CN105047520B - A kind of micro-fluidic electron spray chip device and preparation method - Google Patents
A kind of micro-fluidic electron spray chip device and preparation method Download PDFInfo
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- CN105047520B CN105047520B CN201510299992.7A CN201510299992A CN105047520B CN 105047520 B CN105047520 B CN 105047520B CN 201510299992 A CN201510299992 A CN 201510299992A CN 105047520 B CN105047520 B CN 105047520B
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- 238000007592 spray painting technique Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
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Abstract
The present invention relates to electron spray device, specially a kind of micro-fluidic electron spray chip device and preparation method, it provides the more uniform secondary air for being close to electron spray nozzle needle, ensure the electron spray uniformity of nozzle needle device with unique electrode structure, overcome non-uniformity problem, preparation method conveniently realizes the making of electron spray chip device, and micro-fluidic electron spray chip device includes liquid chip）With gas chip, liquid chip includes passage, the electron spray nozzle needle of conduction liquid, groove of the gas chip comprising conduction gas and second electrode structure, and liquid chip and gas chip bonding form micro-fluidic electron spray chip device, and preparation method comprises the following steps：The processing of gas chip and the processing of liquid chip, the fluted of gas chip carry out bonding together to form micro-fluidic electron spray chip when having electron spray nozzle needle with liquid chip；Accurately it is aligned with the alignment mark on silicon chip during bonding, the electron spray nozzle needle on liquid chip is inserted in the perforation in gas chip.
Description
Technical field
The present invention relates to electron spray device, especially as the electron spray device of mass spectrometer ion gun；The present invention
Device be related to microfluidic chip technology or microfluidic chip technology；The manufacturing technology of the device of the present invention is related to micro Process skill
Art, microelectronics micromachining technology, specially a kind of micro-fluidic electron spray chip device and preparation method.
Background technology
Electron spray is typically liquid under the effect of highfield power, forms taylor cone in the nozzle needle mouthful of tubulose, cone is ejected
Small charged drop.Electrospray techniques are widely used in mass spectral analysis as a kind of main ion gun, are liquid chromatogram matter
The important component of analytical technology is used in conjunction in spectrum, in the analysis and research of large biological molecule, serves the effect of key.EFI
Mist is divided into milliliter level as connection liquid chromatogram and mass spectrographic ion gun according to the size of flow velocity（Flow velocity is in ml/min amount
Level）, micro updating（Flow velocity is in a mul/min magnitude）And nanoliter level（Flow velocity is in nanoliter/minute magnitude）Three kinds.Milliliter level electron spray
The analysis system that big chromatogram column liquid chromatographic for mm dia is used in conjunction with mass spectrum, such as 4.6 traditional mm dia chromatographic columns.
Micro updating electron spray is generally used for diameter less than 1 millimeter and the chromatogram column system more than 100 microns.Nanoliter level electron spray is used for straight
Footpath is less than 100 microns of chromatogram column system.Nanoliter level electron spray is minimum due to flow velocity, the nozzle needle of very little can be used, in electric field force
Effect is lower directly to be sprayed, and efficiently molecules detected is gasified and ionized.Microlitre and milliliter level electron spray due to flow velocity it is larger,
Larger nozzle needle is needed, the liquid-drop diameter of ejection gasifies also than larger and Ionization Efficiency is low, so needing secondary air.It is logical
Method is to add uniform coaxial jet-stream wind, Henion et al. around nozzle needle（U.S. Patent number 4861988）,
Electron spray pin one coaxial sleeve pipe of outer surface cover, nozzle needle is slightly protruding from outside sleeve pipe, the gap that air-flow passes through nozzle needle and sleeve pipe
Eject to form secondary air, to improve electron spray gasification and Ionization Efficiency, while being also greatly enhanced the weight of electron spray
Renaturation and stability.This electrospray techniques with secondary air have obtained the inspection and widest application in market, are always
Connect liquid chromatogram and mass spectrographic standard technique.
In the technology that Henion et al. is invented, a potential is added on liquid, and another potential is added in from electron spray
On the electrode of one distance of pin, the difference of the two potentials produces an electric field at nozzle needle mouth, and liquid flows out from needle tubing, in electricity
Electron spray is formed under field force effect；The gap of gas from nozzle needle and sleeve pipe is ejected, the drop gasification for helping electron spray to produce
Ionized with testing molecule in drop.One important directions of technology development in recent years are to be made of micro-processing technology on chip
Electron spray device.One reason for this is that the miniaturization of liquid chromatogram and integrated, that is, liquid chromatographic system is accomplished one
Inside individual chip, this needs matched chip electric spray ion source.Another reason is that chip electric spray ion source can
Multiple nozzle needles are fabricated on chip on the region of a very little, wafer ion source is there is high Ionization Efficiency and sensitive
Degree, while can also be used to the chromatogram and mass spectrometry system of bigger flow velocity.
Published electron spray wafer ion source uses micro-processing technology and made.Moon et al. microelectronics micromechanics skills
Art（MENS）Make electron spray chip（United States Patent (USP) US6800202 B2）.They pass through plasma with the silicon chip of a monolithic
Lithographic technique etches perforation on silicon chip and electron spray nozzle needle is formed on silicon chip.Staats micro injection molding fabrication techniques bases
In the electron spray chip of plastic material（United States Patent (USP) US6800849 B2）, perforation and EFI with Laser Micro-Machining formation chip
Atomizing nozzle.These electron spray chips can not all add secondary air at nozzle needle, and they are all nanoliter level electron spray device.But
It is that in the market overwhelming majority demand is the micro updating and milliliter level electron spray of big flow velocity, chip electron spray needs to bigger stream
Fast and more stable performance direction is developed.Rossier et al.（United States Patent (USP) US7265348 B2）EFI atomizing nozzle is made in core
On the edge of piece, and the raceway groove of an air guide is done in the chips secondary air is incorporated at nozzle.Li et al.（United States Patent (USP) Shen
Please Pub. No.: US2007/0257190 A1 ）Also EFI atomizing nozzle is made on the edge of chip, and done in the chips
The raceway groove of two air guides is symmetrically introduced jet-stream wind the right and left at nozzle.The side of their this introducing secondary airs
Method is different from the method being verified that in the market is general.The method that in the market is used is that secondary air is close to EFI spray painting
Pin and equably coaxially eject around nozzle needle（Henion et al. U.S. Patent number 4861988）, in practice it has proved that, this
The secondary air of sample help electron spray gasification while, make again electron spray more repeat and stably.Existing electron spray chip
Air-flow in device is not equably around electron spray nozzle needle, it is easy to cause unstable electron spray.Brekenfeld et al.
（U.S. Patent application Pub. No.: US2014/0284406 A1）Chip electron spray nozzle needle perpendicular to chip, liquid from
The one side of chip is flowed into, and the nozzle needle mouthful of the another side under electric field force effect from chip sprays；On the chip at nozzle needle
There are several perforation, gas ejects to form secondary air from hole.This can not equally form uniform ring around electron spray nozzle needle
Air-flow.Such structure also causes air-flow to be close to electron spray nozzle needle, and air-flow subtracts to the shearing booster action of electron spray
It is small.
The content of the invention
The defect existed for existing electron spray chip device, the invention provides a kind of micro-fluidic electron spray chip device
Part and preparation method, it provides the more uniform secondary air for being close to electron spray nozzle needle, is ensured to spray with unique electrode structure
The electron spray uniformity of pin device, overcomes non-uniformity problem, and preparation method conveniently realizes the system of electron spray chip device
Make.
The present invention is the micro-fluidic chip made of micro-processing technology or is called micro-fluid chip, realizes electron spray work(
Energy.Chip includes the micro-fluidic chip for providing gas flow path（Hereinafter referred to as gas chip）With the micro-fluidic core for providing liquid flow path
Piece（Hereinafter referred to as liquid chip）, two parts chip bonding form micro-fluidic electron spray chip
Technical scheme is such：A kind of micro-fluidic electron spray chip device, it include the liquid chip that is mutually bonded and
Gas chip, the liquid chip is with being provided with electron spray nozzle needle, opening on another side in the one side of the gas chip bonding
There is the inlet opening being in fluid communication with the electron spray nozzle needle, the gas chip surface covers dielectric film, the gas core
Outlet perforation and groove are provided with piece, the electron spray nozzle needle is placed in outlet perforation, the electron spray nozzle needle with it is described
Gap is left between the inwall of outlet perforation, groove one end connection outlet perforation, other end connection are arranged at described
Air admission hole on liquid chip or gas chip or two chip interfaces, the air admission hole is to be located at the liquid chip and the gas
A perforation on the hole that edge after body chip bonding is formed by bonding at interface, or the liquid chip, or
It is to be provided with first electrode structure, the gas chip to set on a perforation on the gas chip, the liquid chip
Second electrode structure is equipped with, the electrode position of second electrode structure is remote with air-prevention enough from the liquid in the liquid chip
Electrical breakdown a, potential is added on gas chip by second electrode structure.
It is preferred that, what the liquid chip included being generally parallel to each other enters liquid level and to go out liquid level, the almost parallel fingering
Liquid level and go out the angle of liquid level at 0 degree to 30 degree, the inlet opening be arranged at described in enter liquid level, the electron spray nozzle needle is arranged at
It is described go out liquid level, the spout of the electron spray nozzle needle is liquid outlet, the electron spray nozzle needle for be approximately perpendicular to it is described go out liquid level
Tubulose nozzle needle, it is described it is substantially vertical refer to the electron spray nozzle needle with it is described go out liquid level into 90 degree of ± 10 degree of angles, the tubulose
Electron spray nozzle needle is formed by being etched around a region of liquid outlet edge perpendicular to the direction of the liquid chip.It is above-mentioned substantially to put down
In going and being substantially vertical, it is parallel to each other and is mutually perpendicular to as preferred plan.
It is preferred that, the gas chip includes air inlet face and the outlet face being generally parallel to each other, the almost parallel fingering
The angle in gas face and outlet face is at 0 degree to 30 degree, and air inlet face and the liquid chip of the gas chip are mutually bonded, described
Outlet perforated vertical is in the air inlet face and outlet face, and the substantially vertical outlet perforation and the air inlet face of referring to is into 90 degree
The groove is etched with ± 10 degree of angles, the air inlet face.It is above-mentioned it is substantially parallel and substantially vertical in, be parallel to each other and mutually
It is vertically preferred plan.
It is preferred that, the electron spray nozzle needle external diameter of tubulose is less than the internal diameter that the outlet is perforated, the electron spray nozzle needle
Perforate coaxially arranged with the outlet, the electron spray nozzle needle is perforated through the outlet and the spout of electron spray nozzle needle is exposed
In outlet perforation.
It is preferred that, the liquid chip makes the electron spray nozzle needle on the liquid chip with the gas chip bonding
Be inserted in the perforation of the outlet of the gas chip and make groove formation connection outlet perforation on the gas chip with
The gas passage of the air admission hole.
It is furthermore preferred that the air admission hole is located at the liquid chip and the edge after the gas chip bonding, Huo Zhewei
A perforation on the liquid chip, or be a perforation on the gas chip, gas is under pressure from institute
State air admission hole inflow, by the gas passage from the electron spray nozzle needle and the outlet perforate inwall between clearance flow
Go out, form the secondary air of electron spray.
It is preferred that, the first electrode structure on described liquid chip gives the liquid for entering the liquid chip plus an electricity
Gesture, the first electrode structure be the liquid chip being made up of conductive chip material in itself, or be placed in by insulating core sheet material
Expect to be located at the conductive film at the inlet opening on the surface of liquid chip being made, or to be placed in surface covering dielectric medium thin
It is located at the conductive film at the inlet opening on the surface of the liquid chip of film, or is placed in liquid into the feed liquor
The electric conductor contacted in stream before hole with liquid.
It is preferred that, the gas chip material is the conductor or semiconductor of electricity, and the gas chip surface is covered with electric exhausted
The dielectric film of edge, the second electrode structure setting on the gas chip for remove the dielectric film and with the gas
Body chip conductive is contacted.
It is preferred that, in the electron spray nozzle needle side of the micro-fluidic electron spray chip, the spray apart from the electron spray nozzle needle
Three-electrode structure is provided with a certain distance from head；Three-electrode structure can be the sampling air inlet of mass spectrometer.
Liquid chip and gas chip bonding described above, refers to be combined together two chips with any method,
Can be closed, combined with welding manner with the atom bond between chip surface, with adhesive bond etc.；Specific method can be
But it is not limited to anode linkage, gold-silicon eutectic bonding, silicon/glass electrostatic bonding, silicon/Si direct bonding, glass solder sintering key
Close and Adhesive bonding.
The electron spray nozzle needle is perforated through the outlet and has one section to stretch out outlet perforation, can be real with the following method
It is existing：It is less than the height of the electron spray nozzle needle on liquid chip using the thickness of gas chip, electron spray nozzle needle passes through gas after bonding
Body chip, the shower nozzle of electron spray nozzle needle exposes going out on liquid level in gas chip；Or it is more than electricity using the thickness of gas chip
Spray nozzle needle height, but outlet perforation region has been etched into a depth on the outlet face of gas chip, makes bonding
Electron spray nozzle needle has one section to stretch out outlet perforation afterwards.
The internal diameter size of electron spray nozzle needle on liquid chip can be at 5 microns to 10 micrometer ranges, can be at 10 microns
, can be at 30 microns to 100 micrometer ranges to 30 micrometer ranges.The external diameter size of electron spray nozzle needle on liquid chip can be
10 microns to 20 micrometer ranges, can be at 20 microns to 50 micrometer ranges, can be at 50 microns to 150 micrometer ranges.
Electron spray nozzle needle on liquid chip is inserted in the corresponding outlet perforation in gas chip, and electron spray nozzle needle is with going out
Gas perforation is substantially coaxial or coaxial；Spatial joint clearance between electron spray nozzle needle and the inwall of outlet perforation can be at 10 microns
, can be at 30 microns to 60 micrometer ranges to 30 micrometer ranges, can be at 60 microns to 100 micrometer ranges.
After structure using the present invention, the liquid that gas chip is coupled with a potential, liquid chip is coupled with another
Individual potential, the difference of the two potentials is the operating voltage of electron spray chip device；This voltage is in electron spray chip device
The nozzle of electron spray nozzle needle produces an electric field, and electric field force acts on the liquid of nozzle, pulls out drop, forms electron spray,
Gas flows into the electron spray chip from the air admission hole under pressure, the inwall perforated from electron spray nozzle needle and outlet it
Between gap spray, formed and be close to the secondary air around electron spray of nozzle needle, overcome non-uniformity problem in the prior art；
The spout of electron spray nozzle needle exposes to outlet perforation, and electron spray nozzle needle perforates coaxially arranged with outlet, so as to produce uniform auxiliary
Air-flow is helped to improve the repeated stability and reliability of electron spray.
A kind of preparation method of micro-fluidic electron spray chip device, it comprises the following steps,
（1）The processing of gas chip and the processing of liquid chip：
The microelectronics micro-machining of gas chip includes：In the one side of silicon wafer of the surface with silicon dioxide layer
With photoetching technique formation figure, etching silicon dioxide；Again with photoetching technique formation figure, deep reaction ion etching is used（DRIE）Skill
One depth of art etching silicon wafer, etches a depth formation groove again after removing photoresist；Plasma enhanced chemical gas is used on this face
Phase sedimentation（PECVD）Applying silica film；Again on the other surface with photoetching technique formation figure, etching silicon dioxide；So
Silicon chip formation perforation is cut through with deep reaction ion etching technology with photoetching technique formation figure again afterwards；Again with deep reaction after removing photoresist
Ion etching silicon chip, in one depth of a region etch where perforation；Finally use thermal oxidation process and low pressure chemical phase
Deposition（LPCVD）Dielectric film of the method in chip surface formation insulation；
The microelectronics micro-machining of liquid chip includes：In the one side of silicon wafer of the surface with silicon dioxide layer
With photoetching technique formation figure, etching silicon dioxide；One depth of deep reaction ion etching technology etching silicon wafer is used after photoresist；
Again in another face photoetching technique formation figure, etching silicon dioxide；Again with photoetching technique formation figure, deep reactive ion is used
Lithographic technique etching silicon wafer is until perforation；Go to use one depth of deep reaction ion etching technology etching silicon wafer after photoresist again, make
Tubulose electron spray nozzle needle is formed at the fluid hole for going out liquid level；The dielectric finally insulated with thermal oxidation process in chip surface formation
Matter film；
（2）The fluted of gas chip carries out bonding together to form micro-fluidic electricity when having electron spray nozzle needle with liquid chip
Spraying chip；Accurately it is aligned with the alignment mark on silicon chip during bonding, the electron spray nozzle needle on liquid chip is inserted in gas core
Perforation in piece.
After method using the present invention, the making of electron spray chip device can be conveniently realized.
Brief description of the drawings
Fig. 1 show several structure examples of the present invention；
Fig. 2 show other several concrete structure citings of the present invention；
Fig. 3 show the process flow diagram that gas chip is made of microelectronics micro-machining；
Fig. 4 show the process flow diagram that liquid chip is made of microelectronics micro-machining；
Fig. 5 is liquid chip and gas chip bonding schematic diagram；
Fig. 6 is plus the micro-fluidic electron spray chip device schematic diagram after electrode；
Fig. 7 is the schematic three dimensional views of liquid chip；
Fig. 8 is the schematic three dimensional views of gas chip；
Fig. 9 is schematic enlarged-scale view at the schematic three dimensional views and electron spray nozzle needle of electron spray chip device after bonding.
Embodiment
A kind of structure such as Fig. 1 of specific embodiment of the present invention（a）Shown, liquid chip 102 has generally parallel two
Individual face, one is that, into liquid level, one is liquid level；Entering the up to rare inlet opening 104 of liquid level allows liquid to flow into；Going out liquid level has
At least one fluid hole 105 allows liquid to flow out；It is in fluid communication between inlet opening 104 and fluid hole 105.Going out on liquid level, surrounding
One region of fluid hole 105, a depth is etched perpendicular to liquid chip 102, makes the electricity that tubulose is formed at fluid hole 105
Spraying nozzle needle 103；Gas chip 101 has two generally parallel faces, and one is air inlet face, and one is outlet face；In air inlet
There is at least one outlet perforation 108 between face and outlet face；There are the groove 107 of etching, outlet perforation 108 and groove in air inlet face
107 are in fluid communication；Liquid chip 102 and gas chip 101 are bonded, and make the coaxial sleeve of electron spray nozzle needle 103 on liquid chip 102
Enter in the outlet perforation 108 of gas chip 101 and be exposed to outlet perforation 108, and form the groove on gas chip 101
Gas passage 107 and at least one air inlet 106 is connected, air inlet 106 flows with the outlet perforation 108 in gas chip 101
Body phase is led to；Air inlet 106 is connected by a perforation in liquid chip 102 with outer gas circuit.Liquid chip and gas chip list
Face can have an electrode and dielectric film structure, but succinct for display, and (electrode and dielectric film are not drawn in figure
Structure can refer to the embodiment shown in subsequent figures 6).
Structure such as Fig. 1 of another specific embodiment of the present invention（b）It is shown, in addition to air inlet 106, structure and Fig. 1
（a）Illustrated embodiment is identical.The air inlet 106 of the embodiment is in side.
Structure such as Fig. 1 of another specific embodiment of the present invention（c）It is shown, in addition to air inlet 106, structure and Fig. 1
（a）Illustrated embodiment is identical.The air inlet 106 of the embodiment is a perforation on gas chip 101.
Structure such as Fig. 2 of another specific embodiment of the present invention（a）Shown, liquid chip 109 has generally parallel
Two faces, one is that, into liquid level, one is liquid level；Entering the up to rare inlet opening 110 of liquid level allows liquid to flow into；Go out liquid level
There is at least one fluid hole 111 to allow liquid to flow out；It is in fluid communication between inlet opening 110 and fluid hole 111；Surrounded going out on liquid level
One region of fluid hole 111, etches a depth along the direction perpendicular to liquid chip 109, makes to be formed at fluid hole 111
The electron spray nozzle needle 112 of tubulose；Gas chip 117 has two generally parallel faces, and one is air inlet face, and one is outlet
Face；There is at least one outlet perforation 113 between air inlet face and outlet face；One on outlet face where outlet perforation 113
Region, gas chip 117 is etched a depth 114；There is the outlet in the groove 115 of etching, gas chip 117 in air inlet face
Perforation 113 and groove 115 are in fluid communication；Liquid chip 109 and gas chip 117 are bonded, and make the electron spray on liquid chip 109
Nozzle needle 112 is inserted in the outlet of gas chip 117 perforation 113 and the shower nozzle of electron spray nozzle needle 112 exposes to the quilt of gas chip 117
The lower surface of a depth 114 is etched, and makes the formation gas passage of groove 115 and the connection at least one on gas chip 117
Individual air inlet 116, air inlet 116 is communicated with outlet 113 streams of perforation in gas chip 117；Air inlet 116 passes through liquid core
The perforation of piece 109 is connected with outer gas circuit.Liquid chip and gas chip surface can have electrode and dielectric film structure, but be
Display it is succinct, do not drawn in figure (electrode and dielectric film structure can refer to the embodiment shown in subsequent figures 6).
Structure such as Fig. 2 of another specific embodiment of the present invention（b）It is shown, in addition to air inlet 116, structure and Fig. 2
（a）Illustrated embodiment is identical.The air inlet 116 of the embodiment is in side.
Structure such as Fig. 2 of another specific embodiment of the present invention（c）It is shown, in addition to air inlet 116, structure and Fig. 2
（a）Illustrated embodiment is identical.The air inlet 116 of the embodiment is a perforation on gas chip 117.
A kind of preparation method of the micro-fluidic electron spray chip device of the present invention is to use microelectronics micromachining technology, its
The technological process of specific embodiment is as shown in Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
Electron spray nozzle needle side is corresponded in the present invention, can be set at a certain distance from the shower nozzle of the electron spray nozzle needle
Three-electrode structure is equipped with, so that all the space electric field of three potential formation can drive the charged particle court that electron spray is produced
Moved at three-electrode structure.
The microelectronics miromaching flow of gas chip is as shown in Fig. 3, and chip material is silicon chip 212, silicon chip table
There is silicon dioxide layer 211 in face.Specific procedure of processing and processing sequence embody in figure 3 successively（1）Arrive（9）Figure in, successively
It is：（1）Air inlet face resist coating 213, figure, etching silicon dioxide are formed with first piece of mask plate exposure and development；（2）Air inlet
Resist coating 214 again after face is removed photoresist, figure is formed with second piece of mask plate exposure and development；（3）Deep reaction is carried out in air inlet face
Ion etching（DRIE）, one depth 215 of etching silicon wafer；（4）Air inlet face carries out deep reaction ion etching again after removing photoresist, etch silicon
One depth of piece is so as to the formation groove 216 in air inlet face；（5）Plasma enhanced chemical vapor deposition method is used in air inlet face
（PECVD）Applying silica film 217；（6）In outlet face resist coating, figure is formed with the 3rd piece of mask plate exposure and development,
Etching silicon dioxide；（7）After outlet face photoresist removes photoresist, then resist coating, form figure with the 4th piece of mask plate exposure and development
Shape, carries out deep reaction ion etching and cuts through silicon chip, forms outlet perforation 213；（8）After outlet face is removed photoresist, then carry out it is deep react from
Sub- etching silicon wafer, one depth 214 of a region etch on outlet face where outlet perforation；（9）Silicon chip removes silica,
Then substantially 2.5 microns of thick silicon dioxide films are formed on surface with thermal oxide, low-pressure chemical vapor deposition can be used（LPCVD）Side
Method deposits substantially 1 micron of thick silicon nitride film in chip surface again, so that in the dielectric film of silicon chip surface formation laminated construction.
The microelectronics miromaching flow of liquid chip is as shown in figure 4, chip material is silicon chip 202, silicon chip table
There is silicon dioxide layer 201 in face.Specific procedure of processing and processing sequence embody in Fig. 4 successively（1）Arrive（6）Figure in, successively
It is：（1）Enter liquid level resist coating 203, figure, etching silicon dioxide are formed with the 5th piece of mask plate exposure and development；（2）Deluster
Entering liquid level progress deep reaction ion etching, one depth of etching silicon wafer after photoresist；（3）Go out liquid level resist coating 204, with the 6th
Block mask plate exposure and development form figure, etching silicon dioxide；（4）Going out liquid level resist coating 205 after removing photoresist, with the 7th piece
Mask plate exposure and development form figure, and deep reaction ion etching, etching silicon wafer are carried out until perforation 207,208 going out liquid level；
（5）Go after photoresist to carry out deep reaction ion etching going out liquid level, one depth 206 of etching silicon wafer makes to go out liquid go out liquid level
Tubulose electron spray nozzle needle 209 is formed at hole；（6）Silicon chip removes silica, then forms substantially 2.5 microns on surface with thermal oxide
Thick silicon dioxide dielectric film 210.
The gas chip of processing and liquid chip bonding form electron spray chip above；During bonding on silicon chip to fiducial mark
The accurate alignment of note, makes the electron spray needle guard on liquid chip enter the outlet perforation in gas chip, and make as far as possible electron spray pin with
Perforation is coaxial；Bonding uses adhesive bonds；Fig. 5 is bonding schematic diagram.
As shown in fig. 6, deposit conductive film electrode 221 at inlet opening 208 on liquid level is entered, so that influent chip
Liquid contacted with conductive film electrode 221, be coupled with a potential.On gas chip surface one at, remove dielectric medium
Film, deposit conductive film electrode 220 makes the silicon sheet material electrical contact with gas chip；Gas chip is coupled with another electricity
Gesture；The difference of this potential and the potential being added on liquid is the electron spray operating voltage of device；Electricity of this voltage in device
The nozzle of spraying nozzle needle 209 forms enough highfields, pulls out charged drop and produces electron spray, gas enters from air admission hole 207
By gas passage 216 secondary air is formed from the outflow of outlet perforation 213.
In order to more intuitively show the structure of micro-fluidic electron spray chip device of the invention, Fig. 7, Fig. 8 and Fig. 9 are
The schematic three dimensional views of chip.
Fig. 7（a）It is the top view of gas chip；Fig. 7（b）It is the lower view of gas chip.The visible outlet in figure
A depth 214 and entering that a region where perforation 213, the outlet perforation on outlet face is etched perpendicular to outlet face
Groove 216 on gas face.
Fig. 8（a）It is the top view of liquid chip；Fig. 8（b）It is the lower view of liquid chip.In figure it is visible go out liquid level on
Tubulose electron spray nozzle needle 209, the air admission hole 207 being produced on liquid chip, in order to form tubulose electron spray nozzle needle and around
A depth 206 and be located at into entering on liquid level that one region of liquid outlet is etched along the direction perpendicular to the liquid chip
Fluid apertures 208.
Fig. 9 is the electron spray chip figure after liquid chip and gas chip bonding, and the amplification at electron spray nozzle needle
Figure.In figure in the visible gas chip outlet perforation 213, stretch out in outlet perforation electron spray nozzle needle 209 and in gas
The depth 214 that a region where outlet perforation on the outlet face of chip is etched perpendicular to outlet face.
Above to the structure and all specific descriptions of manufacture craft of device of the invention, image is intended only to and directly perceived
The ground displaying present invention, is not limited in any way to the present invention.The skilled worker of association area can be in the right without departing from the present invention
Change is made to above description on the premise of claimed range and claim spirit.
Claims (9)
1. a kind of micro-fluidic electron spray chip device, it is characterised in that：It includes the liquid chip being mutually bonded and gas chip,
The liquid chip is with being provided with electron spray nozzle needle, being provided with and the electricity on another side in the one side of the gas chip bonding
The inlet opening that nozzle needle of spraying is in fluid communication, the gas chip surface is covered to be provided with out on dielectric film, the gas chip
Gas is perforated and groove, and the electron spray nozzle needle is placed in the outlet perforation, and the electron spray nozzle needle is perforated with the outlet
Gap is left between inwall, described groove one end connects the outlet perforation, other end connection and is arranged on the liquid chip
Or the air admission hole on the interface on the gas chip or after the liquid chip and the gas chip bonding, the liquid core
It is provided with piece on first electrode structure, the gas chip and is provided with second electrode structure.
2. a kind of micro-fluidic electron spray chip device according to claim 1, it is characterised in that：The liquid chip includes
Enter liquid level and go out liquid level, it is described enter liquid level with it is described go out liquid level angle at 0 degree to 30 degree, the inlet opening be arranged at described in enter
Liquid level, the electron spray nozzle needle be arranged at it is described go out liquid level, the spout of the electron spray nozzle needle is liquid outlet, the EFI spray painting
Pin be tubulose nozzle needle and with it is described go out liquid level into 90 degree of ± 10 degree of angles, the tubulose nozzle needle is by an area around liquid outlet
Domain edge etches to be formed perpendicular to the direction of the liquid chip.
3. a kind of micro-fluidic electron spray chip device according to claim 1, it is characterised in that：The gas chip includes
Air inlet face and outlet face, the angle in the air inlet face and the outlet face at 0 degree to 30 degree, the air inlet face of the gas chip and
The liquid chip is mutually bonded, and outlet perforation and the air inlet face are into 90 degree ± 10 degree of angles, quarter in the air inlet face
Erosion has the groove.
4. a kind of micro-fluidic electron spray chip device according to claim 1, it is characterised in that：The electron spray of tubulose
Nozzle needle external diameter is less than the internal diameter that the outlet is perforated, the electron spray nozzle needle and coaxially arranged, the EFI of outlet perforation
Spray painting pin is perforated through outlet and the spout of electron spray nozzle needle exposes to the outlet perforation.
5. a kind of micro-fluidic electron spray chip device according to claim 4, it is characterised in that the air admission hole is to be located at
The hole that the liquid chip is formed with the edge after the gas chip bonding by being bonded at interface, or the liquid core
A perforation on piece, or a perforation on the gas chip, gas is under pressure from the air admission hole stream
Enter, flowed out by gap of the gas passage between the electron spray nozzle needle and outlet perforation inwall, form EFI
The secondary air of mist.
6. a kind of micro-fluidic electron spray chip device according to claim 1, it is characterised in that：On the liquid chip
First electrode structure gives the liquid for entering the liquid chip plus a potential, and the first electrode structure is by conductive chip
The liquid chip that material is made in itself, or is placed in being located on the surface of liquid chip that is made up of insulation chip material described
Conductive film at inlet opening, or be placed on the surface of the liquid chip of surface covering dielectric film positioned at described
Conductive film at inlet opening, or liquid is placed in into the conduction contacted with liquid in the stream before the inlet opening
Body.
7. a kind of micro-fluidic electron spray chip device according to claim 1, it is characterised in that：The gas chip material
For the conductor or semiconductor of electricity, the dielectric film of the gas chip surface covered with electric insulation, the second electrode structure
It is arranged on the gas chip for removing the dielectric film and is contacted with the gas chip conductive.
8. a kind of micro-fluidic electron spray chip device according to claim 1, it is characterised in that：The correspondence EFI spray painting
Pin side, at a certain distance from the shower nozzle of the electron spray nozzle needle it is provided with three-electrode structure.
9. a kind of preparation method of micro-fluidic electron spray chip device, it is characterised in that：It comprises the following steps,
（1）The processing of gas chip and the processing of liquid chip：
The microelectronics micro-machining of gas chip includes：On surface, the one side of the silicon wafer with silicon dioxide layer is used up
Lithography formation figure, etching silicon dioxide；Again with photoetching technique formation figure, deep reaction ion etching is used（DRIE）Technology is carved
One depth of silicon chip is lost, a depth formation groove is etched after removing photoresist again；It is heavy with PECVD on this face
Area method（PECVD）Applying silica film；Again on the other surface with photoetching technique formation figure, etching silicon dioxide；Then again
With photoetching technique formation figure, silicon chip formation perforation is cut through with deep reaction ion etching technology；Deep reactive ion is used after removing photoresist again
Etching silicon wafer, in one depth of a region etch where perforation；Finally use thermal oxidation process and low-pressure chemical vapor deposition
（LPCVD）Dielectric film of the method in chip surface formation insulation；
The microelectronics micro-machining of liquid chip includes：On surface, the one side of the silicon wafer with silicon dioxide layer is used up
Lithography formation figure, etching silicon dioxide；One depth of deep reaction ion etching technology etching silicon wafer is used after photoresist；Exist again
Another face photoetching technique formation figure, etching silicon dioxide；Again with photoetching technique formation figure, deep reaction ion etching is used
Technology etching silicon wafer is until perforation；Go to use one depth of deep reaction ion etching technology etching silicon wafer after photoresist again, make
Tubulose electron spray nozzle needle is formed at the fluid hole of liquid level；It is finally thin in the dielectric medium of chip surface formation insulation with thermal oxidation process
Film；
（2）The fluted of gas chip carries out bonding together to form micro-fluidic electron spray when having electron spray nozzle needle with liquid chip
Chip；Accurately it is aligned with the alignment mark on silicon chip during bonding, the electron spray nozzle needle on liquid chip is inserted in gas chip
Perforation.
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| CN109142473A (en) * | 2018-09-29 | 2019-01-04 | 厦门大学 | A kind of electrode reaction in-situ detection mass spectrometry device |
| CN110317728A (en) * | 2019-07-12 | 2019-10-11 | 中国科学院深圳先进技术研究院 | Single cell whole genome amplification system and method based on micro-fluidic electron spray |
| WO2021007710A1 (en) * | 2019-07-12 | 2021-01-21 | 中国科学院深圳先进技术研究院 | Microfluidic electrospray-based single-cell whole-genome amplification system and method |
| CN110729200A (en) * | 2019-09-24 | 2020-01-24 | 杭州臻镭微波技术有限公司 | Manufacturing method of three-dimensional heterogeneous module for controlling flow of radiator |
| CN111330072B (en) * | 2020-03-03 | 2021-11-23 | 南京鼓楼医院 | Preparation method and application of bionic porous MSCs microspheres |
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| DE20210784U1 (en) * | 2001-11-14 | 2003-11-27 | CARBOTEC Gesellschaft für instrumentelle Analytik mbH | Electrostatic spraying unit used in mass spectrometry directs gas flow to avoid direct influence on tip or capillary |
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| CN1793921A (en) * | 2005-12-07 | 2006-06-28 | 中国科学院上海微系统与信息技术研究所 | Biological microspray array point sample device and its manufacturing method |
| GB2471520B (en) * | 2009-07-03 | 2013-08-21 | Microsaic Systems Plc | An electrospray pneumatic nebuliser ionisation source |
| US8373116B2 (en) * | 2009-09-21 | 2013-02-12 | Queen's University At Kingston | Multi-channel electrospray emitter |
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| CN204706538U (en) * | 2015-06-05 | 2015-10-14 | 杨金金 | A kind of electric spray ion source device |
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