CN102937607B - A kind of series-connection flexible vibration piezoelectric diaphragm type biosensor and preparation method thereof - Google Patents
A kind of series-connection flexible vibration piezoelectric diaphragm type biosensor and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of series-connection flexible vibration piezoelectric diaphragm type biosensor and preparation method thereof.It utilizes micro-processing technology to prepare flexible vibration piezoelectricity barrier film on soi wafer substrate, and wherein the Device layer of soi wafer is as the supporting layer of barrier film, the driving layer that piezoelectric membrane vibrates as barrier film, and upper/lower electrode lays respectively at piezoelectric layer upper and lower surface.Sensor of the invention designs from principle and structure, avoids cost height, the piezoelectric layer patterning process of weak effect dexterously, and meanwhile, the existence of reference cell greatly improves the accuracy of detection of sensor.It addition, compared to QCM biosensor, sensor of the present invention is the sensitiveest, when liquid phase in situ detection, quality factor are high, and are easy to microminiaturization and mass manufacture；Compared to flexible vibration beam type sensor, sensor construction of the present invention is firm, and when liquid phase in situ detection, quality factor are high.
Description
Technical field
The invention belongs to biosensor technology field, relate to a kind of biosensor, a kind of series-connection flexible vibration piezoelectric diaphragm type biosensor being applied to biological detection and preparation method thereof.
Background technology
Biosensor is the technique for fixing utilizing certain biological or chemical, biological identification element (enzyme, antibody, antigen, albumen, nucleic acid, receptor, cell, microorganism, animal vegetable tissue etc.) is fixed on the transducer, when after determinand with biological identification element generation specific reaction, by transducer produced reaction result (formed complex or generation sound, optical, electrical, hot etc.) is changed into can export, the signal of telecommunication that detects and optical signal etc., with this, test substance carried out qualitative and quantitative analysis, thus reach to detect analysis purpose.Piezoelectric biological sensor is a kind of Novel Biosensor that development in recent years is got up, and this kind of sensor need not any labelling, and has instrument and be simple and convenient to operate, respond sensitive, selectivity good, is easy to the advantages such as automatization.Piezoelectric biological sensor in early days is mainly by the piezoelectric quartz resonator sensitivity to quality, and by monitoring resonator after immunoreation, the resonant frequency change caused because surface quality changes detects determinand, and piezoelectrics used herein are single crystal quartz.Develop to microminiaturization however as system, the highly desirable piezoelectrics that can use film morphology of those skilled in the art, therefore, then the piezoelectric transducer that research can be made up with film forming piezoelectric of other, it is that those skilled in the art are desired.
The present invention will introduce a kind of series-connection flexible vibration piezoelectric diaphragm type biosensor and preparation method thereof.The preparation of this sensor have employed micro-processing technology and piezoelectric membrane technology of preparing, designs from principle and structure simultaneously and avoids cost height, the piezoelectric membrane patterning process of weak effect dexterously.The another advantage of this sensor there is provided primary reference unit, makes measurement result the most accurately and reliably.
Summary of the invention
It is an object of the invention to the shortcoming overcoming above-mentioned prior art, a kind of series-connection flexible vibration piezoelectric diaphragm type biosensor and preparation method thereof is provided, the preparation of this sensor uses micro-processing technology and piezoelectric membrane technology of preparing, can design from principle and structure simultaneously and avoid cost height, the piezoelectric membrane patterning process of weak effect dexterously；Further, this sensor can provide primary reference unit, makes measurement result the most accurately and reliably.
It is an object of the invention to solve by the following technical programs:
This series-connection flexible vibration piezoelectric diaphragm type biosensor, including soi wafer, wherein the Device layer surface at soi wafer is sequentially provided with hearth electrode adhesion layer, piezoelectric layer；Described piezoelectric layer is provided with two adjacent flexible vibration piezoelectricity barrier films: barrier film one and barrier film two；The upper/lower electrode of described flexible vibration piezoelectricity barrier film is respectively arranged at the upper and lower surface of piezoelectric layer；On the Handle layer surface of described soi wafer with one layer of silicon nitride film layer, wherein Handle layer and the silicon nitride film layer of soi wafer is offering silicon cup corresponding to described barrier film one and barrier film two position；Described barrier film one, as probe unit, is provided with bioprobe molecule on barrier film one on electrode；Described barrier film two is as reference cell.
Further, above-mentioned flexible vibration piezoelectricity barrier film is square.Described flexible vibration piezoelectricity barrier film is circle.The upper electrode of described flexible vibration piezoelectricity barrier film is connected by upper contact conductor upper electrode pad.Described piezoelectric layer is PZT thin film, barium strontium titanate or the bismuth-sodium titanate thin film using sol-gal process, magnetron sputtering or pulse laser deposition process to prepare.The bottom electrode of described flexible vibration piezoelectricity barrier film is to stick to platinum, aluminum or the thin nickel metal film on hearth electrode adhesion layer (13).
The present invention also proposes the preparation method of a kind of series-connection flexible vibration piezoelectric diaphragm type biosensor, comprises the following steps:
1) take SOI silicon substrate, it is stipulated that the side of its Device layer is front, be reverse side in the side of Handle layer；
2) in the front of SOI silicon substrate, use radio-frequency magnetron sputter method deposition of titanium oxide thin film as depositing the metallic film bottom electrode as flexible vibration piezoelectricity barrier film on hearth electrode adhesion layer, then hearth electrode adhesion layer；The bottom electrode of hearth electrode adhesion layer and flexible vibration piezoelectricity barrier film is all deposition gained in rf magnetron sputtering instrument；
3) in the front of SOI silicon substrate, on the bottom electrode of described flexible vibration piezoelectricity barrier film, depositing piezoelectric thin film is as piezoelectric layer, and the thickness of depositing piezoelectric thin film is 0.1 ~ 10 μm；
4) using LPCVD method at front cvd nitride silicon thin film, the thickness of silicon nitride film is 80 ~ 200nm；
5) in front, utilize photoetching and dry etch process that silicon nitride film is patterned, expose the piezoelectric layer performing flexible vibration barrier film；
6) in front, utilize photoetching and rf magnetron sputtering and combine stripping technology and prepare on Ti/Au electrode and lead-in wire thereof and pad；The Ti/Au wherein contacted with piezoelectric layer is upper electrode, is connected on the silicon nitride film on side by upper electrode, and the Ti/Au being easy to bonding wire is referred to as lead-in wire and pad；Wherein Ti layer thickness be 10 ~ 20nm, Au layer thickness be 100 ~ 500nm；
7) at reverse side, using LPCVD method cvd nitride silicon thin film, the thickness of silicon nitride film is 80 ~ 200nm；
8) at reverse side, utilize photoetching and dry etch process that silicon nitride film is patterned, expose the Handle layer silicon corrosion window corresponding with upper electrode；
9) at reverse side, utilizing anisotropic silicon wet etching or dry corrosion process to remove the silicon in Handle layer silicon corrosion window region, form silicon cup, release performs flexible vibration barrier film；Corrosive liquid is potassium hydroxide solution or tetramethyl ammonium hydroxide solution；Etch stop layer is the buried regions SiO between SOI substrate Device layer and Handle layer2；
10) in front, dry etching is utilized to remove surfaces nitrided silicon thin film；
11) two adjacent barrier films constitute a series-connection flexible vibration piezoelectric diaphragm type biosensor；
12) piezoelectric layer of biosensor diaphragm area is polarized；Then the surface of a barrier film in series connection barrier film is carried out functionalization, as probe unit；Another barrier film in series connection barrier film is as reference cell.
Further, above-mentioned steps 1) in, the Device layer thickness of described SOI silicon substrate is 0.5 ~ 10 μm, is oriented to (100) or (110) or (111)；The buried regions SiO of SOI silicon substrate2Thickness is 0.1 ~ 1 μm；The Handle layer thickness of SOI silicon substrate is 200 ~ 900 μm, is oriented to (100).
Further, above-mentioned steps 2) in, the thickness as the titanium deoxid film of hearth electrode adhesion layer is 10 ~ 20nm；The bottom electrode thickness of metal film of flexible vibration piezoelectricity barrier film is 100 ~ 500nm；Bottom electrode is distribution continuous film over the entire substrate.
Compared with prior art, the method have the advantages that
1. the upper electrode of two neighboring separators of the present invention and lead-in wire thereof and pad, in order to ac-excited signal is applied to sensor, and the frequency response of sensor is measured, and the hearth electrode being connected in series through connection of two neighboring separators realizes, and (hearth electrode is distribution continuous metal thin film over the entire substrate, effectively prevent cost height, the piezoelectric layer patterning process of weak effect the most in a manufacturing process.Need not graphically piezoelectric layer and hearth electrode, shorten manufacturing time, reduce manufacturing cost, improve processed finished products rate.
2., due to the existence of reference cell of the present invention, reduce the impact on sensor detection results of the extraneous factor such as non-specific adsorption, temperature drift, thus drastically increase the accuracy of detection of sensor.
3. because present invention employs micro fabrication, so compared to crystal microbalance (QCM) biosensor, sensor of the invention is the most highly sensitive, and it is easy to microminiaturization and mass manufacture, hundreds and thousands of sensors (particular number is depending on the size of single sensor) can be prepared on a piece of silicon chip, and provide possibility for associated drives and testing circuit being integrated on silicon chip further.
4., compared to flexible vibration beam type sensor and QCM biosensor, there are when sensor of the invention detects in the liquid phase higher quality factor.
5. compared to QCM and FBAR (FBAR) and SAW device (SAW), sensor of the invention has relatively low resonant frequency, is conducive to relevant driving and measurement circuit design.
6., compared to flexible vibration beam type sensor, sensor of the invention structural strength is higher.
Accompanying drawing explanation
Fig. 1 is a kind of series-connection flexible vibration piezoelectric diaphragm type biosensor structural representation three-view diagram；Wherein, (a) is top view, and (b) is the A-A ' sectional view of (a)；C () is the B-B ' sectional view of (b)；
Fig. 2 is another kind of series-connection flexible vibration piezoelectric diaphragm type biosensor structural representation three-view diagram；Wherein, (a) is top view, and (b) is the A-A ' sectional view of (a)；C () is the B-B ' sectional view of (b)；
In fig. 1 and 2: 1 is electrode on reference cell；2 is contact conductor on reference cell；3 is the upper electrode pad of reference cell；4 is electrode pad on probe unit；5 is contact conductor on probe unit；6 is electrode on probe unit；7 is bioprobe molecule；8 is silicon cup；9 is silicon nitride film or metallic aluminium thin film；10Handle layer；11 is buried silicon dioxide layer；12 is Device layer；13 is hearth electrode adhesion layer；14 is piezoelectric layer；15 is as contact conductor on barrier film and the silicon nitride film of pad sealing coat.
Fig. 3 flexible vibration piezoelectricity barrier film single order flexible vibration schematic diagram；
Fig. 4 is resonance peak and the Cleaning Principle figure of inventive sensor.
Detailed description of the invention
This kind of series-connection flexible vibration piezoelectric diaphragm type biosensor of the present invention, including soi wafer, wherein Device layer 12 surface at soi wafer is sequentially provided with hearth electrode adhesion layer 13, piezoelectric layer 14；Piezoelectric layer 14 is provided with two adjacent flexible vibration piezoelectricity barrier films: barrier film one and barrier film two；The upper/lower electrode of flexible vibration piezoelectricity barrier film is respectively arranged at the upper and lower surface of piezoelectric layer 14；On Handle layer 10 surface of described soi wafer with one layer of silicon nitride film layer 9, wherein Handle layer 10 and the silicon nitride film layer 9 of soi wafer is offering silicon cup 8 corresponding to described barrier film one and barrier film two position；Barrier film one, as probe unit, is provided with bioprobe molecule 7 on barrier film one on electrode 6；Barrier film two is as reference cell.The upper electrode of described flexible vibration piezoelectricity barrier film is connected by upper contact conductor upper electrode pad.Piezoelectric layer 14 is PZT thin film, barium strontium titanate or the bismuth-sodium titanate thin film using sol-gal process, magnetron sputtering or pulse laser deposition process to prepare.The bottom electrode of flexible vibration piezoelectricity barrier film is to stick to platinum, aluminum or the thin nickel metal film on hearth electrode adhesion layer 13.Contact conductor 2 on reference cell；For there being the silicon nitride film 15 as contact conductor on barrier film and pad sealing coat between upper electrode pad 3 and the piezoelectric layer 14 of reference cell.
The shape of the flexible vibration piezoelectricity barrier film of the present invention can be square or circular, as depicted in figs. 1 and 2.
On the upper electrode pad of two neighboring separators, apply ac-excited voltage, because whole bottom electrode layer is connection, so self-assembling formation series connection membrane configuration, and in two barrier films, evoke flexible vibration because of piezoelectric effect.When ac-excited electric voltage frequency is consistent with barrier film resonant frequency, the piezoelectric resonator peak that can be detected by measuring circuit will be produced in two barrier films.
Provide several specific embodiments of series-connection flexible vibration piezoelectric diaphragm type biosensor preparation method of the present invention below in conjunction with the accompanying drawings:
Embodiment 1
The present embodiment series-connection flexible vibration piezoelectric diaphragm type biosensor structural representation is as shown in Figure 1.The barrier film that in this embodiment, each sensor is comprised is the square that the length of side is 200 μm.
Concrete processing technology comprises the steps:
1) use SOI silicon substrate, and specify front with reverse side hereinafter to describe, it is front on the surface of Device side, is reverse side on the surface of Handle side.Device layer 12 thickness of SOI silicon substrate is 1 μm, is oriented to (100), buried regions SiO2Thickness is 0.1 μm, and Handle layer 10 thickness is 400 μm, is oriented to (100).
2) in front, radio-frequency magnetron sputter method deposition of titanium oxide (TiO is used2) thin film is as hearth electrode adhesion layer 13, redeposited metal platinum (Pt) thin film is as hearth electrode (i.e. the bottom electrode of flexible vibration piezoelectricity barrier film).The bottom electrode of hearth electrode adhesion layer 13 and flexible vibration piezoelectricity barrier film is all deposition gained, TiO in rf magnetron sputtering instrument2The thickness of thin film be 10nm, Pt film thickness be 100nm.
3) in front, pulse laser deposition process is used to prepare barium strontium titanate (BST) piezoelectric membrane that thickness is 1 μ m-thick as piezoelectric layer 14.
4) in front, then LPCVD method deposited silicon nitride (Si is used3N4) thin layer, the thickness of silicon nitride film is 100nm.
5) in front, utilize photoetching and dry etch process that silicon nitride film is patterned, expose perform flexible vibration barrier film piezoelectric layer 14, the piezoelectric layer 14 exposed is identical with the size and shape of barrier film, be also the length of side be the square of 200 μm.Should be noted during photoetching that crystal orientation is directed at, the limit making the square area that piezoelectric layer exposes is parallel with the breach limit that substrate instruction (100) is orientated.
6) in front, utilize photoetching and rf magnetron sputtering and combine stripping technology and prepare the upper electrode (i.e. electrode 6 on probe unit) of titanium/gold (Ti/Au) and upper contact conductor 5 and electrode pad 4 on probe unit.Titanium layer thickness is 10nm, and gold layer thickness is 100nm.On probe unit, electrode 6 is also square, and the square area centering exposed with piezoelectric layer 14, and limit is parallel to each other.On probe unit, the length of side of electrode 6 is 160 μm, and wire widths is 50 μm, and the pad length of side is 150 μm.Same mode, contact conductor 2 and the upper electrode pad 3 of reference cell on electrode 1 and reference cell is prepared on reference cell on the side of electrode 6 on the detection unit.
7) at reverse side, LPCVD method deposited silicon nitride (Si is used3N4) thin film 9, the thickness of silicon nitride film 9 is 100nm；
8) at reverse side, utilize double-sided alignment photoetching and dry etch process that silicon nitride film 9 is patterned, expose the Handle layer 10 silicon corrosion window corresponding with upper electrode.Window is square, and with upper electrode (include on probe unit on electrode 6 and reference cell electrode 1) centering, limit is parallel to each other, a length of 760 μm of edge of window.
9) at reverse side, utilizing anisotropic silicon wet corrosion technique to remove the silicon in Handle layer 10 silicon corrosion window region, form silicon cup 8, release performs flexible vibration barrier film.Corrosive liquid is 30% potassium hydroxide (KOH) solution, and corrosion temperature is 80 DEG C.Etch stop layer is the buried silicon dioxide layer (SiO between SOI substrate Device layer 12 and Handle layer 102) 11.
10) in front, dry etching is utilized to remove surfaces nitrided silicon thin film.
11) two adjacent barrier films constitute a series-connection flexible vibration piezoelectric diaphragm sensor.
12) piezoelectric layer 14 in sensor membrane region is carried out thermal poling；Then the surface of the barrier film being used as probe unit in series connection barrier film being carried out functionalization, fixing bioprobe molecule 7 is protein A, and fixing means is physisorphtion, and blocking agent is caseic TBS(TRIS buffer) buffer agent.Use this sensor can detect goat IgG.
Embodiment 2
Fig. 1 gives a kind of series-connection flexible vibration piezoelectric diaphragm type biosensor structural representation three-view diagram.The barrier film that in this example, each sensor is comprised is the square that the length of side is 200 μm, and concrete processing technology comprises the steps:
1) use SOI silicon substrate, and specify front with reverse side hereinafter to describe, it is front on the surface of Device side, is reverse side on the surface of Handle side.The Device layer thickness of SOI silicon substrate is 1 μm, is oriented to (100), buried regions SiO2Thickness is 0.1 μm, and Handle layer thickness is 400 μm, is oriented to (100).
2) in front, radio-frequency magnetron sputter method deposition of titanium oxide (TiO is used2) thin film is as adhesion layer, redeposited metal platinum (Pt) thin film is as hearth electrode.Adhesion layer and hearth electrode are all deposition gained, TiO in rf magnetron sputtering instrument2The thickness of thin film be 10nm, Pt film thickness be 100nm.
3) in front, pulse laser deposition process is used to prepare barium strontium titanate (BST) piezoelectric membrane that thickness is 1 μ m-thick.
4) LPCVD method deposited silicon nitride (Si is used3N4) thin layer, the thickness of silicon nitride film is 100nm.
5) in front, utilize photoetching and dry etch process that silicon nitride film is patterned, expose perform flexible vibration barrier film piezoelectric layer, the piezoelectric layer exposed is identical with the size and shape of barrier film, be also the length of side be the square of 200 μm.Should be noted during photoetching that crystal orientation is directed at, the limit making the square area that piezoelectric layer exposes is parallel with the breach limit that substrate instruction (100) is orientated.
6) in front, utilize photoetching and rf magnetron sputtering and combine stripping technology and prepare the upper electrode of titanium/gold (Ti/Au) and lead-in wire thereof and pad.Titanium layer thickness is 10nm, and gold layer thickness is 100nm.Upper electrode is also square, and the square area centering exposed with piezoelectric layer, and limit is parallel to each other.The length of side of upper electrode is 160 μm, and wire widths is 50 μm, and the pad length of side is 150 μm.
7) LPCVD method deposited silicon nitride (Si is used3N4) thin film, the thickness of silicon nitride film is 100nm.
8) at reverse side, utilize double-sided alignment photoetching and dry etch process that silicon nitride film is patterned, expose the Handle layer silicon corrosion window corresponding with upper electrode.Window be square, and with upper electrode centering, limit is parallel to each other, a length of 760 μm of edge of window.
9) at reverse side, utilizing anisotropic silicon wet corrosion technique to remove the silicon in Handle layer silicon corrosion window region, form silicon cup, release performs flexible vibration barrier film.Corrosive liquid is 30% potassium hydroxide (KOH) solution, and corrosion temperature is 80 DEG C.Etch stop layer is the buried regions SiO between SOI substrate Device layer and Handle layer2。
10) in front, dry etching is utilized to remove surfaces nitrided silicon thin film.
11) two adjacent barrier films constitute a series-connection flexible vibration piezoelectric diaphragm sensor.
12) piezoelectric layer in sensor membrane region is carried out thermal poling；Then the surface of the barrier film being used as probe unit in series connection barrier film being carried out functionalization, fixing bioprobe molecule is protein A, and fixing means is physisorphtion, and blocking agent is caseic TBS(TRIS buffer) buffer agent.Use this sensor can detect goat IgG.
Embodiment 3
Fig. 2 gives another kind of series-connection flexible vibration piezoelectric diaphragm type biosensor structural representation three-view diagram.The barrier film that in this example, each sensor is comprised is the circle of a diameter of 300 μm, and concrete processing technology comprises the steps:
1) use SOI silicon substrate, and specify front with reverse side hereinafter to describe, it is front on the surface of Device side, is reverse side on the surface of Handle side 10.Device layer 12 thickness of SOI silicon substrate is 2 μm, is oriented to (111), buried regions SiO2Thickness is 0.5 μm, and Handle layer thickness is 400 μm, is oriented to (111).
2) in front, radio-frequency magnetron sputter method deposition of titanium oxide (TiO is used2) thin film is as hearth electrode adhesion layer 13, redeposited platinum (Pt) thin film is as hearth electrode.Hearth electrode adhesion layer 13 and hearth electrode are all deposition gained, TiO in rf magnetron sputtering instrument2The thickness of thin film be 10nm, Pt film thickness be 100nm.
3) in front, radio-frequency magnetron sputter method deposition is used to prepare zinc oxide (ZnO) piezoelectric membrane that thickness is 2 μm as piezoelectric layer 14.
4) LPCVD method deposited silicon nitride (Si is used in front3N4) thin layer, the thickness of silicon nitride film is 100nm.
5) in front, utilize photoetching and dry etch process that silicon nitride film is patterned, expose perform flexible vibration barrier film piezoelectric layer 14, the piezoelectric layer 14 exposed is identical with the size and shape of barrier film, be also the length of side be the circle of 300 μm.
6) in front, utilize photoetching and rf magnetron sputtering and combine stripping technology and prepare the upper electrode of titanium/gold (Ti/Au) of reference cell and probe unit and lead-in wire thereof and pad.Titanium layer thickness is 10nm, and gold layer thickness is 100nm.Upper electrode is also round shape, and the border circular areas centering exposed with piezoelectric layer.A diameter of 240 μm of upper electrode, wire widths is 50 μm, and the pad length of side is 150 μm.
7) at reverse side, utilizing r. f. magnetron sputtering aluminum (Al) thin layer (i.e. metallic aluminium thin film 9), the thickness of aluminum thin film is 200nm.
8) at reverse side, utilize double-sided alignment photoetching and stripping technology that aluminum thin film is patterned, expose the Handle layer 10 silicon corrosion window corresponding with upper electrode.Window is circular, and with electrode centering in each unit, window diameter is 300 μm.
9) at reverse side, utilizing silicon dry corrosion process to remove the silicon in Handle layer 10 silicon corrosion window region, form silicon cup 8, release performs flexible vibration barrier film.Etchant gas is SF6/C4F8.Etch stop layer is the buried silicon dioxide layer 11 between SOI substrate Device layer 12 and Handle layer 10.
10) in front, dry etching is utilized to remove surfaces nitrided silicon thin film.Silicon nitride film 15 as contact conductor on barrier film and pad sealing coat retains.
11) two adjacent barrier films constitute a series-connection flexible vibration piezoelectric diaphragm type sensor.
12) piezoelectric layer in sensor membrane region is carried out thermal poling；Then the surface of the barrier film being used as probe unit in series connection barrier film being carried out functionalization, fixing bioprobe molecule 7 is protein A, and fixing means is physisorphtion, and blocking agent is caseic TBS(TRIS buffer) buffer agent.Use this sensor can detect goat IgG.
During detection, as shown in Figure 3, target biological molecules will be captured by the bioprobe molecule on the probe unit of functionalization, this capture is presented as the change of sensor surface additional mass, and then cause its resonant frequency to change, by contrast probe unit and the movement of reference cell resonance peak, target biological molecules can be detected.
Fig. 4 is resonance peak and the Cleaning Principle figure of the present invention.Wherein f1And f2It is respectively sensor and carries out detecting the single order resonance peak of front probe unit and reference cell, f '1And f '2It is respectively probe unit and the single order resonance peak of reference cell after sensor detects.The frequency shifts amount then caused by capture target molecule is Δ f=(f1-f′1)-(f2-f′2)=(22040-21170)-(24350-24180)=700Hz.
In sum, sensor of the invention designs from principle and structure, avoids cost height, the piezoelectric layer patterning process of weak effect dexterously, and meanwhile, the existence of reference cell greatly improves the accuracy of detection of sensor.It addition, compared to QCM biosensor, sensor of the present invention is the sensitiveest, when liquid phase in situ detection, quality factor are high, and are easy to microminiaturization and mass manufacture；Compared to flexible vibration beam type sensor, sensor construction of the present invention is firm, and when liquid phase in situ detection, quality factor are high.
Claims (2)
1. a series-connection flexible vibration piezoelectric diaphragm type biosensor, it is characterised in that include SOI
Silicon chip, wherein Device layer (12) surface at soi wafer be sequentially provided with hearth electrode adhesion layer (13),
Piezoelectric layer (14)；Described piezoelectric layer (14) is provided with two adjacent flexible vibration piezoelectricity every
Film: barrier film one and barrier film two；The upper/lower electrode of described flexible vibration piezoelectricity barrier film is respectively arranged at piezoelectricity
The upper and lower surface of layer (14)；On Handle layer (10) surface of described soi wafer with one layer
Silicon nitride film layer (9), wherein the Handle layer (10) of soi wafer and silicon nitride film layer (9)
Silicon cup (8) is being offered corresponding to described barrier film one and barrier film two position；Described barrier film one is as detection
Unit, is provided with bioprobe molecule (7) on barrier film one on electrode (6)；Described barrier film two is made
For reference cell；The upper electrode of described flexible vibration piezoelectricity barrier film is powered on by the connection of upper contact conductor
Pole pad, applies ac-excited voltage, with self-assembling formation series connection membrane configuration, and because of piezoelectric effect
Flexible vibration is evoked in two barrier films；Described piezoelectric layer (14) is for using sol-gal process, magnetic control
PZT thin film, barium strontium titanate or bismuth titanates prepared by sputtering or pulse laser deposition process
Sodium thin film；The bottom electrode of described flexible vibration piezoelectricity barrier film is to stick on hearth electrode adhesion layer (13)
Platinum, aluminum or thin nickel metal film；On reference cell, contact conductor (2) is powering on of reference cell
Have between pole pad (3) and piezoelectric layer (14) as contact conductor on barrier film and pad sealing coat
Silicon nitride film (15)；The shape of flexible vibration piezoelectricity barrier film is square or circular.
2. a preparation method for series-connection flexible vibration piezoelectric diaphragm type biosensor, its feature exists
In, comprise the following steps:
1) SOI silicon substrate is taken, it is stipulated that the side of its Device layer is front, at Handle layer
Side is reverse side；Device layer 12 thickness of SOI silicon substrate is 1 μm, is oriented to (100), buries
Layer SiO2Thickness is 0.1 μm, and Handle layer 10 thickness is 400 μm, is oriented to (100)；
2) in the front of SOI silicon substrate, radio-frequency magnetron sputter method deposition of titanium oxide thin film is used to make
For deposition metallic film on hearth electrode adhesion layer (13), then hearth electrode adhesion layer (13) as flexibility
The bottom electrode of vibration piezoelectricity barrier film；Thickness as the titanium deoxid film of hearth electrode adhesion layer (13)
It is 10～20nm；The bottom electrode thickness of metal film of flexible vibration piezoelectricity barrier film is 100～500nm；Under
Electrode is distribution continuous film over the entire substrate；Hearth electrode adhesion layer (13) and flexible vibration pressure
The bottom electrode of electric separator is all deposition gained in rf magnetron sputtering instrument；
3) in the front of SOI silicon substrate, deposit on the bottom electrode of described flexible vibration piezoelectricity barrier film
Piezoelectric membrane is as piezoelectric layer (14), and the thickness of depositing piezoelectric thin film is 0.1～10 μm；
4) employing LPCVD method at front cvd nitride silicon thin film, the thickness of silicon nitride film is
80～200nm；
5) in front, utilize photoetching and dry etch process that silicon nitride film is patterned, expose
Go out to perform the piezoelectric layer (14) of flexible vibration barrier film；
6) in front, utilize photoetching and rf magnetron sputtering and combine stripping technology and prepare Ti/Au and power on
Pole and lead-in wire thereof and pad；The Ti/Au wherein contacted with piezoelectric layer (14) is upper electrode, by upper
Electrode is connected on the silicon nitride film on side, and the Ti/Au being easy to bonding wire is referred to as lead-in wire and weldering
Dish；Wherein Ti layer thickness is 10～20nm, and Au layer thickness is 100～500nm；
7) at reverse side, using LPCVD method cvd nitride silicon thin film, the thickness of silicon nitride film is
80～200nm；
8) at reverse side, utilize photoetching and dry etch process that silicon nitride film is patterned, expose
Go out the Handle layer silicon corrosion window corresponding with upper electrode；
9) at reverse side, anisotropic silicon wet etching or dry corrosion process is utilized to remove Handle layer
The silicon in silicon corrosion window region, forms silicon cup (8), and release performs flexible vibration barrier film；Corrosive liquid is
Potassium hydroxide solution or tetramethyl ammonium hydroxide solution；Etch stop layer is SOI substrate Device layer
And the buried regions SiO between Handle layer2；
10) in front, dry etching is utilized to remove surfaces nitrided silicon thin film；
11) two adjacent barrier films constitute a series-connection flexible vibration piezoelectric diaphragm type biosensor；
12) piezoelectric layer of biosensor diaphragm area is polarized；Then in series connection barrier film
The surface of one barrier film carries out functionalization, as probe unit；Another barrier film in series connection barrier film is made
For reference cell.
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| CN107643228B (en) * | 2017-08-31 | 2021-04-27 | 中国船舶重工集团公司第七一九研究所 | Preparation method of chip for measuring mercury vapor and use method of sensor |
| CN108447979B (en) * | 2018-03-08 | 2019-09-20 | 清华大学 | Piezoelectric film sensor and preparation method thereof |
| CN113970585A (en) * | 2021-09-03 | 2022-01-25 | 江苏大学 | Enhanced adsorption electrochemical immunosensor and preparation method and detection method thereof |
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