JP7317472B2 - Pellicle for photomask, reticle including the same, and method for manufacturing pellicle for photomask - Google Patents

Description

The present invention relates to a photomask pellicle, a reticle including the same, and a method of manufacturing a photomask pellicle.

A photomask pellicle is provided in the form of a film on a photomask to protect the photomask from external contaminants (eg, dust, resist, etc.) during an optical lithography process. Such a pellicle for a photomask should have a high transmittance for light used in a lithography process, and various aspects such as heat dissipation properties, strength, uniformity, durability, and stability are required. must meet the requirements of As the line width of semiconductor devices/electronic circuits decreases, the wavelength of the light used in the lithography process becomes shorter. There is

The problem to be solved by the present invention is to provide a pellicle material suitable for light sources used in optical lithography processes.
The problem to be solved by the present invention is to provide a photomask pellicle that protects a photomask from external contamination, a reticle including the same, and a method of manufacturing such a photomask pellicle.

A photomask pellicle according to one aspect is a photomask pellicle for protecting a photomask,
A substrate, a metal catalyst layer provided on the substrate, and a pellicle membrane containing a two-dimensional (2D) material provided on the metal catalyst layer.

The pellicle membrane can have a central region and an edge region, the edge region at least partially surrounding the central region.

The substrate and the metal catalyst layer collectively support the edge regions of the pellicle membrane and do not support the central region.

The thickness of the metal catalyst layer is also 10 nm to 100 μm.

The thickness of the metal catalyst layer is also between 10 nm and 10 μm.

The pellicle may further include a barrier layer provided between the substrate and the metal catalyst layer.

The barrier layer may include at least one of _SiO2 , _Si3N4 , TiN and TaN _.

The 2D material may include at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene.

The thickness of the pellicle membrane is also between 5 nm and 50 nm.

The metal catalyst layer includes platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd) and ruthenium (Ru). may include at least one of

The light transmittance of the pellicle membrane is also above 80%.

The combined height of the metal catalyst layer and the substrate is also 1 mm to 10 mm.

A protective film may be provided on at least one surface of the pellicle membrane.

The protective film is a carbon-based material, transition metal dichalcogenide (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron (B), and silicon nitride (SiN). At least one may be included.

A method for manufacturing a pellicle for a photomask according to one aspect is a method for manufacturing a pellicle for a photomask for protecting a photomask, comprising:
forming a metal catalyst layer on a substrate; forming a pellicle membrane on the metal catalyst layer; the substrate supporting a central region of the pellicle membrane; and an inner region of the metal catalyst layer. and etching.

The pellicle membrane may comprise a two-dimensional (2D) material. The pellicle membrane includes a central region and an edge region, the edge region at least partially surrounding the central region.

The substrate and the metal catalyst layer collectively support the edge regions of the pellicle membrane and do not support the central region.

The method may further include forming a barrier layer on the substrate.

The method may further include forming a protective layer on at least one surface of the pellicle membrane.

The pellicle membrane is directly formed on the metal catalyst layer.

Etching the substrate and the metal catalyst layer may be performed by at least one of mechanical etching, dry etching, and wet etching.

Another aspect of a method for manufacturing a pellicle for a photomask is a method for manufacturing a pellicle for a photomask for protecting a photomask, comprising:
forming a barrier layer on a substrate; forming a metal catalyst layer on the barrier layer; and forming a pellicle membrane containing a 2D material between the metal catalyst layer and the barrier layer. removing the metal catalyst layer; and etching inner regions of the substrate and the barrier layer supporting a central portion of the pellicle membrane.

The pellicle membrane includes a central region and an edge region, the edge region at least partially surrounding the central region.

The substrate and the barrier layer collectively support the edge regions of the pellicle membrane and do not support the central region.

The method may further include forming a protective layer on at least one surface of the pellicle membrane.

Removing the metal catalyst layer and etching the substrate and the barrier layer may be performed by at least one of mechanical etching, dry etching, and wet etching.

A reticle according to one aspect includes a photomask containing a mask pattern and a pellicle.

The pellicle may include a substrate, a metal catalyst layer provided on the substrate and surrounding the mask pattern, and a pellicle membrane including a two-dimensional (2D) material. The pellicle membrane may include a central region and an edge region, the edge region at least partially surrounding the central region. The edge region is supported by the substrate and the metal catalyst layer, and the central region is unsupported by the substrate and the metal catalyst layer.

The photomask is separated from the pellicle membrane by 1 mm to 10 mm.

The thickness of the metal catalyst layer is also 10 nm to 100 μm.

The thickness of the metal catalyst layer is also between 10 nm and 10 μm.

A barrier layer may be provided between the substrate and the metal catalyst layer.

The barrier layer may include at least one of _SiO2 , _Si3N4 , TiN and TaN _.

The 2D material may include at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene.

The thickness of the pellicle membrane is also between 5 nm and 50 nm.

The metal catalyst layer includes platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd) and ruthenium (Ru). may include at least one of

The light transmittance of the pellicle membrane is also above 80%.

A protective film may be provided on at least one surface of the pellicle membrane.

The protective film includes at least carbon-based material, transition metal dichalcogenide (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron (B), and silicon nitride (SiN). may contain one.

According to one aspect, a pellicle for photomask protection includes a metal catalyst layer and a pellicle membrane overlying the metal catalyst layer. The pellicle membrane may include a two-dimensional (2D) material and have a central region and edge regions. The edge region can at least partially surround the central region. The metal catalyst layer supports the edge regions of the pellicle membrane and does not support the central region.

The pellicle further includes a substrate, wherein the metal catalyst layer is on the substrate, the substrate and the metal catalyst layer collectively supporting the edge regions of the pellicle membrane and the central Do not support territory.

The pellicle may further include a barrier layer between the substrate and the metal catalyst layer.

According to one aspect, a method of manufacturing a pellicle for photomask protection includes forming a pellicle membrane on a metal catalyst layer. The pellicle membrane may comprise a two-dimensional (2D) material. The pellicle membrane may include a central region and edge regions. The edge region can at least partially surround the central region. The method may further comprise etching at least an inner region of the metal catalyst layer supporting the central region of the pellicle membrane. Thus, the metal catalyst layer supports the edge regions of the pellicle membrane and does not support the central region.

The method may further comprise forming the metal catalyst layer on a substrate. The etching step then etches the substrate supporting the central region of the pellicle membrane and an inner region of the metal catalyst layer, whereby the substrate and the metal catalyst layer collectively: The edge regions of the pellicle membrane are supported and the central region is unsupported.

The method may further comprise forming a barrier layer on the substrate.

The method may further comprise forming a protective coating on at least one surface of the pellicle membrane.

Forming the pellicle membrane may include forming the pellicle membrane directly on the surface of the metal catalyst layer.

According to the present invention, the pellicle membrane, which protects the photomask from external contamination sources, has excellent physico-chemical durability that is not damaged by exposure to light in the extreme ultraviolet (EUV) region for a certain period of time or by surface cleaning processes. can have

In addition, after the 2D material is directly formed on the metal catalyst layer, the metal catalyst layer is selectively removed to form a pellicle membrane, thereby removing the pellicle membrane without a transfer process. can be formed.

Also, the metal catalyst layer and the substrate selectively removed for forming the pellicle membrane are also used as a frame for supporting the pellicle membrane.

In addition, by forming a protective film on at least one surface of the pellicle membrane, the durability of the pellicle membrane can be further improved, and deformation of the pellicle membrane that can occur due to heat accumulation can be minimized. , the life of the pellicle can be extended.

1 is a drawing schematically illustrating an exposure apparatus according to an exemplary embodiment; 1 is a diagram illustrating a pellicle for a photomask according to one embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to an embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to an embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to an embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to an embodiment; FIG. 4 is a diagram illustrating a pellicle for a photomask according to another embodiment; FIG. 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to another embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to another embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to another embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to another embodiment; 3A to 3D are diagrams illustrating steps of a method of manufacturing a pellicle for a photomask according to another embodiment; FIG. 10 is a diagram illustrating a pellicle for a photomask according to another embodiment; FIG. 4A to 4D are diagrams illustrating a method of manufacturing a pellicle for a photomask according to another embodiment; 4A to 4D are diagrams illustrating a method of manufacturing a pellicle for a photomask according to another embodiment; 4A to 4D are diagrams illustrating a method of manufacturing a pellicle for a photomask according to another embodiment; 4A to 4D are diagrams illustrating a method of manufacturing a pellicle for a photomask according to another embodiment; 4A to 4D are diagrams illustrating a method of manufacturing a pellicle for a photomask according to another embodiment; 4A to 4D are diagrams illustrating a method of manufacturing a pellicle for a photomask according to another embodiment; 5A to 5D are cross-sectional views showing steps of a method of manufacturing a pellicle for a photomask according to still another embodiment; 5A to 5D are cross-sectional views showing steps of a method of manufacturing a pellicle for a photomask according to still another embodiment; 5A to 5D are cross-sectional views showing steps of a method of manufacturing a pellicle for a photomask according to still another embodiment;

Embodiments are described in detail below with reference to the accompanying drawings so that those skilled in the art can easily implement them. However, many different forms may be implemented and should not be limited to the embodiments set forth herein. In the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

Throughout the specification, when a part "includes" a component, it does not exclude other components, and may further include other components, unless specifically stated to the contrary. That means.

FIG. 1 schematically depicts an exposure apparatus 99 according to an exemplary embodiment.

Referring to FIG. 1, an exposure device 99 is used for a photolithography process, that is, it can perform a photolithography process, and uses light of a predetermined wavelength to form an image on a substrate 70 . A resist layer 80 may be patterned. The exposure apparatus 99 includes a light source 90 emitting light of a predetermined wavelength, a photomask 30 for exposing the resist layer 80 using the light emitted from the light source 90, and a photomask 30 for protecting the photomask 30. pellicle 60 of.

The light source 90 can emit light in a short wavelength region for forming fine patterns on the resist layer 80 . Specifically, the light source 90 may emit light in the extreme ultraviolet (EUV) region having a wavelength of approximately 13.3 nm.

Light in the extreme ultraviolet (EUV) region emitted from the light source 90 is incident on the reticle 95 . Here, the reticle 95 means a structure in which the photomask 30 and the pellicle 60 are combined. On the other hand, although not shown in the drawing, on the optical path between the light source 90 and the reticle 95, for example, light in the extreme ultraviolet (EUV) region emitted from the light source 90 is uniformly incident on the reticle 95. For this purpose, further optics such as a collimating lens may be provided.

The photomask 30 may expose the resist layer 80 formed on the substrate 70 using extreme ultraviolet (EUV) light emitted from the light source 90 . The photomask 30 may include a mask substrate 20 and a mask pattern 10 provided in a predetermined shape on one surface of the mask substrate 20 . Also, the pellicle 60 is provided under the mask substrate 20 so as to cover the mask pattern 10 .

Photomask 30 may include a reflective photomask. In that case, the light in the extreme ultraviolet (EUV) region emitted from the light source 90 passes through the pellicle 60 and enters the photomask 30, and the light in the extreme ultraviolet (EUV) region reflected by the photomask 30 passes through the pellicle 60. , and strikes the resist layer 80 on the substrate 70 . Here, the mask substrate 20 may include a reflective layer that reflects light in the extreme ultraviolet (EUV) region, and the mask pattern 10 may include an absorption pattern that absorbs light in the extreme ultraviolet (EUV) region. On the other hand, although not shown in the drawings, a focusing lens for focusing light in the extreme ultraviolet (EUV) region emitted from the reticle 95 is provided on the optical path between the reticle 95 and the resist layer 80, for example. An optical system such as may be further provided.

The pellicle 60 is installed under the photomask 30 to prevent external contaminants such as dust and resist from adhering to the photomask 30 and protect the photomask 30 . To this end, the pellicle 60 may include a pellicle membrane 40 spaced apart from the photomask 30 by a predetermined distance. Pellicle 60 and photomask 30 thereby delimit an intervening space 44 . Intervening space 44 is between pellicle membrane 40 and photomask 30 . The pellicle membrane 40 may be separated from the photomask 30 by about several millimeters. For example, the distance between the pellicle membrane 40 and the photomask 30 is approximately 1 mm to 10 mm.

A frame 50 may be provided between the pellicle membrane 40 and the photomask 30 . Here, the frame 50 is installed at the edge portion of the photomask 30, and serves to support the pellicle membrane 40 and the photomask 30 with a fixed gap. For example, the height of the frame 50 is about 1 mm to 10 mm so that the distance between the pellicle membrane 40 and the photomask 30 is about 1 mm to 10 mm. A description of the layers forming the frame 50 will be given later.

In the exposure apparatus 99 having the structure described above, light in the extreme ultraviolet (EUV) region emitted from the light source 90 passes through the pellicle membrane 40, is incident on the photomask 30, and is reflected by the photomask 30 as extreme ultraviolet (EUV) light. The light in the EUV) region passes through the pellicle membrane 40 and is incident on the resist layer 80 formed on the substrate 70, thereby performing the exposure process. That is, the exposure device 99 is provided to perform the exposure process.

On the other hand, in the exposure apparatus 99 shown in FIG. 1, a case where a reflective photomask is used as the photomask 30 is illustrated as an example. However, it is not limited to this, and the photomask 30 can also be a transmissive photomask. In that case, the mask substrate 20 may include a transmissive layer that transmits incident light, and the mask pattern 10 may include an absorption pattern that absorbs incident light.

Pellicle 60 illustrated in FIG. 1 can be any of the pellicles described therein and can be any of the pellicles illustrated by any one of the drawings described herein.

In other words, the exposure apparatus 99 according to the exemplary embodiment uses the pellicle 60, which is one of the pellicles described herein, and one of the pellicles illustrated in one of the drawings described herein. A reticle 95 may be included.

FIG. 2 illustrates a photomask pellicle according to one embodiment.

Referring to FIG. 2, the pellicle 100 can perform the same role as the pellicle 60 including the pellicle membrane 40 and the frame 50 shown in FIG. The pellicle 100 may be provided on the mask substrate so as to cover the mask pattern of the photomask.

Pellicle 100 includes substrate 110 , metal catalyst layer 120 formed on substrate 110 , and pellicle membrane 130 . Also, the metal catalyst layer 120 on the substrate 110 can support one or more edge portions 130 e of the pellicle membrane 130 . In other words, the central portion 130c of the pellicle membrane 130 does not have the metal catalyst layer 120 and the substrate 110 formed thereon, and is supported only by one or more edge portions 130e. The substrate 110 and metal catalyst layer 120 so formed can act like the frame 50 of FIG. can surround the mask pattern 10 in combination with the photomask 30 to at least partially define the .

The "central region" of a pellicle membrane is also referred to as the "central portion" of said pellicle membrane. The "edge region" of a pellicle membrane is also referred to as the "edge portion" of said pellicle membrane. According to one embodiment, edge region 130 e of pellicle membrane 130 can at least partially surround central region 130 c of pellicle membrane 130 . For example, edge region 130e of pellicle membrane 130 can at least partially and/or completely surround central region 130c of pellicle membrane 130, as illustrated in FIG.

In other words, the pellicle membrane 130 on the metal catalyst layer 120 may comprise two-dimensional (2D) material. Pellicle membrane 130 can have a central region 130c and an edge region 130e, with edge region 130e at least partially surrounding central region 130c. Substrate 110 and metal catalyst layer 120 can collectively support edge region 130 e of pellicle membrane 130 and not support central region 130 c of pellicle membrane 130 .

The combined height of the substrate 110 and the metal catalyst layer 120 is about 1 mm to 10 mm so that the pellicle membrane 130 and the photomask are separated by a predetermined distance.

The metal catalyst layer 120 provided on the substrate 110 includes platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium ( Pd) and at least one of ruthenium (Ru). The thickness of the metal catalyst layer 120 is also 100 μm or less, for example, 10 nm or more and 100 μm or less. In another embodiment, the thickness of the metal catalyst layer 120 is also between 10 nm and 10 μm.

The pellicle membrane 130 can be formed by directly growing a material on the surface 120 a of the metal catalyst layer 120 . The pellicle membrane 130 may include a material having a two-dimensional shape crystal structure, ie, a 2D material. For example, the pellicle membrane 130 may include a 2D material including at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene. Also, the thickness of the pellicle membrane 130 is approximately 5 nm to 50 nm.

The pellicle membrane 130 can have high physico-chemical durability and optical transparency. For example, the light transmittance of a pellicle membrane is approximately 80% or more.

A protective film is formed on at least one of both surfaces 130 a and 130 b of the pellicle membrane 130 . Such a protective layer further enhances the durability of the pellicle membrane 130 in an exposure process using light in the extreme ultraviolet (EUV) region, and reduces or minimizes deformation of the pellicle membrane 130 that may occur due to heat accumulation. You can let In addition, the protective film provides excellent physical and chemical durability to the pellicle membrane 130 so that the pellicle membrane 130 is not damaged by exposure to light in the extreme ultraviolet (EUV) region for a certain period of time or by surface cleaning processes. can be given.

The protective film can be carbon-based materials, two-dimensional (2D) materials, transition metal dichalcogenides (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron ( B) and at least one of silicon nitride (SiN). Here, the carbon-based material includes, for example, amorphous carbon, graphene, nano graphite, carbon nanosheet, carbon nanotube, SiC and B4C. At least one of them may be included. The TMD includes metal elements, for example, one of Mo, W, Nb, V, Ta, Ti, Zr, Hf, Tc and Re and one of S, Se and Te as a chalcogen element. It's okay. The 2D material may include one of Cu, Ga, In, Sn, Ge, and Pb.

The pellicle membrane 130 and the edge regions of the protective films formed on both sides of the pellicle membrane 130 are also supported by the metal catalyst layer 120 and the substrate 110 . Accordingly, metal catalyst layer 120 and substrate 110 can collectively support at least one edge region 130 e of pellicle membrane 130 and not central region 130 c of pellicle membrane 130 . In other words, the metal catalyst layer 120 and the substrate 110 can act as the frame 50 of FIG.

3A-3D illustrate a step-by-step method for manufacturing a photomask pellicle according to one embodiment.

3A and 3B, a metal catalyst layer 120 is formed on a substrate 110. As shown in FIG. _The substrate 110 may also be made of materials such as Si, glass, quartz, _Al2O3 . Metal catalyst layer 120 includes platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd) and ruthenium (Ru). may include at least one of The thickness of the metal catalyst layer 120 is also 100 μm or less, for example, 10 nm or more and 10 μm or less.

Referring to FIG. 3C, a pellicle membrane 130 containing a 2D material is formed on the surface 120a of the metal catalyst layer 120. Referring to FIG.

The pellicle membrane 130 may be formed directly on the surface 120a of the metal catalyst layer 120, as illustrated in FIG. 3C. As described herein, in other embodiments, the pellicle membrane 130 may also be formed indirectly on the metal catalyst layer 120, in which case the metal catalyst layer 120 and the pellicle membrane 130 are interposed between the metal catalyst layer 120 and the pellicle membrane 130. There may also be an intervening layer (eg, protective layer 150 described below).

When the pellicle membrane 130 is formed directly on the surface of the material layer, for example, when formed directly on the surface 120a of the metal catalyst layer 120, the pellicle membrane 130 grows directly on the surface 120a of the metal catalyst layer 120. be done.

The pellicle membrane 130 may include a material having a two-dimensional shape crystal structure, ie, a 2D material. For example, the pellicle membrane 130 may include at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene. Also, the thickness of the pellicle membrane 130 is approximately 5 nm to 50 nm.

Pellicle membrane 130 may also be formed by methods such as chemical vapor deposition (CVD) and physical vapor deposition (PVD).

Also, in FIG. 3C, a protective film may first be formed on the metal catalyst layer 120 before forming the pellicle membrane 130 on the metal catalyst layer 120 . After forming the protective film, a pellicle membrane 130 is formed on the protective film, and a protective film (eg, protective film 150 as shown in FIG. 3D) is further formed on the surface 130a of the pellicle membrane 130. can do. That is, the protective film is also formed on both surfaces 130 a and 130 b of the pellicle membrane 130 . A protective film 150 may be formed between the pellicle membrane 130 and the metal catalyst layer 120 of FIG. 3C on the surface 130a of the pellicle membrane 130 of FIG. 3D, in addition to or instead of the protective film 150 previously described. However, it is not limited thereto, and the protective film may be formed only on one side of the pellicle membrane 130 . As such, when a protective layer is formed on at least one surface of the pellicle membrane 130 , the protective layer may have a surface roughness similar to that of the pellicle membrane 130 .

Referring to FIG. 3D, at least the inner regions 110b, 120b of the substrate 110 and the metal catalyst layer 120 supporting the central region 130c of the pellicle membrane 130 are etched (eg, selectively removed). The remaining regions of substrate 110 and metal catalyst layer 120 thereby collectively support one or more edge regions 130 e of pellicle membrane 130 and do not support central region 130 c of pellicle membrane 130 . Accordingly, one or more edge regions 130 e of pellicle membrane 130 are understood to be supported by metal catalyst layer 120 and substrate 110 , and central region 130 c of pellicle membrane 130 is understood to be supported by metal catalyst layer 120 and substrate 110 . It is understood that it is not

The remaining regions of substrate 110 and metal catalyst layer 120 that collectively support one or more edge regions 130e of pellicle membrane 130 and do not support central region 130c of pellicle membrane 130 (see FIG. 3D). The remainder region) is simply the substrate 110 and the metal catalyst layer 120 . The substrate 110 and the metal catalyst layer 120 are subjected to at least one of mechanical etching, dry etching and wet etching.

Through the etching steps described above, the substrate 110 and the metal catalyst layer 120 can act as a frame that supports one or more edge regions 130e of the pellicle membrane 130 and does not support the central region 130c of the pellicle membrane 130. . As mentioned herein, and as illustrated at least in FIG. 3D, the layers described as not supporting the central region of the pellicle membrane directly support one or more edge regions of the pellicle membrane, and the It does not directly support the central region of the pellicle membrane, but is also understood to indirectly support the central region of the pellicle membrane via the one or more edge regions of the pellicle membrane.

For example, as illustrated in FIG. 3D, metal catalyst layer 120 and substrate 110 are understood to collectively directly support one or more edge regions 130e of pellicle membrane 130 and center region 130c of pellicle membrane 130. While not collectively providing direct support, it is also understood to indirectly support central region 130c through one or more edge regions 130e. Accordingly, it can be seen that metal catalyst layer 120 and substrate 110 collectively support one or more edge regions 130 e of pellicle membrane 130 and do not support central region 130 c of pellicle membrane 130 .

FIG. 4 illustrates a photomask pellicle according to another embodiment.

Referring to FIG. 4, the pellicle 200 can perform the same function as the pellicle 60 including the pellicle membrane 40 and the frame 50 shown in FIG.

Pellicle 200 includes substrate 210 , barrier layer 220 formed on substrate 210 , metal catalyst layer 230 formed on barrier layer 220 , and pellicle membrane 240 . As illustrated in FIG. 4, barrier layer 220 is between substrate 210 and metal catalyst layer 230 . Substrate 210 , barrier layer 220 and metal catalyst layer 230 support only one or more edge regions 240 e of pellicle membrane 240 and do not support central region 240 c of pellicle membrane 240 . That is, central region 240c is supported only indirectly through one or more edge regions 240e.

The barrier layer 220 provided on the substrate 210 may further firmly bond the metal catalyst layer 230 and the substrate 210 together. Through this, the durability of the pellicle 200 can be further improved. The barrier layer 220 may include at least one of _SiO2 , _Si3N4 , TiN and TaN _.

The metal catalyst layer 230 formed on the barrier layer 220 may be platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium At least one of (Pd) and ruthenium (Ru) may be included.

The structures and materials of the substrate 210, the metal catalyst layer 230, and the pellicle membrane 240 except for the barrier layer 220 are the same as those described with reference to FIG.

5A through 5E are step-by-step illustrations of a method of manufacturing a pellicle for a photomask according to another embodiment.

Referring to FIGS. 5A and 5B, a barrier layer 220 is formed on substrate 210 . _The substrate 210 may also be made of materials such as Si, glass, quartz, _Al2O3 . The barrier layer 220 may include at least one of _SiO2 , _Si3N4 , TiN and TaN _.

Referring to FIG. 5C, a metal catalyst layer 230 is formed on the barrier layer 220 . The metal catalyst layer 230 may be platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd) and ruthenium (Ru). may include at least one of

Referring to FIG. 5D, a pellicle membrane 240 containing a 2D material is directly or indirectly formed on the surface 230a of the metal catalyst layer 230. Referring to FIG. Pellicle membrane 240 may also be formed by methods such as chemical vapor deposition (CVD), physical vapor deposition (PVD), and the like.

Referring to FIG. 5E, the inner regions 210b, 220b and 230b of the substrate 210, the barrier layer 220 and the metal catalyst layer 230 supporting the central portion 240c of the pellicle membrane 240 are etched, respectively. The substrate 210, the barrier layer 220 and the metal catalyst layer 230 are also etched by at least one of mechanical etching, dry etching and wet etching.

Through the etching steps described above, the remaining regions of substrate 210, barrier layer 220, and metal catalyst layer 230 directly support one or more edge regions 240e of pellicle membrane 240, as shown in FIG. 5E; A central region 240c of the pellicle membrane 240 can act as a non-supporting frame directly.

FIG. 6 illustrates a photomask pellicle according to still another embodiment.

Referring to FIG. 6, the pellicle 300 can perform the same role as the pellicle 60 including the pellicle membrane 40 and the frame 50 shown in FIG.

Pellicle 300 includes substrate 310 , barrier layer 320 formed over substrate 310 , and pellicle membrane 330 . Substrate 310 and barrier layer 320 may perform the role of frame 50 of FIG. 1 supporting one or more edge regions 330 e of pellicle membrane 330 .

7A through 7F are step-by-step illustrations of a method of manufacturing a pellicle for a photomask according to still another embodiment.

Referring to FIGS. 7A and 7B, a barrier layer 320 is formed on substrate 310 . _The substrate 310 may also be made of materials such as Si, glass, quartz, _Al2O3 . The barrier layer 320 may include at least one of _SiO2 , _Si3N4 , TiN and TaN _.

Referring to FIG. 7C, a metal catalyst layer 340 is formed on the barrier layer 320 . The metal catalyst layer 340 may be platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd), and ruthenium (Ru ) may include at least one of

Referring to FIG. 7D, a pellicle membrane 330 containing 2D material is directly or indirectly formed on the lower portion of the metal catalyst layer 340, eg, on the lower surface 340f. For example, pellicle membrane 330 is formed between metal catalyst layer 340 and barrier layer 320 . The pellicle membrane 330 may include a material having a two-dimensional shape crystal structure, ie, a 2D material. For example, the pellicle membrane 330 may include at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene. If the 2D material constituting the pellicle membrane 330 is deposited on the metal catalyst layer 340 using a method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), the 2D material is a metal Penetrates inside the catalyst layer 340 . At this time, the pellicle membrane 330 including the 2D material is formed below the metal catalyst layer 340 by controlling the material forming the lower barrier layer 320 and controlling the process temperature and pressure.

Referring to FIG. 7E, the metal catalyst layer 340 is removed. At least one of mechanical etching, dry etching, and wet etching is used to remove the metal catalyst layer 340 . In other words, the metal catalyst layer 340 is removed using at least one of a mechanical etching method, a dry etching method, and a wet etching method.

Referring to FIG. 7F, substrate 310 supporting central region 330c of pellicle membrane 330 and inner regions 310b and 320b of barrier layer 320 are etched, respectively. Etching of the substrate 310 and the barrier layer 320 may also be performed by at least one of mechanical etching, dry etching, and wet etching.

Through the aforementioned etching steps, substrate 310 and barrier layer 320 directly support one or more edge regions 330e of pellicle membrane 330 and central region 330c of pellicle membrane 330 does not.

8A-8C are cross-sectional views illustrating a method of manufacturing a pellicle for a photomask according to an exemplary embodiment.

In an exemplary embodiment, the metal catalyst layer may also act as a substrate. Alternatively, the substrate may act as the metal catalyst layer. Therefore, the substrate as a separate element from the metal catalyst layer is omitted from the pellicle.

Referring to FIG. 8A, a substrate 410 is prepared to serve as a metal catalyst layer. The substrate 410 may include a material including at least one of Pt, Cu, Ni, Co, Ag, W, Mo, Pd and Ru. In one embodiment, the substrate 410 can have a thickness of 100 μm or less, but for example greater than 10 nm and less than 10 μm. Accordingly, the substrate 410 is also referred to as a "metal catalyst layer" having some or all of the properties and/or characteristics of the metal catalyst layer described above.

Referring to FIG. 8B, a pellicle membrane 430 containing 2D material is formed directly on surface 410a of substrate 410. Referring to FIG. Pellicle membrane 430 may include a material having a two-dimensional type crystal structure, ie, a 2D material. For example, the pellicle membrane 430 may include at least one of h-BN, Si, P, B, and graphene. Also, the pellicle membrane 430 can have a thickness of 5 nm to 50 nm.

Pellicle membrane 430 may also be formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD) methods.

Also in FIG. 8B, prior to forming pellicle membrane 430 on substrate 410, a protective film (not shown) may be formed on surface 410a of substrate 410. As shown in FIG. After forming the protective film, a pellicle membrane 430 is formed on the protective film. A protective coating is also formed on the surface of the pellicle membrane 430 remote from the substrate. That is, the protective film is also formed on the facing surface of the pellicle membrane 430 . However, an embodiment is not so limited. That is, the protective film may be formed only on individual surfaces of the pellicle membrane 430 . When a protective film is formed on at least one surface of the pellicle membrane 430 by such a method, the protective film has a surface roughness similar to that of the pellicle membrane 430. be able to.

As illustrated in FIG. 8B, a pellicle membrane 430 is formed over a restricted area 410b of the surface 410a of the substrate 410, thus exposing an edge area 410e of the substrate 410. As shown in FIG. The pellicle membrane 430 is also formed on the restricted area 410b of the substrate 410 to have a particular or predetermined shape and/or size.

Referring to FIG. 8C, at least the inner region 410c of the restricted region 410b of the substrate 410 supporting the central region 430c of the pellicle membrane 430 is etched. That is, inner region 410c is selectively removed. A remaining region 410r of the restricted region 410b of the substrate 410 thereby remains. In addition, one or more edge regions 410e of exposed substrate 410 around pellicle membrane 430 are etched, as shown in FIG. 8C. Thus, the outer sides 430d, 410d of pellicle membrane 430 and substrate 410 are flat or substantially flat. That is, the outer sides 430d, 410d are flat within manufacturing tolerances and/or material tolerances. The substrate 410 is etched using at least one of a mechanical etching method, a dry etching method, and a wet etching method.

Through such an etching process, the remaining region 410r of the substrate 410 directly supports one or more edge regions 430e of the pellicle membrane 430, and the central region 430c of the pellicle membrane 430 does not directly support (i.e., one or more The edge region 430e can serve as a frame that indirectly supports the central region 430c. Thus, a pellicle 800 is formed that includes the pellicle membrane 430 and the remaining region 410r of the substrate 410, as illustrated in FIG. 8C.

In the above method of manufacturing a pellicle for a photomask, the pellicle membrane is directly formed on the material layer using a growth method instead of being formed by the existing transfer method. For example, when the pellicle membrane is the pellicle membrane 130 of FIG. 3C and the material film is the metal catalyst layer 120, the pellicle membrane 130 is formed by an existing transfer method or by a direct growth method. There is a difference in adhesion between the pellicle membrane 130 and the metal catalyst layer 120 when formed.

According to an experimental example, when the pellicle membrane 130 was formed on the metal catalyst layer 120 by a conventional transfer method, the adhesive force between the pellicle membrane 130 and the metal catalyst layer 120 was about 180 MPa.

On the other hand, when the pellicle membrane 130 was formed on the surface 120a of the metal catalyst layer 120 by direct growth, the adhesion between the pellicle membrane 130 and the metal catalyst layer 120 was about 1,200 MPa. Through these experimental results, the adhesion between the pellicle membrane 130 and the metal catalyst layer 120 is higher than that when the pellicle membrane 130 is formed on the metal catalyst layer 120 by the existing electronic method. It can be seen that when formed on the catalyst layer 120, it rises significantly.

In the experimental example, a silicon (Si) substrate was used as the substrate 110, a nickel-copper alloy (Ni—Cu) was used as the metal catalyst layer 120, and graphene having a thickness of several tens of nanometers was used as the pellicle membrane 130. . In addition, a wet transfer method using PMMA is used as an existing transfer method, and a chemical vapor deposition (CVD) method is used as the growth method.

According to one embodiment, the pellicle membrane, which protects the photomask from external sources of contamination, has excellent physico-chemical properties, such as exposure to light in the extreme ultraviolet (EUV) range for extended periods of time, surface cleaning processes, etc. durability.

In addition, after the 2D material is directly formed on the metal catalyst layer, the metal catalyst layer is selectively removed to form a pellicle membrane. can be formed.

In addition, the metal catalyst layer and the substrate selectively removed for forming the pellicle membrane are also used as a frame for supporting the pellicle membrane.

In addition, by forming a protective film on at least one surface of the pellicle membrane, the durability of the pellicle membrane can be further improved, and deformation of the pellicle membrane that can occur due to heat accumulation can be minimized. , the life of the pellicle can be extended.

The foregoing description is for illustrative purposes only and can be easily modified to other specific forms without changing the technical concept or essential characteristics by those skilled in the art. It will be possible to understand that Accordingly, the embodiments described above are to be understood in all respects as illustrative and not restrictive. For example, each component described in a singular form may also be implemented in distributed form, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of rights is indicated by the claims rather than the foregoing detailed description, and all modifications or variations derived from the meaning, scope and equivalents of the claims are included in the scope of rights. must be interpreted as

INDUSTRIAL APPLICABILITY The photomask pellicle, the reticle including the photomask pellicle, and the method of manufacturing the photomask pellicle according to the present invention can be effectively applied to, for example, optical lithography-related technical fields.

10 Mask pattern 20 Mask substrate 30 Photomask 40, 130, 240, 330 Pellicle membrane 44 Intervening space 50 Frame 60, 100, 200, 300 Pellicle 70 Substrate 80 Resist layer 90 Light source 95 Reticle 99 Exposure device 110, 210, 310 Substrate 120 , 230, 340 metal catalyst layers 220, 320 barrier layers

Claims (33)

In a photomask pellicle for protecting a photomask,
a substrate including side surfaces and a top surface ;
a metal catalyst layer provided on the substrate;
a barrier layer comprising at least one of Si ₃ N ₄ , TiN and TaN provided between the substrate and the metal catalyst layer;
a pellicle membrane comprising a two-dimensional (2D) material provided on the metal catalyst layer;
the pellicle membrane has a central region and an edge region, the edge region at least partially surrounding the central region;
The substrate , the barrier layer and the metal catalyst layer collectively support the edge regions of the pellicle membrane and do not support the central region of the pellicle membrane, and the barrier layer supports the top portion of the substrate. A pellicle for a photomask , present only on the surface and present only between the top surface of the substrate and the bottom surface of the metal catalyst layer. 2. The pellicle for a photomask according to claim 1, wherein the metal catalyst layer has a thickness of 10 nm to 100 μm. 2. The pellicle for a photomask according to claim 1, wherein the metal catalyst layer has a thickness of 10 nm to 10 μm. 2. The pellicle of claim 1, wherein the 2D material includes at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene. 5. The pellicle for a photomask according to claim 4, wherein the pellicle membrane has a thickness of 5 nm to 50 nm. The metal catalyst layer includes platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd) and ruthenium (Ru). 2. The pellicle for a photomask according to claim 1, comprising at least one of: 2. The pellicle for a photomask according to claim 1, wherein the pellicle membrane has a light transmittance of 80% or more. 2. The pellicle for a photomask according to claim 1, wherein the total height of said metal catalyst layer and said substrate is 1 mm to 10 mm. 2. The pellicle of claim 1, further comprising a protective film provided on at least one surface of the pellicle membrane. The protective film includes at least carbon-based material, transition metal dichalcogenide (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron (B), and silicon nitride (SiN). 10. The photomask pellicle of claim 9, comprising one. In a method for manufacturing a photomask pellicle for protecting a photomask,
forming a barrier layer including at least one of _Si3N4 , TiN and TaN on a substrate _;
forming a metal catalyst layer on the barrier layer;
forming a pellicle membrane comprising a two-dimensional (2D) material and including a central region and edge regions at least partially surrounding the central region over the metal catalyst layer;
etching the substrate supporting the central region of the pellicle membrane and an inner region of the metal catalyst layer;
The substrate , the barrier layer and the metal catalyst layer collectively support the edge regions of the pellicle membrane and do not support the central region, and after the etching step the barrier layer is formed on the upper surface of the substrate. A method of manufacturing a photomask pellicle that exists only on the substrate and only between the top surface of the substrate and the bottom surface of the metal catalyst layer. 12. The method of claim 11, further comprising forming a protective layer on at least one surface of the pellicle membrane. 12. The method of manufacturing a pellicle for a photomask according to claim 11, wherein the pellicle membrane is formed directly on the surface of the metal catalyst layer. 12. The pellicle of claim 11, wherein etching the substrate and the metal catalyst layer is performed by at least one of mechanical etching, dry etching, and wet etching. manufacturing method. a photomask including a mask pattern;
a pellicle according to any one of claims 1 to 10,
The metal catalyst layer is a reticle surrounding the mask pattern. 16. The reticle of claim 15, wherein the photomask is separated from the pellicle membrane by 1 mm to 10 mm. a barrier layer provided on the substrate;
a metal catalyst layer provided on the barrier layer ;
a pellicle membrane provided on the metal catalyst layer,
the pellicle membrane includes a two -dimensional (2D) material and has a central region and an edge region;
the edge region at least partially surrounds the central region;
the substrate, the barrier layer and the metal catalyst layer collectively support the edge regions and not support the central region of the pellicle membrane;
A pellicle for photomask protection, wherein the barrier layer is present only on the top surface of the substrate and only between the top surface of the substrate and the bottom surface of the metal catalyst layer. 18. The method of claim 17, wherein the barrier layer includes at least one of TiN and TaN. 18. The pellicle of _claim 17 , wherein the barrier layer comprises at least one of _SiO2 , _Si3N4 , TiN and TaN. 18. The pellicle for photomask protection according to claim 17 , wherein the sum of the height of the metal catalyst layer and the height of the substrate is 1 mm to 10 mm. 18. The pellicle for photomask protection according to claim 17, wherein the metal catalyst layer has a thickness of 10 nm to 100 μm. 18. The pellicle for photomask protection according to claim 17, wherein the metal catalyst layer has a thickness of 10 nm to 10 μm. 18. The pellicle of claim 17, wherein the 2D material includes at least one of h-BN, Si, P, B, and graphene. 18. The pellicle for photomask protection according to claim 17, wherein the pellicle membrane has a thickness of 5 nm to 50 nm. 18. The pellicle of claim 17, wherein the metal catalyst layer comprises at least one of Pt, Cu, Ni, Co, Ag, W, Mo, Pd and Ru. 18. The pellicle for protecting a photomask according to claim 17, wherein the pellicle membrane has a light transmittance of 80% or more. 18. The pellicle for photomask protection of claim 17, further comprising a protective film formed on at least one surface of the pellicle membrane. The protective film includes at least carbon-based material, transition metal dichalcogenide (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron (B), and silicon nitride (SiN). 28. The photomask protective pellicle of claim 27, comprising one. sequentially forming a substrate, a barrier layer and a metal catalyst layer;
forming a pellicle membrane on the metal catalyst layer comprising a two -dimensional (2D) material and including a central region and edge regions at least partially surrounding the central region;
etching at least inner regions of the substrate supporting the central region of the pellicle membrane, the barrier layer, and the metal catalyst layer;
the substrate, the barrier layer, and the metal catalyst layer collectively support the edge regions of the pellicle membrane and do not support the central region;
A method of manufacturing a pellicle for protecting a photomask, wherein after the etching step, the barrier layer exists only on the top surface of the substrate and only between the top surface of the substrate and the bottom surface of the metal catalyst layer. 30. The method of claim 29, further comprising forming a protective layer on at least one surface of the pellicle membrane. 30. The method of claim 29, wherein forming the pellicle membrane includes forming the pellicle membrane directly on the surface of the metal catalyst layer. 3. The etching of the metal catalyst layer comprises etching the metal catalyst layer using at least one of a mechanical etching method, a dry etching method, and a wet etching method. 29. The method for manufacturing a pellicle for photomask protection according to 29 above. 29. The method of claim 28, wherein the 2D material includes at least one of h-BN, Si, P, B, and graphene.

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