CN106876584A - A kind of Graphene flexibility resistance-variable storing device containing black phosphorus alkene and preparation method thereof - Google Patents
A kind of Graphene flexibility resistance-variable storing device containing black phosphorus alkene and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- -1 black phosphorus alkene Chemical class 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000010408 film Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 40
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000011247 coating layer Substances 0.000 claims abstract description 26
- 239000010409 thin film Substances 0.000 claims abstract description 26
- 239000002346 layers by function Substances 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 238000012546 transfer Methods 0.000 claims abstract description 9
- 238000000059 patterning Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 238000011161 development Methods 0.000 claims description 14
- 238000004528 spin coating Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 235000009161 Espostoa lanata Nutrition 0.000 claims description 8
- 240000001624 Espostoa lanata Species 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001652 electrophoretic deposition Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 239000002096 quantum dot Substances 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 6
- 230000001066 destructive effect Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000316887 Saissetia oleae Species 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/884—Switching materials based on at least one element of group IIIA, IVA or VA, e.g. elemental or compound semiconductors
- H10N70/8845—Carbon or carbides
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- Carbon And Carbon Compounds (AREA)
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Abstract
The present invention provides a kind of Graphene flexibility resistance-variable storing device containing black phosphorus alkene and preparation method thereof, and the preparation method of the resistance-variable storing device is：Cleaning Al2O3Substrate；Ni/Au laminated films are deposited using electron beam evaporation technique, bottom electrode layer is obtained；The Graphene composite thin film material containing black phosphorus alkene is shifted on bottom electrode layer using transfer method, resistive functional layer is obtained；Top electrode figure is formed by photoresist patterning processes, the film of Ag, Cu or Ni is deposited using electron beam evaporation technique, form top electrode layer, remove photoresist, peeled off, form memory cell；Coating layer pattern is formed by photoresist patterning processes, using technique for atomic layer deposition in depositing Al2O3Film, forms coating layer, removes photoresist, peels off, and forms the Graphene flexibility resistance-variable storing device containing black phosphorus alkene.The simple structure of resistance-variable storing device prepared by the present invention, erasable speed is fast, and operating voltage is small, non-Destructive readout, can be used to be made large area and flexible device.
Description
Technical field
The invention belongs to storage material technical field, and in particular to a kind of Graphene flexibility resistance-change memory containing black phosphorus alkene
Device and preparation method thereof.
Background technology
Two dimensional crystal is the flat crystal of the nano thickness stacked by basic unit monoatomic layer, with unique electricity,
The characteristic such as optics and magnetics, and have the structural advantage of itself uniqueness, common two-dimensional material has Graphene, silene, two sulphur
Change molybdenum and black phosphorus alkene etc..
Black squama is a kind of waveform stratiform structure crystal of similar graphite, and atom interlayer is combined by Van der Waals force, it is easy to quilt
The nano flake of individual layer or few layer is peeled off into, in monoatomic layer, each phosphorus atoms forms tool with three adjacent phosphorus atoms
There is the pleated honeycomb of covalent bond.Black phosphorus alkene is natural P-type semiconductor, is to jump vertically when valence-band electrons transit to conduction band
Move, electron waves mistake is constant, with direct band gap, and with obvious anisotropy, therefore black phosphorus alkene has electronics higher
Mobility, and research represents that, when two-dimentional black squama material thickness is less than 7.5nm, with good element performance of handoffs, individual layer is black
Phosphorus alkene electron mobility is up to 104cm2/ Vs, thickness is the multilayer black phosphorus alkene electron mobility of 10nm up to 103cm2/V·s。
The preparation method of current black phosphorus alkene includes mechanical stripping method, liquid phase stripping method and chemical synthesis, wherein machinery stripping
It is to apply mechanical force so as to the method for separating its thin layer by stratified material from method, the method is simple, but efficiency
Low, crystalline size controlling is poor；Liquid phase stripping method is that stratified material is placed into suitable organic solvent, is shelled using ultrasonic wave
The method for separating out crystal microchip, the method is simple and easy to apply, and the thickness of thin slice is controllable, can mass production；Chemical synthesis is mesh
Preceding main research direction, compared with mechanical stripping method and liquid phase stripping method, product stabilised quality is good, low cost, efficiency high.In
A kind of stability multilayer black phosphorus alkene and preparation method disclosed in state patent CN 106348263A, during black scale added into ethanol, warp
After high-speed stirred, ultrasonic wave dispersion and ultrasonic cavitation make black exfoliation from into black phosphorus alkene under nitrogen atmosphere, after filtration drying, with
The stabilizers such as the chelating agents such as ethylenediamine tetra-acetic acid, acyl chlorides mix, under nitrogen atmosphere cryogrinding, add the sulphur simple substance envelope of melting
Dress, obtains stability multilayer black phosphorus alkene.With the understanding to black phosphorus alkene material, black phosphorus alkene gradually scene effect transistor,
The aspects such as opto-electronic device, gas sensor and solar cell have been applied, but the application in terms of memory is simultaneously few
See.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of Graphene flexibility resistance-variable storing device containing black phosphorus alkene and its system
Preparation Method, is resistive functional layer, the Al by the Graphene composite thin film material containing black phosphorus alkene2O3Material is substrate, and Ni/Au is multiple
Conjunction film is bottom electrode layer, and the film of Ag, Cu or Ni is top electrode layer, Al2O3Material is coating layer, prepares read-write speed
Degree is fast, the flexible resistance-variable storing device of voltage stabilization.
In order to solve the above technical problems, the technical scheme is that：
A kind of Graphene flexibility resistance-variable storing device containing black phosphorus alkene, the Graphene flexibility resistance-variable storing device containing black phosphorus alkene
From bottom to up successively include substrate, bottom electrode layer, resistive functional layer, top electrode layer and coating layer, the resistive functional layer be containing
The Graphene composite thin film material of black phosphorus alkene, the substrate is Al2O3Material, the bottom electrode layer is Ni/Au laminated films, institute
The film that top electrode layer is Ag, Cu or Ni is stated, the coating layer is Al2O3Material.
Used as the preferred of above-mentioned technical proposal, black phosphorus alkene is with quantum in the Graphene composite thin film material containing black phosphorus alkene
The form of point or nanometer sheet is present.
The present invention also provides a kind of Graphene flexibility resistance-variable storing device of preparation method containing black phosphorus alkene, including following step
Suddenly：
(1) Al is cleaned2O3Substrate；
(2) Ni/Au laminated films are deposited on substrate prepared by step (1) using electron beam evaporation technique, obtains electricity on earth
Pole layer；
(3) the graphene composite film material containing black phosphorus alkene is shifted on bottom electrode layer prepared by step (2) using transfer method
Material, obtains resistive functional layer；
(4) top electrode figure is formed by photoresist patterning processes, is prepared in step (3) using electron beam evaporation technique
The film of Ag, Cu or Ni is deposited in resistive functional layer, top electrode layer is formed, photoresist is removed, peeled off, form memory cell；
(5) coating layer pattern is formed by photoresist patterning processes, is prepared in step (4) using technique for atomic layer deposition
Depositing Al in top electrode layer2O3Film, forms coating layer, removes photoresist, peels off, and forms the flexible resistance of the Graphene containing black phosphorus alkene
Transition storage.
As the preferred of above-mentioned technical proposal, in the step (1), Al is cleaned2O3The method of substrate is：By Al2O3Substrate
Surface ethanol cotton balls wiped clean, is 3 in volume ratio:Boiled in 1 sulfuric acid and the mixed solution of phosphoric acid, then respectively with ethanol and
Deionized water rinsing, nitrogen drying.
Used as the preferred of above-mentioned technical proposal, in the step (2), the thickness of bottom electrode layer is 5-500nm, preferably
20-80nm, more preferably 80nm.
As the preferred of above-mentioned technical proposal, in the step (3), the system of the Graphene composite thin film material containing black phosphorus alkene
Preparation Method is：Black phosphorus alkene quantum dot or black phosphorus alkene nanometer sheet are added in the dispersion in organic solvent containing graphene oxide,
Water bath sonicator is mixed to form dispersion liquid, using the method for electrophoretic deposition, the graphene oxide film containing black phosphorus alkene is obtained, in nitrogen
High temperature reduction obtains the Graphene composite thin film material containing black phosphorus alkene under atmosphere.
As the preferred of above-mentioned technical proposal, in the step (3), the Graphene composite thin film material containing black phosphorus alkene is moved
Thickness is 0.5-100nm, preferably 5-50nm, more preferably 7.5nm.
Used as the preferred of above-mentioned technical proposal, in the step (4) or (5), photoresist patterning processes are to use spin coating
Mode deposit photoresist, then by exposure, development form figure.
Used as the preferred of above-mentioned technical proposal, in the step (4), top electrode layer thickness is 5-500nm, preferably 20-
80nm, more preferably 50nm.
Used as the preferred of above-mentioned technical proposal, in the step (5), coating layer thickness is 5-500nm, preferably 20-
80nm, more preferably 50nm.
Compared with prior art, the invention has the advantages that：
(1) the resistive functional layer in the flexibility resistance-variable storing device of the Graphene containing black phosphorus alkene that prepared by the present invention is alkene containing black phosphorus
Graphene composite thin film material, Graphene have specific surface area very high, black phosphorus alkene have migration velocity very high, by black phosphorus
Both alkene and Graphene combine, and form the composite film material with both excellent physical characteristics.
(2) the flexibility resistance variation memory structure of the Graphene containing black phosphorus alkene that prepared by the present invention is simple, and rate of transformation is fast, operation
Voltage is small and stabilization, non-destructive read, repeatability is high and flexible, and size can realize large area, can be used to make flexible
During large area electron, suitable application area is extensive.
Brief description of the drawings
Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the part of the application, not
Inappropriate limitation of the present invention is constituted, in the accompanying drawings：
Accompanying drawing 1 is the black phosphorus alkenyl resistance variation memory structure schematic diagram of electromagnetism interference.
Wherein, 1, substrate 2, bottom electrode layer 3, resistive functional layer 4, top electrode layer 5, coating layer
Specific embodiment
Describe the present invention in detail below in conjunction with specific embodiment, herein illustrative examples of the invention and explanation
It is for explaining the present invention but not as a limitation of the invention.
Embodiment 1：
(1) Al is cleaned2O3Substrate：By Al2O3Substrate surface ethanol cotton balls wiped clean, is 3 in volume ratio:1 sulfuric acid with
Boiled in the mixed solution of phosphoric acid, then use ethanol and deionized water rinsing respectively, nitrogen drying.
(2) it is the Ni/Au laminated films of 80nm to use electron beam evaporation technique deposit thickness on substrate, obtains hearth electrode
Layer.
(3) black phosphorus alkene quantum dot is added in the dispersion in organic solvent containing graphene oxide, water bath sonicator mixing shape
Into dispersion liquid, using the method for electrophoretic deposition, the graphene oxide film containing black phosphorus alkene is obtained, under nitrogen atmosphere high temperature reduction
The Graphene composite thin film material containing black phosphorus alkene is obtained, it is 7.5nm containing black to use transfer method that thickness is shifted on bottom electrode layer
The Graphene composite thin film material of phosphorus alkene, obtains resistive functional layer.
(4) photoresist is deposited by the way of spin coating, top electrode figure is then formed by exposure, development, using electronics
Beam evaporation technology deposit thickness in resistive functional layer is the Ag films of 50nm, forms top electrode layer, removes photoresist, is peeled off,
Form memory cell.
(5) photoresist is deposited by the way of spin coating, coating layer pattern is then formed by exposure, development, using atom
Layer deposition techniques deposit thickness in top electrode layer is the Al of 50nm2O3Film, forms coating layer, removes photoresist, peels off, shape
Into the Graphene flexibility resistance-variable storing device containing black phosphorus alkene.
Embodiment 2：
(1) Al is cleaned2O3Substrate：By Al2O3Substrate surface ethanol cotton balls wiped clean, is 3 in volume ratio:1 sulfuric acid with
Boiled in the mixed solution of phosphoric acid, then use ethanol and deionized water rinsing respectively, nitrogen drying.
(2) it is the Ni/Au laminated films of 5nm to use electron beam evaporation technique deposit thickness on substrate, obtains hearth electrode
Layer.
(3) black phosphorus alkene quantum dot is added in the dispersion in organic solvent containing graphene oxide, water bath sonicator mixing shape
Into dispersion liquid, using the method for electrophoretic deposition, the graphene oxide film containing black phosphorus alkene is obtained, under nitrogen atmosphere high temperature reduction
The Graphene composite thin film material containing black phosphorus alkene is obtained, it is 0.5nm containing black to use transfer method that thickness is shifted on bottom electrode layer
The Graphene composite thin film material of phosphorus alkene, obtains resistive functional layer.
(4) photoresist is deposited by the way of spin coating, top electrode figure is then formed by exposure, development, using electronics
Beam evaporation technology deposit thickness in resistive functional layer is the Ni films of 5nm, forms top electrode layer, removes photoresist, is peeled off, shape
Into memory cell.
(5) photoresist is deposited by the way of spin coating, coating layer pattern is then formed by exposure, development, using atom
Layer deposition techniques deposit thickness in top electrode layer is the Al of 5nm2O3Film, forms coating layer, removes photoresist, peels off, and is formed
Graphene flexibility resistance-variable storing device containing black phosphorus alkene.
Embodiment 3：
(1) Al is cleaned2O3Substrate：By Al2O3Substrate surface ethanol cotton balls wiped clean, is 3 in volume ratio:1 sulfuric acid with
Boiled in the mixed solution of phosphoric acid, then use ethanol and deionized water rinsing respectively, nitrogen drying.
(2) it is the Ni/Au laminated films of 20nm to use electron beam evaporation technique deposit thickness on substrate, obtains hearth electrode
Layer.
(3) black phosphorus alkene nanometer sheet is added in the dispersion in organic solvent containing graphene oxide, water bath sonicator mixing shape
Into dispersion liquid, using the method for electrophoretic deposition, the graphene oxide film containing black phosphorus alkene is obtained, under nitrogen atmosphere high temperature reduction
The Graphene composite thin film material containing black phosphorus alkene is obtained, it is 5nm containing black phosphorus to use transfer method that thickness is shifted on bottom electrode layer
The Graphene composite thin film material of alkene, obtains resistive functional layer.
(4) photoresist is deposited by the way of spin coating, top electrode figure is then formed by exposure, development, using electronics
Beam evaporation technology deposit thickness in resistive functional layer is the Cu films of 20nm, forms top electrode layer, removes photoresist, is peeled off,
Form memory cell.
(5) photoresist is deposited by the way of spin coating, coating layer pattern is then formed by exposure, development, using atom
Layer deposition techniques deposit thickness in top electrode layer is the Al of 20nm2O3Film, forms coating layer, removes photoresist, peels off, shape
Into the Graphene flexibility resistance-variable storing device containing black phosphorus alkene.
Embodiment 4：
(1) Al is cleaned2O3Substrate：By Al2O3Substrate surface ethanol cotton balls wiped clean, is 3 in volume ratio:1 sulfuric acid with
Boiled in the mixed solution of phosphoric acid, then use ethanol and deionized water rinsing respectively, nitrogen drying.
(2) it is the Ni/Au laminated films of 500nm to use electron beam evaporation technique deposit thickness on substrate, obtains electricity on earth
Pole layer.
(3) black phosphorus alkene nanometer sheet is added in the dispersion in organic solvent containing graphene oxide, water bath sonicator mixing shape
Into dispersion liquid, using the method for electrophoretic deposition, the graphene oxide film containing black phosphorus alkene is obtained, under nitrogen atmosphere high temperature reduction
The Graphene composite thin film material containing black phosphorus alkene is obtained, it is 50nm containing black phosphorus to use transfer method that thickness is shifted on bottom electrode layer
The Graphene composite thin film material of alkene, obtains resistive functional layer.
(4) photoresist is deposited by the way of spin coating, top electrode figure is then formed by exposure, development, using electronics
Beam evaporation technology deposit thickness in resistive functional layer is the film of the Ag of 500nm, forms top electrode layer, removes photoresist, stripping
From formation memory cell.
(5) photoresist is deposited by the way of spin coating, coating layer pattern is then formed by exposure, development, using atom
Layer deposition techniques deposit thickness in top electrode layer is the Al of 500nm2O3Film, forms coating layer, removes photoresist, peels off, shape
Into the Graphene flexibility resistance-variable storing device containing black phosphorus alkene.
Embodiment 5：
(1) Al is cleaned2O3Substrate：By Al2O3Substrate surface ethanol cotton balls wiped clean, is 3 in volume ratio:1 sulfuric acid with
Boiled in the mixed solution of phosphoric acid, then use ethanol and deionized water rinsing respectively, nitrogen drying.
(2) it is the Ni/Au laminated films of 50nm to use electron beam evaporation technique deposit thickness on substrate, obtains hearth electrode
Layer.
(3) black phosphorus alkene quantum dot or black phosphorus alkene nanometer sheet are added to the dispersion in organic solvent containing graphene oxide
In, water bath sonicator is mixed to form dispersion liquid, using the method for electrophoretic deposition, obtains the graphene oxide film containing black phosphorus alkene,
High temperature reduction obtains the Graphene composite thin film material containing black phosphorus alkene under nitrogen atmosphere, is shifted on bottom electrode layer using transfer method
Thickness is the Graphene composite thin film material containing black phosphorus alkene of 100nm, obtains resistive functional layer.
(4) photoresist is deposited by the way of spin coating, top electrode figure is then formed by exposure, development, using electronics
Beam evaporation technology deposit thickness in resistive functional layer is the film of Ag, Cu or Ni of 80nm, forms top electrode layer, removes light
Photoresist, peels off, and forms memory cell.
(5) photoresist is deposited by the way of spin coating, coating layer pattern is then formed by exposure, development, using atom
Layer deposition techniques deposit thickness in top electrode layer is the Al of 80nm2O3Film, forms coating layer, removes photoresist, peels off, shape
Into the Graphene flexibility resistance-variable storing device containing black phosphorus alkene.
Embodiment 6：
(1) Al is cleaned2O3Substrate：By Al2O3Substrate surface ethanol cotton balls wiped clean, is 3 in volume ratio:1 sulfuric acid with
Boiled in the mixed solution of phosphoric acid, then use ethanol and deionized water rinsing respectively, nitrogen drying.
(2) it is the Ni/Au laminated films of 100nm to use electron beam evaporation technique deposit thickness on substrate, obtains electricity on earth
Pole layer.
(3) black phosphorus alkene quantum dot or black phosphorus alkene nanometer sheet are added to the dispersion in organic solvent containing graphene oxide
In, water bath sonicator is mixed to form dispersion liquid, using the method for electrophoretic deposition, obtains the graphene oxide film containing black phosphorus alkene,
High temperature reduction obtains the Graphene composite thin film material containing black phosphorus alkene under nitrogen atmosphere, is shifted on bottom electrode layer using transfer method
Thickness is the Graphene composite thin film material containing black phosphorus alkene of 80nm, obtains resistive functional layer.
(4) photoresist is deposited by the way of spin coating, top electrode figure is then formed by exposure, development, using electronics
Beam evaporation technology deposit thickness in resistive functional layer is the Ni films of 300nm, forms top electrode layer, removes photoresist, is peeled off,
Form memory cell.
(5) photoresist is deposited by the way of spin coating, coating layer pattern is then formed by exposure, development, using atom
Layer deposition techniques deposit thickness in top electrode layer is the Al of 250nm2O3Film, forms coating layer, removes photoresist, peels off, shape
Into the Graphene flexibility resistance-variable storing device containing black phosphorus alkene.
After testing, on-off ratio, the work electricity of the flexibility resistance-variable storing device of the Graphene containing black phosphorus alkene that prepared by embodiment 1-6
The result of pressure, operating current and long term data stability is as follows：
As seen from the above table, the on-off ratio of the flexibility resistance-variable storing device of the Graphene containing black phosphorus alkene that prepared by the present invention is high, work
Voltage and operating current are low, and maintain ability, good stability with good data.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under without prejudice to spirit and scope of the invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
Into all equivalent modifications or change, should be covered by claim of the invention.
Claims (10)
1. it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device, it is characterised in that：The Graphene containing black phosphorus alkene is flexible
Resistance-variable storing device includes substrate, bottom electrode layer, resistive functional layer, top electrode layer and coating layer, the resistive successively from bottom to up
Functional layer is the Graphene composite thin film material containing black phosphorus alkene, and the substrate is Al2O3Material, the bottom electrode layer is multiple for Ni/Au
Film is closed, the top electrode layer is the film of Ag, Cu or Ni, and the coating layer is Al2O3Material.
2. it is according to claim 1 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device, it is characterised in that：It is described to contain
Black phosphorus alkene exists in the form of quantum dot or nanometer sheet in the Graphene composite thin film material of black phosphorus alkene.
3. a kind of preparation method contains the Graphene flexibility resistance-variable storing device of black phosphorus alkene, it is characterised in that comprise the following steps：
(1) Al is cleaned2O3Substrate；
(2) Ni/Au laminated films are deposited on substrate prepared by step (1) using electron beam evaporation technique, obtains bottom electrode layer；
(3) Graphene composite thin film material containing black phosphorus alkene is shifted on bottom electrode layer prepared by step (2) using transfer method, is obtained
To resistive functional layer；
(4) top electrode figure, the resistive prepared in step (3) using electron beam evaporation technique are formed by photoresist patterning processes
The film of Ag, Cu or Ni is deposited in functional layer, top electrode layer is formed, photoresist is removed, peeled off, form memory cell；
(5) coating layer pattern is formed by photoresist patterning processes, the top electricity prepared in step (4) using technique for atomic layer deposition
The upper depositing Al of pole layer2O3Film, forms coating layer, removes photoresist, peels off, and forms the flexibility resistive of the Graphene containing black phosphorus alkene and deposits
Reservoir.
4. it is according to claim 3 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device preparation method, its feature
It is in the step (1), to clean Al2O3The method of substrate is：By Al2O3Substrate surface ethanol cotton balls wiped clean, in body
Product is than being 3:Boiled in 1 sulfuric acid and the mixed solution of phosphoric acid, then use ethanol and deionized water rinsing respectively, nitrogen drying.
5. it is according to claim 3 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device preparation method, its feature
It is：In the step (2), the thickness of bottom electrode layer is 5-500nm, more preferably preferably 20-80nm, 80nm.
6. it is according to claim 3 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device preparation method, its feature
It is：In the step (3), the preparation method of the Graphene composite thin film material containing black phosphorus alkene is：By black phosphorus alkene quantum dot or
Person's black phosphorus alkene nanometer sheet is added in the dispersion in organic solvent containing graphene oxide, and water bath sonicator is mixed to form dispersion liquid, adopts
With the method for electrophoretic deposition, the graphene oxide film containing black phosphorus alkene is obtained, high temperature reduction is obtained containing black phosphorus under nitrogen atmosphere
The Graphene composite thin film material of alkene.
7. it is according to claim 3 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device preparation method, its feature
It is：In the step (3), the thickness for moving the Graphene composite thin film material containing black phosphorus alkene is 0.5-100nm, preferably 5-
50nm, more preferably 7.5nm.
8. it is according to claim 3 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device preparation method, its feature
It is：In the step (4) or (5), photoresist patterning processes are that photoresist is deposited by the way of spin coating, then by exposing
Light, development form figure.
9. it is according to claim 3 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device preparation method, its feature
It is：In the step (4), top electrode layer thickness is 5-500nm, more preferably preferably 20-80nm, 50nm.
10. it is according to claim 3 it is a kind of containing black phosphorus alkene Graphene flexibility resistance-variable storing device preparation method, its feature
It is：In the step (5), coating layer thickness is 5-500nm, more preferably preferably 20-80nm, 50nm.
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