CN105776129B - A kind of manufacture method of the controllable flexible micro-nano post array of form - Google Patents

Abstract

A method for manufacturing a form-controllable flexible micro-nano pillar array. Firstly, a hydrosol adhesive layer is coated on the surface of the substrate, and then a micro-nano patterned photoresist is obtained on the hydrosol adhesive layer through a photolithography process. The surface of the resist is patterned with micro-nano particles by scraping, and the photoresist is removed to obtain a patterned template of micro-nano particles; the polymer is coated on the surface of the substrate, and then the substrate is preheated; the patterned template The micro-nano particles on the surface contact and embed the polymer; then pull the patterned template to make the polymer stretched into a micro-nano column array, and then heat the substrate to solidify the micro-nano column array; then heat the patterned template to make the micro-nano column array The nanoparticles are detached from the hydrosol adhesion layer to obtain a micro-nano column array with micro-nano particles on the top; finally, the micro-nano particles on the top of the micro-nano column array are removed to obtain a polymer micro-nano column array. The present invention has the advantages of simple operation, low cost Advantages of low cost and short cycle time.

Description

A method for fabricating a shape-controllable flexible micro-nano pillar array

technical field

The invention belongs to the technical field of micro-nano manufacturing, and in particular relates to a method for manufacturing a shape-controllable flexible micro-nano column array.

Background technique

High-aspect-ratio polymer micro-nanopillar arrays have large specific surface area and good electromagnetic wave modulation ability, and are widely used in the enhanced absorption of electrons in solar cells, cell inspection and particle separation in the biological field, functional coatings (superhydrophobic and superoleophobic) ), microfluidic chips and other fields. At present, the preparation methods of high-aspect-ratio polymer micro-nano-column arrays mainly include: electrospinning, nanoimprinting, electrical induction molding, and mold replicating. Among them, the electrospinning method refers to the process in which a polymer solution (or melt) forms fibers under the action of a high-voltage electric field. Its core is to make the charged polymer solution or melt flow and deform in an electrostatic field, and then undergo The solvent evaporates or the melt cools and solidifies, so that micro-nano columnar substances are obtained; nano-imprinting methods mainly include thermal embossing, ultraviolet nano-imprinting and micro-contact printing. After heating/ultraviolet light treatment, a polymer micro-column structure complementary to the pattern structure of the mold is obtained; the electric induction molding method uses electrostatic force to realize the rheological drive of the dielectric polymer, and realizes the preparation of the micro-nano column structure; the mold complex The molding method is to pour the flowing polymer on the mold of the micro-hole array, and realize the polymer to fully fill the micro-holes through a vacuum environment. After heating and curing, the polymer micro-nano column array is obtained by demoulding.

At this stage, the manufacturing process of high aspect ratio polymer micro-nano column arrays has the following problems: the micro-nano column or fiber prepared by electrospinning method has low strength, and it is difficult to obtain nanofiber filaments or short fibers separated from each other, and the yield is very low ; The mechanical pressure introduced by the nanoimprint method will cause problems such as geometric deformation of the nanostructure and uneven filling of the variable-size structure; the electric induction molding method and the mold replica method rely on the template, which is generally obtained by dry etching, and its manufacturing cost In addition, the problem of micro-column breakage is prone to occur during the demoulding process of the mold replica method. In addition, the existing technology is difficult to realize the fabrication of inclined or complex polymer micro-nano column arrays. These issues severely restrict the functional reliability of devices containing polymeric micro-nanopillar arrays.

Contents of the invention

In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a method for manufacturing a flexible micro-nano column array with controllable morphology, which can realize low-cost and rapid manufacturing of polymer micro-nano column arrays, and at the same time realize polymer micro-nano column arrays. The regulation of the morphology and the patterning of the polymer micro-nano pillar array has the advantages of simple operation, low cost and short cycle.

In order to achieve the above object, the technical scheme that the present invention takes is:

A method for manufacturing a shape-controllable flexible micro-nano pillar array, comprising the following steps:

1) Coating a hydrosol adhesive layer on the surface of the substrate first, and then obtaining a micro-nano patterned photoresist on the hydrosol adhesive layer through a photolithography process; Micro-nanoparticles are patterned, and then the photoresist is removed to obtain a patterned template for micro-nanoparticles;

2) Coating the polymer on the surface of the substrate, and then preheating the substrate, the preheating parameters: the temperature is 60-90°C, and the time is 2-10 minutes;

3) Contacting and embedding the micro-nano particles on the surface of the patterned template into the polymer, the embedding depth is T=1-500 μm;

4) Pull the patterned template again, so that the polymer is stretched into an array of micro-nano pillars, the angle between the pulling direction and the horizontal direction is α, 0<α<180°, the pulling rate is 10-1000 μm/s, and the time for 1-10s, and then heat the substrate to solidify the micro-nano pillar array, the heating temperature is 100-180°C, and the time is 10-30 minutes;

5) reheating the patterned template at a heating temperature of 100-200° C. for 1-5 minutes, so that the micro-nano particles are separated from the hydrosol adhesion layer, and an array of micro-nano pillars with micro-nano particles on the top is obtained;

6) Finally, the micro-nano particles on the top of the micro-nano column array are removed to obtain the polymer micro-nano column array.

The step 1) micro-nano particles are spherical polystyrene, cubic indium trioxide or columnar sodium chloride.

The polymer in the step 2) is PDMS (polydimethylsiloxane), PS (polystyrene) or PTT (polyurethane).

The relationship between the particle size D of the micro-nano particles and the embedding depth T of the embedded polymer in the step 3) is: D>T>0.

The step 6) uses toluene, nitric acid or deionized water to remove micro-nano particles.

The advantages of the present invention are:

Through the graphic manipulation of micro-nano particles, the morphology of polymer micro-nano column and the patterning of polymer micro-nano column array can be realized; The adjustment of the aspect ratio of the polymer micro-nano column has the advantages of precise controllability and simple operation; at the same time, by changing the angle α (0<α<180°) between the pulling direction and the horizontal direction, the micro-nano column can be regulated. Inclination angle; the viscosity of the hydrosol adhesive layer is reduced by heating the template, so that the micro-nano particles fall off, and the separation of the polymer micro-nano column array and the template is completed, which effectively avoids the problem that the micro-nano column is easy to break in the traditional demoulding process. The invention has the advantages of simple operation, low cost and short period.

Description of drawings

FIG. 1 is a schematic diagram of a template for patterning micro-nanoparticles produced in Example 1. FIG.

Fig. 2 is a schematic diagram of the template-embedded polymer in Example 1.

Fig. 3 is a schematic diagram of stretching the polymer in the pulling template of Example 1.

Fig. 4(a) is a schematic diagram of heating the template to separate the micro-nano particles from the adhesion layer, and Fig. 4(b) is a schematic diagram of the micro-nano particles from the adhesion layer.

Fig. 5 is a schematic diagram of obtaining a polymer micro-nano pillar array by removing micro-nano particles in Example 1.

Figure 6(a) is a schematic diagram of the template-embedded polymer in Example 2, Figure 6(b) is a schematic diagram of the template-stretched polymer in Example 2, and Figure 6(c) is a schematic diagram of polymer microparticles obtained by removing micro-nano particles in Example 2. Schematic of the nanopillar array.

Figure 7(a) is a schematic diagram of the template for patterning micro-nanoparticles produced in Example 3, Figure 7(b) is a schematic diagram of the template embedded in the polymer in Example 3, and Figure 7(c) is a template drawing polymer in Example 3 Schematic diagram, FIG. 7( d ) is a schematic diagram of removing micro-nano particles to obtain a polymer micro-nano column array in Example 3.

detailed description

The present invention will be further described below by means of the accompanying drawings and examples.

Example 1

A method for manufacturing a shape-controllable flexible micro-nano pillar array, comprising the following steps:

1) With reference to Fig. 1 and Fig. 2, first coat the hydrosol adhesive layer 2 on the surface of the substrate 1, then obtain the micro-nano patterned photoresist on the hydrosol adhesive layer 2 by a photolithography process; The surface is patterned with micro-nanoparticles 3 with particle diameter D1=5 μm by scraping method, and then the photoresist is removed to obtain a patterned template of micro-nanoparticles 3, and the micro-nanoparticles 3 are spherical polystyrene;

2) Referring to Fig. 2, the polymer 4 is coated on the surface of the substrate 5, and then the substrate 5 is preheated, the preheating parameters: the temperature is 60°C, the time is 10 minutes, and the polymer 4 is PDMS (Polydimethylene base siloxane);

3) Referring to FIG. 2, the micro-nano particles 3 on the surface of the patterned template are contacted and embedded in the polymer 4, and the embedding depth is T1=2 μm;

4) Referring to Figure 3, pull the patterned template again, so that the polymer 4 is stretched into a micro-nano column array 6, the pulling parameters: the angle between the pulling direction and the horizontal direction is α=90°, and the pulling rate is 10 μm /s, the time is 10s; the length of the pulled micro-nano column array 6 is S1=100 μm, and then the substrate 5 is heated to solidify the micro-nano column array 6, and the heating temperature is 100° C., and kept for 30 minutes;

5) Referring to Figure 4(a), reheat the patterned template at a heating temperature of 100°C for 5 minutes to separate the micro-nanoparticles 3 from the hydrosol adhesion layer 2, and refer to Figure 4(b), to obtain A micro-nano pillar array 6 of micro-nano particles 3;

6) Referring to FIG. 5 , finally dissolve the micronanoparticles 3 at the top of the micronanocolumn array 6 with toluene to obtain the micronanocolumn array 6 of the polymer 4, thereby obtaining the polymerization of PDMS with an angle of α=90° to the horizontal direction The micro-nano column array 6 of the object 4.

Example 2

A method for manufacturing a shape-controllable flexible micro-nano pillar array, comprising the following steps:

1) Coating a hydrosol adhesion layer 2 on the surface of the substrate 1 first, and then obtaining a micro-nano patterned photoresist on the hydrosol adhesion layer 2 through a photolithography process; Patterning of micro-nanoparticles 3 with a diameter D2=10 μm, and then removing the photoresist to obtain a patterned template of micro-nanoparticles 3, where the micro-nanoparticles 3 are cubic indium trioxide;

2) Coating the polymer 4 on the surface of the substrate 5, and then preheating the substrate 5, the preheating parameters: the temperature is 75°C, the time is 6 minutes, and the polymer 4 is PS (polystyrene);

3) Referring to FIG. 6(a), contact and embed the micronanoparticles 3 on the surface of the patterned template into the polymer 4, and the embedding depth T2=5 μm;

4) Referring to Figure 6(b), pull the patterned template again, so that the polymer 4 is stretched into a micro-nano pillar array 6, the pulling parameters: the angle between the pulling direction and the horizontal direction is α=45°, and the The pulling rate is 500 μm/s, and the time is 5 s; the length of the pulled micro-nano column array 6 is S2=2500 μm, and then the substrate 5 is heated to cure the micro-nano column array 6, and the heating temperature is 140° C., and kept for 15 minutes;

5) Reheating the patterned template at a heating temperature of 150° C. for 2 minutes to separate the micro-nano particles 3 from the hydrosol adhesion layer 2 to obtain a micro-nano pillar array 6 with micro-nano particles 3 on the top,

6) Referring to Figure 6(c), finally dissolve the micronanoparticles 3 at the top of the micronanocolumn array 6 by nitric acid solution to obtain the micronanocolumn array 6 of the polymer 4, so that the angle between the horizontal direction and the horizontal direction is α=45° 6 arrays of PS polymers with 4 micro-nanopillars.

Example 3

A method for manufacturing a shape-controllable flexible micro-nano pillar array, comprising the following steps:

1) Referring to Fig. 7(a), the surface of the substrate 1 is coated with a hydrosol adhesion layer 2, and then a micro-nano patterned photoresist is obtained on the hydrosol adhesion layer 2 through a photolithography process; The surface is patterned with a 3-shaped micro-nano particle with a particle diameter of D3=200 μm by a scraping method; the photoresist is removed to obtain a 3-shaped patterned template of the micro-nano particle, and the micro-nano particle 3 is columnar sodium chloride;

2) Coating the polymer 4 on the surface of the substrate 5, and then preheating the substrate 5, the preheating parameters: the temperature is 90°C, the time is 2 minutes, and the polymer 4 is PTT (polyurethane);

3) Referring to FIG. 7(b), contact and embed the micronanoparticles 3 on the surface of the patterned template into the polymer 4, and the embedding depth T3=50 μm;

4) Referring to Figure 7(c), pull the patterned template again, so that the polymer 4 is stretched into a micro-nano column array 6, the pulling parameters: the angle between the pulling direction and the horizontal direction is α=135°, and the pulling The rate is 1000 μm/s, and the time is 6s; the length of the pulled micro-nano column array 6 is S3=6000 μm, and then the substrate 5 is heated to cure the micro-nano column array 6, and the heating temperature is 180° C., and kept for 10 minutes;

5) heating the patterned template at a heating temperature of 200° C. for 1 minute to separate the micro-nano particles 3 from the hydrosol adhesion layer 2 to obtain a micro-nano pillar array 6 with micro-nano particles 3 on the top;

6) Referring to Figure 7(d), finally dissolve the micro-nano particles 3 at the top of the micro-nano column array 6 with deionized water to obtain the micro-nano column array 6 of the polymer 4, so that the angle with the horizontal direction is α=135 ° Micro-nanopillar arrays 6 of PTT polymers 4 .

Claims (4)

1. the manufacture method of the controllable flexible micro-nano post array of a kind of form, it is characterised in that comprise the following steps：

1) first hydrosol adhesion layer is coated in substrate surface, then obtain micro-nano by photoetching process on hydrosol adhesion layer Patterned photoresist；It is graphical by the micro-nano granules that knife coating obtains particle diameter D on photoresist surface again, then remove light Photoresist, obtains the graphical template of micro-nano granules；

2) then polymer-coated is preheated to substrate in substrate surface, pre-add thermal parameter：Temperature 60-90 DEG C, time For 2-10 minutes；

3) micro-nano granules on graphical template surface are contacted and is embedded in polymer, T=1-500 μm of insert depth, micro-nano The particle diameter D of rice grain with the relation of its embedded polymer insert depth T is：D ＞ T ＞ 0；

4) graphical template being lifted again, making polymer be drawn as micro-nano post array, dip direction with horizontal direction angle is α, 0 180 ° of ＜ α ＜, the rate of pulling are 10-1000 μm/s, and the time is 1-10s, then make micro-nano post array solid to silicon Change, heating-up temperature 100-180 DEG C, the time is 10-30 minutes；

5) graphical template is reheated, heating-up temperature is 100-200 DEG C, and the time is 1-5 minutes, departs from micro-nano granules water-soluble Glue adhesion layer, obtains micro-nano post array of the top with micro-nano granules；

6) finally the micro-nano granules on micro-nano post array top are removed, obtains the micro-nano post array of polymer.

2. the manufacture method of the controllable flexible micro-nano post array of a kind of form according to claim 1, it is characterised in that：Institute The step of stating 1) in micro-nano granules be spherical polystyrene, square indium sesquioxide or column Sodium Chloride.

3. the manufacture method of the controllable flexible micro-nano post array of a kind of form according to claim 1, it is characterised in that：Institute The step of stating 2) in polymer be PDMS (polydimethylsiloxane), PS (polystyrene) or PTT (polyurethane).

4. the manufacture method of the controllable flexible micro-nano post array of a kind of form according to claim 1, it is characterised in that：Institute The step of stating 6) used in toluene, nitric acid or deionized water remove micro-nano granules.