KR100800304B1 - Gray-tone blankmask, photomask and manufacturing method thereof - Google Patents

Abstract

The present invention provides a gray tone blank mask, a photo mask, and a manufacture thereof so that a gray tone photomask having high back reflectance can be manufactured in order to facilitate photomask position alignment in a flat panel display or a semiconductor device exposure apparatus such as a liquid crystal display device. Provide a method. In the present invention, a semi-transmissive film having a low reflectance is not formed or removed on the transparent substrate of the portion where the alignment pattern is formed in the gray tone photomask, and a light shielding film having a high reflectance is positioned. Thereby, the rear reflectance of the part in which the alignment pattern is formed can be improved, and alignment is easy.

LCD, blank mask, photo mask, transflective film, alignment

Description

Grey-tone blankmask, photomask and manufacturing method

1 is a top view of a conventional slit pattern photomask.

2 is a top view of a conventional gray tone photomask.

3 is a cross-sectional view of a conventional gray tone blank mask.

Figure 4 schematically shows the deposition of a thin film in the vacuum chamber of the sputtering equipment.

5 is a process flowchart showing a gray tone blank mask and a method of manufacturing the same according to the first embodiment of the present invention.

6 shows an example in which a photomask position alignment pattern is to be formed among transparent substrates.

7 shows a top view and a cross-sectional view of a state in which a sputtering screen component is mounted on a substrate holder according to a first embodiment of the present invention.

8 is a process flowchart showing a gray tone photomask and a method of manufacturing the same according to the first embodiment of the present invention.

9A and 9B are graphs showing back reflectances according to wavelengths of portions in which photomask position alignment patterns are to be formed in the gray tone blank mask according to the related art and the present invention, respectively.

10 is a process flowchart showing a gray tone blank mask and a method of manufacturing the same according to the second embodiment of the present invention.

11 is a process flowchart showing a gray tone photomask and a method of manufacturing the same according to the second embodiment of the present invention.

12 is a process flowchart showing a gray tone blank mask and a method of manufacturing the same according to a third embodiment of the present invention.
FIG. 13 is a process flowchart showing a gray tone photomask and a method of manufacturing the same according to the third embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

30: vacuum chamber 32: target 36: substrate holder

37 sputtering screen parts 38 target holder 52 transparent substrate

54: semi-permeable membrane 56: etch stop membrane 58: light shielding membrane

60: antireflection film 62: resist film

68: portion where photomask position alignment pattern is to be formed

The present invention relates to a gray tone blank mask, a photo mask, and a method for manufacturing the same, and more particularly, to a gray tone blank mask, a photo mask, and a method for manufacturing the same.

Recently, due to the rapid development of thin film transistor liquid crystal display (TFT-LCD), the application range is expanded, it is required to develop a cheaper and more productive manufacturing process technology. In particular, TFT-LCDs deposit or apply numerous films and pattern them by photolithography processes, where the number of photomasks used is becoming a measure of process simplification. Because one cycle of photolithography proceeds as a single photomask, a significant reduction in manufacturing costs can be achieved by reducing the number of photomasks by only one.

The TFT-LCD consists of a color filter panel, an active panel, and a liquid crystal filled between the two panels. In the active panel, a TFT composed of a gate, a source, and a drain is located. Conventionally, a total of five photomasks should be used to manufacture the active panel TFTs. Recently, after forming a TFT, a TFT is manufactured from a total of four photomasks by forming an active region and a source / drain using a single photomask.

As an example of the photomask used to reduce the number of photomasks in the TFT-LCD manufacturing process, there is a slit pattern photomask as shown in FIG. 1. As shown in FIG. 1, the slit pattern photomask 20 generally includes a light shielding region 10, a transmission region 12, and a slit region 14. The light shielding region 10 is a portion where a source pattern 10a and a drain pattern 10b for defining the source and drain of the TFT are formed. The slit region 14 is a portion where the slit patterns 13 are formed to define a channel of the TFT.

In the slit pattern photomask 20 as shown in FIG. 1, the exposure light that passes through the slit region 14 is diffracted by the slit pattern 13, thereby exhibiting a lower transmittance than when passing through the transmission region 12. Accordingly, the light corresponding to the resist on the TFT substrate is completely exposed by the light passing through the transmissive region 12, whereas the exposure amount of the resist on the TFT substrate, that is, the channel portion is exposed by the light passing through the slit region 14. Is reduced, resulting in incomplete exposure. As a result, there is a difference in solubility in the developing solution during the development process, so that a resist pattern is formed on a portion corresponding to the source pattern 10a and the drain pattern 10b while the resist of the fully exposed portion is removed, and incomplete exposure is performed. The remaining resist film remains in the channel region. Therefore, in the photolithography process using the slit pattern photomask 20, the source and the drain of the TFT are defined in the TFT substrate by the first etching using the thus formed resist pattern, and then the resist remaining film of the channel portion is ashed. By removing and opening the channel region and defining the channel of the TFT by the second etching using this resist pattern, the source, drain and channel of the TFT can be patterned using one photomask.

However, the slit pattern photomask 20 has a disadvantage in that it is difficult to uniformly control the diffracted light by the diffraction phenomenon of the light transmitted between the slit patterns 13. In particular, with the development of TFT-LCD technology, the slit pattern is becoming finer, which makes it more difficult to control the diffracted light passing between the slit patterns. This causes a problem that the thickness of the resist film remaining in the channel portion cannot be uniformly controlled, resulting in a large loss in terms of production and yield.

In order to solve this problem, a gray tone photomask using a semi-permeable membrane has been proposed. In the gray tone photomask, the variation in line width can be reduced compared to the slit pattern photomask by adjusting the thickness according to the material and the amount of permeation of the transflective film.

As shown in FIG. 2, the gray tone photomask 22 is formed in the light blocking region 10 formed of the source pattern 10a and the drain pattern 10b corresponding to the source and the drain of the TFT, and the channel region of the TFT. The transflective area 16 and the transmissive area 12 which form the periphery of these area | regions are comprised. The gray tone photomask 22 includes a gray tone blank mask composed of a transflective film 2, a light shielding film 3, an antireflection film 4, and a resist film 5 on the transparent substrate 1 as shown in FIG. It is formed by patterning A).

However, the conventional gray tone blank mask A and the photo mask 22 have the following problems. As mentioned above, TFTs of TFT-LCDs and general semiconductor devices are manufactured through a photolithography process. The photolithography process is generally performed by attaching a photomask to a stepper exposure apparatus and transferring a pattern of the same shape as that of the photomask, and a plurality of sheets having different patterns formed to form a fine and complicated circuit. Exposure is repeated using a photomask. At this time, the positions between the patterns of the semiconductor or the TFT must be identical.

For this purpose, after forming the alignment pattern on the photomask, the photomask is inspected by inspecting the reflectance of the rear surface. In the case of the conventional gray-tone photomask for TFT-LCD manufacturing, the reflectance at the alignment wavelength on the transparent substrate is used. Since the light shielding film is formed after the low transflective film is formed, the back reflectance for the alignment of the photomask has a value of 20% or less in the wavelength region of 400 nm to 600 nm, which is the wavelength for alignment. Therefore, there is a problem in that the photomask alignment is very difficult and defects due to positional alignment errors between patterns occur.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a gray tone photomask capable of obtaining high back reflectance at a wavelength for photomask alignment and a method of manufacturing the same to facilitate alignment.

Another technical problem to be achieved by the present invention is to provide a gray tone blank mask that can be used as the raw material of the gray tone photo mask as described above and a method of manufacturing the same.

In order to achieve the above technical problem, in the gray tone blank mask according to the present invention, a transflective film is formed on a transparent substrate except for a portion on which a alignment pattern is to be formed, and a transparent substrate including a portion on which a alignment pattern is to be formed. A light shielding film is formed on the front side of the. A gray tone photomask is manufactured by etching this light shielding film.

As such, the light blocking film is formed on the portion where the alignment pattern is to be formed, and the semi-transmissive film is not formed, and the transflective film and the light blocking film are formed on the remaining portions of the transparent substrate. The back reflectance of the portion where the alignment pattern is to be formed shows high reflectance by the light shielding film.

The method for manufacturing the gray tone blank mask includes the steps of preparing a transparent substrate, forming a semi-transmissive film on the remaining portions except for a portion where a photomask position alignment pattern is to be formed on the prepared transparent substrate, and a light shielding film on the semi-transparent film. Forming an antireflection film on the formed light shielding film; and forming a resist film on the formed antireflection film.

On the other hand, in order to protect the transflective film when etching the light shielding film of the gray tone blank mask in the subsequent process for manufacturing the gray tone photomask, it is preferable to further form an etch stopper between the transflective film and the light shielding film. . Another gray tone blank mask manufacturing method according to the above, preparing a transparent substrate, forming a semi-permeable film on the remaining portion except the portion where the photomask position alignment pattern is to be formed on the prepared transparent substrate, the etch-stop film on the semi-transmissive film Forming a light shielding film on the etch stop film; forming an antireflection film on the light shielding film; and forming a resist film on the antireflection film.

In particular, in order to prevent the semi-permeable film from being formed in the portion where the alignment pattern is to be formed as described above, the sputtering screen part is installed to correspond to the portion where the alignment pattern is to be formed between the sputtering target and the transparent substrate. It is desirable to. More preferably, the sputtering screen part is installed at a distance of 0.1 to 30 mm from the surface of the transparent substrate. If the distance between the transparent substrate and the sputtering screen component is less than 0.1 mm, the transparent substrate and the sputtering screen component may contact each other and cause defects. If the distance is 30 mm or more, a semi-permeable film is formed at the portion where the alignment pattern is to be formed. Will be.

In more detail, the method for manufacturing a gray tone blank mask according to the present invention uses a sputtering screen component on a transparent substrate to form a semi-transmissive layer on the remaining portions except for the portion where the photomask alignment pattern is to be formed. And removing the sputtering screen component and forming a light shielding film on the semi-transmissive film, forming an antireflection film on the light shielding film, and forming a resist film on the antireflection film.

In addition, another method of manufacturing a gray tone blank mask of the present invention comprises the steps of preparing a transparent substrate, forming a transflective film on the transparent substrate, forming a first resist film on the transflective film, a photomask of the first resist film Exposing and developing the portion where the alignment pattern is to be formed to form a first resist pattern, etching the semi-transmissive layer using the first resist pattern as a mask, removing the first resist pattern, and cleaning the etched semi-transmissive layer Forming a light shielding film on the film, forming an antireflection film on the light shielding film, and forming a second resist film on the antireflection film.

In manufacturing the gray tone blank mask according to the present invention, the rear reflectance of the portion where the alignment pattern is to be formed is preferably 20 to 70% at a wavelength of 400 to 800 nm, or a wavelength of 400 to 600 nm. If the rear reflectance is less than 20%, the reflectance is not sufficient to make it difficult to accurately check the position alignment. If the rear reflectance is 70% or more, the light reflected from the back of the photomask during the lithography process is multiplied. Scattering is likely to cause exposure failure. The remaining portion other than the portion where the alignment pattern is to be formed preferably has a back reflectance of 1 to 20% at a wavelength of 400 to 800 nm, or a wavelength of 400 to 600 nm.

In the manufacturing of the gray tone blank mask according to the present invention, the light transmittance of the transflective film or the laminated film of the transflective film and the etchstop film on the transparent substrate is one of a specific exposure wavelength, such as 157 nm, 193 nm, 248 nm, 365 nm, 405 nm, and 436 nm. 20 to 70% at an exposure wavelength, and the optical phase difference between the transparent substrate and the transflective film (or the laminated film of the transflective film and the etchstop film) is preferably 100 degrees or less. Controlling the light transmittance at the exposure wavelength to 20 to 70% is to control the remaining thickness of the resist during the exposure and development process when manufacturing the TFT-LCD by the 4-mask process using a gray tone photomask. When the light transmittance is 20% or less, the resist residual thickness becomes too thick, making it difficult to perform the 4-mask process. When the light transmittance is 70% or more, the resist residual thickness becomes too thin, which makes it difficult to perform the 4-mask process again. Because it becomes. In addition, when the optical phase difference is 100 degrees or more, the destructive interference is increased due to the interference of adjacent light, resulting in poor uniformity of the resist surface. The thickness of the transflective film (or a laminated film of the transflective film and the etchstop film) may be 50 to 4,500 mm 3.

In addition, the semi-permeable membrane (or the laminated membrane of the semi-permeable membrane and the etch stop membrane) on the transparent substrate is composed of a continuous membrane (single membrane) having a change in composition from the transparent substrate toward the upper layer but having no membrane separation, or a low permeable membrane. It can be comprised with what laminated | stacked two or more layers of the high permeable membranes. At this time, the low permeable membrane can control the transmittance and the high permeable membrane can control the phase difference. The etch stop membrane may be manufactured to have a different composition ratio from the semi-permeable membrane to the upper membrane, and it is preferable to manufacture the etch stop membrane in combination with the semi-permeable membrane to facilitate phase and permeation control.

When forming the semi-permeable membrane, the transparent substrate is heated for 1 second to 30 minutes at a temperature of 100 to 800 ° C. to form a semi-permeable membrane or an etch stop membrane in order to improve adhesion and growth of the membrane. ) It is preferable to perform annealing or heat treatment for 1 second to 30 minutes at a temperature of 100 to 800 ° C. as a method of alleviating and improving resistance to acids and light.

When forming the light shielding film and the antireflection film, it can be composed of a continuous film (single film) or two or more layers in which the nitrogen content increases toward the transparent substrate, and at a temperature of 100 to 800 ° C. in order to improve adhesion and film growth. After heating for 2 seconds to 30 minutes, forming a light shielding film and an anti-reflection film, and performing annealing or heat treatment at a temperature of 100 to 800 ° C. for 1 second to 30 minutes in order to reduce stress by vacuum deposition and improve resistance to acids and light. It is preferable.

Also, resists coated on the anti-reflection film include optical photoresist THMR-iP3500, THMR-iP3600 (manufacturer; Tokyo Ohka Kogyo), DPR-i7000 (manufacturer; Dongjin Semichem), AZ-1500 (manufacturer; Clariant) , GXR (manufacturer; Clariant) and e-beam resist EBR-9 (manufacturer; Toray), PBS (manufacturer; Chisso), ZEP-7000 (manufacturer; Nippon ZEON), positive chemically amplified resist FEP -171 (manufacturer; FUJIFILM), negative chemically amplified resist FEN-270 (manufacturer; FUJIFILM), NEB-22 (manufacturer; Sumitomo) and other alkali-soluble resins and PAG (photo acid generator) It can select from a resist and can use.

The coating method of the resist may be spin coating or capillary coating, the thickness of the resist film is preferably in the range of 1,000 to 15,000 1, and after applying the resist film using a hot plate approximately 50 It is more preferable to produce a gray tone blank mask according to the present invention by carrying out soft bake in the temperature range of ℃ to 250 ℃, for example 80 ℃ to 250 ℃.

In addition, after the semi-transmissive film is removed in advance and the light-transmitting region is formed in the portion where the alignment pattern is to be formed in the manufacturing of the gray tone blank mask, it has a back reflectance of 20% or more, such as 20 to 70% in the wavelength region of 400 nm to 800 nm. It is preferable to form a light shielding film or an etch stop film so as to be able to do so.

The transparent substrate refers to a blank mask substrate for a flat panel display and a blank mask substrate for a semiconductor composed of glass or quartz, and the flat display includes a liquid crystal display (TFT-LCD), an organic light emitting diode (OLED), and a plasma display. (PDP), electroluminescent display (FED), and the like.

The method for manufacturing a gray tone photomask of the present invention uses a gray tone blank mask manufactured according to the present invention and having a transflective film, a light shielding film, an antireflection film, and a resist film, and exposing and developing the resist film with an electron beam or a laser of monochromatic light. Forming a first resist pattern, sequentially etching an anti-reflection film, a light shielding film, and a semi-transmissive film using the first resist pattern as a mask to form a first pattern, removing and cleaning the first resist pattern, 1 Forming a new resist film on the photomask in which the difference pattern is formed; exposing and developing the resist film with an electron beam or a laser of monochromatic light to form a second resist pattern; using the second resist pattern as a mask as a primary pattern Etching the anti-reflection film and the light shielding film and removing the second resist pattern And a step of washing.

Another method for manufacturing a gray tone photomask of the present invention uses a gray tone blank mask manufactured according to the present invention and having a transflective film, an etch stop film, a light shielding film, an antireflection film, and a resist film, wherein the resist film is an electron beam or a laser of monochromatic light. Exposing and developing to form a first resist pattern; sequentially etching an antireflection film, light blocking film, etch stop film, and semi-transmissive film using a first resist pattern as a mask to form a first pattern; first resist Removing and cleaning the pattern, forming a new resist film on the photomask in which the primary pattern is formed, exposing and developing the resist film with an electron beam or a laser of monochromatic light to form a second resist pattern, and a second resist Etching the anti-reflection film and the light shielding film in the primary pattern using the pattern as a mask, Using the second resist pattern as a mask by a step and the second step of removing the resist pattern for etching and cleaning the etch stop film of the first pattern.

Another method of manufacturing a gray tone photomask of the present invention includes preparing a transparent substrate, forming a transflective film on the transparent substrate, forming a first resist film on the transflective film, and a photomask position of the first resist film. Exposing and developing a portion on which the alignment pattern is to be formed to form a first resist pattern, etching the semi-transmissive layer using the first resist pattern as a mask, removing the first resist pattern, and cleaning the etched semi-transmissive layer Forming a light shielding film on the light shielding film; forming an antireflection film on the light shielding film; forming a second resist film on the antireflection film; exposing and developing the second resist film with an electron beam or a laser of monochromatic light to form a second resist pattern And sequentially etching the anti-reflection film and the light shielding film using the second resist pattern as a mask and the second level Removing and cleaning the gist pattern.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. The embodiments described below may be modified in many different forms, and the scope of the present invention is not limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art. In the drawings illustrating embodiments of the present invention, like reference numerals in the drawings refer to like elements, and overlapping descriptions will be omitted.

(First embodiment)

Figure 4 schematically shows the deposition of a thin film in the vacuum chamber of the sputtering equipment.

Referring to FIG. 4, a thin film is formed on the surface of the transparent substrate 52 by installing a target 32 for thin film deposition under the vacuum chamber 30 and by installing a transparent substrate 52 thereon. Referring to the process of forming a thin film by typical sputtering, first, the transparent substrate 52 is mounted on the substrate holder 36, the target 32 is mounted on the target holder 38, and then the vacuum chamber is used using the exhaust part 40. A vacuum is formed in and maintained at 30. Subsequently, gas is injected into the gas injection unit 42 to perform sputtering from the target 32, which is then deposited on the transparent substrate 52.

In the method for manufacturing a gray tone blank mask according to the present invention, a semi-transmissive film, an etch stop film, a light shielding film, and an anti-reflection film are formed. At least one of these films is inert gas and reactive in the vacuum chamber 30 as shown in FIG. 4. It is preferable to form using reactive sputtering or vacuum deposition methods (PVD, CVD, ALD) formed by introducing a gas.

In this case, the metal matrix forming the films may include cobalt (Co), tantalum (Ta), tungsten (W), molybdenum (Mo), chromium (Cr), vanadium (V), palladium (Pd), and titanium (Ti). ), Niobium (Nb), zinc (Zn), hafnium (Hf), germanium (Ge), aluminum (Al), platinum (Pt), manganese (Mn), iron (Fe), silicon (Si), nickel (Ni ), Cadmium (Cd), zirconium (Zr), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), yttrium (Y), sulfur (S), indium tin oxide (InSnO) It may be one or more metals or compounds thereof selected from the group, and an appropriate target 32 of such a matrix is provided upon deposition of each film.

As an inert gas, at least one selected from the group consisting of argon (Ar), helium (He), neon (Ne), and xenon (Xe) is used, and as a reactive gas, oxygen (O ₂ ), nitrogen (N ₂ ), and carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), nitrogen oxides (NO), nitrogen dioxide (NO ₂ ), ammonia (NH ₃ ), methane (CH ₄ ) and fluorine (F ₂ ) It can select and use 1 or more types from.

Under the condition that the vacuum degree of the vacuum chamber 30 is 1 to 5 mTorr and applied power is 0.5 to 2 kW, the mixing ratio of the reactive gas is argon: nitrogen: carbon dioxide: methane: fluorine 5 ~ 90sccm: 0 ~ 95sccm: 0 ~ 30sccm: 0 ~ 30sccm: You can choose from 0 to 30sccm. Alternatively, argon: nitrogen: carbon dioxide: methane: fluorine can be selected from 5 to 80 sccm: 10 to 95 sccm: 0 to 30 sccm: 0 to 30 sccm: 0 to 30 sccm. Instead of carbon dioxide (CO ₂ ), at least one of oxygen (O ₂ ), carbon monoxide (CO), nitrous oxide (N ₂ O), nitrogen oxides (NO), and nitrogen dioxide (NO ₂ ) may be used.

5 is a schematic diagram sequentially showing a gray tone blank mask and a method of manufacturing the same according to the first embodiment of the present invention.

First, referring to FIG. 5C, the gray tone blank mask B1 according to the first exemplary embodiment of the present invention has the remaining portions except for the portion 68 on which the photomask alignment pattern is to be formed on the transparent substrate 52. A semi-transmissive film 54 is formed on the light shielding film 58, and a light shielding film 58 is formed on the entire surface of the transparent substrate 54 including the portion 68 on which the alignment pattern is to be formed. The antireflection film 60 and the resist film 62 are sequentially formed on the light shielding film 58. In this way, only the light shielding film 58 having a high reflectance is formed in the portion 68 where the alignment pattern is to be formed without the transflective film 54, so that the rear reflectance of the portion 68 where the alignment pattern is to be formed is the light shielding film 58. This results in high reflectance.

The back reflectance of the portion 68 where the alignment pattern is to be formed is preferably 20 to 70% at a wavelength of 400 to 800 nm, or a wavelength of 400 to 600 nm. If the rear reflectance is less than 20%, the reflectance is not enough to make it difficult to check the alignment accurately.If the rear reflectance is 70% or more, the light reflected from the back of the photomask during the lithography process This multiple scattering is likely to cause exposure failure. The remaining portion other than the portion 68 where the alignment pattern is to be formed preferably has a back reflectance of 1 to 20% at a wavelength of 400 to 800 nm, or a wavelength of 400 to 600 nm.

The light transmittance of the transflective film 54 is 20 to 70% at a specific exposure wavelength, for example, at any one of 157 nm, 193 nm, 248 nm, 365 nm, 405 nm, and 436 nm, and the transparent substrate 52 and the transflective film ( It is preferable that the optical phase difference of 54) is 100 degrees or less. The semi-permeable membrane 54 may be composed of a continuous membrane (single membrane) in which the constituents are changed from the transparent substrate 52 to the upper layer, and the two or more low-permeable and high-permeable membranes are laminated. Can be. At this time, the low permeable membrane can control the transmittance and the high permeable membrane can control the phase difference.

When the transflective film 54, the light shielding film 58, or the antireflection film 60 is a chromium (Cr) compound, chromium nitride (CrN), chromium oxide (CrO), chromium carbide (CrC), and chromium carbide (CrCO) , Chromium nitride (CrCN), chromium oxynitride (CrON), chromium oxynitride (CrCON), chromium fluoride (CrF), chromium fluoride (CrNF), chromium fluoride (CrOF), chromium fluorocarbon (CrCF), It may include one or more of chromium oxynitride (CrCNF), chromium oxynitride (CrONF), chromium fluoronitride (CrCONF). In the case of molybdenum silicide (MoSi) compounds, molybdenum silicide (MoSiN), molybdenum silicide (MoSiO), molybdenum carbide (MoSiC), molybdenum carbide carbide (MoSiCO), molybdenum nitride (MoSiCN), and molybdenum nitride (MoSiON), molybdenum oxynitride (MoSiCON), molybdenum fluoride (MoSiF), molybdenum fluoride (MoSiNF), molybdenum fluoride (MoSiOF), molybdenum fluoride (MoSiCF), molybdenum fluoride (MoSiCNF), molybdenum oxynitride silicide (MoSiONF), molybdenum oxynitride silicide (MoSiCONF) may include at least one or more. In the case of aluminum (Al) compounds, aluminum oxide (AlO), aluminum nitride (AlN), aluminum carbide (AlC), aluminum nitride carbide (AlCN), aluminum carbide oxide (AlCO), aluminum oxynitride (AlON), oxynitride Aluminum (AlCON), aluminum fluoride (AlF), aluminum fluoride (AlNF), aluminum fluoride (AlOF), aluminum fluorocarbon (AlCF), aluminum fluoronitride (AlCNF), aluminum oxynitride (AlONF), fluorocarbon It may include at least one of the aluminum image quality (AlCONF).

At this time, the component ratio of the transflective film 54, the light shielding film 58, and the antireflection film 60 is 0 to 20 at% of carbon, 0 to 60 at% of oxygen, 0 to 60 at% of nitrogen, and 0 to 40 at% of fluorine. It is in a range and it is preferable that a remainder consists of a metal.

6 shows, by way of example, a portion 68 of the transparent substrate 52 on which a photomask alignment pattern is to be formed. Here, the portion 68 in which the alignment pattern is to be formed at the center of the four sides of the transparent substrate 52 is defined. The position and quantity of the portion 68 in which the photomask alignment pattern is to be formed may be changed according to the equipment specification requiring the alignment of the stepper or the like.

In order to perform the process of preventing the transflective film 54 from being formed in the portion 68 of the transparent substrate 52 made of glass or quartz, where the photomask alignment pattern is to be formed, the following process is performed.

First, a sputtering screen component having a desired shape is mounted on the substrate holder 36 of FIG. 7 shows a top view and a cross-sectional view of the sputtering screen component 37 mounted on the substrate holder 36. The sputtering screen component 37 is installed so as to correspond to the portion 68 in which the photomask alignment pattern is to be formed. More preferably, the sputtering screen component 37 is installed at a distance of 0.1 to 30 mm from the surface of the transparent substrate 52 so as not to contact the transparent substrate 52. If the distance between the transparent substrate 52 and the sputtering screen component 37 is 0.1 mm or less, the transparent substrate 52 and the sputtering screen component 37 may contact each other and may cause defects. The transflective film 54 is formed in the portion 68 where the alignment pattern is to be formed.

In the production of the sputtering screen component 37, the shape and size of the pattern when considering the position on the transparent substrate 52 and the photomask in the region where the position alignment is performed by the stepper equipment in the reflection method are considered. For ease of design, it is designed and manufactured as in 7 with a wider area than the yarn pattern.

The sputtering screen component 37 required for photomask alignment is mounted on four centers and four locations of the transparent substrate 52 as shown in FIG. 7 to facilitate mask handling. At this time, the position and the number of mounting the sputtering screen component 37 are changed correspondingly according to the position and the quantity of the portion 68 on which the photomask position alignment pattern is to be formed.

In order to prevent the semi-permeable membrane 54 from being formed in the portion 68 where the alignment pattern is to be formed when the semi-permeable membrane 54 is formed, screen the desired position according to the shape and size of the photomask alignment pattern. After mounting and adjusting the sputtering screen component 37 to form the semi-permeable membrane 54 and a preferable process thereafter, the process proceeds as follows and refer to FIG. 5.

(Step 1) Install the sputtering screen component 37. The transparent substrate 52 is heated at a temperature of 100 to 800 ° C. for 1 second to 30 minutes in order to improve the adhesion of the semi-permeable film 54 to be formed on the transparent substrate 52 and the growth of the film. For example, the transparent substrate 52 is heated at 150 ° C. for 10 minutes in the vacuum chamber 30.

Using a mixed target of molybdenum (Mo) and silicon (Si) components on the transparent substrate 52 by reactive sputtering under a mixed gas atmosphere with argon: nitrogen of 5 to 90 sccm: 10 to 95 sccm and a pressure of 1 to 5 mTorr The content of nitrogen (N) is 0 to 60 at%, and the remainder forms a semi-permeable membrane 54 of molybdenum nitride nitride, which is a metal component. The semi-transmissive film 54 is formed by the sputtering screen component 37 in the regions other than the region 68 in which the photomask alignment pattern is to be formed.

(Step 2) The semi-transmissive film 54, which is molybdenum nitride, has a transmittance of 20 to 70% with respect to the exposure wavelength, has an optical retardation (phase shift) of 100 degrees or less, and a thickness of 50 to 4,500 kPa. Controlling the light transmittance at the exposure wavelength to 20 to 70% is to control the remaining thickness of the resist during the exposure and development process when manufacturing the TFT-LCD by the 4-mask process using a gray tone photomask. When the light transmittance is 20% or less, the resist residual thickness becomes too thick, making it difficult to perform the 4-mask process. When the light transmittance is 70% or more, the resist residual thickness becomes too thin, which makes it difficult to perform the 4-mask process again. Because it becomes. In addition, when the optical phase difference is 100 degrees or more, the destructive interference is increased due to the interference of adjacent light, resulting in poor uniformity of the resist surface.

On the other hand, the semi-permeable membrane 54 is composed of a continuous membrane (single membrane), the composition of the component changes as the upper layer from the transparent substrate 52 to the upper layer, or a low-permeable membrane and a high-permeable membrane is laminated two or more layers Can be configured. At this time, the low permeable membrane can control the transmittance and the high permeable membrane can control the phase difference.

(Step 3) Annealing or heat treatment at a temperature of 100 to 800 ° C. for 1 second to 30 minutes in order to reduce stress by vacuum deposition and to improve resistance to acid and light after forming the semi-permeable film 54. Conduct. (Refer to (a) of FIG. 5 above.)

(Step 4) Remove the sputtering screen component 37, and target the chromium (Cr) and semi-permeate by reactive sputtering under a mixed gas atmosphere with argon: nitrogen of 5 to 90 sccm: 10 to 95 sccm and a pressure of 1 to 5 mTorr. On the film 54, a light-shielding film 58 of chromium nitride having a thickness of 300 to 2,000 kPa having a component content of nitrogen (N) of 0 to 60 at% and the rest of the metal is formed. In order to improve adhesion and growth of the film, the light blocking film 58 may be formed after first heating the transparent substrate 52 at a temperature of 100 to 800 ° C. for 1 second to 30 minutes.

(Step 5) When the light shielding film 58 is formed, the back reflectance in the region 68 in which the alignment pattern is to be formed has a reflectance of 20 to 70% at a wavelength of 400 to 800 nm or 400 to 600 nm, which is a wavelength for alignment. It is preferable to have. If the rear reflectance is less than 20%, the reflectance is not sufficient to make it difficult to accurately check the position alignment. If the rear reflectance is 70% or more, the light reflected from the back of the photomask during the lithography process is multiplied. Scattering is likely to cause exposure failure.

(Stage 6) Reactive under argon (Ar): Nitrogen (N ₂ ): Oxygen (O ₂ ) in a mixed gas atmosphere with 5 to 90 sccm: 10 to 95 sccm: 0 to 30 sccm and a pressure of 1 to 5 mTorr By sputtering, the antireflection film 60 of chromium oxynitride having a thickness of 50 to 500 kPa having a component content of 0 to 60 at% of oxygen (O), 0 to 60 at% of nitrogen (N), and a metal component of the rest is sputtered. To form. When forming the light shielding film 58 and the anti-reflection film 60, it is possible to form a continuous film (single film) or two or more layers in which the nitrogen content increases toward the transparent substrate 52.

(Step 7) For stress relief by vacuum deposition and resistance to acid and light after the anti-reflection film 60 is formed, and for excellent adhesion between the interface of the resist film 62 and the anti-reflection film 60 to be formed subsequently Annealing or heat treatment is carried out at a temperature of 100 to 800 ° C. for 1 to 30 minutes. (Refer to (b) of FIG. 5 above.)

(Step 8) A gray tone blank mask B1 according to the present invention, in which a resist film 62 is formed by applying a resist on the antireflection film 60, is manufactured. The resist to be applied may be selected from an optical photoresist, a positive chemically amplified resist, a negative chemically amplified resist, a resist composed of PAG, and the like, and the coating method of the resist may be spin coating or capillary coating. The thickness of the resist film is preferably in the range of 1,000 to 15,000 Pa, and more preferably soft bake in the temperature range of 50 ° C to 250 ° C using a hot plate after applying the resist film. (Refer to (c) of FIG. 5 above.)

A method for performing the photomask process with the gray tone blank mask B1 manufactured according to the above process is schematically illustrated in FIG. 8, as follows.

(Step 1) Exposure is performed using an electron beam to form a pattern on the gray tone blank mask B1 on which the resist film 62 is formed.

(Step 2) A development process is performed on the exposed portion to form a first resist pattern corresponding to the anti-reflection film 60 on the gray tone blank mask. (Refer to (a) of FIG. 8 above.)

(Step 3) The anti-reflection film 60 and the light shielding film 58 are sequentially dry-etched by dry etching using Cl ₂ and O ₂ gas using the formed first resist pattern as a mask.

(Step 4) When the anti-reflective film 60 and the light shielding film 58 are etched to expose the transflective film 54, molybdenum nitride, which is a material of the transflective film 54, may be formed using CF ₄ and O ₂ gas. Using the first resist pattern as a mask, dry etching is performed until the transparent substrate 52 is exposed to form the primary pattern P1.

(Step 5) After the remaining first resist pattern is removed in a sulfuric acid solution by dipping, a cleaning process is performed to remove foreign substances that may remain on the surface of the anti-reflection film 60. (Refer to (b) of FIG. 8 above.)

(Step 6) In order to manufacture a gray-tone photomask for TFT-LCD, the transflective pattern corresponding to the pattern of the antireflection film 60 and the light shielding film 58 corresponding to the source and the drain and the channel portion corresponding to the channel portion between the source and the drain are shown. In order to prepare the design data on which the film 54 pattern is formed first, in order to proceed to the next process, gray tone in which the primary pattern P1 of the anti-reflection film 60, the light shielding film 58, and the semi-transmissive film 54 is sequentially formed A new resist film 64 is formed over the blank mask.

(Step 7) Laser exposure is performed on the position where the semi-transmissive film 54 corresponding to the channel portion is to be exposed according to the design data.

(Step 8) A development process is performed on the exposed portion to form a second resist pattern corresponding to the channel portion on the gray tone blank mask. (Refer to (c) of FIG. 8 above.)

(Step 9) The semi-transmissive film 54 may be exposed by sequentially dry etching the anti-reflection film 60 and the light shielding film 58 using Cl ₂ and O ₂ gas using the formed second resist pattern as a mask. The difference pattern P2 is formed.

(Step 10) The remaining second resist pattern is removed by dipping in sulfuric acid solution, and then cleaned to remove foreign substances that may remain on the surface of the anti-reflection film 60, the semi-transmissive film 54, and the transparent substrate 52. The process is carried out to complete the photomask 70 manufacturing process. (Refer to (d) of FIG. 8 above.)

As described above, the photomask manufacturing process using the gray tone mask blank according to the first embodiment of the present invention is completed.

A back reflectance graph according to the wavelength of the portion where the alignment pattern is to be formed in the existing gray tone blank mask is shown in FIG. 9A. In the gray tone blank mask according to the present invention, the reflectance of the portion 68 on which the alignment pattern is to be formed, in which the transflective film 54 is not formed, was measured to be 30% or more in the wavelength range of 400 to 800 nm as shown in FIG. 9B. , The reflectance of the rest portion was measured as showing a reflectance of 8 to 15% in the wavelength range of 400 ~ 800nm, as shown in Figure 9a was found to be a precise position alignment.

(Example 2)

10 is a schematic diagram showing a gray tone blank mask and a method of manufacturing the same according to a second embodiment of the present invention.

As shown in (c) of FIG. 10, the gray tone blank mask B2 according to the second exemplary embodiment of the present invention except for the portion 68 on which the photomask position alignment pattern is to be formed on the transparent substrate 52. The transflective film 54 and the etch stop film 56 are formed on the part, and the light shielding film 58 is formed on the front surface of the transparent substrate 54 including the part 68 on which the alignment pattern is to be formed. It is. The antireflection film 60 and the resist film 62 are sequentially formed on the light shielding film 58. In this way, only the light shielding film 58 having a high reflectance is formed in the portion 68 where the alignment pattern is to be formed without the transflective film 54, so that the rear reflectance of the portion 68 where the alignment pattern is to be formed is the light shielding film 58. This results in high reflectance.

Hereinafter, a method of manufacturing such gray tone blank mask B2 will be described.

First, the sputtering screen component 37 is installed on the transparent substrate 52 to correspond to the portion 68 on which the alignment pattern is to be formed in the same manner as in the first embodiment. 56). The composition and the component ratio range of the etch stop film 56 are the same as those of the semi-transmissive film 54, the light shielding film 58, and the anti-reflection film 60 as mentioned above.

Hereinafter, the process will be described based on differences from the first embodiment. Portions where the description is omitted may use the description of the first embodiment as it is.

(Step 1) Targeting chromium (Cr) Argon (Ar): Nitrogen (N ₂ ): Carbon dioxide (CO ₂ ): Methane (CH ₄ ) 5 ~ 80sccm: 1 ~ 95sccm: 0 ~ 30sccm: 0 ~ 30sccm Reactive sputtering under phosphorus mixed gas atmosphere and pressure of 1 ~ 5mTorr, the component content is 0 ~ 20at% of carbon (C), 0 ~ 60at% of oxygen (O) and nitrogen (N) on transparent substrate 52. 0 to 60 at%, the rest of which forms a semi-permeable film 54 of chromium carbide oxynitride. The semi-transmissive film 54 is formed by the sputtering screen component 37 in the regions other than the region 68 in which the photomask alignment pattern is to be formed.

(Step 2) The semi-transmissive film 54, which is chromium oxynitride, has a transmittance of 20 to 70% with respect to the exposure wavelength, has an optical retardation (phase shift) of 100 degrees or less, and a thickness of 50 to 4,500 kPa. .

(Step 3) After the semi-permeable film 54 is formed, annealing or heat treatment is performed at a temperature of 100 to 800 ° C. to reduce stress by vacuum deposition and to improve resistance to acids and light.

(Step 4) Reactive sputtering under a mixed gas atmosphere with argon: nitrogen of 5 to 90 sccm: 10 to 95 sccm and a pressure of 1 to 5 mTorr using an aluminum (Al) target while the sputtering screen part 37 is still mounted. As a result, an etchstop film 56 of aluminum nitride having a thickness of 20 to 500 kPa having a component content of nitrogen (N) of 0 to 60 at% and the remainder of the metal component is formed on the transflective film 54. The etch stop membrane 56 may be manufactured to have a different composition ratio from the semi-permeable membrane 54 to the upper layer, and is preferably manufactured in combination with the semi-permeable membrane 54 to facilitate phase and permeation control.

The process of forming the light shielding film 58, the antireflection film 60 and the resist 62 after the (step 5) (step 4) is the same as that of the (step 4) to the (step 8) of the first embodiment.

A method for performing the photomask process with the gray tone blank mask B2 prepared by (step 1) to (step 5) is schematically illustrated in FIG. 11, as follows.

(Step 1) In order to form a pattern in the gray tone blank mask B2 in which the resist film 62 was formed, it exposes using the laser of monochromatic light.

(Step 2) A development process is performed on the exposed portion to form a first resist pattern corresponding to the anti-reflection film 60 on the gray tone blank mask. (Refer to (a) of FIG. 11 above.)

(Step 3) The pattern is formed by sequentially wet etching the anti-reflection film 60 and the light shielding film 58 using the formed resist pattern as a mask.

(Step 4) When the anti-reflection film 60 and the light shielding film 58 are etched, the etch stop film 56 is exposed, and aluminum nitride, which is a material of the etch stop film 56, is exposed to the transparent film 54. Wet etching to form a pattern.

(Step 5) The chromium carbide oxynitride film, which is a material of the semi-transmissive film 54, is formed by using a pattern composed of a first resist pattern, an antireflection film 60, a light shielding film 58, and an etchstop film 56 as a mask. Wet etch to form a pattern until 52) is exposed. In this way, the primary pattern P1 is completed.

After (step 6), the remaining first resist pattern is removed by a resist ashing method, and then a cleaning process is performed to remove foreign substances that may remain on the surface of the anti-reflection film 60. (Refer to (b) of FIG. 11 above.)

(Step 7) A semi-transmissive film corresponding to the pattern of the anti-reflection film 60 and the light shielding film 58 corresponding to the source and the drain and the channel portion corresponding to the source and the drain in order to fabricate the gray-tone photomask for TFT-LCD (54) The design data on which the pattern is formed is prepared first, and then the gray tone in which the primary pattern P1 of the anti-reflection film 60, the light shielding film 58, the etch stop film 56, and the semi-transmissive film 54 is formed is sequentially formed. A new resist film 64 is formed on the blank mask to form a pattern through which the semi-transmissive film 54 portion can be exposed.

(Step 8) Laser exposure is performed on the position where the semi-transmissive film 54 corresponding to the channel portion should be exposed according to the design data.

(Step 9) A development process is performed on the exposed portion to form a second resist pattern corresponding to the channel portion on the gray tone blank mask. (Refer to (c) of FIG. 11 above.)

(Step 10) The anti-reflective film 60 and the light shielding film 58 are sequentially wet-etched using the second resist pattern as a mask to form a pattern to expose the etch stop film 56.

(Step 11) The aluminum nitride, which is the material of the exposed etchstop layer 56, is wet etched to form a secondary pattern P2 through which the semi-transmissive layer 54 may be exposed.

(Step 12) After removing the remaining second resist pattern by ashing, a cleaning process is performed to remove foreign substances that may remain on the surface of the anti-reflection film 60, the semi-transmissive film 54, and the transparent substrate 52. This completes the photomask 72 manufacturing process. (Refer to (d) of FIG. 11 above.)

(Example 3)

12 is a schematic diagram showing a gray tone blank mask and a method of manufacturing the same according to a third embodiment of the present invention.

Referring first to FIG. 12D, the gray tone blank mask B3 according to the present embodiment includes a transparent substrate 52, a semi-transmissive layer 54 patterned on the transparent substrate 52, and a semi-transmissive layer. The light shielding film 58 and the antireflection film 60 are sequentially formed on the 54, and then the resist film 64 is formed on the antireflection film 60.

The manufacturing method of the gray tone blank mask B3 is as follows.

delete

(Step 1) Prepare the transparent substrate 52. Using a mixed target of molybdenum (Mo) and silicon (Si) components on the transparent substrate 52 by reactive sputtering under a mixed gas atmosphere with argon: nitrogen of 5 to 90 sccm: 10 to 95 sccm and pressure of 1 to 5 mTorr Nitrogen (N) is 0 to 60 at%, and the remainder forms a semi-permeable membrane 54 of molybdenum nitride, which is a metal component.

(Step 2) The semi-transmissive film 54 of molybdenum nitride is a semi-transmissive film having a transmittance of 20 to 70% at a specific wavelength and having a thickness of 50 to 4,500 Hz with a phase shift of 100 degrees or less.

(Step 3) A first resist film 62 is formed on the semi-transmissive film 54 in order to manufacture a gray tone blank mask which can obtain a back reflectance of 20% or more in the wavelength region of 400 nm to 800 nm. (Refer to (a) of FIG. 12 above.)

(Step 4) A portion 68 on which the photomask alignment pattern is to be formed on the first resist film 62 and a portion for describing the information on the design data to describe the information on the design data including the photomask position alignment. It exposes using an electron beam.

(Step 5) A first resist pattern corresponding to the transflective film 54 is formed on the exposed portion through the developing process. (Refer to (b) of FIG. 12 above.)

(Step 6) CF ₄ and so that the transparent substrate 52 including the portion 68 to form the photomask alignment pattern and the portion for describing the information on the design data are exposed using the first resist pattern formed as a mask. The semi-permeable membrane 54 is etched by a dry etching method using O ₂ gas to form a pattern.

(Step 7) The remaining first resist pattern is completely removed by the dipping method in sulfuric acid solution, and then the foreign substances that may remain on the surface of the transflective film 54 and the surface of the transparent substrate 52 exposed by the pattern formation are removed. Carry out a cleaning process.

(Step 8) Heat treatment is performed at a temperature of 100 to 800 ° C. in order to have excellent stress relaxation on the surface of the semi-transmissive film 54 having the pattern formed thereon and resistance to acids and light. (Refer to (c) of FIG. 12 above.)

 (Step 9) Then, a light shielding film 58, an antireflection film 60 and a second resist film 64 are formed on the semi-transmissive film 54 where the pattern is formed to manufacture a gray tone blank mask B3. The process is carried out in the same manner as in (step 4) to (step 8) of the first embodiment. (Refer to (d) of FIG. 12 above.)

Next, referring to FIG. 13B, the gray tone photomask 74 according to the present embodiment is formed by further etching the light shielding film 58 and the anti-reflection film 60 of the gray tone blank mask B3. .
A method for performing the photomask process with the gray tone blank mask B3 prepared by the above (1 step) to (9 step) is schematically illustrated in FIG. 13, as follows.
(Step 1) Exposure is performed using an electron beam to form a pattern on the gray tone blank mask B3 on which the second resist film 64 is formed.

(Step 2) A second resist pattern corresponding to the anti-reflection film 60 is formed on the exposed portion of the gray tone blank mask B3 through a developing process. (Refer to (a) of FIG. 13 above.)

(Step 3) Using the second resist pattern as a mask, the antireflection film 60 and the light shielding film 58 are sequentially dry-etched using Cl ₂ and O ₂ gases to form a pattern.

(Step 4) The remaining second resist pattern is completely removed from the sulfuric acid solution by dipping, and then a cleaning process is performed to remove foreign substances that may remain on the surface of the anti-reflection film 60 and the surface of the transflective film 54. .

According to the above process, the gray tone mask blank and the photomask manufacturing process according to the present embodiment are discontinuously obtained, so that the back reflectance of 20% or more in the region 68 where the alignment pattern is to be formed can be obtained in the wavelength region of 400 to 800 nm. Gray tone photomasks for TFT-LCDs can be produced.

In the first to third embodiments, the source pattern, the drain pattern, and the channel pattern of the TFT-LCD manufacturing process are manufactured. However, the present invention can be applied to other patterns or other products. For example, the present invention can be applied to manufacturing a passivation pattern of TFT-LCD manufacturing, and can also be used to manufacture color filters of TFT-LCD manufacturing. In addition to the TFT-LCD manufacturing process, it can be used to manufacture semiconductor circuits, plasma display panels (PDPs), organic light emitting diodes (OLEDs), and the like.

As mentioned above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the technical spirit of the present invention. It is obvious.

According to the gray tone blank mask and the photomask manufacturing method of the present invention, since the reflectance of the alignment pattern is high, the photomask position alignment can be made very easily and accurately.

Therefore, when the gray tone photomask according to the present invention is used in the lithography process, not only the mask shortening process such as the 4-mask process of the TFT-LCD manufacturing process can be used, but also the occurrence of defects due to the alignment error of each pattern can be reduced. In addition, it is possible to produce high quality products in which the position of each pattern is very precisely controlled. It can contribute to improving productivity and yield in the manufacture of flat panel displays and semiconductor devices.

The present invention can also be applied to flat panel displays other than 3-mask processes, semiconductor integrated circuits, and liquid crystal displays.

Claims (23)

Transparent substrate; A semi-transmissive layer formed on the transparent substrate except for a portion where a photomask alignment pattern is to be formed; And And a light blocking film formed on an entire surface of the transparent substrate, including a portion where the alignment pattern is to be formed. The method of claim 1, The gray tone blank mask, characterized in that further comprising an etch stop film between the transflective film and the light shielding film. The method of claim 1, The gray tone blank mask, characterized in that further comprising an anti-reflection film and a resist film sequentially on the light shielding film. The method of claim 3, The back reflectance of the portion where the photomask alignment pattern is to be formed is 20 to 70% in the wavelength range of 400 to 800 nm, and the back reflectance of the remaining portion is 1 to 20% in the wavelength range of 400 to 800 nm. Tone blank mask. The method of claim 3, At least one of the transflective film, the light shielding film, and the anti-reflection film is formed in a vacuum chamber by using a reactive sputtering or vacuum deposition method in which an inert gas and a reactive gas are introduced. The method of claim 5, At least one of the transflective film, the light shielding film, and the antireflection film is cobalt (Co), tantalum (Ta), tungsten (W), molybdenum (Mo), chromium (Cr), vanadium (V), palladium (Pd), titanium (Ti), niobium (Nb), zinc (Zn), hafnium (Hf), germanium (Ge), aluminum (Al), platinum (Pt), manganese (Mn), iron (Fe), silicon (Si), nickel 1 type selected from the group consisting of (Ni), cadmium (Cd), zirconium (Zr), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), yttrium (Y), and sulfur (S) It consists of the above metal or a compound thereof, As the inert gas, at least one selected from the group consisting of argon (Ar), helium (He), neon (Ne), and xenon (Xe) is used, and as the reactive gas, oxygen (O ₂ ), nitrogen (N ₂ ) With carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), nitrogen oxides (NO), nitrogen dioxide (NO ₂ ), ammonia (NH ₃ ), methane (CH ₄ ), fluorine (F ₂ ) Gray tone blank mask, characterized in that prepared using one or more selected from the group consisting of. The method of claim 6, When at least one of the transflective film, the light shielding film, and the antireflection film is formed of chromium, the chromium combination is chromium nitride (CrN), chromium oxide (CrO), chromium carbide (CrC), chromium carbide (CrCO), or carbonization. Chromium nitride (CrCN), chromium oxynitride (CrON), chromium carbide oxynitride (CrCON), chromium fluoride (CrF), chromium fluoride (CrNF), chromium fluoride (CrOF), chromium fluorocarbon (CrCF), fluorocarbon Gray tone blank mask, characterized in that it comprises at least one selected from the group consisting of chromium (CrCNF), chromium oxynitride (CrONF) and chromium oxynitride (CrCONF). The method of claim 6, When at least one of the semi-transmissive film, the light shielding film, and the antireflection film is made of molybdenum silicide combination, the molybdenum silicide combination is molybdenum silicide (MoSiN), molybdenum silicide (MoSiO), molybdenum carbide (MoSiC), silicon carbide oxide silicide Molybdenum (MoSiCO), Molybdenum Nitride Nitride (MoSiCN), Molybdenum Nitride Nitride (MoSiON), Molybdenum Nitride Nitride (MoSiCON), Molybdenum Nitride (MoSiF), Molybdenum Nitride (MoSiNF), Molybdenum Nitride MoSiOF), molybdenum carbide silicide (MoSiCF), molybdenum nitride silicide (MoSiCNF), molybdenum nitride silicide (MoSiONF) and molybdenum oxynitride silicide (MoSiCONF), characterized in that it comprises one or more selected from the group consisting of Gray tone blank mask to make. The method of claim 6, When at least one of the transflective film, the light shielding film, and the antireflection film is made of an aluminum combination, the aluminum combination is aluminum oxide (AlO), aluminum nitride (AlN), aluminum carbide (AlC), aluminum nitride carbide (AlCN), or carbide Aluminum oxide (AlCO), aluminum oxynitride (AlON), aluminum carbide oxynitride (AlCON), aluminum fluoride (AlF), aluminum fluoride (AlNF), aluminum fluoride (AlOF), aluminum fluoride (AlCF), fluorocarbon Graytone blank mask, characterized in that it comprises at least one selected from the group consisting of aluminum nitride (AlCNF), aluminum oxynitride (AlONF) and aluminum oxynitride (AlCONF). The method according to any one of claims 6 to 9, The component ratio of at least one of the transflective film, the light shielding film, and the antireflection film is 0 to 20 at% of carbon (C), 0 to 60 at% of oxygen (O), 0 to 60 at% of nitrogen (N), and fluorine (F). Is in the range of 0 to 40 at%, the remainder being made of metal. The method of claim 5, The vacuum degree of the vacuum chamber is 1 to 5 mTorr, and the mixing ratio of the reactive gas is argon (Ar): nitrogen (N ₂ ): carbon dioxide (CO ₂ ): methane (CH ₄ ): fluorine (F ₂ ) 90 sccm: 0 to 95 sccm: 0 to 30 sccm: 0 to 30 sccm: Gray tone blank mask, characterized in that the production is selected from the range of 0 to 30 sccm. The method of claim 5, The vacuum degree of the vacuum chamber is 1 to 5 mTorr, and the mixing ratio of the reactive gas is argon (Ar): nitrogen (N ₂ ): oxygen (O ₂ ), carbon monoxide (CO), nitrous oxide (N ₂ O), and oxidation One or more gases selected from nitrogen (NO) and nitrogen dioxide (NO ₂ ): methane (CH ₄ ): fluorine (F ₂ ) 5 to 90 sccm: 0 to 95 sccm: 0 to 30 sccm: 0 to 30 sccm: 0 to 30 sccm Gray tone blank mask, characterized in that manufactured by The method of claim 1, The semi-permeable membrane is a continuous membrane manufactured so that the constituents change from the transparent substrate toward the upper layer, or the low-permeable membrane and the high-permeable membrane are configured to overlap two or more layers. The transflective film has a transmittance of 20 to 70% at an exposure wavelength of any one of 157 nm, 193 nm, 248 nm, 365 nm, 405 nm, and 436 nm, and has an optical retardation of 100 degrees or less at the exposure wavelength and a thickness of 50 to 4,500 Hz. Characteristic gray tone blank mask. The method of claim 2, The semi-permeable membrane and the etch stop membrane may be a continuous membrane manufactured so that the composition changes from the transparent substrate toward the upper membrane, or the low-permeable membrane and the high-permeable membrane are configured to overlap two or more layers. The transflective film and the etch stop film have a transmittance of 20 to 70% at an exposure wavelength of any one of 157 nm, 193 nm, 248 nm, 365 nm, 405 nm, and 436 nm, and have an optical phase difference of 100 degrees or less at the exposure wavelength, and a thickness of 50 to 50 nm. Gray mask blank, characterized in that 4,500Å. The method of claim 3, The resist film is formed to a thickness of 1,000 to 15,000Å by spin formation or capillary formation, After applying the resist film, a gray tone blank mask, characterized in that manufactured by performing a soft bake at a temperature range of 50 to 250 ℃ using a hot plate. Preparing a transparent substrate; Forming a transflective layer on the transparent substrate except for a portion where a photomask alignment pattern is to be formed; And And sequentially forming a light shielding film, an antireflection film, and a resist film on the transflective film. 17. The sputtering method of claim 16, wherein a sputtering layer is formed to correspond to a portion where a alignment pattern is to be formed between the sputtering target and the transparent substrate in order to form a semi-transmissive layer on a portion other than a portion where a photomask alignment pattern is to be formed on the transparent substrate. The gray component blank mask manufacturing method, characterized in that the screen component is installed at a distance of 0.1 to 30mm distance to the transparent substrate. Preparing a transparent substrate; Forming a transflective film on the transparent substrate; Forming a first resist film on the transflective film; Forming a first resist pattern by exposing and developing a portion including a portion where a photomask alignment pattern of the first resist film is to be formed; Etching the semi-transmissive layer using the first resist pattern as a mask, removing the first resist pattern, and then cleaning the semi-transmissive layer; And And sequentially forming a light blocking film, an antireflection film, and a resist film on the etched semi-transmissive film. The method according to any one of claims 16 to 18, And forming an etch stop film between the transflective film and the light shielding film. The method according to any one of claims 16 to 18, Preparation of the gray mask blank, characterized in that for heating for 1 second to 30 minutes at a temperature of 100 to 800 ℃ at any one or more of the steps before the semi-transmissive film, after the semi-transmissive film is formed, before forming the light-shielding film, after forming the light-shielding film. Way. In a graytone photomask, It is produced by patterning the gray tone blank mask of claim 3, A photomask alignment pattern is formed by patterning a light shielding film, and patterns other than the alignment pattern are formed by patterning a transflective film and a light shielding film. Exposing and developing the resist film of the gray tone blank mask according to claim 3 to form a first resist pattern; Sequentially etching the anti-reflection film, the light shielding film, and the semi-transmissive film by using the first resist pattern as a mask to form a primary pattern; Removing and cleaning the first resist pattern; Forming a new resist film on the photomask in which the primary pattern is formed; Exposing and developing the new resist film to form a second resist pattern; Etching the anti-reflection film and the light shielding film in the primary pattern using the second resist pattern as a mask; And And removing the second resist pattern and cleaning the gray resist photomask. Preparing a transparent substrate; Forming a transflective film on the transparent substrate; Forming a first resist film on the transflective film; Forming a first resist pattern by exposing and developing the photoresist alignment pattern of the first resist film to be formed and the portion of the semi-transmissive film to be formed; Etching the transflective layer using the first resist pattern as a mask; Removing and cleaning the first resist pattern; Sequentially forming a light blocking film, an antireflection film, and a second resist film on the etched semitransmissive film; Exposing and developing the second resist film to form a second resist pattern; Sequentially etching the anti-reflection film and the light blocking film by using the second resist pattern as a mask; And And removing the second resist pattern and cleaning the gray resist photomask.

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