JP4834203B2 - Photomask blank manufacturing method and photomask manufacturing method - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention is suitable for a dry etching process for forming a light-shielding film pattern, and for photomask blanks and photomasks with reduced surface reflectance of the light-shielding film for a short wavelength region of 190 to 300 nm (particularly near 200 nm). It relates to a manufacturing method.

  In general, in a manufacturing process of a semiconductor device, a fine pattern is formed using a photolithography method. In addition, a number of substrates called photomasks are usually used for forming this fine pattern. This photomask is generally provided with a light-shielding fine pattern made of a metal thin film or the like on a translucent glass substrate, and a photolithography method is also used in the production of this photomask.

  For manufacturing a photomask by photolithography, a photomask blank having a light-shielding film on a light-transmitting substrate such as a glass substrate is used. The production of a photomask using this photomask blank consists of an exposure process in which a desired pattern exposure is performed on a resist film formed on the photomask blank, and the resist film is developed in accordance with the desired pattern exposure to develop a resist pattern. A developing step for forming the light shielding film, an etching step for etching the light-shielding film along the resist pattern, and a step for peeling and removing the remaining resist pattern. In the above development process, the resist film formed on the photomask blank is subjected to a desired pattern exposure, and then a developer is supplied to dissolve a portion of the resist film soluble in the developer to form a resist pattern. To do. In the etching process, using this resist pattern as a mask, the exposed portion of the light-shielding film on which the resist pattern is not formed is dissolved by wet etching, for example, thereby forming a desired mask pattern on the translucent substrate. To do. Thus, a photomask is completed.

For example, Patent Document 1 has a laminated film of a halftone material film and a metal film on a transparent substrate as a mask blank suitable for wet etching, and this metal film is directed from the surface side toward the transparent substrate side. There are regions composed of materials having different etching rates. For example, a halftone phase shift mask blank made of a CrN / CrC metal film and a CrON antireflection film is described.

By the way, in order to miniaturize the pattern of a semiconductor device, in addition to miniaturization of a mask pattern formed on a photomask, it is necessary to shorten the wavelength of an exposure light source used in photolithography. As an exposure light source for manufacturing semiconductor devices, in recent years, the wavelength has been shortened from a KrF excimer laser (wavelength 248 nm) to an ArF excimer laser (wavelength 193 nm) and further to an F2 excimer laser (wavelength 157 nm).
On the other hand, in photomasks and photomask blanks, dry etching is required instead of conventional wet etching as a patterning method for manufacturing photomasks when miniaturizing the mask pattern formed on the photomask. It is becoming.

Even if the mask pattern is miniaturized, if the exposure light is reflected on the surface of the light-shielding film pattern (mask pattern) when pattern transfer is performed using the photomask, the pattern transfer accuracy deteriorates due to the generation of stray light. Therefore, in order to prevent the generation of such stray light, an antireflection film made of a material such as CrO or CrON is provided on the surface of the light shielding film in the photomask blank or photomask.
In Patent Document 2, the uppermost layer portion of the light shielding film in the halftone phase shift mask blank is used as a reflectance adjustment unit, and the wavelength of exposure light or the like on the surface of the light shielding film depends on the nitrogen content in the reflectance adjustment unit. It is described that the reflectance with respect to is adjusted.

Japanese Patent No. 2983020 Japanese Patent Laid-Open No. 2003-322956

By the way, as shown in FIG. 4 to be described later, a halftone type in which a light shielding film is formed in a region where a mask pattern of a phase shifter film is formed, except for a boundary portion with a light transmitting portion in the mask pattern. The phase shift mask is suitable for realizing miniaturization of the pattern of the semiconductor device. In such a halftone phase shift mask, a phase shifter having a high transmittance (15% or more) with respect to the exposure wavelength. The surface reflectance of the light-shielding film at a wavelength of 193 nm of an ArF excimer laser, for example, which is becoming the mainstream in recent years as an exposure light source in the manufacture of semiconductor devices accompanying the miniaturization of semiconductor device patterns is as low as possible, especially less than 20% It is hoped that.
However, as described in Patent Document 2, even if the reflectance with respect to the exposure light wavelength on the surface of the light shielding film is adjusted by the nitrogen content in the reflectance adjustment portion of the uppermost layer portion of the light shielding film, the reflection at the exposure wavelength of 193 nm is considered. Even if the rate is lowered, the limit is 20% at most (see, for example, FIG. 3 of the patent document), and a sufficient reflectance reduction effect cannot be obtained.

  Therefore, the present invention has been made to solve the conventional problems, and the object of the present invention is firstly to effectively surface the light shielding film in a short wavelength region of 190 to 300 nm (particularly in the vicinity of 200 nm). It is an object to provide a photomask blank and a photomask manufacturing method capable of sufficiently reducing the reflectance and obtaining good pattern transfer accuracy even with respect to an exposure light source that tends to have a shorter wavelength. Second, by increasing the dry etching rate of the light-shielding film, the dry etching time can be shortened and the film loss of the resist film can be reduced. As a result, the resist film is thinned to improve resolution and pattern accuracy ( It is to provide a photomask blank and a photomask manufacturing method capable of improving the (CD accuracy) and forming a light-shielding film pattern having a good cross-sectional shape by shortening the dry etching time. Thirdly, the present invention provides a photomask blank and a photomask manufacturing method capable of forming a light-shielding film pattern having a good cross-sectional shape by reducing the thickness of the light-shielding film while having the light-shielding performance necessary for the light-shielding film. That is.

In order to solve the above problems, the present invention has the following configuration.
(Configuration 1) In a method of manufacturing a photomask blank having a light-shielding film made of a material containing chromium on a light-transmitting substrate, the light-shielding film is formed with a reflectance adjusting part including at least carbon in an upper layer part of the light-shielding film. The reflectance adjusting unit is formed by sputtering so that the surface reflectance in a wavelength range of 190 to 300 nm is less than 20% in an atmosphere containing at least hydrocarbon gas using a target containing chromium. A method for producing a photomask blank, characterized by comprising:
(Structure 2) The photo according to structure 1, wherein the reflectance adjusting section is formed by adjusting a content of the hydrocarbon gas in the atmosphere and / or a film formation pressure during sputtering film formation. Mask blank manufacturing method.
(Structure 3) The method for manufacturing a photomask blank according to Structure 1 or 2, wherein the light shielding film further contains at least one of oxygen and nitrogen.
(Structure 4) A photomask blank manufacturing method according to any one of Structures 1 to 3, wherein a halftone phase shifter film is formed between the light transmitting substrate and the light shielding film.

(Structure 5) The method for producing a photomask blank according to Structure 4, wherein the transmittance of the halftone phase shifter film in a short wavelength region of 150 to 200 nm is 10% or more and 40% or less.
(Structure 6) The photomask blank is a photomask for dry etching processing corresponding to a photomask manufacturing method for patterning the light shielding film by dry etching using a resist pattern formed on the light shielding film as a mask. The method for manufacturing a photomask blank according to any one of configurations 1 to 5, wherein the photomask blank is a blank.
(Structure 7) A photomask manufacturing method comprising a step of patterning the light-shielding film in the photomask blank obtained by the manufacturing method according to any one of structures 1 to 6 by a dry etching process.
(Configuration 8) After patterning the light-shielding film in the photomask blank obtained by the manufacturing method according to Configuration 4 or 5 by dry etching, and forming a light-shielding film pattern on the halftone phase shifter film, A method for producing a photomask, comprising patterning the halftone phase shifter film by a dry etching process using a light shielding film pattern as a mask to form a halftone phase shifter film pattern on the translucent substrate .

As in Structure 1, the photomask blank manufacturing method of the present invention is a photomask blank manufacturing method having a light-shielding film made of a material containing chromium on a light-transmitting substrate, wherein the light-shielding film is the light-shielding film. A reflectance adjustment part including at least carbon is formed in the upper layer part of the light shielding film, and the reflectance adjustment part uses a target containing chromium and has a thickness of 190 to 300 nm of the light shielding film in an atmosphere containing at least hydrocarbon gas. It is formed by sputtering film formation so that the surface reflectance in the wavelength region is less than 20%.
Thus, the reflectance adjustment part of the upper part of the light shielding film in the wavelength region of 190 to 300 nm is formed by sputtering film formation in an atmosphere containing at least hydrocarbon gas so that the surface reflectance is less than 20%. Thus, the surface reflectance in the wavelength range of 190 to 300 nm (particularly in the vicinity of 200 nm) can be effectively reduced. Therefore, good pattern transfer accuracy can be obtained even for an exposure light source that tends to have a shorter wavelength due to the demand for miniaturization of the pattern of the semiconductor device.

  In the case of a photomask blank equipped with a light shielding film suitable for conventional wet etching processing, the wet etching time of the entire light shielding film is controlled by the carbon content of the light shielding film, so that the light shielding film is intended to reduce reflectivity. In particular, there was a limitation in arbitrarily including carbon in the upper layer portion. Therefore, the upper layer portion of the light shielding film is made of, for example, a material such as CrON, and the surface reflectance of the light shielding film with respect to the exposure light is adjusted by the contents of O and N. As described above, a sufficient reflectance reduction effect in a short wavelength region, for example, an exposure wavelength of 193 nm was not obtained. In the photomask blank of the present invention, by including a light-shielding film suitable for dry etching treatment, restrictions on carbon content are relaxed, and the surface of the light-shielding film depends on the carbon content in the reflectance adjustment part of the light-shielding film upper layer part. The reflectance can be adjusted so as to be sufficiently reduced. Thereby, the surface reflectance in a 190-300 nm wavelength range (especially 200 nm vicinity) can be made into less than 20%.

  As in Configuration 2, the reflectance adjustment unit is formed by adjusting the hydrocarbon gas content in the atmosphere during sputtering film formation and / or the film formation pressure during sputtering film formation. The surface reflectance in the wavelength range of 190 to 300 nm (especially in the vicinity of 200 nm) can be effectively reduced.

As in Structure 3, it is preferable that the light shielding film containing chromium further contains at least one element of oxygen and nitrogen. A light-shielding film made of a material containing chromium and at least one element of oxygen and nitrogen has a higher dry etching rate than a light-shielding film made of chromium alone, and the dry etching time can be shortened. By shortening the dry etching time, it is possible to reduce film loss during dry etching of the resist film formed on the light shielding film. As a result, the resist can be thinned, and the pattern resolution and pattern accuracy (CD accuracy) can be improved. Further, such a light-shielding film of a chromium-based material containing oxygen and nitrogen is desired to be a thin film to some extent without increasing the film thickness at an exposure wavelength of 200 nm or less, which is effective for achieving pattern miniaturization. The optical density (for example, preferably 2.5 or more) can be obtained, and the light shielding film can be made thin while having the light shielding performance necessary for the light shielding film.

  Further, as in Configuration 4, a halftone phase shifter film may be formed between the translucent substrate and the light shielding film. In particular, in a halftone phase shift mask in which a mask pattern of a phase shifter film is formed and a light shielding film is formed on a portion of the mask pattern excluding a boundary portion with a light transmitting portion, 190. The present invention that can sufficiently reduce the surface reflectance of the light-shielding film in a short wavelength region of ˜300 nm (particularly in the vicinity of 200 nm) is preferable (less than 20%).

In that case, as described in Configuration 5, the present invention is particularly suitable when the transmittance of the halftone phase shifter film to exposure light is 10% or more and 40% or less. That is, in a halftone phase shift mask having a phase shifter film having a high transmittance for exposure light, a light transmission portion (a mask pattern is formed in a region where the mask pattern of the phase shifter film is formed). By forming a light-shielding film on the portion excluding the boundary with the portion where the light-transmitting substrate is exposed), it is possible to more completely shield the portion that is originally desired to be completely shielded from light. This is because the surface reflectance of the light shielding film in the short wavelength range of 190 to 300 nm (particularly in the vicinity of 200 nm) has a great influence on the pattern accuracy and the like.
Further, as described in Structure 6, the photomask blank is dry-etched corresponding to a photomask manufacturing method for patterning the light-shielding film by a dry etching process using a resist pattern formed on the light-shielding film as a mask. A photomask blank for processing is preferred.

Moreover, according to the manufacturing method of the photomask which has the process of patterning the light shielding film in the photomask blank of the structures 1 to 6 using the dry etching process as in the structure 7, the dry etching time can be shortened, A photomask in which a light-shielding film pattern having a good cross-sectional shape is accurately formed can be obtained.
Further, as in Configuration 8, after the light shielding film in the photomask blank of Configuration 4 or 5 is patterned by dry etching, a light shielding film pattern is formed on the halftone phase shifter film, and then the light shielding film pattern is masked. Then, according to the photomask manufacturing method of patterning the halftone type phase shifter film by dry etching process and forming the halftone type phase shifter film pattern on the translucent substrate, corresponding to the miniaturization of the pattern, A photomask capable of obtaining good pattern transfer accuracy can be obtained.

According to the present invention, a photomask blank that can effectively reduce the surface reflectance of the light-shielding film in a short wavelength region of 190 to 300 nm (especially in the vicinity of 200 nm) and obtain good pattern accuracy even for a fine pattern. In addition, a method for manufacturing a photomask can be provided.
In addition, according to the present invention, by increasing the dry etching rate of the light shielding film, the dry etching time can be shortened, and the reduction of the resist film can be reduced. As a result, the resist film can be thinned, and the pattern resolution and pattern accuracy (CD accuracy) can be improved. Furthermore, by shortening the dry etching time, it is possible to provide a photomask blank and a photomask manufacturing method capable of forming a light-shielding film pattern having a good cross-sectional shape.
In addition, according to the present invention, a photomask blank and a photomask that can form a light-shielding film pattern having a good cross-sectional shape by reducing the thickness of the light-shielding film while having the light-shielding performance necessary for the light-shielding film. A method can be provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a sectional view showing a first embodiment of a photomask blank obtained by the present invention.
The photomask blank 10 in FIG. 1 is in the form of a binary mask photomask blank having a light-shielding film 2 on a translucent substrate 1.
The photomask blank 10 is a dry etching mask blank corresponding to a photomask manufacturing method for patterning the light shielding film 2 by dry etching using a resist pattern formed on the light shielding film 2 as a mask. is there.
Here, as the translucent substrate 1, a glass substrate is generally used. Since the glass substrate is excellent in flatness and smoothness, when pattern transfer onto a semiconductor substrate using a photomask is performed, highly accurate pattern transfer can be performed without causing distortion of the transfer pattern.

In the present invention, the light-shielding film 2 remains at the end of the light-shielding film patterning even if the resist film is reduced when patterning by dry etching using the resist pattern formed thereon as a mask. Thus, in the dry etching process, it is preferable to use a material having a selectivity with respect to the resist exceeding 1. The selection ratio is represented by the ratio of the amount of reduction of the resist film to the amount of reduction of the light shielding film (= the amount of reduction of the light shielding film / the amount of reduction of the resist) with respect to the dry etching process. Preferably, from the viewpoint of preventing the deterioration of the cross-sectional shape of the light-shielding film pattern and suppressing the global loading phenomenon, the light-shielding film has a selection ratio with the resist of more than 1 and 10 or less, more preferably more than 1 and 5 or less. Is desirable.

Specific examples of the material for the light shielding film 2 include a material containing chromium and an additive element whose dry etching rate is higher than that of chromium alone. It is preferable that the additive element whose dry etching rate is faster than that of chromium alone includes at least one of oxygen and nitrogen.
The oxygen content when oxygen is contained in the light shielding film 2 is preferably in the range of 5 to 80 atomic%. When the oxygen content is less than 5 atomic%, it is difficult to obtain the effect of increasing the dry etching rate as compared with chromium alone. On the other hand, if the oxygen content exceeds 80 atomic%, the absorption coefficient in, for example, an ArF excimer laser (wavelength 193 nm) with a wavelength of 200 nm or less decreases, so that a desired optical density (for example, 2.5 or more) is obtained. Therefore, it becomes necessary to increase the film thickness. Further, from the viewpoint of reducing the amount of oxygen in the dry etching gas, the oxygen content in the light shielding film 2 is particularly preferably in the range of 60 to 80 atomic%.

Further, the nitrogen content in the case where the light shielding film 2 contains nitrogen is preferably in the range of 20 to 80 atomic%. When the nitrogen content is less than 20 atomic%, it is difficult to obtain the effect of increasing the dry etching rate as compared with chromium alone. Further, when the nitrogen content exceeds 80 atomic%, the absorption coefficient in, for example, an ArF excimer laser (wavelength 193 nm) with a wavelength of 200 nm or less becomes small, so that a desired optical density (for example, 2.5 or more) is obtained. Therefore, it becomes necessary to increase the film thickness.
Further, the light shielding film 2 may contain both oxygen and nitrogen. The content in that case is preferably such that the sum of oxygen and nitrogen is in the range of 10 to 80 atomic%. Further, the content ratio of oxygen and nitrogen when the light shielding film 2 contains both oxygen and nitrogen is not particularly limited, and is appropriately determined in consideration of the absorption coefficient and the like.

  The method for forming the light-shielding film 2 is not particularly limited, but a sputtering film forming method is particularly preferable. The sputtering film formation method is suitable for the present invention because it can form a uniform film with a constant film thickness. When the light shielding film 2 is formed on the translucent substrate 1 by a sputtering film forming method, a chromium (Cr) target is used as a sputtering target, and sputtering gas introduced into the chamber is argon gas or helium gas. A mixture of an inert gas and a gas such as oxygen, nitrogen, carbon dioxide, or nitric oxide is used. When a sputtering gas in which oxygen gas or carbon dioxide gas is mixed with an inert gas such as argon gas can be used, a light shielding film containing oxygen in chromium can be formed, and nitrogen gas is mixed with an inert gas such as argon gas. When a sputtering gas is used, a light shielding film containing nitrogen can be formed in chromium, and when a sputtering gas in which nitrogen monoxide gas or a mixture of nitrogen gas and oxygen gas is used as an inert gas such as argon gas, chromium is used. A light shielding film containing nitrogen and oxygen can be formed. When a sputtering gas in which methane gas is mixed with an inert gas such as argon gas is used, a light shielding film containing carbon in chromium can be formed.

  The film thickness of the light shielding film 2 is set so that the optical density with respect to the exposure light is 2.5 or more. Specifically, the thickness of the light shielding film 2 is preferably 90 nm or less. The reason for this is that in order to cope with pattern miniaturization to a submicron level pattern size in recent years, when the film thickness exceeds 90 nm, the formation of a fine pattern is caused by the microloading phenomenon of the pattern during dry etching. This is because it may be difficult. By reducing the film thickness to some extent, the pattern aspect ratio (ratio of pattern depth to pattern width) can be reduced, and line width errors due to the global loading phenomenon and microloading phenomenon can be reduced. Furthermore, by reducing the film thickness to some extent, it becomes possible to prevent damage (collapse or the like) to the pattern, particularly for a pattern having a pattern size of a submicron level. The light-shielding film 2 in the present invention can obtain a desired optical density (for example, 2.5 or more) even at a film thickness of 90 nm or less at an exposure wavelength of 200 nm or less. The lower limit of the thickness of the light shielding film 2 can be reduced as long as a desired optical density is obtained.

In the present invention, the light shielding film 2 includes a reflectance adjusting portion in the surface layer portion (upper layer portion) in order to reduce the reflectance with respect to the exposure light. In that case, as a reflectance adjustment part, materials, such as CrCO and CrCNO, are mentioned preferably, for example.
In the present invention, the reflectance adjusting part contains carbon, and the surface reflectance in the short wavelength region of 190 to 300 nm (especially around 200 nm) of the light shielding film is adjusted by the carbon content in the reflectance adjusting part. Yes. By providing this reflectance adjustment part containing carbon, the surface reflectance of the light shielding film in a short wavelength region of 190 to 300 nm (particularly in the vicinity of 200 nm) can be reduced to, for example, less than 20%. Since it can be preferably suppressed to 15% or less, when the mask pattern is transferred to the transfer target, multiple reflections with the projection exposure surface can be suppressed, and deterioration in imaging characteristics can be suppressed. Furthermore, it is desirable that the reflectance with respect to a wavelength (for example, 257 nm, 364 nm, 488 nm, etc.) used for defect inspection of a photomask blank or photomask is, for example, 30% or less in order to detect defects with high accuracy. In particular, by using a film containing carbon as the reflectance adjusting section, the reflectance with respect to the exposure wavelength in the short wavelength region is reduced as described above, and the reflectance with respect to the inspection wavelength (especially 257 nm) is 20% or less. This is desirable.

Specifically, the carbon content in the reflectance adjusting unit is preferably in the range of 1 to 20 atomic%. By containing carbon within the above range in the reflectance adjusting portion, an effect of sufficiently reducing the surface reflectance of the light shielding film in a short wavelength region of 190 to 300 nm (particularly in the vicinity of 200 nm) is obtained. When the carbon content is less than 1 atomic%, the effect of reducing the reflectance in the short wavelength region is reduced. On the other hand, if the carbon content is more than 20 atomic%, the tendency of the dry etching rate to decrease is not preferable. The more preferable carbon content is desirably 2 to 15 atomic%.

As described above, the light-shielding film can be formed by sputtering film formation using a target made of chromium. In that case, the light-shielding film film is formed by sputtering film formation in an atmosphere containing at least a hydrocarbon-based gas. A reflectance adjusting portion containing at least carbon can be formed in the upper layer portion. This reflectivity adjusting unit has a desired surface reflectivity in the short wavelength region of 190 to 300 nm (especially in the vicinity of 200 nm) of the light shielding film with respect to the hydrocarbon gas content and / or film formation pressure in the atmosphere. The film is formed by sputtering film formation by adjusting the reflectivity (for example, less than 20%). Examples of the hydrocarbon hydrogen gas include methane, propane, butane, and ethane. As the atmosphere containing the hydrocarbon gas, and a mixed gas atmosphere of an inert gas and methane, such as argon or helium (CH _4). As shown in FIGS. 6 and 7 described later (Examples), in the mixed gas atmosphere of argon and methane (CH ₄ ), the increase in the content of methane gas and / or the increase in the film formation pressure causes 190 to increase. The surface reflectance in a short wavelength region of ˜300 nm (particularly in the vicinity of 200 nm) can be reduced.

In this case, the correlation between the hydrocarbon gas content and / or film formation pressure in the atmosphere and the surface reflectance in the short wavelength region of 190 to 300 nm (particularly around 200 nm) of the light shielding film is obtained in advance. The hydrocarbon gas content and / or the film forming pressure in the atmosphere so that the surface reflectance becomes a desired reflectance (for example, less than 20%) is obtained from the correlation, and the hydrocarbon gas It is preferable to form the reflectance adjusting part by sputtering film formation in an atmosphere of the content of and / or film formation pressure.
Further, the light shielding film 2 may contain carbon in a layer (light shielding layer) other than the reflectance adjustment part of the surface layer part. In this case, it is preferable that the carbon content of the entire light shielding film including the carbon contained in the reflectance adjusting unit is 20 atomic% or less. When the carbon content is more than 20 atomic%, the dry etching rate is decreased, the dry etching time required for patterning the light shielding film by dry etching is increased, and it is difficult to reduce the thickness of the resist film. Absent. In addition, when carbon is included as the reflectance adjustment unit, the dry etching rate tends to decrease when the carbon content is large. Therefore, in order to shorten the dry etching time, the reflectance adjustment unit occupies the entire light shielding film. The ratio is desirably 0.45 or less, more preferably 0.30 or less, and still more preferably 0.20 or less.

In addition, you may provide a reflectance adjustment part also in the translucent board | substrate side as needed.
Further, the light shielding film 2 is different in content of chromium and elements such as oxygen, nitrogen, and carbon in the depth direction, and is stepwise in the reflectance adjustment part of the surface layer part and the other layers (light shielding layer). Alternatively, a composition gradient film having a composition gradient continuously may be used. In order to use such a light-shielding film as a composition gradient film, for example, a method of appropriately switching the type (composition) of the sputtering gas during the above-described sputtering film formation during film formation is suitable.

  The photomask blank may have a form in which a resist film 3 is formed on the light shielding film 2 as shown in FIG. The film thickness of the resist film 3 is preferably as thin as possible in order to improve the pattern accuracy (CD accuracy) of the light shielding film. In the case of a so-called binary mask photomask blank as in this embodiment, specifically, the thickness of the resist film 3 is preferably 300 nm or less. More preferably, it is 200 nm or less, and more preferably 150 nm or less. The lower limit of the thickness of the resist film is set so that the resist film remains when the light shielding film is dry etched using the resist pattern as a mask. In order to obtain high resolution, the resist film 3 is preferably a chemically amplified resist having high resist sensitivity.

Next, a method for manufacturing a photomask using the photomask blank 10 shown in FIG. 1 will be described.
The photomask manufacturing method using the photomask blank 10 includes a step of patterning the light-shielding film 2 of the photomask blank 10 using dry etching. Specifically, the photomask blank 10 is formed on the photomask blank 10. A step of performing desired pattern exposure (pattern drawing) on the resist film, a step of developing the resist film in accordance with the desired pattern exposure to form a resist pattern, and etching the light-shielding film along the resist pattern And a step of peeling and removing the remaining resist pattern.

FIG. 2 is a cross-sectional view sequentially illustrating a photomask manufacturing process using the photomask blank 10.
FIG. 2A shows a state in which a resist film 3 is formed on the light shielding film 2 of the photomask blank 10 of FIG. As the resist material, either a positive resist material or a negative resist material can be used.
Next, FIG. 2B shows a step of performing desired pattern exposure (pattern drawing) on the resist film 3 formed on the photomask blank 10. Pattern exposure is performed using an electron beam drawing apparatus or the like. As the above-mentioned resist material, those having photosensitivity corresponding to an electron beam or a laser are used.
Next, FIG. 2C shows a process of developing the resist film 3 in accordance with desired pattern exposure to form a resist pattern 3a. In this step, the resist film 3 formed on the photomask blank 10 is subjected to a desired pattern exposure, and then a developing solution is supplied to dissolve a portion of the resist film that is soluble in the developing solution. Form.

Next, FIG. 2D shows a step of etching the light shielding film 2 along the resist pattern 3a. Since the photomask blank of the present invention is suitable for dry etching, dry etching is preferably used for etching. In the etching process, the resist pattern 3a is used as a mask to remove the exposed portion of the light shielding film 2 on which the resist pattern 3a is not formed by dry etching, thereby allowing the desired light shielding film pattern 2a (mask pattern) to pass through. It is formed on the optical substrate 1.
For this dry etching, it is preferable for the present invention to use a chlorine-based gas or a dry etching gas composed of a mixed gas containing a chlorine-based gas and an oxygen gas. The light-shielding film 2 made of a material containing chromium and an element such as oxygen or nitrogen in the present invention can be dry-etched using the above-described dry etching gas to increase the dry etching rate. Since the etching time can be shortened, a light shielding film pattern having a good cross-sectional shape can be formed. Examples of the chlorine-based gas used for the dry etching gas include Cl ₂ , SiCl ₄ , HCl, CCl ₄ , and CHCl ₃ .

  In the case of a light-shielding film made of a material containing at least oxygen in chromium, chromyl chloride is generated by the reaction of oxygen, chromium, and chlorine-based gas in the light-shielding film. Therefore, a mixture of chlorine-based gas and oxygen gas is used for dry etching. When a dry etching gas made of a gas is used, the oxygen content in the dry etching gas can be reduced according to the oxygen content contained in the light shielding film. By performing dry etching using a dry etching gas with a reduced amount of oxygen in this way, the amount of oxygen that adversely affects the resist pattern can be reduced, preventing damage to the resist pattern during dry etching. Therefore, a photomask with improved pattern accuracy of the light shielding film can be obtained. Depending on the content of oxygen contained in the light shielding film, it is possible to use a dry etching gas not containing oxygen in which the amount of oxygen in the dry etching gas is zero.

FIG. 2E shows a photomask 20 obtained by peeling off and removing the remaining resist pattern 3a. In this way, a photomask having a light-shielding film pattern with a good cross-sectional shape formed with high accuracy is completed.
The present invention is not limited to the embodiment described above. That is, the photomask blank is not limited to a so-called binary mask photomask blank in which a light-shielding film is formed on a translucent substrate, and may be a photomask blank for use in manufacturing a halftone phase shift mask, for example. In this case, as shown in a second embodiment to be described later, a light shielding film is formed on the halftone phase shifter film on the translucent substrate, and the halftone phase shifter film and the light shielding film are combined. Since it is sufficient that a desired optical density (for example, 2.5 or more) is obtained, the optical density of the light shielding film itself can be set to a value smaller than 2.5, for example.

Next, a second embodiment of the photomask blank of the present invention will be described with reference to FIG.
The photomask blank 30 shown in FIG. 3A has a light-shielding film 2 including a halftone phase shifter film 4, a light-shielding layer 5 thereon, and a reflectance adjusting unit 6 on a light-transmitting substrate 1. Is. Since the translucent substrate 1 and the light shielding film 2 have been described in the first embodiment, description thereof is omitted.
The halftone phase shifter film 4 transmits light having an intensity that does not substantially contribute to exposure (for example, 1% to 30% with respect to the exposure wavelength) and has a predetermined phase difference. is there. The halftone type phase shifter film 4 has a light semi-transmitting portion obtained by patterning the halftone type phase shifter film 4 and light having an intensity that substantially contributes to the exposure without the halftone type phase shifter film 4 formed thereon. The light transmission part is made to transmit the light semi-transmission part so that the phase of the light is substantially inverted with respect to the phase of the light transmitted through the light transmission part. The light that passes through the vicinity of the boundary between the light and the light transmitting part and wraps around each other due to the diffraction phenomenon cancels each other, and the light intensity at the boundary is almost zero to improve the contrast or resolution of the boundary It is.

The halftone phase shifter film 4 is preferably made of a material having etching characteristics different from those of the light shielding film 2 formed thereon. For example, the halftone phase shifter film 4 includes a material mainly composed of metal such as molybdenum, tungsten, tantalum, and hafnium, silicon, oxygen, and / or nitrogen. The halftone phase shifter film 4 may be a single layer or a plurality of layers.
The light shielding film 2 in the second embodiment is set to have an optical density of 2.5 or more with respect to exposure light in a laminated structure in which a halftone phase shift film and a light shielding film are combined. The thickness of the light-shielding film 2 set as such is preferably 50 nm or less. The reason is the same as in the first embodiment, and it is considered that the formation of a fine pattern may be difficult due to the microloading phenomenon of the pattern during dry etching. In the present embodiment, the film thickness of the resist film formed on the reflectance adjusting unit 6 is preferably 250 nm or less. More preferably, it is 200 nm or less, and more preferably 150 nm or less. The lower limit of the thickness of the resist film is set so that the resist film remains when the light shielding film is dry etched using the resist pattern as a mask. As in the case of the above-described embodiment, in order to obtain high resolution, the resist film material is preferably a chemically amplified resist having high resist sensitivity.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. In addition, a comparative example for the embodiment will be described.
Example 1
A light-shielding film was formed on a translucent substrate made of synthetic quartz glass whose main surface and end face were precisely polished, and a photomask blank for a binary mask was produced.
A chromium target is used as a sputtering target on the substrate using an in-line sputtering apparatus, and a mixed gas of argon, nitrogen and helium (Ar: 30% by volume, N ₂ : 30% by volume, He: 40% by volume) A light shielding layer was formed by performing reactive sputtering in an atmosphere. During the formation of the light shielding layer, the total gas pressure of the sputtering apparatus was adjusted to 0.17 Pascal (Pa). Next, the total gas pressure of the sputtering apparatus is adjusted to 0.52 Pascal (Pa), and a mixed gas of Ar, Methane, and Helium (Ar: 48.75% by volume, CH ₄ : 11.25% by volume, He: 40% by volume) Reactive sputtering is performed in an atmosphere, and then by performing reactive sputtering in a mixed gas atmosphere of argon and nitric oxide (Ar: 90% by volume, NO: 10% by volume), the reflectivity is obtained. An adjustment part (antireflection layer) was formed. When forming the reflectance adjustment part, the amount of methane gas added in the atmosphere was 11.25% by volume, and the partial pressure of argon and methane gas in the mixed gas was adjusted to 0.52 Pascal (Pa). In this way, a photomask blank was obtained in which a light shielding layer having a total film thickness of 68 nm and a light shielding film composed of a reflectance adjusting unit was formed.

In addition, at the time of film formation of the reflectance adjusting unit, the methane gas addition amount (content) in the atmosphere is 0% (indicated by a in the figure), 8% by volume (indicated by b in the figure), 11.25 volume FIG. 6 shows changes in the surface reflectance spectrum of the light-shielding film when changed to% (indicated by c in the figure). Further, the amount of methane gas added to the atmosphere mixed gas is set to 11.25% by volume, and the gas pressure (deposition pressure) is set to 0.24 Pa (indicated by a in the figure) by increasing the flow rates of argon and methane gas. When changed to 32 Pa (indicated by b in the figure), 0.38 Pa (indicated by c in the figure), 0.46 Pa (indicated by d in the figure), 0.52 Pa (indicated by e in the figure) FIG. 7 shows changes in the surface reflectance spectrum of the light shielding film. From this result, it can be seen that the surface reflectance of the light-shielding film tends to decrease in the short wavelength region near 200 nm due to an increase in the amount of methane gas added and / or an increase in the film formation pressure.

According to the results of analysis of the formed light-shielding film by Auger spectroscopy (see FIG. 5), the light-shielding layer of the light-shielding film is slightly mixed with chromium and nitrogen, and oxygen and carbon used for forming the reflectance adjusting portion. A composition gradient film was obtained. Moreover, the reflectance adjusting part was a composition gradient film in which chromium, nitrogen, oxygen, and carbon were mixed. The carbon content in the reflectance adjusting part was 8 atomic%.
The light shielding film of this example had an optical density of 3.0. Further, the surface reflectance of the light shielding film with respect to the ArF excimer laser (wavelength 193 nm) was very low at 16.2%. Further, for the photomask defect inspection wavelength of 257 nm or 364 nm, they were 15.4% and 25.1%, respectively, and the reflectance was not problematic even in the inspection.

Next, using the obtained photomask blank, a photomask was produced according to the above-described process of FIG. That is, an electron beam resist (CAR-FEP171 manufactured by Fuji Film Electronics Materials), which is a chemically amplified resist, was spin-coated on the photomask blank 10 and subjected to a predetermined heat drying treatment.
Next, a desired pattern was drawn on the resist film formed on the photomask blank 10 using an electron beam drawing apparatus, and then developed with a predetermined developer to form a resist pattern 3a.

Next, the light shielding film 2 was dry-etched along the resist pattern 3a to form the light shielding film pattern 2a. As a dry etching gas, a mixed gas of Cl ₂ and O ₂ (Cl ₂ : O ₂ = 4: 1) was used. The etching rate at this time was 3.6 K / sec in terms of the total film thickness of the light shielding film / etching time, and was very fast. Further, the film reduction rate of the resist was 2.1 kg / sec, and the selectivity of the light-shielding film to the resist was 1.7. Thus, since the light shielding film 2 is thin, the etching rate is fast, and the etching time is also fast, the cross-sectional shape of the light shielding film pattern 2a is vertical and good. Further, the resist film remained on the light shielding film pattern 2a.
The remaining resist pattern was peeled off to obtain a photomask 20. The obtained photomask 20 maintained a very low reflectance of 16.2% for the surface reflectance of the light shielding film pattern at the exposure wavelength of 193 nm.

(Example 2)
FIG. 3 is a cross-sectional view showing a photomask blank according to the present embodiment and a photomask manufacturing process using the photomask blank. The photomask blank 30 of this example is formed from a halftone phase shifter film 4, a light shielding layer 5 thereon, and a reflectance adjusting unit 6 on a translucent substrate 1 as shown in FIG. The light shielding film 2 is formed.
The photomask blank 30 can be manufactured by the following method.
On the translucent substrate made of the same synthetic quartz glass as in Example 1, using a single-wafer sputtering apparatus, the sputtering target is a mixed target of molybdenum (Mo) and silicon (Si) (Mo: Si = 8: 92 mol). %), In a mixed gas atmosphere of argon (Ar) and nitrogen (N ₂ ) (Ar: N ₂ = 10 vol%: 90 vol%), by reactive sputtering (DC sputtering), molybdenum, silicon, and A halftone phase shifter film for ArF excimer laser (wavelength 193 nm) composed of a single layer containing nitrogen as a main component was formed to a thickness of 69 nm. This halftone phase shifter film is an ArF excimer laser (wavelength 193 nm), has a transmittance of 5.5% and a phase shift amount of about 180 °.

  Next, a light-shielding film composed of a light-shielding layer having a total film thickness of 48 nm and a reflectance adjusting portion was formed on the halftone phase shifter film in exactly the same manner as in Example 1. In addition, this light shielding film had an optical density of 3.0 in a laminated structure with a halftone phase shifter film. Further, the surface reflectance of the light shielding film at an exposure wavelength of 193 nm could be suppressed to a very low 16.2%. Further, for the photomask defect inspection wavelength of 257 nm or 364 nm, they were 15.4% and 25.1%, respectively, and the reflectance was not problematic even in the inspection.

Using the photomask blank for the halftone phase shift mask thus obtained, a halftone phase shift mask was produced as follows.
An electron beam resist film (CAR-FEP171 manufactured by Fuji Film Electronics Materials), which is a chemically amplified resist, was formed on the photomask blank 30. The resist film was formed by spin coating using a spinner (rotary coating apparatus). In addition, after apply | coating the said resist film, the predetermined | prescribed heat drying process was performed using the heat drying apparatus.
Next, a desired pattern was drawn on the resist film formed on the photomask blank 30 using an electron beam drawing apparatus, and then developed with a predetermined developer to form a resist pattern 7 (FIG. 3 ( b)).
Next, along the resist pattern 7, the light shielding film 2 composed of the light shielding layer 5 and the antireflection layer 6 was dry-etched to form a light shielding film pattern 2a (see FIG. 3C). As a dry etching gas, a mixed gas of Cl ₂ and O ₂ (Cl ₂ : O ₂ = 4: 1) was used. The etching rate at this time was 3.6 K / sec in terms of the total film thickness of the light shielding film / etching time, and was very fast. Thus, since the light shielding film 2 is thin, the etching rate is fast, and the etching time is also fast, the cross-sectional shape of the light shielding film pattern 2a is vertical and good. Further, the pattern accuracy of the light shielding film 2 was also good. Further, the resist film remained on the light shielding film pattern 2a.

Next, the halftone phase shifter film 4 was etched using the light shielding film pattern 2a and the resist pattern 7 as a mask to form a halftone phase shifter film pattern 4a (see FIG. 4D). The etching of the halftone phase shifter film 4 is affected by the cross-sectional shape of the light-shielding film pattern 2a, and therefore the cross-sectional shape of the light-shielding film pattern 2a is good. The shape was also good.
Next, after the remaining resist pattern 7 is peeled off, a resist film 8 is applied again, pattern exposure is performed to remove an unnecessary light-shielding film pattern in the transfer region, and then the resist film 8 is developed to form a resist. A pattern 8a was formed (see FIGS. 9E and 9F). Next, an unnecessary light shielding film pattern was removed using wet etching, and the remaining resist pattern was peeled off to obtain a photomask 40 (see FIG. 5G).

  In the example shown in FIG. 3G, a light shielding film is formed on the phase shifter film in the peripheral region other than the transfer region (mask pattern formation region). This light-shielding film prevents exposure light from passing through this peripheral area, and solves the problem that defects may occur due to overlapping exposure in the peripheral area when pattern transfer is performed using a mask. It is to do. As shown in FIG. 4, in the region where the mask pattern of the phase shifter film is formed, a light shielding film can be formed in a portion excluding the boundary portion with the light transmitting portion in the mask pattern ( See Example 3 below). The present invention is particularly suitable for a halftone phase shift mask in which a light shielding film pattern is formed on a phase shifter film even in such a transfer region.

(Example 3)
On a light-transmitting substrate made of the same synthetic quartz glass as in Example 1, using a single-wafer sputtering apparatus, a mixed target of tantalum (Ta) and hafnium (Hf) (Ta: Hf = 90: 10 at) is used as a sputtering target. %), And a TaHf film having a thickness of 75 mm is formed by DC magnetron sputtering in an argon (Ar) gas atmosphere, and then reacted in a mixed gas atmosphere of argon, oxygen, and nitrogen using a Si target. A SiON film (Si: O: N = 40: 27: 33 at%) having a thickness of 740 mm was formed by reactive sputtering. That is, a half-tone phase shifter film for an ArF excimer laser (wavelength 193 nm) composed of a TaHf film as a lower layer and an SiON film as an upper layer was formed. This halftone phase shifter film has an ArF excimer laser (wavelength: 193 nm) and has a high transmittance of 15.0% and a phase shift amount of about 180 °.

Next, a light-shielding film composed of a light-shielding layer having a total film thickness of 48 nm and a reflectance adjusting portion was formed on the halftone phase shifter film in the same manner as in Example 1. This light-shielding film had an optical density of 3.0 in a laminated structure with the halftone phase shifter film. Further, the surface reflectance of the light shielding film at an exposure wavelength of 193 nm could be suppressed to a very low 16.2%. Further, for the photomask defect inspection wavelength of 257 nm or 364 nm, they were 15.4% and 25.1%, respectively, and the reflectance was not problematic even in the inspection.
Using the photomask blank for the halftone phase shift mask obtained in this way, the halftone phase shift mask shown in FIG. The obtained photomask 20 maintained a very low reflectance of 16.2% for the surface reflectance of the light shielding film pattern at the exposure wavelength of 193 nm.

In this embodiment, as shown in FIG. 4, without removing the light-shielding film pattern in the transfer region, the light transmission part in the mask pattern (the part where the mask pattern is not formed and the transparent substrate is exposed) A light shielding film was formed on the portion excluding the boundary portion.
The halftone phase shift mask shown in FIG. 4 is in the region where the mask pattern of the phase shifter film is formed, and the light transmitting portion in the mask pattern (the mask pattern is not formed and the transparent substrate is exposed). By forming a light-shielding film in a portion excluding the boundary portion with the portion), light shielding of a portion that is originally desired to be completely shielded from light is made more complete. That is, in the region where the mask pattern is formed, the function originally required for the phase shifter film which is the mask pattern can pass light whose phase is shifted only at the boundary with the light transmitting portion. This is because it is desirable that the other most part (the part excluding the boundary part) should be completely shielded from light. When a phase shifter film having a high transmittance for exposure light is provided as in this embodiment, the photomask form of this embodiment is particularly suitable.

(Comparative example)
On the translucent substrate made of the same synthetic quartz glass as in Example 1, an inline sputtering apparatus was used, a chromium target was used as a sputtering target, and a mixed gas of argon and nitrogen (Ar: 80% by volume, N ₂ : Reactive sputtering is performed in an atmosphere of 20 volume%, gas pressure: 0.3 Pascal, and then mixed gas of argon, methane and helium (Ar: 32 volume%, CH ₄ : 8 volume%, He: 60 volume%) Gas pressure: 0.3 Pascal) A light shielding layer was formed by performing reactive sputtering in an atmosphere. Subsequently, the reflectance adjustment unit was formed by performing reactive sputtering in a mixed gas atmosphere of argon and nitric oxide (Ar: 90% by volume, NO: 10% by volume, gas pressure: 0.3 Pascal). In this way, a light-shielding film composed of a light-shielding layer having a total film thickness of 68 nm and a reflectance adjusting unit was formed.
The light shielding film of this comparative example had an optical density of 3.0. The surface reflectance of this light-shielding film at an exposure wavelength of 193 nm was 24.2%. In addition, at the time of film formation of the reflectance adjusting unit, the ratio of nitric oxide in the atmosphere is increased or the flow rate of nitric oxide is increased, but the minimum point where the surface reflectance becomes the smallest is effective. Even when the wavelength was changed to the short wavelength side and the low reflection side, the surface reflectance at the exposure wavelength of 193 nm of the light shielding film did not decrease from 20.0%.

  Next, using the obtained photomask blank, a photomask was produced in the same manner as in Example 1 described above. The dry etching rate of the light shielding film was 1.9 Å / sec in terms of the total film thickness of the light shielding film / etching time, and was very slow. Thus, since the light shielding film of this comparative example has a high etching rate and a long etching time, the cross-sectional shape of the formed light shielding film pattern was also poor. Also, the damage to the resist film was significant. In addition, since the surface reflectance at the exposure wavelength of 193 nm of the light-shielding film of this comparative example is 24.2%, which is higher than that of the above-described embodiment, projection exposure is performed when a mask pattern is transferred using a photomask. It is conceivable that multiple reflections occur with the surface and a desired pattern transfer cannot be performed.

It is sectional drawing which shows one Embodiment of the photomask blank obtained by this invention. It is sectional drawing which shows the manufacturing process of the photomask using a photomask blank. It is sectional drawing which shows the manufacturing process of the photomask blank which used the photomask blank which concerns on 2nd embodiment of this invention, and this photomask blank. It is sectional drawing which shows other embodiment of the halftone type | mold phase shift mask obtained by this invention. It is a figure which shows the result by the Auger spectroscopic analysis of the light shielding film of an Example. It is a figure which shows the surface reflectance spectrum change by the methane gas addition amount increase in the atmosphere at the time of the reflectance adjustment part film-forming. It is a figure which shows the surface reflectance spectrum change by the film-forming pressure rise at the time of film-forming of a reflectance adjustment part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Translucent substrate 2 Light-shielding film 3 Resist film 4 Halftone type phase shifter film 5 Light-shielding layer 6 Antireflection layer 2a Light-shielding film pattern 3a Resist pattern 10, 30 Photomask blank 20, 40 Photomask

Claims (8)

In a method for manufacturing a photomask blank having a light-shielding film made of a material containing chromium on a light-transmitting substrate,
The light-shielding film is formed by forming a reflectance adjustment part containing at least carbon in an upper layer part of the light-shielding film,
The reflectance adjusting unit is formed by sputtering film formation using a target containing chromium so that the surface reflectance in a wavelength range of 190 to 300 nm is less than 20% in an atmosphere containing at least a hydrocarbon gas .
In the sputtering film formation, the correlation between the hydrocarbon gas content and / or film formation pressure in the atmosphere and the surface reflectance in the short wavelength region of 190 to 300 nm of the light shielding film is obtained in advance. Based on the obtained hydrocarbon gas content and / or film formation pressure in the atmosphere where the surface reflectance is less than 20%, and based on the obtained hydrocarbon gas content and / or film formation pressure Done
The method of manufacturing a photomask blank, wherein the correlation is a relationship in which the surface reflectance in the vicinity of 200 nm is reduced by increasing the hydrocarbon gas content and / or increasing the film forming pressure . 2. The photomask blank manufacturing method according to claim 1, wherein the correlation is a relationship in which a minimum point at which the surface reflectance is minimized is shifted to a short wavelength side as the deposition pressure of hydrocarbon gas is increased. Method.   The method for manufacturing a photomask blank according to claim 1, wherein the light shielding film further contains at least one of oxygen and nitrogen.   4. The method of manufacturing a photomask blank according to claim 1, wherein a halftone phase shifter film is formed between the translucent substrate and the light shielding film. 5.   5. The method for producing a photomask blank according to claim 4, wherein the transmittance of the halftone phase shifter film in a short wavelength region of 150 to 200 nm is 10% or more and 40% or less.   The photomask blank is a photomask blank for dry etching corresponding to a photomask manufacturing method for patterning the light shielding film by dry etching using a resist pattern formed on the light shielding film as a mask. A method for producing a photomask blank according to any one of claims 1 to 5.   A method for manufacturing a photomask, comprising: a step of patterning the light-shielding film in the photomask blank obtained by the manufacturing method according to claim 1 by a dry etching process.   The said light shielding film in the photomask blank obtained by the manufacturing method of Claim 4 or 5 is patterned by dry etching process, and after forming a light shielding film pattern on the said halftone type phase shifter film, this light shielding film pattern The halftone phase shifter film is patterned by a dry etching process using the mask as a mask to form a halftone phase shifter film pattern on the translucent substrate.

Images