KR102675777B1 - Pellicle for photomask, reticle including the same and method for manufacturing the same - Google Patents

Abstract

A photomask pellicle that protects a photomask from external contamination and a method of manufacturing the photomask pellicle are disclosed. The disclosed pellicle for a photomask includes a metal catalyst layer and a pellicle membrane provided on the metal catalyst layer and including a 2D material. The metal catalyst layer supports the edge area of the pellicle membrane, but does not support the central area of the pellicle membrane. The metal catalyst layer may be on a substrate, where the substrate and the metal catalyst layer collectively support the edge region of the pellicle membrane and do not support the central region. The pellicle may be formed based on growing a 2D material on the metal catalyst layer and etching the inner region of the metal catalyst layer that supports the central region of the formed pellicle membrane.

Description

Pellicle for photomask, reticle including same, and method for manufacturing pellicle for photomask {Pellicle for photomask, reticle including the same and method for manufacturing the same}

The disclosed embodiments relate to a pellicle for a photomask, a reticle including the same, and a method of manufacturing a pellicle for a photomask.

A pellicle for a photomask may be provided in the form of a film on a photomask to protect the photomask from external contaminants (eg, dust, resist, etc.) during the optical lithography process. This photomask pellicle must have high transmittance for light used in the lithography process and must satisfy various requirements such as heat dissipation characteristics, strength, uniformity, durability, and stability. As the line width of semiconductor devices/electronic circuits decreases, the wavelength of light used in the lithography process may become shorter to implement this, and there is a need to develop pellicle materials suitable for the light source used in the lithography process.

Exemplary embodiments provide pellicle materials suitable for light sources used in optical lithography processes.

An exemplary embodiment provides a photomask pellicle that protects the photomask from external contamination, a reticle including the same, and a method of manufacturing the photomask pellicle.

A pellicle for a photomask according to one aspect,

A pellicle for a photomask to protect a photomask, comprising: a substrate;

a metal catalyst layer provided on the substrate; and a pellicle membrane provided on the metal catalyst layer and including a 2D material.

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

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

The thickness of the metal catalyst layer may be 10 nm to 100 μm.

The thickness of the metal catalyst layer may be 10 nm to 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 may be 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). It can contain at least one.

The light transmittance of the pellicle membrane may be 80% or more.

The combined height of the metal catalyst layer and the substrate may be 1 mm to 10 mm.

It may further include a protective film provided on at least one side of the pellicle membrane.

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

A method of manufacturing a pellicle for a photomask according to one aspect,

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

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

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

It may further include forming a barrier layer on the substrate.

It may further include forming a protective film on at least one side of the pellicle membrane.

The pellicle membrane may be formed directly on the metal catalyst layer.

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

The method of manufacturing a pellicle for a photomask according to another aspect is,

A method of manufacturing a pellicle for a photomask to protect a photomask, comprising: forming a barrier layer on a substrate; forming a metal catalyst layer on the barrier layer; forming a pellicle membrane including a 2D material between the metal catalyst layer and the barrier layer; removing the metal catalyst layer; and etching the inner region of the substrate and the barrier layer supporting the central portion of the pellicle membrane.

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

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

It may further include forming a protective film on at least one side of the pellicle membrane.

The step of removing the metal catalyst layer and the step of 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 side,

A photo mask including a mask pattern; and

Includes 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 includes a central region and an edge region, and the edge region may at least partially surround the central region. The edge region may be supported by the substrate and the metal catalyst layer, and the central region may not be supported by the substrate and the metal catalyst layer.

The photo mask may be spaced apart from the pellicle membrane by 1 mm to 10 mm.

The thickness of the metal catalyst layer may be 10 nm to 100 μm.

The thickness of the metal catalyst layer may be 10 nm to 10 μm.

It may 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 may be 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). It can contain at least one.

The light transmittance of the pellicle membrane may be 80% or more.

It may further include a protective film provided on at least one side of the pellicle membrane.

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

A pellicle for protecting a photomask according to one aspect includes a metal catalyst layer; and a pellicle membrane provided on the metal catalyst layer. The pellicle membrane includes a two-dimensional (2D) material and may have a central region and an edge region. The edge area may at least partially surround the central area. The metal catalyst layer may support the edge area of the pellicle membrane, but may not support the central area.

The pellicle may further include a substrate, wherein the metal catalyst layer is on the substrate, and the substrate and the metal catalyst layer collectively support the edge region of the pellicle membrane and do not support the central region. .

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

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

The method may further include forming the metal catalyst layer on the substrate. At this time, the etching step etches the inner region of the substrate and the metal catalyst layer supporting the central region of the pellicle membrane, and thus the substrate and the metal catalyst layer collectively support the edge region of the pellicle membrane. Supports and does 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 film 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 an embodiment, the pellicle membrane that protects the photomask from external contaminants may have excellent physical and chemical durability that is not damaged even by exposure to light in the extreme ultraviolet (EUV) region for a certain period of time or by a surface cleaning process.

Additionally, by forming a 2D material directly on a metal catalyst layer and then selectively removing the metal catalyst layer to form a pellicle membrane, the pellicle membrane can be formed without going through a transfer process.

Additionally, the metal catalyst layer and substrate selectively removed to form the pellicle membrane can be used as a frame to support the pellicle membrane.

In addition, by forming a protective film on at least one side of the pellicle membrane, the durability of the pellicle membrane can be further improved, and deformation of the pellicle membrane that may occur due to heat accumulation can be minimized, thereby increasing the lifespan of the pellicle membrane. there is.

Figure 1 schematically shows an exposure apparatus according to an exemplary embodiment.
Figure 2 shows a pellicle for a photomask according to one embodiment.
Figures 3a to 3d show step-by-step a method of manufacturing a pellicle for a photomask according to an embodiment.
Figure 4 shows a pellicle for a photomask according to another embodiment.
Figures 5A to 5E show step-by-step a method of manufacturing a pellicle for a photomask according to another embodiment.
Figure 6 shows a pellicle for a photomask according to another embodiment.
Figures 7a to 7f show step-by-step a method of manufacturing a pellicle for a photomask according to another embodiment.
8A to 8C are cross-sectional views showing step by step a method of manufacturing a pellicle for a photomask according to another embodiment.

Below, with reference to the attached drawings, embodiments will be described in detail so that those skilled in the art can easily perform them. However, the implemented form may vary in many ways, and is not limited to the embodiment described here. In addition, parts that are not related to the description are omitted in the drawings, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

Figure 1 schematically shows an exposure apparatus 99 according to an exemplary embodiment.

Referring to FIG. 1, the exposure device 99 is used in the photo lithography process, that is, it is capable of performing the photo lithography process, and is a resist layer formed on the substrate 70 using light of a predetermined wavelength. , 80) can be patterned. This exposure device 99 includes a light source 90 that emits light of a predetermined wavelength, a photomask 30 that performs an exposure operation on the resist layer 80 using the light emitted from the light source 90, and a photomask ( It includes a pellicle (60) to protect the 30).

The light source 90 may emit light in a short wavelength range for forming a fine pattern in 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 refers to a structure in which the photomask 30 and the pellicle 60 are combined. Meanwhile, 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 distributed uniformly to the reticle 95. An optical system such as a collimating lens may be further provided to allow incident light.

The photomask 30 may perform an exposure operation on the resist layer 80 formed on the substrate 70 using light in the extreme ultraviolet (EUV) region 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 . Additionally, the pellicle 60 may be provided under the mask substrate 20 to cover the mask pattern 10.

The photomask 30 may include a reflective photomask. In this case, 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 from the photomask 30 The light may pass through the pellicle 60 and be incident on 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. . Meanwhile, although not shown in the drawing, on the optical path between the reticle 95 and the resist layer 80, there is, for example, a focusing lens that focuses light in the extreme ultraviolet (EUV) region coming from the reticle 95. ), etc., may be further provided with an optical system.

The pellicle 60 is provided at the bottom of the photomask 30 and serves to protect the photomask 30 by preventing external contaminants such as dust or resist from being adsorbed on the photomask 30. To this end, the pellicle 60 may include a pellicle membrane 40 that is spaced apart from the photomask 30 at a predetermined interval. Accordingly, the range of the intervening spacer 44 is limited by the pellicle 60 and the photo mask 30. The intervening space 44 is between the pellicle membrane 40 and the photomask 30. The pellicle membrane 40 may be spaced apart from the photomask 30 by approximately several mm. For example, the gap between the pellicle membrane 40 and the photomask 30 may be 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 provided at the edge of the photomask 30 and may serve to support the pellicle membrane 40 so that the pellicle membrane 40 is spaced apart from the photomask 30 at a regular interval. For example, the height of the frame 50 may also be about 1 mm to 10 mm so that the gap between the pellicle membrane 40 and the photomask 30 is about 1 mm to 10 mm. A description of the layers constituting the frame 50 will be provided later.

In the exposure device 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 and is incident on the photomask 30. The light in the extreme ultraviolet (EUV) region reflected from passes through the pellicle membrane 40 and is incident on the resist layer 80 formed on the substrate 70, thereby performing an exposure process. That is, the exposure device 99 is provided to perform an exposure process.

Meanwhile, in the exposure apparatus 99 shown in FIG. 1, a case in which a reflective photomask is used as the photomask 30 is shown as an example. However, the photomask 30 is not limited to this and may be a transmissive photomask. In this case, the mask substrate 20 may include a transmission layer that transmits incident light, and the mask pattern 10 may include an absorption pattern that absorbs incident light.

The pellicle 60 described in FIG. 1 may be any of the pellicles described herein, or may be any pellicle described in any one of the drawings described herein.

In other words, the exposure apparatus 99 according to the exemplary embodiment is any of the pellicles described herein and includes a pellicle 60 that is any of the pellicles described in any of the drawings described herein. May include a reticle 95.

Figure 2 shows a pellicle for a photomask according to an embodiment.

Referring to FIG. 2, the pellicle 100 may perform the same role as the pellicle 60 including the pellicle membrane 40 and frame 50 shown in FIG. 1. The pellicle 100 may be provided on a mask substrate to cover the mask pattern of the photomask.

The pellicle 100 includes a substrate 110, a metal catalyst layer 120 formed on the substrate 110, and a pellicle membrane 130. Additionally, the metal catalyst layer 120 on the substrate 110 may support one or more edge portions 130e of the pellicle membrane 130. In other words, the metal catalyst layer 120 and the substrate 110 may not be formed in the central portion 130c of the pellicle membrane 130, and only one or more edge portions 130e may be supported. The substrate 110 and the metal catalyst layer 120 formed in this way can function like the frame 50 of FIG. 1, and when forming a reticle (e.g., the reticle 95), such as the intervening space 44 The mask pattern 10 may be surrounded by combining with the photomask 30 to at least partially define the intervening space.

The “central region” of the pellicle membrane may also be expressed as the “central portion” of the pellicle membrane. The “edge region” of a pellicle membrane may also be expressed as the “edge portion” of the pellicle membrane. According to one embodiment, the edge area 130e of the pellicle membrane 130 may at least partially surround the central area 130c of the pellicle membrane 130. For example, as shown in FIG. 2, the edge region 130e of the pellicle membrane 130 may at least partially and/or completely surround the central region 130c of the pellicle membrane 130.

In other words, the pellicle membrane 130 on the metal catalyst layer 120 may include a two-dimensional (2D) material. The pellicle membrane 130 may have a central region 130c and an edge region 130e, and the edge region 130e at least partially surrounds the central region 130c. The substrate 110 and the metal catalyst layer 120 may collectively support the edge region 130e of the pellicle membrane 130 and may not support the central region 130c of the pellicle membrane 130. there is.

The combined height of the substrate 110 and the metal catalyst layer 120 may be approximately 1 mm to 10 mm so that the pellicle membrane 130 and the photomask are spaced apart at a predetermined interval.

The metal catalyst layer 120 provided on the substrate 110 is platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), and palladium. It may include at least one of (Pd) and ruthenium (Ru). The thickness of the metal catalyst layer 120 may be 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 may be 10 nm or more and 10 μm or less.

The pellicle membrane 130 can be formed by directly growing a material on the surface 120a of the metal catalyst layer 120. The pellicle membrane 130 may include a material having a two-dimensional crystal structure, that is, 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. Additionally, the thickness of the pellicle membrane 130 may be approximately 5 nm to 50 nm.

The pellicle membrane 130 may have high physical and chemical durability and light transmittance. For example, the light transmittance of the pellicle membrane may be approximately 80% or more.

A protective film may be formed on at least one of both surfaces 130a and 130b of the pellicle membrane 130. This protective film can further strengthen the durability of the pellicle membrane 130 in the exposure process using light in the extreme ultraviolet (EUV) region and reduce or minimize deformation of the pellicle membrane 130 that may occur due to heat accumulation. there is. In addition, the protective film can provide 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 a surface cleaning process.

The protective film is made of carbon-based materials, transition metal dichalcogenide (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron (B), and silicon nitride (SiN). It may include at least one of: Here, carbon-based materials include, for example, amorphous carbon, graphene, nano graphite, carbon nanosheet, carbon nanotube, SiC, and B4C. It may include at least one of: And, TMD is a metal element of one of Mo, W, Nb, V, Ta, Ti, Zr, Hf, Tc, Re, Cu, Ga, In, Sn, Ge, and Pb and one of S, Se, and Te. May contain cogen element.

The pellicle membrane 130 and the edge areas of the protective film formed on both sides of the pellicle membrane 130 may be supported by the metal catalyst layer 120 and the substrate 110. Accordingly, the metal catalyst layer 120 and the substrate 110 can collectively support at least one edge region 130e of the pellicle membrane 130, and do not support the central region 130c of the pellicle membrane 130. . In other words, the metal catalyst layer 120 and the substrate 110 may function as the frame 50 of FIG. 1 .

Figures 3a to 3d show step-by-step a method of manufacturing a pellicle for a photomask according to an embodiment.

Referring to FIGS. 3A and 3B, a metal catalyst layer 120 is formed on the substrate 110. The substrate 110 may be formed of a material such as Si, glass, quartz, or Al2O3. The metal catalyst layer 120 is 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 may be 100㎛ or less, for example, 10㎚ or more and 10㎛ or less.

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

As shown in FIG. 3C, the pellicle membrane 130 may be formed directly on the surface 120a of the metal catalyst layer 120. As described herein, in other embodiments, pellicle membrane 130 may be formed indirectly on metal catalyst layer 120, in which case an intervening layer between metal catalyst layer 120 and pellicle membrane 130. layer) (e.g., protective layer 150 described below).

When the pellicle membrane 130 is formed directly on the surface of the material layer, for example, on the surface 120a of the metal catalyst layer 120, the pellicle membrane 130 is formed directly on the surface 120a of the metal catalyst layer 120. ) can be grown directly on

The pellicle membrane 130 may include a material having a two-dimensional crystal structure, that is, 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. Additionally, the thickness of the pellicle membrane 130 may be approximately 5 nm to 50 nm.

The pellicle membrane 130 may be formed by a method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD).

Additionally, 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, the pellicle membrane 130 is formed on the protective film, and a protective film (e.g., protective film 150 as shown in Figure 3D) is formed again on the surface 130a of the pellicle membrane 130. You can. That is, the protective film may be formed on both surfaces 130a and 130b of the pellicle membrane 130. In addition to or instead of the protective film 150 described on the surface 130a of the pellicle membrane 130 in Figure 3D, a protective film 150 may be formed between the metal catalyst layer 120 and the pellicle membrane 130 in Figure 3C. It may be possible. However, the present invention is not limited to this, and the protective film may be formed only on one side of the pellicle membrane 130. In this way, when a protective film is formed on at least one surface of the pellicle membrane 130, the protective film may have a surface roughness similar to that of the pellicle membrane 130.

Referring to FIG. 3D, at least the inner regions 110b and 120b of the substrate 110 and the metal catalyst layer 120 supporting the central region 130c of the pellicle membrane 130 are etched (e.g., selectively etched). is removed). Accordingly, the remaining regions of the substrate 110 and the metal catalyst layer 120 collectively support one or more edge regions 130e of the pellicle membrane 130, and do not support the central region 130c of the pellicle membrane 130. No. Therefore, one or more edge regions 130e of the pellicle membrane 130 can be understood as being supported by the metal catalyst layer 120 and the substrate 110, and the central region 130c of the pellicle membrane 130 is supported by the metal catalyst layer ( It may be understood that it is not supported by 120) and the substrate 110.

As shown in FIG. 3D, a substrate 110 and a metal catalyst layer collectively support one or more edge regions 130e of the pellicle membrane 130 and do not support the central region 130c of the pellicle membrane 130. The remaining region of (120) is simply referred to as the substrate 110 and the metal catalyst layer 120. The substrate 110 and the metal catalyst layer 120 may be etched using at least one of mechanical etching, dry etching, and wet etching.

Through the above etching step, the substrate 110 and the metal catalyst layer 120 serve 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. can perform its role. As mentioned herein and at least as shown in Figure 3D, a layer described as not supporting the central region of the pellicle membrane directly supports one or more edge regions of the pellicle membrane and directly supports the central region of the pellicle membrane. It may be understood as indirectly supporting the central region of the pellicle membrane through the one or more edge regions of the pellicle membrane without doing so.

For example, as shown in FIG. 3D, the metal catalyst layer 120 and the substrate 110 may be understood as collectively directly supporting one or more edge regions 130e of the pellicle membrane 130, and the pellicle Although it does not collectively directly support the central region 130c of the membrane 130, it may be understood as indirectly supporting the central region 130c through one or more edge regions 130e. Therefore, it can be understood that the metal catalyst layer 120 and the substrate 110 collectively support one or more edge regions 130e of the pellicle membrane 130, and do not support the central region 130c of the pellicle membrane 130. There will be.

Figure 4 shows a pellicle for a photomask according to another embodiment.

Referring to FIG. 4, the pellicle 200 may perform the same role as the pellicle 60 including the pellicle membrane 40 and frame 50 shown in FIG. 1.

The pellicle 200 includes a substrate 210, a barrier layer 220 formed on the substrate 210, a metal catalyst layer 230 formed on the barrier layer 220, and a pellicle membrane 240. As shown in FIG. 4, the barrier layer 220 may be between the substrate 210 and the metal catalyst layer 230. The substrate 210, barrier layer 220, and metal catalyst layer 230 may support only one or more edge regions 240e of the pellicle membrane 240 and may not support the central region 240c of the pellicle membrane 240. there is. That is, the central area 240c is supported only indirectly through one or more edge areas 240e.

The barrier layer 220 provided on the substrate 210 can bond the metal catalyst layer 230 and the substrate 210 more firmly. 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 is platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), It may contain at least one of palladium (Pd) and ruthenium (Ru).

The structures and materials of the substrate 210, metal catalyst layer 230, and pellicle membrane 240, excluding the barrier layer 220, are the same as those in the description of FIG. 2 and are therefore omitted.

Figures 5A to 5E show step-by-step 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 the substrate 210. The substrate 210 may be formed of a material such as Si, glass, quartz, or 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 is 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 including a 2D material is formed directly or indirectly on the surface 230a of the metal catalyst layer 230. The pellicle membrane 240 may be formed by a method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD).

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

Through the above etching step, as shown in Figure 5e, the remaining areas of the substrate 210, barrier layer 220, and metal catalyst layer 230 directly support one or more edge areas 240e of the pellicle membrane 240. And, the central region 240c of the pellicle membrane 240 may function as a frame that does not directly support it.

Figure 6 shows a pellicle for a photomask according to another embodiment.

Referring to FIG. 6, the pellicle 300 may perform the same role as the pellicle 60 including the pellicle membrane 40 and frame 50 shown in FIG. 1.

The pellicle 300 includes a substrate 310, a barrier layer 320 formed on the substrate 310, and a pellicle membrane 330. The substrate 310 and the barrier layer 320 may serve as the frame 50 of FIG. 1 supporting one or more edge regions 330e of the pellicle membrane 330.

Figures 7a to 7f show step-by-step a method of manufacturing a pellicle for a photomask according to another embodiment.

Referring to FIGS. 7A and 7B, a barrier layer 320 is formed on the substrate 310. The substrate 310 may be formed of a material such as Si, glass, quartz, or 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 is 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 including a 2D material is formed directly or indirectly on the lower part of the metal catalyst layer 340, for example, on the lower surface 340f. For example, the pellicle membrane 330 is formed between the metal catalyst layer 340 and the barrier layer 320. The pellicle membrane 330 may include a material having a two-dimensional crystal structure, that is, 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. When 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 penetrates into the metal catalyst layer 340. I do it. At this time, by adjusting the materials constituting the lower barrier layer 320 and the process temperature and pressure, a pellicle membrane 330 containing a 2D material can be formed under the metal catalyst layer 340.

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

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

Through the above etching step, the substrate 310 and the barrier layer 320 directly support one or more edge regions 330e of the pellicle membrane 330, and do not directly support the central region 330c of the pellicle membrane 330. It may not be possible.

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

In example embodiments, the metal catalyst layer may serve as a substrate. Alternatively, the substrate may serve as the metal catalyst layer. Therefore, the substrate as an element separated 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 may have a thickness of less than 100 μm, for example, thicker than 10 nm and thinner than 10 μm. Accordingly, the substrate 410 may be expressed as a “metal catalyst layer” having some or all of the properties and/or characteristics of the metal catalyst layers described above.

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

The pellicle membrane 430 may be formed using a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method.

Additionally, in FIG. 8B , a protective film (not shown) may be formed on the surface 410a of the substrate 410 before forming the pellicle membrane 430 on the substrate 410. After forming the protective film, a pellicle membrane 430 may be formed on the protective film. Again, a protective film may be formed on the surface of the pellicle membrane 430 away from the substrate. Soon, a protective film may be formed on opposing surfaces of the pellicle membrane 430. However, the embodiment is not limited to this. In other words, 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 in this way, the protective film may have a surface roughness similar to that of the pellicle membrane 430.

As shown in Figure 8b, pellicle membrane 430 may be formed on a limited area 410b of the surface 410a of the substrate 410, such that the edge area 410e of the substrate 410 is exposed. . The pellicle membrane 430 may be formed to have a specific or predetermined shape and/or size on the limited area 410b of the substrate 410.

Referring to FIG. 8C, at least the inner region 410c of the limited region 410b of the substrate 410 supporting the central region 430c of the pellicle membrane 430 is etched. Soon, the inner area 410c is selectively removed. Accordingly, the remaining area 410r of the limited area 410b of the substrate 410 remains. Additionally, as shown in FIG. 8C, one or more edge regions 410e of the exposed substrate 410 around the pellicle membrane 430 may be etched. Accordingly, the outer sides 430d and 410d of the pellicle membrane 430 and the substrate 410 are flat or substantially flat. That is, the outer sides 430d and 410d may be flat within manufacturing process tolerances and/or material tolerances. The substrate 410 may be etched based on using at least one of a mechanical etching method, a dry etching method, and a wet etching method.

Through this 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 it. It may serve as a frame (that is, indirectly supporting the central area 430c through one or more edge areas 430e). Therefore, as shown in FIG. 8C, a pellicle 800 including the pellicle membrane 430 and the remaining area 410r of the substrate 410 can be formed.

In the above-described pellicle manufacturing method for a photomask, the pellicle membrane is not formed using a conventional transfer method, but is formed directly on the material layer using a growth 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 can be formed by a conventional transfer method or by a direct growth method. When this occurs, there is a difference in adhesion between the pellicle membrane 130 and the metal catalyst layer 120.

According to an experimental example, when the pellicle membrane 130 was formed on the metal catalyst layer 120 using a conventional transfer method, the adhesion 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 force between the pellicle membrane 130 and the metal catalyst layer 120 was about 1200 MPa. Through these experimental results, the adhesion between the pellicle membrane 130 and the metal catalyst layer 120 is greater than when the pellicle membrane 130 is formed on the metal catalyst layer 120 using a conventional electronic method. )) When it is formed in the phase, it can be seen that it increases significantly.

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

The above description is for illustrative purposes, and those skilled in the art will understand that it can be easily transformed into another specific form without changing the technical idea or essential features. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of rights is indicated by the patent claims described later rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of rights.

10: Mask pattern 20: Mask substrate
30: Photomask 40: Pellicle membrane
50:Frame 60:Pellicle
70: Substrate 80: Resist layer
100, 200, 300: pellicle 110, 210, 310: substrate
120, 230, 340: Metal catalyst layer 130, 240, 330: Pellicle membrane
220, 320: barrier layer

Claims (51)

In the pellicle for a photomask to protect the photomask,
Board;
a barrier layer provided on the substrate;
a metal catalyst layer provided on the barrier layer; and
A pellicle membrane provided on the metal catalyst layer and including a 2D material,
The pellicle membrane has 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 region of the pellicle membrane and do not support the central region of the pellicle membrane,
A pellicle for a photomask in which the barrier layer exists only between the upper surface of the substrate and the lower surface of the metal catalyst layer corresponding to the upper surface. According to claim 1,
A pellicle for a photomask wherein the metal catalyst layer has a thickness of 10 nm to 100 μm. According to claim 1,
A pellicle for a photomask wherein the metal catalyst layer has a thickness of 10 nm to 10 μm. delete According to claim 1,
The barrier layer is a pellicle for a photomask containing at least one of Si3N4, TiN, and TaN. According to claim 1,
The 2D material is a pellicle for a photomask containing at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene. According to claim 6,
A pellicle for a photomask where the thickness of the pellicle membrane is 5nm to 50nm. According to claim 1,
The metal catalyst layer includes platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd), and ruthenium (Ru). A pellicle for a photomask comprising at least one. According to claim 1,
A pellicle for a photomask wherein the pellicle membrane has a light transmittance of 80% or more. According to claim 1,
A pellicle for a photomask where the combined height of the metal catalyst layer and the substrate is 1 mm to 10 mm. According to claim 1,
A pellicle for a photomask further comprising a protective film provided on at least one side of the pellicle membrane. According to claim 11,
The protective film is at least one of a carbon-based material, transition metal dichalcogenide (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron (B), and silicon nitride (SiN). A pellicle for a photomask containing a. In the method of manufacturing a pellicle for a photomask to protect the photomask,
forming a barrier layer on a substrate;
Forming a metal catalyst layer on the substrate such that the barrier layer is provided between the substrate and the metal catalyst layer;
forming a pellicle membrane on the metal catalyst layer, including a 2D material, and including a central region and an edge region at least partially surrounding the central region; and
A step of etching the inner region of the metal catalyst layer and the substrate supporting the central region of the pellicle membrane,
the substrate and the metal catalyst layer collectively support the edge region of the pellicle membrane and do not support the central region,
A method of manufacturing a pellicle for a photomask in which the barrier layer exists only between the upper surface of the substrate and the lower surface of the metal catalyst layer corresponding to the upper surface. delete According to claim 13,
A method of manufacturing a pellicle for a photomask, further comprising forming a protective film on at least one surface of the pellicle membrane. According to claim 13,
A method of manufacturing a pellicle for a photomask in which the pellicle membrane is formed directly on the surface of the metal catalyst layer. According to claim 13,
A method of manufacturing a pellicle for a photomask, wherein the step of etching the substrate and the metal catalyst layer is performed by at least one of mechanical etching, dry etching, and wet etching. In the method of manufacturing a pellicle for a photomask to protect the photomask,
forming a barrier layer on a substrate;
forming a metal catalyst layer on the barrier layer;
forming a pellicle membrane between the metal catalyst layer and the barrier layer, comprising a 2D material and having a central region and an edge region at least partially surrounding the central region;
removing the entire metal catalyst layer; and
A step of etching the inner region of the substrate and the barrier layer supporting the central region of the pellicle membrane,
A method of manufacturing a pellicle for a photomask, wherein the substrate and the barrier layer collectively support the edge area of the pellicle membrane and do not support the central area of the pellicle membrane. According to claim 18,
A method of manufacturing a pellicle for a photomask, further comprising forming a protective film on at least one surface of the pellicle membrane. According to claim 19,
The step of removing the metal catalyst layer and the step of etching the substrate and the barrier layer are performed by at least one of mechanical etching, dry etching, and wet etching. A photo mask including a mask pattern; and
Including a pellicle;
The pellicle is,
Board,
A metal catalyst layer provided on the substrate and surrounding the mask pattern,
a barrier layer provided between the substrate and the metal catalyst layer, and
It includes a pellicle membrane containing a two-dimensional (2D) material,
The pellicle membrane includes a central region and an edge region,
The edge region at least partially surrounds the central region,
The edge region is supported by the substrate and the metal catalyst layer, and the central region is not supported by the substrate and the metal catalyst layer,
The barrier layer is a reticle that exists only between the upper surface of the substrate and the lower surface of the metal catalyst layer corresponding to the upper surface. According to claim 21,
The photo mask is a reticle spaced apart from the pellicle membrane by 1 mm to 10 mm. According to claim 21,
A reticle where the metal catalyst layer has a thickness of 10 nm to 100 μm. According to claim 21,
A reticle where the thickness of the metal catalyst layer is 10 nm to 10 μm. delete According to claim 21,
A reticle wherein the barrier layer includes at least one of Si3N4, TiN, and TaN. According to claim 21,
The 2D material is a reticle including at least one of h-BN, silicon (Si), phosphorus (P), boron (B), and graphene. According to clause 27,
A reticle where the pellicle membrane has a thickness of 5 nm to 50 nm. According to claim 21,
The metal catalyst layer includes platinum (Pt), copper (Cu), nickel (Ni), cobalt (Co), silver (Ag), tungsten (W), molybdenum (Mo), palladium (Pd), and ruthenium (Ru). A reticle containing at least one. According to claim 21,
A reticle wherein the pellicle membrane has a light transmittance of 80% or more. According to claim 21,
The pellicle further includes a protective film provided on at least one surface of the pellicle membrane. According to claim 31,
The protective film is at least one of a carbon-based material, transition metal dichalcogenide (TMD), ruthenium (Ru), molybdenum (Mo), silicon (Si), zirconium (Zr), boron (B), and silicon nitride (SiN). A reticle containing a. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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