nm;
As the preferred embodiments of the present invention, carry out UV-irradiation after described film is at room temperature dry when removing the residual organism of film surface, described ultraviolet light wavelength is 184.9nm.
The method of a kind of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment of the present invention at least has the following advantages: the present invention is in conjunction with liquid phase self-assembly reverse adsorption technology, carry out treatment with ultraviolet light non-crystalline state ferrous acid bismuth thin film, irradiate the ozone of air generation by short wave ultraviolet light (λ=184.9nm) by the oxidation of organism chain, to reach the quick gentle organic object of removing.And because being removes organism in room temperature, the contraction of film is very little, while having prevented at high temperature decomposing organic matter, film shrinks excessive and cracks.Smooth by short wave ultraviolet light (λ=184.9nm) film surface densification after treatment, there is no crackle.In addition, technique of the present invention is simple, and requirement for experiment condition is low, and the bismuth ferrite thin film even compact, the crystal grain that obtain connect perforation and there is no crackle.
Brief description of the drawings
Fig. 1 is through the SEM of short wave ultraviolet light (λ=184.9nm) bismuth ferrite thin film after treatment figure;
Fig. 2 be without short wave ultraviolet light (λ=184.9nm) process, the SEM figure of the bismuth ferrite thin film of decomposing organic matter at high temperature;
Fig. 3 is through the section SEM of short wave ultraviolet light (λ=184.9nm) bismuth ferrite thin film after treatment figure.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the method for preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment of the present invention is described in further detail:
Embodiment 1
Step 1: the configuration of precursor liquid.Take Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, measures Glacial acetic acid, is dissolved in distilled water and is configured to the solution of 200ml.Stirring at room temperature, to clarification completely, adds citric acid, continues stirring at room temperature until solution clarification, obtain precursor liquid, in this precursor liquid, described 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 is 2%.
Step 2: the functionalization of substrate.Substrate is placed in respectively to deionized water, acetone, dehydrated alcohol supersound washing 10min.Under UV-light, irradiate after 20min, in OTS (1vol%)-toluene solution, soak 30min and prepare OTS unitary film, in 120 DEG C of dry 5min with remove organism.Finally under UV-light, irradiate 40min, obtain the substrate of functionalization.
Step 3: the deposition of film.Face down and be suspended in precursor liquid surface prepared by step 1 one of functional substrate, prepare noncrystalline membrane at 60 DEG C～90 DEG C deposition 6h～30h.
Step 4: treatment with ultraviolet light.Prepared noncrystalline membrane is carried out after drying at room temperature to treatment with ultraviolet light 20min～60min, while being positioned over UV-irradiation, the ozone oxidation organism chain producing by UV-irradiation air, to remove organism.
Step 5: the crystallization of film.Film after step 4 is processed obtains the film of crystallization in 550 DEG C of insulation annealing 10min～120min.
Step 6: the sign of film.Characterize surface and the cross-section morphology of film with SEM.
Embodiment 2
Step 1: the configuration of precursor liquid.Take Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, measures Glacial acetic acid, is dissolved in distilled water and is configured to the solution of 200ml.Stirring at room temperature, to clarification completely, adds citric acid, continues stirring at room temperature until solution clarification, obtain precursor liquid, in this precursor liquid, described 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 is 2%.
Step 2: the functionalization of substrate.Substrate is placed in respectively to deionized water, acetone, dehydrated alcohol supersound washing 10min.Under UV-light, irradiate after 20min, in OTS (1vol%)-toluene solution, soak 30min and prepare OTS unitary film, in 120 DEG C of dry 5min with remove organism.Finally under UV-light, irradiate 40min, obtain the substrate of functionalization.
Step 3: the deposition of film.Face down and be suspended in solution surface one of functional substrate, prepare noncrystalline membrane at 60 DEG C～90 DEG C deposition 6h～30h.
Step 4: pyrolytic decomposition organism.Prepared noncrystalline membrane is incubated to 30min to remove organism in 300 DEG C after drying at room temperature.
Step 5: the crystallization of film.The film of crystallization will be obtained in 550 DEG C of insulation annealing 10min～120min through the organic film of pyrolytic decomposition.
Step 6: the sign of film.Characterize the surface topography of film with SEM.
Surface and the cross-section morphology of measuring film with SEM, its result as shown in figs. 1 and 3.Therefrom known, to prepare with the pre-treatment of short wave ultraviolet light (λ=184.9nm) irradiation the film even compact that the method for bismuth ferrite function film obtains even, and there is no crackle, grain-size is about 100～300nm.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of any equivalence that those of ordinary skill in the art take technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.

Claims (5)

1. a method for preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment, is characterized in that: with Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o is raw material, is dissolved in distilled water together with Glacial acetic acid, then adds complexing agent citric acid, 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 fraction of Glacial acetic acid is 2%, and citric acid concentration is 0.02mol/L; Taking functionalization self-assembled monolayer as template, template is suspended in to precursor liquid surface reverse adsorption at 60～90 DEG C and prepares film, then, after being at room temperature dried, film carries out UV-irradiation, to remove the residual organism of film surface, last, at 550 DEG C of insulation annealings; The preparation method of described functionalization self-assembled monolayer is: first by substrate washes clean, then under UV-light, irradiate 20min, then, in OTS-toluene solution, soak 30min, wherein, in OTS-toluene solution, the volume fraction of OTS is 1%, finally, under UV-light, irradiate 40min at 120 DEG C again after dry.
2. the method for a kind of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment as claimed in claim 1, is characterized in that: the depositing time that described template is suspended in precursor liquid surface is 6～30h.
3. the method for a kind of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment as claimed in claim 1, is characterized in that: described bismuth ferrite function film thickness is 40nm.
4. the method for a kind of preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment as claimed in claim 1, it is characterized in that: after described film is at room temperature dry, carry out UV-irradiation when removing the residual organism of film surface, described ultraviolet light wavelength is 184.9nm.
5. a method for preparing bismuth ferrite functional film by short wave ultraviolet irradiation pretreatment, is characterized in that: comprise the following steps:
Step 1: the preparation of precursor liquid: take Bi (NO 3) 35H 2o, Fe (NO 3) 39H 2o, measure Glacial acetic acid, be dissolved in distilled water and be mixed with the solution of 200mL, stirring at room temperature is to clarification completely, add citric acid, continue stirring at room temperature until solution clarification obtains precursor liquid, in this precursor liquid, described 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 fraction of Glacial acetic acid is 2%;
Step 2: the functionalization of substrate: substrate is placed in respectively to deionized water, acetone, dehydrated alcohol supersound washing 10min, under UV-light, irradiate after 20min, in OTS-toluene solution, soak 30min and prepare OTS unitary film, then in 120 DEG C of dry 5min with remove organism, finally under UV-light, irradiate 40min, obtain the substrate of functionalization, wherein, in OTS-toluene solution, the volume fraction of OTS is 1%;
Step 3: the deposition of film: face down and be suspended in precursor liquid surface one of functional substrate, prepare noncrystalline membrane at 60 DEG C～90 DEG C deposition 6h～30h;
Step 4: prepared noncrystalline membrane is carried out after drying at room temperature to treatment with ultraviolet light 20min～60min, wherein, ultraviolet light wavelength is 184.9nm;
Step 5: the crystallization of film: the film that treatment with ultraviolet light film is later obtained to crystallization in 550 DEG C of insulation annealing 10min～120min.
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