WO2006028168A1 - フォトマスクブランク及びフォトマスク - Google Patents
フォトマスクブランク及びフォトマスク Download PDFInfo
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- WO2006028168A1 WO2006028168A1 PCT/JP2005/016511 JP2005016511W WO2006028168A1 WO 2006028168 A1 WO2006028168 A1 WO 2006028168A1 JP 2005016511 W JP2005016511 W JP 2005016511W WO 2006028168 A1 WO2006028168 A1 WO 2006028168A1
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- film
- light
- transition metal
- photomask
- shielding film
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals 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
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals 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
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/46—Antireflective coatings
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals 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
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals 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
- G03F1/54—Absorbers, e.g. of opaque materials
- G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals 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
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
Definitions
- the present invention relates to a photomask blank and a photomask used for fine processing of semiconductor integrated circuits, CCDs (charge coupled devices), color filters for LCDs (liquid crystal display devices), magnetic heads, and the like.
- CCDs charge coupled devices
- LCDs liquid crystal display devices
- magnetic heads and the like.
- circuit patterns have become increasingly finer, especially due to the high integration of large-scale integrated circuits.
- circuit patterns there is an increasing demand for miniaturization technology of contact hole patterns for wiring between layers constituting cells. Therefore, even in the manufacture of photomasks with circuit patterns written in optical lithography that forms these wiring patterns and contact hole patterns, circuit patterns can be written more finely and accurately with the above miniaturization.
- the circuit pattern to be drawn is a size that is considerably smaller than the wavelength of the light to be used. If a photomask pattern that is four times the shape of the circuit is used as it is, The shape according to the photomask pattern is not transferred to the resist film due to the influence of light interference or the like generated during actual photolithography. Therefore, in order to reduce these effects, the photomask pattern covers a more complex shape than the actual circuit pattern (a shape that applies so-called OPC: Optical and Process Correction). Needs may also arise. Therefore, photomask Even in lithography technology for obtaining patterns, more accurate processing methods are currently required. Lithography performance may be expressed at the limit resolution. This resolution limit is equivalent to or higher than the resolution limit required for optical lithography used in semiconductor processing processes using photomasks. The critical resolution accuracy is required for lithography technology in the photomask-cage process.
- a photoresist film is usually formed on a photomask blank having a light-shielding film on a transparent substrate, the pattern is drawn with an electron beam !, and the resist pattern is developed through development. Then, using the obtained resist pattern as an etching mask, the ability to etch the light-shielding film and process it into the light-shielding pattern
- the resist film thickness is the same as before the miniaturization If the processing is carried out while maintaining the film thickness, the ratio of the film thickness to the pattern, the so-called aspect ratio, increases, the pattern shape of the resist deteriorates, and the pattern transfer cannot be performed properly. Or cause peeling. Therefore, it is necessary to reduce the resist film thickness with miniaturization.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-195479
- Patent Document 2 Japanese Patent Application Laid-Open No. 2003-2003
- Patent Document 3 Japanese Patent No. 3093632 Publication
- Patent Document 3 have reported chromium compound films having a film thickness of 50 to 77 nm.
- chlorine-based dry etching containing oxygen which is a general dry etching condition for chromium-based films such as chromium compound films, often has a property of etching to an organic film to some extent.
- etching with a very thin resist film it is very difficult to obtain resist with high resolution that makes it difficult to accurately transfer the resist pattern and etching resistance that enables high-precision etching at the same time. It is a problem. Therefore, in order to achieve high resolution and high accuracy, it is necessary to reexamine the light shielding film material that should be switched from a method that relies only on resist performance to a method that improves the performance of the light shielding film.
- Patent Document 5 Japanese Patent Laid-Open No. Sho 63-85553
- metal silicide films that can be etched more easily under the etching conditions by fluorine-based dry etching that do not easily damage the resist film, in particular, molybdenum silicide films, have been studied for a long time.
- Patent Document 5 Japanese Patent Laid-Open No. 63-85553
- Patent Document 6 Japanese Patent Laid-Open No. 1-142637
- Patent Document 7 Japanese Patent Laid-Open No. 3-116147
- the metal silicide film is also insufficient in chemical stability for chemical cleaning in the final process of photomask fabrication. In particular, when the film thickness is reduced, the physical properties required for the film in the cleaning process may be impaired. .
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-195479
- Patent Document 2 Japanese Patent Laid-Open No. 2003-195483
- Patent Document 3 Japanese Patent No. 3093632
- Patent Document 4 Japanese Patent Laid-Open No. 2001-312043
- Patent Document 5 Japanese Patent Laid-Open No. 63-85553
- Patent Document 6 Japanese Patent Laid-Open No. 1-142637
- Patent Document 7 Japanese Patent Laid-Open No. 3-116147
- Patent Document 8 Japanese Patent Laid-Open No. 4-246649
- Patent Document 9 Japanese Patent Laid-Open No. 7-140635
- the present invention has been made to solve the above problems, and is a photolithographic device that exposes light using an exposure wavelength of 250 nm or less, such as a finer photomask pattern, particularly an ArF excimer laser.
- a photomask blank that can achieve both high resolution and high-precision etching in the photomask used therefor, that is, an etching mask.
- An object of the present invention is to provide a photomask in which a mask pattern is formed using.
- the present inventor contains a light and an exposure wavelength of 250 nm or less, particularly, an ArF excimer laser, with a specific ratio of silicon and transition metal.
- the film was found to have higher light-shielding properties than the conventionally used chromium-based film, and the chemical stability that was previously considered to be low is stable within this specific ratio range.
- the inventors have made the present invention.
- the present invention provides the following photomask blank and photomask.
- a photomask blank which is a photomask material provided with a mask pattern having a transparent area for exposure light and an effective opaque area on a transparent substrate, and another film ( One or two or more light shielding films are formed with or without A), and at least one of the layers constituting the light shielding film (B) contains, as main components, silicon and a transition metal.
- At least one of the layers constituting the light shielding film (B) is further composed of oxygen, nitrogen and carbon. 3.
- An antireflection film is further laminated on the light shielding film, and the antireflection film is made of transition metal silicide oxide, transition metal silicide nitride, transition metal silicide oxynitride, transition metal silicide oxycarbide, transition metal silicide.
- An antireflection film is further laminated on the light shielding film, and the antireflection film is mainly composed of chromium oxide, chromium nitride, chromium oxynitride, chromium oxycarbide, chromium nitride carbide, or chromium oxynitride carbide.
- a mask pattern having a region transparent to exposure light and an effective opaque region is formed on a transparent substrate using the photomask blank according to any one of claims 1 to 8. Characteristic photomask.
- the antireflection film may be a transition metal silicide oxide, a transition metal silicide nitride, a transition metal silicide.
- the light shielding film and the antireflection film must be fluorine-based dry. Since etching can be performed by etching, particularly high etching cacheability can be obtained.
- the antireflection film is a chromium compound such as chromium oxide, chromium nitride, chromium oxynitride, chromium oxycarbide, chromium nitride carbide, or chromium oxynitride carbide
- the light shielding film is thin enough to be processed with a resist film, so that it can be processed without damaging the resist, and the chemical stability during cleaning is satisfactory.
- the light-shielding film of the photomask blank has the structure of the present invention
- a photomask blank having a light-shielding film with high light-shielding properties and chemical stability is obtained, and when an antireflection film is further laminated.
- the resist can be formed with a relatively thin thickness because it can be covered with etching conditions or etching time with little damage to the resist during etching, thereby increasing the aspect ratio of the resist film.
- Various problems can be avoided, and a more accurate photomask pattern can be formed.
- FIG. 1 is a schematic view showing a DC sputtering apparatus provided with two targets used in an example.
- FIG. 2 is a graph showing the film thickness dependence of the optical density of the light shielding film of Example 1 with respect to light having wavelengths of 248 nm and 193 nm.
- FIG. 3 is a graph showing the film thickness dependence of optical density with respect to light with a wavelength of 193 nm of the light shielding films of Example 1 and Comparative Examples 1 and 2.
- FIG. 4 is a graph showing the film thickness dependence of optical density with respect to light having a wavelength of 193 nm of a chromium film.
- FIG. 5 is a graph showing the wavelength dependence of the optical density of the light-shielding film of Example 1.
- FIG. 6 is a graph showing the wavelength dependence of the reflectance of the antireflection film of the photomask blanks of Examples 6 to 9. BEST MODE FOR CARRYING OUT THE INVENTION
- the photomask blank of the present invention is an area that is transparent to exposure light on a transparent substrate, that is, an area that is effectively opaque when used as a photomask for pattern exposure.
- the light shielding film may be a single layer film or a multilayer film, but at least one of the layers constituting this film contains a key element and a transition metal.
- the film is a single-layer film.
- a tungsten layer, a tantalum layer, or the like is used as a layer other than the layer containing the above-mentioned key and transition metal, and in particular, between the layer containing the above-mentioned key and transition metal and the transparent substrate. Formed into! /
- the light-shielding film is required to have chemical stability so that the film thickness does not change during cleaning, and the photomask for ArF is required to have a change in film thickness of 3 nm or less due to cleaning. It must be noted that the light-shielding film is damaged and the light-shielding performance is impaired in the cleaning conditions essential in the mask manufacturing process, especially in the cleaning with sulfuric acid hydrogen peroxide solution (sulfuric acid / hydrogen peroxide). . In addition, it is necessary to pay attention to the conductivity of the film in order to avoid the occurrence of charge-up when it is irradiated with an electron beam in the lithography process for forming the mask pattern.
- the chemical stability and conductivity of the light-shielding film are within the range of acceptable physical properties that do not cause a problem in practice. It can be.
- Transition metals constituting the light-shielding film include molybdenum, tantalum, tungsten, and cover. Examples of suitable materials such as iron, nickel, vanadium, titanium, niobium, zirconium, hafnium, etc. Molybdenum is the most preferred dry etching cache point.
- the film formed on the photomask In order for the film formed on the photomask to function as having sufficient light-shielding properties, in a binary mask blank having a light-shielding film and an antireflection film that are generally used, The light-shielding film and the antireflection film are combined.In the halftone phase shift mask blank, the halftone phase shift film, the light-shielding film, and the antireflection film are combined, and the optical density OD is 2. It is required to be 5 or more, especially 2.8 or more, especially 3.0 or more.
- the above-mentioned film mainly composed of a key metal and a transition metal contains light elements such as oxygen, nitrogen, and carbon as other components even if the film substantially includes only the key element and the transition element.
- the ArF excimer with a wavelength of 193 nm to which the photomask blank of the present invention is particularly preferably applied As photomask blanks for laser exposure, the nitrogen and carbon content should be 20 atom% or less, the oxygen content should be 10 atom% or less, especially the total of nitrogen, carbon and oxygen should be 40 atom% or less. Is preferred.
- the thickness of the light shielding film is preferably 20 to 50 nm! If the film thickness is less than 20 nm, a sufficient light-shielding effect may not be obtained.If it exceeds 50 nm, high-precision processing becomes difficult with a thin resist with a thickness of 250 nm or less, and the film stress causes warping of the substrate. There is a risk that
- the light-shielding film can be formed by a known method, but the film formation by sputtering is commonly used as the most easy method for obtaining a film having excellent homogeneity, and the sputtering method is preferable also in the present invention.
- This is a film forming method.
- a target in which the content ratio of the key element to the transition metal is adjusted to 4: 1 to 15: 1 may be used alone, or from the target element, the transition metal target, and the key element and the transition metal.
- the target (transition metal silicide target) force may be appropriately selected, and the sputtering area of the target or the power applied to the target may be adjusted to adjust the ratio of the key to the transition metal.
- light-shielding films contain light elements such as oxygen, nitrogen, and carbon
- reactive sputtering is performed by appropriately introducing oxygen-containing gas, nitrogen-containing gas, and carbon-containing gas as the reactive gas into the sputtering gas. It is possible to form a film.
- an antireflection film can be further laminated on the light shielding film as described above.
- the antireflection film basically, any known one can be used. In view of the force workability, there are two configurations.
- the first is an antireflection film suitable for the case where an antireflection film and a light shielding film are etched simultaneously using a resist as an etching mask.
- the main component is a transition metal silicide compound such as silicide oxynitride, transition metal silicide oxycarbide, transition metal silicide oxynitride, transition metal silicide oxynitride carbide.
- molybdenum is most preferred.
- the film thickness of this antireflection film varies depending on the wavelength of light used for inspection necessary for the production or use of the photomask, but an antireflection effect is usually obtained by setting the film thickness to 15 to 30 nm.
- the light shielding film and the antireflection film can be etched by one etching process to form a light shielding pattern.
- Such an antireflection film can be obtained by a known method. Commonly used methods are a key target, a transition metal target, and a target composed of a key and a transition metal.
- Metal silicide target force A method in which a target is appropriately selected and reactive sputtering is performed in a reactive gas or a mixed gas stream of a reactive gas and an inert gas such as argon (for example, Patent Document 9: 7—See 140635.
- another aspect of the antireflection film is one comprising, as a main component, a chromium compound such as chromium oxide, chromium nitride, chromium oxynitride, chromium oxide carbide, chromium nitride carbide, or chromium oxynitride carbide.
- a chromium compound such as chromium oxide, chromium nitride, chromium oxynitride, chromium oxide carbide, chromium nitride carbide, or chromium oxynitride carbide.
- the light shielding film of the present invention cannot be etched.
- the antireflection film of the chromium compound When an anti-reflection film is used as an etching mask and a light-shielding film containing silicon and a transition metal is etched by fluorine-based dry etching, the anti-reflection film functions as an etching mask due to the high etching resistance of the chromium compound. Etching can be expected, and it is suitable, for example, when digging deeply at this etching stage, such as when used as a Levenson mask.
- the optical density OD with respect to exposure light is 0.3 or more and 1.5 or less, preferably 0.5 or more 1 It is preferable to set it to be in the range of 0 or less.
- the film thickness of this anti-reflective film varies depending on the wavelength of light used for the inspection required when manufacturing or using a photomask. Usually, an anti-reflective effect is obtained by setting the film thickness to 15 to 30 nm, especially for ArF exposure. Is preferably 20 to 25 nm.
- Such an antireflection film is a force that can be obtained by a known method.
- a commonly used method uses a chrome target, and a reactive gas or a mixed gas stream of a reactive gas and an inert gas such as argon is used. (See, for example, Patent Document 9: Japanese Patent Publication No. 7-140635).
- the above-described light shielding film and antireflection such as an etch stopper film, a semi-transparent film, a phase shift film such as a MoSi type and a MoZrSi type, etc.
- Other films different from the film can be provided.
- a resist pattern for writing a circuit diagram is formed on a photomask blank having an antireflection film of a transition metal silicide compound.
- a surface treatment for reducing the surface energy of the substrate (photomask blank) surface before applying the resist.
- the most preferable treatment method is a method in which the surface is alkylsilylated with HMDS or other organosilicon surface treatment agent commonly used in the semiconductor manufacturing process.
- a method of directly applying to is preferably used. By performing this process, it is possible to reduce the occurrence of problems such as fine pattern peeling and falling.
- a resist is applied on the substrate (photomask blank) subjected to the surface treatment and dried to obtain a resist film.
- the resist must be selected according to the lithography system used. For EB lithography that is normally used, a positive or negative resist having an aromatic skeleton in the polymer, and For production of a photomask for a fine pattern in which the present invention is particularly effectively used, it is preferable to use a chemically amplified resist.
- the resist film thickness needs to be in a range where a good pattern shape can be obtained and can function as an etching mask, but particularly when trying to form a fine pattern as an ArF exposure mask.
- the film thickness is preferably 350 nm or less, and more preferably 250 nm or less.
- the lower limit of the resist film thickness is a force due to the etching resistance of the resist. Generally, 75 nm or more is preferable, and more preferably lOOnm or more.
- a method using EB irradiation for drawing on a resist, there is a method using EB irradiation or a method using light irradiation.
- a method using EB irradiation is a preferable method for forming a fine pattern.
- the energy in the range of usually 3 ⁇ 30MCZcm 2 is used, and then the resist film is developed to obtain a resist pattern.
- the light shielding film is etched using the resist pattern obtained above as an etching mask.
- Etching is performed by known fluorine-based dry etching, and in the case of the antireflection film of this aspect, the antireflection film and the light shielding film can be etched simultaneously. It is also possible to etch the light-shielding film by chlorine dry etching after etching the antireflection film. In this case, the transition metal silicide compound film containing a large amount of oxygen is not etched, and the oxygen content is low. Since the transition metal silicide compound film is etched, if the oxygen content of the antireflection film is set higher than the oxygen content of the light shielding film, the antireflection film can be used as an etching mask. Accurate machining can be performed.
- the resist is peeled off with a predetermined stripping solution to obtain a photomask on which the light shielding film pattern is formed.
- a typical phase shift material such as an acid silicate film or a semi-transparent film such as a metal silicide oxynitride film is used. Since the metal silicide compound film can be etched at the same time under the condition for etching the light shielding film, it is also preferable to apply the present invention to a halftone phase shift mask or a Levenson mask.
- phase shift mask in general, after the phase shift pattern is formed, a part of the light shielding film pattern is removed.
- the antireflection film and the light shielding film can be removed by fluorine-based dry etching.
- the end of etching of the light shielding film can be determined by a known method, for example, detection of etching atoms or detection of reflectance.
- overetching can be prevented by etching the antireflection film and then removing the light shielding film by etching using chlorine-based dry etching.
- the photomask blank is covered with a mask.
- a case where an auto mask is manufactured will be described.
- the resist pattern can be obtained by the same operation as that in which the antireflection film is a transition metal silicide compound.
- the next dry etching process can be performed by chlorine dry etching, particularly chlorine dry etching in which oxygen is contained in chlorine. In this chlorine-based dry etching, an organic film such as a resist is etched compared to fluorine-based etching.
- the etching is changed to fluorine-based dry etching.
- the chromium compound film which is an antireflection film
- the photomask is completed by removing the resist by a predetermined method.
- a chromium compound antireflection film can be used as an etching mask. This is advantageous when it is necessary to dig deeply and accurately in the lower layer.
- the photomask obtained by the above process is completed by final cleaning with sulfuric acid / hydrogen peroxide solution and Z or ammonia water / hydrogen peroxide solution.
- the light-shielding film has chemical stability that can withstand the cleaning conditions. If this is the case, the light-shielding film part will be more etched than the anti-reflection film, especially binary masks and high transmission halftone masks. Tritone masks using blanks greatly reduce mask accuracy, and even if there is a light-shielding film only on the outer periphery, as in the case of low-transmission halftone masks, problems arise due to the reduced antireflection function. .
- the film thickness change amount under both conditions is 5 nm or less, especially 3 nm or less.
- the film thickness change amount in such a resistance test satisfies the above range and is excellent in chemical stability (chemical resistance).
- a photomask blank with a light-shielding film formed on the substrate was fabricated by the method described below. Using a DC sputtering system with two targets as shown in Fig. 1, the silicon and molybdenum were formed on the quartz substrate.
- a light shielding film consisting of In FIG. 1, 1 is a substrate, 101 is a chamber, 102a and 102b are targets, 103 is a sputter gas inlet, 104 is an exhaust port, 105 is a substrate turntable, and 106a and 106b are power supplies.
- the sputtering gas was introduced in a predetermined amount shown in Table 1, and the gas pressure in the sputtering chamber was set to 0.05 Pa.
- the Mo target as the transition metal source and the Si (single crystal) target as the key source
- a predetermined discharge power shown in Table 1 is applied to each target.
- the MoSi film or MoSiON film is formed to a predetermined film thickness by adjusting the film formation time so that the content ratios of silicon and molybdenum are as shown in Table 1. Filmed.
- Table 1 also shows the light element content (measured by ESCA) in the obtained light-shielding film.
- sulfuric acid sulfuric acid: hydrogen peroxide
- the conductivity of the light-shielding film was measured using a MCP-T600, a 4-end needle sheet resistance meter manufactured by Mitsubishi Chemical Corporation. The results are shown in Table 2.
- Thickness 14 Thickness 24 nm Thickness 32 nm Thickness 46 nm
- the light shielding film of Example 1 has an optical density of about 3.0 at a wavelength of 193 nm and 248 nm at a film thickness of about 40 nm, and is a chromium-based light shielding film (FIG. 4). It can be seen that the light-shielding property superior to that of the reference can be secured.
- the light shielding film of Comparative Example 1 has an optical density of about 2.5 at a wavelength of 193 nm, as shown in FIG. 3, and is compared with the metal chromium light shielding film (see FIG. 4). As a result, there was no significant difference in light-shielding performance.
- the light-shielding film of Comparative Example 3 does not satisfy the conductivity with high sheet resistance.
- the photomask blank of the present invention can secure an optical density of about 3 with a film thickness of about 40 nm for light having a wavelength of 248 nm or less by the light shielding film. It was confirmed that the photomask blank and the photomask obtained from the photomask blank were superior in light-shielding properties compared to those using a chromium-based film as a conventional light-shielding film. This makes it possible to reduce the thickness of the light-shielding film, thereby reducing the dry etching time. This means that the patterning accuracy can be improved by the thin film of the resist film thickness.
- the photomask blank of the present invention has a light-shielding film that is excellent in resistance to ammonia and hydrogen peroxide, which are common cleaning liquids in the mask manufacturing process, and the pattern dimensions even when cleaning is repeated. It can be seen that the fluctuation can be minimized.
- a photomask blank (binary mask blank) in which a light shielding film and an antireflection film were formed on a substrate was produced by the method described below.
- the gas pressure in the chamber was set to 0.1 lPa.
- the target is a Mo target as a transition metal source and a Si (single crystal) target as a key source.
- a discharge power of 150 W is applied to the Mo target and 850 W is applied to the Si target.
- Chromium compound anti-reflection coating (Examples 10 to 12)
- a chromic oxynitride antireflection film was formed on the light shielding film using a commonly used single target magnetron DC sputtering apparatus.
- Ar gas 10 sccm, N gas 30 sccm and O gas 15 sccm were introduced as the sputtering gas.
- the gas pressure in the chamber was set to 0.1 lPa.
- a Cr target is used as the target, a 1000 W discharge power is applied to the Cr target, the CrON film is adjusted while rotating the substrate at 30 rpm, and the film formation time shown in Table 4 is adjusted. Thick A film was formed.
- the optical density of the light shielding film at the time of entering light from the transparent substrate side was measured with the spectrophotometer with the spectrophotometer.
- the results are shown in Table 5.
- the film thickness of the antireflection film is 23 nm (48 nm when combined with the light shielding film) and the light density is 193 nm, the optical density is about 3.0. Since a total film thickness of about 56 nm is usually required, it can be seen that a thin film can be formed even when the photomask blank of the present invention is formed by laminating a light shielding film and an antireflection film.
- the change in reflectivity after 1 hour of immersion was measured with a spectrophotometer UV-2400PC manufactured by Shimadzu Corporation.
- the change in reflectance at a wavelength of 365 nm was 1% or less under any condition, confirming that there were no practical problems.
- a resist pattern was formed by electron beam lithography using a chemically amplified resist (film thickness 180 nm), and this was used as an etching mask for CF.
- the etching cross-sectional shape is good, no step is confirmed between the light shielding film and the antireflection film, and the light shielding film and the antireflection film can be patterned with one operation by fluorine-based dry etching. I was able to confirm.
- this CrON antireflection film can be used as a hard mask for patterning the light shielding film.
- the photomask blank force of the present invention can also dramatically reduce the required film thickness of a resist when manufacturing a photomask.
- a halftone phase shift mask blank was prepared and processed into a halftone phase shift mask as follows. First, MoZrSi sintered body and Si single crystal are used as sputtering targets, and MoZrSi
- the substrate is 30rpm
- Sputter film formation was performed while rotating at 1 to form a first layer having a thickness of 1 Onm on a 6-inch square quartz substrate.
- As sputtering gas 8 sccm Ar, 20 sccm N and 5 sccm
- a mixed gas of O was introduced.
- the gas pressure during sputtering is set to 0.15 Pa.
- the discharge power is set to MoZrSi target power 30W and Si target 1000W.
- the second layer having a thickness of 40 nm shown in Table 1 was formed at a gas pressure of 0.25 Pa while changing the substrate at 30 rpm.
- the discharge power is set to MoZrSi target power 30W and Si target 1000W.
- a third layer having a thickness of 20 nm was formed at a gas pressure of 0.1 lPa to obtain a halftone phase shift film.
- a molybdenum silicide light-shielding film and a molybdenum silicide nitride anti-reflection film similar to those in Example 6 are formed on the halftone phase shift film by the same method as in Example 6.
- the thickness of the film was 10 nm
- the thickness of the antireflection film was 20 nm
- a black-tone phase shift mask blank having a light shielding film and an antireflection film was obtained.
- the anti-reflection film, the light shielding film, and the noise tone phase shift film were etched.
- the etching end point was also determined by the reflectivity changing force by the reflectivity monitor.
- the resist pattern was peeled off by a conventional method, and a negative resist was formed again by coating. After irradiating the outer frame part where the light shielding pattern is left on this, in order to further protect the substrate surface of the part where the halftone pattern has already been removed by etching, the entire substrate is irradiated from the back side with light.
- each membrane ethtin 80 sccm 60 W 2 Pa) to etch the light shielding film.
- each membrane ethtin 80 sccm 60 W 2 Pa
- the end point was determined from the change in reflectance by the reflectance monitor.
- a halftone phase shift film is formed on a quartz substrate in the same manner as in Example 13, and the molybdenum silicide light-shielding film and chrome oxynitride are prevented from being reflected on the halftone phase shift film as in Example 10.
- the film was laminated in the same manner as in Example 10 with a light-shielding film thickness of 10 ⁇ m and an antireflection film thickness of 20 nm to obtain a black-tone phase shift mask blank in which the light-shielding film and the antireflection film were laminated. It was.
- a resist pattern is formed by electron beam lithography using a chemically amplified resist (film thickness lOOnm).
- a chemically amplified resist film thickness lOOnm.
- the light shielding film was etched by Pa). The etching end point of each film was determined by the reflectivity changing force using a reflectivity monitor.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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KR1020077005657A KR101165242B1 (ko) | 2004-09-10 | 2005-09-08 | 포토마스크 블랭크 및 포토마스크 |
US11/662,183 US7691546B2 (en) | 2004-09-10 | 2005-09-08 | Photomask blank and photomask |
CN2005800365654A CN101052917B (zh) | 2004-09-10 | 2005-09-08 | 光掩模坯料及光掩模 |
EP05782284A EP1801647B1 (en) | 2004-09-10 | 2005-09-08 | Photomask blank and photomask |
US12/709,116 US8007964B2 (en) | 2004-09-10 | 2010-02-19 | Photomask blank and photomask |
Applications Claiming Priority (2)
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JP2004-263161 | 2004-09-10 | ||
JP2004263161A JP4407815B2 (ja) | 2004-09-10 | 2004-09-10 | フォトマスクブランク及びフォトマスク |
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Application Number | Title | Priority Date | Filing Date |
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US11/662,183 A-371-Of-International US7691546B2 (en) | 2004-09-10 | 2005-09-08 | Photomask blank and photomask |
US12/709,116 Division US8007964B2 (en) | 2004-09-10 | 2010-02-19 | Photomask blank and photomask |
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Publication Number | Publication Date |
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WO2006028168A1 true WO2006028168A1 (ja) | 2006-03-16 |
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PCT/JP2005/016511 WO2006028168A1 (ja) | 2004-09-10 | 2005-09-08 | フォトマスクブランク及びフォトマスク |
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US (2) | US7691546B2 (ja) |
EP (4) | EP1801647B1 (ja) |
JP (1) | JP4407815B2 (ja) |
KR (1) | KR101165242B1 (ja) |
CN (1) | CN101052917B (ja) |
TW (1) | TW200623233A (ja) |
WO (1) | WO2006028168A1 (ja) |
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TWI476508B (zh) * | 2008-02-27 | 2015-03-11 | Hoya Corp | 光罩基板、光罩及光罩之製造方法 |
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EP1801647B1 (en) | 2011-11-16 |
CN101052917A (zh) | 2007-10-10 |
EP2302453A3 (en) | 2011-05-25 |
EP2302453A2 (en) | 2011-03-30 |
EP1801647A1 (en) | 2007-06-27 |
EP2302452B1 (en) | 2015-04-01 |
EP2246737B1 (en) | 2015-12-02 |
US7691546B2 (en) | 2010-04-06 |
JP4407815B2 (ja) | 2010-02-03 |
TW200623233A (en) | 2006-07-01 |
TWI320579B (ja) | 2010-02-11 |
EP2246737A1 (en) | 2010-11-03 |
EP2302452A2 (en) | 2011-03-30 |
US20100143831A1 (en) | 2010-06-10 |
US8007964B2 (en) | 2011-08-30 |
EP2302453B1 (en) | 2015-04-01 |
JP2006078807A (ja) | 2006-03-23 |
EP1801647A4 (en) | 2008-01-23 |
EP2302452A3 (en) | 2011-05-25 |
KR101165242B1 (ko) | 2012-09-13 |
US20080063950A1 (en) | 2008-03-13 |
CN101052917B (zh) | 2010-11-03 |
KR20070054198A (ko) | 2007-05-28 |
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