KR20060072864A - Porous mask via colloidal self-assembly and uses thereof - Google Patents

Abstract

The present invention provides a film-type mask base material in which spherical particles are laminated inside a matrix by colloidal self-assembly from a solution containing monodisperse particles constituting the matrix and monodisperse particles forming a sphere, The present invention relates to a porous mask in which holes are formed by etching spherical particles, porous particles prepared by using the same, nanocomposites, and bio and optoelectronic devices. It is easy to manufacture masks, and it is possible to use not only single layer masks but also multilayer masks composed of multilayers, and mask holes have three-dimensional structures instead of two-dimensional planar structures, which enables curved patterning and uniform holes. Branch can produce particles, Various bio devices and optoelectronic devices can be manufactured.

Colloidal self-assembly, nanomasks, nanocomposites, biodevices, optoelectronic devices

Description

Porous mask via colloidal self-assembly and uses             

1 is a scanning electron microscope (SEM) photograph of a porous silica mask prepared in one embodiment according to the present invention.

2 is an explanatory diagram of nanolithography using a self-assembled porous mask according to the present invention.

FIG. 3 is an explanatory diagram for explaining a step of preparing nanocomposite particles by inserting a third material having different properties into the pores of particles having uniform pores; FIG.

4 is an explanatory diagram for explaining an example of manufacturing a nanodevice using the nanocomposite particles produced by the present invention.

5a to 5d are scanning electron micrographs showing the process of manufacturing a porous nanomask in accordance with an embodiment of the present invention.

6a to 6c are scanning electron micrographs showing a mask made from different stacking water.

7A is a scanning electron micrograph showing the shape of particles with three uniform holes.

FIG. 7B is a scanning electron micrograph showing the shape of particles with four uniform holes. FIG.

FIG. 8 is a scanning electron micrograph showing nanocomposite particles prepared by adding platinum as a third material to particles having uniform pores. FIG.

The present invention relates to a nano-etching process and a patterning process, and more particularly to the production of a porous mask by self-assembly of colloidal particles, the production of monodisperse particles and nanocomposite particles using the manufactured mask.

As electronics become smaller and more integrated, micro or nanometer pattern processes are needed to store more information. Until now, photolithography was mainly used to manufacture such a pattern. However, photolithography has a limited line width that can be realized by diffraction and interference of light, and thus, electron beam lithography or X-ray lithography has been introduced to manufacture microscopic patterns. However, these methods have a disadvantage in that they require longer processing time and more cost than photolithography.

The self-assembly patterning method that can implement a simpler and cheaper fine pattern in a larger area has attracted attention. Among them, colloidal lithography using the monolithic dispersing of particles is used to produce particles of uniform size of micro or less, and then spin or dip coating on the base material, chemical vapor deposition, and electroplating. After lamination, a variety of patterns can be created from this and can be manufactured at the laboratory level without the need for a clean room requiring extreme cleanliness. In addition, this method uses the self-assembly of particles, which makes it possible to easily create a pattern with a large array of uniform arrays at low cost.

For this reason, studies have been actively conducted to manufacture micropatterns of several tens of nanometers in size by using colloid self-assembly. (Related patents: 1. Ozin. GA: Yang. SM; Miguez, H., WO0101436, EP01975922, WO02 / 33461 A2. 2. Winningham, Thomas Andrew; Douglas, Kenne, US200220123, 3. Van Duyne et al., US00401803 References: 1.Hanenes, CL; Van Duyne, RPJ Phys. Chem. V, 2001, 105, 5599. 2. Yi, DK; Kim, DY Chem. Commun., 2003, 982. 3.Kuo, CW Shiu, JY; Chen, P. Chem. Mater., 2003, 15, 2917. 4.Love, JC; Gates, BD; Wolfe, DB; Paul, KW; Whitesides, GM Nano.Let. 2002, 2, 891. ).

However, since the nanopatterning process and etching process using the colloidal site assembly including the above findings use the self-assembled patterned particles as a sacrificial layer or finally lift off (Lift-off process), the self-assembly pattern It is limited to the use for single use and has the inconvenience of having to recreate the self-assembly pattern in every use.

One object of the present invention is to propose a new method for utilizing a film having an inverted photonic crystal structure prepared by colloidal self-assembly as a porous mask for nanoetching and patterning.

In addition, another object of the present invention is to produce monodisperse particles having a uniform hole by using a continuous colloid layer, and to put nanomaterials into a third material therein to make nanocomposite particles and use them in bio and optoelectronic devices. .

According to the present invention which achieves the above object, a film-shaped mask substrate in which spherical particles are laminated inside a matrix by colloidal self-assembly from a solution containing the monodisperse particles constituting the matrix and the monodisperse particles forming a sphere. Manufacturing;

There is provided a method of manufacturing a porous mask comprising the step of forming a hole by etching the spherical particles of the prepared mask substrate.

According to the present invention, there is also provided a porous mask prepared by the above-described method.

In addition, according to the present invention, a patterning method using the porous mask described above is provided.

According to the present invention, there is also provided a porous particle produced by the above patterning method.

In addition, according to the present invention, a composite particle provided with a nanomaterial to the porous particles is provided.

In addition, according to the present invention, there is provided a bio device and an optoelectronic device using the composite particles.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

1 is a SEM photograph showing an example of a porous mask manufactured by colloidal self-assembly according to the present invention.

In the porous mask according to the present invention, after preparing a film-shaped mask substrate in which spherical particles are laminated inside the matrix by colloidal self-assembly from a solution containing monodisperse particles constituting the matrix and monodisperse particles forming a sphere, It manufactures by etching a spherical particle of this base material and forming a hole.

Colloidal self-assembly may use techniques known in the art, such as dip coating, spin coating, Langmuir-Blozet, chemical vapor deposition, sputtering, electroplating and the like.

Although not particularly limited, according to the present invention, a method of self-assembling the monodisperse particles may be used to prepare a mask substrate according to the present invention by using Langmuir-Bjett, dip coating or spin coating from a solution in which monodisperse particles are dispersed. have.

The self-assembly process is described in detail in several literatures (Fengqiang Sun ey al., Adv Mater., 2004, 16, 1116 .; Chen. X. Chen, Z. Fu, N. Lu, G Yang, B. Adv. Mater., 2003, 15, 1413., Peng Jiang, Michael J. McFarland, J. Am. Chem. Soc., 2004, 126, 13778, Feng Yang, Werner A. Goedel, Adv. Mater., 2004, 16, 911, Xu Dong Wang et al., Nano Lett., 2004, 4, 2003., Aaron E. Saunders et al., Nano Lett., 2004, 4.1943.)

The colloidal particles used to form the porous mask do not require any particular limitation on the size or shape of the particles as long as the particles can be laminated on the base material. Preferred sizes are advantageously monodisperse particles ranging from several micrometers to tens of nanometers.

 The degree or number of layers of spherical particles deposited inside the matrix by colloidal site assembly can be varied by changing the conditions of the method applied. For example, when the dip coating is used, the degree of lamination may be controlled by the concentration of the solution containing the particles, the rate of lifting the base material from the solution, and the evaporation rate of the solvent.

Although not particularly limited, etching of spherical particles to prepare a mask having a hole formed from a mask substrate includes high temperature firing, reactive ion etching using plasma, etching using laser and light, and chemical etching solution. Can be used. As the etching source, for example, heat; Strong acid solutions such as hydrofluoric acid, organic and inorganic etching solutions such as toluene, acetone, and photoresist (PR) remover; Etching gases such as plasma, high energy electron beam, ultraviolet irradiation, and ozone can be used.

In addition, although not particularly limited in the present invention, as a material for forming the skeleton (metrics) of the porous mask by forming an inverted photonic crystal structure, a polymer, an inorganic ceramic, or a metal material may be used, but is not particularly limited. In order to remain in the process, the material may be resistant to chemical and physical etching in comparison with the sacrificial material (spherical particles) forming holes.

For example, the material forming the matrix may be a polymer or organic molecule such as polystyrene, polymethyl methacrylate, polyurethane, epoxy, or the like; Ceramic particles such as silica, titania and the like; Metal particles such as gold, silver, platinum, copper, nickel, and the like; Compound semiconductor particles, such as cadmium-sulfur, gallium-nitrogen, and the like, may be used, and the above-mentioned ones may also be used as monodisperse particles forming a sphere. When selecting the particles which form a matrix and the particle | grains which form a sphere among these particles, the particle | grains which are well etched shall be used as the particle | grains which form a sphere, and the particle | grains which form a matrix which are resistant to an etching are used for the etching method applied.

According to the present invention, when the spherical forming particles of the mask substrate are etched, holes are formed, and the size and number of the holes can be variously adjusted according to the etching method, the degree of etching, the type of particles, and the like. Preferably it is etched to one spherical particle, ie to form three or four holes per unit matrix.

Figure 2 illustrates that the mask is used as a mask of the nano-etching and patterning process through a porous mask manufactured using colloidal self-assembly. The size of the hole to be formed can be easily adjusted according to the size of the nanoparticles used and the degree of etching, and the size can be varied from about several nanometers to several hundred nanometers. The porous mask of the present invention has a regular hole, and through this hole through the etching source, for example, light, plasma, electron beam, laser, chemical etching solution, etc. can produce a pattern corresponding to the hole size. Will be.

For example, when the porous mask of the present invention is placed on a substrate to be patterned and an etching source is applied through a hole (window) of the mask, a hole having a shape corresponding to the hole of the mask is formed in the substrate. For example, when a self-assembled layer of monodisperse particles is used as a substrate, monodisperse particles having uniformly formed pores can be obtained.

In this case, an etching solution, an etching gas, an etching plasma, an ultraviolet ray, an electron beam, or the like may be used.

  As described above, the monodisperse particles having pores may be used to prepare nanocomposites, and the nanocomposites to be prepared may be used in bio devices or optoelectronic devices. 3 illustrates the preparation of a nanocomposite by inserting a third material such as a biomaterial, an electronic material, an optical material, and other organic or inorganic materials into a hole-shaped particle. Specific examples of such materials include biomaterials such as DNA, proteins, and the like; Ceramic materials such as silica, titania and the like; Compound semiconductors such as cadmium-sulfur, gallium-nitrogen and the like; Metal materials such as gold, silver, platinum, copper, and the like, and various other materials such as organic materials and polymers, are not particularly limited as long as they can be made into composite particles in a hole.

In order to make the nanocomposite, the third material is filled into the pores by the sputtering method, which is a vapor phase method, the electron beam deposition method (E-beam), the chemical vapor deposition method (CVD and ALD), and the chemical solvent, which is a liquid method. Gel adsorption and physical adsorption and chemical reactions through covalent bonding and surface treatment can be used.

The composite particles prepared in this way can be applied to various application fields, and depending on the materials put therein, biosensors such as biosensors, biochips, and drug delivery, optoelectronic devices such as photonic crystal displays, experimental and industrial applications such as reagent separation and detection, etc. It can be applied in various ways.

For example, as illustrated in FIG. 4, a composite prepared by inserting a material having a bio-friendly or surface-specific property that binds to or adsorbs a body part or a specific part of a material surface inside a pore of the porous particle manufactured by the present invention. The particles can be attached to the desired area and then a reagent can be spread from the site for treatment or chemical experiments. Depending on what kind of material is in the middle core, it can be applied to various fields. In addition to the liquid, the inorganic part in the solid state such as metal, ceramic, etc. may be used depending on the application.

Hereinafter, the present invention will be described by way of examples. However, these examples are only presented to make the contents of the present invention easy to understand, and the scope of the present invention should not be construed as being limited to these examples.

EXAMPLE

Preparation of Porous Mask

In order to manufacture a porous mask, 1.01 μm polystyrene polymer particles and a matrix forming material and silica particles of 50 nm were selected as a material for forming a sphere, put together in a solution, and laminated through dip coating. In this case, the number of layers in which the particles are stacked may be adjusted according to the concentration of the solution containing the particles, the speed of lifting the base material from the solution, and the evaporation rate of the solvent.

The mask base material thus prepared is formed by the self-assembly of particles to form a normal order, and the material forming the matrix is made of silica, and the inner large sphere is made of polystyrene polymer particles (see SEM photograph in FIG. 5A). .

In order to form a film-type mask having a porous structure, polystyrene particles having a spherical shape are etched by anisotropic reactive ion etching, which is a kind of dry etching. 5B is a SEM photograph taken when only about 10% of the polystyrene particles are removed, and FIG. 5C is a SEM photograph taken when 50% or more of the polystyrene particles are removed. Figure 5d is a SEM image of the mask finally formed a porous hole.

According to the degree of lamination in the manufacture of the mask base material, that is, the film base material of the single layer (FIG. 6A), the double layer (FIG. 6B), and the triple layer (FIG. 6C) can be made. Figure 6a is a SEM photograph taken to produce a mask by etching in a single layer, Figure 6b is a SEM photograph taken to manufacture a mask by etching in a double layer, Figure 6c is a mask by etching in a triple layer SEM picture taken to manufacture the. In this way, not only a single layer mask but also a multilayer mask composed of multiple layers can be utilized, and since the mask hole has a three-dimensional structure instead of a two-dimensional planar structure, curved patterning is possible.

In this example, a mask is manufactured by using a deep coating method and a dry etching method. For example, the spin coating method can form a structure as in the present example, and the etching method also uses a matrix material and a sacrificial layer to form a film. It can vary depending on the large spherical particles used. For example, if the large spherical particles of the sacrificial layer are polymers and the matrix material is ceramics or metals, the porous structure can be formed by removing the polymers using high temperature firing, whereas the matrix material is a polymer and the spherical particles of the inner sacrificial layer In the case of ceramics such as metals or silica, an acid solution such as hydrofluoric acid (HF) may be used to remove the internal metal or silica.

Preparation of Porous Particles

The prepared porous mask is placed on a substrate to be patterned, and the substrate may be patterned by injecting an etching solution, an etching gas, or a high energy electron beam and light through the pores of the mask.

When the mask prepared in the above example is placed on the substrate to be patterned (in this example, spherical monodisperse polystyrene self-assembled layer) and oxygen plasma is flowed into the hole of the mask, the spherical layer of polystyrene particles in the lower layer is etched and inserted into the mask hole. Polystyrene particles having holes of the corresponding size can be obtained.

As shown in Figure 7a and 7b the size and shape of the hole of the polymer particles having a hole can be adjusted according to the shape and size of the porous mask used. For example, in the case of using a mask in which three holes are alternately arranged, as shown in FIG. 7A, the polymer particles under the mask also have three holes, and the size depends on the size of the mask hole. In addition, in the case of using a mask in which four holes are alternately arranged, as shown in FIG. 7B, the polymer particles under the mask also have four holes. Since the pore size of the patterned or etched polymer particles depends on the pore size of the mask, the pore size can be easily adjusted depending on the size of the particles used in the manufacture of the mask.

Preparation of the complex

8 is a polystyrene-platinum composite particle prepared by wrapping the outer structure with silica matrix and preparing a polystyrene particle having a uniform hole by a lithography process according to the present invention, and then inserting platinum (Pt) therein by a sputtering method therein. SEM picture taken.

According to the present invention as described above, it is possible to easily produce a porous mask having a hole of less than 10nm difficult to manufacture in a general etching process, it is possible to use not only a single layer mask but also a multilayer mask composed of a multi-layered mask, Since it has a three-dimensional structure instead of a two-dimensional planar structure, curved surfaces can be patterned, particles having uniform holes can be manufactured, and various bio- and opto-electronic devices can be manufactured using such particles.

Claims (14)

Manufacturing a film-shaped mask base material in which spherical particles are laminated inside the matrix by colloidal self-assembly from a solution containing particles constituting the matrix and particles forming a sphere; Method for producing a porous mask comprising the step of forming a hole by etching the spherical particles of the prepared mask substrate. The method of claim 1, wherein the particles forming the matrix are organic molecules such as polystyrene, polymethylmethacrylate, polyurethane, epoxy; Ceramic particles such as silica and titania; Metal particles such as gold, silver, platinum, copper and nickel; , Cadmium-sulfur, gallium-nitrogen, such as a compound semiconductor particles, characterized in that selected from the group consisting of. The method of claim 1, wherein the particles forming the sphere is an organic molecule such as polystyrene, polymethyl methacrylate, polyurethane, epoxy; Ceramic particles such as silica and titania; Metal particles such as gold, silver, platinum, copper and nickel; , Cadmium-sulfur, gallium-nitrogen, such as a compound semiconductor particles, characterized in that selected from the group consisting of. The method of claim 1, wherein the colloid self-assembly is selected from the group consisting of dip coating, spin coating, Langmuir-Blozet, chemical vapor deposition, sputtering and electroplating. The method of claim 1, further comprising: hot baking the etching; Solution etching using a strong acid solution such as hydrofluoric acid, an organic or inorganic etching solution such as toluene, acetone, a photoresist (PR) remover; Etching gas such as plasma, high energy electron beam, ultraviolet irradiation, ozone is used. The method according to claim 1, wherein the etching is carried out to the extent that three or four holes are formed in one spherical particle of the mask substrate. A porous mask prepared by the method of any one of claims 1 to 6. The patterning method using the porous mask of Claim 7. The method of claim 8, wherein the surface of the substrate is etched with an etching source selected from the group consisting of etching solution, etching gas, etching plasma, ultraviolet rays and electron beams by placing the porous mask on the substrate to be patterned. Patterning method characterized by. 10. The method of claim 9, wherein said substrate is a self-assembled layer of monodisperse particles. Porous particles prepared by the patterning method of any one of claims 7 to 9. 11. A composite particle in which nanomaterials are imparted to porous particles of the substrate. The bio device using the composite particle of claim 12. An optoelectronic device using a composite particle of claim 12.

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