KR101270659B1 - Substrate for Blank Mask, Blank Mask and Manufacturing Method Thereof - Google Patents

Abstract

The present invention provides a binary blank mask or a phase inverted blank mask in which a transparent substrate, a phase inversion film, a metal film, and a resist film are sequentially formed, wherein the transparent substrate is made of synthetic quartz glass. A flatness of 1.0 μm in the effective area of 150 × 150 mm of the transparent substrate was applied by applying a slurry containing a functional additive having a thickness of at least 6.3 mm and a size of 152 × 152 ± 0.2 mm, in particular a slurry containing a functional additive having an etching or protecting effect. Hereinafter, it relates to a blank mask substrate and a blank mask using the same, characterized in that the surface roughness is manufactured to 0.5 nmRa or less.

Description

Blank mask substrate, blank mask and manufacturing method thereof {Substrate for Blank Mask, Blank Mask and Manufacturing Method Thereof}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blank mask and a blank mask substrate, which are key raw materials of a photomask used in a lithography process in semiconductor manufacturing, and more particularly to the flatness of a blank mask substrate. And a method for producing a high quality blank mask by excellent Surface Roughness. Specifically, the present invention relates to a method for producing a blank mask substrate and a blank mask having excellent performance by applying a polishing slurry containing a functional additive having an effect of etching or protecting the surface of a transparent substrate to a multi-step polishing process.

The photomask, which is a key component material used in lithography, a core technology of semiconductor device fabrication, is manufactured by forming a pattern by a lithography process using an e-beam on a blank mask. The performance of the photomask is determined by the performance of the blank mask and the performance of the blank mask is determined by the properties of components such as the transparent substrate, the phase shift film, the metal film and the resist film constituting the blank mask. In particular, in order for the transparent substrate to be used as the substrate of the blank mask, characteristics such as high transmittance, low thermal expansion coefficient, excellent flatness and surface roughness at short wavelengths are determined by the processing technology of the transparent substrate. Therefore, substrate processing technologies such as lapping and polishing are increasingly emerging as key technologies. With the recent development of high density and high precision of VLSI devices, 6-inch transparent substrates for electronic devices such as blank mask substrates require even greater flatness and surface roughness over the 132 × 132 mm effective area where the mask pattern is formed. As shown in FIG. 1, the current trend is to expand to the effective area 10 of 150 × 150 mm to form more patterns within a limited substrate area. Acquisition of excellent flatness of the transparent substrate can secure a margin of depth (Depth of Focus, DOF) during wafer transfer in the semiconductor process, and obtaining excellent surface roughness of the transparent substrate is gradually reduced in exposure wavelength. By minimizing light scattering in the semiconductor process, the contrast ratio can be maximized during wafer transfer in the semiconductor process. To this end, precision lapping and polishing processes have been proposed to improve the flatness and surface roughness in the processing technology of the transparent substrate for the blank mask. In the lapping and polishing process, the synthetic quartz glass is placed between the upper and lower plates and supplied with a slurry containing abrasive particles while applying relative pressure to the synthetic quartz glass, the surface plate and the polishing pad, and then the synthetic quartz glass is subjected to several steps. It is a process to control the excellent flatness and surface roughness by removing several hundred micrometers. The flatness of the transparent substrate has a principle that the flatness of the lapping surface is transferred as it is in the lapping process, and excellent flatness may be obtained through optimization of the slurry, the surface characteristics, and the process conditions of the lapping equipment. Surface roughness is determined by at least two steps of polishing process through optimization of the process conditions of slurry, polishing pad and polishing equipment. The abrasive particles are contained in the slurry and transfer the pressure applied from the equipment to the synthetic quartz glass to cause the polishing to occur. The type, size and content of the abrasive particles are different depending on the purpose of the polishing process. In general, the lapping process uses mainly hardened alumina (Al ₂ O ₃ ), silicon carbide (SiC), and zirconia (ZrO ₂ ) for efficient removal of synthetic quartz glass. Cerium oxide (CeO ₂ ) and colloidal silica (SiO ₂ ) with low hardness and spherical shape are used. In the case of lapping table, the polishing properties vary according to the surface material, groove shape, and polishing pad depending on hardness, density, compression rate, and elastic recovery rate. Therefore, in the present lapping and polishing process, since the flatness and surface roughness of the synthetic quartz glass are controlled by the characteristics of the physical abrasive particles, the surface plate and the polishing pad as described above, there is a limit in the reproducibility and efficiency of the process. Therefore, in order to manufacture a transparent substrate for a blank mask having even more excellent flatness and surface roughness, efficient and precise processing of the transparent substrate is required. Therefore, in addition to slurry, surface plate, polishing pad and process optimization, the introduction of Chemical Mechanical Planarization (CMP) process in which complex polishing is performed by addition of chemical elements such as oxidizing agent and functional additive is required.

The problem to be solved by the present invention was created to solve the above problems, over a multi-step to provide a method for manufacturing a blank mask substrate having excellent flatness and surface roughness in the enlarged 150 × 150 mm effective area A polishing step and a method for producing a good blank mask substrate and a blank mask using a polishing slurry of a different composition to which each functional additive is added in the step.

The problem to be solved by the present invention is not limited to the above-mentioned problems, and other tasks not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, a blank mask manufacturing method comprising the steps of providing a transparent substrate; First polishing the transparent substrate using a first slurry comprising a first abrasive particle of cerium oxide and a first functional additive of ammonium molybdate; And second polishing the transparent substrate using a second slurry containing colloidal silica having a smaller particle size than the first abrasive particle and a second slurry containing the first functional additive and a second functional additive of ammonium dichromate. Steps. Herein, the transparent substrate may have a flatness of 1.0 μm or less and a surface roughness of 0.5 nm Ra or less in an effective area of 150 × 150 mm.
The first slurry may include 1 to 30 wt% of the cerium oxide, and the second slurry may include 1 to 50 wt% of the colloidal silica.
The first slurry and the second slurry each further comprise 0.1 to 5 wt% of hydrogen peroxide (H ₂ O ₂ ), and the first slurry and the second slurry comprise 0.01 to 1 mole of the ammonium molybdate and the Ammonium dichromate may be included, respectively.
The first slurry and the second slurry may further include any one of nitric acid or potassium hydroxide (KOH).
The cerium oxide may have a particle diameter of 0.5 to 5 μm, and the colloidal silica may have a particle size of 20 to 200 nm.
The first slurry may be pH 4.0, and the second slurry may be pH 6.0.
In the first polishing step and the second polishing step, porous or porous and soft pads may be used simultaneously.

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As described above, according to the problem solving means of the present invention by applying a slurry containing a functional additive having the effect of etching or protecting the transparent substrate in the polishing process, the flatness is 1.0 ㎛ in 150 × 150 mm effective area of the transparent substrate Hereinafter, there exists an effect which can manufacture the transparent substrate for blank masks whose surface roughness is 0.5 nmRa or less.

1 is a plan view schematically showing a transparent substrate for a blank mask.
2 is a cross-sectional view showing the flatness of the transparent substrate manufactured according to an embodiment of the present invention.
3 is a cross-sectional view of a blank mask according to an embodiment of the present invention.
4 is a cross-sectional view of a phase inversion blank mask according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in different forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the concept of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. As used herein, the terms 'comprises' and / or 'comprising' mean that the stated element, step, operation and / or element does not imply the presence of one or more other elements, steps, operations and / Or additions. In addition, since they are in accordance with the preferred embodiment, the reference numerals presented in the order of description are not necessarily limited to the order. In addition, in this specification, when it is mentioned that a film is on another film or substrate, it means that it may be formed directly on another film or substrate, or a third film may be interposed therebetween.

In addition, the embodiments described herein will be described with reference to cross-sectional views and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of films and regions are exaggerated for effective explanation of technical content. Thus, the shape of the illustrations may be modified by manufacturing techniques and / or tolerances. Accordingly, the embodiments of the present invention are not limited to the specific forms shown, but also include variations in forms generated by the manufacturing process. For example, the etched area shown at right angles may be rounded or may have a shape with a certain curvature. Thus, the regions illustrated in the figures have schematic attributes, and the shapes of the regions illustrated in the figures are intended to illustrate specific types of regions of the elements and are not intended to limit the scope of the invention.

In order to achieve the above-described object, the present invention is to form a transparent substrate through a two-step lapping and polishing process and substrate cleaning process of the Slicing, Grinding, Chamfer processing is completed, and the phase inversion on the transparent substrate In a blank mask in which a film, a metal film is formed, and a resist film is sequentially stacked, flatness is 1.0 μm or less in an effective area of 150 × 150 mm through a polishing process of a transparent substrate using a polishing slurry to which a functional additive is added during the manufacture of a transparent substrate. In addition, the surface roughness is made of an excellent blank mask substrate of 0.5 nmRa or less, characterized in that for producing an excellent blank mask.

In the case of the manufacturing method of the transparent substrate for blank masks by the said invention,

a1) preparing a synthetic quartz glass substrate,

b1) wrapping the synthetic quartz glass formed in step a1);

c1) polishing the synthetic quartz glass formed in step b1);

d1) manufacturing the transparent substrate for the blank mask, including cleaning the transparent substrate formed in step c1).

The binary blank mask manufactured using the prepared transparent substrate,

a2) preparing a transparent substrate formed in step d1);

b2) forming a metal film on the transparent substrate,

C2) forming a resist film on the metal film and manufacturing the resist film by the binary blank mask manufacturing method.

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

a3) preparing a transparent substrate formed in step d1);

b3) forming a phase inversion film on the transparent substrate prepared in step a3),

c3) forming a metal film on the phase inversion film formed in step b3);

d3) forming a resist film on the metal film formed in step c3) to manufacture a phase shift blank mask.

In the step a1), the transparent substrate is made of soda-lime, natural quartz or synthetic quartz glass, the base material slicing from the quartz ingot (thickness) of 6.3 mm or more, the size is 152 × 152 ± 0.2 mm It features.

In step b1), the lapping process is characterized by consisting of two steps. When the lapping process is performed in one step, the lapping process is performed under high pressure by using abrasive particles of large size in consideration of process efficiency. The target thickness reduction can then be easily achieved, but damage including cracks generated in the depth direction at the surface of the substrate can occur and can develop into substrate defects due to residual stress. It is also difficult to obtain good surface conditions. Poor surface conditions result in lower productivity because the first polishing process is relatively more time consuming. Therefore, it is desirable to proceed the lapping process in two stages to achieve the target thickness accuracy while minimizing substrate defects.

In the step b1), the abrasive particles used in the lapping process is characterized by alumina (Al ₂ O ₃ ) as the main component and the size of the abrasive particles is 4 ~ 20 ㎛. If the size of the abrasive grain is 4 μm or less, productivity decreases as the process time increases. If the size of the abrasive grain is 20 μm or more, many damages including cracks generated in the depth direction occur on the surface of the synthetic quartz glass, and it is difficult to obtain a good surface state. It is also difficult to adjust the thickness accuracy. Therefore, the size of the abrasive particles used in the lapping process is preferably 4 ~ 20 ㎛.

In the step c1), the slurry used in the primary polishing process contains cerium oxide abrasive particles, hydrogen peroxide (H ₂ O ₂ ) and a functional additive ammonium molybdate ((NH ₄ ) ₂ Mo ₂ O ₇ ) and pH Is adjusted to nitric acid (HNO ₃ ) or potassium hydroxide (KOH) to adjust the total composition to 100 wt%. The slurry used in the secondary polishing process contains colloidal silica abrasive grains, hydrogen peroxide (H ₂ O ₂ ) and functional additive ammonium dichromate ((NH ₄ ) ₂ Cr ₂ O ₇ ), and the pH is nitric acid (HNO ₃ ). Or adjust to potassium hydroxide (KOH) to adjust the total composition to 100 wt%.

In the step c1), the content of the cerium oxide abrasive particles used in the primary polishing process is 1 to 30 wt%. If the content of cerium oxide abrasive grains in the polishing slurry is less than or equal to 1 wt%, the amount of abrasive grains reaching the synthetic quartz glass by the slurry decreases, making uniform polishing difficult in the effective area of 150x150 mm and the content of abrasive grains is 30 wt%. If it is abnormal, the slurry dispersibility decreases due to agglomeration of abrasive particles, and the viscosity increases, so that when used as a blank mask substrate in the effective area of 150x150 mm, such as unwanted scratches or chips on the surface of the substrate Surface defects may occur. Therefore, the content of cerium oxide abrasive particles is preferably 1 to 30 wt%. In the secondary polishing process, the secondary polishing is performed for the purpose of maintaining or improving the flatness and surface roughness of the 150x150 mm effective area of the transparent substrate secured by the primary polishing process, and the silica abrasive grains used in the secondary polishing slurry. The content of is characterized in that 1 to 50 wt%. If the abrasive grain content in the polishing slurry is 1 wt% or less, it is impossible to uniformly polish. If the abrasive grain content is 50 wt% or more, the slurry dispersibility is reduced due to agglomeration of abrasive particles due to an increase in slurry viscosity. This may cause defects such as unwanted scratches or chips on the surface of the substrate. Since the abrasive grains used in the secondary polishing process are much smaller than the cerium oxide abrasive grains, it is necessary to add more abrasive grains than the primary polishing process for uniform polishing of 150x150 mm effective area. . Therefore, the content of silica abrasive particles is preferably 1 to 50 wt%.

In the step c1), the size of the cerium oxide abrasive particles used in the primary polishing process is 0.5 to 5 ㎛. The abrasive grains receive the pressure applied from the polishing equipment through the polishing pad to physically remove the synthetic quartz glass.If the abrasive grain size is 5 ㎛ or more, it is impossible to secure good surface roughness. It must be done, which results in a decrease in productivity. And if the size of the cerium oxide abrasive particles is 0.5 ㎛ or less, the target surface roughness can be easily achieved, but as the processing time for achieving the target thickness reduction of the synthetic quartz glass increases, it also results in a decrease in productivity. Therefore, the size of the cerium oxide abrasive particles in the primary polishing process is preferably 0.5 to 5 ㎛. And the size of the colloidal silica (SiO ₂ ) abrasive particles used in the secondary polishing process is characterized in that the 20 ~ 200 nm. In order to improve the surface roughness obtained in the primary polishing process, abrasive particles smaller in size than cerium oxide are used.If the size is 20 nm or less, the process efficiency decreases due to the increase of the process time. It is hard to do. Therefore, the size of the colloidal silica abrasive grains in the secondary polishing process is preferably 20 to 200 nm.

In step c1), the hydrogen peroxide used as the oxidant in the first and second polishing processes is characterized in that the addition of 0.1 to 5 wt%. Hydrogen peroxide decomposes in the slurry to form OH ions or Radicals to etch a relatively high step surface of the substrate. In particular, the resulting OH Radical is being used as a more powerful oxidant than hydrogen peroxide. Hydrogen peroxide has an oxidation potential of 1.8 V, but Hydroxyl Radical has an oxidation potential equal to 3.0 V of the fluorine having the highest oxidation potential of about 2.8 V. In addition, the higher the content of hydrogen peroxide, the more OH ions or radicals decompose in the slurry, which increases the etching rate and amount of the synthetic quartz glass, but adding 5 wt% or more of hydrogen peroxide makes it difficult to control the target thickness reduction due to excessive etching. It has the disadvantage of poor reproducibility of the process. When the hydrogen peroxide is added below 0.1 wt%, the etching effect on the surface of the synthetic quartz glass has little effect, resulting in a decrease in the efficiency of the process. Therefore, the content of hydrogen peroxide added to the slurry is preferably 0.1 to 5 wt%.

In step c1), ammonium molybdate ((NH ₄ ) ₂ Mo ₂ O ₇ ) used as a functional additive in the primary polishing process is characterized in that it contains 0.01 to 1 mol. Ammonium molybdate is added as a functional additive to promote decomposition of hydrogen peroxide (H ₂ O ₂ ). The addition of ammonium molybdate in the polishing slurry enhances the decomposition rate of hydrogen peroxide by the catalytic reaction with hydrogen peroxide to promote the production of more OH Radicals. Thus formed OH Radical increases the etching action of the surface of the synthetic quartz glass to improve the polishing efficiency due to the effect of shortening the process time. Therefore, it is preferable that ammonium molybdate and hydrogen peroxide are added simultaneously. If ammonium molybdate is added in an amount of 0.01 mol or less, the etching effect of the surface cannot be expected. If more than 1 mol is added, the etching action of ammonium molybdate is maximized, resulting in lower surface roughness and poor reproducibility of the process. Therefore, the content of ammonium molybdate, which is a functional additive, is preferably 0.01 to 1 mol. And ammonium bichromate ((NH ₄ ) ₂ Cr ₂ O ₇ ) added as a functional catalyst in the secondary polishing process is characterized in that the addition of 0.01 to 1 mole. Ammonium dichromate is adsorbed on the surface of the synthetic quartz glass in the form of metal ions or metal oxides in the slurry to form a protective layer of several nm thickness that protects the surface of the synthetic quartz glass globally. Becomes possible. When more than 1 mole of ammonium dichromate is added, the thickness of the protective layer formed on the surface of the synthetic quartz glass becomes thick, and the efficiency of polishing decreases. If the amount is less than 0.01 mole, the thickness of the protective layer becomes too thin, thus losing its role as a functional catalyst. . Therefore, the content of ammonium dichromate added to the secondary polishing slurry is preferably 0.01 to 1 mol.

In step c1), the overall pH of the polishing slurry in the first and second polishing processes is adjusted to pH 4-12 using nitric acid (HNO ₃ ) or potassium hydroxide (KOH). In particular, an inorganic alkali such as potassium hydroxide (KOH) has a synthetic quartz glass etching effect has the advantage of showing a synergistic effect. Therefore, the pH of the slurry is preferably adjusted with potassium hydroxide (KOH).

In step c1), the pressure of the first and second polishing process is characterized in that 50 ~ 150 g / cm ² . If the pressure is 50 g / cm ² or less, the polishing efficiency is reduced, and if the polishing process is performed at a pressure greater than 150 g / cm ² , defects such as scratches or cracks may occur on the synthetic quartz glass substrate. Therefore, it is preferable that the pressure of a 1st, 2nd polishing process is 50-150 g / cm <^2> .

In the step c1), the lower platen rotating speed of the polishing equipment in the first and second polishing process is characterized in that 20 ~ 40 RPM. If the rotation speed is less than 20 RPM, the moving distance of the synthetic quartz glass moving on the polishing pad during the unit time is reduced, resulting in the decrease of the efficiency of the process. If the rotation speed is more than 40 RPM, the target thickness accuracy is controlled. It is difficult and has the disadvantage that the supplied polishing slurry is discharged without causing friction with the synthetic quartz glass for a sufficient time. Therefore, the rotational speed of the lower plate of the primary and secondary polishing processes is preferably 20 to 40 RPM.

In the step c1), the RPM ratio of the internal gear and the sun gear in the first and second polishing processes is 9: 1. If the RPM ratio is 9: 5 or 9: 7, there will be a local difference in the trajectory of rotation of the synthetic quartz glass, resulting in deterioration of uniformity characteristics. As the RPM ratio approaches 9: 7, the difference in removal rate between edge and center becomes larger. Therefore, the polishing rate of 9: 1 increases the rotation speed of the carrier supporting the transparent substrate to the maximum, which improves the polishing efficiency and uniformity. Therefore, the RPM ratio of the internal gear and the sun gear in the primary and secondary polishing equipments is preferably 9: 1.

In the step c1), the supply amount of the slurry in the first and second polishing process is characterized in that 3 ~ 10 L / min. Since the supply amount of the slurry affects the fluidity of the abrasive particles, it is preferable that the slurry supply amount is 3 to 10 L / min in order to reach the synthetic quartz glass sufficiently and uniformly.

In step c1), the polishing pad used in the primary polishing process is a porous cerium pad. In the first polishing process, since a removal rate is relatively higher than that of the second or more polishing process, it is preferable to use a cerium pad having a high hardness. The pad used in the secondary polishing process is characterized in that the soft pad SUBA # 400 ~ 800. The polishing pad determines the removal amount and surface condition of the synthetic quartz glass according to the type. The use of polishing pads below # 400 results in lower processing efficiency due to relatively high compression rate, elastic recovery rate and low hardness. When the polishing pad of # 800 or more is used, it is difficult to achieve the target surface roughness because of the low compressibility, elastic recovery rate and high hardness. Therefore, in the secondary polishing process, it is preferable to use a pad having a soft SUBA # 400 to 800 as the polishing pad.

In step c1), the first and second polishing processes are characterized in that the temperature is 20 to 30 ° C, humidity is carried out in an environment of 40% or more. Higher temperature and humidity during the polishing process increases the material removal rate (MRR) of the substrate, enabling efficient polishing. However, in order to maintain a constant MRR, it is desirable to narrow the setting of the appropriate temperature and humidity intervals.

In step c1), the dressing and brushing operations of the polishing pad are performed for 10 to 50 minutes before the first and second polishing processes are performed. The continuous polishing process causes glazing of the polishing pad, which degrades the pad's performance, resulting in a significant reduction in the removal rate. Diamond dressing can restore the pad's performance. And foreign matter accumulated in the pore of the pad after dressing work can be removed by brushing work. Since there is a direct relationship between the occurrence of defects and the removal rate in the polishing process, it may be selectively applied according to the number of times of the polishing process and the state of the pad.

In step d1), the cleaning of the transparent substrate after the first and second polishing processes is divided into one or two or more cleaning processes, and the first cleaning is characterized in that an alkaline solution is added. The order of cleaning is ultrapure rinse, scrub for 2 to 5 minutes using Detergent, ultrapure rinse, Standard Cleaning 1 (SC-1, NH ₄ OH: H ₂ O ₂ : H ₂ O = 1: 1: 5, 23 ° C) ) Scrub in solution, followed by ultrapure rinse. Scrub using Detergent aims to remove colloidal silica abrasive grains present on the transparent substrate surface. In SC-1 cleaning, ammonia water (NH ₄ OH) etches the surface of the transparent quartz glass substrate and hydrogen peroxide (H ₂ O ₂ ) directly dissolves contaminants on the surface of the transparent substrate. Therefore, it is preferable to wash | clean by the washing | cleaning method in which alkali solution was included by the 1st washing after a 1st and 2nd polishing process. In addition, a solution of hydrofluoric acid (HF), which is effective for removing silica-based materials, may be applied according to the purpose.

In the step d1), the second or more cleaning is intended to remove organic matter and particles on the surface of the transparent substrate, and Sulfuric Acid Peroxide Mixture (SPM, H ₂ SO ₄ : H ₂ O ₂ = 1: 10, 85 ° C) characterized in that the cleaning method is applied. The cleaning sequence is followed by SPM, Hot QDR (Hot Quick Dump Rinse), QDR, Megasonic, and Spin Dry. The SPM process is carried out to remove organic matter and particles on the surface, and hot QDR to remove residual sulfuric acid residues on the surface, and is carried out at 60 ~ 70 ° C to protect from thermal shock of the transparent substrate. Then, using a rinse process and nozzle type megasonic generator, the remaining particles are removed and finally the transparent substrate is dried through spin drying at 300 to 1500 RPM. In each of the above steps, the cleaning process may be selectively applied.

In the above steps a2) and a3), the transparent substrate is made of quartz or synthetic quartz glass and the like, and has a transmittance of at least 85% or more with respect to the lithographic light source i-line (365 nm) and the exposure wavelength of monochromatic light having even shorter wavelengths ( It features a substrate with a thickness of 6.3 ± 0.1 mm and a size of 152 x 152 ± 0.2 mm.

In the step b3), the phase inversion film is formed by sputtering in a vacuum chamber in which active and inert gases are introduced using a metal matrix, and cobalt (Co), chromium (Cr), tantalum (Ta) and tungsten are formed. (W), molybdenum (Mo), vanadium (V), palladium (Pd), titanium (Ti), niobium (Nb), zinc (Zn), hafnium (Hf), germanium (Ge), aluminum (Al), platinum (Pt), manganese (Mn), iron (Fe) and silicon (Si) characterized in that the thin film containing at least one selected from the group consisting of, the inert gas is argon (Ar), helium (He), At least one selected from the group consisting of neon (Ne), krypton (Kr) and xenon (Xe) is used, and the active gas is oxygen (O ₂ ), nitrogen (N ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), from the group consisting of nitrous oxide (N ₂ O), nitric oxide (NO), nitrogen dioxide (NO ₂ ), ammonia (NH ₃ ) and methane (CH ₄ ) At least one gas selected is used. And when the matrix of the phase inversion film is molybdenum silicide (MoSi) combination, molybdenum silicide (MoSiN), molybdenum silicide (MoSiO), molybdenum carbide (MoSiC), molybdenum carbide (MoSiCO), molybdenum carbide (MoSiCN) ), Molybdenum nitride silicide (MoSiON), and molybdenum nitride nitride molybdenum (MoSiCON), characterized in that the thin film comprising any one or more components.

In the steps b2) and c3), the metal film has a chromium matrix and is chromium (Cr), chromium carbide (CrC), chromium nitride (CrN), chromium oxide (CrO), chromium carbide (CrCN), and chromium carbide oxide. (CrCO), chromium oxynitride (CrON), and chromium carbide oxynitride (CrCON).

In the steps b2) and c3), the metal film is composed of a three-layered film of MoSi-based light-shielding film / MoSi-based anti-reflection film / Cr-based hard mask (silicon nitride) when the matrix of the light-shielding film is a molybdenum silicide (MoSi) combination Molybdenum nitride (MoSiN), when the antireflection film is composed of a molybdenum silicide (MoSi) combination and consists of a thin film comprising at least one of molybdenum (MoSiN), molybdenum silicide (MoSiO) and molybdenum carbide (MoSiC) At least one of molybdenum silicide (MoSiO), molybdenum carbide (MoSiC), molybdenum carbide oxide (MoSiCO), molybdenum nitride nitride (MoSiCN), molybdenum nitride nitride (MoSiON) and molybdenum nitride nitride (MoSiCON) Consists of a thin film containing and the parent of the hard mask is chromium (Cr) combination, chromium (Cr), chromium carbide (CrC), chromium nitride (CrN), chromium oxide (CrO), chromium carbide (CrCN), carbonization It is characterized by consisting of a thin film comprising any one or more of chromium oxide (CrCO), chromium oxynitride (CrON), chromium carbide oxynitride (CrCON) components.

In steps c2) and d3), a resist is coated on the metal film in the step by a spin coating method. The resist film is a chemically amplified resist and has a thickness of 4000 GPa or less.

[Example]

(Example 1 and Comparative Example 1)

Example 1 is an example in which a blank mask substrate is manufactured by applying a slurry containing a functional additive to a polishing step of a multi step.

First, in the primary polishing process of the 150x150 mm effective area 10 with reference to FIG. 1, 7 wt% of cerium oxide (CeO ₂ ) abrasive particles having 1.0 μm in deionized water and 1 wt% of hydrogen peroxide (H ₂ O ₂ ) are present. To prepare a primary polishing slurry, 0.02 mol of ammonium molybdate ((NH ₄ ) ₂ Mo ₂ O ₇ ) was added and the pH was adjusted to 4 to a total weight of 100 wt%, followed by high-speed stirring for 30 minutes. The polishing slurry thus obtained was polished for 70 minutes under the conditions of Table 1, and then the transmittance, flatness, and surface roughness change generated by polishing were measured.

And in the secondary polishing process of 150x150 mm effective area 10, such as primary polishing, the slurry is 24 wt% of colloidal silica (SiO ₂ ) of 80 nm size in deionized water and 1 wt% hydrogen peroxide (H ₂ O ₂ ). %, Ammonium dichromate ((NH ₄ ) ₂ Cr ₂ O ₇ ) 0.04 mol was added and adjusted to pH 10 to a total weight of 100, followed by high-speed stirring for 30 minutes. The secondary polishing slurry thus obtained was polished for 30 minutes under the conditions of Table 1, and then the change in transmittance, flatness and surface roughness produced by polishing was measured, and the results are shown in Table 2.

Process conditions Primary Polishing 2nd Polishing Abrasive slurry Cerium oxide 1.0 μm Colloidal Silica 80 nm Abrasive pad Porous Cerium Pad SUBA # 600 pad Rotation speed 25 RPM 20 RPM pressure 108 g / cm ² 75 g / cm ² Slurry flow rate 5 L / min 5 L / min Process time 70 min 30 min

On the other hand, Comparative Example is a functional additive of ammonium molybdate ((NH ₄ ) ₂ Mo ₂ O ₇ ) and ammonium dichromate ((NH ₄ ) ₂ Cr ₂ O ₇ ) among the components of the slurry prepared for the first and second polishing The polishing process was performed in the same manner as the polishing conditions shown in Table 1 above without the addition of the slurry.

At this time, after the polishing process, the thickness of the synthetic quartz glass was measured using LS-7000 laser micrometer (KEYENC Co., Ltd.) for evaluation of transmittance, flatness and surface roughness. Using an analyzer, the average value was calculated by measuring the transmittance at 49 points (A) at 193 nm wavelength, and the surface roughness was also spread over 49 points (A) in the 150x150 mm effective area 10 using SPM (Veeco) equipment. The average value was calculated by measuring. Flatness was measured using a Flatmaster 200 instrument.

Here, Total Indicated Reading (TIR, μm) refers to the sum of the absolute values of the height of the highest part and the height of the lowest part in the state where an imaginary line is drawn on the cross section of the synthetic quartz glass with reference to FIG. 2. The smaller the TIR value, the better the flatness can be expressed.

Slurry composition Example 1 Comparative Example 1 Primary Polishing Secondary polishing Primary Polishing Secondary polishing Abrasive Particle (wt%) CeO ₂ (7) SiO ₂ (24) CeO2 (7) SiO2 (24) Oxidizer (wt%) H ₂ O ₂ (1) H ₂ O ₂ (1) H ₂ O ₂ (1) H ₂ O ₂ (1) Catalyst (Mole) (NH ₄ ) ₂ Mo ₂ O ₇
(0.02) (NH ₄ ) ₂ Cr ₂ O ₇
(0.04) - - pH 4 10 4 10 Evaluation item Effective area After primary polishing After secondary polishing After primary polishing After secondary polishing Transmittance (%) at 193 nm 150 × 150 mm 88.5 91.7 87.2 89.3 TIR (μm) 0.77 0.68 1.12 0.98 Ra (nm) 0.494 0.185 0.525 0.287

According to Table 2 above, the content and pH of the abrasive particles, the oxidizing agent were kept constant, and ammonium molybdate ((NH ₄ ) ₂ Mo ₂ O ₇ ) and ammonium dichromate ((NH ₄ ) ₂ Cr ₂ O ₇ added as a functional additive. The transmittance, surface roughness, and flatness with or without the addition of) were measured to determine the possibility of application to the blank mask substrate. When the polishing was performed with the slurry to which the functional additives shown in Table 2 were not added, it could be confirmed that the results were insufficient to be used as the blank mask substrate. And a high transmittance of 91.7% when ammonium molybdate, which shows the etching effect on the surface of synthetic quartz glass, and ammonium bichromate, which forms a protective layer due to the adsorption of metal ions or metal oxides on the surface, adds precise polishing, A high flatness of 0.68 μm and excellent surface roughness of 0.185 nmRa were obtained. Therefore, through the above embodiment, a blank mask substrate having excellent quality could be manufactured by applying the polishing slurry to which the functional additive was added to the polishing process.

(Example 2 and Comparative Example 2)

Meanwhile, various kinds of blank masks may be manufactured using the transparent substrate manufactured by the polishing process to which the functional additive is added. For example, as shown in FIG. 3, a metal film on the transparent substrate 1 may be manufactured. (5), the binary blank mask in which the resist film 6 is sequentially formed or as shown in FIG. 4, the phase inversion film 2, the metal film 5, and the resist film 6 are formed on the transparent substrate 1; Phase inverted blank masks and the like that are sequentially formed may be manufactured.

In Example 2 and Comparative Example 2, a phase inversion blank mask was manufactured using the transparent substrates prepared in Example 1 and Comparative Example 1, and the performance as a photomask was evaluated.

First, referring to FIG. 4, a phase inversion film 2 having a composition of MoSiN was formed on the transparent substrate 1. At this time, the phase inversion film was formed through DC magnetron sputtering, and a sputtering target having a composition of 20:80 at% of Mo: Si and having a thickness of 6 mm was used. In this case, the sputtering gas was applied with 3 to 7 sccm of argon, 1 to 19 sccm of nitrogen, 0.9 to 1.5 kw of power, and 0.07 Pa of pressure. The phase shift film continuously changed composition while changing the flow rate and power of the sputtering gas. It was formed into a continuous film. In addition, the heat treatment temperature of the substrate during sputtering was applied to 180 ℃.

The phase inversion film formed on the substrate of Example 1 had a thickness of 870 Å, a transmittance of 5.32%, and a phase inversion of 178 degrees. And in the case of the phase inversion film formed on the board | substrate of the comparative example 1, the phase inversion of 875 GPa of thickness, 5.29% of transmittance, and 177 degree | times was measured.

In addition, the metal film 5 including the light shielding film 3 and the antireflection film 4 was formed on the phase inversion film 2 formed above by DC magnetron sputtering. As the sputtering target, a Cr target was used, and a target having a purity of 99.999% (5N) and a thickness of 6 mm was used. In this case, the sputtering gas is applied to 7 to 3 sccm of argon, 0 to 6 sccm of nitrogen, 0 to 7 sccm of nitrogen oxide, 1.7 to 5.8 sccm of methane, 1 to 0.71 kw of power, and 0.06 Pa of pressure. The metal film was formed into a continuous film whose composition was continuously changed while changing the sputtering gas flow rate and power.

The metal film formed on the substrate of Example 1 was 726 mm thick and the metal film formed on the substrate of Comparative Example 1 was 730 mm thick.

Further, a chemically amplified resist 6 was formed on the metal film 5 formed by the spin coating method. The thickness of the resist film formed on the substrate of Example 1 was 4003 mm 3 and the thickness of the resist film formed on the substrate of Comparative Example 1 was 3995 mm.

As a result of measuring the pattern minimum line width uniformity by manufacturing the blank mask formed as described above with a 65 nm class photomask, in Example 2 using the substrate of Example 1, a minimum line width uniformity of 5.0 nm was measured, and the substrate of Comparative Example 1 In Comparative Example 2 using the showed a minimum line width uniformity of 5.8 nm.

The photomask formed as described above was applied to a lithography process of forming a pattern on a wafer to fabricate a semiconductor device, thereby obtaining excellent results with a low defect rate. Therefore, the blank mask substrate having excellent quality and an excellent blank mask using the same may be manufactured through the polishing process using the slurry to which the functional additive is added through the above embodiment.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood. It is therefore to be understood that the above-described embodiments are illustrative and non-restrictive in every respect.

1: transparent substrate
2: phase inversion film
3, 4: metal film
6: resist film
10: effective area in the transparent substrate (150 x 150 mm)
A: the point where the transmittance, flatness and surface roughness in the effective area were measured

Claims (12)

Providing a transparent substrate;
First polishing the transparent substrate using a first slurry comprising a first abrasive particle of cerium oxide and a first functional additive of ammonium molybdate; And
Second polishing the transparent substrate using a second slurry comprising colloidal silica having a particle size smaller than the first abrasive particle and a second slurry containing the first functional additive and a second functional additive of ammonium dichromate Including but not limited to:
And the transparent substrate has a flatness of 1.0 μm or less and a surface roughness of 0.5 nm Ra or less in an effective area of 150 × 150 mm. delete delete The method of claim 1,
Wherein the first slurry comprises 1 to 30 wt% of the cerium oxide and the second slurry comprises 1 to 50 wt% of the colloidal silica. The method of claim 1,
The first slurry and the second slurry each further comprise 0.1 to 5 wt% of hydrogen peroxide (H ₂ O ₂ ), and the first slurry and the second slurry comprise 0.01 to 1 mole of the ammonium molybdate and the A blank mask manufacturing method comprising each of ammonium dichromate. The method of claim 1,
The first slurry and the second slurry further comprises any one of nitric acid or potassium hydroxide (KOH). The method of claim 1,
The cerium oxide has a particle size of 0.5 ~ 5 ㎛, the colloidal silica has a particle size of 20 ~ 200 nm blank mask manufacturing method. The method of claim 1,
Wherein said first slurry is pH 4.0 and said second slurry is pH 6.0. The method of claim 1,
The first polishing step and the second polishing step, a blank mask manufacturing method using a porous or porous, and a soft pad at the same time. A blank mask made by the method of any one of claims 1 and 4-9. A blank mask having at least one of a phase inversion film, a metal film, and a resist film formed on said transparent substrate manufactured by the method of any one of claims 1 and 4-9. delete

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