CN102768854B - A kind of magnetoelectric composite multi-state memory unit and preparation method thereof - Google Patents
A kind of magnetoelectric composite multi-state memory unit and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000005294 ferromagnetic effect Effects 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000000151 deposition Methods 0.000 claims abstract description 20
- 230000008021 deposition Effects 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000004549 pulsed laser deposition Methods 0.000 claims description 11
- 238000007669 thermal treatment Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910002367 SrTiO Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 2
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- 238000003860 storage Methods 0.000 abstract description 118
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Abstract
A kind of magnetoelectric composite multi-state memory unit and preparation method thereof, to be included on substrate depositions of bottom electrode, ferroelectric layer and top electrode successively, described hearth electrode is ferromagnetic layer, and described top electrode is ferromagnetic layer or material is the thin layer of Ag, Au, Pt, Cu or Al; The material of this ferromagnetic layer is La
1-xsr
xmnM
yo
3, wherein 0.15≤x≤0.5,0≤y≤0.1, M is at least one in Ag, Bi, Cu, Co, Ni and Sc element; The material of ferroelectric layer is BaTiO
3; The material of ferromagnetic layer and ferroelectric layer all has (110) orientation; The Thickness Ratio of described ferromagnetic layer and ferroelectric layer is 0.1-20.Ferromagnetic, the ferroelectric two phase structure of magnetoelectric composite multi-state memory unit of the present invention mates and interface coupling is better, Composition Control is easy, preparation technology is simple, not only achieve the multiple-state storage function of data, and have store data non-volatile, digital independent is simple, speed is fast, with the conventional semiconductor processing compatibility advantage such as better.
Description
Technical field
The present invention relates to a kind of magnetoelectric composite multi-state memory unit and preparation method thereof, belong to microelectronic component and preparing technical field thereof.
Background technology
Along with people's increasing sharply to storage requirement, memory technology is just towards high speed, highdensity future development.Multi-state memory can store multiple information state in a storage unit, and comparing traditional two condition storer (each cell stores 0,1 two states) can improve memory capacity exponentially when not changing number of memory cells.Therefore, multiple-state storage technology is considered to the important directions of Future high-density Development of storage technology.
At present, the material with multiple-state storage function mainly contains phase-change material and multi-ferroic material two class.The principle of phase-change material multiple-state storage mainly obtains the resistance states of different resistance by the crystallization degree of control Ge-Sb-Te based material, thus realizes multiple-state storage.The major defect of phase transformation multiple-state storage is that the intermediateness resistance fluctuation between high-impedance state and low resistance state is comparatively large, and noise margin is poor, circuit design and verification error correcting routine complexity.Multi-ferroic material is that the four kinds of different polarized states (± P, ± M) utilizing material to show under different Electric and magnetic fields realize multiple-state storage.Multi-ferroic material according to chemical composition can be divided into two large classes, and a class is single-phase multi-ferroic material, and another kind of is multiferroic magnetic electric compound material.Single-phase multi-ferroic material realizes multiple-state storage and normally utilizes magnetotunneling to tie under different polarized states, to show four kinds and then wear resistance to realize, but its Curie temperature of single-phase multi-ferroic material or Neel temperature, generally all far below room temperature, cannot realize multiple-state storage under normal temperature.The multiple-state storage principle of multiferroic magnetoelectric composite film material is that the four kinds of different conditions (voltage swing is different with direction) utilizing alternating magnetic field induction magnetic composite magnetoelectricity to output signal to show realize multiple-state storage.Comparatively speaking, magnetoelectricity compound multiple-state storage have that structure is simple, normal temperature applicability is good, reading speed is fast, the advantage such as non-volatile (non-volatile).Therefore, multiferroic magnetoelectric composite film as multiple-state storage medium be applicable to very much Contemporary storage technologies at a high speed, highdensity development trend, potential huge commercial value in Future Information industry.
Chinese patent application 201010570946.3 discloses a kind of multiferroic magnetoelectric composite film of all-perovskite structure, but this thin film alignment is (100), and is two-layer composite, and does not have the function of multiple-state storage.
Summary of the invention
The object of the present invention is to provide magnetoelectric composite multi-state memory unit that a kind of structure is simple, four state output characteristics are good and preparation method thereof.This magnetoelectric composite multi-state memory unit realizes data write by change multiferroic magnetoelectric composite film material residual polarization and remanent magnetization direction, realize data reading by the size and Orientation difference of alternating magnetic field induction magnetic composite magnetoelectricity output voltage, thus realize four states storages.
For achieving the above object, the present invention is by the following technical solutions:
A kind of magnetoelectric composite multi-state memory unit, be included in the hearth electrode of compound successively on substrate, ferroelectric layer and top electrode, described hearth electrode is ferromagnetic layer, and described top electrode is ferromagnetic layer or material is the thin layer of Ag, Au, Pt, Cu or Al; The material of described ferromagnetic layer is La
1-xsr
xmnM
yo
3, wherein 0.15≤x≤0.5,0≤y≤0.1, M is at least one in Ag, Bi, Cu, Co, Ni and Sc element; The material of described ferroelectric layer is BaTiO
3; The material of described ferromagnetic layer and ferroelectric layer all has (110) orientation; The Thickness Ratio of described ferromagnetic layer and ferroelectric layer is 0.1-20.
Because the ferromagnetic layer in magnetoelectric composite multi-state memory unit of the present invention at room temperature has good electric conductivity, (resistivity is generally 10
-2Ω about .cm), therefore this ferromagnetic layer can directly use as low/top electrode.
In magnetoelectric composite multi-state memory unit of the present invention, ferromagnetic layer and ferroelectric layer choose the LaSrMnO with perovskite structure respectively
3material and BaTiO
3material, both structure matching are better, and belong to oxide system, in heat treatment process, not easily occur phase reaction.Ferromagnetic layer LaSrMnO
3can mix Ag, Bi, Cu, Co, Ni, Sc element in material, wherein elements A g, Bi, Cu, Sc are conducive to improving LaSrMnO
3the electric conductivity of film, Co and Ni is conducive to improving LaSrMnO
3the temperature applicability of film.
In order to realize four state storage characteristicss, under room temperature, ferromagnetic layer should have suitably large HCJ H as much as possible
cj, thus when data reading, one can be applied and be less than H
cjbias magnetic field change the remanent magnetization direction of ferromagnetic layer, so that the magnetoelectricity distinguishing the storage unit that residual polarization and remanent magnetization direction are contrary outputs signal.Inventor studies the LaSrMnO of discovery at room temperature (110) orientation
3the H of film
cjgenerally be greater than 2.5kA/m, the requirement that four states store can be met preferably, and work as LaSrMnO
3the H of film
cjthe magnetoelectricity output signal of same electrical polarised direction can be distinguished better when data reading when being greater than 5.0kA/m.But the LaSrMnO of (100) orientation
3the H of film
cjbeing generally less than 2.5kA/m, easily occurring obscuring or mistake when reading the magnetoelectricity output signal of same electrical polarised direction.Therefore, the present invention forms texture preferably (110) orientation of the ferromagnetic layer of magnetoelectric composite multi-state memory unit, the HCJ 2.5kA/m≤H of ferromagnetic layer
cj≤ 40kA/m.
In the present invention, the magnetoelectricity output characteristics of Thickness Ratio η on magnetic electric compound material of ferromagnetic layer and ferroelectric layer affects very large.Inventor studies discovery: when η is less than 0.1, magnetoelectricity conversion coefficient is less, four state output characteristics are poor, when 2.1≤η≤5, magnetoelectric composite multi-state memory unit has good four state output characteristics, when 5 < η≤20, four state output characteristics changes are not obvious, and four state output characteristics are deteriorated on the contrary when η is greater than 20, be unfavorable for storing data reading.Therefore thickness 0.1≤η≤20 of ferromagnetic layer and ferroelectric layer in the present invention, are preferably 2.1≤η≤5.
In the present invention, the gross thickness of ferromagnetic layer and ferroelectric layer is preferably less than 1 μm, by LaSrMnO
3with BaTiO
3the magnetoelectric composite film that the hundreds of nanometers formed is thick can export the voltage signal of tens μ V under the AC magnetic field of 10Oe, the needs of data reading can be met completely, and when the thickness of laminated film is more than 1 μm, the interface coupling coefficient of ferroelectric layer and ferromagnetic layer declines, cause magnetoelectricity conversion performance to decline on the contrary, and consider that the gross thickness of laminated film is also no more than 1 μm from the angle of storer preparation technology.
The relative dielectric constant of ferroelectric phase larger magnetoelectricity changing voltage is less in theory, and less relative dielectric constant is conducive to the magnetoelectricity output voltage improving magnetoelectric composite film.Inventor studies discovery: thickness arrives the BaTiO of hundreds of nanometers tens
3the relative dielectric constant ε of film
rbe generally 50-800 (under 1000Hz), and work as ε
rfor its laminated film during 150-300 has good magnetoelectricity output characteristics, be relatively applicable to the data reading of magnetoelectricity storer.Therefore, in the present invention, the relative dielectric constant of ferromagnetic layer is preferably 50≤ε r≤800, is more preferably 150≤ε
r≤ 300.
Due to single crystal La AlO
3, SrTiO
3or (LaSr) (AlTa) O
3material is perovskite structure, and on such substrate of (110) orientation, easier epitaxial growth goes out to have the LaSrMnO of (110) orientation of perovskite structure
3/ BaTiO
3laminated film.Therefore, the preferred backing material of the present invention is LaAlO
3, SrTiO
3or (La
1-xsr
x) (Al
1-ytay) O
3the monocrystalline of (110) orientation, wherein 0.15≤x≤0.5,0.15≤y≤0.5.
In the present invention, as Material selec-tion Ag, Au, Pt, Cu or Al of top electrode, be preferably Ag thin layer.
The present invention also provides a kind of preparation method of described magnetoelectric composite multi-state memory unit, when top electrode be material is the thin layer of Ag, Au, Pt, Cu or Al, to comprise the steps: at 600-800 DEG C on substrate deposited iron magnetosphere film and ferroelectric layer film successively, then in oxygen atmosphere in 700-860 DEG C of thermal treatment 30-120min; Again at ferroelectric layer surface deposition top electrode film;
When top electrode is ferromagnetic layer, to comprise the steps: at 600-800 DEG C on substrate deposited iron magnetosphere film, ferroelectric layer film and ferromagnetic layer film successively, then in oxygen atmosphere in 700-860 DEG C of thermal treatment 30-120min;
Described deposition process is magnetron sputtering, pulsed laser deposition, ion beam sputtering or ion plating.
The invention has the advantages that:
Ferromagnetic, the ferroelectric two phase structure of magnetoelectricity composite memory unit provided by the invention mates and interface coupling is better, Composition Control is easy, preparation technology is simple, not only achieve the multiple-state storage function of data, and have store data non-volatile, digital independent is simple, speed is fast, with the conventional semiconductor processing compatibility advantage such as better.
Accompanying drawing explanation
Fig. 1 is the structural representation of magnetoelectric composite multi-state memory unit of the present invention.Wherein, 1 is top electrode, and 2 is ferroelectric layer, and 3 is ferromagnetic layer, and 4 is substrate.
Embodiment
The invention will be further described below to use example.Scope is not by the restriction of these embodiments, and scope is determined by claims.
Embodiment 1
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 200nm
0.5sr
0.5mnO
3film and thickness are the BaTiO of 10nm
3(mode of deposition is film: operating air pressure is 0.5Pa, Ar and O
2throughput ratio be 16: 4, sputtering power is 100W, and underlayer temperature is 600 DEG C, and target-substrate distance is 70mm), then by film 700 DEG C of thermal treatment 60min under oxygen atmosphere, and then adopt magnetron sputtering technique at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, and (mode of deposition is: operating air pressure is 1Pa, Ar gas atmosphere, sputtering power is 100W, underlayer temperature is 23 DEG C, target-substrate distance is 70mm), again three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.5sr
0.5mnO
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The measurement of memory cell: relative dielectric constant ε
rmeasure with Agilent 4294A type precise impedance analyser, HCJ H
cjmeasure by VersLab many merits magnetic measurement systems, crystal orientation SmartLab X-ray diffractometer is measured, and magnetoelectricity changing voltage Signal recovery 7265 digital lock-in amplifier is measured.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 3kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 3kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 1.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 1 (above-mentioned all measurements are all carried out at 23 DEG C, and following examples are identical).
Table 1
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 50 | 20 | 2.5 | 0.14 |
| 2 | 110 | 50 | 20 | 2.5 | -0.11 |
| 3 | 110 | 50 | 20 | 2.5 | -0.15 |
| 4 | 110 | 50 | 20 | 2.5 | 0.10 |
Embodiment 2
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (001) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 200nm
0.5sr
0.5mnO
3film and thickness are the BaTiO of 10nm
3film (mode of deposition is same embodiment 1), then by film 700 DEG C of thermal treatment 60min under oxygen atmosphere, and then adopt magnetron sputtering technique with embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.5sr
0.5mnO
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 2kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 2kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 0.2kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 2.
Table 2
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 001 | 45 | 20 | 1.5 | 0.12 |
| 2 | 001 | 45 | 20 | 1.5 | -0.10 |
| 3 | 001 | 45 | 20 | 1.5 | -0.11 |
| 4 | 001 | 45 | 20 | 1.5 | 0.09 |
Embodiment 3
The magnetoelectric composite multi-state memory unit of the present embodiment adopts the preparation of pulsed laser deposition (PLD) technique.First, (110) the orientation SrTiO first cleaned up
3on substrate with PLD method respectively deposit thickness be the La of 20nm
0.85sr
0.15mnAg
0.1o
3film and thickness are the BaTiO of 200nm
3(mode of deposition is film: high purity oxygen gas atmosphere, operating air pressure is 10Pa, each pulsed laser energy 280mJ, pulsed frequency 10Hz, underlayer temperature is 800 DEG C, target-substrate distance is 50mm), then by film 860 DEG C of thermal treatment 30min under oxygen atmosphere, and then adopt magnetron sputtering technique with embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.85sr
0.15mnAg
0.1o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 5.0kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 5.0kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.
(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 1.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 3.
Table 3
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 172 | 0.1 | 3.1 | 0.22 |
| 2 | 110 | 172 | 0.1 | 3.1 | -0.15 |
| 3 | 110 | 172 | 0.1 | 3.1 | -0.21 |
| 4 | 110 | 172 | 0.1 | 3.1 | 0.12 |
Embodiment 4
The magnetoelectric composite multi-state memory unit of the present embodiment adopts the preparation of pulsed laser deposition (PLD) technique.First, (110) the orientation SrTiO first cleaned up
3on substrate with PLD method respectively deposit thickness be the La of 15nm
0.85sr
0.15mnAg
0.1o
3film and thickness are the BaTiO of 200nm
3(mode of deposition is film: high purity oxygen gas atmosphere, operating air pressure is 10Pa, each pulsed laser energy 280mJ, pulsed frequency 10Hz, underlayer temperature is 800 DEG C, target-substrate distance is 50mm), then by film 860 DEG C of thermal treatment 30min under oxygen atmosphere, and then adopt magnetron sputtering technique with embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.85sr
0.15mnAg
0.1o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 5.0kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 5.0kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 1.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 4.
Table 4
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 50 | 0.075 | 3.2 | 0.15 |
| 2 | 110 | 50 | 0.075 | 3.2 | -0.14 |
| 3 | 110 | 50 | 0.075 | 3.2 | -0.16 |
| 4 | 110 | 50 | 0.075 | 3.2 | 0.13 |
Embodiment 5
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 210nm
0.5sr
0.5mnO
3film and thickness are the BaTiO of 10nm
3film (mode of deposition is same embodiment 1), then by film 700 DEG C of thermal treatment 60min under oxygen atmosphere, and then adopt magnetron sputtering technique with embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.5sr
0.5mnO
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 5kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 5kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 0.2kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 5.
Table 5
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 150 | 21 | 2.5 | 0.11 |
| 2 | 110 | 150 | 21 | 2.5 | -0.10 |
| 3 | 110 | 150 | 21 | 2.5 | -0.11 |
| 4 | 110 | 150 | 21 | 2.5 | 0.09 |
Embodiment 6
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 210nm
0.70sr
0.30mnBi
0.05o
3film and thickness are the BaTiO of 100nm
3(mode of deposition is film: operating air pressure is 1.5Pa, the throughput ratio of Ar and O2 is 16: 4, sputtering power is 100W, underlayer temperature is 800 DEG C, target-substrate distance is 70mm), again by film 860 DEG C of thermal treatment 30min under oxygen atmosphere, and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.70sr
0.30mnBi
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε r of memory cell, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 6.
Table 6
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 150 | 2.1 | 5.0 | 0.56 |
| 2 | 110 | 150 | 2.1 | 5.0 | -0.23 |
| 3 | 110 | 150 | 2.1 | 5.0 | -0.55 |
| 4 | 110 | 150 | 2.1 | 5.0 | 0.25 |
Embodiment 7
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 210nm
0.67sr
0.33mnBi
0.05o
3film and thickness are the BaTiO of 100nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.67sr
0.33mnBi
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 7.
Table 7
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 150 | 2.1 | 5.6 | 0.67 |
| 2 | 110 | 150 | 2.1 | 5.6 | -0.33 |
| 3 | 110 | 150 | 2.1 | 5.6 | -0.65 |
| 4 | 110 | 150 | 2.1 | 5.6 | 0.32 |
Embodiment 8
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 500nm
0.67sr
0.33mnBi
0.05o
3film and thickness are the BaTiO of 100nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.67sr
0.33mnBi
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 8.
Table 8
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 150 | 5.0 | 5.6 | 0.72 |
| 2 | 110 | 150 | 5.0 | 5.6 | -0.35 |
| 3 | 110 | 150 | 5.0 | 5.6 | -0.72 |
| 4 | 110 | 150 | 5.0 | 5.6 | 0.32 |
Embodiment 9
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 350nm
0.67sr
0.33mnBi
0.05o
3film and thickness are the BaTiO of 100nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.67sr
0.33mnBi
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 9.
Table 9
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 150 | 3.5 | 5.6 | 0.85 |
| 2 | 110 | 150 | 3.5 | 5.6 | -0.45 |
| 3 | 110 | 150 | 3.5 | 5.6 | -0.82 |
| 4 | 110 | 150 | 3.5 | 5.6 | 0.43 |
Embodiment 10
The magnetoelectric composite multi-state memory unit of the present embodiment adopts the preparation of pulsed laser deposition (PLD) technique.First, (110) the orientation SrTiO first cleaned up
3on substrate with PLD method successively respectively deposit thickness be the La of 150nm
0.67sr
0.33mnAg
0.01co
0.01o
3film, thickness are the BaTiO of 100nm
3film and thickness are the La of 150nm
0.67sr
0.33mnAg
0.01co
0.01o
3(mode of deposition is film: high purity oxygen gas atmosphere, operating air pressure is 5Pa, each pulsed laser energy 280mJ, pulsed frequency 10Hz, underlayer temperature is 700 DEG C, and target-substrate distance is 50mm), then by film 800 DEG C of thermal treatment 120min under oxygen atmosphere, again three layers of laminated film are etched into the identical storage unit of four sizes, the bottom of each storage unit and top layer La
0.67sr
0.33mnAg
0.01co
0.01o
3film is as hearth electrode and top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 10.
Table 10
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 156 | 3.0 | 5.2 | 0.66 |
| 2 | 110 | 156 | 3.0 | 5.2 | -0.35 |
| 3 | 110 | 156 | 3.0 | 5.2 | -0.65 |
| 4 | 110 | 156 | 3.0 | 5.2 | 0.34 |
Embodiment 11
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 660nm
0.60sr
0.40mnSc
0.05o
3film and thickness are the BaTiO of 300nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.60sr
0.40mnSc
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 11.
Table 11
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 900 | 2.2 | 4.8 | 0.32 |
| 2 | 110 | 900 | 2.2 | 4.8 | -0.35 |
| 3 | 110 | 900 | 2.2 | 4.8 | -0.35 |
| 4 | 110 | 900 | 2.2 | 4.8 | 0.31 |
Embodiment 12
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 440nm
0.60sr
0.40mnSc
0.005o
3film and thickness are the BaTiO of 200nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.60sr
0.40mnSc
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 12.
Table 12
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 800 | 2.2 | 4.8 | 0.44 |
| 2 | 110 | 800 | 2.2 | 4.8 | -0.32 |
| 3 | 110 | 800 | 2.2 | 4.8 | -0.46 |
| 4 | 110 | 800 | 2.2 | 4.8 | 0.33 |
Embodiment 13
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 330nm
0.60sr
0.40mnSc
0.05o
3film and thickness are the BaTiO of 150nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.60sr
0.40mnSc
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 13.
Table 13
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 300 | 2.2 | 4.8 | 0.64 |
| 2 | 110 | 300 | 2.2 | 4.8 | -0.41 |
| 3 | 110 | 300 | 2.2 | 4.8 | -0.65 |
| 4 | 110 | 300 | 2.2 | 4.8 | 0.40 |
Embodiment 14
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) the orientation LaAlO first cleaned up
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 400nm
0.60sr
0.40mnSc
0.05o
3film and thickness are the BaTiO of 180nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.60sr
0.40mnSc
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 14.
Table 14
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 220 | 2.2 | 4.8 | 0.66 |
| 2 | 110 | 220 | 2.2 | 4.8 | -0.40 |
| 3 | 110 | 220 | 2.2 | 4.8 | -0.65 |
| 4 | 110 | 220 | 2.2 | 4.8 | 0.42 |
Embodiment 15
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) orientation (La first cleaned up
0.3sr
0.7) (Al
0.65ta
0.35) O
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 350nm
0.67sr
0.33mnBi
0.05o
3film and thickness are the BaTiO of 100nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 100nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.67sr
0.33mnBi
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 6kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 6kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 15.
Table 15
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 150 | 3.5 | 5.6 | 0.88 |
| 2 | 110 | 150 | 3.5 | 5.6 | -0.42 |
| 3 | 110 | 150 | 3.5 | 5.6 | -0.85 |
| 4 | 110 | 150 | 3.5 | 5.6 | 0.46 |
Embodiment 16
The magnetoelectric composite multi-state memory unit of the present embodiment adopts magnetron sputtering technique preparation.First, (110) orientation (La first cleaned up
0.3sr
0.7) (Al
0.65ta
0.35) O
3on substrate with magnetically controlled sputter method respectively deposit thickness be the La of 5nm
0.67sr
0.33mnBi
0.05o
3film and thickness are the BaTiO of 2nm
3film (mode of deposition is same embodiment 6), and then adopt with the magnetron sputtering technique of embodiment 1 at BaTiO
3film surface deposits the Ag film that a layer thickness is 30nm, then three layers of laminated film are etched into the identical storage unit of four sizes, the bottom La of each storage unit
0.67sr
0.33mnBi
0.05o
3film is as hearth electrode, top layer Ag film as top electrode, and after top electrode and hearth electrode line, namely four unit can be used as four independently storage unit.
The relative dielectric constant ε of memory cell
r, HCJ H
cj, crystal orientation, magnetoelectricity changing voltage measuring method with embodiment 1.
Memory cell magnetoelectricity four state output characteristics measuring method is: (1) data write: above-mentioned four storage unit being compiled respectively is 1,2,3, No. 4, first No. 1 and No. 2 unit edges are carried out saturated polarization perpendicular to face direction upwards, No. 3 are carried out saturated polarization with No. 4 unit edges perpendicular to the prone direction of film, then (are greater than H to No. 1 and No. 3 unit along parallel membrane towards the magnetic field of the direction on right side applying 50kA/m
cj) magnetize, along parallel membrane towards the direction on a left side, 50kA/m is applied to No. 2 and No. 4 unit and (is greater than H
cj) magnetic field magnetize, like this because namely difference four storage unit of residual electric polarization and remanence polarized state have been written into four different signals.(2) data reading: the bias magnetic field that four storage unit are placed in respectively along parallel membrane towards right direction size 2.5kA/m (is less than H
cj), then the AC magnetic field of 1kHz size 80A/m is applied along parallel face direction, measure magnetoelectricity changing voltage size and the phase place of each unit with lock-in amplifier, phase place is used for the positive and negative of regulation magnetoelectricity changing voltage, then can read four kinds of different magnetoelectricity changing voltages.Measurement result is in table 16.
Table 16
| Element number | Orientation | ε r | Thickness Ratio η | H cj(kA/m) | Magnetoelectricity voltage (μ V) |
| 1 | 110 | 60 | 2.5 | 40 | 0.12 |
| 2 | 110 | 60 | 2.5 | 40 | -0.08 |
| 3 | 110 | 60 | 2.5 | 40 | -0.13 |
| 4 | 110 | 60 | 2.5 | 40 | 0.07 |
Claims (9)
1. a magnetoelectric composite multi-state memory unit, is characterized in that, is included in the hearth electrode of compound successively on substrate, ferroelectric layer and top electrode, and it is La that described hearth electrode and top electrode are material
1-xsr
xmnM
yo
3ferromagnetic layer, wherein 0.15≤x≤0.5,0≤y≤0.1, M is at least one in Ag, Bi, Cu, Co, Ni and Sc element; The material of described ferroelectric layer is BaTiO
3; The material of described ferromagnetic layer and ferroelectric layer all has (110) orientation; The Thickness Ratio of described ferromagnetic layer and ferroelectric layer is 2.1 ~ 5; HCJ 2.5kA/m≤the H of described ferromagnetic layer
cj≤ 40kA/m; The relative dielectric constant of described ferroelectric layer is 50 ~ 800.
2. a magnetoelectric composite multi-state memory unit, is characterized in that, is included in the hearth electrode of compound successively on substrate, ferroelectric layer and top electrode, and described hearth electrode is material is La
1-xsr
xmnM
yo
3ferromagnetic layer, wherein 0.15≤x≤0.5,0≤y≤0.1, M is at least one in Ag, Bi, Cu, Co, Ni and Sc element; The material of described ferroelectric layer is BaTiO
3; The thin layer of described top electrode to be material be Ag, Au, Pt, Cu or Al; The material of described ferromagnetic layer and ferroelectric layer all has (110) orientation; The Thickness Ratio of described ferromagnetic layer and ferroelectric layer is 2.1 ~ 5; HCJ 2.5kA/m≤the H of described ferromagnetic layer
cj≤ 40kA/m; The relative dielectric constant of described ferroelectric layer is 50 ~ 800.
3. magnetoelectric composite multi-state memory unit according to claim 1 and 2, is characterized in that, the material of described ferromagnetic layer and ferroelectric layer all has perovskite structure.
4. magnetoelectric composite multi-state memory unit according to claim 1 and 2, is characterized in that: the gross thickness of described ferromagnetic layer and ferroelectric layer is less than 1 μm.
5. magnetoelectric composite multi-state memory unit according to claim 1, is characterized in that: the relative dielectric constant of described ferroelectric layer is 150 ~ 300.
6. magnetoelectric composite multi-state memory unit according to claim 1 and 2, is characterized in that: described backing material is LaAlO
3, SrTiO
3or (La
1-xsr
x) (Al
1-yta
y) O
3(110) oriented single crystal, wherein 0.15≤x≤0.5,0.15≤y≤0.5.
7. a preparation method for magnetoelectric composite multi-state memory unit according to claim 1, is characterized in that comprising the steps:
At 600-800 DEG C on substrate deposited iron magnetosphere film, ferroelectric layer film and ferromagnetic layer film successively, then in oxygen atmosphere in 700-860 DEG C of thermal treatment 30-120min.
8. a preparation method for magnetoelectric composite multi-state memory unit according to claim 2, is characterized in that comprising the steps:
At 600-800 DEG C on substrate deposited iron magnetosphere film and ferroelectric layer film successively, then in oxygen atmosphere in 700-860 DEG C of thermal treatment 30-120min; Again at ferroelectric layer surface deposition top electrode film.
9. the preparation method according to claim 7 or 8, is characterized in that: described deposition process is magnetron sputtering, pulsed laser deposition, ion beam sputtering or ion plating.
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