CN110137353A

CN110137353A - A kind of semiconductor material, device and its manufacturing method

Info

Publication number: CN110137353A
Application number: CN201910317111.8A
Authority: CN
Inventors: 陳柏瑞; 冯国昆
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-04-19
Filing date: 2019-04-19
Publication date: 2019-08-16

Abstract

A kind of semiconductor material, device and its manufacturing method.The semiconductor material, comprising: the length being made of CCCGGG or TTTAAA continuous mrna sequence is the DNA material of 20-30 base-pair, and the proton of amino or imino group in the DNA material base-pair is replaced by bivalent metal ion；The semiconductor devices is made using the semiconductor material.

Description

A kind of semiconductor material, device and its manufacturing method

Technical field

The present invention relates to bioengineering, Automated library system circuit, technical field of semiconductors, and in particular to a kind of semiconductor material Material, device and its manufacturing method.

Background technique

The saturation bombing of artificial intelligence AI information now, if we carefully comb these concepts, all these concepts It is exactly behind semiconductor, instantly, but occurs the overturning of undercurrent in semi-conductor industry, main cause is exactly in AI concept especially fire Conductive semiconductor material is limited by theoretical limit, it is difficult to which the rule for supporting integrated circuit to continue Moore's Law continues to develop.

At rear mole and surpass mole epoch, general nano material, quanta point material, carbon nano-tube material, graphene occurs Material etc. attempt be applied to integrated circuit in new material, but due to the defect of its technology itself, quantum-mechanical theory limitation, Its commercial application prospect of various reasons such as manufacturing cost is more remote.

Each base-pair diameter of DNA molecular is 2nm, and the screw pitch of every 10 base-pairs is 3.4nm, can theoretically be incited somebody to action Electronic device spacing accomplishes the advantage of only 0.34nm, is the ideal material for constructing nano-scale structures.Recently, many scientists by Method by covering metallic atom or high-molecular compound on the surface of DNA has synthesized conductive DNA chain or tool characteristic of semiconductor Material, such as DNA- hexadecyltrimethylammonium chloride (DNA-CTMA) adulterates substrate, DNA-CTMA etc. as fluorescent dye Compound DNA material shows good optical gain property and photo and thermal stability.But it since DNA is covered by material completely, only rises A kind of effect of bracket, cannot good application DNA line width 2nm, single electronic device reaches the advantage of 0.34nm, and no longer has The characteristic of selective binding other biological molecule.

Achievement of the DNA CHIP " genetic chip " on medical test is distinguished, but DNA CHIP " genetic chip " (biological core Piece Bio-chip) it is not DNA semiconductor, semiconductor chip is the integrated various electronics electricity with specific Physical Electronics function Road unit, and the birth of " biochip " is mainly used in biosensor, is only applied to micro physiology or biological sampling To detect the characteristic of different biological cells, biomolecule and DNA and the interaction between them, it is microcosmic to obtain life Movable rule.Its action principle is still Common biochemical redox reaction, and the research with semiconductor is not produced with utilization Raw association.

Summary of the invention

In view of problems of the prior art, one of the objects of the present invention is to provide a kind of semiconductor materials, device And its manufacturing method, the DNA half of quantum effect when specifically one kind is different from traditional " bulk " field but enters small ruler Conductor material, DNA semiconductor devices and its manufacturing method, as a preferred embodiment, the DNA semiconductor material can break through existing There is the theoretical limit of conventional semiconductor material in technology, existing integrate can substantially be reduced by being applied to semiconductor integrated circuit The size of circuit, the working efficiency for greatly improving traditional integrated circuit.

To achieve this purpose, the present invention adopts the following technical scheme:

A kind of semiconductor material, comprising: the length being made of CCCGGG or TTTAAA continuous mrna sequence is 20-30 alkali The proton of the DNA material of base pair, amino or imino group in the DNA material base-pair is replaced by bivalent metal ion.

As a preferred embodiment, the bivalent metal ion is Fe²⁺Ion.

As a preferred embodiment, the length of the gene order is 24 base-pairs.

As a preferred embodiment, the gene order of the DNA material are as follows: 5 '-CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG- 3。

A kind of manufacturing method of semiconductor material, the DNA semiconductor material are amino or imino group in base-pair The semiconductor material that proton is replaced by bivalent metal ion, described method includes following steps:

Target dna is replicated using PCR system；

The target dna digestion of duplication is dealt with, it is 20-30 base-pair that the length of DNA is excellent after processing；

It the DNA performed will be cut is placed in bivalent metal ion alkaline buffer and form bifilar M-DNA；

Extra bivalent metal ion is removed with buffer.

As a preferred embodiment, the bivalent metal ion is Fe²⁺Ion.

As a preferred embodiment, the length of the gene order is 24 base-pairs.

As a preferred embodiment, the gene order of the target dna are as follows: 5 '-CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG- 3。

A kind of semiconductor devices, comprising: substrate is formed with one or more electrodes pair on substrate, the electrode pair Two electrodes are conllinear on the longitudinal direction of the electrode pair, and the longitudinal direction is first straight line direction, two conllinear electricity Extremely opposite end has tip, and the clearance distance between two tips is not more than 8nm；Amino or imino group in base-pair Proton is bonded by way of bonding with the tip of the electrode by the DNA material that bivalent metal ion replaces, and is connected to It states between two tips.

As a preferred embodiment, the bivalent metal ion is Fe²⁺Ion.

A kind of manufacturing method of semiconductor devices, comprising:

Electrode base board is prepared, is formed with electrode structure on the substrate, the electrode structure includes first electrode and more A second electrode, the multiple second electrode include one or more electrodes pair, and two electrodes of each electrode pair are two-by-two in institute It states on the longitudinal direction of electrode pair collinearly, the longitudinal direction is first straight line direction, the opposite end of two conllinear electrodes With tip, the clearance distance between two tips is not more than 8nm, and the multiple electrode is located at the gap between two tips Along the same straight line in second straight line direction, the first straight line direction and second straight line direction are vertical, the first electrode On second straight line direction；

The bonding of DNA material electrophoresis, applies negative potential on the first electrode, applies in the multiple second electrode equal Positive potential, voltage difference are 0.5-2 volt DC；After applying electric field, by the proton quilt containing amino or imino group in base-pair The solution for the DNA material that bivalent metal ion replaces micropipet drips on device, and maintains electrophoresis state 20 minutes or more, So that the DNA material binds are between two opposite electrode tips of the electrode pair；

The substrate for being bonded with DNA material is placed in container by freeze-drying, in 10-18 DEG C of low temperature bath, is dried using cold pumping Case continuously vacuumizes 4~7 days, then the substrate for being bonded with DNA material is put into merging liquid nitrogen refrigeration system, in liquid nitrogen At a temperature of at least save 3 days, further be dehydrated.

As a preferred embodiment, the bivalent metal ion is Fe²⁺Ion.

Detailed description of the invention

Fig. 1 is DNA base to electronics orbital π-π overlapping schematic diagram；

Fig. 2 is the particularly conjugated double bond system schematic that will form between DNA adjacent base pair；

Fig. 3 is that the Pz electronics orbital of vertical phenyl ring plane can overlap mutually to form mixing orbital schematic diagram；

Fig. 4 is the schematic diagram by being inserted into intercalator regulating DNA molecular semiconductor energy gap in DNA molecular；

Fig. 5 is M-DNA helical molecule overall situation schematic diagram；

Fig. 6 A and Fig. 6 B are two kind bond schematic diagrams of the bivalent metal ion in base-pair；

Fig. 7 is M-DNA of the present invention and essence (intrinsic) DNA C-V characteristic schematic diagram；

Fig. 8 is the method flow diagram using DNA semiconductor material of the present invention manufacture DNA semiconductor devices；

Fig. 9 is electrode SEM striograph of the present invention；

Figure 10 is the empty electrode background signal test experiments result figure of non-loading of the present invention；

Figure 11 is the electrode lay-out structural schematic diagram that the semiconductor devices is manufactured using electrophoretic techniques；

Figure 12 is Electronic Speculum (AFM) image using the semiconductor devices after electrophoretic techniques of the present invention bonding Fe-DNA Figure；

Figure 13 is to be bonded fixed Fe-DNA semiconductor with the bridge-type in the gold electrode surfaces of device that fluorescence microscope is shot The striograph of material；

Figure 14 is the C-V characteristic schematic diagram under background signal, M-DNA and essence (intrinsic) DNA circulation voltage scanning；

Figure 15 is the C-V characteristic signal of the background signal, M-DNA and essence (intrinsic) DNA under different frequency scan round Figure；

Figure 16 A, 16B, 16C, 16D are the C-V characteristic signal of the M-DNA and essence (intrinsic) DNA within the scope of different voltages Figure (dotted line indicates M-DNA, and wherein Figure 16 B, 16C, 16D show the result of Multiple-Scan).

The present invention is described in more detail below.But following examples is only simple example of the invention, not generation Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.

Specific embodiment

To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.

In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting Embodiment is as follows:

The purpose of the present invention is to provide a kind of semiconductor material, device and its manufacturing method, a kind of specifically DNA Semiconductor material, device and its manufacturing method.DNA semiconductor material and its manufacturing method are introduced separately below, and utilize institute State the method and DNA semiconductor devices of DNA semiconductor material manufacturing semiconductor devices.

DNA DNA (de-oxy-nucleic-acid) is the inhereditary material of life control trait expression, tool There is double-spiral structure.DNA is a kind of very long molecule, is linked to be long spire shape by many nucleotide per one.DNA has bifilar spiral shell Revolve the stereochemical structure of (double helix), two terraced sides are exactly that the deoxyriboses of five carbon replaces the two long of composition with phosphoric acid Chain, two strands of direction are just opposite.Base connects on the position of the first carbon of pentose, and phosphoric acid then connects in the position of the 5th carbon It sets, and in succession with the third carbon of adjacent nucleotide pentose, so the bifilar of DNA has by 5 ' to 3 ' directionality.This Four kinds of bases are adenine (A, adenine), thymidine (T, thymine), guanine (G, guanine) and cytimidine respectively (C, cytosine).The diameter of DNA spiral is about 2nm, the handrail of both sides be by phosphoric acid and degassing nucleic acid (deoxyribose) with The long key double helix that the double rouge keys (phosphodiester bond) of phosphoric acid are conspired to create, centre is using base as pedal, every ten pairs of alkali Base rotation is turned around, distance about 3.4nm.A, C, G, T order that base arranges on DNA, the referred to as sequence of DNA, between double helix Base be complementary, i.e. A and T pairing, and G and C are matched, they are connected together in a manner of hydrogen bond, A in any section of DNA Ratio with T or C and G must be 1；Therefore only it is to be understood that the sequence of DNA wherein one base is it is known that another strand of sequence Column.

Calculate DNA length when, commonly use how many a base-pairs to indicate, such as 1,000bp be exactly 3,400nm (3.4 × 10^-7M) long.Different place between DNA molecular, the order that only nitrogenous base occurs, that is exactly the password of life information, certainly The type of protein produced by after fixed.

In semiconductor industry, the aggregation degree of integrated circuit depends on the maturity of optical lithography, due to DNA molecular Diameter only has 2nm or so, not only avoids line width bottleneck encountered in the integrated circuit manufacture process based on existing optical lithography, and Spacing between base only has 0.34nm, can make minimum feature much smaller than contemporary semiconductor industrial technology, with the processing procedure control of DNA System is gradually to replace the manufacture of semiconductor with optical lithography now, it is possible to provide next-generation chip technology is broken through to 0.34nm.

The nanoscale of DNA only has 2 nanometers of diameter, is a kind of natural molecule nano line, DNA is perpendicular to bifilar helix side To nucleotide element in have the planar structure of similar phenyl ring, electronics orbital possessed by base can generate overlapping along axis, The phenomenon that this orbital overlaps overlaps (such as Fig. 1) for referred to as π-π, will form special conjugated double bond between adjacent base pair at this time System (such as Fig. 2), and the Pz electronics orbital of vertical phenyl ring plane can overlap mutually to form mixing orbital (such as Fig. 3), be considered It can promote the electric conductivity of DNA molecular；DNA internal base is to after the formation of continuous π-π storehouse and hybridized orbital, as giving Electronics one transmission channel of creation is general, allows electronics mobile along the direction of DNA long-chain through this orbital.Work as pi-electron When number increases, the energy gap of semiconductor can reduce, and molecular crystalline composed by 20 pi-electrons, possessed energy gap is about 1.5 ±0.5eV；10 pi-electrons, possessed energy gap are about 3.0 ± 1eV.DNA double stock helical structure is combined closely when bifilar When, each pair of base-pair contains 20 pi-electrons, and in the case where DNA molecular combination is not very close situation, per share DNA molecular is had The pi-electron number that contains of base be 10, therefore the pi-electron number that base possessed by DNA molecular contains is arrived between 10 Between 20, the energy gap having is between 1.5 ± 0.5eV and 3.0 ± 1eV.It can be seen that possessed by regulating DNA molecule The pi-electron number that base contains, so that it may realize the regulation (such as Fig. 4) to the semiconductor energy gap of DNA molecular.

The electrical property of traditional " bulk " semiconductor material some can mix (miscellaneous) matter and adjust the electricity of material itself by adulterating Property, allow to be used as the design and fabrication of semiconductor devices.Since DNA conductive effect is not so good as common metal nano wire, In order to increase DNA electric conductivity, it is necessary to find and be adapted to adulterate to change electrical ion or compound.By DNA molecular institute The special construction and property having, such dopant material and not phase used in doping way and conventional semiconductors processing procedure Together.

Intercalator (Intercalator) is a kind of compound that can link DNA molecular, is miscellaneous with plane fragrance The cation of ring can be inserted into the bifilar a chain for binding criminals rotation structure of DNA such as ethidium (ethidium), DNA molecular is caused to be squeezed and had The phenomenon that extension and screw diameter become smaller, an insertion agent molecule can be inserted in the distance every 1.02nm, these can connect Knot DNA molecular compound include (Pt (terpy) (SCH2CH2OH))+, [Pt (bpy) (en)]²⁺、[Pt(o-phen) (en)]²⁺[Pt (py) 2 (en)]²⁺Deng.

In addition to this, there are also some planar metal misfit object (Planar Metal that can link DNA molecular Complexes), such as MPE-Fe (II) and [Pt (AO-en) Cl₂] etc., M-DNA (Metallic-DNA) material is formed, wherein M is Metal ion with tetravalence or divalent, synthesis mode are (to be greater than 8.0) under specific pH value condition, the metal ion of divalent It is easy to replace the proton of the amino or imino group in base-pair, becomes M-DNA (such as Fig. 5) with base-pair misfit.

It forgoing describes and uses DNA for material, may be implemented by way of doping to the semiconductor energy gap of DNA molecular The basic principle and approach of regulation, below with Fe-DNA, it may be assumed that the amino or imino group of divalent Fe ionic compartmentation DNA base centering Proton for, introduce the preparation process of the M-DNA semiconductor material.

One, target dna is replicated using PCR system:

Raw material:

Design or selection Sequentially continuous and length can be connected across the DNA profiling at metal electrode both ends, and the DNA profiling is CCCGGG or TTTAAA continuous mrna sequence；Design said gene sequence advantage first is that: the gene order of the DNA profiling It is dealt with convenient for digestion, gene order length is easily controllable.

As a preferred embodiment, the gene order of the DNA profiling can be with are as follows: 5 '-CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG-3。

Design primer (Primer), the gene order of the primer can be with are as follows: 5 '-CCC ↓ GGG-3, ↓ indicate consecutive gene Sequence.In situation known to gene order, above-mentioned DNA profiling and primer can be prepared by existing nucleic acid production method and be obtained , special Commercial nucleic acid manufacturing company can also be entrusted, such as: Japanese Illumina company.

4 kinds of nucleic acid raw material dNTPs are as follows: dATP, dGTP, dCTP, dTTP.

DNA Polymerase polymerase: can by 4 kinds of nucleic acid raw materials (dNTPs:dATP, dGTP, dCTP, dTTP) according to DNA profiling password, correctly singly adds up, and synthesizes one new genetic fragment.It polymerize many kinds of of Enzyme, according to Its characteristic can generally be distinguished into general Taq polymerization Enzyme (Taq), thermal starting (Hot-Start) polymerization Enzyme, correction (Proofreading) it polymerize Enzyme three classes.The present embodiment is using Taq polymerization Enzyme (Taq).

The buffer that buffer solution is deployed by Tris, KCl.

Preparation method:

1. weighing 6.055g Tris to be placed in 1L beaker.

2. the deionized water of about 800ml is added, dissolution is sufficiently stirred.

3. pH value required for concentrated hydrochloric acid is adjusted is added, required pH value is greater than 8.

4. solution is settled to 1L.

5. after autoclave sterilization, room temperature preservation.

Specific reproduction process:

1.DNA template deformation:

The DNA profiling of 1-100ng is dissolved in the distilled water of 50L, is made using high temperature (about 90 DEG C~100 DEG C) double Stock DNA denaturation, is opened into single-stranded DNA, as PCT reaction template；

2.DNA template and primer annealing:

Reducing temperature (generally about 50 DEG C~60 DEG C) makes with the primer to DNA template sequence complementation in conjunction with DNA profiling. Single-stranded DNA may also be combined into bifilar once again at this time.But since the concentration of primer is far more than the concentration of DNA profiling, so sub-thread It is little that DNA is combined into bifilar chance once again；Reaction density is about 0.2~0.4 μM/L.

3. primer extend:

The felicity condition (generally 72 DEG C) for raising the temperature to DNA polymerase reaction, makes it with primer beginning, foundation DNA template sequence carries out progradation, synthesizes the DNA fragmentation of complementary stock.

The buffer that the buffer solution of the present embodiment is deployed by Tris, KCl, specific formula as previously mentioned, pH about 8.4, PCR reactions constantly repeat aforementioned three steps, and product is able to geometric progression and promptly increases, and improves the spirit of experiment significantly Sensitivity and the degree of difficulty for reducing work.

The preparation of Fe-DNA:

Firstly, DNA is dealt with two kinds of digestions of BamHI and EcoRI, both restrictive digestions can be in DNA spy Fixed base stack position forms point of contact, DNA is switched to certain length, length is preferably 20-30 base-pair, more preferably 24 base-pairs.Such as: as previously described due to the continuous sequence that selected DNA length is CCC GGG, will wherein one design It is 20-30 base-pair that DNA can be switched to length when relatively short.After determining DNA length, DNA is just placed in Fe²⁺Buffering (10mM/L Tris, 2.5Mm/L, FeCl in liquid₂, pH=9.0) and bifilar Fe-DNA is formed, trihydroxy methyl amino first is finally used again Alkane buffer (10mM/L Tris, pH=9.0) removes extra Fe²⁺Ion.

Furthermore also using source Wako Pure Chemical Industries, Ltd., Ogata Materials The aqueous solution that the concentration that Science Lab is provided is the DNA (hereinafter referred to as b form dna) of 2mM/L prepares M-DNA.Or it utilizes and is purchased from The MCl of the Sigma-Aldrich concentration 20mM/L of Wako Pure Chemicals and Sigma-Aldrich₂, fallen at -20 DEG C Enter excessive ethyl alcohol DNA and MCl₂In aqueous solution, M-DNA can be obtained.

Fe-DNA is in DNA and FeCl₂Mixed solution in synthesize, wherein Fe²⁺By providing electronics to the base of base-pair And it is converted into Fe³⁺。Fe³⁺Ion is hydrated by hydrone, prevents Fe ion and the nitrogen-atoms of base from forming covalent bond.In addition to phosphoric acid Except root anion, Fe³⁺Strong ionic bond between the transfer charge of base-pair enhances the combination of duplex, and passes through enhancing Electric dipole moment strengthen the combination between adjacent double bonds body.

Front describes the DNA of divalent Fe ion misfit by taking Fe as an example, in fact, most bivalent metal ion can be with With DNA misfit.The DNA framework of metal ion misfit as shown in figure 5, the position of bivalent metal ion misfit probably in base-pair Centre, the dark ball in Fig. 5 among base-pair represent bivalent metal ion, link the electricity that dark first ball ball linkage lines represent Subchannel.Bond mode of the bivalent metal ion in base-pair is divided into two kinds of such as Fig. 6 A and 6B, replaces the middle imido grpup of T and G (- NH) proton (Fig. 6 A), or replace the amino (- NH of A and C²) proton and enol tautomeric isomers (figure is formed with T and G 6B).Both bond modes are needed could misfit under the situation of base pair matches.

Electric conductivity, ion cobalt (Co) or iron ion (Fe) can be increased with bivalent metal ion with modifying DNA structure In C of the misfit in spiral long-chain and G base, it can be observed that compared to the DNA of script, highest occupied molecular orbital (HOMO) And lowest unoccupied molecular orbital (LOMO) obviously broadens, and the increase of π-π storehouse quantity also allows the type shape of long-chain to change, and The distance between base-pair is caused obviously to become close, and mistake in pi-electron possessed by these polycyclic compounds and metal misfit object The free electron that metal cation is had is crossed, DNA energy gap is also made also obviously to narrow, the above results M-DNA's shown in Fig. 7 VA characteristic curve can also be verified.

The empty electrode for being spaced about 8nm is made using electron beam lithographic and hot evaporation technology, recycles DNA sulphur gold key from group The mode of dress or electrophoresis, DNA is placed among electrode, device is made, and is measured the electrical transmission of DNA two o'clock nano wire, can be sought The characteristic electron (such as Fig. 7) of DNA electronic device.Compared to the energy gap of original DNA (can also be known as: essential DNA or intrinsic DNA) 2.0eV, Co-DNA the and Fe-DNA energy gap after misfit are obviously reduced, respectively 0.50eV and 0.27eV, so that charge more holds Easily transmission (as shown in Figure 7).It can be seen that data are shown, and when there is good metal ion mixing, its spy of metal misfit DNA Property can be used as the semiconductor long-chain for having satisfactory electrical conductivity similar to conductor.

The specific preparation process for forgoing describing DNA semiconductor material, the DNA semiconductor will be utilized by being described in detail below The method (Fig. 8) of material manufacture DNA semiconductor devices.

DNA nano-wire devices are made, the process technique mainly used has: e-beam lithography (electron-beam Lithography) and hot evaporation system (thermal evaporation), drawn using e-beam lithography desired Electrode shape, then by hot evaporation system by metal-plated, the empty electrode after lifting off is via scanning electron microscope (Scanning Electron Microscope, be abbreviated as SEM) is checked and measurement system carries out leakage tests, after completing i.e. Nano wire sample can be confined among electrode, be easily produced simple device.More specifically, of the present invention DNA semiconductor material is to adulterate Intercalator or the DNA semiconductor material using metal cation misfit, specific preparation side Method is as follows:

Embodiment one

E-beam e-beam lithography

Substrate used in the present embodiment is highly dope p-type Si substrate, by E-beam lithographic, by designed light shield figure Type is exposed on the thereon of coated photoresist, then via development output figure groove, finally against hot evaporation technology, vapor deposition Upper metal generates electrode, and the present embodiment used is Au/Ti electrode.

E-beam lithography is to regard exposure source in smaller working region using electron beam, write out smaller scale Electrode pattern.Since the limit of optical diffraction limits, the resolution limitations of deep ultraviolet light lithographic techniques are not short enough in optical wavelength Limitation, resolution ratio can not be improved, therefore the present invention selects the electron beam accelerated to do exposure source.Since electron beam has height Energy, matter wave is very short, so resolution ratio is very good.In manufacturing process it may first have to uniformly hinder positive light and be coated on base On plate, recycle e-beam lithography by the graph exposure of nanoscale in working region later, and by developer solution (methyl Isobutyl ketone (methyl isobutyl ketone, MIBK): isopropanol (isopropyl alcohol, IPA)=1: 3) will be electric The exposed photoresist dissolution of beamlet, and generate the groove of wanted figure.To complete minimum line width, it has to be noted that electron beam is beaten The diffraction that entering light generates when hindering, will lead to aliasing, it is therefore necessary to by the selection and exposure of control solution level, photoresist Between light time with the control of developing time, to improve this phenomenon.Due to being completely dried the electrical conductivity of the DNA without the crystallization water itself not Good, when macromolecular sequence, is not easy to measure the electrical property for arriving DNA, while avoiding the influence of bulk effect, and with being limited to etched electrodes Yield and technology, the present embodiment use the accessible 8nm spacing of E-beam etching technique.

Hot evaporation system

The manufacturing method thereof of film is to be broadly divided into chemical vapour deposition technique (Chemical vapor deposition, CVD) With two kinds of physical vaporous deposition (Physiscal vapor deposition, PVD), and hot evaporation belongs to physical vapour deposition (PVD) One kind, cardinal principle be in vacuum cavity, sample is inverted in the surface of target, and target is placed in high temperature resistant Tungsten boat on, pass to electric current heating tungsten boat through the fixed copper post in tungsten boat both ends, melted at high temperature to target and evaporate gas Micel, these micels can condense into film after encountering substrate, can control the rate and matter of plated film through the size of electric current Amount.

During plated film, chamber vacuum degree must be maintained at about 5 × 10^-6(Torr) is held in the palm hereinafter, reducing the micel of vapor deposition With the chance of molecular collision in air, increase film quality.Because Au is not easy to be attached on Si substrate, therefore Au is plated after first plating Ti, More Ti target is placed in tungsten boat, on plated film to substrate before, first empty plating a period of time, purpose are the micel for utilizing Ti The intracorporal gas molecule of chamber will be remained on to take away, vacuum degree in cavity is allowed to improve.Just Ti and Au is distinguished when vacuum degree is enough good Upper substrate is sequentially plated, Ti is mainly the adhesive layer between Si substrate and Au.

Another embodiment is then first to be dipped in substrate in acetone soln with ultrasonic wave cleaning concussion about before sputter 10-20 minutes, preferably 15 minutes, then with deionized water flushing 10-20 minutes, preferably 15 minutes after, with being dried with nitrogen.It will Substrate after cleaning is placed on clamping disk, and position is from center about 3cm, substrate and palladium material at a distance of about 8cm.Pressure is tieed up when sputter It holds in 5~10mTorr, power is about 150W.Start to cover substrate with masking piece (shutter) metal plate before formal sputter, it is first pre- Sputtered target material 10 minutes, to remove target material surface oxide and impurity, and in sputtering process, substrate temperature about maintained 200 ℃.Resulting test piece still first will analyze crystal structure with XRD diffraction analysis instrument, likewise, crystallinity preferably film test piece, Its micro-structure can be observed with scanning electron microscope (SEM), its component ratio is analyzed with EDS, using spectrometer measurement can The load of light-exposed penetrance, resistivity measure analysis its conductive characteristic, Hall measurement instrument (Hall measurement) analysed film The physical characteristic of the correlation such as sub- concentration (carrier density, n) and carrier mobility (hall mobility, μ).

More specifically:

(S1) cleaning base plate (Cleaning)

By the 10mm x 10mm substrate of the good deep ultraviolet light electrode of cloth, it is placed in clean beaker, is firstly added suitable capacity Acetone, and the sealing of beaker mouth is fallen with aluminium-foil paper to prevent dust, places the beaker in ultrasonic vibrating machine shake and wash 10 minutes, Then it changes solution into alcohol and removes metal ion water (DI-water) and repeat above-mentioned movement, finally use elevated pressure nitrogen air gun by base Plate surface residual liquid is removed, and finally checks on substrate whether still there is residual impurity via optical microscopy, if still there is impurity residual It stays, repeats the above steps.

(S2) light blockage coating (Spin coating)

Substrate is placed in spin coater center, and opens mechanical vacuum side Pu and fixation is sucked in substrate, is then existed Upper 2~3 drop photoresist is dripped on substrate, is finally uniformly thrown photoresist away using the centrifugal force that high speed rotation generates, the present embodiment light Resist selects Polymethyl methacrylate, and (select this photoresist reason is thinner thickness to PMMA model 950A2, compares energy Control the line width of electron beam lithographic), coating first stage revolving speed sets 1500rpm, 15 seconds, and purpose is uniformly distributed photoresist； Second stage revolving speed sets 5500rpm, 35 seconds, and purpose is control photoresist thickness.

(S3) soft roasting (Soft baking)

The substrate for being coated with uniform photoresist is placed on heater, temperature sets 180 DEG C, heating time 60 seconds.Purpose is It allows solvent volatilization extra on photoresist, avoids the distortion in electron beam lithographic.

(S4) electron beam lithographic (Electron beam lithography)

Figure required for designing is finished, and by it is soft it is roasted after substrate be put into scanning electron microscope (model: JSM-6500F), map file is being changed into exposure shelves with spectrum assignment program (Expose Control Program, ECP), adjusted Electric current required for good and dosage (Dose, μ C/cm^-2) and then using the mark point on substrate find mesh target area, then By the position of program-controlled optical gate (Beam Blanker) control electron beam exposure, final program will shine exposure file for pattern It is exposed on desired position.

(S5) develop (Develoption)

The photoresist as used in the embodiment of the present invention is positive photoresist, so can be readily soluble by the region that electron beam exposure is crossed Solution (methyl iso-butyl ketone (MIBK) (methyl isobutyl ketone, MIBK): isopropanol (isopropyl in developer solution Alcohol, IPA)=1: 3), developer temperatur control at 25 DEG C, soaking time about 30 second, and immersion is finished is cleaned with isopropanol, Finally check whether development is completed.

(S6) hot evaporation (Thermal evaporation)

Since the present embodiment photoresist selects relatively thin photoresist (about 100nm), therefore, the parameter control of Ti when hot evaporation System is in plated film rateThickness 15nm；The state modulator of Au is in plated film rate Thickness 25nm, and plate The speed of film rate will affect coating quality, can optionally make the appropriate adjustments.

(S7) (Lift off) is lifted off

Substrate after plated film is soaked among the beaker equipped with acetone, and beaker mouth is sealed with aluminium-foil paper, stands 1 Hour or more, because photoresist can be dissolved in acetone, film can be removed since substrate outside, after film automatically strips.It crosses It avoids shaking as far as possible in journey, electrode is avoided to peel off because external stress is excessive.After the completion of electrode preparation, SEM image such as Fig. 9, Electrode background signal is measured through thus ammeter, caused by confirming that the sample signal of measurement not leaks electricity, the empty electrode of not upper sample must It must first ensure that resistance value could use more than 1012 nurses difficult to understand, such as Figure 10.

Next task is that DNA semiconductor material of the present invention is assembled to the electrode manufactured by above-mentioned technique On electrode base board of the interval no more than 8nm.Present inventor studies discovery: the DNA sheet of the crystallization water is free of due to being completely dried The electrical conductivity of body is bad, and when macromolecular sequence is not easy to measure the electrical property for arriving DNA, while avoiding the influence of bulk effect, and limited Yield and technology in etched electrodes ground, the present embodiment is selected using the electrode spacing of E-beam etching technique is not more than 8nm, Advantage will further be embodied in the explanation below.

Further below by taking Fe-DNA material as an example:

Electrophoretic techniques is bonded Fe-DNA

So-called electrophoresis exactly allows charged particle that can be carried out movement by extra electric field in special pH value solution A kind of mode, since Fe-DNA itself is negatively charged, the present invention can increase success rate using this technology, in design electrode figure When type, certain branch electrode foot position can be used as electric field is generated, as shown in figure 11, including first electrode and multiple second electrodes, institute Stating multiple second electrodes includes one or more electrodes pair, and two electrodes of each electrode pair are two-by-two in the longitudinal direction of the electrode pair Conllinear on direction, the longitudinal direction is first straight line direction, and the opposite end of two conllinear electrodes has tip, two points Clearance distance between portion is not more than 8nm, and the multiple electrode is located at along second straight line direction the gap between two tips Same straight line on, the first straight line direction and second straight line direction are vertical, and the first electrode is located at second straight line side Upwards, apply negative potential on the first electrode, apply equal positive potential, voltage difference 0.5- in the multiple second electrode 2 volt direct currents, preferably 1 volt direct current.After applying electric field, the micropipet of the solution containing Fe-DNA is dripped in device On, and maintaining electrophoresis state 30 minutes, Fe-DNA will assemble with electric field to the eletrode tip of positive potential in electrophoresis process, from And the Fe-DNA semiconductor material is bonded between two opposite electrode tips of the electrode pair.Institute in the present invention Stating and maintaining the time of electrophoresis state is for example, it will be appreciated by those skilled in the art that the electrophoresis time can be according to electricity The needs of swimming process and set, such as 20 minutes or more, etc..Figure 12 is to be bonded Fe-DNA using electrophoretic techniques of the present invention Semiconductor scanning electron microscope (AFM) striograph afterwards.

In a further preferred embodiment Fe-DNA can also be bonded using bridge-type bond techniques

Figure 13 is to be bonded fixed Fe-DNA semiconductor with the bridge-type in the gold electrode surfaces of device that fluorescence microscope is shot The striograph of material.

In order to allow Fe-DNA semiconductor material to be fixed in the gold electrode surfaces of device, selection with two kinds of digestion BamHI and EcoRI carrys out the connector as Fe-DNA and gold electrode, this two kinds of connectors can be divided into forward primer due to building form difference (forward primer, fp) and reverse primer (reverse primer, rp), first by the BamHI-fp and EcoRI- of 2 μ l Fp (concentration is 2 μM/L) drop is kept for 8 hours or more being preferred at 4 DEG C, be impregnated 5 times later in clean gold electrode surfaces Go metal ion water (pH 9.0) to remove the redundant solution that is not yet bonded, then by 2 μ l BamHI-rp and EcoRI-rp (2 μM, In 10mM buffer, 2.5mM FeCl2, pH=9.0) drop upper electrode surface, 30 minutes are held at 4 DEG C, and connector is just at this time It can be completed, then equally impregnate 5 times and remove metal ion water (pH 9.0), finally by 2 μ l Fe-DNA (2 μM/L), in 10mM Buffer, 2.5mM MCl2, pH=9.0) drop upper electrode surface, and kept for 8 hours or more at 4 DEG C, allow Fe-DNA with connect Device generates self assembly bond, finally impregnates 5 times and removes metal ion water (pH 9.0), and the remnants Fe-DNA not being bonded and salt are gone It removes.The above process all preferably must be held under moist environment and operate, avoid the solution being layered on gold electrode because environmental drying and Volatilization.

Freeze-drying

In order to avoid the influence of the crystallization water, Fe-DNA device is placed in beaker, in 15 DEG C of low temperature bath, is dried using cold pumping Case continuously vacuumizes 4~7 days, then Fe-DNA device is put into merging liquid nitrogen refrigeration system, at least protects under liquid-nitrogen temperature It deposits 3 days, is further dehydrated, the device for being dehydrated can test completely can be completed.

Pass through the electrical performance testing of semiconductor devices prepared by the above method:

Fe metal ions M-DNA device memory behavior electrical testing

In the electron motion of semiconductor, the quantum charge transport phenomena for having one kind special is negative differential resistance (negative differential resistance, NDR) usually occurs among the quantum well structures of semiconductor, similar The phenomenon that be also found in various conjugation oligomerizations or a variety of organic molecules with electric characteristics.

That the present invention inquires into is M after dehydration and drying DNA molecular misfit²⁺Metal ion and M³⁺Current potential between metal ion Change procedure.

After the completion of M-DNA element manufacturing, device, which is passed to scan round voltage after measured current maps to voltage, to be sent out Its existing current characteristics has apparent variation (Fig. 7), is mainly the misfit against M metal ion to increase its DNA electric conductivity, (Fig. 7) significantly different compared to the current response of essential DNA, the background signal in addition enclosing sky electrode (are schemed compared with both 14).Due to the reaction of M metal ion in M-DNA, negative differential resistance (NDR) is had during voltage scanning and sluggishness is existing The generation of elephant, and peak value size and voltage are related with sweep speed.Because of the characteristic of negative differential resistance, M-DNA nano wire can be allowed It is designed to memory devices.

In a preferred embodiment, the voltage of different frequency scanning is to take 0 volt to be raised to 9 volts to drop to -9 volts again most After return to 0 volt as a circulation, voltage-current characteristic shows sluggish and negative differential resistance (NDR) characteristic (such as Figure 15). According to the M that the Crack cause of studies have shown that negative differential resistance characteristic is in DNA base²⁺And M³⁺Between occur electrically reaction, can Significantly observe scanning voltage ion-electron transition current potential peak value (Ep, a) and ion reduction current potential peak value (E_{P, c}) position About 5 volts and -5 volts.During voltage scanning, volt (i to iv), M from -9 volts to 9²⁺Electronics gradually occurs Transition becomes M3+ (ii to iii) and observes electron transition current potential peak value (E_{P, a}), electron transition reaction causes to pass through sample Electric current be gradually increased, after whole M metal ion electron transitions, electric current, which can be reduced rapidly, finally tends to a certain platform (iii to iv).And voltage sweeps to -9 volts (iv to i) then conversely, M from 9 volts³⁺It gradually generates reduction reaction and becomes M again²⁺(v To vi), electric current can also tend to a platform (vi to i) after also observing that reduction potential peak value (Ep, c) and all reduction.

After the voltage cycle sweep test being repeated several times, these reactions can occur again, and can determine that, in essence DNA in not can be appreciated that these phenomenons, therefore can determine that the increase of electric conductivity and the generation electrically reacted all be attributable to M gold Caused by the implantation for belonging to ion.

Thus voltage scanning recycles, it can be seen that M²+ and M³⁺Between the process converted mutually, and know as M-DNA device M The all M of metal ion²⁺When, the electric current of reaction is in circulation (i to iv), conversely, all M of M metal ion³⁺When, reaction Electric current is that using the different resistance characteristic of two kinds of M metal ions and curent change difference, can differentiate not in circulation (iv to i) Same state.

The memory devices characteristic of M-DNA

Electrical transmission characteristic is measured after M-DNA is connected with two end electrodes, it can be it has also been found that M-DNA in voltage be more than a certain electricity Property current potential when, can also occur NDR effect (Figure 16 A dotted line), current value is decreased obviously, curent change compared to λ-DNA (figure 16A solid black lines are inside inserted as Y-axis amplification display), can exclude this NDR effect is DNA itself caused, and deducibility is M²⁺? Electron transition occurs after to enough energy and becomes M³⁺, therefore cause the appearance of NDR phenomenon.Figure 16 B and Figure 16 C also verify this peak value Almost only appear in first and scan process (Figure 16 B, Figure 16 C solid black lines), in other words unidirectional scanning (0 →+ 10V or 0 → -10V) during, the scanning of first time just allows total metal ion electron transition or reduction enough.And Figure 16 D Also confirm that the result consistency and repeatability of this gamut scanning (0 →+10 → 0 → -10 → 0V).

When by M-DNA nano wire as memory materials'use, it can pass through and export electric current under input voltage reading different proportion Asymmetry, differentiate M-DNA state.And in the case where exchange is with direct current reading manner compared with, it is found that direct current reading manner can allow shape State maintains a more long.Furthermore it is also possible to control the different bias write times, a variety of distinguishable shapes are observed with direct current reading manner State has the phenomenon that similar internal storage state is divided into 1,0, -1, compared to two states that general memory only has 1 and 0, M-DNA's If multiple case is applied on memory, the capacity of memory can be greatly increased.Using these mechanism, can design device to The memory of multiple case uses, and can also design device to logical device using this condition discrimination.

The Applicant declares that the present invention is explained by the above embodiments detailed construction feature of the invention, but the present invention is simultaneously It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention must rely on above-mentioned detailed construction feature and could implement.Institute Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention And increase, selection of concrete mode of accessory etc., all of which fall within the scope of protection and disclosure of the present invention.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims

1. a kind of semiconductor material, comprising: the length being made of CCCGGG or TTTAAA continuous mrna sequence is 20-30 base Pair DNA material, the proton of amino or imino group in the DNA material base-pair replaced by bivalent metal ion.

2. semiconductor material as described in claim 1, the bivalent metal ion is Fe²⁺Ion or other containing divalent or trivalent it Metal ion.

3. semiconductor material as described in claim 1, the gene order of the DNA material are as follows: 5 '-CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG -3 GGG CCC or other continuous sequence genes column.

4. a kind of manufacturing method of semiconductor material, the DNA semiconductor material is the matter of the amino or imino group in base-pair The semiconductor material that son is replaced by bivalent metal ion, described method includes following steps:

Target dna is replicated using PCR system；

The target dna digestion of duplication is dealt with, the length of DNA is 20-30 base-pair after processing；

Extra bivalent metal ion is removed with buffer.

5. the manufacturing method of semiconductor material as claimed in claim 4, the bivalent metal ion is Fe²⁺Ion or other contain The metal ion of divalent or trivalent.

6. the manufacturing method of semiconductor material as claimed in claim 4, the gene order of the target dna are as follows: 5 '-CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG CCC GGG GGG -3 GGG CCC GGG CCC CCC or other continuous sequence genes column.

7. a kind of semiconductor devices, comprising: substrate is formed with one or more electrodes pair on substrate, and the two of the electrode pair A electrode is conllinear on the longitudinal direction of the electrode pair, and the longitudinal direction is first straight line direction, two conllinear electrodes Opposite end has tip, and the clearance distance between two tips is not more than 8nm；The matter of amino or imino group in base-pair Son is bonded by way of bonding with the tip of the electrode by the DNA material that bivalent metal ion replaces, and is connected to above-mentioned Between two tips.

8. semiconductor devices as claimed in claim 7, the bivalent metal ion is Fe²⁺Ion or other containing divalent or trivalent it Metal ion.

9. a kind of manufacturing method of semiconductor devices, comprising:

Electrode base board is prepared, is formed with electrode structure on the substrate, the electrode structure includes first electrode and multiple Two electrodes, the multiple second electrode include one or more electrodes pair, and two electrodes of each electrode pair are two-by-two in the electricity Conllinear on longitudinal direction extremely pair, the longitudinal direction is first straight line direction, and two conllinear opposite ends of electrode have Tip, the clearance distance between two tips are not more than 8nm, and the multiple electrode is located at along the gap between two tips On the same straight line of two rectilinear directions, the first straight line direction and second straight line direction are vertical, and the first electrode is located at On second straight line direction；

The bonding of DNA material electrophoresis, applies negative potential on the first electrode, applies equal positive electricity in the multiple second electrode Position, voltage difference are 0.5-2 volt DC；After applying electric field, by the proton containing amino or imino group in base-pair by divalent The solution for the DNA material that metal ion replaces micropipet drips on device, and maintains electrophoresis state 20 minutes or more, so that The DNA material binds are between two opposite electrode tips of the electrode pair；

The substrate for being bonded with DNA material is placed in container by freeze-drying, in 10-18 DEG C of low temperature bath, is connected using cold pumping baking oven It is continuous to vacuumize 4~7 days, then the substrate for being bonded with DNA material is put into merging liquid nitrogen refrigeration system, in liquid-nitrogen temperature Under at least save 3 days, further dehydrate.

10. the manufacturing method of semiconductor devices as claimed in claim 9, the bivalent metal ion is Fe²⁺Ion or other Metal ion containing divalent or trivalent.