CN108318533A - Biochemical sensor and its production method - Google Patents

Biochemical sensor and its production method Download PDF

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Publication number
CN108318533A
CN108318533A CN201711244390.7A CN201711244390A CN108318533A CN 108318533 A CN108318533 A CN 108318533A CN 201711244390 A CN201711244390 A CN 201711244390A CN 108318533 A CN108318533 A CN 108318533A
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nano wire
mentioned
conductive
layer
nano
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殷华湘
张青竹
张兆浩
徐忍忍
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Institute of Microelectronics of CAS
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Institute of Microelectronics of CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance

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Abstract

This application provides a kind of biochemical sensors and its production method.The biochemical sensor includes:Substrate has conductive surface and the insulating surface opposite with conductive surface;Conductive structure, on a conducting surface, conductive structure includes the nano thread structure along the multiple parallel connections set gradually far from conductive surface for setting, and nano thread structure includes nano wire, the nano wire interval setting of arbitrary neighborhood;Two electrodes are arranged on the surface of the separate substrate of conductive structure, and two electrodes are electrically connected with the both ends of each nano wire respectively;Sensitive material is arranged on each nano wire, and the mutually isolated setting of sensitive material on each nano wire.The biochemical sensor includes the stacking three-dimensional structure of nano wire, and sensitive material is arranged on each nano thread structure, increases the contact area of test substance and sensitive material, and then improves responsiveness and the sensitivity of sensor.

Description

Biochemical sensor and its production method
Technical field
This application involves sensor fields, in particular to a kind of biochemical sensor and its production method.
Background technology
Biological and chemical sensor (biochemical sensor) is in chemical industry, pharmacy, biomedicine, environmental monitoring and food security etc. Numerous areas has extensive and important application, closely bound up with the production and living of people.Resistor-type biochemical sensor is tied because of it Structure is simple, precision is high, wide range of measurement, long lifespan and be easily achieved micromation etc., research it is the most extensive.
The operation principle of resistor-type biochemical sensor is:The variation of measurand is converted into the variation of resistance value, then The variation of tested magnitude is shown or recorded through corresponding measuring circuit.
The responsiveness of resistor-type biochemical sensor and sensitivity are to determine the key parameter of its performance quality, still, mesh Before, the responsiveness of resistor-type biochemical sensor and sensitivity are generally relatively low.
Invention content
The main purpose of the application is to provide a kind of biochemical sensor and its production method, to solve to give birth in the prior art Change the responsiveness of sensor and the problem that sensitivity is relatively low.
To achieve the goals above, according to the one side of the application, a kind of biochemical sensor is provided, the biochemical sensitive Device includes:Substrate has conductive surface and the insulating surface opposite with above-mentioned conductive surface;Conductive structure is arranged above-mentioned On conductive surface, above-mentioned conductive structure includes the nano thread structure along the multiple parallel connections set gradually far from above-mentioned conductive surface, Each above-mentioned nano thread structure includes nano wire, the above-mentioned nano wire interval setting of arbitrary neighborhood;Two electrodes, setting are led above-mentioned On the surface far from above-mentioned substrate of electric structure, and two above-mentioned electrodes are electrically connected with the both ends of each above-mentioned nano wire respectively;It is quick Feel material, is arranged on each above-mentioned nano wire, and the mutually isolated setting of above-mentioned sensitive material on each above-mentioned nano wire.
Further, above-mentioned conductive structure further includes:Support construction, above-mentioned support construction are used to support above-mentioned nanowire-junction Structure.
Further, above-mentioned support construction is multiple and is arranged on above-mentioned conductive surface that each above-mentioned support construction includes Two spaced support portions in a first direction, each above-mentioned nano thread structure further include two on above-mentioned first direction between Every the interconnecting piece of setting, above-mentioned nano wire is connected between two above-mentioned interconnecting pieces, in the both sides of above-mentioned nano wire, above-mentioned support Portion is alternately stacked setting with above-mentioned interconnecting piece, and above-mentioned first direction is parallel to above-mentioned conductive surface, and two above-mentioned electrodes are set respectively It sets on the surface of above-mentioned interconnecting piece or above-mentioned support portion.
Further, above-mentioned substrate includes insulating layer and the top substrate layer that is arranged on above-mentioned insulating layer, above-mentioned roof liner The surface far from above-mentioned insulating layer of bottom is above-mentioned conductive surface, and the surface far from above-mentioned top substrate layer of above-mentioned insulating layer is Above-mentioned insulating surface.
Further, above-mentioned substrate further includes bottom liner bottom, and above-mentioned bottom liner bottom is arranged on above-mentioned insulating surface, preferably Above-mentioned substrate is SOI substrate.
Further, it is above-mentioned support construction that setting is contacted with above-mentioned conductive surface, and setting is contacted with above-mentioned electrode For above-mentioned nano thread structure.
Further, the material of above-mentioned support construction and the etching selection ratio of the material of above-mentioned nano thread structure are more than 100.
Further, the material of above-mentioned support construction is selected from least one of germanium and germanium silicon.
Further, the material of above-mentioned nano thread structure is selected from silicon.
Further, above-mentioned sensitive material is selected from 3- (2,3 the third oxygen of epoxy) propyl trimethoxy silicane, three second of 3- aminopropyls At least one of oxysilane, glutaraldehyde and graphene.
According to the another aspect of the application, a kind of production method of biochemical sensor is provided, which includes:It carries For substrate, above-mentioned substrate has conductive surface and the insulating surface opposite with above-mentioned conductive surface;On above-mentioned conductive surface Conductive structure and two electrodes are formed, above-mentioned conductive structure is arranged on above-mentioned conductive surface, and above-mentioned conductive structure includes along remote Nano thread structure from multiple parallel connections that above-mentioned conductive surface is set gradually, each above-mentioned nano thread structure includes nano wire, arbitrarily Adjacent above-mentioned nano wire interval setting;Two electrodes are arranged on the surface far from above-mentioned substrate of above-mentioned conductive structure, and Two above-mentioned electrodes are electrically connected with the both ends of each above-mentioned nano wire respectively;Sensitive material is set on each above-mentioned nano wire.
Further, conductive structure is formed on above-mentioned conductive surface and the process of two electrodes includes:In above-mentioned conduction The nano wire layer at the multiple intervals set gradually on surface forms pre- conductive structure;In above-mentioned pre- conductive structure far from above-mentioned Two electrodes are set on the surface of substrate;Above-mentioned pre- conductive structure is performed etching, the part of each above-mentioned nano wire layer, shape are removed At the nano thread structure at multiple intervals, and then conductive structure is formed, each above-mentioned nano thread structure includes nano wire, and two above-mentioned Electrode is electrically connected with the both ends of above-mentioned nano wire respectively.
Further, above-mentioned pre- conductive structure further includes multiple supporting layers, and above-mentioned conductive structure further includes that multiple intervals are set The support construction set, the process for forming above-mentioned pre- conductive structure include:It is arranged alternately supporting layer on above-mentioned conductive surface and receives Rice noodles layer;The process for forming above-mentioned conductive structure further includes:Remove the portion of each above-mentioned supporting layer corresponding with each above-mentioned nano wire Point material, remaining part is above-mentioned support construction in each above-mentioned supporting layer, and between the above-mentioned nano wire of arbitrary neighborhood not It is provided with above-mentioned support construction.
Further, during forming above-mentioned conductive structure, the part being removed in above-mentioned nano wire layer is centre The part in region, and then formation includes the nanometer of two interconnecting pieces and the above-mentioned nano wire being connected between two interconnecting pieces Cable architecture;The part being removed in above-mentioned supporting layer is region corresponding with the intermediate region of above-mentioned nano wire layer, to be formed Include the support construction of two support portions.
Further, during being arranged alternately supporting layer on above-mentioned conductive surface with nano wire layer, first above-mentioned Conductive surface is provided that above-mentioned supporting layer, and the layer structure being finally arranged is above-mentioned nano wire layer.
Using the technical solution of the application, which includes multiple in parallel and spaced nano thread structures, The stacking three-dimensional structure of nano wire is formd, and sensitive material is set on each nano thread structure, determinand can be increased in this way The contact area of matter and sensitive material, and then improve responsiveness and the sensitivity of sensor.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.In the accompanying drawings:
Fig. 1 shows a kind of structural schematic diagram of biochemical sensor according to the application;And
Fig. 2 to Fig. 7 shows the structural schematic diagram of the manufacturing process of the biochemical sensor in Fig. 1.
Wherein, above-mentioned attached drawing includes the following drawings label:
1, substrate;10, conductive surface;11, bottom liner bottom;12, insulating layer;13, top substrate layer;2, support construction;21, it props up Support part;3, nano thread structure;20, supporting layer;30, nano wire layer;31, interconnecting piece;32, nano wire;4, electrode;5, sensitive material Material;6, photoresist mask layer.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
It should be understood that when element such as layer, film, region or substrate are described as in another element "upper", the element Can be directly on another element, or intermediary element also may be present.Moreover, in specification and following claims In, when description has element " connected " to another element, which " can be directly connected to " to another element, or pass through third Element " electrical connection " is to another element.
As background technology is introduced, the responsiveness of biochemical sensor in the prior art and sensitivity are relatively low, are Solution technical problem as above, present applicant proposes a kind of biochemical sensors and its production method.
In a kind of typical embodiment of the application, a kind of biochemical sensor is provided, as shown in Figure 1, the biochemistry passes Sensor includes substrate 1, conductive structure, two electrodes 4 and sensitive material 5.Wherein, substrate 1 have conductive surface 10 and with The opposite insulating surface of above-mentioned conductive surface 10;Conductive structure is arranged on above-mentioned conductive surface 10, and above-mentioned conductive structure includes Along the nano thread structure 3 of the multiple parallel connections set gradually far from above-mentioned conductive surface 10, each above-mentioned nano thread structure 3 includes nanometer Line 32, the interval of above-mentioned nano wire 32 setting of arbitrary neighborhood;Two electrodes 4 are arranged in above-mentioned conductive structure far from above-mentioned substrate On 1 surface, and two above-mentioned electrodes 4 are electrically connected with the both ends of each above-mentioned nano wire 32 respectively;Sensitive material 5 is arranged on each It states on nano wire 32, and the 5 mutually isolated setting of sensitive material on each above-mentioned nano wire 32.
Above-mentioned biochemical sensor includes multiple in parallel and spaced nano thread structures, forms the stacking of nano wire Three-dimensional structure, and sensitive material is set on each nano thread structure, contact of the test substance with sensitive material can be increased in this way Area, and then improve responsiveness and the sensitivity of sensor.
In order to further steadily be supported to nano thread structure, to be further ensured that receiving in the biochemical sensor The stable fastness of nanowire structure, the reliability to be further ensured that the biochemical sensor is higher, a kind of implementation of the application In example, as shown in Figure 1, above-mentioned conductive structure further includes support construction 2, above-mentioned support construction 2 is used to support above-mentioned nanowire-junction Structure 3.
In a kind of embodiment of the application, as shown in Figure 1, above-mentioned support construction 2 is multiple and is arranged in above-mentioned conductivity meter On face 10, each above-mentioned support construction 2 includes two spaced support portions 21 in a first direction, each above-mentioned nano thread structure 3 further include two spaced interconnecting pieces 31 on above-mentioned first direction, the above-mentioned nano wire 32 of each above-mentioned nano thread structure 3 It is connected between two above-mentioned interconnecting pieces 31, in the both sides of above-mentioned nano wire 32, above-mentioned support portion 21 is handed over above-mentioned interconnecting piece 31 Be arranged for stacking, above-mentioned first direction is parallel to above-mentioned conductive surface 10, two electrodes be separately positioned on above-mentioned interconnecting piece 31 or On the surface of above-mentioned support portion 21.In this way in the both sides of nano wire, a support portion corresponds to one interconnecting piece of support, further protects The stable fastness for having demonstrate,proved nano thread structure, to further ensure the biochemical sensor performance stability with it is reliable Property.
Certainly, the support construction of the application is not limited to above-mentioned structure, can also be other structures in this field, Those skilled in the art can select suitable support construction to support nano thread structure according to actual conditions.
In a kind of embodiment of the application, as shown in Figure 1, above-mentioned substrate 1 includes insulating layer 12 and is arranged above-mentioned exhausted The surface far from above-mentioned insulating layer 12 of top substrate layer 13 in edge layer 12, above-mentioned top substrate layer 13 is above-mentioned conductive surface 10, The surface far from above-mentioned top substrate layer 13 of above-mentioned insulating layer 12 is above-mentioned insulating surface.
In the another embodiment of the application, as shown in Figure 1, above-mentioned substrate 1 further includes bottom liner bottom 11, above-mentioned bottom substrate Layer 11 is arranged on above-mentioned insulating surface.
In order to further ensure there is preferable insulation performance, the other side to have good electric conductivity for the side of the substrate Can, in a kind of embodiment of the application, above-mentioned substrate 1 is SOI substrate.
Certainly, the substrate of the application is not limited to above-mentioned substrate, can also be other structures in the prior art and The substrate of material.
In order to preferably support nano thread structure, and maximize the contact area of sensitive material and determinand as possible simultaneously, It saves cost of manufacture and improves producing efficiency, as shown in Figure 1, being contacted with above-mentioned conductive surface 10 in a kind of embodiment of the application Setting is above-mentioned support construction 2, and it is above-mentioned nano thread structure 3 that setting is contacted with above-mentioned electrode 4.
Certainly, the not necessarily support construction that setting is contacted with conductive surface, can also be nano thread structure, i.e. nanometer Cable architecture is set up directly on conductive surface, and substrate is supported nano thread structure.Similarly, setting is contacted with above-mentioned electrode Not necessarily nano thread structure, can also be that the other structures of support construction etc., those skilled in the art can be according to realities Border situation selects suitable set-up mode to form the biochemical sensor of the application.
In order to be more convenient for making, and ensure that the biochemical sensor formed is expected structure, a kind of embodiment of the application In, the material of above-mentioned support construction 2 and the etching selection ratio of the material of above-mentioned nano thread structure 3 are more than 100.I.e. for same Etching process, the rate that is etched of support construction 2 are more than 100 times of the rate that is etched of nano thread structure.
The material of the support construction of the application is conductive material, and specific material can be selected according to actual conditions It selects, but should be ensured that the biochemical sensor can make to obtain, such as, the structure of predetermined pattern in order to obtain will basis The etching selection ratio of the material of the material selection support construction of corresponding nano thread structure, the two is more than some value.
In order to further ensure the support construction has good electric conductivity, and it is further ensured that the biochemical biography to be formed simultaneously The structure of sensor is scheduled structure, and in a kind of embodiment of the application, the material of above-mentioned support construction 2 is in germanium and germanium silicon At least one.
In the another embodiment of the application, the material of above-mentioned nano thread structure 3 is selected from silicon.Certainly, receiving in the application Nanowire structure is not limited to above-mentioned silicon materials, can be according to actual conditions with other materials, those skilled in the art Selection suitable material forms the nano thread structure of the application.
The sensitive material of the application can be any type sensitive material in the prior art, and those skilled in the art can be with Suitable sensitive material is selected according to actual conditions.
As shown in Figure 1, when test, apply voltage between two electrodes 4, incident light is got on sensitive material, and electricity is utilized Flow table surveys the electric current at two 4 both ends of electrode, and size of current is corresponding with luminous intensity.
In another embodiment of the application, above-mentioned sensitive material 5 is selected from 3-2,3 glycidoxypropyl trimethoxy silicon At least one of alkane, 3- aminopropyl triethoxysilanes, glutaraldehyde and graphene.
In the typical embodiment of another kind of the application, a kind of production method of biochemical sensor, above-mentioned system are provided Include as method:As shown in Fig. 2, provide substrate, above-mentioned substrate has conductive surface and opposite with above-mentioned conductive surface exhausted Edge surface;Conductive structure and two electrodes are formed on above-mentioned conductive surface 10, above-mentioned conductive structure is arranged in above-mentioned conductivity meter On face 10, above-mentioned conductive structure includes the nano thread structure 3 along the multiple parallel connections set gradually far from above-mentioned conductive surface 10, respectively Above-mentioned nano thread structure 3 includes nano wire 32, and the interval of above-mentioned nano wire 32 setting of arbitrary neighborhood forms knot as shown in FIG. 6 Structure;Two electrodes 4 are arranged on surface of the above-mentioned conductive structure far from above-mentioned substrate 1, and two above-mentioned electrodes 4 respectively with respectively The both ends of above-mentioned nano wire 32 are electrically connected;Sensitive material 5 is set on each above-mentioned nano wire, forms structure as shown in Figure 7.
In above-mentioned production method, the nano thread structure of multiple intervals and parallel connection is set on the surface of substrate, and respectively receiving Sensitive material is set on nanowire structure, the contact area of test substance and sensitive material can be increased in this way, and then improves biography The responsiveness of sensor and sensitivity.
In another embodiment of the application, the mistake of conductive structure and two electrodes 4 is formed on above-mentioned conductive surface 10 Journey includes:The nano wire layer 30 at the multiple intervals set gradually on above-mentioned conductive surface 10, forms pre- conductive structure;Above-mentioned Two electrodes 4 are set on the surface far from above-mentioned substrate of pre- conductive structure;Above-mentioned pre- conductive structure is performed etching, removal is each The part of above-mentioned nano wire layer forms the nano thread structure 3 at multiple intervals, and then forms conductive structure, each above-mentioned nanowire-junction Structure 3 includes nano wire 32, and two above-mentioned electrodes 4 are electrically connected with the both ends of above-mentioned nano wire 32 respectively.
It, can also be it should be noted that the electrode in the application might not be arranged before conductive structure is formed It forms conductive structure to be configured later, specifically, can electrode be set before sensitive material is set, it can also be quick in setting Electrode is set after sense material, those skilled in the art can be according to being that the setting steps of electrode are set in certain steps by situation Later.
In order to further preferably support nano thread structure, in a kind of embodiment of the application, above-mentioned pre- conductive structure is also Including multiple supporting layers 20, above-mentioned conductive structure further includes multiple spaced support constructions 2, forms above-mentioned pre- conductive structure Process include:It is arranged alternately supporting layer 20 and nano wire layer 30 on above-mentioned conductive surface, forms structure shown in Fig. 3;Shape Process at above-mentioned conductive structure further includes:Remove the part material of each above-mentioned supporting layer corresponding with each above-mentioned nano wire 32 20 Expect, remaining part is above-mentioned support construction 2 in each above-mentioned supporting layer 20, forms structure as shown in FIG. 6, and arbitrary neighborhood Above-mentioned nano wire 32 between be not provided with above-mentioned support construction 2, the sensitivity on nano thread structure can be further increased in this way The contact area of material and determinand.
In the another embodiment of the application, during forming above-mentioned conductive structure, as shown in fig. 6, above-mentioned nanometer The part being removed in line layer 30 is a part for intermediate region, that is, is not whole intermediate region, but one therein Point, then form the above-mentioned nano wire as shown in FIG. 6 for including two interconnecting pieces 31 and being connected between two interconnecting pieces 31 32 nano thread structure 3;The part being removed in above-mentioned supporting layer 20 is corresponding with the intermediate region of above-mentioned nano wire layer 30 Region, i.e., the part being removed in supporting layer 20 is in-between region, and the intermediate region is gone with nano wire layer 30 The part removed be up and down it is corresponding, to formed it is as shown in FIG. 6 include two support portions 21 support construction 2.
In order to further increase the contact area of sensitive material and determinand as possible, and further decrease cost of manufacture simultaneously Producing efficiency is improved, in a kind of embodiment of the application, as shown in figure 3, being arranged alternately supporting layer on above-mentioned conductive surface 10 20 with nano wire layer 30 during, be provided that above-mentioned supporting layer 20 in above-mentioned conductive surface first, the layer knot being finally arranged Structure is above-mentioned nano wire layer 30.
In the another embodiment of the application, the etching selection of the material of above-mentioned supporting layer and the material of above-mentioned nano wire layer Than being more than 100.I.e. for the same etching process, the rate that is etched of support construction 2 is more than the speed that is etched of nano thread structure 100 times of rate.It may further ensure that prepared structure is expected structure in this way, and producing efficiency can be improved, letter Change manufacturing process.
The material of the support construction of the application is conductive material, and specific material can be selected according to actual conditions It selects, but should be ensured that the biochemical sensor can make to obtain, such as, the structure of predetermined pattern in order to obtain will basis The etching selection ratio of the material of the material selection support construction of corresponding nano thread structure, the two is more than some value.
In order to further ensure the support construction has good electric conductivity, and it is further ensured that the biochemical biography to be formed simultaneously The structure of sensor is scheduled structure, and in a kind of embodiment of the application, the material of above-mentioned support construction 2 is in germanium and germanium silicon At least one.
In the another embodiment of the application, the material of above-mentioned nano thread structure 3 is selected from silicon.Certainly, receiving in the application Nanowire structure is not limited to above-mentioned silicon materials, can be according to actual conditions with other materials, those skilled in the art Selection suitable material forms the nano thread structure of the application.
The sensitive material of the application can be any type sensitive material in the prior art, and those skilled in the art can be with Suitable sensitive material is selected according to actual conditions.
In another embodiment of the application, above-mentioned sensitive material 5 is selected from 3-2,3 glycidoxypropyl trimethoxy silicon At least one of alkane, 3- aminopropyl triethoxysilanes, glutaraldehyde and graphene.
It is feasible that the set-up mode of nano wire layer and supporting layer in the application can be selected from any type in the prior art Mode, such as:CVD, PVD, MOCVD, ALD or PLD.Those skilled in the art can select suitable side according to actual conditions Method forms supporting layer and nano wire layer.
Wet etching may be used in the step of removal part supporting layer and nano wire layer of the application or dry etching is implemented, Both lithographic methods can carry out under atmospheric pressure environment, can also be carried out under reduced pressure atmosphere.Those skilled in the art can To select suitable lithographic method and etching condition according to actual conditions.
The electrode of the application can be that method in the prior art is formed, such as:Photoetching technique successively, thermal evaporation and (lift-off) technology of stripping.Thermal evaporation therein can be replaced with deposited by electron beam evaporation or magnetron sputtering technique.A kind of tool In the embodiment of body, an electrode layer is first deposited, then etches again, forms two electrodes.Those skilled in the art can basis Actual conditions select suitable method to form two electrodes of the application.
The material of the electrode of the application can be that any type in the prior art can be as the material of electrode, this field Technical staff can select suitable material form corresponding electrode according to actual conditions, for example can select gold, chromium or zinc etc..
Two electrodes in the application can be identical, can also be different, those skilled in the art can basis Actual conditions select identical or different electrode.
In order to enable those skilled in the art can become more apparent upon the technical solution of the application, below with reference to specific reality Example is applied to illustrate the technical solution of the application.
Embodiment
SOI substrate is provided, as shown in Fig. 2, and to substrate surface progress cleaning treatment, silicon chip is put into seven-star rinse bath 10min is rinsed in APM solution to remove silicon chip surface particle, is then rinsed 5min with deionized water and is dried;Then Lam is used 203 monolithic cleaning equipments of Research, in diluted HF solution (HF:H2O=1:100) in, 120s is cleaned;
The chip that cleaning is completed is sent into ASM E2000plusRpcvd equipment (reduced Pressure-chemical vapor deposition, RPCVD) epitaxial reaction chamber in carry out epitaxial growth.It is outer in decompression Prolong in reaction chamber environment, toast silicon chip 20min in hydrogen environment at high temperature first, it is therefore an objective to remove oneself of surface possibility remaining Right oxide layer.Then cavity temperature is down to 650 DEG C, is passed through SiH2Cl2And GeH4Gas 90s grows GeSi layers, i.e. supporting layer, Then GeH is cut off4Gas trap is only passed through SiH2Cl2Gas, extension 160s form Si layers, i.e. nano wire layer.Repeat above-mentioned two step Epitaxial gas technique forms six layer heap stack structures of Si/GeSi, forms structure shown in Fig. 3.
Using using photoetching technique, magnetron sputtering technique and stripping (lift-off) technology to prepare electrode successively, in Fig. 3 Shown in structure exposed surface be arranged photoresist layer, by photoetching pre-set electrode region formed photoresist trepanning, connect It and deposits metal material chrome gold (10nm/30nm) with magnetron sputtering technique, finally use stripping technology removal photoresist and attachment Metal material on a photoresist, leaves electrode pattern, completes the preparation of electrode, forms structure shown in Fig. 4.Magnetic control therein Sputtering technology could alternatively be thermal evaporation or electron beam evaporation.
Photoresist mask layer 6 is formed in nano wire region using electron beam lithography, as shown in Figure 5;Then it uses anti- Ion etching is answered to remove the six layer heap stack structure layers of Si/GeSi of unglazed photoresist covering;Photoresist finally is cleaned with acetone, completes to receive The etching of rice noodles figure.
Discharge nano wire:Using hydrofluoric acid (HF), hydrogen peroxide (H2O2) and acetic acid (CH3COOH mixed solution) is selected The GeSi corrosion of selecting property, corrosion temperature are 20 DEG C of room temperature.The concentration and proportioning (volume ratio) of wherein three kinds solution are HF (6%):H2O2 (30%):CH3COOH (99.8%)=1:2:3, the preparation of experimental solutions has used the HF aqueous solutions of 200ml, the H of 400ml2O2 The high-purity C H of aqueous solution and 600ml3COOH solution.Solution is stirred evenly after placing the regular hour, chip is put into molten In liquid, etching time 9min.Then, the chip etched is taken out and the water for spending ion immediately cleans 5min, finally It is dried up with high pressure nitrogen, forms structure shown in fig. 6.
Active agent (i.e. sensitive material) is modified:The concentrated sulfuric acid of 70 DEG C of structure immersion that Fig. 6 is formed and mixing for hydrogen peroxide It closes in solution, 1~5h of constant temperature carries out hydroxylating processing;It cleans, dries immediately after, it is 1 to be immersed in volume ratio:1 concentrated hydrochloric acid With carry out sour processing in the mixed liquor of absolute ethyl alcohol, processing time is 1~for 24 hours;It is immersed in active agent 3- ammonia after cleaning drying In the solution of propyl-triethoxysilicane, soaking time is 0.5~7d;5min is cleaned with ethyl alcohol and deionized water successively later, It is put into baking oven drying, active agent modification is completed, forms structure shown in Fig. 7.
It can be seen from the above description that the application the above embodiments realize following technique effect:
1), the biochemical sensor of the application includes multiple in parallel and spaced nano thread structures, forms nano wire Stacking three-dimensional structure, and sensitive material is set on each nano thread structure, test substance and sensitive material can be increased in this way Contact area, and then improve responsiveness and the sensitivity of sensor
2) nano thread structure of multiple intervals and parallel connection is arranged on the surface of substrate in, the production method of the application, and each Sensitive material is set on nano thread structure, the contact area of test substance and sensitive material can be increased in this way, and then is improved The responsiveness of sensor and sensitivity.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.

Claims (15)

1. a kind of biochemical sensor, which is characterized in that the biochemical sensor includes:
Substrate (1) has conductive surface (10) and the insulating surface opposite with the conductive surface (10);
Conductive structure is arranged on the conductive surface (10), and the conductive structure includes along far from the conductive surface (10) The nano thread structure (3) of the multiple parallel connections set gradually, each nano thread structure (3) includes nano wire (32), arbitrary neighborhood The nano wire (32) interval setting;
Two electrodes (4) are arranged on the surface far from the substrate (1) of the conductive structure, and two electrodes (4) It is electrically connected respectively with the both ends of each nano wire (32);And
Sensitive material (5) is arranged on each nano wire (32), and the sensitive material on each nano wire (32) (5) mutually isolated setting.
2. biochemical sensor according to claim 1, which is characterized in that the conductive structure further includes:
Support construction (2), the support construction (2) are used to support the nano thread structure (3).
3. biochemical sensor according to claim 2, which is characterized in that the support construction (2) is multiple and setting exists On the conductive surface (10), each support construction (2) includes two spaced support portions (21) in a first direction, Each nano thread structure (3) further includes two spaced interconnecting pieces (31) in said first direction, the nano wire (32) be connected between two interconnecting pieces (31), the both sides in the nano wire (32), the support portion (21) with it is described Interconnecting piece (31) is alternately stacked setting, and the first direction is parallel to the conductive surface (10), and two electrodes (4) are respectively It is arranged on the surface of the interconnecting piece (31) or the support portion (21).
4. biochemical sensor according to claim 1, which is characterized in that the substrate (1) include insulating layer (12) and The top substrate layer (13) being arranged on the insulating layer (12), the table far from the insulating layer (12) of the top substrate layer (13) Face is the conductive surface (10), and the surface far from the top substrate layer (13) of the insulating layer (12) is the insulation meter Face.
5. biochemical sensor according to claim 4, which is characterized in that the substrate (1) further includes bottom liner bottom (11), The bottom liner bottom (11) is arranged on the insulating surface, and the preferably described substrate (1) is SOI substrate.
6. biochemical sensor according to claim 2, which is characterized in that contacting setting with the conductive surface (10) is The support construction (2), it is the nano thread structure (3) that setting is contacted with the electrode (4).
7. biochemical sensor according to claim 2, which is characterized in that the material of the support construction (2) is received with described The etching selection ratio of the material of nanowire structure (3) is more than 100.
8. biochemical sensor according to claim 2, which is characterized in that the material of the support construction (2) be selected from germanium with At least one of germanium silicon.
9. biochemical sensor according to claim 1, which is characterized in that the material of the nano thread structure (3) is selected from silicon.
10. biochemical sensor according to claim 1, which is characterized in that the sensitive material (5) is selected from 3- (2,3 epoxies At least one of third oxygen) propyl trimethoxy silicane, 3- aminopropyl triethoxysilanes, glutaraldehyde and graphene.
11. a kind of production method of biochemical sensor, which is characterized in that the production method includes:
Substrate is provided, the substrate has conductive surface and the insulating surface opposite with the conductive surface;
Conductive structure and two electrodes are formed on the conductive surface, the conductive structure is arranged on the conductive surface, The conductive structure includes the nano thread structure along the multiple parallel connections set gradually far from the conductive surface, each nano wire Structure includes nano wire, the nano wire interval setting of arbitrary neighborhood;Two electrodes are arranged in the separate of the conductive structure On the surface of the substrate, and two electrodes are electrically connected with the both ends of each nano wire respectively;And
Sensitive material is set on each nano wire.
12. production method according to claim 11, which is characterized in that on the conductive surface formed conductive structure and The process of two electrodes includes:
The nano wire layer at the multiple intervals set gradually on the conductive surface forms pre- conductive structure;
Two electrodes are set on the surface far from the substrate of the pre- conductive structure;And
The pre- conductive structure is performed etching, the part of each nano wire layer is removed, forms the nanowire-junction at multiple intervals Structure, and then form conductive structure, each nano thread structure includes nano wire, and two electrodes respectively with the nano wire Both ends electrical connection.
13. production method according to claim 12, which is characterized in that the pre- conductive structure further includes multiple supports Layer, the conductive structure further includes multiple spaced support constructions,
The process for forming the pre- conductive structure includes:
It is arranged alternately supporting layer and nano wire layer on the conductive surface;
The process for forming the conductive structure further includes:
The some materials of each supporting layer corresponding with each nano wire are removed, remaining part is in each supporting layer The support construction, and the support construction is not provided between the nano wire of arbitrary neighborhood.
14. production method according to claim 13, which is characterized in that during forming the conductive structure, institute The part that the part that is removed in nano wire layer is intermediate region is stated, and then is formed and is included two interconnecting pieces and be connected to two The nano thread structure of the nano wire between a interconnecting piece;The part being removed in the supporting layer is and the nano wire layer The corresponding region in intermediate region, to formed include two support portions support construction.
15. production method according to claim 13, which is characterized in that be arranged alternately supporting layer on the conductive surface During nano wire layer, the supporting layer is provided that in the conductive surface, the layer structure being finally arranged is institute first State nano wire layer.
CN201711244390.7A 2017-11-30 2017-11-30 Biochemical sensor and its production method Pending CN108318533A (en)

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CN101830509A (en) * 2010-05-20 2010-09-15 武汉理工大学 Beta-AgVO3 nanowire hydrogen sulfide gas sensing material and method for manufacturing gas sensor by using same
CN102945791A (en) * 2012-11-29 2013-02-27 上海集成电路研发中心有限公司 Preparation method of silicon nanowire array
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Application publication date: 20180724