CN111606298B - Directional passive self-driven film and preparation method thereof - Google Patents
Directional passive self-driven film and preparation method thereof Download PDFInfo
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- CN111606298B CN111606298B CN202010360444.1A CN202010360444A CN111606298B CN 111606298 B CN111606298 B CN 111606298B CN 202010360444 A CN202010360444 A CN 202010360444A CN 111606298 B CN111606298 B CN 111606298B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
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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
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00134—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
- B81C1/00158—Diaphragms, membranes
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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
Abstract
The invention provides a directional passive self-driven film and a preparation method thereof. The preparation method of the oriented passive self-driven film comprises the following steps: depositing a metal film on a substrate; writing directional passive self-driven patterns on the metal film by adopting a laser writing technology; performing wet etching on the metal film on which the directional passive self-driven pattern is engraved to obtain a directional passive self-driven film; the directional passive self-driven pattern comprises a plurality of directional passive self-driven pattern units which are connected end to end; each of the directional passive self-driven pattern units includes: the driving region is gradually increased in width, and the contraction region is connected with the driving region and gradually reduced in width, wherein the length of the driving region is longer than that of the contraction region. The directional passive self-driven thin film with the suspended cutting edge is prepared by combining the laser writing technology with the wet etching method, a mask is not needed in the whole preparation process, and the preparation process is very simple and convenient.
Description
Technical Field
The invention relates to the field of micro-nano manufacturing, in particular to a directional passive self-driven film and a preparation method thereof.
Background
There are many organisms in nature with anisotropic surface structures, whose surfaces exhibit typical differences in directionality for liquid manipulation, such as beetles, spider silks, cactus and nepenthes, which exhibit excellent directional transport capabilities due to their specific micro-nano structures on their surfaces.
In recent years, the construction of surface microstructures has attracted extensive research interest. The bionic water collection technology at home and abroad is inspired mainly by the biological micro-nano structure, for example, the micro-nano structure is designed based on the water collection principle of desert beetles, cactus and pitcher plant at present, and unprecedented liquid drop growth and transportation are realized; artificial spider silks with controllable spindle geometry were successfully produced and showed excellent water-collecting ability; the directional transport of water from the inside to the outside on the surface of artificial nepenthes has been achieved. However, from the perspective of micro-nano processing, designing and manufacturing a bionic structure are relatively complex, the processing flexibility is relatively low, and it is a major problem facing the present time to develop an artificial structure which can exceed the nature and can flexibly and accurately realize directional passive self-driving and long-distance transportation.
Therefore, the prior art has yet to be developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an oriented passive self-driven thin film and a preparation method thereof, and aims to solve the problem that the existing process method for preparing an oriented passive self-driven artificial structure is complex.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing an oriented passive self-driven film comprises the following steps:
depositing a metal film on a substrate;
writing directional passive self-driven patterns on the metal film by adopting a laser writing technology;
performing wet etching on the metal film on which the directional passive self-driven pattern is engraved to obtain a directional passive self-driven film;
the directional passive self-driven pattern comprises a plurality of directional passive self-driven pattern units which are connected end to end;
each of the directional passive self-driven pattern units includes: the driving region is gradually increased in width, and the contraction region is connected with the driving region and gradually reduced in width, wherein the length of the driving region is longer than that of the contraction region.
The preparation method of the directional passive self-driven film comprises the following step of preparing a substrate, wherein the substrate is one of a glass sheet, a quartz sheet and a silicon sheet.
The preparation method of the directional passive self-driven film is characterized in that the metal film is a titanium film.
The preparation method of the directional passive self-driven thin film comprises the step of preparing a titanium thin film, wherein the thickness of the titanium thin film is 20-200 nm.
The preparation method of the directional passive self-driven film comprises the step of depositing the metal film on the substrate by using one of an ion sputtering deposition process, an electron beam evaporation deposition process, a thermal evaporation deposition process, a laser pulse deposition process and a magnetron sputtering deposition process.
The preparation method of the directional passive self-driven film comprises the following steps of (1) preparing a directional passive self-driven film, wherein the laser writing technology is a laser direct writing technology;
the writing parameters of the laser direct writing technology are as follows: the laser power is 1-10 mW; the pulse width of the laser is 0.1-10 ms.
The preparation method of the directional passive self-driven film comprises the step of etching the film by a wet method, wherein the etching liquid for the wet etching is hydrogen fluoride solution.
The preparation method of the directional passive self-driven film is characterized in that the wet etching time is 10-60 min.
The preparation method of the directional passive self-driven thin film, wherein the directional passive self-driven pattern unit further comprises: and the strip-shaped robust region is positioned at one side of the driving region and the contraction region.
An oriented passive self-driven film is prepared by the preparation method of the oriented passive self-driven film.
Has the advantages that: the invention makes the property of the directional passive self-driven pattern on the surface of the receptor metal film change suddenly by the laser writing technology to obtain the anisotropic etching-resistant directional passive self-driven pattern, thereby realizing selective etching; and then, the directional passive self-driven film with the suspended edge is prepared by wet etching, a mask is not needed in the whole preparation process, and the preparation process is very simple and convenient.
Drawings
Fig. 1 shows an oriented passive self-driven pattern in the method for manufacturing an oriented passive self-driven thin film according to the present invention.
Fig. 2 is a schematic structural diagram of the directional passive self-driven thin film according to the present invention.
Detailed Description
The invention provides a directional passive self-driven film and a preparation method thereof. In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the present invention provides a method for preparing an oriented passive self-driven thin film, comprising the steps of:
depositing a metal film on a substrate;
writing directional passive self-driven patterns on the metal film by adopting a laser writing technology;
performing wet etching on the metal film on which the directional passive self-driven pattern is engraved to obtain a directional passive self-driven film;
the directional passive self-driven pattern comprises a plurality of directional passive self-driven pattern units which are connected end to end;
each of the directional passive self-driven pattern units includes: the driving area 1 with gradually increasing width, and the contraction area 2 which is connected with the driving area 1 and has gradually decreasing width, wherein the length of the driving area 1 is longer than that of the contraction area 2.
The laser direct writing technology has high resolution, low cost and high flexibility, but the laser direct writing is generally used for two-dimensional processing at present. The three-dimensional suspension cutting structure has more excellent performance in liquid drop transportation, and is favorable for realizing long-distance transportation of liquid drops. Based on the method, a novel three-dimensional structure is developed by combining a laser direct writing technology and a wet etching technology, so that long-distance transportation of liquid drops is realized.
The invention prepares the film with the anisotropic patterned surface of the overhang cutting edge based on the combination of the laser writing technology and a wet etching method, wherein the laser writing technology is mainly characterized in that the etching property of the surface of the metal film is mutated through laser scanning, so that the surface of the metal film forms an anti-etching directional passive self-driven pattern, the wet etching is mainly used for etching the metal material which is not protected by the anti-etching directional passive self-driven pattern, and thus, the overhang cutting structure with the upper surface wider than the lower bottom surface is formed, and the flow of liquid drops in the non-target direction can be well limited. The invention does not need a mask in the whole processing process, directly writes the preprocessed prototype structure on the metal film, and then carries out subsequent wet etching, and the method is very simple and convenient.
The directional passive self-driven pattern can also be called as an anisotropic pattern, and the purpose of the directional passive self-driven pattern is to selectively etch the directional passive self-driven pattern which is etched and written to form a directional passive self-driven structure. As shown in fig. 1, the directional passive self-driven pattern of the present invention includes a plurality of directional passive self-driven pattern units connected end to end; each of the directional passive self-driven pattern units includes: the driving area 1 with gradually increasing width, and the contraction area 2 which is connected with the driving area 1 and has gradually decreasing width, wherein the length of the driving area 1 is longer than that of the contraction area 2. Specifically, the shape of the driving region 1 may be a triangle, and the constriction region 2 is also a triangle, wherein the base of the triangle of the driving region 1 is connected to the base of the triangle of the constriction region 2, and the height of the triangle of the driving region 1 is longer than that of the triangle of the constriction region 2, for example, the height of the triangle of the driving region 1 is 3-7 times that of the triangle of the constriction region 2. The directional passive self-driven pattern units are connected in a tail-ending way to form a column of directional passive self-driven patterns, for example, the contraction zone of the first passive self-driven pattern unit is connected with the driving zone of the second passive self-driven pattern unit, the contraction zone of the second passive self-driven pattern unit is connected with the driving zone of the third passive self-driven pattern unit, and the like to form a column of directional passive self-driven patterns. The multiple columns of directional passive self-driven patterns are arranged in parallel to form a complete directional passive self-driven pattern.
It should be noted that the direction of the change of the width of the head and tail of the directional passive self-driven pattern unit and the width of the driving area or the shrinking area of the directional passive self-driven pattern unit are relative to the direction of the movement of the liquid drop set during the pattern design.
The driving area 1 can generate a driving force to drive the liquid drop to the right to convert the kinetic energy of the liquid drop due to the characteristic of the anisotropic structure, and the contraction area 2 is an inevitable liquid drop state resetting link designed for realizing the long-range driving pattern of the liquid drop and can cause the liquid drop to decelerate. The invention designs the shape and length ratio of the driving area 1 and the contraction area 2, so that the kinetic energy of the liquid drop is not 0 when the liquid drop passes through the contraction area 2, and then the liquid drop enters the next driving area connected with the contraction area to be driven again, and the circulation is continued, so that the liquid drop can be driven all the time.
The invention carries out wet etching on the metal film with the directional passive self-driven pattern to obtain the directional passive self-driven film with the structure as shown in figure 2. Compared with the existing driving structure, the directional passive self-driving structure has the following advantages in self-driving long-distance transportation: 1. the directional passive self-driven film has a sharp overhang cutting edge, can inhibit and pin the liquid drop in a non-target direction, and promotes the flow of the liquid drop in the target direction; 2. the laplace pressure caused by the anisotropic characteristic of the directional passive self-driven pattern can form a directional driving force for liquid drops. The invention can convert the redundant surface energy of the liquid drop into the kinetic energy at the contraction area 2 to the maximum extent to break the pinning, thereby realizing the controllable directional long-distance transportation of the liquid drop.
The invention can prepare the film with the anisotropic patterned surface with the suspended trimming edge by combining the laser writing technology and the wet etching method, and realizes long-distance transportation of liquid drops.
The substrate provided by the invention can be corroded in an etching solution. After the etching liquid finishes etching the metal film, the substrate below the etched directional passive self-driven pattern can be further etched against, and the directional passive self-driven film with the cantilever structure can be obtained by controlling the etching time. In one implementation of the invention, the substrate is one of a glass sheet, a quartz sheet, and a silicon sheet. Specifically, the substrate is one of substrates such as a glass slide, a silicon wafer and a glass sheet.
The material of the metal film in the invention is a directional passive self-driven pattern layer (heterostructure layer) which can be etched through laser writing and can be etched through wet etching. In one implementation of the invention, the metal thin film is a titanium thin film (Ti thin film). The titanium film can form anti-etching titanium dioxide (TiO) on the surface of the titanium film in the laser etching process2) That is to say, the surface of the titanium film is provided with the anti-etching directional passive self-driven pattern layer made of the titanium dioxide material, so that selective etching is realized. Moreover, because titanium dioxide has excellent hydrophilicity, the super-hydrophilicity characteristic of the surface of the oriented passive self-driven film prepared by the invention enables surface droplets to be continuous in long range, and the attractive force between droplet molecules enables the droplets to flow towards the driven direction without interruption.
In one embodiment of the present invention, wherein the thickness of the titanium thin film is 20 to 200 nm. Tests prove that the Ti film deposited on the substrate has the thickness of 20-200nm, and the directional passive self-driven film with the overhang cutting edge can be prepared.
In one implementation manner of the present invention, the deposition process used for depositing the metal film on the substrate is one of an ion sputtering deposition process, an electron beam evaporation deposition process, a thermal evaporation deposition process, a laser pulse deposition process, and a magnetron sputtering deposition process. The deposition process of the present invention is directed to forming a metal film on a substrate, and it is understood that the metal film can be formed by other physical vapor deposition processes.
The laser writing technology aims to write an anti-etching directional passive self-driven pattern on a metal film by a laser scanning method. In one implementation of the invention, the laser writing technology is a laser direct writing technology. Compared with other processing modes, the laser direct writing technology has the characteristics of high flexibility and multi-scale processing, so that the diversity of directional passive self-driven patterns can be increased, and the diversity of droplet control is realized. The invention can also adopt other laser writing systems, and is not limited to the laser direct writing technology.
The invention can control the width of the upper surface of the cantilever structure by controlling the writing parameters. In an implementation manner of the present invention, the writing parameters of the laser direct writing technology are as follows: the laser power is 1-10 mW; the pulse width of the laser is 0.1-10 ms. Further, the writing parameters of the laser direct writing technology are as follows: the laser power is 4 mW; the laser pulse width is 1ms, so that the driving effect of the prepared directional passive self-driven film on liquid drops can reach the best. The invention also finds that the surface width of the cantilever structure is directly related to laser parameters, and the change is not obvious after wet etching, which further indicates that the laser direct writing technology has excellent controllability. The invention selects proper laser writing power during laser writing, thereby achieving the purpose of regulating and controlling the surface wettability of the sample by laser.
In one implementation mode of the invention, the etching liquid for wet etching is a hydrogen fluoride solution (HF solution). Specifically, the hydrogen fluoride solution is an HF diluted solution with the mass percent of 4% -5%. The hydrogen fluoride solution can etch the metal film and can also corrode the substrate to a certain degree.
The invention utilizes the characteristic that HF diluent has isotropic etching on the substrate, and can prepare the directional passive self-driven structure with the suspended beam shape, in particular to the directional passive self-driven structure with the suspended beam shape which is obtained by etching the metal film by the etching liquid and then etching the substrate below the directional passive self-driven pattern for resisting etching. The invention discovers that the wet etching time can influence the etching effect, namely, if the etching time is too long, the etching is excessive, and if the etching time is too short, the etching is insufficient. In one implementation mode of the invention, the time of the wet etching is 10-60 min.
Furthermore, the wet etching time is 20min, and the directional passive self-driven structure with uniform appearance and a suspended beam shape can be obtained. Specifically, the etching liquid finishes etching a 50nm metal film within 15min, and the substrate below the anti-etching directional passive self-driven pattern is continuously etched for 5min to obtain a directional passive self-driven structure which is uniform in appearance and has a suspended beam shape.
As shown in fig. 1, in one implementation of the present invention, the directional passive self-driven pattern unit further includes: a strip-shaped robust region 3 located at one side of the drive region and the pinch region. The robust region 3 can form a robust layer after wet etching is completed, and the robust layer is used for improving the robustness of directional driving of liquid drops and preventing the liquid drops from collapsing in a non-target direction, so that the self-driven directional transportation capacity and the robustness of liquid are realized. In particular, the robust region 3 varies according to the shape of the side of the directional passive self-driven pattern, for example, the robust region 3 has the same width from the side of the directional passive self-driven pattern. The robust region 3 of the present invention has a strip shape. Similarly, the robust region 3 and the directional passive self-driven pattern are periodically distributed to form an anti-etching pattern on the metal film.
As shown in fig. 2, the invention provides an oriented passive self-driven thin film, wherein the oriented passive self-driven thin film is prepared by the preparation method of the oriented passive self-driven thin film. Specifically, the directional passive self-driven film comprises: the self-driven pattern structure comprises a substrate 4, a metal thin film layer 5 positioned on the substrate 4 and an oriented passive self-driven pattern layer 6 positioned on the metal thin film layer 5. That is, the directional passive self-driven pattern layer 6 and the metal thin film layer 5 form an anisotropic structure having directional passive self-driving on the substrate 4. Corresponding to the preparation method, the robust region 3 correspondingly obtains a robust layer, the driving region 1 correspondingly obtains a driving layer with gradually increased width, the contraction region 2 correspondingly obtains a contraction layer with gradually decreased width, and the length of the driving layer is longer than that of the contraction layer, so that an asymmetric anisotropic morphology is formed on the surface of the substrate 4; at the same time, the anisotropic structure has an overhang edge, i.e. the width of the upper surface is wider than the width of the lower base surface, and the interface is wedge-shaped. A trapezoidal groove is formed between the robust layer and the driving layer and the contraction layer. Further, the metal thin film layer 5 may be a titanium thin film layer, and the directional passive self-driving pattern layer 6 may be a titanium dioxide layer, providing a strongly hydrophilic surface.
Compared with the traditional method for generating the anisotropic surface by utilizing the chemical gradient, the oriented passive self-driven film disclosed by the invention is based on an asymmetric anisotropic structure, combines the Laplace pressure and the strong hydrophilicity of the surface, can realize spontaneous flow of liquid on the surface along any designed target direction, and has the advantages of relatively high speed, long distance of far output and high robustness.
The technical solution of the present invention will be described below by specific examples.
Example 1
The method comprises the following steps: and depositing a layer of 50nm Ti film on the glass substrate by a magnetron sputtering deposition process.
Step two: and (3) writing the directional passive self-driven pattern on a 50nm metal Ti film by a laser direct writing technology to obtain a patterned film. Wherein, the writing parameters of the laser direct writing technology are as follows: the laser power is 4 mW; the laser pulse width is 1 ms.
Step three: and immersing the obtained patterned film into an HF (hydrogen fluoride) diluent with the mass fraction of 4.5% for 20min to obtain the oriented passive self-driven film.
Step four: when the water mist is sprayed on the surface of the prepared directional passive self-driven film, the liquid drops can move along the direction shown by a dotted arrow shown in figure 1, and long-range transportation is realized.
It was found experimentally that 50nm Ti films could be completely etched in about 15 minutes while the laser oxidized TiO2The pattern is preserved. Since the HF diluent has an isotropic etching effect on the glass, the sample is continuously immersed into the etching solution, TiO2The glass substrate at the bottom of the pattern starts to be etched away, and by controlling the etching time of the HF diluent (for example, etching for 5min), the structure shown in FIG. 1 with uniform morphology and overhanging edges is obtained.
Example 2
The method comprises the following steps: and depositing a layer of Ti film with the thickness of 200nm on the glass substrate by a magnetron sputtering deposition process.
Step two: and (3) writing the directional passive self-driven pattern on the 200nm metal Ti film by a laser direct writing technology to obtain the patterned film. Wherein, the writing parameters of the laser direct writing technology are as follows: the laser power is 4 mW; the laser pulse width is 1 ms.
Step three: and immersing the obtained patterned film into an HF (hydrogen fluoride) diluent with the mass fraction of 4.5% for 100min to obtain the oriented passive self-driven film.
Step four: when the water mist is sprayed on the surface of the prepared directional passive self-driven film, the liquid drops can move along the direction shown by a dotted arrow shown in figure 1, and long-range transportation is realized.
Example 3
The method comprises the following steps: and depositing a layer of 20nm Ti film on the glass substrate by a magnetron sputtering deposition process.
Step two: and (3) writing the directional passive self-driven pattern on the 20nm metal Ti film by a laser direct writing technology to obtain the patterned film. Wherein, the writing parameters of the laser direct writing technology are as follows: the laser power is 4 mW; the laser pulse width is 1 ms.
Step three: and immersing the obtained patterned film into an HF (hydrogen fluoride) diluent with the mass fraction of 4.5% for 10min to obtain the oriented passive self-driven film.
Step four: when the water mist is sprayed on the surface of the prepared directional passive self-driven film, the liquid drops can move along the direction shown by a dotted arrow shown in figure 1, and long-range transportation is realized.
Compared with the prior art that the movement speed of the liquid drop is low and the distance for long distance transportation is limited due to the adoption of the anisotropic surface generated by chemical gradient, the invention adopts the asymmetric anisotropic structure to spontaneously drive the liquid drop, and can convert the redundant surface energy of the liquid into the kinetic energy at the advancing edge by combining the spreading capacity of the liquid drop caused by the hydrophilicity of the surface of the anisotropic structure, the Laplace pressure caused by the shape and the shape of the asymmetric structure and the controllable anisotropic wetting of the suspended edge structure formed by etching on the liquid drop so as to break the pinning phenomenon in the conventional technology and realize the self-driven controllable directional long-distance transportation of the liquid drop.
It should be understood that the technical solutions and concepts of the present invention may be equally replaced or changed by those skilled in the art, and all such changes or substitutions should fall within the protection scope of the appended claims.
Claims (7)
1. A method for preparing a directional passive self-driven film is characterized by comprising the following steps:
depositing a metal film on a substrate;
writing directional passive self-driven patterns on the metal film by adopting a laser writing technology;
performing wet etching on the metal film on which the directional passive self-driven pattern is engraved to obtain a directional passive self-driven film;
the metal film is a titanium film;
forming anti-etching titanium dioxide on the surface of the titanium film in the laser etching process of the titanium film;
the etching liquid for wet etching is hydrogen fluoride solution;
the directional passive self-driven pattern comprises a plurality of directional passive self-driven pattern units which are connected end to end;
each of the directional passive self-driven pattern units includes: the driving area is gradually increased in width, and the contraction area is connected with the driving area and gradually reduced in width, wherein the length of the driving area is longer than that of the contraction area;
the directional passive self-driven pattern unit further includes: the strip-shaped robust region is positioned on one side of the driving region and the contraction region;
the robust region varies according to the shape of the sides of the directional passive self-driven pattern, wherein the robust region is the same width as the directional passive self-driven pattern sides.
2. The method for preparing the directional passive self-driven film according to claim 1, wherein the substrate is one of a glass sheet, a quartz sheet and a silicon sheet.
3. The method for preparing the directional passive self-driven thin film according to claim 1, wherein the thickness of the titanium thin film is 20-200 nm.
4. The method for preparing the directional passive self-driven film according to claim 1, wherein the deposition process for depositing the metal film on the substrate is one of an ion sputtering deposition process, an electron beam evaporation deposition process, a thermal evaporation deposition process, a laser pulse deposition process and a magnetron sputtering deposition process.
5. The method for preparing the directional passive self-driven film according to claim 1, wherein the laser writing technology is a laser direct writing technology;
the writing parameters of the laser direct writing technology are as follows: the laser power is 1-10 mW; the pulse width of the laser is 0.1-10 ms.
6. The method for preparing the directional passive self-driven thin film according to claim 1, wherein the wet etching time is 10-60 min.
7. An oriented passive self-driven film, which is prepared by the method for preparing the oriented passive self-driven film according to any one of claims 1 to 5.
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| CN110374963A (en) * | 2019-07-01 | 2019-10-25 | 大连理工大学 | A kind of structure that achievable liquid is transported from driving over long distances |
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| WO2021217891A1 (en) | 2021-11-04 |
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