CN105720188A - Magnetoelectric effect based magnetoelectric memory element of ferroelectric/ferromagnetic composite thin film - Google Patents
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Abstract
Disclosed is a magnetoelectric effect based magnetoelectric memory element of a ferroelectric/ferromagnetic composite thin film. Ferroelectric and ferromagnetic thin films are deposited on a Pt/Ti/SiO<2>/Si composite substrate in sequence to prepare a laminated structure; the chemical structural formula of the ferroelectric thin film with a piezoelectric effect is 0.5Ba(Zr<0.2>Ti<0.8>) O<3>-0.5(Ba<0.3>Ca<0.7>)TiO<3>(BZT-BCT); the thin film with a magnetostrictive effect is Fe<0.7>Ga<0.3>; the preparation method comprises the steps of preparing the ferroelectric ceramic thin film through radio frequency magnetron sputtering, and preparing the ferromagnetic thin film by direct current magnetron sputtering. The magnetoelectric effect based magnetoelectric memory element has the advantages as follows: the memory element is nonvolatile, capable of keeping the polarized and magnetized states under externally-applied voltage, and low in power consumption; the memory unit has good ferroelectric, piezoelectric and ferromagnetic performances at the room temperature; and the maximum electric field control magnetic resistance effect 6% is obtained when the externally applied bias voltage is 20V.
Description
Technical field
The present invention be more particularly directed to magnetoelectricity memory element of a kind of ferroelectricity/ferromagnetic composite film based on magnetoelectric effect and preparation method thereof.
Background technology
Along with the high speed development of information technology, information storage technology is proposed the highest requirement.To having high memory density, low read-write energy consumption, the research and development of the high-performance storage device of high read or write speed, have become as one of most active field in current scientific research forward position and information technology.In traditional information recording method formula, magnetic recording is prone to the advantage of reading with it, becomes the main flow of present information memory technology；But the restriction of its memory density and the write difficulty difficult problem that always magnetic storage technology is faced.By contrast, ferroelectricity storage has high memory density and is prone to the feature of write, but the complexity of the process of reading and destructive problem, greatly limit its application as memorizer.To this end, the researcher of association area always strives to advantages ferromagnetic, two kinds of recording modes of ferroelectricity be combined and overcome respective shortcoming, thus constantly explore in terms of new device, new construction and the new material that informational function is relevant；New ideas memorizer related to this is also constantly being designed；And one of them feasible approach, it is simply that by magnetoelectric effect (magnetoelectric coupling, ME coupling) and multi-ferroic material.
Magnetoelectric effect (ME Coupling Effect) refers to that material produces spontaneous polarization under additional the action of a magnetic field and forms electric field, otherwise, magnetization can also be produced under DC Electric Field.There is the magnetoelectric material of magnetoelectric effect due to the magneto-electric coupled characteristic of its multiple physical field, be not only related to the new problem of physically strong correlation electron system, there is important scientific meaning；Provide extra degree of freedom in the design that application aspect is also multifunction electronic device of future generation simultaneously.Magnetoelectricity memorizer (Magnetoelectric Memory based on magnetoelectric effect, MERAM) available electric field realizes information ablation process, magnetic head is utilized to realize readout, the advantage of ferroelectric random storage (FeRAM) and magnetic memory (MRAM) is combined, so that current memory member speed improves more than an order of magnitude again and is substantially reduced the energy expenditure of information ablation process by the high-performance memory of " autotelegraph/magnetic is read " formula integrating the high speed of ferroelectricity write, low energy consumption characteristic and the high speed of magnetic reading, non-destructive.
The magnetoelectricity memory element of the ferroelectricity/ferromagnetic composite film based on magnetoelectric effect that the present invention relates to, selects Fe0.7Ga0.3Alloy is as ferromagnetic layer, and BZT-BCT, as ferroelectric layer, prepares a kind of environmentally friendly magnetoelectricity memory device with big electroluminescent magnetoelectric effect, and magnetoelectric composite film device involved in the present invention is to propose first, has no relevant report the most both at home and abroad.
Summary of the invention
It is an object of the invention to for above-mentioned existing problems, it is provided that the preparation method of the magnetoelectricity memory element of a kind of ferroelectricity/ferromagnetic composite film based on magnetoelectric effect, the present invention is with Ba (Zr0.2Ti0.8)O3-(Ba0.3Ca0.7)TiO3Ceramic target and Fe0.7Ga0.3Alloy target material is raw material, the method using magnetron sputtering prepares magnetoelectric composite film device, this memory element have non-volatile, can keep when applied voltage polarization and magnetized state, owing to the change of resistance states can be overturn by the voltage between upper/lower electrode, need not the generation in the big magnetic field of big electric current, the advantage with low-power consumption.
Technical scheme:
The magnetoelectricity memory element of a kind of ferroelectricity/ferromagnetic composite film based on magnetoelectric effect, at Pt/Ti/SiO2Being sequentially depositing ferroelectricity in/Si compound substrate and ferromagnetic thin film makes laminated construction, wherein compound substrate is respectively Si, SiO from bottom to top2, Ti and Pt hearth electrode, the ferroelectric thin film chemical structural formula with piezoelectric effect is 0.5Ba (Zr0.2Ti0.8)O3-0.5(Ba0.3Ca0.7)TiO3(BZT-BCT), thickness is 200-400nm, and the thin film with magnetostrictive effect is Fe0.7Ga0.3, thickness is 200-400nm.
The preparation method of the magnetoelectricity memory element of a kind of described ferroelectricity based on magnetoelectric effect/ferromagnetic thin film structure, wherein ferroelectric ceramic thin film utilizes rf magnetron sputtering to prepare, and ferromagnetic thin film is by Fe0.7Ga0.3Alloy target material utilizes magnetically controlled DC sputtering to prepare, and step is as follows:
1) by Pt/Ti/Si/SiO2Substrate puts into sputtering chamber together with BZT-BCT ceramic target, is evacuated to (1-2) × 10-4Then pass to pressure be 2-2.5Pa, the gaseous mixture that volume ratio is 12:8-9 of argon and oxygen, underlayer temperature is 500-700 DEG C, radio-frequency power is 50-60w, sputtering time is 1.5-4h, after sputtering chamber takes out under 800 DEG C and air atmosphere heat treatment 30 minutes, prepare ferroelectric ceramic thin film；
2) using the ferroelectric ceramic thin film of above-mentioned preparation as substrate and Fe0.7Ga0.3Alloy target material puts into sputtering chamber together, is evacuated to (1-2) × 10-4, then passing to the argon that pressure is 1-1.5Pa, argon flow amount is 10sccm, and radio-frequency power is 30-50w, sputtering time is 10-30min, prepares the magnetoelectricity memory element of ferroelectricity/ferromagnetic composite film after sputtering chamber takes out.
The technical Analysis of the present invention:
The memory element that the present invention relates to is with the Magnetoelectric film of laminated construction as medium, extra electric field changes the polarized state of ferroelectric layer to be affected the magnetized state of ferromagnetic layer by magnetoelectric effect and realizes electric field controls magneto-resistor state, write medium is electric field, storage medium is the magneto-resistor state of ferromagnetic layer, and the change of electroluminescent magneto-resistor state is based on BZT-BCT and Fe0.7Ga0.3Between the magnetoelectric effect of ess-strain mechanism, the present invention uses has the BZT-BCT and the Fe of big magnetostriction effect of big piezoelectric modulus0.7Ga0.3Lamination is prepared memory element and is conducive to the acquisition of electroluminescent magneto-resistance effect.Compared with traditional nonvolatile memory, magnetoelectricity memory device has the advantage that power consumption is little, read or write speed is fast, has great importance for meeting the actual demand of future memory part.Utilizing magnetron sputtering to prepare layered composite film device, technique is simple, compatible with semiconductor technology.
The invention have the advantage that this memory element have non-volatile, can keep when applied voltage polarization and magnetized state, owing to the change of resistance states can be overturn by the voltage between upper/lower electrode, need not the generation in the big magnetic field of big electric current, the advantage with low-power consumption；This memory element is capable of writing direct information data with electric field, the change utilizing magneto-resistor carries out the reading of information, this magnetoelectric composite film device at room temperature has good ferroelectricity, piezoelectricity and ferromagnetic property, is that 20V obtains maximum electric field controls magneto-resistance effect 6% at applying bias voltage.
Accompanying drawing explanation
Fig. 1 is the laminated construction schematic diagram of the magnetoelectricity memory element of embodiment 1 preparation.
Fig. 2 is the XRD figure of the magnetoelectricity memory element of embodiment 1 preparation.
Fig. 3 is the normalization hysteresis curve figure of the magnetoelectricity memory element of embodiment 1 preparation.
Fig. 4 is the piezoelectric effect butterfly curve chart of the magnetoelectricity memory element of embodiment 1 preparation.
Fig. 5 is the electroluminescent magneto-resistance effect curve chart under the different bias voltages of the magnetoelectricity memory element of embodiment 1 preparation.
Detailed description of the invention
The present invention is with Ba (Zr0.2Ti0.8)O3-(Ba0.3Ca0.7)TiO3Ceramic target and Fe0.7Ga0.3Alloy target material is raw material, uses the method for magnetron sputtering to prepare magnetoelectric composite film device.Specific embodiment is as follows:
Embodiment 1:
The magnetoelectricity memory element of a kind of ferroelectricity/ferromagnetic composite film based on magnetoelectric effect, at Pt/Ti/SiO2Being sequentially depositing ferroelectricity in/Si compound substrate and ferromagnetic thin film makes laminated construction, wherein compound substrate is respectively Si, SiO from bottom to top2, Ti and Pt hearth electrode, the ferroelectric thin film chemical structural formula with piezoelectric effect is 0.5Ba (Zr0.2Ti0.8)O3-0.5(Ba0.3Ca0.7)TiO3(BZT-BCT), thickness is 200nm, and the thin film with magnetostrictive effect is Fe0.7Ga0.3, thickness is 200nm.
The preparation method of the magnetoelectricity memory element of described ferroelectricity based on magnetoelectric effect/ferromagnetic thin film structure, wherein ferroelectric ceramic thin film utilizes rf magnetron sputtering to prepare, and ferromagnetic thin film is by Fe0.7Ga0.3Alloy target material utilizes magnetically controlled DC sputtering to prepare, and step is as follows:
1) by Pt/Ti/Si/SiO2Substrate puts into sputtering chamber together with BZT-BCT ceramic target, is evacuated to (1-2) × 10-4, then pass to pressure be 2Pa, the gaseous mixture that volume ratio is 4:3 of argon and oxygen, underlayer temperature is 500 DEG C, radio-frequency power is 60w, sputtering time is 2h, after sputtering chamber takes out under 800 DEG C and air atmosphere heat treatment 30 minutes, prepare ferroelectric ceramic thin film；
2) using the ferroelectric ceramic thin film of above-mentioned preparation as substrate and Fe0.7Ga0.3Alloy target material puts into sputtering chamber together, is evacuated to (1-2) × 10-4, then passing to the argon that pressure is 1Pa, argon flow amount is 10sccm, and radio-frequency power is 50w, sputtering time is 12min, prepares the magnetoelectricity memory element of ferroelectricity/ferromagnetic composite film after sputtering chamber takes out.
Fig. 1 is the laminated construction schematic diagram of the magnetoelectricity memory element of preparation.
Fig. 2 is the XRD figure of the magnetoelectricity memory element of preparation.In figure visible: thin film is by Perovskite Phase Ba (Zr0.2Ti0.8)O3-(Ba0.3Ca0.7)TiO3And Fe (111)0.7Ga0.3(110) two phase composition mutually.
Fig. 3 is the normalization hysteresis curve figure of the magnetoelectricity memory element of preparation.
Fig. 4 is the piezoelectric effect butterfly curve chart of the magnetoelectricity memory element of preparation.
Fig. 5 is the electroluminescent magneto-resistance effect curve chart under the different bias voltages of the magnetoelectricity memory element of preparation.In figure visible: the most not only there is ferroelectricity but also there is ferromagnetism, and there is bigger electroluminescent magneto-resistance effect.
Embodiment 2:
The magnetoelectricity memory element of a kind of ferroelectricity/ferromagnetic composite film based on magnetoelectric effect, at Pt/Ti/SiO2Being sequentially depositing ferroelectricity in/Si compound substrate and ferromagnetic thin film makes laminated construction, wherein compound substrate is respectively Si, SiO from bottom to top2, Ti and Pt hearth electrode, the ferroelectric thin film chemical structural formula with piezoelectric effect is 0.5Ba (Zr0.2Ti0.8)O3-0.5(Ba0.3Ca0.7)TiO3(BZT-BCT), thickness is 250nm, and the thin film with magnetostrictive effect is Fe0.7Ga0.3, thickness is 250nm.
The preparation method of the magnetoelectricity memory element of described ferroelectricity based on magnetoelectric effect/ferromagnetic thin film structure, wherein ferroelectric ceramic thin film utilizes rf magnetron sputtering to prepare, and ferromagnetic thin film is by Fe0.7Ga0.3Alloy target material utilizes magnetically controlled DC sputtering to prepare, and step is as follows:
1) by Pt/Ti/Si/SiO2Substrate puts into sputtering chamber together with BZT-BCT ceramic target, is evacuated to (1-2) × 10-4Then pass to pressure be 2.5Pa, the gaseous mixture that volume ratio is 4:3 of argon and oxygen, underlayer temperature is 700 DEG C, radio-frequency power is 60w, sputtering time is 2.5h, after sputtering chamber takes out under 800 DEG C and air atmosphere heat treatment 30 minutes, prepare ferroelectric ceramic thin film；
2) using the ferroelectric ceramic thin film of above-mentioned preparation as substrate and Fe0.7Ga0.3Alloy target material puts into sputtering chamber together, is evacuated to (1-2) × 10-4, then passing to the argon that pressure is 1Pa, argon flow amount is 10sccm, and radio-frequency power is 30-50w, sputtering time is 15min, prepares the magnetoelectricity memory element of ferroelectricity/ferromagnetic composite film after sputtering chamber takes out.
The testing result of the magnetoelectricity memory element of preparation is similar with embodiment 1.
Embodiment 3:
The magnetoelectricity memory element of a kind of ferroelectricity/ferromagnetic composite film based on magnetoelectric effect, at Pt/Ti/SiO2Being sequentially depositing ferroelectricity in/Si compound substrate and ferromagnetic thin film makes laminated construction, wherein compound substrate is respectively Si, SiO from bottom to top2, Ti and Pt hearth electrode, the ferroelectric thin film chemical structural formula with piezoelectric effect is 0.5Ba (Zr0.2Ti0.8)O3-0.5(Ba0.3Ca0.7)TiO3(BZT-BCT), thickness is 300nm, and the thin film with magnetostrictive effect is Fe0.7Ga0.3, thickness is 300nm.
The preparation method of the magnetoelectricity memory element of a kind of described ferroelectricity based on magnetoelectric effect/ferromagnetic thin film structure, wherein ferroelectric ceramic thin film utilizes rf magnetron sputtering to prepare, and ferromagnetic thin film is by Fe0.7Ga0.3Alloy target material utilizes magnetically controlled DC sputtering to prepare, and step is as follows:
1) by Pt/Ti/Si/SiO2Substrate puts into sputtering chamber together with BZT-BCT ceramic target, is evacuated to (1-2) × 10-4Then pass to pressure be 2Pa, the gaseous mixture that volume ratio is 3:2 of argon and oxygen, underlayer temperature is 600 DEG C, radio-frequency power is 60w, sputtering time is 3h, after sputtering chamber takes out under 800 DEG C and air atmosphere heat treatment 30 minutes, prepare ferroelectric ceramic thin film；
2) using the ferroelectric ceramic thin film of above-mentioned preparation as substrate and Fe0.7Ga0.3Alloy target material puts into sputtering chamber together, is evacuated to (1-2) × 10-4, then passing to the argon that pressure is 1Pa, argon flow amount is 10sccm, and radio-frequency power is 50w, sputtering time is 20min, prepares the magnetoelectricity memory element of ferroelectricity/ferromagnetic composite film after sputtering chamber takes out.
The testing result of the magnetoelectricity memory element of preparation is similar with embodiment 1.
Claims (2)
1. the magnetoelectricity memory element of ferroelectricity/ferromagnetic composite film based on magnetoelectric effect, it is characterised in that:
At Pt/Ti/SiO2It is sequentially depositing ferroelectricity in/Si compound substrate and ferromagnetic thin film makes laminated construction, wherein composite lining
The end, is respectively Si, SiO from bottom to top2, Ti and Pt hearth electrode, there is the ferroelectric thin film chemical constitution of piezoelectric effect
Formula is 0.5Ba (Zr0.2Ti0.8)O3-0.5(Ba0.3Ca0.7)TiO3(BZT-BCT), thickness is 200-400nm, has magnetic
The thin film causing flex effect is Fe0.7Ga0.3, thickness is 200-400nm.
2. the magnetoelectricity storage of ferroelectricity based on magnetoelectric effect/ferromagnetic thin film structure as claimed in claim 1 is first
The preparation method of part, it is characterised in that: wherein ferroelectric ceramic thin film utilizes rf magnetron sputtering to prepare, ferromagnetic thin
Film is by Fe0.7Ga0.3Alloy target material utilizes magnetically controlled DC sputtering to prepare, and step is as follows:
1) by Pt/Ti/Si/SiO2Substrate puts into sputtering chamber together with BZT-BCT ceramic target, is evacuated to
(1-2)×10-4, then pass to pressure be 2-2.5Pa, the mixing that volume ratio is 12:8-9 of argon and oxygen
Gas, underlayer temperature is 500-700 DEG C, radio-frequency power is 50-60w, sputtering time is 1.5-4h, from sputtering
Room take out after under 800 DEG C and air atmosphere heat treatment 30 minutes, prepare ferroelectric ceramic thin film；
2) using the ferroelectric ceramic thin film of above-mentioned preparation as substrate and Fe0.7Ga0.3Alloy target material is put into together and is spattered
Penetrate room, be evacuated to (1-2) × 10-4, then passing to the argon that pressure is 1-1.5Pa, argon flow amount is
10sccm, radio-frequency power is 30-50w, sputtering time is 10-30min, prepares ferrum after sputtering chamber takes out
The magnetoelectricity memory element of electricity/ferromagnetic composite film.
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Cited By (13)
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| CN106783173A (en) * | 2016-11-23 | 2017-05-31 | 东莞理工学院 | A kind of new all-transparent BZT film varactors and preparation method thereof |
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| CN107488833A (en) * | 2017-08-08 | 2017-12-19 | 电子科技大学 | A kind of new Magnetoelectric film material and preparation method thereof |
| WO2018068266A1 (en) * | 2016-10-13 | 2018-04-19 | Qualcomm Incorporated | Ferroelectric resistive memory elements using schottky junctions |
| CN108411256A (en) * | 2018-03-28 | 2018-08-17 | 天津大学 | A kind of preparation method of BTS/BST/BZT multilayered structures dielectric tuning film |
| CN108531867A (en) * | 2018-03-28 | 2018-09-14 | 天津大学 | A kind of preparation method of flexibility BTS/BZT/BTS plural layers varactors |
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| CN109904307A (en) * | 2019-02-01 | 2019-06-18 | 电子科技大学 | A kind of voltage-controlled storage unit and its implementation based on anisotropic magnetoresistance |
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