CN100507569C - Process for preparing polymer microfluidic chips - Google Patents
Process for preparing polymer microfluidic chips Download PDFInfo
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- CN100507569C CN100507569C CNB2004100427164A CN200410042716A CN100507569C CN 100507569 C CN100507569 C CN 100507569C CN B2004100427164 A CNB2004100427164 A CN B2004100427164A CN 200410042716 A CN200410042716 A CN 200410042716A CN 100507569 C CN100507569 C CN 100507569C
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Abstract
The invention relates to a method for making macromolecule micro flow control chip, which comprises three steps: first etching and making form master model with split channel network on glass, quartz and silicon based plate, then using form master model as matrix to batch press rigid many organic polymer material male mould with dimpling channel network, at last using the male mould as template and adopting mould method to batch press macromolecule micro flow control chip base-plate which has the same split channel network with form master model, then sealing a plate cover on the surface of the said base-plate to form macromolecule micro flow control chip.
Description
Technical field
The invention belongs to the production technical field of micro-fluidic chip, the low-cost simple preparation method that relates to a kind of high polymer micro-flow control chips that is suitable for producing in batches, promptly duplicate a plurality of rigid organic polymer material sun submodules, with the method for making of positive submodule batch molding high polymer micro-flow control chips by cloudy master mold; This method is applicable to the industrialization production of multiple curing type polymkeric substance and solvent evaporates type polymer chip, is particularly useful for the batch process of the disposable chip in the fields such as environmental contaminants detection, biochemical analysis and clinical examination.
Background technology
Micro-total analysis is the emerging analysis technical field that grows up early 1990s.Micro-total analysis is to utilize micro fabrication to pass through to make functional units such as little valve, microchannel, microreactor, microsensor, little detecting device on chip to constitute the very small chemical system, the operations such as pre-treatment, mixing, reaction, separation and detection of sample in the traditional chemical all are integrated in finish on the chip, have fast, efficient, characteristics such as the sample reagent dosage is little.Wherein, micro-fluidic chip is little with volume, analysis speed is fast, flexible etc., and advantage becomes the most active frontier development in this field, has been used for the detection of multiple material, and huge application potential is particularly arranged in biochemical analysis and clinical examination.Micro-fluidic chip promote the use of the low-cost manufacture method that need be suitable for producing in enormous quantities.Therefore, the attention that has been subjected to many developed countries in recent years as the chip material and the Study on Processing Technology on microfluidic analysis chip basis.
At present, the material that is used to make micro-fluidic chip develops into glass, quartz and multiple organic polymer material such as epoxy resin, polymethylmethacrylate (PMMA), polystyrene, dimethyl silicone polymer (PDMS), Polyvinylchloride, phenolics, polyurethane, poly-several lactams etc. from initial silicon chip.Process technology is also developed into new methods such as pressure sintering, method of molding, laser ablation method, LIGA technology and soft lithographic by traditional photoetching and etching technique.Glass and quartzy because good optical property, thermal diffusivity and electric osmose character is the most frequently used material of micro-fluidic chip always.But their shortcoming is the cost of manufacture height, little process complexity, and matter is crisp frangible, must use severe corrosive acid during etching, and reproducible not, be difficult to produce in batches.Organic polymer material is because cheap, easy to process, and being easy to modify characteristics such as assembling and realization batch process becomes the micro-fluidic chip material that has development prospect most.Wherein, because it is dimethyl silicone polymer (PDMS) has low price, excellent electric insulating, desirable optical characteristics and bio-compatibility, reusable, be suitable for producing in batches and be easy to multiple material and form characteristics such as reversible sealing and be widely used as host material in micro-fluidic chip.
The high polymer micro-flow control chips process technology of report has following several method at present:
(1) pressure sintering
Pressure sintering is a kind of method of quick copy high polymer micro-flow control chips, is suitable for the preparation of micro-fluidic chips such as thermoplastic, polymeric materials such as polymethylmethacrylate (PMMA) and polycarbonate.In hot press polymer matrix film is heated to softening temperature, heat-retaining condition is transferred formpiston and is applied certain pressure, can suppress on the polymer matrix film with formpiston on the corresponding concave channel of protruding passage.The silicon mould that used formpiston is normally processed by photoetching and engraving method.(Martynova?L.，Locascio?L.E.，Gaitan?M.，Kramer?G.W.，Christensen?R.G.，MacCrehan?W.A.，Fabrication?of?Plastic?Microfluid?Channels?by?Imprinting?Methods，Anal.Chem.，1997，69，4783-4789)
(2) method of molding
Method of molding also is the process technology of the micro-fluidic superpolymer chip of a kind of quick copy, and fidelity is better than pressure sintering.Make formpiston earlier, then the high polymer material of pouring liquid on formpiston with protruding passage.High polymer material after solidifying and formpiston peeled off promptly get substrate with concave channel.The high polymer material of cast usefulness should have low-viscosity, and low solidification temperature under action of gravity, can be full of microchannel on the mould and groove etc. and locate.This method is usually used in the making of curing type polymer chip and solvent evaporates type polymer chip.
The formpiston that method of molding is commonly used generally is silicon materials, glass, the negative optical cement of epoxy radicals SU-8 and PDMS etc.Silicon formpiston and glass mold plungers are made of photoetching and etching method; Can on the negative optical cement of epoxy radicals SU-8, obtain high-aspect-ratio (20: 1) and the protruding figure of resolution by photoetching, promptly can be used as formpiston after the oven dry of developing up to several microns; Be cast in PDMS on female former that materials such as silicon or glass make, solidify the back and peel off mutually with master mold and promptly obtain the PDMS formpiston.These moulds all have a fatal shortcoming and are unsuitable for large-scale batch process---short life.Silicon materials template and glass template are frangible, and the protruding figure on negative optical cement of epoxy radicals SU-8 and the PDMS template is easy to peel off.(Ng?J.M.K.，GitlinI.，Stroock?A.D.，Whitesides?G.M.，Components?for?IntegratedPoly(dimethylsiloxane)Microfluidic?Systems，Electrophoresis，2002，23，3461-3473)
(3) LIGA technology
The LIGA technology is micro-machined new method, comprises deep layer photoetching, little electroforming and littlely duplicates three steps.The first step is to adopt synchrotron radiation X optical depth layer photoetching, and the figure transfer on the mask to the photoresist that the hundreds of micron thickness is arranged, is obtained the optical cement mould the same with mask graph.Second step was by electrochemical plating the space on the optical cement mould to be filled with metallic nickel on the conductive metal film that utilizes below the photoresist, formed the caster of a nickel that complements one another with the optical cement mode configuration.Copy a plurality of nickel subtemplates with the nickel master mold again.The 3rd step was to make formpiston with the nickel subtemplate, copied a plurality of superpolymer chips with injection moulding.This method is used for the making of PMMA polymer chip more.(McCormick?R.M.，Neison?R.J.，Goretty?Alonso-Amigo?M.，Benvegnu?D.J.，Hooper?H.H.，MicrochnnelElectrophoretic?Separations?of?DNA?in?Injection-molded?Plastic?Substrates.Anal.Chem.，1997，69，2626-2630)
(4) laser is cut the erosion method
Laser cut the erosion method be with Ultra-Violet Laser by the Copper Foil mask focusing on light degradable high polymer material such as polystyrene, polycarbonate, polyphenyl dioctyl phthalate glycol ester, moment forms the recessed figure consistent with mask graph with ablating corresponding to the graphics field on the mask on the superpolymer substrate.Because the Ultra-Violet Laser energy is big, and is big to the human injury, must in special Laser Experiments chamber, carry out, the manufacturing conditions harshness, instrument and equipment is relatively more expensive.(Roberts?M.A.，Rosier?J.S.，Bercier?P.，Girault?H.，UV?Laer?Machined?Polymer?Substrates?for?theDevelopment?of?Microdiagnostic?System，Anal.Chem.，1997，69，2035-2042)
In above-mentioned several superpolymer chip processing methods, though the micro-fluidic superpolymer chip of formpiston quick copy of pressure sintering and the enough preparations of method of molding energy, but a template once can only be duplicated a substrate, and template is perishable not to be durable, and is unsuitable for coml so can only satisfy the needs of laboratory fundamental research and produces in batches.At present, micro-fluidic chip is made the transition to application fields and degree of depth industrialization by fundamental research in the laboratory at initial stage.So seeking industrialization micro-fluidic chip process technology simple to operate, cheap becomes people's question of common concern.
Summary of the invention
The objective of the invention is to propose a kind of low-cost simpler production method of the high polymer micro-flow control chips that is suitable for producing in enormous quantities.For the first time the rigid organic polymer material is used as template, based on stamped method and these two kinds of quick copy technology of method of molding, the master mold system of utilization submodule, the job operation of submodule system substrate realizes the batch making of multiple curing type polymkeric substance and solvent evaporates type high polymer micro-flow control chips.
Technical scheme of the present invention
The method for making of high polymer micro-flow control chips provided by the invention comprises: photoengraving is scribed cloudy master mold, a plurality of rigid organic polymer material sun submodules of imprinting and copying and molding and is duplicated three steps of high polymer micro-flow control chips; The first step that described photoengraving is scribed cloudy master mold is: with wet etching or be dry-etched in and make the cloudy master mold that has recessed microchannel network on the substrate of glass, quartz and silicon material; Positive submodule second step of described imprinting and copying rigid organic polymer material is: the cloudy master mold that has recessed microchannel network that uses first step to make adopts hot pressing or cold-press method to copy the positive submodule of having of a plurality of rigid organic polymer materials of protruding microchannel network; The third step that described method of molding duplicates high polymer micro-flow control chips is: the rigid organic polymer sun submodule of using second step to make is made template and is adopted method of molding to copy the high polymer micro-flow control chips substrate that has with the identical recessed microchannel of described cloudy master mold network, again this high polymer micro-flow control chips substrate with the surface of recessed microchannel network on sealed composite one dull and stereotyped cover plate, promptly make high polymer micro-flow control chips of the present invention;
The cloudy master mold that has recessed microchannel network that described first step makes is for being the cloudy master mold that has recessed microchannel network that is produced on glass, quartz, silicon or the metal substrate;
The positive submodule of the rigid organic polymer material that has protruding microchannel network that described second step makes is the on-chip positive submodule with rigid organic polymer material of having of high softening temperature of protruding microchannel network that is produced on PMMA, polystyrene, epoxy resin, polycarbonate or any one multipolymer material between them;
The high polymer micro-flow control chips substrate that described third step makes is the high polymer micro-flow control chips substrate that has recessed microchannel network that has low solidification temperature and do not react with described positive submodule, and the recessed microchannel network on this high polymer micro-flow control chips is identical with recessed microchannel network on the described cloudy master mold;
The method for making of high polymer micro-flow control chips provided by the invention also can comprise being placed on described the 3rd step the 4th step afterwards; The 4th step is filled for the high polymer micro-flow control chips that obtains being carried out finishing or microchannel.
The present invention only need carry out the complexity of a described cloudy master mold of first step and make, and just can mass-produce high polymer micro-flow control chips.Wherein, the rigid organic polymer sun submodule material that has a protruding microchannel network is that any multipolymer is between the two appointed in polymethylmethacrylate (PMMA), polystyrene, polycarbonate, polyurethane or they; Described high polymer micro-flow control chips substrate material should be not and the material generation chemical reaction of the rigid organic polymer sun submodule that has protruding microchannel network, can be multiple curing type polymkeric substance or solvent evaporates type polymkeric substance, as dimethyl silicone polymer (PDMS) silicon rubber or rubber etc.
The preparation method of high polymer micro-flow control chips provided by the invention, as described below;
1, the making of mask:
With Adobe Illustrator 8.0 software design micro-fluidic chip figures, make mask by high-resolution laser printer.Network graphic district, microchannel is transparent photic zone, and non-graph area is the light tight district of black.
2, the making of cloudy master mold:
A, the cloudy master mold of wet etching
With glass, quartz or the silicon materials that scribble chromium film protective seam and optical cement layer successively is substrate, and mask is covered on this substrate, exposes under UV-irradiation, develops in developer solution then, and the micro-fluidic figure on the mask just is copied on the optical cement layer.Use chromium film etching liquid (cerous sulfate under the room temperature; Perchloric acid: the exposed chromium film of corrosion water=50 grams: 15 milliliters: 300 milliliters), after high purity water is rinsed well, oven dry.Micro-fluidic figure on the optical cement layer is transferred on the substrate.With the hydrofluoric acid solution is etching agent wet etching microchannel figure, controls the etching depth of microchannel by controlling etching time, and this process is lasted a few minutes and do not waited by several hours, and obtaining xsect is trapezoidal recessed microchannel.At last remove optical cement layer remaining on the substrate and chromium film with acetone and chromium film etching liquid successively, rinse well with high purity water and promptly get totally transparent cloudy master mold.
Perhaps
B, the cloudy master mold of dry etching
Be coated with the positive optical cement of last layer on the substrate of glass, quartz or silicon material, behind the low temperature drying, mask covered on the substrate, exposure under the ultraviolet ray irradiation is developed in developer solution then, and the fluid channel figure on the mask is copied on the optical cement layer.Use active CHF
3The plasma etching substrate, no glue pattern district can produce the concave channel or the microstructure of certain depth on the substrate.Remove optical cement remaining on the substrate with acetone at last, rinse well with high purity water and promptly get totally transparent cloudy master mold.
3, the making (as depicted in figs. 1 and 2) of rigid organic polymer sun submodule:
A, pressure sintering are made rigid organic polymer sun submodule
With commercially available rigid organic polymer sheet 2, be cut into a plurality of small pieces by the size of the cloudy master mold 11 of glass, use ethanol, deionized water wash clean successively, nitrogen dries up.This organic polymer sheet 2 and cloudy master mold 11 are clipped between the thick aluminium sheet 3 of two surface finish with " sandwich " sandwich method, and integral body is placed in the hot-press arrangement, heating.When temperature is higher than the softening temperature of organic polymer, after pressurizeing and continuing for some time, be cooled to room temperature under the pressurized conditions, the demoulding can obtain having the rigid organic polymer sun submodule 22 of convex microchannel network.
Perhaps
B, cold-press method are made PMMA sun submodule
Commercially available rigid organic polymer sheet 2 is pressed the cloudy master mold 11 size cuttings of glass, use ethanol, deionized water wash clean successively, nitrogen dries up.Be clipped in this organic polymer sheet 2 and cloudy master mold 11 between the thick aluminium sheet 3 of two surface finish with " sandwich " sandwich method, integral body is placed in the pressue device, pressurization 450 to 2700psi under the room temperature, and the demoulding can obtain having the rigid organic polymer sun submodule 22 of convex microchannel network behind the removal pressure.
4, the making of high polymer micro-flow control chips substrate (as shown in Figure 3):
Method of molding is made the superpolymer chip substrate: in the performed polymer of polymer monomer, preliminary polymerization or the polycondensation of new distillation, the initiating agent that adds appropriate amount, water after the vacuum outgas and cast from the rigid organic polymer sun submodule 22, after the high temperature polymerization, be cooled to room temperature, lift-off stencil must be with the high polymer micro-flow control chips substrate 4 (as shown in Figure 4) with concave channel network.
5, the method for making of high polymer micro-flow control chips (as shown in Figure 5):
The making of A mono-material high polymer micro-flow control chips
Water after will the prepolymer vacuum outgas identical and cast from the sheet glass, after the high temperature polymerization, be cooled to room temperature, peel off glass plate with making superpolymer chip substrate 4, superpolymer cover plate 41.At the liquid storage tank position of the superpolymer chip substrate 4 that has microchannel network structure mechanical punching, after superpolymer chip substrate 4 and 41 surface treatments of superpolymer cover plate, sealing promptly gets mono-material high polymer micro-flow control chips of the present invention (assembly that is made of superpolymer chip substrate 4 and superpolymer cover plate 41 among Fig. 5).According to the difference of material, can select different disposal routes and air-proof condition for use.
The making of B superpolymer hydridization high polymer micro-flow control chips
Cover plate 41 is the various glass that are different from the substrate material that has the microchannel network, quartz or the organic polymer sheet of method preparations such as commercially available, hot padding or method of molding.Liquid storage tank at the superpolymer substrate that has the microchannel network structure is put place's mechanical punching.After superpolymer chip substrate 4 and 41 surface treatments of superpolymer cover plate, seal and promptly get hydridization high polymer micro-flow control chips of the present invention (assembly that constitutes by superpolymer chip substrate 4 and superpolymer cover plate 41 among Fig. 5).According to the difference of selected materials, can adopt different disposal routes and air-proof condition.
Description of drawings
Fig. 1 is a rigid organic polymer sun submodule manufacturing process synoptic diagram;
Fig. 2 is the structural representation of rigid organic polymer sun submodule;
Fig. 3 is the making synoptic diagram of high polymer micro-flow control chips substrate 4;
Fig. 4 is the structural representation of mono-material or hydridization high polymer micro-flow control chips substrate;
Fig. 5 is the structural representation of high polymer micro-flow control chips of the present invention;
Wherein: organic polymer sheet 2 cloudy master mold 11 thick aluminium sheets 3
Rigid organic polymer sun submodule 22 superpolymer chip substrates 4 superpolymer cover plates 41
Embodiment
Embodiment 1:
(1) making of mask
With Adobe Illustrator 8.0 software design micro-fluidic chip figures, make mask by high-resolution laser printer.Network graphic district, microchannel is transparent photic zone, and non-graph area is the light tight district of black.
(2) the cloudy master mold of wet etching glass
The mask that will have the microchannel network covers even glue chromium plate (the chromium type: LRC of 63mm * 63mm * 1.5mm; The thick T:145nm glue of chromium class: positive-working photoresist; Glue is thick: 570nm), 210 seconds (wavelength 365nm) of exposure developed 80 seconds in the developer solution under UV-irradiation, removed the optical cement of network area, microchannel on the chromium plate.High purity water is dried half an hour for 100 ℃ in the baking oven after developer solution remaining on the chromium plate is rinsed well; The chromium film that exposes with chromium film etching liquid (cerous sulfate: perchloric acid: water=50 restrain: 15 milliliters: 300 milliliters) corrosion network place, microchannel under the room temperature 120 seconds is rinsed oven dry then well with high purity water.By the digit microscope shooting, the microchannel width dimensions that records on the chromium plate is 60 μ m.With 0.5M HF/0.5M NH
4The exposed glass in F etching agent corrosion channel network place, speed is about 10 μ m/h, after the etching 2.5 hours, remove optical cement layer and chromium film remaining on the substrate with acetone, chromium film etching liquid successively again, rinse well with high purity water and promptly get the cloudy master mold of the glass that has recessed microchannel network.Record recessed microchannel size by contourgraph: go up bottom width 117 μ m, following bottom width 65 μ m, the degree of depth 25 μ m.
(2) thermal marking method is made PMMA sun submodule
With commercially available rigid organic polymer PMMA sheet material, be cut into the small pieces of a plurality of 63mm of being of a size of * 63mm * 2.0mm, use ethanol, deionized water wash clean successively, nitrogen dries up.PMMA flat board and cloudy master mold " sandwich " sandwich method are clipped between the thick aluminium sheet of two surface finish, and integral body places hot-press arrangement.When temperature is higher than the softening temperature (106 ℃) of PMMA, when reaching 110～115 ℃, add 1.0～1.2MP pressure, 30～60s after, water flowing is cooled to room temperature, the demoulding can obtain having the PMMA sun submodule of protruding microchannel.Aforesaid operations is 100 times continuously, records the average protruding microchannel size of these PMMA sun submodules by contourgraph: go up bottom width 66 μ m, following bottom width 120 μ m, height 25.2 μ m.This shows that this method has higher fidelity, saved the complex process of many glass template etching.
(3) making of dimethyl silicone polymer (PDMS) chip
The A method of molding is made the PDMS substrate: PDMS monomer (dimethyl siloxane) is mixed with the part by weight of initiating agent (Sylard184) with 10: 1, water after the degassing and cast from 50 PMMA sun submodules,, be cooled to room temperature 65 ℃ of polymerizations 1.5 hours, lift-off stencil gets water white transparency PDMS substrate.Electron-microscope scanning records the on-chip average recessed microchannel of these PDMS size: go up bottom width 120.5 μ m, following bottom width 66.2 μ m, the degree of depth 25.1 μ m.
The making of B PDMS cover plate: PDMS monomer (dimethyl siloxane) is mixed with the part by weight of initiating agent (Sylard184) with 10:1, water after the degassing and cast from the clean glass sheet,, be cooled to room temperature 65 ℃ of polymerizations 1.5 hours, lift-off stencil gets water white transparency PDMS cover plate.
The PDMS substrate that C will have the microchannel network structure is cut into identical size with dull and stereotyped PDMS cover plate.The cylindrical hole that diameter is 5mm is beaten with card punch in liquid storage tank position at substrate, as the chip liquid storage tank.
After D will have the PDMS substrate of microchannel network structure and dull and stereotyped PDMS cover plate and clean with absolute ethyl alcohol, dry up in the clean cabinet, in distance 6W low pressure mercury lamp 3cm place's illumination 3 hours.After the taking-up, in 1 minute, two are closed up, on smooth glass sheet, place 48h, promptly obtain the PDMS micro-fluidic chip of irreversible sealing.
Embodiment 2:
(1) the cloudy master mold of dry etching glass
With the glass sheet of 63mm * 63mm * 1.5mm with acetone, high purity water wash clean successively after, oven dry.On glass sheet, get rid of positive photoresist BP-213 with photoresist spinner, 90 ℃ of following preliminary dryings 5 minutes.The set mask that has the microchannel network is covered on the glass sheet of gluing, 120 seconds (wavelength 365nm) of UV-irradiation exposure developed 80 seconds in the developer solution, removed the optical cement of network area, microchannel on the chromium plate.After with high purity water developer solution remaining on the glass sheet being rinsed well, 100 ℃ of baking half an hour in the baking oven.Use active CHF
3The network area, microchannel of no glue on the plasma etching glass sheet has just formed the microchannel network of spill on the glass sheet.Record recessed microchannel size by contourgraph: go up bottom width 120 μ m, following bottom width 60 μ m, the degree of depth 29.5 μ m.
(2) cold-press method is made PMMA sun submodule
A is cut into the small pieces of a plurality of 63mm of being of a size of * 63mm * 2.0mm with commercially available rigid organic polymer PMMA sheet material, uses ethanol, deionized water wash clean successively, and nitrogen dries up.Be clipped between the thick aluminium sheet of two surface finish with cloudy master mold " sandwich " sandwich method PMMA is dull and stereotyped, integral body is placed in the pressue device, and the 2500psi that pressurizes under the room temperature removes the demoulding behind the pressure, can obtain having the positive submodule of PMMA of convex microchannel network.Aforesaid operations is 100 times continuously, records the average protruding microchannel size of these PMMA sun submodules by contourgraph: go up bottom width 60.3 μ m, following bottom width 120.1 μ m, height 29.5 μ m.
(3) make PDMS/ glass hydridization chip
The A method of molding is made the PDMS substrate: PDMS monomer (dimethyl siloxane) is mixed with the part by weight of initiating agent (Sylard184) with 10: 1, water after the degassing and cast from 50 PMMA sun subtemplates, 65 ℃ of polymerizations 1.5 hours, be cooled to room temperature, lift-off stencil must have the water white transparency PDMS substrate of spill microchannel network.Electron-microscope scanning records the on-chip average recessed microchannel of these PDMS size: go up bottom width 120.3 μ m, following bottom width 60.5 μ m, the degree of depth 29.3 μ m.
B is cut into the size of 70mm * 70mm with flat glass film, soaks 1 hour in potassium bichromate solution earlier, and after rinsing well with deionized water then, nitrogen dries up.
C beats the cylindrical hole that diameter is 5mm in the liquid storage tank position of the PDMS substrate that has the microchannel network structure with card punch, as the chip liquid storage tank.With acetone ultrasonic cleaning 5 minutes, after rinsing well with deionized water, nitrogen dried up again earlier.In distance 6W low pressure mercury lamp 3cm place's illumination 3 hours, after the taking-up, in 1 minute, PDMS substrate and sheet glass are closed up, place the PDMS/ glass hydridization chip that promptly obtains irreversible sealing on the smooth glass sheet behind the 48h.
Embodiment 3:
The cloudy master mold of wet etching glass
The mask that will have the microchannel network covers even glue chromium plate (chromium type: LRC; The thick T:145nm glue of chromium class: positive-working photoresist; Glue is thick: 570nm), 210 seconds (wavelength 365nm) of ultraviolet ray irradiation exposure developed 80 seconds in the developer solution, removed the optical cement of network area, microchannel on the chromium plate.High purity water is dried half an hour for 100 ℃ in the baking oven after developer solution remaining on the chromium plate is rinsed well; With chromium film etching liquid (cerous sulfate: perchloric acid: water=50 restrain: 15 milliliters: 300 milliliters) the exposed chromium film in etch pattern place, rinse oven dry then well with high purity water under the room temperature.By the digit microscope shooting, the microchannel width dimensions that records on the chromium plate is 60 μ m.Use 0.5MHF/0.5M NH
4The exposed glass in zone, F etching agent corrosion microchannel, speed is about 10 μ m/h, and etching is removed residual light glue-line and chromium film with acetone, chromium film etching liquid after 2.5 hours more successively, rinses well with high purity water and promptly gets the cloudy master mold of the glass that has recessed microchannel network.Record recessed microchannel size by contourgraph: go up bottom width 117 μ m, following bottom width 65 μ m, the degree of depth 25 μ m.
(2) thermal marking method is made PMMA sun submodule
With commercially available rigid organic polymer PMMA sheet material, be cut into the sheet of a plurality of 63mm of being of a size of * 63mm * 2.0mm, use ethanol, deionized water wash clean successively, nitrogen dries up.PMMA flat board and cloudy master mold " sandwich " sandwich method are clipped between the thick aluminium sheet of two surface finish, and integral body places hot-press arrangement.When temperature is higher than the softening temperature (105 ℃) of PMMA, when reaching 110～115 ℃, add 1.0～1.2MP pressure, 30～60s after, water flowing is cooled to room temperature, the demoulding can obtain having the PMMA sun submodule of protruding microchannel.Aforesaid operations is 100 times continuously, records the average protruding microchannel size of these PMMA sun submodules by contourgraph: go up bottom width 66 μ m, following bottom width 120 μ m, height 25.2 μ m.
(3) make the PDMS/PMMA chip
The A method of molding is made the PDMS substrate: PDMS monomer (dimethyl siloxane) is mixed with the part by weight of initiating agent (Sylard184) with 10: 1, water respectively after the degassing and cast from 50 PMMA sun submodules, 60 ℃ of polymerizations 2 hours, be cooled to room temperature, lift-off stencil must have the water white transparency PDMS substrate of spill microchannel network.Electron-microscope scanning records the on-chip average recessed microchannel of these PDMS size: go up bottom width 120.5 μ m, following bottom width 66.2 μ m, the degree of depth 25.1 μ m.
B is cut into the size identical with the PDMS substrate with dull and stereotyped PMMA sheet, use ethanol, deionized water rinsing clean successively after, nitrogen dries up.
C beats the cylindrical hole that diameter is 5mm in the liquid storage tank position of the PDMS substrate that has the microchannel network structure with card punch, as the chip liquid storage tank.With acetone ultrasonic cleaning 5 minutes, after rinsing well with deionized water, nitrogen dried up again earlier.In distance 6W low pressure mercury lamp 3cm place's illumination 3 hours, after the taking-up, in 1 minute,, place the PDMS/PMMA hydridization chip that promptly obtains irreversible sealing on the smooth glass sheet behind the 48h with PDMS substrate and dull and stereotyped PMMA sheet.
Claims (4)
1, a kind of method for making of high polymer micro-flow control chips is characterized in that, comprising: photoengraving is scribed cloudy master mold, a plurality of rigid organic polymer material sun submodules of imprinting and copying and molding and is duplicated three steps of high polymer micro-flow control chips; The first step that described photoengraving is scribed cloudy master mold is: with wet etching or be dry-etched in and make the cloudy master mold that has recessed microchannel network on the substrate of glass, quartz and silicon material; Positive submodule second step of described imprinting and copying rigid organic polymer material is: the cloudy master mold that has recessed microchannel network that uses first step to make adopts hot pressing or cold-press method to copy the positive submodule of having of a plurality of rigid organic polymer materials of protruding microchannel network; The third step that described method of molding duplicates high polymer micro-flow control chips is: the rigid organic polymer sun submodule of using second step to make is made template and is adopted method of molding to copy the high polymer micro-flow control chips substrate that has with the identical recessed microchannel of described cloudy master mold network, again this high polymer micro-flow control chips substrate with the surface of recessed microchannel network on sealed composite one dull and stereotyped cover plate, promptly make high polymer micro-flow control chips of the present invention.
2, the method for making of high polymer micro-flow control chips as claimed in claim 1, it is characterized in that the positive submodule of the rigid organic polymer material that has protruding microchannel network that described second step makes is the on-chip positive submodule with rigid organic polymer material of having of high softening temperature of protruding microchannel network that is produced on polymethylmethacrylate, polystyrene, epoxy resin or polycarbonate material.
3, the method for making of high polymer micro-flow control chips as claimed in claim 1, it is characterized in that, the high polymer micro-flow control chips substrate that described third step makes is the high polymer micro-flow control chips substrate that has recessed microchannel network that has low solidification temperature and do not react with described positive submodule, and the on-chip recessed microchannel of this high polymer micro-flow control chips network is identical with recessed microchannel network on the described cloudy master mold.
4, the method for making of high polymer micro-flow control chips as claimed in claim 1 is characterized in that, also comprises being placed on described the 3rd step the 4th step afterwards: the 4th step is filled for the high polymer micro-flow control chips that obtains being carried out finishing or microchannel.
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| CNB2004100427164A CN100507569C (en) | 2004-05-21 | 2004-05-21 | Process for preparing polymer microfluidic chips |
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| CN100406888C (en) * | 2006-02-28 | 2008-07-30 | 东北大学 | Method for producing passive micro-mixer and micro-reactor in micro-flow control chip |
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| CN102001615B (en) * | 2010-09-02 | 2012-05-09 | 浙江大学 | Method for preparing high polymer nanofluidic chip |
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| CN102198926A (en) * | 2011-04-06 | 2011-09-28 | 哈尔滨工业大学 | Micro-channel processing method for micro-fluidic chip |
| CN102721820B (en) * | 2012-05-21 | 2013-11-13 | 浙江大学 | Method for preparing assembly type polymer micro fluidic chip equipped with integrated pneumatic micro valve |
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| CN102962107B (en) * | 2012-11-13 | 2014-08-20 | 浙江大学 | Manufacture method for three-dimensional micro-fluidic chip |
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| CN105538587B (en) * | 2016-01-22 | 2018-07-06 | 苏州汶颢芯片科技有限公司 | Soft chip adapted to injection system and the method for making soft chip |
| CN107305214B (en) * | 2016-04-22 | 2019-01-04 | 清华大学 | A kind of production method of hard micro-fluid chip |
| CN106540762B (en) * | 2016-11-09 | 2018-05-25 | 太原理工大学 | The preparation method of polystyrene micro-fluidic chip under a kind of room temperature |
| CN107262173B (en) * | 2017-08-03 | 2020-04-17 | 广东顺德工业设计研究院(广东顺德创新设计研究院) | PDMS (polydimethylsiloxane) micro-fluidic chip and method for preparing PDMS micro-fluidic chip based on wet etching |
| CN108545692B (en) * | 2018-03-27 | 2020-12-08 | 浙江大学 | Method for manufacturing microfluidic chip with inner wall of channel coated with parylene |
| CN109550526A (en) * | 2018-12-04 | 2019-04-02 | 西北农林科技大学 | A kind of micro-fluidic chip prepares mold and its preparation process and application |
| CN109823030B (en) * | 2018-12-30 | 2022-01-21 | 深圳博华仕科技有限公司 | Micro-fluidic chip printing system and printing method |
| CN112808335B (en) * | 2021-01-21 | 2022-03-01 | 中国科学技术大学 | Preparation method of micro-fluidic chip for multi-parameter detection of water body |
| CN117244599B (en) * | 2023-11-15 | 2024-02-02 | 湘潭大学 | Method for manufacturing PDMS micro-fluidic chip |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001157855A (en) * | 1999-12-03 | 2001-06-12 | Inst Of Physical & Chemical Res | Microchip for capillary gel electrophoresis and method of manufacture |
| CN1320818A (en) * | 2001-04-23 | 2001-11-07 | 清华大学 | Process for preparing capillary electrophoresis chip used in chemical analysis |
| CN1464303A (en) * | 2002-06-20 | 2003-12-31 | 中国科学院理化技术研究所 | Process for preparing high polymer micro-flow control chips |
-
2004
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001157855A (en) * | 1999-12-03 | 2001-06-12 | Inst Of Physical & Chemical Res | Microchip for capillary gel electrophoresis and method of manufacture |
| CN1320818A (en) * | 2001-04-23 | 2001-11-07 | 清华大学 | Process for preparing capillary electrophoresis chip used in chemical analysis |
| CN1464303A (en) * | 2002-06-20 | 2003-12-31 | 中国科学院理化技术研究所 | Process for preparing high polymer micro-flow control chips |
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