CN109865541A - A kind of scanning electron microscope home position Electrochemical Detection chip and preparation method thereof - Google Patents
A kind of scanning electron microscope home position Electrochemical Detection chip and preparation method thereof Download PDFInfo
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Abstract
A kind of scanning electron microscope home position Electrochemical Detection chip and preparation method thereof, is related to Electrochemical Detection chip.Scanning electron microscope home position Electrochemical Detection chip is equipped with upper piece and bottom sheet, it is described upper piece be made of two sides with the silicon chip of silicon nitride layer, with setting on the silicon chip of silicon nitride layer, there are two symmetrical liquid injection port and a viewing windows on the two sides；The bottom sheet is made of two sides with the silicon chip of insulating layer and silicon nitride layer, and the two sides is equipped with reference electrode, working electrode and to electrode with the silicon chip of insulating layer and silicon nitride layer on one side；It is described upper piece and bottom sheet by metal bonding layer bonding.Production method: 1) production upper piece；2) bottom sheet is made；3) pass through metal bonding layer with bottom sheet for upper piece to be bonded, form integral scanning Electronic Speculum electrochemical in-situ detection chip.Sample directly can be added by liquid injection port when use, close liquid injection port, it is easy to operate.
Description
Technical field
The present invention relates to Electrochemical Detection chip, more particularly, to a kind of scanning electron microscope home position Electrochemical Detection chip and its
Production method.
Background technique
Scanning electron microscope (Scanning Electron Microscope, SEM) is between transmission electron microscope and optics
A kind of microscopic appearance Observations Means between microscope, can directly using the materiality of sample surfaces material can be carried out it is microcosmic at
Picture, the advantages of observing the fine structure on various samples uneven surface.Its sample carrier sample stage collocation in situ detection chip,
Resolution ratio can be made to reach atom level, in situ detection chip can integrate the functions such as physics, chemistry, realize patterning, functionalization,
There is high application value (Nishiyama, H.et in terms of molecular biosciences, chemical industry, medicine semiconductor electronic material
al.Atmospheric scanning electron microscope observes cells and tissues in
open medium through silicon nitride film.J.Struct.Biol.169,438–449(2010)；
Kirk,S.E.,Skepper,J.N.&Donald,A.M.Application of environmental scanning
electron microscopy to determine biological surface structure.J.Microsc.233,
205–224(2009)；Niels de Jonge,Frances M.Ross.Electron microscopy of specimens
in liquid.Nature Nanotechnology volume 6,pages 695–704(2011)).It is taken in scanning electron microscope
Visual window is built, the such as outer field actions such as thermal field, light field, electrochemical field are introduced, sample is carried out dynamic in real time in situ
Observation.Researcher can capture sample by in-situ techniques and incude to the dynamic of environment, including size, pattern, crystal structure
The important informations such as variation.Material increasingly becomes the root of investigation of materials and exploitation in the metamorphosis of atomic scale under outer field action
This.
Currently used for scanning electron microscope home position Electrochemical Detection chip major design be all upper piece and bottom sheet separate, use unit
It is packaged again after installing sample additional, it is inconvenient, and be easy because the problems such as leakproofness is poor caused by individual operations difference, leakage,
Detection quality is influenced, destroys Electronic Speculum what is more.And many electrochemical in-situ detection chips use bipolar electrode, two electrodes on the market
System can not accurately control current potential, test poor controllability.
Summary of the invention
The purpose of the present invention is to provide the integrated designs of achievable electrochemical in-situ detection chip, while solving above-mentioned
Chip in situ introduces a kind of scanning electron microscope home position Electrochemical Detection chip and its production side for the problems such as control current potential after electric field is inaccurate
Method.
The scanning electron microscope home position Electrochemical Detection chip is equipped with upper piece and bottom sheet, it is described upper piece silicon nitride had by two sides
The silicon chip of layer is made, and with setting on the silicon chip of silicon nitride layer, there are two symmetrical liquid injection port and a forms on the two sides
Mouthful；The bottom sheet is made of two sides with the silicon chip of insulating layer and silicon nitride layer, and the two sides has insulating layer and silicon nitride
The silicon chip of layer is equipped with reference electrode, working electrode and to electrode on one side；It is described upper piece and bottom sheet by metal bonding layer bonding.
The production method of the scanning electron microscope home position Electrochemical Detection chip, comprising the following steps:
1) production upper piece；
2) bottom sheet is made；
3) pass through metal bonding layer with bottom sheet for upper piece to be bonded, form integral scanning Electronic Speculum electrochemical in-situ and detect core
Piece.
In step 1), it is described upper piece have first surface and with the opposite facing second surface of first surface, upper piece production
Method is as follows:
1.1 silicon chips of the preparation two sides with silicon nitride layer, 4 cun of the size of the silicon chip, 200 μm of thickness；
1.2 utilize photoetching process, expose 10~30s in ultraviolet photolithographic machine, and liquid injection port pattern is shifted from lithography mask version
To the first surface of the silicon chip in step 1.1, then develop in developer for positive photoresist 30~60s, then is cleaned with deionized water
Surface；
1.3 utilize reactive ion etching process, the silicon nitride at silicon chip first surface upper liquid filling mouth in step 1.2
It etches away, then silicon chip first surface is put into 10~30s of acetone soak upward, is finally rinsed with deionized water；
The silicon chip second surface produced in step 1.3 is put into mass percent concentration upward as 5% hydrogen tetramethyl by 1.4
Wet etching is carried out in base ammonium hydroxide (TMAH) solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind viewing window
Insulating silicon nitride layer film takes out silicon chip and is rinsed with ionized water；
1.5 utilize photoetching process, and the silicon chip that step 1.4 is produced exposes 10~30s in ultraviolet photolithographic machine, by form
Mouthful pattern is transferred to silicon chip first surface from lithography mask version, and then develop in developer for positive photoresist 30~60s, then spend from
Sub- water rinses clean the surface；
1.6 utilize reactive ion etching process, the nitrogen on the silicon chip second surface that step 1.5 is produced at viewing window
SiClx etches away, and then silicon chip second surface is put into 10~30s of acetone soak upward, is finally rinsed with deionized water, gone
Fall photoresist；
The silicon chip second surface that step 1.6 is produced is put into mass percent concentration upward as 5% tetramethyl hydrogen by 1.7
Wet etching is carried out in amine-oxides (TMAH) solution, etching temperature is 90 DEG C, it is etched to first surface and leaves behind silicon nitride film,
Silicon chip is taken out to be rinsed with ionized water；
1.8 silicon chips for producing step 1.7 carry out laser scribings, are divided into independence upper piece.
In step 2), the bottom sheet has third surface and the 4th surface with third surface opposite pair, bottom sheet production
Method is as follows:
2.1 silicon chips of the preparation two sides with insulating layer and silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
2.2 utilize photoetching process, expose 10~30s in ultraviolet photolithographic machine, and three electrode patterns are shifted from lithography mask version
The silicon chip third surface produced to step 2.1, then develop in developer for positive photoresist 30~60s, then clear with deionized water
Wash surface；
2.3 utilize electron beam evaporation, the silicon chip third surface that step 2.2 is produced be deposited a layer thickness be 80~
The Au of 200nm, then silicon chip third surface is put into upward in acetone and impregnates 10~30s of removing, finally use acetone rinsing, removal
Photoresist leaves metal electrode；
2.4 utilize thermal evaporation, and it is 50~2000nm gold that a layer thickness, which is deposited, in the silicon chip third face that step 2.3 is produced
Belong to, silicon chip plated film third is subjected to 10~30s of photolithographic exposure up, develop 30~60s, is then placed in hydrochloric acid and impregnates
2min removes the bonding layer metals of redundance on silicon chip, is finally putting into 10~30s of acetone soak, then rushed with deionized water
It washes, removes photoresist, leave live part metal bonding layer；
2.5 silicon chips for producing step 2.4 carry out laser scribing, are divided into independent bottom sheet.
In step 3), it is described upper piece and bottom sheet by metal bonding layer bonding, the production method is as follows:
By step 1.8 and step 2.5 make upper piece and bottom sheet by metal bonding layer be bonded, be assembled integrally formula scan
Electronic Speculum electrochemical in-situ detection chip.
It is described upper piece and the silicon chip two sides of bottom sheet be covered with one layer of silicon nitride layer, the thickness of the silicon nitride layer can be 5
~200nm.The silicon nitride film can be used for the thin-film material of a viewing window, effectively improve imaging effect, reduces background and makes an uproar
Sound.
The silicon chip two sides of the bottom sheet is covered with a layer insulating, and aluminium oxide can be used in the material of the insulating layer, thick
Degree can be 20~500nm, and alumina insulating layer is covered on silicon nitride layer.The silicon nitride layer and alumina insulating layer can be used as
A kind of composite insulation layer.The silicon chip and reference electrode, working electrode of composite insulation layer isolation bottom sheet, to electrode；It is described
The silicon chip and metal bonding layer of composite insulation layer isolation bottom sheet.
Upper piece the viewing window may be provided in symmetrical two liquid injection port lines center.
The bottom sheet is equipped with reference electrode, working electrode and comparison electrode three-electrode system, the three-electrode system control electricity
Position is more accurate, and outside access power supply can be regulated and controled by professional electrochemical workstation.The electrode material of the three-electrode system can be
80~200nm Au.The working electrode area is located at chip center, working electrode area be (0.3mm × 0.3mm)~
(0.8mm×0.8mm).Described can be 0.3~0.5mm to the width of electrode and reference electrode, between electrode and reference electrode
It is divided into 0.3~0.8mm.
The thickness of the metal bonding layer can be 50~2000nm, the metal of metal bonding layer can be selected from aluminium, copper, titanium, iron,
The thickness of one of gold, platinum, palladium, indium, tin etc., bonded layer determines observing samples liquid layer thickness.
It is described upper piece with the bonding way of bottom sheet upper piece second surface can be bonded in bottom sheet by way of thermal evaporation
Third surface on, formed integral scanning Electronic Speculum electrochemical in-situ detection chip.
Technical effect of the invention is as follows:
A kind of scanning electron microscope home position Electrochemical Detection chip provided by the invention has reference electrode, to electrode and work
Electrode three-electrode system, this three-electrode system control current potential is more accurate, and outside access power supply can be by professional electrochemical workstation
Regulation.
A kind of scanning electron microscope home position Electrochemical Detection chip provided by the invention has using aluminium oxide and silicon nitride as again
Insulating layer is closed, it is highly-safe, while using silicon nitride layer as support layer, imaging effect is effectively improved, background noise is reduced.
A kind of scanning electron microscope home position Electrochemical Detection chip manufacture method provided by the invention, it is manufactured upper piece and bottom sheet it is logical
Metal bonding layer bonding is crossed, realizes integrated design and production, can sample, closing fluid injection directly be added by liquid injection port in when use
Mouthful, it is easy to operate.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of scanning electron microscope home position Electrochemical Detection chip embodiment of the present invention.
Fig. 2 is a kind of structural representation of upper piece embodiment of scanning electron microscope home position Electrochemical Detection chip of the present invention
Figure.
Fig. 3 is that a kind of decomposition texture of upper piece embodiment of scanning electron microscope home position Electrochemical Detection chip of the present invention shows
It is intended to.
Fig. 4 is a kind of structural representation of the bottom sheet embodiment of scanning electron microscope home position Electrochemical Detection chip of the present invention
Figure.
Fig. 5 is that a kind of decomposition texture of the bottom sheet embodiment of scanning electron microscope home position Electrochemical Detection chip of the present invention shows
It is intended to.
Specific embodiment
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.It should be noted that explanation of the invention
Book and claims and term " first " in above-mentioned attached drawing, " second " etc. are to be used to distinguish similar objects, without with
In the specific sequence of description or precedence.
Embodiment 1
The embodiment of the present invention 1 discloses a kind of scanning electron microscope home position Electrochemical Detection chip, as shown in Fig. 1~5, structure
Including upper piece 1 and bottom sheet 7.It is described upper piece 1 be made of upper silicon chip 3, the upper silicon chip 3 is equipped on the 1st silicon nitride layer 2 and the
1 lower silicon nitride layer 4；Set that there are two symmetrical notes on upper silicon chip 3 equipped with silicon nitride layer 2 on the 1st and the 1st lower silicon nitride layer 4
Liquid mouth 5 and a viewing window 6；The bottom sheet is made of lower silicon chip 12, and insulating layer on the 1st is equipped with above the lower silicon chip 12
Silicon nitride layer 11 on 10 and the 2nd is equipped with the 1st lower insulating layer 14 and the 2nd lower silicon nitride layer 13, the lower silicon below lower silicon chip 12
12 one side of substrate is equipped with reference electrode, working electrode and to electrode three-electrode system 9；It is described upper piece 1 and bottom sheet 7 pass through metallic bond
Layer 8 is closed to be bonded.
Meanwhile the embodiment of the present invention 1 discloses a kind of production method of scanning electron microscope home position Electrochemical Detection chip, the system
Make method the following steps are included:
Step 1: production upper piece 1；
Step 2: production bottom sheet 7；
Step 3: upper piece 1 and bottom sheet 7 be bonded by metal bonding layer 8, form the inspection of integral scanning Electronic Speculum electrochemical in-situ
Survey chip.
It is described upper piece 1 have first surface and with the opposite facing second surface of first surface, upper piece 1 production method is such as
Under:
The silicon chip of step 1.1, preparation two sides with silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
Step 1.2, using photoetching process, expose 15s in ultraviolet photolithographic machine, liquid injection port pattern shifted from lithography mask version
To the second surface of the silicon chip in step 1.1, then develop in developer for positive photoresist 45s, then with deionized water clean the surface；
Step 1.3, using reactive ion etching process, at the silicon chip first surface upper liquid filling mouth in step 1.2
Silicon nitride etch falls, and then silicon chip first surface is put into acetone soak 10s upward, is finally rinsed with deionized water；
Step 1.4, the silicon chip second surface produced in step 1.3 is put into upward mass percent concentration be 5%
Wet etching is carried out in hydrogen tetramethylammonium hydroxide (TMAH) solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind
Viewing window insulating silicon nitride layer film takes out silicon chip and is rinsed with ionized water；
Step 1.5, using photoetching process, the silicon chip that step 1.4 is produced ultraviolet photolithographic machine expose 15s, will regard
Pattern of windows is transferred to silicon chip first surface from lithography mask version, and then develop in developer for positive photoresist 45s, then uses deionization
Water rinses clean the surface；
Step 1.6, using reactive ion etching process, the viewing window on the silicon chip second surface that step 1.5 is produced
The silicon nitride etch at place falls, and then silicon chip second surface is put into acetone soak 10s upward, is finally rinsed with deionized water,
Remove photoresist；
Step 1.7, the silicon chip second surface that step 1.6 is produced is put into upward mass percent concentration be 5% 4
Wet etching is carried out in ammonium hydroxide (TMAH) solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind nitridation
Silicon thin film takes out silicon chip and is rinsed with ionized water；
Step 1.8, the silicon chip for producing step 1.7 carry out laser scribing, be divided into it is independent upper piece 1, size 8mm ×
4mm。
The bottom sheet 7 has third surface and the 4th surface with third surface opposite pair, and 7 production method of bottom sheet is such as
Under:
The silicon chip of step 2.1, preparation two sides with insulating layer and silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
Step 2.2, using photoetching process, expose 15s in ultraviolet photolithographic machine, three electrode patterns shifted from lithography mask version
The silicon chip third surface produced to step 2.1, then develop in developer for positive photoresist 45s, then cleans table with deionized water
Face；
Step 2.3, using electron beam evaporation, a layer thickness, which is deposited, in the silicon chip third surface that step 2.2 is produced is
Silicon chip third surface is put into acetone upward impregnates removing 10s later, finally use acetone rinsing, removes light by the Au of 100nm
Photoresist leaves metal electrode；
Step 2.4, using thermal evaporation, it is 50nm gold that a layer thickness, which is deposited, in the silicon chip third face that step 2.3 is produced
Belong to aluminium or copper or titanium, silicon chip plated film third is subjected to photolithographic exposure 15s up, develop 45s, is then placed in dilute hydrochloric acid and soaks
2min is steeped, the bonding layer metals of redundance on silicon chip is removed, is finally putting into acetone soak 10s, then rinsed with deionized water,
Photoresist is removed, live part metal bonding layer is left；
Step 2.5, the silicon chip for producing step 2.4 carry out laser scribing, are divided into independent bottom sheet 7, and size 10mm ×
4mm。
On described 1st insulating layer 10 and the 1st lower insulating layer 14 with a thickness of 200nm, material is aluminium oxide, on the described 1st
Insulating layer 10 and the 1st lower insulating layer 14 are arranged on the 2nd under silicon nitride layer 11 and the 2nd on silicon nitride layer 13.
Silicon nitride layer 2 on described 1st, the 1st lower silicon nitride layer 4, silicon nitride layer 11 and the 2nd lower silicon nitride layer 13 on the 2nd
With a thickness of 100nm.
The viewing window 6 is located at symmetrical two liquid injection ports, 5 line center.
The metal bonding layer 8 with a thickness of 50nm, the metal of metal bonding layer is aluminium or copper or titanium.
It is described upper piece 1 with the bonding way of bottom sheet 7 be by 8 thermal evaporation methods of metal bonding layer by upper piece 1 the second table
Face is bonded on the third surface of bottom sheet 7, forms integral scanning Electronic Speculum electrochemical in-situ detection chip.
Embodiment 2
The embodiment of the present invention 2 discloses a kind of scanning electron microscope home position Electrochemical Detection chip, as shown in Fig. 1~5, structure
Including upper piece 1 and bottom sheet 7.It is described upper piece 1 be made of upper silicon chip 3, the upper silicon chip 3 is equipped on the 1st silicon nitride layer 2 and the
1 lower silicon nitride layer 4；Set that there are two symmetrical notes on upper silicon chip 3 equipped with silicon nitride layer 2 on the 1st and the 1st lower silicon nitride layer 4
Liquid mouth 5 and a viewing window 6；The bottom sheet is made of lower silicon chip 12, and insulating layer on the 1st is equipped with above the lower silicon chip 12
Silicon nitride layer 11 on 10 and the 2nd is equipped with the 1st lower insulating layer 14 and the 2nd lower silicon nitride layer 13 below lower silicon chip 12, is equipped with the 1st
Upper insulating layer 10, the one side of the silicon chip 12 of silicon nitride layer 11, the 1st lower insulating layer 14 and the 2nd lower silicon nitride layer 13 is equipped on the 2nd
Reference electrode, working electrode and to electrode three-electrode system 9；It is described upper piece 1 and bottom sheet 7 be bonded by metal bonding layer 8.
The embodiment of the present invention 2 discloses a kind of production method of scanning electron microscope home position Electrochemical Detection chip, the system simultaneously
Make method the following steps are included:
Step 1: production upper piece 1；
Step 2: production bottom sheet 7；
Step 3: upper piece 1 and bottom sheet 7 be bonded by metal bonding layer 8, form the inspection of integral scanning Electronic Speculum electrochemical in-situ
Survey chip.
It is described upper piece 1 have first surface and with the opposite facing second surface of first surface, upper piece 1 production method is such as
Under:
The silicon chip of step 1.1, preparation two sides with insulating layer and silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
Step 1.2, using photoetching process, expose 20s in ultraviolet photolithographic machine, liquid injection port pattern shifted from lithography mask version
To the second surface of the silicon chip in step 1.1, then develop in developer for positive photoresist 52s, then with deionized water clean the surface；
Step 1.3, using reactive ion etching process, at the silicon chip first surface upper liquid filling mouth in step 1.2
Silicon nitride etch falls, and then silicon chip first surface is put into acetone soak 15s upward, is finally rinsed with deionized water；
Step 1.4, the silicon chip second surface produced in step 1.3 is put into upward mass percent concentration be 5%
Wet etching is carried out in hydrogen tetramethylammonium hydroxide (TMAH) solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind
Viewing window insulating silicon nitride layer film takes out silicon chip and is rinsed with ionized water；
Step 1.5, using photoetching process, the silicon chip that step 1.4 is produced ultraviolet photolithographic machine expose 20s, will regard
Pattern of windows is transferred to silicon chip first surface from lithography mask version, and then develop in developer for positive photoresist 52s, then uses deionization
Water rinses clean the surface；
Step 1.6, using reactive ion etching process, the viewing window on the silicon chip second surface that step 1.5 is produced
The silicon nitride etch at place falls, and then silicon chip second surface is put into acetone soak 15s upward, is finally rinsed with deionized water,
Remove photoresist；
Step 1.7, the silicon chip second surface that step 1.6 is produced is put into upward mass percent concentration be 5% 4
Wet etching is carried out in ammonium hydroxide (TMAH) solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind nitridation
Silicon thin film takes out silicon chip and is rinsed with ionized water；
Step 1.8, the silicon chip for producing step 1.7 carry out laser scribing, be divided into it is independent upper piece 1, size 8mm ×
4mm。
The bottom sheet 7 has third surface and the 4th surface with third surface opposite pair, and 7 production method of bottom sheet is such as
Under:
The silicon chip of step 2.1, preparation two sides with insulating layer and silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
Step 2.2, using photoetching process, expose 20s in ultraviolet photolithographic machine, three electrode patterns shifted from lithography mask version
The silicon chip third surface produced to step 2.1, then develop in developer for positive photoresist 52s, then cleans table with deionized water
Face；
Step 2.3, using electron beam evaporation, a layer thickness, which is deposited, in the silicon chip third surface that step 2.2 is produced is
Silicon chip third surface is put into acetone upward impregnates removing 10s later, finally use acetone rinsing, removes light by the Au of 100nm
Photoresist leaves metal electrode；
Step 2.4, using thermal evaporation, it is 500nm gold that a layer thickness, which is deposited, in the silicon chip third face that step 2.3 is produced
Belong to iron or gold or platinum, silicon chip plated film third is subjected to photolithographic exposure 20s up, develop 52s, is then placed in dilute hydrochloric acid and soaks
2min is steeped, the bonding layer metals of redundance on silicon chip is removed, is finally putting into acetone soak 18s, then rinsed with deionized water,
Photoresist is removed, live part metal bonding layer is left；
Step 2.5, the silicon chip for producing step 2.4 carry out laser scribing, are divided into independent bottom sheet 7, and size 10mm ×
4mm。
On described 1st insulating layer 10 and the 1st lower insulating layer 14 with a thickness of 250nm, material is aluminium oxide, on the described 1st
Insulating layer 10 and the 1st lower insulating layer 14 are arranged on the 2nd under silicon nitride layer 11 and the 2nd on silicon nitride layer 13.
Silicon nitride layer 2 on described 1st, the 1st lower silicon nitride layer 4, silicon nitride layer 11 and the 2nd lower silicon nitride layer 13 on the 2nd
With a thickness of 150nm.
The viewing window 6 is located at symmetrical two liquid injection ports, 5 line center.
The metal bonding layer 8 with a thickness of 500nm, the metal of metal bonding layer is iron or gold or platinum.
It is described upper piece 1 with the bonding way of bottom sheet 7 be by 8 thermal evaporation methods of metal bonding layer by upper piece 1 the second table
Face is bonded on the third surface of bottom sheet 7, forms integral scanning Electronic Speculum electrochemical in-situ detection chip.
Embodiment 3
The embodiment of the present invention 3 discloses a kind of scanning electron microscope home position Electrochemical Detection chip, as shown in Fig. 1~5, structure
Including upper piece 1 and bottom sheet 7.It is described upper piece 1 be made of upper silicon chip 3, the upper silicon chip 3 is equipped on the 1st silicon nitride layer 2 and the
1 lower silicon nitride layer 4；Set that there are two symmetrical notes on upper silicon chip 3 equipped with silicon nitride layer 2 on the 1st and the 1st lower silicon nitride layer 4
Liquid mouth 5 and a viewing window 6；The bottom sheet is made of lower silicon chip 12, and insulating layer on the 1st is equipped with above the lower silicon chip 12
Silicon nitride layer 11 on 10 and the 2nd is equipped with the 1st lower insulating layer 14 and the 2nd lower silicon nitride layer 13 below lower silicon chip 12, is equipped with the 1st
Upper insulating layer 10, the one side of the silicon chip 12 of silicon nitride layer 11, the 1st lower insulating layer 14 and the 2nd lower silicon nitride layer 13 is equipped on the 2nd
Reference electrode, working electrode and to electrode three-electrode system 9；It is described upper piece 1 and bottom sheet 7 be bonded by metal bonding layer 8.
The embodiment of the present invention 3 discloses a kind of production method of scanning electron microscope home position Electrochemical Detection chip, the system simultaneously
It is as follows to make method:
Step 1: production upper piece 1；
Step 2: production bottom sheet 7；
Step 3: upper piece 1 and bottom sheet 7 be bonded by metal bonding layer 8, form the inspection of integral scanning Electronic Speculum electrochemical in-situ
Survey chip.
It is described upper piece 1 have first surface and with the opposite facing second surface of first surface, upper piece 1 production method is such as
Under:
The silicon chip of step 1.1, preparation two sides with insulating layer and silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
Step 1.2, using photoetching process, expose 25s in ultraviolet photolithographic machine, liquid injection port pattern shifted from lithography mask version
To the second surface of the silicon chip in step 1.1, then develop in developer for positive photoresist 52s, then with deionized water clean the surface；
Step 1.3, using reactive ion etching process, at the silicon chip first surface upper liquid filling mouth in step 1.2
Silicon nitride etch falls, and then silicon chip first surface is put into acetone soak 25s upward, is finally rinsed with deionized water；
Step 1.4, the silicon chip second surface produced in step 1.3 is put into upward mass percent concentration be 5%
Wet etching is carried out in hydrogen tetramethylammonium hydroxide (TMAH) solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind
Viewing window insulating silicon nitride layer film takes out silicon chip and is rinsed with ionized water；
Step 1.5, using photoetching process, the silicon chip that step 1.4 is produced ultraviolet photolithographic machine expose 25s, will regard
Pattern of windows is transferred to silicon chip first surface from lithography mask version, and then develop in developer for positive photoresist 52s, then uses deionization
Water rinses clean the surface；
Step 1.6, using reactive ion etching process, the viewing window on the silicon chip second surface that step 1.5 is produced
The silicon nitride etch at place falls, and then silicon chip second surface is put into acetone soak 25s upward, is finally rinsed with deionized water,
Remove photoresist；
Step 1.7, the silicon chip second surface that step 1.6 is produced is put into upward mass percent concentration be 5% 4
Wet etching is carried out in ammonium hydroxide (TMAH) solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind nitridation
Silicon thin film takes out silicon chip and is rinsed with ionized water；
Step 1.8, the silicon chip for producing step 1.7 carry out laser scribing, be divided into it is independent upper piece 1, size 8mm ×
4mm。
The bottom sheet 7 has third surface and the 4th surface with third surface opposite pair, and 7 production method of bottom sheet is such as
Under:
The silicon chip of step 2.1, preparation two sides with insulating layer and silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
Step 2.2, using photoetching process, expose 25s in ultraviolet photolithographic machine, three electrode patterns shifted from lithography mask version
The silicon chip third surface produced to step 2.1, then develop in developer for positive photoresist 52s, then cleans table with deionized water
Face；
Step 2.3, using electron beam evaporation, a layer thickness, which is deposited, in the silicon chip third surface that step 2.2 is produced is
Silicon chip third surface is put into acetone upward impregnates removing 10s later, finally use acetone rinsing, removes light by the Au of 100nm
Photoresist leaves metal electrode；
Step 2.4, using thermal evaporation, it is 2000nm that a layer thickness, which is deposited, in the silicon chip third face that step 2.3 is produced
Silicon chip plated film third is carried out photolithographic exposure 25s by Metal Palladium or indium up, and develop 52s, is then placed in dilute hydrochloric acid and is impregnated
2min removes the bonding layer metals of redundance on silicon chip, is finally putting into acetone soak 30s, then rinsed with deionized water, goes
Except photoresist, live part metal bonding layer is left；
Step 2.5, the silicon chip for producing step 2.4 carry out laser scribing, are divided into independent bottom sheet 7, and size 10mm ×
4mm。
On described 1st insulating layer 10 and the 1st lower insulating layer 14 with a thickness of 500nm, insulating layer 10 and the 1st on the described 1st
Lower insulating layer 14 is arranged on the 2nd under silicon nitride layer 11 and the 2nd on silicon nitride layer 13.
Silicon nitride layer 2 on described 1st, the 1st lower silicon nitride layer 4, silicon nitride layer 11 and the 2nd lower silicon nitride layer 13 on the 2nd
With a thickness of 200nm.
The viewing window 6 is located at symmetrical two liquid injection ports, 5 line center.
The metal bonding layer 8 with a thickness of 2000nm, the metal of metal bonding layer is palladium or indium.
It is described upper piece 1 with the bonding way of bottom sheet 7 be by 8 thermal evaporation methods of metal bonding layer by upper piece 1 the second table
Face is bonded on the third surface of bottom sheet 7, forms integral scanning Electronic Speculum electrochemical in-situ detection chip.
Claims (10)
1. a kind of scanning electron microscope home position Electrochemical Detection chip, it is characterised in that be equipped with upper piece and bottom sheet, it is described upper piece by two sides
Silicon chip with silicon nitride layer is made, the two sides with setting on the silicon chip of silicon nitride layer there are two symmetrical liquid injection port and
One viewing window；The bottom sheet is made of two sides with the silicon chip of insulating layer and silicon nitride layer, and the two sides has insulating layer
It is equipped with reference electrode, working electrode on one side with the silicon chip of silicon nitride layer and to electrode；It is described upper piece and bottom sheet pass through metallic bond
Close layer bonding.
2. the production method of scanning electron microscope home position Electrochemical Detection chip as described in claim 1, it is characterised in that including following
Step:
1) production upper piece；
2) bottom sheet is made；
3) pass through metal bonding layer with bottom sheet for upper piece to be bonded, form integral scanning Electronic Speculum electrochemical in-situ detection chip.
3. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that in step 1)
In, it is described upper piece have first surface and with the opposite facing second surface of first surface, upper piece the production method is as follows:
1.1 silicon chips of the preparation two sides with silicon nitride layer, 4 cun of the size of the silicon chip, 200 μm of thickness；
1.2 utilize photoetching process, expose 10~30s in ultraviolet photolithographic machine, liquid injection port pattern is transferred to step from lithography mask version
The first surface of silicon chip in rapid 1.1, then develop in developer for positive photoresist 30~60s, then with deionized water clean the surface；
1.3 utilize reactive ion etching process, and the silicon nitride at the silicon chip first surface upper liquid filling mouth in step 1.2 is carved
Then silicon chip first surface is put into 10~30s of acetone soak upward, is finally rinsed with deionized water by eating away；
The silicon chip second surface produced in step 1.3 is put into mass percent concentration upward as 5% hydrogen tetramethyl by 1.4
Carry out wet etching in Ammonia, etching temperature is 90 DEG C, and being etched to first surface, to leave behind viewing window silicon nitride exhausted
Edge layer film takes out silicon chip and is rinsed with ionized water；
1.5 utilize photoetching process, and the silicon chip that step 1.4 is produced exposes 10~30s in ultraviolet photolithographic machine, by viewing window
Pattern is transferred to silicon chip first surface from lithography mask version, and then develop in developer for positive photoresist 30~60s, then uses deionization
Water rinses clean the surface；
1.6 utilize reactive ion etching process, the nitridation on the silicon chip second surface that step 1.5 is produced at viewing window
Silicon etching falls, and then silicon chip second surface is put into 10~30s of acetone soak upward, is finally rinsed with deionized water, removed
Photoresist；
The silicon chip second surface that step 1.6 is produced is put into mass percent concentration upward as 5% tetramethyl hydrogen-oxygen by 1.7
Change and carry out wet etching in ammonium salt solution, etching temperature is 90 DEG C, is etched to first surface and leaves behind silicon nitride film, takes out silicon substrate
Piece is rinsed with ionized water；
1.8 silicon chips for producing step 1.7 carry out laser scribings, are divided into independence upper piece.
4. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that in step 2)
In, the bottom sheet have third surface and the 4th surface with third surface opposite pair, bottom sheet the production method is as follows:
2.1 silicon chips of the preparation two sides with insulating layer and silicon nitride layer, 4 cun of silicon chip size, 200 μm of thickness；
2.2 utilize photoetching process, expose 10~30s in ultraviolet photolithographic machine, three electrode patterns are transferred to step from lithography mask version
The rapid 2.1 silicon chip third surfaces produced, then develop in developer for positive photoresist 30~60s, then cleans table with deionized water
Face；
2.3 utilize electron beam evaporation, and it is 80~200nm that a layer thickness, which is deposited, in the silicon chip third surface that step 2.2 is produced
Au, then by silicon chip third surface be put into upward in acetone impregnate removing 10~30s, finally use acetone rinsing, remove photoetching
Glue leaves metal electrode；
2.4 utilize thermal evaporation, and it is 50~2000nm metal that a layer thickness, which is deposited, in the silicon chip third face that step 2.3 is produced,
Silicon chip plated film third is subjected to 10~30s of photolithographic exposure up, develop 30~60s, and it is then placed in hydrochloric acid and impregnates 2min,
The bonding layer metals for removing redundance on silicon chip, are finally putting into 10~30s of acetone soak, then rinsed with deionized water, go
Except photoresist, live part metal bonding layer is left；
2.5 silicon chips for producing step 2.4 carry out laser scribing, are divided into independent bottom sheet.
5. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that in step 3)
In, it is described upper piece and bottom sheet by metal bonding layer bonding, the production method is as follows:
By step 1.8 and step 2.5 make upper piece and bottom sheet by metal bonding layer bonding, be assembled integrally formula scanning electron microscope
Electrochemical in-situ detection chip.
6. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that it is described upper piece
Be covered with one layer of silicon nitride layer with the silicon chip two sides of bottom sheet, the silicon nitride layer with a thickness of 5~200nm；The silicon nitride
Thin-film material of the film for upper piece viewing window.
7. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that the bottom sheet
Silicon chip two sides be covered with a layer insulating, the material of the insulating layer uses aluminium oxide, with a thickness of 20~500nm, oxidation
Aluminum insulation layer is covered on silicon nitride layer；The silicon nitride layer and alumina insulating layer are as a kind of composite insulation layer；It is described multiple
Close insulator separation bottom sheet silicon chip and reference electrode, working electrode, to electrode；The silicon of the composite insulation layer isolation bottom sheet
Substrate and metal bonding layer.
8. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that it is described upper piece
Viewing window be located at symmetrical two liquid injection port lines center.
9. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that the bottom sheet
Equipped with reference electrode, working electrode and comparison electrode three-electrode system, outside access power supply is regulated and controled by professional electrochemical workstation；
The electrode material of the three-electrode system is 80~200nm Au, and the working electrode area is located at chip center, working electrode
Area is (0.3mm × 0.3mm)~(0.8mm × 0.8mm)；The width to electrode and reference electrode is 0.3~
0.5mm, to being divided into 0.3~0.8mm between electrode and reference electrode.
10. the production method of scanning electron microscope home position Electrochemical Detection chip as claimed in claim 2, it is characterised in that the metal
Bonded layer with a thickness of 50~2000nm, the metal of metal bonding layer in aluminium, copper, titanium, iron, gold, platinum, palladium, indium, tin one
Kind, the thickness of bonded layer determines observing samples liquid layer thickness；
It is described upper piece upper piece second surface is bonded in by way of thermal evaporation the third of bottom sheet with the bonding way of bottom sheet
On surface, integral scanning Electronic Speculum electrochemical in-situ detection chip is formed.
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