KR20200063945A - Pellicle structure and method of manufacturing the pellicle structure - Google Patents

Abstract

The present invention relates to a pellicle structure. The pellicle structure comprises: a graphene film formed of multi-layer graphene; and a frame support body attached to or coupled to a lower portion of the graphene film and having a through opening port exposing the graphene film to a center portion, wherein the frame support body comprises: a silicon frame portion formed of n-type silicon (Si) or p-type silicon (Si); and a diffusion preventing frame portion disposed between the graphene film and the silicon frame portion to prevent element diffusion between the silicon frame portion and the graphene film.

Description

Pelicle structure and its manufacturing method{PELLICLE STRUCTURE AND METHOD OF MANUFACTURING THE PELLICLE STRUCTURE}

The present invention relates to a pellicle structure that protects a mask from various contaminants during an extreme ultraviolet exposure process and a method for manufacturing the same.

Recently, in order to increase the degree of integration of semiconductor devices, many studies have been conducted on a technique for miniaturizing a pattern formed on a substrate such as a wafer, and an extreme ultraviolet exposure process technique for forming a pattern using ultraviolet rays as one method thereof ( Extreme Ultraviolet Lithography (EUVL) is being developed.

Extreme ultraviolet exposure process technology (Extreme Ultraviolet Lithography: EUVL) is a method of manufacturing a pattern having a line width of about 7 nm or less using extreme ultraviolet light having a wavelength of about 13.5 nm. In order to secure the yield of the extreme ultraviolet exposure process, it is very important to protect the mask containing the pattern information from various contaminants.

In order to protect the mask, a pellicle structure for an extreme ultraviolet exposure process is mainly applied, and development of its manufacturing method and structure is required.

One object of the present invention is to provide a pellicle structure including a graphene film and/or a silicon nitride (SiNx) film as a pellicle film.

Another object of the present invention is to provide a method for manufacturing the pellicle structure.

The pellicle structure according to the embodiment of the present invention includes a pellicle film formed of multilayer graphene; And a frame support attached to or coupled to the lower portion of the pellicle film and having a through opening exposing the graphene film at a center portion, wherein the frame support is crystalline silicon doped with an n-type dopant material (n-type Si). Or a silicon frame formed of p-type Si doped with p-type dopant material; And a diffusion preventing frame part having the same planar shape as the silicon frame part and having a thickness smaller than that of the silicon frame and disposed between the graphene film and the silicon frame part to prevent element diffusion between the silicon frame part and the graphene film. Includes.

In one embodiment, the pellicle film may have a thickness of 1 to 50 nm.

In one embodiment, the silicon frame portion may have a thickness of 700 to 800 μm, and the diffusion prevention frame portion may have a thickness of 25 nm or more and 1 μm or less.

In one embodiment, the diffusion preventing frame portion may be formed of silicon oxide (SiOx) or silicon nitride (SiNx).

The manufacturing method of the pellicle structure according to the embodiment of the present invention is a first step of sequentially forming a diffusion barrier layer, an amorphous carbon layer, a metal catalyst layer, and a capping layer formed of a metal having a higher melting point than the metal of the metal catalyst layer on a silicon substrate step; A second step of converting the amorphous carbon layer to a graphene layer by heat treatment; A third step of removing the catalyst layer and the capping layer; A fourth step of forming a mask pattern on the bottom surface of the silicon substrate; A fifth step of forming a frame support by etching the silicon substrate and the diffusion barrier layer region exposed by the mask pattern through a radical etching process; And a sixth step of removing the mask pattern.

In one embodiment, the silicon substrate may include a single crystal silicon wafer doped with phosphorus (P), arsenic (As), or antimony (Sb) from 0.0000015% to 0.3%.

In one embodiment, the diffusion barrier layer may be formed by depositing silicon oxide (SiOx) or silicon nitride (SiNx) to a thickness of 25 nm or more and 1 μm or less.

In one embodiment, the catalyst layer is formed of nickel (Ni), the capping layer may be formed of tungsten (W), molybdenum (Mo) or tantalum (Ta).

In one embodiment, the heat treatment for converting the amorphous carbon layer to the graphene layer may be performed in a hydrogen (H2), nitrogen (N2) or inert gas atmosphere at 700 to 1000 ℃.

In one embodiment, the mask pattern may be formed of silicon oxide (SiO2), silicon nitride (SiNx), PDMS, or metal.

In one embodiment, the fifth step uses radicals extracted from one or more plasmas selected from the group consisting of ClF ₃ , ClF ₂ , ClF, Cl ₂ , CF ₄ , C ₄ F ₈ , SF ₆ and N _X O. Can be performed.

The pellicle structure according to the sealing example of the present invention includes a pellicle film formed of a silicon nitride film; And a frame support attached to or coupled to the lower portion of the pellicle film and having a through opening exposing the graphene film to a central portion, wherein the frame support includes a first silicon oxide frame portion to which the pellicle film is directly attached or coupled; A silicon frame formed on the first silicon oxide frame portion and formed of crystalline silicon doped with n-type dopant material (n-type Si) or crystalline silicon doped with p-type dopant material (p-type Si); A second silicon oxide frame portion stacked on the silicon frame portion; And a silicon nitride frame part stacked on the second silicon oxide frame part.

A method of manufacturing a pellicle structure according to an embodiment of the present invention sequentially forms a first silicon oxide layer and a first silicon nitride layer on a lower surface of a silicon substrate, and a second silicon oxide layer on an upper surface of the silicon substrate And a first step of sequentially forming a second silicon nitride layer; A second step of forming a mask pattern on the second silicon nitride layer; A third step of forming a silicon nitride frame portion and a second silicon oxide frame portion by removing exposed areas of the second silicon nitride layer and the second silicon oxide layer through a first reactive ion etching process using the mask pattern; A fourth step of forming a silicon frame part by removing an exposed region of the silicon substrate through a radical etching process using the silicon nitride frame part and the second silicon oxide frame part as a mask; And removing the exposed region of the first silicon oxide layer through the second reactive ion etching process using the silicon nitride frame portion, the second silicon oxide frame portion, and the silicon frame portion as a mask to form the first silicon oxide frame portion. It may include a fifth step.

In one embodiment, the first and second reactive ion etching processes are performed using ions generated using argon (Ar), oxygen (O2), and SF6 gas, and the radical etching process is ClF ₃ , It may be performed using radicals extracted from one or more plasmas selected from the group consisting of ClF ₂ , ClF, Cl ₂ , CF ₄ , C ₄ F ₈ , SF ₆ and N _X O.

In one embodiment, during the radical etching process, the first silicon oxide layer may function as an etch stop layer.

The pellicle structure according to the embodiment of the present invention includes a pellicle film including a stacked structure of a silicon nitride film and a multilayer graphene; And a frame support attached to or coupled to the lower portion of the silicon nitride film and having a through opening exposing the graphene film to a central portion, wherein the frame support is a first silicon oxide frame part to which the silicon nitride film is directly attached or bonded. ; A silicon frame formed on the first silicon oxide frame portion and formed of crystalline silicon doped with n-type dopant material (n-type Si) or crystalline silicon doped with p-type dopant material (p-type Si); A second silicon oxide frame portion stacked on the silicon frame portion; And a silicon nitride frame part stacked on the second silicon oxide frame part.

A method of manufacturing a pellicle structure according to an embodiment of the present invention sequentially forms a first silicon oxide layer, a first silicon nitride layer, an amorphous carbon layer, a catalyst layer and a capping layer on a lower surface of a silicon substrate, and A first step of sequentially forming a second silicon oxide layer and a second silicon nitride layer on the upper surface; A second step of changing the amorphous carbon layer to a graphene layer; A third step of removing the catalyst layer and the capping layer; A fourth step of forming a mask pattern on the second silicon nitride layer; A fifth step of forming a silicon nitride frame portion and a second silicon oxide frame portion by removing exposed areas of the second silicon nitride layer and the second silicon oxide layer through a first reactive ion etching process using the mask pattern; A sixth step of forming a silicon frame part by removing an exposed region of the silicon substrate through a radical etching process using the silicon nitride frame part and the second silicon oxide frame part as a mask; And removing the exposed region of the first silicon oxide layer through the second reactive ion etching process using the silicon nitride frame portion, the second silicon oxide frame portion, and the silicon frame portion as a mask to form the first silicon oxide frame portion. It may include a seventh step.

According to the pellicle structure of the present invention and a method for manufacturing the same, not only can the silicon nitride film and/or graphene film acting as the pellicle film be significantly damaged in the manufacturing process, but also the process time for manufacturing the pellicle is significantly reduced I can do it.

1 is a cross-sectional view illustrating a pellicle structure according to an embodiment of the present invention.
2 is a flowchart illustrating a method of manufacturing the pellicle structure illustrated in FIG. 1.
3A to 3F are cross-sectional views illustrating a method of manufacturing the pellicle structure illustrated in FIG. 1.
4 is a cross-sectional view illustrating a pellicle structure according to another embodiment of the present invention.
5 is a flowchart illustrating a method of manufacturing the pellicle structure shown in FIG. 4.
6A to 6D are cross-sectional views illustrating a method of manufacturing the pellicle structure illustrated in FIG. 4.
7 is a cross-sectional view illustrating a pellicle structure 300 according to another embodiment of the present invention.
8 is a flowchart illustrating a method of manufacturing the pellicle structure illustrated in FIG. 7.
9A to 9E are cross-sectional views illustrating a method of manufacturing the pellicle structure illustrated in FIG. 7.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention can be applied to various changes and may have various forms, and specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific disclosure form, and it should be understood as including all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

The terms used in this application are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "include" or "have" are intended to indicate the presence of features, steps, actions, components, parts or combinations thereof described in the specification, one or more other features or steps. It should be understood that it does not preclude the existence or addition possibility of the operation, components, parts or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. Terms, such as those defined in a commonly used dictionary, should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

1 is a cross-sectional view for describing a pellicle structure according to an embodiment of the present invention.

Referring to FIG. 1, a pellicle structure 100 according to an embodiment of the present invention includes a pellicle film 120 and a frame support 110.

The pellicle film 120 is formed of pure graphene and has a single pass transmission of about 13.5 nm wavelength applied to extreme ultraviolet exposure process (EUVL) of about 90% or more. It can have a thickness. In one embodiment, the pellicle film 120 may be formed of graphene having a thickness of about 1 to 50 nm. For example, in consideration of mechanical strength, the pellicle film 120 may be preferably formed of graphene having a thickness of about 3 to 50 nm. For example, the pellicle film 120 may be formed of a graphene composed of about 5 to 50 carbon atom layers so that the transmittance to the extreme ultraviolet rays is 90% or more while having a certain strength.

The planar shape of the pellicle film 120 is not particularly limited. For example, the pellicle layer 120 may have a planar shape such as circular, elliptical, polygonal, and the like.

The frame support 110 is attached or coupled to the lower portion of the pellicle film 120 so that the pellicle structure 100 according to the present invention can stand alone, exposing the pellicle film 120 to the middle portion A through opening can be formed. In one embodiment, when the pellicle film 120 has a rectangular planar shape, the frame support 110 is attached to the edge portion of the pellicle film 120 so as to support it, a constant thickness and width It may have a square frame structure in which an opening through which the extreme ultraviolet rays passing through the pellicle film 120 can be passed is formed by exposing the pellicle film 120 to the center portion. If attached to the edge portion of the pellicle film 120 to support it, the thickness and width of the frame support 110 is not particularly limited.

In one embodiment, the frame support 110 has the same shape as the rim of the pellicle film 120 and the diffusion preventing frame portion 111 and the diffusion preventing frame to which the pellicle film 120 is directly attached or combined. It may include a silicon frame portion 112 having the same plane shape as the portion 111 and coupled to one side of the diffusion preventing frame portion 111 and having a thickness greater than that of the diffusion preventing frame portion 111.

The silicon frame portion 112 may have a thickness of about 700 to 800 μm, and n-type dopant material doped with high concentration of crystalline silicon (n ⁺⁺ -type Si) or p-type dopant material doped crystalline It may be formed of silicon (p-type Si). When the silicon frame portion 111 is formed of crystalline silicon (n ⁺⁺ -type Si) doped with the n-type dopant element at a high concentration, the n-type dopant element includes one or more selected from group 5 elements. The doping content of the n-type dopant element may be about 0.0000015% or more and 0.3% or less.

The diffusion preventing frame part 111 is an atomic diffusion between the silicon frame part 112 and the pellicle film 120 in the process of manufacturing or using the pellicle structure 100, silicon carbide (SiC), other silicide ( Silicide) and the like can be prevented. To this end, the diffusion preventing frame 111 may be formed to a thickness of about 25 nm or more and 1 μm or less. When the thickness of the diffusion preventing frame part 111 is less than 50 nm, a problem that an atomic diffusion between the silicon frame part 112 and the pellicle film 120 cannot be blocked may occur, and the diffusion preventing frame part 111 When the thickness of) exceeds 1 μm, a problem that an excessively increased process time and cost of manufacturing the diffusion preventing frame part 111 may occur. In one embodiment, the diffusion preventing frame portion 111 may be formed of a dielectric material such as silicon oxide (SiOx), aluminum oxide (AlOx), hafnium oxide (HfOx) or silicon nitride (SiNx).

Hereinafter, a method of manufacturing the pellicle structure illustrated in FIG. 1 will be described.

2 is a flowchart illustrating a method of manufacturing the pellicle structure illustrated in FIG. 1, and FIGS. 3A to 3F are cross-sectional views illustrating a method of manufacturing the pellicle structure illustrated in FIG. 1.

Referring to FIGS. 2 and 3A to 3H together with FIG. 1, a method of manufacturing a pellicle structure according to an embodiment of the present invention includes a diffusion barrier layer (111' amorphous carbon layer (120' catalyst layer) on a silicon substrate 112' 130) and a first step (S110) of sequentially forming the capping layer 140; a second step of converting the amorphous carbon layer 120' into a graphene layer 120 (S120); the catalyst layer 130 and the A third step (S130) of removing the capping layer 140; a fourth step of forming a mask pattern 150 on the lower surface of the silicon substrate 112' (S140); and using the mask pattern 150 A fifth step (S150) of forming the frame support 110 by etching the silicon substrate 112' and the diffusion barrier layer 111' through a radical etching process; and a sixth step of removing the mask pattern 150 (S160).

In the first step (S110), the silicon substrate 112 ′ may be prepared by first doping an n-type dopant or a p-type dopant on a silicon wafer having a thickness of about 700 to 800 μm. In the silicon wafer, the n-type dopant element may be doped at a high concentration, and in this case, the n-type dopant element may include one or more selected from group 5 elements.

Subsequently, the diffusion barrier layer 111' may be formed on the silicon substrate 112'. In one embodiment, the diffusion barrier layer 111' includes silicon oxide (SiOx), aluminum oxide (AlOx), and hafnium oxide (HfOx). ), or a dielectric material such as silicon nitride (SiNx).

The method for forming the diffusion barrier layer 111' is not particularly limited. For example, the diffusion barrier layer 111' may be formed on the silicon substrate 112' by a vapor deposition method. May be formed to a thickness of about 50 nm or more to prevent element diffusion between the silicon substrate 112' and the amorphous carbon layer 120' during the heat treatment process performed in the second step (S120).

Subsequently, an amorphous carbon layer 120' may be formed on the diffusion preventing layer 111'. The method of forming the amorphous carbon layer 120' is not particularly limited. For example, the amorphous carbon layer 120' Silver may be formed through chemical vapor deposition using a carbon source material, a solution process, and the like.

In one embodiment, the amorphous carbon layer 120 ′ has a thickness of about 50 nm or less so that the pellicle film 120 manufactured therefrom has a single pass transmission of 90% or more at a wavelength of about 13.5 nm. It can be formed of.

Subsequently, the catalyst layer 130 may be formed on the amorphous carbon layer 120'. The catalyst layer 130 may replace the amorphous carbon layer 120' during the heat treatment process performed in the second step (S120). It can serve as a catalyst to convert to a graphene layer 120. In one embodiment, the catalyst layer 130 may be formed of nickel (Ni), in this case, in order to perform the catalytic role, the The catalyst layer 130 may be formed to a thickness of about 300 nm or more, for example, about 300 to 60 nm.

Subsequently, the capping layer 140 may be formed on the catalyst layer 130. The capping layer 140 may prevent nickel (Ni) from volatilization from the catalyst layer 130 during a high temperature heat treatment process performed in the second step (S120). When nickel (Ni) is volatilized from the catalyst layer 130 during a high-temperature heat treatment process of about 700 to 1000°C performed in the second step (S120), at least a part of the amorphous carbon layer 120' due to lack of catalyst There may be a problem that is not converted to the graphene.

In one embodiment, the capping layer 140 is a metal having a melting point of 2500°C or higher, for example, tungsten (W) (melting point: 3422°C), molybdenum (Mo) (melting point: 2610 °C), tantalum (Ta) (melting point: 3017 °C) and the like.

In the second step (S120), by performing a heat treatment process for a period of time at a temperature of about 700 to 1000 ℃ for the structure formed in the first step (S120), the amorphous carbon layer 120' to the graphene layer When the heat treatment temperature is less than 700°C, a problem that the amorphous carbon layer 120' is not converted into graphene may occur, and when it exceeds 1000°C, the metal of the capping layer 140 may be converted. Element may be diffused into the catalyst layer 130 may cause a problem that a uniform graphene layer 120 is not formed.

In one embodiment, the amorphous carbon layer 120 ′ may be converted into a multi-layer graphene composed of carbon atom layers of about 50 or less layers by a heat treatment process at a temperature of about 700 to 1000°C.

On the other hand, in order to prevent the oxidation of the nickel or the graphene of the catalyst layer 130, the heat treatment process may be performed in a hydrogen (H2), nitrogen (N2) or inert gas atmosphere, for about 30 to 120 minutes Can be performed.

In the third step (S130), the method of removing the capping layer 140 and the catalyst layer 130 is not particularly limited. For example, the capping layer 140 and the catalyst layer 130 may be sequentially removed through a wet etching process using metal etchants.

In the fourth step, a mask material layer may be formed by forming a mask material layer on a lower surface of the silicon substrate 111 ′ and patterning the mask material 150. The mask pattern 150 includes the silicon substrate ( It may be formed of a material that is not etched by a radical that etches 111' and the diffusion barrier layer 112', or is etched significantly slower than the silicon substrate 112' and the diffusion barrier layer 111'. For example, The mask pattern 150 may be formed of a single material selected from silicon oxide (SiO2), silicon nitride (SiNx), PDMS, metal, etc. The relatively thick silicon substrate exposed by the mask pattern 150 ( Since the mask pattern 150 must be maintained while radically etching the entire region of 111' and the diffusion barrier layer 112', the mask pattern 150 is preferably formed relatively thick.

In the fifth step (S150), the frame support 110 may be formed by etching the silicon substrate 112' and the diffusion preventing layer 111' through a radical etching process using the mask pattern 150. .

The radical etching process may be performed using a remote plasma etching apparatus. The pellicle film 120 made of the graphene may be damaged by ions. In order to prevent damage to the graphene pellicle film 120, only the highly reactive radicals in plasma are selectively extracted and then used. By doing so, the entire silicon substrate 111' and the diffusion barrier layer 112' exposed by the mask pattern 150 may be etched. At this time, chlorine (Cl) and fluorine may be used as reaction gases for generating the plasma. (F), nitrogen (N)-based highly reactive gases, for example, chlorine-based gas such as ClF ₃ , ClF ₂ , ClF, Cl ₂ , fluoride-based CF ₄ , C ₄ F ₈ , SF ₆ A gas or a nitrogen-containing oxide-based gas such as N _X O may be used, etc. Since the radical etching process may be performed at a low temperature from room temperature to 300°C, damage due to heat of the graphene layer may be additionally prevented. .

Meanwhile, as shown in the present invention, after forming an amorphous carbon layer 120' between the diffusion barrier layer 111' and the catalyst layer 130, the amorphous carbon layer 120' is converted into a graphene pellicle film 120 through a heat treatment process. In the case of, the graphene has no surface dangling bond and is in a chemically stable state, so it is impossible to perform chemical adsorption, so that the silicon substrate 112' and the diffusion prevention layer 111' are radically etched. During the etching process, the graphene layer has an advantage of not being etched or damaged at all by the radical.

On the other hand, when a silicon wafer doped with an n-type dopant at a high concentration is used as the silicon substrate 112', even for a relatively thick silicon wafer of about 700 to 800 µm through the radical etching process, tens of minutes to The etching process can be completed very quickly in a few hours, which is about 2 to 10 times faster than the p-type silicon wafer, which can significantly reduce the process time for manufacturing the pellicle structure.

In the sixth step (S160), the method of removing the mask pattern 150 is not particularly limited.

4 is a cross-sectional view illustrating a pellicle structure according to another embodiment of the present invention.

Referring to FIG. 4, the pellicle structure 200 according to another embodiment of the present invention includes a pellicle film 220 and a frame support 210.

The pellicle film 120 may be formed of a silicon nitride film, and transmits at least about 90% transmittance (single pass transmission) of extreme ultraviolet light having a wavelength of about 13.5 nm applied to an extreme ultraviolet exposure process (EUVL). It may have a thickness of about 1 to 100nm to have.

The planar shape of the pellicle film 220 is not particularly limited. For example, the pellicle layer 120 may have a planar shape such as circular, elliptical, polygonal, and the like.

The frame support 210 is attached or coupled to the lower portion of the pellicle film 220 so that the pellicle structure 200 can stand alone, and a through opening is formed in the middle portion to expose the pellicle film 220. Can be. In one embodiment, when the pellicle film 220 has a rectangular planar shape, the frame support 210 is attached to the edge portion of the pellicle film 220 so as to support it, a constant thickness and width It may have a square frame structure in which an opening through which the extreme ultraviolet rays passing through the pellicle film 220 is passed is formed by exposing the pellicle film 220 to the center portion. If attached to the edge portion of the pellicle film 220 to support it, the thickness and width of the frame support 210 is not particularly limited.

In one embodiment, the frame support 210 has the same shape as the rim of the pellicle film 220, the first silicon oxide frame portion 211 to which the pellicle film 220 is directly attached or combined, the agent A silicon frame part 212, a second silicon oxide frame part 213, and a silicon nitride frame that have the same plane shape as the one silicon oxide frame part 212 and are successively stacked on the first silicon oxide frame part 211. A portion 214 may be included. The silicon frame part 212 may have a greater thickness than the first silicon oxide frame part 211, the second silicon oxide frame part 213, and the silicon nitride frame part 214.

The first and second silicon oxide frame portions 211 and 213 may be formed of silicon oxide, for example, silicon dioxide, and the silicon nitride frame portion 214 may be formed of silicon nitride. Each of the first silicon oxide frame part 211, the second silicon oxide frame part 213, and the silicon nitride frame part 214 may be formed to a thickness of about 25 nm or more and 1 μm or less.

The silicon frame part 212 may have a thickness of about 700 to 800 μm, and n-type dopant material doped with high concentration of crystalline silicon (n ⁺⁺ -type Si) or p-type dopant material doped It may be formed of silicon (p-type Si). When the silicon frame portion 111 is formed of crystalline silicon (n ⁺⁺ -type Si) doped with the n-type dopant element at a high concentration, the n-type dopant element includes one or more selected from group 5 elements. The doping content of the n-type dopant element may be about 0.0000015% or more and 0.3% or less.

Hereinafter, a method of manufacturing the pellicle structure illustrated in FIG. 4 will be described.

5 is a flowchart illustrating a method of manufacturing the pellicle structure illustrated in FIG. 4, and FIGS. 6A to 6D are cross-sectional views illustrating a method of manufacturing the pellicle structure illustrated in FIG. 4.

Referring to FIGS. 5 and 6A to 6D together with FIG. 4, a method of manufacturing a pellicle structure according to another embodiment of the present invention includes a first silicon oxide layer 211 ′ and a first silicon oxide layer 211 ′ on the lower surface of the silicon substrate 212 ′. A first step of sequentially forming one silicon nitride layer 220 and sequentially forming a second silicon oxide layer 213' and a second silicon nitride layer 214' on the upper surface of the silicon substrate 212' ( S210); a second step (S220) of forming a mask pattern 250 on the second silicon nitride layer 214'; the second silicon nitride through a first reactive ion etching process using the mask pattern 250 A third step (S230) of forming the silicon nitride frame portion 214 and the second silicon oxide frame portion 213 by removing the exposed regions of the layers 214' and the second silicon oxide layer 213'; An agent for forming the silicon frame part 212 by removing the exposed region of the silicon substrate 212' through a radical etching process using the silicon nitride frame part 214 and the second silicon oxide frame part 213 as a mask. Step 4 (S240); the first silicon oxide through a second reactive ion etching process using the silicon nitride frame portion 214, the second silicon oxide frame portion 213, and the silicon frame portion 212 as a mask. A fifth step (S250) of forming the first silicon oxide frame portion 211 by removing the exposed region of the layer 211 ′ may be included.

In the first step (S210 ), first, the silicon substrate 212 ′ may be prepared by doping an n-type dopant or a p-type dopant on a silicon wafer having a thickness of about 700 to 800 μm. In the silicon wafer, the n-type dopant element may be doped at a high concentration, and in this case, the n-type dopant element may include one or more selected from group 5 elements.

Subsequently, a first silicon oxide layer 211' and a first silicon nitride layer 220 are sequentially formed on the lower surface of the silicon substrate 212', and the second silicon on the upper surface of the silicon substrate 212'. The oxide layers 213' and the second silicon nitride layer 220 may be sequentially formed. The first and second silicon oxide layers 211'213' are made of silicon oxide, for example, silicon dioxide (SiO2). The first and second silicon nitride layers 220 and 214' may be formed of silicon nitride, and may be formed of the same thickness or different thicknesses from each other. The first silicon nitride layer 220 may be the pellicle film 220 illustrated in FIG. 4.

In the second step (S220), after forming a mask material layer on the second silicon nitride layer 214', the mask pattern 250 may be formed by patterning the mask material 250. Since the material and the manufacturing method are substantially the same as the mask pattern 150 described above, a duplicate detailed description thereof will be omitted.

In the third step (S230), the exposed areas of the second silicon nitride layer 214' and the second silicon oxide layer 213' are removed through a first reactive ion etching process using the mask pattern 250. By doing so, the silicon nitride frame portion 214 and the second silicon oxide frame portion 213. The first reactive ion etching process is performed using argon (Ar), oxygen (O2), and SF6 gas. Can be.

In the fourth step (S240), after removing the mask pattern 250 or while maintaining the mask pattern 250, the silicon nitride frame portion 214 and the second silicon oxide frame portion 213 The silicon frame portion 212 may be formed by removing the exposed region of the silicon substrate 212' through a radical etching process using as a mask. The radical etching process may include the pellicle illustrated in FIG. 1 previously described. Since it is substantially the same as the radical etching process applied in the method for manufacturing the structure, a duplicate detailed description thereof will be omitted.

Meanwhile, in the radical etching process, since the first silicon oxide layer 211 ′ is hardly etched by radicals, it can function as an etch stop layer for the radical etching process, and as a result, the During the radical etching process, it is possible to prevent the surface of the first silicon nitride layer 220 that is a pellicle film from being rough.

In the fifth step (S250), after removing the mask pattern 250 or while maintaining the mask pattern 250, the silicon nitride frame portion 214, the second silicon oxide frame portion 213 And removing the exposed region of the first silicon oxide layer 211 ′ through the second reactive ion etching process using the silicon frame portion 212 as a mask to form the first silicon oxide frame portion 211. The second reactive ion etching process may be performed using argon (Ar), oxygen (O2), and SF6 gas.

During the second reactive ion etching process, the first silicon nitride layer 220, which is the pellicle film, is hardly damaged and only the first silicon oxide layer 211' is removed, so that a pellicle film of excellent quality can be formed.

7 is a cross-sectional view illustrating a pellicle structure 300 according to another embodiment of the present invention.

Referring to FIG. 7, the pellicle structure 300 according to another embodiment of the present invention includes a pellicle film 320 and a frame support 310. The pellicle structure 300 according to the present embodiment has the pellicle structure described with reference to FIG. 5 except that the pellicle film 320 is formed of a stacked structure of a silicon nitride layer 321 and a multi-layer graphene film 322. Since it is substantially the same as 200), a duplicate detailed description thereof will be omitted.

The frame support 310 may be directly attached or coupled to the silicon nitride layer 321 of the pellicle film 320.

Hereinafter, a method of manufacturing the pellicle structure illustrated in FIG. 7 will be described.

8 is a flowchart illustrating a method of manufacturing the pellicle structure illustrated in FIG. 7, and FIGS. 9A to 9E are cross-sectional views illustrating a method of manufacturing the pellicle structure illustrated in FIG. 7.

Referring to FIGS. 8 and 9A to 9E together with FIG. 7, a method of manufacturing a pellicle structure according to another embodiment of the present invention includes a first silicon oxide layer 311 ′ made on a lower surface of a silicon substrate 312 ′. One silicon nitride layer 320, an amorphous carbon layer 322', a catalyst layer 330 and a capping layer 340 are sequentially formed, and a second silicon oxide layer 313' and an upper surface of the silicon substrate 312' are formed. A first step (S310) of sequentially forming a second silicon nitride layer 314'; A second step (S320) of changing the amorphous carbon layer 322' to a graphene layer; The catalyst layer 330 and the capping layer 340 Step 3 (S330) for removing ); Step 4 (S340) for forming a mask pattern 350 on the second silicon nitride layer 314'; First reactive ion etching using the mask pattern 350 The silicon nitride frame portion 314 and the second silicon oxide frame portion 313 are formed by removing exposed areas of the second silicon nitride layer 314 ′ and the second silicon oxide layer 313 ′ through a process. The fifth step (S350); the silicon frame by removing the exposed region of the silicon substrate 312' through a radical etching process using the silicon nitride frame portion 314 and the second silicon oxide frame portion 313 as a mask A sixth step (S360) of forming a portion 312; a second reactive ion etching using the silicon nitride frame portion 314, the second silicon oxide frame portion 313, and the silicon frame portion 312 as a mask. A seventh step (S370) of forming the first silicon oxide frame portion 311 by removing an exposed region of the first silicon oxide layer 311 ′ through a process may be included.

In the first step (S310), the process of forming the first silicon oxide layer 311' first silicon nitride layer 320, second silicon oxide layer 313' and second silicon nitride layer 314' is Formation of the first silicon oxide layer 211' first silicon nitride layer 220, second silicon oxide layer 213' and second silicon nitride layer 214' described with reference to FIGS. 5 and 6A to 6D. The process of forming the amorphous carbon layer 322' catalyst layer 330 and the capping layer 340 is substantially the same as the process, and the amorphous carbon layer 120' catalyst layer (described in reference to FIGS. 2 and 3A to 3F) 130) and the process of forming the capping layer 140 is substantially the same, so detailed descriptions thereof will be omitted.

In the second step (S320) and the third step (S330), the process of removing the catalyst layer 330 and the capping layer 340 after converting the amorphous carbon layer 322' into a graphene layer is shown in FIG. And the process of removing the catalyst layer 130 and the capping layer 140 after converting the amorphous carbon layer 120 ′ to the graphene layer described with reference to FIGS. 3A to 3F, and thus overlapping detailed Description is omitted.

The fifth step (S350), the sixth step (S360) and the seventh step (S370) are substantially the second steps (S220) to the fifth step (S250) described with reference to FIGS. 5 and 6A to 6D. Since it is the same, redundant detailed description of them is omitted.

According to the pellicle structure of the present invention and a method for manufacturing the same, not only can the silicon nitride film and/or graphene film acting as the pellicle film be significantly damaged in the manufacturing process, but also the process time for manufacturing the pellicle is significantly reduced I can do it.

Although described above with reference to the preferred embodiments of the present invention, those skilled in the art may variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that you can.

100: pellicle structure 110: frame support
111: silicone frame portion 112: diffusion preventing frame portion
120: graphene film

Claims (17)

A pellicle film formed of multilayer graphene; And
Includes a frame support attached to or coupled to the lower portion of the pellicle film, a through opening exposing the graphene film in the center portion,
The frame support may include a silicon frame portion formed of n-type dopant-doped crystalline silicon (n-type Si) or p-type dopant-doped crystalline silicon (p-type Si); And a diffusion preventing frame part having the same planar shape as the silicon frame part and having a thickness smaller than that of the silicon frame and disposed between the graphene film and the silicon frame part to prevent element diffusion between the silicon frame part and the graphene film. Pelicle structure, characterized in that it comprises. According to claim 1,
The pellicle film is characterized in that it has a thickness of 1 to 50 nm, pellicle structure. According to claim 1,
The silicon frame portion has a thickness of 700 to 800㎛, characterized in that the diffusion-prevention frame portion has a thickness of 25 nm or more and 1 μm or less, a pellicle structure. According to claim 1,
The diffusion preventing frame portion is characterized in that formed of silicon oxide (SiOx) or silicon nitride (SiNx), a pellicle structure. A first step of sequentially forming a diffusion barrier layer, an amorphous carbon layer, a metal catalyst layer, and a capping layer formed of a metal having a higher melting point than the metal of the metal catalyst layer on a silicon substrate;
A second step of converting the amorphous carbon layer to a graphene layer by heat treatment;
A third step of removing the catalyst layer and the capping layer;
A fourth step of forming a mask pattern on the bottom surface of the silicon substrate;
A fifth step of forming a frame support by etching the silicon substrate and the diffusion barrier layer region exposed by the mask pattern through a radical etching process; And
And a sixth step of removing the mask pattern. The method of claim 5,
The silicon substrate is characterized in that it comprises a single crystal silicon wafer doped with phosphorus (P), arsenic (As) or antimony (Sb) of 0.0000015% or more and 0.3% or less, a method of manufacturing a pellicle structure. The method of claim 5,
The diffusion barrier layer is characterized in that formed by depositing a silicon oxide (SiOx) or silicon nitride (SiNx) to a thickness of 25 nm or more and 1 μm or less, a method of manufacturing a pellicle structure. The method of claim 5,
The catalyst layer is formed of nickel (Ni), the capping layer is characterized in that formed of tungsten (W), molybdenum (Mo) or tantalum (Ta), a method of manufacturing a pellicle structure. The method of claim 5,
Heat treatment for converting the amorphous carbon layer to the graphene layer is characterized in that is carried out in a hydrogen (H2), nitrogen (N2) or inert gas atmosphere at 700 to 1000 ℃, the method of manufacturing a pellicle structure. The method of claim 5,
The mask pattern is characterized in that it is formed of silicon oxide (SiO2), silicon nitride (SiNx), PDMS or metal, a method of manufacturing a pellicle structure. The method of claim 5,
The fifth step is characterized in that it is performed using radicals extracted from one or more plasmas selected from the group consisting of ClF ₃ , ClF ₂ , ClF, Cl ₂ , CF ₄ , C ₄ F ₈ , SF ₆ and N _X O. A method of manufacturing a pellicle structure. A pellicle film formed of a silicon nitride film; And
Includes a frame support attached to or coupled to the lower portion of the pellicle film, a through opening exposing the graphene film in the center portion,
The frame support includes a first silicon oxide frame portion to which the pellicle film is directly attached or coupled; A silicon frame portion formed of crystalline silicon (n-type Si) doped with an n-type dopant material or doped crystalline silicon doped with a p-type dopant material (p-type Si); A second silicon oxide frame portion stacked on the silicon frame portion; And a silicon nitride frame portion stacked on the second silicon oxide frame portion. A first silicon oxide layer and a first silicon nitride layer are sequentially formed on a lower surface of the silicon substrate, and a second silicon oxide layer and a second silicon nitride layer are sequentially formed on the upper surface of the silicon substrate. step;
A second step of forming a mask pattern on the second silicon nitride layer;
A third step of forming a silicon nitride frame portion and a second silicon oxide frame portion by removing exposed areas of the second silicon nitride layer and the second silicon oxide layer through a first reactive ion etching process using the mask pattern;
A fourth step of forming a silicon frame part by removing an exposed region of the silicon substrate through a radical etching process using the silicon nitride frame part and the second silicon oxide frame part as a mask;
The silicon nitride frame portion, the second silicon oxide frame portion, and the first silicon oxide frame portion are formed by removing the exposed region of the first silicon oxide layer through a second reactive ion etching process using the silicon frame portion as a mask. A method of manufacturing a pellicle structure comprising the fifth step. The method of claim 13,
The first and second reactive ion etching processes are performed using ions generated using argon (Ar), oxygen (O2), and SF6 gas,
The radical etching process is performed using radicals extracted from one or more plasmas selected from the group consisting of ClF ₃ , ClF ₂ , ClF, Cl ₂ , CF ₄ , C ₄ F ₈ , SF ₆ and N _X O Characterized in that, the method of manufacturing a pellicle structure. The method of claim 13,
During the radical etching process, the first silicon oxide layer is characterized in that it functions as an etch stop layer (etch stop layer), a method of manufacturing a pellicle structure. A pellicle film including a stacked structure of a silicon nitride film and a multilayer graphene; And
The silicon nitride film is attached to or attached to the lower portion, and includes a frame support having a through opening exposing the graphene film in the center portion,
The frame support includes a first silicon oxide frame portion to which the silicon nitride film is directly attached or coupled; A silicon frame formed on the first silicon oxide frame portion and formed of crystalline silicon doped with n-type dopant material (n-type Si) or crystalline silicon doped with p-type dopant material (p-type Si); A second silicon oxide frame portion stacked on the silicon frame portion; And a silicon nitride frame portion stacked on the second silicon oxide frame portion. A first silicon oxide layer, a first silicon nitride layer, an amorphous carbon layer, a catalyst layer and a capping layer are sequentially formed on a lower surface of the silicon substrate, and a second silicon oxide layer and a second silicon on the upper surface of the silicon substrate A first step of sequentially forming a nitride layer;
A second step of changing the amorphous carbon layer to a graphene layer;
A third step of removing the catalyst layer and the capping layer;
A fourth step of forming a mask pattern on the second silicon nitride layer;
A fifth step of forming a silicon nitride frame portion and a second silicon oxide frame portion by removing exposed areas of the second silicon nitride layer and the second silicon oxide layer through a first reactive ion etching process using the mask pattern;
A sixth step of forming a silicon frame part by removing an exposed region of the silicon substrate through a radical etching process using the silicon nitride frame part and the second silicon oxide frame part as a mask;
The silicon nitride frame portion, the second silicon oxide frame portion, and the first silicon oxide frame portion are formed by removing the exposed region of the first silicon oxide layer through a second reactive ion etching process using the silicon frame portion as a mask. A method of manufacturing a pellicle structure comprising the seventh step.

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