CN107199060B - A kind of three-dimensional electrofocusing's micro-fluidic chip and preparation method thereof for solid phase microextraction - Google Patents
A kind of three-dimensional electrofocusing's micro-fluidic chip and preparation method thereof for solid phase microextraction Download PDFInfo
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- CN107199060B CN107199060B CN201710348908.5A CN201710348908A CN107199060B CN 107199060 B CN107199060 B CN 107199060B CN 201710348908 A CN201710348908 A CN 201710348908A CN 107199060 B CN107199060 B CN 107199060B
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Classifications
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01L2300/0893—Geometry, shape and general structure having a very large number of wells, microfabricated wells
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- 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
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Abstract
A kind of three-dimensional electrofocusing's micro-fluidic chip and preparation method thereof for solid phase microextraction, the chip include gas circuit fluid path layer and gas circuit layer or identical two layers of gas circuit fluid path layer；Gas circuit fluid path layer includes gas circuit runner and gas circuit storage pool, and fluid path runner and fluid path storage pool, fluid path runner are formed with the bottleneck structure for storing Solid Phase Extraction particle；Gas circuit layer is identical as 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, and two gas circuit runners are divided into halfway, is symmetrically distributed in fluid path runner two sides, and finally communicates at fluid path runner, forms nozzle；The depth of gas circuit runner is greater than the depth of fluid path runner, and the outlet of fluid path runner is respectively positioned on the middle position of gas circuit runner in transverse direction and flow channel depth direction.Solid phase microextraction and chip-in series Mass Spectrometer Method dual function can be achieved in the present invention.
Description
Technical field
Three-dimensional electrofocusing's micro-fluidic chip and preparation method thereof that the present invention relates to a kind of for solid phase microextraction, the miniflow
Control chip can carry out Solid Phase Extraction and with mass spectrometry, in biphase gas and liquid flow for generating fine droplet.
Background technique
Solid phase microextraction is being used for of early 1990s being put forward for the first time and grown up by Arthur and Pawliszy
Adsorb and be concentrated the sample treatment of target substance in determinand.SPME is a kind of sampling, extraction, concentration, the sample introduction of collecting in one
The solvent-free Sample Pretreatment Technique of body is to grow 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 based on test analyte between stationary phase and solution
Several differences and target analytes are extracted from sample substrate.The process of traditional Solid Phase Extraction generally comprises adsorbent
Pretreatment, sample absorption, washing, elution and eluent evaporation and concentration.Solid phase microextraction also includes some of steps.
Solid phase microextraction in recent years based on micro-fluidic chip platform more and more attention has been paid to, compared with traditional SPE,
SPME platform is easy to operate, test is fast, expense is low, sampling is synchronous with enrichment carries out, is small to sample contamination, not destroying sample system
Original equilibrium, easily efficiently analytical technology is combined with mass spectrum, chromatography and electrophoresis etc., realizes that on-line automaticization operates, so that at sample
It is reason technology and analysis, easy to operate time saving.
Micro-fluidic chip (microfluidic), also known as chip lab, result from earliest in the 1970s, smooth by this
The Terry et al. of good fortune university is studied at first, they are led with the silicon wafer to manufacture blank of early stage micro-fluidic chip, the chip at that time
It is used for the detection and analysis of composition of air.Micro-fluidic chip is usually with dimethyl silicone polymer (PDMS), poly- methyl-prop at present
High molecular polymers, glass, the silicon such as e pioic acid methyl ester (PMMA) etc. are that material is processed.With traditional chemical experiment and biology
Experiment is compared, and micro-fluidic chip has the characteristics that size is small, large specific surface area, channel size in the micron-scale, 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 high sensitivity
Detection means is the optimal selection that qualitative and quantitative analysis is carried out to unknown micro substance.The combination of the two 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 be measure a kind of analysis method of ion mass-to-charge ratio, the basic principle is that make in sample each component from
It being ionized in component, generates the positively charged ion of different mass-to-charge ratioes, the effect of accelerated electric field forms ion beam, into
Enter mass analyzer, so that ion is deflected using electric and magnetic fields, they are focused respectively and obtains mass spectrogram, so that it is determined that its
Quality.Mass spectrograph is exactly the instrument analyzed using this principle unknown materials.Electrospray ionization mass spectrum (Electrospray
Ion-Mass Spectrometer, ESI-MS) combination is more already applied to species analysis field, however have in mass spectrograph
While this highly sensitive advantage, the requirement to ion source is often also very high.Traditional spray needle ion source is needed to sample
The problems such as product are handled before carrying out on other platforms, sample consumption is big, separative efficiency and efficiency of transmission be not high.It is combined mass spectrographic
Microfluid electric spray ion source comes into being, and micro-fluid chip can integrate the function such as the pre-treatment, pre-separation, electron spray of sample
Can, the sensitivity of detection is substantially increased, the consumption of sample is reduced.
Summary of the invention
It is a primary object of the present invention to overcome the deficiencies of the prior art and provide a kind of three-dimensional electricity for solid phase microextraction
Micro-fluidic chip and preparation method thereof is focused, which is used to carry out solid phase microextraction, and it is used for pre-treatment reagent, generates micron,
Even the fine droplet of Nano grade, tandem mass spectrometer carry out the detection of material composition.
To achieve the above object, the invention adopts the following technical scheme:
A kind of three-dimensional electrofocusing's micro-fluidic chip for solid phase microextraction, including upper layer and lower layer, 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 includes gas circuit
Runner and the gas circuit storage pool being connected with the gas circuit runner, fluid path runner and the fluid path being connected with fluid path runner storage
Pond, the fluid path runner are formed with the bottleneck structure for storing Solid Phase Extraction 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
It states gas circuit runner and initially forms a runner from the gas circuit storage pool, two gas circuit runners are divided into halfway, are symmetrically distributed in
Fluid path runner two sides, and finally communicated at the fluid path runner, form nozzle；Upper layer and lower layer merge described
The depth of gas circuit runner is greater than the depth of the fluid path runner, and the outlet of the fluid path runner is in transverse direction and flow channel depth direction
It is respectively positioned on the middle 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 greater than second width, and second width is greater 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 knot
Structure layer includes gas circuit runner and fluid path runner, and in addition a piece of PDMS substrate layer includes gas circuit runner and fluid path runner, two panels PDMS
Respective gas circuit runner and the corresponding merging up and down of fluid path runner after merging up and down, alternatively, wherein a piece of PDMS structure sheaf includes gas
Road runner and fluid path runner, in addition a piece of PDMS substrate layer includes gas circuit runner, respective gas circuit after two panels PDMS or more merges
Runner is corresponding to be merged up and down.
The gas circuit runner and the fluid path runner angle are between 0-90 °, and optimized angle is between 35 ° and 45 °.
It is that 50 μm of contraction is sprayed aperture that the nozzle, which has width,.
The nozzle is formed by directly from the mold that photoresist is formed by the gas circuit runner and the fluid path runner
Stripping forming.
A kind of production method making three-dimensional electrofocusing's micro-fluid chip, 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 includes corresponding to gas circuit runner and gas circuit storage pool, fluid path stream
The region in road and fluid path storage pool, for defining gas circuit runner and gas circuit storage in the photoresist exposure process on silicon chip
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 defining gas circuit runner and gas circuit storage pool in the photoresist exposure process on silicon chip；
During Mold Making, after bottom photoresist is got rid of on the first silicon chip, pass through gas circuit fluid path layer mask plate pair
The exposure of bottom photoresist, forms gas circuit fluid path layer after development；After getting rid of upper layer photoresist on the first silicon chip again, pass through gas circuit
Layer mask plate exposes upper layer photoresist, and gas circuit layer is formed after development, to be used to deepen to expose the gas circuit runner formed for the first time,
Thus the mold for corresponding to and forming PDMS structure sheaf is produced；The second silicon chip is repeated the above process again, alternatively, to the second silicon
Substrate only carries out whirl coating, exposure, developing process for gas circuit layer mask plate, thus produces to correspond to and forms PDMS substrate layer
Mold；
Then, PDMS structure sheaf and PDMS substrate layer are separately formed out using corresponding mould；
After again, PDMS structure sheaf and PDMS substrate layer are aligned, 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 when for exposing
The existing structure that glue is formed is aligned in the rear mask plate used.
Further:
Gas circuit fluid path layer mask plate be corresponding to complete that primary or whirl coating, exposure, developing process, gas circuit layer are covered twice
The corresponding manufacturing process of film version completes at least whirl coating, exposure, developing process three times, so that the thickness of gas circuit runner is much larger than liquid
Road gate thickness, thus be conducive to liquid from fluid path spray after be suspended in gas, without with flow path wall face contact.
The photoresist uses SU-8 glue.
Beneficial effects of the present invention:
The present invention realizes that one kind is able to carry out solid phase microextraction, can generate the micro-fluidic chip knot of small spray droplet
Structure, especially useful biphase gas and liquid flow form the fluid spray form of liquid-in-gas.It especially solves in biphase gas and liquid flow, forms liquid-in-gas
Fluid spray form, generate micron, even Nano grade fine droplet.Solve keeps micro-fluid chip micro- with mass spectrometry
Difficulty and going against accepted conventions in runner production cutting is combined that micro-fluid chip runner is single, lacks the function of gas assisted atomization.It adopts
It with the present invention, can finally realize that Solid Phase Extraction-micro-fluidic chip-Mass Spectrometer Method whole system is built, and realize the micro- extraction of solid phase
It takes and chip-in series Mass Spectrometer Method dual function.
Detailed description of the invention
Fig. 1 shows the flow diagram that the present invention implements micro flow chip preparation method；
Fig. 2 a to Fig. 2 d shows the schematic diagram of two pieces of mask plates of the present invention, and wherein Fig. 2 a shows gas circuit fluid path layer
Mask plate 201, Fig. 2 b show gas circuit layer mask plate 202, and Fig. 2 c is the enlarged drawing of part 203 in Fig. 2 a, and Fig. 2 d is office in Fig. 2 a
The enlarged drawing in portion 204；
Fig. 3 shows the detailed process figure of multiple whirl coating in Fig. 1, exposure and imaging；
Fig. 4 a to Fig. 4 f shows two panels PDMS molding schematic top plan view, wherein Fig. 4 a shows the PDMS knot that molding obtains
Structure layer 401, Fig. 4 b show the PDMS structure sheaf 402 after cutting, and Fig. 4 c shows the scanning electron microscope (SEM) photograph of PDMS structure sheaf atomizing nozzle, scheme
4d shows the PDMS substrate layer 404 that molding obtains, and Fig. 4 e shows the PDMS substrate layer 405 after cutting, and Fig. 4 f shows PDMS substrate
The scanning electron microscope (SEM) photograph of structure sheaf atomizing nozzle；
Fig. 5 a shows the whole PDMS chip schematic top plan view after bonding；
Fig. 5 b is the Section A-A figure in Fig. 5 a；
Fig. 6, which is shown, is combined schematic diagram for the three-dimensional electrofocusing's micro-fluidic chip and mass spectrograph of solid phase microextraction；
Fig. 7 a to Fig. 7 d shows filling Solid Phase Extraction in three-dimensional electrofocusing's micro-fluidic chip for solid phase microextraction
Grain MCX, electron spray experiment and mass spectrograph are combined schematic diagram, and wherein Fig. 7 a, which is shown, inserts solid phase in the bottleneck structure of fluid path runner
Extract particle MCX；Fig. 7 b shows three-dimensional electrofocusing's micro-fluidic chip interior spray effect for solid phase microextraction；Fig. 7 c be
During the loading of solid phase microextraction, chip and mass spectrograph combination detection signal graph, Fig. 7 d is stripping in solid phase microextraction
Cheng Zhong, chip and mass spectrograph combination detection signal graph.
Description of symbols:
Silicon chip (100), mask plate (101), photoresist (102), PDMS (103), glass slide (104), PDMS substrate
(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 sheaf
(401), PDMS structure sheaf (402) after cutting, scanning electron microscope (SEM) photograph (403), PDMS substrate layer (404), PDMS substrate layer after cutting
(405), scanning electron microscope (SEM) photograph (406), the complete three-dimensional electrofocusing's micro-fluidic chip (500) for being used for solid phase microextraction, are completely used for
Three-dimensional electrofocusing's micro-fluidic chip Section A-A (501) of solid phase microextraction, mass spectrograph injection port (600), Solid Phase Extraction particle
(700)。
Specific embodiment
It elaborates below to embodiments of the present invention.It is emphasized that following the description is only exemplary,
The range and its application being not intended to be limiting of the invention.
Refering to Fig. 2 a to Fig. 6, in one embodiment, a kind of micro-fluidic core of three-dimensional electrofocusing for solid phase microextraction
Piece, including upper layer and lower layer, 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 Solid Phase Extraction particle；The gas circuit layer is identical as the gas circuit structure in the 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 the gas circuit fluid path layer, the gas circuit runner 206 is from described
Gas circuit storage pool 205 initially forms a runner, and two gas circuit runners are divided into halfway, is symmetrically distributed in the fluid path runner
210 two sides, and finally communicated at the fluid path runner 210, form nozzle 204；The gas that upper layer and lower layer merge
The depth of road runner 206,209 be greater than the fluid path runner 210 depth, and the outlet of the fluid path runner 210 laterally and
Flow channel depth direction is respectively positioned on the middle 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 greater than second width, and second width is greater 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, that is, PDMS, three-dimensional focal micro-fluid chip include the two panels PDMS up and down being mutually bonded, respectively
PDMS structure sheaf 401 and PDMS substrate layer 404, and two panels PDMS includes flow passage structure；Wherein a piece of PDMS structure sheaf 401
Comprising gas circuit runner 206 and fluid path runner 210, in addition a piece of PDMS substrate layer 404 includes gas circuit runner and fluid path runner, two panels
Respective gas circuit runner and the corresponding merging up and down of fluid path runner after PDMS or more merges, alternatively, wherein a piece of PDMS structure sheaf packet
Runner containing gas circuit 206 and fluid path runner 210, in addition a piece of PDMS substrate layer 404 includes gas circuit runner 209, two panels PDMS or more
Respective gas circuit runner 206,209 is corresponding after merging merges up and down.
In a preferred embodiment, the gas circuit runner 206 and 210 angle of fluid path runner are between 0-90 °, preferably
Angle is between 35 ° and 45 °.
In a preferred embodiment, it is that 50 μm of contraction is sprayed aperture 211 that the nozzle 204, which has width,.
In a preferred embodiment, the nozzle is formed by with the fluid path runner 210 by the gas circuit runner 206
204 directly from photoresist formed mold in stripping forming.
Refering to fig. 1 to Fig. 3, in another embodiment, a kind of system making three-dimensional electrofocusing's micro-fluid chip
Make method, 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 206 and gas circuit storage pool 205,
The region of fluid path runner 210 and fluid path storage pool 207, for defining gas circuit stream in the photoresist exposure process on silicon chip
Road 206 and gas circuit storage pool 205, fluid path runner 210 and fluid path storage pool 207；The transmission region of gas circuit layer mask plate includes pair
It should be in the region of gas circuit runner 209 and gas circuit storage pool 208, for defining gas in the photoresist exposure process on silicon chip
Road runner 209 and gas circuit storage pool 208；
During Mold Making, after bottom photoresist is got rid of on the first silicon chip, pass through gas circuit fluid path layer mask plate 201
Bottom photoresist is exposed, forms gas circuit fluid path layer after development；After getting rid of upper layer photoresist on the first silicon chip again, pass through gas
Road floor mask plate 202 exposes upper layer photoresist, and gas circuit layer is formed after development, to be used to deepen to expose the gas circuit formed for the first time
Thus runner 206 produces the mold for corresponding to and forming PDMS structure sheaf；The second silicon chip is repeated the above process again, alternatively,
The whirl coating for gas circuit layer mask plate 202, exposure, developing process are only carried out to the second silicon chip, are thus produced corresponding to shape
At the mold of PDMS substrate layer；
Then, PDMS structure sheaf 401 and PDMS substrate layer 404 are separately formed out using corresponding mould；
After again, PDMS structure sheaf 401 and PDMS substrate layer 404 are aligned, it is micro- to bond together to form one piece of complete three-dimensional focal
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 that photoresist is formed is aligned in the rear mask plate used when for exposing.
In a preferred embodiment, gas circuit fluid path layer mask plate 201 it is corresponding complete it is primary or twice whirl coating, expose
Light, developing process, the corresponding manufacturing process of gas circuit layer mask plate 202 complete at least whirl coating, exposure, developing process three times, so that
The thickness of the gas circuit runner 206,209 finally merged is obtained much larger than 210 thickness of fluid path runner, to be conducive to liquid from fluid path
Be suspended in gas after ejection, without with flow path wall face contact.
In a preferred embodiment, the photoresist uses SU-8 glue.
The feature and its advantage of specific embodiments of the present invention are further described below in conjunction with attached drawing.
Fig. 2 a to Fig. 2 d shows two pieces of mask plates that embodiment is related to, and gas circuit fluid path layer mask plate 201 contains corresponding 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 is used for bottom photoresist
Exposure, for forming gas circuit fluid path layer；Gas circuit layer mask plate 202 mainly comprising corresponding 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 layer photoresist, for deepening gas circuit runner.According to gas circuit liquid
The definition of road floor mask plate 201,207 diameter 2.16mm of fluid path liquid storage tank, fluid path runner 210 are connected wide 235 μ of section with liquid storage tank
M, and be connected at nozzle 75 μm of width, 25 μm of 203 width of bottleneck structure, 35 μm of length, the contraction formed by gas circuit runner
Spraying 211 wide 50 μm of aperture；According to the definition of gas circuit layer mask plate 202,208 diameter 2.16mm of gas circuit liquid storage tank, gas circuit runner
209 connect with gas circuit liquid storage tank 208 place it is 100 μm wide；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 209 middle position of gas circuit runner, and gas circuit runner 209 is symmetrically distributed in 210 two sides of fluid path runner,
It ensure that the realization of chip core structure.
Preparation method according to an embodiment of the present invention, photoresist use SU-8 glue, it is a kind of negativity, near ultraviolet ray photoetching
Glue, i.e. ultraviolet light irradiation portion branch generate cross-linking reaction, and developing process can remain, and are formed spatially lucky with chip channel
Complementary structure, it is suitable for super thick processed, the micro-structure of high-aspect-ratio.
Whirl coating process includes three steps: drying, whirl coating, front baking.3 cun of silicon wafer wafers 100 are put in oxygen plasma first
In machine, plasma is stamped；Then silicon wafer wafer 100 is fixed on the vacuum chuck of sol evenning machine, it will appropriate thin shape with dropper
SU-8 glue is dripped in crystal circle center, with 2500 revs/min of revolving speed whirl coating 30 seconds；It goes on hot plate and is dried with 65 DEG C after five minutes 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 wafer wafer 100 of the front baking after air-cooled is put into ultraviolet
Quarter machine silicon wafer stage on, gas circuit fluid path layer mask plate 201 is gently placed on photoresist, silicon wafer wafer 100 and gas circuit are kept
Fluid path layer mask plate 201 is generally centered, and it is 18 seconds that the time for exposure is arranged after clamping, starts to expose；After the completion carefully by silicon wafer crystalline substance
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, is dried process after the completion.
Developing process: cooling silicon wafer wafer 100 is transferred in the big culture dish for filling developer solution, guarantees developer solution energy
It is totally submerged silicon wafer, development is taken out after five minutes, rinsed well with ethyl alcohol.
So far, the whirl coating of gas circuit fluid path layer mask plate 201, exposure, developing process are completed, what is generated is microfluid
Gas circuit fluid path layer in chip, including bottleneck structure 203.
Whirl coating, exposure, developing process for gas circuit layer mask plate 202, it is substantially consistent with above-mentioned process.However 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 and silicon wafer wafer 100 thereon
212 alignments can guarantee that the gas circuit runner 209 generated is symmetrically distributed in 210 two sides of fluid path runner, fluid path runner 210 exports just
It is located at 209 intersection of gas circuit runner well, to ensure that gas after flowing out in gas circuit runner 205, just by gas circuit runner 209
In gas wrapping vacantly spray.
As shown in figure 3, the corresponding production 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 whirl coating, exposure, developing process three times.Make gas circuit runner 209 in this way
Thickness is much larger than 210 thickness of fluid path runner, is suspended in gas after the outflow of fluid path runner 210 to be conducive to liquid, without
With flow path wall face contact.Molding PDMS structure is as PDMS structure sheaf 401, the spray of PDMS structure sheaf on this silicon wafer wafer 100
204 scanning electron microscope (SEM) photograph 403 of mist mouth clearly illustrates relative position and the depth relationship of fluid path runner 210 and gas circuit runner 209.
Take second silicon wafer wafer again, this time only to mask plate 202 carry out whirl coating, exposure, development, experimentation with it is upper
State that process is unanimous on the whole, ultimately form second only include continuous phase layer SU-8 structure.It is molding on this silicon wafer wafer
PDMS structure clearly illustrates continuous phase stream as PDMS substrate layer 404,204 scanning electron microscope (SEM) photograph 406 of PDMS substrate layer atomizing nozzle
Road 209.
Preparation method according to an embodiment of the present invention makes two panels with the PDMS polymer that different proportion mixes respectively
PDMS, PDMS structure after molding are as shown in Figure 4.It places it under microscope, with blade along micro-fluid chip outer contour
It is cut, PDMS structure sheaf 402 and PDMS substrate layer 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 production.Then under the microscope by two panels PDMS
Alignment, bonds together to form one piece of complete three-dimensional focal micro-fluid chip, as shown in figure 5 a and 5b.
Final three-dimensional focal micro-fluid chip obtained is placed on baking oven by preparation method according to an embodiment of the present invention
In, 120 DEG C are toasted 24 hours, or the longer time.
The entire manufacturing process of PDMS chip in the present embodiment is as described above, preparation method is also carried out in the present embodiment
It embodies.Three-dimensional electrofocusing's micro-fluidic chip for solid phase microextraction in the present embodiment is mainly used to extract related targeted conjunction
Object 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 through mass spectrograph injection port 600 after three-dimensional electrofocusing's micro-fluidic chip ejection for solid phase microextraction
Carry out sample analysis.Fig. 7 a is illustrated fills solid phase extraction from three-dimensional electrofocusing's micro-fluidic chip bottleneck for solid phase microextraction
Particle micrograph and Fig. 7 b is taken to show spray effect outside the fluid sample sprayed, the loading process extraction of Solid Phase Extraction is full
Start moment mass spectrogram with rear mass spectrogram and Solid Phase Extraction elution.
The above content is combine it is specific/further detailed description of the invention for preferred embodiment, cannot recognize
Fixed specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs,
Without departing from the inventive concept of the premise, some replacements or modifications can also be made to the embodiment that these have been described,
And these substitutions or variant all shall be regarded as belonging to protection scope of the present invention.
Claims (8)
1. a kind of three-dimensional electrofocusing's micro-fluidic chip for solid phase microextraction, which is characterized in that including upper layer and lower layer, 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
Include gas circuit runner and the gas circuit storage pool being connected 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 are formed with the bottleneck structure for storing Solid Phase Extraction 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, two gas circuit runners is divided into halfway, symmetrically
Fluid path runner two sides are distributed in, and are finally communicated at the fluid path runner, nozzle is formed；Upper layer and lower layer merge
The depth of the gas circuit runner be greater 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 middle position of the gas circuit runner of merging, wherein what the fluid path runner was connected with the fluid path storage pool
Section has 235 μm of width, and the section that the fluid path runner is connected with the fluid path storage pool is being filled at bottleneck structure
There is Solid Phase Extraction particle, the section that the fluid path runner is connected with the nozzle has 75 μm of width, the bottleneck structure
Width is 25 μm, and length is 35 μm, and the fluid path runner extracts related target compound by the bottleneck structure, and described in warp
The biphase gas and liquid flow that fluid path runner and the gas circuit runner merge forms the fluid spray form of liquid-in-gas, generates small atomized liquid
Drop.
2. three-dimensional electrofocusing's micro-fluidic chip as described in claim 1, which is characterized in that three-dimensional electrofocusing's microfluid core
Piece material therefor is high polymer dimethyl silicone polymer i.e. PDMS, and three-dimensional focal micro-fluid chip includes the two panels up and down being mutually bonded
PDMS, and two panels PDMS includes flow passage structure；Wherein a piece of PDMS structure sheaf includes gas circuit runner and fluid path runner, in addition
A piece of PDMS substrate layer includes gas circuit runner and fluid path runner, respective gas circuit runner and fluid path stream after two panels PDMS or more merges
Road is corresponding to be merged up and down, alternatively, wherein a piece of PDMS structure sheaf includes gas circuit runner and fluid path runner, other a piece of PDMS substrate
Layer includes gas circuit runner, and respective gas circuit runner is corresponding after two panels PDMS or more merging merges up and down.
3. such as the described in any item three-dimensional electrofocusing's micro-fluidic chips of claim 1 to 2, which is characterized in that the gas circuit runner
With the fluid path runner angle between 0-90 °.
4. such as the described in any item three-dimensional electrofocusing's micro-fluidic chips of claim 1 to 2, which is characterized in that the nozzle has
Width is that 50 μm of contraction is sprayed aperture.
5. such as the described in any item three-dimensional electrofocusing's micro-fluidic chips of claim 1 to 2, which is characterized in that by the gas circuit stream
Road and the fluid path runner are formed by nozzle stripping forming directly from the mold that photoresist is formed.
6. a kind of production method for making three-dimensional electrofocusing's micro-fluid chip described in any one of claim 1 to 5, feature exist
In, the following steps are included:
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 defined in the photoresist exposure process on silicon chip gas circuit runner 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 defining gas circuit runner and gas circuit storage pool in the photoresist exposure process on silicon chip；
During Mold Making, after bottom photoresist is got rid of on the first silicon chip, by gas circuit fluid path layer mask plate to most bottom
Layer photoresist exposure, forms gas circuit fluid path layer after development；After getting rid of upper layer photoresist on the first silicon chip again, covered by gas circuit layer
Film version exposes upper layer photoresist, and gas circuit layer is formed after development, to be used to deepen to expose the gas circuit runner formed for the first time, thus
Produce the mold for corresponding to and forming PDMS structure sheaf；The second silicon chip is repeated the above process again, alternatively, to the second silicon chip
Whirl coating, exposure, the developing process for gas circuit layer mask plate are only carried out, the mould for corresponding to and forming PDMS substrate layer is thus produced
Tool；
Then, PDMS structure sheaf and PDMS substrate layer are separately formed out using corresponding mould；
After again, PDMS structure sheaf and PDMS substrate layer are aligned, one piece of complete three-dimensional focal micro-fluid chip is bonded together to form；
Gas circuit fluid path layer mask plate and gas circuit layer mask plate contain alignment structures, have when for exposing by what photoresist was formed
Structure is aligned in the rear mask plate used.
7. the production method of three-dimensional electrofocusing's micro-fluid chip as claimed in claim 6, which is characterized in that gas circuit fluid path layer is covered
Film version is corresponding to complete that primary or whirl coating, exposure, developing process, the corresponding manufacturing process of gas circuit layer mask plate are complete twice
At at least whirl coating, exposure, developing process three times, so that the thickness of gas circuit runner is much larger than fluid path gate thickness, thus favorably
In liquid from fluid path spray after be suspended in gas, without with flow path wall face contact.
8. the production method of three-dimensional electrofocusing's micro-fluid chip as claimed in claims 6 or 7, which is characterized in that the photoetching
Glue uses SU-8 glue.
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| DE102017202918A1 (en) * | 2017-02-23 | 2018-08-23 | Robert Bosch Gmbh | Sensor device and method for detecting substances in a fluid |
| CN109603932B (en) * | 2018-12-12 | 2020-11-03 | 深圳大学 | Double-focusing micro-fluid chip |
| CN112827517B (en) * | 2019-11-25 | 2023-05-02 | 杭州微著生物科技有限公司 | Use method and device of micro-fluidic chip |
| CN111714931B (en) * | 2020-06-28 | 2024-04-16 | 清华大学深圳国际研究生院 | Permeation type solid phase microextraction micro-fluidic device and manufacturing method thereof |
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| WO2012004296A1 (en) * | 2010-07-09 | 2012-01-12 | Sophion Bioscience A/S | A chip assembly for use in a microfluidic analysis system |
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