KR20120057502A - Photomask blank, Binary photomask and Phase shift photomask - Google Patents

Abstract

PURPOSE: A multi-functional photo-mask blank, a binary photo-mask, and a phase shift photo-mask are provided to improve the uniformity in plates and between plates and to improve the critical dimension characteristic of the photo-mask. CONSTITUTION: A multi-functional photo-mask blank includes a functional film(104) and a hard mask film(106). The functional film is arranged on a transparent substrate(102). The hard mask film is arranged on the functional film. The functional film functions as a transmission rate adjusting film in addition to a phase rate adjusting film and the hard mask film with respect to exposing light. The functional film includes silicon(Si) and one metal material selected from titanium(Ti), vanadium(V), cobalt(Co), nickel(Ni), zirconium(Zr), niobium(Nb), palladium(Pd), zinc(Zn), chrome(Cr), aluminum(Al), manganese(Mn), cadmium(Cd), magnesium(Mg), lithium(Li), selenium(Se), copper(Cu), molybdenum(Mo), hafnium(Hf), tantalum(Ta) and tungsten(W). The functional film further includes one of nitrogen(N), oxygen(O), and carbon(C).

Description

Photomask blank, Binary photomask and Phase shift photomask

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photomask blank and a photomask capable of implementing a high precision critical dimension (CD) in a semiconductor photo-lithography process. More particularly, the present invention relates to a blank mask using one type of blank mask. Binary masks and phase-inverted photomasks with hard masks are formed, and they can be applied to 193nm ArF lithography and immersion lithography that can achieve minimum line widths of 65nm and below, especially 45nm and below 32nm. Photomask blanks and photomasks.

In line with the demand for miniaturization of circuit patterns associated with the high integration of large scale integrated circuits, advanced semiconductor microprocessing technology is becoming a very important factor. In the case of high integrated circuits, circuit wiring is becoming finer for low power and high speed operation, and technical requirements for contact hole patterns for interlayer connection and arrangement of circuit components due to integration are increasing. Therefore, in order to meet these demands, there is a need for a technique capable of recording a more precise circuit pattern with the above miniaturization even in photomask fabrication in which the original of the circuit pattern is recorded.

This photolithography technique has shortened the exposure wavelength to 436 nm g-line, 365 nm i-line, 248 nm KrF, and 193 nm ArF to improve the resolution of semiconductor circuit patterns. However, shortening the exposure wavelength greatly contributes to the improvement of the resolution, but has a bad effect on the depth of focus (DoF), causing a lot of 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 that simultaneously improves resolution and depth of focus by using a phase shift layer that inverts the phase of exposure light by 180 degrees.

The phase inversion mask is mainly formed using a halftone phase inversion blank mask, as shown in " registered patent 10-0373317. &Quot; Referring to FIG. 1, the phase inversion blank mask has a structure in which a metal film and a resist film, each consisting of a phase inversion film, a light shielding film, and an antireflection film, are sequentially formed on a transparent substrate. On the other hand, as the pattern size becomes finer and denser to 45 nm or less, especially 32 nm or less, strict CD Mean to Target (MTT), CD Uniformity, and CD Linearity are required as well as resolution when manufacturing a photomask. To solve this problem, referring to FIGS. 2 and 3, a blank mask for a hard mask for etching a lower metal layer has been recently developed using the hard mask layer as an etch mask.

1 to 3, in the case of the conventional phase inversion blank mask 100, the hard mask blank mask 200, and the hard mask phase inversion blank mask 300, the phase inversion film 20 and the light shielding film 30 ), A multilayer thin film including an antireflection film (not shown), a hard mask film 40, and optionally an etch stop film 50, is formed, thereby increasing the complexity of the manufacturing process and the incidence of defects. This has a high problem. In particular, as the CD size to be implemented becomes more and more miniaturized, the control of defects becomes more and more strict.

In addition, the uniformity of the transmittance, reflectance, phase shift amount, and thickness of the target thin film is different due to the complicated structure of the multilayer as described above, and the stress of the thin film generated by the difference between the materials of each layer is also high. Have The problem also affects the plate surface, but also affects between the plates produced in a large amount of continuous production causes a problem of lowering the production yield.

Furthermore, the above-described complex blank mask structure repeats the exposure, development, etching and cleaning processes for photomask fabrication, thereby resulting in a problem of change in alignment and characteristics of the thin film.

The present invention relates to a blank mask for photomasks used in ArF lithography and ArF immersion lithography at 193 nm to solve the above problems.

The present invention provides a photomask blank capable of simultaneously implementing a binary photomask and a phase inversion photomask to which a hard mask film is applied in one photomask blank structure.

In addition, the present invention provides a blank mask manufacturing method in the photomask blank structure in which a multi-layered thin film is formed, in order to improve the in-plane and inter-plate uniformity.

In this way, when manufacturing the photomask blank and photomask, the process provides a photomask blank and a photomask having excellent CD characteristics along with improved product yield through a simplified process.

The photomask blank according to the embodiment of the present invention is a multifunctional photomask blank, which may be manufactured as one selected from a binary photomask and a phase inversion photomask, and includes a functional film disposed on a transparent substrate and disposed on the functional film. And a hard mask film, wherein the functional film serves as a transmittance control film together with a phase rate control film for exposure light and the hard mask film.

The functional film is titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn), chromium (Cr), aluminum ( Al), manganese (Mn), cadmium (Cd), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), molybdenum (Mo), hafnium (Hf), tantalum (Ta) and tungsten ( At least one metal material selected from W) and silicon (Si).

The functional film further includes at least one of nitrogen (N), oxygen (O) and carbon (C).

The functional film has more content of the silicon (Si) than the metal material.

The functional film has a content of 50% or more of the silicon (Si).

The functional film has a single layer or a multi-layer structure, has a single film having a uniform composition in the depth direction, or a continuous film structure having a variable composition, and has a thickness of 300 mW to 1000 mW.

The functional film has a transmittance of 0.1% to 10%, a reflectance of 10% to 30%, and a phase change amount of 170 ° to 190 ° with respect to the exposure light.

The exposure light has a wavelength of 300 nm or less.

The hard mask layer includes titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn), chromium (Cr), aluminum (Al), manganese (Mn), cadmium (Cd), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), molybdenum (Mo), hafnium (Hf), tantalum (Ta) and tungsten At least one metal material selected from (W).

The hard mask layer further includes at least one of nitrogen (N), oxygen (O), and carbon (C).

The hard mask film has a single layer or a multilayer structure, has a single film having a uniform composition in the depth direction, or a continuous film structure having a variable composition, and has a thickness of 50 kPa to 300 kPa.

The functional layer and the hard mask layer have an etching selectivity of 50: 1 or more.

In the laminated structure of the functional film and the hard mask film, the optical density with respect to the exposure wavelength is 2.0 to 4.0, the reflectance is 10% to 40% on the hard mask film, and the sheet resistance is 3 kΩ / □ or less.

Further comprising a photoresist film disposed on the hard mask film, the photoresist film is made of a material containing an acid, and has a thickness of 50nm to 300nm.

In addition, the binary photomask manufactured using the multifunctional photomask blank according to the embodiment of the present invention has a light shielding area and a light transmitting area, and the light blocking area is a region in which at least a functional film and a hard mask film are stacked on a transparent substrate. The transmissive area is an area where the transparent substrate is exposed.

In addition, the phase inversion photomask manufactured using the multifunctional photomask blank according to the embodiment of the present invention has a light shielding area, a phase inversion area and a light transmitting area, and the light shielding area is formed on at least a functional film and a hard substrate on a transparent substrate. A mask film is a stacked region, and the phase inversion region is a region in which a functional film is formed on a portion of the transparent substrate, and the light transmissive region is a region where the transparent substrate is exposed.

According to the present invention having the above-described configuration, by providing a photomask blank that can implement a binary photomask and a phase inversion photomask at the same time in one photomask blank structure, the process of manufacturing a photomask blank and photomask, Simplification can provide photomask blanks and photomasks with superior CD properties with improved product yield.

In addition, in the photomask blank structure in which a multilayer thin film is formed, it is possible to provide a photomask blank and a photomask with improved in-plane and inter-plate uniformity.

1 is a cross-sectional view showing a conventional phase inversion photomask blank.
2 is a cross-sectional view illustrating a binary photomask blank to which a conventional hard mask film is applied.
3 is a cross-sectional view illustrating a phase inversion photomask blank to which a conventional hard mask film is applied.
4 is a cross-sectional view illustrating a multifunctional photomask blank according to an embodiment of the present invention.
5A through 5B are cross-sectional views illustrating a method of manufacturing a binary photomask blank using a multifunctional photomask blank according to an embodiment of the present invention.
6A through 6D are cross-sectional views illustrating a method of manufacturing a phase shift photomask blank using a multifunctional photomask blank according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail through embodiments of the present invention with reference to the drawings, but the embodiments are only used for the purpose of illustrating and explaining the present invention, and the present invention described in the meaning limitations and claims. It is not intended to limit the scope of. Therefore, it will be appreciated that various modifications and equivalent other embodiments may be made from those skilled in the art. Therefore, the true technical protection scope of the present invention will be defined by the technical details of the claims.

4 is a cross-sectional view illustrating a multifunctional photomask blank according to an embodiment of the present invention.

Referring to FIG. 4, the multifunctional photomask blank according to the embodiment of the present invention is a blank mask used to fabricate a photomask applied to exposure light having a wavelength of 300 nm or less, particularly, 200 nm or less, and the transparent substrate 102. The functional film 104, the hard mask film 106, and the resist film 108 are sequentially stacked on the substrate. The photomask blank according to the embodiment of the present invention is a blank mask capable of manufacturing a binary photomask and a phase inversion photomask to which a hard mask film is applied, and the photomasks may be implemented from the structure of the photomask blank.

The transparent substrate 102 has a width of 6 inches x 6 inches x 0.25 inches in width, length, and thickness of Synthetic Fused Silica, Calcium Fluoride (CaF2), F-Doped Quartz, and Oxidation. At least one transparent substrate selected from titanium doped quartz (SiO 2 -TiO). The transparent substrate 102 preferably has a birefringence of 2 nm / 6.35 mm or less, a transmittance of 90% or more at an exposure wavelength, a flatness of less than 0.3 um, and a surface roughness of 0.3 nmRa or less. .

The functional film 104 includes titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn), and chromium (Cr). , Aluminum (Al), manganese (Mn), cadmium (Cd), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), molybdenum (Mo), hafnium (Hf), tantalum (Ta) And at least one material selected from tungsten (W) and silicon (Si), and may include at least one material of nitrogen (N), oxygen (O), and carbon (C).

The functional film 104 includes both a light shielding function and a phase inversion function. In order for the functional film 104 to have a light shielding function, the functional film 104 should be made of a material having a high extinction coefficient as compared to chromium (Cr), which is a typical material used as a conventional light shielding film, and should be able to substantially reduce its thickness. Since silicon (Si) is a material having a high extinction coefficient compared to chromium (Cr) among various material compounds, the thickness can be reduced, and accordingly, a thin film of the photoresist film is also possible. The thinning of the photoresist film reduces scattering of electrons in the exposure process and improves linearity, thereby finally achieving excellent resolution. However, when the functional film 104 is formed by the DC sputtering method using a target made of only metal and a target made of only silicon (Si), plasma discharge becomes unstable. Accordingly, the functional film 104 may be formed by improving the instability of the sputtering discharge using a target containing at least one of the metals constituting the functional film 104 and silicon (Si) together. Can be. In this case, the metal to be applied to the target is one of the above-mentioned metal, in particular, the material of molybdenum (Mo), titanium (Ti), tungsten (W), tantalum (Ta), zirconium (Zr). desirable.

On the other hand, in order for the functional film 104 to have a phase inversion function, it must have a certain amount of transmittance and a phase amount at a predetermined thickness. To this end, the functional film 104 preferably includes at least one of oxygen (O), nitrogen (N), and carbon (C) in order to increase the refractive index in addition to the metal and silicon (Si). In particular, when the functional film 104 contains oxygen (O) and nitrogen (N), it is possible to increase the phase amount at a low thickness by increasing the refractive index, while ensuring the desired predetermined transmittance. Through this, the functional film 104 has a transmittance of 0.1% to 10% at an exposure wavelength of 300 nm or less, particularly 193 nm or less, preferably, within 1 to 5%, more preferably 1% to 3%. Have When the functional film 104 has a transmittance of 0.1% or less, the exposure intensity for the destructive interference is lowered, and the effective intensity required for phase control is insufficient, and when the functional film 104 is 10% or more, the light blocking function is not performed. In addition, considering the light shielding function of the hard mask film 106 formed on the functional film 104, the functional film 104 may have a transmittance of 1% to 10%. In addition, the functional film 104 has a phase change amount of 170 degrees to 190 degrees, and more preferably has a phase change amount of 175 degrees to 185 degrees. If the phase amount of the metal film is 170 degrees or less and 190 degrees or more, the substantial phase reversal effect is difficult compared to the phase of the light transmitting portion passing through the transparent substrate.

In order to reduce the loading effect, the functional film 104 needs to be reduced in thickness compared to about 1,000 mm3 of the conventional binary blank mask, and has a thickness of 300 mm3 or more for the actual light shielding function. Therefore, the functional film 104 preferably has a thickness of 300 kPa to 1000 kPa. This means that when the functional film 104 has a thickness of less than 300 mW, a thickness for phase inversion is not substantially formed, so that only the existing light shielding function is possible. It can be performed, but due to the relatively high thickness in terms of the loading effect is small. More preferably, the functional film 104 has a thickness of 400 kPa to 900 kPa.

The functional film 104 may be composed of a single layer or multiple layers, and may be formed of a single film having a uniform composition in the depth direction and a continuous film having a composition that is selectively changed. The functional film 104 has a surface reflectance of 10% to 30% at an exposure wavelength of 300 nm or less, for example, at an exposure wavelength of 193 nm or 248 nm, and the uniformity of characteristics such as the amount of phase change, transmittance, reflectance and thickness is determined by the in-plane average value. Within 10%, the surface roughness is 0.1 nmRa to 1.0 nmRa, and the flatness is within 0.5 um of the absolute value of the change compared to the transparent substrate.

The functional film 104 has a chemical resistance property of 1% or less in transmittance and reflectance at an exposure wavelength after 2 hours of immersion in SC-1 (ammonia water: hydrogen peroxide water: ultrapure water = 1: 1: 5), and in ozone water (DIO3). After 2 hours of immersion, the transmittance and reflectance change in the exposure wavelength are 1% or less, and the surface resistance on the surface is 2kΩ / □ or less.

In addition, the silicon (Si) of the functional film 104 is higher than the metal material, the composition ratio of the silicon (Si) is preferably 50% or more, more preferably 55% or more in the functional film 104. It has a cleaning process step using a variety of cleaning solutions, for example, acidic, basic and ozone water in the manufacture of the photomask, wherein, if the silicon content of the functional film 104 is within 50%, cleaning This is because the damage caused by the solution becomes thin, which causes problems such as a decrease in optical density, a change in phase amount, and an increase in transmittance.

The hard mask film 106 may be formed in a single layer or multiple layers, and may be formed of a single film having a uniform composition in the depth direction and a continuous film having a variable composition. In order to improve the resolution of the hard mask layer 106, the thickness of the resist layer 108 may be thinner than that of the existing light shielding layer, and thus, the thickness of the resist layer 108 may be 50 μm to 300 μm.

Since the hard mask film 106 may be used as an etching mask with respect to the functional film 106 disposed below, the hard mask film 106 may be formed of a material different from that of the functional film 104 and the functional film 104 and 50. It is preferable to form from a material having a selectivity of at least 1: 1. To this end, the hard mask layer 106 may include titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn), Chromium (Cr), Aluminum (Al), Manganese (Mn), Cadmium (Cd), Magnesium (Mg), Lithium (Li), Selenium (Se), Copper (Cu), Molybdenum (Mo), Hafnium (Hf), It is formed of one or more materials selected from tantalum (Ta) and tungsten (W). Since the lower functional film 104 of the hard mask film 106 includes silicon (Si) that is etched with a florin (F) -based gas, the lower functional film 104 may be formed of a material that is etched with the chlorine (Cl) gas-based. In consideration of the selectivity with respect to the functional film 104, it is preferable that it consists of at least 1 sort (s) of chromium (Cr), hafnium (Hf), tantalum (Ta), tungsten (W), and titanium (T). In addition, the hard mask layer 106 may include at least one of nitrogen (N), oxygen (O), and carbon (C) in the above-described metal material.

The blank mask according to the present invention has an optical density of 2.0 to 4.0 for an exposure wavelength of 300 nm or less in the functional film 104 and the hard mask film 106 stacked structure, and 10% to 40% on the hard mask film 106. It has a reflectivity of and has a sheet resistance of 3 kΩ / □ or less.

Functional film 104 and hardmask film 106 are selected from reactive DC magnetron sputtering, reactive RF magnetron sputtering, ion beam sputtering, and co-sputtering devices. It is formed using a device of the species. For example, the functional film 104 and the hard mask film 106 have a distance of 10 cm to 40 cm in a linear distance between the transparent substrate 102 and the sputtering target, and the sputtering target and the transparent substrate are inclined at 10 degrees to 40 degrees. It can be formed using a long throw sputtering apparatus having a true incidence incident structure.

The functional film 104 and the hard mask film 106 may be selectively heat treated before, during, and after formation to improve chemical resistance to stress, acid, and alkali chemicals. The heat treatment method can be performed using, for example, a vacuum hot plate, a vacuum rapid heat treatment apparatus, or the like. Through this, the resist film 108 formed on the hard mask film 106 uses a chemically amplified resist including an acid, and has a thickness of 50 nm to 300 nm to improve resolution. In addition, an intermediate layer including an acid and containing an acid may be further formed between the hard mask film 106 and the resist film 108.

(Example 1)

Multifunctional  Preparation of the blank mask

In the method for manufacturing a multifunctional blank mask according to an embodiment of the present invention, referring to FIG. 4, first, a transparent substrate having a size of 6 inch x 6 inch x 0.25 inch and having a birefringence of 2 nm or less is prepared. A MoSi (10: 90 at%) target with a purity of 4N or higher was placed on top of the DC magnetron reactive sputtering device chamber for multifunctional film formation.

Thereafter, the initial vacuum degree is set to 0.02 Pa or less to completely remove impurities such as moisture inside the chamber. Subsequently, 5-8 sccm of argon gas (Ar) and 12-15 sccm of nitrogen (N) gas are inject | poured, sputtering for 500-600 second with process power 0.9-1.4 kW and pressure 0.05-0.20 Pa. The functional film 104 made of MoSiN was formed. At this time, the transparent substrate is rotating at 30 RPM, and the bottom of the transparent substrate is heat-treated at 200 degrees by a hot plate. In addition, at least one selected from the group consisting of helium (He), neon (Ne), and xenon (Xe) may be used as an inert gas in addition to argon gas (Ar). In addition, when the structure of the functional film 104 is changed, oxygen (O 2), nitrogen (N 2), carbon monoxide (CO), carbon dioxide (CO 2), nitrogen dioxide (NO 2), nitrogen monoxide (NO), nitrous oxide ( N2O), ammonia (NH3) and methane (CH4) at least one gas selected from the group consisting of can be used.

Then, using a chromium (Cr) target, 3 to 5 sccm of argon gas and 1 to 3 sccm of methane (CH4) gas are injected, and the process power is 0.4 to 0.8 kW and the pressure is 0.05 to 0.20 Pa. Sputtering was performed for 20 to 80 seconds to form a hard mask film 106 on the functional film 104.

Thereafter, the chemically amplified resist film was spin-coated to a thickness of 1500 Å to prepare a multifunctional blank mask.

In order to evaluate the characteristics of the functional film 104, the transmittance was measured using a Varian Cary-5000 device. It was 8.3% and the reflectance was 15.0-20.0% at 193 nm. In addition, as a result of measuring the phase amount of the functional film 104 using the MPM-193 equipment, the phase change was 175 to 184 degrees at 193 nm, and the thickness was measured using the XRR equipment to be 600 to 680 Å. The thickness was excellent, showing excellent results with the functional film. In addition, as a result of using the MAGICS M6640 equipment of Lasertec for the defect inspection such as particles (Particle) for the prepared metal film first, the particles of 100nm ~ 150 nm 3ea, particles of 150nm ~ 200nm size 2ea Particles of 200 nm or more were 0ea, and the particles were excellent as 5ea in the entire 142 mm ² region. In addition, the surface roughness of the metal film was measured in an area of 1 μm × 1 μm using an AFM (Atomic Force Micrometer) device, and the result showed excellent surface roughness of 0.35 nmRa. In addition, the impurity content of the surface of the metal film was analyzed using ICS-3000, an ion chromatography apparatus, and the impurity concentration was 129 ppbv or less, which showed good results. In addition, in order to observe the flatness change of the metal film, the flatness (average 0.62um) of the functional film 104 was compared with the flatness (average 0.35um) of the transparent substrate in the 142 mm ² area using the Tropel Flatmater-200 device. As a result of the measurement, the change in TIR (Total Indicated Reading) value showed an average change of 0.27um, which showed excellent results.

In order to evaluate the characteristics of the hard mask film 106, the thickness of the hard mask film 106 was measured using XRR. The results were 50Å? 350Å. The transmittance and reflectance of the hardmask film 106 were measured at 193nm. It exhibited a transmittance of 0.15% to 0.08%, and a reflectance of 18.0 to 19.3%. In addition, the optical density of 2.8 ~ 3.1 was shown, and the sheet resistance (Sheet Resistance) was measured using a 4-point probe device, and the result showed excellent sheet resistance by showing 358 Ω / ㅁ.

As such, the multifunctional blank mask according to the present invention exhibited excellent properties without problems for use as a photomask.

(Example 2)

Multifunctional  Binary with Blank Mask Photomask  Produce

5A to 5B are cross-sectional views illustrating a method of manufacturing a binary photomask using the multifunctional photomask blank of the present invention.

Referring to FIG. 5A, after manufacturing the above-mentioned multifunctional blank mask of FIG. 4, an exposure process is performed on a multifunctional photomask blank using an exposure equipment of 50 keV, and a PEB (Post Exposure Bake) process is performed at 110 ° C. FIG. It was carried out for 10 minutes. Thereafter, a development process was performed using THMA 2.38% Developer to form a resist film pattern 108a.

5B, the lower hard mask layer 106 may be a chlorine (Cl) -based gas, for example, a Cl ₂ gas and an O ₂ , using the resist film pattern 108 as an etching mask. The hard mask layer pattern 106a was formed by etching using gas. Thereafter, the functional film 104 is etched based on the fluorine (F) -based gas, for example, SF ₆ , using the gas to expose a portion of the transparent substrate 102 in the light-transmitting region ( 104a). Then, the resist film was removed to prepare a binary photomask.

The binary photomask according to the present invention has sufficient light shielding property against exposure light as the functional film 104 and the hard mask film 106 are stacked.

(Example 3)

Multifunctional  Phase Inversion Using Blank Mask Photomask  Produce

6A to 6D are cross-sectional views illustrating a method of manufacturing a phase inversion photomask using the multifunctional blank mask of the present invention.

6A and 6B, after manufacturing the above-described multifunctional photomask blank of FIG. 4, an exposure process is performed using an exposure apparatus of 50 keV on the multifunctional photomask blank, and a post exposure bake (PEB) process. Was carried out at 110 ° C. for 10 minutes. Thereafter, a development process was performed using THMA 2.38% Developer to form a first resist film pattern 108a.

Then, using the first resist film pattern 108a as an etching mask, the lower hard mask film 106 may be a chlorine (Cl) -based gas, for example, Cl ₂ gas and O ₂ gas. The hard mask film pattern 106a was formed by etching. Thereafter, the functional film 104 is etched again based on the fluorine (F) -based gas, for example, SF ₆ , using the gas to expose a portion of the transparent substrate 102 in the light-transmitting region ( 104a) was formed and the first resist film was removed.

Subsequently, after forming a second resist film on the resultant, the second resist film was patterned to form a second resist film pattern 108b on the hard mask film pattern 106a.

Subsequently, a portion of the hard mask layer exposed so that the hard mask layer pattern 106b remains only in the light shielding region using the second resist layer pattern 108b as an etch mask was etched to prepare a phase inversion photomask in which the phase inversion region is exposed.

As described above, the present invention was able to manufacture a binary photomask and a phase reversal photomask to which a hard mask film was applied using a multifunctional photomask blank having a structure, wherein a process of forming a film when manufacturing the photomask blank is performed. As a two-step structure, a three-step structure of the conventional phase inversion blank mask and a five-step structure of the phase inversion blank mask to which the hard mask film was applied were easily manufactured.

The following is the result of evaluating the uniformity inside and between plates when 100 sheets were continuously produced by applying Examples 1 and 2. FIG.

Continuous evaluation result
Example 1

Example 2 Transmittance Average 3.23% 4.27% Range (Max-Min) 0.02% 0.03% reflectivity Average 21.85% 19.1% Range (Max-Min) 0.87% 0.67% thickness Average 572.4 Å 576 yen Range (Max-Min) 8.1Å 7.8Å flatness Average 0.61 μm 0.58 μm Range (Max-Min) 0.08μm 0.04μm

Referring to [Table 1], when 100 sheets were produced, the transmittance, reflectance, thickness, and flatness were all excellent in reproducibility, and the range also showed excellent results within 10% of the average value. .

On the other hand, Comparative Example 1 relates to the production of a phase reversal photomask blank and a hard mask photomask blank prepared in order to compare the above embodiment.

First, the manufacturing method of a phase inversion photomask blank is demonstrated.

A phase inversion film was formed using a MoSi (10: 90at%) target to form a phase inversion film on a 6 inch by 6 inch by 0.25 inch size transparent substrate. In this process, 5 sccm of argon (Ar) and 15 sccm of nitrogen (N2), which is a reactive gas, were used as an inert gas to form a plasma at 1.5 kW, and the process pressure was 0.3 Pa. The process time was 150 seconds.

Subsequently, the transmittance and reflectance of the prepared phase inversion film were measured for 49 Points of 7 x 7 using the n & k Analyzer 1512RT. As a result, the transmittance average was 5.62% at 193 nm. In addition, as a result of measuring the phase amount, the average inversion of the phase inversion film was 178.1 degrees and the uniformity was 0.8 degrees at 193 nm. In addition, as a result of measuring the thickness using a GXR equipment, the thickness was 632.1 어, indicating that the thickness of the phase inversion film was relatively higher than those of Examples 1 and 2.

Subsequently, to form a metal film, the target was replaced with a chromium target, and a light shielding film of 430 kPa was formed using argon gas 3 sccm nitrogen, 10 sccm, process power 0.5 kW, and process pressure 0.03 Pa. In this case, the reflectance was measured in the light shielding film. As a result, the reflectance was 38.5% at 193 nm. Then, the antireflection film was formed on the light-shielding film with an argon gas of 5 sccm, nitrogen of 3 sccm, and nitrogen monoxide gas of 4 sccm to a thickness of 120 Å. The reflectance was measured again. It was.

The following is a comparative example of a method for producing a photomask blank for hard mask.

First, using MoSi (10: 90at%) target to form a metal film was formed for 7 seconds in argon gas and 3.5 sccm in nitrogen for 300 seconds at 0.8kW power. The light-shielding film of the formed metal film had a transmittance of 0.17% and a thickness of 500 Hz at 193 nm, but a reflectance of 48.2%. Anti-reflection film deposition conditions were formed for 7 seconds in argon gas, 9.5 sccm in nitrogen, 0.7W for 150 sec. As a result of measuring the reflectance of the metal film on which the anti-reflection film was formed, the result was 14.5% at 193 nm, showing good results with the reflectance of the metal film. In order to form a hard mask layer on the metal layer, the target was replaced with chromium, and 5 sccm of argon gas, 3 sccm of nitrogen, and 2.5 sccm of nitrogen monoxide gas were deposited at 0.5 kW for 100 sec. Mask film formation was performed.

As such, the binary photomask and the phase reversal photomask using the photomask blank according to the embodiment of the present invention have better physical properties than the photomask blank according to the comparative example.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation in the embodiment in which said invention is directed. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.

10: transparent substrate 20: phase inversion film
30: metal film 40: etch stop film
50: hard mask film 60: resist film
100: halftone phase inversion blank mask
200: Binary Intensity Blank Mask for Hard Mask
300: phase inversion blank mask for hard mask

Claims (16)

A multifunctional photomask blank, which can be manufactured as one selected from binary photomask and phase inversion photomask,
A functional film disposed on the transparent substrate;
And a hard mask film disposed on the functional film.
And the functional film serves as a transmittance control film together with a phase rate control film for exposure light and the hard mask film. The method of claim 1,
The functional film is titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn), chromium (Cr), aluminum ( Al), manganese (Mn), cadmium (Cd), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), molybdenum (Mo), hafnium (Hf), tantalum (Ta) and tungsten ( A multifunctional photomask blank comprising at least one metal material selected from W) and silicon (Si). The method of claim 2,
The functional film is a multi-functional photomask blank, characterized in that further comprises at least one of nitrogen (N), oxygen (O), carbon (C). The method of claim 2,
The functional film is a multifunctional photomask blank, characterized in that the silicon (Si) has a higher content than the metal material. The method of claim 2,
The functional film is a multifunctional photomask blank, characterized in that the content of the silicon (Si) is 50% or more. The method of claim 1,
The functional film has a single layer or a multilayer structure, a single film having a uniform composition in the depth direction, or a continuous film structure having a variable composition, and has a thickness of 300 mW to 1000 mW. The method of claim 1,
The functional film has a transmittance of 0.1% to 10%, a reflectance of 10% to 30%, and a phase change amount of 170 ° to 190 ° with respect to the exposure light. The method of claim 1,
The exposure light has a wavelength of less than 300nm, multifunctional photomask blank. The method of claim 1,
The hard mask layer includes titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), niobium (Nb), palladium (Pd), zinc (Zn), chromium (Cr), aluminum (Al), manganese (Mn), cadmium (Cd), magnesium (Mg), lithium (Li), selenium (Se), copper (Cu), molybdenum (Mo), hafnium (Hf), tantalum (Ta) and tungsten A multifunctional photomask blank comprising at least one metal material selected from (W). 10. The method of claim 9,
The hard mask film is a multi-functional photomask blank, characterized in that further comprises at least one of nitrogen (N), oxygen (O), carbon (C). The method of claim 1,
The hard mask film has a single layer or a multilayer structure, a single film having a uniform composition in the depth direction, or a continuous film structure having a variable composition, and has a thickness of 50 mW to 300 mW. The method of claim 1,
The functional film and the hard mask film is a multi-function photomask blank, characterized in that having an etching selectivity of 50: 1 or more. The method of claim 1,
In the laminated structure of the functional film and the hard mask film, the optical density with respect to the exposure wavelength is 2.0 to 4.0, the reflectance is 10% to 40% on the hard mask film, and the sheet resistance is 3 kΩ / □ or less. Photomask Blanks. The method of claim 1,
And a photoresist film disposed on the hard mask film, wherein the photoresist film is made of a material including an acid and has a thickness of 50 nm to 300 nm. A binary photomask manufactured by using the multifunctional photomask blank of claim 1 and having a light shielding area and a light transmitting area,
The light blocking region is a region in which at least a functional film and a hard mask film are stacked on a transparent substrate, and the light transmitting region is a region where the transparent substrate is exposed. A phase inversion photomask manufactured by using the photomask blank of claim 1 and having a light shielding area, a phase shifting area, and a light transmitting area,
The light blocking region is a region in which at least a functional film and a hard mask film are stacked on a transparent substrate, the phase inversion region is a region in which a functional film is formed on a portion of the transparent substrate, and the light transmitting region is a region where the transparent substrate is exposed. Phase inversion photomask.

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