TWI565650B - Fabricating method of micro/nanospheres structure and application thereof - Google Patents

Description

Micro nanosphere structure manufacturing method and hole manufacturing method thereof

The invention relates to a manufacturing technology of a micro-nanosphere structure, in particular to a method for fabricating a micro-nanosphere structure suitable for large-area coating and a micro-nano hole manufacturing method thereof.

With the extensive development of micro-nano technology, the current technology for fabricating micro-nanostructures has matured. Photolithography, E-beam lithography, and nano-transfer lithography are common. Nano-imprint lithography), nanospheres lithography, etc., in which nanosphere self-assembled lithography is inexpensive to manufacture, does not require expensive equipment, and can be manufactured quickly and in large quantities, so it is widely used. use.

At present, there are many methods for micro-nanosphere self-assembly technology, such as spin coating, Dip coating, Blade coating, etc., although these methods are mentioned. Good micro-nanosphere distribution can be obtained on a millimeter-scale area, but if it is to be extended to a large-scale application of a grade, it is easy to cause defects and reproducibility. Taking China Patent Application No. 101128412 as an example, the patent is preceded by placing a micro-nanosphere solution on a substrate and coating it with a doctor blade, using a heated volatile solution. Brushing the surface of the substrate, scraping the micro-nanospheres not adsorbed on the substrate with a doctor blade, repeating the steps of scouring and scraping several times, and finally drying the volatile solution on the substrate to form a plurality of micro-nano balls on the substrate. structure. The prior patent of this patent is the use of a doctor blade coating method, and there is a problem that it cannot be applied to a large-area mass production, and there may be a defect that a uniform distribution can be obtained only in a partial area.

In view of the above, the present invention provides a method for fabricating a micro-nanosphere structure and a micro-nano hole manufacturing method thereof, which utilizes a modified blade coating micro-nanosphere technology to complete large-area and mass production. The process to overcome the predicament that the prior art cannot be applied to a large area above the cent level.

The main object of the present invention is to provide a method for fabricating a micro-nanosphere structure by using a modified doctor blade to coat a micro-nanosphere technique, and then allowing the substrate to enter and exit the liquid one or more times to remove excess micro-nanospheres. In order to form a uniformly distributed micro-nanosphere structure on a large-area substrate, it is a large-area, mass-produced process, and has high uniformity, high reproducibility, low production cost, and process. The advantages of simplicity and so on.

Another object of the present invention is to provide a method for fabricating micro-nano holes, which utilizes a micro-nanosphere structure to further fabricate micro-nano holes for use on thin films or semiconductor components requiring a micron-hole structure, such as Porous metal films, hole channel processes for organic vertical transistors (SCLT), gas detection holes for gas sensors, etc., are widely used.

In order to achieve the above object, the present invention provides a method for fabricating a micro-nanosphere structure by first contacting at least one scraper with a micro-nanosphere solution and moving the scraper to apply the micro-nanosphere solution thereon. On at least one substrate, the micro-nanospheres of the micro-nanosphere solution are uniformly attached to the surface of the substrate; and then the substrate is allowed to enter the liquid one or more times before leaving, the liquid may be organic A volatile solution or the like to thereby remove micro-nanospheres that are not attached to the surface of the substrate; and finally drying the substrate, a plurality of micro-nanosphere structures can be formed on the substrate.

Furthermore, after the micro-nanosphere structure is formed on the substrate, the micro-nano hole can be further formed by forming a thin film layer on the substrate on which the micro-nanosphere structure has been formed, and the film is formed. The layer also covers the micro-nanosphere; then the micro-nanosphere and the film layer covered thereon are removed to form a film layer having a plurality of micro-nano holes.

The objectives, technical contents, and effects achieved by the present invention will become more apparent from the detailed description of the embodiments and the accompanying drawings.

10‧‧‧Substrate

12‧‧‧Scraper

14‧‧‧Dripper

16‧‧‧Micron Nanosphere Solution

18‧‧‧Organic Volatile Solutions

20‧‧‧hair dryer

22‧‧‧Micron Nanosphere

30‧‧‧Transparent substrate

32‧‧‧ Conductive layer

34‧‧‧Polyvinyl carbitol (PVP) insulation

342‧‧‧Perforation

36‧‧‧Micron Nanosphere

38, 38'‧‧‧Aluminum metal layer

382‧‧‧ hole

40‧‧‧ active layer

42‧‧‧metal layer

50‧‧‧Substrate

52‧‧‧Poly 3-hexylthiophene (P3HT) polymer layer

54‧‧‧Micro-nano balls

56, 56'‧‧‧ metal layer

58‧‧‧ hole

60‧‧‧Ammonia molecules

Fig. 1 is a schematic flow chart showing the structure of a micro-nanosphere in the present invention.

2(a) to 2(e) are respectively schematic views showing the steps of the steps of fabricating the micro-nano structure of the present invention.

Figure 3 is a schematic view showing the position of the 12 regions to be observed on the fabricated substrate of the present invention.

Fig. 4 is a picture taken in correspondence with 12 areas of the third figure, wherein numbers 1 to 12 correspond to the substrate numbers 1 to 12 in Fig. 3.

Fig. 5 is a schematic view showing the flow of the micro-nano hole in the micro-nanosphere structure of the present invention.

6(a) to 6(e) are respectively sectional views showing the steps of the steps of fabricating the vertical type transistor using the present invention.

Figure 7 is a schematic perspective view of a vertical type of transistor fabricated by applying the present invention.

Figure 8 is a schematic diagram of current switching characteristics of a vertical transistor.

9(a) to 9(c) are respectively sectional views showing the steps of the steps of fabricating the gas sensor by applying the present invention.

Figure 10 is a schematic perspective view of a gas sensor fabricated by applying the present invention.

Figure 11 is a graph of current and voltage before and after the gas sensor is introduced into the ammonia gas.

Fig. 12 is a schematic view showing the performance of the transmittance before and after the metal mesh structure produced by the present invention.

The invention mainly adopts a method of coating a micro-nanosphere by a modified blade, and then removing the micro-nanosphere by a soaking method, so that the micro-nano ball is deposited on the surface of the substrate so as to be large or small in area. A uniformly distributed micro-nanosphere structure can be formed on the substrate. The invention first describes a method for fabricating a micro-nanosphere structure, and further describes a method for fabricating a micro-nanosphere structure for a micro-nano hole. Finally, two practical application examples are given to illustrate the technical features of the present invention.

Please refer to FIG. 1 and FIG. 2 simultaneously. First, as shown in step S10, a substrate 10 is provided, and at least one scraper 12 is disposed thereon. As shown in FIG. 2(a), a dropper 14 is used. One of the micro-nanosphere solution drops on the scraper 12, and the micro-nanosphere solution contacts the scraper 12. The surface of the scraper 12 is further provided with a singular or plural slit, so that the micro-nanosphere solution can be uniformly diffused to these In the slit (not shown), wherein the slit has a size of several nanometers to several millimeters; then, as shown in steps S12 and 2(b), the micro-nanosphere solution 16 on which the moving blade 12 is placed is moved. Uniformly coated on the substrate 10, using the force between the substrate 10 and the micro-nanosphere, such as the attraction between the substrate and the opposite electrical properties of the micro-nanosphere, the micro-nanosphere solution 16 Nanosphere attached to the substrate 10 surface. Further, as shown in step S14, the substrate 10 is brought into and out of the liquid one or more times. Here, the second immersion is performed and the vertical immersion is used as an example, but it is not limited thereto; please refer to the second (c) As shown in Fig. 2(d), the substrate 10 is vertically immersed in a heated organic volatile solution 18, and the boiling point of the organic volatile solution 18 can be less than the melting point of the microspheres, such as an alcohol solution, but not To this end, in this case, boiling isopropanol is used as the organic volatile solution 18, and then the substrate 10 is separated from the organic volatile solution 18. This step can be repeated several times, and the soaking time can be several seconds to utilize organic The volatile solution 18 carries away the micro-nanospheres that are not attached to the surface of the substrate 10, and the vertical immersion (the best one is selected for vertical immersion) allows the organic volatile solution 18 to flow smoothly with gravity. The micro-nanospheres that are not adsorbed on the substrate 10 are taken. Finally, as shown in steps S16 and 2(e), the substrate is dried, and the substrate 10 can be dried by hot air or cold air by the blower 20 to dry the substrate 10. Uniformly distributed complex micro-nana 22 structure ball.

The invention utilizes the above-mentioned manufacturing method to actually fabricate the nanosphere on the substrate 10 of 25 cm*18 cm, and sequentially selects 12 regions of the substrate 10 on which the plurality of nanospheres have been formed, as shown in FIG. These numbers are 1 to 12, and these areas are observed by a scanning electron microscope (SEM). The results are shown in Fig. 4, and the numbers 1 to 12 correspond to the substrate numbers 1 to 12 in Fig. 3, From this observation, it is possible to obtain a nanosphere structure having a high density and a uniform distribution regardless of the position of the substrate 10, so that it can be applied to a large-area and mass-produced process.

Furthermore, the present invention is more applicable to the fabrication of nano-holes. Referring to FIG. 5, first, as shown in step S20, a substrate is provided, on which the foregoing method has been used, such as steps S10-S14 or step S10. ~S16 makes a micro nanosphere structure. Then, as shown in step S22, a thin film layer is deposited on the substrate, so that the thin film layer covers both the substrate and the micro-nanospheres. At last, As shown in step S24, an adhesive or tape is attached to the outermost surface of the substrate, and the adhesive or tape is peeled off to physically remove the micro-nanosphere and the film layer covered thereon, thereby forming a plurality of thin film layers of micrometers or nanopores; wherein in the step of removing the micro-nanospheres, chemical removal of the micro-nanospheres may be used in addition to physical removal, which will not be described in detail herein. . The film layer having a plurality of holes produced by the invention can be used as a highly transparent conductive layer, a base metal mesh of a vertical transistor or a reaction hole layer or a hole electrode layer of a gas sensor. The bottom part is respectively for the basic metal mesh of the vertical transistor and the reaction hole layer of the gas sensor. The second practical application example is as follows, but it should not be limited to this.

6(a) to 6(e) are respectively sectional views showing the steps of the steps of applying the present invention to fabricate a vertical type transistor, and referring to the three-dimensional structure diagram shown in FIG. First, as shown in FIG. 6(a), a transparent substrate 30, such as a glass substrate, is provided on which a conductive layer (eg, indium-tin-oxide, ITO) 32 and a polyethylene are sequentially formed as a collector. The ruthenium ketone (PVP) insulating layer 34 is formed on the polyethylene ruthenium ketone insulating layer 34 by the steps S10 to S16 described above. As shown in FIG. 6(b), an aluminum metal layer 38, 38' is formed on the transparent substrate 30 by metal evaporation, which covers both the micro-nanosphere 36 and the polyethylene-xanthone insulation layer 34. The surface. Then, the tape is attached to the outermost surface of the transparent substrate 30, and the tape is peeled off to physically remove the micro-nanosphere 36 and the aluminum metal layer 38' covered thereon to form a pattern as shown in FIG. 6(c). The illustrated hole 382 structure, leaving the aluminum metal layer 38 as the base metal mesh. Then, as shown in FIG. 6(d), the polyethylene ruthenium ketone insulating layer 34 is subjected to a plasma etching process using the aluminum metal layer 38 having the holes 382 as a mask to etch away the bare portion of the polyethylene. The ruthenium ketone insulating layer 34 is formed with a through hole 342 penetrating the polyethylene ruthenium ketone insulating layer 34 and exposing the transparent conductive layer 32. Finally, as shown in FIG. 6(e), an active layer 40 is formed on the transparent substrate 30, and the material thereof may be a poly-3-hexylthiophene (P3HT) polymer. The active layer 40 is also filled with the perforations 342 and is annealed. After completion, a metal layer 42 is formed on the active layer 40, comprising a molybdenum oxide (MoO ₃ ) layer and an aluminum layer for use as an emitter, so that the vertical transistor can be completed by applying the technical features of the present invention. Structure.

After the completion of the vertical transistor, it does have the characteristics of the switching element. Please refer to the current switch characteristic diagram shown in Figure 8. From this result, the current switching ratio (on/off) of the vertical transistor can be seen. Ratio) can indeed reach 104, quite in line with the characteristics of the switching elements.

In addition, in the present invention, the gas sensor can be fabricated by using the above-described micro nanosphere and micron hole manufacturing method, and the steps are as shown in FIGS. 9(a) to 9(c).

Please also refer to the three-dimensional structure diagram shown in Figure 10. First, as shown in Fig. 9(a), a substrate 50, such as a transparent substrate, preferably a glass substrate, having a conductive layer (e.g., ITO) formed thereon, wherein the conductive layer on the transparent substrate 50 is provided, is provided. And forming a sensing layer, such as a poly-3-hexylthiophene (P3HT) polymer layer 52, on the substrate 50; and using the foregoing steps S10 to S16 on the poly-3-hexylthiophene polymer layer 52. A structure of a plurality of micro-nano balls 54 is produced. Next, as shown in FIG. 9(b), a conductive layer 56, 56' is formed on the substrate 50, for example, an aluminum electrode is plated by evaporation, which covers both the microspheres 54 and the poly-3-hexylthiophene. The exposed surface of the polymer layer 52. The tape is attached to the outermost surface of the substrate 50, and the tape is peeled off to physically remove the micro-nanosphere 54 and the metal layer 56' covered thereon to form a film as shown in FIG. 9(c). The hole 58 is structured to leave a conductive layer 56 having a hole 58 as a hole electrode layer of the gas sensor.

As shown in Fig. 10, when the gas sensor is used to detect gas, for example, Ammonia gas (NH3), ammonia molecules 60 will enter the poly-3-hexylthiophene polymer layer 52 through the pores 58 to cause a change in the current voltage signal, as shown in Fig. 11, which is shown in the gas sensor. The experimental results of the current-voltage curve before and after the ammonia gas are introduced. It can be seen from the figure that a reaction occurs at 200 seconds, and the presence of the ammonia gas molecule 60 can be sensed.

In addition, the metal mesh having nanopores produced by the present invention has relatively high light transmittance, and as shown in FIG. 12, the nanosphere is coated on a glass substrate by the process of the present invention, and A layer of aluminum metal is vapor-deposited, and then the nanospheres are removed by tape to form an aluminum metal mesh structure. At the same time, the comparison of the transmittance before and after evaporation of 40 nm of aluminum metal layer on the substrates coated with 2000 Å and 1000 Å nanospheres was compared, in which the nanospheres were removed to form an aluminum metal mesh structure, and the comparison result is shown in Fig. 12. The aluminum metal layer formed directly on the glass substrate has the lowest transmittance, and the aluminum metal structure formed on the substrate has a higher transmittance. Therefore, the metal mesh produced by the present invention can obtain a high transmittance, and can be used as a conductive layer having high light transmittance.

Therefore, the present invention utilizes a modified blade coating micro-nanosphere technology to uniformly coat, and then cooperates with a soaking method, such as vertical immersion, to remove excess micro-nanospheres to form a micro-nanosphere structure, which can avoid more The external force factor and the realization of the large-area process, thereby forming a uniform distribution of the micro-nanosphere structure on the substrate, whether it is suitable for large or small areas, is a process that can be large-area and mass-produced. At the same time, it has the advantages of high uniformity, high reproducibility, low production cost and simple process. Furthermore, the micro-nano structure is used to continue the fabrication of the micro-nano holes, and can be widely applied to thin films or semiconductor components requiring a micro-nano hole structure, such as a hole channel process of an organic vertical transistor (SCLT). Gas sensing holes for gas sensors, etc., are widely used.

The embodiments described above are merely illustrative of the technical idea and features of the present invention. The subject matter of the present invention is to be understood by those skilled in the art, and the scope of the present invention is not limited thereto, that is, the equivalent changes or modifications made in accordance with the spirit of the present invention should still be Within the scope of the patent of the present invention.

Claims (18)

A method for fabricating a micro-nanosphere structure, comprising the steps of: contacting a micro-nanosphere solution with at least one scraper, the surface of the scraper may be provided with a singular or plural slit, so that the micro-nanosphere solution can be located in the narrow Sewing, moving the scraper to apply the micro-nanosphere solution thereon to at least one substrate, and attaching the micro-nanosphere of the micro-nanosphere solution to the surface of the substrate; making the substrate one or more times After entering the liquid, it is removed to remove the excess micro-nanosphere; and after drying the substrate, a plurality of the micro-nanosphere structures are formed on the substrate. The method for producing a micro-nanosphere structure according to claim 1, wherein the liquid is a heated liquid or a volatile liquid. The method for producing a nanosphere structure according to claim 2, wherein the boiling point of the liquid is less than the melting point of the microsphere, and may be an organic volatile liquid such as an alcohol solution. The method for producing a nanosphere structure according to claim 1, wherein in the step of drying the substrate, drying is performed by natural drying, infrared heating, substrate heating, blowing cold air or hot air blowing. The method for fabricating a micro-nanosphere structure according to claim 1, wherein the substrate enters the liquid by immersing in the liquid, or contacting the substrate surface downward to contact the liquid, or atomizing the liquid to adsorb The substrate is placed on the substrate, or the liquid is placed in a permeation tank to leak down onto the substrate. The method for fabricating a micro-nanosphere structure according to claim 5, wherein the substrate is separated from the liquid by removing the substrate from the immersion area, tilting the substrate or facing downward to cause the liquid to flow away or drip away by gravity. The liquid is removed by adhesion to the water absorbing or oil absorbing material. The method for fabricating the micro-nanosphere structure according to claim 5, wherein the immersion is more an oblique or upright immersion. A micro-nano hole manufacturing method comprises the steps of: contacting a micro-nanosphere solution with at least one scraper, the scraper surface may be provided with a singular or plural slit, so that the micro-nanosphere solution can be located in the slits And moving the scraper to apply the micro-nanosphere solution thereon to at least one substrate, and attaching the micro-nanosphere of the micro-nanosphere solution to the surface of the substrate; and allowing the substrate to enter once or more After a heated solution, the solution is removed to remove the micro-nanospheres that are not attached to the surface of the substrate, so that a plurality of the micro-nanospheres are formed on the substrate; a thin film layer is formed on the substrate and Covering the micro-nanospheres; and removing the micro-nanospheres and the film layer overlying them to form a thin film layer having a plurality of micro-nano holes. The method for fabricating a micro-nano hole according to claim 8, wherein the boiling point of the solution is less than the melting point of the micro-nanosphere. The method for producing a micro-nano hole according to claim 8, wherein the solution is an organic solution, a volatile solution or an organic volatile solution, such as an alcohol solution. The micro-nano hole manufacturing method according to claim 8, wherein after the step of forming the plurality of micro-nanosphere structures on the substrate, a drying step may be further performed to dry the substrate. The micro-nano hole manufacturing method according to claim 11, wherein in the step of drying the substrate, drying is performed by natural drying, infrared heating, substrate heating, blowing cold air or hot air blowing. The method for fabricating a micro-nano hole according to claim 8, wherein the substrate enters the liquid in a manner Soaking in the liquid, or contacting the surface of the substrate downward, or atomizing the liquid onto the substrate, or causing the liquid to be deposited in a permeation tank to drop down onto the substrate. And the manner in which the substrate is separated from the liquid may be that the substrate is removed from the immersion area, the substrate is inclined or face down to cause the liquid to flow away or drip away by gravity, and the liquid is removed by water absorbing or oil absorbing material. The micro-nano hole manufacturing method according to claim 13, wherein the immersion is more an oblique or upright immersion. The micro-nano hole manufacturing method according to claim 8, wherein in the step of removing the micro-nanospheres and the film layer covered thereon, the micro-nano is physically removed by using an adhesive colloid or tape. The rice ball and the film above it, or chemically dissolving the micro-nanospheres by using a solvent capable of dissolving the micro-nanospheres and simultaneously removing the film above it, or using high temperature to make the micro-nano The ball is vaporized and the film above it is removed simultaneously. The method for fabricating a micro-nano hole according to claim 8, wherein the film layer having the plurality of holes serves as a highly transparent conductive layer or as a base metal mesh of a vertical transistor. The micro-nano hole manufacturing method according to claim 8, wherein the film layer having the plurality of holes is a hole electrode layer or a reaction hole layer of a gas sensor. The micro-nano hole manufacturing method according to claim 17, wherein the substrate is a substrate having a conductive layer or a semiconductor layer.