CN111170270A - Surface microstructure preparation method based on electric field regulation and control morphology - Google Patents
Surface microstructure preparation method based on electric field regulation and control morphology Download PDFInfo
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- CN111170270A CN111170270A CN202010012436.8A CN202010012436A CN111170270A CN 111170270 A CN111170270 A CN 111170270A CN 202010012436 A CN202010012436 A CN 202010012436A CN 111170270 A CN111170270 A CN 111170270A
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- 230000005684 electric field Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 229920000642 polymer Polymers 0.000 claims abstract description 94
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000009833 condensation Methods 0.000 claims abstract description 18
- 230000005494 condensation Effects 0.000 claims abstract description 18
- 238000007639 printing Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 113
- 238000001723 curing Methods 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000005057 refrigeration Methods 0.000 claims description 13
- 238000004528 spin coating Methods 0.000 claims description 13
- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
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- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00444—Surface micromachining, i.e. structuring layers on the substrate
- B81C1/00492—Processes for surface micromachining not provided for in groups B81C1/0046 - B81C1/00484
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00349—Creating layers of material on a substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a surface microstructure preparation method based on electric field controlled morphology, which comprises the steps of preparing a liquid drop array on the surface of a first polymer by a liquid drop condensation or liquid drop printing method, covering a second polymer on the first polymer, impressing liquid drops into the second polymer, applying an electric field effect between the first polymer and the second polymer, driving the liquid drops to deform so as to control the morphology of the liquid drops, and realizing the solidification of the second polymer by adopting thermal curing or ultraviolet irradiation under the condition of keeping voltage unchanged, so that the microstructure array corresponding to the liquid drops is obtained by impressing on the surface of the second polymer. The invention adopts the liquid drop as the template for preparing the microstructure array, simplifies the preparation process, regulates and controls the appearance of the liquid drop by an external electric field method, further regulates and controls the appearance of the microstructure array, and has the advantages of simple process, low cost and flexible and controllable microstructure appearance.
Description
Technical Field
The invention relates to a preparation technology of an organic colloid surface microstructure, in particular to a preparation method of a surface microstructure based on electric field regulation and control of morphology.
Background
The surface microstructure film is widely applied to the fields of optics, biomedicine, functional materials and the like. At present, the main surface microstructure preparation technologies mainly include methods such as photolithography and mold imprinting. The photoetching method needs to manufacture a mask plate, depends on photoetching machine equipment, comprises the processes of gluing, exposing, developing, pre-baking, post-baking and the like, and has higher cost and complex process. The mold imprinting method generally comprises two steps, namely manufacturing the mold, and then pressing and molding the mold to form the microstructure on the surface of the colloid. The processing of the die still needs to depend on photoetching, etching and laser processing technologies, the defects of high cost, long manufacturing period and complex process cannot be solved, and the microstructure is easy to damage during demoulding. The shape and roughness of the microstructure are completely determined by the shape and quality of the die; in addition, the temperature, pressure, viscosity of the polymer fluid, etc. at the time of molding may affect the quality of the surface of the microstructure, thereby affecting the physical and optical properties of the microstructure, etc.
Chinese patent zl201710351836.x proposes a method of imprinting a microstructure on a polymer surface using droplets as a mold, which has the advantage of simple cost. However, due to the surface tension effect, the topography of the droplets appears spherical, and thus the microstructure topography imprinted by the droplets is also spherical. Therefore, the method cannot realize effective regulation and control of the microstructure morphology. Actually, the microstructure morphology determines the imaging focal length, the light scattering property and the like of the microlens array, so that the microstructure morphology is very important to be regulated and controlled. In the case of micro-nano scale, surface tension effect is dominant, and in order to overcome the surface tension effect, external force must be introduced, which is a very big challenge.
Disclosure of Invention
Aiming at the problems of complex process, high cost and inflexible shape adjustment of the traditional surface microstructure preparation technology at present, the invention aims to provide a surface microstructure preparation method based on electric field shape adjustment and control, which has the advantages of low cost, simple process, flexible and controllable shape.
The purpose of the invention is realized as follows:
a surface microstructure preparation method based on electric field regulation and control morphology is characterized in that: the method comprises the following steps:
A. preparing a first substrate, placing a first polymer on top of the first substrate, preparing droplets on top of the first polymer by droplet coalescence or droplet printing, thereby obtaining an array of droplets, wherein: the droplets are immiscible with the first polymer;
B. preparing a second substrate, placing a second polymer over the second substrate, wherein: the second polymer is immiscible with the first polymer and the droplets;
C. placing a gasket on the edge of the first substrate, placing a second substrate on the gasket, wherein the second polymer faces downwards, and under the action of surface tension, the liquid drops are stamped into the inner part of the second polymer, so that a stable first polymer-liquid drop-second polymer three-phase interface is obtained;
D. an electric field action is applied between the first substrate and the second substrate, so that the electrostatic force borne by the surface of the liquid drop overcomes the action of surface tension, the liquid drop is driven to deform, and the appearance of the liquid drop is regulated, namely: a topography change of the droplets imprinted into the interior of the second polymer;
E. under the condition of keeping voltage unchanged, the second polymer is cured by adopting a heating curing or ultraviolet irradiation curing mode, so that a microstructure corresponding to the liquid drop is obtained by impressing on the surface of the second polymer;
F. and stripping the second polymer from the surface of the first substrate, and cleaning the surface of the second polymer to finally obtain the second polymer with the microstructure array on the surface.
Further, the first polymer in the step A is one of a conventional liquid polymer, an ultraviolet curing polymer or a thermosetting polymer, the first polymer is obtained by spot coating or spin coating, and the thickness of the first polymer is 1-1000 μm.
Further, the droplet array in step a is obtained by a droplet condensation method, wherein the droplet condensation is realized by active refrigeration or solvent evaporation refrigeration: the active refrigeration realizes the temperature regulation of the first polymer through a semiconductor refrigerator, so that the temperature of the first polymer is lower than the ambient temperature, or the solvent volatilization refrigeration dissolves the first polymer in a volatile solvent, and the temperature regulation of the first polymer is realized through the solvent volatilization refrigeration, so that the temperature of the first polymer is lower than the ambient temperature; or, the droplet array in the step a is obtained by a droplet printing method. For the active refrigeration liquid drop condensation method, the size of the liquid drop can be controlled by controlling the condensation time and the refrigeration temperature; for the solvent volatilization refrigeration liquid drop condensation method, the size of the liquid drop can be controlled by controlling the condensation time and the concentration of the solvent; for a droplet printing method, the size of the droplets can be controlled by controlling the printing parameters.
Further, the diameter of the liquid drop in the step A is 0.1-1000 μm, and the liquid drop material is one of water, methanol, ethanol or ethylene glycol.
Further, the second polymer in the step B is an ultraviolet curing polymer, and the curing mode in the corresponding step E is to realize complete curing of the second polymer by ultraviolet lamp irradiation; or, the second polymer in the step B is a thermosetting polymer, and the curing mode in the corresponding step E is to realize complete curing of the second polymer by a heating curing method; the second polymer is obtained by a spot coating or spin coating mode, and the thickness of the second polymer is 1-1000 mu m.
Further, the first polymer does not have the same cured form as the second polymer, i.e., the first polymer cannot be cured by ultraviolet irradiation when the second polymer is an ultraviolet curable material, or the first polymer is not cured by heating when the second polymer is a thermally curable material.
Furthermore, the electric field in the step D can be changed, and the precise control of the appearance of the liquid droplet is realized by changing the electric field, wherein the change of the electric field is realized by the configuration of different electrodes and the application of voltages with different magnitudes;
further, the different electrodes refer to: the first substrate is made of a conductive material, or a planar electrode or a patterned electrode array is prepared on the surface of the first substrate, and the second substrate is made of a conductive material, or a planar electrode or a patterned electrode array is prepared on the surface of the second substrate. The first substrate material can be selected from conductive materials such as copper, aluminum, silicon with high doping concentration, etc., or a layer of conductive materials such as gold, copper, etc., can be prepared on the surface of non-conductive materials such as ceramics, sapphire, etc., and the second substrate material can be selected from the same material as the first substrate material if the second polymer is a heat-curable polymer, or from a transparent conductive material such as Indium Tin Oxide (ITO) if the second polymer is an ultraviolet-curable polymer, or from a transparent material such as glass.
Further, the applying of the voltages with different magnitudes refers to: the voltage is applied by using a direct current power supply, and the voltage regulation range is continuously adjustable within 1V-3000V.
Further, the dielectric constant of the droplets is greater than the dielectric constant of the first polymer and the dielectric constant of the second polymer.
Compared with the prior art, the technical scheme provided by the invention has the characteristics that: the liquid drop is used as a template for preparing the microstructure array, the preparation process is simplified, the appearance of the liquid drop is regulated and controlled by introducing an external electric field, and the flexible and controllable appearance of the microstructure is realized. Therefore, the method has the advantages of simple process, low cost and flexible and controllable microstructure appearance.
Drawings
FIG. 1 is a schematic diagram of an experimental apparatus in step 1 of an experimental process of a method for preparing a surface microstructure according to embodiment 1 of the present invention;
FIG. 2 is a schematic diagram showing the condensation of water droplets in step 1 of the experimental procedure of the method for preparing a surface microstructure according to example 1 of the present invention;
FIG. 3 is a schematic diagram of step 2 of the experimental procedure in the method for preparing a surface microstructure according to embodiment 1 of the present invention;
FIG. 4 is a schematic diagram of step 3 of the experimental procedure of the method for preparing a surface microstructure according to example 1 of the present invention;
FIG. 5 is a schematic diagram of steps 4 and 5 of an experimental process of a method for preparing a surface microstructure according to embodiment 1 of the present invention;
FIG. 6 is a schematic view of a film with a microstructure array on a surface thereof, obtained by the method for preparing a surface microstructure according to embodiment 1 of the present invention;
FIG. 7 is a schematic top view of a planar electrode in the method for manufacturing a surface microstructure according to embodiment 1 of the present invention;
FIG. 8 is a schematic view of an experimental apparatus in step 1 of the experimental process of the method for preparing a surface microstructure according to embodiment 2 of the present invention;
FIG. 9 is a schematic diagram showing the condensation of water droplets in step 1 of the experimental procedure of the method for preparing a surface microstructure according to example 2 of the present invention;
FIG. 10 is a schematic diagram of step 2 of the experimental procedure in the method for preparing a surface microstructure according to embodiment 2 of the present invention;
FIG. 11 is a schematic diagram of step 3 of the experimental procedure of the method for preparing a surface microstructure according to embodiment 2 of the present invention;
FIG. 12 is a schematic diagram of steps 4 and 5 of an experimental process of a method for fabricating a surface microstructure according to embodiment 2 of the present invention;
FIG. 13 is a schematic view of a film with a microstructure array on a surface thereof, obtained by a method for manufacturing a surface microstructure according to embodiment 2 of the present invention;
FIG. 14 is a schematic top view of a planar electrode in the method for manufacturing a surface microstructure according to embodiment 2 of the present invention;
FIG. 15 is a schematic view of an experimental apparatus in step 1 of the experimental process of the method for preparing a surface microstructure according to embodiment 3 of the present invention;
FIG. 16 is a schematic diagram showing the condensation of water droplets in step 1 of the experimental procedure of the method for preparing a surface microstructure according to example 3 of the present invention;
FIG. 17 is a schematic diagram of step 2 of the experimental procedure in the method for preparing a surface microstructure according to embodiment 3 of the present invention;
FIG. 18 is a schematic diagram of step 3 of the experimental procedure of the method for preparing a surface microstructure according to embodiment 3 of the present invention;
FIG. 19 is a schematic diagram of steps 4 and 5 of an experimental process of a method for fabricating a surface microstructure according to embodiment 3 of the present invention;
FIG. 20 is a schematic view of a film with a microstructure array on a surface thereof, obtained by a method for manufacturing a surface microstructure according to embodiment 3 of the present invention;
FIG. 21 is a schematic top view of a planar electrode in the method for manufacturing a surface microstructure according to embodiment 3 of the present invention;
FIG. 22 is a schematic view of an experimental apparatus in step 1 of the experimental process of the method for preparing a surface microstructure according to embodiment 4 of the present invention;
FIG. 23 is a schematic diagram showing the condensation of water droplets in step 1 of the experimental procedure of the method for preparing a surface microstructure according to example 4 of the present invention;
FIG. 24 is a schematic diagram of step 2 of the experimental procedure in the method for preparing a surface microstructure according to embodiment 4 of the present invention;
FIG. 25 is a schematic diagram of step 3 of the experimental procedure of the method for preparing a surface microstructure according to embodiment 4 of the present invention;
FIG. 26 is a schematic diagram of steps 4 and 5 of an experimental process of a method for fabricating a surface microstructure according to embodiment 4 of the present invention;
FIG. 27 is a schematic view of a film with a microstructure array on a surface thereof, obtained by a method for manufacturing a surface microstructure according to embodiment 4 of the present invention;
FIG. 28 is a schematic top view of a planar electrode in the method for manufacturing a surface microstructure according to embodiment 4 of the present invention;
FIG. 29 is a schematic view of an experimental apparatus in step 1 of an experimental process of a method for fabricating a surface microstructure according to embodiment 5 of the present invention;
FIG. 30 is a schematic diagram showing the condensation of water droplets in step 1 of the experimental procedure of the method for preparing a surface microstructure according to example 5 of the present invention;
FIG. 31 is a schematic diagram of step 2 of the experimental procedure in the method for preparing a surface microstructure according to example 5 of the present invention;
FIG. 32 is a schematic view of step 3 of the experimental procedure of the method for preparing a surface microstructure according to example 5 of the present invention;
FIG. 33 is a schematic diagram of steps 4 and 5 of an experimental process of a method for fabricating a surface microstructure according to example 5 of the present invention;
FIG. 34 is a schematic view of a film with a microstructure array on a surface, which is obtained by the method for manufacturing a surface microstructure according to embodiment 5 of the present invention;
fig. 35 is a schematic top view of a space electrode in the method for preparing a surface microstructure according to embodiment 5 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in connection with the accompanying drawings.
Example 1:
as shown in fig. 1 to 6, a method for preparing a surface microstructure based on electric field controlled morphology comprises the following steps:
1. preparing a first substrate 101, wherein the first substrate 101 is a silicon wafer with a gold layer 110 prepared on the surface, and spin-coating silica gel on the surface of the first substrate 101 by using a spin coating method to obtain the silica gel 102 with the thickness of 50 μm on the first substrate 101; preparing a constant-temperature and constant-humidity environment control box 103 with a water vapor atmosphere, placing a first substrate 101 with silica gel 102 on a cold surface of a semiconductor refrigerator 104, realizing temperature adjustment of the silica gel 102 through the semiconductor refrigerator 104, and enabling the temperature of the silica gel 102 to be lower than the ambient temperature, so that water vapor in the air is condensed and nucleated on the surface of the silica gel 102; after 2min of condensation time, the water core is self-assembled on the surface of the silica gel 102 to form a water drop array which is uniformly distributed, and the water drops 105 enter the silica gel 102 due to the action of surface tension; wherein the environmental temperature is controlled to be 15 ℃, the environmental relative humidity is controlled to be 75%, and the refrigerating temperature of the semiconductor refrigerator 104 is 0 ℃;
2. preparing a second substrate 106, wherein the second substrate 106 is a glass sheet with an Indium Tin Oxide (ITO) layer 111 prepared on the surface, and an ultraviolet curing adhesive (NORLAND 61) is spin-coated on the surface of the second substrate 106 by a spin coating method to obtain an ultraviolet curing adhesive 107 with the thickness of 30 μm on the second substrate 106;
3. placing a gasket 108 on the edge of the first substrate 101, and placing a second substrate 106 on the gasket 108 on the first substrate 101, wherein the ultraviolet curing glue 107 faces downwards, and water drops 105 are impressed into the ultraviolet curing glue 107 under the action of surface tension, so that a stable silica gel-water drops-ultraviolet curing glue three-phase interface is obtained;
4. as shown in fig. 7, as described above, the surface of the first substrate 101 has the gold layer planar electrode 110, the surface of the second substrate 106 has the ITO layer planar electrode 111, a voltage of 200V is applied between the first substrate 101 and the second substrate 106 by using the dc power supply 109, and the water droplet 105 is subjected to electrostatic force action by the introduced electrostatic field action, so as to overcome the surface tension action and drive the water droplet 105 to deform, that is, the water droplet is imprinted into the ultraviolet curing adhesive 107 to change the internal appearance;
5. under the condition of keeping the voltage unchanged, the ultraviolet curing adhesive is completely cured by irradiation of an ultraviolet lamp 112, so that a microstructure corresponding to the shape of the water drop 105 is obtained on the surface of the ultraviolet curing adhesive 107, wherein the ultraviolet irradiation energy is 4W/cm2The curing time is 10 min;
6. and stripping the ultraviolet curing adhesive 107 from the surface of the first substrate 101, respectively cleaning the surface of the ultraviolet curing adhesive 107 by using acetone and deionized water, and removing water drops and residual silica gel to finally obtain the ultraviolet curing adhesive 113 with the microstructure array on the surface.
Example 2:
as shown in fig. 8 to 13, a method for preparing a surface microstructure based on electric field controlled morphology includes the following steps:
1. preparing a first substrate 201, wherein the first substrate 201 is a ceramic wafer with a copper layer 209 prepared on the surface, dissolving silica gel in toluene to obtain a silica gel toluene solution, and spin-coating the silica gel toluene solution on the surface of the first substrate 201 by using a spin-coating method to obtain a silica gel toluene solution 202 with the thickness of 300 microns on the first substrate 201; preparing a constant-temperature and constant-humidity environment control box 203 with a water vapor atmosphere, standing the first substrate 201 with the silica gel toluene solution 202 in the environment control box 203, and volatilizing toluene to enable the surface temperature of the silica gel toluene solution to be lower than the ambient temperature, so that water vapor in the air is condensed and nucleated on the surface of the silica gel toluene solution; after 10min of toluene volatilization and water drop condensation, water nuclei are self-assembled on the surface of the silica gel to form a water drop array which is uniformly distributed, and the water drops 204 enter the silica gel 202 due to the action of surface tension; wherein the ambient temperature is controlled to be 25 ℃, and the ambient relative humidity is controlled to be 80%;
2. preparing a second substrate 205, wherein the second substrate 205 is a glass sheet with an ITO layer 210 prepared on the surface, and ultraviolet curing glue (NORLAND 71) is spin-coated on the surface of the second substrate 205 by a spin coating method to obtain the ultraviolet curing glue 206 with the thickness of 20 μm on the second substrate 205;
3. placing a gasket 207 on the edge of the first substrate 201, and covering the gasket 207 on the first substrate 201 with the second substrate 205, wherein the ultraviolet curing glue 206 faces downwards, and under the action of surface tension, the water drops 204 are impressed into the ultraviolet curing glue 206, so that a stable three-phase interface of silica gel-water drops-ultraviolet curing glue is obtained;
4. as shown in fig. 14, as described above, the surface of the first substrate 201 has the planar electrode 209 of the copper layer, the surface of the second substrate 205 has the planar electrode 210 of the ITO layer, and a voltage of 80V is applied between the first substrate 201 and the second substrate 205 by using the dc power supply 208, so that the electrostatic force applied to the surface of the water drop overcomes the action of surface tension, and the water drop 204 is driven to deform, i.e., the water drop 204 is imprinted into the uv-curable adhesive 206, and the internal appearance changes;
5. under the condition of keeping the voltage unchanged, the ultraviolet lamp 211 irradiates to realize the complete curing of the ultraviolet curing glue 206, so that a microstructure corresponding to the shape of the water drop 204 is obtained on the surface of the ultraviolet curing glue 206, wherein the ultraviolet irradiation energy is 8W/cm2The curing time is 5 min;
6. and stripping the ultraviolet curing adhesive 206 from the surface of the first substrate 201, and respectively cleaning the surface of the ultraviolet curing adhesive 206 by using acetone and deionized water to finally obtain the ultraviolet curing adhesive 212 with the microstructure array on the surface.
Example 3:
as shown in fig. 15-20, a method for preparing a surface microstructure based on electric field controlled morphology comprises the following steps:
1. preparing a first substrate 301, wherein the first substrate 301 is a glass sheet with an ITO layer 307 prepared on the surface, and directly printing an ethylene glycol droplet array 302 on the first substrate 301 by adopting a droplet printing mode, wherein the diameter of the ethylene glycol droplet is 10 microns;
2. preparing a second substrate 303, wherein the second substrate 303 is a glass sheet with an ITO layer 308 prepared on the surface, and silica gel is spin-coated on the surface of the second substrate 303 by using a spin coating method to obtain silica gel 304 with the thickness of 500 mu m on the second substrate 303;
3. placing a gasket 305 on the edge of the first substrate 301, and covering the second substrate 303 on the gasket 305 on the first substrate 301, wherein the silica gel 304 faces downwards, and the ethylene glycol droplets 302 are imprinted into the silica gel 304 under the action of surface tension, so that a stable silica gel-ethylene glycol two-phase interface is obtained;
4. as shown in fig. 21, as described above, the ITO layer planar electrode 307 is disposed on the surface of the first substrate 301, the ITO layer planar electrode 308 is disposed on the surface of the second substrate 305, and a voltage of 3000V is applied between the first substrate 301 and the second substrate 303 by using the dc power source 306, so that the electrostatic force applied on the surface of the ethylene glycol droplet 302 overcomes the surface tension effect, and the ethylene glycol droplet 302 is driven to deform, that is, the ethylene glycol droplet 302 is imprinted into the silica gel 304, and the internal appearance thereof changes;
5. under the condition of keeping the voltage unchanged, the complete solidification of the silica gel 304 is realized in a thermal solidification mode, so that a microstructure corresponding to the shape of the ethylene glycol liquid drop 302 is obtained on the surface of the silica gel 304, wherein the solidification temperature is 150 ℃, and the solidification time is 90 min;
6. the silica gel 304 is peeled off from the surface of the first substrate 301, and the surface of the silica gel 304 is cleaned by deionized water, so that the silica gel 309 with a microstructure array on the surface is finally obtained.
Example 4:
as shown in fig. 22 to 27, a method for preparing a surface microstructure based on electric field controlled morphology includes the following steps:
1. preparing a first substrate 401, wherein the first substrate 401 is made of copper, and ultraviolet curing glue (Ormocomp) is spin-coated on the surface of the first substrate 401 by adopting a spin coating method to obtain ultraviolet curing glue 402 with the thickness of 20 microns on the first substrate 401; preparing a constant-temperature and constant-humidity environment control box 403 with a water vapor atmosphere, placing a first substrate 401 with ultraviolet curing glue 402 on a cold surface of a semiconductor refrigerator 404, realizing temperature adjustment of the ultraviolet curing glue 402 through the semiconductor refrigerator 404, and enabling the temperature of the ultraviolet curing glue 402 to be lower than the ambient temperature, so that water vapor in the air is condensed and nucleated on the surface of the ultraviolet curing glue 402; after 10min of condensation time, the water cores are self-assembled on the surface of the ultraviolet curing glue 402 to form a water drop array which is uniformly distributed, and water drops 405 enter the ultraviolet curing glue 402 due to the action of surface tension; wherein the environmental temperature is controlled to be 20 ℃, the environmental relative humidity is controlled to be 60%, and the refrigerating temperature of the semiconductor refrigerator 404 is-10 ℃;
2. preparing a second substrate 406, wherein the second substrate 406 is a glass sheet with an ITO layer 410 prepared on the surface, and epoxy resin is coated on the surface of the second substrate 406 in a spinning mode to obtain epoxy resin 407 with the thickness of 100 microns on the second substrate 406;
3. placing a gasket 408 on the edge of the first substrate 401, and covering the second substrate 405 on the gasket 408 on the first substrate 401, wherein the epoxy resin 407 faces downwards, and under the action of surface tension, the water drops 405 are pressed into the epoxy resin 407, so that a stable ultraviolet curing glue-water drops-epoxy resin three-phase interface is obtained;
4. as shown in fig. 28, as described above, the first substrate 401 is a bottom electrode, the surface of the second substrate 406 is provided with the ITO layer planar electrode 410, and a dc power source 409 is used to apply a voltage of 1500V between the first substrate 401 and the second substrate 406, so that the electrostatic force applied to the surface of the water droplet 405 overcomes the surface tension effect, and the water droplet 405 is driven to deform, that is, the water droplet 405 is imprinted into the epoxy resin 407, and the internal shape of the epoxy resin 407 changes;
5. under the condition of keeping the voltage unchanged, the epoxy resin 407 is completely cured in a thermal curing mode, so that a microstructure corresponding to the shape of the water drop 405 is obtained on the surface of the epoxy resin 407, wherein the curing temperature is 200 ℃, and the curing time is 80 min;
6. and stripping the epoxy resin 407 from the surface of the first substrate 401, respectively cleaning the surface of the epoxy resin 407 by using acetone and deionized water, and removing water drops and residual ultraviolet curing adhesive to finally obtain the epoxy resin 412 with the microstructure array on the surface.
Example 5:
as shown in fig. 29 to 34, a method for preparing a surface microstructure based on electric field controlled morphology includes the following steps:
1. preparing a first substrate 501, wherein the first substrate 501 is a highly doped silicon wafer, a space square electrode array is manufactured on the first substrate 501, polyurethane is coated on the surface of the first substrate 501 in a spinning mode by a spinning method, and polyurethane 502 with the thickness of 100 microns is obtained on the first substrate 501; preparing a constant-temperature constant-humidity environment control box 503 with a water vapor atmosphere, placing a first substrate 501 with polyurethane 502 on a cold surface of a semiconductor refrigerator 504, and realizing temperature adjustment of the polyurethane 502 through the semiconductor refrigerator to enable the temperature of the polyurethane 502 to be lower than the ambient temperature, so that water vapor in the air is condensed and nucleated on the surface of the polyurethane 502; after 3min of condensation time, the water core is self-assembled on the surface of the polyurethane 502 to form a water drop array which is uniformly distributed, and the water drops 505 enter the polyurethane 502 due to the action of surface tension; wherein the ambient temperature is controlled to be 20 ℃, the ambient relative humidity is controlled to be 85%, and the refrigerating temperature of the semiconductor refrigerator 504 is 0 ℃;
2. preparing a second substrate 506, wherein the second substrate 506 is a glass sheet with an ITO layer 507 prepared on the surface, and an ultraviolet curing adhesive (Aroh Alona 3662) is spin-coated on the surface of the second substrate 506 by a spin coating method to obtain an ultraviolet curing adhesive 508 with the thickness of 60 μm on the second substrate 506;
3. placing a gasket 509 at the edge of the first substrate 501, covering the gasket 509 on the first substrate 501 with the second substrate 506, wherein the ultraviolet curing glue 508 faces downwards, and under the action of surface tension, water drops 505 are impressed into the ultraviolet curing glue 508, so as to obtain a stable polyurethane-water drops-ultraviolet curing glue three-phase interface;
4. as shown in fig. 35, as described above, the first substrate 501 is a bottom electrode, the surface of the second substrate 506 is provided with the ITO layer planar electrode 507, and a voltage of 600V is applied between the first substrate 501 and the second substrate 506 by using the dc power supply 510, so that the electrostatic force applied to the surface of the water droplet 505 overcomes the action of surface tension, and the water droplet 505 is driven to deform, that is, the water droplet 505 is imprinted into the uv-curable adhesive 508, and the internal appearance thereof changes;
5. under the condition of keeping the voltage unchanged, the ultraviolet lamp 511 irradiates to realize the complete curing of the ultraviolet curing glue 508, thereby the ultraviolet curing glue is completely cured508 the surface of the film is provided with a microstructure corresponding to the shape of the water droplet 505, wherein the ultraviolet irradiation energy is 4W/cm2The curing time is 8 min;
6. the ultraviolet curing adhesive 508 is peeled off from the surface of the first substrate 501, and acetone and deionized water are adopted to respectively clean the surface of the ultraviolet curing adhesive 508, so as to finally obtain the ultraviolet curing adhesive 512 with the microstructure array on the surface.
Claims (10)
1. A surface microstructure preparation method based on electric field regulation and control morphology is characterized by comprising the following steps: the method comprises the following steps:
A. preparing a first substrate, placing a first polymer on top of the first substrate, preparing droplets on top of the first polymer by droplet coalescence or droplet printing, thereby obtaining an array of droplets, wherein: the droplets are immiscible with the first polymer;
B. preparing a second substrate, placing a second polymer over the second substrate, wherein: the second polymer is immiscible with the first polymer and the droplets;
C. placing a gasket on the edge of the first substrate, placing a second substrate on the gasket, wherein the second polymer faces downwards, and under the action of surface tension, the liquid drops are stamped into the inner part of the second polymer, so that a stable first polymer-liquid drop-second polymer three-phase interface is obtained;
D. an electric field action is applied between the first substrate and the second substrate, so that the electrostatic force borne by the surface of the liquid drop overcomes the action of surface tension, the liquid drop is driven to deform, and the appearance of the liquid drop is regulated, namely: a topography change of the droplets imprinted into the interior of the second polymer;
E. under the condition of keeping voltage unchanged, the second polymer is cured by adopting a heating curing or ultraviolet irradiation curing mode, so that a microstructure corresponding to the liquid drop is obtained by impressing on the surface of the second polymer;
F. and stripping the second polymer from the surface of the first substrate, and cleaning the surface of the second polymer to finally obtain the second polymer with the microstructure array on the surface.
2. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 1, wherein the method comprises the following steps: the first polymer in the step A is one of a conventional liquid polymer, an ultraviolet curing polymer or a thermosetting polymer, the first polymer is obtained in a spot coating or spin coating mode, and the thickness of the first polymer is 1-1000 microns.
3. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 1, wherein the method comprises the following steps: the liquid drop array in the step A is obtained by adopting a liquid drop condensation method, wherein the liquid drop condensation is realized by adopting active refrigeration or solvent volatilization refrigeration: the active refrigeration realizes the temperature regulation of the first polymer through a semiconductor refrigerator, so that the temperature of the first polymer is lower than the ambient temperature, or the solvent volatilization refrigeration dissolves the first polymer in a volatile solvent, and the temperature regulation of the first polymer is realized through the solvent volatilization refrigeration, so that the temperature of the first polymer is lower than the ambient temperature; or, the droplet array in the step a is obtained by a droplet printing method.
4. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 1, wherein the method comprises the following steps: the diameter of the liquid drop in the step A is 0.1-1000 mu m, and the liquid drop material is one of water, methanol, ethanol or ethylene glycol.
5. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 1, wherein the method comprises the following steps: the second polymer in the step B is an ultraviolet curing polymer, and the curing mode in the corresponding step E is to realize the complete curing of the second polymer through the irradiation of an ultraviolet lamp; or, the second polymer in the step B is a thermosetting polymer, and the curing mode in the corresponding step E is to realize complete curing of the second polymer by a heating curing method; the second polymer is obtained by a spot coating or spin coating mode, and the thickness of the second polymer is 1-1000 mu m.
6. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 1, wherein the method comprises the following steps: the first polymer does not have the same form of cure as the second polymer, i.e., the first polymer cannot be cured by ultraviolet radiation when the second polymer is an ultraviolet curable material, or the first polymer is not cured by heat when the second polymer is a thermally curable material.
7. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 1, wherein the method comprises the following steps: and D, the electric field can be changed, and the shape of the liquid drop is accurately regulated and controlled by changing the electric field, wherein the change of the electric field is realized by the configuration of different electrodes and the application of voltages with different sizes.
8. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 7, wherein the method comprises the following steps: the different electrodes are: the first substrate is made of a conductive material, or a planar electrode or a patterned electrode array is prepared on the surface of the first substrate, and the second substrate is made of a conductive material, or a planar electrode or a patterned electrode array is prepared on the surface of the second substrate.
9. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 7, wherein the method comprises the following steps: the voltages with different magnitudes are applied as follows: the voltage is applied by using a direct current power supply, and the voltage regulation range is continuously adjustable within 1V-3000V.
10. The method for preparing the surface microstructure based on the electric field controlled morphology according to claim 1, wherein the method comprises the following steps: the dielectric constant of the droplets is greater than the dielectric constant of the first polymer and the dielectric constant of the second polymer.
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