CN101538156A - Preparation method of induced texture ferroelectric film at buffer layer - Google Patents
Preparation method of induced texture ferroelectric film at buffer layer Download PDFInfo
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- CN101538156A CN101538156A CN200910071930A CN200910071930A CN101538156A CN 101538156 A CN101538156 A CN 101538156A CN 200910071930 A CN200910071930 A CN 200910071930A CN 200910071930 A CN200910071930 A CN 200910071930A CN 101538156 A CN101538156 A CN 101538156A
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Abstract
A preparation method of induced texture ferroelectric film at buffer layer relates to a preparation method of ferroelectric film. The invention solves the problem of bad performance of ferroelectric film prepared and obtained in the existing method. The method is as follows: firstly, LaNiO3 buffer layer sol is prepared; secondly, a buffer layer film is obtained after spin coating, heat preservation and annealing; thirdly, ferroelectric oxide sol is dropped on a substrate to obtain the ferroelectric film after spin coating, heat preservation and annealing. The ferroelectric film prepared and obtained by the invention has good dielectricity and piezoelectric performance; the manufacturing technology in the invention is simple; the ferroelectric film manufactured and obtained by the invention is compatible with integrated devices in silicon technology, and has good application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of ferroelectric membranc.
Background technology
Relaxation ferroelectric ceramic is the very noticeable material of a class in the function ceramics, high speed development along with electronic information technology, demand to laminated ceramic capacitor, ceramic micro positioner and driving mechanism and little electric light machinery etc. grows with each passing day, and this is major cause and background that present relaxation ferroelectric ceramic is developed rapidly.In addition, along with the development of FERROELECTRICS MEMORIES TECHNOLOGY, low-light-electric mechanical and ferroelectric integrated electronics, the preparation of ferroelectric membranc and the research of application have become a very important and active field in the current novel material research.In the research process of ferroelectric membranc, it is found that the performance of electrode pair film has great influence, the existing Pt electrodes that adopt as buffer layer more, but the fatigue resistance of Pt electrode is poor, causes existing ferroelectric membranc poor performance.
Summary of the invention
Purpose of the present invention is for the problem of the ferroelectric membranc poor performance that solves existing method and prepare, and a kind of preparation method of induced texture ferroelectric film at buffer layer is provided.
The preparation method of induced texture ferroelectric film at buffer layer of the present invention carries out according to following steps: one, according to ratio of weight and number 1.6~2 parts lanthanum nitrate, 1~1.2 part nickelous acetate and 10~30 parts ethylene glycol monomethyl ether are mixed, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Buffer layer sol; Two, buffer layer sol is added drop-wise on the substrate, with 1000~2000r/min spin coating, 5~15s, to be incubated 4~5min 300~450 ℃ of conditions behind 3500~4500r/min spin coating, 15~25s, the 5~15min that anneals under 600~800 ℃ of conditions then is cooled to room temperature and is buffer layer thin film again; Three, ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film, with 1000~2000r/min spin coating, 5~15s, again to be incubated 4~5min 300~450 ℃ of conditions behind 3500~4500r/min spin coating, 15~25s, 5~the 15min that anneals under 600~800 ℃ of conditions then is cooled to room temperature and is ferroelectric membranc.
Ferroelectric membranc colloidal sol is Pb (ZrxTi in the inventive method step 3
(1-x)) O
3Ferroelectric membranc colloidal sol or (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3Ferroelectric membranc colloidal sol; Pb (ZrxTi
(1-x)) O
3In 0<x<1, (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3In 0<x<1.
The present invention utilizes LaNiO
3Conductive oxide prepares ferroelectric membranc as buffer layer, LaNiO
3Oxygen in the conducting oxide electrode can be spread to the contact interface of ferroelectric membranc and electrode, reduced the oxygen room at the interface formation and accumulation, improved the ferroelectric membranc fatigue resistance, make the XRD figure of the ferroelectric membranc that obtains composes as can be seen from the present invention, except the Pt (111) and Pt (200) diffraction peak of substrate, the ferroelectric membranc of preparation has strong texture along the growth of (100) crystal orientation preferred orientation, and the dielectricity of ferroelectric membranc and piezoelectric property are good; Manufacture craft of the present invention is simple, makes the ferroelectric membranc uniform film thickness unanimity obtain, and the surface do not have crackle, and compactness is good, and it is good that the present invention makes the ferroelectric membranc performance that obtains, available YBa among the present invention
2Cu
3O
7-x, SrRuO
3Or La
xSr
1-xCO
3Substitute LaNiO
3Conductive oxide can be induced equally and obtain ferroelectric membranc as buffer layer.The present invention make the ferroelectric membranc obtain can with integrated device compatibility such as silicon technology, application prospect is good.
Description of drawings
Fig. 1 makes the XRD figure spectrum of the ferroelectric membranc that obtains for embodiment 14; Fig. 2 is embodiment 14 LaNiO
3The SEM surface picture of buffer layer thin film; The SEM surface picture that Fig. 3 makes the ferroelectric membranc that obtains for embodiment 14.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment induced texture ferroelectric film at buffer layer carries out according to following steps: one, according to ratio of weight and number 1.6~2 parts lanthanum nitrate, 1~1.2 part nickelous acetate and 10~30 parts ethylene glycol monomethyl ether are mixed, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Buffer layer sol; Two, buffer layer sol is added drop-wise on the substrate, with 1000~2000r/min spin coating, 5~15s, to be incubated 4~5min 300~450 ℃ of conditions behind 3500~4500r/min spin coating, 15~25s, the 5~15min that anneals under 600~800 ℃ of conditions then is cooled to room temperature and is buffer layer thin film again; Three, ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film, with 1000~2000r/min spin coating, 5~15s, again to be incubated 4~5min 300~450 ℃ of conditions behind 3500~4500r/min spin coating, 15~25s, 5~the 15min that anneals under 600~800 ℃ of conditions then is cooled to room temperature and is ferroelectric membranc.
The thickness of ferroelectric oxide on buffer layer thin film is 30~400nm in the present embodiment step 3.
Embodiment two: what present embodiment and embodiment one were different is according to ratio of weight and number 1.7~1.9 parts lanthanum nitrate, 1.05~1.15 parts nickelous acetate and 15~25 parts ethylene glycol monomethyl ether to be mixed in the step 1, is heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Colloidal sol.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment two were different is according to ratio of weight and number 1.8 parts lanthanum nitrate, 1.2 parts nickelous acetate and 20 parts ethylene glycol monomethyl ether to be mixed in the step 1, is heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Colloidal sol.Other step and parameter are identical with embodiment two.
Embodiment four: what present embodiment was different with embodiment one or two is that buffer layer is 40~300nm at on-chip thickness in the step 2.Other step and parameter are identical with embodiment one or two.
Embodiment five: what present embodiment and embodiment four were different is that buffer layer sol is added drop-wise on the substrate in the step 2, with 1500r/min spin coating 10s, again with 4000r/min spin coating 20s.Other step and parameter are identical with embodiment four.
Embodiment six: what present embodiment and embodiment one, two or four were different is that ferroelectric membranc colloidal sol is Pb (ZrxTi in the step 3
(1-x)) O
3Ferroelectric membranc colloidal sol or (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3Ferroelectric membranc colloidal sol; Pb (ZrxTi
(1-x)) O
3In 0<x<1, (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3In 0<x<1.Other step and parameter are identical with embodiment one, two or four.
Embodiment seven: that present embodiment and embodiment six are different is (1-x) Pb (Mg in the step 3
1/3Nb
2/3)-xPbTiO
3The preparation method of colloidal sol: one, according to chemical formula (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3By 1: 1/3-1/3x: 2/3-2/3x: the mol ratio of x takes by weighing plumbic acetate, magnesium acetate, ethanol niobium and tetrabutyl titanate, wherein 0<x<1 respectively; Two, add glacial acetic acid and ethylene glycol monomethyl ether in following ratio in the 3.5g plumbic acetate, stirring at room 10~30min gets solution A then; Wherein the glacial acetic acid volume is 1.8~2.5mL, and the volume of ethylene glycol monomethyl ether is 9.0~11.0mL; Three, add glacial acetic acid and ethylene glycol monomethyl ether in following ratio in the magnesium acetate of 0.4g and 3.5g ethanol niobium mixture, reflux stirs 20~60min under 60~100 ℃ of conditions then, solution B; Wherein the glacial acetic acid volume is 1.8~2.5mL, and the volume of ethylene glycol monomethyl ether is 9.0~11.0mL; Four, add tetrabutyl titanate in following ratio in the mixture of step 3, reflux stirs 20~60min under 60~100 ℃ of conditions then, obtains C solution, and wherein the quality of tetrabutyl titanate is 0.9g; Five, add methyl ethyl diketone in following ratio in the mixing solutions of A solution and C solution, stirring at room 10~30min promptly obtains (1-x) Pb (Mg then
1/3Nb
2/3)-xPbTiO
3Colloidal sol, the quality of methyl ethyl diketone are 0.5~1.2g.Other step and parameter are identical with embodiment six.
Embodiment eight: what present embodiment and embodiment seven were different is x=0.2 in the step 3~0.6.Other step and parameter are identical with embodiment seven.
Embodiment nine: that present embodiment and embodiment seven are different is x=0.31 in the step 3.Other step and parameter are identical with embodiment seven.
Embodiment ten: what present embodiment and embodiment one, two, four or six were different is that ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film in the step 3, with 1500r/min spin coating 10s, again with 4000r/min spin coating 20s.Other step and parameter are identical with embodiment one, two, four or six.
Embodiment 11: the preparation method of present embodiment induced texture ferroelectric film at buffer layer carries out according to following steps: one, according to ratio of weight and number 1.7 parts lanthanum nitrate, 1.2 parts nickelous acetate and 30 parts ethylene glycol monomethyl ether are mixed, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Buffer layer sol; Two, buffer layer sol is added drop-wise on the substrate, with 1500r/min spin coating 10s, to be incubated 4min 400 ℃ of conditions behind the 4000r/min spin coating 10s, the 10min that anneals under 700 ℃ of conditions then is cooled to room temperature and is buffer layer thin film again; Three, ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film, and with 1500r/min spin coating 10s, to be incubated 5min 400 ℃ of conditions behind the 4000r/min spin coating 10s, the 10min that anneals under 700 ℃ of conditions then is cooled to room temperature and is ferroelectric membranc again.
Buffer layer is 40~300nm at on-chip thickness in the present embodiment step 2.
Ferroelectric membranc colloidal sol is Pb (ZrxTi in the present embodiment step 3
(1-x)) O
3Colloidal sol or (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3Colloidal sol, wherein Pb (ZrxTi
(1-x)) O
3(1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3In 0<x<1.
Embodiment 12: the preparation method of present embodiment induced texture ferroelectric film at buffer layer carries out according to following steps: one, according to ratio of weight and number 1.6~2 parts lanthanum nitrate, 1~1.2 part nickelous acetate and 10~0.03 parts ethylene glycol monomethyl ether are mixed, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Buffer layer sol; Two, buffer layer sol is added drop-wise on the substrate, with 2000r/min spin coating 13s, to be incubated 5min 380 ℃ of conditions behind the 4000r/min spin coating 13s, the 10min that anneals under 800 ℃ of conditions then is cooled to room temperature and is buffer layer thin film again; Three, ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film, with 1800r/min spin coating 12s, to be incubated 4min 420 ℃ of conditions behind the 4200r/min spin coating 19s, the 12min that anneals under 680 ℃ of conditions then is cooled to room temperature and is ferroelectric membranc again.
Embodiment 13: the preparation method of present embodiment induced texture ferroelectric film at buffer layer carries out according to following steps: one, according to ratio of weight and number 1.5 parts lanthanum nitrate, 1.1 parts nickelous acetate and 18 parts ethylene glycol monomethyl ether are mixed, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Buffer layer sol; Two, step 1 is obtained buffer layer sol and be added drop-wise on the substrate, with 1800r/min spin coating 8s, to be incubated 4min 400 ℃ of conditions behind the 4000r/min spin coating 10s, the 10min that anneals under 700 ℃ of conditions then is cooled to room temperature and is buffer layer thin film again; Three, ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film, with 1500r/min spin coating 10s, to be incubated 5min 400 ℃ of conditions behind the 4000r/min spin coating 10s, the 10min that anneals under 700 ℃ of conditions then is cooled to room temperature and is ferroelectric membranc again.
Present embodiment ferroelectric oxide colloidal sol is Pb (ZrxTi
(1-x)) O
3Colloidal sol, Pb (ZrxTi
(1-x)) O
3The preparation method of colloidal sol is recorded in the article of a piece " performance of different components PZT piezoelectric membrane " by name being delivered on " functional materials and device journal " by the Shao Chun jade.
The thickness of ferroelectric oxide on buffer layer thin film is 30~400nm in the present embodiment step 3.
Embodiment 14: the preparation method of present embodiment induced texture ferroelectric film at buffer layer carries out according to following steps: one, according to ratio of weight and number 1.8 parts lanthanum nitrate, 1.1 parts nickelous acetate and 20 parts ethylene glycol monomethyl ether are mixed, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Buffer layer sol; Two, buffer layer sol is added drop-wise on the substrate, with 2000r/min spin coating 13s, to be incubated 5min 380 ℃ of conditions behind the 4000r/min spin coating 13s, the 10min that anneals under 800 ℃ of conditions then is cooled to room temperature and is buffer layer thin film again; Three, ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film, with 1800r/min spin coating 12s, to be incubated 4min 420 ℃ of conditions behind the 4200r/min spin coating 19s, the 12min that anneals under 680 ℃ of conditions then is cooled to room temperature and is ferroelectric membranc again.
Buffer layer is 200nm at on-chip thickness in the present embodiment step 2.
(1-x) Pb (Mg in the present embodiment step 2
1/3Nb
2/3)-xPbTiO
3The preparation method of ferroelectric membranc colloidal sol: one, according to chemical formula (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3By 1: 1/3-1/3x: 2/3-2/3x: the mol ratio of x takes by weighing plumbic acetate, magnesium acetate, ethanol niobium and tetrabutyl titanate, wherein 0<x<1 respectively; Two, add glacial acetic acid and ethylene glycol monomethyl ether in following ratio in the 3.5g plumbic acetate, stirring at room 10~30min gets solution A then; Wherein the glacial acetic acid volume is 1.8~2.5mL, and the volume of ethylene glycol monomethyl ether is 9.0~11.0mL; Three, add glacial acetic acid and ethylene glycol monomethyl ether in following ratio in the magnesium acetate of 0.4g and 3.5g ethanol niobium mixture, reflux stirs 20~60min under 60~100 ℃ of conditions then, solution B; Wherein the glacial acetic acid volume is 1.8~2.5mL, and the volume of ethylene glycol monomethyl ether is 9.0~11.0mL; Four, add tetrabutyl titanate in following ratio in the mixture of step 3, reflux stirs 20~60min under 60~100 ℃ of conditions then, obtains C solution, and wherein the quality of tetrabutyl titanate is 0.9g; Five, add methyl ethyl diketone in following ratio in A solution and C solution mixing solutions, stirring at room 10~30min promptly obtains (1-x) Pb (Mg then
1/3Nb
2/3)-xPbTiO
3Colloidal sol, the quality of methyl ethyl diketone are 0.5~1.2g.
Present embodiment is made the XRD figure of the ferroelectric membranc that obtains and is composed as shown in Figure 1, as can be seen from Figure 1, except the Pt (111) and Pt (200) diffraction peak of substrate, the ferroelectric membranc of preparation is along the growth of (100) crystal orientation preferred orientation, have stronger texture, present embodiment is made the ferroelectric membranc that obtains will have stronger dielectricity and piezoelectric property.
Present embodiment LaNiO
3The SEM surface picture of buffer layer thin film as shown in Figure 2, as can be seen from Figure 2, the uniform film thickness unanimity of buffer layer thin film, and the surface do not have crackle, compactness is good.
The SEM surface picture that present embodiment is made the ferroelectric membranc obtain as shown in Figure 3, as can be seen from Figure 3, the uniform film thickness unanimity of ferroelectric membranc, and the surface do not have crackle, compactness is good.
Claims (11)
1, the preparation method of induced texture ferroelectric film at buffer layer, the preparation method who it is characterized in that induced texture ferroelectric film at buffer layer carries out according to following steps: one, according to ratio of weight and number 1.6~2 parts lanthanum nitrate, 1~1.2 part nickelous acetate and 10~30 parts ethylene glycol monomethyl ether are mixed, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Buffer layer sol; Two, with LaNiO
3Buffer layer sol is added drop-wise on the substrate, with 1000~2000r/min spin coating, 5~15s, to be incubated 4~5min 300~450 ℃ of conditions behind 3500~4500r/min spin coating, 15~25s, the 5~15min that anneals under 600~800 ℃ of conditions then is cooled to room temperature and is buffer layer thin film again; Three, ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film, with 1000~2000r/min spin coating, 5~15s, again to be incubated 4~5min 300~450 ℃ of conditions behind 3500~4500r/min spin coating, 15~25s, 5~the 15min that anneals under 600~800 ℃ of conditions then is cooled to room temperature and is ferroelectric membranc.
2, the preparation method of induced texture ferroelectric film at buffer layer according to claim 1, it is characterized in that according to ratio of weight and number 1.7~1.9 parts lanthanum nitrate, 1.05~1.15 parts nickelous acetate and 15~25 parts ethylene glycol monomethyl ether being mixed in the step 1, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Colloidal sol.
3, the preparation method of induced texture ferroelectric film at buffer layer according to claim 2, it is characterized in that according to ratio of weight and number 1.8 parts lanthanum nitrate, 1.2 parts nickelous acetate and 20 parts ethylene glycol monomethyl ether being mixed in the step 1, be heated with stirring to dissolving fully then; Promptly obtain LaNiO
3Colloidal sol.
3, the preparation method of induced texture ferroelectric film at buffer layer according to claim 1 and 2 is characterized in that the substrate in the step 2 is SiO
2/ Si or Pt/Ti/SiO
2/ Si.
4, the preparation method of induced texture ferroelectric film at buffer layer according to claim 3 is characterized in that buffer layer is 40~300nm at on-chip thickness in the step 2.
5,, it is characterized in that buffer layer sol is added drop-wise on the substrate in the step 2, with 1500r/min spin coating 10s, again with 4000r/min spin coating 20s according to the preparation method of claim 1,2 or 4 described induced texture ferroelectric film at buffer layer.
6, the preparation method of induced texture ferroelectric film at buffer layer according to claim 5 is characterized in that ferroelectric membranc colloidal sol is Pb (ZrxTi in the step 3
(1-x)) O
3Ferroelectric membranc colloidal sol or (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3Ferroelectric membranc colloidal sol; Pb (ZrxTi
(1-x)) O
3In 0<x<1, (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3In 0<x<1.
7, the preparation method of induced texture ferroelectric film at buffer layer according to claim 6 is characterized in that (1-x) Pb (Mg in the step 3
1/3Nb
2/3)-xPbTiO
3The preparation method of ferroelectric membranc colloidal sol: one, according to chemical formula (1-x) Pb (Mg
1/3Nb
2/3)-xPbTiO
3By 1: 1/3-1/3x: 2/3-2/3x: the mol ratio of x takes by weighing plumbic acetate, magnesium acetate, ethanol niobium and tetrabutyl titanate, wherein 0<x<1 respectively; Two, add glacial acetic acid and ethylene glycol monomethyl ether in following ratio in the 3.5g plumbic acetate, stirring at room 10~30min gets solution A then; Wherein the glacial acetic acid volume is 1.8~2.5mL, and the volume of ethylene glycol monomethyl ether is 9.0~11.0mL; Three, add glacial acetic acid and ethylene glycol monomethyl ether in following ratio in the magnesium acetate of 0.4g and 3.5g ethanol niobium mixture, reflux stirs 20~60min under 60~100 ℃ of conditions then, solution B; Wherein the glacial acetic acid volume is 1.8~2.5mL, and the volume of ethylene glycol monomethyl ether is 9.0~11.0mL; Four, add tetrabutyl titanate in following ratio in the mixture of step 3, reflux stirs 20~60min under 60~100 ℃ of conditions then, obtains C solution, and wherein the quality of tetrabutyl titanate is 0.9g; Five, add methyl ethyl diketone in following ratio in the mixing solutions of A solution and C solution, stirring at room 10~30min promptly obtains (1-x) Pb (Mg then
1/3Nb
2/3)-xPbTiO
3Colloidal sol, wherein the quality of methyl ethyl diketone is 0.5~1.2g.
8, the preparation method of induced texture ferroelectric film at buffer layer according to claim 7 is characterized in that x=0.2 in the step 3~0.6.
9, the preparation method of induced texture ferroelectric film at buffer layer according to claim 7 is characterized in that x=0.31 in the step 3.
10,, it is characterized in that ferroelectric oxide colloidal sol is added drop-wise on the buffer layer thin film in the step 3, with 1500r/min spin coating 10s, again with 4000r/min spin coating 20s according to the preparation method of claim 1,2,4 or 6 described induced texture ferroelectric film at buffer layer.
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CN102136315A (en) * | 2011-03-21 | 2011-07-27 | 四川师范大学 | Multilayer-ceramic total-area LNO (lanthanum nickel oxide)/Ag/LNO composite electrode and preparation method thereof |
CN102154636A (en) * | 2010-12-17 | 2011-08-17 | 济南大学 | Preparation method for p type high transmission rate (100)-oriented LaNiO3 nano film |
CN102184753A (en) * | 2011-03-21 | 2011-09-14 | 四川师范大学 | All-area Ag/LNO compound electrode material and preparation method thereof |
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CN102154636A (en) * | 2010-12-17 | 2011-08-17 | 济南大学 | Preparation method for p type high transmission rate (100)-oriented LaNiO3 nano film |
CN102154636B (en) * | 2010-12-17 | 2012-09-12 | 济南大学 | Preparation method for p type high transmission rate (100)-oriented LaNiO3 nano film |
CN102136315A (en) * | 2011-03-21 | 2011-07-27 | 四川师范大学 | Multilayer-ceramic total-area LNO (lanthanum nickel oxide)/Ag/LNO composite electrode and preparation method thereof |
CN102184753A (en) * | 2011-03-21 | 2011-09-14 | 四川师范大学 | All-area Ag/LNO compound electrode material and preparation method thereof |
CN102795891A (en) * | 2012-08-23 | 2012-11-28 | 同济大学 | Preparation method for barium strontium titanate film taking MgO as buffer layer |
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CN103833358A (en) * | 2012-11-21 | 2014-06-04 | 吉林师范大学 | Preparation method of La0.7Ca0.25Sr0.05MnO3 ferromagnetic thin film |
CN103833358B (en) * | 2012-11-21 | 2015-09-30 | 吉林师范大学 | A kind of La 0.7ca 0.25sr 0.05mnO 3the preparation method of ferromagnetic thin film |
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