CN104897762A - GaN based biosensor and making method thereof - Google Patents

GaN based biosensor and making method thereof Download PDF

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Publication number
CN104897762A
CN104897762A CN201410074971.0A CN201410074971A CN104897762A CN 104897762 A CN104897762 A CN 104897762A CN 201410074971 A CN201410074971 A CN 201410074971A CN 104897762 A CN104897762 A CN 104897762A
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gan
algan
drain electrode
source electrode
biology sensor
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李加东
苗斌
吴东岷
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Abstract

The invention discloses a GaN based biosensor, which comprises: a substrate; an AlGaN/GaN heterojunction formed on the substrate, wherein the AlGaN/GaN heterojunction comprises a first GaN layer, an AlGaN layer and a second GaN layer formed on the substrate in order; a source electrode and a drain electrode located on the AlGaN/GaN heterojunction, with the surface of the second GaN layer having a sensing region located between the source electrode and the drain electrode; and a biomolecular membrane, which is directly modified on the sensing region. According to the invention, by means of surface treatment on the sensing region, the biomolecular membrane can be directly modified on the sensing region, thus not only reducing the cost, but also improving the sensor sensitivity. In addition, the GaN based biosensor and the method provided by the invention also employ silicone to package the source electrode and the drain electrode, and solve the problem that during material testing liquid ions are likely to permeate a protective layer to cause device damage and the technical problem that devices are unsuitable for long-term application in an organic environment.

Description

GaN base biology sensor and preparation method thereof
Technical field
The application belongs to biomedical instrument device and applied technical field thereof, particularly relates to a kind of GaN base biology sensor and preparation method thereof.
Background technology
GaN base III-V semiconductor material has wide direct band gap, excellent physics, chemical stability, high saturated electron drift velocity, the superior function such as high breakdown field strength and high heat conductance, the energy bandmatch that particularly AlGaN/GaN low-dimensional heterostructure interface conduction band is very large and the extremely strong piezoelectricity of AlGaN layer and spontaneous polarization effect, two-dimensional electron gas (2DEG) density exceeding nearly order of magnitude than AlGaAs/GaAs heterojunction structure can be provided, add the breakdown electric field that GaN base material is high, the power density of the GaN base device made is higher than GaAs base device more than 10 times in theory, therefore, GaN base wide bandgap semiconductor, particularly AlGaN/GaN heterogeneous structure material is considered to develop high temperature, high frequency, high power, the most preferably material system of radiation-resistant third generation microelectronic component.
Based on the excellent properties of AlGaN/GaN heterogeneous structure material, researchist has carried out the applied research of AlGaN/GaN heterogeneous structure material in different field, the people such as people and Shanghai Institute of Technical Physics of Chinese Academy of Sciences W. D. Hu such as such as Chinese Academy of Sciences Suzhou nanometer institute J .D. Sun and Y.F.Sun have carried out the research of AlGaN/GaN High Electron Mobility Transistor (HEMT) terahertz detector, have developed the terahertz detector at working and room temperature; The people such as the Z.Xu of the people such as Shanghai Institute of Technical Physics of Chinese Academy of Sciences X.D.Wang and Xian Electronics Science and Technology University have carried out the research of AlGaN/GaN HEMT base RF/Microwave power amplifier and AlGaN/GaN HEMT base frequency converter respectively, and achieve good result.And in the biochemical safety that current people very pay close attention to, environmental monitoring field AlGaN/GaN HEMT base device also has wide application prospects.
In bio-sensing field, compared with traditional silica-based biological devices, the chemical property of GaN base biosensing device is more stable, possesses nontoxicity simultaneously, can reduce the advantages such as adherent cell degeneration.In current research, HEMT device sensitive zones adopts the recognition component of Au film or oxide passivation layer film fixing biological molecules film and molecules detected usually, the formation of Au film needs ultraviolet photolithographic machine, electron beam evaporation platform and stripping technology, and the formation of oxidation film needs plasma enhanced chemical vapor deposition platform (PECVD), ultraviolet photolithographic machine, the equipment such as dry etching machine, this can increase the manufacture difficulty of sensor, improve cost of manufacture, the existence of Au film or oxide film simultaneously also can increase the distance of molecules detected regulation and control 2DEG, thus can have an impact to the performance of sensor.On the other hand; the physical dimension of current GaN base biology sensor is micron dimension; the packaged type that device package adopts photoresist, silicon nitride and monox three kinds different usually; but when adopting the encapsulation of silicon nitride, monox inorganic material; the compatibility of its manufacture craft and device is high, but this material easily occurs that in test process liquid ions infiltrates the problem that protective seam causes device failure.And when adopting photoresist to encapsulate, the unsuitable prolonged application of device, in organic environment, adopts photoresist, silicon nitride and monox three kinds of packaged types also higher to the requirement of equipment, thus adds cost of manufacture simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of GaN base biology sensor and preparation method thereof, solve in prior art adopt Au film or oxidation film cost of manufacture is high, obtain the technical matters of sensor performance difference.
For achieving the above object, the invention provides following technical scheme:
The embodiment of the present application discloses a kind of GaN base biology sensor, comprising:
Substrate;
Be formed at the AlGaN/GaN heterojunction on described substrate, described AlGaN/GaN heterojunction comprises the first GaN layer be formed at successively on described substrate, AlGaN layer and the second GaN layer;
Be positioned at the source electrode on described AlGaN/GaN heterojunction and drain electrode, the surface of described second GaN layer has a sensing unit, and described sensing unit is between described source electrode and drain electrode;
Molecule film, directly modifies on described sensing unit.
Preferably, in above-mentioned GaN base biology sensor, described source electrode and drain electrode are of a size of 0.25 mm 2~ 25mm 2, the distance between described source electrode and drain electrode is 0.5mm ~ 5mm, and the outside of described source electrode and drain electrode is also packaged with silicone.
Preferably, in above-mentioned GaN base biology sensor, the material of described substrate is selected from sapphire or silicon.
Preferably, in above-mentioned GaN base biology sensor, described molecule film adopts and can form biological reagent that tail base is-COOH on the second GaN layer surface or tail base is the biological reagent of-N2H.
Correspondingly, the invention also discloses a kind of method for making of GaN base biology sensor, comprising:
S1, at Grown AlGaN/GaN heterojunction, described AlGaN/GaN heterojunction comprises the first GaN layer be formed at successively on described substrate, AlGaN layer and the second GaN layer;
S2, utilize electron beam evaporation process on AlGaN/GaN heterojunction evaporation Ti/Al/Ni/Au as drain electrode, evaporation Ni/Au as source electrode, surface definition one sensing unit of described second GaN layer, described sensing unit described source electrode and drain electrode between;
S3, in described sensor regions direct modified biological molecular film.
Preferably, in the method for making of above-mentioned GaN base biology sensor, described step s3 is specially: adopt UV/O3 to carry out surface treatment to sensing unit, then the toluene solution of the APTES of 5% is added drop-wise to sensing unit, silanization is carried out to surface, sensing unit, after 2h, adopts toluene respectively, deionized water fully rinses, rear employing nitrogen dries up, and being formed can the molecule film of sessile antibody or DNA.
Preferably, in the method for making of above-mentioned GaN base biology sensor, described source electrode and drain electrode are of a size of 0.25 mm 2~ 25mm 2, the distance between described source electrode and drain electrode is 0.5mm ~ 5mm, in described step s2, also comprises and adopts silicone to carry out the process of packaging protection to source electrode and drain electrode.
Preferably, in the method for making of above-mentioned GaN base biology sensor, the material of described substrate is selected from sapphire or silicon.
Preferably, in the method for making of above-mentioned GaN base biology sensor, described molecule film adopts and can form biological reagent that tail base is-COOH on the second GaN layer surface or tail base is the biological reagent of-N2H.
Compared with prior art, the invention has the advantages that:
(1), by carrying out surface treatment to sensing unit, and then making molecule film to be directly modified on sensing unit, not only reducing cost, and improve the sensitivity of sensor.
(2), GaN base biology sensor of the present invention is of a size of a millimeter magnitude; silicone is adopted to encapsulate source electrode and drain electrode; solve material in test process, easily occur that liquid ions infiltrates the problem that protective seam causes device failure, and the unsuitable technical matters of prolonged application in organic environment of device.Meanwhile, GaN base biology sensor size becomes large and adopts the packaged type of silicone, does not affect the performance of sensor.In addition, the encapsulation of silicone can adopt the plant equipment of manual type or low cost, avoids the problem that the packaging cost of photoresist, silicon nitride and monox three kinds of packaged types is high.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the application, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Figure 1 shows that the structural representation of GaN base biology sensor in the specific embodiment of the invention;
Figure 2 shows that GaN base biology sensor electric current curve over time in the specific embodiment of the invention;
Figure 3 shows that in the specific embodiment of the invention, GaN base biology sensor is to the signal response of the PSA of variable concentrations.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be described in detail the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
Shown in ginseng Fig. 1, GaN base biology sensor comprises substrate 1, and is formed at the first GaN layer 2 on substrate 1, AlGaN layer 3 and the second GaN layer 4, first GaN layer 2, AlGaN layer 3 and the second GaN layer 4 successively and forms AlGaN/GaN heterojunction.
The material of substrate 1 is selected from sapphire or silicon, is preferably sapphire.
AlGaN/GaN heterojunction is formed with source electrode 5 and drain electrode 6, source electrode 5 and drain electrode 6 are preferably dimensioned to be 0.25 mm 2~ 25mm 2, the distance between source electrode 5 and drain electrode 6 is preferably 0.5mm ~ 5mm.The material of source electrode 5 and drain electrode 6 has Ti, the combination of the metals such as Ta, Zr, Co, Al, Pt, Pa, Ni, Cr, Mo, W, Au, is preferably Ti/Al/Ni/Au combination.
Source electrode 5 and drain electrode 6 are electrically connected with contact conductor 7 respectively, and contact conductor 7 is drawn in the side of device.The material of contact conductor 7 has Ti, the metals such as Ta, Zr, Co, Al, Pt, Pa, Ni, Cr, Mo, W, Au, Cu, Fe and combination thereof, is preferably Ni/Au.
Source electrode 5 and drain electrode 6 and contact conductor 7 are packaged with layer of silicone 8, when layer of silicone 8 can prevent from carrying out liquid detecting, liquid and source electrode 5, drain 6 and go between 7 contact.The more important thing is, adopt silicone encapsulate, liquid ions not easily infiltrates protective seam, and device can prolonged application in organic environment.
Source electrode 5 and drain electrode 6 convexedly stretch in the surface of the second GaN layer 4, surround a sensing chamber 9 between source electrode 5 and drain electrode 6, can drip liquid to be detected in sensing chamber 9.The surface of the second GaN layer 4 defines in sensing chamber 9 sensing unit, sensing unit is directly modified with molecule film (not shown), the direct modification at this place refers to that molecule film is directly modified in the second GaN layer 4, does not need by Au film or oxide passivation layer film fixing biological molecules film.
Molecule film can be used for sessile antibody, DNA, preferably adopts to form biological reagent that tail base is-COOH on GaN surface or tail base is the biological reagent of-N2H, such as 3-aminopropyl triethoxysilane.
The method for making of above-mentioned GaN base biology sensor comprises:
S1, first employing metal-organic vapor phase epitaxy method (MOCVD) grow the first GaN layer 2, AlGaN layer 3 and the second GaN layer 4 on a sapphire substrate successively;
S2, photolithographic exposure go out ohmic contact regions, utilize electron beam evaporation, and at ohmic contact regions evaporation Ti/Al/Ni/Au, anneal 45 seconds under N2 environment after stripping, annealing temperature is 880 DEG C, form source electrode 5 and drain electrode 6.The size of source electrode 5 and drain electrode 6 is 2mm × 2mm, and source electrode 5 is 2mm with the spacing of drain electrode 6;
S3, photoetching, expose contact conductor 7 region, utilizes electron beam evaporation technique evaporation Ni/Au, and the rear lift-off of utilization technique separates outside lead;
S4, employing silicone carry out the encapsulation of device, protection source-drain electrode;
S5, device are modified, before HEMT device is used as biological test, need to carry out functional modification on sample cell sensing surface, sample adopts UV/O3 to carry out surface treatment to sample cell sensing surface, is then added drop-wise in sample cell by the toluene solution of the APTES (APTES) of 5%, carries out silanization to sensitive zones surface, after 2h, adopt toluene respectively, deionized water fully rinses, rear employing nitrogen dries up, formed can sessile antibody, DNA molecule film.
In AlGaN/GaN HEMT(High Electron Mobility Transistor) in structure, due to piezoelectricity and spontaneous polarization effect, the interface of AlGaN/GaN HEMT device can form a 2DEG(two-dimensional electron gas) surface channel, 2DEG in potential well is controlled by grid voltage, this structure adopts molecule film to replace as the grid of AlGaN/GaN HEMT during biology sensor, during devices function, the introducing of determined antigen causes the change of molecule film surface voltage, thus cause the change of 2DEG concentration in potential well, and the change of 2DEG concentration can cause the change of electric current between the source electrode (source) of transistor and drain electrode (drain), therefore the change by electric current detects the concentration change introducing determined antigen.
Above-mentioned GaN base biology sensor is utilized to detect prostate specific antigen:
In the sensing chamber of silanization, drip 2.5% glutaraldehyde solution, hydroformylation 1h, adopt deionized water rinsing.After flushing dries up, in sensing chamber, drip the PSA antibody of 10 μ g/ml, seal the interior cultivation of the refrigerator being placed on 4 DEG C 24 hours, carboxyl is fully combined with antibody, after having cultivated, then adopt the bovine serum albumin(BSA) (BSA) of 1% to close avtive spot.
Sensor after sessile antibody, under 50mV constant bias voltage, measures the PSA of 0.1pg/ml, and survey 3 times, average, measurement result as shown in Figure 2.As can be seen from the figure, when test PBS damping fluid and interpolation BSA are to sensitive zones surface, the current signal of device does not all significantly change, and illustrates that sensor has good stability and specificity.When adding concentration and being the PSA of 1pg/ml, the electric current of sensor reduces by 0.473 μ A, this means that PSA there occurs reaction with the antibody in HEMT finishing, and millimeter magnitude device possesses the ability measuring low concentration PSA.
For this device, measure the response of device to the PSA of variable concentrations, often kind of measurement of concetration 3 times, average, measurement result as shown in Figure 3.As can be seen from the figure millimeter magnitude molecule film gate electrode AlGaN/GaN HEMT biology sensor to the detection limit of PSA lower than 0.1pg/ml.This micron dimension gate electrode metal AlGaN/GaN HEMT sensor response to PSA made than people such as B.S.Kang improves 2 orders of magnitude.
Be easy to it is contemplated that in other embodiments, when adopting silicone to encapsulate source electrode and drain electrode, sensing unit also first can form Au film or oxide passivation layer film, then molecule film is modified on Au film or oxide passivation layer film.Same, in the embodiment not adopting Au film or oxide passivation layer film, also can adopt other passivation layers of non-silicone to the encapsulation of device, such as silicon nitride.
It should be noted that, in this article, the such as relational terms of first and second grades and so on is only used for an entity or operation to separate with another entity or operational zone, and not necessarily requires or imply the relation that there is any this reality between these entities or operation or sequentially.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise those key elements, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.When not more restrictions, the key element limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment comprising described key element and also there is other identical element.
The above is only the embodiment of the application; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the protection domain of the application.

Claims (9)

1. a GaN base biology sensor, is characterized in that, comprising:
Substrate;
Be formed at the AlGaN/GaN heterojunction on described substrate, described AlGaN/GaN heterojunction comprises the first GaN layer be formed at successively on described substrate, AlGaN layer and the second GaN layer;
Be positioned at the source electrode on described AlGaN/GaN heterojunction and drain electrode, the surface of described second GaN layer has a sensing unit, and described sensing unit is between described source electrode and drain electrode;
Molecule film, directly modifies on described sensing unit.
2. GaN base biology sensor according to claim 1, is characterized in that: described source electrode and drain electrode are of a size of 0.25 mm 2~ 25mm 2, the distance between described source electrode and drain electrode is 0.5mm ~ 5mm, and the outside of described source electrode and drain electrode is also packaged with silicone.
3. GaN base biology sensor according to claim 1, is characterized in that: the material of described substrate is selected from sapphire or silicon.
4. GaN base biology sensor according to claim 1, is characterized in that: described molecule film adopts and can form biological reagent that tail base is-COOH on the second GaN layer surface or tail base is the biological reagent of-N2H.
5. a method for making for GaN base biology sensor, is characterized in that, comprising:
S1, at Grown AlGaN/GaN heterojunction, described AlGaN/GaN heterojunction comprises the first GaN layer be formed at successively on described substrate, AlGaN layer and the second GaN layer;
S2, utilize electron beam evaporation process on AlGaN/GaN heterojunction evaporation Ti/Al/Ni/Au as drain electrode, evaporation Ni/Au as source electrode, surface definition one sensing unit of described second GaN layer, described sensing unit described source electrode and drain electrode between;
S3, in described sensor regions direct modified biological molecular film.
6. the method for making of GaN base biology sensor according to claim 5, it is characterized in that: described step s3 is specially: adopt UV/O3 to carry out surface treatment to sensing unit, then the toluene solution of the APTES of 5% is added drop-wise to sensing unit, silanization is carried out to surface, sensing unit, after 2h, adopt toluene respectively, deionized water fully rinses, rear employing nitrogen dries up, and being formed can the molecule film of sessile antibody or DNA.
7. the method for making of GaN base biology sensor according to claim 5, is characterized in that: described source electrode and drain electrode are of a size of 0.25 mm 2~ 25mm 2, the distance between described source electrode and drain electrode is 0.5mm ~ 5mm, in described step s2, also comprises and adopts silicone to carry out the process of packaging protection to source electrode and drain electrode.
8. the method for making of GaN base biology sensor according to claim 5, is characterized in that: the material of described substrate is selected from sapphire or silicon.
9. the method for making of GaN base biology sensor according to claim 5, is characterized in that: described molecule film adopts and can form biological reagent that tail base is-COOH on the second GaN layer surface or tail base is the biological reagent of-N2H.
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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN105806913A (en) * 2016-05-17 2016-07-27 西安电子科技大学 GaN biosensor with integrated-type solid film reference electrode and producing method
CN106018527A (en) * 2016-05-17 2016-10-12 西安电子科技大学 GaN biosensor provided with integrated type solid film Pt reference electrode and manufacturing method
CN107121544A (en) * 2017-06-02 2017-09-01 中国科学院半导体研究所 Biology sensor of diagnosing acute heart infarction and preparation method thereof
CN107407653A (en) * 2014-11-07 2017-11-28 蛋白质感官公司 For testing and analyzing the equipment, system and method for thing
CN110534478A (en) * 2018-05-24 2019-12-03 中国科学院苏州纳米技术与纳米仿生研究所 Senser element and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107407653A (en) * 2014-11-07 2017-11-28 蛋白质感官公司 For testing and analyzing the equipment, system and method for thing
CN105806913A (en) * 2016-05-17 2016-07-27 西安电子科技大学 GaN biosensor with integrated-type solid film reference electrode and producing method
CN106018527A (en) * 2016-05-17 2016-10-12 西安电子科技大学 GaN biosensor provided with integrated type solid film Pt reference electrode and manufacturing method
CN106018527B (en) * 2016-05-17 2019-01-08 西安电子科技大学 GaN biosensor and production method with integrated form solid film Pt reference electrode
CN107121544A (en) * 2017-06-02 2017-09-01 中国科学院半导体研究所 Biology sensor of diagnosing acute heart infarction and preparation method thereof
CN110534478A (en) * 2018-05-24 2019-12-03 中国科学院苏州纳米技术与纳米仿生研究所 Senser element and preparation method thereof

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