KR20060117287A - Half-tone type phase shift blank mask and manufacturing method of the same - Google Patents

Abstract

A half-tone type of phase shift blank mask for photo-mask used in lithographic process is provided to show excellent selectivity of a transparent substrate to a phase sift film in wet and dry etching processes, and offer superior chemical- and light-resistance by laminating the phase shift film, etching prevention film, light shielding film and resist film in order on the substrate. The phase shift blank mask(300) includes; a silicon containing thin film(70) formed between an anti-reflective film(60) and a resist film(80) by surface-treating the anti-reflective film with organic material containing silicon; and an etching prevention film(40) which includes wet etching solution, or metal or metal compound to be etched by dry etching gas. The wet etching solution is applied to at least one selected from a phase shift film, a light shielding film(50) and the anti-reflective film. The phase shift film comprises first and second phase shift films(20,30) which are formed with different compounds originated from the same metal.

Description

Half-tone type phase shift blank mask and manufacturing method of the same

1 is a cross-sectional view of a conventional halftone phase inversion blank mask not including an etch stop film;

2A to 2I are cross-sectional views of products produced in respective processes when a halftone type phase shift photomask is manufactured using a halftone type phase shift blank mask that does not include the etch stop film shown in FIG. 1;

3A to 3G are cross-sectional views of the products calculated at each step in performing the manufacturing process of the first embodiment for the halftone phase inversion blank mask according to the present invention;

4A to 4K are cross-sectional views of products calculated at each step in performing the fabrication process of the first embodiment for the halftone phase inversion photomask according to the present invention;

5 is a cross-sectional view of a second embodiment of a halftone phase inversion blank mask according to the present invention; and

6A to 6L are cross-sectional views of the products calculated at each step of performing the manufacturing process of the second embodiment for the halftone phase inversion photomask according to the present invention.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halftone phase shift blank mask and a method for manufacturing the same, and more particularly, to a halftone phase shift blank mask for manufacturing a halftone phase shift photomask used in a lithography process in the manufacture of a semiconductor device, and a method thereof. It relates to a manufacturing method.

Due to the high integration of semiconductor integrated circuits, the design rules of integrated circuits are becoming more and more fine, and a critical level (Critical Dimension: CD) of 0.07 μm or less is required. In order to accommodate this demand, high resolution of patterns through miniaturization of CD by shortening the wavelength of the exposure light source of optical lithography is progressing. As an exposure light source for the high resolution of the pattern, a krypton fluoride (KrF) excimer laser having a wavelength of 248 nm, an argon fluoride (ArF) excimer laser having a wavelength of 193 nm, and a fluorine (F ₂ ) excimer having a wavelength of 157 nm Short wavelength lasers such as lasers are used. Although the resolution can be improved by shortening the wavelength of the exposure light source, there is a problem that the depth of focus (DOF) decreases. In order to solve the problem caused by the short wavelength of the exposure light source, a phase inversion photomask is used. The phase inversion photomask is a material on which an image pattern defining a semiconductor circuit to be transferred on a wafer is formed, and before the image pattern is formed, it is called a phase inversion blank mask.

Among the phase inversion blank masks, halftone phase inversion blank masks are known to be effective for preparing contact holes or isolation patterns. In general, the halftone phase inversion blank mask is a half-tone phase inversion blank mask of a single layer structure that controls phase inversion and transmittance into a single layer, or a halftone phase inversion of two layer structure that controls phase inversion and transmittance control to each film. It may be divided into a blank mask. Typically, a halftone phase inversion blank mask applied to ArF lithography having an exposure wavelength of 193 nm is required to have a transmittance of 6 to 30%. In addition, with the introduction of ArF lithography having an exposure wavelength of 193 nm, the inspection wavelengths used for defect inspection in manufacturing halftone phase inversion blank masks and halftone phase inversion masks are also shortened to 248 nm, 365 nm, and the like. In this case, less than 40% transmittance is required, and if it has more than 40% transmittance, inspection becomes difficult.

In the conventional single film halftone type phase inversion blank mask, a phase inversion film mainly composed of MoSiN, MoSiON, MoSiCN, MoSiCON, etc., formed by a sputtering method, has been used. In order to realize 6% or more transmittance and 180 degree phase inversion at an exposure wavelength of 193 nm with such a phase inversion film, it is necessary to reduce the content of molybdenum (Mo), which is a metal series. However, when the Mo content of the phase inversion film is reduced, the refractive index is also reduced, resulting in a thick thickness of the phase inversion film, which makes it difficult to finely process the pattern. In addition, it is difficult to achieve a transmittance of less than 40% at an inspection wavelength of 248 nm or 365 nm. In addition, there is a problem that only dry etching using a fluorine (F ₂ ) -based gas is possible to form a pattern, and phase reversal during dry etching using a fluorine-based gas in a phase shift film of SiO ₂ and MoSi series, which are main materials of a transparent substrate. There is a problem that the selectivity of the transparent substrate to the film becomes small. Furthermore, the MoSi series phase inversion film has the property of being corroded by ammonia (NH ₃ ), which is generally used in the cleaning process of the halftone type phase inversion mask, so that the characteristics (thickness, transmittance, and phase inversion angle) of the phase inversion film during cleaning process There is a changing problem.

In the halftone phase inversion blank mask of a two-layer film, a phase inversion film of a two-layer film structure by the sputtering method has been used. The phase inversion film of the two-layer film structure has a problem that the thickness of the upper film becomes too thick in order to obtain a transmittance of 6% or more at an exposure wavelength of 193 nm. In addition, the lower layer has a problem that the selectivity for dry etching using fluorine-based gas is not sufficient, and only dry etching is possible to form a pattern. In addition, since the phase inversion film includes a silicon (Si) -based Si compound, it is difficult to control the process because it does not provide a sufficient selection ratio for the transparent substrate during dry etching.

1 is a cross-sectional view of a conventional halftone phase shift blank mask that does not include an etch stop film.

Referring to FIG. 1, the halftone phase inversion blank mask not including an etch stop layer may include a phase inversion film 20, a light shielding film 50, an antireflection film 60, and silicon on a transparent substrate 10. 70) and the resist film 80 are sequentially stacked. The phase inversion film 20 is a single film made of chromium oxynitride (CrCON) and is formed to have a thickness of 100 to 900 mW. In this case, the phase inversion film 20 was measured by the transmittance and phase inversion measuring instrument MPM-193. As a result, 20-30% transmittance and 170-190 degree phase inversion were measured at a wavelength of 193 nm. The transmittance of up to 37.6% was measured with the n & k Analyzer 1512RT. The light shielding film 50 is made of chromium nitride (CrCN), and is formed to a thickness of 100 to 900 Å. The anti-reflection film 60 is made of chromium oxynitride (CrCON), and is formed to a thickness of 10 to 400 kPa. As described above, after the respective films are sequentially stacked, the thin film 70 containing silicon is formed by performing surface treatment with an organic material containing silicon on the antireflection film 60. Next, using a positive chemically amplified resist FEP-171 (manufactured by FUJIFILM Corporation), a resist film 80 is formed to a thickness of 2000 to 4000 GPa and soft baked. Through the above process, the halftone phase inversion blank mask 100 without the etch stop film is obtained.

2A to 2I are cross-sectional views of products produced in respective processes when a halftone type phase shift photomask is manufactured using a halftone type phase shift blank mask that does not include the etch stop film shown in FIG. 1.

First, as shown in FIG. 2A, an energy of 10 μC / cm 2 using an electron beam pattern forming apparatus having an acceleration voltage of 50 kV in a predetermined desired pattern region of the halftone phase inversion blank mask 400 that does not include an etch stop film. The resist exposure is carried out in an amount. Then, a PEB process is performed at 100 ° C. for 10 minutes using a hot plate for acid diffusion and smooth development of the exposed part.

Next, in order to remove the exposed resist, a resist pattern 88 is formed by performing a developing process by a fan spray method using NMD-W containing 2.38% of TMAH. In this case, a thin film pattern 71 including silicon is formed to correspond to the resist pattern 88. Subsequently, the resist pattern 88 is masked to perform wet etching to form the antireflection film pattern 68, the light shielding film pattern 58, and the phase inversion film pattern 28. At this time, the wet etching solution uses CR-7, and the wet etching is performed by spraying. Since the anti-reflection film, the light shielding film, and the phase inversion film are all made of a chromium compound, it is possible to form a pattern for all the films in one etching. 2B and 2C show a cross section after the resist pattern 88 is formed and a cross section after the antireflection film pattern 68, the light shielding film pattern 58, and the phase inversion film pattern 28 are formed, respectively.

Next, by quenching in sulfuric acid at 80 ° C for 60 minutes to remove the unnecessary resist pattern after pattern formation, a cleaning process is performed. At this time, the thin film pattern including silicon is also removed. Subsequently, a resist film 180 having a thickness of 4650 kPa was formed by spin coating using THMR-iP3500, a positive photoresist, and then soft baked at 105 ° C. for 30 minutes on a hot plate. 2D and 2E show a cross section after the resist pattern 88 has been removed, and a cross section after the thin film 71 containing silicon and the resist film 180 are formed, respectively.

Next, as shown in FIG. 2F, resist exposure is performed with an energy amount of 98 mJ / cm 2 using an optical pattern forming apparatus having a wavelength of 364 nm in a predetermined desired pattern region. Subsequently, in order to remove the exposed resist, the resist pattern 181 is formed by developing using a fan spray method using NMD-W containing 2.38% of TMAH. Next, wet etching is performed by using the resist pattern 181 as masking. In this case, the wet etching solution uses CR-7, and the anti-reflection film pattern 69, the light shielding film pattern 59, and the phase inversion film pattern 29 are formed by the wet etching method of the spray method. 2G and 2H show the cross section after the resist pattern 181 is formed and the cross section after the anti-reflection film pattern 69, the light shielding film pattern 59, and the phase inversion film pattern 29 are formed, respectively.

Next, an unnecessary resist pattern was removed by quenching in sulfuric acid at 80 ° C. for 60 minutes, and after the washing process, the antireflection film pattern 69, the light shielding film pattern 59, and the phase shift film pattern 29 were sequentially stacked. A halftone phase inversion mask 200 having a structure is obtained. FIG. 2I illustrates a cross-section of the halftone phase shift mask 200 obtained by performing the above-described process, and as shown in FIG. 2I, the halftone phase shift mask 200 does not include an etch stop film.

As described above, when a halftone phase shift mask is manufactured using a conventional halftone phase shift blank mask without applying an etch stop layer, an antireflection film, a light shielding film, and a phase shift film to which a metal compound of the same series is applied are wet or dry. When the pattern is formed through the process, the half-tone phase inversion is not possible because the phase inversion film pattern for applying the phase inversion effect is not formed due to the absence of the etch stop layer, making it difficult to realize high resolution. It becomes impossible to manufacture a halftone phase inversion mask using a blank mask.

The technical problem to be achieved by the present invention is 6 to 30% transmittance in a lithography process using an argon fluoride excimer laser having a wavelength of 193 nm as an exposure light source, and a transmittance of less than 40% at a wavelength of 248 to 436 nm as an inspection wavelength. Halftone type phase inverted blank with excellent thickness selectivity between transparent substrate and film and excellent chemical resistance to cleaning chemicals to have dry thickness and easy wet etching It is to provide a mask and a method of manufacturing the same.

In order to achieve the above technical problem, the halftone phase inversion blank mask according to the present invention has a structure in which a phase inversion film, an etch stop film, a light shielding film, an antireflection film, and a resist film are sequentially stacked on a transparent substrate, and the reflection And a thin film containing silicon formed at an interface between the anti-reflection film and the resist film by performing a surface treatment with an organic material containing silicon on the anti-reflection film, wherein the etch stop film includes the phase inversion film, the light shielding film, and the reflection. It consists of a metal or a metal compound etched by the wet etching liquid or dry etching gas different from the wet etching liquid or dry etching gas applied to the etching with respect to at least one film among the prevention films.

According to another aspect of the present invention, there is provided a method of manufacturing a halftone phase inversion blank mask, including: forming the phase inversion film on the transparent substrate; The metal is composed of a metal or metal compound etched by a wet etchant or dry etching gas different from the wet etchant or dry etching gas applied to the etching of at least one of the light-shielding film and the anti-reflection film on the phase inversion film Forming an etch stop layer; Sequentially forming the light blocking film and the anti-reflection film on the etch stop film; Forming a thin film containing silicon on the anti-reflection film by performing surface treatment on the anti-reflection film with an organic material including silicon; And forming the resist film on the thin film containing silicon.

Accordingly, by applying the etch stop film to the halftone phase shift mask, the light shielding film, the anti-reflection film, and the phase shift film can be made of the same metal compound, so that one wet etching process is performed on one or more films positioned above or below the etch stop film. The pattern can be formed through a dry etching process. In addition, by further forming a thin film containing silicon on the anti-reflection film, it is possible to form a precise pattern, and to improve the adhesion between the anti-reflective film and the resist film. Therefore, the manufacturing process of the halftone phase inversion mask can be simplified, thereby reducing the production cost and reducing the probability of defect occurrence.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of a halftone phase inversion blank mask and a halftone phase inversion photomask and a method of manufacturing the same according to the present invention.

3A to 3G are cross-sectional views of the products calculated at each step in performing the manufacturing process of the first embodiment for the halftone phase inversion blank mask according to the present invention.

First, the first phase inversion film 20 for controlling the transmittance by a reactive sputtering method under a gas atmosphere including chromium as a target on a 6-inch transparent substrate 10 and at least one of argon, nitrogen, oxygen, and carbon dioxide. A phosphorus carbon oxynitride (CrCON) film 20 is formed. The first phase inversion film preferably has a transmittance of 1 to 60%, a phase shift of 10 to 190 °, and a thickness of 50 to 4500 Hz at a wavelength of 190 to 500 nm. And the mixing ratio between the inert gas and the reactive gas is argon: nitrogen: carbon dioxide: methane = 5 ~ 80sccm: 5 ~ 95sccm: 0 ~ 10sccm: 0 in the vacuum chamber of 0.01 ~ 500mTorr and applied power 0.01 ~ 2 전력 A chromium oxynitride (CrCON) film 20 is formed in a state of ˜10 sccm. FIG. 3A shows a cross section after the first phase inversion film 20 is formed on the quartz substrate 10. At this time, the transparent substrate 10 is made of glass, quartz, calcium fluoride (CaF ₂ ) and the like, 248nm wavelength of krypton fluoride (KrF) excimer laser (Excimer laser) or 193nm wavelength of the argon fluoride (ArF) excimer laser, etc. It is preferred that the substrate is rectangular or circular, having a size of at least 5 inches having a transmission of at least 90% or greater.

Next, a second phase inversion film for controlling the phase inversion amount by a reactive sputtering method under a gas atmosphere including chromium as a target on the first phase inversion film 20 and at least one of argon, nitrogen, and carbon dioxide ( 30) a chromium nitride (CrCN) film 20 is formed to a thickness of 50 to 1000 GPa. At this time, the chromium carbide (CrCN) 30 film contains carbon and nitrogen in the range of 0 to 20 at% and 0 to 60 at%, respectively, and the rest is made of chromium. The chromium nitride (CrCN) film 30 has an argon: nitrogen: methane = 5 ~ 80sccm: mixing ratio between an inert gas and a reactive gas under a condition in which the vacuum chamber has a vacuum degree of 0.01 to 500 mTorr and an applied power of 0.01 to 2 kPa. 5 ~ 95sccm: It is formed into a film at 0 ~ 10sccm. The second phase inversion film 30 preferably has a transmittance of 1 to 60%, a phase shift of 10 to 190 °, and a thickness of 50 to 4500 Hz at a wavelength of 190 to 500 nm.

MPM-193, a device for measuring phase inversion amount and transmittance in a state where the first phase inversion film 20 and the second phase inversion film 30 are sequentially stacked on the transparent substrate 10 (manufactured by Japan Laser Tech Co., Ltd.) As a result of measuring the phase inversion and transmittance, the phase inversion of 10-190 ° and the transmittance of 5-7% were measured at 193nm, which is an ArF lithography wavelength. As described above, the total amount of phase inversion generated by the first phase inversion film 20 and the second phase inversion film 30 is preferably 170 to 190 degrees. As a result of measuring the transmittance at an inspection wavelength of 200 to 500 nm with the n & k Analyzer 1512RT (the equipment of n & k Technology, USA) which measures the transmittance and the reflectance, the transmittance of up to 30-50% was measured. In addition, by dipping in sulfuric acid and SC-1 solution for 2 hours, the changes in thickness, transmittance and phase reversal were measured and showed changes within 20Å, 1% and 10 °, respectively. FIG. 3B shows a cross section after the second phase inversion film 30 is formed on the first phase inversion film 20.

After the first phase inversion film 20 and the second phase inversion film 30 are formed, heat treatment is performed on the substrate to improve adhesion between the films and growth of the film. The temperature used at the time of such heat treatment is 100-1000 degreeC, Preferably it is set to 200-500 degreeC. The degree of vacuum used during the heat treatment is 0 to 0.5 Pa, preferably 0.2 to 0.3 Pa. In addition, the heat treatment time is suitable 1 ~ 60 minutes, preferably 5 to 40 minutes the heat treatment. As the atmosphere gas used in the heat treatment, N ₂ , Ar, He, Ne, Xe, or the like may be used. This heat treatment process is performed by a hot plate, a vacuum hot plate, a vacuum oven, a vacuum chamber, a furnace, a rapid thermal process, a lamp heat treatment device, or the like. Can be performed.

Next, carbonization of the etch stop layer 40 is performed by reactive sputtering under a gas atmosphere including aluminum as a target on the second phase inversion film 30 and at least one of argon, nitrogen, carbon dioxide, and methane gas. An aluminum nitride (AlCON) film 40 is formed to a thickness of 10 to 300 kPa. The aluminum carbide oxynitride (AlCON) film 40 contains carbon, oxygen, and nitrogen in the range of 0 to 20 at%, 0 to 60 at%, and 0 to 60 at%, respectively, and the rest is made of aluminum. The etch stop film 40 has a mixing ratio of inert gas and reactive gas under argon: nitrogen: carbon dioxide: methane = 5 to 80 sccm: 5 to 95 sccm under the condition that the vacuum chamber has a vacuum degree of 0.01 to 500 mTorr and an applied power of 0.01 to 2 kW. : 0 ~ 10sccm: Formed in the state of 0 ~ 10 sccm. FIG. 3C illustrates a cross section after the etch stop film 40 is formed on the second phase inversion film 30.

Next, the chromium nitride (CrN) film 50, which is the light shielding film 50, is formed by a reactive sputtering method under a gas atmosphere including chromium as a target on the etch stop film 40 and at least one of argon and nitrogen. It is formed to a thickness of 900Å. At this time, the chromium nitride (CrN) film 50 contains nitrogen in the range of 1 to 60 at%, and the rest is made of chromium. The light shielding film 50 is formed in a state where the mixing ratio between the inert gas and the reactive gas is argon: nitrogen = 5 to 80sccm: 5 to 95sccm under the condition that the vacuum chamber has a vacuum degree of 0.01 to 500 mTorr and an applied power of 0.01 to 2 kPa. FIG. 3D illustrates a cross section after the light shielding film 50 is formed on the etch stop film 40.

Next, a chromium oxynitride (CrCON) film, which is an antireflection film 60 by a reactive sputtering method under a gas atmosphere containing chromium as a target on the light shielding film 50 and containing at least one of argon, nitrogen, oxygen, and carbon dioxide (60) to form a thickness of 10 ~ 400Å. At this time, the chromium oxynitride (CrCON) film 60 includes oxygen, nitrogen, and carbon in the range of 0 to 60 at%, 0 to 60 at%, and 0 to 20 at%, respectively, and the rest is made of chromium. And the mixing ratio between the inert gas and the reactive gas is argon: nitrogen: carbon dioxide: methane = 5 ~ 80sccm: 5 ~ 95sccm: 0 ~ 10sccm: 0 in the vacuum chamber of 0.01 ~ 500mTorr and applied power 0.01 ~ 2 0.01 The anti-reflection film 60 is formed in a state of ˜10 sccm. After the anti-reflection film 60 is formed, a heat treatment process is performed using a vacuum chamber to improve the stability of the thin film. At this time, the vacuum degree is 0.2Pa, using Ar as the atmosphere gas, heat treatment for 45 minutes at a temperature of 500 ℃. FIG. 3E shows a cross section after the antireflection film 60 is formed on the light shielding film 50.

Meanwhile, the first phase inversion film 20, the second phase inversion film 30, the etch stop film 30, the light shielding film 50, and the anti-reflection film 60 are formed of a metal matrix and are boron (B) and carbon. (C), magnesium (Mg), aluminum (Al), silicon (Si), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), yttrium (Y), zirconium (Zr), niobium (Nb) , Molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb) , Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium (Ir), Platinum (Pt), Gold (Au), Thallium (Tl) And one or two or more compounds selected from the group consisting of lead (Pb) or one or more compounds selected from one or two or more metals selected from these, and their oxidation, nitriding, carbonization, and fluorides.

At this time, when the metal matrix of the first phase inversion film 20 is molybdenum silicide (MoSi) combination, molybdenum silicide (MoSiN), molybdenum silicide (MoSiO), molybdenum carbide (MoSiC), and molybdenum carbide oxide (MoSiCO) , A film of a component selected from molybdenum nitride silicide (MoSiCN), molybdenum nitride nitride (MoSiON), and molybdenum carbide nitride molybdenum carbide (MoSiCON), the component ratio of which is 0 to 20 at%, 0 to 0 at In the range of ˜60 at%, 0 to 60 at% and 20 to 80 at%, the remainder being made of metal. In contrast, when the metal matrix of the first phase inversion film 20 is chromium (Cr), it is a film of a component selected from chromium oxide (CrO), chromium oxynitride (CrON), and chromium carbide oxynitride (CrCON). Is in the range of 0 to 20 at%, 0 to 60 at%, and 0 to 60 at%, respectively, of carbon, oxygen, and nitrogen, and the remainder is made of metal.

On the other hand, when the metal matrix of the second phase inversion film 30 is molybdenum silicide (MoSi) combination, molybdenum silicide (MoSiN), molybdenum silicide (MoSiO), molybdenum carbide (MoSiC), and molybdenum carbide oxide (MoSiCO) , A film made of a component selected from molybdenum nitride silicide (MoSiCN), molybdenum nitride nitride (MoSiON) and molybdenum carbide nitride molybdenum carbide (MoSiCON), the composition ratio of which is 0 to 20at each carbon, oxygen, nitrogen and silicon %, 0-60at%, 0-60at%, and silicon contain in the range of 20-80at%, and remainder consists of a metal. In contrast, when the metal matrix of the second phase inversion film 30 is chromium (Cr), the film is composed of a component selected from chromium nitride (CrN), chromium carbide (CrC), and chromium carbide (CrCN). Carbon, oxygen, and nitrogen are included in the range of 0 to 20 at%, 0 to 60 at%, and 0 to 60 at%, respectively, the remainder being made of metal.

Also, when the metal matrix of the etch stop film 40 is aluminum (Al), aluminum nitride (AlN), aluminum oxide (AlO), aluminum carbide (AlC), aluminum carbide (AlCO), aluminum carbide (AlCN) Aluminum oxynitride (AlON), aluminum carbide oxynitride (AlCON) and the like may be used, and its content is in the range of 0 to 20 at%, 0 to 60 at% and 0 to 60 at% of carbon, oxygen and nitrogen, respectively. The remainder is made of metal. The etch stop film 40 preferably has a transmittance of 0.001 to 60%, a phase shift of 0 to 180 °, and a thickness of 10 to 4500 Hz at a wavelength of 190 to 500 nm.

In addition, when the metal matrix of the light shielding film 50 is chromium, chromium nitride (CrN), chromium carbide (CrC), chromium carbide (CrCN), or the like may be a component of the light shielding film 50. The light shielding film 50 contains carbon, oxygen, and nitrogen in the range of 0 to 20 at%, 0 to 60 at%, and 0 to 60 at%, and the rest is made of metal, and has an optical density of 2 at a wavelength of 190 to 500 nm. It is -4 and it is preferable that thickness is 50-4500 kPa.

In addition, when the metal matrix of the anti-reflection film 60 is chromium (Cr), chromium oxide (CrO), chromium oxynitride (CrON), chromium carbide oxynitride (CrCON), or the like may be used, and the content of carbon is carbon. , Oxygen and nitrogen are contained in the range of 0 to 20 at%, 0 to 60 at% and 0 to 60 at%, respectively, and the remainder is made of metal. The antireflection film 50 preferably has an optical density of 2 to 4, a reflectance of less than 30%, and a thickness of 50 to 4500 Hz at a wavelength of 190 to 500 nm.

Each of the first phase inversion film 20, the second phase inversion film 30, the etch stop film 30, the light shielding film 50, and the anti-reflection film 60 as described above is formed under a gas atmosphere. The inert gas to be formed includes at least one or more selected from the group consisting of argon (Ar), helium (He), neon (Ne), and xenon (Xe), and the reactive gas is oxygen (O ₂ ), nitrogen (N _2). ), At least one selected from the group consisting of carbon monoxide (CO), carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), nitrogen oxides (NO), nitrogen dioxide (NO ₂ ), ammonia (NH ₃ ) and methane (CH ₄ ) It contains 1 or more types. In this case, the mixing ratio of the inert gas and the reactive gas in the vacuum chamber of 0.01 ~ 500mTorr and the applied power of 0.01 ~ 2㎾ is argon (Ar): nitrogen (N ₂ ): carbon dioxide (CO ₂ ): methane (CH ₄ ) It is set selectively within the range of 5 to 80 sccm: 5 to 95 sccm: 0 to 30 sccm: 0 to 30 sccm.

On the other hand, in the characteristics of each film, the first phase inversion film 20 and the second phase inversion film 30 is preferably etched by the wet etching liquid or dry etching gas of the same series, the light shielding film 50 and the anti-reflection film (60) It is also preferably etched by the wet etching liquid or dry etching gas of the same series. In addition, the second phase inversion film 30 and the etch stop film 40 may not be etched by the wet etching solution or the dry etching gas of the same series, and the etch stop film 40 and the light blocking film 50 are also the same series. It is preferable not to be etched by wet etching liquid or dry etching gas.

Next, hexamethyldisilane (HMDS) is surface-treated by vapor priming to improve adhesion between the anti-reflection film 60 and the resist on the heat-treated anti-reflection film 60 to form a thin film 70 containing silicon. do. At this time, argon (Ar) gas was used to move the HMDS vapor, and HMDS vapor priming was performed for 20 seconds while the temperature of the hot plate was set at 100 ° C. FIG. 3F shows a cross section after film formation of a thin film 70 containing silicon on the antireflection film 60.

This surface treatment is performed using an organic material containing silicon, wherein the solution used is hexamethyldisilane, trimethylsilyl diethylamine, O-trimethylsilyacetate acetate), O-trimethylsilylproprionate, O-trimet hylsilylbutyrate, Trimethylsilyltrifluoroacetate, Trimethylmethoxysilane, N-methyl N-methyl-N-trimethyl-silytrifluoroacetamide, O-trimethylsilyacetylacetone, Isopropenoxytrimethylsilane, trimethylsiltrifluoroacetamide Amide (Trimethylsilyltrifluoroacetamide), Methyltrimethylsilyl Dimethylketone Acetate (Methyltrim) ethylsilydimethylketone acetate), trimethylethoxysilane, and the like can be used.

In addition, the surface treatment is performed by spin coating or vapor priming. When the surface treatment is performed on the anti-reflection film 60 by using the spin coating method, the injection amount of the organic material containing silicon is It is determined within the range of about 0.5 ~ 50 kHz, the rotational speed of the substrate is set to 10 ~ 3000rpm. On the other hand, when performing the surface treatment on the anti-reflection film 60 using the vapor priming method, it proceeds at a temperature of 20 ~ 500 ℃ and a pressure of 760mmHg or less, Ar or N ₂ 0.01 ~ 100L / min Used as As described above, when the surface treatment by the organic material containing silicon is performed on the antireflection film 60, the thin film 70 including silicon is formed on the antireflection film 60. At this time, the thickness of the thin film formed by the surface treatment is preferably less than 300 kPa.

Next, a resist film having a thickness of 2000 to 4000 kPa was formed by spin coating using a positive chemically amplified resist FEP-171 (manufactured by FUJIFILM Corporation, Japan) on the heat-treated and HMDS vapor-primed antireflection film 60. ) And soft bake for 20 minutes at a temperature of 50 ~ 250 ℃ (preferably 120 ℃) using a hot plate. The resist film 80 may be formed using a resist such as a photoresist, an electron beam resist, or a chemically amplified resist. At this time, the resist coating is formed by spin coating or capillary coating on the antireflection film 60 which is surface-treated with an organic material including silicon to form a resist film 80. It is preferable that the thickness of the resist film 80 formed in this way is 100-10000 kPa.

FIG. 3G shows a cross section after depositing a resist film 80 on the anti-reflection film 60 subjected to heat treatment and HMDS vapor priming. Through the above steps, the halftone phase inversion blank mask 300 is obtained.

4A to 4K are cross-sectional views of the products calculated at each step of performing the manufacturing process of the first embodiment for the halftone phase inversion photomask according to the present invention.

First, as shown in FIG. 4A, an energy of 10 μC / cm 2 is obtained by using an electron beam pattern forming apparatus having an acceleration voltage of 50 kV in a predetermined desired pattern region in the halftone phase inversion blank mask 300 obtained through the above-described process. The resist exposure is carried out in an amount. The light source for exposure has an energy of 10 to 200 mJ / cm 2 at a wavelength of 190 to 500 nm for a monochromatic laser and an energy of 1 to 100 μC / cm 2 at an acceleration voltage of 10 to 100 kV for an electron beam. Subsequently, a post exposure Bake (PEB) process is performed at 100 ° C. for 10 minutes using a hot plate for acid diffusion and smooth development of the exposed portion. The PEB process is applied when the type of resist used in the resist film is a chemically amplified resist, and the PEB process may be selectively used when the type of resist used in the resist film is a photoresist or an electron beam resist. At this time, the PEB process is performed for 1 to 30 minutes at a temperature of 50 ~ 200 ℃ using a hot plate.

Next, a pan was prepared using Tetramethylammonium Hydroxide (TMAH) (NMD-W manufactured by Tokyo Ohka Kogyo, Japan, which contains 2.38% of (CH ₃ ) ₄ NOH) to remove the exposed resist. The resist pattern 81 is formed through a spray developing process. In the development method used when forming a resist pattern, a resist pattern is formed using a developer in a puddle, fan spray, or dipping method. At this time, the monomolecular film containing silicon is removed at the portion where the resist is developed by the developing process. 4B shows a cross section after the resist pattern 81 is formed.

Next, dry etching is performed using a mixed gas of Cl ₂ and O ₂ . The anti-reflection film pattern 61, the light shielding film pattern 51, the etch stop film pattern 41, the second phase inversion film pattern 31, and the first phase inversion film pattern 21 are formed through the one-time dry etching process. do. An anti-reflection film 60, the light-shielding film 50, a second phase shift film 30 and the first phase shift film 20 is composed of chromium compound film because the film consisting of an Al compound film stop etching, the Cl ₂ based gas Dry etching is possible. When performing dry etching, when the light shielding film and the antireflection film are composed of chromium or a chromium compound, the light shielding film pattern 51 and the antireflection film pattern 61 are formed using chlorine and oxygen mixed gas. In contrast, when wet etching is applied, when the light shielding film and the antireflection film are composed of chromium or chromium compounds, Ceric Ammonium Nitrate (Ce (NH ₄ ) ₂ (NO ₃ ) ₆ ) and Perchloric Acid (HClO) are used. ₄ ) the light shielding film pattern 51 and the anti-reflection film pattern 61 are formed using the mixed solution.

The etch stop layer pattern 41 is formed through a wet etching process or a dry etching process using the anti-reflection layer pattern 61 and the light shielding layer pattern 51 as a mask. When the etch stop layer 60 is aluminum or an aluminum compound, the etch stop layer pattern 42 is formed using a solution in which phosphoric acid and acetic acid are mixed when wet etching is performed. In addition, when the etch stop film 40 is an aluminum or aluminum compound, the etch stop film pattern 41 is formed using a fluorine-based gas as the dry etch gas.

In addition, the first phase inversion film pattern 21 and the second phase inversion film pattern 31 may be wet or dry etched using the antireflection film pattern 61, the light shielding film pattern 51, and the etch stop film pattern 41 as masks. It is formed through the process. In the case where the first phase inversion film 20 and the second phase inversion film 30 are made of chromium or a chromium compound, the light shielding film pattern 51 and the reflection are made of a solution in which cerium nitrate and perchloric acid are mixed when wet etching is performed. The prevention film pattern 61 is formed, and the first phase inversion film pattern 21 and the second phase inversion film pattern 31 are formed using Cl ₂ and O ₂ mixed gas. On the other hand, when the first phase inversion film 20 and the second phase inversion film 30 are composed of molybdenum silicide or molybdenum silicide compounds, the first phase inversion film 21 and the second phase inversion film using fluorine-based gas The pattern 31 is formed. FIG. 4C shows a cross section after pattern formation for each film is completed by dry etching.

Next, it quenched 60 minutes in 80 ℃ sulfuric acid (H ₂ SO ₄₎ to remove the resist pattern became necessary after pattern formation, and then subjected to a cleaning process. In this process, the resist pattern 81 and the thin film 70 including silicon are removed. Removal of the resist pattern is carried out through development after quenching or ultraviolet irradiation with sulfuric acid (H ₂ SO ₄ ). Then, heat treatment is performed in the vacuum chamber to improve the adhesion between the antireflection film pattern 61 and the resist film to be formed later. At this time, the vacuum degree is 0.2Pa and Ar is used as the atmosphere gas, heat treatment is performed for 45 minutes at a temperature of 500 ℃. 4D is a cross-sectional view of the resist pattern 81 and the thin film 70 including silicon removed.

Heat treatment of the antireflection film pattern 61 is performed for 1 to 60 minutes at a temperature of 100 ~ 1000 ℃, preferably 5 to 40 minutes at a temperature of 200 ~ 500 ℃. At this time, N ₂ , Ar, He, Ne, Xe and the like are used as the atmosphere gas, and the degree of vacuum is set to 0 to 0.5 Pa (preferably 0.2 to 0.3 Pa). At this time, a hot plate, a vacuum hot plate, a vacuum oven, a vacuum chamber, a furnace, a rapid heat treatment apparatus, a lamp heat treatment apparatus, etc. may be used for heat treatment.

Next, the thin film 71 including silicon is formed on the heat-treated antireflection film 61 by surface treatment using HMDS in a vapor priming method to improve adhesion between the antireflection film 61 and the resist. At this time, argon gas is used to move the HMDS vapor, and HMDS vapor priming is performed for 20 seconds at a temperature of a hot plate of 100 ° C. FIG. 4E shows a cross section after film formation of the thin film 71 containing silicon by surface treatment using the HMDS on the antireflection film 61. The solution and the surface treatment method used in the surface treatment of the antireflection film 61 are the same as when forming a thin film 70 containing silicon on the antireflection film 60, as shown in FIG.

Next, the resist film 90 nm thick was formed by spin coating using THMR-iP3600 (manufactured by Tokyo Ohka Kogyo, Japan), which is a positive photoresist, on the heat-treated and HMDS vapor-primed antireflection film 61. ) And soft bake for 20 minutes at a temperature of about 50-250 ° C. (preferably 100 ° C.) using a hot plate. 4F shows a cross section after the resist film 90 is formed. The resist film 80 may be formed using a resist such as a photoresist, an electron beam resist, or a chemically amplified resist. At this time, the resist is coated by the spin coating or capillary coating on the anti-reflection film 60 surface-treated with an organic material including silicon to form a resist film 80. It is preferable that the thickness of the resist film 80 formed in this way is 100-10000 kPa.

Next, as shown in FIG. 4G, resist exposure is performed with an energy amount of 95 mJ / cm 2 using an optical pattern forming apparatus having a wavelength of 364 nm in a predetermined desired pattern region. The light source for exposure has an energy of 10 to 200 mJ / cm 2 at a wavelength of 190 to 500 nm for a monochromatic laser and an energy of 1 to 100 μC / cm 2 at an acceleration voltage of 10 to 100 kV for an electron beam. Then, the PEB process is performed for 1 to 30 minutes at a temperature of 50 to 200 ° C using a hot plate for acid diffusion and smooth development of the exposed portion.

Next, in order to remove the exposed resist, a resist pattern 91 is formed by applying a fan spray developing process using NMD-W containing 2.38% of TMAH. The resist pattern 91 is formed using a developer in a puddle, a fan spray, or a immersion method. At this time, the monolayer 71 containing silicon is removed at the portion where the resist is developed by the developing process. 4H shows a cross section after the formation of the resist pattern 91 by exposure.

Next, wet etching is performed with the resist pattern 91 masked. At this time, the wet etching solution uses CR-7, a solution of ammonium cerium nitrate and perchloric acid, and forms the antireflection film pattern 62 and the light shielding film pattern 52 by a spray method. As such, when the wet etching is performed, when the light blocking film 50 and the antireflection film 60 are made of chromium or a chromium compound, the light blocking film pattern 52 and the antireflection film pattern 62 are made of a mixture of cerium ammonium nitrate and perchloric acid. To form. On the other hand, when the dry etching is performed, when the light blocking film 50 and the antireflection film 60 are made of chromium or a chromium compound, the light blocking film pattern 52 and the antireflection film pattern 62 are formed using chlorine and oxygen mixed gas. do.

Next, the etch stop layer pattern 42 is formed through the spray-type wet etching process by masking the anti-reflection layer pattern 62 and the light shielding layer pattern 52 which are chromium compounds. In this case, Al-11K (manufactured by Sciencetec, Inc.), which is a mixture of phosphoric acid (H ₃ PO ₄ ) and acetic acid (CH ₃ COOH), is used as the wet etching solution. On the other hand, when using dry etching, the etch stop film pattern 42 is formed using fluorine-based gas. 4I and 4J illustrate cross-sections after the anti-reflection film pattern 62 and the light shielding film pattern 52 are formed by wet etching and cross-sections after the etch stop film pattern 42 is formed through the wet etching process, respectively.

Next, after immersing in sulfuric acid at 80 ° C. for 60 minutes or irradiating with ultraviolet rays, the development is performed to remove unnecessary resist patterns and the cleaning process is performed. Finally, the anti-reflection film pattern 62, the light shielding film pattern 52, and the etch stop film pattern (42), a halftone phase inversion photomask 400 in which the second phase inversion film pattern 31 and the first phase inversion film pattern 21 are formed is obtained. The cleaning process was a diluted SC-1 (Standard Cleaning 1; H ₂ O ₂ , NH ₄ OH, H ₂ O) mixed solution and SPM (Sulfuric Acid Hydrogen Peroxide Mixture; H ₂ SO ₄ , H ₂ O ₂ , H ₂ O) is carried out using a mixed solution. 4K is a cross-sectional view of the halftone type phase inversion photomask 400 obtained through the above-described process.

The first embodiment of the halftone phase inversion blank mask and the halftone phase inversion mask obtained through the above process has a phase inversion film composed of a two-layer film of a transmittance control film and a phase inversion control film. This makes it possible to control the phase inversion amount and transmittance at a wavelength of 193 nm while having an appropriately thin thickness, and has a transmittance of less than 40% at an inspection wavelength of 200 to 500 nm. In addition, by using chromium, which is generally used in a binary photomask, as a phase inversion film, a conventional wet and dry etching process may be applied, and an excellent selection ratio may be provided for a transparent substrate.

In addition, by inserting an etch stop film of a metal compound other than chromium compound between the second phase inversion film, which is a chromium compound film, and the light shielding film, an etching process for each film can be selected and controlled. Wet etching of metal compounds is possible. In addition, by using a metal capable of dry etching simultaneously with the chromium compound as the same gas used for the dry etching of the chromium compound provides a very good selection ratio. In addition, by using the chromium-based metal compound as the phase inversion film, it provides excellent chemical resistance to the chemical solution used in the cleaning process, thereby reducing the cost and the probability of defect occurrence through the process simplification in the production of the halftone phase inversion photomask. It is possible.

5 is a cross-sectional view of a second embodiment of a halftone phase inversion blank mask according to the present invention. The second embodiment of the halftone phase inversion blank mask shown in FIG. 5 has a single phase inversion film unlike the first embodiment having a phase inversion film composed of a two-layer film of the first phase inversion film and the second phase inversion film.

Referring to FIG. 5, the second embodiment 500 of the halftone phase inversion blank mask according to the present invention is a phase inversion film 20, an etch stop film 40, and a light shielding film 50 on a transparent substrate 10. ), The antireflection film 60, the thin film 70 containing silicon and the resist film 80 are sequentially stacked. The phase inversion film 20 is a single film made of chromium oxynitride (CrCON) and is formed to a thickness of 400 to 800 Å. The phase inversion film 20 is the same as the first phase inversion film or the second phase inversion film of the first embodiment 300 for the halftone phase inversion blank mask according to the present invention described with reference to FIGS. 3A to 3F. Has a composition. At this time, the phase inversion film 20 was measured using the transmittance and phase inversion measuring instrument MPM-193. As a result, 20-30% transmittance and 170-190 ° phase inversion were measured at a wavelength of 193 nm. The transmittance was measured up to 39.8% at the wavelength of 200 ~ 500nm, which was measured by n & k Analyzer 1512RT, and was immersed in sulfuric acid and SC-1 solution for 2 hours to measure changes in thickness, transmittance, and phase shift. The results showed changes within 10Å, 1%, and 10 °, respectively.

The etch stop film 40 is made of aluminum carbide oxynitride (AlCON), and is formed to a thickness of 10 ~ 300Å. In this case, the sum of the phase inversions with respect to the exposure wavelength of the phase inversion film 20 and the etch stop film 40 is in the range of 170 to 190 °, and the sum of the transmittances to the exposure wavelength is in the range of 0.0001 to 40%. The light shielding film 50 is made of chromium nitride (CrCN), and is formed to a thickness of 100 to 900 Å. The anti-reflection film 60 is made of chromium oxynitride (CrCON), and is formed to a thickness of 10 to 400 kPa. As described above, the respective films are sequentially stacked, and the surface treatment is performed with an organic material containing silicon on the antireflection film 60 to form a thin film containing silicon. Next, using NEB-22 (manufactured by Sumitomo, Japan), which is a negative chemically amplified resist, a resist film 80 is formed to a thickness of 2000 to 4000 GPa and soft baked. Through the above process, a halftone phase inversion blank mask 500 having a single phase inversion film is obtained.

6A to 6L are cross-sectional views of the products calculated at each step of performing the manufacturing process of the second embodiment for the halftone phase inversion photomask according to the present invention.

First, as shown in FIG. 6A, an energy of 12 μC / cm 2 using an electron beam pattern forming apparatus having an acceleration voltage of 50 kV in a predetermined desired pattern region of a half-tone phase inversion blank mask 500 having a single phase inversion film. The resist exposure is carried out in an amount. Then, a PEB process is performed at 100 ° C. for 10 minutes using a hot plate for acid diffusion and smooth development of the exposed portion.

Next, in order to remove the exposed resist, a resist pattern 85 is formed by applying a fan spray developing process using NMD-W containing 2.38% of TMAH. In this case, a thin film pattern 71 including silicon is formed to correspond to the resist pattern 85. Subsequently, the resist pattern 85 is masked and the anti-reflection film pattern 65 and the light shielding film pattern 55 are formed by a spray method using a wet etching method using CR-7. 6B and 6C show the cross section after the resist pattern 85 is formed and the cross section after the anti-reflection film pattern 65 and the light shielding film pattern 55 are formed, respectively.

Next, the etch stop layer pattern 45 is formed through the spray-type wet etching process by masking the anti-reflection film pattern 65 and the light shielding film pattern 55 which are chromium compounds. At this time, the wet etching solution uses Al-11K which is a mixture of phosphoric acid and acetic acid. Subsequently, the phase inversion film pattern 25 is formed by the spray method which is a wet etching method using CR-7, immersed in 80 degreeC sulfuric acid for 60 minutes, the unnecessary resist pattern is removed, and a washing process is performed. At this time, the thin film pattern including silicon is also removed. 6D to 6F, the cross section after the etch stop film pattern 45 is formed, the cross section after the phase inversion film pattern 55 is formed, and the thin film pattern 71 including the resist pattern 85 and silicon are removed. A cross section is shown.

Next, after surface-treating with an organic material containing silicon to form a thin film 70 containing silicon, a spin film of THMR-iP3500, a positive photoresist, is formed to form a resist film 95 having a thickness of 4650 GPa. Then soft bake is carried out for 30 minutes at a temperature of 105 ℃ on a hot plate. FIG. 6G shows a cross section after the thin film 70 containing silicon and the resist film 95 are formed.

Next, as shown in FIG. 6H, resist exposure is performed with an energy amount of 98 mJ / cm 2 using an optical pattern forming apparatus having a wavelength of 364 nm in a predetermined desired pattern region. Subsequently, in order to remove the exposed resist, NMD-W containing 2.38% of TMAH is developed using a fan spray method to form a resist pattern 96. Next, wet etching is performed using the resist pattern 96 as masking, and the wet etching solution is formed using the CR-7 to form the anti-reflection film pattern 66 and the light shielding film pattern 56 by spraying. Next, the etch stop layer pattern 46 is formed through the spray-type wet etching process by masking the anti-reflection film pattern 66 and the light shielding film pattern 56 which are chromium compounds. At this time, Al-11K is used as a wet etchant. 6I through 6K show the cross section after the resist pattern 96 is formed, the cross section after the anti-reflection film pattern 66 and the light shielding film pattern 56 are formed, and the cross section after the etch stop film pattern 46 is formed, respectively.

Next, an unnecessary resist pattern was removed by quenching in sulfuric acid at 80 ° C. for 60 minutes, and a cleaning process was performed. Finally, an antireflection film pattern 66, a light shielding film pattern 56, an etch stop film pattern 46, and a phase inversion were performed. A halftone phase inversion photomask 600 in which the film pattern 25 is formed is obtained. 6L is a cross-sectional view of the halftone phase inversion photomask 600 obtained through the above-described process.

In the second embodiment of the halftone phase inversion blank mask and the halftone phase inversion mask obtained through the process as described above, since the light shielding film, the antireflection film, and the phase inversion film are made of the same metal compound, the same wet etching solution may be used. Therefore, it is possible to form a light shielding film, an antireflection film, and a phase inversion film pattern with an excellent selection ratio without the need for an additional etching process. In addition, by applying a chromium-based metal compound as a phase inversion film provides excellent chemical resistance to the chemical solution used in the cleaning process. In addition, by applying an etch stop layer, the process can be simplified, thereby reducing the cost and the probability of defect occurrence.

Although the preferred embodiments of the present invention have been shown and described above, the present invention is not limited to the specific preferred embodiments described above, and the present invention belongs to the present invention without departing from the gist of the present invention as claimed in the claims. Various modifications can be made by those skilled in the art, and such changes are within the scope of the claims.

According to the halftone phase inversion blank mask and a method of manufacturing the same according to the present invention, by applying an etch stop film to the halftone phase inversion mask, the light shielding film, the antireflection film and the phase inversion film can be made of the same metal compound, so that The pattern formation may be performed by one wet etching process or one dry etching process for one or more layers disposed below. In addition, by further forming a thin film containing silicon on the antireflection film, it is possible to form a precise pattern and to improve the adhesion between the reflective radiating film and the resist film. Therefore, the manufacturing process of the half-tone phase inversion mask can be simplified, thereby reducing the production cost and reducing the possibility of defects. In addition, by applying a phase inversion film of a single film or a two-layer film made of a chromium compound, a transmittance of 6 to 30% and a phase inversion of 180 ° can be obtained at an ArF lithography wavelength of 193 nm and an inspection wavelength of 200 to 500 nm. There is an effect that can facilitate the inspection by obtaining a transmittance of less than 40% at the wavelength. In addition, by applying a single or double phase inversion film made of a chromium compound, not only has a good selectivity for the transparent substrate during dry or wet etching, but also chemical resistance to a commonly used photomask cleaning chemical solution. Has an excellent effect.

Claims (17)

In a halftone phase inversion blank mask in which a phase inversion film, an etch stop film, a light shielding film, an antireflection film, and a resist film are sequentially stacked on a transparent substrate, It includes a thin film containing silicon formed on the interface between the anti-reflection film and the resist film by performing a surface treatment with an organic material containing silicon to the anti-reflection film, The etch stop layer may be a metal or a metal compound etched by a wet etchant or dry etching gas different from a wet etchant or a dry etching gas applied to etching at least one of the phase inversion layer, the light shielding layer, and the anti-reflective layer. A halftone phase inversion blank mask, characterized in that. The method of claim 1, And the phase shift film comprises a first phase shift film and a second phase shift film composed of different compounds having the same metal as a matrix. The method of claim 2, The first phase inversion film and the second phase inversion film are boron (B), carbon (C), magnesium (Mg), aluminum (Al), silicon (Si), scandium (Sc), titanium (Ti), vanadium ( V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), Indium (In), Tin (Sn), Antimony (Sb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium It consists of one metal selected from the group consisting of (Ir), platinum (Pt), gold (Au), thallium (Tl), and lead (Pb), consists of two or more metals selected from the group, or the selected It characterized by comprising at least one metal compound selected from the oxidation, nitriding, carbonization and fluoride of one metal or two or more metals It is a halftone phase shift mask blank. The method of claim 2 or 3, The first phase inversion film and the second phase inversion film include carbon, oxygen, and nitrogen, and the component ratios of the carbon, oxygen, and nitrogen contained in the first phase inversion film and the second phase inversion film, respectively, are 0 to. A halftone phase inversion blank mask, characterized in that it is in the range of 20 at%, 0 to 60 at% and 0 to 60 at%. The method of claim 4, wherein The first phase inversion film further includes silicon, and the component ratio of the silicon included in the first phase inversion film is a halftone phase inversion blank mask, characterized in that in the range of 20 ~ 80at%. The method of claim 2 or 3, The half-tone phase shift blank mask of claim 1, wherein the transmittance of at least one of the first phase inversion film and the second phase inversion film with respect to an exposure wavelength in a range of 190 to 500 nm is in a range of 1 to 60%. The method of claim 2 or 3, The thickness of at least one of the first phase inversion film and the second phase inversion film is a halftone phase inversion blank mask, characterized in that in the range of 50 ~ 4500Å. The method of claim 2 or 3, The sum of the transmittances with respect to the exposure wavelength of the first phase inversion film and the second phase inversion film is in the range of 0.0001 to 40%, halftone phase inversion blank mask. The method according to claim 1 or 2, A halftone type phase inverted blank mask, characterized in that the transmittance of the etch stop film to the exposure wavelength in the 190 ~ 500nm range of 0.001 ~ 60%. The method according to claim 1 or 2, The optical density of the at least one film of the light shielding film and the anti-reflection film with respect to the exposure wavelength in the range of 190 ~ 500nm is in the range of 2 ~ 4 half-tone phase inversion blank mask. The method of claim 1, The sum of the phase inversions with respect to the exposure wavelength of the phase inversion film and the etch stop film is in the range of 170 to 190 °, and the sum of the transmittances for the exposure wavelengths of the phase inversion film and the etch stop film is in the range of 0.0001 to 40%. A halftone phase inversion blank mask, characterized in that. The method according to claim 1 or 2, The etch stop layer, the light blocking layer, and the anti-reflection layer may include boron (B), carbon (C), magnesium (Mg), aluminum (Al), silicon (Si), scandium (Sc), titanium (Ti), and vanadium (V). ), Chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As) ), Yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd) ), Indium (In), Tin (Sn), Antimony (Sb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium (Ir) ), Platinum (Pt), gold (Au), thallium (Tl), and lead (Pb), or a metal selected from the group consisting of two or more metals selected from the group, or the selected one Containing at least one metal compound selected from the group consisting of metals or two or more metals oxidized, nitrided, carbonized and fluoride Halftone phase shift mask blank according to. In the method for manufacturing a halftone phase inversion blank mask in which a phase inversion film, an etch stop film, a light shielding film, an antireflection film, and a resist film are sequentially stacked on a transparent substrate, Forming the phase inversion film on the transparent substrate; The metal is composed of a metal or metal compound etched by a wet etchant or dry etching gas different from the wet etchant or dry etching gas applied to the etching of at least one of the light-shielding film and the anti-reflection film on the phase inversion film Forming an etch stop layer; Sequentially forming the light blocking film and the anti-reflection film on the etch stop film; Forming a thin film containing silicon on the anti-reflection film by performing surface treatment on the anti-reflection film with an organic material including silicon; And Forming the resist film on the thin film containing silicon; halftone phase inversion blank mask manufacturing method comprising a. The method of claim 13, The phase inversion film forming step, Forming a first phase inversion film; And Forming a second phase inversion film; The first phase inversion film and the second phase inversion film is a halftone phase inversion blank mask manufacturing method, characterized in that composed of different compounds having the same metal as a parent. The method of claim 13, And performing a heat treatment to improve the adhesion of the film and the growth of the film to at least one of the phase inversion film, the etch stop film, the light shielding film, and the anti-reflection film. Mask manufacturing method. The method of claim 15, The heat treatment step is a halftone phase inversion blank mask manufacturing method, characterized in that carried out at a temperature of 100 ~ 1000 ℃ under a vacuum degree of 0 ~ 0.5Pa. The method according to claim 13 or 14, The phase inversion film, the etch stop film, the light shielding film, and the anti-reflection film are formed under a gas atmosphere in which a mixing ratio of argon, nitrogen, carbon dioxide, and methane is 5 to 80 sccm: 5 to 95 sccm: 0 to 30 sccm: 0 to 30 sccm. A halftone type phase inversion blank mask manufacturing method.

Images