CN102886934A - Completely-crystallized multiferroic film without producing impure phase and preparation method thereof - Google Patents
Completely-crystallized multiferroic film without producing impure phase and preparation method thereof Download PDFInfo
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- CN102886934A CN102886934A CN2012104177533A CN201210417753A CN102886934A CN 102886934 A CN102886934 A CN 102886934A CN 2012104177533 A CN2012104177533 A CN 2012104177533A CN 201210417753 A CN201210417753 A CN 201210417753A CN 102886934 A CN102886934 A CN 102886934A
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Abstract
The invention provides a completely-crystallized multiferroic film without producing impure phase and a preparation method of the completely-crystallized multiferroic film. The invention relates to a multiferroic film and a preparation method of the multiferroic film, solving the problems of conventional BiFeO3 (BFO) based film and conventional method that the film is relatively high in current leakage, low in ferromagnetic performance, and is reacted with a Pt bottom electrode to obtain Bi2Pt alloy, so that the comprehensive performance is reduced, and the completely-crystallized multiferroic film without producing impure phase cannot be prepared by the conventional method. The completely-crystallized multiferroic film without producing impure phase is prepared by barium strontium titanate based sol and BFO based sol. The preparation method comprises the steps as follows: 1, preparing a film for a buffering layer; and 2, depositing a BFO based film, and then carrying out quick annealing technology so as to obtain the completely-crystallized multiferroic film without producing impure phase. The preparation method provided by the invention is mainly used for preparing the completely-crystallized multiferroic film without producing impure phase.
Description
Technical field
The present invention relates to a kind of multiferroic film and preparation method thereof.
Background technology
Along with the progress of science and technology, more and more higher to the requirement of device miniaturization, the new material that this just needs exploitation to have simultaneously two or more function is to develop the new device that can realize simultaneously several functions.In recent years, multi-ferroic material is owing to possess the multiple iron such as ferroelectric, ferromagnetic simultaneously, and owing to the coupling between the different iron has the new performances such as magnetoelectric effect, having broad application prospects aspect the integrated and miniaturization of device.Present single-phase multi-ferroic material is naturally occurring fewer, and BFO is the multi-ferroic material that wherein can at room temperature possess simultaneously ferroelectricity and ferromagnetism.But following problem appears when the BFO practical application, and the first, leakage current is larger; The second, the room temperature magnetic a little less than; The 3rd, in high-temperature heat treatment process, the BFO base film easily with the Pt hearth electrode generation Bi that reacts
2The alloys such as Pt, thus the combination property of BFO base film reduced; Therefore the existing method multiferroic film that can't prepare crystallization fully and produce without dephasign.
Summary of the invention
The present invention will solve existing BiFeO
3(BFO) the base film leakage current is large, ferromagnetic property is relatively poor, reacting with the Pt hearth electrode generates Bi
2The alloys such as Pt, thus cause its combination property to descend and existing method can't prepare crystallization fully and the problem of the multiferroic film that produces without dephasign, and provide a kind of crystallization fully and the multiferroic film that produces without dephasign and preparation method thereof.
A kind of crystallization of the present invention is being passed through the Pt/Ti/SiO that cleans by barium strontium titanate based sols and BFO based sols fully and without the multiferroic film that dephasign produces
2Form by spin-coating method, thermal decomposition method and rta technique legal system are standby on/Si (100) substrate.
A kind of crystallization is specifically finished fully and the preparation method of the multiferroic film that produces without dephasign according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: ratio (1-y) takes by weighing raw material, raw material joined in the solvent through hydrolysis, dehydration and polymerization process namely obtains the barium strontium titanate based sols that concentration is 0.3mol/L, again with the barium strontium titanate based sols by spin coating and thermal decomposition method at the Pt/Ti/SiO through cleaning
2Preparation thickness is the barium strontium titanate base film of 50nm～400nm on/Si (100) substrate, then adopts rta technique heat treatment 1min～15min under 600～800 ℃ of conditions, namely obtains buffer layer thin film; Two, deposition BFO base film: according to chemical formula Bi
zB
1-zFe
kC
1-kO
3Press the Bi element, the B element, the mol ratio of Fe element and C element is z: (1-z): k: ratio (1-k) takes by weighing raw material, raw material is joined in the solvent through hydrolysis, dehydration and polymerization process namely obtain the BFO based sols that concentration is 0.3mol/L, deposit thickness on the buffer layer thin film that obtains through step 1 is the BFO base film of 100nm～1000nm by spin coating and thermal decomposition method with the BFO based sols again, then adopt rta technique heat treatment 1min～15min under 500～700 ℃ of conditions, the multiferroic film that namely obtains crystallization fully and produce without dephasign; Chemical formula Ba described in the step 1
xSr
1-xA
yTi
1-yO
3In, A is Co, Fe or Mn, x is: and 0＜x≤1, y is: 0≤y≤0.5; Multiferroic film Bi described in the step 2
zB
1-zFe
kC
1-kO
3, wherein B is La, Nd, Gd or Ho, and C is Mn, Ti, Nb or Cr, and z is: 0＜z≤1, k is: 0＜k≤1.
Advantage of the present invention: one, the crystallization of the present invention's preparation multiferroic film complete and that produce without dephasign can prevent that BFO base film and Pt hearth electrode from reacting, and is conducive to obtain the multiferroic film of high-crystallinity; Two, the prepared crystallization of the present invention fully and the multiferroic film that produces without dephasign dephasign does not appear, and effectively improved its multi-ferrum property such as ferroelectric and ferromagnetic; Three, preparation technology of the present invention and equipment are simple, and cost is low, are easy to industrialization; Four, the present invention can be applicable to magnetoelectricity memory, sensor field.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram, and a represents to test the BFO film X-ray diffraction spectrogram of a preparation among Fig. 1, and the b among Fig. 1 represents to test the BFO/BSTO film X-ray diffraction spectrogram of two preparations, and the # among Fig. 1 is the dephasign characteristic peak, and the * among Fig. 1 is the substrate feature peak;
Fig. 2 is ferroelectric hysteresis loop figure, and a represents to test the BFO thin-film electro hysteresis line chart of a preparation among Fig. 2, and b represents to test the BFO/BSTO thin-film electro hysteresis line chart of two preparations among Fig. 2;
Fig. 3 is ferroelectric hysteresis loop figure, c represents to test the BFMO/BSTO thin-film electro hysteresis line chart of three preparations among Fig. 3, d among Fig. 3 represents to test the BLFO/BSTO thin-film electro hysteresis line chart of four preparations, and the e among Fig. 3 represents to test the BLFMO/BSTO thin-film electro hysteresis line chart of five preparations;
Fig. 4 is the electron scanning micrograph of the BLFMO/BSTO thin-membrane section of test five preparations, f among Fig. 4 is the BLFMO electron scanning micrograph, g among Fig. 4 is the BSTO electron scanning micrograph, and the h among Fig. 4 is the Pt/Ti electron scanning micrograph, and the i among Fig. 4 is SiO
2/ Si electron scanning micrograph;
Fig. 5 is the X-ray diffraction spectrogram, f represents to test the BLFMO film X-ray diffraction spectrogram of six preparations among Fig. 5, j among Fig. 5 represents to test the BLFMO/BSTCO film X-ray diffraction spectrogram of seven preparations, and the # among Fig. 5 is the dephasign characteristic peak, and the * among Fig. 5 is the substrate feature peak;
Fig. 6 is ferroelectric hysteresis loop figure, k represents to test when test voltage is 40V the BLFMO/BSTCO thin-film electro hysteresis line chart of seven preparations among Fig. 6, the BLFMO/BSTCO thin-film electro hysteresis line chart of test seven preparations when 1 expression test voltage is 60V among Fig. 6, m represents to test when test voltage is 80V the BLFMO/BSTCO thin-film electro hysteresis line chart of seven preparations among Fig. 6;
Fig. 7 is hysteresis curve figure, and the e among Fig. 7 represents to test the BLFMO/BSTO film hysteresis curve figure of five preparations, and the j among Fig. 7 represents to test the BLFMO/BSTCO film hysteresis curve figure of seven preparations;
Fig. 8 is the partial enlarged drawing of Fig. 7 hysteresis curve figure, and the e among Fig. 8 represents to test the partial enlarged drawing of the five BLFMO/BSTO film hysteresis curve figure that prepare, and the j among Fig. 8 represents to test the partial enlarged drawing of the seven BLFMO/BSTCO film hysteresis curve figure that prepare.
The specific embodiment
The specific embodiment one: a kind of crystallization of present embodiment is being passed through the Pt/Ti/SiO that cleans by barium strontium titanate based sols and BFO based sols fully and without the multiferroic film that dephasign produces
2Form by spin-coating method, thermal decomposition method and rta technique legal system are standby on/Si (100) substrate.
The described crystallization of present embodiment multiferroic film complete and that produce without dephasign can prevent that BFO base film and Pt hearth electrode from reacting, and is conducive to obtain the multiferroic film of high-crystallinity.
The described crystallization of present embodiment fully and the multiferroic film that produces without dephasign dephasign does not appear, and effectively improved its multi-ferrum property such as ferroelectric and ferromagnetic.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: the preparation method of described barium strontium titanate based sols carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: the raw material that ratio (1-y) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the barium strontium titanate based sols that will prepare; 3. polymerization process: the barium strontium titanate based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the barium strontium titanate based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the barium strontium titanate based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is: the preparation method of described BFO based sols carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Bi
zB
1-zFe
kC
1-kO
3Mol ratio in Bi element, B element, Fe element and C element is z: (1-z): k: the raw material that ratio (1-k) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the BFO based sols that will prepare; 3. polymerization process: the BFO based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the BFO based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the BFO based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.Other is identical with the specific embodiment one.
The specific embodiment four: a kind of crystallization of present embodiment is specifically finished fully and the preparation method of the multiferroic film that produces without dephasign according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: ratio (1-y) takes by weighing raw material, raw material joined in the solvent through hydrolysis, dehydration and polymerization process namely obtains the barium strontium titanate based sols that concentration is 0.3mol/L, again with the barium strontium titanate based sols by spin coating and thermal decomposition method at the Pt/Ti/SiO through cleaning
2Preparation thickness is the barium strontium titanate base film of 50nm～400nm on/Si (100) substrate, then adopts rta technique heat treatment 1min～15min under 600～800 ℃ of conditions, namely obtains buffer layer thin film; Two, deposition BFO base film: according to chemical formula Bi
zB
1-zFe
kC
1-kO
3Press the Bi element, the B element, the mol ratio of Fe element and C element is z: (1-z): k: ratio (1-k) takes by weighing raw material, raw material is joined in the solvent through hydrolysis, dehydration and polymerization process namely obtain the BFO based sols that concentration is 0.3mol/L, deposit thickness on the buffer layer thin film that obtains through step 1 is the BFO base film of 100nm～1000nm by spin coating and thermal decomposition method with the BFO based sols again, then adopt rta technique heat treatment 1min～15min under 500～700 ℃ of conditions, the multiferroic film that namely obtains crystallization fully and produce without dephasign.
Chemical formula Ba described in the present embodiment step 1
xSr
1-xA
yTi
1-yO
3In, A is Co, Fe or Mn, x is: 0＜x≤1, y is: 0≤y≤0.5.
Multiferroic film Bi described in the present embodiment step 2
zB
1-zFe
kC
1-kO
3, wherein B is La, Nd, Gd or Ho, and C is Mn, Ti, Nb or Cr, and z is: 0＜z≤1, k is: 0＜k≤1; When 0＜z＜1, during k=1, be the prepared film of A position doping BFO; Work as z=1,0＜k＜1 o'clock is the prepared film of B position doping BFO; When 0＜z＜1,0＜k＜1 o'clock, be A and the prepared film of B position co-doped BFO.
The barium-strontium titanate-based film thickness that obtains in the present embodiment step 1 is that (thermal decomposition is once all carried out in every spin coating for number of times by control repetitive operation spin coating and thermal decomposition method, the effect of thermal decomposition is that the solvent that contains in the colloidal sol after will spin coating volatilizees fully or decomposes, forms the solid phase film) realization.
The multiferroic film Bi that obtains in the present embodiment step 2
zB
1-zFe
kC
1-kO
3Thickness is by the number of times of control repetitive operation spin coating and thermal decomposition method (thermal decomposition is once all carried out in every spin coating, and the effect of thermal decomposition is that the solvent that contains in the colloidal sol after will spin coating volatilizees fully or decomposes, forms the solid phase film) realization.
The crystallization of present embodiment preparation multiferroic film complete and that produce without dephasign can prevent that BFO base film and Pt hearth electrode from reacting, and is conducive to obtain the multiferroic film of high-crystallinity.
The crystallization of present embodiment preparation fully and the multiferroic film that produces without dephasign dephasign does not appear, and effectively improved its multi-ferrum property such as ferroelectric and ferromagnetic;
The present embodiment Processes and apparatus is simple, and cost is low, is easy to industrialization.
The specific embodiment five: what present embodiment and the specific embodiment four were different is: the preparation method of the described barium strontium titanate based sols of step 1 carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: the raw material that ratio (1-y) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the barium strontium titanate based sols that will prepare; 3. polymerization process: the barium strontium titanate based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the barium strontium titanate based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the barium strontium titanate based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.Other is identical with the specific embodiment four.
The specific embodiment six: what present embodiment and the specific embodiment four were different is: step 1 is according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: ratio (1-y) takes by weighing raw material, raw material joined in the solvent through hydrolysis, dehydration and polymerization process namely obtains the barium strontium titanate based sols that concentration is 0.3mol/L, again with the barium strontium titanate based sols by spin coating and thermal decomposition method at the Pt/Ti/SiO through cleaning
2Preparation thickness is the barium strontium titanate base film of 100nm～300nm on/Si (100) substrate.Other is identical with the specific embodiment four.
The specific embodiment seven: what present embodiment and the specific embodiment four were different is: step 1 adopts rta technique heat treatment 3min～10min under 650～750 ℃ of conditions.Other is identical with the specific embodiment four.
The specific embodiment eight: what present embodiment and the specific embodiment four were different is: the chemical formula Ba described in the step 1
xSr
1-xA
yTi
1-yO
3In, x is: 0.5≤x≤0.9, y is: 0≤y≤0.2.Other is identical with the specific embodiment four.
The specific embodiment nine: what present embodiment and the specific embodiment four were different is: the preparation method of the described BFO based sols of step 2 carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Bi
zB
1-zFe
kC
1-kO
3Mol ratio in Bi element, B element, Fe element and C element is z: (1-z): k: the raw material that ratio (1-k) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the BFO based sols that will prepare; 3. polymerization process: the BFO based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the BFO based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the BFO based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.Other is identical with the specific embodiment four.
The specific embodiment ten: what present embodiment and the specific embodiment four were different is: step 2 adopts rta technique heat treatment 3min～10min under 550～650 ℃ of conditions.Other is identical with the specific embodiment four.
Adopt following verification experimental verification invention effect:
Test one: preparation BFO (BiFeO
3) film: according to chemical formula BiFeO
3, be that 1: 1 ratio takes by weighing bismuth nitrate and ferric nitrate raw material in the mol ratio of Bi element and Fe element, raw material is joined in the solvent namely obtain BFO colloidal sol through hydrolysis, dehydration and polymerization process, collosol concentration is 0.3mol/L.First with Pt/Ti/SiO
2/ Si (100) substrate cleans through deionized water, absolute ethyl alcohol and acetone successively, adopt spin-coating method to be deposited on the substrate BFO colloidal sol again, rotating speed is 4000r/min, then with its 400 ℃ of lower thermal decomposition 10min on roasting glue machine, repeat again spin coating and thermal decomposition 5 times, adopt at last rta technique heat treatment 5min under 600 ℃ of conditions, namely obtain the BFO film that thickness is about 580nm.
This tests described BFO (BiFeO
3) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: according to chemical formula BiFeO
3Be that bismuth nitrate and the ferric nitrate raw material that 1: 1 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in the mol ratio of Bi element and Fe element, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the BFO solution that will prepare; 3. polymerization process: the BFO solution that 2. step is made at room temperature left standstill 2.5 days, namely got BFO colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares BFO colloidal sol 1.1 times of contained crystallization water molal quantity summation of steps.
Test two: a kind of crystallization is specifically finished fully and the preparation method of the multiferroic film that produces without dephasign according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
0.7Sr
0.3TiO
3, be that 0.7: 0.3: 1 ratio takes by weighing barium acetate, strontium acetate and butyl titanate raw material in Ba element, Sr element and Ti element mol ratio, raw material is joined in the solvent namely obtain Ba through hydrolysis, dehydration and polymerization process
0.7Sr
0.3TiO
3Colloidal sol, collosol concentration are 0.3mol/L; At first with Pt/Ti/SiO
2/ Si (100) substrate cleans through deionized water, absolute ethyl alcohol and acetone successively, then adopts spin coating proceeding to deposit Ba at substrate
0.7Sr
0.3TiO
3Film, rotating speed are 4000r/min, at last with it at 400 ℃ of lower thermal decomposition 10min, repeat again spin coating and thermal decomposition 1 time after, then adopt rta technique heat treatment 5min under 700 ℃ of conditions, namely obtain the buffer layer thin film that thickness is about 240nm; Two, deposition BFO (BiFeO
3) film: according to chemical formula BiFeO
3, be that 1: 1 ratio takes by weighing bismuth nitrate and ferric nitrate raw material in the mol ratio of Bi element and Fe element, raw material is joined in the solvent namely obtain BFO colloidal sol through hydrolysis, dehydration and polymerization process, collosol concentration is 0.3mol/L; Adopt spin-coating method to be deposited on the buffer layer thin film that obtains through step 1 BFO colloidal sol, rotating speed is 4000r/min, then with its 400 ℃ of lower thermal decomposition 10mm on roasting glue machine, repeat again spin coating and thermal decomposition 3 times, deposit 4 layers of BFO film, make the BFO film that thickness is about 380nm, adopt at last rta technique heat treatment 5min under 600 ℃ of conditions, namely obtain BFO/Ba
0.7Sr
0.3TiO
3(BFO/BSTO) film.
This test procedure one described Ba
0.7Sr
0.3TiO
3(BSTO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
0.7Sr
0.3TiO
3Be that barium acetate, strontium acetate and the butyl titanate raw material that 0.7: 0.3: 1 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in Ba element, Sr element and Ti element mol ratio, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Ba that will prepare
0.7Sr
0.3TiO
3Solution; 3. polymerization process: the Ba that 2. step is made
0.7Sr
0.3TiO
3Solution at room temperature left standstill 2.5 days, namely got Ba
0.7Sr
0.3TiO
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Ba to step
0.7Sr
0.3TiO
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
This test procedure two described BFO (BiFeO
3) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula BiFeO
3Be that bismuth nitrate and the ferric nitrate raw material that 1: 1 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in the mol ratio of Bi element and Fe element, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the BFO solution that will prepare; 3. polymerization process: the BFO solution that 2. step is made at room temperature left standstill 2.5 days, namely got BFO colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares BFO colloidal sol 1.1 times of contained crystallization water molal quantity summation of steps.
Adopt X-ray diffractometer to detect the BFO film of test one preparation and the BFO/BSTO film of test two preparations, testing result as shown in Figure 1, Fig. 1 is the X-ray diffraction spectrogram, a represents to test the BFO film X-ray diffraction spectrogram of a preparation among Fig. 1, b among Fig. 1 represents to test the BFO/BSTO film X-ray diffraction spectrogram of two preparations, # among Fig. 1 is the dephasign characteristic peak, and the * among Fig. 1 is the substrate feature peak.As shown in Figure 1, test one does not adopt the BFO film of cushion preparation dephasign to occur, adopts the BFO/BSTO thin film crystallization for preparing behind the cushion to produce fully and without dephasign and test two.
Adopt ferroelectric analyzer to detect the BFO film of test one preparation and the BFO/BSTO film of test two preparations, testing result as shown in Figure 2, Fig. 2 is ferroelectric hysteresis loop figure, a represents to test the BFO thin-film electro hysteresis line chart of a preparation among Fig. 2, and b represents to test the BFO/BSTO thin-film electro hysteresis line chart of two preparations among Fig. 2.As shown in Figure 2, than the BFO film that test one does not adopt cushion to prepare, test two adopts the saturated polarization of the BFO/BSTO film for preparing behind the cushions obviously to improve, and has better ferroelectric properties.
Test three: a kind of crystallization is specifically finished fully and the preparation method of the multiferroic film that produces without dephasign according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
0.7Sr
0.3TiO
3, be that 0.7: 0.3: 1 ratio takes by weighing barium acetate, strontium acetate and butyl titanate raw material in Ba element, Sr element and Ti element mol ratio, raw material is joined in the solvent namely obtain Ba through hydrolysis, dehydration and polymerization process
0.7Sr
0.3TiO
3Colloidal sol, collosol concentration are 0.3mol/L; At first with Pt/Ti/SiO
2/ Si (100) substrate cleans through deionized water, absolute ethyl alcohol and acetone successively, then adopts spin coating proceeding to deposit Ba at substrate
0.7Sr
0.3TiO
3Film, rotating speed are 4000r/min, at last with it at 400 ℃ of lower thermal decomposition 10min, repeat again spin coating and thermal decomposition 1 time after, then adopt rta technique heat treatment 5min under 700 ℃ of conditions, namely obtain the buffer layer thin film that thickness is about 240nm;
Two, deposition BiFe
0.95Mn
0.05O
3Film: according to chemical formula BiFe
0.95Mn
0.05O
3, be that 1: 0.95: 0.05 ratio takes by weighing bismuth nitrate, ferric nitrate and manganese acetate raw material in the mol ratio of Bi element, Fe element and Mn element, raw material is joined in the solvent namely obtain BiFe through hydrolysis, dehydration and polymerization process
0.95Mn
0.05O
3Colloidal sol, collosol concentration are 0.3mol/L; With BiFe
0.95Mn
0.05O
3Colloidal sol adopts spin-coating method to be deposited on the buffer layer thin film that obtains through step 1, rotating speed is 4000r/min, then with its 400 ℃ of lower thermal decomposition 10min on roasting glue machine, repeats spin coating and thermal decomposition 3 times again, deposit 4 layers of BFO film, make the BiFe that thickness is about 380nm
0.95Mn
0.05O
3Film adopts rta technique heat treatment 5min under 600 ℃ of conditions at last, namely obtains BiFe
0.95Mn
0.05O
3/ BSTO (BFMO/BSTO) film.
This test procedure one described Ba
0.7Sr
0.3TiO
3(BSTO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
0.7Sr
0.3TiO
3Be that barium acetate, strontium acetate and the butyl titanate raw material that 0.7: 0.3: 1 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in Ba element, Sr element and Ti element mol ratio, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Ba that will prepare
0.7Sr
0.3TiO
3Solution; 3. polymerization process: the Ba that 2. step is made
0.7Sr
0.3TiO
3Solution at room temperature left standstill 2.5 days, namely got Ba
0.7Sr
0.3TiO
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Ba to step
0.7Sr
0.3TiO
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
This test procedure two described BiFe
0.95Mn
0.05O
3(BFMO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula BiFe
0.95Mn
0.05O
3Be that bismuth nitrate, ferric nitrate and the manganese acetate raw material that 1: 0.95: 0.05 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in the mol ratio of Bi element, Fe element and Mn element, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the BiFe that will prepare
0.95Mn
0.05O
3Solution; 3. polymerization process: the BiFe that 2. step is made
0.95Mn
0.05O
3Solution at room temperature left standstill 2.5 days, namely got BiFe
0.95Mn
0.05O
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare BiFe to step
0.95Mn
0.05O
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
Test four: a kind of crystallization is specifically finished fully and the preparation method of the multiferroic film that produces without dephasign according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
0.7Sr
0.3TiO
3, be that 0.7: 0.3: 1 ratio takes by weighing barium acetate, strontium acetate and butyl titanate raw material in Ba element, Sr element and Ti element mol ratio, raw material is joined in the solvent namely obtain Ba through hydrolysis, dehydration and polymerization process
0.7Sr
0.3TiO
3Colloidal sol, collosol concentration are 0.3mol/L; At first with Pt/Ti/SiO
2/ Si (100) substrate cleans through deionized water, absolute ethyl alcohol and acetone successively, then adopts spin coating proceeding to deposit Ba at substrate
0.7Sr
0.3TiO
3Film, rotating speed are 4000r/min, at last with it at 400 ℃ of lower thermal decomposition 10min, repeat again spin coating and thermal decomposition 1 time after, then adopt rta technique heat treatment 5min under 700 ℃ of conditions, namely obtain the buffer layer thin film that thickness is about 240nm;
Two, deposition Bi
0.9La
0.1FeO
3Film: according to chemical formula Bi
0.9La
0.1FeO
3, be that 0.9: 0.1: 1 ratio takes by weighing bismuth nitrate, lanthanum nitrate and ferric nitrate raw material in the mol ratio of Bi element, La element and Fe element, raw material is joined in the solvent namely obtain Bi through hydrolysis, dehydration and polymerization process
0.9La
0.1FeO
3Colloidal sol, collosol concentration are 0.3mol/L; With Bi
0.9La
0.1FeO
3Colloidal sol adopts spin-coating method to be deposited on the buffer layer thin film that obtains through step 1, and rotating speed is 4000r/min, then with its 400 ℃ of lower thermal decomposition 10min on roasting glue machine, repeats spin coating and thermal decomposition 3 times again, deposits 4 layers of Bi
0.9La
0.1FeO
3Film makes the Bi that thickness is about 380nm
0.9La
0.1FeO
3Film adopts rta technique heat treatment 5min under 600 ℃ of conditions at last, namely obtains Bi
0.9La
0.1FeO
3/ BSTO (BLFO/BSTO) film.
This test procedure one described Ba
0.7Sr
0.3TiO
3(BSTO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
0.7Sr
0.3TiO
3Be that barium acetate, strontium acetate and the butyl titanate raw material that 0.7: 0.3: 1 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in Ba element, Sr element and Ti element mol ratio, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Ba that will prepare
0.7Sr
0.3TiO
3Solution; 3. polymerization process: the Ba that 2. step is made
0.7Sr
0.3TiO
3Solution at room temperature left standstill 2.5 days, namely got Ba
0.7Sr
0.3TiO
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Ba to step
0.7Sr
0.3TiO
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
This test procedure two described Bi
0.9La
0.1FeO
3(BLFO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Bi
0.9La
0.1FeO
3Be that bismuth nitrate, lanthanum nitrate and the ferric nitrate raw material that 0.9: 0.1: 1 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in the mol ratio of Bi element, La element and Fe element, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Bi that will prepare
0.9La
0.1FeO
3Solution; 3. polymerization process: the Bi that 2. step is made
0.9La
0.1FeO
3Solution at room temperature left standstill 2.5 days, namely got Bi
0.9La
0.1FeO
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Bi to step
0.9La
0.1FeO
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
Test five: a kind of crystallization is specifically finished fully and the preparation method of the multiferroic film that produces without dephasign according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
0.7Sr
0.3TiO
3, be that 0.7: 0.3: 1 ratio takes by weighing barium acetate, strontium acetate and butyl titanate raw material in Ba element, Sr element and Ti element mol ratio, raw material is joined in the solvent namely obtain Ba through hydrolysis, dehydration and polymerization process
0.7Sr
0.3TiO
3Colloidal sol, collosol concentration are 0.3mol/L; At first with Pt/Ti/SiO
2/ Si (100) substrate cleans through deionized water, absolute ethyl alcohol and acetone successively, then adopts spin coating proceeding to deposit Ba at substrate
0.7Sr
0.3TiO
3Film, rotating speed are 4000r/min, at last with it at 400 ℃ of lower thermal decomposition 10min, repeat again spin coating and thermal decomposition 1 time after, then adopt rta technique heat treatment 5min under 700 ℃ of conditions, namely obtain the buffer layer thin film that thickness is about 240nm;
Two, deposition Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Film: according to chemical formula Bi
0.9La
0.1Fe
0.95Mn
0.05O
3, be 0.9: 0.1: 0.95 in the mol ratio of Bi element, La element, Fe element and Mn element: 0.05 ratio takes by weighing bismuth nitrate, lanthanum nitrate, ferric nitrate and manganese acetate raw material, raw material is joined in the solvent namely obtain Bi through hydrolysis, dehydration and polymerization process
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol, collosol concentration are 0.3mol/L; With Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol adopts spin-coating method to be deposited on the buffer layer thin film that obtains through step 1, and rotating speed is 4000r/min, then with its 400 ℃ of lower thermal decomposition 10min on roasting glue machine, repeats spin coating and thermal decomposition 3 times again, deposits 4 layers of Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Film makes the Bi that thickness is about 380nm
0.9La
0.1Fe
0.95Mn
0.05O
3Film adopts rta technique heat treatment 5min under 600 ℃ of conditions at last, namely obtains Bi
0.9La
0.1Fe
0.95Mn
0.05O
3/ BSTO (BLFMO/BSTO) film.
This test procedure one described Ba
0.7Sr
0.3TiO
3(BSTO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
0.7Sr
0.3TiO
3Be that barium acetate, strontium acetate and the butyl titanate raw material that 0.7: 0.3: 1 ratio takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water in Ba element, Sr element and Ti element mol ratio, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Ba that will prepare
0.7Sr
0.3TiO
3Solution; 3. polymerization process: the Ba that 2. step is made
0.7Sr
0.3TiO
3Solution at room temperature left standstill 2.5 days, namely got Ba
0.7Sr
0.3TiO
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Ba to step
0.7Sr
0.3TiO
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
This test procedure two described Bi
0.9La
0.1Fe
0.95Mn
0.05O
3(BLFMO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Mol ratio in Bi element, La element, Fe element and Mn element is 0.9: 0.1: 0.95: the bismuth nitrate that 0.05 ratio takes by weighing, lanthanum nitrate, ferric nitrate and manganese acetate raw material join in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Bi that will prepare
0.9La
0.1Fe
0.95Mn
0.05O
3Solution; 3. polymerization process: the Bi that 2. step is made
0.9La
0.1Fe
0.95Mn
0.05O
3Solution at room temperature left standstill 2.5 days, namely got Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Bi to step
0.9La
0.1Fe
0.95Mn
0.05O
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
Adopt ferroelectric analyzer to detect the BFMO/BSTO film of test three preparations, the BLFO/BSTO film that test four prepares and the BLFMO/BSTO film of testing five preparations, testing result as shown in Figure 3, Fig. 3 is ferroelectric hysteresis loop figure, c represents to test the BFMO/BSTO thin-film electro hysteresis line chart of three preparations among Fig. 3, d among Fig. 3 represents to test the BLFO/BSTO thin-film electro hysteresis line chart of four preparations, and the e among Fig. 3 represents to test the BLFMO/BSTO thin-film electro hysteresis line chart of five preparations.As shown in Figure 3, adopt BSTO (Ba
0.7Sr
0.3TiO
3) as cushion, the BFO film behind La, Mn or La and the Mn co-doped all has good ferroelectric properties.
Adopt the section of sem observation test five preparation BLFMO/BSTO films, testing result as shown in Figure 4, Fig. 4 is the electron scanning micrograph of the BLFMO/BSTO thin-membrane section of test five preparations, f among Fig. 4 is the BLFMO electron scanning micrograph, g among Fig. 4 is the BSTO electron scanning micrograph, h among Fig. 4 is the Pt/Ti electron scanning micrograph, and the i among Fig. 4 is SiO
2/ Si electron scanning micrograph; 4 layers of BLFMO that process through high-temperature quick among Fig. 4 and 2 layers of BSTO film are in conjunction with tight, and its gross thickness is about 620nm.
Test six: preparation Bi
0.9La
0.1Fe
0.95Mn
0.05O
3(BLFMO) film: according to chemical formula Bi
0.9La
0.1Fe
0.95Mn
0.05O
3, be 0.9: 0.1: 0.95 in the mol ratio of Bi element, La element, Fe element and Mn element: 0.05 ratio takes by weighing bismuth nitrate, lanthanum nitrate, ferric nitrate and manganese acetate raw material, raw material is joined in the solvent namely obtain Bi through hydrolysis, dehydration and polymerization process
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol, collosol concentration are 0.3mol/L; First with Pt/Ti/SiO
2/ Si (100) substrate cleans through deionized water, absolute ethyl alcohol and acetone successively, again with Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol adopts spin-coating method to be deposited on the substrate, rotating speed is 4000r/min, then with its 400 ℃ of lower thermal decomposition 10min on roasting glue machine, repeats spin coating and thermal decomposition 5 times again, adopt at last rta technique heat treatment 5min under 600 ℃ of conditions, namely obtain the Bi that thickness is about 580nm
0.9La
0.1Fe
0.95Mn
0.05O
3(BLFMO) film.
This tests described Bi
0.9La
0.1Fe
0.95Mn
0.05O
3(BLFMO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Mol ratio in Bi element, La element, Fe element and Mn element is 0.9: 0.1: 0.95: the bismuth nitrate that 0.05 ratio takes by weighing, lanthanum nitrate, ferric nitrate and manganese acetate raw material join in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Bi that will prepare
0.9La
0.1Fe
0.95Mn
0.05O
3Solution; 3. polymerization process: the Bi that 2. step is made
0.9La
0.1Fe
0.95Mn
0.05O
3Solution at room temperature left standstill 2.5 days, namely got Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Bi to step
0.9La
0.1Fe
0.95Mn
0.05O
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
Test seven: a kind of crystallization is specifically finished fully and the preparation method of the multiferroic film that produces without dephasign according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
0.7Sr
0.3Ti
0.95Co
0.05O
3Be 0.7: 0.3: 0.95 in Ba element, Sr element, Ti element and Co element mol ratio: 0.05 ratio takes by weighing barium acetate, strontium acetate, cobalt acetate and butyl titanate raw material, raw material is joined in the solvent namely obtain Ba through hydrolysis, dehydration and polymerization process
0.7Sr
0.3Ti
0.95Co
0.05O
3Colloidal sol, collosol concentration are 0.3mol/L; At first with Pt/Ti/SiO
2/ Si (100) substrate cleans through deionized water, absolute ethyl alcohol and acetone successively, then adopts spin coating proceeding to deposit Ba at substrate
0.7Sr
0.3Ti
0.95Co
0.05O
3Film, rotating speed are 4000r/min, at last with it at 400 ℃ of lower thermal decomposition 10min, repeat again spin coating and thermal decomposition 1 time after, then adopt rta technique heat treatment 5min under 700 ℃ of conditions, namely obtain the buffer layer thin film that thickness is about 240nm; Two, deposition Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Film: according to chemical formula Bi
0.9La
0.1Fe
0.95Mn
0.05O
3, be 0.9: 0.1: 0.95 in the mol ratio of Bi element, La element, Fe element and Mn element: 0.05 ratio takes by weighing bismuth nitrate, lanthanum nitrate, ferric nitrate and manganese acetate raw material, raw material is joined in the solvent namely obtain Bi through hydrolysis, dehydration and polymerization process
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol, collosol concentration are 0.3mol/L; With Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol adopts spin-coating method to be deposited on the buffer layer thin film that obtains through step 1, and rotating speed is 4000r/min, then with its 400 ℃ of lower thermal decomposition 10min on roasting glue machine, repeats spin coating and thermal decomposition 3 times again, deposits 4 layers of Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Film makes the Bi that thickness is about 380nm
0.9La
0.1Fe
0.95Mn
0.05O
3Film adopts rta technique heat treatment 5min under 600 ℃ of conditions at last, namely obtains Bi
0.9La
0.1Fe
0.95Mn
0.05O
3/ Ba
0.7Sr
0.3Ti
0.95Co
0.05O
3(BLFMO/BSTCO) film.
This test procedure one described Ba
0.7Sr
0.3Ti
0.95Co
0.05O
3(BSTCO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
0.7Sr
0.3Ti
0.95Co
0.05O
3Be 0.7: 0.3: 0.95 in Ba element, Sr element, Ti element and Co element mol ratio: the barium acetate that 0.05 ratio takes by weighing, strontium acetate, cobalt acetate and butyl titanate raw material join in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Ba that will prepare
0.7Sr
0.3Ti
0.95Co
0.05O
3Solution; 3. polymerization process: the Ba that 2. step is made
0.7Sr
0.3Ti
0.95Co
0.05O
3Solution at room temperature left standstill 2.5 days, namely got Ba
0.7Sr
0.3Ti
0.95Co
0.05O
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Ba to step
0.7Sr
0.3Ti
0.95Co
0.05O
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
This test procedure two described Bi
0.9La
0.1Fe
0.95Mn
0.05O
3(BLFMO) preparation method of colloidal sol carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Mol ratio in Bi element, La element, Fe element and Mn element is 0.9: 0.1: 0.95: the bismuth nitrate that 0.05 ratio takes by weighing, lanthanum nitrate, ferric nitrate and manganese acetate raw material join in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 1h under 30 ℃ of conditions, namely gets the Bi that will prepare
0.9La
0.1Fe
0.95Mn
0.05O
3Solution; 3. polymerization process: the Bi that 2. step is made
0.9La
0.1Fe
0.95Mn
0.05O
3Solution at room temperature left standstill 2.5 days, namely got Bi
0.9La
0.1Fe
0.95Mn
0.05O
3Colloidal sol; The deionized water of step described in 1. and the volume ratio of EGME are 1: 15, and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: 3, and deionized water and glacial acetic acid volume ratio are 1: 5.5; The volume of the PEG400 of step described in 2. is 10% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is that 1. 1. deionized water molal quantity and the step of mixed solvent prepare Bi to step
0.9La
0.1Fe
0.95Mn
0.05O
3In the raw material of colloidal sol 1.1 times of contained crystallization water molal quantity summation.
Adopt X-ray diffractometer to detect the BLFMO film of test six preparations and the BLFMO/BSTCO film of test seven preparations, testing result as shown in Figure 5, Fig. 5 is the X-ray diffraction spectrogram, f represents to test the BLFMO film X-ray diffraction spectrogram of six preparations among Fig. 5, and the j among Fig. 5 represents to test the BLFMO/BSTCO film X-ray diffraction spectrogram of seven preparations; # among Fig. 5 is the dephasign characteristic peak, and the * among Fig. 5 is the substrate feature peak.As shown in Figure 5, test six does not adopt the BLFMO films of cushion preparation dephasign to occur, and it is higher and produce without dephasign to test the seven BLFMO/BSTCO thin film crystallization degree that prepare after adopting the BSTCO films as cushion.
Adopt ferroelectric analyzer to detect the BLFMO/BSTCO film of test seven preparations, testing result as shown in Figure 6, Fig. 6 is that test voltage is the ferroelectric hysteresis loop figure under 40V, 60V and the 80V, k represents to test when test voltage is 40V the BLFMO/BSTCO thin-film electro hysteresis line chart of seven preparations among Fig. 6, the BLFMO/BSTCO thin-film electro hysteresis line chart of test seven preparations when 1 expression test voltage is 60V among Fig. 6, m represents to test when test voltage is 80V the BLFMO/BSTCO thin-film electro hysteresis line chart of seven preparations among Fig. 6.As shown in Figure 6, film behind the test seven employing magnetic Co element doping BSTO is as cushion, not only effectively raise the saturated polarization of multiferroic film, its remanent polarization and coercive field all are significantly improved simultaneously, has better ferroelectric properties, when electric-field intensity was 1290.3kV/cm, its saturated polarization, remanent polarization and coercive field were respectively 47.5 μ C/cm
2, 37.6 μ C/cm
2And 596.8kV/cm.
Adopt vibrating specimen magnetometer to detect the BLFMO/BSTO film of test five preparations and the BLFMO/BSTCO film of test seven preparations, testing result as shown in Figure 7, Fig. 7 is hysteresis curve figure, e among Fig. 7 represents to test the BLFMO/BSTO film hysteresis curve figure of five preparations, and the j among Fig. 7 represents to test the BLFMO/BSTCO film hysteresis curve figure of seven preparations; Fig. 8 is the partial enlarged drawing of Fig. 7 hysteresis curve figure, and the e among Fig. 8 represents to test the partial enlarged drawing of the five BLFMO/BSTO film hysteresis curve figure that prepare, and the j among Fig. 8 represents to test the partial enlarged drawing of the seven BLFMO/BSTCO film hysteresis curve figure that prepare; By Fig. 7 and Fig. 8 as can be known, test seven adopts the BSTCO of magnetic Co element doping to adopt the BSTO film to compare as cushion as cushion with test five, the ferromagnetic property of the BLFMO/BSTCO film of test seven preparations is greatly improved, and it has higher saturation magnetization, remanent magnetization and coercivity.
Claims (10)
1. a crystallization is fully and without the multiferroic film that dephasign produces, it is characterized in that crystallization fully and the multiferroic film that produces without dephasign by barium strontium titanate based sols and BFO based sols at the Pt/Ti/SiO through cleaning
2Form by spin-coating method, thermal decomposition method and rta technique legal system are standby on/Si (100) substrate.
2. a kind of crystallization according to claim 1 is characterized in that the preparation method of described barium strontium titanate based sols carries out in accordance with the following steps fully and without the multiferroic film that dephasign produces: 1. hydrolytic process: will be according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: the raw material that ratio (1-y) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the barium strontium titanate based sols that will prepare; 3. polymerization process: the barium strontium titanate based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the barium strontium titanate based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the barium strontium titanate based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.
3. a kind of crystallization according to claim 1 is characterized in that the preparation method of described BFO based sols carries out in accordance with the following steps fully and without the multiferroic film that dephasign produces: 1. hydrolytic process: will be according to chemical formula Bi
zB
1-zFe
kC
1-kO
3Mol ratio in Bi element, B element, Fe element and C element is z: (1-z): k: the raw material that ratio (1-k) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the BFO based sols that will prepare; 3. polymerization process: the BFO based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the BFO based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the BFO based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.
4. a kind of crystallization as claimed in claim 1 fully and the preparation method of the multiferroic film that produces without dephasign is characterized in that crystallization fully and the preparation method of the multiferroic film that produces without dephasign finishes according to the following steps:
One, preparation buffer layer thin film: according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: ratio (1-y) takes by weighing raw material, raw material joined in the solvent through hydrolysis, dehydration and polymerization process namely obtains the barium strontium titanate based sols that concentration is 0.3mol/L, again with the barium strontium titanate based sols by spin coating and thermal decomposition method at the Pt/Ti/SiO through cleaning
2Preparation thickness is the barium strontium titanate base film of 50nm～400nm on/Si (100) substrate, then adopts rta technique heat treatment 1min～15min under 600～800 ℃ of conditions, namely obtains buffer layer thin film; Two, deposition BFO base film: according to chemical formula Bi
zB
1-zFe
kC
1-kO
3Press the Bi element, the B element, the mol ratio of Fe element and C element is z: (1-z): k: ratio (1-k) takes by weighing raw material, raw material is joined in the solvent through hydrolysis, dehydration and polymerization process namely obtain the BFO based sols that concentration is 0.3mol/L, deposit thickness on the buffer layer thin film that obtains through step 1 is the BFO base film of 100nm～1000nm by spin coating and thermal decomposition method with the BFO based sols again, then adopt rta technique heat treatment 1min～15min under 500～700 ℃ of conditions, the multiferroic film that namely obtains crystallization fully and produce without dephasign; Chemical formula Ba described in the step 1
xSr
1-xA
yTi
1-yO
3In, A is Co, Fe or Mn, x is: and 0＜x≤1, y is: 0≤y≤0.5; Multiferroic film Bi described in the step 2
zB
1-zFe
kC
1-kO
3, wherein B is La, Nd, Gd or Ho, and C is Mn, Ti, Nb or Cr, and z is: 0＜z≤1, k is: 0＜k≤1.
5. a kind of crystallization according to claim 4 fully and the preparation method of the multiferroic film that produces without dephasign is characterized in that the preparation method of the described barium strontium titanate based sols of step 1 carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: the raw material that ratio (1-y) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the barium strontium titanate based sols that will prepare; 3. polymerization process: the barium strontium titanate based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the barium strontium titanate based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the barium strontium titanate based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.
6. a kind of crystallization according to claim 4 fully and the preparation method of the multiferroic film that produces without dephasign is characterized in that step 1 is according to chemical formula Ba
xSr
1-xA
yTi
1-yO
3Be x in Ba element, Sr element, A element and Ti element mol ratio: (1-x): y: ratio (1-y) takes by weighing raw material, raw material joined in the solvent through hydrolysis, dehydration and polymerization process namely obtains the barium strontium titanate based sols that concentration is 0.3mol/L, again with the barium strontium titanate based sols by spin coating and thermal decomposition method at the Pt/Ti/SiO through cleaning
2Preparation thickness is the barium strontium titanate base film of 100nm～300nm on/Si (100) substrate.
7. a kind of crystallization according to claim 4 fully and the preparation method of the multiferroic film that produces without dephasign is characterized in that step 1 adopts rta technique heat treatment 3min～10min under 650～750 ℃ of conditions.
8. a kind of crystallization according to claim 4 fully and the preparation method of the multiferroic film that produces without dephasign is characterized in that the chemical formula Ba described in the step 1
xSr
1-xA
yTi
1-yO
3In, x is: 0.5≤x≤0.9, y is: 0≤y≤0.2.
9. a kind of crystallization according to claim 4 fully and the preparation method of the multiferroic film that produces without dephasign is characterized in that the preparation method of the described BFO based sols of step 2 carries out in accordance with the following steps: 1. hydrolytic process: will be according to chemical formula Bi
zB
1-zFe
kC
1-kO
3Mol ratio in Bi element, B element, Fe element and C element is z: (1-z): k: the raw material that ratio (1-k) takes by weighing joins in the mixed solvent that is comprised of EGME, acetylacetone,2,4-pentanedione, glacial acetic acid and deionized water, be stirred to abundant dissolving under the room temperature, it is stand-by to get mixed solution; 2. dehydration: the mixed solution that 1. PEG400 and acetic anhydride and step made mixes, and then continues to stir 0.5h～2h under 20～40 ℃ of conditions, namely gets the BFO based sols that will prepare; 3. polymerization process: the BFO based sols that 2. step is made at room temperature left standstill 1 day～4 days, namely got the BFO based sols; The deionized water of step described in 1. and the volume ratio of EGME are 1: (7～23), and deionized water and acetylacetone,2,4-pentanedione volume ratio are 1: (1～5), deionized water and glacial acetic acid volume ratio are 1: (2～9); The volume of the PEG400 of step described in 2. is 5%～15% of the mixed liquor volume that 1. makes of step; The acetic anhydride molal quantity of step described in 2. is 1. in the deionized water molal quantity of mixed solvent and the raw material that 1. step prepares the BFO based sols 1.05～1.1 times of contained crystallization water molal quantity summation of steps.
10. a kind of crystallization according to claim 4 fully and the preparation method of the multiferroic film that produces without dephasign is characterized in that step 2 adopts rta technique heat treatment 3min～10min under 550～650 ℃ of conditions.
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