CN101630662A - Manufacturing method for protein structure quick switch memristor array - Google Patents
Manufacturing method for protein structure quick switch memristor array Download PDFInfo
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- CN101630662A CN101630662A CN200910072709A CN200910072709A CN101630662A CN 101630662 A CN101630662 A CN 101630662A CN 200910072709 A CN200910072709 A CN 200910072709A CN 200910072709 A CN200910072709 A CN 200910072709A CN 101630662 A CN101630662 A CN 101630662A
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Abstract
A manufacturing method for a protein structure quick switch memristor array relates to the manufacturing method for protein structure memristor array. The manufacturing method solves the problems that the existing manufacturing method for a memristor model has low manufacturing cost and the prepared memristor manufacturing model has low on-off speed. The manufacturing method uses a method combining a micro electronic technique and a biochemistry technique for fixing bovine immunity globular protein on semiconductor material, prepares biology cell membranes, and then manufactures the protein structure quick switch memristor array; the preparation method for the nanometer structure memristor array is simple; the used raw materials have low price and low manufacturing cost; and the manufactured memristor array has quicker on-off speed.
Description
Technical field
The present invention relates to the manufacture method of protein structure memristor array
Background technology
Hewlette-packard laboratory research personnel Dmitri B.StruK+ov, Gregory S.Snider, Duncan R.Stewart ﹠amp; The R.Stanley Williams The missing memristor found that publishes thesis on Britain's " nature " magazine of publishing on May 1st, 2008 declares, the 4th kind of primary element-memory resistor in they the are verified circuit world, be called for short memristor (Memristor), and successfully design a workable memristor mock-up, and applied for U.S. Pat 20080090337A1.They are as making sandwich, with nano level titanium dioxide semiconductor film TiO
2-x/ TiO
2Be clipped between two nano wires making by platinum, make Pt/TiO
2-x/ TiO
2/ Pt nanostructure, making the knack recall resistance is to make its part have only 5 nanometer sizes, that is to say, only is equivalent to the 10,000/so thin of a hairline of people.In fact this existing memristor model is exactly a nonlinear resistor that memory function is arranged, variation by Control current can change its resistance, if high value is defined as " 1 ", low resistance is defined as " 0 ", and then this resistance just can realize storing the function of data.Though this memristor model structure is simple, used a large amount of inorganic semiconductor materials and precious metal platinum during this memristor modelling, improved the cost of manufacture of this memristor model, and the memristor switching speed that making obtains is relatively low.
Summary of the invention
The objective of the invention is problem, and the manufacture method of protein structure quick switch memristor array is provided for the switching speed of cost of manufacture height that solves existing memristor model production method existence and the memristor that making obtains.
The manufacture method of protein structure quick switch memristor array of the present invention is made according to following steps: one, adopt the method for magnetron sputtering to make the golden film that a layer thickness is 70～90nm at the upper surface of silicon chip; Two, to immerse solute concentration be 5 * 10 to the silicon chip that will be coated with golden film
-3The ethanolic solution reaction 5～7h of 11-sulfydryl-1-undecyl alcohol of mol/L promptly forms the sulfydryl hydrophilic surface on golden film surface, and wherein the mass concentration of etoh solvent is 70%～90% in the ethanolic solution of 11-sulfydryl-1-undecyl alcohol; Three, the silicon chip with sulfydryl hydrophilic surface of step 2 preparation is immersed in the alkali ethereal solution of epoxychloropropane that solute concentration is 0.6～0.8mol/L and react 3～5h, promptly formed the epoxy material surface at hydrophilic surface, wherein the solvent of the alkali ethereal solution of epoxychloropropane is that the NaOH solution of 0.3～0.5mol/L and quality purity are that 99%～99.9% diethylene glycol dimethyl ether is formed according to 1: 1 volume ratio by concentration; Four, the washed with de-ionized water 3～4min of the silicon chip with epoxy material surface that step 3 is prepared, be that 95% ethanolic solution cleans 1～2min with mass concentration then, again with reacting 18～22h in the aqueous slkali that immerses glucan behind washed with de-ionized water 3～4min, be about to glucose and be fixed on the epoxy material surface, wherein the aqueous slkali of glucan is made up of 9～11 parts of concentration NaOH solution that is 0.8～1.2mol/L and 2～5 parts glucan T-500 according to ratio of weight and number; Five, the silicon chip that the surface of step 4 preparation is fixed with glucose immerses and reacts 15～18h in the hydrogenperoxide steam generator of bromoacetic acid that concentration is 0.8～1.2mol/L and form carboxymethylated matrix, and wherein solvent is that concentration is the hydrogenperoxide steam generator of 1.8～2.2mol/L in the hydrogenperoxide steam generator of bromoacetic acid; Six, it is that 99%～99.9% dichloroethanes and quality purity are to react 5～8h in the mixed solution of 99%～99.9% N-hydroxy-succinamide that the silicon chip with carboxy methylation matrix of step 5 preparation is immersed in quality purity, the silicon chip that will have the carboxy methylation matrix again immerses in the cattle immune globulin matter solution that molar concentration is 0.01～0.03mol/L and reacts 2～3h, be ethanolamine salt acid buffer flushing 10～20min of 0.1～0.3mol/L then with molar concentration, be about to cattle immune globulin matter and be fixed on formation protein molecule film on the carboxy methylation matrix, wherein the mol ratio of dichloroethanes and N-hydroxy-succinamide is 1: 1; Seven, surface-coated one deck polytetrafluoroethyldispersion dispersion of protein molecular film or employing silica gel curing back formation thickness are the film of 100～500nm on the silicon chip of step 6 preparation, adopting laser marking machine to etch bore dia again on film is that the microwell array of 100 μ m obtains the microwell array film, the output facula diameter of control laser marking machine is 100 μ m, the power of laser marking machine is 10W, drips 60～100mmol K on the nano-pore array thin film surface then
+Ion, Na
+Ion or Cl
-The ionic liquid of ion forms biological cell membrane, promptly obtains protein structure memristor unit; Eight, the protein structure memristor unit that step 7 is prepared adopts the sealed package technology with metal electrode to encapsulate and promptly obtains protein structure quick switch memristor array.
The manufacture method of protein structure quick switch memristor array of the present invention is that microelectric technique and biochemical technology are combined, protein molecule is fixed on the silicon materials, the present invention makes the quick switch memristor array of the protein structure that obtains, it is a kind of nonlinear resistor that memory function is arranged, under leement duration D is identical in the disclosed structure of patent US20080090337A1 situation, the switching speed that the present invention makes the memristor array that obtains has improved more than 0.5 times.The manufacture method of nanostructure memristor display of the present invention is simple, employed cost of material is cheap, cost of manufacture is low, it is faster to make the memristor display switching speed that obtains, can satisfy the requirement more and more faster of present digital and electronic field, for the faster more energy-conservation instant opening type PC or the analog computer that will occur provides the novel memristor high-speed switch component structure that can realize storing data function to switching speed.
Description of drawings
Fig. 1 makes the structural representation of the protein structure quick switch memristor array that obtains for embodiment one; Fig. 2 is the schematic diagram of inner impurity motion of the solid-state example switch in the unit of protein molecule memristor of embodiment one and equivalent resistance.Fig. 3 is that the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment two injects a K under the forward bias effect
+Cellular construction figure when ion makes resistance mediate state; Fig. 4 is that two K are injected in the unit solid-state quick switch memristor forward bias effect of the protein molecule memristor of embodiment two down
+Cellular construction figure when ion makes resistance be in minimum state; Fig. 5 does not have K for the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment two under the reverse biased effect
+Ion injects the cellular construction figure when making resistance be in maximum rating; Fig. 6 is that the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment three injects a Na under the forward bias effect
+Cellular construction figure when ion makes resistance mediate state; Fig. 7 is that the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment three injects two Na under the forward bias effect
+Cellular construction figure when ion makes resistance be in minimum state; Fig. 8 does not have Na for the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment three under the reverse biased effect
+Ion injects the cellular construction figure when making resistance be in maximum rating; Fig. 9 is that the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment four injects a Cl under the reverse biased effect
-Cellular construction figure when ion makes resistance mediate state; Figure 10 is that the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment four injects two Cl under the reverse biased effect
-Cellular construction figure when ion makes resistance be in minimum state; Figure 11 does not have Cl for the solid-state quick switch memristor in unit of the protein molecule memristor of embodiment four under the forward bias effect
-Ion injects the cellular construction figure when making resistance be in maximum rating.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the manufacture method of present embodiment protein structure quick switch memristor array is made according to following steps: one, adopt the method for magnetron sputtering to make the golden film that a layer thickness is 70～90nm at the upper surface of silicon chip; Two, to immerse solute concentration be 5 * 10 to the silicon chip that will be coated with golden film
-3The ethanolic solution reaction 5～7h of 11-sulfydryl-1-undecyl alcohol of mol/L promptly forms the sulfydryl hydrophilic surface on golden film surface, and wherein the mass concentration of etoh solvent is 70%～90% in the ethanolic solution of 11-sulfydryl-1-undecyl alcohol; Three, the silicon chip with sulfydryl hydrophilic surface of step 2 preparation is immersed in the alkali ethereal solution of epoxychloropropane that solute concentration is 0.6～0.8mol/L and react 3～5h, promptly formed the epoxy material surface at hydrophilic surface, wherein the solvent of the alkali ethereal solution of epoxychloropropane is that the NaOH solution of 0.3～0.5mol/L and quality purity are that 99%～99.9% diethylene glycol dimethyl ether is formed according to 1: 1 volume ratio by concentration; Four, the washed with de-ionized water 3～4min of the silicon chip with epoxy material surface that step 3 is prepared, be that 95% ethanolic solution cleans 1～2min with mass concentration then, again with reacting 18～22h in the aqueous slkali that immerses glucan behind washed with de-ionized water 3～4min, be about to glucose and be fixed on the epoxy material surface, wherein the aqueous slkali of glucan is made up of 9～11 parts of concentration NaOH solution that is 0.8～1.2mol/L and 2～5 parts glucan T-500 according to ratio of weight and number; Five, the silicon chip that the surface of step 4 preparation is fixed with glucose immerses and reacts 15～18h in the hydrogenperoxide steam generator of bromoacetic acid that concentration is 0.8～1.2mol/L and form carboxymethylated matrix, and wherein solvent is that concentration is the hydrogenperoxide steam generator of 1.8～2.2mol/L in the hydrogenperoxide steam generator of bromoacetic acid; Six, it is that 99%～99.9% dichloroethanes and quality purity are to react 5～8h in the mixed solution of 99%～99.9% N-hydroxy-succinamide that the silicon chip with carboxy methylation matrix of step 5 preparation is immersed in quality purity, the silicon chip that will have the carboxy methylation matrix again immerses in the cattle immune globulin matter solution that molar concentration is 0.01～0.03mol/L and reacts 2～3h, be ethanolamine salt acid buffer flushing 10～20min of 0.1～0.3mol/L then with molar concentration, be about to cattle immune globulin matter and be fixed on formation protein molecule film on the carboxy methylation matrix, wherein the mol ratio of dichloroethanes and N-hydroxy-succinamide is 1: 1; Seven, surface-coated one deck polytetrafluoroethyldispersion dispersion of protein molecular film or employing silica gel curing back formation thickness are the film of 100～500nm on the silicon chip of step 6 preparation, adopting laser marking machine to etch bore dia again on film is that the microwell array of 100 μ m obtains the microwell array film, the output facula diameter of control laser marking machine is 100 μ m, the power of laser marking machine is 10W, drips 60～100mmol K on the nano-pore array thin film surface then
+Ion, Na
+Ion or Cl
-The ionic liquid of ion forms biological cell membrane, promptly obtains protein structure memristor unit; Eight, the protein structure memristor unit that step 7 is prepared adopts the sealed package technology with metal electrode to encapsulate and promptly obtains protein structure quick switch memristor array.
Polytetrafluoroethyldispersion dispersion in the present embodiment step 7 and silica gel all can be bought from the market and obtain.
Present embodiment is made under the protein structure quick switch memristor array the obtain situation identical with leement duration D in the disclosed structure of patent US20080090337A1, and the switching speed of the memristor that the present invention's making obtains has improved more than 0.5 times.
The array structure schematic diagram of the protein structure quick switch memristor array that the present embodiment making obtains as shown in Figure 1,1 is silicon chip among Fig. 1, the 2nd, golden film, the 3rd, sulfydryl hydrophilic surface, the 4th, glucose, the 5th, the peptide bond that carboxymethylated matrix and ox brain immune globulin white matter form, the 6th, ox brain immune globulin white matter, the 7th, micropore, the 8th, microwell array film, the 9th, the liquid of ion, the 10th, metal electrode.
The schematic diagram that present embodiment is made inner impurity motion of the solid-state example switch in the unit obtain the protein molecule memristor and equivalent resistance as shown in Figure 2, (a) is after integral protein matter molecule applies voltage among the figure, do not have any ion and enter integral protein matter molecule, at this moment the resistance maximum of integral protein matter molecule, its resistance R
OFFExpression; (b) be a cation is arranged or negative enter ion and enter integral protein matter molecule, the resistance of the integral protein matter molecule state that mediates at this moment, its resistance is represented with R.(c) be to have two cations or two anions to enter integral protein matter molecule, the resistance minimum of integral protein matter molecule at this moment, its resistance R
ONExpression.(d) be the equivalent circuit diagram of integral protein matter molecular switch state.
Embodiment two: that present embodiment and embodiment one are different is the K that drips 60～100mmol in the step 7 on the nano-pore array thin film surface
+Ionic liquid.Other step and parameter are identical with embodiment one.
Present embodiment obtains that promptly different number K are arranged under the applying bias effect
+The protein structure memristor unit switch array that ion injects.
Embodiment three: that present embodiment and embodiment one are different is the Na that drips 60～100mmol in the step 7 on the nano-pore array thin film surface
+Ionic liquid.Other step and parameter are identical with embodiment one.
Present embodiment promptly obtains having the protein structure memristor unit switch array of different number N a+ ions injections under the applying bias effect.
Embodiment four: that present embodiment and embodiment one are different is the Cl that drips 60～100mmol in the step 7 on the nano-pore array thin film surface
-Ionic liquid.Other step and parameter are identical with embodiment one.
Present embodiment obtains that promptly different number Cl are arranged under the applying bias effect
-The protein structure memristor unit switch array that ion injects.
Embodiment five: present embodiment and embodiment one are different is that the thickness of silicon chip in the step 1 is 100～1500 μ m.Other step and parameter are identical with embodiment one.
Embodiment six: present embodiment is different with embodiment one or two is that the silicon chip that will have the carboxy methylation matrix in the step 6 immerses in the cattle immune globulin matter solution that molar concentration is 0.02mol/L and reacts 2h.Other steps and parameter are identical with embodiment one or two.
Embodiment seven: present embodiment and embodiment five are different is that metal in the metal electrode in the step 8 is platinum, zinc, aluminium, gold, silver or copper, wherein the thickness 50nm of metal electrode～10 μ m.Other steps and parameter are identical with embodiment one.
Embodiment eight: present embodiment and embodiment one are different be in the manufacture method step 7 of protein structure quick switch memristor array on silicon chip the surface of protein molecular film adopt polytetrafluoroethyldispersion dispersion to solidify the back to form thickness be the film of 100～500nm.Other steps and parameter are identical with embodiment one.
Polytetrafluoroethyldispersion dispersion in the present embodiment can be bought from the market and obtain.
Embodiment nine: present embodiment and embodiment one are different be in the manufacture method step 7 of protein structure quick switch memristor array on silicon chip the surface of protein molecular film adopt silica gel to solidify the back to form thickness be the film of 100～500nm.Other steps and parameter are identical with embodiment one.
The silica gel of present embodiment can be bought from the market and obtain.
Claims (4)
1, the manufacture method of protein structure quick switch memristor array is characterized in that the manufacture method of protein structure quick switch memristor array is made according to following steps: one, adopt the method for magnetron sputtering to make the golden film that a layer thickness is 70～90nm at the upper surface of silicon chip; Two, to immerse solute concentration be 5 * 10 to the silicon chip that will be coated with golden film
-3The ethanolic solution reaction 5～7h of 11-sulfydryl-1-undecyl alcohol of mol/L promptly forms the sulfydryl hydrophilic surface on golden film surface, and wherein the mass concentration of etoh solvent is 70%～90% in the ethanolic solution of 11-sulfydryl-1-undecyl alcohol; Three, the silicon chip with sulfydryl hydrophilic surface of step 2 preparation is immersed in the alkali ethereal solution of epoxychloropropane that solute concentration is 0.6～0.8mol/L and react 3～5h, promptly formed the epoxy material surface at hydrophilic surface, wherein the solvent of the alkali ethereal solution of epoxychloropropane is that the NaOH solution of 0.3～0.5mol/L and quality purity are that 99%～99.9% diethylene glycol dimethyl ether is formed according to 1: 1 volume ratio by concentration; Four, the washed with de-ionized water 3～4min of the silicon chip with epoxy material surface that step 3 is prepared, be that 95% ethanolic solution cleans 1～2min with mass concentration then, again with reacting 18～22h in the aqueous slkali that immerses glucan behind washed with de-ionized water 3～4min, be about to glucose and be fixed on the epoxy material surface, wherein the aqueous slkali of glucan is made up of 9～11 parts of concentration Na0H solution that is 0.8～1.2mol/L and 2～5 parts glucan T-500 according to ratio of weight and number; Five, the silicon chip that the surface of step 4 preparation is fixed with glucose immerses and reacts 15～18h in the hydrogenperoxide steam generator of bromoacetic acid that concentration is 0.8～1.2mol/L and form carboxymethylated matrix, and wherein solvent is that concentration is the hydrogenperoxide steam generator of 1.8～2.2mol/L in the hydrogenperoxide steam generator of bromoacetic acid; Six, it is that 99%～99.9% dichloroethanes and quality purity are to react 5～8h in the mixed solution of 99%～99.9% N-hydroxy-succinamide that the silicon chip with carboxy methylation matrix of step 5 preparation is immersed in quality purity, the silicon chip that will have the carboxy methylation matrix again immerses in the cattle immune globulin matter solution that molar concentration is 0.01～0.03mol/L and reacts 2～3h, be ethanolamine salt acid buffer flushing 10～20min of 0.1～0.3mol/L then with molar concentration, be about to cattle immune globulin matter and be fixed on formation protein molecule film on the carboxy methylation matrix, wherein the mol ratio of dichloroethanes and N-hydroxy-succinamide is 1: 1; Seven, surface-coated one deck polytetrafluoroethyldispersion dispersion of protein molecular film or employing silica gel curing back formation thickness are the film of 100～500nm on the silicon chip of step 6 preparation, adopting laser marking machine to etch bore dia again on film is that the microwell array of 100 μ m obtains the microwell array film, the output facula diameter of control laser marking machine is 100 μ m, the power of laser marking machine is 10W, drips 60～100mmolK on the nano-pore array thin film surface then
+Ion, Na
+Ion or Cl
-The ionic liquid of ion forms biological cell membrane, promptly obtains protein structure memristor unit; Eight, the protein structure memristor unit that step 7 is prepared adopts the sealed package technology with metal electrode to encapsulate and promptly obtains protein structure quick switch memristor array.
2, the manufacture method of protein structure quick switch memristor array according to claim 1 is characterized in that in the step 1 at thickness being to prepare gold thin film on 100～1500 μ m silicon chips.
3, the manufacture method of protein structure quick switch memristor array according to claim 1 and 2, the silicon chip that it is characterized in that will having in the step 6 carboxy methylation matrix immerses in the cattle immune globulin matter solution that molar concentration is 0.02mol/L and reacts 2h.
4, the manufacture method of protein structure quick switch memristor array according to claim 3 is characterized in that the metal in the metal electrode in the step 8 is platinum, zinc, aluminium, gold, silver or copper, wherein the thickness 50nm of metal electrode～10 μ m.
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| WO2012050533A1 (en) * | 2010-10-15 | 2012-04-19 | Nanyang Technological University | A memristor comprising a protein and a method of manufacturing thereof |
| CN102931345A (en) * | 2011-08-12 | 2013-02-13 | 中国科学院微电子研究所 | Memristor device based on flexible substrate and manufacturing method thereof |
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| WO2012050533A1 (en) * | 2010-10-15 | 2012-04-19 | Nanyang Technological University | A memristor comprising a protein and a method of manufacturing thereof |
| CN102931345A (en) * | 2011-08-12 | 2013-02-13 | 中国科学院微电子研究所 | Memristor device based on flexible substrate and manufacturing method thereof |
| CN107425119A (en) * | 2017-08-11 | 2017-12-01 | 河北大学 | A kind of resistive neurobionics device with organic-biological compatibility and its preparation method and application |
| CN107681047A (en) * | 2017-08-11 | 2018-02-09 | 河北大学 | A kind of organic degradable resistive neurobionics device and its preparation method and application |
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| CN107968013A (en) * | 2017-11-28 | 2018-04-27 | 清华大学 | A kind of liquid metal switch system combined based on biologic specificity identification |
| CN108596333A (en) * | 2018-03-15 | 2018-09-28 | 江西理工大学 | A kind of cardiac Purkinje fibers memristor perturbation circuit design method based on Hodgkin-Huxley models |
| CN108596333B (en) * | 2018-03-15 | 2021-08-24 | 江西理工大学 | Heart purkinje fiber memristor perturbation circuit design method based on Hodgkin-Huxley model |
| CN109599488A (en) * | 2018-11-06 | 2019-04-09 | 西南交通大学 | A kind of hair is preparing the application in memristor |
| CN109616571A (en) * | 2018-11-13 | 2019-04-12 | 西南交通大学 | A kind of preparation method of collagen memristor |
| CN109756146A (en) * | 2019-01-04 | 2019-05-14 | 西安交通大学 | Nano generator and preparation method containing micro-nano texturing fibroin frictional layer |
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