KR100815679B1 - Halftone phase shift mask blank, halftone phase shift mask, and manufacturing method thereof - Google Patents

Halftone phase shift mask blank, halftone phase shift mask, and manufacturing method thereof Download PDF

Info

Publication number
KR100815679B1
KR100815679B1 KR1020047007952A KR20047007952A KR100815679B1 KR 100815679 B1 KR100815679 B1 KR 100815679B1 KR 1020047007952 A KR1020047007952 A KR 1020047007952A KR 20047007952 A KR20047007952 A KR 20047007952A KR 100815679 B1 KR100815679 B1 KR 100815679B1
Authority
KR
South Korea
Prior art keywords
layer
material
phase shifter
etching
film
Prior art date
Application number
KR1020047007952A
Other languages
Korean (ko)
Other versions
KR20040054805A (en
Inventor
오사무 노자와
히데아키 미츠이
유우키 시오타
리오 오쿠보
Original Assignee
호야 가부시키가이샤
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2001361025A priority Critical patent/JP2002258458A/en
Priority to JPJP-P-2001-00361025 priority
Priority to JP2001394311A priority patent/JP4027660B2/en
Priority to JPJP-P-2001-00394311 priority
Priority to JPJP-P-2002-00047051 priority
Priority to JP2002047051A priority patent/JP3818171B2/en
Priority to JPJP-P-2002-00082021 priority
Priority to JP2002082021A priority patent/JP3993005B2/en
Application filed by 호야 가부시키가이샤 filed Critical 호야 가부시키가이샤
Priority to PCT/JP2002/005479 priority patent/WO2003046659A1/en
Publication of KR20040054805A publication Critical patent/KR20040054805A/en
Application granted granted Critical
Publication of KR100815679B1 publication Critical patent/KR100815679B1/en

Links

Images

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/32Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof

Abstract

According to the present invention, there is provided a liquid crystal display device comprising: a transparent substrate having a light transmitting portion for transmitting exposure light; and a phase shifter portion for shifting a phase of light transmitted through a part of the exposure light by a predetermined amount, Which is used to manufacture a halftone phase shift mask having optical characteristics such that light is canceled out from each other and the contrast of the exposed pattern boundary portion transferred to the surface of the photoreceptor can be satisfactorily maintained and improved, to be. The phase shifter film forming the phase shifter portion is composed of a film mainly composed of silicon, oxygen and nitrogen, and an etching stopper film formed between the film and the transparent substrate.

Description

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

The present invention relates to a halftone phase shift mask blank, a halftone phase shift mask and a manufacturing method thereof, and more particularly to a halftone phase shift mask which is suitable for use in an ArF excimer laser (193 nm) and an F 2 excimer laser (157 nm) A phase shift mask blank, and the like.

At present, DRAM (Dynamic Random Access Memory) has a mass production system of 256 Mbit, and will be more highly integrated from Mbit to Gbit in the future. As a result, the design rule of the integrated circuit is becoming finer and the time required for the fine pattern having a line width (half pitch) of 0.10 탆 or less is also a problem.

As one means for coping with the miniaturization of the pattern, up to now the pattern has been made to have a high resolution by shortening the wavelength of the exposure light source. As a result, KrF excimer laser (248 nm) and ArF excimer laser (193 nm) are mainly used as exposure light sources in current optical lithography.

However, shortening the wavelength of the exposure light improves the resolution, but at the same time, the depth of focus is reduced. This adversely affects the burden on the design of the optical system including the lens, or degrades the process stability.

In order to cope with such a problem, a phase shift method has been used. In the phase shift method, a phase shift mask is used as a mask for transferring a fine pattern.

The phase shift mask is composed of, for example, a phase shifter portion forming a pattern portion on a mask and a non-pattern portion having no phase shifter portion. Under such a configuration, by shifting the phase of the light transmitted through the two by 180 degrees, mutual interference of light occurs at the pattern boundary, thereby improving the contrast of the transferred image.

It is known that the phase shift amount (phi; rad) of light passing through the phase shifter portion depends on the complex refractive index real part n of the phase shifter portion and the film thickness d, and the following equation (1) is established.

? = 2? d (n-1) /?

Where? Is the wavelength of the exposure light. Therefore, to change the phase 180 degrees, the film thickness d

d =? / {2 (n-1)}

. This phase shift mask achieves an increase in the focus depth to obtain the necessary resolution, and it is possible to simultaneously improve the resolution and the applicability of the process without changing the exposure wavelength.

The phase shift mask can be practically distinguished from the full-transmission type (Levenson type) phase shift mask and the halftone type phase shift mask depending on the light transmission characteristics of the phase shifter portion forming the mask pattern. The former is known to be effective for transferring a line-and-space in general as a mask in which the light transmittance of the phase shifter portion is equal to the non-pattern portion (light transmitting portion) and is almost transparent to the exposure wavelength.

On the other hand, the latter halftone type is known to be effective for forming contact holes and isolated patterns with the light transmittance of the phase shifter portion (light semi-transmitting portion) being several to several tens% of the non-pattern portion (light transmitting portion).

Among halftone phase shift masks, there are a two-layered halftone type phase shift mask mainly composed of a layer for adjusting the transmittance and a layer mainly for adjusting the phase, and a single layer type halftone type phase shift mask having a simple structure and easy to manufacture .

The monolayer type is currently mainstream because of its ease of processability, and most of the halftone phase shifter is composed of a single layer film made of MoSiN or MoSiON.

On the other hand, in the two-layer type, the halftone phase shifter portion is mainly composed of a combination of a layer for controlling the transmittance and a layer for mainly controlling the phase shift amount, and the spectral characteristics and the phase shift amount (phase angle) Can be controlled.

On the other hand, the wavelength (exposure wavelength) is an ArF excimer laser (193nm) in the current of a KrF excimer laser (248nm) of the exposure light source in accordance with the miniaturization of LSI patterns, and the future, the short wavelength to the F 2 excimer laser (157nm) It is expected that the upsurge will proceed.

In the current half tone type phase shift mask, the film design is mainly performed so that the exposure light transmittance of the halftone phase shifter portion is close to 6%. However, a high transmittance is required for high resolution, and it is also said that a transmittance of 15% or more is required in the future.

As the exposure light source has a short wavelength and a high transmittance, the width of the material of the halftone phase shifter portion satisfying a predetermined transmittance and phase shift amount tends to be narrowed. Further, as the transmittance increases, a material having high light transmittance is required. In addition, a material having high light transmittance is required in view of the conventional wavelength in accordance with the shortening of the wavelength of the exposure light source. Because of this necessity, there is a problem that the etching selectivity with respect to the quartz substrate during pattern processing becomes small.

In the multilayer half-tone phase shifter having two or more layers, the phase difference and the transmittance can be controlled by a combination of a multilayer film or a two-layer film, thereby facilitating material selection. Further, a material serving as an etching stopper in the upper layer can be selected as the lower layer.

 Furthermore, the manufactured phase shift mask needs to reduce the reflectance in exposure light to some extent. In the step of inspecting the appearance of the pattern, light having a wavelength longer than the wavelength of the exposure light is generally used as the inspection light wavelength, and inspection using a transmission type defect inspection apparatus (for example, KLA 300 series) is conducted. Accordingly, if the transmittance to the inspection wavelength (for example, when the exposure wavelength is KrF excimer laser (248 nm), inspection wavelength is 488 nm or 364 nm) becomes too high (for example, 40% or more), inspection becomes difficult.

Particularly, as described above, a halftone phase shifter having a high light transmittance is required in accordance with the reduction of the wavelength of the exposure light. However, a material with high light transmittance tends to increase the rate of increase of the transmittance with respect to the change of wavelength to the long wavelength side. This makes it more difficult to reduce the light transmittance to the inspection light wavelength to a predetermined range in the single-layer halftone phase shifter.

 Further, in the defect inspection apparatus, an inspection method using transmitted light and reflected light is newly developed. In the case of inspection in this manner, the transmittance at the inspection wavelength may be slightly higher (for example, 50 to 60%) as compared with the case of inspecting using only transmitted light. However, it is necessary to control so that the reflectance at the inspection wavelength becomes a certain difference (for example, 3% or more) from the transparent substrate.

In such a situation, the halftone phase shifter portion is formed into a multilayer structure of two or more layers, whereby the reflection characteristic and the transmission characteristic in the exposure light and the inspection light can be easily controlled.

As the half-tone type phase shift mask of the two-layer type, there is a half-tone phase shifter having a two-layer structure of thin Cr and a coated glass described in Japanese Patent Application Laid-Open No. 4-140635.

Further, as a halftone phase shifter section which can be formed by the same device as a multilayer structure and can be etched by the same etching agent, a multi-layered structure including the same element (refer to Japanese Unexamined Patent Application Publication No. 1994-83034 (For example, a two-layer structure of a Si layer and an SiN layer) (Conventional Example 2).

As a technique for reducing the transmittance to the inspection light wavelength, as described in Japanese Patent Application Laid-Open No. 7 (1995) -168343, a monolayer film such as MoSiO or MoSiON, which is known as a monolayer halftone phase shifter (KrF excimer laser) and inspection light (488 nm) can be obtained by forming a two-layer structure including a transparent film having a small wavelength dependency of transmittance in combination with a single layer film (Conventional Example 3).

As a phase shifter portion of a multi-layer structure noticed by a tantalum silicide-based material, an upper layer mainly composed of tantalum, silicon and oxygen as described in Japanese Patent Laid-Open Publication No. 2001-174973 and an upper layer mainly composed of tantalum, And a halftone type phase shifter portion composed of a two-layer structure of a lower layer (Conventional Example 4).

Further, it has a halftone phase shifter section composed of a tantalum, silicon and oxygen-based upper layer described in Japanese Patent Laid-Open Publication No. 2001-337436 and a lower layer two-layer structure composed mainly of chromium or chromium tantalum alloy Example 5).

However, the above-described conventional example has the following problems.

Usually, a halftone phase shifter film is used as an etching mask layer of a halftone phase shifter film, and then a light shielding Cr layer is formed in order to form a light shielding portion at a desired position on the mask.

In the coated glass / thin Cr layer / glass substrate as in Conventional Example 1, the shielding Cr layer is formed on the coated glass. In such a case, a mask pattern having a three-layer structure of a light-shielding Cr layer / a coated glass / a thin Cr layer transferred with a resist pattern generally used in pattern processing is manufactured. Thereafter, the shielding Cr layer is selectively .

However, since the light-shielding Cr layer and the thin Cr layer are made of the same material, the influence on the thin Cr layer in the selective removal process of the shielding Cr layer becomes a problem. Specifically, the thin Cr layer is etched and the pattern is removed by the same principle as lift-off in some cases. When the thin Cr layer is side-etched, the transmittance in the vicinity of the pattern edge changes.

Next, in Conventional Example 2, for example, the Si layer and the SiN layer can be continuously formed by using the same Si as a target by the same sputtering apparatus. However, when the SiN layer is formed by reactive sputtering using a sputtering atmosphere containing an Si target and nitrogen, poisoning of the target occurs due to reactive sputtering, so that reproducibility can not be obtained and there is a problem in productivity. In addition, when SiN is used, the transmittance is excessively lowered due to the recent shortening of the exposure wavelength.

Next, in Conventional Example 3, MoSiO or MoSiON is used as the material of the single-layer film (upper layer). However, since it contains a metal, the transmittance becomes small and is not suitable for shortening the wavelength of exposure light in recent years. Further, if the metal content is reduced, the refractive index becomes smaller and the film thickness of the halftone phase shifter becomes thick, which is disadvantageous for fine processing.

In Conventional Example 4 and Conventional Example 5, TaSiO is used as the material of the upper layer. However, since it contains a metal, the transmittance becomes small and is not suitable for shortening the wavelength of exposure light in recent years. Further, if the metal content is reduced, the refractive index becomes smaller and the film thickness of the halftone phase shifter becomes thick, which is disadvantageous for fine processing.

Moreover, in these conventional examples, the lower layer serves as an etching stopper for the dry etching by the fluorine gas in the upper layer, and the lower layer is then etched by dry etching by the chlorine gas.

However, in the lower layer made of tantalum of the conventional example 4, the etching selection ratio to the fluorine dry etching of the upper layer is insufficient. In the chromium tantalum alloy of Conventional Example 5, the etch rate due to the chlorine-based gas is slow and a high-precision pattern can not be obtained.

SUMMARY OF THE INVENTION The present invention has been made under the above background, and an object of the present invention is to provide a halftone phase shift mask blank and a halftone phase shift mask which are excellent in the fine workability in etching for forming a halftone phase shifter portion.

In particular, the present invention relates to a high transmittance (transmittance (transmittance)) at an exposure wavelength range of 140 to 200 nm, specifically about 157 nm, which is the wavelength of the F 2 excimer laser, and around 193 nm, which is the wavelength of the ArF excimer laser, 8 to 30%), and a halftone type phase shift mask.

The present invention is characterized in that in the halftone phase shift mask blank, the phase shifter film is composed of a film mainly composed of silicon, oxygen and nitrogen, and an etching stopper film formed between the film and the transparent substrate.

In the present invention, in the halftone phase shifter layer formed on the transparent substrate, the film on the transparent substrate side becomes the lower layer, and the film formed on the lower layer becomes the upper layer.

The present inventors have found that SiN x has a high resistance to irradiation with exposure light and resistance to chemicals such as a cleaning liquid because the Si-N bond tightens the matrix of the film, and SiO x has a relatively high transmittance on the short wavelength side Based on the fact that it is possible to obtain the advantages of these two material systems, attention was paid to SiO x N y .

Further, it has been found that a phase shifter film suitable for use in exposure light of a short wavelength is obtained by controlling the composition of SiO x N y . By making the halftone phase shifter film a two-layer structure of an SiO x N y film (upper layer) and an etching stopper film (lower layer), in addition to resistance to exposure light exposure and tolerance to chemicals, A shifter film can be realized.

Here, the etching stopper film is a film made of a material having a function of inhibiting the progress of etching of the SiO x N y film, or a function capable of easily detecting the end point of etching of the phase shifter film, .

The material of the upper layer is substantially composed of a material consisting of silicon, oxygen and nitrogen. That is, the upper layer is composed of a film in which silicon, oxygen and nitrogen are the main constituent elements. The above material can control the desired transmittance and retardation in combination with the lower layer even when the exposure light is short-wavelength, and also has high resistance to irradiation with exposure light and resistance to chemicals such as a cleaning liquid. In addition, since the refractive index can be made comparatively large, the film thickness of the entire halftone phase shifter film for obtaining a desired phase difference can be suppressed, and the fine workability of the halftone phase shifter film is excellent.

For the upper layer material, the complex refractive index real part (n)

Figure 112004022162911-pct00001
1.7, and the complex index of refraction k is in the range k
Figure 112004022162911-pct00002
0.450. ≪ / RTI > This is advantageous for satisfying the optical characteristics as the half-tone phase shift mask according to the shorter wavelength of the exposure light. In addition, for F 2 excimer laser, k
Figure 112004022162911-pct00003
0.40, and more preferably 0.07
Figure 112004022162911-pct00004
k
Figure 112004022162911-pct00005
0.35 is more preferable.

0.10 for the ArF excimer laser

Figure 112004022162911-pct00006
k
Figure 112004022162911-pct00007
0.45 is preferable. In addition, for F 2 excimer laser, n
Figure 112004022162911-pct00008
2.0 is preferable, and n
Figure 112004022162911-pct00009
2.2 is more preferable. For the ArF excimer laser, n
Figure 112004022162911-pct00010
2.0 is preferable, and n
Figure 112004022162911-pct00011
2.5 is more preferable.

In order to obtain the optical characteristics, the compositional range of the constituent elements was 35 to 45 atomic% of silicon, 1 to 60 atomic% of oxygen, and 5 to 60 atomic% of nitrogen. That is, when silicon is more than 45% or nitrogen is more than 60%, the light transmittance of the film becomes insufficient. Conversely, if the nitrogen content is less than 5% or the oxygen content exceeds 60%, the light transmittance of the film is excessively high, so that the function as the halftone phase shifter film is lost. When the content of silicon is less than 35% or nitrogen exceeds 60%, the structure of the film becomes physically and chemically very unstable.

From the above viewpoint, in the case of the F 2 excimer laser, it is preferable that the composition range of the constituent elements is 35 to 40 atomic% of silicon, 25 to 60 atomic% of oxygen, and 5 to 35 atomic% of nitrogen. Similarly, for the ArF excimer laser, it is preferable that the composition range of the constituent elements is 38 to 45 atomic% of silicon, 1 to 40 atomic% of oxygen and 30 to 60 atomic% of nitrogen. In addition to the above-mentioned composition, a small amount of impurities (metal, carbon, fluorine, etc.) may be contained.

The upper layer according to the present invention may be formed by reactive sputtering in a sputtering atmosphere using a rare gas and a reactive gas containing nitrogen and oxygen, using a target substantially made of silicon. A target substantially composed of silicon can obtain a stable target having a high number density and high purity compared with the case of using a mixed target such as a metal silicide. Therefore, there is an advantage that the particle generation rate of the obtained film is reduced.

The etching stopper layer is a film made of a material having a function of inhibiting the progress of etching of the SiO x N y film or a function capable of easily detecting the end point of etching of the phase shifter film, .

The film having the function of inhibiting the progress of the etching of the former SiO x N y film is preferably a material having a low selectivity for etching the phase shifter layer, that is, an etching rate for the etching medium used for etching the SiO x N y film is SiO x N y film. Specifically, the film is made of a material having an etch selectivity to the phase shifter film of 0.7 or less, preferably 0.5 or less.

The etch stopper film having a function of easily detecting the end point of etching of the latter phase shifter film can be formed by etching the end point of the etching stopper (for example, 680 nm) of a transparent substrate (for example, a synthetic quartz substrate) Is larger than the difference between the transparent substrate and the SiO x N y film.

It is preferable that the material has a refractive index (a complex refractive index real part) higher than that of the SiO x N y film and the transparent substrate. Specifically, the refractive index difference between the SiO x N y film and the etching end point detection light is 0.5 or more Is a film made of a material having a refractive index of at least 1, and is a film made of a material having a difference in refractive index from the transparent substrate of 0.5 or more, preferably 1 or more.

The etch stopper layer preferably has an etch selectivity to the substrate of 1.5 or more, preferably 2.0 or more. That is, if the etching stopper layer can not be removed, the light transmittance at the light transmitting portion is reduced and the contrast at the time of pattern transfer is lowered. Even if it can be removed, if the etching rate is not larger than the substrate, the substrate may also be etched in the vicinity of the end point of etching, and the processing accuracy is deteriorated.

In consideration of the above, suitable materials include one or more materials selected from magnesium, aluminum, titanium, vanadium, chromium, yttrium, zirconium, niobium, tin, lanthanum, tantalum, tungsten, And compounds (oxides, nitrides and oxynitrides) of these compounds.

The thickness of the etching stopper film is preferably 10 to 200 angstroms. That is, if the etching rate is less than 10 angstroms, the etching can not be completely prevented or a significant reflectance change can not be detected, so that there is a possibility that the pattern processing accuracy is deteriorated.

On the other hand, although the enlargement of the pattern due to the progress of the isotropic etching varies depending on the etching process, it progresses to about twice the film thickness at the maximum. Therefore, when a pattern line width of 0.1 占 퐉 = 1000 angstroms or less is machined, if the film thickness exceeds 200 angstroms, a dimensional error of 40% or more is caused, which seriously affects mask quality.

It is preferable that the etching stopper layer has a function of adjusting the transmittance. The transmittance of the etching stopper layer itself to an exposure wavelength (wavelength of 140 to 200 nm or around 157 nm or near 193 nm) is 3 to 40%. This makes it possible to reduce the transmittance of the inspection wavelength longer than the exposure wavelength (by stacking other materials) by the etching stopper layer formed under the phase shifter portion while maintaining the transmittance at the phase shifter portion.

That is, in the current mask inspection in the manufacturing process, a method of measuring the transmitted light intensity using light having a wavelength longer than the exposure wavelength is employed. It is preferable that the light transmittance of the light half portion (phase shifter portion) is 40% or less in the range of the current inspection wavelength of 200 to 300 nm. That is, if it is 40% or more, the contrast with the light transmitting portion can not be obtained and the inspection accuracy is deteriorated. When the etching stopper film is a material having a high light shielding function, a film made of one or more materials selected from aluminum, titanium, vanadium, chromium, zirconium, niobium, molybdenum, lanthanum, tantalum, tungsten, Nitrides thereof and the like.

It is preferable that the etching stopper layer has a thickness sufficiently smaller than that of the phase shifter portion, and a film thickness of 200 angstroms or less is suitable. That is, if it exceeds 200 angstroms, there is a high possibility that the light transmittance at the exposure wavelength is less than 3%. In this case, the phase angle and the transmittance are adjusted in the two layers of the SiO x N y film and the etching stopper film.

Specifically, the transmittance of the etching stopper itself to the exposure wavelength (wavelength of 140 to 200 nm or 157 nm or near 193 nm) is 3 to 40%, and the transmittance when laminated with the SiO x N y film is 3 to 40% It is preferable to adjust it. When the etching stopper layer is provided, the etching stopper layer exposed on the surface corresponding to the light transmitting portion must be removable. This is because if the etching stopper layer covers the light transmitting portion, the transmittance of the light transmitting portion is reduced.

An etching stopper film removal method, the etching stopper film when makil made of a material having a function for preventing the progression of etching SiO x N y film, it is necessary to use a SiO x N y film etching method and other methods. When the etching stopper film is made of a material having a function of easily detecting the end point of the etching of the phase shifter film, the etching method of the SiO x N y film and the etching stopper film may be the same or different.

Dry etching (RIE: Reactive Ion Etching) using, for example, a fluorine-based gas such as CHF 3 , CF 4 , SF 6 or C 2 F 6 and a mixed gas thereof can be used for etching the phase shifter film made of the SiO x N y film . On the other hand, when the etching stopper film is removed by etching in a manner different from that of the phase shifter film, dry etching using a fluorine-based gas other than that used for removing the phase shifter film, or chlorine-based gas such as (Cl 2 , Cl 2 + O 2 ) Wet etching using a dry etching or a wet etching using an acid or an alkali can be used.

MoSi x , TaSi x , WS x , CrSi x , ZrSi x , HfSi x, or the like can be used as the etching stopper film that can be removed by the same fluorine dry etching as the etching of the phase shifter film made of the SiO x N y film Can be mentioned as preferred materials.

Thus, when an etching stopper film capable of etching continuously with the SiO x N y film is provided, the process advantage is large. As the etching stopper film which can be etched by a method different from the etching of the phase shifter film made of the SiO x N y film, a thin film containing Ta or Ta, for example, which can be etched by dry etching of Cl 2 , for example, TaN x , TaZr x , TaCr x , TaHf x , and Cr which can be etched by dry etching of Zr, Hf, and Cl 2 + O 2 .

Thus, when an etching stopper film capable of etching continuously with the SiO x N y film is provided, the process advantage is large. In addition, SiO x N as the phase shifter film is etched with the etching stopper film in another way made in the y-film, such as a thin film, for example TaZr x containing Ta or Ta which can be etched by dry etching in Cl 2, TaCr x, TaHf x or the like, or Cr which can be etched by dry etching of Zr, Hf or Cl + O 2 .

In the case where the etching stopper film is made of a material having a function of inhibiting the progress of etching of the SiO x N y film and is made of a material having high transmittance, it is preferable that the transparent substrate of the halftone phase shift mask having a single- It is also possible to provide an etching stopper film between the transparent films so as not to remove the etching stopper exposed to the light transmitting portions.

The etching stopper layer is particularly effective when the oxygen in the SiO x N y film is 40 atomic% or more, or when the difference in refractive index from the transparent substrate is 0.5 or less, preferably 0.3 or less.

The present inventors have also found that when the upper layer is a layer which is etched using dry etching using a fluorine-based gas, as a lower layer material, a dry etching process using a gas (for example, a chlorine-based gas) different from the fluorine- The present inventors have found a predetermined material which can be etched by using the above-

Examples of the predetermined material include: a single metal selected from the first group consisting of Al, Ga, Hf, Ti, V, and Zr, or a material containing two or more of these metals Hereinafter, referred to as a first material). The monolithic metal or the first material selected from the first group is a material which is resistant to the fluorine-based gas and can be etched by dry etching using a gas (for example, chlorine-based gas) different from the fluorine-based gas.

The single metal or material selected from the first group has a high etching resistance in dry etching using a fluorine-based gas and can be formed by dry etching using a fluorine-based gas (e.g., chlorine-based gas, bromine-based gas, iodine- It is a material that can be easily etched.

The lower layer needs to be resistant to an effect as an etch stop layer for the upper layer in the dry etching using the fluorine-based gas, and the etching rate of the lower layer material is preferably selected from the thickness of the lower layer, the etching rate ratio to the upper layer ), But it is preferably about 0 to several tens Angstroms / min. In the dry etching of the lower layer using a chlorine-based gas, it is preferable that etching can be removed to a degree that is acceptable in a desired etching process, and it is preferable that the etching rate is 5 times or more higher than the selection ratio with respect to the substrate material. The material is more preferable.

In the monolithic metal selected from the first group, Hf, Zr and the like are preferable from the viewpoint of high resistance to chemicals. Al, Ti, V, or the like is preferable from the viewpoint of ease of production of the sputtering target.

The first material is selected from the group consisting of Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, Al, Ga, Hf, Ti, V and Zr) (including an alloy and a mixture, hereinafter referred to as a second material). These materials are obtained by adding the metal selected in the first group to the metal selected from the second group to sufficiently exhibit resistance to the fluorine-based gas and further to remove the fluorine-based gas (for example, chlorine-based gas, bromine- Based gas or the like) by dry etching. That is, it is a material that can have the same action as the first material.

Here, the metal cited in the second group (except for Cr) is less resistant to the fluorine-based gas as compared with the metal cited in the first group. When the metal selected in the first group is added, the resistance to the fluorine-based gas is improved, and when the metal selected in the first group is added, the desired resistance to the fluorine-based gas is sufficiently exhibited . Cr has the same resistance as the metal cited in the first group to the fluorine-based gas.

In addition, the second group of metals is a material whose etch rate to the chlorine-based gas is equal to or slightly lower than that of the first group of metals or can be supplemented by adding the first group. The metal cited in the first group is, for example, a material which is easily etchable to the chlorine-based gas, so that the material cited in the second group to which the metal cited in the first group is added is, for example, It is a material that maintains or improves the etching property with respect to the gas.

Thus, the present inventors have found that by adding a small amount of a metal selected from the first group to the metal selected in the second group, the resistance to the fluorine-based gas is remarkably improved while maintaining the etching property with respect to the chlorine-based gas. The amount of the metal selected from the first group to the metal selected in the second group is 2% or more. If the addition amount is less than the above range, the characteristics of the additive material are not sufficiently exhibited and the effect such as the resistance to the fluorine-based gas can not be sufficiently obtained as described above.

As the predetermined material, thirdly, a material containing nitrogen and / or carbon in the metal of the monolith, the first material or the second material may be mentioned. It is preferable that nitrogen and / or carbon is contained within a range that does not impair desired characteristics.

The fluorine-based gas includes, for example, C x F y (for example, CF 4 and C 2 F 6 ), CHF 3 , a mixed gas thereof, or O 2 and rare gas (He, Ar, Xe) .

As the gas other than the fluorine-based gas, a halogen-based gas other than fluorine (chlorine-based, bromine-based, iodine-based or mixed gas thereof) can be used. Examples of the chlorine-based gas include Cl 2 , BCl 3 , HCl, a mixed gas thereof, and a rare gas (He, Ar, Xe) as an additive gas.

Examples of the bromine-based gas include Br 2 , HBr, a mixed gas thereof, and rare gas (He, Ar, Xe) as an additive gas. Examples of the iodine-based gas include I 2 , HI, a mixed gas thereof, and a rare gas (He, Ar, Xe) as an additive gas.

Here, chlorine-based gas is used as the gas other than the fluorine-based gas, but the etching rate is preferably higher than the bromine-based gas or the iodine-based gas. A gas containing fluorine and a gas other than fluorine may be used at the same time. In this case, it is advantageous that the proportion of excited species in the active species in the plasma is large.

When there are many fluorine-excluded species, it is defined as fluorine-based gas. (For example, chlorine gas) other than the fluorine-based gas when the amount of the excitation species other than the fluorine-based gas (for example, chlorine) is large. In the case where fluorine and other halogen elements are included in the gas composition of the monolith (for example, ClF 3, etc.), the fluorine-based gas is used.

As the gas other than the fluorine-based gas, oxygen is preferably not added as the additive gas. This is because, when oxygen is added, the lowering of the etching rate is considered by surface oxidation. Further, for example, since the etching gas Cl 2 + O 2 commonly used for Cr etching is complicated and the etching distribution is likely to occur, dry etching with a single gas such as Cl 2 is a highly accurate pattern .

Next, the action of each layer satisfying the above requirements will be described.

Since the lower layer has resistance to the fluorine-based gas, the upper layer is dry-etched with a fluorine-based gas to reduce the film thickness of the lower layer even when the lower layer surface is exposed. Therefore, the overetching time of the upper layer can be sufficiently set in consideration of the removal of the remaining film in the upper layer, which is caused by the etching distribution caused by the dense difference in the pattern or the like. As a result, it becomes possible to form a pattern faithful to the mask pattern, and improvement in dimensional accuracy is expected.

Since the lower layer is a material which can be etched using dry etching by a gas other than the fluorine gas (for example, chlorine gas) (having a certain etching rate with respect to the chlorine gas), the lower layer is preferably dry Etching process. Even if the surface of the transparent substrate is exposed, there is almost no cavity in the surface layer of the transparent substrate. Therefore, it is possible to avoid the deviation of the in-plane retardation due to the phase difference variation and the etching imbalance due to the cavity of the substrate surface layer, and to obtain high retardation controllability. This is because the quartz substrate frequently used as the substrate of the phase shift mask has a smaller etching rate than that of the lower layer material for the dry etching of the lower layer removal.

The lower etching rate for the chlorine-based gas is preferably as high as possible, and is preferably 2500 angstroms / min, 3000 angstroms / min or more, and 4000 angstroms / mim or more, depending on the CD dimension accuracy requirement and etching conditions. Specifically, the underlying layer of the phase shift mask is typically less than 100 angstroms. Since the lower layer has a high etching rate, the etching of the lower layer is completed in only a few seconds. The overetching time is very short, and even if the etching rate is 360 angstroms / min, the etching amount (cavity amount) is very small at 6 angstroms / sec for one second.

Further, unlike the configuration of the light-shielding Cr layer / coated glass / thin Cr layer / transparent substrate described in the prior art, in the shielding Cr layer / upper layer / lower layer / transparent substrate of the present invention, It becomes possible to selectively handle in the removal process of the shielding Cr layer. This removal process is not limited to a wet process mainly using a commonly used acetic acid (cerium nitrate) ammonium salt solution, and can be also used by dry etching. That is, irrespective of wet etching or dry etching, it is possible to avoid the adverse effect that the lower layer is etched in the selective removal process of the shielding Cr layer. That is, it has a suitability for this process.

In film formation of the lower layer and the upper layer, the film structure may be formed so as to have an amorphous structure or a very small grain boundary structure, thereby contributing to the improvement of pattern accuracy. When these film structures have a columnar structure or a crystal structure, irregularities (roughness) are generated in pattern side walls when etching is performed. However, if the film structure is an amorphous structure or a structure having a very small grain boundary , And the sidewall of the pattern at the time of etching is substantially flat (substantially straight).

In addition, when these film structures have a columnar structure or a crystal structure, there is a case where film stress is generated and becomes a problem. However, if the film structure is an amorphous structure or a structure having a very small grain boundary, it becomes easy to control the film stress.

In addition, the phase shifter film, the upper layer is SiO x, SiN x, SiO x N y, SiC x, SiC x N y, SiC x O y N z or metal thereto (e.g., M: Mo, Ta, W, Cr, Zr , Hf) is preferably made of a material containing 10 atomic% or less of M / (Si + H) x 100, it can be easily processed by dry etching using a fluorine-based gas And it is preferable because it has high resistance to dry etching using a chlorine-based gas. When the upper layer is made of such a material, even when the exposure wavelength is short-wavelengthed by ArF excimer laser (193 nm) or F 2 excimer laser (157 nm), a predetermined transmittance and phase shift amount can be satisfied, There is a number.

The phase shift mask blank has, for example, a structure composed of a SiO x and an SiO x N y layer / a lower layer made of the above-described material (a layer having the above etching property) / a transparent substrate. In this configuration, the SiO x and SiO x N x layers are patterned by dry etching using a fluorine-based gas, and the portion touching the lower layer is processed by dry etching using a chlorine-based gas so as to reduce damage to the base do.

By using the blanks having such a configuration, the optical characteristics can be controlled even in the generation where the short wavelength is advanced, and the phase shift effect can be obtained. Specifically, the phase shift amount is mainly controlled by the thickness and composition of the upper layer SiO x and the SiO x N y layer, and the transmittance is mainly controlled by the thickness of the lower layer made of the predetermined material. Thus, the optical characteristics can be controlled.

Further, by processing the lower layer by dry etching using a chlorine-based gas, damage to the transparent substrate as the base can be avoided. A change in the phase shift amount due to the cavity of the transparent substrate can be avoided, and the above-described optical characteristics can be controlled, so that a predetermined phase shift effect can be obtained.

In the present invention, a shielding Cr layer is formed by forming a resist pattern on the light-shielding Cr layer with a light shielding Cr layer on the phase shift mask blank. Using the resist pattern, the light shielding Cr pattern, It is preferable to etch the film. After the etching of the phase shifter film, the light shielding Cr pattern leaves a light shielding band portion of the non-transfer region of the phase shift mask. In addition to this, the alignment mark forming part outside the transfer area or the desired area excluding the vicinity of the boundary of the pattern is removed. The light shielding Cr layer may be a single layer or a multilayer film containing oxygen, carbon, nitrogen or the like for Cr or Cr.

In the present invention, the reflectance for the inspection light can be adjusted by making the refractive index of the upper layer film at the inspection wavelength smaller than the refractive index of the lower layer. Furthermore, by adjusting the refractive index of the upper layer film to be smaller than the refractive index of the lower layer film at the exposure wavelength, the reflectance with respect to the exposure light can also be adjusted to be equal to or less than the required value.

Specifically, the transmittance of the exposure light is preferably 3 to 20%, more preferably 6 to 20%, and the exposure light reflectance is preferably 30%, preferably 20%, for transferring the pattern. The inspection light transmittance is preferably 40% or less for defect inspection using transmitted light of the mask. By setting the inspection light transmittance to 60% or less and the inspection light reflectance to 12% or more, defect inspection using the transmitted light and reflected light of the mask is preferable.

As the exposure light when using the halftone phase shift mask of the present invention, in particular, an exposure wavelength range of 140 nm to 200 nm, specifically, a wavelength of 157 nm which is the wavelength of the F 2 excimer laser and a wavelength of 193 nm which is the wavelength of the ArF excimer laser can be used . A high transmittance product in which the halftone phase shifter portion is set to have a high transmittance (transmittance of 8 to 30%) can be manufactured.

Further, in the present invention, the film is designed such that the upper layer is mainly a layer (phase adjustment layer) functioning to adjust the phase shift amount and the lower layer is mainly a layer (transmittance adjustment layer) functioning to adjust the transmittance.

That is, assuming that the phase shift amount (phi; deg) of the exposure light of wavelength? Passing through the upper layer (phase adjustment layer) is?, The film thickness d of the phase adjustment layer is

d = (? / 360) x? / (n-1)

. Here, n is the refractive index of the phase adjusting layer with respect to the light of wavelength?.

When the phase shift amount? Of the halftone phase shifter section is? ', The phase shift amount of the lower layer (transmittance adjustment layer)

Φ = φ + φ '= 180 °

It is necessary to design so as to be. The value of φ 'is approximately -20 °

Figure 112004022162911-pct00012
φ '
Figure 112004022162911-pct00013
20 < / RTI > That is, if it is outside the above range, the film thickness of the lower layer becomes too thick, and the transmittance of exposure light can not be increased. Therefore, the film thickness d of the upper layer is

Figure 112004022162911-pct00014
Figure 112004022162911-pct00015
0.44 x? / (N-1) d0.56 x? / (N-1)

Lt; / RTI >

Specifically, the film thickness of the lower layer may be 1 to 20 nm, and more preferably 1 to 15 nm. As a result, the layer thickness of the halftone phase shifter film can be suppressed to 120 nm or less, more preferably 100 nm or less.

The phase shift amount of the halftone phase shifter film is ideally 180 degrees, but practically, the phase shift amount may be within the range of 180 占 占.

A synthetic quartz substrate or the like can be used as the transparent substrate of the present invention. In particular, when an F 2 excimer laser is used as exposure light, an F-doped synthetic quartz substrate, a calcium fluoride substrate, or the like can be used.

As the material of the lower layer, a material consisting substantially of tantalum and hafnium, or a material substantially consisting of silicon and hafnium is particularly preferable. The lower layer material has resistance to a fluorine dry etching gas and can be removed by a chlorine dry etching gas. Accordingly, as the method (etching method) of the halftone phase shift film, the upper layer can be etched by dry etching using a fluorine-based gas and the lower layer can be dry etched using a chlorine-based gas.

Specifically, tantalum or silicon is a material that can be etched by dry etching using a chlorine-based gas that does not damage the transparent substrate even if it is a single substance. However, the resistance to dry etching using the fluorine-based gas in the upper layer is not very excellent.

On the other hand, monolithic hafnium is excellent in resistance to dry etching using a fluorine-based gas in the upper layer and is a material that can be etched by dry etching using a chlorine-based gas. By adding hafnium to tantalum or silicon, the resistance to dry etching using a fluorine-based gas can be improved more than before the addition, and the etching characteristic can be maintained or improved with respect to the chlorine-based gas. The addition amount of hafnium to tantalum or silicon is preferably 2 atom% or more from the viewpoint of obtaining resistance to the fluorine-based dry etching gas.

When the lower layer is made of a material consisting essentially of tantalum and hafnium or silicon and hafnium, the addition amount of hafnium in the lower layer is preferably 50 atomic% or less. This is because the optical transflective film made of tantalum or silicon has little difference between the light transmittance at the exposure wavelength and the transmittance at the inspection wavelength. Alternatively, the transmittance at the inspection wavelength is larger than the transmittance at the exposure wavelength, and it is suitable for designing the optical characteristics (the transmittance and / or the reflectance of the exposure light and the inspection light), so that the optical characteristics can be easily designed by sufficiently containing tantalum or silicon It is because.

In the halftone phase shift mask blank and the halftone phase shift mask of the present invention, a heat treatment or a laser annealing may be performed after the film formation of the halftone phase shifter film. By the heat treatment, effects such as relaxation of film stress, resistance to chemicals, resistance to irradiation, and fine adjustment of transmittance can be obtained. The heat treatment temperature is 200 DEG C or higher, preferably 380 DEG C or higher.

Further, in the present invention, a light-shielding film containing chromium as a main component can be formed on the halftone phase shifter film. The light shielding film may be used as an etching mask layer of a halftone phase shifter film and then selectively removed to form a light shielding portion at a desired place or area on the halftone phase shift mask. Examples of the light-shielding film containing chromium as a main component include a single-layer or multilayer film (including a film having a continuous composition gradient) containing oxygen, nitrogen, carbon, fluorine, etc. in addition to chromium and chromium. It is also preferable to form an antireflection film containing oxygen (reflection prevention at an exposure wavelength) in the surface layer portion.

When a light shielding film containing chromium as a main component is formed on the halftone phase shifter film of the halftone phase shift mask, a light shielding film formed as a light shielding band on the outer periphery of the transfer region can be formed. Or to increase the contrast of a mark such as an alignment mark, it is possible to form a light-shielding film formed at a mark formation place. Or a light shielding film formed in a region except for the vicinity of the boundary of the light transflective portion can be formed in order to obtain the phase shift effect and reduce the side lobe light.

In addition, the present invention includes aspects other than the limitation of the upper and lower relationships and the limitation of the purpose, taking advantage of the above-described dry etching characteristics of the upper and lower layers. As a result, it can be utilized as a laminate material for dry etching (a laminate material before dry etching) in applications such as application to an etching mask material and utilization as an etching stopper material.

The demand for a material having excellent dry etching characteristics is not limited to the photomask using the above-mentioned phase shift, and an etching stopper layer (etching stopper layer) for the purpose of protecting the base layer, a thin film having a high selectivity, Is applied to the etching mask material which is required.

In this embodiment, the second layer material is a material which has high etching resistance in dry etching using a fluorine-based gas and which can be easily etched under a condition using a chlorine-based gas (hereinafter, a material exhibiting a predetermined action). The second layer material includes any one or more of Al, Ga, Hf, Ti, V, and Zr, and is formed by adding these elements to the film made of the elements of these monomers and other metals, to be. The addition amount to other metals should be 2% or more. If the amount is less than this, the characteristics of the additive material are not sufficiently exhibited, and the above-mentioned predetermined action can not be obtained in etching. Here, the other metal is a material which can be etched against a chlorine-based gas. Examples of the other metals include Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, Po, Mo and W.

By using these materials, etching can be performed at a high selectivity ratio using the difference in dry etching characteristics depending on the kind of gas. This effect contributes to the thinning of the constituent layer (for example, the thinning of the etching mask layer), leading to an improvement in the precision of the fine pattern.

Further, in forming the film of the first layer material and the second layer material, the film structure may be formed to have a non-crystal structure or a very small grain boundary structure, thereby contributing to the improvement of pattern accuracy. This is because, when these film structures have a columnar structure or a crystal structure, irregularities (roughness) are generated in pattern side walls when etching is performed, but if the film structure is a structure having a very small amorphous structure or a very small grain size , And the sidewall of the pattern at the time of etching is substantially flat (substantially straight). In addition, when these film structures have a columnar structure or a crystal structure, there is a case where film stress is generated and becomes a problem. However, if these film structures have an amorphous structure or a very small grain boundary, it becomes easier to control the film stress.

The first layer of the above embodiment also includes the case where the upper layer of the substrate corresponds to the first layer. That is, the present invention includes a case where the second layer is formed as an etching mask layer and a cavity (engraving) pattern is formed in the surface layer portion of the substrate. The laminate of the embodiment includes a laminate of a second layer and a substrate (the upper layer corresponds to the first layer).

1 is a cross-sectional view of a halftone phase shift mask blank and a halftone phase shift mask according to an embodiment of the present invention;

2 is a diagram showing a transmission spectrum of a light semi-transmission portion (phase shifter portion) of the sample manufactured in Example 2. Fig.

3 is a view showing the relationship between the etching time and the intensity of reflected light of the sample manufactured in Example 7. Fig.

4 is a schematic view for explaining a processing procedure of each layer in Example 10. Fig.

5 is a schematic view for explaining a processing procedure of each layer in Example 11. Fig.

6 is a schematic view for explaining a processing procedure of each layer of Reference Example 2. Fig.

7 is a manufacturing process diagram of a halftone phase shift mask blank and a halftone phase shift mask according to the embodiment.

Fig. 8 is a manufacturing process diagram of a halftone phase shift mask blank and a halftone phase shift mask according to the embodiment (subsequent drawings). Fig.

9 is a spectrum chart of optical characteristics of a halftone phase shift mask blank according to Example 13. Fig.

10 is a spectrum diagram of optical characteristics of a halftone phase shifting mask blank according to Example 14. Fig.

11 is a view showing a modified example of a halftone phase shift mask blank and a halftone phase shift mask according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples and Reference Examples, but the present invention is not limited to the following examples.

FIG. 1 (1) shows a cross section of a halftone phase shift mask blank according to the embodiment and the reference example, and FIG. 1 (2) shows a cross section of a halftone phase shift mask according to the embodiment and the reference example .

1, the halftone phase shift mask blank 1 includes a transparent substrate 2 and a halftone phase shifter film 5 (see FIG. 1) formed of a lower layer 3 and an upper layer 4 formed directly on the lower layer ).

1, the halftone phase shift mask 1 'includes a halftone phase shift mask 1' formed on a transparent substrate 2 and composed of a lower layer portion 3 'and an upper layer portion 4' formed directly on the lower layer portion 3 ' And a shifter section 5 '. Under such a configuration, a mask pattern 8 composed of a light transflective portion 6 in which a halftone phase shifter portion is formed and a light transmission portion 7 in which a halftone phase shifter portion is not formed is formed. The halftone phase shifter film 5 and the halftone phase shifter section 5 'have a desired transmittance with respect to the exposure light and the phase shift angle is approximately 180 degrees. Also, the transmittance or the transmittance at the inspection wavelength and the reflectance are designed to be in a desired range.

(Examples 1 to 8)

Examples 1 to 8 are concrete examples of halftone phase shift masks corresponding to F 2 excimer laser exposure, in which a synthetic quartz substrate is used as a substrate, and an etching stopper layer is provided between the substrate and the SiO x N y layer .

(Film formation)

First, a layer A as an etching stopper layer and a layer B composed of SiO x N y are sequentially stacked on a synthetic quartz substrate. In the present embodiment, it was produced by the sputtering method. The basic composition of the layers A and B of the two-layer film, the conditions such as the type of the target and the sputter gas, and the film thickness of each layer are shown in Table 1 for each example. The film thicknesses of the layers A and B are adjusted using the above-described equation (1) so that the total sum of the phase shift amounts of the respective layers becomes 180 DEG at a wavelength of 157 nm.

(Optical characteristics)

When the transmittance of the fabricated two-layer film was measured using a vacuum ultraviolet spectrophotometer, the transmittance of the F 2 excimer laser at a wavelength of 157 nm was as shown in Table 2, and even when an etching stopper layer was provided, A light transmittance in a sufficient range of 3 to 40% was obtained.

target Board Gas ratio (%) Film thickness (nm) argon nitrogen Oxygen Example 1 Layer A: Al 2 O 3 Synthetic quartz 100.0 0.00 0.00 15 Layer B: Si 40.0 59.00 1.00 75 Example 2 Floor A: Ta Synthetic quartz 40.0 60.00 0.00 10 Layer B: Si 40.0 59.00 1.00 72 Example 3 Layer A: Ta-Zr Synthetic quartz 100.0 0.00 0.00 8 Layer B: Si 40.0 59.00 1.00 78 Example 4 Layer A: Ta-Hf Synthetic quartz 100.0 0.00 0.00 8 Layer B: Si 40.0 59.00 1.00 78 Example 5 Floor A: Zr Synthetic quartz 100.0 0.00 0.00 5 Layer B: Si 40.0 59.00 1.00 80 Example 6 Floor A: Hf Synthetic quartz 100.0 0.00 0.00 5 Layer B: Si 40.0 59.00 1.00 80 Example 7 Layer A: Si Synthetic quartz 100.0 0.00 0.00 4 Layer B: Si 40.0 59.00 1.00 80 Example 8 Floor A: MoSi x Synthetic quartz 100.0 0.00 0.00 8 Layer B: Si 10.0 60.00 30.00 86


Light transmittance (%) (157 nm) Example 1 13.1 Example 2 7.6 Example 3 6.6 Example 4 5.8 Example 5 15.7 Example 6 14.2 Example 7 9.8 Example 8 10.1

The transmission spectrum of Example 2 is shown in Fig. Although the inspection wavelength of the half-tone phase shift mask for F 2 excimer laser exposure is about 250 nm, since the transmittance in this range is 40% or less, sufficient inspection accuracy can be expected to be obtained. Similarly, in Examples 1 and 3 to 7, the transmittance before and after 250 nm was 40% or less.

In Examples 1 to 6, a resist is applied on the prepared two-layer film, and an exposure and development process is performed to form a resist pattern. Thereafter, the upper layer (B: SiO x N y film) of the two-layer film is etched by dry etching using the resist pattern as a mask. In this embodiment, CF 4 gas is used, and the etching time is set to be 30% longer than the time for which the film thickness of the SiO x N y layer can be substantially etched. As a result, the SiO x N y film was patterned based on the resist pattern, and the progress of etching stopped at the etching stopper film of the lower layer.

Table 3 shows the etching rates of the synthetic quartz substrate, layer A and layer B (SiO x N y ) of this example obtained through separate experiments.

CF 4 etch rate (Å / min) Selection ratio (A / B) Selection ratio (substrate) Quartz substrate 118.83 The layer B (SiO x N y ) 148.7 1.25 Layer A (AlO x ) ND * 1 <0.1 <0.1 The layer A (TaN x ) 15     0.101     0.13 The layer A (Ta-Zr) 10     0.067     0.08 The layer A (Ta-Hf) 20     0.134     0.17 The layer A (Zr) N.D. <0.1 <0.1 The layer A (Hf) 8     0.054     0.07

[ * 1: ND (not detected); indicates that the measurement is too small to be measurable]

As to the layer B, the etching rate of the layer A is reduced to 1/5 or less, and it is confirmed that the layer A of Examples 1 and 2 is the etching stopper film having the function of inhibiting the progress of the etching of the SiO x N y film .

Subsequently, the layer A exposed to the surface was removed by etching. As for the etchant, in Example 1, hydrous sulfuric acid was used, and in Examples 2 to 6, Cl 2 gas was used, and a favorable pattern shape was obtained. Table 4 shows the etching rates of the synthetic quartz substrate and layer A obtained through separate experiments. The etching rate of the layer A with respect to the synthetic quartz substrate is 5 times or more, and it can be confirmed that the layer A of Examples 1 and 2 is a &quot; removable &quot; layer.

Cl 2 etch rate (Å / min) Selection ratio (vs. substrate) Peroxide sulfuric acid etching rate (Å / min) Selection ratio (vs. substrate) Quartz substrate 269.8 0 The layer B (SiO x N y ) 415.9 1.54 0 Layer A (AlO x ) 101 0.37 Quickly dissolve >> 10 The layer A (TaN x ) 2039.6 7.56 The layer A (Ta-Zr) 4020 14.90 The layer A (Ta-Hf) 3000 11.12 The layer A (Zr) 3300 12.23 The layer A (Hf) 2800 10.38


In Examples 7 and 8, a resist is applied on the prepared two-layer film, and an exposure and development process is performed to form a resist pattern. Thereafter, the upper layer (B: SiO x N y ) and the lower layer (A) of the two-layer film are etched by CF 4 gas using the resist pattern as a mask. The relationship between the etching time at this time and the reflected light intensity of the portion to be etched with respect to the wavelength of 678 nm light was plotted. As for Example 7, as shown in Fig. 3, it was confirmed that the intensity of the reflected light sharply decreased at any time .

When the etching was stopped at that point, both layers A and B had a good pattern shape based on the resist pattern. That is, it can be confirmed that the layer A of Example 7 is an "etching stopper film" having a function of allowing the end point of etching of the SiO x N y film to be easily detected, and is also a "removable" film. The refractive index (complex refractive index real part) of the synthetic quartz substrate, layer A and layer B at a wavelength of 678 nm is 1.47, 4.70, and 1.67, respectively. When the refractive index of the layer B is larger than that of the synthetic quartz substrate and the layer A as described above, the abrupt change of the reflected light intensity as shown in Fig. 3 can be obtained before and after the etching of the layer B, thereby facilitating the detection of the end point. This change in the reflected light intensity was also obtained in the case of Example 8 as well.

The relationship between the etching time and the intensity of the reflected light is also shown in FIG. 3 by plotting the example of the single layer of the SiON layer. The end point can be detected even in the case of the SiON layer monolayer, but the end point becomes more clear in the seventh embodiment.

(Example 9)

In this example, the lower layer material was examined. Table 5 shows the results of confirming the etching characteristics of TaZr x (indicating the material including Ta and Zr, not showing the composition ratio of Ta and Zr, and the same is applied hereinafter) when dry etching was performed using a fluorine-based or chlorine-based gas. Table 6 shows the results of checking the etching characteristics of TaAl and TaHf when dry etching was performed using a fluorine-based or chlorine-based gas. That is, in the present embodiment, mainly Ta was used as a main material, and dry etching characteristics of a film to which a material (Al, Hf, Zr) considered to be related to the effect of the present invention was added were mainly examined.

Zr content (%) Etching gas Etching rate (Å / min) Selection ratio (/ QZ) TaZr x Cl 2 4020 11.2 Zr      100 Cl 2 3370 9.4 QZ        0 Cl 2 360 - TaZr x        1.8 C 2 F 6 40 0.3 TaZr x        2.6 C 2 F 6 40 0.3 TaZr x        4.3 C 2 F 6 10 0.1 Zr      100 C 2 F 6 7 0.1 Qz        0 C 2 F 6 120 -


Each film material is formed by sputtering. As for the material addition, a metal piece of the target material was placed on a Ta target to form a film. The presence or absence of addition to the film was confirmed by X-ray photoelectron spectroscopy (XPS). For the dry etching, the gases shown in Table 6 were used. In this embodiment, etching is performed by high-density plasma using an inductively coupled plasma source.

Etching gas Etching rate (Å / min) Selection ratio (/ QZ) TaAl Cl 2 2880 11.5 TaHf Cl 2 2980 11.0 QZ Cl 2 260 - TaAl C 2 F 6 70 0.6 TaHf C 2 F 6 20 0.2 QZ C 2 F 6 110 -


As a result of the experiment, it was confirmed that the resistance to the fluorine gas was improved while maintaining the chlorine properties by adding a small amount of the material (Al, Hf, Zr). In addition, the Zr metal film as a single body according to the present invention has a high etching resistance (low etching rate) in dry etching using a fluorine-based gas and a low etching rate (high etching rate) in dry etching using chlorine- It was confirmed that it is a material.

(Reference Example 1)

In order to confirm the effect of addition of Example 9, dry etching characteristics of a single Ta metal film to which the above material was not added were confirmed as a reference example. As shown in Table 7, the single Ta metal film had insufficient selectivity with respect to the fluorine gas with respect to the quartz substrate. Incidentally, the etching conditions of this comparative example are carried out in accordance with the ninth embodiment.

Etching gas Etching rate (Å / min) Selection ratio (/ QZ) Ta Cl 2 2900 8.1 QZ Cl 2 360 - Ta C 2 F 6 110 0.9 QZ C 2 F 6 120 -


(Example 10)

In this embodiment, the SiON layer was tried to be processed using the Zr film as an etching mask.

Each film formed on the Si substrate was processed with the film structure of resist / Zr / SiON (Fig. 4 (a)) to confirm the effect as an etching mask material. In this embodiment, the film thickness of each layer was set to 200 angstroms for the Zr layer and 800 angstroms for the SiON layer. After the Zr layer was processed into chlorine gas using the resist pattern as a mask (FIG. 4 (b)), the remaining film of the Zr layer after the processing of the SiON layer was measured. As a result, Etching resistance.

(Example 11)                 

In this embodiment, an attempt was made to produce a photomask having a phase shift effect. In this case, micro-machining of the blank made up of the SiON / TaZr / QZ substrate was carried out in consideration of the selectivity between materials.

The two-layer film on the QZ substrate was formed by using an RF magnetron sputterer to form a SiON layer of about 800 angstroms and a TaZr layer of about 60 angstroms. After forming a Cr film of about 500 angstroms on the SiON layer for pattern processing (or forming a shielding Cr layer), a ZEP resist for an electron beam is applied, and after passing through electron beam lithography and development, (Fig. 5 (a)).

Here, the film thickness of each layer was set in consideration of the phase difference of the mask transmitted light.

Cr processing was performed on the basis of the resist pattern by a mixed gas of chlorine + oxygen (acid consumption of about 20%) (FIG. 5 (b)).

Thereafter, the SiON layer was processed by using C 2 F 6 gas (FIG. 5 (c)). Thereafter, the TaZr layer is etched with chlorine gas (FIG. 5 (d)), and the Cr layer (including the resist film) is removed (or shaded) by a wet process mainly using a cerium (cerium nitrate) (Fig. 5 (e)), thereby forming a desired test pattern.

For pattern processing, a high density plasma etching apparatus using an inductively coupled plasma source was used. As a result of observing the cross section of the pattern shape after the processing using SEM (scanning electron microscope), it was confirmed that a good pattern having almost no cavity with respect to the QZ substrate was formed.                 

It was also confirmed that the same pattern observation was performed on a sample stopped in the processing of the SiON layer, and as a result, the film of the TaZr layer was hardly reduced. By providing an overetching time in consideration of the distribution in a predetermined dry etching time, pattern formation without a residual film of the SiON layer is realized. Further, side etching of the TaZr layer due to removal of the Cr layer was not found.

(Reference Example 2)

In this Reference Example, the TaZr layer of Example 11 is made of TaN whose etching resistance by the fluorine gas is close to that of the SiON layer. The same process as in Example 3 was performed except that the material on the QZ substrate was changed. The TaN film was formed by reactive sputtering using a mixed gas of argon and nitrogen. 6 (a) and 6 (b)). Thereafter, the SiON layer was processed by using C 2 F 6 gas (FIG. 6 (c)), . Thereafter, the TaN layer is etched by chlorine gas (FIG. 6 (d)), and the Cr layer (including the resist film) is removed by a wet process mainly using a cerium (II) ) To form a predetermined test pattern.

As a result of forming a test pattern of 0.5 mu m in the same manner as in Example 11, the pattern shape could be processed to have a good shape as described above, but the cavity for the QZ substrate as the base was confirmed. In addition, the etching rate of the TaN film by the fluorine gas was almost equal to QZ.

(Example 12)                 

In this comparative example, except that the TaZr layer described in Example 11 was replaced with a Hf layer and a Zr layer, the same treatment was performed.

A fine pattern was formed by the same treatment, and the pattern shape was observed by SEM. As a result, it was confirmed that the same pattern as in Example 11 was formed. It was confirmed that there was no difference in the damage to the QZ substrate and good pattern formation was achieved.
(Examples 13 to 18 and Reference Examples 3 to 5)

Examples 13 to 15 and 18 and Reference Examples 3 to 5 are a phase shift mask blank and a phase shift mask prepared by using an F 2 excimer laser (wavelength 157 nm) as exposure light and using light having a wavelength of 257 nm as inspection light. Examples 16 and 17 are a phase shift mask blank and a phase shift mask manufactured by using an ArF excimer laser (wavelength: 193 nm) as exposure light and using light having a wavelength of 364 nm as inspection light.

Next, the manufacturing process of the present invention will be described with reference to Figs. 7 and 8. Fig.

First, on a synthetic quartz-shaped transparent substrate 2, a target of the composition shown in Table 1 (except tantalum and silicon monolith for Reference Examples 3 and 5) and a rare gas (argon gas) were used as a sputtering gas, The lower layer 3 was formed by using a magnetron sputtering apparatus.

Next, the upper layer 4 was formed on the SiON film immediately above the lower layer 3 by a reactive magnetron sputtering method in which Ar, O 2 , and N 2 were sputtered using Si as a target (see, for example, 7 (1)).

Next, the halftone phase shift mask blank obtained above was heat-treated at 400 DEG C for 1 hour.

Next, a light shielding film 9 composed mainly of chromium and an electron beam lithography resist 10 were laminated in this order on the above-mentioned two-layer film (FIG. 7 (2)). Then, pattern lithography with an electron beam was performed on the resist, and development and baking by a dipping method were performed to form a resist pattern 10 '((3) in FIG. 7).

Subsequently, using the resist pattern as a mask, a light shielding film pattern 9 'was formed by dry etching with Cl 2 + O 2 gas. Further, the pattern of the halftone phase shifter portion was formed by changing the gas. At this time, CH 4 + O 2 was used for etching the upper layer 4, and Cl 2 gas was used for etching the lower layer 3 ((4) in FIG. 7). However, in Comparative Example 3, since the lower layer was also etched with CH 4 + O 2 , etching using Cl 2 gas was not performed.

Next, the resist on the formed pattern is peeled off (FIG. 8 (1)), and then the resist 11 is applied again to the entire surface (FIG. 8 (2)) and then subjected to a laser lithography / Thereby forming a resist pattern 11 '(FIG. 8 (3)). Then, the light-shielding band 12 was formed in the non-transfer area excluding the transfer area I by wet etching. Next, the resist pattern was peeled off to obtain a halftone phase shift mask ((4) in FIG. 8).

Tables 8 to 11 show the transparent substrate material, the composition of the upper layer, the film thickness, the optical characteristics of the exposure light and the inspection light, and the etching characteristics. The composition of the lower layer is substantially the same as that of the target.                 

Transparent substrate Upper layer material The upper layer film thickness (A) Underlayer material Underlayer film thickness (A) Exposure wavelength (nm) Exposure wavelength transmittance (%) Exposure wavelength reflectance (%) Inspection wavelength (nm) Inspection wavelength transmittance (%) Inspection Wavelength Reflectance (%) Example 12 F-doped synthetic quartz SiON① 790 Ta-Hf 100 157 6.20 15.60 257 19.91 32.79 Example 13 CaF 2 SiON① 800 Ta-Hf 65 157 9.14 13.55 257 32.39 24.78 Example 14 F-doped synthetic quartz SiON① 810 Ta-Hf 35 157 14.0 12.00 257 49.30 16.80 Example 15 Synthetic quartz SiON② 740 Ta-Hf 75 193 15.1 17.00 364 30.40 21.50 Example 16 Synthetic quartz SiON 960 Hf-Si 100 193 15.83 18.58 364 19.6 38.89 Example 17 CaF 2 SiON 920 Hf-Si 40 157 11.35 9.28 257 46.58 17.83 Reference Example 3 F-doped synthetic quartz SiON 770 Ta 60 157 7.33 14.37 257 35.4 24.06 Reference Example 4 F-doped synthetic quartz SiON 807 TaCr 80 157 6.30 18.20 257 29.40 25.13 Reference Example 5 F-doped synthetic quartz SiON 790 Si 40 157 9.76 11.95 257 43.4 16.93



157 nm 193 nm Composition (atom%) SiON① n k n k Si O N 2.00 0.20 - - 36 48 16 SiON② - - 2.22 0.18 40 27 33 SiON 2.05 0.22 - - 36 46 18 SiON 2.17 0.30 2.05 0.10 38 38 24

Ta Hf Si Cr Zr Ta-Hf 90 10 Ta-Hf 80 20 Hf-Si 17 83 Ta-Cr 96 4

The etching selectivity of the lower layer (SF 6 + He) The lower etch selectivity (Cl 2 ) Example 12 0.25 > 5 Example 13 0.25 > 5 Example 14 0.08 > 5 Example 15 0.25 > 5 Example 16 0.17 > 5 Example 17 0.17 > 5 Reference Example 3 0.67 > 5 Reference Example 4 0.25     2.50 Reference Example 5 8.08 -


Figs. 9 and 10 show transmittance curves and reflectance curves for the wavelengths of Examples 13 and 14, respectively. In Examples 13 and 14, the transmittance for the exposure light (F 2 excimer laser) was realized in the vicinity of the standard product (6%) and the product of high transmittance (around 9%). The reflectance of the exposure light was low and satisfied the required range (20% or less). In addition, the transmittance of the inspection light was also lower than the upper limit of the required value (40% or less), and it was sufficient to cope with the inspection.

In Example 15, a high transmittance (about 15%) for the exposure light (F 2 excimer laser) was realized. The reflectance of the exposure wavelength was low and the required range (20% or less) was satisfied. Also, the transmittance of the inspection wavelength was slightly higher. However, since it satisfies the required value (the transmittance is 60% or less and the reflectance is 10% or more) for the inspection using the transmitted light and the reflected light, it can sufficiently cope with the inspection using the transmitted light and the reflected light.

In Example 16, an exposure ratio (about 15%) was realized. The reflectance of the exposure wavelength was low and the required range (20% or less) was satisfied. In addition, the transmittance of the inspection light was also lower than the upper limit of the required value (40% or less), and it was sufficient to cope with the inspection.

In Examples 17 and 18, the material of the lower layer was HfSi instead of TaHf in Examples 13 to 16. [ Example 17 has realized a high transmittance (about 15%) for the exposure light (ArF excimer laser) and Example 18 has realized a high transmittance product (about 11%) for the exposure light (F 2 excimer laser). The reflectance of the exposure wavelength was low and the required range (30% or less) was satisfied. In addition, the transmittance of the inspection light was also lower than the upper limit of the required value (40% or less), and it was sufficient to cope with the inspection.

In Examples 13 to 18, the etching selection ratio to the SF 6 + He dry etching gas was lower for the lower layer than for the upper layer. Furthermore, the lower layer has sufficient resistance to the upper layer etching, and the lower layer has a larger etching selection ratio to the Cl 2 dry etching gas for the transparent substrate. Thus, since the damage to the transparent substrate was small at the time of removal of the lower layer, it was possible to form a halftone phase shift mask in which the cross-sectional shape was extremely good and the change of the optical characteristic due to overetching of the transparent substrate was suppressed to the utmost.

On the other hand, Reference Example 3 and Reference Example 5 are examples in which the lower layer material is a tantalum and silicon monolith which does not contain hafnium. In these Reference Examples the lower layer is CH 4 + O 2 dry etching selection ratio is greater for the etching gas for the upper layer. Further, when the upper layer is dry-etched using a fluorine-based gas, the film thickness of the lower layer is faster even when the lower layer surface is exposed. As a result, it is difficult to set a sufficient over-etching time in consideration of removing the residual film in the upper layer, which is caused by the etching distribution caused by the dense difference in the pattern.

That is, when the over-etching is not sufficiently performed, a pattern with a good sectional shape can not be formed. When the over-etching is sufficiently performed, the lower layer is also etched and the transparent substrate is also deeply pushed to change the optical characteristics.

In Reference Example 3, the upper layer was not sufficiently over-etched. As a result, a pattern with a good sectional shape was not obtained. In Reference Example 5, the etching selection ratio to the lower layer of CH 4 + O 2 dry etching gas is very large for the upper layer. As a result of thoroughly over-etching the upper layer, the transparent substrate also had a depth loss and the phase shift amount changed.

In addition, in Reference Example 4, since the etching selectivity to the Cl 2 dry etching gas was small, the damage to the substrate during the removal of the underlayer was large, and the optical characteristics were changed.

Another example of forming the light shielding film on the halftone phase shifter portion of the halftone phase shift mask is to form a light shielding layer 13 (see FIG. 11) in a desired region except for the vicinity of the boundary between the light transflecting portion 6 and the light transmitting portion 7 ) Are formed. By forming the light-shielding film 13 in this manner, the phase shift effect can be obtained and the side lobe light can be reduced. This structure is effective particularly in the case of a high transmittance product (the transmittance of the halftone phase shifter portion is 8 to 30%) because the influence of the side lobe light is high when the transmittance of the halftone phase shifter portion is high.

According to the present invention, it is possible to obtain a halftone phase shift mask blank and a halftone phase shift mask having excellent fine processability at the time of etching for forming the halftone phase shifter portion.

In addition, particularly, the fine workability at the time of etching for forming the halftone phase shifter portion is excellent.

Particularly, when the exposure light source has a short wavelength, especially at an exposure wavelength range of 140 to 200 nm, a high transmissivity product (transmittance: 8 to 30%) near 157 nm, which is the wavelength of the F 2 excimer laser, and around 193 nm, Can be used.

As a result, by using the halftone phase shift mask of the present invention, it becomes possible to transfer a high-definition transfer pattern.











Claims (37)

  1. delete
  2. delete
  3. delete
  4. delete
  5. delete
  6. delete
  7. delete
  8. delete
  9. delete
  10. delete
  11. delete
  12. delete
  13. And a phase shifter section for shifting a phase of light transmitted through a part of the exposure light and a phase shifter section for shifting the phase of the transmitted light by a predetermined amount, wherein the light transmitted through each of the light transmitting sections and the phase shifter section As a halftone type phase shift mask blank used for manufacturing a halftone phase shift mask having optical characteristics such that the contrast of the exposed pattern boundary portion transferred onto the surface of the photoreceptor can be satisfactorily maintained and improved And a phase shifter film for forming the phase shifter portion on the transparent substrate,
    Wherein the phase shifter film has a first layer and a second layer sequentially formed on a transparent substrate,
    The first and second layers may be continuously etched with the same etch medium,
    The refractive index difference in the etching end point detection light between the second layer and the transparent substrate is 0.5 or less,
    Wherein the refractive index difference in the etching end point detection light between the first layer and the transparent substrate is larger than the refractive index difference in the etching end point detection light between the second layer and the transparent substrate.
  14. delete
  15. 14. The method of claim 13,
    Wherein the phase shifter film has a two-layer structure of a first layer and a second layer sequentially formed on a transparent substrate,
    The first layer is mainly a layer for adjusting the transmittance,
    Wherein the second layer is a layer that mainly regulates the phase.
  16. 14. The method of claim 13,
    Wherein the first layer is made of one kind of material selected from Si and MSix (M: at least one of Mo, Ta, W, Cr, Zr and Hf)
    Said second layer is SiO x, SiO x N y or a metal thereto: a a (M Mo, Ta, W, Cr, Zr, 1 species or 2 or more species of Hf), M / (Si + M) × 100 To 10 atomic% or less of the total thickness of the halftone phase shift mask blank.
  17. And a phase shifter section for shifting a phase of light transmitted through a part of the exposure light and a phase shifter section for shifting the phase of the transmitted light by a predetermined amount, wherein the light transmitted through each of the light transmitting sections and the phase shifter section As a halftone type phase shift mask blank used for manufacturing a halftone phase shift mask having optical characteristics such that the contrast of the exposed pattern boundary portion transferred onto the surface of the photoreceptor can be satisfactorily maintained and improved And a phase shifter film for forming the phase shifter portion on the transparent substrate,
    The phase shifter film can be etched by dry etching using a fluorine-based gas. The phase-shifter film is formed of an upper layer made of SiOx or SiOxNy, and an intermediate layer formed between the upper layer and the transparent substrate and resistant to the fluorine- And a lower layer which can be etched by dry etching using the above-
    Wherein the lower layer material is made of a metal single substance selected from the first group consisting of Al, Ga, Hf, Ti, V and Zr, or a material (first material) containing two or more of these metals,
    Alternatively, the material of the lower layer is selected from the first group in one kind of metal selected from the second group consisting of Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, (Second material) in which at least one species is added,
    Or the material of the lower layer is made of the metal monolith, the first material, or the material containing nitrogen or carbon in the second material.
  18. And a phase shifter section for shifting a phase of light transmitted through a part of the exposure light and a phase shifter section for shifting the phase of the transmitted light by a predetermined amount, wherein the light transmitted through each of the light transmitting sections and the phase shifter section As a halftone type phase shift mask blank used for manufacturing a halftone phase shift mask having optical characteristics such that the contrast of the exposed pattern boundary portion transferred onto the surface of the photoreceptor can be satisfactorily maintained and improved And a phase shifter film for forming the phase shifter portion on the transparent substrate,
    Wherein the phase shifter film is formed by an upper layer which is etched by dry etching using a fluorine-based gas and a lower layer which is formed between the upper layer and the transparent substrate and which is resistant to the fluorine- At least a lower layer which can be etched,
    Wherein the lower layer material is made of a metal single substance selected from the first group consisting of Al, Ga, Hf, Ti and V, or a material (first material) containing two or more of these metals,
    Alternatively, the material of the lower layer is selected from the first group in one kind of metal selected from the second group consisting of Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, (Second material) in which at least one species is added,
    Or the material of the lower layer is made of the metal monolith, the first material, or the material containing nitrogen or carbon in the second material.
  19. A method of manufacturing a phase shift mask using the halftone phase shift mask blank according to claim 17 or 18,
    The method comprises:
    Etching the upper layer by dry etching using a fluorine-based gas using a desired resist pattern as a mask,
    Etching the lower layer by dry etching using a chlorine-based gas,
    And removing the resist pattern after the step of removing the resist pattern.
  20. A halftone phase shift mask produced by using the method according to claim 19.
  21. And a phase shifter section for shifting a phase of light transmitted through a part of the exposure light and a phase shifter section for shifting the phase of the transmitted light by a predetermined amount, wherein the light transmitted through each of the light transmitting sections and the phase shifter section As a halftone type phase shift mask blank used for manufacturing a halftone phase shift mask having optical characteristics such that the contrast of the exposed pattern boundary portion transferred onto the surface of the photoreceptor can be satisfactorily maintained and improved And a phase shifter film for forming the phase shifter portion on the transparent substrate,
    Wherein the phase shifter film is composed of an upper layer substantially composed of a material consisting of silicon, oxygen and nitrogen and a lower layer substantially composed of a material composed of tantalum and hafnium.
  22. And a phase shifter section for shifting a phase of light transmitted through a part of the exposure light and a phase shifter section for shifting the phase of the transmitted light by a predetermined amount, wherein the light transmitted through each of the light transmitting sections and the phase shifter section As a halftone type phase shift mask blank used for manufacturing a halftone phase shift mask having optical characteristics such that the contrast of the exposed pattern boundary portion transferred onto the surface of the photoreceptor can be satisfactorily maintained and improved And a phase shifter film for forming the phase shifter portion on the transparent substrate,
    Wherein the phase shifter film is composed of an upper layer substantially composed of a material consisting of silicon, oxygen and nitrogen and a lower layer substantially composed of a material consisting of silicon and hafnium.
  23. 23. The method of claim 21 or 22,
    Wherein the content of hafnium in the lower layer is 2 to 50 atomic% or more.
  24. And a phase shifter section for shifting a phase of the transmitted light by a predetermined amount while allowing a part of the exposure light to pass therethrough and a phase shifter section for shifting the light transmitted through each of the light transmitting section and the phase shifter section As a halftone type phase shift mask blank used for manufacturing a halftone phase shift mask having optical characteristics such that the contrast of the exposed pattern boundary portion transferred onto the surface of the photoreceptor can be satisfactorily maintained and improved And a phase shifter film for forming the phase shifter portion on the transparent substrate,
    Wherein the phase shifter film is made of a material containing substantially an upper layer made of a material consisting of silicon, oxygen and nitrogen and at least one of tantalum and silicon, hafnium and nitrogen or carbon. Shift mask blank.
  25. The method according to any one of claims 21, 22 and 24,
    Wherein the upper layer made of a material consisting substantially of silicon, oxygen and nitrogen contains 35 to 45% of silicon, 1 to 60% of oxygen and 5 to 60% of nitrogen in atomic percentages, respectively.
  26. The method according to any one of claims 13, 17, 18, 21, 22, and 24,
    And a light shielding film containing chromium as a main component is formed on the phase shifter film.
  27. Etching the halftone phase shifter film of the halftone phase shift mask blank according to any one of claims 21, 22, and 24 to form a halftone phase shifter film on the transparent substrate, the halftone phase shifter film having a light transmitting portion and a light semi- Wherein a mask pattern is formed on the surface of the mask.
  28. 27. A method of manufacturing a halftone phase shift mask according to claim 27,
    And a halftone phase shifter film etching step of etching the upper layer by dry etching using a fluorine-based gas and etching the lower layer by dry etching using a chlorine-based gas. .
  29. A phase shifter film according to any one of claims 13, 17, 18, 21, 22, and 24, which is obtained by performing patterning processing for selectively removing a phase shifter film so as to obtain a predetermined pattern, And a mask pattern composed of a phase shifter portion and a phase shifter portion.
  30. A pattern transfer method, wherein pattern transfer is performed using the halftone phase shift mask according to claim 29.
  31. The first layer made of SiOx or SiOxNy and the first layer made of SiOx or SiOxNy can be processed by dry etching using a chlorine-based gas, and resistance against the fluorine-based gas can be obtained And a second layer having a thickness of 100 nm or less,
    Wherein the material of the second layer is made of a metal single substance selected from the first group consisting of Al, Ga, Hf, Ti, V and Zr, or a material (first material) containing two or more of these metals,
    Alternatively, the material of the second layer may be added to one kind of metal selected from the second group consisting of Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, (Second material) to which at least one selected material is added,
    Or the material of the second layer is made of a material containing nitrogen or carbon in the metal monolith, the first material, or the second material.
  32. A first layer which can be processed by dry etching using a fluorine-based gas and a second layer which can be processed by dry etching using a chlorine-based gas and which is resistant to the fluorine-based gas, As the laminate,
    Wherein the material of the second layer is composed of a single metal selected from the first group consisting of Al, Ga, Hf, Ti and V, or a material (first material) containing two or more of these metals,
    Alternatively, the material of the second layer may be added to one kind of metal selected from the second group consisting of Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, (Second material) to which at least one selected material is added,
    Or the material of the second layer is made of a material containing nitrogen or carbon in the metal monolith, the first material, or the second material.
  33. 33. The method of claim 32,
    Laminate, characterized in that the material of the first layer is selected from a material that contains a metal in the SiO x, SiN x, SiO x N y, SiC x, SiC x N y, SiC x O y or a combination thereof.
  34. 34. The method according to claim 32 or 33,
    Wherein the second layer is formed on the first layer,
    And the second layer is used as an etching mask layer of the first layer.
  35. 34. The method according to claim 32 or 33,
    Said second layer being formed below said first layer,
    And the second layer is used as an etching stopper of the first layer.
  36. The first layer made of SiOx or SiOxNy and the first layer made of SiOx or SiOxNy can be processed by dry etching using a chlorine-based gas, and resistance against the fluorine-based gas can be obtained Wherein a pattern having at least a second layer of a second layer is formed by performing dry etching using a fluorine-based gas of the first layer and dry etching using a chlorine-based gas of the second layer,
    Wherein the material of the second layer is made of a metal single substance selected from the first group consisting of Al, Ga, Hf, Ti, V and Zr, or a material (first material) containing two or more of these metals,
    Or the second layer is made of a material selected from the group consisting of Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, (Second material) to which at least one selected material is added,
    Or the material of the second layer is made of a material containing nitrogen or carbon in the metal monolith, the first material, or the second material.
  37. A first layer which can be processed by dry etching using a fluorine-based gas and a second layer which can be processed by dry etching using a chlorine-based gas and which is resistant to the fluorine-based gas, Wherein a pattern of the first layer is formed by performing dry etching using the fluorine-based gas of the first layer and dry etching using the chlorine-based gas of the second layer,
    Wherein the material of the second layer is composed of a single metal selected from the first group consisting of Al, Ga, Hf, Ti and V, or a material (first material) containing two or more of these metals,
    Or the second layer is made of a material selected from the group consisting of Cr, Ge, Pd, Si, Ta, Nb, Sb, Pt, Au, (Second material) to which at least one selected material is added,
    Or the material of the second layer is made of a material containing nitrogen or carbon in the metal monolith, the first material, or the second material.
KR1020047007952A 2000-12-26 2002-06-04 Halftone phase shift mask blank, halftone phase shift mask, and manufacturing method thereof KR100815679B1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
JP2001361025A JP2002258458A (en) 2000-12-26 2001-11-27 Halftone phase shift mask and mask blank
JPJP-P-2001-00361025 2001-11-27
JP2001394311A JP4027660B2 (en) 2000-12-26 2001-12-26 Halftone phase shift mask blank and mask
JPJP-P-2001-00394311 2001-12-26
JPJP-P-2002-00047051 2002-02-22
JP2002047051A JP3818171B2 (en) 2002-02-22 2002-02-22 Phase shift mask blank and manufacturing method thereof
JPJP-P-2002-00082021 2002-03-22
JP2002082021A JP3993005B2 (en) 2002-03-22 2002-03-22 Halftone phase shift mask blank, halftone phase shift mask, method of manufacturing the same, and pattern transfer method
PCT/JP2002/005479 WO2003046659A1 (en) 2001-11-27 2002-06-04 Halftone phase shift mask blank, halftone phase shift mask, and manufacturing method thereof

Publications (2)

Publication Number Publication Date
KR20040054805A KR20040054805A (en) 2004-06-25
KR100815679B1 true KR100815679B1 (en) 2008-03-20

Family

ID=27482698

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020047007952A KR100815679B1 (en) 2000-12-26 2002-06-04 Halftone phase shift mask blank, halftone phase shift mask, and manufacturing method thereof

Country Status (3)

Country Link
KR (1) KR100815679B1 (en)
CN (1) CN100440038C (en)
WO (1) WO2003046659A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7556892B2 (en) 2004-03-31 2009-07-07 Shin-Etsu Chemical Co., Ltd. Halftone phase shift mask blank, halftone phase shift mask, and pattern transfer method
JP2006078825A (en) 2004-09-10 2006-03-23 Shin Etsu Chem Co Ltd Photomask blank, photomask and method for manufacturing same
KR100720334B1 (en) * 2005-05-13 2007-05-21 주식회사 에스앤에스텍 Half-tone type phase shift blank mask and manufacturing method of the same
JP4509050B2 (en) * 2006-03-10 2010-07-21 信越化学工業株式会社 Photomask blank and photomask
JP4883278B2 (en) * 2006-03-10 2012-02-22 信越化学工業株式会社 Photomask blank and photomask manufacturing method
CN101046626B (en) * 2006-03-30 2012-03-14 应用材料公司 Method for etching molybdenum when manufacturing photomask
US7635546B2 (en) 2006-09-15 2009-12-22 Applied Materials, Inc. Phase shifting photomask and a method of fabricating thereof
CN101809499B (en) * 2007-09-27 2012-10-10 Hoya株式会社 Mask blank, and method for production of imprint mold
US7820540B2 (en) * 2007-12-21 2010-10-26 Palo Alto Research Center Incorporated Metallization contact structures and methods for forming multiple-layer electrode structures for silicon solar cells
JP4697495B2 (en) * 2010-05-28 2011-06-08 信越化学工業株式会社 Photomask blank and photomask manufacturing method
DE102010061296A1 (en) * 2010-12-16 2012-06-21 Schott Solar Ag Method for producing electrically conductive contacts on solar cells and solar cell
JP4930736B2 (en) * 2011-09-21 2012-05-16 信越化学工業株式会社 Photomask manufacturing method and photomask
JP4930737B2 (en) * 2011-09-21 2012-05-16 信越化学工業株式会社 Photomask blank and binary mask manufacturing method
KR101926614B1 (en) * 2012-07-27 2018-12-11 엘지이노텍 주식회사 Phase shift mask
JP6157832B2 (en) * 2012-10-12 2017-07-05 Hoya株式会社 Electronic device manufacturing method, display device manufacturing method, photomask manufacturing method, and photomask
JP6418035B2 (en) * 2015-03-31 2018-11-07 信越化学工業株式会社 Phase shift mask blanks and phase shift masks
CN109188854B (en) * 2018-10-18 2020-06-09 合肥鑫晟光电科技有限公司 Mask plate, display substrate, manufacturing method of display substrate and display device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980033168A (en) * 1996-10-24 1998-07-25 후지다히로미찌 Blank for halftone phase shift mask, halftone phase shift mask and manufacturing method thereof
KR0130448Y1 (en) * 1994-12-13 1998-12-15 전성원 Device for opening and closing tail door for an automobile
KR100190358B1 (en) * 1990-04-09 1999-06-01 디어터 크리스트, 베르너 뵈켈 Phase mask for photolithographic projection and process for its preparation

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0239153A (en) * 1988-07-29 1990-02-08 Toppan Printing Co Ltd Photomask blank and photomask
JP3339716B2 (en) * 1992-07-17 2002-10-28 株式会社東芝 Manufacturing method of exposure mask
JP3253783B2 (en) * 1993-08-13 2002-02-04 株式会社東芝 Halftone phase shift mask and method of manufacturing the same
JP3351892B2 (en) * 1994-01-19 2002-12-03 大日本印刷株式会社 Halftone phase shift photomask and blank for halftone phase shift photomask
JPH0876353A (en) * 1994-09-08 1996-03-22 Nec Corp Production of phase shift mask
JP3894503B2 (en) * 1995-06-01 2007-03-22 Hoya株式会社 Antistatic film, lithographic mask blank and lithographic mask using this film
JPH10198017A (en) * 1997-01-10 1998-07-31 Toppan Printing Co Ltd Phase shift photomask and blank for phase shift photomask
JP3472528B2 (en) * 1999-06-11 2003-12-02 Hoya株式会社 Phase shift mask and phase shift mask blank
JP2001066756A (en) * 1999-06-23 2001-03-16 Toppan Printing Co Ltd Blank for halftone type phase shift mask, halftone type phase shift mask and production method therefor
JP2001174973A (en) * 1999-12-15 2001-06-29 Dainippon Printing Co Ltd Halftone phase shift photomask and blanks for same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100190358B1 (en) * 1990-04-09 1999-06-01 디어터 크리스트, 베르너 뵈켈 Phase mask for photolithographic projection and process for its preparation
KR0130448Y1 (en) * 1994-12-13 1998-12-15 전성원 Device for opening and closing tail door for an automobile
KR19980033168A (en) * 1996-10-24 1998-07-25 후지다히로미찌 Blank for halftone phase shift mask, halftone phase shift mask and manufacturing method thereof

Also Published As

Publication number Publication date
KR20040054805A (en) 2004-06-25
CN100440038C (en) 2008-12-03
CN1596385A (en) 2005-03-16
WO2003046659A1 (en) 2003-06-05

Similar Documents

Publication Publication Date Title
KR101724046B1 (en) Method of manufacturing photomask blank and method of manufacturing photomask
KR101936976B1 (en) Photomask blank, photomask, and making method
EP2664959B1 (en) Half-tone phase shift mask blank and method for manufacturing half-tone phase shift mask
JP4907688B2 (en) Photomask blank, photomask, and pattern transfer method using photomask
US8293435B2 (en) Photomask blank, photomask, and methods of manufacturing the same
JP5562834B2 (en) Photomask blank, photomask and photomask blank manufacturing method
US9075320B2 (en) Mask blank, transfer mask, method of manufacturing a transfer mask, and method of manufacturing a semiconductor device
US7618753B2 (en) Photomask blank, photomask and method for producing those
EP1860500B1 (en) Phase shift mask blank, phase shift mask, and pattern transfer method
KR101204632B1 (en) Photomask-blank, photomask and fabrication method thereof
KR101135246B1 (en) Method of producing photomask and photomask blank
JP4933753B2 (en) Phase shift mask blank, phase shift mask, and manufacturing method thereof
US7736824B2 (en) Photomask blank, photomask, and method of manufacture
JP3645882B2 (en) Method for manufacturing halftone phase shift mask blank
KR101450947B1 (en) Photomask blank and photomask and method for fabricating in photomask
JP5165833B2 (en) Photomask blank, photomask, and photomask blank manufacturing method
KR100947166B1 (en) Photomask blank and photomask making method
DE10165034B4 (en) Halftone phase shift mask and mask blank
JP4614291B2 (en) Halftone phase shift mask blank and halftone phase shift mask manufactured using the same
TWI437362B (en) Mask blank, method of manufacturing an exposure mask, method of manufacturing an exposure mask, and method of manufacturing an imprint template
KR101709381B1 (en) Halftone phase shift photomask blank, halftone phase shift photomask and pattern exposure method
JP5175932B2 (en) Phase shift mask blank and phase shift mask
DE102009043145B4 (en) Mask blank and method of making a transfer mask
EP1813984B1 (en) Halftone phase shifting mask blank, halftone phase shifting mask, and pattern transfer method
US8409772B2 (en) Mask blank and method of manufacturing a transfer mask

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
G170 Publication of correction
FPAY Annual fee payment

Payment date: 20130227

Year of fee payment: 6

FPAY Annual fee payment

Payment date: 20140220

Year of fee payment: 7

FPAY Annual fee payment

Payment date: 20150224

Year of fee payment: 8

FPAY Annual fee payment

Payment date: 20160219

Year of fee payment: 9

FPAY Annual fee payment

Payment date: 20170221

Year of fee payment: 10

FPAY Annual fee payment

Payment date: 20180220

Year of fee payment: 11

FPAY Annual fee payment

Payment date: 20190219

Year of fee payment: 12

FPAY Annual fee payment

Payment date: 20200219

Year of fee payment: 13