CN109216401A - A kind of two-dimension flexible magnetic storage array and preparation method thereof - Google Patents
A kind of two-dimension flexible magnetic storage array and preparation method thereof Download PDFInfo
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- CN109216401A CN109216401A CN201810803231.4A CN201810803231A CN109216401A CN 109216401 A CN109216401 A CN 109216401A CN 201810803231 A CN201810803231 A CN 201810803231A CN 109216401 A CN109216401 A CN 109216401A
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- H10B—ELECTRONIC MEMORY DEVICES
- H10B61/00—Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices
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- H10B—ELECTRONIC MEMORY DEVICES
- H10B61/00—Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices
- H10B61/10—Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices comprising components having two electrodes, e.g. diodes or MIM elements
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Abstract
The invention discloses a kind of two-dimension flexible magnetic storage arrays and preparation method thereof, it uses sandwich structure, design is reasonable, by the temperature for accurately controlling growth source, ratio, growth time come grow vacancy doping III-VI race chalcogenide layer with reach electricity regulation realizability, to realize storage and the writing function of each magnetic cell device and two-dimension flexible magnetic storage array, its magnetic moment modification scope is 0~1 μ B, it can be in liquid nitrogen cryogenics to room temperature, it is used in air environment or vacuum environment, magnetic storage function-stable, in conjunction with flexible substrates, it has wide range of applications, strong applicability.
Description
Technical field
The invention belongs to magnetic storages and Magnetographic Technology field, and in particular to a kind of two-dimension flexible magnetic storage array and its system
Preparation Method.
Background technique
Since the nineties in last century, electronics and information industry is made remarkable achievements.Present information memory technology
So that information is stored densification, but also combine information storage with quick-searching, it has also become information work development
Basis, in the important people's livelihood such as the storage of industrial automation, embedding assembly, network and data, automobile and aerospace, national defence neck
Domain has huge application value.Wherein magnetic storage technology has that storing data is non-volatile, the service life is long, low-power consumption, anti-radiation
Many advantages, such as, it has also become the pillar of present information memory technology.
Demand with people to carry-on smart machine, wearable electronic and biomedical devices is increasingly vigorous, flexible magnetic
The breakthrough of memory technology battery energy storage technology will become its key further developed.Existing magnetic memory chip in the application by
To considerable restraint, the influence using temperature, environment to magnetic function is often shown, applying so as to cause magnetic memory chip
The scope of application in journey is small, functional poor, unstable etc..
2016, high performance magnetic storage chip was transplanted to one piece of flexiplast surface first by international team, and lossless
Its performance, flexible " intelligent plastics " chip of obtained transparent membrane have excellent data storage and processing ability, are expected to
The key element for designing and developing as flexible light weight equipment.However, this technology is mainly using sides such as removing, transfers
Method can not still be detached from traditional magnetic storage chip preparation method, and technique is complicated, at high cost.Although scientist is in difference
Multinomial research has been carried out on storage chip and material, but directly constructs and apply on a flexible substrate the side of high-performance storage chip
Formula still faces huge challenge.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of two-dimension flexible magnetic storage array and
Preparation method solves the problems, such as the preparation and application of magnetic memory materials in above-mentioned background technique.
The technical solution adopted by the present invention to solve the technical problems is: a kind of two-dimension flexible magnetic storage array is provided,
Including flexible substrates and several magnetic cell devices, the magnetic cell device array is arranged in flexible substrates；
The magnetic cell device include the first conductive electrode being cascading from bottom to top, sandwich structure and
Second conductive electrode；The sandwich structure is followed successively by the III-VI race chalcogenide of the first BN layers/vacancy doping from bottom to top
BN layers of layer/2nd, the chemical formula of III-VI race chalcogenide are MX, and wherein M is at least one of Ga, In, X S, Se
At least one of, the vacancy is the M atom defect in III-VI race chalcogenide；The magnetic cell device passes through the
One conductive electrode and the second conductive electrode applyVertical electric field, adjust the III-VI race of vacancy doping
The magnetic property of chalcogenide layer changes between ferromagnetic half-metal non-magnetic, realizes magnetic storage function, the magnetic cell
The magnetic moment modification scope of device is 0~1 μ B.
In a preferred embodiment of the present invention, the described first BN layers and the 2nd BN layers of thickness is 1~3 molecular layer.
In a preferred embodiment of the present invention, III-VI race chalcogenide layer with a thickness of monolayer to being less than
100nm。
In a preferred embodiment of the present invention, first conductive electrode and the second conductive electrode are non-magnetic material, packet
Include Au, Ti/Au.
In a preferred embodiment of the present invention, the flexible substrates include PET, Kapton.
The present invention also provides the preparation methods of above-mentioned two-dimension flexible magnetic storage array, include the following steps:
1) the first conductive electrode array and lead are prepared using electronic beam photetching process on a flexible substrate；
2) the BN two-dimensional material being grown on copper foil is transferred to the first conductive circuit electrode surface using transfer techniques, repeats to turn
Moving past journey makes BN two-dimensional material with a thickness of 1~3 molecular layer, BN layers of composition the first；
3) two-dimensional material of III-VI race chalcogenide is grown in the first BN layer surface using molecular beam epitaxial method, it is described
The chemical formula of III-VI race chalcogenide is MX, and the vacancy M is formed in situ by the ratio in the control source M and the source X during the growth process,
Constitute the III-VI race chalcogenide layer of vacancy doping；
4) the BN two-dimensional material being grown on copper foil is transferred to vacancy doping using poly- 2) the described transfer techniques of step
III-VI race chalcogenide layer surface, repetitive displacement process make BN two-dimensional material with a thickness of 1~3 molecular layer, BN layers of composition the 2nd；
5) using walk poly- 1) the described electronic beam photetching process prepared in the 2nd BN layer surface the second conductive electrode array and
Lead；
6) model is applied to the III-VI race chalcogenide layer that vacancy is adulterated by the first conductive electrode and the second conductive electrode
Enclose forVertical voltage, complete preparation.
In a preferred embodiment of the present invention, M is at least one of Ga, In, X S, Se in the step 3) chemical formula
At least one of, the ratio in the source M and the source X is concentration than 7~9:1.
In a preferred embodiment of the present invention, walk it is poly- 1) in, the electronic beam photetching process specific steps are as follows: in flexible base
It spin coating PMMA photoresist and is dried on bottom；Then exposure mask and electron beam lithography are carried out, PMMA photoresist is exposed, with development after exposure
Liquid development, fixing drying, the electrode pattern designed；Then conductive electrode metal is evaporated, uses acetone stripping photolithography after the completion
Glue forms the first conductive electrode array, then the welding lead on the first conductive electrode.
In a preferred embodiment of the present invention, walk it is poly- 2) in, the transfer techniques specific steps are as follows: on being grown on copper foil
Large area BN two-dimensional material one layer of PMMA of surface spin coating, after PMMA solidification after, use FeCl3Solution dissolves copper foil, will have
The PMMA of BN two-dimensional material is transferred to the first conductive electrode array surface, is soaked in acetone to PMMA and is dissolved later.
In a preferred embodiment of the present invention, step is poly- 3), the molecular beam epitaxy specific steps are as follows: will be prepared for first and lead
Electrode and the first BN layers of flexible substrates are placed in the vacuum chamber of molecular beam epitaxy system, intracavitary M, X for placing high-purity
Growth source, with mechanical pump, molecular pump by air pressure 10 in growth chamber-7Torr hereinafter, heat the source M and the source X to each spontaneous evaporation temperature respectively
Degree, wherein the ratio of the source M and the source X concentration is 7~9:1 to form the vacancy M；It is room temperature that growth course, which keeps flexible substrates temperature,.
The technical program compared with the background art, it has the following advantages:
1. magnetic storage array of the present invention uses sandwich structure, design is rationally, conductive by the first conductive electrode and second
Electrode applies vertical voltage, the III-VI race sulphur of regulation vacancy doping to the III-VI race chalcogenide two-dimensional material that vacancy is adulterated
Belong to the magnetism and Half-metallic of compound two-dimensional material, to realize each magnetic cell device and two-dimension flexible magnetic storage array
Storage and writing function, magnetic moment modification scope are 0~1 μ B, can be in liquid nitrogen cryogenics to room temperature, air environment or vacuum environment
Middle use, magnetic storage function-stable have wide range of applications in conjunction with flexible substrates, strong applicability.
2. preparation method of the invention is mixed by accurately controlling the temperature, ratio, growth time in growth source to grow vacancy
Miscellaneous III-VI race chalcogenide two-dimensional material effectively solves flexible magnetic memory chip system to reach the realizability that electricity regulates and controls
The problem of making complex process.
Detailed description of the invention
Fig. 1 two-dimension flexible magnetic storage array structure schematic diagram.
Fig. 2 magnetic memory cell structure schematic diagram.
Fig. 3 is the monolayer GaSe two-dimensional material density of electronic states figure of the vacancy 2.8%Ga doping in embodiment 1, wherein a
Voltage is that 0, b voltage isC voltage is
Fig. 4 is that the magnetic moment of the monolayer GaSe two-dimensional material of the vacancy 2.8%Ga doping in embodiment 1 becomes with electric field change
Gesture figure.
Specific embodiment
The contents of the present invention are illustrated with reference to the accompanying drawings and examples:
Embodiment 1
Fig. 1, a kind of two-dimension flexible magnetic storage array of the present embodiment, including PET flexible substrates 6 and several magnetic is please referred to deposit
Storage unit device, the magnetic cell device array are arranged in flexible substrates 6；
Please refer to Fig. 2, the magnetic cell device include the first conductive electrode 1 being cascading from bottom to top,
Sandwich structure and the second conductive electrode 5；The sandwich structure is followed successively by the doping of 2/ vacancy of the first BN layer from bottom to top
The 2nd BN layer 4 of III-VI race chalcogenide layer 3/, the chemical formula of III-VI race chalcogenide are MX, and M is in the present embodiment
Ga, X Se, the vacancy are the Ga atom defect in monolayer GaSe two-dimensional material；The first BN layer 2 and the 2nd BN layers
4 thickness is 3 molecular layers, the monolayer GaSe two-dimensional material comprising Ga atom vacancy with a thickness of monolayer, vacancy
Concentration is 2.8%, and 5 material of the first and second conductive electrodes is Au/Ti (70nm/10nm).
The magnetic cell device is applied by the first conductive electrode 1 and the second conductive electrode 5Hang down
Straight electric field adjusts the magnetic property of the III-VI race chalcogenide layer 3 of vacancy doping non-magnetic between ferromagnetic half-metal
Transformation, realizes magnetic storage function, and the magnetic moment modification scope of the magnetic cell device is 0~1 μ B.
The preparation method of above-mentioned two-dimension flexible magnetic storage array, includes the following steps:
0) clean PET flexible substrates 6 are obtained by chemical cleaning (being cleaned by ultrasonic using acetone, ethyl alcohol, deionized water)；
1) 1 array of the first conductive electrode and lead are prepared in flexible substrates 6 using electronic beam photetching process；
Specific steps are as follows: the electronic beam photetching process specific steps are as follows: spin coating PMMA photoresist is simultaneously in flexible substrates 6
Drying；Then exposure mask and electron beam lithography are carried out, PMMA photoresist is exposed, with developing liquid developing, fixing drying after exposure, is obtained
The electrode pattern of design；Then Au/Ti (70nm/10nm) metal is evaporated, uses acetone stripping photoresist after the completion, first is formed and leads
1 array of electrode, the then welding lead on 1 electrode of the first conductive electrode；
2) the BN two-dimensional material being grown on copper foil is transferred to 1 surface of the first conductive electrode using transfer techniques, repeated
Transfer process makes BN two-dimensional material with a thickness of 1~3 molecular layer, constitutes the first BN layer 2；
Specific steps are as follows: the large area monolayer BN two-dimensional material for taking a small pieces to be grown on copper foil, in monolayer
One layer of PMMA of BN two-dimensional material spin coating；After PMMA solidification, FeCl is used3Solution dissolves copper foil；BN two-dimensional material will be had
PMMA is transferred to the first BN two-dimensional material surface；The sample that displaced BN two-dimensional material is soaked in a few hours in acetone, with thorough
Dissolve PMMA in bottom；3 molecular layer BN two-dimensional material of repetitive displacement.It is soaked in acetone to PMMA and is dissolved later；
3) two-dimensional material using molecular beam epitaxial method in 2 surface of the first BN layer growth III-VI race chalcogenide, institute
The chemical formula for stating III-VI race chalcogenide is MX, and M sky is formed in situ by the ratio in the control source M and the source X during the growth process
Position constitutes the III-VI race chalcogenide layer 3 of vacancy doping；In the present embodiment, in chemical formula M be Ga, X Se, the source M and
The ratio in the source X is concentration ratio 8:1；
Specific steps are as follows: the substrate 6 for being prepared for the first conductive electrode 1 and the first BN layer 2 is placed in molecular beam epitaxy system
In the vacuum chamber of system, growth chamber air pressure is first evacuated to 10 with mechanical pump-3Torr is evacuated to 10 hereinafter, being then turned on molecular pump-6torr
Air pressure is evacuated to 10 hereinafter, opening titanium pump-9torr；Maintenance 6 temperature of substrate is room temperature, by 99.999% high-purity source Ga and the source Se
200 DEG C and 400 DEG C are separately heated to, so that the evaporation rate in the source Ga and the source Se is 8:1, to control the concentration in the source Ga and the source Se
Ratio is 8:1；After growth time is 20min, sample is taken out, and be placed in nitrogen environment to prevent block；
4) the BN two-dimensional material being grown on copper foil is transferred to vacancy doping using poly- 2) the described transfer techniques of step
3 surface of III-VI race chalcogenide layer, repetitive displacement process make BN two-dimensional material with a thickness of 3 molecular layers, constitute the 2nd BN layer 4；
5) 5 array of the second conductive electrode is prepared on 4 surface of the 2nd BN layer using poly- 1) the described electronic beam photetching process of step
And lead；
6) the III-VI race chalcogenide layer 3 that vacancy is adulterated is applied by the first conductive electrode 1 and the second conductive electrode 5
Vertical voltage controls the magnetism of each magnetic cell device, realizes storage and the writing function of two-dimension flexible magnetic storage array.
It is predicted through theoretical calculation, the monolayer GaSe two-dimensional material spin polarizability of the vacancy 2.8%Ga doping is
100%, it is shown as Half-metallic (as shown in Figure 3a), magnetic moment size is 1 μ B (as shown in Figure 4), when application is less than
Vertical voltage when, the vacancy 2.8%Ga doping monolayer GaSe two-dimensional material spin polarizability be still 100%, magnetic moment 1
μ B, display are still magnetic (as shown in Figure 3b), when being applied more thanVertical voltage when, the vacancy 2.8%Ga doping list
Molecular layer GaSe two-dimensional material spin polarizability is changed into rapidly 0%, and magnetic moment is 0 μ B, is shown as non magnetic (as shown in Figure 3c),
Thus it proves, by accurately controlling vertical voltage intensity, the III-VI race chalcogenide two-dimensional material of controllable vacancy doping
Magnetic and Half-metallic, to realize storage and the writing function of magnetic cell device and two-dimension flexible magnetic storage array.
Skilled person will appreciate that when technical parameter of the invention changes in the following range, it is contemplated that obtain
Same as the previously described embodiments or similar technical effect:
The chemical formula of III-VI race chalcogenide is MX, and wherein M is at least one of Ga, In, in X S, Se
At least one, the vacancy are the M atom defect in III-VI race chalcogenide.
III-VI race chalcogenide layer 3 with a thickness of monolayer to be less than 100nm.
First conductive electrode 1 and the second conductive electrode 5 are non-magnetic material, including Au, Ti/Au.
The flexible substrates 6 include PET, Kapton.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (10)
1. a kind of two-dimension flexible magnetic storage array, it is characterised in that: described including flexible substrates and several magnetic cell devices
Magnetic cell device array is arranged in flexible substrates；
The magnetic cell device includes the first conductive electrode being cascading from bottom to top, sandwich structure and second
Conductive electrode；The sandwich structure is followed successively by III-VI race chalcogenide layer/the of the first BN layers/vacancy doping from bottom to top
Two BN layers, the chemical formula of III-VI race chalcogenide is MX, and wherein M is at least one of Ga, In, in X S, Se
At least one, the vacancy are the M atom defect in III-VI race chalcogenide；The magnetic cell device is led by first
Electrode and the second conductive electrode applyVertical electric field, adjust the III-VI race chalcogen of vacancy doping
The magnetic property of compound layer changes between ferromagnetic half-metal non-magnetic, realizes magnetic storage function, the magnetic cell device
Magnetic moment modification scope be 0~1 μ B.
2. a kind of two-dimension flexible magnetic storage array according to claim 1, it is characterised in that: the described first BN layers and second
BN layers of thickness is 1~3 molecular layer.
3. a kind of two-dimension flexible magnetic storage array according to claim 1, it is characterised in that: the III-VI race is chalcogenide
Nitride layer with a thickness of monolayer to be less than 100nm.
4. a kind of two-dimension flexible magnetic storage array according to claim 1, it is characterised in that: first conductive electrode and
Second conductive electrode is non-magnetic material, including Au, Ti/Au.
5. a kind of two-dimension flexible magnetic storage array according to claim 1, it is characterised in that: the flexible substrates include
PET, Kapton.
6. a kind of preparation method of two-dimension flexible magnetic storage array as described in claim any one of 1-5, which is characterized in that including
Following steps:
1) the first conductive electrode array and lead are prepared using electronic beam photetching process on a flexible substrate；
2) the BN two-dimensional material being grown on copper foil is transferred to the first conductive circuit electrode surface, repetitive displacement mistake using transfer techniques
Journey makes BN two-dimensional material with a thickness of 1~3 molecular layer, BN layers of composition the first；
3) two-dimensional material using molecular beam epitaxial method in the first BN layer surface growth III-VI race chalcogenide, the III-
The chemical formula of VI race chalcogenide is MX, and the vacancy M is formed in situ by the ratio in the control source M and the source X during the growth process, is constituted
The III-VI race chalcogenide layer of vacancy doping；
4) the BN two-dimensional material being grown on copper foil is transferred to the III-VI of vacancy doping using poly- 2) the described transfer techniques of step
Race's chalcogenide layer surface, repetitive displacement process make BN two-dimensional material with a thickness of 1~3 molecular layer, BN layers of composition the 2nd；
5) the second conductive electrode array and lead are prepared in the 2nd BN layer surface using poly- 1) the described electronic beam photetching process of step；
6) applying range to the III-VI race chalcogenide layer that vacancy is adulterated by the first conductive electrode and the second conductive electrode isVertical voltage, complete preparation.
7. preparation method according to claim 6, it is characterised in that: in the step 3) chemical formula M be Ga, In in extremely
The ratio in few one kind, at least one of X S, Se, the source M and the source X is concentration than 7~9:1.
8. preparation method according to claim 6, it is characterised in that: step it is poly- 1) in, the electronic beam photetching process is specific
Step are as follows: spin coating PMMA photoresist and dry on a flexible substrate；Then exposure mask and electron beam lithography are carried out, PMMA photoetching is exposed
Glue, with developing liquid developing, fixing drying after exposure, the electrode pattern designed；Then conductive electrode metal is evaporated, after the completion
With acetone stripping photoresist, the first conductive electrode array is formed, then the welding lead on the first conductive electrode.
9. preparation method according to claim 6, it is characterised in that: step it is poly- 2) in, the transfer techniques specific steps are as follows:
FeCl is used after PMMA solidification in the large area BN two-dimensional material one layer of PMMA of surface spin coating being grown on copper foil3Solution is by copper
PMMA with BN two-dimensional material is transferred to the first conductive electrode array surface, is soaked in acetone later by foil dissolution
It is dissolved to PMMA.
10. preparation method according to claim 6, it is characterised in that: step is poly- 3), the molecular beam epitaxy specific steps
Are as follows: the first conductive electrode will be prepared for and the first BN layers of flexible substrates are placed in the vacuum chamber of molecular beam epitaxy system, chamber
Interior M, X for placing high-purity grows source, with mechanical pump, molecular pump by air pressure 10 in growth chamber-7Torr hereinafter, heat the source M respectively
With the source X to respective evaporating temperature, wherein the ratio of the source M and the source X concentration is 7~9:1 to form the vacancy M；Growth course keeps soft
Property base reservoir temperature be room temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531707A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院物理研究所 | Magnetic tunnel junction |
| US20160225424A1 (en) * | 2013-09-24 | 2016-08-04 | National University Of Singapore | Spin orbit and spin transfer torque-based spintronics devices |
| WO2018064143A1 (en) * | 2016-09-27 | 2018-04-05 | Board Of Regents, The University Of Texas System | Bacterial cellulose paper-based flexible electronics employing nanocrystals |
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2018
- 2018-07-20 CN CN201810803231.4A patent/CN109216401B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531707A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院物理研究所 | Magnetic tunnel junction |
| US20160225424A1 (en) * | 2013-09-24 | 2016-08-04 | National University Of Singapore | Spin orbit and spin transfer torque-based spintronics devices |
| WO2018064143A1 (en) * | 2016-09-27 | 2018-04-05 | Board Of Regents, The University Of Texas System | Bacterial cellulose paper-based flexible electronics employing nanocrystals |
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