CN105047520A - Micro fluidic electro-spray chip device and manufacture method - Google Patents
Micro fluidic electro-spray chip device and manufacture method Download PDFInfo
- Publication number
- CN105047520A CN105047520A CN201510299992.7A CN201510299992A CN105047520A CN 105047520 A CN105047520 A CN 105047520A CN 201510299992 A CN201510299992 A CN 201510299992A CN 105047520 A CN105047520 A CN 105047520A
- Authority
- CN
- China
- Prior art keywords
- chip
- electron spray
- liquid
- gas
- nozzle needle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Nozzles (AREA)
- Micromachines (AREA)
Abstract
The invention relates to an electro-spray device, and especially to a micro fluidic electro-spray chip device and a manufacture method. The chip device provides more uniform auxiliary airflow close to an electro-spray pin, a unique electrode structure ensures the electro-spray uniformity of the pin, and the problem of non-uniformity is overcome. The manufacture method can be used to conveniently manufacture the electro-spray chip device. The micro fluidic electro-spray chip device comprises fluid chips and gas chips, each fluid chip comprises a fluid transmission channel and the electro-spray pin, each gas chip comprises a gas transmission groove and a second electrode structure, and the fluid chip is bonded with the gas chip to form the micro fluidic electro-spray chip device. The manufacture method comprises the following steps that the gas chips and the fluid chips are processed, and the side, with the groove, of the gas chip is bonded with the side, with the electro-spray pin, of the fluid chip to form the micro fluidic electro-spray chip device, and during bonding, accurate alignment is realized by aligning marks on a silicon chip, so that the electro-spray pin on the fluid chip can be nested into a through hole of the gas chip.
Description
Technical field
The present invention relates to electron spray device, particularly as the ionogenic electron spray device of mass spectrometer; Device of the present invention relates to microfluidic chip technology or microfluidic chip technology; The manufacturing technology of device of the present invention relates to micro-processing technology, microelectronics micromachining technology, is specially a kind of micro-fluidic electron spray chip device and manufacture method.
Background technology
Normally liquid is under the effect of highfield power for electron spray, and at the nozzle needle interruption-forming taylor cone of tubulose, cone point ejects small charged drop.Electrospray techniques, as a kind of main ion source, is widely used in mass spectral analysis, is the important component part that liquid chromatography mass is used in conjunction analytical technology, in the analysis and research of large biological molecule, serves crucial effect.Electron spray, as connection liquid chromatogram and mass spectrographic ion source, is divided into milliliter level (flow velocity is in ml/min magnitude), micro updating (flow velocity is in mul/min magnitude) according to the size of flow velocity and receives upgrading (flow velocity is receiving a liter/min magnitude) three kinds.Milliliter level electron spray is used for the analytical system that the large chromatographic column liquid chromatogram of mm dia and mass spectrum are used in conjunction, as 4.6 traditional mm dia chromatographic columns.Micro updating electron spray is generally used for diameter and is less than 1 millimeter and be greater than the chromatogram column system of 100 microns.Upgrading electron spray of receiving is less than the chromatogram column system of 100 microns for diameter.Receive upgrading electron spray due to flow velocity minimum, with very little nozzle needle, directly can spray under electric field force effect, efficiently molecules detected gasification and ionization.Microlitre and milliliter level electron spray due to flow velocity comparatively large, needs larger nozzle needle, the liquid-drop diameter of ejection is also larger, gasify and Ionization Efficiency low, so need secondary air.General method adds all even coaxial jet-stream wind around nozzle needle, the people such as Henion (U.S. Patent number 4861988), at the sleeve pipe that the outer surface cover one of electron spray pin is coaxial, nozzle needle stretches out in outside sleeve pipe slightly, air-flow ejects formation secondary air by the gap of nozzle needle and sleeve pipe, to improve electron spray gasification and Ionization Efficiency, also greatly improve repeatability and the stability of electron spray simultaneously.The electrospray techniques of this band secondary air obtains the inspection in market and applies the most widely, is to connect liquid chromatogram and mass spectrographic standard technique always.
In the technology of people's inventions such as Henion, an electromotive force is added on liquid, and another electromotive force is added in from the electrode of an electron spray pin distance, and the difference of these two electromotive forces is at nozzle needle mouth place's generation electric field, liquid flows out from needle tubing, under electric field force effect, form electron spray; Gas ejects from the gap of nozzle needle and sleeve pipe, help electron spray produce droplets vaporize and drop in testing molecule ionization.An important directions of technical development in recent years on chip, makes electron spray device with micro-processing technology.One of them reason is the microminiaturization of liquid chromatogram and integrated, and namely liquid chromatographic system is accomplished inside a chip, this needs chip electric spray ion source supporting with it.Another reason is that chip electric spray ion source can be fabricated into multiple nozzle needle on chip on a very little region, makes wafer ion source have high Ionization Efficiency and sensitivity, can also be used for chromatogram and the mass spectrometry system of larger flow velocity simultaneously.
The multiplex micro-processing technology in published electron spray wafer ion source makes.The people such as Moon make electron spray chip (US Patent No. 6800202B2) with microelectronics micro mechanical technology (MENS).They, with the silicon chip of a monolithic, etch perforation by plasma etching technology and on silicon chip, form electron spray nozzle needle on silicon chip.The Staats electron spray chip (US Patent No. 6800849B2) of micro injection molding fabrication techniques based on plastic material, forms perforation and the electron spray nozzle of chip by Laser Micro-Machining.These electron spray chips all can not add secondary air at nozzle needle place, and they all just receive upgrading electron spray device.But on market, most demand is micro updating and the milliliter level electron spray of large flow velocity, and chip electron spray needs to larger flow velocity and more stable performance future development.The people such as Rossier (US Patent No. 7265348B2) are made in electron spray nozzle on the edge of chip, and the raceway groove doing an air guide is in the chips incorporated into nozzle place secondary air.The people such as Li (U.S. Patent application Pub.No.:US2007/0257190A1) are also made in electron spray nozzle on the edge of chip, and the raceway groove having done two air guides is in the chips incorporated into jet-stream wind the right and left at nozzle place symmetrically.The method of their this introducing secondary air is different from the method be verified general on market.The method that market uses is that secondary air is close to electron spray nozzle needle and coaxially ejects (U.S. Patent number 4861988 of the people such as Henion) around nozzle needle equably, facts have proved, such secondary air, while the gasification of help electron spray, makes again electron spray more repeat and stablize.Air-flow in existing electron spray chip device is not equably around electron spray nozzle needle, is easy to cause unstable electron spray.The nozzle needle of the chip electron spray of the people such as Brekenfeld (U.S. Patent application Pub.No.:US2014/0284406A1) is perpendicular to chip, and liquid flows into from the one side of chip, sprays under electric field force effect from the nozzle needle mouth of the another side of chip; Chip around nozzle needle place has several perforation, and gas ejects formation secondary air from hole.This can not form the air-flow of uniform ring around electron spray nozzle needle equally.Such structure also makes air-flow can not be close to electron spray nozzle needle, and air-flow reduces the shearing booster action of electron spray.
Summary of the invention
For the defect that existing electron spray chip device exists, the invention provides a kind of micro-fluidic electron spray chip device and manufacture method, it provides the more uniform secondary air being close to electron spray nozzle needle, the electron spray uniformity of nozzle needle device is ensured with the electrode structure of uniqueness, overcome non-uniformity problem, manufacture method realizes the making of electron spray chip device easily.
The present invention be with micro-processing technology make micro-fluidic chip or be called micro-fluid chip, realize electron spray function.Chip comprises the micro-fluidic chip (hereinafter referred to as liquid chip) providing the micro-fluidic chip of gas flow path (hereinafter referred to as gas chip) and provide liquid flow path, and two parts chip bonding forms micro-fluidic electron spray chip
Technical scheme is such: a kind of micro-fluidic electron spray chip device, it comprises liquid chip and the gas chip of mutual bonding, described liquid chip with the one side of described gas chip bonding on be provided with electron spray nozzle needle, another side has the inlet opening with described electron spray nozzle needle fluid communication, described gas chip surface covers dielectric film, described gas chip has give vent to anger perforation and groove, give vent to anger in perforation described in described electron spray nozzle needle is placed on, gap is left between described electron spray nozzle needle and the described inwall of boring a hole of giving vent to anger, to give vent to anger described in described groove one end is communicated with perforation, the other end is communicated with the air admission hole be arranged in described liquid chip or gas chip or two chip interface, described air admission hole is the hole that the edge after being positioned at described liquid chip and described gas chip bonding is formed at interface by bonding, or a perforation on described liquid chip, or a perforation on described gas chip, described liquid chip is provided with the first electrode structure, described gas chip is provided with the second electrode structure, the electrode position of the second electrode structure will from the liquid in described liquid chip enough away from air-prevention electrical breakdown, an electromotive force is added on gas chip by the second electrode structure.
Preferably, described liquid chip comprises mutually almost parallel feed liquor face and goes out liquid level, described almost parallel fingering liquid level with go out the angle of liquid level at 0 degree to 30 degree, described inlet opening is arranged at described feed liquor face, liquid level is gone out described in described electron spray nozzle needle is arranged at, the spout of described electron spray nozzle needle is liquid outlet, described electron spray nozzle needle is for going out the tubulose nozzle needle of liquid level described in being approximately perpendicular to, described substantially vertical finger described electron spray nozzle needle with described go out liquid level become 90 degree ± 10 degree angles, described tubulose electron spray nozzle needle is formed along the direction etching perpendicular to described liquid chip by a region around liquid outlet.Above-mentioned almost parallel and substantially vertical in, being parallel to each other with mutually vertical is preferred plan.
Preferably, described gas chip comprises mutually almost parallel air inlet face and face of giving vent to anger, the angle in described almost parallel finger air inlet face and face of giving vent to anger is at 0 degree to 30 degree, the air inlet face of described gas chip and the mutual bonding of described liquid chip, described perforated vertical of giving vent to anger is in described air inlet face and face of giving vent to anger, perforation of giving vent to anger described in described substantially vertical finger becomes 90 degree ± 10 degree angles with described air inlet face, and described air inlet face is etched with described groove.Above-mentioned almost parallel and substantially vertical in, being parallel to each other with mutually vertical is preferred plan.
Preferably, to give vent to anger described in the described electron spray nozzle needle external diameter of tubulose is less than the internal diameter of perforation, described electron spray nozzle needle and described giving vent to anger are bored a hole coaxially arranged, to give vent to anger perforation described in give vent to anger perforation and the spout of electron spray nozzle needle expose to described in described electron spray nozzle needle passes.
Preferably, described liquid chip and described gas chip bonding make the described electron spray nozzle needle on described liquid chip be inserted in described gas chip give vent to anger bore a hole in and give vent to anger described in the groove on described gas chip being formed be connected and bore a hole and the gas passage of described air admission hole.
Preferred, described air admission hole is positioned at the edge after described liquid chip and described gas chip bonding, or be a perforation on described liquid chip, or be a perforation on described gas chip, gas flows into from described air admission hole under pressure, flow out from described electron spray nozzle needle and the described gap of boring a hole between inwall of giving vent to anger through described gas passage, form the secondary air of electron spray.
Preferably, the first electrode structure on said liquid chip adds an electromotive force to the liquid entering described liquid chip, described first electrode structure is the liquid chip itself be made up of conductive chip material, or the surface being placed in the liquid chip be made up of insulating core sheet material is positioned at the conductive film of described inlet opening, or be placed in surface coverage dielectric film described liquid chip surface on be positioned at the conductive film at described inlet opening place, or be placed in the electric conductor that liquid enters the stream before described inlet opening and liquid comes into contact.
Preferably, described gas chip material is conductor or the semiconductor of electricity, described gas chip surface is coated with the dielectric film of electric insulation, described second electrode structure be arranged at remove described dielectric film gas chip on and contact with described gas chip conductive.
Preferably, in the electron spray nozzle needle side of described micro-fluidic electron spray chip, be provided with third electrode structure apart from shower nozzle a distance of described electron spray nozzle needle; Third electrode structure can be the sampling air inlet of mass spectrometer.
Liquid chip described above and gas chip bonding, refer to and by any method, two chips to be combined, and can be to combine with the atomic bond between chip surface, combine, by adhesive bond etc. with welding manner; Concrete grammar can be but be not limited to be anode linkage, gold-silicon eutectic bonding, silicon/glass electrostatic bonding, silicon/Si direct bonding, glass solder sintering bonding and Adhesive bonding.
Give vent to anger described in described electron spray nozzle needle passes and bore a hole and have one section to stretch out perforation of giving vent to anger, can realize with the following method: use the thickness of gas chip to be less than the height of the electron spray nozzle needle on liquid chip, after bonding, electron spray nozzle needle is through gas chip, and the shower nozzle of electron spray nozzle needle exposes and goes out on liquid level at gas chip; Or use the thickness of gas chip to be greater than electron spray nozzle needle height, a degree of depth but perforation region of giving vent to anger in the face of giving vent to anger of gas chip has been etched into, after making bonding, electron spray nozzle needle has one section to stretch out perforation of giving vent to anger.
The internal diameter size of the electron spray nozzle needle on liquid chip can at 5 microns to 10 micrometer ranges, can at 10 microns to 30 micrometer ranges, can at 30 microns to 100 micrometer ranges.The external diameter size of the electron spray nozzle needle on liquid chip can at 10 microns to 20 micrometer ranges, can at 20 microns to 50 micrometer ranges, can at 50 microns to 150 micrometer ranges.
The electron spray nozzle needle correspondence of being inserted in gas chip on liquid chip is given vent to anger perforation, and electron spray nozzle needle with give vent to anger bore a hole substantially coaxial or coaxial; Spatial joint clearance between the inwall that electron spray nozzle needle and giving vent to anger is bored a hole can at 10 microns to 30 micrometer ranges, can at 30 microns to 60 micrometer ranges, can at 60 microns to 100 micrometer ranges.
After adopting structure of the present invention, gas chip is coupled with an electromotive force, and the liquid in liquid chip is coupled with another electromotive force, and the difference of these two electromotive forces is the operating voltage of electron spray chip device; The nozzle of the electron spray nozzle needle of this voltage in electron spray chip device produces an electric field, electric field force acts on the liquid of nozzle, pull-out drop, form electron spray, gas flows into described electron spray chip from described air admission hole under pressure, gap between the inwall that electron spray nozzle needle and giving vent to anger is bored a hole sprays, and forms the secondary air around electron spray being close to nozzle needle, overcomes non-uniformity problem in prior art; The spout of electron spray nozzle needle exposes to perforation of giving vent to anger, and electron spray nozzle needle is bored a hole coaxially arranged with giving vent to anger, thus produces uniform secondary air to improve repeated stability and the reliability of electron spray.
A manufacture method for micro-fluidic electron spray chip device, it comprises the following steps,
(1) processing of gas chip and the processing of liquid chip:
The microelectronics micro-machining of gas chip comprises: the one side photoetching technique on surface with the silicon wafer of silicon dioxide layer forms figure, etching silicon dioxide; Form figure by photoetching technique again, by deep reaction ion etching (DRIE) technology etching silicon wafer degree of depth, etch a degree of depth after removing photoresist again and form groove; With plasma enhanced chemical vapor deposition method (PECVD) applying silica film on this face; Figure is formed on the other surface again, etching silicon dioxide by photoetching technique; And then form figure by photoetching technique, carve by deep reaction ion etching technology and wear silicon chip formation perforation; Deep reaction ion etching silicon chip is used again, in a region etch degree of depth at perforation place after removing photoresist; Thermal oxidation process and low-pressure chemical vapor deposition (LPCVD) method is finally used to form the dielectric film of insulation at chip surface;
The microelectronics micro-machining of liquid chip comprises: the one side photoetching technique on surface with the silicon wafer of silicon dioxide layer forms figure, etching silicon dioxide; By deep reaction ion etching technology etching silicon wafer degree of depth after photoresist; Figure is formed, etching silicon dioxide again in another face photoetching technique; Figure is formed again, with deep reaction ion etching technology etching silicon wafer until perforation by photoetching technique; Use deep reaction ion etching technology etching silicon wafer degree of depth after removing photoresist again, make to form tubulose electron spray nozzle needle at the fluid hole place going out liquid level; Finally form the dielectric film of insulation at chip surface by thermal oxidation process;
(2) fluted one side and the liquid chip of gas chip have electron spray nozzle needle one side to carry out bonding to form micro-fluidic electron spray chip; Alignment mark during bonding on silicon chip is accurately aimed at, and makes the electron spray nozzle needle on liquid chip be inserted in perforation in gas chip.
After adopting method of the present invention, the making of electron spray chip device can be realized easily.
Accompanying drawing explanation
Figure 1 shows that several structure example of the present invention;
Figure 2 shows that other several concrete structure citing of the present invention;
Figure 3 shows that the process flow diagram making gas chip of microelectronics micro-machining;
Figure 4 shows that the process flow diagram making liquid chip of microelectronics micro-machining;
Fig. 5 is liquid chip and gas chip bonding schematic diagram;
Fig. 6 is the micro-fluidic electron spray chip device schematic diagram after adding top 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 three dimensional views and the electron spray nozzle needle place schematic enlarged-scale view of electron spray chip device after bonding.
Embodiment
The structure of a kind of specific embodiment of the present invention is as shown in Fig. 1 (a), and liquid chip 102 has two parallel haply faces, and one is feed liquor face, and one is liquid level; Feed liquor face have at least an inlet opening 104 allow liquid flow into; Going out liquid level has at least one fluid hole 105 to allow liquid flow out; Between inlet opening 104 and fluid hole 105, fluid is communicated with.Going out on liquid level, around a region of fluid apertures 105, etching a degree of depth perpendicular to liquid chip 102, making the electron spray nozzle needle 103 forming tubulose at fluid hole 105 place; Gas chip 101 has two parallel haply faces, and one is air inlet face, and one is the face of giving vent to anger; In air inlet face with give vent to anger between face and have at least one perforation 108 of giving vent to anger; Air inlet face there is the groove 107 of etching, give vent to anger perforation 108 and groove 107 fluid communication; Liquid chip 102 and gas chip 101 bonding, electron spray nozzle needle 103 on liquid chip 102 is coaxially inserted in the perforation 108 of giving vent to anger of gas chip 101 and is exposed to perforation 108 of giving vent to anger, and make the groove on gas chip 101 form gas passage 107 and be communicated with at least one air inlet 106, air inlet 106 and perforation 108 fluid communication of giving vent to anger in gas chip 101; Air inlet 106 is connected with outer gas circuit by a perforation in liquid chip 102.Liquid chip and gas chip surface can have electrode and dielectric film structure, but succinct in order to what show, do not draw (electrode and dielectric film structure can refer to the embodiment shown in subsequent figures 6) in figure.
The structure of another kind of specific embodiment of the present invention is as shown in Fig. 1 (b), and except air inlet 106, structure is identical with Fig. 1 (a) illustrated embodiment.The air inlet 106 of this embodiment is at side.
The structure of another kind of specific embodiment of the present invention is as shown in Fig. 1 (c), and except air inlet 106, structure is identical with Fig. 1 (a) illustrated embodiment.The air inlet 106 of this embodiment is a perforation on gas chip 101.
As shown in Figure 2 (a) shows, liquid chip 109 has two parallel haply faces to the structure of another kind of specific embodiment of the present invention, and one is feed liquor face, and one is liquid level; Feed liquor face have at least an inlet opening 110 allow liquid flow into; Going out liquid level has at least one fluid hole 111 to allow liquid flow out; Between inlet opening 110 and fluid hole 111, fluid is communicated with; Going out around fluid apertures 111 region on liquid level, etching a degree of depth along the direction perpendicular to liquid chip 109, making the electron spray nozzle needle 112 forming tubulose at fluid hole 111 place; Gas chip 117 has two parallel haply faces, and one is air inlet face, and one is the face of giving vent to anger; In air inlet face with give vent to anger between face and have at least one perforation 113 of giving vent to anger; Give vent to anger in the face of giving vent to anger the region at perforation 113 place, gas chip 117 is etched a degree of depth 114; Air inlet face there is the groove 115 of etching, give vent to anger perforation 113 and groove 115 fluid communication in gas chip 117; Liquid chip 109 and gas chip 117 bonding, electron spray nozzle needle 112 on liquid chip 109 is inserted in the perforation 113 of giving vent to anger of gas chip 117 and the shower nozzle of electron spray nozzle needle 112 exposes to gas chip 117 is etched the lower surface of a degree of depth 114, and make the groove 115 on gas chip 117 form gas passage and be communicated with at least one air inlet 116, air inlet 116 communicates with perforation 113 stream of giving vent to anger in gas chip 117; Air inlet 116 is connected with outer gas circuit by the perforation of liquid chip 109.Liquid chip and gas chip surface can have electrode and dielectric film structure, but succinct in order to what show, do not draw (electrode and dielectric film structure can refer to the embodiment shown in subsequent figures 6) in figure.
The structure of another kind of specific embodiment of the present invention is as shown in Fig. 2 (b), and except air inlet 116, structure is identical with Fig. 2 (a) illustrated embodiment.The air inlet 116 of this embodiment is at side.
As shown in Figure 2 (c), except air inlet 116, structure is identical with Fig. 2 (a) illustrated embodiment for the structure of another kind of specific embodiment of the present invention.The air inlet 116 of this embodiment is a perforation on gas chip 117.
A kind of manufacture method of micro-fluidic electron spray chip device of the present invention uses microelectronics micromachining technology, and the technological process of its specific embodiment is as shown in Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
In the present invention corresponding electron spray nozzle needle side, third electrode structure can be provided with apart from shower nozzle a distance of described electron spray nozzle needle, move towards third electrode structure place with the charged particle that the space electric field enabling whole three electromotive forces be formed drives electron spray to produce.
As shown in Figure 3, chip material is silicon chip 212 to the microelectronics miromaching flow process of gas chip, and silicon chip surface has silicon dioxide layer 211.Concrete procedure of processing and processing sequence embody in figure 3 in the figure of (1) to (9) successively, successively: (1) air inlet face resist coating 213, form figure, etching silicon dioxide with first piece of mask plate exposure and development; (2) air inlet face resist coating 214 again after removing photoresist, forms figure with second piece of mask plate exposure and development; (3) deep reaction ion etching (DRIE) is carried out in air inlet face, etching silicon wafer degree of depth 215; (4) air inlet face carries out deep reaction ion etching after removing photoresist again, etching silicon wafer degree of depth thus form groove 216 in air inlet face; (5) in air inlet face, plasma enhanced chemical vapor deposition method (PECVD) applying silica film 217 is used; (6) at face resist coating of giving vent to anger, figure is formed, etching silicon dioxide with the 3rd piece of mask plate exposure and development; (7) after face photoresist of giving vent to anger removes photoresist, then resist coating, form figure with the 4th piece of mask plate exposure and development, carry out deep reaction ion etching and wear silicon chip quarter, form perforation 213 of giving vent to anger; (8) after remove photoresist in the face of giving vent to anger, then deep reaction ion etching silicon chip is carried out, a region etch degree of depth 214 at perforation place of giving vent to anger in the face of giving vent to anger; (9) silicon chip removes silicon dioxide, then roughly 2.5 micron thickness silicon dioxide films are formed with thermal oxidation on surface, low-pressure chemical vapor deposition (LPCVD) method can be used again at chip surface deposit roughly 1 micron thickness silicon nitride film, thus form the dielectric film of laminated construction at silicon chip surface.
As shown in Figure 4, chip material is silicon chip 202 to the microelectronics miromaching flow process of liquid chip, and silicon chip surface has silicon dioxide layer 201.Concrete procedure of processing and processing sequence embody in the diagram in the figure of (1) to (6) successively, successively: (1) feed liquor face resist coating 203, form figure, etching silicon dioxide with the 5th piece of mask plate exposure and development; (2) deep reaction ion etching is carried out in feed liquor face after removing photoresist, etching silicon wafer degree of depth; (3) go out liquid level resist coating 204, form figure, etching silicon dioxide with the 6th piece of mask plate exposure and development; (4) going out liquid level resist coating 205 after removing photoresist, forming figure, carry out deep reaction ion etching going out liquid level with the 7th piece of mask plate exposure and development, etching silicon wafer is until perforation 207,208; (5) carry out deep reaction ion etching, etching silicon wafer degree of depth 206 going out liquid level after removing photoresist, make to form tubulose electron spray nozzle needle 209 at the fluid hole place going out liquid level; (6) silicon chip removes silicon dioxide, then forms roughly 2.5 micron thickness dioxide dielectric matter films 210 with thermal oxidation on surface.
The gas chip more than processed and liquid chip bonding form electron spray chip; Alignment mark during bonding on silicon chip is accurately aimed at, and makes the electron spray needle guard on liquid chip enter perforation of giving vent to anger in gas chip, and makes electron spray pin coaxial with perforation as far as possible; Bonding adopts adhesive bonds; Fig. 5 is bonding schematic diagram.
As shown in Figure 6, the inlet opening 208 place's deposit conductive film electrode 221 on feed liquor face, to make the liquid of influent chip contact with conductive film electrode 221, is coupled with an electromotive force.A place on gas chip surface, removes dielectric film, and deposit conductive film electrode 220 makes the silicon sheet material electrical contact with gas chip; Gas chip is coupled with another electromotive force; This electromotive force is the electron spray operating voltage of device with the difference of the electromotive force be added on liquid; This voltage forms enough highfields at the nozzle of the electron spray nozzle needle 209 of device, and pull-out charged drop produces electron spray, and gas passes into gas passage 216 from air admission hole 207 and flows out formation secondary air from perforation 213 of giving vent to anger.
In order to show the structure of micro-fluidic electron spray chip device of the present invention more intuitively, Fig. 7, Fig. 8 and Fig. 9 are the schematic three dimensional views of chip.
Fig. 7 (a) is the top view of gas chip; Fig. 7 (b) is the lower view of gas chip.Give vent to anger described in visible in figure perforation 213, giving vent to anger perforation place on the face of giving vent to anger a region perpendicular to the degree of depth 214 of face etching of giving vent to anger and the groove in air inlet face 216.
Fig. 8 (a) is the top view of liquid chip; Fig. 8 (b) is the lower view of liquid chip.Go out as seen in figure the tubulose electron spray nozzle needle 209 on liquid level, the air admission hole 207 be produced on liquid chip, in order to form tubulose electron spray nozzle needle at the degree of depth 206 etched along the direction perpendicular to described liquid chip around region of liquid outlet and the inlet opening 208 be positioned on feed liquor face.
Fig. 9 is the electron spray chip figure after liquid chip and gas chip bonding, and the enlarged drawing at electron spray nozzle needle place.Perforation 213 of giving vent to anger in figure in visible described gas chip, the electron spray nozzle needle 209 stretching out in perforation of giving vent to anger and the degree of depth 214 etched perpendicular to face of giving vent to anger in a region at the perforation place of giving vent to anger of giving vent to anger on face of gas chip.
Above to the structure of device of the present invention and all specific descriptions of manufacture craft, be all in order to image and show the present invention intuitively, the present invention is not constituted any limitation.The technology personage of association area can make change to above description under the prerequisite not exceeding right of the present invention and claim spirit.
Claims (10)
1. at the micro-fluidic electron spray chip device of one, it is characterized in that: it comprises liquid chip and the gas chip of mutual bonding, described liquid chip with the one side of described gas chip bonding on be provided with electron spray nozzle needle, another side has the inlet opening with described electron spray nozzle needle fluid communication, described gas chip surface covers dielectric film, described gas chip has give vent to anger perforation and groove, give vent to anger in perforation described in described electron spray nozzle needle is placed on, gap is left between described electron spray nozzle needle and the described inwall of boring a hole of giving vent to anger, to give vent to anger described in described groove one end is communicated with perforation, the other end is communicated with the air admission hole be arranged on described liquid chip or on interface on described gas chip or after described liquid chip and described gas chip bonding, described liquid chip is provided with the first electrode structure, described gas chip is provided with the second electrode structure.
2. the micro-fluidic electron spray chip device of one according to claim 1, it is characterized in that: described liquid chip comprises feed liquor face and goes out liquid level, described feed liquor face and described go out the angle of liquid level at 0 degree to 30 degree, described inlet opening is arranged at described feed liquor face, liquid level is gone out described in described electron spray nozzle needle is arranged at, the spout of described electron spray nozzle needle is liquid outlet, described electron spray nozzle needle is tubulose nozzle needle, and with described go out liquid level become 90 degree ± 10 degree angles, described tubulose nozzle needle is formed along the direction etching perpendicular to described liquid chip by a region around liquid outlet.
3. the micro-fluidic electron spray chip device of one according to claim 1, it is characterized in that: described gas chip comprises air inlet face and face of giving vent to anger, the angle in described air inlet face and described face of giving vent to anger is at 0 degree to 30 degree, the air inlet face of described gas chip and the mutual bonding of described liquid chip, described perforation of giving vent to anger becomes 90 degree ± 10 degree angles with described air inlet face, and described air inlet face is etched with described groove.
4. the micro-fluidic electron spray chip device of one according to claim 1, it is characterized in that: the internal diameter of perforation of giving vent to anger described in the described electron spray nozzle needle external diameter of tubulose is less than, described electron spray nozzle needle and described giving vent to anger are bored a hole coaxially arranged, to give vent to anger perforation described in described electron spray nozzle needle exposes to through give vent to anger perforation and the spout of electron spray nozzle needle.
5. the micro-fluidic electron spray chip device of one according to claim 1, is characterized in that: described liquid chip and described gas chip bonding make the described electron spray nozzle needle on described liquid chip be inserted in described gas chip give vent to anger bore a hole in and give vent to anger described in the groove on described gas chip being formed be connected and bore a hole and the gas passage of described air admission hole.
6. the micro-fluidic electron spray chip device of one according to claim 5, it is characterized in that, described air admission hole is the hole that the edge after being positioned at described liquid chip and described gas chip bonding is formed at interface by bonding, or a perforation on described liquid chip, or a perforation on described gas chip, gas flows into from described air admission hole under pressure, flow out from described electron spray nozzle needle and the described gap of boring a hole between inwall of giving vent to anger through described gas passage, form the secondary air of electron spray.
7. the micro-fluidic electron spray chip device of one according to claim 1, it is characterized in that: the first electrode structure on said liquid chip adds an electromotive force to the liquid entering described liquid chip, described first electrode structure is the liquid chip itself be made up of conductive chip material, or the surface being placed in the liquid chip be made up of insulating core sheet material is positioned at the conductive film of described inlet opening, or be placed in surface coverage dielectric film described liquid chip surface on be positioned at the conductive film at described inlet opening place, or be placed in the electric conductor that liquid enters the stream before described inlet opening and liquid comes into contact.
8. the micro-fluidic electron spray chip device of one according to claim 1, it is characterized in that: described gas chip material is conductor or the semiconductor of electricity, described gas chip surface is coated with the dielectric film of electric insulation, described second electrode structure be arranged at remove described dielectric film gas chip on and contact with described gas chip conductive.
9. the micro-fluidic electron spray chip device of one according to claim 1, is characterized in that: corresponding described electron spray nozzle needle side, shower nozzle a distance of described electron spray nozzle needle is provided with third electrode structure.
10. a manufacture method for micro-fluidic electron spray chip device, is characterized in that: it comprises the following steps,
(1) processing of gas chip and the processing of liquid chip:
The microelectronics micro-machining of gas chip comprises: the one side photoetching technique on surface with the silicon wafer of silicon dioxide layer forms figure, etching silicon dioxide; Form figure by photoetching technique again, by deep reaction ion etching (DRIE) technology etching silicon wafer degree of depth, etch a degree of depth after removing photoresist again and form groove; With plasma enhanced chemical vapor deposition method (PECVD) applying silica film on this face; Figure is formed on the other surface again, etching silicon dioxide by photoetching technique; And then form figure by photoetching technique, carve by deep reaction ion etching technology and wear silicon chip formation perforation; Deep reaction ion etching silicon chip is used again, in a region etch degree of depth at perforation place after removing photoresist; Thermal oxidation process and low-pressure chemical vapor deposition (LPCVD) method is finally used to form the dielectric film of insulation at chip surface;
The microelectronics micro-machining of liquid chip comprises: the one side photoetching technique on surface with the silicon wafer of silicon dioxide layer forms figure, etching silicon dioxide; By deep reaction ion etching technology etching silicon wafer degree of depth after photoresist; Figure is formed, etching silicon dioxide again in another face photoetching technique; Figure is formed again, with deep reaction ion etching technology etching silicon wafer until perforation by photoetching technique; Use deep reaction ion etching technology etching silicon wafer degree of depth after removing photoresist again, make to form tubulose electron spray nozzle needle at the fluid hole place going out liquid level; Finally form the dielectric film of insulation at chip surface by thermal oxidation process;
(2) fluted one side and the liquid chip of gas chip have electron spray nozzle needle one side to carry out bonding to form micro-fluidic electron spray chip; Alignment mark during bonding on silicon chip is accurately aimed at, and makes the electron spray nozzle needle on liquid chip be inserted in perforation in gas chip.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510299992.7A CN105047520B (en) | 2015-06-05 | 2015-06-05 | A kind of micro-fluidic electron spray chip device and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510299992.7A CN105047520B (en) | 2015-06-05 | 2015-06-05 | A kind of micro-fluidic electron spray chip device and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105047520A true CN105047520A (en) | 2015-11-11 |
| CN105047520B CN105047520B (en) | 2017-07-28 |
Family
ID=54453973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510299992.7A Expired - Fee Related CN105047520B (en) | 2015-06-05 | 2015-06-05 | A kind of micro-fluidic electron spray chip device and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105047520B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142473A (en) * | 2018-09-29 | 2019-01-04 | 厦门大学 | A kind of electrode reaction in situ detection mass spectrometric apparatus |
| 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 |
| CN111653490A (en) * | 2019-09-24 | 2020-09-11 | 浙江集迈科微电子有限公司 | Manufacturing method of three-dimensional heterogeneous module for controlling flow of radiator |
| 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 |
| WO2021174640A1 (en) * | 2020-03-03 | 2021-09-10 | 南京鼓楼医院 | Method for preparing biomimetic porous msc microspheres and use thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113799491B (en) | 2021-09-15 | 2022-11-11 | 华中科技大学 | Arrayed electrofluid nozzle without extraction electrode |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317986A (en) * | 1998-09-17 | 2001-10-17 | 阿德文生物科学公司 | Integrated monolithic microfabricated electrospray and liquid chromatography system and method |
| WO2003041869A1 (en) * | 2001-11-14 | 2003-05-22 | CARBOTEC Gesellschaft für instrumentelle Analytik mbH | Focussed electrospray device |
| US20030111599A1 (en) * | 2001-12-19 | 2003-06-19 | Staats Sau Lan Tang | Microfluidic array devices and methods of manufacture and uses thereof |
| US6633031B1 (en) * | 1999-03-02 | 2003-10-14 | Advion Biosciences, Inc. | Integrated monolithic microfabricated dispensing nozzle and liquid chromatography-electrospray system and method |
| 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 |
| US20110000986A1 (en) * | 2009-07-03 | 2011-01-06 | Richard Syms | Electrospray Pneumatic Nebuliser Ionisation Source |
| US20110101122A1 (en) * | 2009-09-21 | 2011-05-05 | Oleschuk Richard D | Multi-Channel Electrospray Emitter |
| WO2011075451A1 (en) * | 2009-12-18 | 2011-06-23 | Thermo Finnigan Llc | Pneumatically-assisted electrospray emitter array |
| CN204706538U (en) * | 2015-06-05 | 2015-10-14 | 杨金金 | A kind of electric spray ion source device |
-
2015
- 2015-06-05 CN CN201510299992.7A patent/CN105047520B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317986A (en) * | 1998-09-17 | 2001-10-17 | 阿德文生物科学公司 | Integrated monolithic microfabricated electrospray and liquid chromatography system and method |
| US6633031B1 (en) * | 1999-03-02 | 2003-10-14 | Advion Biosciences, Inc. | Integrated monolithic microfabricated dispensing nozzle and liquid chromatography-electrospray system and method |
| WO2003041869A1 (en) * | 2001-11-14 | 2003-05-22 | CARBOTEC Gesellschaft für instrumentelle Analytik mbH | Focussed electrospray device |
| US20030111599A1 (en) * | 2001-12-19 | 2003-06-19 | Staats Sau Lan Tang | Microfluidic array devices and methods of manufacture and uses thereof |
| 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 |
| US20110000986A1 (en) * | 2009-07-03 | 2011-01-06 | Richard Syms | Electrospray Pneumatic Nebuliser Ionisation Source |
| US20110101122A1 (en) * | 2009-09-21 | 2011-05-05 | Oleschuk Richard D | Multi-Channel Electrospray Emitter |
| WO2011075451A1 (en) * | 2009-12-18 | 2011-06-23 | Thermo Finnigan Llc | Pneumatically-assisted electrospray emitter array |
| CN204706538U (en) * | 2015-06-05 | 2015-10-14 | 杨金金 | A kind of electric spray ion source device |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142473A (en) * | 2018-09-29 | 2019-01-04 | 厦门大学 | A kind of electrode reaction in situ detection mass spectrometric apparatus |
| 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 |
| CN111653490A (en) * | 2019-09-24 | 2020-09-11 | 浙江集迈科微电子有限公司 | Manufacturing method of three-dimensional heterogeneous module for controlling flow of radiator |
| WO2021174640A1 (en) * | 2020-03-03 | 2021-09-10 | 南京鼓楼医院 | Method for preparing biomimetic porous msc microspheres and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105047520B (en) | 2017-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105047520A (en) | Micro fluidic electro-spray chip device and manufacture method | |
| US8148681B2 (en) | Microengineered vacuum interface for an ionization system | |
| US7973278B2 (en) | Microengineered ionisation device | |
| US7615744B1 (en) | Microengineered nanospray electrode system | |
| EP2512638B1 (en) | Pneumatically-assisted electrospray emitter array | |
| US8227765B2 (en) | Electrospray pneumatic nebuliser ionisation source | |
| US8022361B2 (en) | Monolithic multinozzle emitters for nanoelectrospray mass spectrometry | |
| US6852560B2 (en) | Fabrication of a microchip-based electrospray device | |
| Wright et al. | MEMS-based nanospray-ionization mass spectrometer | |
| CN204706538U (en) | A kind of electric spray ion source device | |
| CA2552086C (en) | Microengineered nanospray electrode system | |
| Sen et al. | Design, fabrication and test of a microfluidic nebulizer chip for desorption electrospray ionization mass spectrometry | |
| Yu et al. | Microfluidic self-aspiration sonic-spray ionization chip with single and dual ionization channels for mass spectrometry | |
| JP5785219B2 (en) | Interface component and manufacturing method thereof | |
| Syms et al. | A microengineered alignment bench for a nanospray ionization source | |
| JP2007027131A5 (en) | ||
| CN210894237U (en) | MEMS-based multi-stationary-phase miniature filling column structure | |
| Wright et al. | MEMS-based Nanospray Ionisation Mass Spectrometer Steven Wright1, Richard RA Syms2, Richard Moseley1, Guodong Hong1, Shane O’Prey1, William E. Boxford1, Neil Dash1 and Peter Edwards1 | |
| Tabourier et al. | A planar on-chip micro-nib interface for NanoESI-MS microfluidic applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170728 |