CN102590309B - Manufacture and application method for graphene transistor and biosensor of graphene transistor - Google Patents

Manufacture and application method for graphene transistor and biosensor of graphene transistor Download PDF

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CN102590309B
CN102590309B CN201210025405.1A CN201210025405A CN102590309B CN 102590309 B CN102590309 B CN 102590309B CN 201210025405 A CN201210025405 A CN 201210025405A CN 102590309 B CN102590309 B CN 102590309B
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graphene
transistor
graphene transistor
electrode
transistorized
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CN102590309A (en
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游学秋
卢家宾
王晓诚
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XIAMEN SIMING INHERE BEAUTY THERAPY SURGERY CLINIC Co.,Ltd.
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游学秋
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Abstract

The invention discloses a manufacture and application method for a graphene transistor and a biosensor of the graphene transistor, which is low in price, avoids chemical pollution of the surface of the graphene transistor, and is suitable for integrated manufacture and mass production of the graphene transistor and the existing electronic devices. A method used for growing zinc oxide nanowires or metal nano-particles on the surface of the graphene transistor and based on the manufacture method for the biosensor of the graphene transistor is further provided. Nanometer materials on the surface of the transistor are favorable for absorbing biological active substances (such as enzyme, deoxyribonucleic acid (DNA), ribonucleic acid (RNA), aptamer, antigen or antibody) with special identification capacity. Therefore, a graphene transistor channel has capacity of absorbing target analyte selectively, and sensitivity and selectivity of a sensor based on the graphene transistor channel are improved.

Description

The exploration and application method of Graphene transistor and biology sensor thereof
Technical field
The present invention relates to a kind of biology sensor and manufacture field, the particularly a kind of exploration and application method of Graphene transistor and biology sensor thereof.
Background technology
Graphene is the monatomic planar crystal with high conductivity, thermal conductivity and outstanding physical strength.Graphene transistor has unique advantage in high-sensitivity detection field.When detecting gas, Graphene has very low noise signal, can accurately survey single gas molecule, and making it has potential application foreground at chemical sensor and molecular probe direction.
In view of the extremely wide application prospect of Graphene, people are just trying hard to find various methods and are obtaining it, and what certainly first expect is how by graphite separation in layer.First Hai Mu etc. use what is called " mechanical stripping method ", be exactly with adhesive tape, the high orientation graphite of arranging neatly especially repeatedly to be pasted and torn in fact, finally sticky Graphene is on tape posted on silicon chip, then with solvent, adhesive tape is dissolved, on silicon chip, just can obtain the Graphene of individual layer or minority layer.This method is fairly simple, and gained Graphene is also more complete, can supply further performance study, but it yields poorly, and is difficult to manufacture large-area material.In research before, the inventor has designed a kind of " electrochemical stripping method ", by electrochemical reaction, non-carbon atom is inserted into interlayer, graphite linings is strutted, reduce the gravitation of interlayer, by the lamella after oxidation separately, the lamella separating makes it deoxidation and reduction by chemical method or high temperature again and becomes Graphene for the micro bubble producing with electrochemical process in water or solvent or high-frequency ultrasonic vibration.This method cost is low, is easy to scale preparation, but the electrochemical reactions such as oxidation and ultrasonic processing and reduction reaction tend to cause the damaged of carbon atom in Graphene, and the Graphene obtaining is of low quality, poor-performing.
Chemical vapour deposition technique has become one of main method of preparing in zinc paste at present.Chemical vapour deposition technique is as methane (CH with the gaseous organic substance of carbon atoms 4), acetylene (C 2h 2) etc. on the metallic matrixes such as nickel or copper pyrolytic, the carbon atom that removes hydrogen atom can deposit and be adsorbed on metal surface and grow into continuously Graphene.This method is simple, can prepare large area Graphene, and gained Graphene is more complete, and quality is better.
Depositing electrode pattern on the Graphene preparing how, and by itself and existing electronic circuit integrated be the problem that first exploitation graphene electronic device will solve.Existing Graphene transistor device is to make electrode pattern with electron beam lithography mostly, the method need to be carried out a plurality of chemical treatment steps on Graphene top layer, such as need being coated with last layer organic photoresist and Graphene need to being immersed in to chemical development in developer on Graphene.These chemical treating processes cause chemical contamination to graphene device, and the surface that most disadvantageous chemical moleculars stick to Graphene is difficult for removing, and has upset the performance of Graphene crystal.And electron beam lithography cost is high, be consuming timely not easy to greatly large-scale production.Simultaneously existing Graphene transistor chemistry sensor has poor selectivity, and Graphene plane of crystal is not easy to Adsorption for Biomolecules, and these problems have seriously limited the application of Graphene aspect high sensitive sensor.
Summary of the invention
It is not enough that object of the present invention overcomes above-mentioned prior art; a kind of Graphene preparation method of transistor is provided; the method is cheap and avoided the chemical contamination on Graphene transistor surface, is applicable to integrated making and the large-scale production of the existing electron device of Graphene transistor AND gate.
For the poor problem of the selectivity of Graphene transistor sensor, the method based on the transistorized biology sensor of Graphene of making has further been proposed, method at Graphene transistor superficial growth zinc oxide nanowire or metal nanoparticle, the nano material on transistor surface be conducive to absorption there is single-minded recognition function power bioactivator (as enzyme, DNA, RNA, fit, antigen or antibody etc.), make Graphene transistor channels there is the ability of selective adsorption target analytes, sensitivity and the selectivity of the sensor based on Graphene transistor channels have been improved.By the gate electrode in solution, apply the gate voltage of certain limit, between source electrode and drain electrode, apply constant channel voltage simultaneously, by the variation of sense channel electric current, the micro-target analytes in solution can be detected with sensitivity.
The object of the invention also comprises a kind of method that application is carried out micro-target analytes detection based on the transistorized biology sensor of Graphene that discloses in addition.
The present invention is achieved by the following scheme:
The transistorized method of making Graphene, is characterized in that: comprise the steps:
Step 1, on silicon wafer, evaporation last layer titanium is as conductive layer;
Step 2, photoresist is coated in titanium-base;
Step 3, photoetching technique is imprinted on designed transistor electrodes pattern on photoresist;
Step 4, immerses the electrically-conductive backing plate that stamps the photoresist of pattern in nickel sulphonic acid and BAS and carries out nickel electro-chemistry deposition;
Step 5, substrate is put into acetone soln, uses high-frequency ultrasonic vibration processing, and nickel mask is separated with substrate;
Step 6, nickel mask is placed in the silicon wafer that has adhered to Graphene crystal, uses evaporator that electrode material is plated to electrode pattern by mask on Graphene transistor.
Step 7 deposits one deck isolation protective material by nickel mask on electrode pattern.
Further, described step 2, can be coated in the thick SU8 photoresist of one deck 100 μ m on titanium-base by the method for spin coating; Described step 4, the thickness of the nickel of deposition is 100 μ m; Described step 5, puts into substrate the acetone soln of 60 ℃; The electrode material of described step 6 is Au/Ti metal electrode material.Described isolation protective material is parylene material.
Make the method based on the transistorized biology sensor of Graphene, it is characterized in that: the Graphene transistor fabrication of described biology sensor adopts described method above to make.
In addition, the method of making based on the transistorized biology sensor of Graphene is except comprising the described transistorized method step of Graphene of preparing, also be included in the region of Graphene exposure by galvanochemistry selectivity sedimentation growth of zinc oxide nano line or metal nanoparticle step, the nano material top layer on transistor surface is adsorbed and is loaded bioactivator step by electrostatic interaction.
Wherein, the region that described Graphene exposes is by galvanochemistry selectivity sedimentation growth of zinc oxide nano line step, the region that Graphene exposes is by galvanochemistry selectivity sedimentation growth of zinc oxide nano line step, elder generation's spin coating ZnO methyl alcohol colloidal solution on substrate, oven dry to be to strengthen the bonding of ZnO micelle, by get rid of cloth the substrate of micelle hang by the feet in zinc nitrate hexahydrate growth solution; Using another platinum wire that immerses growth solution as with reference to electrode, and the electrode pair Graphene by Graphene transistor two ends adds DC voltage; Zinc oxide nanowire is grown at Graphene surface electrochemistry; Afterwards by deionized water rinsing remove remaining solute, dewatering after air-dry grows up to zinc oxide nanowire.
A kind of method that application detects based on the transistorized biology sensor of Graphene, it is characterized in that, by the gate electrode in solution, apply gate voltage, between source electrode and drain electrode, apply constant channel voltage simultaneously, target molecule in sample solution is adsorbed on transistor surface, by changing the electrostatic double layer interface characteristic between transistor AND gate sample solution, thereby changed the transistorized field effect characteristic of Graphene; By the variation of sense channel electric current, the micro-target analytes in solution can be detected.
The present invention has following distinguishing feature and effect in sum:
1). overcome the chemical contamination of having avoided Graphene transistor surface, be applicable to integrated making and the large-scale production of the existing electron device of Graphene transistor AND gate; Make Graphene transistor channels there is the ability of selective adsorption target analytes, improved sensitivity and the selectivity of the sensor based on Graphene transistor channels.
2). the Graphene transistor biology sensor of high sensitivity and high selectivity, Graphene transistor sensor has low noise, highly sensitive feature.In Graphene superficial growth nano material as zinc oxide nanowire, make transistor surface can load a large amount of Zhuan mono-Shi Do functions bioactivator (as enzyme, DNA, RNA, fit, antigen or antibody etc.), the ability of giving transistor channels selective adsorption target analytes.The target analytes of trace is adsorbed on Graphene transistor surface, can change significantly transistor resistance characteristic.Therefore the resistance characteristic of Graphene changes the micro-target analytes in reflected sample in high sensitivity.
Accompanying drawing explanation
Fig. 1 nickel Mask Fabrication process schematic diagram;
Fig. 2 prepares Graphene transistor schematic by mask evaporation;
Fig. 3 is based on the transistorized biology sensor preparation process of Graphene schematic diagram;
Based on Graphene, transistorized biosensor test experiment arranges and test circuit schematic diagram Fig. 4.
Embodiment
Below in conjunction with accompanying drawing, the transistorized method of making Graphene of the present invention, method and the biosensor application method of making based on the transistorized biology sensor of Graphene are described further:
One, the first preparation of Graphene crystal.The chemical vapour deposition technique generally using at present of take is example, first on monox/silicon wafer, deposits the transition metal layers such as nickel that 500nm is thick or copper, uses the gaseous organic substance of carbon atoms as methane (CH 4), acetylene (C 2h 2) and the mixed gas of hydrogen as the source of carbon, in the high temperature of 1000 ℃, the gaseous organic substance of carbon atoms pyrolytic on the metallic matrixes such as nickel or copper, the carbon atom deposition that removes hydrogen atom is adsorbed on metal surface and grows into continuously Graphene.The support film of using while applying last layer polymethylmethacrylate (PMMA) as transfer Graphene on the substrate of Graphene of having grown.Graphene substrate is immersed to hydrogen chloride solution (HCl: H 2o=1: 10), after approximately 8 hours, the metallic matrix of Graphene bottom is dissolved, and PMMA/ graphene film floats over solution top layer.PMMA/ graphene film is transferred to and deposited 300nm silicon oxide sio 2highly doped conductive silicon wafer on.Then use acetone solution PMMA layer, by deionized water clean wafers repeatedly.The hot stove thermal treatment that wafer is put into the hydrogen of 450 ℃ and argon gas more than 20 minutes, is removed remaining PMMA molecule, makes large-area Graphene crystal well stick to SiO 2on/highly doped Si wafer.
Two, the preparation of nickel mask.As shown in Figure 1, first on silicon wafer evaporation last layer titanium as conductive layer.By the method for spin coating, the thick SU-8 photoresist of one deck approximately 100 μ m is coated on titanium-base.Then use mask exposure, the photoetching techniques such as development are imprinted on designed transistor electrodes pattern on photoresist.The SU-8/ titanium-base that stamps pattern is immersed in nickel sulphonic acid and BAS and carries out nickel electro-chemistry deposition.The thickness approximately 100 μ m of the nickel of deposition.Substrate is put into the acetone soln of 60 ℃, used high-frequency ultrasonic vibration processing, nickel mask is separated with substrate.
Three, electrode mask evaporation.As shown in Figure 2, nickel mask is placed on the monox or silicon wafer that has adhered to Graphene crystal, use evaporator that electrode material (as Au/Ti metal electrode material) is plated to electrode pattern by mask at Graphene transistor two, as source electrode and drain electrode.Then with same method, on electrode, deposit one deck isolation protective material (as parylene material).Avoid electrode directly to contact with sample solution.
Four, the perform region nano material grown exposing at Graphene transistor is as zinc oxide nanowire.With reference to accompanying drawing 3, the method for the region growing zinc oxide nanowire exposing at Graphene can be used galvanochemistry selectivity sedimentation.Spin coating ZnO methyl alcohol colloidal solution on substrate, then through 150 ℃ of oven dry 10min, to strengthen the bonding of ZnO micelle, ZnO methyl alcohol colloidal solution is mixed and heated to 60 ℃ of preparations by NaOH methanol solution and zinc acetate methanol solution.ZnO growth solution is the zinc nitrate hexahydrate (Zn (NO of 0.025ML 3) 2.6H 2o) aqueous solution.By get rid of cloth the substrate of micelle hang by the feet in ZnO growth solution, heating water bath to 95 ℃, usings another platinum wire that immerses growth solution as with reference to electrode, the DC voltage of the add-1V of electrode pair Graphene by Graphene transistor two ends.Zinc oxide nanowire is grown at Graphene surface electrochemistry.After approximately 6 hours, take out Graphene substrate and remove remaining solute with deionized water rinsing, absolute ethyl alcohol dehydration is air-dry.
Five, the bioactivator (as enzyme, DNA, RNA, fit, antigen or antibody etc.) with single-minded recognition function is loaded on the nano material on Graphene transistor (ZnO nano-wire) top layer.With reference to accompanying drawing 3, zinc oxide nanowire has higher isoelectric point (about 9.5IEP), the bioprobe molecule of low isoelectric point is (as DNA, RNA is fit, antibody protein etc.) can by electrostatic interaction, be adsorbed on the nano zinc oxide material surface of higher isoelectric point, play immobilizing biologically active materials in the effect on Graphene transistor surface.The RNA aptamers of C reactive protein of take is example as molecular probe detection of a target molecule (C reactive protein), and the sequence of the RNA aptamers of c reactive protein is 5 '-GCC UGU AAG GUG GUC GGU GUG GCG AGU GUG UUA GGA GAG AUUGC-3 '.Graphene/ZnO nano-wire transistor is immersed in the Tris buffer solution (pH6.8) contain lnM C reactive protein aptamers 12 hours.Because of RNA aptamers electronegative in damping fluid, and ZnO nano-wire positively charged in damping fluid, so RNA aptamers is adsorbed on zinc oxide nanowire surface by electrostatic interaction, thereby make Graphene/zinc-oxide nano line transistor there is the ability of optionally identifying C reactive protein.C reactive protein in sample can be combined and be attached to transistor surface with RNA aptamers, converts the electric signal that can be identified to.
Six, biosensor test experiment arranges and test, with reference to figure 4, analyte sample solution is dropped in to transistor operationg region territory, Ag/AgCl electrode is immersed in sample solution as with reference to electrode, another and the direct-connected termination electrode of Graphene passage are as working electrode, electrostatic double layer interface by transistor AND gate solution applies gate voltage to Graphene transistor, the gate voltage scope applying at+1V between-1V.Be carried in the channel voltage at Graphene passage two ends between 50mV, to guarantee that the gate voltage loading can distribute relatively uniformly on whole Graphene passage.Target molecule in sample solution (C reactive protein) is adsorbed on transistor surface, change the electrostatic double layer interface characteristic (being equivalent to change the dielectric property of gate electrode and interchannel dielectric layer) between transistor AND gate sample solution, thereby changed the transistorized field effect characteristic of Graphene.Under constant gate voltage and channel voltage, the absorption of target molecule (C reactive protein) causes channel current to change.By the variation of sense channel electric current, the micro-target analytes (C reactive protein) in solution can be detected with sensitivity.
In sum, concrete material, parameter and technique in embodiment, have been enumerated.The content part according to the present invention, manufactures in process, and concrete material, parameter and technique can be adjusted according to prior art, substitute etc.In the equivalence that does not depart from content scheme of the present invention, replace and should belong to the scope of protection of the invention.

Claims (5)

1. make the transistorized method of Graphene, it is characterized in that: comprise the steps:
Step 1, on silicon wafer, evaporation last layer titanium forms titanium-base as conductive layer;
Step 2, is coated in photoresist on titanium-base;
Step 3, photoetching technique is imprinted on designed transistor electrodes pattern on photoresist;
Step 4, immerses the electrically-conductive backing plate that stamps the photoresist of pattern in nickel sulphonic acid and BAS and carries out nickel electro-chemistry deposition;
Step 5, substrate is put into acetone soln, uses high-frequency ultrasonic vibration processing, and nickel mask is separated with substrate;
Step 6, nickel mask is placed in the silicon wafer that has adhered to Graphene crystal, uses evaporator that electrode material is plated to electrode pattern by mask on Graphene transistor, as source electrode and drain electrode.
2. the transistorized method of making Graphene as claimed in claim 1, is characterized in that, also comprises step 7, by nickel mask, deposits one deck isolation protective material on electrode pattern.
3. the method for making based on the transistorized biology sensor of Graphene, is characterized in that: the Graphene transistor fabrication of described biology sensor adopts as claim 1,2 arbitrary described method making.
4. the method for making as claimed in claim 3 based on the transistorized biology sensor of Graphene, it is characterized in that, also be included in the region of Graphene exposure by galvanochemistry selectivity sedimentation growth of zinc oxide nano line or metal nanoparticle step, the nano material top layer on transistor surface is used for adsorbing loading bioactivator step.
5. the method for making as claimed in claim 4 based on the transistorized biology sensor of Graphene, it is characterized in that, the region that described Graphene exposes is by galvanochemistry selectivity sedimentation growth of zinc oxide nano line step, elder generation's spin coating ZnO methyl alcohol colloidal solution on substrate, oven dry to be to strengthen the bonding of ZnO micelle, by get rid of cloth the substrate of micelle hang by the feet in zinc nitrate hexahydrate growth solution; Using another platinum wire that immerses growth solution as with reference to electrode, and the electrode pair Graphene by Graphene transistor two ends adds DC voltage; Zinc oxide nanowire is grown at Graphene surface electrochemistry; Afterwards by deionized water rinsing remove remaining solute, dewatering after air-dry grows up to zinc oxide nanowire.
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Patentee after: XIAMEN SIMING INHERE BEAUTY THERAPY SURGERY CLINIC Co.,Ltd.

Address before: Room 105, Building No. 37, Nancheng Huanxi Road, Xinluo District, Longyan City, Fujian Province

Patentee before: You Xueqiu

CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140402

Termination date: 20210203