CN1301198C - Method of performing micro contact printing using colloidal crystal as ink - Google Patents
Method of performing micro contact printing using colloidal crystal as ink Download PDFInfo
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- CN1301198C CN1301198C CNB2004100110845A CN200410011084A CN1301198C CN 1301198 C CN1301198 C CN 1301198C CN B2004100110845 A CNB2004100110845 A CN B2004100110845A CN 200410011084 A CN200410011084 A CN 200410011084A CN 1301198 C CN1301198 C CN 1301198C
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Abstract
The present invention relates to a method for patterning and transferring colloid crystals by an improved micro contact printing technology and constructing patterned heterogeneous colloid crystals used as ink for performing micro contact printing, which comprises five steps: preparing ordered colloid crystals; preparing ordered microstructure PDMS mould plates; patterning two-dimensional colloid crystals on the surfaces of the PDMS mould plates; preparing a substrate coated with a polymer film layer; printing colloid crystals by micro contact. The material of the polymer film layer is polyvinyl alcohol, polystyrene or polymethyl methacrylate. The method has the advantages that the colloid crystals are microcosmically patterned, and the colloid crystals are transferred to base sheets made of different material. The method has the characteristics of simplicity, rapidness, convenience and flexibility. Micro contact printing can be performed for many times on the same substrate to obtain heterogeneous colloid crystal films, and the method can be widely used for designing and preparing colloid crystal optical devices and further promotes the development of new material and optical devices.
Description
Technical field
The present invention relates to a kind of combination and uncover the technology of the novel patterning colloid crystal of technology and micro-contact printing technical development, relate to particularly that a kind of what utilize that improved micro-contact printing technology carries out patterning and transfer and the heterogeneous colloidal crystal of structure patterning to colloidal crystal is the method that ink carries out micro-contact printing with the colloidal crystal.
Background technology
Diameter is that sub-micron, monodispersed inorganic or polymeric colloid microballoon (colloidal microspheres) can self assembly form two dimension or three-dimensional orderly arrangement under the effect of gravity, electrostatic force or capillary force.These microsphere aggregation bodies of arranging in order are commonly called colloidal crystal (colloidal crystals) or synthetic proteins stone (syntheticopals).Colloidal crystal has been represented a kind of new-type functional material, and this class material is in electronics, optics and the sensory field background that has a very wide range of applications.Usually specific microstructure need be introduced the colloidal crystal system in order to realize the application of colloidal crystal on device.Based on this purpose, there have been large quantities of methods to grow up at present.Though these methods can effectively be controlled the size of colloidal crystal, structure and crystalline form orientation, field at the colloidal crystal patterning also exists some difficult problems, for example: the technology of colloidal crystal patterning on curved surface also can not set up, the method for preparation and the heterogeneous colloidal crystal of patterning does not have complete yet.
Micron and little processing of nanoscale surface structure and character or the center that patterning becomes contemporary science and technology gradually.The chance of many modern technologies development all derives from the successful structure of new microstructures or the miniaturization of existing structure.The microelectronic industry of develop rapidly is exactly a most typical example.Though the demand of microelectronic industry once was, and also be in the future the motive force of patterned surface development, the application of patterned surface technology in other field promptly increases.For example, the long-pending reactor of chemistry and biological substance microanalysis, biochip, microbody, combination are synthesized, micro optical element, micro-electro-mechanical systems are unified microstream system etc.Simultaneously, the patterned surface technology also provides chance for the research of the physics, chemistry and the biological phenomenon that are taken place in the range of small.Wetting and the phenomenon etc. of drying on the growth of crystal and cell and the patterned surface on the quantum confinement in nanostructured, the patterned surface for example.
Current and the potential application of these patterned surface technology is also promoting constantly development of patterning techniques itself simultaneously.Various in recent years physics, chemistry, biological new patterned surface technology continue to bring out, and utilize these technology, and people can realize on micron and nanoscale the structure on the surface of various materials and the control of character such as physics, chemistry and biology.Soft lithography is most widely used so far general, the patterned surface technology of reliable non-photoetching.Soft lithography is that the Whitesides research group by U.S. Harvard university in 1993 at first develops, and relates to the general designation of a class integrated technology in fields such as conventional lithography, organic molecule (for example mercaptan and siloxanes etc.) self assembly, electrochemistry, polymer science.Soft lithography has comprised the method for a series of patterning materials flexibly.Mainly comprise micro-contact printing (microcontact printing, μ CP), duplicating molded (replicamolding, REM), micrometastasis molding (microtransfer molding, μ TM), little molding (micromolding in capillaries in the capillary, MIMIC) and solvent assist little molding (solvent assistedmicromolding, SAMIM).In these methods, little molding (MIMIC-Micromoldingin capillaries) has been applied directly to the patterning colloid crystal in the capillary.Micro-contact printing (μ CP-microcontactprinting) has been used to substrate surface is modified upward different electric charge and hydrophilic and hydrophobics, and induces colloid micro ball at specific area deposition with this surface.Based on different interaction forces, as covalent bond, electrostatic interaction, physical absorption etc., many materials (as organic molecule, protein, polymer, nano particle, colloid, metal) can carry out patterning by the method for micro-contact printing on solid substrate.
Huskens and Reinhoudt etc. have developed a kind of μ CP technology that does not need ink.Dimethyl silicone polymer (PDMS) template of this technology employing surface oxidation contacts as the monolayer of seal and a kind of labile acid, because the existing acidity of PDMS template surface of oxidation is enough to the hydrolysis regional labile acid that contacts with the PDMS seal, thereby realized the patterning of substrate surface.Delamarche group also uses the PDMS on plane of the molecular ink layer be stained with patterning as seal in μ CP technology.The deformation that the PDMS that the use of plane P DMS template not only can provide the required tight contact of molecular transfer can also avoid patterning is caused when contact.Delamarche etc. adopt pentaerythrite-four (3-mercaptopropionic acid ester), and (pentaerythritol～tetrakis (3～mercaptopropionate), (PTMP)) as molecular ink, developed a kind of eurymeric μ CP technology, the pattern that this eurymeric μ CP technology is constructed can reach the precision of sub-micron.
Summary of the invention
The purpose of this invention is to provide that a kind of what utilize that improved micro-contact printing technology carries out patterning and transfer and the heterogeneous colloidal crystal of structure patterning to colloidal crystal is the method that ink carries out micro-contact printing with the colloidal crystal.
Purpose of the present invention can be achieved through the following technical solutions: adopt the monodisperse silica microspheres of colloidal sol-gel method preparation and carry out self assembly with the polystyrene microsphere that the suspension emulsion polymerization prepares to prepare orderly colloidal crystal, utilize the micro-contact printing technology that the orderly colloidal crystal that has obtained is carried out little processing and shifts its structure in suprabasil patterning of arbitrary surface and plane and the heterogeneous colloidal crystal microstructure of patterning of realization then.
Method of the present invention comprises four steps:
1. the in order preparation of colloidal crystal: (preparation method of silicon dioxide microsphere is referring to W.St ber with the monodisperse silica microspheres of colloidal sol-gel method preparation, A.Fink, J.Colloid Interface Sci.1968,26,62), with (preparation method of polystyrene microsphere is referring to X.Chen with the monodisperse polystyrene microsphere of suspension emulsion polymerization preparation, Z.Cui, Z.Chen, K.Zhang, G.Lu, G.Zhang, B.Yang, Polymer, 2002,43,4147.), add the deionized water dilution, being adjusted to mass percentage concentration is 0.5～2.0%, 10～20 microlitre silicon dioxide microspheres or monodisperse polystyrene microsphere emulsion is dripped to (substrate descends processing 30 minutes to 24 hours with the mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide at 80～100 degrees centigrade, and the consumption volume ratio of two kinds of solution is 7: 3 on 50～60 degree angle substrates after treatment, through dry under nitrogen or air atmosphere after the rinsed with deionized water), be under 30～60% the atmosphere solvent to be volatilized naturally at room temperature humidity, just can obtain orderly colloidal crystal, the thickness of the colloidal crystal that we constructed is generally 100 nanometers to 2 micron as stated above.(adjust the concentration and the amount of emulsion, can control the thickness of colloidal crystal)
2. the preparation that has the PDMS template of ordered micro-configuration: at first the dimethyl siloxane performed polymer of liquid state is mixed in 15: 1～3: 1 ratio of mass ratio with corresponding curing agent, irritate after the vacuum outgas in the mould of being made up of the photoresist sheet of smooth sheet glass and patterned surface, 40 ℃～80 ℃ solidified 3～10 hours.After the cooling polymer film that is cured is taken off from photoresist sheet carefully, thereby obtained the dimethyl silicone polymer template of patterned surface, i.e. silicon rubber (PDMS) template, the thickness of template is 50 microns to 1.5 millimeters usually.The photoresist sheet of patterned surface can utilize the light of different size and shape to cover plate, and the pattern of light being covered on the plate by photoetching technique copies on the photoresist sheet, obtains the photoresist sheet of patterned surface.(preparation of the photoresist sheet of patterned surface is referring to document: Y.N.Xia, E.Kim, X.M.Zhao, J.A.Rogers, M.Prentiss, G.M.Whitesides, Science 1996,273,347.Y.N.Xia, G.M.Whitesides, Angew.Chem.Int.Ed.Engl.1998,37,550.).
3. utilize and uncover soft lithography and realize the patterning of two-dimensional colloidal crystal at the PDMS template surface: with patterned PDMS template and the colloidal crystal that obtained 0.2 * 10
5～1.0 * 10
5Form closely contact under Pascal's the pressure, and heated 3～20 hours down, this sample is cooled to room temperature, again the silicon rubber template is carefully taken off in 100～110 ℃ environment.At this moment, the colloidal crystal individual layer that closely contacts with the PDMS template surface (thickness of the colloid monolayer crystal that we constructed in the experiment be generally 100 nanometers to 1 micron) will be transferred on the PDMS template surface, form orderly arrangement, and form the micro-structural of patterning in the superiors of colloidal crystal.The structure of the colloidal crystal on PDMS template and substrate surface is the secondary ordered structure: being formed by the microballoon self assembly in order of submicron order micron-sizedly provided by the silicon rubber template in order.In the said method, colloidal crystal is mainly made by monodisperse silica microspheres and monodisperse polystyrene microsphere, and used substrate requires surfacing, and roughness is little.Generally be silicon chip, sheet glass, gold plaque or quartz plate.
4. scribble polymer film (polyvinyl alcohol for example, polystyrene, polymethyl methacrylate etc.) (substrate can have different materials in any substrate, silicon chip, sheet glass, gold plaque or quartz plate that it is not limited in the step 3 can be the materials of polymer, polymer rete thereon arbitrarily.) preparation: being 1.0%～5.0% polymer solution with mass percent concentration is spin-coated on the planar substrates with the speed of 1000～3000rpm, thickness is about 40～100nm, or adopt the method for dip-coating in the curved surface substrate, to be coated with polymer film, the curved surface substrate is soaked in polymer solution, take out, vertically place, allow volatilization naturally under the solvent room temperature, thickness is about 40～100nm.
5. the micro-contact printing of colloidal crystal: the PDMS template of the patterning that has two-dimensional colloidal crystal that will in step 3, form and scribble polymer foil (thickness is about the substrate of any material of 40～100nm) 0.2 * 10
5～1.0 * 10
5Form closely contact under the Pascal, and heated 1.5～5 hours down in 100～160 ℃.After sample was cooled to room temperature, careful the taking off away of PDMS template, the colloidal crystal that sequential 2 D is arranged just had been transferred on the surface of substrate, and the material of substrate is not subjected to any restriction, can be the plane also can be curved surface.
Further, utilize the micro-contact printing process of twice colloidal crystal, we have realized the preparation first of the heterogeneous colloidal crystal of patterning, have obtained for the first time the heterogeneous colloidal crystal film that the colloid micro ball band by two kinds of different-grain diameters and material constitutes.This heterogeneous colloidal crystal film can be used for the preparation of the photaesthesia rete of two waveband.
In the present invention, we improve and have developed the micro-contact printing technology, we have introduced polymer film as " glue ", because the heating-up temperature when step 5 colloidal crystal micro-contact printing is on glass transition temperature of polymer, colloid micro ball on polymer film softening transform can take place and covers the PDMS template forms tight the contact, increased the contact area between polymer film and the colloid micro ball, the point of colloid micro ball and hard polymer film is contacted be converted into the face of colloid micro ball and softening polymer film to contact, active force has between the two increased, this active force is greater than the active force of colloid micro ball and PDMS template surface, thereby realized the transfer of " ink " colloid micro ball on solid substrate, just realized the micro-contact printing of colloidal crystal.
Utilize this method can realize transfer and the patterning of colloidal crystal to any substrate surface, while is by the flexibility of micro-contact printing, the two-dimensional colloidal crystal rete that the micro-contact printing technology of our development can realize patterning from the silicon rubber template surface of patterning to the transfer of the substrate surface that is covered with thin polymer film, can obtain the two-dimensional colloidal crystal film of patterning at the substrate surface of the plane of any material and curved surface, use our technology can also prepare the heterogeneous colloidal crystal film of patterning.
This method provides a kind of new " ink " and the interaction between the substrate for the transfer of material in the micro-contact printing technology, and this method also will widen making field based on the device of colloidal crystal to micro-contact printing The Application of Technology scope, and will further promote the development of new material and optics.
Description of drawings
Fig. 1: realize the schematic diagram of colloidal crystal at any suprabasil patterning with the micro-contact printing technology;
Fig. 2 (a): at the sem photograph of the lip-deep sequential 2 D colloidal crystal of silicon rubber template of the wide straight-line groove structure of micron order;
The partial enlarged drawing of Fig. 2 (b): Fig. 2 (a) sem photograph;
Fig. 3 (a): with the polyvinyl alcohol rete is that adhesion layer is realized micro-contact printing, transfers to the sem photograph of the parallel band of two-dimensional colloidal crystal that is made of silicon dioxide microsphere on the planar substrates;
The partial enlarged drawing of Fig. 3 (b): Fig. 3 (a) sem photograph;
Fig. 4 (a): with the polyvinyl alcohol rete is that adhesion layer is realized micro-contact printing, transfers to the sem photograph of the parallel band of two-dimensional colloidal crystal that is made of polystyrene microsphere on the planar substrates;
The partial enlarged drawing of Fig. 4 (b): Fig. 4 (a) sem photograph;
Fig. 5 (a): with the polyvinyl alcohol rete is that adhesion layer is realized micro-contact printing, transfers to the sem photograph of the parallel band of the suprabasil two-dimensional colloidal crystal of curved surface;
The partial enlarged drawing of Fig. 5 (b): Fig. 5 (a) sem photograph;
Fig. 6 (a): with the polyvinyl alcohol rete is that adhesion layer is realized micro-contact printing, transfers to the two-dimentional atom of the parallel band of the suprabasil two-dimensional colloidal crystal of curved surface and tries hard to;
The profile of the parallel band of two-dimensional colloidal crystal of Fig. 6 (b): Fig. 6 (a);
Fig. 7 (a): with the polyvinyl alcohol rete is that adhesion layer is realized micro-contact printing, the microscope figure of the two-dimentional heterogeneous colloidal crystal that constitutes by the micron order band of polystyrene microsphere with by the micron order band of silicon dioxide microsphere of constructing on planar substrates;
The sem photograph that amplify the part of Fig. 7 (b): Fig. 7 (a) microscope figure;
Fig. 8 (a): with the polyvinyl alcohol rete is that adhesion layer is realized micro-contact printing, and the two-dimentional atom of the two-dimentional heterogeneous colloidal crystal that constitutes by the micron order band of polystyrene microsphere with by the micron order band of silicon dioxide microsphere of constructing on planar substrates is tried hard to;
The profile of the parallel band of the two-dimentional heterogeneous colloidal crystal of Fig. 8 (b): Fig. 8 (a);
Fig. 9 (a): with the polystyrene rete is that adhesion layer is realized micro-contact printing, transfers to the atom of the parallel band of two-dimensional colloidal crystal that is made of silicon dioxide microsphere on the planar substrates and tries hard to;
The enlarged drawing that Fig. 9 (b): Fig. 9 (a) atom is tried hard to.
The specific embodiment
The present invention is further elaborated below in conjunction with embodiment, rather than will limit the invention with this.
Embodiment 1:
1. the preparation method of polystyrene microsphere:
Under nitrogen protection; with 100 milliliters distilled water is decentralized medium; with 10 gram styrene; 0.5 4 of gram, 4 '-methacryloxy-2,2 '-diphenyl propane; 1.2 (methyl) acrylic acid of gram and 0.08 gram potassium peroxydisulfate or ammonium persulfate; 0.24 the sodium acid carbonate of gram adds and is equipped with in the reactor of mechanical agitator and reflux condensing tube, mechanical agitation speed is at 300 rev/mins.In 70 ℃ water-bath, carry out the emulsifier-free emulsion polymerization reaction, need not add any surfactant and dispersant herein, react and obtain stablizing the milky surface after 24 hours and be rich in the emulsion that carboxyl and surface have the monodisperse cross-linked polystyrene microsphere of negative electrical charge, diameter of micro ball is 220 nanometers, and the emulsion solid content of polystyrene microsphere is 5.0% (mass percent).
2. the preparation method of silicon dioxide microsphere:
Average grain diameter is that the preparation of monodispersed silica spheres of 230 ± 30 nanometers is with reference to St ber method (W.St ber in the ethanol, A.Fink, J.Colloid Interface Sci.1968,26,62): under the room temperature, with 45 milliliters of tetraethyl orthosilicates, 45.4 milliliters of ammonium hydroxide, 272 ml waters and 638 milliliters of absolute ethyl alcohols addings are equipped with in the reactor of mechanical agitator and reflux condensing tube.The reaction that at room temperature is hydrolyzed, the reaction time is 24 hours.The milky silica spheres emulsion that obtains is removed impurity in the emulsion through the process of four times centrifugal (centrifugal speeds are 9500 change per minutes, each 15 minutes), then the silica spheres that obtains is placed in the baking oven of constant temperature 45 degree and dries.
3. the preparation that has the PDMS template of ordered micro-configuration: according to the method for conventional lithography, buy the plate of covering of different size and shape earlier, make the photoresist sheet of correspondingly-sized, adopt the soft lithographic method that Pattern is turned over again and be carved into the silicon rubber template with photoetching method.
The preparation of photoresist sheet: with spin coater spin coating photoresist on clean sheet glass, heating is 20-50 minute in 80-100 ℃ of baking oven, to cover plate and be placed between photoresist sheet and the 1000 watts of uviol lamps exposure 0.5-3 minute, photoresist sheet after exposure usefulness and the supporting developer solution of photoresist are developed, deionized water rinsing, nitrogen dries up.
The preparation of silicon rubber template: the dimethyl siloxane performed polymer of liquid state is mixed in 15: 1～3: 1 ratio of mass ratio with corresponding curing agent, irritate after the vacuum outgas in the mould of being made up of the photoresist sheet of smooth sheet glass and patterned surface, 40～80 ℃ solidified 3～10 hours.After the cooling polymer film that is cured is taken off from photoresist sheet carefully, thereby obtained the dimethyl silicone polymer template of patterned surface, i.e. silicon rubber (PDMS) template, the thickness of template is 50 microns to 1.5 millimeters usually.
4. the preparation of colloidal crystal in order: regulating microballoon emulsion (silicon dioxide microsphere or polystyrene microsphere) mass percentage concentration is 0.5～2.0%, 10.0～2.0 microlitre microballoon emulsions are dripped on the substrate at 50～60 degree angles, substrate was handled 30 minutes to 24 hours down at 80～100 degrees centigrade with the mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide, the consumption volume ratio of two kinds of solution is 7: 3, dries up through nitrogen after the rinsed with deionized water.Be under 30～60% the atmosphere solvent to be volatilized naturally at room temperature humidity, obtain orderly colloidal crystal.The mass concentration of microballoon emulsion and large usage quantity, angle of inclination hour, the colloidal crystal number of plies that obtains is more; Otherwise the number of plies that obtains reduces.
5. use and uncover soft lithography at PDMS template surface structure two-dimensional colloidal crystal ordered micro-configuration: with colloidal crystal (silicon dioxide colloid crystal or polystyrene colloid crystal) with have the silicon rubber template 0.2 * 10 of the wide straight-line groove structure of micron order
5～1.0 * 10
5Pascal's pressure forms down closely contact, and this sample is placed in 100～110 ℃ the baking oven and heated 3～20 hours, this sample is cooled to room temperature again, and the silicon rubber template is carefully taken off.Shown in Fig. 2 (a), Fig. 2 (b), on silicon rubber template surface, form the colloidal crystal film of the silica of sequential 2 D.If pressure is little, heat time heating time is short, then the surface of transferring to the silicon rubber template that colloidal crystal can not be complete.
Embodiment 2:
1.PDMS the preparation of the two-dimensional colloidal crystal ordered micro-configuration of silicon dioxide microsphere is as described in the embodiment 1 on the template surface.
2. scribble polymer film (polyvinyl alcohol for example, polystyrene, the preparation of any substrate polymethyl methacrylate etc.): to be 1.0%～5.0% poly-vinyl alcohol solution with the speed of 1000～3000rpm be spin-coated on the planar substrates (adopts silicon chip, sheet glass, gold plaque, quartz plate or other material substrate with mass percent concentration, the invention effect is identical), thickness is about 40～100nm.Adopt the method for dip-coating in the curved surface substrate, to be coated with polymer film, with glass tube (polystyrene in poly-vinyl alcohol solution, polymethyl methacrylates etc. are all filmed according to this method, the thickness that obtains is only relevant with the mass percent concentration of polymer solution) soak, take out, vertically place, allow solvent volatilize naturally, thickness is about 40～100nm.
3. use with the micro-contact printing technology of polyvinyl alcohol rete as adhesion layer, the parallel band of two-dimensional colloidal crystal of realizing silicon dioxide microsphere is from the enforcement of PDMS template surface to the transfer of planar substrates: with the PDMS template of the patterning that has two-dimensional colloidal crystal that forms the embodiment 1 and the planar substrates of any material that scribbles the polyvinyl alcohol rete 0.2 * 10
5～1.0 * 10
5Pascal forms closely contact down, is placed in 100～110 degrees centigrade of baking ovens and heats 1.5～5 hours.After sample was cooled to room temperature, careful the taking off away of PDMS template, the silicon dioxide colloid crystal film of PDMS template surface just had been transferred on the surface of substrate, shown in Fig. 3 (a), Fig. 3 (b).
Embodiment 3:
1.PDMS the preparation of the two-dimensional colloidal crystal ordered micro-configuration of polystyrene microsphere is as described in the embodiment 1 on the template surface.
2. scribble the polyvinyl alcohol polymer rete substrate preparation as described in example 2 above.
3. use with the micro-contact printing technology of polyvinyl alcohol film as adhesion layer, the parallel band of two-dimensional colloidal crystal of realizing polystyrene microsphere is from the enforcement of PDMS template surface to the transfer of planar substrates: with the PDMS template of the patterning that has two-dimensional colloidal crystal that forms the embodiment 1 and the planar substrates (adopt in this method be silicon chip or sheet glass) that scribbles any material of polyvinyl alcohol thin layer 0.2 * 10
5～1.0 * 10
5Pascal forms closely contact down, is placed in 100～110 degrees centigrade of baking ovens and heats 1.5～5 hours.After sample was cooled to room temperature, careful the taking off away of PDMS template, the polystyrene colloid crystal that the sequential 2 D of PDMS template surface is arranged just had been transferred on the surface of substrate.Shown in Fig. 4 (a), Fig. 4 (b).
Embodiment 4:
1.PDMS the preparation of the two-dimensional colloidal crystal ordered micro-configuration of silicon dioxide microsphere is as described in the embodiment 1 on the template surface.
2. scribble the polyvinyl alcohol polymer rete substrate preparation as described in example 2 above.
3. use with the micro-contact printing technology of polyvinyl alcohol film as adhesion layer, the parallel band of two-dimensional colloidal crystal of realizing silicon dioxide microsphere is from the enforcement of PDMS template surface to the transfer of curved surface substrate: the surface of glass tube that with the PDMS template of the patterning that has two-dimensional colloidal crystal that forms the embodiment 1 and the radius that scribbles the polyvinyl alcohol rete is 3.7 millimeters is 0.2 * 10
5～1.0 * 10
5Pascal forms closely contact down, is placed in 100～110 degrees centigrade of baking ovens and heats 1.5～5 hours.After sample was cooled to room temperature, careful the taking off away of PDMS template, the colloidal crystal that the sequential 2 D of PDMS template surface is arranged just had been transferred on the surface of substrate, as Fig. 5 (a), Fig. 5 (b).At this moment, the silicon dioxide microsphere of transferring to substrate surface all is absorbed in the polymer film uniformly, and the degree of depth is about 20～40 nanometers, shown in Fig. 6 (a), Fig. 6 (b).
Embodiment 5:
1.PDMS the preparation of the two-dimensional colloidal crystal ordered micro-configuration of silicon dioxide microsphere and polystyrene microsphere is as described in the embodiment 1 on the template surface.
2. scribble the polyvinyl alcohol polymer rete substrate preparation as described in example 2 above.
3. use with the micro-contact printing technology of polyvinyl alcohol film the enforcement of the two-dimentional heterogeneous colloidal crystal that structure constitutes by the micron order band of polystyrene microsphere with by the micron order band of silicon dioxide microsphere on planar substrates as adhesion layer: with the PDMS template of the patterning of the two-dimensional colloidal crystal that has a kind of microballoon that forms among the embodiment 1 and the planar substrates of any material that scribbles the polyvinyl alcohol thin layer 0.2 * 10
5～1.0 * 10
5Pascal forms closely contact down, this sample is placed in 100～110 degrees centigrade of baking ovens heated 1.5～5 hours then.After sample was cooled to room temperature, careful the taking off away of PDMS template, the colloidal crystal of orderly arrangement of two dimension just had been transferred on the surface of substrate.PDMS template with a new colloidal crystal that has another kind of microballoon forms tight the contact with the colloidal crystal film that the micron order band of transferring on the polymeric substrates is arranged along orthogonal direction again, this sample is placed in 100～110 degrees centigrade of baking ovens heated 1.5～5 hours then.After sample was cooled to room temperature, careful the taking off away of PDMS template, the colloidal crystal of orderly arrangement of two dimension just had been transferred on the surface of substrate.Shown in Fig. 7 (a), Fig. 7 (b).Fig. 7 (a) has provided the optical microscope photograph of reflective-mode of the heterogeneous colloidal crystal of a patterning, under light microscope, constitute two kinds of bands of heterogeneous colloidal crystal because diffraction of light presents the color of two kinds of homogeneous, this phenomenon has reflected the long-range order that colloid micro ball is arranged, and color is different to the dependence of microballoon size and two kinds of colloid micro ball material refractive indexes.This heterogeneous colloidal crystal is to prepare by the two micro-contact printing processes that go on foot.What shift in primary micro-contact printing process is the colloidal crystal band of polystyrene microsphere, and this band is continuous, is light green color, and the width of band is 9.0 microns, and the interband distance is 18.0 microns.What shift in secondary micro-contact printing process is the colloidal crystal band of silicon dioxide microsphere, the arrangement of this band is arranged with the polystyrene band and is become an angle of 90 degrees approximately, is discontinuous, is light yellow, the width of band is 5.5 microns, and the interband distance is 4.0 microns.The band that can observe two kinds of crystal in Fig. 7 (b) exists a width to be about the crack of 200nm at infall, the formation in this crack may be because the colloidal crystal film that forms in the print steps of the first step has certain height, therefore, some zone with the PDMS template of second kind of colloidal crystal in the print steps in second step can not form tight the contact with polymer film, thereby has caused the crack of two kinds of band infalls.From then on the heterogeneous colloidal crystal that we can also observe that our method forms among the figure is proper two-dimensional colloidal crystal, and through after twice printing process, the silicon dioxide microsphere that is not scattered is stayed on the polystyrene colloid crystalline film that forms earlier.
Two kinds of colloid micro balls transferring to substrate surface by twice micro-contact printing process also all are absorbed in the polymer film uniformly, and the degree of depth is about 20～40 nanometers.Be the microstructure of two-dimentional heterogeneous colloidal crystal of explanation patterning, we have provided the AFM photo of the two dimension of two kinds of colloidal crystal band infalls in Fig. 8 (a).As can be seen from the figure, the particle diameter of silicon dioxide microsphere is about 230nm, and the particle diameter of polystyrene microsphere is 200nm.The profile analysis of infall also demonstrates the height difference of two kinds of colloid micro balls on polymer film from Fig. 8 (b): the former height is 205nm, and the latter's height is 175nm.This result proves that two kinds of colloid micro balls all have been absorbed in the polymer film in transfer process, the degree of depth is approximately 25nm.Can infer that the structure that this just microballoon is absorbed in the polymer film provides powerful interaction from the jut of PDMS template surface to the on-chip transfer of overlie polymer film for realizing colloidal crystal.
Embodiment 6:
1.PDMS the preparation of the two-dimensional colloidal crystal ordered micro-configuration of silicon dioxide microsphere is as described in the embodiment 1 on the template surface.
2. scribble the poly styrene polymer rete substrate preparation as described in example 2 above.
3. use with the micro-contact printing technology of polystyrene film as adhesion layer, the parallel band of two-dimensional colloidal crystal of realizing silicon dioxide microsphere is from the enforcement of PDMS template surface to the transfer of planar substrates: with the PDMS template of the patterning that has two-dimensional colloidal crystal that forms the embodiment 1 and the planar substrates (adopting silicon chip, sheet glass, gold plaque or quartz plate) that scribbles any material of polystyrene film thin layer 0.2 * 10
5～1.0 * 10
5Pascal forms closely contact down, is placed in 110～130 degrees centigrade of baking ovens and heats 1.5～5 hours.After sample was cooled to room temperature, careful the taking off away of PDMS template, the colloidal crystal of orderly arrangement of two dimension just had been transferred on the surface of substrate.Shown in Fig. 9 (a), Fig. 9 (b).Because glass transition temperature 90-100 ℃ of polystyrene is higher than 80 ℃ of the glass transition temperatures of polyvinyl alcohol, selected temperature will be higher than the employed temperature of polyvinyl alcohol in the micro-contact printing process that with the polystyrene film is adhesion layer, and the effect that two kinds of polymer films are done adhesion layer is identical.
Embodiment 7:
1.PDMS the preparation of the two-dimensional colloidal crystal ordered micro-configuration of silicon dioxide microsphere is as described in the embodiment 1 on the template surface.
2. scribble the poly methyl methacrylate polymer rete substrate preparation as described in example 2 above.
3. use with the micro-contact printing technology of polymethyl methacrylate film as adhesion layer, the parallel band of two-dimensional colloidal crystal of realizing silicon dioxide microsphere is from the enforcement of PDMS template surface to the transfer of planar substrates: with the PDMS template of the patterning that has two-dimensional colloidal crystal that forms the embodiment 1 and the planar substrates (adopting silicon chip, sheet glass, gold plaque or quartz plate) that scribbles any material of polymethyl methacrylate film thin layer 0.2 * 10
5～1.0 * 10
5Pascal forms closely contact down, is placed in 130～160 degrees centigrade of baking ovens and heats 1.5～5 hours.After sample was cooled to room temperature, careful the taking off away of PDMS template, the colloidal crystal of orderly arrangement of two dimension just had been transferred on the surface of substrate.Its result is same shown in accompanying drawing 9 (a), Fig. 9 (b).Because 114 ℃ of the glass transition temperatures of polymethyl methacrylate are higher than 80 ℃ of the glass transition temperatures of polyvinyl alcohol, selected temperature will be higher than the employed temperature of polyvinyl alcohol in the micro-contact printing process that with the polymethyl methacrylate film is adhesion layer, and the effect that two kinds of polymer films are done adhesion layer is identical.
Claims (3)
1, with the colloidal crystal is the method that ink carries out micro-contact printing, comprise the preparation of orderly colloidal crystal, preparation, two-dimensional colloidal crystal five steps of micro-contact printing, it is characterized in that at the patterning of dimethyl silicone polymer template surface, the preparation that scribbles the substrate of polymer film, colloidal crystal with dimethyl silicone polymer template of ordered micro-configuration:
1. the preparation of colloidal crystal in order: with monodispersed silicon dioxide microsphere or polystyrene microsphere, add the deionized water dilution, being adjusted to mass percentage concentration is 0.5～2.0%, 10～20 microlitre microballoon emulsions are dripped on 50～60 degree angle silicon chip, sheet glass, gold plaque or the quartz plate substrates after treatment, be under 30～60% the atmosphere solvent to be volatilized naturally at room temperature humidity, obtain orderly colloidal crystal;
2. the preparation that has the dimethyl silicone polymer template of ordered micro-configuration: at first the dimethyl siloxane performed polymer of liquid state is mixed in 15: 1～3: 1 ratio of mass ratio with corresponding curing agent, irritate in the mould of forming by the photoresist sheet of smooth sheet glass and patterned surface after the vacuum outgas, 40 ℃～80 ℃ solidified 3～10 hours, after the cooling polymer film that is cured is taken off from photoresist sheet carefully, thereby obtain the dimethyl silicone polymer template of patterned surface, i.e. the dimethyl silicone polymer template;
3. two-dimensional colloidal crystal is at the patterning of dimethyl silicone polymer template surface: with patterned dimethyl silicone polymer template and the colloidal crystal that obtained 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and under 100～110 ℃ environment, heated 3～20 hours, this sample is cooled to room temperature, again the silicon rubber template is carefully taken off, thereby colloidal crystal individual layer feasible and that the dimethyl silicone polymer template surface closely contacts is transferred on the dimethyl silicone polymer template surface, form orderly arrangement, and form the micro-structural of patterning in the superiors of colloidal crystal;
4. scribble the preparation of the substrate of polymer film: being 1.0%～5.0% polymer solution with mass percent concentration is spin-coated on the planar substrates with the speed of 1000～3000rpm, and thickness is about 40～100nm; Or adopt the method for dip-coating in the curved surface substrate, to be coated with polymer film, and the curved surface substrate is soaked in polymer solution, take out, vertically place, allow volatilization naturally under the solvent room temperature, thickness is about 40～100nm;
5. the micro-contact printing of colloidal crystal: the dimethyl silicone polymer template of the patterning that has two-dimensional colloidal crystal that will form in 3. in step and scribble the substrate of polymer foil 0.2 * 10
5～1.0 * 10
5Form closely contact under the Pascal, and heated 1.5～5 hours down in 100～160 ℃, after sample was cooled to room temperature, careful the taking off away of dimethyl silicone polymer template, the colloidal crystal that sequential 2 D is arranged just was transferred on the surface of substrate.
2, as claimed in claim 1 is the method that ink carries out micro-contact printing with the colloidal crystal, it is characterized in that: substrate is silicon chip, sheet glass, gold plaque or quartz plate.
3, as claimed in claim 1 is the method that ink carries out micro-contact printing with the colloidal crystal, it is characterized in that: the polymer film layer material is polyvinyl alcohol, polystyrene or polymethyl methacrylate.
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