CN107199060A - It is a kind of for three-dimensional electrofocusing's micro-fluidic chip of SPME and preparation method thereof - Google Patents
It is a kind of for three-dimensional electrofocusing's micro-fluidic chip of SPME and preparation method thereof Download PDFInfo
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- CN107199060A CN107199060A CN201710348908.5A CN201710348908A CN107199060A CN 107199060 A CN107199060 A CN 107199060A CN 201710348908 A CN201710348908 A CN 201710348908A CN 107199060 A CN107199060 A CN 107199060A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502769—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by multiphase flow arrangements
- B01L3/502784—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by multiphase flow arrangements specially adapted for droplet or plug flow, e.g. digital microfluidics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/68—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0861—Configuration of multiple channels and/or chambers in a single devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0887—Laminated structure
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0893—Geometry, shape and general structure having a very large number of wells, microfabricated wells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
- B01L2300/12—Specific details about materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2400/00—Moving or stopping fluids
- B01L2400/02—Drop detachment mechanisms of single droplets from nozzles or pins
- B01L2400/021—Drop detachment mechanisms of single droplets from nozzles or pins non contact spotting by inertia, i.e. abrupt deceleration of the nozzle or pin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2400/00—Moving or stopping fluids
- B01L2400/04—Moving fluids with specific forces or mechanical means
- B01L2400/0403—Moving fluids with specific forces or mechanical means specific forces
- B01L2400/0463—Hydrodynamic forces, venturi nozzles
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Abstract
It is a kind of for three-dimensional electrofocusing's micro-fluidic chip of SPME and preparation method thereof, the chip includes gas circuit fluid path layer and gas circuit layer, or two layers of gas circuit fluid path layer of identical；Gas circuit fluid path layer includes gas circuit runner and gas circuit storage pool, fluid path runner and fluid path storage pool, and fluid path runner is formed with the bottleneck structure for storing SPE particle；Gas circuit layer is identical with the gas circuit structure in gas circuit fluid path layer, the gas circuit storage pool being connected comprising gas circuit runner with gas circuit runner；In gas circuit fluid path layer, gas circuit runner initially forms a runner from gas circuit storage pool, is divided into two gas circuit runners in midway, is symmetrically distributed in fluid path runner both sides, and is finally communicated at fluid path runner, forms nozzle；The depth of gas circuit runner is more than the depth of fluid path runner, and the outlet of fluid path runner is respectively positioned on the centre position of gas circuit runner in transverse direction and flow channel depth direction.The achievable SPME of the present invention and chip-in series Mass Spectrometer Method dual-use function.
Description
Technical field
The present invention relates to a kind of for three-dimensional electrofocusing's micro-fluidic chip of SPME and preparation method thereof, the miniflow
Control chip can carry out SPE and be used to produce fine droplet with mass spectrometry, in biphase gas and liquid flow.
Background technology
SPME is early 1990s by being used for that Arthur and Pawliszy is proposed and grown up first
Adsorb and concentrate the sample treatment of target substance in determinand.SPME is that one kind collects sampling, extraction, concentration, sample introduction in one
The solvent-free Sample Pretreatment Technique of body, grows up on the basis of solid phase extraction techniques, due to the volume of its stationary phase
Micro-extraction is defined as much smaller than sample volume.The technology is the distribution system between stationary phase and solution based on test analyte
Several differences and target analytes are extracted from sample substrate.The process of traditional SPE generally comprises adsorbent
Pretreatment, sample adsorption, washing, elution and eluent evaporation and concentration.SPME is also comprising some of steps.
SPME in recent years based on micro-fluidic chip platform increasingly attracts attention, compared with traditional SPE,
SPME platform operations are easy, test is fast, expense is low, sampling and enrichment it is synchronous carry out, it is small to sample contamination, do not destroy sample system
Original equilibrium, easily efficiently analytical technology is combined with mass spectrum, chromatogram and electrophoresis etc., realizes on-line automaticization operation so that at sample
It is reason technology and analysis, simple to operate time saving.
Micro-fluidic chip (microfluidic), also known as chip lab, are resulted from the 1970s, smooth by this earliest
Terry of good fortune university et al. is studied at first, and they use the silicon wafer to manufacture blank of early stage micro-fluidic chip, and the chip is led at that time
It is used for the detection and analysis of composition of air.Current micro-fluidic chip is generally with dimethyl silicone polymer (PDMS), poly- methyl-prop
High molecular polymer, glass, the silicon such as e pioic acid methyl ester (PMMA) etc. are processed for material.With traditional chemical experiment and biology
Experiment is compared, and micro-fluidic chip has the characteristics of size is small, specific surface area is big, and channel size is in micron order, with cell size
It is close, it is particularly suitable for the research for carrying out cell grade.And mass spectrum (mass spectrometer) is as a kind of highly sensitive
Detection means, is the optimal selection that qualitative and quantitative analysis is carried out to unknown micro substance.Both combinations will be to unknown materials point
The development of the pertinent instruments such as analysis, food inspection, biochemical analysis has very important significance.
Mass spectral analysis is a kind of analysis method for measuring ion mass-to-charge ratio, its general principle be make in sample each component from
Ionized in component, generate the positively charged ion of different mass-to-charge ratioes, the effect of accelerated electric field forms ion beam, entered
Enter mass analyzer, ion is deflected using electric field and magnetic field, they are focused on respectively and obtains mass spectrogram, so that it is determined that its
Quality.The instrument that mass spectrograph is exactly analyzed unknown materials using this principle.Electrospray ionization mass spectrum (Electrospray
Ion-Mass Spectrometer, ESI-MS) combination is more already applied to species analysis field, but have in mass spectrograph
While this advantage of high sensitivity, its requirement to ion gun is often also very high.Traditional spray needle ion gun is needed to sample
Before product are carried out on other platforms the problems such as processing, big sample consumption, separative efficiency and not high efficiency of transmission.Combination is mass spectrographic
Microfluid electric spray ion source arises at the historic moment, and micro-fluid chip can be with work(such as the pre-treatments, pre-separation, electron spray of integrated sample
Can, the sensitivity of detection is substantially increased, the consumption of sample is reduced.
The content of the invention
It is a primary object of the present invention to overcome the deficiencies in the prior art, there is provided a kind of three-dimensional electricity for SPME
Micro-fluidic chip and preparation method thereof is focused on, the chip is used for carrying out SPME, for pre-treatment reagent, produces micron,
Even the fine droplet of Nano grade, tandem mass spectrometer, carry out the detection of material composition.
To achieve the above object, the present invention uses following technical scheme：
A kind of three-dimensional electrofocusing's micro-fluidic chip for SPME, including two layers, respectively gas circuit fluid path up and down
Layer and gas circuit layer, or be two layers of gas circuit fluid path layer with identical gas circuit fluid path structure；The gas circuit fluid path layer includes gas circuit
Runner and the gas circuit storage pool being connected with the gas circuit runner, fluid path runner and the fluid path storage being connected with the fluid path runner
Pond, the fluid path runner is formed with the bottleneck structure for storing SPE particle；The gas circuit layer and the gas circuit fluid path
Gas circuit structure in layer is identical, the gas circuit storage pool being connected comprising gas circuit runner with gas circuit runner；In the gas circuit fluid path layer, institute
State gas circuit runner and initially form a runner from the gas circuit storage pool, be divided into two gas circuit runners in midway, be symmetrically distributed in
The fluid path runner both sides, and finally communicated at the fluid path runner, form nozzle；Two layers of merging is described up and down
The depth of gas circuit runner be more than the fluid path runner depth, and the fluid path runner outlet in transverse direction and flow channel depth direction
It is respectively positioned on the centre position of the gas circuit runner of merging.
Further：
The section that the fluid path runner is connected with the fluid path storage pool have the first width, the fluid path runner with it is described
The section that nozzle is connected has the second width, and first width is more than second width, and second width is more than described
The width of bottleneck structure.
The width for the section that the fluid path runner is connected with the liquid storage tank is 235 μm, the section being connected with the nozzle
Width be 75 μm, the width of the bottleneck structure is 25 μm, and length is 35 μm.
Three-dimensional electrofocusing's micro-fluid chip material therefor is high polymer dimethyl silicone polymer i.e. PDMS, three-dimensional focal
Micro-fluid chip includes the two panels PDMS up and down being mutually bonded, and two panels PDMS includes flow passage structure；Wherein a piece of PDMS knots
Structure layer includes gas circuit runner and fluid path runner, and a piece of PDMS substrate layers include gas circuit runner and fluid path runner, two panels PDMS in addition
Up and down merge after respective gas circuit runner it is corresponding with fluid path runner above and below merge, or, wherein a piece of PDMS structure sheafs include gas
Road runner and fluid path runner, in addition a piece of PDMS substrate layers include gas circuit runner, above and below two panels PDMS merge after respective gas circuit
Merge above and below runner correspondence.
The gas circuit runner and the fluid path runner angle are between 0-90 °, and optimized angle is between 35 ° and 45 °.
The nozzle has the contraction spraying aperture that width is 50 μm.
The nozzle formed by the gas circuit runner and the fluid path runner is directly from the mould that photoresist is formed
Stripping forming.
A kind of preparation method for making described three-dimensional electrofocusing's micro-fluid chip, comprises the following steps：
Mold Making is carried out using gas circuit fluid path layer mask plate and gas circuit layer mask plate；
Wherein, the transmission region of gas circuit fluid path layer mask plate includes corresponding to gas circuit runner and gas circuit storage pool, fluid path stream
The region in road and fluid path storage pool, is stored for gas circuit runner defined in the photoresist exposure process on to silicon chip and gas circuit
Pond, fluid path runner and fluid path storage pool；The transmission region of gas circuit layer mask plate includes corresponding to gas circuit runner and gas circuit storage pool
Region, for gas circuit runner and gas circuit storage pool defined in the photoresist exposure process on to silicon chip；
During Mold Making, got rid of on the first silicon chip after bottom photoresist, pass through gas circuit fluid path layer mask plate pair
Bottom photoresist is exposed, and gas circuit fluid path layer is formed after development；Got rid of again on the first silicon chip after the photoresist of upper strata, pass through gas circuit
Layer mask plate is exposed to upper strata photoresist, and gas circuit layer is formed after development, for deepening the gas circuit runner that exposure is formed for the first time,
Thus produce corresponding to the mould for forming PDMS structure sheafs；Said process is repeated to the second silicon chip again, or, to the second silicon
Substrate only carries out whirl coating, exposure, the developing process for gas circuit layer mask plate, thus produces corresponding to forming PDMS substrate layers
Mould；
Then, PDMS structure sheafs and PDMS substrate layers are molded respectively using corresponding mould；
After again, PDMS structure sheafs and PDMS substrate layers are alignd, one piece of complete three-dimensional focal microfluid core is bonded together to form
Piece；
Preferably, gas circuit fluid path layer mask plate and gas circuit layer mask plate contain alignment structures, by photoetching during for exposing
The existing structure of glue formation aligns with the rear mask plate used.
Further：
Gas circuit fluid path layer mask plate be corresponding to be completed once or twice whirl coating, exposure, developing process, and gas circuit layer is covered
The corresponding manufacturing process of film version completes at least three times whirl coatings, exposure, developing process, so that the thickness for obtaining gas circuit runner is much larger than liquid
Road gate thickness, so as to be conducive to liquid to be suspended in after being sprayed from fluid path in gas, without being contacted with runner wall.
The photoresist uses SU-8 glue.
Beneficial effects of the present invention：
The present invention realizes that one kind can carry out SPME, can produce the micro-fluidic chip knot of small spray droplet
Structure, the fluid spray form of especially useful biphase gas and liquid flow formation liquid-in-gas.Especially solve in biphase gas and liquid flow, form liquid-in-gas
Fluid spray form, produce the fine droplet of micron, even Nano grade.Solve makes micro-fluid chip micro- with mass spectrometry
Runner makes the difficulty in cutting and the combination micro-fluid chip runner that goes against accepted conventions is single, lacks the function of gas assisted atomization.Adopt
With the present invention, building for SPE-micro-fluidic chip-Mass Spectrometer Method whole system can be finally realized, and realize the micro- extraction of solid phase
Take and chip-in series Mass Spectrometer Method dual-use function.
Brief description of the drawings
Fig. 1 shows that the present invention implements the schematic flow sheet of micro flow chip preparation method；
Fig. 2 a to Fig. 2 d show the schematic diagram of two pieces of mask plates of the present invention, and wherein Fig. 2 a show gas circuit fluid path layer
Mask plate 201, Fig. 2 b show gas circuit layer mask plate 202, and the enlarged drawing that Fig. 2 c are in Fig. 2 a local 203, Fig. 2 d are office in Fig. 2 a
The enlarged drawing in portion 204；
Fig. 3 shows multiple whirl coating, exposed and developed detailed process figure in Fig. 1；
Fig. 4 a to Fig. 4 f show that two panels PDMS is molded schematic top plan view, wherein, Fig. 4 a show to mould obtained PDMS knots
Structure layer 401, Fig. 4 b show the PDMS structure sheafs 402 after cutting, and Fig. 4 c show the scanning electron microscope (SEM) photograph of PDMS structure sheaf nozzles, scheme
4d shows to mould obtained PDMS substrate layers 404, and Fig. 4 e show the PDMS substrate layers 405 after cutting, and Fig. 4 f show PDMS substrates
The scanning electron microscope (SEM) photograph of structure sheaf nozzle；
Fig. 5 a show the overall PDMS chips schematic top plan view after bonding；
Fig. 5 b are the Section A-A figure in Fig. 5 a；
Fig. 6 shows that three-dimensional electrofocusing's micro-fluidic chip for SPME is combined schematic diagram with mass spectrograph；
Fig. 7 a to Fig. 7 d, which are shown in three-dimensional electrofocusing's micro-fluidic chip for SPME, inserts SPE
Grain MCX, electron spray experiment and mass spectrograph are combined schematic diagram, and wherein Fig. 7 a show to insert solid phase in the bottleneck structure of fluid path runner
Extract particle MCX；Fig. 7 b show three-dimensional electrofocusing's micro-fluidic chip interior spray effect for SPME；Fig. 7 c be
During the loading of SPME, chip and mass spectrograph combination detection signal graph, Fig. 7 d are stripping in SPME
Cheng Zhong, chip and mass spectrograph combination detection signal graph.
Description of reference numerals：
Silicon chip (100), mask plate (101), photoresist (102), PDMS (103), slide (104), PDMS substrates
(105), gas circuit fluid path layer mask plate (201), gas circuit layer mask plate (202), bottleneck structure (203), nozzle (204), gas circuit storage
Liquid pool (205), gas circuit runner (206), fluid path liquid storage tank (207), gas circuit liquid storage tank (208), gas circuit runner (209), fluid path stream
Road (210), shrinks spraying aperture (211), alignment mark (212), photoresist (300,301,302,303), PDMS structure sheafs
(401), PDMS structure sheafs (402) after cutting, scanning electron microscope (SEM) photograph (403), PDMS substrate layers (404), PDMS substrate layers after cutting
(405), scanning electron microscope (SEM) photograph (406), it is complete to be used for three-dimensional electrofocusing's micro-fluidic chip (500) of SPME, completely it is used for
Three-dimensional electrofocusing's micro-fluidic chip Section A-A (501) of SPME, mass spectrograph injection port (600), SPE particle
(700)。
Embodiment
Embodiments of the present invention are elaborated below.It is emphasized that what the description below was merely exemplary,
The scope being not intended to be limiting of the invention and its application.
Refering to Fig. 2 a to Fig. 6, in one embodiment, a kind of micro-fluidic core of three-dimensional electrofocusing for SPME
Piece, including two layers up and down, respectively gas circuit fluid path layer and gas circuit layer, or be two layers of gas circuit with identical gas circuit fluid path structure
Fluid path layer；The gas circuit fluid path layer includes gas circuit runner 206 and the gas circuit storage pool 205 being connected with the gas circuit runner 206, liquid
Road runner 210 and the fluid path storage pool 207 being connected with the fluid path runner 210, the fluid path runner 210 are formed with for storing
The bottleneck structure of SPE particle；The gas circuit layer is identical with the gas circuit structure in gas circuit fluid path layer, includes gas circuit stream
The gas circuit storage pool 208 that road 209 is connected with gas circuit runner 209；In gas circuit fluid path layer, the gas circuit runner 206 is from described
Gas circuit storage pool 205 initially forms a runner, is divided into two gas circuit runners in midway, is symmetrically distributed in the fluid path runner
210 both sides, and finally communicated at the fluid path runner 210, form nozzle 204；Up and down two layers merging the gas
The depth of road runner 206,209 be more than the fluid path runner 210 depth, and the fluid path runner 210 outlet laterally and
Flow channel depth direction is respectively positioned on the centre position of the gas circuit runner of merging, for forming three-dimensional focal electron spray.
Refering to Fig. 2 c, in a preferred embodiment, the fluid path runner 210 is connected with the fluid path storage pool 207
Section has the first width, and the section that the fluid path runner 210 is connected with the nozzle 204 has the second width, and described first is wide
Degree is more than second width, and second width is more than the width of the bottleneck structure.
In a preferred embodiment, the width for the section that the fluid path runner 210 is connected with the liquid storage tank is 235 μm,
The width for the section being connected with the nozzle 204 is 75 μm, and the width of the bottleneck structure is 25 μm, and length is 35 μm.
Refering to Fig. 4 a to Fig. 4 f, in a preferred embodiment, three-dimensional electrofocusing's micro-fluid chip material therefor is high
Polymers dimethyl silicone polymer is PDMS, and three-dimensional focal micro-fluid chip includes the two panels PDMS up and down being mutually bonded, is respectively
PDMS structure sheafs 401 and PDMS substrate layers 404, and two panels PDMS includes flow passage structure；Wherein a piece of PDMS structure sheafs 401
Comprising gas circuit runner 206 and fluid path runner 210, a piece of PDMS substrate layers 404 include gas circuit runner and fluid path runner, two panels in addition
Above and below PDMS merge after respective gas circuit runner it is corresponding with fluid path runner above and below merging, or, wherein a piece of PDMS structure sheafs bag
Runner containing gas circuit 206 and fluid path runner 210, in addition a piece of PDMS substrate layers 404 include gas circuit runner 209, above and below two panels PDMS
Merge after merging above and below the respective correspondence of gas circuit runner 206,209.
In a preferred embodiment, the gas circuit runner 206 and the angle of fluid path runner 210 are between 0-90 °, preferably
Angle is between 35 ° and 45 °.
In a preferred embodiment, the nozzle 204 has the contraction spraying aperture 211 that width is 50 μm.
In a preferred embodiment, the nozzle formed by the gas circuit runner 206 and the fluid path runner 210
Stripping forming in 204 moulds directly formed from photoresist.
Refering to Fig. 1 to Fig. 3, in another embodiment, a kind of system for making described three-dimensional electrofocusing's micro-fluid chip
Make method, comprise the following steps：
Mold Making is carried out using gas circuit fluid path layer mask plate and gas circuit layer mask plate；
Wherein, the transmission region of gas circuit fluid path layer mask plate include corresponding to gas circuit runner 206 and gas circuit storage pool 205,
The region of fluid path runner 210 and fluid path storage pool 207, for gas circuit stream defined in the photoresist exposure process on to silicon chip
Road 206 and gas circuit storage pool 205, fluid path runner 210 and fluid path storage pool 207；Gas circuit layer mask plate transmission region include pair
Should be in the region of gas circuit runner 209 and gas circuit storage pool 208, for gas defined in the photoresist exposure process on to silicon chip
Road runner 209 and gas circuit storage pool 208；
During Mold Making, got rid of on the first silicon chip after bottom photoresist, pass through gas circuit fluid path layer mask plate 201
Bottom photoresist is exposed, gas circuit fluid path layer is formed after development；Got rid of again on the first silicon chip after the photoresist of upper strata, pass through gas
Road floor mask plate 202 is exposed to upper strata photoresist, and gas circuit layer is formed after development, for deepening the gas circuit that exposure is formed for the first time
Runner 206, is thus produced corresponding to the mould for forming PDMS structure sheafs；Said process is repeated to the second silicon chip again, or,
Whirl coating, exposure, the developing process for gas circuit layer mask plate 202 are only carried out to the second silicon chip, is thus produced corresponding to shape
Into the mould of PDMS substrate layers；
Then, PDMS structure sheafs 401 and PDMS substrate layers 404 are molded respectively using corresponding mould；
After again, PDMS structure sheafs 401 and PDMS substrate layers 404 are alignd, one piece of complete three-dimensional focal is bonded together to form micro-
Fluid chip.
In a preferred embodiment, gas circuit fluid path layer mask plate 201 and gas circuit layer mask plate 202 contain alignment structures,
Such as alignment mark 212, the existing structure for forming photoresist during for exposing aligns with the rear mask plate used.
In a preferred embodiment, gas circuit fluid path layer mask plate 201 it is corresponding complete once or twice whirl coating, expose
Light, developing process, the corresponding manufacturing process of gas circuit layer mask plate 202 complete at least three times whirl coatings, exposure, developing process, so that
The thickness for obtaining the gas circuit runner 206,209 finally merged is much larger than the thickness of fluid path runner 210, so as to be conducive to liquid from fluid path
It is suspended in after ejection in gas, without being contacted with runner wall.
In a preferred embodiment, the photoresist uses SU-8 glue.
The feature and its advantage of the specific embodiment of the present invention are further described below in conjunction with accompanying drawing.
Fig. 2 a to Fig. 2 d show two pieces of mask plates that embodiment is related to, and gas circuit fluid path layer mask plate 201 contains correspondence gas circuit
The region of liquid storage tank 205 and gas circuit runner 206, fluid path liquid storage tank 207 and fluid path runner 210, it is used for bottom photoresist
Exposure, for forming gas circuit fluid path layer；Gas circuit layer mask plate 202 mainly comprising correspondence gas circuit liquid storage tank 208 and with gas circuit liquid storage
The region of the connected gas circuit runner 209 in pond 208, for the exposure of upper strata photoresist, for deepening gas circuit runner.According to gas circuit liquid
The definition of road floor mask plate 201, the diameter 2.16mm of fluid path liquid storage tank 207, fluid path runner 210 is connected wide 235 μ of section with liquid storage tank
M, with 75 μm of width being connected at nozzle, 25 μm of 203 width of bottleneck structure, 35 μm of length, the contraction formed by gas circuit runner
211 wide 50 μm of aperture of spraying；According to the definition of gas circuit layer mask plate 202, the diameter 2.16mm of gas circuit liquid storage tank 208, gas circuit runner
209 be connected with gas circuit liquid storage tank 208 it is local wide 100 μm；After two pieces of mask plates press 212 positioned in alignment of mark structure, fluid path
The outlet of runner 210 is located exactly at the centre position of gas circuit runner 209, and gas circuit runner 209 is symmetrically distributed in the both sides of fluid path runner 210,
It ensure that the realization of chip core structure.
Preparation method according to embodiments of the present invention, photoresist uses SU-8 glue, and it is a kind of negativity, near ultraviolet ray photoetching
Glue, i.e. ultraviolet irradiation portion branch produce cross-linking reaction, and developing process can be remained, and are formed spatially lucky with chip raceway groove
Complementary structure, it is suitable to super thick processed, the micro-structural of high-aspect-ratio.
Whirl coating process includes three steps：Drying, whirl coating, front baking.3 cun of silicon chip wafers 100 are put in oxygen plasma first
In machine, plasma is stamped；Then silicon chip wafer 100 is fixed on the vacuum cup of sol evenning machine, will appropriate thin shape with dropper
SU-8 glue drops in crystal circle center, with 2500 revs/min of rotating speed whirl coating 30 seconds；Go to after being dried 5 minutes with 65 DEG C on hot plate again with 95
DEG C dry 10 minutes, complete front baking, be air-cooled to room temperature.
Exposure process includes two steps：Exposure, rear baking.Silicon chip wafer 100 after front baking air cooling is put into ultraviolet
Quarter machine silicon wafer stage on, gas circuit fluid path layer mask plate 201 is gently placed with photoresist, silicon chip wafer 100 and gas circuit is kept
Fluid path layer mask plate 201 is generally centered, and is set the time for exposure to be 18 seconds after clamping, is started exposure；After the completion of it is careful that silicon chip is brilliant
Circle 100 is gone on hot plate, is dried 10 minutes with 95 DEG C again after being dried 15 minutes with 65 DEG C, after the completion of dry process.
Developing process：The silicon chip wafer 100 of cooling is transferred in the big culture dish for filling developer solution, it is ensured that development liquid energy
Silicon chip is totally submerged, development is taken out after 5 minutes, clean with alcohol flushing.
So far, completed for the whirl coating of gas circuit fluid path layer mask plate 201, exposure, developing process, what it was produced is microfluid
Gas circuit fluid path layer in chip, including bottleneck structure 203.
It is substantially consistent with above-mentioned process for whirl coating, exposure, the developing process of gas circuit layer mask plate 202.But in order to
Thicker photoresist layer is obtained, whirl coating speed is reduced to 1000 revs/min；It is then to put gas circuit layer mask plate 202 in exposure process
It is placed on photoresist, utilizes the photoresist mark structure of crosslinking curing on mark structure 212 thereon and silicon chip wafer 100
212 alignments, you can ensure that the gas circuit runner 209 produced is symmetrically distributed in the both sides of fluid path runner 210, fluid path runner 210 is exported just
It is located at the intersection of gas circuit runner 209 well, so that after ensure that gas flows out from gas circuit runner 205, just by gas circuit runner 209
In gas wrapping vacantly spray.
As shown in figure 3, the corresponding making of gas circuit fluid path layer mask plate 201 only completes whirl coating, exposure, a developing process,
The corresponding manufacturing process of gas circuit layer mask plate 202 completes three whirl coatings, exposure, developing process.So cause gas circuit runner 209
Thickness is much larger than the thickness of fluid path runner 210, so that be conducive to liquid from gas is suspended in after the outflow of fluid path runner 210, without
Contacted with runner wall.The PDMS structures being molded on this silicon chip wafer 100 are used as PDMS structure sheafs 401, the spray of PDMS structure sheafs
The scanning electron microscope (SEM) photograph 403 of mist mouthful 204 clearly illustrates the relative position and depth relationship of fluid path runner 210 and gas circuit runner 209.
Take second silicon chip wafer again, this time only to mask plate 202 carry out whirl coating, exposure, develop, experimentation with it is upper
State that process is unanimous on the whole, ultimately form second SU-8 structure for only including continuous phase layer.It is molded on this silicon chip wafer
PDMS structures clearly illustrate continuous phase stream as PDMS substrate layers 404, the scanning electron microscope (SEM) photograph 406 of PDMS substrate layers nozzle 204
Road 209.
Preparation method according to embodiments of the present invention, the PDMS polymer mixed respectively with different proportion makes two panels
PDMS, the PDMS structures after shaping are as shown in Figure 4.Place it under microscope, with blade along micro-fluid chip outer contour
Cut, PDMS structure sheafs 402 and PDMS substrate layers 405 after cutting after being cut, due to designed micro-fluid chip, nothing
Nanospray tip need to be formed by cutting, so being easily accomplished chip cutting making.Then by two panels PDMS under the microscope
Alignment, bonds together to form one piece of complete three-dimensional focal micro-fluid chip, as shown in figure 5 a and 5b.
Preparation method according to embodiments of the present invention, baking oven is placed on by final obtained three-dimensional focal micro-fluid chip
In, 120 DEG C are toasted 24 hours, or the longer time.
The whole manufacturing process of PDMS chips in the present embodiment is as described above, preparation method is also carried out in the present embodiment
Embody.Three-dimensional electrofocusing's micro-fluidic chip for SPME in the present embodiment is mainly used to extract related targeted conjunction
Thing and the small atomized drop of generation, are detected for mass spectrograph, and microchip and mass spectrograph combination schematic diagram are as shown in Figure 6.Liquid
Sample enters mass spectrograph after three-dimensional electrofocusing's micro-fluidic chip for SPME sprays through mass spectrograph injection port 600
Carry out sample analysis.Fig. 7 a are illustrated fills solid phase extraction from three-dimensional electrofocusing's micro-fluidic chip bottleneck for SPME
Particle micrograph, and the fluid sample outside spray effect that Fig. 7 b displayings spray are taken, the loading process extraction of SPE is full
Start moment mass spectrogram with rear mass spectrogram and SPE elution.
Above content is to combine specific/preferred embodiment made for the present invention be further described, it is impossible to recognized
The specific implementation of the fixed present invention is confined to these explanations.For general technical staff of the technical field of the invention,
Without departing from the inventive concept of the premise, it can also make some replacements or modification to the embodiment that these have been described,
And these are substituted or variant should all be considered as belonging to protection scope of the present invention.
Claims (10)
1. a kind of three-dimensional electrofocusing's micro-fluidic chip for SPME, it is characterised in that including two layers up and down, be respectively
Gas circuit fluid path layer and gas circuit layer, or be two layers of gas circuit fluid path layer with identical gas circuit fluid path structure；The gas circuit fluid path layer
The gas circuit storage pool being connected comprising gas circuit runner and with the gas circuit runner, fluid path runner and the liquid being connected with the fluid path runner
Road storage pool, the fluid path runner is formed with the bottleneck structure for storing SPE particle；The gas circuit layer and the gas
Gas circuit structure in the fluid path floor of road is identical, the gas circuit storage pool being connected comprising gas circuit runner with gas circuit runner；The gas circuit fluid path
In layer, the gas circuit runner initially forms a runner from the gas circuit storage pool, is divided into two gas circuit runners in midway, symmetrically
The fluid path runner both sides are distributed in, and are finally communicated at the fluid path runner, nozzle is formed；Two layers of merging up and down
The depth of the gas circuit runner be more than the depth of the fluid path runner, and the outlet of the fluid path runner is deep in transverse direction and runner
Degree direction is respectively positioned on the centre position of the gas circuit runner of merging.
2. three-dimensional electrofocusing's micro-fluidic chip as claimed in claim 1, it is characterised in that the fluid path runner and the fluid path
The section that storage pool is connected has the first width, and the section that the fluid path runner is connected with the nozzle has the second width, institute
The first width is stated more than second width, second width is more than the width of the bottleneck structure.
3. three-dimensional electrofocusing's micro-fluidic chip as claimed in claim 2, it is characterised in that the fluid path runner and the liquid storage
The width for the section that pond is connected is 235 μm, and the width for the section being connected with the nozzle is 75 μm, the width of the bottleneck structure
For 25 μm, length is 35 μm.
4. three-dimensional electrofocusing's micro-fluidic chip as described in any one of claims 1 to 3, it is characterised in that the three-dimensional voltolisation
Burnt micro-fluid chip material therefor is high polymer dimethyl silicone polymer i.e. PDMS, and three-dimensional focal micro-fluid chip includes mutually being bonded
Two panels PDMS up and down, and two panels PDMS includes flow passage structure；Wherein a piece of PDMS structure sheafs include gas circuit runner and liquid
Road runner, in addition a piece of PDMS substrate layers include gas circuit runner and fluid path runner, above and below two panels PDMS merge after respective gas circuit
Merge above and below runner is corresponding with fluid path runner, or, wherein a piece of PDMS structure sheafs include gas circuit runner and fluid path runner, in addition
A piece of PDMS substrate layers include gas circuit runner, and above and below two panels PDMS merges after merging above and below respective gas circuit runner correspondence.
5. three-dimensional electrofocusing's micro-fluidic chip as described in any one of Claims 1-4, it is characterised in that the gas circuit runner
With the fluid path runner angle between 0-90 °, optimized angle is between 35 ° and 45 °.
6. three-dimensional electrofocusing's micro-fluidic chip as described in any one of claim 1 to 5, it is characterised in that the nozzle has
Width is 50 μm of contraction spraying aperture.
7. three-dimensional electrofocusing's micro-fluidic chip as described in any one of claim 1 to 6, it is characterised in that by the gas circuit stream
The nozzle that road is formed with fluid path runner stripping forming directly from the mould of photoresist formation.
8. a kind of preparation method of the three-dimensional electrofocusing's micro-fluid chip made described in any one of claim 1 to 6, its feature exists
In comprising the following steps：
Mold Making is carried out using gas circuit fluid path layer mask plate and gas circuit layer mask plate；
Wherein, the transmission region of gas circuit fluid path layer mask plate include corresponding to gas circuit runner and gas circuit storage pool, fluid path runner and
The region of fluid path storage pool, for gas circuit runner defined in the photoresist exposure process on to silicon chip and gas circuit storage pool,
Fluid path runner and fluid path storage pool；The transmission region of gas circuit floor mask plate includes the area corresponding to gas circuit runner and gas circuit storage pool
Domain, for gas circuit runner and gas circuit storage pool defined in the photoresist exposure process on to silicon chip；
During Mold Making, got rid of on the first silicon chip after bottom photoresist, by gas circuit fluid path layer mask plate to most bottom
Layer photoresist exposure, forms gas circuit fluid path layer after development；Get rid of after the photoresist of upper strata, covered by gas circuit layer on the first silicon chip again
Film version exposes to upper strata photoresist, gas circuit layer is formed after development, for deepening the gas circuit runner that exposure is formed for the first time, thus
Produce corresponding to the mould for forming PDMS structure sheafs；Said process is repeated to the second silicon chip again, or, to the second silicon chip
Whirl coating, exposure, the developing process for gas circuit layer mask plate are only carried out, is thus produced corresponding to the mould for forming PDMS substrate layers
Tool；
Then, PDMS structure sheafs and PDMS substrate layers are molded respectively using corresponding mould；
After again, PDMS structure sheafs and PDMS substrate layers are alignd, one piece of complete three-dimensional focal micro-fluid chip is bonded together to form；
Preferably, gas circuit fluid path layer mask plate and gas circuit layer mask plate contain alignment structures, by photoresist shape during for exposing
Into existing structure alignd with the rear mask plate used.
9. the preparation method of three-dimensional electrofocusing's micro-fluid chip as claimed in claim 8, it is characterised in that gas circuit fluid path layer is covered
Film version corresponding complete once or twice whirl coating, exposure, developing process, the corresponding manufacturing process of gas circuit layer mask plate are complete
Into at least three times whirl coatings, exposure, developing process, so that the thickness for obtaining gas circuit runner is much larger than fluid path gate thickness, so that favorably
It is suspended in after liquid sprays from fluid path in gas, without being contacted with runner wall.
10. the preparation method of three-dimensional electrofocusing's micro-fluid chip as claimed in claim 8 or 9, it is characterised in that the photoetching
Glue uses SU-8 glue.
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