KR101230059B1 - Method for manufacturing porous layers using patterned substrate and Board manufactured by the same - Google Patents

Abstract

The present invention relates to a method for producing a porous membrane using a patterned substrate and a substrate produced by the method, and more particularly, to a method for producing a nanoporous membrane based on spin coating on a nano-pattern or micro-patterned substrate. It relates to a porous film-forming substrate produced using the production method.
According to the present invention, a sufficient specific surface area is based on spin coating method on a nano-patterned or micro-patterned substrate as compared with a method of dispersing and printing nanoparticles used to form a large specific surface in a solvent and a binder. Can be obtained.

Description

Method for manufacturing porous membrane using a patterned substrate and a porous film forming substrate manufactured by the method {Method for manufacturing porous layers using patterned substrate and Board manufactured by the same}

The present invention relates to a method for producing a porous membrane using a patterned substrate and a substrate produced by the method, and more particularly, to a method for producing a nanoporous membrane based on spin coating on a nano-pattern or micro-patterned substrate. It relates to a porous film-forming substrate produced using the production method.

In all catalytic materials and sensor devices, the specific surface area can be increased to improve the properties or performance by extending the areas where physical or chemical reactions occur. Therefore, it is very important to improve the specific surface area in such materials.

In particular, the production of a porous membrane having an appropriate size and space according to the type and size, state, and the like of the species to be detected in the sensor element and the type of material involved in the catalytic reaction in the catalyst material.

In addition, the catalytic material needs to be applied and used on a suitable material to impart selective reactivity, and in the case of a sensor element, a porous membrane may be fabricated on a suitable substrate for improved detection capability and large area, mass production, and efficiency. There is a need.

In addition, in a solar cell, which is a photo-voltaic energy conversion system for converting light energy emitted from the sun into electrical energy, it is necessary to form a large specific surface area in order to improve the generation of electrons and holes. Dye-sensitized solar cells (DSSC), which are currently used as a form of solar cells, also use porous membranes for large specific surface areas.

In particular, in the case of dye-sensitized solar cells, the area between the electrolyte and the dye should be maximized to maximize the generation of electrons and holes in the electrolyte and dye. Therefore, there is a need for fabrication of porous membranes having a large specific surface area where dyes can be efficiently transferred and attached.

In addition, increasing the specific surface area by patterning the electrodes of the solar cell is one way to improve the solar cell efficiency. In particular, in the case of a dye-sensitized solar cell, high efficiency can be achieved by improving the efficiency of charge (electron or hole) transfer and shortening the charge transfer distance through patterning of the electrode.

However, in the conventional method for producing a porous membrane, the shape and distribution of pores are uneven or the pore size or distribution control is almost impossible. In addition, even if the size is uniform, it is possible to manufacture a porous membrane having only one size has a limitation in various applications.

In addition, the porous membrane formed on the substrate also had a problem in improving performance because it was produced in a flat form on a flat substrate through a printing method or the like.

Therefore, according to the prior art, it is not possible to obtain a sufficient specific surface (amount of surface area to volume) for the development of materials or devices having new characteristics or performance.

In addition, only one type of porous membrane is formed on the substrate.

In addition, it is difficult to control the film thickness, porosity, etc. formed on the substrate.

The present invention provides a method for producing a porous membrane using a patterned substrate capable of obtaining a sufficient specific surface based on a spin coating method on a nano-patterned or micro-patterned substrate, and a porous film-forming substrate prepared by the method. There is this.

In addition, another object of the present invention is to provide a method for preparing a porous membrane using a patterned substrate capable of controlling the thickness of the porous membrane, and a porous membrane-forming substrate prepared by the method.

In addition, another object of the present invention is to provide a method for preparing a porous membrane using a patterned substrate that can also control the size of nanocrystal grains and a porous film forming substrate prepared by the method.

It is another object of the present invention to provide a method for preparing a porous membrane using a patterned substrate capable of forming a porous film of any form, and a porous film-forming substrate prepared by the method.

The present invention also provides a method for producing a porous membrane using a patterned substrate that forms a hybrid porous membrane of mesoporous and nanoporous membranes, and a porous membrane-forming substrate prepared by the method. have.

The present invention provides a method for producing a porous membrane using a patterned substrate to solve the problems posed above. The method for producing the porous membrane may include a nanosphere pattern forming step of forming a first nanosphere pattern on a substrate; Forming a second nanosphere pattern and a porous groove on the substrate by etching the nanosphere patterned substrate to form a porous groove; A mask removing step of removing the two nanosphere patterns to form only the pattern recesses and the pattern convex portions on the substrate; A source material deposition film forming step of forming a source material deposition film by applying a source material on the substrate using a source material applying device; Forming a mesoporous film on the substrate by using the substrate on which the source material deposition film is formed by spin coating; And forming a crystalline porous film through a drying and heat treatment process.

Here, the porous groove is formed between the recess and the iron portion and the crystalline porous membrane is characterized in that the nanoporous and micro-sized hybrid (hybrid) porous membrane.

In this case, the source material is characterized in that the liquid precursor.

Here, the characteristics of the crystalline porous membrane is characterized in that it is determined by adjusting the time, temperature in the step of forming the crystalline porous membrane.

In addition, the thickness of the crystalline porous film is controlled by repeating the source material deposition film forming step to the crystalline porous film forming step.

On the other hand, another embodiment of the present invention provides a porous film forming substrate prepared by the method for producing a porous film using the above patterned substrate.

According to the present invention, compared to a method of dispersing and printing nanoparticles used to form a wide specific surface in a solvent and a binder, a sufficient specific surface based on the spin coating method on a nano-patterned or micro-patterned substrate. Can be obtained.

In addition, another effect of the present invention is to simplify the process and to adjust the spin rate or the concentration of the source material (or precursor) during the spin coating process. It is possible to produce a porous membrane using a substrate.

In addition, another effect of the present invention is that it is possible to produce a porous film using a patterned substrate that can also control the size of the nano-crystal grains by adjusting the time, temperature, etc. in the heat treatment process.

In addition, another effect of the present invention is that it is possible to produce a porous membrane using a patterned substrate capable of forming various types of porous membrane.

In addition, the present invention is able to produce a porous membrane using a patterned substrate to form a hybrid porous membrane of mesoporous membrane and nanoporous membrane.

Figure 1 (a) is a cross-sectional view showing a nanosphere pattern formed on a substrate (or device) using spin coating.
FIG. 1B is a cross-sectional view illustrating a process of transferring a pattern formed in FIG. 1A to a substrate or a utilization device by using an etching (or etching) process according to an embodiment of the present invention.
1C is a cross-sectional view illustrating a process of removing a mask after transferring a pattern to a substrate according to an embodiment of the present invention.
FIG. 2A is a cross-sectional view showing a process of depositing a source material (liquid precursor) to be formed on the pattern fabricated in FIGS. 1A to 1C.
Figure 2 (b) is a cross-sectional view showing a process for forming a source material deposition film according to an embodiment of the present invention.
Figure 2 (c) is a cross-sectional view showing a process of forming a porous membrane formed by a spin coating process according to an embodiment of the present invention.
FIG. 2D is a cross-sectional view illustrating a process in which a crystalline porous membrane 240 formed by drying the porous membrane 230 formed in FIG. 2C is formed.
Figure 3 is a flow chart showing the manufacturing process of a porous membrane using a patterned substrate according to an embodiment of the present invention.
Figure 4 (a) is a cross-sectional view of a plurality of layers of crystalline porous membrane according to an embodiment of the present invention.
Figure 4 (b) is a cross-sectional view of three layers of crystalline porous membrane according to an embodiment of the present invention.
Figure 5 (a) is a cross-sectional view of the porous groove 101 in accordance with an embodiment of the present invention.
Figure 5 (b) is a cross-sectional view of the porous groove 101 according to another embodiment of the present invention.
6 is a screen example of a process of forming a pattern by coating a nanospheres on a substrate according to an embodiment of the present invention.
Figure 7 is an enlarged screen example after the etching process of the nanosphere pattern according to an embodiment of the present invention.
8 is a screen example of removing the nanospheres in accordance with the mask removal process according to an embodiment of the present invention.
9 is a screen example of a process for forming a hybrid porous film on a patterned substrate and controlling the size of pores using a spin coating method according to an embodiment of the present invention.
10 is a screen example of the porous groove 101 and the nanocrystalline particles 1001 shown in (a) or (b) of FIG.

As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing.

Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component. And / or < / RTI > includes any combination of a plurality of related listed items or any of a plurality of related listed items.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "having" are intended to indicate that there is a feature, number, process, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present disclosure does not exclude the possibility of the presence or the addition of numbers, processes, operations, components, components, or a combination thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Hereinafter, a method of manufacturing a porous membrane using a patterned substrate and a substrate manufactured by the method will be described in detail with reference to the accompanying drawings.

Figure 1 (a) is a cross-sectional view showing a nano-sphere (nano-sphere) pattern formed on a substrate (or device) using spin coating. Referring to FIG. 1A, a nanosphere pattern 110 formed on a substrate 100 (or a device) using spin coating is illustrated.

The pattern 110 may be manufactured by various methods including a bottom-up method such as nano-sphere lithography and a top-down method such as photo-lithography. The size of the nanosphere pattern 110 may be controlled by the nanosphere size and the selective etching (ie etching) of the nanospheres.

In other words, the cross section formed after the spin coating after applying the mixed solution (which is a mixed solution of silica particles and water) to the substrate 100 is shown in FIG.

FIG. 1B is a cross-sectional view illustrating a process of transferring a pattern formed in FIG. 1A to a substrate or a utilization device by using an etching (or etching) process according to an embodiment of the present invention. Referring to FIG. 1B, a diagram illustrating a substrate formed after a reactive ion etching (RIE) or wet-etching (wet etching) process is performed. Of course, in this case, the size of the nanosphere pattern 110 is reduced by etching, and the porous groove 101 is formed between the nanosphere patterns 110.

FIG. 1B is a step of transferring the pattern formed in FIG. 1A to a substrate or a utilization device by using an etching (or etching) process. The pattern shape and size to be transferred can be controlled according to the etching process conditions (time, gas atmosphere, etc.), and both the mask (nanosphere in this figure) and the substrate used for pattern formation can be etched.

1C is a cross-sectional view illustrating a process of removing a mask after transferring a pattern to a substrate according to an embodiment of the present invention. Referring to FIG. 1C, the mask is removed after transferring the nanosphere pattern 110 to the substrate 100.

Of course, the mask removal process may include a process of removing the oxide film formed on the surface after removing the nanosphere pattern 110 by using ultrasonic vibration or using a wet etching process. Therefore, irregularities are periodically formed on the upper end of the substrate 100.

2A to 2D are schematic views illustrating a process of forming a porous film using the substrate 100 formed by FIGS. 1A to 1C, and controlling a thickness and a shape of the film.

FIG. 2A is a cross-sectional view illustrating a process of depositing a source material (liquid precursor) to be formed on the patterns fabricated in FIGS. 1A to 1C. Referring to FIG. 2A, after the process of transferring the nanosphere pattern 110 to the substrate 100 and removing the mask, the source material 210 is transferred to the substrate 100 using the source material applying apparatus 200. Apply on). As a source material, a liquid precursor is used. This liquid precursor is a liquid phase reaction method using a reaction in a liquid phase.

Coprecipitation, sol-gel, and hydrothermal methods using liquid precursors are the most commonly used methods.

In other words, the liquid precursor is mixed with water or water and ethylene glycol with precursor 201 (ie, nanospheres) such as TiO ₂ , SiO ₂ , ZrO ₂ , BaTiO ₃ , Al ₂ O ₃ , and Y ₂ O ₃ . Produced by dispersing well in solution.

In FIG. 2A, the source material applying apparatus 200 is shown to proceed from right to left, but the hydrophobic material applying apparatus 200 is fixed and the substrate 100 proceeds from right to left by the conveyor system. It is also possible to do it.

2B is a cross-sectional view illustrating a process in which a source material deposition film is formed in accordance with an embodiment of the present invention. Referring to FIG. 2B, when the source material (see 210 of FIG. 2A) is applied on the substrate 100 by FIG. 2A, the source material deposition film is deposited on the substrate 100. 220 is formed.

Figure 2 (c) is a cross-sectional view showing a process in which a porous membrane formed by a spin coating process according to an embodiment of the present invention. Referring to FIG. 2C, the source material deposition film 220 formed by FIG. 2B is converted into a mesoporous film 230 by spin coating. Since the spin coating method is a well known technique, it will be omitted for a clear understanding of the present invention.

FIG. 2D is a cross-sectional view illustrating a process in which the crystalline porous membrane 240 formed through the post-treatment process of the mesoporous membrane 230 formed in FIG. Referring to FIG. 2D, the mesoporous membrane 230 formed by FIG. 2C is a process of forming a porous membrane through a drying (or heat treatment) process.

In the case of the mesoporous membrane 230, the characteristics of the mesoporous membrane 230 can be controlled according to the conditions (spin coating thickness, spin coating number, concentration of the source material, etc.) for depositing the source material. In addition, the drying process is performed using a hot plate, oven, wind or the like.

3 is a flowchart illustrating a process of preparing a porous membrane using a patterned substrate according to an embodiment of the present invention. 3 will be described with reference to FIGS. 1A to 1C and FIGS. 2A to 2D.

Referring to FIG. 3, the nanosphere pattern 110 is formed on the substrate 100 of FIG. 1A (step S300). An example of this is shown in FIG. 6. Referring to FIG. 6, the screen on the upper left is a low magnification screen 600, and when viewed in a clockwise direction, a high magnification 610 and an ultra high magnification screen 620 are illustrated.

 In this pattern process, nanospheres having various sizes are well dispersed in water or a mixed solution of water and ethylene glycol. The substrate 100 may be immersed in a piranha solution for 24 hours in a silicon substrate or subjected to oxygen plasma treatment so as to have hydrophilicity. The speed and time of spin coating is controlled to form single or multiple layers of silica nanospheres.

3, the nanosphere patterned substrate 100 formed in step S300 is etched (step S310). After the etching process, as shown in FIG. 1B, the nanosphere pattern 110 is reduced, and the porous groove 101 is formed on the top surface of the substrate 100. An example of this is shown in FIG. Referring to FIG. 7, a planar photograph, a cross-sectional photograph, and the like of an ultra-high magnification screen 700 and a high magnification screen 710 are shown in a clockwise direction.

By adjusting variables such as the type of gas used in the etching process, process pressure, and time, it is possible to find a condition that can control the nanosphere size only or the pattern transferred on the nanosphere and the substrate reproducibly at the nanometer level. In one embodiment of the present invention it was controllable at the 2 nm / s level. Such control of the pattern size or characteristics can ensure more controllability by introducing a sacrificial film.

After the etching process, a process of removing the mask of the nanosphere pattern 110 is performed (step S330). 8 shows an example of a screen after removing a mask. Referring to FIG. 8, the left screen is an ultra high magnification screen 800 and a high magnification screen 810. Looking at the ultra-high magnification screen 800, only the convex portion 801 and the recessed portion 802 is formed.

In the case of silica nanospheres, it can be removed by using ultrasonic vibration or HF (fluoric acid) solution.

After the mask removing process, a liquid precursor is applied onto the substrate 100 as shown in FIG. 2A, and spin coating is performed (steps S340 and S350). 9 shows an example of a screen after such spin coating. Referring to FIG. 9, FIG. 9 shows a porous membrane fabricated using a spin coating method. The thickness and shape of the porous membrane exhibits properties that depend on the number of spin coatings. In detail, the spin coating screen 900, the spin coating screen 910, the spin coating screen 920, and the spin coating screen 930 are shown in the clockwise direction.

As shown in FIG. 9, as the number of spin coatings increases, it can be seen that the porous grooves (see (a) 101 of FIG. 1) existing between the patterns become smaller.

In particular, by controlling the space between the nanoparticles as well as the space between the patterns it is possible to form a hybrid porous film of the nano-size and micro-size coexist.

When the spin coating process is completed, the substrate 100 is dried (step S360). The drying process may be performed by blowing the solvent using a method of drying the substrate 100 at a low temperature or a high temperature by placing the substrate 100 in a hot plate, an oven, or the like, as described above.

4A is a cross-sectional view of a convex portion (see 102 of FIG. 1 and 801 of FIG. 8) of a pattern formed according to an embodiment of the present invention. Referring to FIG. 4A, FIG. 4A is a cross-sectional view illustrating a state in which the first crystalline porous membrane 400 is formed in the convex portions 102 and 801 of the pattern.

4B is a cross-sectional view of the convex portions 102 and 801 of the pattern according to another embodiment of the present invention. Referring to FIG. 4B, FIG. 4B shows the first crystalline porous membrane 400, the second crystalline porous membrane 410, and the third crystalline porosity in the convex portions 102 and 801 of the pattern. The film 420 is formed in a sequential manner.

Therefore, in FIG. 5A, the first gap h1 is formed in the porous groove 101 due to the one-time crystalline porous membrane 400. On the contrary, in the case of FIG. 5B, the second gap h2 is formed in the porous groove 101 due to the two crystalline porous membranes 400 and 410. In other words, it can be seen that the gap between the membrane thickness and the porous membrane can be adjusted.

10 is a screen example of the porous groove 101 shown in (a) or (b) of FIG. 5. Referring to FIG. 10, FIG. 10 is screen examples 1000 and 1010 showing a successful fabrication of a nanoporous membrane composed of nanocrystalline particles 1001 by transmission electron micrographs.

In one embodiment of the present invention, the porous groove is shown in a triangular shape, but for easy understanding, other shapes, such as a circle, are possible. Thus, unlike conventional planar substrates, the surface area for reactions such as photoelectron incidence is increased.

100 substrate 101 porous groove
102: pattern convex portion 110: nanosphere pattern
200: source material application device 201: precursor (precusor)
210: source material 220: source material deposition film
230: mesoporous membrane 240: crystalline porous membrane
400: first crystalline porous membrane 410: second crystalline porous membrane
420: third crystalline porous membrane 801: pattern convex
802: pattern recess 1001: nanocrystalline particles
h1: first interval h2: second interval

Claims (6)

A nanosphere pattern forming step of forming a first nanosphere pattern on the substrate;
Forming a second nanosphere pattern and a porous groove on the substrate by etching the nanosphere patterned substrate to form a porous groove;
Removing the second nanosphere pattern to form only a pattern recess and a pattern iron part on the substrate;
A source material deposition film forming step of forming a source material deposition film by applying a source material on the substrate using a source material applying device;
Forming a mesoporous film on the substrate by using the substrate on which the source material deposition film is formed by spin coating; And
Method for producing a porous membrane using a patterned substrate comprising the step of forming a crystalline porous membrane to form a crystalline porous membrane through the drying and heat treatment process. The method of claim 1,
The porous groove is formed between the recessed portion and the iron portion and the crystalline porous membrane is a method for producing a porous membrane using a patterned substrate is a hybrid porous membrane of nano size and micro size. The method of claim 2,
And the source material is a liquid precursor. The method of claim 2,
The thickness of the crystalline porous film is a method of manufacturing a porous film using a patterned substrate is determined by controlling the time, temperature in the crystalline porous film forming step. The method of claim 2,
And repeating the forming of the source material deposition film and the forming of the crystalline porous film, wherein the thickness of the crystalline porous film is controlled. delete

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