KR101655154B1 - Method for manufacturing of substrate and substrate - Google Patents

Abstract

The present invention provides a method of manufacturing a semiconductor device, comprising: preparing a substrate; And coating and oxidizing two or more different block copolymers in sequence on the substrate, wherein the refractive index of the coated and oxidized block copolymer is greater than the coating and oxidation of the coating and the oxidized later, Wherein the copolymer comprises two or more blocks different from each other, wherein one of the blocks comprises silicon and the substrate.

Description

[0001] METHOD FOR MANUFACTURING SUBSTRATE AND SUBSTRATE [0002]

The present invention relates to a method for producing a high anti-reflection coating substrate using a block copolymer containing silicon and a high anti-reflection coating substrate.

Glass substrates are generally known to be transparent in the region of visible light above 400 nm. However, Fresnel reflections reflect about 8% of total light on the front and back sides of the substrate, about 4% each. This causes a decrease in efficiency in various optical elements such as an optical lens using a glass substrate, a solar cell, a display, and an opto-electric device, and researches on antireflection coating films for solving the problems have been actively conducted.

In order to impart the antireflection property to the glass substrate, a method of coating a film such that incident light and reflected light are canceled each other is common. For a typical single-layer antireflective coating film, the following conditions must be met. (1) The thickness of the antireflection coating film is 1/4 of the incident light wavelength; (2) The refractive index of the coating film is determined by n _c = (n _air × n _s ) ^1/2 (where n _c , n _air and n _s are the refractive indices of the coating film, air and substrate, respectively) , The refractive index of the ideal coating film becomes 1.20.

However, in the case of a homogeneous single-layer antireflection coating film, the reflectance is close to 0% only at a specific wavelength band depending on the thickness of the coating film, and the antireflection characteristic is greatly reduced according to the angle of the incident beam.

This can be overcome through a coating film whose refractive index gradually decreases from the glass substrate to the air. At this time, the top coating film requires a material whose refractive index is close to 1, which is close to air, but the dielectric materials used in the optical element do not have a refractive index of 1.35 or less, making it difficult to produce a coating film whose refractive index gradually changes.

The recent research trend is that a porous film composed of a composite material of a coating material and air can realize a low refractive index that a conventional material can not have, and by using the coating film, a refractive index gradually changes to form a coating film so that the reflectance becomes 0% in a wide range of visible light I am trying to get a curtain.

In order to provide a porous coating film, a vacuum deposition method such as PVD, CVD or oblique-angle deposition having strong bonding force with a glass substrate is used, but it has drawbacks such as high cost and long process time. In order to solve this problem, the solution is etched using a micelle coating, a sol-gel, a polyelectrolyte multilayer structure, a polymer blend, etc., and a post-treatment such as UV, heat, .

Among them, the polymer mixing method can easily and quickly produce a porous film having a low refractive index by removing one polymer easily through solution etching after coating.

However, the porous film made of organic polymer is not only poor in thermal, mechanical, and chemical durability but also has difficulty in fine adjustment of refractive index.

Therefore, it is required to develop an antireflection coating film in which the refractive index is gradually changed by forming a high density porous film having mechanical and chemical durability while easily controlling the refractive index through a solution process.

One embodiment of the present invention provides a method of making a high anti-reflection coating substrate comprising a high density, low refractive silica thin film layer.

Another embodiment of the present invention provides a high anti-reflection coating substrate produced by the above-described method.

One embodiment includes the steps of preparing a substrate; And coating and oxidizing two or more different block copolymers in sequence on the substrate, wherein the refractive index of the coated and oxidized block copolymer is greater than the coating and oxidation of the coating and the oxidized later, Wherein the copolymer comprises two or more different blocks, and one of the blocks comprises silicon.

The step of sequentially coating and oxidizing two or more different block copolymers on the substrate may include coating and oxidizing the first block copolymer on the substrate; And coating and oxidizing the second block copolymer on the coated and oxidized first block copolymer, wherein a refractive index of the first block copolymer is larger than a refractive index of the second block copolymer, The copolymer and the second block copolymer each independently include two or more different blocks, and any one of the blocks may include silicon.

The coating of the block copolymer may be a solvent in which two or more organic solvents are mixed.

The coating may be of a method including dip-coating, spin-coating, spray-coating, or a combination thereof.

The oxidation of the block copolymer may be performed by a two-step reactive ion etching process including CH ₄ etching and O ₂ etching.

The two-step reactive ion etching process may be to perform, O ₂ CH ₄ etching after performing the first etching.

The CH ₄ etching can be performed at 10W to 200W for 10 seconds to 200 seconds.

The O ₂ etching may be performed at 10 W to 200 W for 100 seconds to 200 seconds.

The oxidized block copolymer has a porous structure including pores, and the size of the pores may be smaller than a wavelength of visible light.

The size of the pores may be between 10 nm and 200 nm.

The block copolymer may be selected from the group consisting of polystyrene-b-polydimethylsiloxane, polyacrylonitrile-b-polydimethylsiloxane, poly (4-vinylpyridine) B-polydimethylsiloxane, polyethyleneoxide-b-polydimethylsiloxane, poly (2-vinylpyridine) -b-polydimethylsiloxane (poly (2- vinylpyridine-b-polydimethylsiloxane, polymethylmethacrylate-b-polydimethylsiloxane, polybutadiene-b-polydimethylsiloxane, polyisobutylene- Polyisobutylene-b-polydimethylsiloxane, polydimethylsiloxane-b-polybutylacrylate, polydimethylsiloxane-b-polyacrylic acid d), or a combination thereof.

The block containing silicon with respect to 100% by volume of the block copolymer may be contained in an amount of 9% by volume to 90% by volume.

The oxidized block copolymer may have a refractive index of 1.05 to 1.46 in a wavelength region of 550 nm to 700 nm.

The oxidized block copolymer may have a porosity of 30% to 90%.

The block copolymer may have a molecular weight of 40 kg / mol to 60 kg / mol.

The step of sequentially coating and oxidizing two or more different block copolymers on the substrate may be a step of successively coating and oxidizing two or more different block copolymers on one or both sides of the substrate.

The substrate may be a glass substrate.

Another embodiment includes a substrate; And at least two porous silica thin film layers formed on the substrate, wherein the porous silica thin film layers have different refractive indices, and a porous silica thin film layer closer to the substrate among the porous silica thin film layers has a higher refractive index.

The two or more porous silica thin film layers may have a thickness of 10 nm to 200 nm.

The porous silica thin film layer has pores, and the pore size may be smaller than the visible light wavelength.

The size of the pores may be between 10 nm and 200 nm.

The porous silica thin film layer may have a refractive index of 1.05 to 1.46 in a wavelength region of 550 nm to 700 nm.

The porous silica thin film layer may have a porosity of 30% to 90%.

The substrate may have at least two porous silica thin film layers formed on one side or both sides of the substrate.

The substrate may be a glass substrate.

Another embodiment provides a substrate produced by the method of manufacturing the substrate.

Other details of the embodiments of the present invention are included in the following detailed description.

The present invention can provide a substrate coated with a high density low refractive silica thin film which can easily adjust the refractive index by controlling the volume fraction ratio of two blocks by using a block copolymer containing silicon. The silica thin film is composed of two or more layers and functions as an antireflection coating film to minimize the reflection of the substrate in the entire visible light region and to increase the transmittance. In addition, since it is composed of a porous silicon thin film formed by an oxidation process, it has strong bonding with a substrate and is excellent in mechanical and chemical durability, and can be applied to optical devices and optical-electronic devices.

1 is a schematic view showing a method of manufacturing a substrate including two layers of porous silica films according to an embodiment of the present invention.
FIG. 2 is a SEM photograph showing the change of the pore size according to the volume fraction of PDMS using four block copolymers having different molecular weights.
FIG. 3 is a chart comparing the Psi and Delta values of the porous silica membrane through an effective approximation model.
4 is a graph comparing the refractive index and the porosity ratio of the porous silica thin film.
FIG. 5 is a graph comparing permeabilities when a uniform coating film is formed using a solvent in which PGMEA having a high viscosity is coated when a block copolymer is coated.
6 is a top (left) and cross (right) SEM photograph of the porous silica thin film of the substrate according to Example 1. Fig.
7 is a graph comparing transmittances of the substrates according to Example 1, Example 2, Comparative Example 1, and Comparative Example 2. Fig.
8 is a graph comparing changes in transmittance of the substrate according to Example 1 and Comparative Example 1 according to an incident beam.
9 is a graph comparing the transmittance at 420 nm after the mechanical, chemical, and thermal durability tests of the porous silica thin film used in the substrate according to Example 1. Fig.
10 is a photograph of a substrate according to Example 1 and Comparative Example 1. Fig.

Hereinafter, the production of the antireflection coating film according to the present invention will be described in detail with reference to the accompanying drawings. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the embodiments described below, but may be embodied in other forms. In the drawings, the width, length, thickness, etc. of components may be exaggerated for convenience. Like reference numerals and like-like patterns throughout the specification denote like elements.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. Where a section of a layer, film, area, plate, or the like is referred to as being "on" another part, it includes not only the case where it is "directly on" another part but also the case where there is another part in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

One embodiment includes the steps of preparing a substrate; And coating and oxidizing two or more different block copolymers in sequence on the substrate, wherein the refractive index of the coated and oxidized block copolymer is greater than the coating and oxidation of the coating and the oxidized later, Wherein the copolymer comprises two or more different blocks, and one of the blocks comprises silicon.

Since any one of the blocks in the block copolymer necessarily contains silicon, it is possible to form a high-density low-refractive porous silica film and to coat it with two or more layers to have broadband antireflection characteristics over the entire visible light range It is possible to manufacture a substrate having an average transmittance of 99% over the entire range of the visible light region.

Such substrates provide advantages for optics and opto-electronic devices, such as optical lenses, solar cells, displays, etc., that require antireflective properties because they are used outdoors.

The step of sequentially coating and oxidizing two or more different block copolymers on the substrate includes coating and oxidizing the first block copolymer on the substrate; And coating and oxidizing the second block copolymer on the coated and oxidized first block copolymer.

Wherein the refractive index of the first block copolymer is larger than the refractive index of the second block copolymer and the first block copolymer and the second block copolymer each independently comprise two or more blocks different from each other, May comprise silicon.

1 is a schematic view showing a method of manufacturing a substrate including two layers of porous silica films according to an embodiment of the present invention. From this, it can be seen that a porous silica thin film having a relatively high refractive index is formed directly on a substrate through a coating and oxidation process, and then a porous silica thin film having a low refractive index is continuously formed thereon through a coating and oxidation process, It can be understood that a glass substrate having broad-band antireflection characteristics in the entire range of the visible light region can be manufactured. 1, the volume fraction of _PDMS (f _PDMS ) after oxidation of the block copolymer, which is the source of the porous silica thin film having a large refractive index, is about 49%, that is, about 49%, and the oxidation of the block copolymer as a source of the porous silica thin film having a small refractive index It can be seen that the volume ratio of _PDMS (f _PDMS ) after the process is 0.09, i.e. about 9%.

The coating of the block copolymer may be a solvent in which two or more organic solvents are mixed. When a solvent in which two or more organic solvents are mixed is used, the transmittance of the substrate can be improved compared with the case where only a single organic solvent is used. When two kinds of organic solvents are used, they can be mixed at a volume ratio of 1: 1, respectively.

5 is a graph comparing permeabilities when a uniform coating film is formed using a solvent in which PGMEA having a high viscosity is coated when a block copolymer is coated. From this, it can be seen that when the block copolymer is coated with PGMEA having high viscosity at a ratio of 1: 1 with toluene, PS-PDMS is uniformly coated as compared with toluene alone . That is, it can be seen that the uniformity of the initial block copolymer coating is greatly related to the improvement of the transparency of the substrate after the oxidation process, and the uniformity of the coating depends on the organic solvent used in the coating.

The coating may be of a method including dip-coating, spin-coating, spray-coating, or a combination thereof.

The oxidation of the block copolymer may be performed by a two-step reactive ion etching process including CH ₄ etching and O ₂ etching.

The two-step reactive ion etching process may be to perform, O ₂ CH ₄ etching after performing the first etching.

The CH ₄ etch may be performed at 10 W to 200 W for 10 seconds to 200 seconds, and the O ₂ etch may be performed at 10 W to 200 W for 100 seconds to 200 seconds.

Specifically, the block copolymer is coated on a substrate to be coated through a wet coating technique such as dip coating, spin-coating, or spray-coating, and then CH ₄ And 2-step reactive ion etching process using O ₂ gas. (For example, 10 W to 200 W, 10 seconds to 100 seconds) in the case of CH ₄ etching, 10 W to 200 W, 100 seconds to 200 W in the case of O ₂ etching, 200 sec. ≪ / RTI > CH ₄ if the etching time is more than 200 seconds, or O ₂ etching time exceeds 200 seconds, the transmittance to the aggregation of the SiO ₂ particles is lowered, CH ₄ etching time is less than 10 seconds, or O ₂ etching time is 100 seconds , The organic matter removal is not completely performed and the conversion to SiO ₂ is lowered. In addition, when the CH ₄ etching time is out of the above range, it may become difficult to control the thickness of the formed porous silica thin film to 10 nm to 200 nm.

Through the oxidation process, a block containing no silicon among the blocks in the block copolymer containing two or more different blocks is easily removed to form pores, and the block containing silicon is converted into silica. That is, the porous silica thin film composed of two or more layers is formed on the substrate through the coating and oxidation process.

The oxidized block copolymer has a porous structure including pores, and the size of the pores may be smaller than a wavelength of visible light. For example, the size of the pores may be between 10 nm and 200 nm, for example between 10 nm and 100 nm.

As described above, in the block copolymer, the block containing no silicon is easily removed through the oxidation process to form pores, and the block containing silicon is converted into silica. For example, the block copolymer may be selected from the group consisting of polystyrene-b-polydimethylsiloxane, polyacrylonitrile-b-polydimethylsiloxane, poly (4-vinylpyridine) b-polydimethylsiloxane, poly (4-vinylpyridine) -b-polydimethylsiloxane, polyethyleneoxide-b-polydimethylsiloxane, poly (2- vinylpyridine) 2-vinylpyridine-b-polydimethylsiloxane, polymethylmethacrylate-b-polydimethylsiloxane, polybutadiene-b-polydimethylsiloxane, polyisobutylene- polyisobutylene-b-polydimethylsiloxane, polydimethylsiloxane-b-polybutylacrylate, polydimethylsiloxane-bp (polydimethylsiloxane-bp) olyacrylic acid, or a combination thereof. For example, the block copolymer may be a polystyrene-b-polydimethylsioxane (PS-PDMS) block copolymer.

The block containing silicon with respect to 100% by volume of the block copolymer may be contained in an amount of 9% by volume to 90% by volume, for example, 9% by volume to 50% by volume. When the block containing silicon in the block copolymer is included in the above range, a porous silica thin film having excellent antireflection characteristics can be obtained.

The oxidized block copolymer may have a refractive index of 1.05 to 1.46 in a wavelength region of 550 nm to 700 nm, for example, a refractive index of 1.10 to 1.40 in a wavelength region of 600 nm to 650 nm.

The oxidized block copolymer may have a porosity of 30% to 90%, for example, 35% to 85%.

The block copolymer may have a molecular weight of 40 kg / mol to 60 kg / mol, such as 43 kg / mol to 55 kg / mol. The block copolymer should have a molecular weight within the above range to have an appropriate pore size and porosity, and thus to have excellent antireflection properties.

FIG. 2 is a SEM photograph showing the change of the pore size according to the volume fraction of PDMS using four block copolymers having different molecular weights. From this, it can be seen that as the volume ratio of PDMS decreases, the size of the pores in the porous silica thin film increases as the oxidation process proceeds after coating the four types of PS-PDMS having different PDMS volume ratios. At this time, the generated pore size is smaller than the visible ray region, and the scattering phenomenon can be almost neglected. The pore volume ratio formed after the oxidation process is determined by the relative volume fraction of PS-PDMS. That is, the smaller the volume fraction of PDMS containing silicon in the PS-PDMS, the higher the volume fraction of PS, which is an organic block removed in the oxidation process, and finally the larger the pore volume ratio after the oxidation process. As the PDMS molecular weight of the block copolymers used were fixed and the PS molecular weight was increased only, the volume fraction of PDMS decreased with increasing total molecular weight, and finally the volume ratio of pores after the oxidation process increased. FIG. 4 also shows the tendency that the volume ratio of the pores increases as the volume ratio of PDMS decreases after the oxidation process of the block copolymer.

The block copolymer coated and oxidized on the substrate becomes a porous silica thin film, and the thickness of the porous silica thin film is determined by the molecular weight of the block copolymer. The thickness of the porous silica thin film may be 10 nm to 200 nm, for example, 120 nm to 160 nm. When the thickness of the porous silica thin film is less than 10 nm, the effect of reducing the reflectance due to the optical interference is remarkably deteriorated. When the thickness is more than 200 nm, the reflectance reduction effect is also decreased for the same reason. The thickness of the porous silica thin film is adjusted by adjusting the CH ₄ etching process time to 10 seconds to 200 seconds.

The step of sequentially coating and oxidizing two or more different block copolymers on the substrate may be a step of sequentially coating and oxidizing two or more different block copolymers on one or both sides of the substrate.

7 is a graph comparing transmittances of the substrates according to Example 1, Example 2, Comparative Example 1, and Comparative Example 2. Fig. From this, a porous silica thin film consisting of two layers of coated and oxidized layers of a block copolymer having a molecular weight of 43 kg / mol and a coated copolymer layer having a molecular weight of 55 kg / mol was coated on one side It can be seen that the transmittance is 96% on average in the visible light region. In addition, when the above-mentioned porous silica thin film is coated on both sides of the glass substrate, the radiation prevention characteristic is excellent at the entire range of the visible light region, and the transmittance is 99.9% at the maximum at the wavelength of 420 nm and 99.1% Able to know. This is a great advantage in increasing the efficiency of the optical element with a transmittance that is improved by about 7% or more as compared with the 92% transmittance of a general glass substrate.

The substrate may be a glass substrate.

Another embodiment includes a substrate; And at least two porous silica thin film layers formed on the substrate, wherein the porous silica thin film layers have different refractive indices, and a porous silica thin film layer closer to the substrate among the porous silica thin film layers has a higher refractive index.

The two or more porous silica thin film layers may have a thickness of 10 nm to 200 nm, for example, 120 nm to 160 nm.

The porous silica thin film layer has pores, and the pore size may be smaller than the visible light wavelength. For example, the size of the pores may be between 10 nm and 200 nm, for example between 10 nm and 100 nm.

The porous silica thin film layer may have a refractive index of 1.05 to 1.46 in a wavelength region of 550 nm to 700 nm, for example, a refractive index of 1.10 to 1.40 in a wavelength region of 600 nm to 650 nm.

The porous silica thin film layer may have a porosity of 30% to 90%, for example, 35% to 85%.

The substrate may have at least two porous silica thin film layers formed on one side or both sides of the substrate.

The substrate may be a glass substrate.

The effects of the above-described configuration and other configurations and the like are all as described above.

Another embodiment provides a substrate produced by the above substrate manufacturing method. The substrate can function as a high anti-reflection coating substrate.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

(Example)

Example  One

Polystyrene-b-polydimethylsiloxane (PS-PDMS) block copolymer having a molecular weight of 43 kg / mol and a volume fraction of PDMS of 48.8% was coated on one side of the glass substrate and then oxidized. Thereafter, a polystyrene-b-polydimethylsiloxane (PS-PDMS) block copolymer having a molecular weight of 55 kg / mol and a PDMS volume fraction of 9.1% was coated on the block copolymer And oxidized to prepare a glass substrate on which two porous silica thin films were coated on one side. During the coating, a mixture of PGMEA and toluene mixed at a volume ratio of 1: 1 was used as a solvent. The thickness of the coating layer was 142 nm.

Example  2

A glass substrate coated with two layers of porous silica thin films on both sides was prepared in the same manner as in Example 1 except that the block copolymer was coated on both sides of the glass substrate instead of one side thereof.

Comparative Example  One

A glass substrate on which nothing was coated was regarded as Comparative Example 1.

Comparative Example  2

Except that polystyrene-b-polydimethylsioxane (PS-PDMS) block copolymer having a molecular weight of 55 kg / mol and a volume fraction of PDMS of 9.1% was not used. , A glass substrate having a single-layer porous silica thin film coated on one side thereof was prepared.

Comparative Example  3

The molecular weight was 45.5 kg / mol instead of the polystyrene-b-polydimethylsioxane (PS-PDMS) block copolymer having a molecular weight of 43 kg / mol and a volume fraction of PDMS of 48.8% A polystyrene-b-polydimethylsioxane (PS-PDMS) block copolymer having a fraction of 32.2% was used,

A glass substrate coated with a single layer of a porous silica thin film on one side was prepared in the same manner as in Comparative Example 2 except that toluene alone was used as a solvent instead of a mixed solution of PGMEA and toluene in a volume ratio of 1: .

Comparative Example  4

A glass substrate coated with a single layer of a porous silica thin film on one side was prepared in the same manner as in Comparative Example 3 except that a mixture of PGMEA and toluene in a volume ratio of 1: 1, instead of toluene, .

Evaluation 1: Properties of block copolymer

Polystyrene-b-polydimethylsioxane (PS-PDMS) block copolymer having a molecular weight of 43 kg / mol and a volume fraction of PDMS of 48.8%, a molecular weight of 45.5 kg / mol, Polystyrene-b-polydimethylsioxane (PS-PDMS) block copolymer having a molecular weight of 51.5 kg / mol and a volume fraction of PDMS of 16.5%, a polystyrene-b-polydimethylsiloxane Polystyrene-b-polydimethylsioxane (PS-PDMS) block copolymer having a molecular weight of 55 kg / mol and a volume fraction of PDMS of 9.1% PDMS) block copolymers were named BCP 1, BCP 2, BCP 3 and BCP 4, respectively, and these were oxidized to obtain a porous silica thin film. Psi and Delta values of the four porous silica thin films were measured using an ellipsometer, and a porous silica film was designated as a layer composed of a Caucy model and a void applied to a transparent material, and applied to an effective approximation model The results shown in Fig. 3 and Table 1 were obtained. SEM photographs of BCP 1, BCP 2, BCP 3 and BCP 4 are shown in FIG.

Block copolymer Molecular Weight
(kg / mol) f _PDMS
(%) Porosity
(%) Refractive index after oxidation
(? = 632.8 nm) BCP 1 43 48.8 39.9 1.346 BCP 2 45.5 32.2 63.1 1.221 BCP 3 51.5 16.5 74.1 1.131 BCP 4 55 9.1 82.8 1.111

As can be seen from Table 1, the four block copolymers having different molecular weights show that the volume ratio of pores increases as the volume ratio of _PDMS (f _PDMS ) decreases after the oxidation process. This corresponds to the result shown in FIG. 2, and the tendency can be confirmed by a graph showing the relation between the pore and the refractive index in FIG. It can be confirmed that the refractive index of the formed porous silica thin film can be adjusted from 1.111 to 1.346.

Evaluation 2: Evaluation of permeability according to solvent in coating

The transmittance of the glass substrate according to Comparative Example 1, Comparative Example 3, and Comparative Example 4 was measured, and the results are shown in FIG. It can be seen that Comparative Examples 3 and 4 using a solvent show better transmittance than Comparative Example 1 not using a solvent. In addition, it can be seen that Comparative Example 4 using a mixed solvent shows better transmittance than Comparative Example 3 using a single solvent.

Evaluation 3: Porous silica Thin-film layer  Evaluation of permeability according to the number and the number of coated surfaces

The transmittance of the glass substrates according to Example 1, Example 2, Comparative Example 1, and Comparative Example 2 was measured, and the results are shown in FIG. It can be seen that a glass substrate coated with a porous silica thin film has better transmittance than a glass substrate coated with nothing. In addition, it can be seen that the glass substrate coated with the porous silica thin film layer of two layers rather than the single porous silica thin film layer has excellent transmittance. It is also understood that coating the porous silica thin film layer on both sides of one side of the glass substrate can have a better transmittance.

Rating 4: Of the incident beam  Evaluation of transmittance according to angle change

The transmittance of the glass substrate according to Example 1 and Comparative Example 1 was measured according to changes in angles (0 °, 30 °, 45 °, and 60 °) of the incident beam, and the results are shown in FIG. It can be confirmed that the glass substrate according to Example 1 is excellent in antireflection characteristics even when the angle of the incident beam increases from 0 ° to 60 ° gradually and the rate of decrease in transmittance is smaller than that of the glass substrate according to Comparative Example 1.

Evaluation 5: Durability evaluation

The permeability change after the durability test of the porous silica thin film used in the glass substrate according to Example 1 was measured, and the result is shown in Fig. It can be confirmed that the transmittance at 420 nm is more than 98% even when the glass substrate according to Example 1 is immersed in an organic solvent such as Acetone, Toluene, Hepate, DMF, IPA, and Pyridine. It is also found that the chemical durability is excellent since the permeability is 98% or more even after treatment with KOH strong base or HCl strong acid treatment. It can be seen that the bond strength between the thin film coated with 98% of the transmittance and the substrate is excellent even after the sonic treatment, and the transmittance is 99% even after the heat treatment at 500 ° C for 1 hour, showing excellent thermal durability.

(Ref in Fig. 9 means a glass substrate different from Example 1).

Evaluation 6: Color under the substrate Reconstruction  evaluation

1 is a photograph of a glass substrate according to Example 1 and Comparative Example 1. Fig. The actual reflection phenomenon was observed under the sun or a fluorescent lamp. In the glass substrate of Example 1, the reflection was hardly occurred in the entire range of the visible light region, so that the color under the glass substrate was transparent. In this case, a ghost image appears in which all the light in the visible region is reflected, and the color under the glass substrate can not be reconstructed.

From the above Evaluation 1 to 6, it can be seen that the substrate produced by the substrate manufacturing method of the present invention has an excellent antireflection characteristic in the entire range of the visible light region, and has an average transmittance of 99% or more on average and excellent durability. It can be seen that there is an advantage in that the performance can be improved.

While the preferred embodiments of the present invention have been shown and described, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (26)

Preparing a substrate; And
Coating and oxidizing two or more different block copolymers in sequence on the substrate
Lt; / RTI >
The refractive index of the coated and oxidized block copolymer is greater than that of the coated and oxidized first, coated and oxidized later,
Wherein the block copolymer comprises two or more different blocks, wherein one of the blocks comprises silicon,
Wherein a solvent in which at least two organic solvents are mixed is used in coating the block copolymer, the solvent includes propylene glycol methyl ether acetate (PGMEA)
The oxidation of the block copolymer
Performing a two-step reactive ion etching process comprising etching CH ₄ and O ₂ etching,
The two-step reactive ion etching process is carried out to, O _2, CH ₄ etching after performing the first etching,
The CH ₄ etching is carried out from 10W to 200W for 10 seconds to 200 seconds,
The O ₂ etching is performed at 10 W to 200 W for 100 seconds to 200 seconds
≪ / RTI >
The method of claim 1,
The step of sequentially coating and oxidizing two or more different block copolymers on the substrate
Coating and oxidizing the first block copolymer on the substrate; And
Coating and oxidizing the second block copolymer on the coated and oxidized first block copolymer,
The refractive index of the first block copolymer is larger than the refractive index of the second block copolymer,
Wherein the first block copolymer and the second block copolymer each independently include two or more different blocks, and one of the blocks includes silicon
≪ / RTI >
delete The method of claim 1,
Wherein the coating uses a method comprising dip-coating, spin-coating, spray-coating, or a combination thereof.
delete delete delete delete The method of claim 1,
The oxidized block copolymer has a porous structure containing pores,
Wherein the pore size is smaller than the visible light wavelength.
The method of claim 9,
Wherein the pore size is from 10 nm to 200 nm.
The method of claim 1,
The block copolymer may be selected from the group consisting of polystyrene-b-polydimethylsiloxane, polyacrylonitrile-b-polydimethylsiloxane, poly (4-vinylpyridine) B-polydimethylsiloxane, polyethyleneoxide-b-polydimethylsiloxane, poly (2-vinylpyridine) -b-polydimethylsiloxane (poly (2- vinylpyridine-b-polydimethylsiloxane, polymethylmethacrylate-b-polydimethylsiloxane, polybutadiene-b-polydimethylsiloxane, polyisobutylene- Polyisobutylene-b-polydimethylsiloxane, polydimethylsiloxane-b-polybutylacrylate, polydimethylsiloxane-b-polyacrylic acid, Or a combination thereof.
The method of claim 1,
Wherein the block containing silicon is contained in an amount of from 9 vol% to 90 vol% based on 100 vol% of the block copolymer.
The method of claim 1,
Wherein the oxidized block copolymer has a refractive index of 1.05 to 1.46 in a wavelength region of 550 nm to 700 nm.
The method of claim 1,
Wherein the oxidized block copolymer has a porosity of 30% to 90%.
The method of claim 1,
Wherein the block copolymer has a molecular weight of 40 kg / mol to 60 kg / mol.
The method of claim 1,
The step of sequentially coating and oxidizing two or more different block copolymers on the substrate
And coating and oxidizing two or more different block copolymers in sequence on one or both sides of the substrate.
The method of claim 1,
Wherein the substrate is a glass substrate.
delete delete delete delete delete delete delete delete A substrate produced by the method of any one of claims 1, 2, 4, and 9 to 17.

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