KR100836872B1 - Fabrication of microstructures for micro/nano-fluidic devices and MEMS microdevices using inorganic polymers and hydrophilic polymers - Google Patents

Abstract

The present invention provides a photocrosslinkable inorganic polymer photoresist such as photolithography, micro-transfer molding (μ-TM), imprint lithography, stereolithography, and the like. The method is to produce various functional patterns and structures. The molded patterns and structures undergo post-curing or high temperature heat treatment to produce microfluidic patterns and devices of inorganic polymer or ceramic composition with chemical and thermal stability and light transmittance. In addition, similar processes are applied to hydrophilic polymers to produce hydrophilic nanofluidic patterns and devices, which will be used in various MEMS / NEMS devices in the future.

Soft Lithography, Inorganic Polymers, Ceramics, Ceramic Precursors, MEMS, Microfluidic Devices, Superhydrophilic Polymers, Nanochannels

Description

Fabrication of microstructures for micro / nano-fluidic devices and MEMS microdevices using inorganic polymers and hydrophilic polymers

INDUSTRIAL APPLICABILITY The present invention provides a method for forming an economical and large-area pattern using an exposure process, micro transfer molding, imprint lithography, stereolithography process as an inorganic polymer precursor, and a polymer or ceramic microfluidic channel and device manufactured by the method. It is about.

MEMS (Microelectromechanical Systems) originally meant micro-mechanical devices or systems containing them with electrical and electronic drive characteristics, but now they are miniaturized, high precision, and complex in optical, thermal, hydrodynamic, chemical and biological functions. It is a general term for micro system that provides core technology.

Current MEMS technologies include surface microfabrication, a selective etching technique for deposited thin films, substrate microfabrication techniques for etching silicon substrates themselves, laser micromachining, electron emission micromachining, LIGA (Lithographie, Galvanoformung und Abformung, and German abbreviation). ) Process is utilized. Current MEMS devices manufactured using silicon, glass, polymers, and metal materials require deterioration due to friction / wear, adhesion, and fatigue due to repeated operation and high integration. Therefore, other materials need to be utilized.

In addition, the microfluidic device combines microelements such as valves, chemical reaction parts, microdetection systems, and separation filter parts that are interconnected with microchannels ranging from tens of nm to hundreds of micrometers in the MEMS device, and search for compounds. It refers to a system that can produce chemical transformations and associated processes, including production.

Recently, researches on nanotechnology have been actively conducted, and as a result, active researches on the fabrication of devices using microfluidics have been made [IEEE, vol. 86, 1594, 1998; Science, vol. 285, 699, 1999]. In order to manufacture microfluidic devices, a patterning process using a MEMS technique is required. Pattern formation methods can be divided into bottom-up materials (top-down) or top-down methods from bulk materials by various etching methods. Methods of producing the desired levels of structures and patterns belong to the latter. Photolithography, which is currently used in semiconductor processes, is a process that uses photo technology to irradiate light on a patterned mask to crosslink a photosensitive polymer applied to a substrate in a fluid pattern form and to form a pattern through an etching process. Various MEMS devices, including nano devices with line widths of less than 100 nm, are currently used in surface micromachining, electron beam lithography, LIGA, reactive ion etching, and X-ray lithography. . Processes such as dip-pen lithography are applied to materials such as metals, plastics and glass, but other materials are not required for highly integrated driving devices and microchemical reaction systems requiring high temperature heat resistance and chemical stability. It is required. In other words, silicon, glass, polymer, and metal materials are mainly used as materials for MEMS, and interest in ceramic materials having high strength, high temperature, and chemical stability is increasing.

In order to implement MEMS modules as well as high temperature reactors or microchemical ceramic reactors that can operate under chemically harsh conditions, non-oxide ceramics (SiC, SiCN, SiCBN, BN) that are stable at high temperatures and have chemical stability are suitable. [Adv. Mat., Vol. 13, 54 2001]. Such carbides, nitrides, silicides, borides, and sulfides have already been applied to a variety of applications including fibers, thin films, and composites [Journal of the American Ceramic Society, vol. . 75, 1300, 1992; United States Patent, 4,336,215, 1982. In particular, aerospace, heat engines and cutting tools, and as a material that can be used in extreme environments are spotlighted. Since the general manufacturing method of the non-oxidized ceramic is made from high melting point and insoluble powder, it is required to go through an expensive process, and researches for overcoming the disadvantages of the conventional powder process are being conducted. In addition, the ceramic materials such as SiC, SiCN, and the like have excellent thermal and chemical stability, and thus exhibit low etching rates. Therefore, the development of new processes has been required due to the difficulty in manufacturing ceramic microstructures and fluid patterns using existing semiconductor etching processes. Materials Science Forum, vol. 510-511, 774, 2006; Key Eng. Mat. vol. 287, 96, 2005].

Accordingly, chemical vapor deposition using molecular precursors, pyrolysis of inorganic molecular precursors, and organic-inorganic hybrid composites have been studied as alternatives, but in the 1980s, Nippon Carbon Co. developed SiC fibers (trade name: Nicalon) using inorganic polymers. Since its commercialization, various inorganic polymer precursors have been synthesized and used as composite materials of ceramic fibers, coatings and ceramic fiber / ceramic matrices. Oxide-based ceramics using various sol-gel processes are widely used as electronic and structural materials, while SiC or Si ₃ N ₄ ceramics made from inorganic polymers have been commercialized in parts such as fibers. The types of inorganic polymers used as ceramic precursors and the yield of pyrolysis production are shown in Table 1. In general, inorganic polymers have a relatively high thermal stability and high chemical stability, as compared with organic polymers, which are pyrolyzed at 200 ~ 300 ℃ or below, and the deterioration of physical properties occurs rapidly. Have Liquid polymer precursors (Preceramic polymer) is mixed with other materials, and the molding is simple, so that various types of ceramics can be produced, the importance of the method of manufacturing a fine ceramic structure is gradually increasing. Recently, various soft lithography processes have been spotlighted as economic production processes, and new processes such as stereolithography processes have been continuously developed to manufacture various three-dimensional microstructures that cannot be manufactured by existing processes. .

Table 1 Kinetics and yield of pyrolysis of inorganic polymers used as ceramic precursors

Existing water-soluble microfluidic devices are manufactured using PDMS (Polydimethylsiloxane) or glass and silicon materials, which are mostly silicone rubber. The former has been used in the manufacture of various types of devices because of its excellent physicochemical properties, low cost, and excellent moldability, but has the disadvantage of being a hydrophobic polymer with a high contact angle of 110˚ or more. There was a difficulty in the application of the device. In order to overcome this problem, physicochemical coating, surface modification, silanization, radical group or protein conjugation have been attempted, but surface modification through surface treatment using plasma is most common.

Patent Registration No. 10-0126891 proposes a method of applying a hydrophilic material after forming a radical on the surface of a hydrophobic polymer using plasma, but in this case, it is formed on the nano-sized microchannels that are formed to form a nanostructure. It is possible to change the shape and size, and low stability that easily changes the properties when repeated use is a problem. In addition, in the case of Patent Registration No. 10-0508961, by applying the fine particle titanium dioxide having a plate-like structure to improve the hydrophilicity and shielding of the surface, it is a difficult process for producing a fluid pattern in the micro area. On the other hand, hydrophilic glass and silicon devices have very stable characteristics, but manufacturing costs are very high. Therefore, there is a demand for the manufacture of micro / nano fluid devices using materials having low cost and stable properties.

In order to overcome the limitations of existing processes with low etching rate and expensive process cost in the process of ceramic material, the process applied to plastic material such as soft lithography technology such as micro transfer molding and imprint lithography is applied to inorganic polymer By manufacturing the structure, it is possible to reduce the cost and manufacturing time compared to the manufacturing method using a conventional semiconductor process.

The process applies an inorganic polymer thin film to a substrate material for producing a microelement, such as a silicon wafer, and then heats the coated substrate to evaporate the solvent in the photoresist film. The coated side of the heated substrate is then exposed by imaging to cause chemical deformation. After the exposure process, the substrate is treated with a developer to dissolve and remove the non-exposed portions of the coated surface of the substrate. The polymer fluid pattern and the structure itself prepared through the post-curing process are used in the device as it is, or additionally heat treated up to 1200 ° C. in an inert atmosphere, thereby making silicon carbide (SiC), silicon carbide (SiOC), and silicon nitride (Si ₃ N ₄ ) System-based ceramic fluid patterns and structures are prepared.

The manufacturing process of the ceramic fluid pattern and the channel using the inorganic polymer precursor is shown in FIG. 1, and a desired pattern is added to the liquid inorganic polymer precursor by adding a reaction initiator capable of performing a crosslinking reaction by radical reaction by ultraviolet rays or heating. After molding, the resin is cured through photocrosslinking or thermal crosslinking reaction. At this time, high molecular fluid devices that have undergone only a hardening process are superior to conventional PDMS-based fluid devices, and have chemical stability comparable to those of glass and silicon fluid devices, but their manufacturing cost is expected to have similar advantages as plastic devices. Applicability is great as. Thereafter, according to the purpose of use, heat treatment may be performed at a temperature of 600 to 1200 ° C. under inert gas conditions such as nitrogen and argon to manufacture a ceramic MEMS device having chemical resistance, corrosion resistance, and abrasion resistance.

On the other hand, PDMS as a channel material for a water-soluble fluid micro / nanofluidic device has a disadvantage of being a hydrophobic polymer, so the wettability of the aqueous solution is very low, and thus does not exhibit flow characteristics in the microfluidic device channel of several micrometers or less. The manufacturing method of microfluidic channels using a new hydrophilic polymer and a soft lithography process rather than a surface modified coating method has an advantage of expecting stable physicochemical surface properties while performing accurate transfer from a master during molding. To this end, the hydrophilic polymer is coated on the silicon master fabricated by the exposure process, and then PDMS is further poured on it to prepare a composite polymer pattern having a two-layer structure. In order to increase the mechanical strength of the composite polymer, an organic-inorganic composite hydrophilic polymer channel formed through secondary curing is bonded to a glass substrate to prepare a micro / nano fluid channel. The hydrophilic polymer used at this time uses the patent application 10-2005-0123594 material. That is, it is more stable than the existing surface-modified hydrophilic fluid elements, and has high utility in the future due to the low manufacturing cost compared to expensive hydrophilic glass and silicon elements.

The present invention provides a method for forming an economical and large-area pattern by using an exposure process, micro transfer molding, imprint lithography, stereolithography process as an inorganic polymer precursor, and a polymer or ceramic microfluidic channel produced by the method, It aims at manufacturing an element.

Similar processes are also applied to hydrophilic polymers to produce water soluble nanochannels and devices. In addition, it can be used as a related part of MEMS / NEMS devices by manufacturing polymer and ceramic shapes of various three-dimensional structures by stereo lithography process.

In order to solve the above problems, in the present invention, the microfluidic channel and the structure are manufactured by the soft lithography method and the material mixed with the inorganic polymer by adding the ultraviolet ray and the thermal sensitive initiator. SiC-based ceramic channels and structures are manufactured by using the same as it is in the device or by heat-treating up to 1200 ° C. in an inert atmosphere. In addition, nanofluidic channels and devices are fabricated by hydrophilic polymers and soft lithography. In the present invention, an overview of the steps up to the preparation of the microfluidic pattern and the structure using the inorganic polymer precursor or the hydrophilic polymer is shown in FIG.

First, a pattern is formed using an inorganic polymer precursor using an exposure process and various soft lithography methods. Soft lithography designed to date includes MIMIC (Micromolding in capillaries), micro transfer molding, transfer molding, microcontact printing (μ-CP), capillary force lithography (CFL), imprint lithography, etc. [ Nature , vol. 376, 581, 1995; Adv . Mater , vol. 8, 837, 1996; Adv . Eng . Mater , vol. 2 (5), 290; 2000].

Figure 3 is as follows for the purpose of explaining the micro transfer molding and imprint lithography utilized in the present invention during the above process.

In other words, it includes the development of processes that can produce two-dimensional and three-dimensional fluid patterns and structures up to 1 cm in size and at least 10 nm using photolithography or imprint lithography processes using inorganic polymers and hydrophilic polymers. According to the heat treatment process, a process for mass-producing a ceramic pattern excellent in high temperature stability, friction and wear characteristics is included. This will be used in the manufacture of application devices that can be utilized in MEMS / NEMS devices by establishing a mass production technology of ceramic fluid patterns and structures of various shapes.

In addition, in the present invention, various fluid patterns and structures of hydrophilic polymers and inorganic polymers are formed by using a stereolithography process. This process utilizes catalysts or two-photon absorbing dyes containing noble metals selected from platinum or rhodium catalysts, which are necessary to cause steric limited selective crosslinking reactions by two-photon absorption methods during exposure. Stereolithography enables the fabrication of structures with nano-scale precision by limiting the area where the photopolymerization reaction occurs by absorbing two long-wavelength photons to a small focal size of at least 100 nm. It is also possible to manufacture structures [Applied Physic A. Vol 73, 561, 2001]. The stereolithography process using a two-photon absorption photopolymerization method using a laser is known to be able to manufacture high-precision three-dimensional structures without expensive semiconductor processing equipment and masks. No application has been applied to the fabrication of structures [Applied Physic B. Vol. 77, 485, 2003]. In general, as a method of manufacturing nanoscale fluid patterns and structures, an electron-beam lithography process using quartz material is used. This method has a disadvantage of using expensive equipment. In contrast, micro transfer molding, imprint lithography, and stereo lithography processes are inexpensive and have the advantage of easily forming fluid patterns and structures under laboratory conditions. In the case of the inorganic polymer precursor, a heat treatment process is performed at 600 to 1200 ° C. under an inert atmosphere such as nitrogen and argon to finally form a silicon carbide (SiC), silicon carbide (SiOC), and silicon nitride (Si ₃ N ₄ ) ceramic fluid pattern. And structures.

To form fluid patterns and structures using inorganic polymers and hydrophilic polymers, PDMS (Polydimethylsiloxane) mold, a kind of silicone rubber, is used to promote crosslinking reaction by PDMS polymer and radicals on a silicon master imprinted with a fluid pattern or structure formed through exposure process. It can be formed by crosslinking at 50-60 ^o C after mixing the initiator. In this process, the size of the mask pattern can be controlled by mixing the organic photoresist with an organic solvent having a relatively high spin rate and volatility. When forming fluid patterns and structures of organic-inorganic hybrid hydrophilic polymers using microtransfer molding, imprinting lithography, and stereolithography processes, heat is added without adding a thermal initiator or photoinitiator. It has the advantage of crosslinking and UV curing.

In the formation of ceramic fluid patterns and structures using inorganic polymer precursors, the control of the crosslinking speed affects the overall fluid pattern formation, so the crosslinking process is very important in the overall process. Conventional crosslinking process has been improved by adding a photocuring initiator for rapid UV curing. However, UV-cured patterns have a weak thermal, chemical and mechanical strength. Therefore, in the present invention, a two-step curing method through UV crosslinking and thermal crosslinking using a long wavelength was used for curing the inorganic polymer precursor. That is, the photocrosslinking initiator and the thermosetting initiator may be simultaneously mixed with the inorganic polymer precursor solution to form a pattern by UV curing by soft lithography, and then a ceramic pattern having thermal and chemical stability may be formed through thermosetting.

The irradiation area for UV curing is determined with reference to the ultraviolet / visible absorption peak of the photocuring initiator. Table 2 shows chemical composition and maximum absorption peak of representative photocuring initiators produced by Ciba Specialty Chemicals. On the other hand, the temperature for thermosetting is set to the Tg temperature or more with reference to the glass transition temperature (Tg) when the thermosetting initiator is mixed with the precursor of the inorganic polymer. The ascent rate is increased slowly to about 1-5 ^o C / min and maintained for 1-3 hours at the set temperature.

Table 2. Photocuring Initiators

Ceramic microfluidic devices can be fabricated using a series of soft lithography methods that form a master on a substrate using an exposure process, then form a PDMS mold and then form a cured inorganic polymer precursor channel. The substrate may be silicon or glass, depending on the application, but may be any material as long as it is stable at the heat treatment temperature for transition to ceramic. The exposure process is preferably performed at an exposure energy of 1 to 100 mJ / cm ² using mainly UV (selection of wavelength 250 to 850 nm), electron beam, laser beam or ion beam as a light source. The mechanism of action of the inorganic polymer negative photoresist utilized in the present invention is insoluble due to crosslinking reaction upon receiving ultraviolet light, so that it is present as a pattern or structure without being removed in a subsequent development process. On the other hand, since the crosslinking reaction does not occur in the case of non-exposed sites, the mask phase may be left as a negative image by being dissolved and removed in a subsequent development process. If the transferred channel on the glass or silicon wafer is sealed, its applicability as a microfluid may increase. Sutures include inorganic polymer precursors, plasma treatment, organic polymers, and the like. In order to increase adhesion, an additive for heat or UV curing may be added. At this time, the roughness of the channel and the pattern affects the sealing effect.

To form a hydrophilic polymer pattern, an embossed nanofluidic pattern mold was formed on the silicon master surface through an exposure process, and then perfluorooctyltrichlorosilane as a release agent to facilitate desorption of the microfluidic pattern to be formed later. The 1H, 1H, 2H, 2H-perfluorooctyl-tri-chlorosilane was deposited onto the mold of the silicon master under reduced pressure of 100 mmHg After spin-coating the hydrophilic polymer on the surface treated with the release agent, the organic solvent was decompressed. Remove the organic solvent remaining in the hydrophilic compound The hydrophilic polymer coated on the template prepared to form the nanochannel of the organic-inorganic complex hydrophilic polymer is present in a gel state by removing a considerable amount of the organic solvent. Pour the mixed liquid of the polymer support and the curing agent, where the hydrophilic compound and the polymer support Due to the very large polarity difference, the bulk is not formed between each other and the interface is formed, but from the microscopic viewpoint, the bonding force is formed between the intermolecular molecules and the bonding force is formed between the two phases during the curing process of the polymer support. The micropattern is formed on the hydrophilic polymer by the bonding between the hydrophilic polymer and the support. Secondary curing is performed to increase the hardness of the hydrophilic polymer, and crosslinking is formed between the molecules constituting the hydrophilic polymer and the strength is increased.

As described above, a low-cost exposure process, a micro transfer molding, an imprint lithography, and a stereolithography process are applied to an inorganic polymer to produce a polymer microfluidic pattern and a structure having excellent organic solvent permeability through a post-crosslinking process. In addition, through the high temperature pyrolysis process, it is possible to manufacture ceramic microfluidic patterns and structures having excellent high temperature stability, friction, and wear characteristics, as well as three-dimensional microstructures. In addition, the nanofluidic device having excellent flow characteristics of the water-soluble fluid was fabricated using a hydrophilic organic-inorganic polymer having chemical resistance and high light transmittance.

Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.

Example 1 Preparation of Master and Mold Using Exposure Process

In order to obtain a master for pattern formation using an inorganic polymer precursor in the present invention, a commercially available epoxy photocrosslinkable polymer, SU-8-50 (MicroChem, USA), is spin coated on a silicon wafer for 90 seconds at 95 ° C. After heating, ultraviolet light of 20 mJ / cm 2 was exposed for 1 minute using a photomask and an ultraviolet exposure equipment, and then heated again at 95 ° C. for 1 hour. After the completion of the heating, the portion not irradiated with ultraviolet rays through the developing step was removed using a developer to obtain a silicon master having a pattern imprinted on the silicon substrate by a photomask.

Then, on the silicon master pattern as described above, Sylgard 184 (dimethylvinyl-terminated dimethyl siloxane, Dimethylvinylated and trimethyllated silica, Tetra- (trimethylsiloxy) silane mixture) of Dow Corning PDMS (Polydimethylsiloxane) as a crosslinking agent (dimethyl, methylhydrogensiloxane, dimethylvinyl) mixed with the same weight ratio of -terminated dimethylsiloxane, Dimethylvinylated and trimethyllatedsilica) mixed at a mass ratio of 10: 1, poured and crosslinked at 60 ^o C for 5 hours, and then detached from the silicon master to form a PDMS mold on which the master pattern was transferred. Produced. An overview of the specific process is shown in FIG. 4.

Example 2 Confirmation of Ultraviolet Ray and Thermocrosslinkability of Inorganic Polymer Precursor

Polysilazane (Polysilazane, KiON Corp., USA), a liquid inorganic polymer having vinyl group and Si-H functional group, is used as a precursor of inorganic polymer (Ceraset, KiON Corp.) for SiCN ceramics and spins of liquid polymer Irgacure 500 is used as the photocrosslinking initiator to increase the rate of UV and thermal crosslinking in a mixture of 10: 1 of polysilazane: PGMEA by using PGMEA (Propyleneglycol-monomethyletheracetate) to increase wettability during coating. After 0.5 wt% of the content of crosslinking and DCP (Dicumyl peroxide), which is a thermal crosslinking initiator, was added 0.5 wt% of the content of the inorganic polymer precursor, and irradiated for 20 minutes under the condition of 20 mJ / cm ² , followed by ultraviolet crosslinking. Thermal crosslinking was carried out in two stages: 100 ^o C and 150 ^o C. Thereafter, the temperature was again raised at a rate of 5 ^o C / min. Under nitrogen, and then maintained at 300 ^o C for 60 minutes. Then, the temperature was reduced at a rate of 5 ^o C / min. In addition, an inorganic polymer for SiCN ceramic was prepared by heat treatment at 400 ^° C. for 60 minutes at the same temperature and temperature reduction rate, and the transmittance of the cured inorganic polymer was investigated. As shown in Figure 5 shows a high transmittance of more than 95% in the wavelength range of more than 300 nm.

Example 3 Pattern Preparation Using Inorganic Polymer Imprint Lithography Process

A pattern was prepared using polysilazane (KiON Corp., USA, molecular weight: 270), which is a SiCN ceramic inorganic polymer precursor. After the inorganic polymer precursor solution to which the same amount of the thermal crosslinking initiator (DCP) was added was coated on the surface of the glass substrate, a pattern was manufactured by using an imprint lithography process as shown in FIG. 3 (b). In the preparation of the pattern, first, the same Sylgard 184 as described in Example 1 and a crosslinking agent were mixed in a 10: 1 to make a PDMS mold, and the inorganic polymer precursor was added dropwise onto the PDMS by coating or dropping the pattern. Formed. After the PDMS mold was physically desorbed and removed, heat crosslinking was performed at 100 ^° C. for 6 hours. The microfluidic pattern using the inorganic polymer precursor was analyzed using a scanning microscope (SEM), and FIG. 6 shows a photograph of the scanning microscope of the inorganic polymer pattern.

Example 4 Preparation of Microfluidic Channel Using Inorganic Polymers

After preparing the inorganic polymer precursor solution as shown in Examples 2 and 3 and evenly spread on the silicon wafer substrate, a microfluidic channel was prepared by an imprint lithography process using a PDMS mold. Ultraviolet light with an intensity of 20 mJ / cm ² was irradiated for 10 minutes to form an inorganic polymer channel, and then the PDMS mold was removed. Thermal crosslinking was carried out while raising the inorganic polymer channels to 100 ^o C and 150 ^o C. The total length of the prepared channel was 45 mm, the width of the channel was 50 μm, and the thickness was 20 μm. 7 shows the shape of the designed channel and the results of scanning microscope analysis of the prepared microfluidic channel.

Example 5 Microfluidic Channel Preparation by Simultaneously Performing Channel and Suture by UV Irradiation

Photosensitive polymers including photoresists, inorganic polymers, and the like can increase photoreactivity by adding photocrosslinking initiators. Using this, the channel formation and the sealing can be simultaneously performed through the exposure process. 0.4 mg of the SiCN inorganic polymer precursor of Example 2 was added 2 mg of Igaucre 500 as a photocrosslinker, coated on a glass substrate, and then contacted with a cover substrate punched to a predetermined position. At this time, the inorganic polymer in the liquid state plays the role of an adhesive and occupies a certain thickness, and irradiated with ultraviolet rays after attaching a photo mask on the cover substrate. After post-heating at 95 ^° C. after UV irradiation, channels were formed between the two substrates by removing inorganic polymers not crosslinked with ethanol.

Example 6: Preparation of Hydrophilic Nanochannels with Polymeric Supports

The silicon master pattern prepared through the exposure process as described in Example 1 was placed in a vacuum desiccator and perfluorooctyltrichlorosilane (1H, 1H, 2H, 2H-perfluorooctyl-tri) as a release agent in a small dish inside. After dropping 2-3 drops of chlorosilane, it is maintained at a reduced pressure of 100 mmHg and deposited on the mold of the silicon master for 4 hours. The hydrophilic polymers used in this Example were prepared by the method of Example 2 as described in the previously filed patent No. 10-2005-0123594, ethanol, TEOS (Tetraethylorthosilicate), Pluronic P123 (ethylene / propylene oxide block) Copolymer), Titanium Chloride (TiCl ₄ ) and Tiron (4,5-dihydroxyl-m-benzenedisulfonic acid, disodium salt). When the hydrophilic polymer synthesized as shown in FIG. 8 is applied on the master to have a thickness of 5 μm using a spin coater, the same PDMS solution as in Example 1, which will serve as a supporter, will be applied. The mixture is mixed so that the weight ratio of the crosslinking agent is 5: 1, and poured in a liquid state from 6 to 8 mm from the master surface to the liquid surface. After that, while maintaining a reduced pressure of 100mmHg for 10 minutes using a vacuum desiccator, the PDMS forms an interface with the hydrophilic polymer coated on the silicon master and is left in close contact with the hydrophilic polymer. Harden. After the hardening of the PDMS is completed, the Petri dish is removed from the incubator and cooled to room temperature, and then the hydrophilic polymer layer and the PDMS are detached from the silicon wafer master by applying a physical force.

Since the junction between the hydrophilic polymer and the PDMS is formed in the liquid-liquid state, the micropattern is engraved in the hydrophilic polymer so that the hydrophilic polymer is fixed and detached on the surface of the PDMS. Hydrophilic polymers are physically dried and have strength and elasticity similar to those of PDMS, requiring secondary curing to increase their strength. When the hydrophilic polymer is cured at 100 ° C. for 5 hours, crosslinks are formed between the molecules constituting the hydrophilic polymer and the strength is increased. As a result of measuring the cross section of the prepared microchannel to confirm the hydrophilic microchannel transfer state, a microchannel having a depth of 1.4 μm, which is the height of the master, was formed and is illustrated in FIG. 9. In addition, nanochannels were fabricated by fabricating a silicon wafer master having a height of 400 nm using SU-8-50 diluted to 20% by weight with PGMEA (propylene glycol monomethyl ether acetate) to form nanochannels.

Example 7: Fabrication of Hydrophilic Microfluidic Devices

In order to fabricate the hydrophilic polymer microchannel fabricated as described in Example 6 as a microfluidic device, holes for injecting a fluid having a diameter of 1 mm into a glass plate having a width, a length, and a thickness of 75 mm, 25 mm, and 1 mm, respectively The processed glass plate and the surface of the hydrophilic polymer were modified with plasma to form radicals, and then adhered to each other by leaving them at 60 ° C. for 5 hours to produce a closed microchannel. To verify the performance of the fabricated microfluidic device, a drop of water-soluble dye was added dropwise to the sample injection mold attached to the microchannel fluid apparatus having a depth of 1.4 μm.

In order to perform the comparative group experiments, the experiment was conducted under the same conditions as the microchannel fluid apparatus manufactured only with the PDMS fabricated with the same master. As a result, in the microfluidic apparatus fabricated with the hydrophobic polymer PDMS, due to the low adhesion between the aqueous solution and the surface. Convex forms of meniscus were formed and spontaneous flow of aqueous solution by capillary phenomenon was impossible. However, in the microfluidic device made of the hydrophilic polymer, spontaneous fluid flow occurred due to capillary action due to the high adhesion between the aqueous solution and the hydrophilic polymer, and the flow phenomenon of the liquid was uniformly observed throughout the connected channels. Through the method described as described above, the electrophoretic apparatus, which was previously constructed using capillaries of several centimeters to tens of centimeters in length, could be manufactured as a size of 75 mm in width, 25 mm in length, and 10 mm in height.

Example 8 Fabrication of Microfluidic Devices with Hydrophilic-hydrophobic Composite Channels

Part of the mold formed on the master described in Example 6 is covered with a masking tape so that the hydrophilic polymer is not applied as shown in FIG. 11, and then the hydrophilic polymer is applied using a spin coating apparatus. Thereafter, after removing the masking tape, the PDMS solution was injected in the same manner as in Example 6, cured for 12 hours in a 50 ° C thermostat, and then detached and subjected to a secondary curing process at 100 ° C for 5 hours to remove microchannels. Made. As such, the portions to which the hydrophilic polymer has been applied form a hydrophilic channel, and the portions not to be coated may form the hydrophobic polymer PDMS to form microchannels and may have hydrophilicity / hydrophobicity in a continuous channel. In order to fabricate the final microfluidic device, a closed microfluidic device was fabricated by joining the perforated glass plates as described in Example 7. Through this, it is possible to induce discontinuous flow between polar and nonpolar solutions, or to immobilize hydrophobic proteins and the like.

Example 9 Ceramic Structure Formation by Two-photon Absorption in Stereolithography Process

0.05 wt% of the cyclopentadienylmethyl trimethylplatinum liquid polymer used as a catalyst for the 0.5 g polysilazane polymer used in Example 2 was mixed uniformly in 1 g of tetrahydrofuran, an organic solvent, and then the photoresist mixed composition was used. After dropping on transparent quartz, the solvent was removed by vacuum volatilization. The photoresist mixed composition was subjected to exposure crosslinking using an optical femtolaser exposure apparatus (variable range 750 to 850 nm). At this time, the exposure region that absorbs two photons of long wavelength and causes photopolymerization can be selectively controlled in a three-dimensional space. Accordingly, by continuously crosslinking the exposure area in two or three dimensions, it is possible to manufacture a two-dimensional or three-dimensional structure having nano-scale precision. After developing ethanol, heat treatment was performed at 600 ^° C. under nitrogen to form a ceramic pattern. FIG. 12 shows a 230 nm line in an embodiment of ceramic fluid pattern and structure formation by two photon absorption method utilizing a two-dimensional exposure process.

1 is a description of the ceramic fluid pattern and structure formation using the inorganic polymer precursor of the present invention.

Figure 2 is a schematic description of the formation of the fluid pattern and structure using the organic-inorganic composite hydrophilic polymer and inorganic polymer of the present invention.

Figure 3 is a schematic illustration of the micro-transfer molding and imprint lithography process during the process for patterning of the present invention.

4 is a description of a process of forming a polymer mold for an inorganic polymer fluid pattern and a structure according to Example 1 of the present invention.

5 is an analysis result of the UV transmission characteristics of the inorganic polymer cured by heat treatment according to Example 2 of the present invention.

6 is a scanning microscope (SEM) photograph of a microfluidic pattern using an inorganic polymer according to Example 3 of the present invention.

7 is a scanning microscope photograph of an inorganic polymer channel for microfluidic substrate of a silicon wafer substrate according to Example 4 of the present invention.

8 is a description of the manufacturing process of the microchannels and structures through the molding between the organic-inorganic composite hydrophilic polymer and the support polymer.

FIG. 9 is an atomic force microscope (AFM) stereogram of a mask and a molded microfluidic channel used for channel formation of the hydrophilic polymer according to Example 6 in the present invention.

10 is an optical micrograph for comparing the spontaneous flow phenomenon of the aqueous solution in the microchannel of the hydrophilic polymer according to Example 7 of the present invention.

11 is a description of a method for manufacturing a microfluidic device having a hydrophilic-hydrophobic mixed microchannel according to Example 8 of the present invention.

12 is a scanning micrograph showing the results of forming a nanostructure using a stereolithography process according to Example 9 of the present invention.

Claims (4)

Manufacturing a silicon master with a fine pattern imprinted thereon; Depositing a release agent on a side surface of the pattern of the master; Applying a hydrophilic polymer to the deposition surface; Stacking or curing a crosslinkable polydimethylsiloxane solution on the hydrophilic polymer layer; Removing the silicon master after the curing; Microchannel formation method comprising a hydrophilic polymer layer comprising a. The method of claim 1, The crosslinked polydimethylsiloxane solution is any one or more components selected from dimethyl vinyl terminal dimethyl siloxane, dimethyl vinyl group and trimethyl group terminally substituted silica, dimethyl or methyl hydrogen siloxane, dimethyl vinyl terminal substituted dimethyl siloxane or dimethyl vinylation and A method of forming a microchannel in which a hydrophilic polymer layer is complex, characterized by using a crosslinking agent of at least one component selected from trimethylated silica. The method of claim 1, A method for forming a microchannel in which hydrophilicity and hydrophobicity are complexed by forming a liquid interface between a hydrophilic polymer and a hydrophobic polymer which are not mixed to form a hydrophilic microchannel, and then curing the liquid interface. Apparatus comprising nanofluidic channels with improved flow characteristics of water-soluble fluids prepared by the method of any one of claims 1 to 3.

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