CN108630811A - A kind of resistance-variable storing device and preparation method based on small peptide assembly - Google Patents

A kind of resistance-variable storing device and preparation method based on small peptide assembly Download PDF

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Publication number
CN108630811A
CN108630811A CN201810366934.5A CN201810366934A CN108630811A CN 108630811 A CN108630811 A CN 108630811A CN 201810366934 A CN201810366934 A CN 201810366934A CN 108630811 A CN108630811 A CN 108630811A
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small peptide
resistance
storing device
variable storing
preparation
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CN201810366934.5A
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CN108630811B (en
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韩素婷
周晔
吕子玉
徐振庭
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Shenzhen University
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Shenzhen University
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/50Bistable switching devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/761Biomolecules or bio-macromolecules, e.g. proteins, chlorophyl, lipids or enzymes

Abstract

The invention discloses a kind of resistance-variable storing device and preparation method based on small peptide assembly, wherein resistance-variable storing device includes change resistance layer, using small peptide assembly as the change resistance layer.Small peptide assembly is easily obtained as a kind of biomaterial, and cost is relatively low, with good biocompatibility and degradability, be conducive to prepare environmentally protective memory device, and small peptide assembly also has good thermal stability and chemical stability, electron-transport efficient.

Description

A kind of resistance-variable storing device and preparation method based on small peptide assembly
Technical field
The present invention relates to memory technology field more particularly to a kind of resistance-variable storing devices and preparation based on small peptide assembly Method.
Background technology
Resistance-variable storing device(Resistive random access memory, RRAM)With simple three-decker, tool Body presss from both sides one layer of dielectric material as change resistance layer between double layer of metal.Compared with other kinds of nonvolatile memory, RRAM The advantages that simple in structure, low in energy consumption, small, it is considered to be the excellent selection of next-generation nonvolatile memory.
Dielectric material in RRAM is the carrier that electric resistance changing occurs for RRAM, can be divided by its essential attribute inorganic and organic Material two major classes.Common inorganic material has binary oxide, ternary and multivariant oxide, sulfur family solid electrolyte etc., these Material is difficult to degrade and recycling mostly either with relative complex crystal growth condition or containing toxic, It is completed by United Nations University, International Telecommunication Association and International Solid waste association《Global electronic rubbish monitoring in 2017》Report is aobvious Show, for global electronic refuse production in 2016 up to 4470 tons, and with digitlization further development, electronic waste amount will by 2021 It is further added by 17%.Organic material(Organic molecule and high molecular polymer)Although overcoming some disadvantages of inorganic material, oxygen To change stability or sustainability is weaker, chromatography relatively narrower, and usually needs to adulterate heavy metal, building-up process is also more complex, this A little features hinder the popularization of the resistance-variable storing device based on organic material.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of resistives based on small peptide assembly to deposit Reservoir and preparation method, it is intended to solve in existing resistance-variable storing device that resistive material can not degrade, environment is unfriendly and stablize Property insufficient problem.
Technical scheme is as follows:
A kind of resistance-variable storing device, including change resistance layer, using small peptide assembly as the change resistance layer.
The resistance-variable storing device, wherein the small peptide assembly is prepared by small peptide, and the small peptide is selected from phenylpropyl alcohol ammonia In sour dipeptides, Aspartame, glutamine dipeptide, phenylalanine-phenylalanine-phenylalanine and arginine-glycine-aspartic acid It is one or more.
The resistance-variable storing device, wherein the small peptide is threadiness or spherical.
The resistance-variable storing device, wherein the thickness of the small peptide assembly is 20-150nm.
A kind of preparation method of resistance-variable storing device, including:
Step A, the substrate containing hearth electrode is done into hydrophilic treated;
Step B, small peptide assembly is made on the hearth electrode;
Step C, top electrode is made on the small peptide assembly, resistance-variable storing device completes.
The preparation method of the resistance-variable storing device, wherein the small peptide assembling is made using the method for spin coating or vapor deposition Body.
The preparation method of the resistance-variable storing device, wherein the small peptide assembly, packet are made using the method for spin coating It includes:
Step B1, small peptide is scattered in polar solvent, obtains small peptide solution;
Step B2, the small peptide solution is spin-coated on the speed of 900-5000 rpm on the hearth electrode, and annealed, obtained To the small peptide assembly.
The preparation method of the resistance-variable storing device, wherein in the step B1, the polar solvent is water, hexafluoro is different Propyl alcohol or DMF.
The preparation method of the resistance-variable storing device, wherein in the step B1, the polar solvent is DMF, small peptide A concentration of 4-50mg/ml of DMF solution.
The preparation method of the resistance-variable storing device, wherein in the step B2, the temperature of annealing is 60-120 DEG C.
Advantageous effect:The present invention is using small peptide assembly as change resistance layer, and small peptide assembly is as a kind of biomaterial, easily In acquisition, cost is relatively low, can produce in enormous quantities on a flexible substrate, and small peptide assembly have good biocompatibility and Degradability is conducive to prepare environmentally protective memory device;The piezoelectric effect of small peptide assembly makes memory in addition to electricity There can also be response to pressure;The resistance-variable storing device of the present invention shows single-write and multiple-read simultaneously(Write-once-and- Read-many-times, WORM)Storage characteristics, test show resistance-variable storing device of the invention cut-in voltage be 3V, open Ratio is closed up to 100000, and there is good thermal stability and chemical stability, electron-transport is efficient.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of FF assemblies in the embodiment of the present invention 1.
Fig. 2 is that current-voltage of the aluminium/FF assemblies/ITO memories in electric performance test is bent in the embodiment of the present invention 1 Line.
Specific implementation mode
The present invention provides a kind of resistance-variable storing device and preparation method based on small peptide assembly, to make the mesh of the present invention , technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that described herein Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
Resistance-variable storing device provided by the invention, using small peptide assembly as change resistance layer.Wherein, the small peptide assembly by It is prepared by small peptide(Spin coating or vapor deposition)It forms, small peptide refers to the short-chain peptide for including 2-9 amino acid, it is preferable that small peptide is selected from phenylpropyl alcohol Propylhomoserin dipeptides, Aspartame, glutamine dipeptide, phenylalanine-phenylalanine-phenylalanine and arginine-glycine-aspartic acid In it is one or more, small peptide assembly be threadiness or it is spherical.Preferably, the thickness of the small peptide assembly is 20- 150nm(Further preferably 50nm), it is ensured that device steadily works.
Using small peptide assembly as change resistance layer, small peptide assembly is easily obtained the present invention as a kind of biomaterial, at This is relatively low, can produce in enormous quantities on a flexible substrate, and peptide assembly has good biocompatibility and degradability, has Conducive to preparing environmentally protective memory device;The piezoelectric effect of small peptide assembly makes memory can also be to pressure in addition to electricity With response;The resistance-variable storing device of the present invention shows single-write and multiple-read simultaneously(Write-once-and-read-many-times, WORM)Storage characteristics, test show resistance-variable storing device of the invention cut-in voltage be 3V, on-off ratio up to 100000, and With good thermal stability and chemical stability, electron-transport is efficient.
It is further preferred that small peptide selects phenylalanine dipeptide(L, L-diphenylalanine, abbreviation FF).FF is can It is self-assembled into one of the minimum peptide monomer that nanostructure assembles body by non-covalent bond effect, synthetic method is simple, amphipathic Matter can help its self assembly, and FF can be made to form many different knots by modes such as the use of different solvents, extra electric fields Structure, such as nanometer rods, nanotube, nanosphere etc..FF micro nano structures have good thermal stability and chemical stability, nanotube Electron-transport is efficient.Light weight is that the necessary of electronic material is measured with biocompatibility, and FF not only meets this 2 demands, also It is a kind of natural small molecule, there is good biocompatibility and biological degradability;Finally, FF has higher conjugated system, It is easy to be self-assembly of the assembly with different photoelectric properties.
The present invention also provides a kind of preparation methods of resistance-variable storing device, including:
Step A, the substrate containing hearth electrode is done into hydrophilic treated.
Specifically, first detergent and ultra-pure water is used to carry out ultrasonic cleaning to the substrate containing hearth electrode, N is used in combination2Rifle is blown It is dry, it is put into vacuum drying chamber drying;Hydrophilic treated is done again, and the substrate after cleaning is put into UVO cleaners(Electrode is face-up) Handle 30min.
Step B, small peptide assembly is made on the hearth electrode.
The specific method making that spin coating or vapor deposition can be used.By taking spin-coating method as an example, manufacturing process includes:
Step B1, small peptide is scattered in polar solvent, obtains small peptide solution.It is preferred that water, hexafluoroisopropanol or DMF(N, N- bis- Methylformamide solution)As solvent.
Step B2, the small peptide solution is spin-coated on the speed of 900-5000 rpm on the hearth electrode, and is moved back Fire obtains the small peptide assembly.
The concentration and spin speed of small peptide solution contribute to the thickness of regulation and control institute small peptide assembly, and the bigger thickness of concentration is more Greatly, the bigger thickness of spin speed is smaller.Excessive thickness can make dielectric layer be hardly formed guide passage, cannot achieve electroluminescent resistance and turn Become;Thickness is too small can be so that the tolerance of device declines, and the thickness of small peptide assembly is preferably controlled in 20-150nm, in above-mentioned rotation It applies in velocity interval, the concentration of the aqueous solution of small peptide is preferably 0.3-5.5 mg/ml, the hexafluoroisopropanol solution and small peptide of small peptide The concentration of DMF solution be both preferably 4-50mg/ml, under the conditions of this, orderly group is more readily formed in small peptide in polar solvent Body is filled, evenly, device stability is more preferable for the dielectric layer prepared.There is the substrate of small peptide solution to be placed on drying station spin coating to dry Dry, preferably 60-120 DEG C drying 1-3h, the dielectric layer of small peptide assembly completes.
Step C, top electrode is made on the small peptide assembly.Specifically mask plate is used to cover, steamed on the dielectric layer Plate the metallic top electrode of 18-40nm thickness(Gold, silver, aluminium, magnesium), the resistance-variable storing device based on small peptide assembly completes.
Below by embodiment, the present invention is described in detail.
Embodiment 1
(1)Glass containing ITO electrode is done into hydrophilic treated.Specifically, first the glass containing ITO electrode is put into container, is added Cleaning agent(Such as Decon)With appropriate ultra-pure water, 10 min of ultrasound;Then substrate is rinsed to non-foam, finally using ultra-pure water Again plus ultra-pure water 5 min of ultrasound, it is repeated 3 times, the substrate N that will have been cleaned2Rifle dries up, and is put into vacuum drying chamber, with 120 DEG C Toast 30min;Hydrophilic treated is done again, and the glass after cleaning is put into UVO cleaners(ITO electrode is upward)Handle 30min.
(2)FF assemblies are made in the ito surface of glass.Configuration concentration is the DMF solution of the FF of 10mg/ml, then in base The ito surface at bottom is with the speed spin coating FF solution of 1000 rpm, spin coating 30s, then 2h is dried in 95 DEG C of baking oven, and FF assembles system It completes.
(3)Top electrode is made on FF assemblies.It is covered using mask plate, the aluminium electricity of 30nm thickness is deposited on FF assemblies Pole, the resistance-variable storing device based on FF assemblies complete.
Structural characterization and performance test
Electronic Speculum test is scanned to the FF assemblies in embodiment 1, the results are shown in Figure 1, and FF assemblies are threadiness.
Electric performance test is carried out to the resistance-variable storing device based on FF assemblies in embodiment 1, the results are shown in Figure 2, device The cut-in voltage of part is 3V, and on-off ratio shows the storage characteristics of single-write and multiple-read up to 100000.
In conclusion the present invention provides a kind of resistance-variable storing device and preparation method based on small peptide assembly, the present invention Change resistance layer using small peptide assembly as resistance-variable storing device, small peptide assembly are easily obtained as a kind of biomaterial, cost It is relatively low, it can produce in enormous quantities on a flexible substrate, and peptide assembly has good biocompatibility and degradability, favorably In preparing environmentally protective memory device;The piezoelectric effect of small peptide assembly makes memory in addition to can also have to pressure to electricity There is response;The resistance-variable storing device of the present invention shows the storage characteristics of single-write and multiple-read simultaneously, and test shows that resistive of the invention is deposited The cut-in voltage of reservoir is 3V, and on-off ratio has good thermal stability and chemical stability, electron-transport up to 100000 It is efficient.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention Protect range.

Claims (10)

1. a kind of resistance-variable storing device, including change resistance layer, which is characterized in that using small peptide assembly as the change resistance layer.
2. resistance-variable storing device according to claim 1, which is characterized in that the small peptide assembly is prepared by small peptide, The small peptide is selected from phenylalanine dipeptide, Aspartame, glutamine dipeptide, phenylalanine-phenylalanine-phenylalanine and smart ammonia It is one or more in acid-Gly-Asp.
3. resistance-variable storing device according to claim 2, which is characterized in that the small peptide is threadiness or spherical.
4. resistance-variable storing device according to claim 1, which is characterized in that the thickness of the small peptide assembly is 20- 150nm。
5. a kind of preparation method of resistance-variable storing device, which is characterized in that including:
Step A, the substrate containing hearth electrode is done into hydrophilic treated;
Step B, small peptide assembly is made on the hearth electrode;
Step C, top electrode is made on the small peptide assembly, resistance-variable storing device completes.
6. the preparation method of resistance-variable storing device according to claim 5, which is characterized in that using spin coating or the method for vapor deposition Make the small peptide assembly.
7. the preparation method of resistance-variable storing device according to claim 6, which is characterized in that make institute using the method for spin coating Small peptide assembly is stated, including:
Step B1, small peptide is scattered in polar solvent, obtains small peptide solution;
Step B2, the small peptide solution is spin-coated on the speed of 900-5000 rpm on the hearth electrode, and annealed, obtained To the small peptide assembly.
8. the preparation method of resistance-variable storing device according to claim 7, which is characterized in that in the step B1, the pole Property solvent be water, hexafluoroisopropanol or DMF.
9. the preparation method of resistance-variable storing device according to claim 8, which is characterized in that in the step B1, the pole Property solvent be DMF, a concentration of 4-50mg/ml of the DMF solution of small peptide.
10. the preparation method of resistance-variable storing device according to claim 7, which is characterized in that in the step B2, annealing Temperature is 60-120 DEG C.
CN201810366934.5A 2018-04-23 2018-04-23 Resistive random access memory based on short peptide assembly and preparation method Active CN108630811B (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
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