CN102534587A - Method for preparing BiFeO3 film through sol-gel method - Google Patents
Method for preparing BiFeO3 film through sol-gel method Download PDFInfo
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- CN102534587A CN102534587A CN201110449902XA CN201110449902A CN102534587A CN 102534587 A CN102534587 A CN 102534587A CN 201110449902X A CN201110449902X A CN 201110449902XA CN 201110449902 A CN201110449902 A CN 201110449902A CN 102534587 A CN102534587 A CN 102534587A
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Abstract
The invention provides a method for preparing BiFeO3 film through a sol-gel method, which comprises the following steps of: (1) taking bismuth nitrate and ferric nitrate as raw materials, respectively dissolving the bismuth nitrate and the ferric nitrate into ethylene glycol monomethyl ether and glacial acetic acid, mixing fully to dissolve completely, and forming precursor liquid after mixing; and (2) evenly gluing a cleaned and ultraviolet light irradiated substrate by the precursor liquid, after finishing even gluing, putting a sample film at the temperature of 350 DEG C immediately for pre-annealing for 3 minutes so as to decompose organic matters, and finally preserving heat at the temperature of 500-600 DEG C. The method integrates the advantages of a one-time annealing system and a gradual annealing system, after the film is preprocessed, heat processing is carried out at the temperature of 450 DEG C, the film is annealed for 15-30 minutes at the temperature of 500-600 DEG C after being partially crystallized, volume shrunk and evenly glued for several times, so that on the premise that the density of the BiFeO3 film is ensured, the space charge is reduced as much as possible, and the leakage conductance of the film is inhibited.
Description
Technical field
The invention belongs to field of functional materials, relate to a kind of Prepared by Sol Gel Method BiFeO
3The method of film and method for annealing thereof.
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.
Be used to prepare BiFeO at present
3The method of film has a lot, like sol-gel (Sol-Gel) method, chemical vapor deposition (CVD) method, magnetron sputtering (magnetron sputtering) method, metallorganics deposit (MOD) method, metal organic chemical vapor deposition (MOCVD) method, liquid phase deposition (LPD), molecular beam epitaxy (MBE) method and pulsed laser deposition (PLD) method etc.The presoma of sol-gel method is the organic salt and the inorganic salt compound of metal, and solvent is an organic solvent.According to certain ratio presoma is dissolved in the organic solvent, forms three-dimensional network shape colloid, through even glue,, remove organic composition and moisture in the gel, and annealed crystallization obtains crystalline film then again through pervaporation and decomposition through hydrolysis condensation reaction.Usually the method for using has crystal pulling method and spin-coating method.Select spin-coating method, equipment is cheap, simple to operate, and does not need exacting terms such as high temperature, vacuum, and raw material consumption is less, and the film forming even compact.
The sol-gel legal system is equipped with BiFeO at present
3Film is mainly used annealed mode successively, can obtain that crystallization is effective, the film of even compact, and obtains easily to obtain the epitaxial film through heterogeneous nucleation.But annealing successively can't make crystal grain connect and connect, and has more space charge, and this can cause bigger leakage conductance electric current in test.Shrink and exist in the crystallization process, therefore once annealing causes the not fine and close of structure easily.
Summary of the invention
Technical problem to be solved by this invention provides a kind of Prepared by Sol Gel Method BiFeO
3The method of film can obtain even compact by this method, and space charge is less, the BiFeO that leakage conductance is lower
3Film.
For realizing above-mentioned purpose, the invention provides a kind of Prepared by Sol Gel Method BiFeO
3The method of film may further comprise the steps:
Step 1: selecting the FTO/glass substrate for use is substrate, and the FTO substrate of well cutting is cleaned to remove the impurity of FTO/glass substrate surface;
Step 2: place ultraviolet radiation instrument to shine the FTO substrate of cleaning, make substrate surface reach " atomic cleanliness degree ";
Step 3: with Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2O is dissolved in respectively in EGME and the Glacial acetic acid min. 99.5, and the formation precursor liquid is mixed in the dissolving back, regulates precursor liquid concentration and makes the concentration of Fe and Bi be 0.3mol/L, and magnetic agitation obtains stable BiFeO
3Presoma;
Step 4: the precursor that on the substrate that step 2 obtains, obtains with step 3 is spared the glue processing, behind the even glued bundle, under 350 ℃, carries out pre-treatment 3min so that organism decomposes, and then 450 ℃ of thermal treatments, repeats to spare the thickness that glue obtains setting several times;
Step 5: the sample that step 4 is obtained places rapid heat-treatment furnace, is incubated 15～30min down at 500～600 ℃.
Prepared by Sol Gel Method BiFeO of the present invention
3The method of film has the following advantages at least: the inventive method combines the advantage of the once annealing and the two kinds of annealing schedules of successively annealing; After the film pre-treatment, at first heat-treat, so that film crystallization and retraction volume at 450 ℃; After even glue obtains setting thickness thin film several times; 550 ℃ of annealing, so on the one hand can be at low temperatures nucleation uniformly, in preventing once to anneal under the high temperature excessive grain grow the decline of the density that causes; In can avoiding again successively annealing crystal grain grow inadequately fully, development degree heterogeneity and the electricdomain dysplasia that causes; Can improve the density and the crystallization degree of film like this, reduce space charge, to suppress the leakage conductance of film.Therefore, the present invention is through simple technology, and lower experiment condition has obtained even compact, crystal grain connection perforation and the lower pure phase bismuth ferric film of the less leakage conductance electric current of space charge.The present invention can be through control heat treatment period and temperature, and the growth of control crystal grain is grown up, and obtains the film that different crystal grain are formed, distributed.
Description of drawings
Fig. 1 is the XRD figure (450 ℃ of thermal treatments successively, 550 ℃ of annealing 30min) of bismuth ferrite thin film of the present invention;
Fig. 2 is the SEM figure ((a) 500 ℃ of annealing successively, (b) 450 ℃ of thermal treatments successively, 550 ℃ of annealing 30min, (c) 550 ℃ of once annealing) of bismuth ferrite thin film of the present invention;
Fig. 3 is the dielectric properties collection of illustrative plates of bismuth ferrite thin film of the present invention, and wherein (a) is the dielectric frequency spectrum, (b) is the loss frequency spectrum.
Embodiment
Embodiment 1
Step 1: selecting the FTO/glass substrate for use is substrate; The FTO/glass substrate of well cutting is placed washing composition, acetone (volume percent is more than or equal to 99.5%) and absolute ethyl alcohol (volume percent is more than or equal to 99.5%) ultrasonic cleaning 10min successively; Remove the impurity such as grease of FTO/glass substrate surface; With a large amount of distilled water flushing substrates, dry up with nitrogen at last after each ultrasonic cleaning;
Step 2: place ultraviolet radiation instrument to shine 20min the FTO/glass substrate of cleaning; Make substrate surface reach " atomic cleanliness degree "; The high-energy of uv irradiating can make the bond rupture of oxide compound wherein, forms wetting ability hydroxyl preferably, improves the wetting ability of substrate;
Step 3: with Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2O is dissolved in respectively in EGME and the Glacial acetic acid min. 99.5, and the formation precursor liquid is mixed in the dissolving back, and Bi, Fe ionic concn are 0.3mol/L in the adjusting precursor liquid, and magnetic agitation 0.5h obtains stable BiFeO
3Presoma;
Step 4: the precursor that on the substrate that step 2 obtains, obtains with step 3 is spared glue and is handled; Wherein, Even glue speed is 3000～5000r/min, behind the even glued bundle, under 350 ℃, carries out pre-treatment 3min so that organism decomposes; Then at 450 ℃ of thermal treatment 3min, the thickness that obtains setting after repeating several times;
Step 5: the sample that step 4 is obtained places rapid heat-treatment furnace, is incubated 0.5 hour down at 500～600 ℃, promptly forms BiFeO at substrate surface
3Film.
Step 1: selecting the FTO/glass substrate for use is substrate; The FTO/glass substrate of well cutting is placed washing composition, acetone (volume percent of acetone is >=99.5%) and absolute ethyl alcohol (volume percent is more than or equal to 99.5%) ultrasonic cleaning 10min successively; Remove the impurity such as grease of FTO/glass substrate surface; With a large amount of distilled water flushing substrates, dry up with nitrogen at last after each ultrasonic cleaning;
Step 2: place ultraviolet radiation instrument to shine 20min the FTO/glass substrate of cleaning; Make substrate surface reach " atomic cleanliness degree "; The high-energy of uv irradiating can make the bond rupture of oxide compound wherein, forms wetting ability hydroxyl preferably, improves the wetting ability of substrate;
Step 3: with Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2O is dissolved in respectively in EGME and the Glacial acetic acid min. 99.5, and the formation precursor liquid is mixed in the dissolving back, and Bi, Fe ionic concn are 0.3mol/L in the adjusting precursor liquid, and magnetic agitation 0.5h obtains stable BiFeO
3Presoma;
Step 4: the precursor that on the substrate that step 2 obtains, obtains with step 3 is spared glue and is handled; Wherein, Even glue speed is 4000～5000r/min, behind the even glued bundle, under 300 ℃, carries out pre-treatment 3min so that the decomposition of machine thing; Make the film portion crystallization and shrink at 450 ℃ of thermal treatment 3min then, the thickness that obtains setting after repeating several times;
Step 5: the sample that step 4 is obtained places rapid heat-treatment furnace, insulation 15min under 500～600 ℃ high temperature.
Embodiment 3
Step 1: selecting the FTO/glass substrate for use is substrate; The FTO/glass substrate of well cutting is placed washing composition, acetone (volume percent of acetone is >=99.5%) and absolute ethyl alcohol (volume percent is more than or equal to 99.5%) ultrasonic cleaning 10min successively; Remove the impurity such as grease of FTO/glass substrate surface; With a large amount of distilled water flushing substrates, dry up with nitrogen at last after each ultrasonic cleaning;
Step 2: place ultraviolet radiation instrument to shine 20min the FTO substrate of cleaning, make substrate surface reach " atomic cleanliness degree ", the high-energy of uv irradiating can make the wherein bond rupture of oxide compound, forms wetting ability hydroxyl preferably, improves the wetting ability of substrate;
Step 3: with Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2O is dissolved in respectively in EGME and the Glacial acetic acid min. 99.5, and mix the dissolving back, and Bi, Fe ionic concn are 0.3mol/L in the adjusting precursor liquid, and magnetic agitation 0.5h obtains stable BiFeO
3Presoma;
Step 4: the precursor that on the substrate that step 2 obtains, obtains with step 3 is spared glue and is handled; Wherein, Even glue speed is 4500～7000r/min, behind the even glued bundle, under 300～350 ℃, carries out pre-treatment 3min then so that organism decomposes; Then at 450 ℃ of thermal treatment 3min, repeat even glue and obtain the thickness set several times;
Step 5: the sample that step 4 is obtained places rapid heat-treatment furnace, insulation 15～30min under 500 ℃ high temperature.
Embodiment 4
Step 1: selecting the FTO/glass substrate for use is substrate; The FTO/glass substrate of well cutting is placed washing composition, acetone (volume percent of acetone is >=99.5%) and absolute ethyl alcohol (volume percent is more than or equal to 99.5%) ultrasonic cleaning 10min successively; Remove the impurity such as grease of FTO/glass substrate surface; With a large amount of distilled water flushing substrates, dry up with nitrogen at last after each ultrasonic cleaning;
Step 2: place ultraviolet radiation instrument to shine 20min the FTO/glass substrate of cleaning; Make substrate surface reach " atomic cleanliness degree "; The high-energy of uv irradiating can make Sn-O bond rupture wherein, forms wetting ability hydroxyl preferably, improves the wetting ability of substrate;
Step 3: with Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2O is dissolved in respectively in EGME and the Glacial acetic acid min. 99.5, and the formation precursor liquid is mixed in the dissolving back, and Bi, Fe ionic concn are 0.3mol/L in the adjusting precursor liquid, and magnetic agitation 0.5h obtains stable BiFeO
3Presoma;
Step 4: the precursor that on the substrate that step 2 obtains, obtains with step 3 is spared glue and is handled; Wherein, Even glue speed is 5000～6500r/min, behind the even glued bundle, under 350 ℃, carries out pre-treatment 3min then so that organism decomposes; Then at 400 ℃ of thermal treatment 3min, repeat even glue and obtain the thickness set several times;
Step 5: the sample that step 4 is obtained places rapid heat-treatment furnace, is incubated 15～30min down at 550 ℃.
With the thing phase composite structure of XRD determining film, with the microscopic appearance of SEM mensuration film, its result is as depicted in figs. 1 and 2; Fig. 3 is the dielectric properties collection of illustrative plates of bismuth ferrite thin film of the present invention; Can know that therefrom the film of sol-gel method preparation has the distortion calcium titanium ore structure, pure do not have impurity mutually.The film even compact, grain-size is about 100～300nm.
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 (3)
1. Prepared by Sol Gel Method BiFeO
3The method of film is characterized in that: may further comprise the steps:
Step 1: selecting the FTO/glass substrate for use is substrate, and the FTO substrate of well cutting is cleaned to remove the impurity of FTO/glass substrate surface;
Step 2: place ultraviolet radiation instrument to shine the FTO substrate of cleaning, make substrate surface reach " atomic cleanliness degree ";
Step 3: with Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2O is dissolved in respectively in EGME and the Glacial acetic acid min. 99.5, and the formation precursor liquid is mixed in the dissolving back, regulates precursor liquid concentration and makes the ionic concn of Fe and Bi be 0.3mol/L, and magnetic agitation obtains stable BiFeO
3Presoma;
Step 4: the precursor that on the substrate that step 2 obtains, obtains with step 3 is spared the glue processing, behind the even glued bundle, under 350 ℃, carries out pre-treatment 3min so that organism decomposes, and then 450 ℃ of thermal treatments, repeats to spare the thickness that glue obtains setting several times;
Step 5: the sample that step 4 is obtained places rapid heat-treatment furnace, is incubated 15～30min down at 500～600 ℃.
2. Prepared by Sol Gel Method BiFeO as claimed in claim 1
3The method of film is characterized in that: the time that said FTO substrate shines in ultraviolet radiation instrument is 20 minutes.
3. Prepared by Sol Gel Method BiFeO as claimed in claim 1
3The method of film is characterized in that: in the said step 4, the speed of even glue is 3000～7000r/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145192A (en) * | 2013-03-28 | 2013-06-12 | 新疆大学 | Method for preparing manganese, nickel codoped bismuth ferrite film by sol-gel process |
| CN103693694A (en) * | 2013-12-20 | 2014-04-02 | 陕西科技大学 | Bi(1-x)DyxFeO3 low leakage current film and preparation method thereof |
| CN104891821A (en) * | 2015-05-04 | 2015-09-09 | 桂林电子科技大学 | Method for preparing multilayer BiFeO3 film from precursor solutions with different concentrations |
| CN105859273A (en) * | 2016-03-29 | 2016-08-17 | 陕西科技大学 | 2-2 type BiFeO3-CuFe2O4 composite film and preparation method therefor |
| CN109023313A (en) * | 2018-09-20 | 2018-12-18 | 山东建筑大学 | A kind of raising BiFeO3The method for annealing of film magnetoelectric effect |
| CN111416006A (en) * | 2020-02-27 | 2020-07-14 | 北京科技大学 | Two-dimensional layered perovskite ferroelectric multifunctional film and preparation process thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145192A (en) * | 2013-03-28 | 2013-06-12 | 新疆大学 | Method for preparing manganese, nickel codoped bismuth ferrite film by sol-gel process |
| CN103145192B (en) * | 2013-03-28 | 2016-04-27 | 新疆大学 | Sol-gel technology prepares the method for manganese, nickel co-doped bismuth ferrite thin film |
| CN103693694A (en) * | 2013-12-20 | 2014-04-02 | 陕西科技大学 | Bi(1-x)DyxFeO3 low leakage current film and preparation method thereof |
| CN103693694B (en) * | 2013-12-20 | 2015-11-11 | 陕西科技大学 | A kind of Bi 1-xdy xfeO 3low-leakage current film and preparation method thereof |
| CN104891821A (en) * | 2015-05-04 | 2015-09-09 | 桂林电子科技大学 | Method for preparing multilayer BiFeO3 film from precursor solutions with different concentrations |
| CN104891821B (en) * | 2015-05-04 | 2017-08-11 | 桂林电子科技大学 | Multilayer BiFeO is prepared using the precursor liquid of various concentrations3The method of film |
| CN105859273A (en) * | 2016-03-29 | 2016-08-17 | 陕西科技大学 | 2-2 type BiFeO3-CuFe2O4 composite film and preparation method therefor |
| CN105859273B (en) * | 2016-03-29 | 2019-07-30 | 陕西科技大学 | A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof |
| CN109023313A (en) * | 2018-09-20 | 2018-12-18 | 山东建筑大学 | A kind of raising BiFeO3The method for annealing of film magnetoelectric effect |
| CN109023313B (en) * | 2018-09-20 | 2020-06-19 | 山东建筑大学 | BiFeO is improved3Annealing method for film magnetoelectric coupling effect |
| CN111416006A (en) * | 2020-02-27 | 2020-07-14 | 北京科技大学 | Two-dimensional layered perovskite ferroelectric multifunctional film and preparation process thereof |
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Application publication date: 20120704 |