A kind of method and application for preparing three-dimensional micro-pipe or cavity
Technical field
The present invention relates to a kind of method and application for preparing three-dimensional micro-pipe or cavity.
Background technology
The processing of three-dimensional micro-pipe or cavity will be processed little ditch and microflute (Fig. 1) usually earlier, more little ditch or microflute is closed, and just the encapsulation bonding of often saying (Fig. 2) stacks bonding with substrate and the cover plate aligning that is processed with little groove; The encapsulation back forms microchannel and the microcavity body (Fig. 3) that needs.The advantage of this method is that groove can pass through conventional manufacturing process, and high-precision realization still, can realize the method for high precision encapsulation at present, has only anode linkage, eutectic bonding etc.The plastic and glass micro-fluid chip encapsulates methods such as available thermocompression bonding, gluing, adhesive sticker stickup.
Anode linkage is at a certain temperature with silicon chip and a kind of special Pyrex that contain alkali metal atom (lithium or sodium), by apply high-voltage electric field between silicon and glass, makes the method that forms permanent bonding between silicon and glass.The condition that anode linkage requires is than higher: 1) glass used of bonding must contain alkali metal ion lithium or sodium, at a certain temperature, can move under electric field action, make glass and silicon interface form one deck oxygen-rich layer, the silicon atom of oxygen and silicon chip forms very strong chemical bond; 2) thermal expansivity of glass must with the matched coefficients of thermal expansion of silicon, and the glass heatproof generally will be more than 200 ℃, like this in temperature behind the high temperature bonding when dropping to room temperature more than 200 ℃, glass just can not break because of the greatest differences that exists between thermal expansivity and silicon, and this is one of essential condition that realizes anode linkage; 3) glass and silicon face flatness will be got well, and surface step 100nm is above just can to examine under a microscope step tangible bonding region not on every side.On silicon chip, make pipeline, use the encapsulation of soda-lime glass (for example the Pyrex7740 of Corning etc.) anode linkage to form closed conduct again, have only this method can guarantee to encapsulate to finish the not variation of size of back pipeline and cavity.The condition strictness that anode linkage requires, and conductive wafer apply the situation of high pressure such as this needs of Capillary Electrophoresis, and anode linkage is also inapplicable.Monocrystalline silicon piece and contain alkali metal atom can be all very high with the glass price of silicon matched coefficients of thermal expansion, cause the cost of anode linkage chip very high.
Eutectic bonding need be made large-area metal level at substrate surface, can't use in the microfluid field equally.
Adopt plastic and glass to make microchannel and microcavity body, process groove on these materials, precision can guarantee, still will accomplish high-precision encapsulation, does not also have a kind of very efficient ways.The most frequently used is thermocompression bonding: the plastic sheet that will process groove adds certain pressure with the plastic sheet that another piece is used for encapsulating to good position, is heated near the resin glass temperature, keeps certain hour, and two sector-meetings are bonded to together.There is the shortcoming of following several respects in the encapsulation of this method: 1) a little less than the adhesion, though can satisfy common use, as running into bigger external force collision, bonding face can separate behind the bonding; 2) size of original pipeline and cavity changes through bonding hot pressing meeting behind the bonding, and this variation has certain uncertainty, is difficult to control; 3) control electrode is difficult to integratedly, because bonding temperature is higher, it is very big that the thermal expansivity of metal and plastics differs, and when temperature was elevated to certain numerical value, plastics will be broken metal wire, for the integrated difficulty of metal control electrode of the not enough micron of thickness; 4) two of bonding parts also have the position corresponding relation if all have between figure and figure, accurately aiming at needs special instrument and equipment to realize; 5) in bonding process because plastics softening also can cause displacement, even before the bonding to very will definitely two parts, through hot pressing, also can send out small skew, influence alignment precision.
With respect to the thermocompression bonding packaged type, also have gluing method, adopt liquid gluing, glue can flow in the small groove and destroy groove structure, is difficult to control on the processes.The adhesive sticker mode only bonds and to be fit to encapsulating structure to have a side at least be the situation of soft material, and be not suitable for the little situation of gash depth, because the adhesive sticker above the self-adhesive film is to have certain thicknessly, for the very shallow situation of groove, adhesive sticker also can obviously change the depth dimensions of groove.If the material of two bondings is all very thick very hard, can there be a large amount of bubbles in bonding face, causes leaking gas leakage and can't use.
Sacrificial layer technology is a kind of micro-processing technology that has extensively used in the MEMS field.In the cavity or mobilizable microstructure process that form micro mechanical structure, on lower film, make required various special construction spares earlier with structured material, method with chemical etchant or dissolving erodes this layer film again, but do not damage parts with microstructure, obtain superstructure (cavity or parts with microstructure) then.Because the lower film that is removed only plays the separating layer effect, so be called sacrifice layer.Sacrificial layer technology is usually used in making three-dimensional cantilever design, three-dimensional tube and cavity, in the microfluid processing use is arranged also.Conventional sacrificial layer technology is applicable to the situation that three-dimensional dimension is less, and such as semi-girder, several microns to tens micron thickness, tens microns wide, 100 microns long solid beams.Certainly, also the someone is used for making micro-fluid chip, make the positive photoresist of figure by lithography as sacrifice layer such as using, after the covering of Parylene (Parylene) deposition, the stomidium etching of pipeline is come out, entire chip is put into acetone soak, with acetone positive photoresist is dissolved and form the microfluid pipeline.Because the microfluid size has only tens microns square xsects usually, the length of several centimetres even tens centimetres is but arranged, the sacrifice layer of whole pipe is all dissolved needs several to dozens of hours.The sacrifice layer of pipe end is easy to dissolving, but the saturated solution of lysed sacrifice layer need just can leave the interface through diffusion, and novel solvent need could arrive the interface by diffusion and continue the dissolving sacrifice layer.This diffusion process is along with the lengthening of lysigenous duct length, and the mass exchange that diffuses to form is slow more, difficult more, thus with conventional sacrificial layer technology make the microfluid pipeline time long, efficient is low.
U.S. Gergia Tech Research Corporation applied for a series of patents in 2004, propose a kind of sacrificial layer technology and make micro-fluid chip, they adopt under the low temperature can thermal decomposition organic material as sacrifice layer, after making structural sheet on the sacrifice layer, make the sacrificial layer material thermal decomposition form pipeline by heating.The advantage of this method avoids foregoing sacrifice layer to remove difficulty and pipeline precision control problem, still, the organism that low temperature can decompose down, uncommon means can access.Their patent series has also comprised the organic compound that some can low-temperature decomposition, and these compounds are not the chemical materials that generally uses, and needs special synthetic.In addition, between structural sheet and sacrifice layer, also will increase one deck inorganic material and make structural sheet and sacrifice layer separately, otherwise structural sheet and sacrifice layer can be had an effect, and make the structural sheet sex change.Sacrifice layer is removed still needs 1 to 2 hours time, and this method is used significant limitation.
Summary of the invention
The purpose of this invention is to provide a kind of method and application for preparing three-dimensional micro-pipe or cavity.
The method for preparing three-dimensional micro-pipe or cavity of the present invention, be to coat the solid mould of making by material 2 (low melting point sacrificial layer material) with material 1 (high-melting-point structural material) to form clad, described solid mould is identical with three-dimensional micro-pipe or cavity geometry, described clad is provided with at least one liquid flowing outlet, and the fusing point of described material 1 is greater than the fusing point of material 2; Be lower than under the temperature of fusing point of material 1 at the fusing point that is higher than material 2 then, remove described solid mould, obtain three-dimensional micro-pipe or the cavity made by material 1.
Wherein, described clad is provided with at least two liquid flowing outlets.The fusing point of described material 1 is greater than at least 1 ℃ of the fusing point of material 2.
This method is based on that the phase transformation of material realizes, by heating material 2 is undergone phase transition, and from solid-state liquefy or gaseous state, the material of liquid state or gaseous state is easy to be removed, and stays the microstructure of the microchannel, microcavity body and the various three-dimensionals that need.Because the effect of low melting point sacrificial layer material just forms structure, in final structure, do not have the low melting point sacrificial layer material, therefore, this is a kind of sacrificial layer technology, is referred to as hot sacrificial layer technology.This hot sacrificial layer technology is different with conventional sacrificial layer technology, and conventional sacrificial layer technology is with solvent the sacrifice layer dissolving to be removed, or with mordant sacrifice layer corrosion is fallen, and only keeps structural sheet, forms three-dimensional various structure.Hot sacrificial layer technology whole low melting point sacrificial layer material in process all melts, whole removing is removed, from being heated to the fusing of low melting point sacrificial layer material, to the low melting point sacrificial layer material is removed the time that only needs a few minutes, this time is subjected to the influence of planform little again.
One of key point of the present invention be the high-melting-point structural material can be under the melting temperature that is lower than the low melting point sacrificial layer material can be by liquid synthetic or gas solidify the low melting point sacrificial layer material coated, form the structure that the high-melting-point structural material coats the low melting point sacrificial layer material.
The method of described formation clad is low temperature monomer polymerization, physical vapour deposition (PVD), liquid deposition or chemical vapor deposition.
The low temperature monomer polymerization is under the melting temperature that is lower than the low melting point sacrificial layer material, monomer and initiating agent by liquid state carry out polymerization, the fusing point of synthetic high-melting-point structural material, be higher than the low melting point sacrificial layer material, or the decomposition temperature of high-melting-point structural material is higher than the fusing point of low melting point sacrificial layer material.Physical vapour deposition (PVD) is that the high-melting-point structural material is heated into gaseous state in a container, by pipeline the gas feeding is filled in the container of low-melting described solid mould, the high-melting-point structural material is freezed on low melting point sacrificial layer material surface, also can form the structure that the high-melting-point structural material coats the low melting point sacrificial layer material.Liquid deposition is the high-melting-point structural material to be deposited on low melting point sacrificial layer material surface become coated state from solution, can be the crystallization process of hypersaturated state solution, also can be deposition process such as plating.Chemical vapor deposition is under the melting temperature that is lower than the low melting point sacrificial layer material, and in the container of the low-melting described solid mould of splendid attire, several gas generation chemical reactions form the structure that dystectic material coats the low melting point sacrificial layer material.
Material heats up because entire method needs a person with the qualifications of a general, and cryogenic material thermal expansion meeting causes the high-melting-point structural material to bear very big stress, and therefore, described high-melting-point structural material thermal expansivity needs and the low melting point sacrificial layer material is complementary.Dystectic material can be that resilient material also can be a non-elastic material; For non-elastic material, the thermal expansivity of used low melting point sacrificial layer material is littler than high-melting-point structural material.The thermal expansivity of low melting point sacrificial layer material has negative temperature coefficient the best.The high-melting-point structural material is if resilient material, can be any value to the thermal expansivity of low melting point sacrificial layer material.
Described resilient material can be dimethyl silicone polymer, organic silica gel, EVA, epoxy resin, polyurethane or polyamide.PDMS can be in 50-100 ℃ mixes the back by the monomer of liquid state and initiating agent and solidifies and form, and PDMS can maintain a good state under 200 ℃, itself is elastomeric material, and the material of PDMS does not undergo phase transition under the temperature that is lower than its fusing point or softening point.
Described material 2 can be metal, alloy or plastics.Be lower than under the high-melting-point structural material melting temperature, these materials can dissolve into liquid and take out smoothly.Described metal can be indium.It is that low-melting alloy, tin are that low-melting alloy, bismuth are that low-melting alloy, lead are that low-melting alloy or gallium are low-melting alloy that described alloy can be indium.Described alloy specifically can be SnPb alloy or InSn alloy.Alloy related among the present invention can be the alloy of various different proportion of composing.Described plastics are polymethylmethacrylate, polycarbonate, nylon or the like.
Prepare in the method for three-dimensional micro-pipe or cavity, can be by the described solid mould that the low melting point sacrificial layer material is made with existing several different methods preparation, as photoetching corrosion, casting, injection mo(u)lding, mechanical stamping, cut, machining etc.The micro-processing technology of photoetching corrosion can be realized the High Accuracy Control of line size.
The method of the described solid mould of the little processing of photoetching corrosion is as follows:
1) the three-dimensional structure layer of making adhesion layer, indium metal layer successively and being complementary at substrate surface with three-dimensional micro-pipe or cavity geometry;
2) plated metal indium is removed described adhesion layer and three-dimensional structure layer, obtains described solid mould.
Wherein, described solid mould also can pass through surfacing, and described surfacing is that described solid mould is rapidly heated it more than fusing point, again cooling fast.
Another key point of the present invention is that the low melting point sacrificial layer material can or take place under the temperature of thermal denaturation at the melting temperature that is lower than the high-melting-point structural material that coats it, form flowable liquid, flowable liquid can flow out automatically or remove by methods such as suction, air pressure discharges.Can with the way of decompression suction, the low melting point sacrificial layer material that melts be pumped out from outlet one end of pipeline for the microfluid pipeline; Also can carry out air pressure with gases at high pressure to a port with the microfluid pipeline discharges; With the PDMS pipeline that the SnPb alloy welding wire is made, behind wire melting, the SnPb of fusing can flow out automatically, without any need for external force.
The method for preparing three-dimensional micro-pipe or cavity of the present invention is applicable to that the high-melting-point structural material is that in elastic material structure or the high-melting-point structural material structure part material to be arranged be the structure of resilient material, and low melting point sacrificial layer material thermal expansivity is less than or equal to the high-melting-point structural material or with the material of temperature rising smaller volume.
The method for preparing three-dimensional micro-pipe or cavity of the present invention can be applicable in the preparation electrocapillary phoresis chip.
The method for preparing three-dimensional micro-pipe or cavity of the present invention does not have encapsulation step, the fast efficient height of process velocity, and can guarantee the dimensional accuracy of microchannel and microcavity body.The dimensional accuracy of three-dimensional structure depends on the machining precision of low melting point sacrificial layer material, utilizes micro-processing technology promptly can make high-precision low-melting described solid mould.The method for preparing three-dimensional micro-pipe or cavity of the present invention does not have Alignment Process and bonding technology step, therefore can simplify technology, reduce technology difficulty, and being easy to make the cross section is round pipeline and cavity, the fusing point of material therefor is all more than room temperature, be easy to process, especially be fit to three-dimensional micro-pipe or cavity with elastic material.
Description of drawings
Fig. 1 is substrate surface processing microflute.
Fig. 2 is substrate and cover plate parallel alignment encapsulation bonding.
Fig. 3 is the good microchannel skeleton view of bonding.
Fig. 4 is for through surfacing and mould three-dimensional micro-pipe coupling.
Fig. 5 is for removing microchannel or the microcavity body that the low melting point sacrificial layer material forms substrate and high-melting-point structural material formation.
Fig. 6 bends the Capillary Electrophoresis sample channel for the metallic tin galvanized wire.
Fig. 7 bends the capillary electrophoresis separation pipeline for the metallic tin galvanized wire.
Fig. 8 places for sample channel and separating pipe intersection that the metallic tin galvanized wire is made, and the cross intersection point drips one 502 gluing connecing.
Fig. 9 is that the 502 gluing crosses that connect link amplification assumption diagram.
Figure 10 puts into the PDMS monomer for the plumbous structure of the tin that will make, solidifies PDMS.
Figure 11 forms microchannel for removing tin galvanized wire structure.
Figure 12 deposits Cr on the glass substrate.
Figure 13 applies photoresist on the indium metal.
Figure 14 electroplates window for the photoetching Capillary Electrophoresis.
Figure 15 adds charging plating window for the plated metal indium.
Figure 16 is for removing photoresist.
Figure 17 erodes the Metal Cr that is not covered by the plated metal indium, forms the mould of Capillary Electrophoresis coupling.
Figure 18 is the finishing mould.
Figure 19 is the die surface after repairing.
Figure 20 is the organic silica gel full solidification.
Figure 21 is for making port.
Figure 22 is whole the intensification, removes low-melting indium metal, forms capillary electrophoresis chip.
Embodiment
Following embodiment is an example to make the electrocapillary phoresis chip, illustrates the method for making three-dimensional micro-pipe of the present invention or cavity.
Embodiment 1, making capillary electrophoresis chip
One, makes solid mould with the low-melting-point metal line
Low-melting-point metal is selected the SnPb alloy for use, 63% Sn wherein, and 37% Pb, the fusing point of its alloy are 183 ℃.
The low-melting-point metal line is made solid mould and is comprised the steps:
1) gets two sections alloy silks, curve Fig. 6 and shape shown in Figure 7, as the sample channel and the separating pipe of electrophoresis;
2) it is good to bend good pipeline cross fixation, forms shape as shown in Figure 8;
3) fit tightly at middle right-angled intersection place two pipelines, with the solid mould of a bonding formation structure shown in Figure 9 of 502 glue;
Two, with solid Mold Making electrocapillary phoresis chip
1) the solid mould that will fix and bond is put into the PDMS dimethyl silicone polymer performed polymer (monomer and initiating agent were according to 10: 1 proportionings) for preparing and is mixed, and the degassing 20 minutes in vacuum drying oven then makes among the PDMS bubble remove fully; PDMS adopts Dowcorning Sylgard 184.
2) intensification is solidified: the vacuum drying oven venting, and be warming up to 80 ℃ and solidified 2 hours, form structure as shown in figure 10, take out;
3) in a vacuum, be warmed up to 200 ℃, the metal alloy after the fusing can flow out automatically, forms structure shown in Figure 11;
4) cooling is taken out, and uses the acetone rinsing pipe interior, and 502 glue are rinsed well, obtains the electrocapillary phoresis chip.
Embodiment 2, making capillary electrophoresis chip
One, the low-melting-point metal line is made solid mould
Low-melting-point metal is selected the InSn alloy for use, wherein 52%In and 48%Sn, 118 ℃ of fusing points.
The low-melting-point metal line is made solid mould and is comprised the steps:
1) gets two sections alloy silks, curve Fig. 6 and shape shown in Figure 7, as the sample channel and the separating pipe of electrophoresis;
2) it is good to bend good pipeline cross fixation, forms shape as shown in Figure 8;
3) fit tightly at middle right-angled intersection place two pipelines, with the solid mould of a bonding formation structure shown in Figure 9 of 502 glue;
Two, with solid Mold Making electrocapillary phoresis chip
1) the solid mould that will fix and bond is put into the PDMS dimethyl silicone polymer performed polymer (monomer and initiating agent were according to 10: 1 proportionings) for preparing and is mixed, and outgases 20 minutes in vacuum drying oven then; PDMS adopts Dowcorning Sylgard 184.
2) intensification is solidified: the vacuum drying oven venting, and be warming up to 80 ℃ and solidified 2 hours, form structure as shown in figure 10, take out;
3) in a vacuum, be warmed up to 200 ℃, the metal alloy after the fusing can flow out automatically, forms structure shown in Figure 11;
4) cooling is taken out, and uses the acetone rinsing pipe interior, and 502 glue are rinsed well, obtains the electrocapillary phoresis chip.
Embodiment 3, making capillary electrophoresis chip
One, low-melting-point metal is made solid mould
Make microstructure, 167 ℃ of the fusing points of indium metal with indium metal as the low melting point sacrificial layer material.
1) at glass substrate surface sputter one deck 50
Metal Cr, sputter one deck 1000 then
Metal In, form structure shown in Figure 12;
2) coating photoresist forms structure shown in Figure 13:
The method of coating photoresist is as follows: spin coating AZ4620 photoresist, the thickness of photoresist are determined with big height by the xsect of microchannel, highly are 20 microns pipeline, and the thickness of gluing should be greater than 20 microns;
A) spin coating AZ4620: initial velocity 300rpm, acceleration 50krpm/sec, 3 seconds, spin coating, 2500rpm, 60 seconds, acceleration 50krpm/sec, 10 microns of glue thickness;
B) preceding baking: 110 ℃, 90 seconds;
C) secondary spin coating AZ4620: initial velocity 300rpm, acceleration 50krpm/sec, 2 seconds, spin coating: 1600rpm, 60 seconds, acceleration 50krpm/sec, 14 microns of glue thickness, 24 microns of photoresist gross thickness;
D) baking before the secondary: 110 ℃, 90 seconds.
3) photoetching making is electroplated window, forms structure shown in Figure 14:
A) exposure: with mask 15.3mw/cm on the EV620 litho machine that Austrian company produces
2Exposure, 180 seconds;
B) develop: 0.2%NaOH solution developed about 180 seconds.
4) indium plating 10, and 20 microns of thickness form structure shown in Figure 15:
Electroplate liquid: amidosulphuric acid indium 105.36 grams per liters, amidosulphuric acid sodium 150 grams per liters, sulfaminic acid 26.4 grams per liters, sodium chloride 45.84 grams per liters, glucose 8.0 grams per liters, triethanolamine 2.29 grams per liters, pH=2; 20 milliamperes/square centimeter of current densities were electroplated 20 microns of thickness 30 minutes.
5) remove photoresist and form structure shown in Figure 16, ultrasonic acetone soaked 1 minute, repeated 3 times, washed 3 times with absolute ethyl alcohol again, and deionized water rinsing is clean.
6) remove indium and the chromium that does not have plated metal indium zone, as shown in figure 17:
With the mixed liquor corroding metal chromium of cerous ammonium nitrate, perchloric acid, water, cerous ammonium nitrate: perchloric acid: water=50g: 12ml: 300ml; Rare nitric acid corroding metal indium with 10: 1.
7) surfacing obtains structure as shown in figure 18, obtains solid mould:
With 180 ℃ of nitrogen heat guns, the plated metal indium is melted, again cooling rapidly rapidly.The xsect that makes metal electrophoresis pipeline is a shape shown in Figure 4, and Figure 19 is the indium metal pattern synoptic diagram behind local the amplification.
Two, with solid Mold Making capillary electrophoresis chip
Step with solid Mold Making capillary electrophoresis chip is as follows:
1) gets a container, the solid mould that processes is previously put into, add the transparent organic silicon glue HT902T glue of saving the situation again and cover the slide that processes in the step 1; Film thickness is less than 3mm.
2) vacuum outgas is 20 minutes, and the bubble in the organic silica gel is all removed;
3) solidify: solidify and made the organic silica gel full solidification in 24 hours, form structure shown in Figure 20; If film thickness is greater than 3mm, will prolong set time.
4) make port: with thin metallic tubd four ports of punching press Capillary Electrophoresis pipeline gently, cut the organic silica gel in the hole, expose the indium metal of port, form structure as shown in figure 21;
5) device heats to 180 that obtains of step 4) ℃ is waited for a few minutes, and the alignment tube road junction blows out the indium metal of melting with high pressure nitrogen, forms shape of cross section shown in Figure 5, forms structure shown in Figure 22 at last;
6) the remaining Cr metal in the corrosion pipeline.With the mixed liquor corroding metal chromium of cerous ammonium nitrate, perchloric acid, water, cerous ammonium nitrate: perchloric acid: water=50g: 12ml: 300ml flushing pipe.Wash one's hands and face pipeline with HCl, remove the metal remained atom, obtain the electrocapillary phoresis chip.