CN1654311A - Method for constructing non-close packing colloid balls ordered arrangement using soft-graving technology - Google Patents
Method for constructing non-close packing colloid balls ordered arrangement using soft-graving technology Download PDFInfo
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Abstract
The present invention relates to soft etching process to constitute ordered arrangement of colloid balls in non-compact accumulation, and is especially soft etching process for precise control of interval and lattice structure of colloid balls. The process includes five steps of: preparing ordered colloid crystal, preparing and separating PDMS template, soft etching to transfer the 2D colloid crystal to the PDMS template, preparing substrate with PVA film, and forming ordered arrangement of colloid balls in non-compact accumulation. Swelling PDMS template with colloid balls in mixed toluene/acetone solution can form 2D hexagonal non-compact colloid ball arrangement and 2D non-hexagonal colloid ball arrangement with flat surface or patterned surface on the substrate with PVA film. The present invention has attractive application foreground in optics, photonics, sensor, surface micro structure and other fields.
Description
Technical field
The present invention relates to a kind of soft lithography that utilizes and construct the method that non-closelypacked colloidal spheres is arranged in order, particularly relate to a kind of soft lithography that utilizes the sphere gap of colloidal spheres, the method that lattice structure is accurately controlled.
Background technology
Diameter is between the formed non-tightly packed arrangement of the colloidal spheres of nanometer, micron level, because it has tempting application prospect in fields such as optics, photonic propulsion, sensor and surperficial micro-structures, has therefore caused people's extensive concern at many scientific research fields.Various technology also grow up thereupon, all are used to carry single colloid micro ball to appointed positions as optical tweezers (opticaltweezers), nanometer robot (microrobot), laser beam (laser beams), AFM.Though this method can accurately be controlled the position of each colloidal spheres and control lattice structure arbitrarily, this process of carrying continuously one by one itself just proves that this method productive rate is low.In order to arrange by the controlled large-area two-dimensional colloid crystalline substance of disposable acquisition lattice, people have been developed the method for many template confinements, as utilize the microcosmic of how much patterns of template surface or chemical property difference limit colloidal spheres to arrange.In order to obtain the lithographic technique that this template just need can be as accurate as sub-micron, as senior photoetching (advancedphotolithography), focused-ion-beam lithography (focused ion beam lithography) and dip in tattooing needle point technology (dip-pen nanolithography) etc. obtains but these methods are difficult in common lab.
The colloidal spheres self assembly can form two dimension or the tightly packed arrangement of three-dimensional six sides, and the colloidal spheres of utilizing lithographic technique or use to have electric charge also can realize the accurately controlled of sphere gap, but is difficult to change lattice structure.The someone reports recently, and the polymer performed polymer is poured in the brilliant slit of colloid, solidifies then, has so just obtained the colloid crystalline substance compound of polymer overmold, by swelling or make polymer generation deformation, just can adjust the sphere gap and the lattice structure of colloid crystalline substance.The brilliant composite construction of this polymer-colloid gets a good chance of being prepared into new optics and sensor component.Yet the structure of this non-closelypacked ball is difficult to break away from polymer and individualism.
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.
Summary of the invention
The purpose of this invention is to provide a kind of soft lithography that utilizes and construct the method that non-tightly packed two-dimensional colloidal ball is arranged in order, and adopting said method can accurately be controlled the sphere gap and the lattice structure of colloid crystalline substance within the specific limits.
The monodisperse silica microspheres that the present invention prepares with sol-gel process carries out self assembly and prepares orderly colloidal crystal, utilize soft lithography that the colloidal crystal that obtains is processed then and make it to change sphere gap or lattice structure, use the present invention combines the non-tightly packed colloidal spheres that can also obtain having patterning with patterning techniques in the soft lithography orderly arrangement.
Utilize soft lithography in substrate, can construct the orderly arrangement of two kinds of non-tightly packed colloidal spheres by method of the present invention, a kind of is that the non-closelypacked colloidal spheres of structure two dimension six sides is arranged, another kind is that the colloidal spheres of the two-dimentional non-hexagonal structure of structure is arranged, and wherein the method for the non-closelypacked colloidal spheres arrangement of structure two dimension six sides comprises following five 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 sol-gel process preparation, A.Fink, J.Colloid Interface Sci.1968,26,62), add the absolute ethyl alcohol dilution, being adjusted to mass percent concentration is 0.5～2.0%, the silicon dioxide microsphere emulsion that 10～20 microlitres are above-mentioned drips to that (substrate generally is silicon chip, sheet glass, gold plaque or quartz plate on the substrate at 10～20 degree angles that tilt, require surfacing, roughness is little.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 earlier, the consumption volume ratio of two kinds of solution is 7: 3, 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, by adjusting the concentration and the consumption of emulsion, just can obtain the colloidal crystal of two dimension or three-dimensional order, if the concentration and the large usage quantity of microballoon emulsion, the colloidal crystal number of plies that obtains is more; Otherwise the number of plies that obtains is less.
2.PDMS the preparation of template: two kinds of PDMS templates of main use in this patent, a kind of is flat PDMS template, a kind of is the template that the surface has ordered micro-configuration.The preparation method of two kinds of templates is basic identical, 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, vacuum outgas, again this mixture is spin-coated on smooth glass surface or has on the photoresist sheet of patterning, rotating speed is 1000～1500 rev/mins, the spin coating time is 1～5 minute, again this sheet glass or photoresist sheet are put in 60 ℃ of baking ovens and heated 3～10 hours, after the cooling with careful the taking off of the polymer film that is cured, thereby obtain dimethyl silicone polymer flat or patterned surface (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, thereby 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.Whitesies, Science 1996,273,347.Y.N.Xia, G.M.Whitesides, Angew.Chem.Int.Ed.Engl.1998,37,550.).
3. utilize and uncover soft lithography two-dimensional colloidal crystal is transferred to the PDMS template surface: flat or surface are had the PDMS template of ordered micro-configuration (patterned surface) and the colloidal crystal that obtained 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 3～20 hours, then this sample is cooled to room temperature, again the silicon rubber template is carefully taken off.At this moment, just be transferred on the PDMS template surface with the colloid monolayer crystal that the PDMS template surface closely contacts, in this layer colloid crystalline substance, colloidal spheres is still keeping six side's close-packed structures.If contact 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.
4. (substrate can be a unlike material to scribble any substrate of polyvinyl alcohol rete, it is not limited to silicon chip, sheet glass, gold plaque or quartz plate in the step 1, can be the material of spin on polymers rete thereon arbitrarily) preparation: being 5.0%～8.0% polyvinyl alcohol water solution with mass percent concentration is spin-coated on the planar substrates with 1000～3000 rev/mins speed, thickness is about 50～400nm, with the increase of polyvinyl alcohol concentration, suprabasil polyvinyl alcohol rete thickens; Adopt silicon chip, sheet glass, gold plaque, quartz plate or other material substrate, the invention effect is identical.
5. the two dimension six sides non-tightly packed colloidal spheres formation and the transfer of arrangement in order: the PDMS template that has colloidal spheres that obtains in the step 3 was put in toluene/acetone mixed solution 10～60 minutes, the molar content of toluene is 100%～0% in the mixed solution, because toluene can make PDMS template swelling, and acetone can not, the ratio of regulating two kinds of raw materials in the mixed solution just can be controlled the degree of swelling of PDMS template, in the time of PDMS template swelling, its surperficial two-dimensional colloidal crystalline substance will become the non-close-packed structure of six sides by six side's close-packed structures.Just can control the PDMS degree of swelling by control toluene/acetone ratio, just can regulate the sphere gap of the non-tightly packed colloidal spheres of PDMS surface six sides.Again with the PDMS template of swelling rapidly with scribble the substrate of polyvinyl alcohol rete 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 1.5～5 hours.After sample is cooled to room temperature, the PDMS template is carefully taken off away, the non-closelypacked colloidal spheres of two dimension six sides is arranged and just has been transferred on the substrate surface, and is held again.
Preceding 4 steps of colloidal spheres aligning method of constructing two-dimentional non-hexagonal structure are with above identical, the 5th step is: formation and transfer that the colloidal spheres of two-dimentional non-hexagonal structure is arranged: get the template that has colloidal spheres in the above-mentioned steps 3, apply different power along the mutually perpendicular direction of stencil plane, make PDMS template generation deformation, and the colloidal spheres sphere gap on the PDMS template surface will be directly proportional with the deformation of PDMS template, that is to say that if the PDMS template is extended one times on a certain direction, sphere gap also will double in that this side up so.Therefore can regulate the arrangement mode of colloidal spheres on the microcosmic by the shape that macro adjustments and controls PDMS is stretched.Again with this PDMS template 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms tight the contact with the substrate that scribbles the polyvinyl alcohol rete down, and in 100～110 ℃ baking oven, heated 1.5～5 hours, sample is carefully taken off away the PDMS template after being cooled to room temperature again, and the two-dimensional colloidal ball of non-hexagonal structure has been arranged on the surface that just is transferred and is fixed to substrate.
Utilize this method can control lattice structure and sphere gap that the two-dimensional colloidal ball is arranged accurately, and this method is simple, just can operate in common lab.
Description of drawings
Fig. 1: construct non-closelypacked colloidal spheres aligning method schematic diagram with soft lithography;
Fig. 2: the closelypacked colloidal spheres Pareto diagram of six sides that utilizes the method preparation of self assembly;
Fig. 3: the non-closelypacked colloidal spheres Pareto diagram of six sides that utilizes the method preparation of swelling; Wherein the employed solution of swelling is toluene/acetone mixed solution, and the toluene molar content is 15.5%;
Fig. 4: the non-closelypacked colloidal spheres Pareto diagram of six sides that utilizes the method preparation of swelling; Wherein the employed solution of swelling is toluene/acetone mixed solution, and the toluene molar content is 28.8%;
Fig. 5: the non-closelypacked colloidal spheres Pareto diagram of six sides that utilizes the method preparation of swelling; Wherein the employed solution of swelling is toluene/acetone mixed solution, and the toluene molar content is 58.2%;
Fig. 6: the non-closelypacked colloidal spheres Pareto diagram of six sides that utilizes the method preparation of swelling; Wherein the employed solution of swelling is toluene;
Fig. 7: the non-closelypacked colloidal spheres of preparation six sides is arranged the graph of relation of its sphere gap and toluene concentration;
Fig. 8: the stretching principle schematic for preparing the colloidal spheres arrangement of two-dimentional non-hexagonal structure; When the PDMS template remains unchanged, and make the other direction elongation on a certain direction, will obtain two kinds of different lattice structures as shown in the figure;
Fig. 9: be to keep X-axis constant, the cubic non-close-packed structure schematic diagram that on Y direction, stretches and obtain;
Figure 10: be to keep Y-axis constant, the structural representation that the row shape is arranged that is that on X-direction, stretches and obtain;
Figure 11 (a): be to use the PDMS template that has band shape pattern, stretch, keep PDMS template constant result who obtains on direction simultaneously perpendicular to band shape pattern along being parallel to PDMS template band shape pattern direction;
Figure 11 (b): the partial enlarged drawing that is Figure 11 (a).
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 silicon dioxide microsphere:
Average grain diameter is that the preparation of monodispersed silica spheres of 566 ± 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 14 milliliters of tetraethyl orthosilicates, 31 milliliters of ammonium hydroxide, 56 ml waters and 150 milliliters of isopropyl 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, can obtain milky silica spheres emulsion.
2. the preparation of colloidal crystal in order: with the monodisperse silica microspheres (diameter is 566 nanometers) of sol-gel process preparation, adding absolute ethyl alcohol, to be diluted to mass percent concentration be 0.5～2.0%, 10.0～20.0 microlitre microballoon emulsions are 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 on the substrate that tilts about 10 degree, the consumption volume ratio of two kinds of solution is 7: 3, 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 the closelypacked colloidal crystal of six sides, sphere gap equals the diameter 568nm of ball, as Fig. 2.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.
3. use and uncover soft lithography the tightly packed colloidal crystal of two dimension is transferred to the flat PDMS template surface in surface: with PDMS template and the colloidal crystal that obtained 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 3～20 hours, and this sample is cooled to room temperature, again the silicon rubber template is carefully taken off.At this moment, just be transferred on the PDMS template surface with the colloid monolayer crystal that the PDMS template surface closely contacts.And six side's close-packed structures that this layer colloidal crystal still keeping self assembly to form.
4. scribble the preparation of any material substrate of polyvinyl alcohol: be that the aqueous solution of 5.0%～8.0% polyvinyl alcohol is spin-coated on the speed of 1000～3000rpm that (substrate can be a silicon chip on the planar substrates with mass percent concentration, quartz plate, sheet glass, gold plaque etc.), thickness 50～400 nanometers.
5. the method construct sphere gap with swelling is the non-closelypacked colloidal spheres arrangement of six sides of 670 nanometers: preparation toluene/acetone mixed solution, regulating toluene concentration is 15.5% (mole percent level), get in the step 3 the PDMS template that has two-dimensional colloidal crystal that forms and be put in toluene/acetone mixed solution and take out after 30 minutes, immediately with this PDMS template with scribble the substrate of polyvinyl alcohol rete 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 1.5～5 hours.After sample is cooled to room temperature, the PDMS template is carefully taken off away, the non-closelypacked colloid crystalline substance of two dimension six sides just has been transferred on the substrate surface, and is held again, and sphere gap is 670 nanometers, as Fig. 3.
Embodiment 2:
The preparation of silicon dioxide microsphere, the preparation of colloidal crystal in order, the tightly packed colloidal crystal of two dimension is transferred to the PDMS template surface, the preparation method of any material substrate who scribbles polyvinyl alcohol is as described in the embodiment 1, be that the non-closelypacked colloidal spheres of six sides of 720 nanometers is arranged with the method construct sphere gap of swelling then: the PDMS template that has two-dimensional colloidal crystal that forms in embodiment 1 step 3 is put in the toluene that toluene concentration is 28.8% (mole percent level)/acetone mixed solution takes out after 30 minutes, immediately with this PDMS template rapidly with scribble the substrate of polyvinyl alcohol rete 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 1.5～5 hours.After sample is cooled to room temperature, the PDMS template is carefully taken off away, the non-closelypacked colloid crystalline substance of two dimension six sides just has been transferred on the substrate surface, and is held again, and sphere gap is 720 nanometers, as Fig. 4.
Embodiment 3:
The preparation of silicon dioxide microsphere, the preparation of colloidal crystal in order, the tightly packed colloidal crystal of two dimension is transferred to the PDMS template surface, the preparation method of any material substrate who scribbles polyvinyl alcohol is as described in the embodiment 1, be that the non-closelypacked colloidal spheres of six sides of 798 nanometers is arranged with the method construct sphere gap of swelling then: the PDMS template that has two-dimensional colloidal crystal that forms in embodiment 1 step 3 is put in the toluene that toluene concentration is 58.2% (mole percent level)/acetone mixed solution takes out after 30 minutes, immediately with this PDMS template rapidly with scribble the substrate of polyvinyl alcohol rete 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 1.5～5 hours.After sample is cooled to room temperature, the PDMS template is carefully taken off away, the non-closelypacked colloid crystalline substance of two dimension six sides just has been transferred on the substrate surface, and is held again, and sphere gap is 798 nanometers, as Fig. 5.
Embodiment 4:
The preparation of silicon dioxide microsphere, in order preparation, the two-dimentional tightly packed colloidal crystal of colloidal crystal are transferred to the PDMS template surface, are scribbled the preparation method of any material substrate of polyvinyl alcohol as described in the embodiment 1, be that the non-closelypacked colloidal spheres of six sides of 843 nanometers is arranged with the method construct sphere gap of swelling then: the PDMS template that has two-dimensional colloidal crystal that forms in embodiment 1 step 3 is put in the toluene solution takes out after 30 minutes, immediately with this PDMS template rapidly with scribble the substrate of polyvinyl alcohol rete 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 1.5～5 hours.After sample is cooled to room temperature, the PDMS template is carefully taken off away, the non-closelypacked colloid crystalline substance of two dimension six sides just has been transferred on the substrate surface, and is held again, and sphere gap is 843 nanometers, as Fig. 6.
Embodiment 5:
The preparation of silicon dioxide microsphere, in order preparation, the two-dimentional tightly packed colloidal crystal of colloidal crystal are transferred to the PDMS template surface, are scribbled the preparation method of any material substrate of polyvinyl alcohol as described in the embodiment 1, arrange with the non-closelypacked colloidal spheres in method construct four directions that stretches then: get the PDMS template that has two-dimensional colloidal crystal in embodiment 1 step 3, as shown in Figure 8, when keeping X-axis constant, on Y direction, stretch, make the PDMS template on Y direction, increase by 0.66 times, again with this PDMS template 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms tight the contact with the substrate that scribbles the polyvinyl alcohol rete down, and in 100～110 ℃ baking oven, heated 1.5～5 hours, sample is carefully taken off away the PDMS template after being cooled to room temperature again, just having obtained cubic non-closelypacked colloidal spheres arranges, sphere gap is 657 nanometers, as Fig. 9.
Embodiment 6:
The preparation of silicon dioxide microsphere, in order preparation, the two-dimentional tightly packed colloidal crystal of colloidal crystal are transferred to the PDMS template surface, are scribbled the preparation method of any material substrate of polyvinyl alcohol as described in the embodiment 1, be the colloidal spheres arrangement that the row shape is arranged with the method construct that stretches then: get the PDMS template that has two-dimensional colloidal crystal in embodiment 1 step 3, as shown in Figure 8, when keeping Y-axis constant, on X-direction, stretch, make the PDMS template on X-direction, increase by 0.63 times, again with this PDMS template 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms tight the contact with the substrate that scribbles the polyvinyl alcohol rete down, and in 100～110 ℃ baking oven, heated 1.5～5 hours, sample is carefully taken off away the PDMS template after being cooled to room temperature again, just obtained being the colloidal spheres arrangement that the row shape is arranged, each colloidal spheres that lists is closely contact each other, and spacing equals diameter 566 nanometers of ball; And the spacing between row and the row is 798 nanometers, as Figure 10.
Embodiment 7:
The preparation of silicon dioxide microsphere, in order the preparation of colloidal crystal is as described in the embodiment 1.
The PDMS template surface that soft lithography is transferred to the tightly packed colloidal crystal of two dimension patterning is uncovered in use: the surface is had the PDMS template of band shape pattern and the colloidal crystal that obtained 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and heats in 100～110 ℃ baking oven 3～20 hours, and this sample is cooled to room temperature, again the silicon rubber template is carefully taken off.Transfer to the PDMS template surface with regard to the colloidal spheres that has one deck patterning, and still keep six side's close-packed structures between the colloidal spheres.
The preparation of any substrate that scribbles polyvinyl alcohol is as described in the embodiment 1.
The non-tightly packed colloidal spheres that has patterning by the method construct that stretches is arranged: get the PDMS template that the patterning colloid ball is arranged that has that obtains in the top step, be stretched to original 1.51 times along being parallel to PDMS template band shape pattern direction, and remaining unchanged perpendicular to PDMS template band shape pattern direction, again with this PDMS template 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms tight the contact with the substrate that scribbles the polyvinyl alcohol rete down, and in 100～110 ℃ baking oven, heated 1.5～5 hours, sample is carefully taken off away the PDMS template after being cooled to room temperature again, just obtained as Figure 11 (a), the result of 11 (b), figure discal patch band chart case is wide 5.0 microns, and the spacing between the band is 11.0 microns, each colloidal spheres that lists is closely contact each other, and spacing equals diameter 566 nanometers of ball; Spacing between row and the row is 740 nanometers.
Claims (2)
1, utilizes soft lithography to construct the method that non-tightly packed colloidal spheres is arranged in order, comprise the steps:
1. the preparation of colloidal crystal in order: prepare monodisperse silica microspheres with sol-gel process, add the absolute ethyl alcohol dilution, being adjusted to mass percent concentration is 0.5～2.0%, the above-mentioned silicon dioxide microsphere emulsion of 10～20 microlitres is dripped on the substrate at 10～20 degree angles, be under 30～60% the atmosphere solvent to be volatilized naturally at room temperature humidity, obtain the colloidal crystal of two dimension or three-dimensional order;
2. the preparation of PDMS template: the dimethyl siloxane performed polymer of liquid state is mixed in 15: 1～3: 1 ratio of mass ratio with corresponding curing agent, vacuum outgas, again this mixture is spin-coated on smooth glass surface or has on the photoresist sheet of patterning, rotating speed is 1000～1500 rev/mins, the spin coating time is 1 minute, again this sheet glass or photoresist sheet are put in 60 ℃ of baking ovens and heated 3～10 hours, after the cooling with careful the taking off of the polymer film that is cured, thereby obtain dimethyl silicone polymer flat or patterned surface (PDMS) template;
3. utilize and uncover soft lithography two-dimensional colloidal crystal is transferred to the PDMS template surface: with PDMS template flat or patterned surface and the colloidal crystal that obtained 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and in 100～110 ℃ baking oven, heated 3～20 hours, then this sample is cooled to room temperature, again the silicon rubber template is carefully taken off, at this moment, just be transferred on the PDMS template surface with the colloid monolayer crystal that the PDMS template surface closely contacts;
4. scribble the preparation of polyvinyl alcohol rete substrate: being 5.0%～8.0% polyvinyl alcohol water solution with mass percent concentration is spin-coated on the planar substrates with 1000～3000 rev/mins speed, thickness is about 50～400nm, thereby obtains scribbling the substrate of polyvinyl alcohol rete;
5. the formation that non-tightly packed colloidal spheres is arranged in order: the PDMS template that has colloidal spheres that step is obtained in 3. was put in toluene/acetone mixed solution 10～60 minutes, the molar content of toluene is 100%～0% in the mixed solution, then with the PDMS template of swelling rapidly with scribble the substrate of polyvinyl alcohol rete 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms closely contact down, and in 100～110 ℃ baking oven, heated 1.5～5 hours, after treating that sample is cooled to room temperature, again the PDMS template is carefully taken off away, arrange thereby in the substrate that scribbles the polyvinyl alcohol rete, obtain the non-closelypacked colloidal spheres of surface two dimension six sides flat or patterned surface; Perhaps, get the template that step has colloidal spheres in 3., apply different power, make PDMS template generation deformation along the mutually perpendicular direction of stencil plane, again with this PDMS template 0.2 * 10
5～1.0 * 10
5Pascal's pressure forms tight the contact with the substrate that scribbles the polyvinyl alcohol rete down, and in 100～110 ℃ baking oven, heated 1.5～5 hours, sample is carefully taken off away the PDMS template after being cooled to room temperature again, thereby the two-dimensional colloidal ball that obtains surface non-hexagonal structure flat or patterned surface in the substrate that scribbles the polyvinyl alcohol rete is arranged.
2, the soft lithography that utilizes as claimed in claim 1 is constructed the method that non-tightly packed colloidal spheres is arranged in order, it is characterized in that: substrate is surfacing, the silicon chip that roughness is little, sheet glass, gold plaque or quartz plate, substrate was handled 30 minutes to 24 hours down at 80～100 degrees centigrade at the mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide, the consumption volume ratio of two kinds of solution is 7: 3, through dry back effect under nitrogen or air atmosphere after the rinsed with deionized water.
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| CN102583226A (en) * | 2012-03-12 | 2012-07-18 | 吉林大学 | Preparation method for multielement dissymmetrical microsphere and heterogeneous microsphere shell |
| CN102583226B (en) * | 2012-03-12 | 2014-06-04 | 吉林大学 | Preparation method for multielement dissymmetrical microsphere and heterogeneous microsphere shell |
| CN102786028A (en) * | 2012-07-17 | 2012-11-21 | 西南交通大学 | Manufacturing method of multi-needle point array used for large area friction induced micro/nano-processing |
| CN102786028B (en) * | 2012-07-17 | 2015-05-06 | 西南交通大学 | Manufacturing method of multi-needle point array used for large area friction induced micro/nano-processing |
| CN104108680B (en) * | 2014-06-19 | 2016-02-03 | 北京大学深圳研究生院 | A kind of preparation method of micro-sphere array needle point |
| CN105951049A (en) * | 2016-05-13 | 2016-09-21 | 中山大学 | Preparation method of metal particles with nanoscale gaps |
| CN105951049B (en) * | 2016-05-13 | 2018-04-13 | 中山大学 | A kind of metallic particles manufacture method with nanoscale gap |
| CN106430089A (en) * | 2016-09-27 | 2017-02-22 | 中国农业大学 | Diatom shell micro particle single layer array method |
| CN108796604A (en) * | 2017-05-03 | 2018-11-13 | 中国科学院化学研究所 | A kind of colloidal photon crystal and preparation method thereof with curved-surface structure |
| CN107159072A (en) * | 2017-05-10 | 2017-09-15 | 浙江工业大学 | A kind of preparation method of the self-driven microreactor of regulatable drop |
| CN107159072B (en) * | 2017-05-10 | 2019-03-19 | 浙江工业大学 | A kind of regulatable drop drives the preparation method of microreactor certainly |
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