CN105762275A - Multiferroic/piezoelectric composite structure, storage device and preparation method thereof - Google Patents
Multiferroic/piezoelectric composite structure, storage device and preparation method thereof Download PDFInfo
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- 238000003860 storage Methods 0.000 title abstract description 11
- 239000002131 composite material Substances 0.000 title abstract 3
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- 239000000758 substrate Substances 0.000 claims abstract description 30
- 229910009567 YMnO3 Inorganic materials 0.000 claims abstract description 14
- 238000003475 lamination Methods 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 146
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- 238000000034 method Methods 0.000 claims description 27
- 238000004528 spin coating Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
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- 230000015572 biosynthetic process Effects 0.000 claims description 6
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- 229910019651 Nb(OC2H5)5 Inorganic materials 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
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- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910003334 KNbO3 Inorganic materials 0.000 description 2
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 description 2
- 229910002340 LaNiO3 Inorganic materials 0.000 description 2
- 229910020347 Na2WO3 Inorganic materials 0.000 description 2
- 229910003378 NaNbO3 Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910002353 SrRuO3 Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
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- 230000005621 ferroelectricity Effects 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 2
- 229910019438 Mg(OC2H5)2 Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N50/00—Galvanomagnetic devices
- H10N50/80—Constructional details
- H10N50/85—Magnetic active materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10N50/00—Galvanomagnetic devices
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Abstract
Disclosed is a multiferroic/piezoelectric composite structure, comprising a substrate; a bottom electrode layer formed by conductive oxides and located on the substrate; and laminations formed by alternatively stacked multiferroic thin film layers and piezoelectric layers located on the bottom electrode layer; wherein multiferroic thin film layers and adjacent piezoelectric layers are in contact to form sandwich structures. The multiferroic / piezoelectric composite structure utilizes piezoelectric layers and a multiferroic thin film layer similar structure formed by low temperature multiferroic materials to form interfacial effect and exchange coupling, furthermore improves multiferroic thin film performs under low temperature environments such as the south pole and space exploration, substantially improves multiferroic material (such as YMnO3) application in ferroelectric storage, and thereby meets people demands on hard disk rapid write-in and read-out, computer nonvolatile storage and device miniaturization and multifunction under low temperature environments.
Description
Technical field
The present invention relates to multi-ferroic material, physics and device arts, more particularly, to for the many ferrum/Piezoelectric anisotropy structure under low temperature environment and memory device, preparation method.
Background technology
Ferroelectric memory is that a kind of volume worked out in nearly more than 10 years is little, access speed fast, life-span length, novel memory devices low in energy consumption, has fabulous application background.Along with the development of IT technology, the demand for nonvolatile memory is increasing, and read or write speed requires increasingly faster, and power consumption requirements is more and more less.All functions of the compatible RAM of ferroelectric memory energy, and the same with ROM technology, it is a kind of non-volatile memorizer.Ferroelectric memory is asked in this two classes storage class and has been set up an a kind of non-volatile RAM of bridge crossing over gully.Comparing with traditional nonvolatile memory, ferroelectric memory has the advantages such as power consumption is little, read or write speed is fast, Radiation hardness is strong, and the actual demand for meeting future memory part has great importance.
Multi-ferroic material (mutliferroics) refers to have in ferroelectricity, ferromagnetism and ferroelasticity the Multifunction material of both or both above performances simultaneously, there is magnetoelectric effect produced by ferromagnetism and ferroelectricity and two kinds of property, provide the probability simultaneously utilizing electric polarization and magnetization to carry out code storage information, such that it is able to prepare the New Magnetic Field Controlled storage medium of the superelevation speed read-write process that magnetic recording reading speed is fast, ferrum electrographic recording write is fast.In recent years, along with people's raising to device miniaturization, sensitivity and polyfunctional requirement, in the urgent need to researching and developing a kind of new material or new structure, to realize an urgent demand of people.At present, magnetoelectric effect has been carried out substantial amounts of research by people, research finds that multi-iron material can carry out independent electricity regulation and control (mainly regulating polarised direction) respectively under the regulation and control in external electric field and magnetic field, magnetic tuning (mainly regulates the direction of magnetization), and magnetoelectricity intermodulation control.At present, electric field to the regulation and control of magnetic moment direction and utilizes the magnetic recording read head that magneto-resistance effect is prepared for multiferroic to have been carried out.These achievements in research have confirmed the feasibility of magnetoelectricity cross complaint non-volatile memory device.Wherein, low temperature multi-ferroic material has YMnO3、BiWO3、TiMnO3、BiMnO3Deng single phase multi-iron material;And the doped derivatives of above-mentioned different materials and solid solution derivant.
Piezoelectricity ferro material is widely used in the detection of information, conversion, process, display and storage, is a kind of important high-tech functional material.The application of piezoelectric can be roughly classified into two big classes: i.e. vibrational energy and Under Ultrasonic Vibration kinetic energy-electric energy transducer application, including electroacoustic transducer, underwater acoustic transducer and ultrasonic transducer etc., and other sensor and driver applications.These characteristics utilizing piezoelectric can realize the mutual conversion of mechanical vibration (sound wave) and alternating current.Thus piezoelectric is widely used in sensor element, for instance seismic sensor, the measuring cell of power, speed and acceleration and electroacoustic transducer etc..
But for single multi-iron material or piezoelectric, no matter it is solid or thin film, all has such as that electric leakage is big, polarize the shortcomings such as coefficient difficult, magneto-electric coupled is little, which prevent the practical application of these materials.In order to pursue memory device better performance, improve the susceptiveness of its read-write process, it is achieved high density storage etc., the basis of existing material must be prepared there is excellent new construction.The research of forefathers is it has been proved that utilize the multilayer film of the Material cladding of different materials or heterogeneity gradient can improve the performance of material.
Stacked piezoelectric/many iron constructions can improve the overall piezoelectric property of structure under the premise keeping multiferroic and make to exist between piezoelectric layer with many iron thin films layer to couple and obtain that better ferrum is electric, ferromagnetic and piezoelectric property, piezoelectric layer can play the effect of cushion simultaneously, reduce the movement of Lacking oxygen/defect between many iron thin films layer and electrode, optimize interface environments, improve the electrical property of many iron thin films layer further.
Summary of the invention
In view of this, the present invention provides a kind of many ferrum/Piezoelectric anisotropy structure and memory device, preparation method.
According to an aspect of the present invention, it is provided that a kind of many ferrum/Piezoelectric anisotropy structure, including substrate;It is positioned on described substrate the bottom electrode layer formed by conductive oxide;And it is positioned at the piezoelectric layer on described bottom electrode layer and lamination that many iron thin films layer is alternately stacked and is formed;Wherein, many iron thin films layer collectively forms sandwich structure with adjacent piezoelectric layer.
Preferably, described substrate includes the one in silicon chip, silicon dioxide substrates, ITO substrate, STO substrate and LAO substrate.
Preferably, the thickness of described bottom electrode layer is 50-300nm.
Preferably, the thickness of described piezoelectric layer is 0.75-1.25 with the ratio of the thickness of described many iron thin films layer.
Preferably, the thickness of described piezoelectric layer is 50-300nm.
Preferably, the thickness of described many iron thin films layer is 50-300nm.
According to a further aspect in the invention, it is provided that a kind of memory device, including many ferrum/Piezoelectric anisotropy structure as above;And it is positioned at the top electrode layer in the intermediate laminate of described many ferrum/Piezoelectric anisotropy structure.
According to the third aspect of the invention we, it is provided that the preparation method of a kind of many ferrum/Piezoelectric anisotropy structure, including: step one, utilize spin-coating method to be coated with conductive oxide colloidal sol on substrate, after heat treatment form bottom electrode layer;Step 2, utilize spin-coating method to be coated with piezoelectricity colloidal sol on described bottom electrode layer, after heat treatment form piezoelectric layer;Step 3, utilize piezoelectric layer described in spin-coating method is coated with many ferrum collosols, after heat treatment form many iron thin films layer;Step 4, utilize spin-coating method to be coated with piezoelectricity colloidal sol on described many iron thin films layer, after heat treatment form piezoelectric layer;The lamination that repetition step 3 and step 4 formation piezoelectric layer and many iron thin films layer are alternately stacked and are formed.
Preferably, forming the rotating speed of spin coating during described hearth electrode is 3800r/min, and the time of spin coating is 30s.
Preferably, heat treatment when forming described hearth electrode is short annealing 30min at 500 DEG C-800 DEG C.
Preferably, forming the rotating speed of spin coating when described piezoelectric layer and many iron thin films layer is 3600r/min, and the time of spin coating is 30s.
Preferably, heat treatment when forming described piezoelectric layer and many iron thin films layer is short annealing 45min at 500 DEG C-800 DEG C.
Preferably, described conductive oxide is nickel acid lanthanum, and the preparation process of nickel acid lanthanum colloidal sol is: Lanthanum (III) nitrate, nickel acetate are dissolved in ethylene glycol monomethyl ether, are subsequently adding ethanolamine, be stirred at room temperature, and obtains nickel acid lanthanum colloidal sol.
Preferably, described many iron thin films layer is mangaic acid yttrium thin film, and the preparation process of this mangaic acid yttrium colloidal sol is: YMnO3: Y (CH3CO2)3·4H2O and Mn (CH3CO2)2·4H2O 1:1:1 in molar ratio puts in ethylene glycol monomethyl ether and stirs at 60 DEG C, obtains mangaic acid yttrium colloidal sol.
Preferably, described piezoelectric layer is PMN-PT thin film, and the preparation process of PMN-PT colloidal sol is: Pb (C2H5O2)2·3H2O、Mg(OC2H5)2、Nb(OC2H5)5、 Ti(OCH(CH3)2)4It is mixed into ethylene glycol monomethyl ether in chemical formula ratio and obtains PMN-PT colloidal sol.
Many ferrum/Piezoelectric anisotropy structure provided by the invention utilizes the analog structure of many iron thin films layer of piezoelectric layer and the formation of low temperature multi-iron material to form interfacial effect and spin-exchange-coupled, and then cause that the performance of many iron thin films under the low temperature environment such as environment such as the South Pole, space probation improves, substantially increase multi-iron material such as YMnO3Application in ferrum electricity storage, reads hard disk no write de-lay at low ambient temperatures thus meeting people, computer non-volatile memories, and the demand of device miniaturization multifunction.
Accompanying drawing explanation
By referring to the accompanying drawing description to the embodiment of the present invention, above-mentioned and other purposes of the present invention, feature and advantage will be apparent from, in the accompanying drawings:
Fig. 1 illustrates the schematic diagram of many ferrum/Piezoelectric anisotropy structure according to embodiments of the present invention;
Fig. 2 illustrates the flow chart of the preparation method of many ferrum/Piezoelectric anisotropy structure according to embodiments of the present invention.
Detailed description of the invention
It is more fully described the present invention hereinafter with reference to accompanying drawing.In various figures, identical element adopts similar accompanying drawing labelling to represent.For the sake of clarity, the various piece in accompanying drawing is not necessarily to scale.Furthermore, it is possible to some known part not shown.
It is to be understood that, when describing the structure of ceramic material, when one layer, one region is called be positioned at another layer, another region " above " or when " top ", can refer to be located immediately at above another layer, another region, or itself and another layer, also comprise other layer or region between another region.Further, if overturn by device, this layer, one region will be located in another layer, another region " below " or " lower section ".
If being located immediately at another layer, another region above scenario to describe, the form of presentation of " A is directly on B " or " A is on B and adjoins with it " will be adopted herein.In this application, " A is located immediately in B " represents that A is arranged in B, and A and B abuts directly against, but not A is arranged in the B doped region formed.
Describe hereinafter the many specific details of the present invention, for instance the structure of ceramic material, material, size, process technique and technology, in order to be more clearly understood that the present invention.But just as the skilled person will understand, it is possible to do not realize the present invention according to these specific details.
The present invention can present in a variety of manners, some of them example explained below.
Described in Fig. 1 is the schematic diagram of the many ferrum/Piezoelectric anisotropy structure 100 of the embodiment of the present invention.Substrate 101 can be silicon chip, silicon dioxide substrates, ITO substrate, STO substrate or LAO substrate.Bottom electrode layer 102 is positioned at above substrate 101, by La0.7Sr0.3MnO3、LaNiO3、SrRuO3Being formed Deng conductive oxide, the thickness of bottom electrode layer 102 is about 50-300nm.
Piezoelectric layer 1031Being positioned at above bottom electrode layer 102, piezoelectric formed, its thickness is about 50-300nm.
Described piezoelectric layer is formed by piezoelectric, and described piezoelectric can be with the PTO strong piezoelectric material being representative, such as PMN-PT 0.7Pb (Mg1/3Nb2/3)O3]-0.3[PbTiO3](PMN-PT)、PbZrTiO3、PbTiO3、PbSrTiO3、PbZnNbPbTiO3、BaTiO3、Bi4Ti3O12、KNbO3、Na2WO3、NaNbO3、Ba2NaNb5O5, the piezoelectric etc. such as ZnO.The adulterant used in the piezoelectric of doping includes following at least one element: Na, Sr and Nd.
Many iron thin films layer 1041It is positioned at described piezoelectric layer 1031Top, is formed by the multi-iron material of undoped multi-iron material or doping, and thickness is about 50-300nm.
Wherein, multi-iron material can be with low temperature multi-iron material mangaic acid yttrium YMnO3、BiWO3、BiMnO3、LuFe2O4、RMn2O5(R=Y, Tb, Dy, Gd, Bi, Eu) etc..The adulterant used in the multi-iron material of doping includes following at least one element: Ca, La and Mo.Mangaic acid yttrium YMnO3Ne&1&el temperature be-193 DEG C.
Subsequently, piezoelectric layer 1032-103NRespectively at many iron thin films layer 1041-104N-1Top is alternatively formed, and a layer of top is piezoelectric layer 103N。
Utilize spin-coating method to form piezoelectric layer 1031-103NAnd many iron thin films layer 1041-104N-1, piezoelectric layer and many iron thin films layer random growth.Total cycle N >=2.
Wherein, adjacent with both sides for many iron thin films layer 104m piezoelectric layer 103mWith piezoelectric layer 103m+1Contact with each other and collectively form sandwich structure.The ratio of the thickness of piezoelectric layer and the thickness of many iron thin films layer is 0.75-1.25.When the thickness of many iron thin films layer is 200nm, the thickness of piezoelectric layer is 150-250nm.
Only being formed with many iron thin films layer in existing many iron constructions on bottom electrode layer, the ferroelectric remnant polarization (Pr) of such many iron constructions is 2uC/cm2, and the ferroelectric remnant polarization (Pr) of many ferrum/Piezoelectric anisotropy structure provided by the invention has reached 10uC/cm2。
Many ferrum/Piezoelectric anisotropy structure provided by the invention utilizes the analog structure of many iron thin films layer of piezoelectric layer and the formation of low temperature multi-iron material to form interfacial effect and spin-exchange-coupled, and then cause that the performance of many iron thin films under the low temperature environment such as environment such as the South Pole, space probation improves, substantially increase multi-iron material such as YMnO3Application in ferrum electricity storage, reads hard disk no write de-lay at low ambient temperatures thus meeting people, computer non-volatile memories, and the demand of device miniaturization multifunction.
Memory device (not separately shown) according to the present invention includes above-mentioned many ferrum/Piezoelectric anisotropy structure 100 and the top electrode layer 201 being positioned in the intermediate laminate of many ferrum/Piezoelectric anisotropy structure 100.Described top electrode layer 201 can be the conducting metals such as Au, Pt, Ag, Cu.
Fig. 2 illustrates the flow chart of the preparation method of many ferrum/Piezoelectric anisotropy structure according to embodiments of the present invention.The preparation method of described many ferrum/Piezoelectric anisotropy structure comprises the following steps.
In step S01, utilize spin-coating method to be coated with conductive oxide colloidal sol on substrate, after heat treatment form bottom electrode layer.
In the present embodiment, described substrate can be silicon chip, silicon dioxide substrates, ITO substrate, STO substrate or LAO substrate.Described bottom electrode layer is by La0.7Sr0.3MnO3、LaNiO3、SrRuO3Formed Deng conductive oxide.
First preparing conductive oxide colloidal sol, and placed on a spinstand by cleaned silicon chip, drip on silicon chip by conductive oxide colloidal sol in the process rotated, wherein, the rotating speed of turntable is 3800r/min, and rotational time is 30s.Short annealing 30min at 500 DEG C-800 DEG C, finally gives the conductive oxide film that resistivity is relatively low subsequently.
For nickel acid lanthanum (LNO), the preparation process of described LNO colloidal sol is: 0.864g Lanthanum (III) nitrate, 0.497g nickel acetate is dissolved in 9ml ethylene glycol monomethyl ether, is subsequently adding 1ml ethanolamine, is stirred at room temperature, and finally obtains nickel acid lanthanum colloidal sol.
In step S02, utilize spin-coating method to be coated with piezoelectricity colloidal sol on described bottom electrode layer, after heat treatment form piezoelectric layer.
In the present embodiment, preparing piezoelectricity colloidal sol, placed on a spinstand by the silicon chip including bottom electrode layer, drip on bottom electrode layer by piezoelectricity colloidal sol in the process rotated, wherein, the rotating speed of turntable is 3600r/min, and rotational time is 30s.Short annealing 45min at 500 DEG C-800 DEG C, obtains piezoelectric layer subsequently.
Described piezoelectric layer is formed by piezoelectric, and described piezoelectric can be with the PTO strong piezoelectric material being representative, such as PMN-PT 0.7Pb (Mg1/3Nb2/3)O3]-0.3[PbTiO3](PMN-PT)、PbZrTiO3、PbTiO3、PbSrTiO3、PbZnNbPbTiO3、BaTiO3、Bi4Ti3O12、KNbO3、Na2WO3、NaNbO3、Ba2NaNb5O5, the piezoelectric etc. such as ZnO.The adulterant used in the piezoelectric of doping includes following at least one element: Na, Sr and Nd.
With PMN-PT 0.7Pb (Mg1/3Nb2/3)O3]-0.3[PbTiO3] (PMN-PT) be example.The preparation process of PMN-PT colloidal sol is: Pb (C2H5O2)2·3H2OMg(OC2H5)2、Nb(OC2H5)5、Ti(OCH(CH3)2)4It is mixed into ethylene glycol monomethyl ether in chemical formula ratio and obtains PMN-PT colloidal sol.
In step S03, utilize and piezoelectric layer described in spin-coating method is coated with many ferrum collosols, after heat treatment form many iron thin films layer.
At the present embodiment, prepare many ferrum collosols, by include piezoelectric layer, bottom electrode layer silicon chip place on a spinstand, rotate process in many ferrum collosols are dripped on piezoelectric layer, wherein, the rotating speed of turntable is 3600r/min, and rotational time is 30s.Short annealing 45 minutes at 500-800 DEG C, obtain many iron thin films layer subsequently.
Wherein, multi-iron material can be with low temperature multi-iron material mangaic acid yttrium YMnO3、BiWO3、BiMnO3、LuFe2O4、RMn2O5(R=Y, Tb, Dy, Gd, Bi, Eu) etc..The adulterant used in the multi-iron material of doping includes following at least one element: Ca, La and Mo.
With mangaic acid yttrium (YMnO3) for example, this YMnO3The preparation process of colloidal sol is: YMnO3: Y (CH3CO2)3·4H2O and Mn (CH3CO2)2·4H2O 1:1:1 in molar ratio puts in ethylene glycol monomethyl ether and stirs at 60 DEG C, obtains YMnO3Colloidal sol.
In step S04, utilize spin-coating method to be coated with piezoelectricity colloidal sol on described many iron thin films layer, after heat treatment form piezoelectric layer.
The same with step S02, do not repeat them here.
In step S05, the lamination that repetition step 3 and step 4 formation piezoelectric layer and many iron thin films layer are alternately stacked and are formed.
Wherein, piezoelectric layer is alternatively formed respectively above many iron thin films layer, and a layer of top is piezoelectric layer.The piezoelectric layer that many iron thin films layer is adjacent with both sides forms sandwich structure.
Finally, in step S06, magnetron sputtering is utilized to be splashed on piezoelectric layer by the mask plate of diameter 0.1mm by conducting metal.Described conducting metal can be Au, Pt, Ag, Cu etc..
Many ferrum/Piezoelectric anisotropy structure provided by the invention utilizes the analog structure of many iron thin films layer of piezoelectric layer and the formation of low temperature multi-iron material to form interfacial effect and spin-exchange-coupled, and then cause that the performance of many iron thin films under the low temperature environment such as environment such as the South Pole, space probation improves, substantially increase multi-iron material such as YMnO3Application in ferrum electricity storage, reads hard disk no write de-lay at low ambient temperatures thus meeting people, computer non-volatile memories, and the demand of device miniaturization multifunction.
Should be noted that, in this article, the relational terms of such as first and second or the like is used merely to separate an entity or operation with another entity or operating space, and not necessarily requires or imply the relation that there is any this reality between these entities or operation or sequentially.And, term " includes ", " comprising " or its any other variant are intended to comprising of nonexcludability, so that include the process of a series of key element, method, article or equipment not only include those key elements, but also include other key elements being not expressly set out, or also include the key element intrinsic for this process, method, article or equipment.When there is no more restriction, statement " including ... " key element limited, it is not excluded that there is also other identical element in including the process of described key element, method, article or equipment.
According to embodiments of the invention as described above, these embodiments do not have all of details of detailed descriptionthe, are not intended to the specific embodiment that this invention is only described yet.Obviously, as described above, can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is to explain principles of the invention and practical application better, so that skilled artisan can utilize the present invention and the amendment on basis of the present invention to use well.The present invention is limited only by the restriction of claims and four corner thereof and equivalent.
Claims (15)
1. ferrum more than/Piezoelectric anisotropy structure, including:
Substrate;
It is positioned on described substrate the bottom electrode layer formed by conductive oxide;And
It is positioned at the piezoelectric layer on described bottom electrode layer and lamination that many iron thin films layer is alternately stacked and is formed;
Wherein, many iron thin films layer contacts with each other with adjacent piezoelectric layer and collectively forms sandwich structure.
2. many ferrum/Piezoelectric anisotropy structure according to claim 1, wherein, described substrate includes the one in silicon chip, silicon dioxide substrates, ITO substrate, STO substrate and LAO substrate.
3. many ferrum/Piezoelectric anisotropy structure according to claim 1, wherein, the thickness of described bottom electrode layer is 50-300nm.
4. many ferrum/Piezoelectric anisotropy structure according to claim 1, wherein, the ratio of the thickness of described piezoelectric layer and the thickness of described many iron thin films layer is 0.75-1.25.
5. many ferrum/Piezoelectric anisotropy structure according to claim 5, wherein, the thickness of described piezoelectric layer is 50-300nm.
6. many ferrum/Piezoelectric anisotropy structure according to claim 5, wherein, the thickness of described many iron thin films layer is 50-300nm.
7. a memory device, including:
Many ferrum/Piezoelectric anisotropy structure as described in claim 1-7;And
It is positioned at the top electrode layer in the intermediate laminate of described many ferrum/Piezoelectric anisotropy structure.
8. a preparation method for ferrum more than/Piezoelectric anisotropy structure, including:
Step one, utilize spin-coating method to be coated with conductive oxide colloidal sol on substrate, after heat treatment form bottom electrode layer;
Step 2, utilize spin-coating method to be coated with piezoelectricity colloidal sol on described bottom electrode layer, after heat treatment form piezoelectric layer;
Step 3, utilize piezoelectric layer described in spin-coating method is coated with many ferrum collosols, after heat treatment form many iron thin films layer;
Step 4, utilize spin-coating method to be coated with piezoelectricity colloidal sol on described many iron thin films layer, after heat treatment form piezoelectric layer;
The lamination that repetition step 3 and step 4 formation piezoelectric layer and many iron thin films layer are alternately stacked and are formed.
9. preparation method according to claim 8, wherein, forming the rotating speed of spin coating during described hearth electrode is 3800r/min, and the time of spin coating is 30s.
10. preparation method according to claim 8, wherein, heat treatment when forming described hearth electrode is short annealing 30min at 500 DEG C-800 DEG C.
11. preparation method according to claim 8, wherein, forming the rotating speed of spin coating when described piezoelectric layer and many iron thin films layer is 3600r/min, and the time of spin coating is 30s.
12. preparation method according to claim 8, wherein, heat treatment when forming described piezoelectric layer and many iron thin films layer is short annealing 45min at 500 DEG C-800 DEG C.
13. preparation method according to claim 8, wherein, described conductive oxide is nickel acid lanthanum, and the preparation process of nickel acid lanthanum colloidal sol is: Lanthanum (III) nitrate, nickel acetate are dissolved in ethylene glycol monomethyl ether, are subsequently adding ethanolamine, be stirred at room temperature, and obtains nickel acid lanthanum colloidal sol.
14. preparation method according to claim 8, wherein, described many iron thin films layer is mangaic acid yttrium thin film, and the preparation process of this mangaic acid yttrium colloidal sol is: YMnO3: Y (CH3CO2)3·4H2O and Mn (CH3CO2)2·4H2O 1:1:1 in molar ratio puts in ethylene glycol monomethyl ether and stirs at 60 DEG C, obtains mangaic acid yttrium colloidal sol.
15. preparation method according to claim 8, wherein, described piezoelectric layer is PMN-PT thin film, and the preparation process of PMN-PT colloidal sol is: Pb (C2H5O2)2·3H2OMg(OC2H5)2、Nb(OC2H5)5、Ti(OCH(CH3)2)4It is mixed into ethylene glycol monomethyl ether in chemical formula ratio and obtains PMN-PT colloidal sol.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108493289A (en) * | 2018-03-09 | 2018-09-04 | 华南师范大学 | Based on hexagonal YMnO3Plane ultraviolet light detector of epitaxial film and preparation method thereof |
US20230240149A1 (en) * | 2022-01-25 | 2023-07-27 | Eagle Technology, Llc | Multi-level multiferroic memory device and related methods |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007157221A (en) * | 2005-12-02 | 2007-06-21 | Tdk Corp | Magnetoresistive effect element, thin film magnetic head provided with this element, and manufacturing method thereof |
CN203521478U (en) * | 2013-09-26 | 2014-04-02 | 北京科技大学 | Ferroelectric/ferromagnetic superlattice structure and memory thereof |
CN104518081A (en) * | 2013-09-29 | 2015-04-15 | 中芯国际集成电路制造(上海)有限公司 | Formation method of magnetic tunnel junction |
-
2016
- 2016-03-14 CN CN201610143309.5A patent/CN105762275A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007157221A (en) * | 2005-12-02 | 2007-06-21 | Tdk Corp | Magnetoresistive effect element, thin film magnetic head provided with this element, and manufacturing method thereof |
CN203521478U (en) * | 2013-09-26 | 2014-04-02 | 北京科技大学 | Ferroelectric/ferromagnetic superlattice structure and memory thereof |
CN104518081A (en) * | 2013-09-29 | 2015-04-15 | 中芯国际集成电路制造(上海)有限公司 | Formation method of magnetic tunnel junction |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108493289A (en) * | 2018-03-09 | 2018-09-04 | 华南师范大学 | Based on hexagonal YMnO3Plane ultraviolet light detector of epitaxial film and preparation method thereof |
US20230240149A1 (en) * | 2022-01-25 | 2023-07-27 | Eagle Technology, Llc | Multi-level multiferroic memory device and related methods |
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