KR20140095955A - Phase shift blankmask and method for fabricating the same - Google Patents

Abstract

The present invention relates to a phase shift blank mask obtained by forming a phase shift layer in a continuous layer or a multilayer containing a metal and at least one of silicon (Si), oxygen (O) and nitrogen (N), and forming an uppermost phase shift layer in an oxidative phase shift layer. Thus, a phase shift blank mask including a phase shift layer having improved chemical resistance and durability in a washing solution during performing a washing process using the washing solution containing ozone (O_3), Hot-DI, and chemicals such as ammonia (NH_4OH), sulfuric acid (H_2SO_4), etc., may be provided.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phase shift blank mask and a manufacturing method thereof,

The present invention relates to a phase inversion blank mask and a method of manufacturing the same, and more particularly to a phase inversion blank mask having a thin thickness suitable for a semiconductor device manufacturing process using an excimer laser for KrF and ArF and having improved chemical resistance and durability And a method of manufacturing the same.

In order to meet the demand for miniaturization of circuit patterns accompanied with the integration of large scale integrated circuits today, advanced semiconductor fine processing technology is becoming a very important factor. In the case of a highly integrated circuit, the circuit wiring is miniaturized for low power and high speed operation, and a contact hole pattern for interlayer connection and a circuit arrangement for integration are increasingly required. Therefore, in order to meet such demands, there is also a demand for a technology capable of recording a circuit pattern with fine patterning in the production of a photomask in which an original of a circuit pattern is recorded.

This photolithography technique has been made to shorten the exposure wavelength by 436 nm of g-line, 365 nm of i-line, 248 nm of KrF and 193 nm of ArF in order to improve the resolution of the semiconductor circuit pattern. However, the shortening of the exposure wavelength contributes greatly to the improvement of the resolution, but it has a bad influence on the depth of focus (DoF), which causes an increase in the burden on the design of the optical system including the lens.

Accordingly, in order to solve the above problem, a phase inversion mask has been developed which simultaneously improves resolution and depth of focus using a phase shift layer which inverts the phase of the exposure light by 180 degrees. The phase inversion blank mask has a structure in which a phase reversal film, a light shielding film, and a photoresist film are stacked on a transparent substrate and is used as a blank mask for realizing a critical dimension (CD) of 90 nm or less in a semiconductor photolithography process , In particular KrF at 248 nm and ArF lithography and Immersion exposure lithography at 193 nm.

However, photomasks formed with conventional phase inversion blank masks are susceptible to the chemicals used in the cleaning process, such as basic chemicals including acidic and ammonia, such as sulfuric acid, and recently, ozone water cleaning, The change of the thickness of the phase reversal film by the process showed a weak point. Such a change in the thickness of the phase reversal film causes an optical property change such as a phase reversal amount, a transmittance, and a reflectance of the photomask. Also, the surface roughness and the flatness are changed due to the surface damage due to the repeated cleaning process, so that the durability of the phase reversal film is not maintained for a long time, which makes it difficult to manufacture a reliable photomask.

In addition, the conventional phase inversion blank mask is formed on the phase reversal film by increasing the oxygen content to improve the chemical resistance and durability. However, when the oxygen content is excessively increased in the phase reversal film, the chemical resistance to the cleaning material is deteriorated, There is a problem that the thickness of the phase reversal film becomes thick in order to compensate for the refractive index and phase inversion amount of the film being lowered.

The present invention relates to a method for manufacturing a photomask, which comprises the steps of: forming a phase reversal film having excellent chemical resistance and durability so as to prevent deterioration such as dissolution or corrosion in a cleaning material including ozone water used in a cleaning process repeatedly performed repeatedly in a photomask manufacturing process; And a method of manufacturing the same.

The method of manufacturing a phase inversion blank mask for forming a phase inversion film on a transparent substrate according to an embodiment of the present invention is characterized in that the phase inversion film is formed by a sputtering method using one target, Wherein the phase reversal film formed on the uppermost portion of the phase reversal film includes at least a metal, silicon (Si), oxygen (O), and nitrogen (N) (O) in an amount of 0.1 at% to 5 at% in order to improve the chemical resistance of the cleaning material including water, and is formed to have a thickness of 10 Å to 100 Å.

The uppermost phase reversal film is formed to contain oxygen (O) of 0.1 at% to 3 at%.

The uppermost phase reversal film is formed by implanting a gas containing oxygen (O) at a ratio of 1 vol% to 60 vol% of the total gas.

After the formation of the phase reversal film, heat treatment is performed at a temperature of 250 ° C to 400 ° C for 10 minutes to 60 minutes.

The phase reversal film is formed using a metal and a target made of silicon (Si), and the ratio of the metal: silicon (Si) is 1 at% to 40 at%: 99 at% to 60 at%.

The two or more phase reversal films are formed to have the form of a continuous film or a multilayer film.

The phase reversal film formed on the uppermost portion of the phase reversal film is formed of MoSiON and has a composition ratio of molybdenum (Mo) of 1 at% to 30 at%, silicon (Si) of 30 at% to 80 at%, and nitrogen (N) of 10 at% .

The phase reversal film formed under the uppermost phase reversal film of the phase reversal film is formed to include at least a metal, silicon (Si), and nitrogen (N).

Wherein the phase reversal film formed under the uppermost phase reversal film of the phase reversal film is made of MoSiN and includes 1 at% to 30 at% of molybdenum (Mo), 30 at% to 80 at% of silicon (Si) 50 at%.

The phase reversal film formed under the uppermost phase reversal film of the phase reversal film is formed to have a thickness of 300 ANGSTROM to 1,000 ANGSTROM.

The uppermost phase reversal film is formed to have a thickness of 10 ANGSTROM to 80 ANGSTROM.

The phase reversal film may be formed of at least one selected from the group consisting of titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn) (Al), Mn, Cd, Mg, Li, Se, Cu, Mo, Hf, Ta and tungsten (W). ≪ / RTI >

The phase reversal film has a transmittance of 1% to 30% and is formed to have a phase reversal amount of 170 ° to 190 °. ,

Shielding film is formed on the upper or lower portion of the phase reversal film.

The light shielding film is formed to be a light shielding film and an antireflection film, and is formed to have a thickness of 200 ANGSTROM to 800 ANGSTROM.

The light-shielding film may be formed of at least one of titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn) (Al), Mn, Cd, Mg, Li, Se, Cu, Mo, Hf, Ta and tungsten (W) or at least one of silicon (Si), oxygen (O), nitrogen (N), and carbon (C).

The light shielding film is formed of a light shielding film and an antireflection film, and the light shielding film and the antireflection film are formed of a chromium (Cr) compound of one of CrO, CrN, CrC, CrON, CrCO, CrCN and CrCON.

The light shielding film is formed so as to have an optical density of 2.5 or more with respect to the exposure wavelength for ArF and KrF with respect to the laminated structure together with the phase reversal film.

The phase inversion blank mask according to the present invention has a form of a multi-layered or continuous film of two or more layers, and forms a phase reversal film so that the topmost portion is oxidized by including oxygen (O).

Accordingly, it is possible to provide a phase inversion blank mask having a phase reversal film in which the refractive index and the phase inversion amount can be prevented from being lowered and the thickness is prevented from being increased by forming the thin oxide film at the top of the phase reversal film.

Accordingly, it is possible to provide a phase inversion blank mask excellent in chemical resistance and durability by preventing deterioration such as dissolution or corrosion of a phase reversal film to a cleaning material including ozone water used in a cleaning process in manufacturing a photomask.

1 is a cross-sectional view illustrating a phase inversion blank mask according to an embodiment of the present invention;
2 is a cross-sectional view showing part A of Fig.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a cross-sectional view showing a phase inversion blank mask according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view showing part A of FIG.

1 and 2, a phase inversion blank mask 100 according to the present invention includes a phase reversal film 104, a light shielding film 106, and a photoresist film 108 on a transparent substrate 102 .

The transparent substrate 102 has a size of 6 inches by 6 inches by 0.25 inches (width by length by thickness) and has a transmittance of 90% or more at an exposure wavelength of 200 nm or less.

The phase reversal film 104 may be formed of at least two films having mutually different materials using one target having the same structure, for example, a target made of a transition metal and silicon (Si). At this time, the target may have a ratio of transition metal: silicon (Si) of 1% to 40%: 99% to 60%. The phase reversal film 104 can be formed as a two-layer film of the first phase reversal film 110 and the second phase reversal film 112, for example. The first phase reversal film 110 and the second phase reversal film 112 constituting the phase reversal film 104 may have the form of a continuous film or a multilayer film of two or more layers as constituent materials different films. Here, the continuous film means a film formed by changing a reactive gas injected in a state in which the plasma is turned on during the sputtering process. In addition, when the phase reversal film 104 is composed of two or more layers, the constituent materials may have a structure in which the same films are alternately stacked.

The phase reversal film 104 made of the first phase reversal film 110 and the second phase reversal film 112 includes a metal and silicon Si and is composed of oxygen (O), nitrogen (N), and carbon (C) ≪ / RTI > The metal of the phase reversal film 104 includes, for example, a transition metal, and preferably includes at least one of titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr) Nb, Pd, Zn, Cr, Al, Mn, Cd, Mg, Li, Se, (Cu), molybdenum (Mo), hafnium (Hf), tantalum (Ta) and tungsten (W).

The phase reversal film 104 can be formed using, for example, a target containing molybdenum (Mo) and silicon (Si) as a transition metal. At this time, the first phase reversal film 110 can be formed of, for example, a nitriding phase reversal film including a metal, silicon (Si) and nitrogen (N), and is preferably made of MoSiNx which is a nitride film. The second phase reversal film 112 may be formed of an oxidative phase reversal film containing metal, silicon (Si), oxygen (O), and nitrogen (N), and is preferably made of MoSiOyNx which is a nitride oxide film. The second phase reversal film 112 has an oxygen (O) content of 0.1 at% to 10 at%, and preferably an oxygen (O) content of 0.1 at% to 3 at%.

The second phase reversal film 112 is formed to prevent deterioration such as dissolution or corrosion of the phase reversal film caused by the cleaning solution in the cleaning process for manufacturing the photomask. In detail, when the phase reversal film is made of a MoSi-based compound whose main component is a transition metal and silicon (Si), for example, the phase reversal film is composed of ozone (O ₃ ), Hot- DI and chemical ammonia (NH ₄ OH) It is liable to be damaged in a cleaning process using a cleaning solution containing sulfuric acid (H ₂ SO ₄ ) or the like. When the phase reversal film is damaged in the cleaning process using the cleaning solution, the thickness of the phase reversal film is thinned, the transmittance is increased, and the phase reversal amount is changed, so that the required optical properties of the phase reversal film can not be realized. Therefore, the first phase reversal film 110 including the metal, silicon (Si), and nitrogen (N) has excellent chemical resistance and durability, and is excellent in durability against metals, silicon (Si), oxygen (O), and nitrogen The phase reversal film 104 is formed in the form of a continuous film or a multilayer film to improve the durability of the phase reversal film 104 so that the phase inversion It is possible to prevent the film 104 from being damaged. In addition, after the formation of the phase reversal film 104, a heat treatment process may be performed to improve the physical properties of the thin film if necessary.

The phase reversal film 104 can be formed in the form of a continuous film or a multilayer film through a sputtering process using a change in the reactive gas ratio, a change in power applied to the target, or a plasma on / off have. In addition, the second phase reversal film 112 may be formed by ion plating in an oxygen atmosphere using a reactive oxidizing gas such as NO, O ₂ , NO ₂ , N ₂ O, CO, CO ₂ or the like containing oxygen Ion plating, ion beam, plasma surface treatment, rapid thermal process (RTP) device, vacuum hot-plate bake device, and heat treatment method using a furnace As shown in FIG.

The first phase reversal film 110 has a thickness of 300 ANGSTROM to 800 ANGSTROM, preferably 600 ANGSTROM to 700 ANGSTROM. The second phase reversal film 112 has a thickness of 10 to 100 angstroms and the second phase reversal film 112 has a thickness of 1 to 40 percent of the total phase reversal film thickness and preferably 1 to 10% And the thickness ratio of the first phase reversal film 110 to the second phase reversal film 112 is preferably 1: 5 to 1:30. When the second phase reversal film 112 has a thickness exceeding 50 angstroms, the thickness of the first phase reversal film 110 may be thinner in consideration of the thickness of the total phase reversal film 104 in a short wavelength of 200 nm or less The transmittance becomes high and the refractive index and the phase reversal amount become low. In order to compensate for this, when the thickness of the first phase reversing film 110 is increased, it is difficult to form a fine pattern of the phase reversing film 104 and it is difficult to realize the optical and physical properties of the phase reversing film pattern.

The phase reversal film 104 has a transmittance of 5% to 10%, and preferably has a transmittance of about 6%. The phase reversal film 104 has a phase reversal amount of 170 DEG to 190 DEG, and preferably has a phase reversal amount of 180 DEG.

The light shielding film 104 may be disposed on the top or bottom of the phase reversal film 104. The light shielding film 104 is formed of a metal film and is formed of a metal film such as Ti, V, C, Ni, Zr, Nb, Pd, Zn ), Cr, Al, Mn, Cd, Mg, Li, Selenium, Cu, Mo, (Si), oxygen (O), nitrogen (N), carbon (C) or the like is added to the metal material, or a transition metal such as tantalum And may further comprise one or more substances.

The light shielding film 106 may be formed as a single layer or a multilayer, and may further include, for example, a layer for controlling the back surface reflectance and stress of the metal film. If the light shielding film 106 has, for example, a two-layer structure, the lower layer may be formed of a light shielding film that mainly shields exposure light, and the upper layer may be an anti-reflection film that reduces reflection of exposure light. When the metal film is composed of multiple layers, it is preferable that the outermost surface layer has a lower reflectance at an exposure wavelength than any of the layers below.

It is more preferable that the light shielding film 106 has a thickness of 200 ANGSTROM to 800 ANGSTROM and a thickness of 400 ANGSTROM to 600 ANGSTROM. When the thickness of the metal film is 200 Å or less, the function of shielding the exposure light is not substantial. When the thickness of the metal film is 800 Å or more, the resolution and accuracy for implementing the auxiliary shape pattern are lowered due to the high thickness of the metal film. The light shielding film 106 has an optical density of 2.5 to 3.5 and a surface reflectance of 10% to 30% at an exposure wavelength of 200 nm or less.

EXAMPLES The present invention will now be described in detail with reference to the following examples, but 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. It is not. Thus, it will be understood that various modifications and equivalent embodiments may be made by those skilled in the art without departing from the scope of the present invention. Accordingly, the true scope of protection of the present invention should be determined by the technical matters of the claims.

(Example)

Phase reversal film  design

A phase reversal film 104 according to an embodiment of the present invention is formed in a two-layer structure of a first phase reversal film 110 made of MoSiN and a second phase reversal film 112 made of MoSiON on a transparent substrate 102 do.

The phase reversal film 104 is formed by injecting NO gas among N ₂ gas and oxygen (O) -containing gases using a DC magnetron sputtering apparatus equipped with a single target made of MoSi, . The phase reversal film 104 was injected while changing the N ₂ gas ratio of the reactive gases to 30% to 80% and the NO gas ratio to 0% to 80%. The phase reversal film 104 was formed to have a total thickness of 650 ANGSTROM ± 20 ANGSTROM so that the transmittance was about 5.8% to 6.2% at a wavelength of 193 nm. At this time, the second phase reversal film 112 was formed to a thickness less than 50 ANGSTROM.

In order to compare the optical and physical characteristics of the phase reversal film 104 according to the embodiment of the present invention, a single-phase phase reversal film made of MoSiN was formed. The phase reversal film used in the comparative example was formed by injecting N ₂ in a range of 30% to 80% with a reactive gas using a DC magnetron sputtering machine equipped with an MoSi target in the same manner as the embodiment of the present invention. Of the total thickness is in the range of 650 짹 20 Å so as to be about 5.8% to 6.2%.

The phase change of the phase reversal film formed according to the examples and comparative examples of the present invention was measured using an MPM-193 instrument, and the transmittance was measured using an N & K analyzer.

≪ Phase quantity and transmittance of the phase reversal film > Example No. 2. target 1 layer
N2 Ratio (%)
N2 / (Ar + N2) 2 stratum
NO Ratio (%)
NO / (Ar + N2 + NO) Phase amount (˚)
@ 193 nm Transmittance (%)
@ 193 nm Example 1

MoSi 70 0 179.8 5.87 Example 2 70 10 180.1 6.03 Example 3 70 30 180.3 6.04 Example 4 70 60 179.7 6.01 Example 5 75 60 179.9 6.02 Comparative Example 1
MoSi
80 - 180.2 5.81 Comparative Example 2 75 - 180.3 5.94 Comparative Example 3 70 - 179.8 6.16

As in Examples 2 to 4 of the embodiments of the present invention, the phase reversal film including NO in the phase reversal film of the bilayer film exhibited a phase amount of 180 ° ± 0.3 ° at 193 nm and a transmittance of 6 ± 0.4% at 193 nm %, Indicating excellent results as a phase reversal film.

Ozonated water  evaluation

The ozone water was evaluated for the phase reversal film formed according to the example of the present invention and the comparative example. The photomask formed by using the blank mask is subjected to repeated cleaning using ozone water, and the chemical resistance characteristic of the phase reversal film is important in this process. The concentration of the ozonated water used in the evaluation was 80 ppm. The phase reversal film formed according to the examples and the comparative example was subjected to a cleaning process 15 times, and the changes in phase amount and transmittance before and after the cleaning process were measured.

≪ Measurement results of phase amount and transmittance change due to ozone water washing > Example No. 2. @ 193 nm Before cleaning After 15 times cleaning delta Example 1 T% 5.87 5.97 0.10 Phase) 179.8 178.8 1.0 Example 2 T% 6.03 6.10 0.07 Phase) 180.1 179.3 0.8 Example 3 T% 6.04 6.07 0.03 Phase) 180.3 180.1 0.2 Example 4 T% 6.01 6.06 0.05 Phase) 179.7 179.1 0.6 Example 5 T% 6.02 6.08 0.06 Phase) 179.9 179.4 0.5 Comparative Example 1 T% 5.81 6.30 0.49 Phase) 180.2 172.0 7.2 Comparative Example 2 T% 5.94 6.31 0.37 Phase) 180.3 174.7 5.6 Comparative Example 3 T% 6.16 6.41 0.25 Phase) 179.8 175.6 4.2

As in Examples 2 to 4 of the embodiments of the present invention, the phase reversal film including NO in the phase reversal film of the two-layer film was subjected to 15 times cleaning with ozone water and then the phase amount was changed from 0.2 to 0.8 at 193 nm , And the transmittance varied from 0.03% to 0.07%.

On the other hand, the phase reversal film made of the MoSiN monolayer according to the comparative example exhibited a phase shift of 1.0 ° to 7.2 ° at 193 nm and a transmittance variation of 0.1% to 0.49% after 15 cycles of cleaning with ozone water . It can be understood that the phase reversal film made of MoSiN is dissolved or deteriorated in the ozonated water due to the ozonated water washing.

Accordingly, by forming the second phase reversal film 112 of a thin thickness made of MoSiON on the uppermost layer of the phase reversal film as in the embodiment of the present invention, the change in phase amount is within 2 占 and the change in transmittance is within 0.1% It was found that the phase reversal film 104 of the present invention had excellent chemical resistance and durability against ozone water.

SPM  evaluation( SPM  : H ₂ SO ₄  + H ₂ O ₂ )

The SPM evaluation was performed on the phase reversal films formed according to Examples and Comparative Examples of the present invention. The SPM evaluation is a cleaning process for removing a resist layer in manufacturing a photomask formed using a blank mask. In this process, the chemical resistance characteristic of the phase reversal film is important. The SPM evaluation uses a solution of H ₂ SO ₄ and H ₂ O ₂ mixed with H ₂ SO ₄ : H ₂ O ₂ = 10: 1, washing at a temperature of about 90 ° C. for 10 minutes three times And the changes in phase amount and transmittance before and after the cleaning process were measured.

≪ Measurement results of phase quantity and transmittance according to the number of times of SPM cleaning > Example No. 2. @ 193 nm Before cleaning After 3 rinses delta Example 1
T% 5.87 5.96 0.09 Phase) 179.8 178.7 1.1 Example 2
T% 6.03 6.08 0.05 Phase) 180.1 179.5 0.6 Example 3 T% 6.04 6.06 0.02 Phase) 180.3 180.2 0.1 Example 4 T% 6.01 6.05 0.04 Phase) 179.7 179.3 0.4 Example 5 T% 6.02 6.06 0.04 Phase) 179.9 179.5 0.4 Comparative Example 1 T% 5.81 6.27 0.46 Phase) 180.2 172.3 6.9 Comparative Example 2 T% 5.94 6.29 0.35 Phase) 180.3 174.2 5.2 Comparative Example 3 T% 6.16 6.40 0.24 Phase) 179.8 175.9 3.9

As in Examples 2 to 4 of the embodiments of the present invention, the phase reversal film including NO in the phase reversal film of the two-layer film was cleaned three times using the SPM solution, and the phase amount was changed from 0.1 to 0.6 degrees at 193 nm And the transmittance varied from 0.02% to 0.05%.

On the other hand, the phase reversal film made of the MoSiN monolayer according to the comparative example exhibited a phase shift of 1.1 ° to 6.9 ° at 193 nm and a transmittance change of 0.09% to 0.46% after three cycles of cleaning with the SPM solution .

Accordingly, by forming the second phase reversal film 112 of a thin thickness made of MoSiON on the uppermost layer of the phase reversal film as in the embodiment of the present invention, the change in phase amount is within 2 占 and the change in transmittance is within 0.1% It was found that the phase reversal film 104 of the present invention had excellent chemical resistance and durability against the SPM solution.

SC  - 1 rating ( SC -One : NH ₄ OH : H ₂ SO ₄ : H ₂ O )

SC-1 evaluation was performed on the phase reversal films formed according to the examples and comparative examples of the present invention. The SC-1 evaluation was carried out in order to evaluate the chemical resistance of the aqueous ammonia used in the cleaning process of the MoSi-based compound in the production of the photomask formed by using the blank mask. The SC-1 evaluation was carried out using a solution of NH ₄ OH, H ₂ SO ₄ and H ₂ O mixed in a volumetric ratio of NH ₄ OH: H ₂ SO ₄ : H ₂ O = 1: 1: 3, The reaction was conducted under harsh conditions at room temperature for 2 hours at 23 DEG C, and the changes in phase amount and transmittance before and after the washing step were measured.

≪ Measurement results of phase quantity and transmittance according to SC-1 cleaning > Example No. 2. @ 193 nm I'm after delta Example 1
T% 5.87 6.18 0.31 Phase) 179.8 178.7 1.1 Example 2
T% 6.03 6.20 0.17 Phase) 180.1 178.6 1.5 Example 3 T% 6.04 6.17 0.13 Phase) 180.3 179.1 1.2 Example 4 T% 6.01 6.22 0.21 Phase) 179.7 177.9 1.8 Example 5 T% 6.02 6.24 0.22 Phase) 179.9 178.1 1.8 Comparative Example 1 T% 5.81 7.67 1.86 Phase) 180.2 151.8 28.4 Comparative Example 2 T% 5.94 7.21 1.27 Phase) 180.3 161.6 18.7 Comparative Example 3 T% 6.16 7.18 1.02 Phase) 179.8 164.5 15.3

As in Examples 2 to 4 of the embodiments of the present invention, the phase reversal film including NO in the phase reversal film of the two-layer film was cleaned with SC-1 solution, and the phase amount was changed from 1.2 to 1.8 degrees at 193 nm , And the transmittance varied from 0.13% to 0.22%.

On the other hand, the phase reversal film made of the MoSiN monolayer according to the comparative example exhibited a phase shift of 1.1 ° to 28.4 ° at 193 nm after cleaning with the SC-1 solution, and the transmittance varied from 0.31% to 1.86% .

Accordingly, by forming the second phase reversal film 112 of a thin thickness made of MoSiON on the uppermost layer of the phase reversal film as in the embodiment of the present invention, the change of the phase amount is within 4 degrees and the change of the transmittance is within 0.3% It was found that the phase reversal film 104 of the present invention had excellent chemical resistance and durability for the SC-1 solution.

HOT - DIW  evaluation

HOT-DIW (Deionized Water) cleaning evaluation was performed on the phase reversal films formed according to the examples and comparative examples of the present invention. The HOT-DIW evaluation was carried out under the condition of immersing in DIW at 95 ° C for 50 minutes, and the changes in the amount of phase and the change in the transmittance before and after the washing step were measured.

≪ Measurement results of phase amount and transmittance according to Hot-DIW & Example No. 2. @ 193 nm I'm after delta Example 1
T% 5.87% 6.47% 0.60% Phase) 179.8 175.7 4.1 Example 2
T% 6.03% 6.27% 0.24% Phase) 180.1 177.8 2.3 Example 3 T% 6.04% 6.23% 0.19% Phase) 180.3 178.5 1.8 Example 4 T% 6.01% 6.28% 0.27% Phase) 179.7 177.1 2.6 Example 5 T% 6.02% 6.30% 0.28% Phase) 179.9 177.2 2.7 Comparative Example 1 T% 5.81% 7.98% 2.17% Phase) 180.2 148.8 31.4 Comparative Example 2 T% 5.94% 7.78% 1.84% Phase) 180.3 154.2 26.1 Comparative Example 3 T% 6.16% 7.68% 1.52% Phase) 179.8 159.4 20.4

In the phase reversal film of the two-layer film according to the embodiment of the present invention, the phase reversal film containing NO showed a change in the amount of phase from 1.8 to 2.7 at 193 nm after cleaning with HOT-DIW, and the transmittance was 0.19% 0.28%, respectively.

On the other hand, the phase reversal film made of the MoSiN monolayer according to the comparative example exhibited a change in the phase amount from 4.1 ° to 31.4 ° at 193 nm and a transmittance variation from 0.6% to 2.17% after cleaning with HOT-DIW .

Accordingly, by forming the second phase reversal film 112 of a thin thickness made of MoSiON on the uppermost layer of the phase reversal film as in the embodiment of the present invention, the change of the phase amount is within 4 占 and the change of the transmissivity is within 0.3% It can be seen that the phase reversal film 104 of the present invention has excellent durability against HOT-DIW.

As shown in Tables 2 to 4, the phase reversal film of the two-layer structure according to the present embodiment, that is, the phase reversal film having the oxidized second phase reversal film 112 made of MoSiON having a thickness of 50 angstroms or less, (104) was superior in chemical resistance and durability to the phase reversal film formed of the MoSiN nitride film in the comparative example. It is also seen that the phase reversal film having the best physical properties is formed when the ratio of NO gas among the gases for forming the uppermost phase reversal film among the embodiments of the present invention is about 30% of the total injected gas.

As described above, in the present invention, the phase reversal film made of MoSi-based compound is formed into a two-layer structure of a nitriding phase reversal film and an oxidative phase reversal film.

As a result, a cleaning process using a cleaning solution having a thin thickness and including ozone (O ₃ ), hot-DI, and chemical ammonia (NH ₄ OH), sulfuric acid (H ₂ SO ₄ ) It is possible to provide a phase inversion blank mask having a phase reversal film whose chemical resistance and durability against the cleaning solution are improved with respect to the process.

100: Phase inversion blank mask
102: transparent substrate
104: phase reversal film
106: Shading film
108: resist film
110: first phase reversal film
112: second phase reversal film

Claims (18)

A phase inversion blank mask manufacturing method for forming a phase inversion film on a transparent substrate,
Wherein the phase reversal film is formed by a sputtering method using one target, the film being formed of at least two layers having mutually different materials,
Wherein the phase reversal film formed on the uppermost portion of the phase reversal film includes at least a metal, silicon (Si), oxygen (O), and nitrogen (N)
The phase reversal film disposed on the uppermost portion of the phase reversal film contains oxygen (O) of 0.1 at% to 5 at% in order to improve the chemical resistance of the cleaning material including ozonated water and hot water, and has a thickness of 10 Å to 100 Å Forming a phase inversion blank mask. The method according to claim 1,
Wherein the uppermost phase reversal film is formed to contain oxygen (O) of 0.1 at% to 3 at%. The method according to claim 1,
Wherein the heat treatment is performed in a temperature range of 250 ° C to 400 ° C for 10 minutes to 60 minutes after formation of the phase reversal film. The method according to claim 1,
Wherein the phase reversal film is formed using a target made of a metal and silicon (Si), and the ratio of the metal to the silicon (Si) is 1 at% to 40 at%: 99 at% to 60 at% Way. The method according to claim 1,
Wherein the phase reversal film of two or more layers is formed so as to have a shape of a continuous film or a multilayer film. The method according to claim 1,
The phase reversal film formed on the uppermost portion of the phase reversal film is formed of MoSiON and has a composition ratio of molybdenum (Mo) of 1 at% to 30 at%, silicon (Si) of 30 at% to 80 at%, and nitrogen (N) of 10 at% Is formed so as to have a predetermined width. The method according to claim 1,
Wherein the phase reversal film formed below the uppermost phase reversal film of the phase reversal film is formed to include at least a metal, silicon (Si), and nitrogen (N). The method according to claim 1,
Wherein the phase reversal film formed under the uppermost phase reversal film of the phase reversal film is made of MoSiN and includes 1 at% to 30 at% of molybdenum (Mo), 30 at% to 80 at% of silicon (Si) And the composition ratio is 50 at%. The method according to claim 1,
Wherein the phase reversal film formed below the uppermost phase reversal film of the phase reversal film is formed to have a thickness of 300 ANGSTROM to 1,000 ANGSTROM. The method according to claim 1,
Wherein the uppermost phase reversal film is formed to have a thickness of 10 ANGSTROM to 80 ANGSTROM. The method according to any one of claims 1, 4, and 7,
The phase reversal film may be formed of at least one selected from the group consisting of titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn) (Al), Mn, Cd, Mg, Li, Se, Cu, Mo, Hf, Ta and tungsten And at least one metal material selected from the group consisting of tantalum nitride (W) and tantalum nitride (W). The method according to claim 1,
Wherein the phase reversal film has a transmittance of 1% to 30% and is formed to have a phase inversion amount of 170to 190 °. The method according to claim 1,
Shielding film is formed on the upper or lower portion of the phase reversal film. 14. The method of claim 13,
Wherein the light shielding film is formed to be a light shielding film and an antireflection film, and is formed to have a thickness of 200 ANGSTROM to 800 ANGSTROM. 14. The method of claim 13,
The light-shielding film may be formed of at least one of titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn) (Al), Mn, Cd, Mg, Li, Se, Cu, Mo, Hf, Ta and tungsten (W), or at least one of silicon (Si), oxygen (O), nitrogen (N), and carbon (C) is included in the metal. / RTI > 14. The method of claim 13,
Wherein the light shielding film is formed of a light shielding film and an antireflection film, and the light shielding film and the antireflection film are formed of a chromium (Cr) compound of one of CrO, CrN, CrC, CrON, CrCO, CrCN, and CrCON. A method of manufacturing a blank mask. 14. The method of claim 13,
Wherein the light shielding film is formed so as to have an optical density of 2.5 or more with respect to the ArF and KrF exposure wavelengths for the laminated structure together with the phase reversal film. A phase inversion blank mask produced by at least one of claims 1 to 17.

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