KR102085976B1 - Multi-functional transparent photomask with preventing electrostatic discharge damage and anti-fouling and Manufacturing method of the Same - Google Patents

Abstract

The present invention relates to a multi-functional transparent photomask which effectively disperses electrostatic charge generated by repeated disadhesion in a contact or proximity photolithography process by sequentially forming a transparent conductive layer, an adhesion enhancing layer, and an anti-fouling functional layer on the top of a photomask manufactured by a conventional method, prevents adsorption of a photoresist and floating foreign body, and can solve various problems which occur in the contact or proximity photolithography process at once by improving the service life of functional coating.

Description

Multi-functional transparent photomask with preventing electrostatic discharge damage and anti-fouling and Manufacturing method of the Same}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photomask and a method of manufacturing the same. In the photomask used in the contact photolithography process, a transparent conductive material is used to form a pattern in the photomask by electrostatic discharge generated during the contact photolithography process. The present invention relates to a transparent photomask manufacturing technology that effectively prevents damage and improves transmittance and cleaning power by applying an antifouling functional material to a surface.

In the photomask used in the contact photolithography process, static electricity generated by repeated desorption with the product accumulates in the metal pattern in the photomask, and when the surface item voltage is exceeded, the metal pattern melts or vaporizes and the pattern is damaged. Electro-static discharge (ESD) is one of the major process challenges. As a countermeasure, it is currently applying a method of changing the pattern design to shorten the replacement cycle of the photomask or to minimize the electrostatic discharge. However, such a method is causing problems such as a decrease in productivity or an increase in process cost, and thus, there is an increasing demand for a photomask which prevents pattern damage due to electrostatic discharge in a contact photolithography process.

The main cause of pattern damage by electrostatic discharge is when an air layer exists between the metal patterns on the photomask to form a single capacitor-like structure or a large amount of electrostatic charge is momentarily concentrated in a narrow pattern. Therefore, in order to prevent damage to the pattern caused by electrostatic discharge, charge accumulation and rapid discharge in the metal pattern should be prevented. For this purpose, it is most effective to form a charge transfer path between the metal patterns.

Conventionally, a technology of forming a conductive material layer under a metal pattern has been commercialized to form a charge transfer path.

However, the technology for forming a conductive material under the conventionally commercialized metal pattern has various problems as follows, and its use is limited. First, there is a phenomenon in which a part of the metal pattern is peeled off as the adhesion between the conductive material formed on the lower part of the metal pattern and the metal is lowered, as shown in FIG. 2, thereby shortening the production yield and the photomask life of the photomask.

Second, the transmittance is reduced by about 15% or more compared to the general photomask by the conductive material formed under the metal pattern as shown in FIG. Since the photomask is a key optical component of the exposure process, the reduction in transmittance is a very serious problem that not only shortens the lifetime of the light source of the exposure equipment but also seriously affects the product quality of the exposure process.

The commercially available conductive material has tantalum as its main component. Since tantalum itself does not have a transmittance, it has been applied in the form of increasing the transmittance by forming a conductive layer having a thickness of several nm and partially oxidizing it. The problem is that since it is a few nm thin film, it is not easy to control the degree of oxidation over the entire area of the photomask, so that the uniformity of the permeability decreases and the resistance increases as it is oxidized, thereby failing to effectively conduct the electrostatic charge.

As described above, since currently commercially available technologies have many problems, they must possess not only a certain level of permeability, excellent electrostatic charge conductivity, but also chemical resistance to photomask processing, and high durability that is not damaged during the exposure process. There is a need for a new alternative technique.

Korea Patent Registration 10-0526527 (2005.10.28) Korea Patent Registration 10-1703654 (2017.02.01)

The present invention can form a transparent conductive material layer which is a passage through which the electrostatic charge between the chromium metal patterns of the photomask can be moved, and at the same time, the cleaning power can be improved on the transparent conductive material layer to increase the chemical resistance and the life of the transparent conductive material layer. It is an object to provide a process for producing a photomask in which a layer of antifouling functional material is present.

The formation of the transparent conductive material and the antifouling functional material layer aims at securing the scalability of the technology by using a general technology rather than a new material and manufacturing technology. In addition, an object of the present invention is to provide a transparent photomask manufactured by the above-described method having excellent quality.

The multifunctional transparent photomask of the present invention for solving the above problems is to form a transparent conductive material on top of the photomask so as to move the electrostatic charge between the chromium pattern and to form an adhesion enhancing layer for enhancing adhesion with the final antifouling functional material. The step, and finally forming the antifouling functional material layer on top of the photomask can be prepared by performing a process.

Herein, the transparent conductive material has sufficient conductivity, and includes a material having optically excellent transmittance with respect to the wavelength of the light source used in the contact photolithography process, and has a sufficient adhesive strength with the glass substrate of the photomask. .

In addition, by forming an antifouling coating layer on the top, it is characterized in that it simultaneously retains antistatic function and antifouling functionality.

At this time, in order to improve the adhesion between the transparent conductive material and the top antifouling coating layer, it is characterized in that the adhesion strength layer is formed thin.

In addition, a wet deposition method that achieves the above-mentioned characteristics is preferred to a physical deposition method for excellent and uniform electrical conductivity, high permeability uniformity, excellent antifouling functionality, and excellent adhesion between the glass substrate of the photomask or each layer. Include.

By forming a conductive transparent conductive layer on top of the photomask, a passage through which electrostatic charge is transferred is formed between the chromium patterns, thereby preventing damage to the chromium pattern due to static electricity generated during contact and detachment of a contact photolithography process. Can provide an effect. In addition, by using a conductive material having a compliant transmittance in the visible region and realizing an optimal thickness through optical design, it is possible to provide an effect of minimizing the exposure energy loss of contact photolithography.

Conventionally, in the contact photolithography process, it is possible to provide the same antifouling function effect that lowers the foreign matter adsorption rate and improves the cleaning power, and in particular, by forming an adhesion enhancing layer between the transparent conductive layer and the antifouling functional layer, It is effective to improve adhesion and antifouling properties.

In addition, generally, a transparent conductive layer, an adhesion enhancing layer, and an antifouling functional layer are sequentially formed on the prepared photomask, and are not physically mixed or chemically formed between the layers.

1 is a cross-sectional view of a photomask that implements an antistatic function by forming a conductive material layer under a conventional chromium layer.
FIG. 2 is an image of a pin-hole due to peeling of a chromium pattern generated in the conventional photomask of FIG. 1.
3 is a result of measuring the transmission spectra of the antistatic function photomask and the general photomask implemented in FIG. 1, the antistatic function photomask of FIG. 1 shows about 15% lower transmittance than the general photomask. .
4 to 9 are cross-sectional views illustrating a method of manufacturing a photomask having various functions according to the present invention.

Hereinafter, a photomask having various functions such as antistatic and antifouling, and a method of manufacturing the same will be described in detail based on the above object of the present invention.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments and drawings described below in detail. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims.

As an embodiment for carrying out the present invention, a transparent conductive layer having a transparent and conductive layer on top of a photomask fabricated through a general manufacturing method in order to protect the transparent conductive layer, while improving adhesion to the upper antifouling coating layer, And it provides a method for forming an antifouling coating layer for implementing the antifouling functionality on the top. In more detail, the present invention will be described.

The transparent photomask of the present invention comprises the steps of preparing a photomask; Performing a plasma treatment on the surface of the photomask to modify the surface of the photomask; Forming a transparent conductive layer by depositing a transparent conductive material on the surface-modified photomask; Depositing an adhesion improving material on the transparent conductive layer to form an adhesion improving layer; Performing a plasma treatment on the surface of the adhesion enhancing layer to modify the surface; And after applying the antifouling coating agent on the adhesion improving layer, the step of heat treatment to form an antifouling coating layer; can be prepared by performing a process comprising a.

The photomask of the first step may be a general photomask, for example, a concave-convex pattern consisting of a concave portion and a convex portion is formed on the transparent glass substrate 100, the convex portion chrome from the upper direction of the transparent glass substrate The layer 110 and the chromium oxide layer 120 are laminated in this order, and only the transparent glass substrate exists in the recessed portion (see FIG. 4).

The transparent glass substrate 100 may mainly use soda lime or quartz, and the transparent glass substrate 100 is not always limited to the material, and all materials for manufacturing a photomask generally used may be used.

The second step is a pretreatment process before forming the transparent conductive layer, and is a process of modifying the surface of the glass substrate 100 of the concave portion, which is the surface of the photomask, and the surface of the chromium oxide layer 120, which is the outermost surface of the convex portion. The surface modification treatment method may perform a plasma treatment.

The surface modification is performed at a speed of 28 to 32 mm / s, preferably at a speed of 29 to 31 mm / s, more preferably 29.5 to 30.5 at 2,000 V power under a vacuum degree of 5.0 × 10 ^-6 Torr. The plasma is irradiated at a speed of mm / s.

Through such a modification process, as shown in the schematic diagram in FIG. 4, the transparent glass substrate 105 with the surface modified and the chromium oxide layer 125 with the surface modified can be secured.

Next, the third step is to form a transparent conductive layer on the surface of the modified photomask.

The transparent electrode material may include at least one selected from oxide materials having conductivity such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IGW), and fluorine tin oxide (FTO).

Alternatively, the conductive material may include at least one selected from materials in which conductive materials such as carbon nanotubes, silver nanowires, and graphene are dispersed.

And it may include one or more selected from conductive polymers such as polyacetylene (Polyacetylene), P3HT (Poly 3-Hexylthiophene) and PEDOT (Polytthylene di-oxythiophene).

A transparent conductive layer is formed on the surface of the photomask modified with the transparent conductive material having the composition. At this time, the transparent conductive layer should be thinner than the chromium layer 110 and the chromium oxide layer 120, in order to satisfy the light transmittance and electrical conductivity characteristics, preferably 10 to 50nm, more preferably 10 to 10 20 nm is preferable, and when the thickness of the transparent conductive layer exceeds 30 nm, there may be a problem in the optical properties.

The formation of the transparent conductive layer on the ITO material is carried out in a vacuum of 5.2 ~ 5.8 × 10 ^-6 Torr, preferably 5.4 ~ 5.6 × 10 ^-6 Torr of 98 ~ 102sccm and 7 ~ 9sccm, preferably 99 ~ Injection at 101 sccm and 7.5 to 8.5 sccm and may be carried out through dry deposition under process conditions of power 1.98 to 2.02 kW, preferably 1.99 to 2.01 kW.

The transparent conductive layer thus formed was made of a material having excellent electrical conductivity and high optical transmittance, and has a surface resistance of 1 × 10 ^{4 s} / squre or less, preferably 2.0 to 5.0 × 10 ³ Ω / squre. Can have.

In addition, the transparent conductive layer may have an average transmittance of 85% or more in the 380-450 nm visible light region, preferably 85-87%, and more preferably 85.5-86.5%.

Next, step 4 is a process of forming an adhesion improving layer by coating an adhesion improving agent on top of the transparent conductive layer, wherein the adhesion improving layer also has sufficient acid resistance, alkali resistance, While the material is thin, wear-resistant, it is formed by using a material having high adhesion with the transparent conductive layer and the antifouling coating layer on the top.

The adhesion improving agent may include a ceramic and an inorganic polymer.

The ceramic may include at least one selected from silicon oxide, silicon nitride, silicon carbide, and aluminum oxide, and preferably, at least one selected from silicon oxide and silicon nitride.

In addition, the inorganic polymer may include at least one selected from polysilazane and silane.

An adhesion improving layer 210 is formed on the transparent conductive layer (see FIG. 7), wherein the adhesion improving layer has an average thickness of 50 nm or less, preferably 10 to 35 nm, and more preferably 10 to 20 nm in the case of silicon oxide. If the thickness of the adhesion improving layer exceeds 20nm, there may be a problem that the characteristics of the top antifouling functional coating are not expressed by the unidirectional growth characteristic.

Formation of the adhesion enhancing layer uses a deposition method commonly used in the industry, preferably a dry deposition method can be used. In more detail, argon and oxygen at 38 to 42 sccm and 24 to 28 sccm, preferably 39 to 41 sccm and 25, respectively, under a vacuum degree of 1.0 to 1.4 × 10 ^-5 Torr, preferably 1.1 to 1.3 × 10 ^-6 Torr, respectively. It can be injected at ˜27 sccm and dry deposition can be performed under process conditions with a power of 2.86-2.90 kW, preferably 2.87-2.89 kW.

The adhesion enhancing layer thus formed may have a light transmittance of 95% or more in the 380-450 nm visible light region, preferably 96-99%, and more preferably 96-98%.

Next, step 5 is a step of surface modification by plasma treatment of the surface of the adhesion strength layer before forming the antifouling coating layer. The surface modification is to improve the adhesion between the adhesion improving layer and the antifouling coating agent by forming a hydroxide (-OH) group used for bonding to the surface of the photomask while allowing the coating to be applied more uniformly when applying the antifouling coating agent. .

The plasma treatment of the five stages is 0.45 ~ 0.6W / 1mm, preferably about 0.48 ~ 0.55W / 1mm, more preferably 0.49 ~ 0.52W / 45 to 60% level to minimize the damage of the product to the atmospheric pressure plasma At a speed of 28 to 32 mm / s, preferably at a speed of 29 to 31 mm / s, more preferably at a speed of 29.5 to 30.5 mm / s, and argon and oxygen at about 780 to 820: 1 volume ratio under the conditions of 1 mm. It is carried out using a mixed gas.

In addition, an ionizer treatment may be preceded to neutralize foreign substances adsorbed on the photomask surface and photomask surface charging characteristics before plasma treatment, and ionizer treatment may be performed by a general method used in the art. have.

Thus, the adhesion improving layer 215 surface-modified by the surface modification of five steps is formed on the outermost top layer of the photomask (see FIG. 8).

Next, the sixth step is a process for forming an antifouling coating layer, the general coating method used in the art, it is possible to coat the antifouling coating agent on the adhesion enhancing layer of the surface-modified photomask, preferably through a wet coating method. More preferably, it may be carried out by a wet spray coating method of high pressure spraying the antifouling coating agent in the liquid form on the surface of the modified photomask. In more detail, the antifouling coating agent is discharged at a discharge rate of 1.5 to 2.5 ml / min, preferably 1.8 to 2.2 ml / min, and a nitrogen pressure of 11 to 13 L / min, preferably 11.5 to 12.5 L. Acceleration with a nitrogen pressure of / min may be carried out by spraying on the surface of the photomask. Then, the entire photomask is scanned at a speed of 560 to 650 mm / s, preferably at a speed of 580 to 620 mm / s, more preferably at a speed of about 590 to 610 mm / s, and applied to the entire photomask. In this case, the direction of movement of the spray nozzle is set to 'ㄹ', and a wet coating process is performed to prevent excessive spraying of the coating liquid on the outside of the photomask by setting the direction change to be outside the photomask. can do. By coating in this manner, an antifouling coating layer 220 coated with an antifouling coating agent may be formed on the upper surface of the transparent glass substrate 100 having the surface modified and the adhesion improving layer 215 having the surface modified (see FIG. 9). ).

The antifouling coating agent may include an antifouling agent and an organic solvent, and is preferably an antifouling coating agent containing 0.1 to 0.7 wt% of the antifouling agent and a residual amount of solvent, and preferably 0.15 to 0.5 wt% of the antifouling agent and the residual amount of the solvent. To be more preferably formed by coating 0.2 to 0.4% by weight of the antifouling agent and the remaining amount of the solvent. In this case, if the antifouling agent content is less than 0.1% by weight, there may be a problem that it is difficult to express sufficient properties, and when the amount of the antifouling agent is greater than 0.7% by weight, there may be a problem that the nozzle is clogged or uncured during the process.

The antifouling agent is polytrialkylene oxide, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, perfluoroalkoxy polymer, fluorinated ethylene-propylene, polyethylenetetrafluoroethylene , Polyethylene-chlorotrifluoroethylene, perfluoroelastomer, fluorocarbon, perfluoropolyether, perfluorosulfonic acid, fluorinated polyimide, and perfluoropolyoxetane. And, preferably, may include one or two selected from polytrialkylene oxide, perfluoropolyether.

In addition, the polytrialkylene oxide (Perfluoro polytrialkyleneoxide) may include a perfluoro polytri (C1 ~ C3 alkylene) oxide, preferably perfluoro polytrimethylene oxide.

In addition, the organic solvent does not react with the antifouling agent component, and serves to dissolve the antifouling agent component, and includes a fluorine-containing organic solvent such as fluorine-containing alkanes, fluorine-containing halo alkanes, and fluorine. It may include one or two or more selected from a containing aromatic compound and a fluorine-containing ether (hydrofluoroether), preferably alkyl fluoroalkyl ether, more preferably C1 to C3 alkyl nonafluoroisobutyl It may include one or more selected from ethers (C1 ~ C3 alkyl Nonafluoroisobutyl Ether), more preferably methyl nonafluoroisobutyl ether (MethylNonafluoroisobutyl Ether) and ethyl nonafluoroisobutyl ether (EthylNonafluoroisobutyl Ether).

And, the heat treatment of step 6 may be carried out a general heat treatment method used in the art, preferably by heating the hot air treatment for 10 to 15 minutes at 140 ~ 150 ℃, by curing the solvent in the antifouling coating layer volatilized The antifouling coating layer 220 may be formed.

The antifouling coating layer may be formed with an average thickness of 50 nm or less, preferably 30 to 45 nm, more preferably 30 to 40 nm. At this time, if the average thickness of the antifouling coating layer exceeds 50nm, there may be a problem that the film removal due to a decrease in abrasion resistance due to weakening of the bonding force in the coating film, and if the thickness is too thin, sufficient antifouling effect and uniform optical properties May not be implemented.

In the present invention, the antifouling coating layer may have a light transmittance of 98% or more, preferably 98.0 to 99.2%, and more preferably 98.5 to 99.0% in the 380 to 450 nm visible light region.

In addition, an initial contact angle measured using ultrapure water may be 100 ° or more, preferably 105 ° to 110 °, for the convex part with the pattern and the concave part without the pattern based on the KS L 2110 standard.

The photomask having the antifouling coating layer of the present invention thus prepared is a dust-free wiper for a clean room, which is generally used in the electric and electronic industries, unlike a general photomask that performs cleaning based on sulfuric acid fruit water or solvent-based chemicals. The cleaning can be easily performed using only.

In addition, the present invention can provide an eco-friendly cleaning method that can secure the safety of workers, shorten the working time, reduce the production cost because it does not need to use existing expensive equipment and chemicals.

In addition, since the defects generated in the photolithography process can be improved by reducing the foreign matter adsorption rate by the antifouling coating layer, the utility thereof can be maximized through differentiation from the prior art.

In addition, a transparent conductive layer is provided with a path through which the electrostatic charge can be transferred between the chromium patterns, thereby providing an effect of preventing damage to the chromium pattern caused by static electricity generated during repeated contact and detachment in a contact photolithography process. By using a conductive material having a compliant transmittance to the visible region and implementing an optimal thickness through optical design, it is possible to provide an effect of minimizing exposure energy loss of contact photolithography.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are provided to aid the understanding of the present invention and should not be construed as limiting the scope of the present invention to the following examples.

EXAMPLE

Preparation Example 1 Preparation of Transparent Conductive Layer

A dry conductive target was prepared by mixing 90 wt% indium oxide and 10 wt% tin oxide and pressing at high temperature, and coated it on a 4.8 mm thick soda-lime glass by dry deposition to form a transparent conductive layer. Prepared.

At this time, the dry deposition method is injecting argon and oxygen at 99 ~ 101sccm and 7.5 ~ 8.5sccm respectively under a vacuum degree of 5.4 ~ 5.6 × 10 ^-6 Torr. Dry deposition was performed under process conditions applying 11.99 to 2.01 kW of power.

Preparation Example 2 Preparation of Adhesion Enhancer

A target for silicon dry deposition having a purity of 99% or more was prepared and coated on a 4.8 mm thick soda-lime glass by a dry deposition method under conditions of high oxygen concentration to prepare an adhesion improving coating layer.

In the dry deposition method, argon and oxygen are injected at 39 to 41 sccm and 25 to 27 sccm, respectively, under a vacuum degree of 1.1 to 1.3 × 10 ^-6 Torr, and dry deposition is performed under a process condition of applying 22.87 to 2.89 kW of power. It was.

Preparation Example 3 Preparation of an Antifouling Coating

An antifouling coating was prepared by mixing and stirring 0.3% by weight of perfluoro polytrimethyleneoxide and 99.7% by weight of ethyl Nonafluoroisobutyl ether as a solvent.

Next, the antifouling coating agent was accelerated at a nitrogen discharge rate of about 2.0 ml / min and about 12.0 L / min to spray a 4.8 mm thick soda-lime glass surface to form an antifouling coating layer.

Experimental Example 1 Measurement of Light Transmittance and Electrical Conductivity

Each of Preparation Examples 1 to 3 was measured for light transmittance based on the KS M ISO 9211-3 method, and the results except for the decrease in transmittance due to soda-lime glass as a substrate are shown in Table 1 below.

In addition, the surface resistance of the transparent conductive layer (film) was measured based on the KS L 2109 method, and the results are shown in Table 1 below.

division 365nm 405 nm 436 nm Surface resistance Transparent conductive layer (thickness 20 nm) 79.9% 86.2% 90.3% 3.36 × 10 ³ μs / squre Adhesion Enhancement Layer (Thickness 15nm) 97.5% 96.9% 97.0% - Antifouling coating layer (thickness 40nm) 99.1% 98.4% 98.4% -

Example 1 Preparation of Multifunctional Transparent Photomask

A blank mask in which a chromium layer 110, a chromium oxide layer, and a photoresist layer are sequentially formed on a 20-inch by 24-inch transparent glass substrate 100 (soda lime), which is generally used in a contact photolithography process, is prepared. It was.

Next, a blank mask was irradiated with laser to induce development and etching reaction to prepare a photomask having a convex pattern and a concave pattern in which a chromium layer and a chromium oxide layer were stacked on the chromium layer on the transparent glass substrate (FIG. 4). Reference).

At this time, the thickness of the transparent glass substrate was 4.8 mm, the chromium layer thickness was about 95 nm, and the chromium oxide layer thickness was about 15 nm.

Next, the photomask was placed in a vacuum facility, and plasma treatment was performed under argon (Ar) gas under a condition of 0.5 W / mm to perform surface modification.

Next, 100 sccm of oxygen and 8 sccm of oxygen were injected into the transparent conductive material prepared in Preparation Example 1 on the plasma-treated photomask under 5.5 × 10 ^-6 Torr vacuum degree, and a dry deposition process was performed at a power of 2 kW to the photomask surface. The transparent conductive layer was formed evenly. At this time, the length of the target of ITO was 1,000mm or more to proceed the process once to form a transparent conductive layer with an average thickness of 20nm.

Next, the photomask on which the transparent conductive layer was formed was injected with 40 sccm of argon and 26 sccm of oxygen under a vacuum degree of 1.2 × 10 ^-5 Torr, followed by a dry deposition process using the adhesion enhancer of Preparation Example 2 at a power of 2.88 kW, to evenly apply the photomask to the surface of the photomask. The transparent adhesive improvement layer was formed. At this time, the target of Si was 1,000 mm or more in length, and the transparent adhesive improvement layer was formed in 18 nm of average thickness by performing a one time process.

Next, the photomask on which the adhesion force always layer was formed was subjected to surface modification by performing atmospheric pressure plasma treatment under a gas of argon (Ar) and oxygen (O ₂ ) under a condition of 0.5 W / mm.

Next, the antifouling coating agent discharged at 2 ml / min prepared in Preparation Example 3 on the plasma treated photomask was accelerated to nitrogen pressure of 12 L / min so that the entire surface of the photomask could be evenly sprayed. The antifouling coating was wet coated by high pressure spraying at a speed of 600 mm / s. At this time, the moving direction of the spray nozzle is set to 'ㄹ', and the wet coating process was performed to prevent the spraying of the coating liquid excessively on the outer side of the photomask by setting the direction change to the outside of the photomask.

Next, a photomask coated with a coating agent is heat-treated and cured under conditions of supplying thermal energy by a hot air method for 15 minutes at 150 ° C. to form an antifouling coating layer having a thickness of about 30 nm on the transparent glass substrate. A photomask was prepared in which an antifouling coating layer was formed as shown.

Comparative Example 1: Multifunctional photomask using a raw material having a conductive material formed under the metal pattern

A blank mask (Clean Surface Technology, brand name EP blankmask (ESD Protected blankmask) manufactured by CST) was prepared.

Next, the convex pattern and the concave pattern in which the conductive layer of the conductive material is formed on the transparent glass substrate and the chromium oxide layer is stacked on the chromium layer are irradiated with a blank mask by irradiating a laser and inducing development and etching reaction. The antistatic photomask formed was prepared.

Next, the antifouling coating agent discharged at 2 ml / min prepared in Preparation Example 3 on the plasma treated photomask was accelerated to nitrogen pressure of 12 L / min so that the entire surface of the photomask could be evenly sprayed. The antifouling coating was wet coated by high pressure spraying at a speed of 600 mm / s. At this time, the moving direction of the spray nozzle is set to 'ㄹ', and the wet coating process was performed to prevent the spraying of the coating liquid excessively on the outer side of the photomask by setting the direction change to the outside of the photomask.

Next, a photomask coated with a coating agent was heat-treated and cured under conditions of supplying thermal energy in a hot air manner for 15 minutes at 150 ° C. to form an antifouling coating layer having a thickness of about 30 nm on the transparent glass substrate.

Comparative Example 2 photomask in which a conductive layer was formed using silver nanowires

A blank mask in which a chromium layer 110, a chromium oxide layer, and a photoresist layer are sequentially formed on a 20-inch by 24-inch transparent glass substrate 100 (soda lime), which is generally used in a contact photolithography process, is prepared. It was.

Next, a blank mask was irradiated with a laser to induce development and etching to prepare a photomask having a convex pattern and a concave pattern in which a chromium layer was laminated on the transparent glass substrate and a chromium oxide layer was stacked on the chromium layer.

At this time, the thickness of the transparent glass substrate was 4.8 mm, the chromium layer thickness was about 95 nm, and the chromium oxide layer thickness was about 15 nm.

Next, an atmospheric pressure plasma treatment was performed under a gas mixed with argon (Ar) and oxygen (O ₂ ) under a condition of 0.5 W / mm to perform surface modification.

Next, the conductive layer was formed by high pressure injection of the silver nanowire solution on the plasma treated photomask. At this time, the silver nanowire is 60nm in diameter, 45㎛ in length, 5mg per ml in ethanol is dissolved in solution, and the coating agent discharged at 2ml / min accelerated to nitrogen pressure of 15L / min to be evenly sprayed on the photomask surface The coating was wet coated by high pressure spraying the entire photomask at a speed of 600 mm / s. At this time, the moving direction of the spray nozzle is set to 'd', and the wet coating process was performed to prevent the spraying of the coating liquid excessively on the outside of the photomask by setting the direction change to be outside the photomask.

Next, the photomask coated with the coating agent was heat-treated and cured under a condition of supplying thermal energy by hot air for 15 minutes at 150 ° C. to form a conductive layer on the surface of the photomask.

Next, an atmospheric pressure plasma treatment was performed under a gas mixed with argon (Ar) and oxygen (O ₂ ) under a condition of 0.5 W / mm to perform surface modification of the conductive layer.

Next, the antifouling coating agent discharged at 2 ml / min prepared in Preparation Example 3 on the plasma treated photomask was accelerated to nitrogen pressure of 12 L / min so that the entire surface of the photomask could be evenly sprayed. The antifouling coating was wet coated by high pressure spraying at a speed of 600 mm / s. At this time, the moving direction of the spray nozzle is set to 'ㄹ', and the wet coating process was performed to prevent the spraying of the coating liquid excessively on the outer side of the photomask by setting the direction change to the outside of the photomask.

Next, a photomask coated with a coating agent is heat-treated and cured under conditions of supplying thermal energy by a hot air method for 15 minutes at 150 ° C. to form an antifouling coating layer having a thickness of about 30 nm on the transparent glass substrate. A photomask was prepared in which an antifouling coating layer was formed as shown.

Experimental Example 2 Measurement of Light Transmittance of Photomask

The light transmittance according to the wavelength of the photomasks prepared in Example 1 and Comparative Examples 1 to 2 was measured. The results are shown in Table 2 below and Table 3 shows the results excluding optical characteristics of the substrate.

The light transmittance was 300-500 nm wavelength irradiation, and the light transmittance of the photomask was measured based on KS M ISO 9211-3 method.

division 365nm 405 nm 436nm Example 1 68.1% 78.0% 80.3% Comparative Example 1 68.7% 73.3% 73.3% Comparative Example 2 76.8% 82.8% 84.4%

division 365nm 405 nm 436nm Example 1 80.7% 87.3% 90.1% Comparative Example 1 81.4% 82.0% 82.5% Comparative Example 2 91.0% 92.7% 94.6%

Experimental Example 3 Measurement of Contact Angle, Durability, Haze and Surface Resistance of Antifouling Coating Layer

The initial contact angle for the distilled water of the above example was measured based on the KS L 2110 method, and the results are shown in Table 4 below.

In addition, the contact angle was measured after the anti-wear test to evaluate the durability of the antifouling coating layer, the results are shown in Table 4 below. At this time, the wear resistance test conditions were performed 250g, 40rpm, 5,000 times for the dust-free.

In this case, in order for the antifouling coating to be applied to the actual contact or proximity exposure process, the contact angle difference before and after the abrasion resistance test should be within 10 °.

In addition, haze was measured based on KS M ISO 14782, and the results are shown in Table 4 below.

In addition, the surface resistance was measured according to the KS L 2109 method, and the results are shown in Table 4 below. In this case, the surface resistance is a surface resistance of the transparent conductive layer, and more specifically, the measurement result of the ITO layer in Example 1, the conductive layer under the metal pattern in Comparative Example 1, and the silver nanowire layer in Comparative Example 2.

division Initial contact angle (°) Contact angle after wear test (°) Haze (%) Surface resistance (Ω / squre) Example 1 116.0 ± 1.2 111.2 ± 1.5 0.09 ± 0.01 (1.3 ± 0.1) × 10 ³ Comparative Example 1 114.2 ± 1.3 42.5 ± 1.2 0.05 ± 0.03 (2.9 ± 0.7) × 10 ⁴ Comparative Example 2 113.7 ± 2.1 95.5 ± 1.8 1.50 ± 0.30 (4.8 ± 0.5) × 10 ⁴

As can be seen in Example 3 and Table 4, Example 1 may have a somewhat lower or similar level of optical characteristics than Comparative Example 1 and Comparative Example 2.

However, as can be seen in Table 5, it has excellent conductive properties by having the lowest surface resistance, and it can be seen that the durability of the top antifouling coating is also excellent.

On the other hand, in the case of Comparative Example 1 has a surface resistance of 10 ⁴ or more, and the durability of the top antifouling coating is very low, it can be confirmed that the antifouling coating application is impossible.

In addition, in the case of Comparative Example 2, the surface resistance is 10 ⁴ or more, and the transmittance is excellent, but the haze characteristic is much lower than that of Example 1, which is improved than Comparative Example 1, but the durability of the top antifouling coating is actually lower. It can be confirmed that it is difficult to apply.

Although the embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above embodiments and can be modified in various forms, and a person of ordinary skill in the art to which the present invention pertains. It will be appreciated that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

100: transparent glass substrate
105: transparent glass substrate modified surface
110: patterned chrome layer
120: patterned chromium oxide layer
125: surface modified chromium oxide pattern
200: transparent conductive layer
210: adhesion layer
215: surface modified adhesion improving layer
220: antifouling coating layer

Claims (12)

delete delete delete delete delete delete Preparing a photomask;
Performing a surface modification on the surface of the photomask by plasma treatment;
Forming a transparent conductive layer by depositing a transparent conductive material on the surface-modified photomask;
Depositing an adhesion homeostatic agent on the transparent conductive layer to form an adhesion improving layer;
Performing a plasma treatment on the surface of the adhesion enhancing layer to modify the surface; And
And applying the antifouling coating agent containing 0.1 to 0.7 wt% of the antifouling agent and the remaining amount of the organic solvent on the adhesion improving layer, followed by heat treatment to form the antifouling coating layer.
In the photomask of the first stage, an uneven pattern composed of recesses and protrusions is formed on the transparent glass substrate. Only the substrate exists,
The three-step transparent conductive material includes at least one selected from conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IGW) and fluorine tin oxide (FTO), Or conductive materials such as carbon nanotubes, silver nanowires, and graphenes dispersed in one or more selected materials, or polyacetylene, poly 3-hexylthiophene (P3HT), and polythylene (PEDOT) di-oxythiophene) and at least one selected from conductive polymers,
Adhesion enhancers of the four stages include at least one selected from inorganic materials such as silicon oxide, silicon nitride and aluminum oxide, or at least one selected from inorganic polymers such as polysilazane and silane,
The antifouling agent is polytrialkylene oxide, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, perfluoroalkoxy polymer, fluorinated ethylene-propylene, polyethylenetetrafluoroethylene At least one selected from polyethylene-chlorotrifluoroethylene, perfluoroelastomer, fluorocarbon, perfluoropolyether, perfluorosulfonic acid, fluorinated polyimide, and perfluoropolyoxetane,
The organic solvent is an organic solvent capable of dissolving the antifouling agent without reacting with the antifouling agent, and the organic solvent is a fluorine-containing alkane, a fluorine-containing halo alkane, a fluorine-containing aromatic and a fluorine-containing At least one selected from ethers,
Plasma treatment in the second and fifth steps precedes the ionizer treatment for neutralizing the foreign matter adsorbed on the photomask surface and the photomask surface charging characteristics before the plasma treatment,
The five stages of plasma treatment is performed at a speed of 28 to 32 mm / s under conditions of 0.45 to 0.6 W / 1 mm based on the plasma header length.
In the three-step transparent conductive material deposition process, argon (Ar) and oxygen (O ₂ ) gases were injected at 99 ~ 101 sccm and 7.5 ~ 8.5 sccm under vacuum of 5.4 ~ 5.6 × 10 ^-6 Torr and 1.98 ~ 2.02kW, respectively. Do it with power,
In the four-step adhesion enhancement layer deposition process, argon (Ar) and oxygen (O ₂ ) gases were injected at 38 to 42 sccm and 24 to 28 sccm, respectively, under vacuum degrees of 1.0 to 1.4 × 10 ^-5 Torr, and 2.86 to 2.90 kW, respectively. Method for producing a multi-functional transparent photomask having antistatic and antifouling properties, characterized in that performed by power. delete delete delete delete The method of claim 7, wherein the heat treatment in six steps is performed by hot air treatment for 10 to 15 minutes at 140 to 150 ° C. 9.

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