KR20220117560A - A photomask with a pellicle structure that prevents growth of growable residue and haze - Google Patents

Abstract

The present invention relates to a photomask of a pellicle structure and a manufacturing method thereof, capable of exhibiting the same level of performance as that of a quartz (quartz) substrate while the photomask is manufactured using a relatively low-cost sodalime substrate, and in particular, capable of minimizing an occurrence of haze caused by growth type foreign matters such as sodium (Na+), calcium (Ca2+) and magnesium (Mg2+) protruding from the inside of the sodalime substrate to a surface thereof due to a Yake phenomenon during a photomask exposure process. The photomask according to the present invention can improve an antifouling performance of a substrate due to a coating layer formed on the substrate, while preventing in advance repetitive detachments of pellicle for cleaning the substrate due to generation of the growth type foreign matters, thereby improving economics of a process. According to the present invention, the manufacturing method of a photomask comprises the steps of: forming a mask pattern on a substrate of a sodalime material; individually forming a coating layer on upper and lower surfaces of the substrate with a composition comprising at least one selected from silicon dioxide (SiO2 ) and fluorine (fluorine); and forming a pellicle membrane on the substrate to be supported by a pellicle frame and spaced apart from the substrate at a predetermined interval.

Description

A photomask with a pellicle structure that prevents growth of growable residue and haze

The present invention relates to a photomask having a pellicle structure in which growth of foreign substances and haze is suppressed.

A lithography process is performed to integrate a semiconductor device onto a wafer. The lithography process is performed including a photomask manufacturing process of designing a layout of a circuit pattern to be formed on a wafer, and implementing a mask pattern conforming to the layout of the designed circuit pattern on a transparent quartz substrate. . The mask pattern is transferred to the photoresist layer on the wafer by performing an exposure process using the manufactured photomask.

On the other hand, an exposure light source of a shorter wavelength band is used to transfer a pattern of a smaller line width during the exposure process, and as the exposure light source of a shorter wavelength band is introduced, the relatively high exposure energy of the light source of the short wavelength band is reduced. Thus, growth of foreign substances or haze is caused more frequently on the surface of the photomask.

In the case of a quartz (quartz) substrate generally used in a photomask, since the cost is relatively high, the production cost is reduced by using less expensive sodalime substrates, while at the same time as the quartz (quartz) substrate. Research is being done to demonstrate its performance. The components of this soda lime glass are about 73% of silicon oxide (SiO ₂ ), about 14% of sodium oxide (Na ₂ O), about 9% of calcium oxide (CaO), about 3% of magnesium oxide (MgO), and the remaining amount is oxidized. It is known to contain aluminum (Al ₂ O ₃ ) and the like, and when such a soda-lime substrate is used, a yake phenomenon occurs between exposure processes, and sodium (Na ⁺ ) ions as a component included in the soda-lime substrate , Calcium (Ca ²⁺ ) ions, magnesium (Mg ²⁺ ) ions, etc. protrude from the surface of the substrate and grow on the surface, thereby forming a growthable foreign material and thus generating haze between use of the photomask.

In addition, a pellicle widely used to extend the service life and cleaning cycle of the photomask and to protect the photomask is attached to the front surface of the photomask through the pellicle frame. , since repeated detachment of the pellicle for cleaning the substrate becomes inevitable, the difficulty in use is great. In addition, the growth foreign material or haze lowers the peripheral transmittance, and induces a pattern defect in which a pattern portion is formed in a portion where an actual pattern does not exist. Since bridge defects may occur, efforts are being made to prevent pattern defects caused by such growth foreign substances or haze.

On the other hand, as a conventional document that presents contents related to haze suppression of a photomask substrate, there is Korean Patent Application Laid-Open No. 10-2009-0074558 (July 7, 2009). Regarding the content of increasing haze resistance by preventing reactants such as cargo (SO _x ), nitroxide (NO _x ), carbon dioxide or moisture from combining with materials remaining during photomask cleaning, and preventing growth foreign substances from adhering Although only disclosed, there is a limitation in that there is no suggestion for preventing a growing foreign material protruding from the inside of the substrate due to the use of the sodalime substrate and the use of the soda lime substrate.

Prior Document 1: Republic of Korea Patent Publication No. 10-2009-0074558 (2009.07.07.)

In order to solve the problems of the prior art, the present invention can exhibit the same level of performance as that of a quartz (quartz) substrate while manufacturing a photomask using a relatively low-cost sodalime substrate. , haze caused by growing foreign substances such as sodium (Na ⁺ ), calcium (Ca ²⁺ ), magnesium (Mg ²⁺ ), etc. that protrude from the inside of the soda lime substrate to the surface by the yake phenomenon during the photomask exposure process ), to provide a photomask having a pellicle structure and a method for manufacturing the same, which can minimize the occurrence.

In addition, the technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned are clearly to those of ordinary skill in the art to which the present invention belongs from the description below. can be understood

In the present specification, a) forming a mask pattern on a substrate of soda lime (sodalime) material; b) forming a coating layer on each of the upper and lower surfaces of the substrate with a composition comprising at least one selected from among silicon dioxide (SiO ₂ ) and fluorine; and c) forming, on the substrate, a pellicle membrane supported by a pellicle frame and spaced apart from the substrate by a predetermined distance; It provides a photomask manufacturing method comprising a.

In addition, in the present specification, the coating layer forming step of step b is performed through one or more methods selected from spray coating and sputtering, to provide a photomask manufacturing method.

In addition, in the present specification, the coating layer is formed in a thickness range of 100 to 800 Å, provides a photomask manufacturing method.

In the present specification, a photomask manufactured according to the above method, comprising: a substrate made of a sodalime material on which a mask pattern is formed; a coating layer covering the upper and lower surfaces of the substrate, respectively, and comprising at least one selected from silicon dioxide (SiO ₂ ) and fluorine; and a pellicle membrane supported on the substrate by a pellicle frame and spaced apart from the substrate by a predetermined distance.

In addition, the thickness of the coating layer in the present specification provides a photomask having a thickness range of 100 to 800 Å.

In addition, in the present specification, the coating layer on the upper surface of the substrate includes silicon dioxide (SiO ₂ ) and fluorine in a ratio of 100: 10 to 20 parts by weight and is formed in a thickness range of 300 to 400 Å, and the coating layer on the lower surface of the substrate is Silicon dioxide (SiO ₂ ) and fluorine (Fluorine) is included in a ratio of 100: 80 to 120 parts by weight and is formed in a thickness range of 100 to 200 Å, to provide a photomask.

In addition, in the present specification, the photomask is selected from sodium (Na ⁺ ), calcium (Ca ²⁺ ) and magnesium (Mg ²⁺ ) series formed by a yake phenomenon by a reaction between a soda lime substrate and a UV light source during exposure To provide a photomask that suppresses the occurrence of haze due to one or more growth-prone foreign substances.

In addition, in the present specification, the photomask has a light transmittance of 88 to 90% at a wavelength of 436 nm, and a light reflectance of 8.0 ± 5.0%, providing a photomask.

The photomask manufactured according to the present invention exhibits performances such as light transmittance and light reflectance equivalent to those of a quartz substrate while manufacturing the photomask using a relatively low-cost sodalime substrate.

In addition, the photomask manufactured according to the present invention is sodium (Na ⁺ ) ions, calcium (Ca ²⁺ ) or magnesium (Mg ²⁺ ) that protrude from the inside of the soda-lime substrate to the surface by the Yake phenomenon during the exposure process. It can be suppressed to a minimum by the occurrence of haze due to growth-prone foreign substances such as.

In addition, the photomask according to the present invention improves the antifouling performance of the substrate due to the coating layer formed on the substrate, and on the other hand, it is possible to prevent in advance the repeated detachment of the pellicle for cleaning the substrate due to the generation of growth foreign substances, so the economic feasibility of the process This is improved.

1 schematically illustrates a photomask including a pellicle structure according to an embodiment of the present invention.
2 illustrates a light path during an exposure process of a photomask including a pellicle structure according to an embodiment of the present invention.
Figure 3 schematically shows a mechanism by which a growthable foreign material is grown on the surface of the substrate by the yak phenomenon when the coating layer is not formed on the soda lime substrate according to the comparative example of the present invention.

The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "having" are intended to designate the presence of an embodied feature, step, component, or a combination thereof, but one or more other features or steps; It should be understood that the possibility of the presence or addition of components, or combinations thereof, is not precluded in advance.

Further, in the present invention, when it is said that each layer or element is formed "on" or "over" each layer or element, it means that each layer or element is formed directly on each layer or element, or It means that other layers or elements may additionally be formed between each layer, on the object, on the substrate.

Since the invention may have various changes and may have various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the invention.

As described above, a pellicle attached to the front surface of the photomask is widely used to extend the service life and cleaning cycle of the photomask and to protect the photomask. On the other hand, in the case of a quartz (quartz) substrate generally used in a photomask, since the cost is relatively high, the production cost is reduced by using less expensive sodalime substrates, while the equivalent to the quartz (quartz) substrate Although research is being conducted to demonstrate the level of performance, when such a soda-lime substrate is used, a yake phenomenon occurs between exposure processes, and sodium (Na ⁺ ) ions, calcium, as components included in the soda-lime substrate (Ca ²⁺ ) ions, magnesium (Mg ²⁺ ) ions, and the like protrude from the surface of the substrate and grow on the surface, thereby forming a growthable foreign material and thus generating haze between use of the photomask.

The present inventors, when forming a coating layer with a composition containing silicon dioxide (SiO ₂ ) and fluorine in a specific weight part ratio on each of the upper and lower surfaces of the sodalime material substrate on which the mask pattern is formed, the photomask In the exposure process, haze caused by growth foreign substances such as sodium (Na ⁺ ), calcium (Ca ²⁺ ), magnesium (Mg ²⁺ ), etc. It can be suppressed to a minimum, and a photomask can be manufactured using a relatively low-cost sodalime substrate, while exhibiting the same level of light transmittance and light reflectance as that of a quartz substrate. And the coating layer formed on the substrate improves the antifouling performance of the substrate, while the repeated detachment of the pellicle for cleaning the substrate can be prevented in advance due to the occurrence of growth foreign substances, so that the economic feasibility of the process is improved. It was confirmed and the present invention was completed.

Hereinafter, a photomask and a manufacturing method thereof according to a specific embodiment of the present invention will be described in detail.

Photomask manufacturing method including pellicle structure

According to one embodiment of the present invention, a photomask manufacturing method includes the steps of: a) forming a mask pattern on a substrate made of a sodalime material; b) forming a coating layer on each of the upper and lower surfaces of the substrate with a composition comprising at least one selected from among silicon dioxide (SiO ₂ ) and fluorine; and c) forming, on the substrate, a pellicle membrane supported by a pellicle frame and spaced apart from the substrate by a predetermined distance; includes

First, a mask pattern is formed on a substrate made of sodalime (step a).

Sodalime is a glass containing a large amount of sodium oxide (Na ₂ O) and calcium oxide (CaO), specifically silicon oxide (SiO ₂ ) about 73%, sodium oxide (Na ₂ O) about 14 %, about 9% of calcium oxide (CaO), about 3% of magnesium oxide (MgO), and the remaining amount may include aluminum oxide (Al ₂ O ₃ - ). On the other hand, soda lime has the advantage of being relatively inexpensive compared to quartz, but unlike a quartz substrate, it contains a number of impurities such as sodium oxide and calcium oxide. ⁺ ), calcium (Ca ²⁺ ), magnesium (Mg ²⁺ ), etc., there is a problem that the growth of foreign matter protrudes (see FIG. 3).

On the other hand, in the present invention, as in step b to be described later, by forming a coating layer on the surface of the substrate, that is, on the upper and lower surfaces of the substrate, respectively, the soda lime substrate is caused by a yak phenomenon due to high exposure energy in the photomask exposure process. It is possible to minimize the occurrence of growth-generating foreign substances such as sodium (Na ⁺ ), calcium (Ca ²⁺ ) and magnesium (Mg ²⁺ ) that protrude from the inside to the surface and the occurrence of haze.

In more detail, the yake phenomenon is a phenomenon that occurs in soda-lime glass, and the substrate temperature rises due to high exposure energy generated during photomask exposure, and the elevated temperature and moisture content, carbon dioxide As the substrate deteriorates due to the amount of (CO ₂ ), etc., sodium (Na ⁺ ), calcium (Ca ²⁺ ), and magnesium (Mg ²⁺ ) as impurities present inside the soda-lime substrate protrude from the outer surface of the substrate, It means growing by forming particles. On the other hand, when the coating layer is formed on the surface of the substrate according to the present invention, when the impurities protrude to the surface when the substrate is deteriorated, the coating layer acts as a physical barrier, thereby effectively preventing the phenomenon.

Meanwhile, the mask pattern formed on the soda-lime substrate may be, for example, an uneven pattern including concave and convex portions formed on the substrate, and the convex portion may have a configuration in which a chromium layer and a chromium oxide layer are sequentially stacked. . On the other hand, the concave portion may be configured with only a soda lime substrate. Meanwhile, the mask pattern may be formed by a method generally used in the art, and the formed chromium layer is, for example, 90 to 100 nm thick, and the chromium oxide layer is, for example, 10 to 20 nm thick. may be formed with

Next, a coating layer is formed on each of the upper and lower surfaces of the substrate with a composition including at least one selected from silicon dioxide (SiO ₂ ) and fluorine (step b).

In the above step, sodium (Na ⁺ ), calcium (Ca ²⁺ ) or magnesium protruding from the inside of the soda lime substrate to the surface due to the yake phenomenon when a photomask made of a substrate made of soda lime is used for exposure. (Mg ²⁺ ) By blocking the growth foreign material in advance, it corresponds to the step of forming a coating layer that suppresses the occurrence of haze due to the growth foreign material (see FIG. 1).

The step may be performed through one or more methods selected from spray coating and sputtering, and the composition for forming the coating layer is silicon dioxide (SiO ₂ ) and one selected from fluorine (Fluorine), as will be described later. It may include more than one.

Meanwhile, in an embodiment of the present invention, the coating layer may be formed in a thickness range of 100 to 800 Å.

For example, on the upper surface of the substrate on which the mask pattern is formed, a coating layer may be formed in a thickness range of 300 to 400 Å using a composition containing silicon dioxide (SiO ₂ ) and fluorine in a ratio of 100: 10 to 20 parts by weight. And, silicon dioxide (SiO ₂ ) and fluorine (Fluorine) on the lower surface of the substrate may be formed in a thickness range of 100 to 200 Å using a composition containing 100: 80 to 120 parts by weight.

On the other hand, the coating layer formed on the upper surface of the substrate has the effect of exhibiting excellent barrier effect and antifouling performance within the thickness range and composition ratio, and, in particular, the thickness range and composition ratio range of the coating layer formed on the upper surface is within the above range, yak phenomenon By effectively suppressing the growth of foreign substances and haze, and at the same time securing improved antifouling performance.

On the other hand, the coating layer formed on the lower surface of the substrate is maintained in a state exposed to the outside unlike the upper surface coating layer provided inside the pellicle structure. ), it is possible to have a light path substantially equivalent to that of an exposure light path of a general photomask that does not use a pellicle by minimizing secondary refraction caused by a difference in refractive index (see FIG. 2 ).

On the other hand, the coating layer forming step of step b may be performed through spray coating and sputtering, for example, 70 ~ 150 ℃, vacuum 3.0 * 10 ^-3 ~ 5.0 * 10 ^-5 Torr, Ar: 5 ~ 10 sccm , O ₂ : 5 ~ 10 sccm, power 270 ~ 290 mA, Rate 2 ~ 10 Å / sec under dry conditions, each sputtering can be performed.

Next, a pellicle membrane supported by a pellicle frame and spaced apart from the substrate by a predetermined distance is formed on the substrate (step c).

The pellicle is a component for protecting the mask, and may include a pellicle frame and a pellicle membrane. Meanwhile, the pellicle membrane covers the exposure area of the mask, and may have, for example, a planar shape such as a circle, an ellipse, or a polygon, but is not particularly limited. On the other hand, the pellicle membrane may be a carbon-containing thin film, for example, graphene, graphite, or may include a carbon nanotube (carbon nanotube), the carbon nanotube SWCNT (Single wall carbon nanotube), It may be a multiwall CNT (MWCNT) or a combination thereof. Meanwhile, the pellicle may further include a reinforcing layer coated on the surface of the carbon-containing thin film, and the reinforcing layer may be made of, for example, a boron (B)-containing material, a silicon (Si)-containing material, or a transition metal. have. Meanwhile, the pellicle membrane may have a thickness of about 1 to 200 nm.

Meanwhile, the pellicle frame may be made of a metal or a polymer, and for example, may be made of carbon, diamond like carbon (DLC), aluminum, stainless steel, or polyethylene. On the other hand, the pellicle frame may be black, and in this case, it is possible to prevent reflection of exposure light and easily perform an inspection for the presence or absence of an attached foreign material. On the other hand, an adhesive layer for adhesion may be additionally provided between the pellicle frame and the substrate, and for example, may be formed using an adhesive such as an acrylic resin, an epoxy resin, a silicone resin, or a fluorine resin.

The photomask according to an embodiment of the present invention manufactured by the above-described method includes a substrate made of a sodalime material on which a mask pattern is formed; a coating layer covering the upper and lower surfaces of the substrate, respectively, and comprising at least one selected from silicon dioxide (SiO ₂ ) and fluorine; and a pellicle membrane supported on the substrate by a pellicle frame and spaced apart from the substrate by a predetermined distance (see FIG. 1 ).

As described above, each coating layer may be formed in a thickness range of 100 to 800 Å, for example, the coating layer on the upper surface of the substrate is silicon dioxide (SiO ₂ ) and fluorine (Fluorine) 100: 10 to 20 parts by weight It is included in a ratio, and is formed in a thickness range of 300 to 400 Å, specifically 100: 15 parts by weight, and may be formed to a thickness of 350 Å. In addition, the coating layer on the lower surface of the substrate contains silicon dioxide (SiO ₂ ) and fluorine in a ratio of 100: 80 to 120 parts by weight, and is formed in a thickness range of 100 to 200 Å, specifically 100: 100 parts by weight. included, and may be formed to a thickness of 150 Å.

On the other hand, the coating layer formed on the upper surface of the substrate has the effect of exhibiting excellent barrier effect and antifouling performance within the thickness range and composition ratio, and, in particular, the thickness range and composition ratio range of the coating layer formed on the upper surface is within the above range, yak phenomenon By effectively suppressing the growth of foreign substances and haze, and at the same time securing improved antifouling performance.

On the other hand, the coating layer formed on the lower surface of the substrate is maintained in a state exposed to the outside unlike the upper surface coating layer provided inside the pellicle structure. ), it is possible to have a light path substantially equivalent to that of an exposure light path of a general photomask that does not use a pellicle by minimizing secondary refraction caused by a difference in refractive index (see FIG. 2 ).

On the other hand, due to the formation of the coating layer as described above, sodium (Na ⁺ ), calcium (Ca ²⁺ ) or magnesium (Mg ²⁺ ), etc. While minimizing the occurrence of haze due to growth-prone foreign substances, and manufacturing a photomask using a relatively low-cost sodalime substrate, the light transmittance and light reflectance equivalent to those of a quartz substrate etc., and also improves the antifouling performance of the substrate due to the coating layer, while the repeated detachment of the pellicle for cleaning the substrate can be prevented in advance due to the occurrence of growth foreign substances, so the economic feasibility of the process is improved. .

On the other hand, the photomask according to an embodiment of the present invention has a light transmittance in the range of 88 to 90% and a light reflectance in the range of 8.0 ± 5.0% at a wavelength of 436 nm, a soda lime substrate that is relatively inexpensive compared to a quartz (quartz) substrate It has the effect of realizing the same level of light transmittance and light reflectance performance as that of a quartz (quartz) substrate.

Hereinafter, the operation and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention and the scope of the invention is not limited in any way by this.

[Example]

Example 1

As a substrate in which a chromium layer and a chromium oxide layer are sequentially stacked, silicon oxide (SiO ₂ ) about 73%, sodium oxide (Na ₂ O) about 14%, calcium oxide (CaO) about 9%, magnesium oxide (MgO) about A glass substrate of 20 inch × 24 inch size containing aluminum oxide (Al ₂ O ₃ ), etc., including 3%, the remaining amount, etc., is prepared, and 70 to 150 respectively on the upper and lower surfaces of the photomask substrate ℃, vacuum 3.0 * 10 ^-3 ~ 5.0 * 10 ^-5 Torr, Ar: 5 ~ 10 sccm, O ₂ : 5 ~ 10 sccm, power 270 ~ 290 mA, Rate 2 ~ 10 Å/sec A coating layer was formed, and at this time, a coating layer was formed on the upper surface of the substrate to a thickness of 350 Å using silicon dioxide and fluorine in a ratio of 100: 15 parts by weight, and silicon dioxide and fluorine were added to a ratio of 100: 150 parts by weight on the lower surface of the substrate. A coating layer was formed in a thickness range of Å. Next, a frame-shaped pellicle frame facing the upper surface of the photomask substrate and a carbon pellicle membrane were formed.

Comparative Example 1

A photomask was manufactured in the same manner as in Example 1, except that a quartz substrate was used instead of a glass substrate made of soda lime, and a coating layer was not separately formed.

Comparative Examples 2-1, 2-2, 2-3

A photomask was prepared in the same manner as in Example 1, but the coating layer was not separately formed (Comparative Example 2-1), the upper surface coating layer was not formed (Comparative Example 2-2), and the lower surface coating layer was not formed Only (Comparative Example 2-3) was different.

Comparative Examples 3-1 to 3-4

A photomask was prepared in the same manner as in Example 1, but the thickness of the top coating layer was formed to be 250 Å (Comparative Example 3-1), the thickness of the top coating layer was formed to be 450 Å (Comparative Example 3-2), Only that the thickness of the lower surface coating layer was formed to be 50 Å (Comparative Example 3-3), and the thickness of the lower surface coating layer was formed to be in the range of 250 Å.

Comparative Examples 4-1, 4-2, 4-3, 4-4, etc.

A photomask was prepared in the same manner as in Example 1, but containing silicon dioxide and fluorine in a ratio of 100: 5 parts by weight (Comparative Example 4-1), silicon dioxide and fluorine at 100: 25 weight when forming the upper coating layer One including part ratio (Comparative Example 4-2), one containing silicon dioxide and fluorine in a ratio of 100:60 parts by weight when forming the lower surface coating layer (Comparative Example 4-3), and one containing silicon dioxide and fluorine in a ratio of 100:130 parts by weight Only those included (Comparative Example 4-4) were different.

Composition and thickness of top coating layer Lower surface coating layer composition and thickness SiO ₂ (parts by weight) Fluorine
(parts by weight) Thickness (Å) SiO ₂
(parts by weight) Fluorine
(parts by weight) Thickness (Å) Example 1 100 15 350 100 95 150 Comparative Example 1 - - - - - - Comparative Example 2-1 - - - - - - Comparative Example 2-2 - - - 100 95 150 Comparative Example 2-3 100 15 350 - - - Comparative Example 3-1 100 15 250 100 95 150 Comparative Example 3-2 100 15 450 100 95 150 Comparative Example 3-3 100 15 350 100 95 100 Comparative Example 3-4 100 15 350 100 95 250 Comparative Example 4-1 100 5 350 100 95 150 Comparative Example 4-2 100 25 350 100 95 150 Comparative Example 4-3 100 15 350 100 60 150 Comparative Example 4-4 100 15 350 100 130 150

[Experiment 1: Confirmation of growth-prone foreign matter (haze occurrence) and contact angle measurement experiment]

After applying the photomasks prepared in Examples 1 to Comparative Examples 100 times in the contact exposure process, whether haze was generated due to the growthable foreign matter was measured according to the KS M ISO 14782 method. In addition, the initial contact angle with respect to distilled water was measured by the KS L 2110 method, and 250 g, 40 rpm, 5,000 times were performed on Mujincheon to measure the antifouling performance, and then the contact angle was measured again, and the results are shown in Table 2 shown in

[Experiment 2: Photomask Transmittance and Reflectance Confirmation Experiment]

When a photomask is manufactured according to Example 1 and Comparative Examples, the transmittance is repeatedly measured 10 times in order to check whether uniform transmittance and reflectance can be obtained over the entire area of the finally manufactured photomask product, and The results obtained by measuring the deviation are shown below. Specifically, the light transmittance was measured according to the KS M ISO 9211-3 method, and the results are shown in Table 2.

division Haze (%) Initial contact angle (°) Contact angle after wear test (°) at 436 nm
light transmittance
(Transmittance) at 436 nm
light reflectance
(Reflectance) Example 1 0.07 ± 0.01 118.7° 115.6 ± 1.2° 89 ± 1.0% 8.0 ± 5.0% Comparative Example 1 0.06 ± 0.03 118.9° 116.4 ± 1.5° 89 ± 1.5% 8.0 ± 5.0% Comparative Example 2-1 4.07 ± 0.20 115.4° 94.2 ± 1.5° 87 ± 1.0% 8.0 ± 7.0% Comparative Example 2-2 4.06 ± 0.15 115.7° 96.1 ± 1.5° 87 ± 1.5% 8.0 ± 7.0% Comparative Example 2-3 0.07 ± 0.02 117.8° 112.6 ± 1.8° 88 ± 2.0% 8.0 ± 7.0% Comparative Example 3-1 0.07 ± 0.03 118.8° 114.6 ± 1.0° 89 ± 1.0% 8.0 ± 6.0% Comparative Example 3-2 0.07 ± 0.04 118.7° 115.5 ± 1.2° 87 ± 1.5% 8.0 ± 7.0% Comparative Example 3-3 0.08 ± 0.15 117.9° 112.3 ± 1.5° 89 ± 1.5% 8.0 ± 6.0% Comparative Example 3-4 0.07 ± 0.15 118.5° 113.1 ± 1.2° 87 ± 1.2% 8.0 ± 7.0% Comparative Example 4-1 0.07 ± 0.05 118.5° 111.1 ± 1.2° 88 ± 1.0% 8.0 ± 6.0% Comparative Example 4-2 0.07 ± 0.02 118.6° 115.8 ± 1.2° 87 ± 1.5% 8.0 ± 7.0% Comparative Example 4-3 0.07 ± 0.02 118.7° 114.6 ± 1.5° 88 ± 1.5% 8.0 ± 6.0% Comparative Example 4-4 0.07 ± 0.01 118.9° 115.1 ± 1.2° 87 ± 1.2% 8.0 ± 7.0%

Referring to the results of Table 2, the photomask manufactured according to Example 1 has excellent antifouling performance while significantly suppressing haze generation due to growth of foreign substances compared to Comparative Examples, and has a light transmittance equivalent to that of a quartz substrate and It could be confirmed that the light reflectance performance was exhibited, and when the top coating layer was not formed, it was confirmed that haze due to the growth foreign matter occurred. In addition, when the coating layer has the composition ratio and thickness range according to the present invention when manufacturing the photomask, as described above, the variation in light transmittance and light reflectance is significantly reduced, and the variation in light transmittance and light reflectance is significantly reduced, while suppressing haze generation and securing excellent antifouling performance, as described above. It was confirmed that it can have transmission and reflection characteristics.

In the foregoing, specific embodiments of the present invention have been described and illustrated, but it is common knowledge in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. It is self-evident to those who have Accordingly, such modifications or variations should not be individually understood from the technical spirit or point of view of the present invention, and modified embodiments should be said to belong to the claims of the present invention.

100: soda lime substrate
200: coating layer
300: pellicle
310: pellicle membrane membrane
320: pellicle frame
330: adhesive layer

Claims (8)

a) forming a mask pattern on a substrate made of a sodalime material;
b) forming a coating layer on each of the upper and lower surfaces of the substrate with a composition comprising at least one selected from silicon dioxide (SiO ₂ ) and fluorine; and
c) forming, on the substrate, a pellicle membrane supported by a pellicle frame and spaced apart from the substrate by a predetermined distance; A photomask manufacturing method comprising a. The method of claim 1,
The coating layer forming step of step b is performed through one or more methods selected from spray coating and sputtering, a photomask manufacturing method. The method of claim 1,
The coating layer is formed in a thickness range of 100 to 800 Å, a photomask manufacturing method. A photomask manufactured according to the method of claim 1, comprising:
a substrate made of a sodalime material on which a mask pattern is formed;
a coating layer covering the upper and lower surfaces of the substrate, respectively, and comprising at least one selected from silicon dioxide (SiO ₂ ) and fluorine; and
A photomask comprising a pellicle membrane supported on the substrate by a pellicle frame and spaced apart from the substrate by a predetermined distance. 5. The method of claim 4,
The thickness of the coating layer has a thickness ranging from 100 to 800 Å, a photomask. 5. The method of claim 4,
The coating layer on the upper surface of the substrate contains silicon dioxide (SiO ₂ ) and fluorine in a ratio of 100: 10 to 20 parts by weight and is formed in a thickness range of 300 to 400 Å,
The coating layer on the lower surface of the substrate includes silicon dioxide (SiO ₂ ) and fluorine in a ratio of 100: 80 to 120 parts by weight and is formed in a thickness range of 100 to 200 Å. 5. The method of claim 4,
The photomask is one or more selected from sodium (Na ⁺ ), calcium (Ca ²⁺ ), and magnesium (Mg ²⁺ ) series formed by a Yake phenomenon by a reaction between a soda lime substrate and a UV light source during exposure. A photomask that suppresses haze caused by foreign substances. 5. The method of claim 4,
The photomask has a light transmittance of 88 to 90% at a wavelength of 436 nm, and a light reflectance of 8.0 ± 5.0%, a photomask.

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