CN107910030B - Preparation method of flexible BNT ferroelectric film - Google Patents
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- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 4
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- 208000037656 Respiratory Sounds Diseases 0.000 claims description 3
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- QYFRTHZXAGSYGT-UHFFFAOYSA-L hexaaluminum dipotassium dioxosilane oxygen(2-) difluoride hydrate Chemical compound O.[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O QYFRTHZXAGSYGT-UHFFFAOYSA-L 0.000 claims description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
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- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims 2
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N50/00—Galvanomagnetic devices
- H10N50/10—Magnetoresistive devices
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C11/00—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor
- G11C11/02—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using magnetic elements
- G11C11/14—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using magnetic elements using thin-film elements
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C11/00—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor
- G11C11/21—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using electric elements
- G11C11/22—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using electric elements using ferroelectric elements
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Abstract
The invention discloses a preparation method of a flexible BNT ferroelectric film, which comprises the following steps: 1) preparing a strontium ruthenate bottom electrode on a muscovite substrate by a laser pulse deposition method; 2) preparing a precursor solution of the BNT ferroelectric film by adopting a sol-gel method, wherein the concentration of the precursor solution is 0.05-0.1 mol/L; 3) a BNT precursor solution is spin-coated on the strontium ruthenate bottom electrode by adopting a spin-coating method to obtain a uniform wet film; 4) drying, pyrolyzing and annealing the prepared uniform wet film; 5) repeating the steps 3) -4) for 4-6 times to obtain the flexible BNT ferroelectric film, wherein the thickness of the film is 200-300 nm. The invention provides a flexible BNT ferroelectric film material with simple process and excellent ferroelectric property.
Description
Technical Field
The invention belongs to the technical field of ferroelectric film and device preparation, and particularly relates to a preparation method of a flexible BNT ferroelectric film.
Background
The ferroelectric thin film material is a two-dimensional material which has spontaneous polarization at a certain temperature, and the direction of the spontaneous polarization can be reversed due to the reversal of the direction of an external electric field. The ferroelectric film has important characteristics of ferroelectricity, dielectricity, piezoelectricity and the like, and can be used for manufacturing important novel components such as a ferroelectric memory, a dielectric phase shifter, a voltage-controlled filter and the like. Due to the advantages of small volume, low working voltage, convenience for developing small devices and the like, the micro-electromechanical device has wide application prospect in high technical fields of microelectronics, micromachine, micro-electro-mechanics and the like. The ferroelectric memory prepared by utilizing the ferroelectricity of the ferroelectric film material enables high-speed reading and writing and high-density storage. Ferroelectric memories are widely used in various fields such as IC cards, aerospace, computers and automation technology. A conventional lead zirconate titanate (PZT) ferroelectric material of a perovskite structure has a large remanent polarization. But the fatigue property of the PZT ferroelectric thin film is poor. And importantly, the PZT material system contains lead, has irreversible damage to human organs and the nervous system of the brain, causes serious pollution to the ecological environment and is difficult to meet the requirement of human on environmental protection in the new century. To further improve the quality of a ferroelectric thin film, particularly to improve fatigue resistance characteristics to meet the demand of a ferroelectric memory, and to solve lead contaminationEnvironmental issues, new ferroelectric thin film materials are being sought. The ferroelectric oxide with bismuth layer perovskite structure is a special ferroelectric oxide with perovskite structure. Bi4Ti3O12The ferroelectric crystal (hereinafter referred to as BIT) has a layered perovskite structure, and has good fatigue characteristics and high field mobility due to its special electrode inversion mode. Bi doped with lanthanide neodymium (Nd) after BIT(4-x)NdxTi3O12The (BNT) film has large residual polarization, good fatigue resistance and high Curie temperature, and is a good ferroelectric material.
On the other hand, in order to meet the demand of the next generation of intelligent electronic devices, flexible electronic devices are increasingly widely applied to the fields of display screens, medical devices and the like due to the characteristics of lightness and flexibility.
Flexible electronics can be summarized as a new electronic technology for manufacturing organic/inorganic material electronic devices on flexible substrates, and has wide application prospects in the fields of electronic information, energy, medical treatment and the like, such as flexible electronic displays, Organic Light Emitting Diodes (OLEDs), thin-film solar panels and the like, due to unique flexibility and ductility and efficient and low-cost manufacturing processes. As with conventional IC technology, manufacturing processes are a major driver in the development of flexible electronic technology. Flexible ferroelectric memories using ferroelectric thin film materials have attracted attention because of their high read speed, high storage density, low operating voltage, radiation resistance, non-volatility, flexibility, and the like. Some organic flexible substrates such as Polyimide (PI), polyethylene naphthalate (PEN), and other organic materials cannot tolerate the high annealing temperatures of ferroelectric materials such as BNT. Muscovite mica (Muscovite mica) this material tears layer by layer like graphene. It can withstand high temperatures of over one thousand degrees. And has a series of excellent performances of acid and alkali resistance, transparency, elasticity and the like. Creates conditions for manufacturing the flexible BNT ferroelectric film.
Disclosure of Invention
The invention aims to overcome the defects of poor thermal stability of a substrate, poor fatigue performance of a perovskite structure ferroelectric material and the like in the prior art, and provides a preparation method of a flexible BNT ferroelectric film, which is simple, convenient, low in cost, stable in preparation process and good in performance.
The specific technical scheme is as follows:
a preparation method of a flexible BNT ferroelectric film comprises the following steps: step 1) preparing a perovskite structure oxide strontium ruthenate SRO bottom electrode on muscovite by adopting a laser pulse deposition method; step 2) preparing a precursor solution of the BNT ferroelectric film by adopting a sol-gel method, wherein the concentration of the precursor solution is 0.05-0.1 mol/L; step 3) preparing a flexible BNT ferroelectric film, and spin-coating a precursor solution on the SRO bottom electrode by adopting a spin-coating method to obtain a uniform wet film; step 4) drying, pyrolyzing and annealing the uniform wet film prepared in the step 3); and 5) repeating the steps 3) -4) for 4-6 times to obtain the target flexible BNT ferroelectric film, wherein the thickness of the film is 200-300 nm.
Further, in the step 1), the specific preparation steps of the laser pulse deposition method comprise: taking a muscovite sheet, preparing a layer of cobalt ferrite on the muscovite sheet as a seed layer, and then preparing a layer of SRO oxide conductive material on the cobalt ferrite.
Further, the thickness of the cobalt ferrite is 5-10nm, and the thickness of the SRO oxide is 30-50 nm; the thickness of the mica sheet is less than 50 μm.
Still further, the preparation method of the muscovite sheet comprises the following steps: selecting smooth, crackless and impurity-free muscovite sheets, then pasting the muscovite sheets on an operation table, and tearing up the muscovite sheets layer by using a pointed forceps until the thickness of the mica sheets is less than 50 mu m.
Further, in step 2), the preparation method of the precursor solution of the BNT ferroelectric thin film comprises the following steps: 20ml of BNT precursor solution with 0.05mol/L is prepared in a laboratory. Bi. The ratio of the amounts of Nd and Ti substances is 3.15:0.85: 3. Due to volatilization of bismuth ions during annealing. So the molar excess of bismuth nitrate is 10% when weighing. a. Dissolving about 1.6808g of bismuth nitrate in ethylene glycol monomethyl ether, heating and stirring until the bismuth nitrate is completely dissolved, thus obtaining a solution I; b. dissolving about 0.2807g of neodymium nitrate in ethylene glycol monomethyl ether to obtain a solution II; c. dissolving about 1.0210g of tetrabutyl titanate in ethylene glycol monomethyl ether, adding acetylacetone with the volume fraction of 1% and acetic acid with the volume fraction of 5%, and stirring until the tetrabutyl titanate is completely dissolved to obtain a solution III; d. dropwise adding the solution II into the solution I while stirring until the solution is uniform and clear, and adding acetic acid with the volume fraction of 10% into the mixed solution to obtain a solution A; e. dropwise adding the solution III into the solution A while stirring, then adding formamide with the volume fraction of 1% into the mixed solution, adding ethylene glycol monomethyl ether to a constant volume, and stirring for 24 hours until the solution is uniform and clear to obtain a solution B; f. and standing the solution B for 3 days, and then filtering to obtain a precursor solution of the BNT ferroelectric film.
Further, in the step 3), the spin-coating rotation speed of the gel is as follows: the low speed is 300-500 rmp, the time is 12-30 s, and the high speed is 4000-5000 rmp, the time is 24-30 s.
Further, in the step 4), the drying temperature in the drying step is 150-200 ℃, and the time is 100-200 s.
Further, in the step 4), the temperature in the pyrolysis step is 300-500 ℃ and the time is 200-300 s.
Further, in the step 4), the annealing temperature is 600-750 ℃ and the time is 200-500 s.
Further, in the step 5), the thickness of the thin film is 200-300 nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention optimizes the solution concentration of the precursor of the BNT ferroelectric film, optimizes the bottom electrode and performs thickness treatment on the substrate to ensure that the thin-layer muscovite sheet cannot crack under the bending condition, so that the prepared flexible BNT ferroelectric film still keeps excellent ferroelectric property under the bending condition.
(2) The preparation technology of the precursor solution of the BNT ferroelectric film with the bismuth-layer perovskite structure is optimized to ensure that the film has correct components and excellent ferroelectric property.
(3) And secondly, optimizing the drying, pyrolysis and annealing time and temperature of the film to ensure that the obtained flexible BNT ferroelectric film has excellent performance.
Drawings
FIG. 1 is a flow chart for preparing a flexible BNT ferroelectric thin film in an embodiment, wherein a in FIG. 1 is a flow chart for preparing a BNT precursor sol, and b in FIG. 1 is a flow chart for preparing a BNT flexible ferroelectric thin film;
FIG. 2 is a schematic XRD of a flexible BNT ferroelectric thin film in accordance with the invention;
FIG. 3 is a graph of the hysteresis loop (i.e., PE) of a flexible BNT ferroelectric film of the present invention;
FIG. 4 is a butterfly curve (i.e., CE) plot of a flexible BNT ferroelectric thin film in accordance with the invention;
FIG. 5 is a graph of the hysteresis loop (PE) of a flexible BNT ferroelectric film of the present invention at different bending radii of curvature;
fig. 6 is a graph of the butterfly Curve (CE) for different radii of curvature of bending for a flexible BNT ferroelectric thin film in accordance with the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific embodiments of the drawings.
A method for preparing a flexible BNT ferroelectric film by a sol-gel method is characterized by comprising the following steps:
1.1 preparation of single crystal muscovite sheet and preparation of bottom electrode: selecting smooth, crackless and impurity-free muscovite sheets, then pasting the mica sheets on an operation table, and tearing up the mica sheets layer by using a pointed-end tweezers until the thickness of the single crystal flexible mica sheets is less than 50 mu m; then preparing a layer of cobalt ferrite CoFe on the single crystal flexible mica sheet by adopting a laser pulse deposition method2O4(CFO) is used as a seed layer, and then an SRO layer which is consistent with the structure of the ferroelectric material is grown on the CFO layer, wherein the thickness of the CFO layer is 10nm, and the thickness of the SRO layer is 40 nm.
1.2 prepare 20ml BNT precursor solution of 0.05mol/L in the laboratory. Bi. The ratio of the amounts of Nd and Ti substances is 3.15:0.85: 3. The molar excess of bismuth nitrate was weighed out as 10% due to volatilization of bismuth ions during annealing. a. Dissolving about 1.6808g of bismuth nitrate in ethylene glycol monomethyl ether, heating and stirring until the bismuth nitrate is completely dissolved, thus obtaining a solution I; b. dissolving about 0.2807g of neodymium nitrate in ethylene glycol monomethyl ether to obtain a solution II; c. dissolving about 1.0210g of tetrabutyl titanate in ethylene glycol monomethyl ether, adding acetylacetone with the volume fraction of 1% and acetic acid with the volume fraction of 5%, and stirring until the tetrabutyl titanate is completely dissolved to obtain a solution III; d. dropwise adding the solution II into the solution I while stirring until the solution is uniform and clear, and adding acetic acid with the volume fraction of 10% into the mixed solution to obtain a solution A; e. dropwise adding the solution III into the solution A while stirring, then adding formamide with the volume fraction of 1% into the mixed solution, adding a proper amount of ethylene glycol monomethyl ether to a constant volume, and stirring for 24 hours until the solution is uniform and clear to obtain a solution B; f. and standing the solution B for 3 days, and then filtering to obtain a precursor solution of the BNT ferroelectric film.
1.3 preparation of BNT flexible ferroelectric film: 1) dripping a BNT precursor solution on a flexible mica sheet substrate with an SRO bottom electrode by a dropper, and spin-coating the precursor solution on the SRO electrode of the substrate by a spin-coating method to obtain a uniform wet film, wherein the spin-coating rotating speed is as follows: at low speed 400rmp for 12s and at high speed 4000rmp for 30 s.
1.4, drying, pyrolyzing and annealing the prepared uniform wet film; the drying temperature is 180 ℃ and the drying time is 200 s; the pyrolysis temperature is 400 ℃, and the time is 300 s; the annealing temperature is 700 ℃, and the time is 300 s; the molar ratio of Bi, Nd and Ti in the obtained film is 3.15:0.85:3, and the thickness of the ferroelectric film is 240 nm.
1.5 repeating the step for 1.3-1.44-6 times to obtain the target film, wherein the molar ratio of Bi, Nd and Ti in the obtained film is 3.15:0.85:3, and the thickness of the ferroelectric film is 240 nm.
1.6 testing the ferroelectric property of the BNT flexible ferroelectric film under the bending condition: in order to test the ferroelectric properties of the flexible BNT ferroelectric thin film, a platinum or SRO dot electrode is grown on top of the thin film, and then the test is performed under different curvature radii, and fig. 1 is a flow chart of the preparation of the flexible BNT ferroelectric thin film of the example.
The structure and ferroelectric properties of the flexible BNT ferroelectric film were tested by taking the examples as research objects.
As shown in fig. 2, the XRD pattern of the flexible BNT ferroelectric thin film is shown.
As shown in FIG. 3 and FIG. 4, the flexible BNT ferroelectric film prepared by the sol-gel method has good ferroelectric property, PV has good rectangularity, and the remanent polarization value reaches 50 μ C/cm2The CV has a butterfly curve of the ferroelectric material, which greatly meets the storage requirement of the ferroelectric memory.
As shown in fig. 5 and fig. 6, the flexible BNT ferroelectric thin film prepared by the sol-gel method has small performance change under bending conditions, which proves that the flexible BNT ferroelectric thin film prepared by the method has good bending characteristics and meets the preparation requirements of the flexible ferroelectric memory.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (6)
1. Flexible Bi3.15Nd0.85Ti3O12The preparation method of the ferroelectric film is characterized by comprising the following steps:
step 1) preparing a perovskite structure oxide strontium ruthenate bottom electrode on muscovite by adopting a laser pulse deposition method; the thickness of the muscovite is less than 50 μm;
step 2) preparing Bi by adopting sol-gel method3.15Nd0.85Ti3O12Precursor solution of the ferroelectric film, wherein the concentration of the precursor solution is 0.05-0.1 mol/L; preparation of Bi by gel method3.15Nd0.85Ti3O12The precursor solution of the ferroelectric thin film comprises the following steps:
bi. The molar ratio of Nd to Ti is 3.15:0.85: 3; due to volatilization of bismuth ions during annealing, the molar weight of bismuth nitrate is excessive by 10 percent when the bismuth nitrate is weighed according to the molar ratio of Bi to Nd to Ti of 3.15:0.85: 3; a. 1.6808g of bismuth nitrate is dissolved in ethylene glycol monomethyl ether, and the solution I is obtained by heating and stirring until the bismuth nitrate is completely dissolved; b. neodymium nitrate 0.2807g of the compound is dissolved in ethylene glycol monomethyl ether to obtain a solution II; c. dissolving 1.0210g of tetrabutyl titanate in ethylene glycol monomethyl ether, adding acetylacetone with the volume fraction of 1% and acetic acid with the volume fraction of 5%, and stirring until the tetrabutyl titanate is completely dissolved to obtain a solution III; d. dropwise adding the solution II into the solution I while stirring until the solution is uniform and clear to obtain a mixed liquid, and adding acetic acid with the volume fraction of 10% into the mixed liquid to obtain a solution A; e. dropwise adding the solution III into the solution A while stirring, then adding formamide with the volume fraction of 1%, adding ethylene glycol monomethyl ether to a constant volume of 20ml, and stirring for 24 hours until the solution is uniform and clear to obtain a solution B; f. standing the solution B for 3 days, and then filtering to obtain Bi3.15Nd0.85Ti3O12Precursor solution of ferroelectric film;
step 3) Flexible Bi3.15Nd0.85Ti3O12Preparing a ferroelectric film, namely spin-coating a precursor solution on a strontium ruthenate bottom electrode by adopting a spin-coating method to obtain a uniform wet film; spin-coating the gel at the spin-coating speed: 300-500 rmp at low speed for 12-30 s, 4000-5000 rmp at high speed for 24-30 s;
step 4) drying, pyrolyzing and annealing the uniform wet film prepared in the step 3); in the annealing treatment step, the annealing temperature is 600-750 ℃ and the time is 200-500 s;
step 5) repeating the steps 3) -4) 4-6 times to obtain the target flexible Bi3.15Nd0.85Ti3O12Ferroelectric thin film, said flexible Bi3.15Nd0.85Ti3O12The thickness of the film is 200nm-300 nm.
2. The preparation method according to claim 1, wherein the specific preparation steps of the laser pulse deposition method in step 1) comprise: taking white mica, preparing a layer of cobalt ferrite on the white mica as a seed layer, and then preparing a layer of ruthenic acid strontium oxide conductive material on the cobalt ferrite.
3. The preparation method according to claim 2, wherein the thickness of the cobalt ferrite is 5-10nm, and the thickness of the strontium ruthenate oxide is 30-50 nm.
4. The method according to claim 2, wherein the muscovite mica is prepared by: selecting smooth, crackless and impurity-free muscovite, sticking the muscovite on an operating table, and tearing up the muscovite layer by layer with a pointed forceps until the thickness of the muscovite is less than 50 μm.
5. The method according to claim 1, wherein in the step 4), the drying temperature of the drying step is 150-200 ℃ and the drying time is 100-200 s.
6. The method according to claim 1, wherein in the step 4), the temperature of the pyrolysis step is 300-500 ℃ and the time is 200-300 s.
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| CN110042466A (en) * | 2019-04-01 | 2019-07-23 | 肇庆市华师大光电产业研究院 | A kind of preparation method of the strontium doping barium titanate polycrystal film based on flexible substrate growth |
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