CN104659034A - Ferroelectric unit based on LaMn3Cr4O12 and ferroelectric memory - Google Patents

Ferroelectric unit based on LaMn3Cr4O12 and ferroelectric memory Download PDF

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CN104659034A
CN104659034A CN201510068294.6A CN201510068294A CN104659034A CN 104659034 A CN104659034 A CN 104659034A CN 201510068294 A CN201510068294 A CN 201510068294A CN 104659034 A CN104659034 A CN 104659034A
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ferroelectric
storage cell
media layer
lamn
ferroelectric storage
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CN104659034B (en
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龙有文
王潇
周龙
殷云宇
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Institute of Physics of CAS
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Institute of Physics of CAS
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Abstract

The invention provides a ferroelectric memory unit which comprises a lower electrode, a ferroelectric dielectric layer formed on the lower electrode, and an upper electrode formed on the ferroelectric dielectric layer, wherein the ferroelectric dielectric layer is a LaMn3Cr4O12 film. The invention further provides a method for preparing the ferroelectric memory unit on a silicon substrate, and the method comprises the following steps: generating a layer of silicon dioxide on the silicon substrate through thermal oxidation; forming the lower electrode on the silicon dioxide layer through sputtering or electron beam evaporation; taking LaMn3Cr4O12 as a target material and forming the ferroelectric dielectric layer on the lower electrode through pulsed laser deposition or sputtering; forming the upper electrode on the ferroelectric dielectric layer through sputtering or electron beam evaporation. The ferroelectric memory unit has the advantages of high speed, low power consumption, corrosion resistance, high-temperature resistance, long service life, ordered anti-ferromagnetic coupling, controllable magnetic field and the like.

Description

Based on LaMn 3cr 4o 12ferroelectric cell and ferroelectric memory
Technical field
The present invention relates to memory area, be specifically related to a kind of based on LaMn 3cr 4o 12ferroelectric cell and ferroelectric memory.
Background technology
Non-volatility memorizer has still can keep data message at once in non-transformer confession, has a wide range of applications in field of data storage.Ferroelectric memory (FeRAM) is a kind of memory construction utilizing the ferroelectric effect of ferroelectric crystal to realize data storage.When ferroelectric effect refers to and apply certain electric field on ferroelectric crystal, germ nucleus atom at the move under influence of electric field, and reaches a kind of stable state, and after extra electric field is removed, central atom can remain on this position.Therefore ferroelectric memory keeps data not need voltage, and also not needing periodic refresh, is a kind of non-volatility memorizer.Ferroelectric memory has read or write speed faster, and lower power consumption and almost unlimited erasable number of times, have wide application prospect.Pb (Zr 1-xti x) O 3and SrBi (PZT) 2ta 2o 9(SBT) film is that two kinds of maximum ferroelectric thin-flim materialss applied by current ferroelectric memory, uses new ferroelectric material to be an important channel of improving ferroelectric memory performance further.
Summary of the invention
In view of this, the invention provides one based on LaMn 3cr 4o 12ferroelectric cell and preparation method, the invention allows for a kind of based on LaMn 3cr 4o 12ferroelectric memory.
First aspect, the present invention proposes a kind of ferroelectric storage cell, comprising: bottom electrode; Be formed at the ferroelectric media layer on described bottom electrode; And the top electrode be formed on described ferroelectric media layer; Wherein, described ferroelectric media layer is LaMn 3cr 4o 12film.
Preferably, the thickness of described ferroelectric media layer is 10nm-200nm.
Preferably, described in power on the alloys of one or more compositions in very Pt, Al, Ni, Ti, Cu, Au, Poly-Si, described bottom electrode is alloys of one or more compositions in Pt, Al, Ni, Ti, Cu, Au, Poly-Si.
Preferably, the working temperature of described ferroelectric storage cell is lower than 170K.
Preferably, the polarization of described ferroelectric media layer and antiferromagnetic order coupling.
Preferably, the electric polarization intensity of controllable magnetic field ferroelectric media layer.
Second aspect, the present invention proposes a kind of ferroelectric memory based on described ferroelectric storage cell, comprise a described ferroelectric storage cell and a metal-oxide semiconductor fieldeffect transistor, the grid of described metal-oxide semiconductor fieldeffect transistor connects wordline, the source electrode of described metal-oxide semiconductor fieldeffect transistor connects bit line, the drain electrode of described metal-oxide semiconductor fieldeffect transistor connects the bottom electrode of described ferroelectric storage cell, and the top electrode of described ferroelectric storage cell connects printed line.
The third aspect, the present invention proposes a kind of method preparing described ferroelectric storage cell, comprising:
Layer of silicon dioxide is generated on a silicon substrate by thermal oxidation;
Silicon dioxide layer forms bottom electrode by sputtering or electron beam evaporation;
With LaMn 3cr 4o 12for target, form ferroelectric media layer by pulsed laser deposition or sputtering on the bottom electrode;
Ferroelectric media layer forms top electrode by sputtering or electron beam evaporation.
Preferably, described LaMn 3cr 4o 12the preparation method of target comprises:
By La 2o 3(99.99%), Mn 2o 3and Cr (99.99%) 2o 3(99.99%) stoichiometrically 1:3:4 mixes and obtains raw mixture;
By described raw mixture grinding 30-90 minute;
Raw mixture after grinding is loaded in gold or platinum capsule and seals;
In cubic hinge press, carry out high pressure temperature high-pressure synthesis, synthesis pressure is 6-10GPa, and synthesis temperature is 900-1100 DEG C, is incubated and is quenched to room temperature after 30-60 minute.
Preferably, the diameter of described gold or platinum capsule is 2-10mm, and length is 2-10mm, and wall thickness is 1-2mm.
The present invention propose based on LaMn 3cr 4o 12the feature that ferroelectric memory has that speed is fast, low in energy consumption, corrosion-resistant, the life-span is long and compatible with silicon technology.
Accompanying drawing explanation
By referring to the description of accompanying drawing to the embodiment of the present invention, above-mentioned and other objects, features and advantages of the present invention will be more clear, in the accompanying drawings:
Fig. 1 is LaMn 3cr 4o 12the lattice structure figure of material;
Fig. 2 is LaMn 3cr 4o 12the dielectric constant of material, magnetic susceptibility and electric polarization intensity vary with temperature curve;
Fig. 3 be the present invention propose based on LaMn 3cr 4o 12ferroelectric storage cell schematic diagram;
Fig. 4 is that the one that proposes of the present invention is based on LaMn 3cr 4o 12the FeRAM structure chart of the 1T1C of ferroelectric storage cell;
Fig. 5 is the equivalent circuit diagram of the FeRAM shown in Fig. 4; And
Fig. 6 is the LaMn that the present invention proposes 3cr 4o 12the preparation method of target.
Embodiment
Based on embodiment, present invention is described below, but the present invention is not restricted to these embodiments.In hereafter details of the present invention being described, detailedly describe some specific detail sections.Do not have the description of these detail sections can understand the present invention completely for a person skilled in the art yet.In order to avoid obscuring essence of the present invention, known method, process, flow process, element and circuit do not describe in detail.In addition, it should be understood by one skilled in the art that the accompanying drawing provided at this is all for illustrative purposes, and accompanying drawing is not necessarily drawn in proportion.
Unless the context clearly requires otherwise, similar words such as " comprising ", " comprising " otherwise in whole specification and claims should be interpreted as the implication that comprises instead of exclusive or exhaustive implication; That is, be the implication of " including but not limited to ".
Fig. 1 is LaMn 3cr 4o 12the lattice structure figure of material.As shown in Figure 1, LaMn 3cr 4o 12belong to cubic system, space group is Im-3, and lattice constant is a LaMn 3cr 4o 12primitive unit cell comprises 2 La atoms, 6 Mn atoms, and 8 Cr atoms and 24 O atoms, each Cr atom connects 6 O atoms, is positioned at the center of the regular octahedron surrounded by 6 O atoms.When there being extra electric field, what produce position movement is Cr atom.
Fig. 2 is LaMn 3cr 4o 12the dielectric constant of material, magnetic susceptibility and electric polarization intensity vary with temperature curve.When temperature is lower than 170K, LaMn 3cr 4o 12in positive polarization direction and contrapolarization direction, there is different electric polarization intensitys.As shown in the first half of Fig. 2, when temperature is higher than 90K, along with the frequency of the alternating current used in the measurement of dielectric constant drops to 1 KHz from 1 megahertz, LaMn 3cr 4o 12dielectric constant increase; When temperature is between 20K to 90K, LaMn 3cr 4o 12dielectric constant do not change with ac frequency, its dielectric property remains unchanged in frequency separation widely, is stable ferroelectric material.In addition, LaMn 3cr 4o 12also there is the character of polarization and antiferromagnetic order coupling, the electric polarization intensity of controllable magnetic field ferroelectric media layer.
Fig. 3 be the present invention propose based on LaMn 3cr 4o 12the schematic diagram of ferroelectric storage cell.Based on LaMn 3cr 4o 12ferroelectric storage cell comprise: top electrode 2, ferroelectric media layer 1 and bottom electrode 3.Wherein ferroelectric media layer 1 is formed between top electrode 2 and bottom electrode 3, is LaMn 3cr 4o 12film, film thickness is 10nm-200nm.Top electrode 2 and bottom electrode 3 are the alloy of one or more compositions in Pt, Al, Ni, Ti, Cu, Au, Poly-Si.Operationally, positive polarised direction stores " 1 ", and negative polarised direction stores " 0 ".
A kind of on a silicon substrate prepare the present invention propose based on LaMn 3cr 4o 12the method of ferroelectric storage cell comprise: the first step, generate layer of silicon dioxide as barrier layer by thermal oxidation on a silicon substrate, described barrier layer is for stopping that the metal in bottom electrode spreads to silicon substrate; Second step, silicon dioxide layer forms bottom electrode by sputtering or electron beam evaporation; 3rd step, with LaMn 3cr 4o 12for target, form ferroelectric media layer by pulsed laser deposition or sputtering on the bottom electrode; 4th step, ferroelectric media layer forms top electrode by sputtering or electron beam evaporation; 5th step, by photoetching, the figure needed for etching is formed, described etching can be wet etching, sputtering, plasma etching, reactive ion etching etc.
Fig. 4 is that the one that proposes of the present invention is based on LaMn 3cr 4o 12the FeRAM structure chart of the 1T1C of ferroelectric storage cell, Fig. 5 is the equivalent circuit diagram of the FeRAM shown in Fig. 4.The FeRAM of 1T1C comprises one based on LaMn 3cr 4o 12ferroelectric storage cell and a metal-oxide semiconductor fieldeffect transistor.The grid 4 of metal-oxide semiconductor fieldeffect transistor connects wordline, the source electrode 5 of metal-oxide semiconductor fieldeffect transistor connects bit line, the drain electrode 6 of metal-oxide semiconductor fieldeffect transistor connects the bottom electrode 3 of ferroelectric storage cell, and the top electrode 2 of ferroelectric storage cell connects printed line.Fig. 4 also show ferroelectric media layer 3, silicon substrate 7, gate dielectric layer 8 and embolism 9.The read-write theory of the FeRAM of described 1T1C is as follows: after wordline gating, realizes forward polarization or the reverse polarization of ferroelectric media layer 3, complete write operation by applying voltage at bit line and printed line; The read operation of FeRAM is realized by write " 1 ", if ferroelectric media layer stores " 1 ", the change in electrical charge of top electrode and bottom electrode is very little, if ferroelectric media layer stores " 0 ", positive and negative appearances of electric charge of write " 1 " top electrode and bottom electrode is afterwards reversed, the peripheral amplifying circuit that reads utilizes the change in electrical charge of top electrode and/or bottom electrode to judge the data stored, and after reading completes, re-writes the original data stored.
Fig. 6 is the LaMn that the present invention proposes 3cr 4o 12the preparation method of target.Described LaMn 3cr 4o 12the preparation method of target:
Step S1, by La 2o 3(purity is greater than 99.99%), Mn 2o 3(purity is greater than 99.99%) and Cr 2o 3(purity is greater than 99.99%) stoichiometrically 1:3:4 mix and obtain raw mixture;
Step S2, by described raw mixture grinding 30-90 minute;
Step S3, it is 2-10mm that the raw mixture after grinding is loaded diameter, and length is 2-10mm, seals in the gold of wall thickness 1-2mm or platinum capsule;
Step S4, sends into described goldleaf capsule in cubic hinge press and carries out high temperature high pressure process synthesis LaMn 3cr 4o 12, synthesis pressure is 6-10GPa, and synthesis temperature is 900-1100 DEG C, insulation 30-90 minute;
Step S5, is quenched to room temperature.
The present invention propose based on LaMn 3cr 4o 12the feature that ferroelectric memory has that speed is fast, low in energy consumption, corrosion-resistant, the life-span is long and compatible with silicon technology.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to those skilled in the art, the present invention can have various change and change.All do within spirit of the present invention and principle any amendment, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a ferroelectric storage cell, comprising:
Bottom electrode;
Be formed at the ferroelectric media layer on described bottom electrode; And
Be formed at the top electrode on described ferroelectric media layer;
Wherein, described ferroelectric media layer is LaMn 3cr 4o 12film.
2. ferroelectric storage cell according to claim 1, wherein, the thickness of described ferroelectric media layer is 10nm-200nm.
3. ferroelectric storage cell according to claim 1, wherein, alloys of one or more compositions in described power on very Pt, Al, Ni, Ti, Cu, Au, Poly-Si, described bottom electrode is alloys of one or more compositions in Pt, Al, Ni, Ti, Cu, Au, Poly-Si.
4. ferroelectric storage cell according to claim 1, wherein, the working temperature of described ferroelectric storage cell is lower than 170K.
5. ferroelectric storage cell according to claim 1, wherein, the polarization of described ferroelectric media layer and antiferromagnetic order coupling.
6. ferroelectric storage cell according to claim 5, wherein, the electric polarization intensity of controllable magnetic field ferroelectric media layer.
7. a ferroelectric memory, comprise ferroelectric storage cell and a metal-oxide semiconductor fieldeffect transistor according to any one of claim 1-6, the grid of described metal-oxide semiconductor fieldeffect transistor connects wordline, the source electrode of described metal-oxide semiconductor fieldeffect transistor connects bit line, the drain electrode of described metal-oxide semiconductor fieldeffect transistor connects the bottom electrode of described ferroelectric storage cell, and the top electrode of described ferroelectric storage cell connects printed line.
8. the method preparing ferroelectric storage cell according to claim 1 comprises:
Layer of silicon dioxide is generated on a silicon substrate by thermal oxidation;
Silicon dioxide layer forms bottom electrode by sputtering or electron beam evaporation;
With LaMn 3cr 4o 12for target, form ferroelectric media layer by pulsed laser deposition or sputtering on the bottom electrode;
Ferroelectric media layer forms top electrode by sputtering or electron beam evaporation.
9. the method preparing ferroelectric storage cell according to claim 8, wherein, described LaMn 3cr 4o 12the preparation method of target comprises:
By La 2o 3(99.99%), Mn 2o 3and Cr (99.99%) 2o 3(99.99%) stoichiometrically 1:3:4 mixes and obtains raw mixture;
By described raw mixture grinding 30-90 minute;
Raw mixture after grinding is loaded in gold or platinum capsule and seals;
In cubic hinge press, carry out high pressure temperature high-pressure synthesis, synthesis pressure is 6-10GPa, and synthesis temperature is 900-1100 DEG C, is incubated and is quenched to room temperature after 10-60 minute.
10. LaMn according to claim 9 3cr 4o 12the preparation method of target, wherein, the diameter of described gold or platinum capsule is 2-10mm, and length is 2-10mm, and wall thickness is 1-2mm.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104882462A (en) * 2015-06-18 2015-09-02 中山大学 Active integrated structure of non-volatile resistive random access memory
CN106083053A (en) * 2016-06-24 2016-11-09 中国科学院地球化学研究所 A kind of preparation method of marmatite electrode
CN110426656A (en) * 2019-07-09 2019-11-08 中国科学院物理研究所 The DyCrO of scheelite phase4Application, magnetoelectric transducer unit in magnetoelectric transducer unit and preparation method thereof

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CN101436597A (en) * 2008-12-10 2009-05-20 华中科技大学 Ferro-electricity film capacitor for ferro-electric memory and preparation method thereof
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104882462A (en) * 2015-06-18 2015-09-02 中山大学 Active integrated structure of non-volatile resistive random access memory
CN104882462B (en) * 2015-06-18 2018-03-16 中山大学 A kind of active integrated morphology of non-volatile resistance-variable storing device
CN106083053A (en) * 2016-06-24 2016-11-09 中国科学院地球化学研究所 A kind of preparation method of marmatite electrode
CN106083053B (en) * 2016-06-24 2018-10-19 中国科学院地球化学研究所 A kind of preparation method of marmatite electrode
CN110426656A (en) * 2019-07-09 2019-11-08 中国科学院物理研究所 The DyCrO of scheelite phase4Application, magnetoelectric transducer unit in magnetoelectric transducer unit and preparation method thereof

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