CN108630811B - Resistive random access memory based on short peptide assembly and preparation method - Google Patents
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/50—Bistable switching devices
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/761—Biomolecules or bio-macromolecules, e.g. proteins, chlorophyl, lipids or enzymes
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Abstract
The invention discloses a resistive random access memory based on a short peptide assembly and a preparation method thereof, wherein the resistive random access memory comprises a resistive layer, and the short peptide assembly is used as the resistive layer. The short peptide assembly is used as a biological material, is easy to obtain, has low cost, good biocompatibility and degradability, is beneficial to preparing green and environment-friendly storage devices, and also has good thermal stability and chemical stability and high electron transmission efficiency.
Description
Technical Field
The invention relates to the technical field of memories, in particular to a resistive random access memory based on a short peptide assembly and a preparation method thereof.
Background
A Resistive Random Access Memory (RRAM) has a simple three-layer structure, specifically, a layer of dielectric material is sandwiched between two layers of metal as a Resistive layer. Compared with other types of nonvolatile memories, RRAM has the advantages of simple structure, low power consumption, small size, and the like, and is considered as an excellent choice for the next-generation nonvolatile memory.
The dielectric material in the RRAM is a carrier for resistance transition of the RRAM, and can be classified into two broad categories, inorganic and organic materials, according to its basic properties. Inorganic materials commonly used are binary oxides, ternary and multicomponent oxides, chalcogen solid electrolytes and the like, which either have relatively complicated crystal growth conditions or contain toxicity and are mostly difficult to degrade and recycle, and reports of 2017 global electronic waste monitoring, which are completed by university of united nations, international union of telecommunication and international solid waste association, show that the global electronic waste production in 2016 reaches 4470 tons, and the electronic waste production increases by 17% to 2021 years with further development of digitization. Although some defects of inorganic materials are overcome by organic materials (organic micromolecules and high molecular polymers), the oxidation stability or sustainability is weak, the chromatogram is narrow, heavy metal is often required to be doped, the synthesis process is complex, and the characteristics hinder the popularization of the resistive random access memory based on the organic materials.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a resistive random access memory based on a short peptide assembly and a preparation method thereof, and aims to solve the problems that a resistive random access material in the conventional resistive random access memory cannot be degraded, is not environment-friendly and has insufficient stability.
The technical scheme of the invention is as follows:
a resistive random access memory comprises a resistive layer, and a short peptide assembly is adopted as the resistive layer.
The resistive random access memory is characterized in that the short peptide assembly is prepared from short peptides, and the short peptides are selected from one or more of phenylalanine dipeptide, aspartame, glutamine dipeptide, phenylalanine-phenylalanine and arginine-glycine-aspartic acid.
The resistive random access memory is characterized in that the short peptide is fibrous or spherical.
The resistive random access memory is characterized in that the thickness of the short peptide assembly is 20-150 nm.
A preparation method of a resistive random access memory comprises the following steps:
a, performing hydrophilic treatment on a substrate containing a bottom electrode;
b, manufacturing a short peptide assembly on the bottom electrode;
and C, manufacturing a top electrode on the short peptide assembly, and finishing manufacturing the resistive random access memory.
The preparation method of the resistive random access memory comprises the step of preparing the short peptide assembly by adopting a spin coating or evaporation method.
The preparation method of the resistive random access memory comprises the following steps of:
b1, dispersing the short peptide in a polar solvent to obtain a short peptide solution;
and step B2, spin-coating the short peptide solution on the bottom electrode at the speed of 900-5000rpm, and annealing to obtain the short peptide assembly.
In the preparation method of the resistive random access memory, in the step B1, the polar solvent is water, hexafluoroisopropanol or DMF.
In the preparation method of the resistive random access memory, in the step B1, the polar solvent is DMF, and the concentration of the DMF solution of the short peptide is 4-50 mg/ml.
The preparation method of the resistive random access memory comprises the step B2, wherein the annealing temperature is 60-120 ℃.
Has the beneficial effects that: the short peptide assembly is used as a resistance change layer, is used as a biological material, is easy to obtain, has low cost, can be produced on a flexible substrate in large batch, has good biocompatibility and degradability, and is favorable for preparing a green and environment-friendly storage device; the piezoelectric effect of the short peptide assembly enables the memory to have a response to pressure in addition to electricity; meanwhile, the resistive random access memory disclosed by the invention shows the storage characteristics of Write-once-and-read-many-times (WORM), and tests show that the starting voltage of the resistive random access memory disclosed by the invention is 3V, the switching ratio reaches 100000, and the resistive random access memory has good thermal stability and chemical stability and high electronic transmission efficiency.
Drawings
Fig. 1 is a scanning electron micrograph of an FF assembly in example 1 of the present invention.
FIG. 2 is a current-voltage curve of the aluminum/FF assembly/ITO memory in the electrical performance test in example 1 of the present invention.
Detailed Description
The invention provides a resistive random access memory based on a short peptide assembly and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The resistive random access memory provided by the invention adopts the short peptide assembly as the resistive layer. The short peptide assembly is prepared by short peptide (spin coating or evaporation coating), the short peptide is short chain peptide containing 2-9 amino acids, preferably, the short peptide is selected from one or more of phenylalanine dipeptide, aspartame, glutamine dipeptide, phenylalanine-phenylalanine and arginine-glycine-aspartic acid, and the short peptide assembly can be fibrous or spherical. Preferably, the short peptide assembly has a thickness of 20-150nm (more preferably 50 nm), which ensures stable operation of the device.
The invention adopts the short peptide assembly as the resistance change layer, the short peptide assembly is used as a biological material, the acquisition is easy, the cost is lower, the mass production can be carried out on a flexible substrate, and the peptide assembly has good biocompatibility and degradability, thereby being beneficial to preparing a green and environment-friendly memory device; the piezoelectric effect of the short peptide assembly enables the memory to have a response to pressure in addition to electricity; meanwhile, the resistive random access memory disclosed by the invention shows the storage characteristics of Write-once-and-read-many-times (WORM), and tests show that the starting voltage of the resistive random access memory disclosed by the invention is 3V, the switching ratio reaches 100000, and the resistive random access memory has good thermal stability and chemical stability and high electronic transmission efficiency.
Further preferably, the short peptide is phenylalanine dipeptide (L, L-diphenylalanine, FF for short). FF is one of the smallest peptide monomers capable of self-assembling into a nano-structure assembly through non-covalent bond, the synthesis method is simple, the self-assembly of FF can be facilitated by the amphiphilic property of FF, and FF can form a plurality of different structures such as nano-rods, nano-tubes, nano-spheres and the like through the use of different solvents, an external electric field and the like. The FF micro-nano structure has good thermal stability and chemical stability, and the electron transmission efficiency of the nanotube is high. The light weight and the biocompatibility are necessary measures of electronic materials, and FF not only meets the two requirements, but also is a natural small molecule and has good biocompatibility and biodegradability; finally, FF has a higher conjugated system and is easy to self-assemble to form an assembly with different photoelectric properties.
The invention also provides a preparation method of the resistive random access memory, which comprises the following steps:
and step A, carrying out hydrophilic treatment on the substrate containing the bottom electrode.
Specifically, a substrate containing a bottom electrode is subjected to ultrasonic cleaning by using a cleaning agent and ultrapure water, and N is used2Drying with a gun, and drying in a vacuum drying oven; the substrate was then hydrophilized and treated in a UVO cleaner (electrode side up) for 30 min.
And B, manufacturing a short peptide assembly on the bottom electrode.
The film can be manufactured by a spin coating or evaporation method. Taking the spin coating method as an example, the manufacturing process comprises:
and step B1, dispersing the short peptide in a polar solvent to obtain a short peptide solution. Water, hexafluoroisopropanol or DMF (N, N-dimethylformamide solution) is preferred as solvent.
And step B2, spin-coating the short peptide solution on the bottom electrode at the speed of 900-5000rpm, and annealing to obtain the short peptide assembly.
The concentration of the short peptide solution and the spin-coating speed are used for regulating the thickness of the short peptide assembly, and the thickness is larger when the concentration is larger, and the thickness is smaller when the spin-coating speed is larger. The dielectric layer is difficult to form a guide path due to the excessive thickness, and the electroresistance transformation cannot be realized; the short peptide assembly has the advantages that the tolerance of the device is reduced, the thickness of the short peptide assembly is preferably controlled to be 20-150nm, the concentration of an aqueous solution of the short peptide is preferably 0.3-5.5mg/ml, and the concentration of a hexafluoroisopropanol solution of the short peptide and the concentration of a DMF solution of the short peptide are preferably 4-50mg/ml in the range of the spin coating speed, under the condition, the short peptide can form an ordered assembly in a polar solvent more easily, the prepared dielectric layer is more uniform, and the stability of the device is better. And (3) drying the substrate spin-coated with the short peptide solution on a drying table, preferably drying at 60-120 ℃ for 1-3h, and finishing the manufacture of the dielectric layer of the short peptide assembly.
And C, manufacturing a top electrode on the short peptide assembly. Specifically, a metal top electrode (gold, silver, aluminum and magnesium) with the thickness of 18-40nm is evaporated on a dielectric layer by adopting a mask plate for covering, and the resistive random access memory based on the short peptide assembly is manufactured.
The present invention will be described in detail below with reference to examples.
Example 1
(1) And carrying out hydrophilic treatment on the glass containing the ITO electrode. Specifically, glass containing an ITO electrode is placed into a container, a cleaning agent (such as Decon) and a proper amount of ultrapure water are added, and ultrasonic treatment is carried out for 10 min; then, the substrate is washed by ultrapure water until no foam exists, finally, the ultrapure water is added for 5 min in an ultrasonic mode, the ultrasonic processing is repeated for 3 times, and the cleaned substrate is treated by N2Drying with a gun, baking in a vacuum drying oven at 120 deg.C for 30 min; and (4) performing hydrophilic treatment, and putting the cleaned glass into a UVO cleaner (with an ITO electrode facing upwards) for treatment for 30 min.
(2) An FF assembly was made on the ITO side of the glass. Preparing a DMF solution of FF with the concentration of 10mg/ml, spin-coating the FF solution on the ITO surface of the substrate at the speed of 1000 rpm for 30s, and baking in an oven at the temperature of 95 ℃ for 2h to complete the preparation of the FF assembly.
(3) A top electrode was fabricated on the FF assembly. And covering by using a mask, evaporating and plating an aluminum electrode with the thickness of 30nm on the FF assembly, and manufacturing the resistive random access memory based on the FF assembly.
Structural characterization and Performance testing
As a result of the scanning electron microscope test, the FF assembly in example 1 was fibrous as shown in fig. 1.
The FF assembly-based resistance change memory in example 1 was subjected to an electrical property test, and as a result, as shown in fig. 2, the turn-on voltage of the device was 3V, the on-off ratio reached 100000, and the memory characteristics of write once and read many were exhibited.
In summary, the invention provides a resistive random access memory based on a short peptide assembly and a preparation method thereof, the short peptide assembly is used as a resistive layer of the resistive random access memory, the short peptide assembly is used as a biological material, the short peptide assembly is easy to obtain and low in cost, the short peptide assembly can be produced on a flexible substrate in large batch, and the peptide assembly has good biocompatibility and degradability, so that the preparation of a green and environment-friendly memory device is facilitated; the piezoelectric effect of the short peptide assembly enables the memory to have a response to pressure in addition to electricity; meanwhile, the resistive random access memory of the invention has the storage characteristics of single-writing and multi-reading, and tests show that the starting voltage of the resistive random access memory of the invention is 3V, the on-off ratio reaches 100000, and the resistive random access memory has good thermal stability and chemical stability and high electron transmission efficiency.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A resistive random access memory comprises a resistive layer and is characterized in that a short peptide assembly is adopted as the resistive layer;
the starting voltage of the resistive random access memory is 3V, and the switching ratio reaches 100000;
dispersing the short peptide in a polar solvent to obtain a short peptide solution, wherein the solvent is water, hexafluoroisopropanol or DMF;
the concentration of the short peptide solution and the spin-coating speed are used for regulating and controlling the thickness of the short peptide assembly, wherein the spin-coating speed is 900-5000rpm, the concentration of the aqueous solution of the short peptide is 0.3-5.5mg/ml, the concentrations of the hexafluoroisopropanol solution of the short peptide and the DMF solution of the short peptide are both 4-50mg/ml, and the thickness of the short peptide assembly is 20-150 nm.
2. The RRAM of claim 1, wherein the short peptide assembly is prepared from a short peptide selected from one or more of phenylalanine dipeptide, aspartame, glutamine dipeptide, phenylalanine-phenylalanine, and arginine-glycine-aspartic acid.
3. The resistive-switching memory according to claim 2, wherein the short peptide is fibrous or spherical.
4. The method for manufacturing the resistive random access memory according to claim 1, comprising:
a, performing hydrophilic treatment on a substrate containing a bottom electrode;
b, manufacturing a short peptide assembly on the bottom electrode, wherein the thickness of the short peptide assembly is 20-150 nm;
and C, manufacturing a top electrode on the short peptide assembly, and finishing manufacturing the resistive random access memory.
5. The method for manufacturing a resistive random access memory according to claim 4, wherein the short peptide assembly is manufactured by a spin coating or evaporation method.
6. The method for preparing a resistive random access memory according to claim 5, wherein the short peptide assembly is prepared by a spin coating method, and the method comprises the following steps:
b1, dispersing the short peptide in a polar solvent to obtain a short peptide solution;
and step B2, spin-coating the short peptide solution on the bottom electrode at the speed of 900-5000rpm, and annealing to obtain the short peptide assembly.
7. The method for manufacturing a resistive random access memory according to claim 6, wherein in the step B1, the polar solvent is water, hexafluoroisopropanol or DMF.
8. The method for preparing a resistive random access memory according to claim 7, wherein in the step B1, the polar solvent is DMF, and the concentration of the DMF solution of the short peptide is 4-50 mg/ml.
9. The method for manufacturing a resistive random access memory according to claim 6, wherein in the step B2, the annealing temperature is 60-120 ℃.
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