KR101593390B1 - Blank mask and photo mask and method for manufacturing thereof - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blank mask, a photomask, and a method of manufacturing the same. More particularly, the present invention relates to a blank mask, a photomask, And a rapid thermal annealing process is carried out on all or at least one thin film to have a concentration of sulfuric acid and ammonium ions of not more than 100 ppbv, a flatness of not more than 1.0 탆 and a density of not less than 1.0 g / cm ³ at the surface of the uppermost layer of the blank mask Characterized in that a resist film is applied.

The present invention relates to a method of forming a resist pattern having a superior shape by reducing the concentration of sulfuric acid and ammonium ions and densifying a thin film by reducing the flatness by performing a rapid thermal annealing process on a thin film of any one of a phase reversal film, It is possible to manufacture a high-quality photomask capable of manufacturing a high-quality photomask that can reduce the occurrence of scum in the lithography process.

A blank mask, a photomask, a rapid thermal annealing, a chemically amplified resist

Description

FIELD OF THE INVENTION [0001] The present invention relates to a blank mask, a photomask,

The present invention relates to a method of manufacturing a blank mask for manufacturing a photomask for use in a lithography process in a semiconductor manufacturing process, and more particularly, to a method of manufacturing a blank mask using KrF (KrF) or ArF excimer laser lithography And a rapid thermal process is performed on the phase reversal film, the light-shielding film or the antireflection film so as to be suitable for the process of manufacturing the blank mask.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photomask used in a lithography process for transferring a specific pattern onto a wafer using a photomask in the manufacture of semiconductor devices and a blank mask used for manufacturing a photomask, A bare mask and a photomask to which a rapid thermal process suitable for fluorine argon excimer laser lithography is applied, and a manufacturing method thereof.

The photolithography process, which is a process of transferring a pattern onto a wafer using a photomask, requires finer and more precise pattern size and uniformity as semiconductor circuits become more highly integrated.

In order to realize this, in the photolithography process, the exposure light source has been short-wavelengthed by an i-line having a wavelength of 365 nm, a KrF excimer laser having a wavelength of 248 nm, and an ArF excimer laser having a wavelength of 193 nm. It is becoming high energy. Chemical amplified resist (CAR) is used to form finer and more precise patterns in the production of blank masks and photomasks. The chemically amplified type resist generates strong acid (Proton, H +) in the exposed portion after the exposure, and the generated strong acid is diffused by the post exposure bake (PEB) process performed after the exposure process. (OH Radical) is formed in the chemically amplified resist due to the generation of strong acid, and formation of the resist film pattern as described above is prevented by a developer (Developer) using TMAH (Tetra-methyl Ammonium Hydroxide) It proceeds. However, nitrogen (N), which is a basic material included in the antireflection film of the blank mask, is combined with H + generated by the exposure light to cause defects such as scum, which makes wet etching and dry etching difficult, There is a problem of substrate dependency. Also, when the multilayer thin film is formed by the reactive sputtering method, the substrate is warped by the thin film stress and the flatness is increased, which causes warping of the transferred pattern by distorting the pattern during the lithography process.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a blank mask and a photomask capable of reducing the generation of sulfuric acid and ammonium ions by nitrogen (N) contained in the antireflection film and reducing the flatness.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems described above, and it is an object of the present invention to minimize the dependency of the resist on the substrate, minimize the change in sensitivity of the resist, and reduce the concentration of sulfuric acid and ammonium ions And a method of manufacturing a blank mask and a photomask having an excellent resist pattern that suppresses the occurrence of scum or the like through minimization, reduction in flatness, and densification of a thin film.

In order to accomplish the above object, the present invention provides a method of manufacturing a semiconductor device, comprising: forming a light shielding film or an antireflection film on a blank mask in which a phase reversal film, a light shielding film, an antireflection film and a chemically amplified type resist are sequentially formed on a transparent substrate, The concentration of sulfuric acid and ammonium ions is 100 ppbv or less, the flatness is 1.0 m or less, and the density is 1.0 g / cm ³ or more on the surface of the uppermost layer of the blank mask.

According to an aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising: forming a resist film on a transparent substrate by sequentially laminating a phase reversal film, a light-shielding film, Wherein the rapid thermal annealing process is performed on the thin film forming the interface with the resist film or the thin film forming the selected one or more kinds of interfaces.

In particular, when the method of manufacturing a blank mask according to the present invention is used in a manufacturing process of a binary blank mask,

a1) forming a transparent substrate,

b1) forming a light-shielding film on the transparent substrate,

c1) forming an antireflection film on the light-shielding film,

d1) subjecting the antireflection film to rapid thermal annealing,

e1) a step of surface-modifying the rapidly heat-treated antireflection film

f1) coating the resist on the surface-modified anti-reflection film.

In addition, when the method of manufacturing a blank mask according to the present invention is used in a phase shift blank mask manufacturing process,

a2) forming a transparent substrate,

b2) forming a phase reversal film on the transparent substrate,

c2) forming a light shielding film on the phase reversal film,

d2) forming an antireflection film on the light-shielding film,

e2) subjecting the antireflection film to rapid thermal annealing,

f2) modifying the surface of the rapid thermal annealed anti-reflection film,

g2) applying a resist on the surface-modified anti-reflection film to manufacture a phase shift mask.

In the method of manufacturing a binary photomask according to the present invention,

a3) After forming a resist film pattern, an antireflection film pattern, and a light-shielding film pattern on a binary blank mask produced by the above-described methods (a1) to f1) And a step of stripping the resist film pattern to manufacture a binary photomask.

Further, in the method of manufacturing a phase reversal photomask according to the present invention,

a4) In the phase inversion blank mask produced by the above-described methods (a2) to g2), a resist film pattern, an antireflection film pattern, a light-shielding film pattern, a phase reversal film Removing the unnecessary resist film pattern after forming the pattern,

b4) removing the resist pattern and then cleaning the resist pattern,

c4) rapid thermal processing after the cleaning,

d4) modifying the surface after the rapid thermal annealing,

e4) forming a resist film by applying the resist after the surface modification,

f4) removing the unnecessary resist film pattern after forming the resist film, forming a resist film pattern, an antireflection film pattern and a light-shielding film pattern through a secondary pattern forming process generally used in manufacturing a phase reversal photomask,

g4) cleaning after removing the resist film pattern,

and (h4) a step of performing rapid thermal annealing after the cleaning step to manufacture a phase reversal photomask.

Hereinafter, each step will be described in detail.

In the above a1) and a2), the transparent substrate is made of glass, quartz or the like and has a size of 6 inches or more, which has a transmittance of at least 90% or more with respect to a laser having a lithography light source i-line (365 nm) Lt; / RTI >

In the step b2), the phase reversal film is formed by sputtering in a vacuum chamber in which an active and an inert gas are introduced using a metal as a matrix, and the phase reversal film is formed of Co, Cr, W, molybdenum, vanadium, palladium, titanium, niobium, zinc, cobalt, tantalum, tungsten, molybdenum, Mo, Cr, Vanadium, Pd, Ti, Nb, Zn, Hf, Ge, Al, Wherein the inert gas is at least one selected from the group consisting of argon (Ar), helium (He), neon (Ne), krypton at least using at least one active gas selected from the group consisting of (Kr) and xenon (Xe) is oxygen (O _2), nitrogen (N _2), carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), Quality small (NO), nitrogen dioxide (NO _2), ammonia (NH ₃₎ and methane and (CH ₄₎ using at least one kind or more gases selected from the group consisting of. When the mother phase of the phase reversal film is a combination of molybdenum silicide (MoSi), the molybdenum silicide (MoSiN), molybdenum oxide (MoSiO), molybdenum carbide (MoSiC), molybdenum carbide molybdenum (MoSiCO) (MoSiCN), molybdenum oxynitride (MoSiON) and molybdenum carbide oxynitride (MoSiCON).

The antireflection film in the steps b1) and c2) and the antireflection film in the steps c1) and d2) are chrome and chromium (Cr), chromium carbide (CrC), chromium nitride (CrN) Refers to a thin film containing at least one of CrO, CrCN, CrCO3, CrON, and CrO3.

The cleaning process in step c4) may be performed by using all or one selected cleaning solution selected from the group consisting of sulfuric acid, hydrogen peroxide, ammonia water and ultrapure water. Ultrasonic or Megasonic may be all or selectively At least one of them is applied, and the drying method using spin or isopropyl alcohol (IPA) is finally applied in the cleaning process. The cleaning process in each of the above steps can be selectively applied.

In the steps d1) and e2), a heat treatment process is applied for minimizing the concentration of sulfuric acid and ammonium, reducing the flatness and densifying the thin film, and the heat treatment method that can be used in each of the above steps is a vacuum oven, A vacuum chamber, and the like. In this case, the heat treatment in each step is carried out at a temperature of 100 ° C. to 1000 ° C., preferably 200 ° C. to 700 ° C., and is preferably carried out at a vacuum degree of 0 Pa to 0.5 Pa, preferably a vacuum degree of 0.1 to 0.3 Pa . Also, the heating method used in the heat treatment in the above steps d1 and e2) is preferably a rapid heat treatment method. Such a heat treatment can be performed for 1 minute to 60 minutes. And cooling after the heat treatment step, and the cooling is performed at atmospheric pressure or vacuum. At this time, the heat treatment in each step may be selectively applied.

In order to remove the skin layer and improve the adhesive strength in the above steps e1) and f2), an organic material containing silicon such as hexamethyldisilane, trimethylsilyldiethylamine, O-trimethylsilyl acetate (O trimethylsilylbutyrate, trimethylsilyltrifluoroacetate, trimethylmethoxy silane, N-methylmethoxy silane, N, N-dimethylformamide, Methyl-N-trimethylsilyltrifluoroacetamide, O-trimethylsilylacetylacetone, isopropenoxy-trimethylsilane, trimethylsilyltrifluoro Trimethylsilyl-trifluoroacetamide, methyltrimethylsilyldimethylketoneacetate A surface treating solution such as methyltrimethyl-silyldimethylketoneacetate, trimethylethoxysilane and the like may be used.

In the e1) and the f2), spin coating or vapor priming may be used as a surface treatment with an organic material containing silicon. In the step of surface-treating the antireflection film by the spin coating method in the above step, the injection amount of the organic material including silicon may be about 0.4 cc to 45 cc, and the number of revolutions may be 20 rpm to 2500 rpm.

As mentioned above, the blank and photomask according to the present invention provide the following effects.

First, the surface of the light-shielding film and antireflection film containing chromium is subjected to rapid thermal annealing to have a concentration of sulfuric acid and ammonium ions of 100 ppbv or less, a flatness of the substrate of 300 nm or less, and a thin film is densified. Provided are a blank mask and a photomask capable of improving the yield, such as scum, footing, skin layer and the like due to dependency on the substrate during mask fabrication, at the time of forming a fine pattern.

Second, in the above blank mask and photomask, a blank mask and a photomask capable of applying a fine pattern by adding a phase reversal film in addition to the light-shielding film and the antireflection film are provided.

Through the above process, the blank mask and the photomask according to the present invention were manufactured. Hereinafter, the present invention will be described in detail with reference to the examples. However, it should be understood that the examples have been used for the purposes of illustration and description only and are not intended to limit the scope of the present invention. no. Therefore, it will be understood by those skilled in the art that various modifications and other equivalent embodiments may be made by those skilled in the art. Accordingly, the true scope of the present invention should be determined by the technical scope of the claims.

(Example 1)

This embodiment relates to the concentration of sulfuric acid and ammonium ions on the surface of the antireflection film.

A light shielding film made of chromium carbide nitride (CrCN) was formed on the transparent substrate made of quartz through reactive sputtering to a thickness of 780 Å. At this time, argon (Ar) was used as a reactive gas, and methane (CH ₄ ) and carbon dioxide (CO ₂ ) were used as an inert gas. On the light-shielding film, an antireflection film made of chromium carbide oxynitride (CrCON) was formed to a thickness of 250 ANGSTROM. Methane (CH ₄ ), oxygen (O ₂ ), and carbon dioxide (CO ₂ ) were used as reactive gases.

Subsequently, rapid thermal annealing was performed to remove sulfuric acid and ammonium ions from the surface of the antireflection film. The chamber was heated in a chamber maintained at a high vacuum through a halogen lamp. The heat treatment was performed at a pressure of 0.2 Pa and a temperature of 400 캜 for 10 minutes, a time of 5 to 40 minutes, a pressure of 0.1 to 0.3 Pa, Lt; 0 > C to 700 < 0 > C.

At this time, when the rapid thermal annealing process is performed at atmospheric pressure or weak vacuum, the desorbed sulfuric acid and ammonium ions are reabsorbed. If the temperature exceeds 700 ° C., the transparent substrate, the light-shielding film, and the antireflection film may be defective due to excessive heat energy. If the heat treatment is performed at a temperature of less than 200 ° C., sufficient desorption energy is not provided.

At this time, on the transparent substrate on which the heat-treated antireflection film and the light-shielding film were formed by ion chromatography (Ion Chromatography) and gas chromatography / mass spectrometer (GC / MS), the concentration of sulfuric acid and ammonium ion And analyzed.

In the case of the transparent substrate on which the antireflection film was formed, the concentration of sulfuric acid and ammonium ion was 80 ppbv. It seems that the sulfuric acid and ammonium ions that cause problems such as scum, footing, skin layer and the like have been reduced considerably by the rapid heat treatment process.

In addition, to measure the flatness of the thin film subjected to the rapid thermal annealing, the flatness was 0.5 μm as measured by a flatness measuring apparatus FM-200. This is because the flatness is reduced due to the rapid thermal annealing process, and the warpage of the pattern, which is caused by the increase of the flatness, is considerably reduced due to the warp of the substrate due to the thin film stress of the multilayer. In addition, the density of the heat-treated thin film was measured by X-ray reflectivity (XRR), and it was found that the film was densified by measuring a value of 1.4 g / cm ^3. As a result, the light resistance , The chemical resistance and the anti-redness are improved, and the precision in the fine pattern is improved.

(Example 2)

The present embodiment relates to a blank mask 100 in which a light-shielding film 30, an antireflection film 40 and a resist 60 are sequentially formed on a transparent substrate 10 as shown in FIG. 1F.

A light shielding film 30 made of chromium carbide nitride (CrCN) was deposited on the transparent substrate 10 made of quartz through reactive sputtering to a thickness of 780 Å. Methane (CH ₄ ) and carbon dioxide (CO ₂ ) were used as the reactive gas. The thickness of the light-shielding film 30 is preferably in the range of 100 to 2500 angstroms.

An antireflection film 40 made of chromium carbide oxynitride (CrCON) was laminated on the light-shielding film to a thickness of 250 ANGSTROM. The thickness of the antireflection film is preferably laminated in a range of 100 ~ 1500Å, and the reactive gas is carbon dioxide (CO _2), methane (CH ₄₎ oxygen in addition to gas (O _2), carbon monoxide (NO), ammonia (NH ₃₎ and One or more of the fluorine (F) gases can be selectively applied.

In the light-shielding film 30 and the antireflection film 40, the optical density has a value of 3.0 and preferably has a value between 2.8 and 3.2. Further, it is preferable that the surface has a reflectance value of 11% at an exposure wavelength of 365 nm and a reflectance of 5 to 20%. The thickness of the light-shielding film 30 and the antireflection film 40 is preferably in the range of 100 to 1200 angstroms.

Subsequently, the mask laminated up to the antireflection film 40 was subjected to a rapid thermal annealing process (41) in a vacuum atmosphere. The concentration of sulfuric acid and ammonium ions after the rapid thermal annealing process of the surface of the antireflection film is preferably 100 ppbv or less, and 80 ppbv in this embodiment. Hexamethyldisilane was treated at 150 ° C. for 10 minutes after a rapid thermal annealing process on the surface of the antireflection film 40. At this time, trimethylsilyldiethylamine, O-trimethylsilyl acetate (O- trimethylsilylbutyrate, trimethylsilyltrifluoroacetate, trimethylmethoxy silane, N-methylmethoxysilane, N-methylmethoxy silane, N-trimethylsilyltrifluoroacetamide, O-trimethylsilylacetylacetone, isopropenoxy-trimethylsilane, trimethylsilyltrifluoroacetate, N-methyl- Amide (Trimethylsilyl-trifluoroacetamide), methyltrimethylsilyldimethylketoneacetate (Methyltrimethyl-silyldimethylketoneacetate), trimethylethoxysilane, and the like.

A blank mask was prepared by coating a resist with FEP-171, which is a type of chemically amplified resist, using a spin coating apparatus, which is one of thin film deposition methods. The thickness of the resist is preferably in the range of 1000 to 5000 angstroms. In this embodiment, the resist is laminated to a thickness of 3000 angstroms. After the resist is formed, a soft bake process is performed at 150 ° C. for 15 minutes. The soft bake application temperature is preferably 50 ° C. to 200 ° C., and the application time is preferably 5 minutes to 60 minutes.

(Example 3)

In this embodiment, as shown in FIG. 3, MoTaSiN is deposited on the transparent substrate 10 to a thickness of 870 ANGSTROM using reactive sputtering. Nitrogen (N 2) is used as the reactive gas and at least one or more of argon (Ar), helium (He), neon (Ne), and xenon (Xe) gases can be selectively used as the inert gas. At this time, it is preferable that the phase inversion is measured at 180 degrees, and the transmittance is preferably 6% at a wavelength of 248 nm. In addition to MoTaSiN used in the above phase reversal film, MoSi, MoSiN, MoSiO, and MoSiCO can be selectively stacked. Subsequently, a light shielding film and an antireflection film were formed on the phase reversal film in the same manner as in Example 2, and then the surface modification process was performed to form a monomolecular film. Then, a chemically amplified resist was applied to form a resist film, Phase inversion blank mask.

Referring to Figure 3a, it proceeds to the exposure process in an area having a predetermined pattern to the phase shift blank of using an electron beam with an acceleration of 50kV 9μC / cm ² to about 10μC / cm ² of energy to the mask completed through the above process , Followed by 15 minutes at 150 ° C on a hot plate, and then the post-exposure baking process is preferably performed at a temperature of 90 to 150 ° C for 5 to 15 minutes.

As shown in FIG. 3B, a development process was performed for 55 seconds with NMD-W (manufacturer: Tokyo Ohka Kogyo), which was a developer containing 2.38% of TMAH (Tetramethylammonium Hydroxide), and a resist pattern 60a was formed. . At this time, since the bonding between the resist and the antireflection film is prevented by the heat treatment process and the surface modification process in manufacturing the phase inversion blank mask, the resist pattern 60a having a good shape can be formed.

Subsequently, the antireflection film 40 and the light-shielding film 30 were dry-etched using the resist pattern 60a as a mask to form an antireflection film pattern 40a and a light-shielding film pattern 30a as shown in FIG. 3C. At this time, the dry etching process was performed for 400 to 600 seconds using Cl ₂ , O ₂ , and He gas.

Next, the phase reversal film pattern 20a is formed by dry etching using SF6, O2, and He gas for 500 seconds, and is preferably performed for 400 to 600 seconds.

In order to remove unnecessary resist patterns, the resist pattern was removed by quenching with sulfuric acid at 85 ° C for 30 minutes

Referring to FIG. 3E, a cleaning process is performed to remove foreign substances, and heat treatment is performed in the same manner as in the heat treatment conditions used in the production of the phase inversion blank mask in order to reduce air movement molecule contamination and to reduce stress and chemical resistance of the film. , Shielding film, antireflective film and resist film by blocking the bond between strong acid generated in the exposure and post-exposure baking process and forming the excellent resist pattern, the surface modification process is performed under the same condition as the surface modification process applied in the production of the phase inversion blank mask Respectively.

Next, as shown in FIG. 3F, a positive chemical amplification resist FEP 171 was spin-coated to form a resist film 150 having a thickness of 3000 Å, and then a soft bake process was performed on a hot plate. At this time, the soft bake temperature is preferably 150 ° C. for 10 minutes and preferably 100 ° C. to 150 ° C. for 5 minutes to 30 minutes.

After the formation of the resist film 150, also with the use of electron beams with an acceleration of 50kV 9μC / cm ² to about 10μC / cm ² of energy, as shown in 3g and exposed to an area having a predetermined pattern, a hot plate To perform a post-exposure baking process at 150 占 폚 for 15 minutes.

Referring to FIG. 3H, a resist pattern 150a is formed by performing a development process with NMD-W (manufacturer Tokyo Ohka Kogyo) containing 2.38% of TMAH (Tetramethylammonium Hydroxide) for 55 seconds, desirable. At this time, the bond between the resist and the antireflection film is prevented by the heat treatment process and the surface modification process, and the resist pattern 150a having a good shape can be formed.

Next, as shown in FIG. 3I, the antireflection film and the light-shielding film were dry-etched using the resist pattern as a mask to form the radiation prevention film pattern 40b and the light-shielding film pattern 30b. In this case, it is preferable to perform dry etching using O ₂ , He, Cl ₂ gas for 500 seconds and 400 to 600 seconds.

Thereafter, in order to remove the unnecessary resist pattern, the resist pattern was removed as shown in FIG. 3J by immersing in sulfuric acid at 85 ° C for 30 minutes, and a cleaning process was performed to remove foreign matter.

In order to desorb the sulfuric acid and ammonium ions of the thin film after the cleaning, a phase reversal photomask was prepared by heat treatment in the same manner as the above rapid thermal annealing conditions.

(Comparative Example 1)

In Comparative Example 1, a phase reversal film was formed by selecting MoSiON, MoSiN, MoSiO, MoSiC, MoSiCO, MoSiCN, MoSiON, or MoSiCON on a transparent substrate in the same manner as in Example 2, followed by forming a light shielding film and an antireflection film in this order. Then, a chemically amplified resist is laminated on the antireflection film to a thickness of 3000 Å to form a phase inversion blank mask without performing a heat treatment process, and the thickness of the resist is preferably 1,000 to 5,000 Å.

The concentration of sulfuric acid and ammonium ion was measured without laminating the antireflective film and subjected to the rapid thermal annealing process. As a result, it was 347 ppbv. This is a concentration at which a growth defect can occur during KrF or ArF excimer laser exposure.

This phenomenon is caused by adding nitrogen to the antireflection film as a reactive gas in the thin film formation by reactive sputtering considering the film stability, etch rate, reflectance, optical density, etc. of the antireflection film In the interface between the antireflection film and the chemically amplified resist, H + of the chemically amplified resist, which is Lewis Acid, which is supplied with N and electron pairs of the antireflection film serving as a Lewis Base, which provides electron pairs by covalent bonding, When H + is neutralized near the interface and rapid heat treatment is not performed, footing is generated in the case of the positive chemical amplification type resist, and undercut occurs in the case of the negative chemical amplification type resist.

If the rapid thermal annealing process is not carried out in the phase inversion blank mask manufacturing process, a resist pattern having defects caused by substrate dependency is formed, and thus it is difficult to manufacture a high quality photomask, and a considerable amount of sulfuric acid and ammonium ions Contamination occurs on the surface, and exposure to KrF and ArF excimer lasers causes growth defects, resulting in defects of the photomask.

The flatness of the thin film was measured to be 1.6 탆. This is due to the bending of the substrate due to the thin film stress of the rapid multilayer, and the pattern warpage is expected to occur as the flatness increases. In addition, the density of the thin film was measured to be 0.6 g / cm ^3. As a result, the light resistance, chemical resistance and antistatic property to the acid and alkali were deteriorated and the precision in the fine pattern was lowered.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a step of a method for manufacturing a binary blank mask.

FIGS. 2A to 2D are cross-sectional views illustrating a method of manufacturing a binary photomask according to an exemplary embodiment of the present invention.

3 is a cross-sectional view of a phase inversion blank mask according to one embodiment of the present invention.

3A to 3J are cross-sectional views illustrating a method of fabricating a phase inversion photomask according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS FIG.

10: transparent substrate

20: Phase reversal film

30:

30a: a light-shielding film pattern

40: Antireflection film

40a: Antireflection film pattern

41: Rapid heat treatment process

50: monolayer

60, 150: resist film

60a, 150a: resist film pattern

100: Binary blank mask

110: Phase inversion blank mask

200: Binary photomask

210: Phase Inversion Photomask

Claims (10)

1. A blank mask in which a film of at least one of a phase reversal film, a light-shielding film, and an antireflection film is laminated on a transparent substrate, The film provided on the uppermost layer of the films is surface-treated so that the concentration of sulfuric acid and ammonium ions is 100 ppbv or less, the flatness is 1.0 탆 or less, and the density is 1.0 g / cm ³ or more, Wherein the surface treatment is a rapid heat treatment under a pressure of 0.1Pa to 0.3Pa. delete delete delete The method according to claim 1, Further comprising a polymer compound including a resist film provided on the uppermost layer film and silicon provided between the resist film and the uppermost layer film. 6. The method of claim 5, The above-mentioned silicon-containing polymer may be used in combination with hexamethyldisilane, trimethylsilyldiethylamine, O-trimethylsilylacetate, O-trimethylsilyl-proprionate, Trimethylsilylbutyrate, trimethylsilyltrifluoroacetate, trimethylmethoxysilane, N-methyl-N-trimethylsilyltrifluoroacetamide (N-methyl-N- trimethylsilyltrifluoroacetate, O-trimethylsilylacetylacetone, isopropenoxy-trimethylsilane, trimethylsilyl-trifluoroacetamide, methyltrimethyl-silyldimethylketoneacetate ), Trimethylethoxysilane, Mask blank, characterized in that one of the. delete The method according to claim 1, Wherein the phase reversal film, the light shielding film or the antireflection film is in an amorphous form. delete The method according to claim 1, Wherein the rapid thermal annealing is performed at a temperature of 200 ° C to 700 ° C.

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