CN101986145A - Nanopore electrical sensor - Google Patents
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- CN101986145A CN101986145A CN 201010298015 CN201010298015A CN101986145A CN 101986145 A CN101986145 A CN 101986145A CN 201010298015 CN201010298015 CN 201010298015 CN 201010298015 A CN201010298015 A CN 201010298015A CN 101986145 A CN101986145 A CN 101986145A
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Abstract
The invention discloses a nanopore electrical sensor, which comprises a substrate, a first insulation layer, a nano functional layer, an electrical contact layer, a second insulation layer and nanopores, wherein the first insulation layer and the nano functional layer are formed on the substrate in turn; the electrical contact layer is formed on the first insulation layer and on the edge of the nano functional layer; and the second insulation layer is formed on the nano functional layer; and nanopores are formed in the centers of the substrate, the first insulation layer, the nano functional layer and the second insulation layer. The thickness of the nano functional layer of the nanopore electrical sensor can be kept between 0.3 and 0.7 nanometers and meets the requirements for detecting the resolution of the electrical characteristics of single basic groups in a single-chain DNA, so the nanopore electrical sensor is suitable for convenient and quick electronic gene sequencing. The nanopore electrical sensor disclosed by the invention solves the technical problem of integrating the nano functional layer in nano pores, and the method for preparing the nano functional layer is simple; and the mutual influences between the basic groups and the nano functional layer, which are generated due to the possible different orientation of the basic groups of the DNA passing through the nano pores, are eliminated.
Description
Technical field
The present invention relates to sensor, relate in particular to a kind of nano-pore electric sensor.
Background technology
Nano-pore (nanopore) can be surveyed and characterising biological molecule such as DNA in the unimolecule level of resolution, RNA and poly-peptide, the potential unimolecule gene sequencing technology based on nano-pore does not need fluorescent marker, does not need PCR reaction, and being expected to can be directly and " reading " goes out DNA fast base sequence; This sequencing technologies is expected to reduce greatly the order-checking cost, realizes personalized medicine.Unimolecule gene sequencing technology based on nano-pore mainly contains three kinds of detection methods: ion blocks electric current (Strand-sequencing using ionic current blockage), transverse electric electron current (Strand-sequencing using transverse electron currents), optical information (Nanopore sequencing using synthetic DNA and optical readout).The degree of depth of the nano-pore of preparation is generally greater than 10 nm at present, and well beyond single-chain DNA base spacing 0.3-0.7 nm, that is to say has 15 bases to pass through simultaneously in the hole, therefore can't reach the resolution of single base of gene sequencing; Therefore, reach the resolution of single base, must possess the single base element in can the identification form chain DNA.In addition, ion blocks electric current and has only the pA magnitude, and signal to noise ratio (S/N ratio) is very low, is difficult to really be used for dna sequencing.
Because the base of each DNA structurally and chemically all differences to some extent, so all may there be unique electronic characteristic in each base, utilizes these subcharacters to check order to DNA.2007, people such as Xu Mingsheng were at Small(
Small 2007,
3, the paper of delivering " Electronic Performance of DAN base (The electronic properties of DNA bases) " on 1539-1543) has been reported between the different DNA bases and has been had the electronic fingerprint feature.In 2005, the M Zwolak in California, USA university San Diego branch school etc. were at nanometer wall bulletin (Nano Letters
2005,
5, publish thesis on 421-424): the characteristic electron of the DNA base of lateral transport (Electronic signature of DNA nucleotides via transverse transport) M Zwolak etc. thinks by Theoretical Calculation: can measure the transverse tunnel electronic current of DNA base as DNA during by nano-pore and it is checked order.This requirement is integrated in the nano-pore system with nano-electrode, and nano-electrode will be recorded in the electric current vertical with the DNA chain that produces when DNA passes through nano-pore like this.Yet, although prepare the technology comparative maturity of nano-pore at present,, also do not have technical method will have single base resolution nano-electrode up to now and be integrated in the nano-pore system.On the other hand, the distance between nano-electrode and the DNA base and the orientation of DNA base are very big to tunnel current influence, so must solve this influence to measuring-signal that may be caused by different orientations during by nano-pore owing to the DNA base.2007, people such as Xu Mingsheng were at Small(
Small 2007,
3Deliver the paper of " Electronic Performance of DAN base (The electronic properties of DNA bases) " 1539-1543): four kinds of bases that they utilize ultrahigh vacuum tunnel flying-spot microscope to disclose DNA first experimentally exist different electronic fingerprint characteristics on the surface of monocrystalline Au, have different interactions between four kinds of bases that this means DNA and the electrode function material; Therefore, different interactional principle between four kinds of bases utilizing DNA and the nano functional layer material is measured when DNA passes through nano-pore the electrology characteristic difference that causes owing to different interactions between four kinds of different bases and the nano functional layer material or optical characteristics difference etc. and is expected to realize the gene sequencing quick, that cost is low.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, propose a kind of nano-pore electric sensor.
Realize that the technical scheme that the foregoing invention purpose is adopted is: a kind of nano-pore electric sensor, comprise the substrate, first insulation course, nano functional layer and second insulation course that stack gradually from top to bottom, center at substrate, first insulation course, nano functional layer and second insulation course is provided with nano-pore, and described nano functional layer is the laminar of center band nano-pore.The nano functional layer clamps between first insulation course and second insulation course, the nano-pore periphery is the shape of full wafer, the different orientation problem that may exist when having solved base by nano-pore has guaranteed that there is optimal and different interactions in four kinds of bases of DNA with the nano functional layer.
As preferably, the first insulation course upper surface, nano functional layer edge are provided with electric contacting layer, help the transmission of nano functional layer signal.
As preferably, described nano functional layer is meant between four kinds of bases of itself and DNA and has different interactional functional materials, when the base of nano functional layer and DNA takes place to interact, measure the variation of the electricity that causes by different interactions or other correlated performance and difference and obtain the information of dna sequence dna.
As preferably, the material of described nano functional layer is a layered conductive material, and layered conductive material is the graphene oxide of graphite, reduction, partially hydrogenated Graphene, BNC, MoS
2, NbSe
2Or Bi
2Sr
2CaCu
2O
x
As preferably, the thickness of nano functional layer is 0.3～3.5 nm, and optimal thickness is 0.3～1 nm.
As preferably, described graphite is 1～10 layer graphene film, and its thickness is within 0.3～3.5 nm scope like this.
As other preferred, the graphene oxide of described reduction is served as reasons graphene oxide film is carried out reduction reaction and the redox graphene film of the conduction that obtains, and its thickness is 0.3～3.5 nm.
As other preferred, described partially hydrogenated Graphene is for to be reacted by graphene film and hydrogen, thereby makes the part of Graphene
Sp 2 Key is converted into C-H
Sp 3 Key, its thickness are 0.3～3.5 nm.
As other preferred version, described layered conductive material is BNC, BNC is the stratiform conductive film by boron nitride and Graphene hydridization, be by boron, nitrogen, three kinds of elements of carbon are formed, its electric property is between the boron nitride of Graphene that conducts electricity and insulation, and its conductive characteristic can be by changing boron, nitrogen, three kinds of elements of carbon in film content and obtain regulation and control, can be referring to document [Lijie Ci etc. " Atomic layers of hybridized boron nitride and graphene domains (atomic layer of boron nitride and Graphene territory hydridization) ", Nature Materials (nature material) 9 (2010) 430-435].The BNC film is preferably 1～10 layer, and its thickness is 0.3～3.5 nm like this, more preferably 1～3 layer.
As preferably, described MoS
2Be that thickness is the MoS of 0.3～3.5 nm
2Film.
As preferably, described NbSe
2Be that thickness is the NbSe of 0.3～3.5 nm
2Film.
As preferably, described Bi
2Sr
2CaCu
2O
xBe that thickness is the Bi of 0.3～3.5 nm
2Sr
2CaCu
2O
xFilm.
As preferably, the material of described substrate is semiconductor material or insulating material, and semiconductor material is one or more the potpourri among Si, GaN, Ge or the GaAs, and insulating material is SiC, Al
2O
3, SiN
x, SiO
2, HfO
2, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate.
As preferably, the material of described first insulation course and second insulation course is SiO
2, Al
2O
3, BN, SiC, SiN
x, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate.The material of the described substrate and first insulation course can be same material.
As preferably, the material of described electric contacting layer is one or more the potpourri among Au, Cr, Ti, Pd, Pt, Cu, Al, Ni or the PSS:PEDOT.Because the thickness of described nano functional layer is in 0.3-3.5 nm scope, described electric contacting layer be used to improve the nano functional layer to being electrically connected of external measurement devices.
As preferably, described nano functional layer clamps as sandwich between first insulation course and second insulation course, dielectric protection layer nano functional layer.
As preferably, described nano-pore is a circular hole, and the aperture of nano-pore is 1～50 nm, and the aperture of more excellent nano-pore is 1～10 nm, and the aperture of optimum nano-pore is 1～3 nm.Nano-pore is that circular hole can better guarantee the sensor isotropy.As other scheme, nano-pore also can be changeable shape hole or elliptical aperture, and the ultimate range around the nano-pore between last 2 is 1～50 nm.
The thickness of nano functional layer of the present invention can be controlled between 0.3～0.7 nm, reaches the resolution requirement of the electrical characteristic that detects the single base in the single stranded DNA, thereby is suitable for cheap, rapid gene electronics order-checking.Nano-pore electric sensor of the present invention has solved the technological difficulties that the nano functional layer are integrated in nano-pore, and its method for preparing the nano functional layer is simple.The nano functional layer clamps between two insulation courses, can avoid polluting and unnecessary environmental impact, such nano functional layer sound construction.The different orientation that may exist owing to base when the nano-pore periphery has solved for the shape of the nano functional layer of full wafer that the DNA base is passed through nano-pore causes the interactional influence to base and nano functional layer.
Description of drawings
Fig. 1 is the preparation flow synoptic diagram of nano-pore electric sensor of the present invention; Wherein the graphene nano functional layer is to be transferred on the insulation course by preparation back on other substrate.
Fig. 2 is the transmission electron microscope shape figure of the single-layer graphene nano-pore of nano-pore electric sensor of the present invention; Wherein Graphene is placed on the grid of transmission electron microscope.
Fig. 3 is the preparation flow synoptic diagram of nano-pore electric sensor of the present invention; Wherein the graphene nano functional layer is that directly preparation is on the SiC insulation course.
Fig. 4 is the preparation flow synoptic diagram of nano-pore electric sensor of the present invention; Wherein BNC is as the nano functional layer.
Fig. 5 is the preparation flow synoptic diagram of nano-pore electric sensor of the present invention; Wherein the graphene nano functional layer is to be transferred on the insulation course by solid carbon source preparation back.
Among the figure, substrate 1, first insulation course 2, nano functional layer 3, nano-pore 4, electric contacting layer 5, second insulation course 6, insulating protective layer 7, square openings 10, hole 11, metal catalytic layer 12.
Embodiment
Also the present invention is further described in conjunction with the accompanying drawings below by specific embodiment.
Embodiment 1:
Adopt chemical gaseous phase depositing process synthesizing graphite alkene film on Cu: will have thickness is that 25 μ m Cu sheets carry out the surface finish cleaning, then it is positioned in the ultrahigh vacuum (1.0 * 10
-9Torr) carry out 900 ℃ of thermal treatments 30 minutes; Logical C
2H
4Gas (10 Pa) growth 10 minutes; Last fast cooling arrives room temperature, thereby obtains graphene film on the Cu sheet.
As shown in Figure 1: in thick monocrystalline silicon＜100 of 600 μ m〉prepare 50 nm SiO successively on the substrate 1
2With 30 nm Si
3N
4Composite insulation layer 2(Fig. 1 a).
Adopt photoetching technique, and corrode silicon substrate and SiO respectively with the HF solution of KOH solution and buffering
2And prepare square openings 10(Fig. 1 b that is approximately 80 μ m * 80 μ m).
Adopt electron beam lithography and SF
6The plasma reaction lithographic technique prepares hole 11(Fig. 1 c that a diameter is approximately 2 μ m on silicon nitride film).
The graphene film for preparing is transferred on the silicon nitride film as nano functional layer 3, graphene film covers silicon nitride fenestra 11(Fig. 1 d): spin coating 1000 nm Polymethylmethacrylate (PMMA) layer on the graphene film that is synthesized, graphene film/the Cu that scribbles PMMA is positioned in the iron nitrate solution Cu erosion is fallen, thereby obtains the PMMA/ graphene film; Then on the PMMA surface, drip isopropyl alcohol, with Si
3N
4/ SiO
2/ Si is placed on PMMA and goes up (Si
3N
4Face contacts with the PMMA face), then with it in about 250 degree thermal treatment ~ 3 minute, with acetone PMMA is dissolved at last.Graphene film has just been transferred to Si like this
3N
4/ SiO
2On the hole 11 of/Si (Fig. 1 d).
Be used to prepare graphene nano hole 4: the enlargement factor of transmission electron microscope is transferred to about 800,000 zoom and focus on Graphene, was approximately for 10 seconds from the electron beam of transmission electron microscope (JEOL 2010F), thereby preparation graphene nano hole 4(Fig. 1 e), Fig. 2 is the shape figure of nano-pore 4 under transmission electron microscope, and wherein nano-pore is placed on the grid of transmission electron microscope.
Because the thickness of graphene film nano functional layer 3 has only the degree of 0.335 nm, electrically contact in order to set up effectively, adopt photoetching and corrosion technology to prepare Cr(5 nm at the edge of Graphene)/Au(50 nm) as electric contacting layer 5(Fig. 1 f).
Adopt the plasma reinforced chemical vapour deposition method on the Graphene face, to prepare 10 nm SiN
xAnd technique for atomic layer deposition prepares 10 nm Al
2O
3Composite insulation layer is as second insulation course 6(Fig. 1 g); In order to protect graphene layer, preparation 5 nm SiN on the Graphene face of monocrystalline silicon face and exposure
xLayer is as insulating protective layer 7(Fig. 1 h).
Effect and parsing: the material of nano functional layer 3 can be the graphene oxide of graphene film, reduction, partially hydrogenated Graphene, BNC, MoS
2, NbSe
2Or Bi
2Sr
2CaCu
2O
xEtc. layered conductive material, this example adopts graphene film as nano functional layer 3 material.
Graphene film can prepare with diverse ways, comprises that chemical gaseous phase depositing process prepares graphene film on metal catalytic layer, also comprises as the synthesizing graphite alkene film with the method for solid carbon source such as graphite, SiC.The metal catalytic layer material of preparation graphene film can also be Cu, Ni, and Pt, Pd, Ir, Zn, Al, Fe, Mn, Ru, Re, Cr, one or more among the Co etc., its thickness are 5 nm～100 μ m.
The carbonaceous gas source of adopting chemical gaseous phase depositing process to prepare graphene film comprises methane, ethane, ethene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, amylene, cyclopentadiene, normal hexane, cyclohexane, benzene etc.; This example is selected the gaseous carbon sources material of ethene as synthesizing graphite alkene for use.
This example adopts chemical gaseous phase depositing process synthesizing graphite alkene film on metal Cu sheet, prepares the single-layer graphene of high uniformity easily in its surface, and, be easy to graphene film be transferred on the insulation course by corrosion Cu Catalytic Layer.
Usually, the insulating film material of preparation nano-pore comprises SiO
2, Al
2O
3, SiN
xDeng, but also can be one or more potpourri in other material such as BN, SiC, polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or the polymethylmethacrylate; This example adopts Si
3N
4/ SiO
2As first insulating layer material.
And the substrate supporting layer material of insulating film material, promptly substrate often is Si, but also can be other material such as GaN, Ge, GaAs, SiC, Al
2O
3, SiN
x, SiO
2, HfO
2, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate; It is substrate that this example adopts Si.
The thickness of nano functional layer can be at 0.3～3.5 nm, and the thickness of the graphene film nano functional layer 3 of this example preparation is 0.335 nm.
With graphene nano functional layer 3 contacted materials can be one or more potpourri among Au, Cr, Ti, Pd, Pt, Cu, Al, Ni or the PSS:PEDOT, can adopt vacuum thermal evaporation, the solution spin coating, thermal oxide, low-pressure chemical vapor deposition, plasma reinforced chemical vapour deposition, technical methods such as ald prepare electric contacting layer, and its thickness is generally 15～600 nm; This example utilizes photoetching and lithographic technique to prepare Cr(5 nm on the edge of graphene nano functional layer 3)/Au(50 nm) as electric contacting layer 5.
The preparation in graphene nano hole can be adopted the nanometer technology of preparing, as electron beam lithography, and focused-ion-beam lithography, the pulsed ionizing beam etching, He ion beam etching etc., the aperture of nano-pore can be 1～50 nm; It is 8 nm that this example adopts the aperture from the graphene nano hole 4 of the electron beam lithography technology preparation of transmission electron microscope.
Embodiment 2:
As shown in Figure 3: { 0001} substrate 1(Fig. 3 is a) in ultrahigh vacuum (1.0 * 10 at the monocrystal SiC of the thick insulation of 100 μ m
-10Torr) carry out heat (1000 ℃～1500 ℃) surface treatment and epitaxial growth obtains graphene film layer 3(Fig. 3 b).
Because the thickness of graphene film nano functional layer 3 is approximately the degree of 0.7 nm, electrically contacts in order to set up effectively, utilizes photoetching and lithographic technique to prepare Pd(50 nm on the edge of Graphene functional layer 3) electric contacting layer 5(Fig. 3 c).
Adopt low-pressure chemical vapor deposition method to prepare 50 nm Si
3N
4Insulation course is as second insulation course 6, and with its surface polishingization (Fig. 3 d).
Adopt electron beam lithography and in fluorinated gas, carry out reaction particle bundle etching SiC substrate 1 and the preparation diameter is approximately hole 10(Fig. 3 e of 2.5 μ m).
Adopt He ion beam etching technology etching Si
3N
4 Second insulation course 6 and graphene nano functional layer 3 and the preparation aperture is approximately nano-pore 4(Fig. 3 f of 1.6 nm).
In order to protect the graphene nano functional layer, preparation 5 nm SiN on the Graphene face of SiC and exposure
xLayer is as insulating protective layer 7(Fig. 3 g).
Effect and parsing: usually, the insulating film material of preparation nano-pore comprises SiO
2, Al
2O
3, SiN
xDeng, but also can be one or more potpourri in other material such as BN, SiC, polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or the polymethylmethacrylate; This example adopts SiC as first insulating layer material.
And the substrate supporting layer material of insulating film material, promptly substrate 1, often is Si, but also can be other material such as GaN, Ge, GaAs, SiC, Al
2O
3, SiN
x, SiO
2, HfO
2, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate; It is substrate that this example adopts SiC.
The material of nano functional layer can be the graphene oxide of graphene film, reduction, partially hydrogenated Graphene, BNC, MoS
2, NbSe
2Or Bi
2Sr
2CaCu
2O
xEtc. layered conductive material, this example adopts graphene film as nano functional layer 3 material.
This example adopts synthesizing graphite alkene film nano functional layer 3 on the SiC of insulation, SiC both had been the solid carbon source material of synthesizing graphite alkene thin layer 3, also be the substrate 1 and first insulation course, 2 materials of preparation nanometer electric sensor, thereby the graphene film that does not need to prepare shift.
The thickness of the graphene film functional layer 3 of this example preparation is 0.7 nm.
Can be one or more the potpourri among Au, Cr, Ti, Pd, Pt, Cu, Al, Ni or the PSS:PEDOT with graphene nano functional layer 3 contacted materials, can adopt vacuum thermal evaporation, the solution spin coating, thermal oxide, low-pressure chemical vapor deposition, plasma reinforced chemical vapour deposition, technical methods such as ald, its thickness is generally 15～600 nm; This example prepares Pd(50 nm on the edge of graphene nano functional layer) as electric contacting layer 5.
The preparation of nano-pore 4 can be adopted the nanometer technology of preparing, as electron beam lithography, and focused-ion-beam lithography, the pulsed ionizing beam etching, He ion beam etching etc., the aperture of nano-pore can be 1～50 nm; The aperture in the graphene nano hole 4 of this routine He ion beam etching preparation is 1.6 nm.
Embodiment 3:
As shown in Figure 4: preparation 100 nm Si on the thick monocrystalline silicon substrate 1 of 600 μ m
3N
4First insulation course 2(Fig. 4 a); Si at insulation course
3N
4Last preparation 100 nm metal Ni Catalytic Layer 12(Fig. 4 b), this metal catalytic layer 12 BNC nano functional layer 3(Fig. 4 c that is used for growing).
After preparation 100 nm metal Ni Catalytic Layer 12, adopt chemical vapour deposition technique to prepare the BNC laminar film as nano functional layer 3: to be placed in the ultrahigh vacuum (1 * 10
-8Torr), then at Ar/H
2In the atmosphere (
~20 vol% H
2) carry out about 120 minutes of 750 ℃ of thermal treatments, then temperature is elevated to 950 ℃ and handled 30 minutes; Turn off Ar/H
2, and change ventilating methane and ammonia synthesizes the BNC film, and growth time is 20 minutes, its thickness is about 0.7 nm.
After BNC nano functional layer 3 synthesizes, it is put in the FeCl of 1M
3In the solution metal Ni Catalytic Layer 12 is reacted away, BNC nano functional layer 3 is just automatically stayed Si like this
3N
4On the insulation course 2 (Fig. 4 d).
The thickness of BNC nano functional layer 3 is approximately 1.05 nm degree, electrically contacts in order to set up effectively, utilizes photoetching and lithographic technique to prepare Pt(50 nm on the edge of BNC nano functional layer 3) electric contacting layer 5(Fig. 4 e).
Adopt technique for atomic layer deposition to prepare 50 nm Al
2O
3Layer, and surface polishingization are as second insulation course 6(Fig. 4 f).
Adopt photoetching technique, and form square openings 10(Fig. 4 g that is approximately 40 μ m * 40 μ m) with KOH solution corrosion silicon substrate.
Adopt electron beam lithography and SF
6The plasma reaction lithographic technique prepares hole 11(Fig. 4 h that a diameter is approximately 2 μ m on silicon nitride film).
Adopt electron beam lithography and argon reaction particle bundle lithographic technique corrosion Al
2O
3With the BNC layer, thereby the preparation aperture is 30 nm nano-pore 3(Fig. 4 i).
In order to protect BNC nano functional layer 3, at the Si of Si substrate and exposure
3N
4With preparation 5 nm SiN on the BNC face
xLayer is as insulating protective layer 7(Fig. 4 j).
Effect and parsing: the material of nano functional layer comprises the graphene oxide of graphene film, reduction, partially hydrogenated Graphene, BNC, MoS
2, NbSe
2Or Bi
2Sr
2CaCu
2O
xEtc. layered conductive material, this example adopts the BNC film as nano functional layer 3 material.
The metal catalytic layer material that chemical vapour deposition technique prepares the BNC film comprises Cu, Ni, and Pt, Pd, Ir, Zn, Al, Fe, Mn, Ru, Re, Cr, one or more among the Co etc., its thickness are 15 nm～600 nm.In this example, select 100 nm metal Ni Catalytic Layer 12 to be used for preparing BNC film nano functional layer 3.
The carbonaceous gas source that is used to prepare the BNC film comprises methane, ethane, ethene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, amylene, cyclopentadiene, normal hexane, cyclohexane, benzene etc., this example is selected the gaseous carbon sources material of methane as synthetic BNC film for use; This example adopts the nitrogenous gas source of ammonia for preparation BNC film, but also can be other nitrogenous material such as nitrous oxide etc.Can change its electric conductivity by the content of N and C among the adjusting BNC.
Usually, the insulating film material of preparation nano-pore comprises SiO
2, Al
2O
3, SiN
xDeng, but also can be one or more potpourri in other material such as BN, SiC, polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or the polymethylmethacrylate; This example adopts Si
3N
4As first insulating layer material.
And the substrate supporting layer material of insulating film material, promptly substrate often is Si, but also can be other material such as GaN, Ge, GaAs, SiC, Al
2O
3, SiN
x, SiO
2, HfO
2, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate; It is substrate that this example adopts Si.
The thickness of the BNC film nano functional layer 3 of this example preparation is 1.05 nm.
With nano functional layer 3 contacted material can be one or more potpourri among Au, Cr, Ti, Pd, Pt, Cu, Al, Ni or the PSS:PEDOT, can adopt vacuum thermal evaporation, the solution spin coating, thermal oxide, low-pressure chemical vapor deposition, plasma reinforced chemical vapour deposition, technical methods such as ald, its thickness is generally 15～600 nm; This example utilizes photoetching and lithographic technique to prepare Pt(50 nm on the edge of BNC nano functional layer 3) as electric contacting layer 5.
The preparation of nano-pore can be adopted the nanometer technology of preparing, as electron beam lithography, and focused-ion-beam lithography, the pulsed ionizing beam etching, He ion beam etching etc., the aperture of nano-pore can be 1～50 nm; It is 30 nm that this example adopts the aperture of the nano-pore 4 of electron beam lithography and the preparation of argon reaction particle bundle lithographic technique.
This embodiment prepares metal catalytic layer on first insulation course, behind synthetic BNC film on this metal catalytic layer, metal catalytic layer is reacted away, and the BNC film is just directly stayed on first insulation course as the nano functional layer, does not so just need to shift the BNC film.
Embodiment 4:
Utilize solid carbon source synthesizing graphite alkene film: be orientated preparation 100 nm Ni metal catalytic layers on cracking graphite (HOPG) substrate at the thick height of 60 μ m; Be placed in the ultrahigh vacuum (2 * 10
-8Torr) under, then at H
2(10 Pa) carries out about 15 hours of 650 ℃ of thermal treatments in the atmosphere; Be cooled to room temperature at last, so just synthesized the single-layer graphene film.
Shift graphene film: after graphene film is synthetic, spin coating 500 nm Polymethylmethacrylate (PMMA) layer on the graphene film that is synthesized, graphene film/the Ni/HOPG that scribbles PMMA is positioned in the iron nitrate solution Ni erosion is fallen, the PMMA/ Graphene just separates with HOPG like this, thereby obtains the PMMA/ graphene film.Then, the PMMA/ Graphene is transferred to the Al that is used to prepare the nano-pore sensor
2O
3The Al of (100 nm)/GaN (250 μ m)
2O
3On first insulation course; At last, with acetone PMMA is dissolved, the graphene film layer has just been transferred to Al like this
2O
3/ GaN is last and as nano functional layer 3(Fig. 5 a).
The thickness of graphene film nano functional layer 3 is approximately 0.35 nm degree, electrically contacts in order to set up effectively, utilizes photoetching and corrosion technology to prepare Pd(30 nm on the edge of graphene nano functional layer 3) electric contacting layer 5(Fig. 5 b).
Adopt technique for atomic layer deposition to prepare 50 nm SiN
xLayer, and surface polishingization are as second insulation course 6(Fig. 5 c).
Adopt photoetching technique, solution corrosion and plasma reaction lithographic technique prepare the aperture in the position at center be 50 nm nano-pore 4(Fig. 5 d).
Effect and parsing: the material of nano functional layer can be the graphene oxide of graphene film, reduction, partially hydrogenated Graphene, BNC, MoS
2, NbSe
2Or Bi
2Sr
2CaCu
2O
xEtc. layered conductive material, this example adopts the single-layer graphene film as the nano functional layer material.
Graphene film can prepare with diverse ways, as on metal catalytic layer, preparing graphene film with chemical gaseous phase depositing process, and the method for solid carbon source such as also available graphite, SiC and synthesizing graphite alkene film.This example adopts high orientation cracking graphite to prepare graphene film as solid carbon source.
The metal catalytic layer material of preparation graphene film can be Cu, Ni, and Pt, Pd, Ir, Zn, Al, Fe, Mn, Ru, Re, Cr, one or more among the Co etc., its thickness are 15 nm～600 nm.In this example, select 100 nm metal Ni Catalytic Layer to be used for preparing graphene film nano functional layer 3.
Usually, the insulating film material of preparation nano-pore comprises SiO
2, Al
2O
3, SiN
xDeng, but also can be one or more potpourri in other material such as BN, SiC, polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or the polymethylmethacrylate; This example adopts Al
2O
3As first insulating layer material.
And the substrate supporting layer material of insulating film material, promptly substrate often is Si, but also can be other material such as GaN, Ge, GaAs, SiC, Al
2O
3, SiN
x, SiO
2, HfO
2, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate; It is substrate that this example adopts GaN.
The thickness of the graphene film nano functional layer 3 of this example preparation is approximately 0.35 nm.
Comprise one or more potpourri among Au, Cr, Ti, Pd, Pt, Cu, Al, Ni or the PSS:PEDOT with graphene nano functional layer 3 contacted materials, can adopt vacuum thermal evaporation, the solution spin coating, thermal oxide, low-pressure chemical vapor deposition, plasma reinforced chemical vapour deposition, technical methods such as ald, its thickness is generally 15～600 nm; This example utilizes photoetching and lithographic technique to prepare Pd(30 nm on the edge of graphene nano functional layer 3) as electric contacting layer 5.
The preparation of nano-pore can be adopted the nanometer technology of preparing, as electron beam lithography, and focused-ion-beam lithography, the pulsed ionizing beam etching, He ion beam etching etc., the aperture of nano-pore can be 1～50 nm; It is 50 nm that this example adopts the aperture of the nano-pore 4 of electron beam lithography and the preparation of argon reaction particle bundle lithographic technique.
Above embodiment has been described in detail the basic structural feature and the preparation of nano-pore electric sensor of the present invention, but the architectural feature of nano-pore electric sensor of the present invention and preparation are not limited to above embodiment.
Claims (10)
1. nano-pore electric sensor, it is characterized in that comprising the substrate (1), first insulation course (2), nano functional layer (3) and second insulation course (6) that stack gradually from top to bottom, center at substrate (1), first insulation course (2), nano functional layer (3) and second insulation course (6) is provided with nano-pore (4), and described nano functional layer (3) is the laminar of center band nano-pore (4).
2. a kind of nano-pore electric sensor according to claim 1 is characterized in that being provided with the electric contacting layer (5) that is connected with nano functional layer (3) at first insulation course (2) upper surface, nano functional layer (3) edge.
3. a kind of nano-pore electric sensor according to claim 1, the thickness that it is characterized in that described nano functional layer (3) is 0.3～3.5 nm.
4. according to claim 1 or 2 or 3 described a kind of nano-pore electric sensors, the material that it is characterized in that described nano functional layer (3) is a layered conductive material, and layered conductive material is the graphene oxide of graphite, reduction, partially hydrogenated Graphene, BNC, MoS
2, NbSe
2Or Bi
2Sr
2CaCu
2O
x
5. a kind of nano-pore electric sensor according to claim 4 is characterized in that described layered conductive material is a graphite, and graphite is 1～10 layer graphene film.
6. according to claim 1 or 2 or 3 described a kind of nano-pore electric sensors, the material that it is characterized in that described substrate (1) is semiconductor material or insulating material, semiconductor material is one or more the potpourri among Si, GaN, Ge or the GaAs, and insulating material is SiC, Al
2O
3, SiN
x, SiO
2, HfO
2, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate.
7. according to claim 1 or 2 or 3 described a kind of nano-pore electric sensors, it is characterized in that the material of described first insulation course (2) and second insulation course (6) is SiO
2, Al
2O
3, BN, SiC, SiN
x, one or more the potpourri in the polyvinyl alcohol (PVA), poly-(4-vinylphenol), divinyl tetramethyl disiloxane-two (benzocyclobutene) or polymethylmethacrylate.
8. according to claim 1 or 2 or 3 described a kind of nano-pore electric sensors, it is characterized in that described nano-pore (4) is a circular hole, the aperture of nano-pore (4) is 1～50 nm.
9. according to claim 1 or 2 or 3 described a kind of nano-pore electric sensors, it is characterized in that described nano-pore (4) is polygonal hole or elliptical aperture, the ultimate range around its hole between 2 is 1～50 nm.
10. a kind of nano-pore electric sensor according to claim 2, the material that it is characterized in that described electric contacting layer (5) are one or more the potpourri among Au, Cr, Ti, Pd, Pt, Cu, Al, Ni or the PSS:PEDOT.
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