WO2004017140A1 - マスクブランクの製造方法、転写マスクの製造方法、マスクブランク製造用スパッタリングターゲット - Google Patents
マスクブランクの製造方法、転写マスクの製造方法、マスクブランク製造用スパッタリングターゲット Download PDFInfo
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- WO2004017140A1 WO2004017140A1 PCT/JP2003/010438 JP0310438W WO2004017140A1 WO 2004017140 A1 WO2004017140 A1 WO 2004017140A1 JP 0310438 W JP0310438 W JP 0310438W WO 2004017140 A1 WO2004017140 A1 WO 2004017140A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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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
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
-
- 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
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
- G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof
-
- 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
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
-
- 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
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70216—Mask projection systems
- G03F7/70283—Mask effects on the imaging process
Definitions
- Mask blank manufacturing method transfer mask manufacturing method, mask blank manufacturing spatter ring
- the present invention relates to a method of manufacturing a mask blank having a thin film for forming a mask pattern on a substrate, a method of manufacturing a transfer mask for manufacturing by patterning a thin film of the mask blank, and a method of manufacturing the mask blank.
- a sputtering target to be used.
- phase shift lithography is a method of improving the resolution of optical lithography only by changing the mask without changing the optical system.
- a mask having a phase shift effect (hereinafter referred to as a phase shift mask) is used.
- the phase shift mask is a mask having both light intensity information and phase information, and various types such as a Levenson type, an auxiliary pattern type, and a self-aligned type (edge enhanced type) are known.
- These phase shift masks have a more complicated structure than conventional photomasks having only light intensity information, and require a high level of technology for manufacturing.
- phase shift masks As one of the phase shift masks, a phase shift mask called a so-called halftone type phase shift mask has recently been developed.
- the provided light semi-transmissive portion has a light blocking function of transmitting light having an intensity that does not substantially contribute to exposure light, and shifts the phase of light (usually inversion. Since it has both functions of the phase shift function and the phase shift function, the light shielding film pattern and the phase shift film pattern do not need to be formed separately, and the feature is that the structure is simple and the manufacturing is easy. .
- the halftone type phase shift mask 5 is composed of a light transmitting portion 2 on the transparent substrate 1, through which the transparent substrate 1 is exposed to transmit light having an intensity substantially contributing to exposure, and a light transmitting portion 2 having an intensity substantially not contributing to exposure.
- a mask pattern is formed by the light semi-transmissive portion 3 provided with a light semi-transmissive film that transmits light and shifts the phase of transmitted light.
- the phase shift of the light transmitted through the light transmissive portion 3 causes the phase of the light transmitted through the light semitransmissive portion 3 to be substantially inverted with respect to the phase of the light transmitted through the light transmissive portion 2. It is.
- a halftone type phase shift mask uses the effect of making the light intensity almost zero to improve the contrast at the boundary, that is, the resolution.
- the light transflective portion in the above-described halftone type phase shift mask needs to have the required optimum values for both the light transmittance and the phase shift amount.
- the applicant of the present application has previously filed an application for a phase shift mask capable of realizing the required optimum value with a single-layer semi-transmissive portion (Japanese Patent No. 2837803, Patent No. 2,966,369).
- the light semi-transmissive portion is composed of a metal such as molybdenum or tungsten and a thin film containing silicon, oxygen and Z or nitrogen as main constituent elements.
- Molybdenum silicide specifically, oxidized Molybdenum and silicon (abbreviated as MoSiNO), or oxynitrided molybdenum and silicon (abbreviated as MoSiN), or molybdenum and silicon nitride (abbreviated as MoSiN) Abbreviated).
- MoSiNO oxidized Molybdenum and silicon
- MoSiN oxynitrided molybdenum and silicon
- MoSiN molybdenum and silicon nitride
- the transmittance of these thin films can be controlled by selecting the oxygen content or the content of oxygen and nitrogen, and the phase shift can be controlled by the thickness.
- the mask pattern is made of silicon from the viewpoint of controllability of the light shielding function of the mask pattern and workability of the mask pattern It is often a material that contains. That is, in a mask blank, which is a member of the transfer mask before the patterning process, a portion (film) serving as a mask pattern is often formed by sputtering using a sputter target containing silicon.
- a silicon-containing target is used, many particles are generated during film formation. This is considered to be because discharge tends to be unstable when forming a film using a target containing silicon.
- the particles will be mixed into the film. If the particles fall out of the film due to cleaning, etc., for example, in the case of a light-shielding film, depending on the degree to which the film thickness is reduced, the light-shielding function may not be achieved, and white defects may occur.
- a silicon target containing a large amount of silicon is often used, and a silicon target containing a silicon target is often used.
- the problem of the generation of particles when using a laser beam becomes even more pronounced. Further, when particles are mixed into the light translucent film and the particles fall out of the film due to washing or the like, the problem becomes more remarkable than in the case of the above-described light shielding film.
- the phase shift amount and the transmittance change when the film thickness is smaller than the originally required film thickness, which directly affects the transfer characteristics. Therefore, reducing the generation of particles when using a silicon-containing target is effective in reducing the phase shift mask defect.
- the phase shift mask blank which is a member of the phase shift mask before pattern processing
- the light semi-transmission portion is formed of the above-mentioned thin film
- the light semi-transmission is realized by a single layer film made of one kind of material.
- the film forming process can be simplified and a single etching medium can be used, so that the phase shift mask can be changed from the phase shift mask to the phase shift mask.
- the phase difference and the transmittance are controlled only by controlling the oxygen and / or nitrogen content during the reactive sputtering described above. It's getting harder to control. Therefore, a target containing metal and silicon, which contains a larger amount of silicon than a stoichiometrically stable composition (hereinafter referred to as silicon-rich (silicon-rich)), is applied, and the phase difference, The transmittance is controlled.
- silicon-rich silicon-rich
- the silicon main component indicates that silicon is contained at 70 atm% or more.
- a light semi-transmissive film is formed by performing the above-described reactive sputtering using such a silicon-based target, particles generated during the film formation cause the light semi-transmissive film to be in the light semi-transmissive film.
- the particles are, for example, fine particles having a diameter of more than 0.3 to 2 m. If particles are mixed in the formed light semi-transmissive film, the particles fall out of the light semi-transmissive film in a cleaning process performed after the film formation, resulting in a pinhole or half-hole to be described later. Pinholes or particles remain in the semi-transmissive film without being removed, resulting in defects. This defect causes a pattern defect called a white defect to occur in a process of forming a phase shift mask by patterning the light translucent film.
- the pinhole is defined as a light-semitransmissive film that is formed while particles generated during the film formation are adhered to the substrate, and when the particles fall out of the light-semitransmissive film in the cleaning process, light is emitted.
- Depressions on the surface of the semi-permeable membrane Means that the bottom reaches the substrate.
- a half-pinhole is a phenomenon in which particles adhere when the formation of the light semi-transmissive film on the substrate has progressed to some extent, and when the particles fall out of the light semi-transmissive film in the cleaning process, the light half-transparent film is formed. This means that the bottom of the concave portion generated on the surface of the permeable membrane does not reach the substrate.
- the problems specific to evening getters and reactive sputtering can be considered as a cause of the generation of particles during film formation.
- the target of the main component of silicon to be used is a target that is not formed from a single compound, but is a simple target (often containing a single silicon) and / or a mixed target formed from a mixture of two or more compounds. is there. Since it is a mixed target, there is a problem of uniformity in its composition and characteristics. If the composition and characteristics are not uniform, discharge stability during film formation cannot be obtained, causing particles to be generated.
- oxygen and / or nitrogen are used to control the phase difference and transmittance of the light semi-transmissive film. However, when oxygen is used, there is a problem that discharge stability is reduced. .
- FIG. 4 is a cross-sectional view of a phase shift mask described in Japanese Patent Application Laid-Open No. 7-128840.
- the halftone type phase shift mask described in this publication has a patterned half by removing a part of the film formed on the entire surface of the transparent substrate to form a light transmitting portion.
- FIG. 5 is a halftone type phase shift mask blank for manufacturing the halftone type phase shift mask of FIG. 5.
- the halftone phase shift mask blank in FIG. 5 if the light-shielding film (light-shielding layer) is formed while particles are mixed in the light semi-transmissive film (semi-transparent layer), the film is formed.
- the present invention has been made in view of the above-described problems, and produces a high quality phase shift mask blank with a high incidence of defects of a light semi-transmissive film at a desired value or less at a high yield.
- the present invention has been made to achieve the above object, and comprises the following means.
- the first means is a method of manufacturing a mask blank having a thin film for forming a mask pattern on a substrate
- the thin film is formed by a sputtering method using a sputtering target containing silicon,
- the target containing silicon includes a target composed of silicon and a small amount of a multi-component. Since the target containing silicon has low discharge stability, particles are generated at the time of film formation, and there is a problem that particles are mixed in the thin film, resulting in defects.However, the target hardness is Vickers hardness. By setting it to 900 HV or more, it was possible to greatly reduce the occurrence of defects. Further, in order to more effectively suppress the occurrence of defects, it is preferable that the hardness of the glass getter is set to a Vickers hardness of 980 HV or more, preferably 110 HV or more. As a result, it was possible to suppress the occurrence of defects even in reactive sputtering using a gas having low discharge stability.
- the incidence of defects existing in the light semi-transmissive film could be more effectively suppressed.
- the picker hardness of the present invention is measured by the test method specified in JISZ2244 and the corresponding international standard ISO6507, and the test load is 9. It was measured as 807 N.
- a second means is the method for producing a mask plank according to the first means, wherein the sputtering target is a target having a Vickers hardness of 980 HV or more.
- the hardness of the target is preferably set to a Vickers hardness of 980 HV or more, more preferably 110 HV or more.
- a third means is the method for manufacturing a mask blank according to the first or second means, wherein the thin film is formed by a reactive sputtering method in an atmosphere containing oxygen, nitrogen, or nitrogen.
- a fourth means is the method for producing a mask blank according to any one of the first to third means, wherein the sputtering target contains 70 to 95 atm% of silicon.
- the silicon content is less than 70 atm%, it is difficult for the thin film to obtain desired properties (such as transmittance), and if it is more than 95 atm%, discharge stability may not be obtained.
- a fifth means is the method for producing a mask blank according to any one of the first to fourth means, wherein the thin film is a light translucent film, and the mask blank is a phase shift mask blank. is there.
- Defects that do not cause a problem in the light-shielding film (defects due to half-pinholes or minute pinholes that can maintain the light-shielding function) occur in the light semi-transmissive film of the phase shift mask blank. As a result, a phase difference and a change in transmittance occur, which causes a problem that the phase shift mask blank becomes unsatisfactory.
- the hardness of the target By setting the hardness of the target to 980 HV or more in Vickers hardness, the incidence of defects having a size of 1 zm or more in the light semi-transmissive film can be suppressed to a desired value or less.
- the incidence of defects having a size of 1 zm or more in the light semi-transmissive film is suppressed to a desired value or less. I was able to.
- the sixth means is the method for producing a mask blank according to any one of the first to fifth means, wherein a metal film is formed on the thin film.
- a metal film is formed on the thin film.
- the sixth means when particles are mixed in the thin film, there is a problem that when the particles fall out, the upper metal film is excessively peeled off. This can suppress this problem.
- a metal film made of a material having a different etching characteristic under the etching conditions for forming a mask pattern from the thin film as the metal film it is possible to pattern the thin film with high accuracy. Become. Furthermore, it prevents exposure light from leaking. It is preferable to select a material having a light-shielding function and a film thickness so that the metal film functions as both a mask material and a light-shielding material.
- a seventh means is to manufacture a transfer mask by patterning a thin film of a mask blank manufactured by the mask blank manufacturing method according to any one of the first to sixth means, thereby manufacturing a transfer mask. Is the way. When manufacturing a transfer mask from the mask blank, it becomes possible to manufacture a transfer mask with a low defect, so that the process of defect correction and the like can be significantly shortened, and the manufacturing can be performed by the shortened manufacturing process. did it.
- Examples of the transfer mask include a mask having a light-shielding pattern on a transparent substrate, a halftone-type phase shift mask having a halftone phase-shift pattern on a transparent substrate, and a digging-type phase shift having a light-shielding film or a halftone film.
- Masks, electron beam masks, etc. Photomasks include KrF, ArF, F2 excimer laser, EUV, X-ray, etc. The method of the present invention is applied to these various masks. Applicable.
- the hardness of the target of the present invention is selected according to the exposure wavelength, various characteristics of the film, the material of the evening getter, and the like.
- the Vickers hardness is preferably 140 HV or less, and more preferably 130 HV or less.
- Eighth means is a sputtering target containing silicon as a main component
- a sputtering target for manufacturing a mask blank wherein the hardness of the target is not less than 900 HV in Vickers hardness.
- a target containing silicon as a main component has a low discharge stability, so that particles are generated during film formation and particles are mixed into the thin film, thereby causing a defect.
- the hardness of the target is preferably set to a Vickers hardness of 980 HV or more, and more preferably 110 HV.
- Ninth means is the sputtering target for producing mask plank according to eighth means, wherein the sputtering target contains a metal silicide compound.
- a silicon powder and a metal powder are sintered to produce a metal silicide compound powder, and the metal silicide powder and the silicon powder are combined with each other.
- metal in the metal silicide compound there is a method of selecting a metal for controlling the transmittance of a thin film.
- metals for controlling the transmittance of the thin film include Mo, Ta, W, Ti, and Cr.
- a target is manufactured by sintering a desired amount of silicon powder and a previously prepared metal silicide powder. There is a way.
- a tenth means is the sputtering target for producing a mask blank according to the eighth or ninth means, wherein the sputtering target contains 70 to 95 atm% of silicon.
- the silicon content is less than 70 atm%, desired characteristics (such as transmittance) cannot be obtained, and if it is more than 95 atm%, discharge stability may not be obtained.
- the first means is to perform sputtering in an atmosphere containing oxygen and Z or nitrogen using a target containing metal and silicon, and to place a metal, silicon, oxygen and / or nitrogen on a transparent substrate.
- the defect occurrence rate of the light semi-permeable film has a correlation
- the method for manufacturing a phase shift mask blank, wherein the light semi-transmissive film is formed using the target having a predetermined hardness so that the defect occurrence rate is equal to or less than a desired value. is there.
- An evening get containing metal and silicon is manufactured by sintering a metal powder and a silicon powder, and the hardness of the target and the defect occurrence rate of the light semi-permeable film have a correlation. Therefore, by performing the sputtering using the target having a hardness that suppresses the defect occurrence rate of the light semi-transmissive film to a desired value or less, the defect occurrence rate existing in the light semi-transmissive film is desired. Was able to be suppressed below.
- the hardness of the glass getter having a larger amount of silicon than the stoichiometrically stable composition of the metal and silicon to a predetermined value or more, it is possible to reduce the defect occurrence rate of the light translucent film to a desired value. It was possible to produce a phase shift mask blank having a desired transmittance and a desired phase difference at a predetermined exposure wavelength while keeping the value at or below the value.
- the hardness of the target By setting the hardness of the target to 980 HV or more in Vickers hardness, the incidence of defects having a size of 1 m or more in the light semi-transmissive film can be suppressed to a desired value or less.
- the hardness of the target By setting the hardness of the target to 980 HV or more in Vickers hardness, the incidence of defects having a size of 1 m or more in the light semi-transmissive film can be suppressed to a desired value or less.
- FIG. 1 is a table showing the hardness of a sunset and the number of defects of a phase shift mask blank according to the present invention.
- FIG. 2 is a schematic sectional view of a DC magnetron sputtering apparatus.
- FIG. 3 is a schematic cross-sectional view of a halftone type phase shift mask.
- FIG. 4 is a schematic cross-sectional view of an eighteen-tone phase shift mask with a light-shielding film.
- FIG. 5 is a schematic cross-sectional view of a halftone type phase shift mask blank with a light shielding film.
- the metal contained in the sputtering target according to the present invention one or more metals selected from molybdenum, titanium, tantalum, tungsten, and chromium are preferably used. It is preferable that the purity of metal and silicon, which are the raw materials of the target, be 5 N or more and that impurities such as Fe, Ni, Cu, and A1 be suppressed to several Ppm or less in order to enhance reliability. .
- the amount of silicon contained in the evening target should be greater than the stoichiometrically stable ratio of the silicon-based component (silicon-rich).
- a melting method using electron beam (EB) melting for example, a hot press (hereinafter, referred to as HP), a hot isostatic press (hereinafter, referred to as HIP), or the like is applied. It can be manufactured by the powder sintering method.
- EB electron beam
- HP hot press
- HIP hot isostatic press
- a powder sintering method using HP ⁇ HIP is preferable from the viewpoint that the density, silicon particle size, silicon content, and the like can be controlled with a high degree of freedom. Then, by controlling the pressure and the heating temperature in the pressure sintering step in HP and HIP, a sunset having a desired hardness can be obtained.
- the hardness of the manufactured target can be conveniently measured by, for example, a Pickers hardness tester.
- molybdenum silicide compound (chemical formula: MoSi 2) is first prepared by adjusting molybdenum powder and silicon powder as a target material at a ratio that provides a stoichiometrically stable composition. .
- the amounts of the obtained molybdenum silicide powder and silicon powder were adjusted, and pressure sintering was performed by HP or HIP to produce a silicon main component having a hardness of about 110 HV.
- the pressure and heating temperature of pressure sintering the hardness of the target can be controlled, but the heating temperature must be lower than the melting point of silicon (about 1414 ° C). In order to reduce the generation, it is preferable that the temperature is set to preferably 130 ° C. or lower, more preferably 1250 or lower.
- This target is based on silicon And mainly contains molybdenum silicide particles and silicon particles.
- the transparent substrate is not particularly limited as long as it is a material transparent to the exposure wavelength to be used. Synthetic quartz glass, fluorite, and various other glasses (for example, soda lime glass, aluminosilicate glass, and aluminoporosilicate glass) Etc.) are preferably used.
- FIG. 2 is a schematic sectional view of a DC magnetron sputtering device (hereinafter, referred to as a sputtering device).
- the sputtering apparatus 10 has a vacuum chamber 11 and a DC power supply 19, and the vacuum chamber 11 has an exhaust port 17 and a gas inlet 18, and is further provided inside the vacuum chamber 11.
- the magnetron force source 12 and the substrate holder 15 are arranged to face each other.
- a sputtering target 14 is mounted on the magneto opening 12 via a backing plate 13, and a transparent substrate 1 is mounted on the substrate holder 15.
- the vacuum chamber 11 is evacuated by a vacuum pump (not shown) through an exhaust port 17.
- an atmosphere gas is introduced from the gas inlet 18 and the negative power is applied to the magnetron cathode 12 using the DC power supply 19.
- the DC power supply 19 has an arc detection function and can monitor the discharge state during sputtering.
- the pressure inside the vacuum chamber 11 is measured by a pressure gauge.
- oxygen-free steel is used for the backing plate 13.
- the bonding between the evening gate 14 and the backing plate 13 described above is performed by an ink jet. Uses a pum.
- the backing plate 13 is cooled directly or indirectly by a water cooling mechanism (not shown).
- the magnetron force sword 12, the backing plate 13 and the target 14 are electrically connected.
- an atmosphere gas at the time of sputtering an inert gas such as Ar or He, or a mixed gas of an inert gas such as Ar or He, oxygen gas and Z or nitrogen gas is used.
- an inert gas such as Ar or He
- a mixed gas of an inert gas such as Ar or He
- oxygen gas and Z or nitrogen gas is used as the oxygen gas and / or nitrogen gas.
- NO gas, N20 gas, CO gas, and C02 gas can be used in addition to NO2 gas and N2 gas.
- the atmosphere contains 0 to 40% (preferably 0 to 20%) of oxygen and 0 to 90% (preferably 50 to 80%) of nitrogen in the atmosphere gas at the time of sputtering,
- 0 to 40% preferably 0 to 20%
- 0 to 90% preferably 50 to 80%
- nitrogen in the atmosphere gas at the time of sputtering
- the advantageous effects of the invention are easily obtained. Further, from the problem of oxygen discharge stability, it is preferable to perform the sputtering in a state where the amount of nitrogen is larger than the amount of oxygen.
- the content of metal, silicon, oxygen and / or nitrogen in the light semi-transmissive film formed on the transparent substrate 1 depends on the desired light transmittance (1) at the applied exposure wavelength of the manufactured phase shift mask. ⁇ 20%) and the phase difference may be appropriately adjusted. Further, from the viewpoint of reducing the film stress of the light semi-transmissive film, it is preferable that the light semi-transmissive film contains carbon, fluorine, helium, etc. in addition to oxygen and / or nitrogen. In this case, CO gas, C02 gas, CH4 gas, He gas, etc. may be added to the atmosphere gas at the time of sputtering. Thus, a light translucent film formed on the transparent substrate 1 is obtained.
- the method for cleaning the light semi-transmissive film formed on the transparent substrate is not particularly limited.
- a cleaning method generally performed in a phase shift mask blank cleaning process for example, immersion in a cleaning solution to which ultrasonic waves are applied.
- a cleaning method, a cleaning method using functional water such as hydrogen water, a scrub cleaning method, or the like may be applied.
- a phase shift mask blank is obtained.
- the obtained semi-transmissive film of the phase shift mask blank is subjected to a defect inspection apparatus to have a thickness of less than 0.3 ⁇ m, 0.3 ⁇ m or more and less than 0.5 ⁇ m, or 0.5 ⁇ m or more and 1 ⁇ m.
- the number of defects (pinholes including particles and half pinholes) having a size of less than m and 1 im or more was measured.
- the yield of phase shift mask plank having no defects of ⁇ or more hereinafter referred to as “1 m defect-free” increased as the hardness of the target used for sputtering increased. did.
- the yield of a more preferable phase shift mask blank having no defect of 0.5 / m or more (hereinafter referred to as 0.5 m defect-free) is obtained, and the more preferable defect of 0.3 m or more is obtained. It has also been found that the yield of a phase shift mask blank (absolutely 0.3 m defect-free) that does not exist at all increases with the hardness of the target.
- a target containing metal and silicon is manufactured by sintering a metal powder and a silicon powder as described above. (Specifically, a metal silicide powder prepared in advance from a metal powder and a silicon powder is used.) And silicon powder are sintered.) In general, it is necessary that this sinterability be good. It is.
- the particles constituting the target mainly, metal silicide particles and silicon particles
- the particles constituting the target will sputter out of the target and adhere to the substrate during sputtering
- the foreign matter contained in the target jumps out of the target and adheres to the substrate
- the foreign matter remains on the light semi-transmissive film and becomes particles.
- the particles are removed from the light semi-transmissive film.
- it is considered to be a half pinhole or pinhole.
- the present inventors quantitatively grasped the quality of the sinterability of the target, and managed the sinterability of the target to reduce the incidence of defects in the light semi-transmissive film to a desired value or less. It was difficult to quantitatively grasp the quality of sinterability.
- the density of the target as a means to quantitatively determine the quality of the sinterability of the target, but the density of the target and the incidence of defects in the light translucent film did not necessarily It was found that the correlation could not be obtained in some cases.
- the present inventors examined the correlation between the defect of the light semi-transmissive film and various physical properties of the target. Then, as an indirect means of grasping the quality of the sinterability of the target, we found the hardness of the evening get by Pickers hardness.
- the present inventor manufactured a phase shift mask blank using a plurality of targets having different hardnesses, and investigated the defect occurrence rate of the light semi-transmissive film caused by particles generated during sputtering. Then, it was found that there is a correlation between the hardness of the target and the defect occurrence rate of the light semi-transmissive film that the defect occurrence rate of the light semi-transmissive film decreases as the hardness of the target increases. It has been found that by using this correlation, it is possible to suppress the defect occurrence rate of the light semi-transmissive film to a desired value or less by setting the hardness of the target to a predetermined value or more. In particular, the hardness of the target is high.
- a resist film was formed on the light translucent film of the phase shift mask blank, and subjected to pattern exposure and development to form a resist pattern.
- a pattern (holes, dots, etc.) of the light semi-transmissive film was obtained by dry etching using CF 4 +02 gas as a single etching medium.
- the resist was peeled off, immersed in 10098% sulfuric acid for 15 minutes, washed with sulfuric acid, and then rinsed with pure water or the like. Then, high-quality phase shift masks in which the incidence of defects in the light semi-transmissive film was suppressed to a desired value or less could be manufactured with a high yield.
- phase shift mask blank a metal film serving as a mask when patterning the light semi-transmissive film is formed on the light semi-transmissive film.
- a metal film is formed on the light semi-transmissive film. Formed into a light-shielding film or an anti-reflection film.
- the metal film materials having etching characteristics different from those of the light semi-transmissive film, for example, when the light semi-transmissive film is a molybdenum-silicon-based material, the metal film is made of a Cr-based material (Cr alone or C (r oxides, nitrides, carbides, etc.) can be preferably used.
- a Cr-based material Cr alone or C (r oxides, nitrides, carbides, etc.
- Molybdenum silicide powder and silicon powder are mixed together and subjected to pressure sintering under appropriate pressure and heating temperature according to the HP method, and a molybdenum silicide target with a Pisces hardness of 870 HV
- Three types of molybdenum silicide targets with different hardnesses (Sample 1), molybdenum silicide target with Vickers hardness of 980 HV (Sample 2), and molybdenum silicide target with Vickers hardness of 110 HV (Sample 3) were manufactured. .
- the hardness of the target was measured using a Vickers hardness tester and the test load was determined to be 9.8 by the Pitzkas hardness test method specified by JISZ 2244 and the corresponding international standard ISO 6507. It was measured as 07 N.
- the measured value is a value obtained by measuring five points on the polished target surface and averaging the measured values.
- the quartz glass substrate as the above-mentioned target and the transparent substrate was set in the above-mentioned DC magnetron sputtering apparatus.
- a thin film of MoSiN was formed as a semi-transmissive film on a transparent substrate with a thickness of about 672 ⁇ by a reactive sputtering method.
- the transparent substrate on which the MoSiN thin film was formed was scrubbed to clean the thin film surface, thereby producing a phase shift mask blank.
- the optical properties of the thin film obtained here were measured, it had a transmittance of 5.5% and a phase difference of 180 ° at the wavelength of the ArF excimer laser (193 nm).
- the film had optimal optical characteristics as a light translucent film for a phase shift mask blank.
- the phase shift mask blank (sample 1) is used as the target (sample 1)
- the phase shift mask blank is used as the target (sample 2).
- 100 blanks (sample 2) and 100 phase shift mask blanks (sample 3) were manufactured from the target (sample 3).
- 1 shows the defects detected in individual mask blanks classified by the largest size. For example, “less than 0.3 m” indicates that there were no defects of 0.3 zm or more (ie, “ 0.3 m defect free ”) means mask blank. Also, “0.5 m defect-free” means that there is no defect of 0.5 m or more, and “0.3 im less than” and “0.5 or more and less than 0” in FIG. Is the total number of Similarly, “ri rn defect free” means that there was no defect of 1 im or more, and "0.3 m or less and 0.3 m or more and less than 0."
- a phase shift mask blank having no defect of 1 m or more in the light semi-transparent film is used. It can be manufactured with a yield of 0% or more, and a phase shift mask blank with no defect of 0.5 xm or more in the optical semi-permeable film can be manufactured with a yield of 40% or more. .
- a phase shift mask blank that has no defect with a size of 1 m or more in the light semi-transparent film is used. It can be manufactured with a yield of 90% or more, and it is possible to manufacture a phase shift mask blank having no defect of 0.5 m or more in the optical semi-permeable film with a yield of 80% or more. did it.
- phase shift mask blank having a defect free of 1 m or the like could be easily applied to the phase shift mask by the patterning process described in the embodiment.
- Example 1 Using the target (samples 1, 2, and 3) used in Example 1, a MoSIN (film thickness of about 672 angstroms) was formed on a transparent substrate in the same manner as in Example 1. Then, a film (about 600 ⁇ ) of Cr and CrO was continuously formed as a metal film on the MoSiN film. After forming the metal film, the surface of the metal film was scrub-cleaned to produce a phase shift mask blank. At the wavelength of the ArF excimer laser (193 nm), the obtained metal film has a light shielding function, and the surface of the metal film has an antireflection function.
- a resist film was formed on the metal film of the phase shift mask blank, followed by pattern drawing and development to form a resist pattern.
- wet etching was performed using an etching solution containing ceric ammonium nitrate, perchloric acid, and pure water to form a metal film pattern.
- a MoSiN pattern was formed by the passing process described in the embodiment. Next, a part of the metal film was removed to obtain a phase shift mask.
- phase shift masks made using the evening get of Samples 2 and 3 showed Pattern defects were observed in which particles adhered and the metal film was excessively peeled off due to the particles falling off during the cleaning process.
- molybdenum silicide was described as the target.
- the present invention is not limited to this, and a target containing one or more metals selected from titanium, tantalum, tungsten, and chromium and silicon is used as the target. It may be. Industrial applicability
- a method of manufacturing a mask blank having a thin film for forming a mask pattern on a substrate comprising the steps of: using an evening getter containing silicon and having a Vickers hardness of 900 HV or more.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003257547A AU2003257547A1 (en) | 2002-08-19 | 2003-08-19 | Mask blank manufacturing method, transfer mask manufacturing method, sputtering target for manufacturing mask blank |
US10/523,470 US8652306B2 (en) | 2002-08-19 | 2003-08-19 | Method for manufacturing mask blank, method for manufacturing transfer mask, sputtering target for manufacturing mask blank |
KR1020097003311A KR101140115B1 (ko) | 2002-08-19 | 2003-08-19 | 마스크 블랭크의 제조방법, 전사 마스크의 제조방법, 마스크 블랭크 제조용 스퍼터링 타깃 |
JP2004528898A JP4488892B2 (ja) | 2002-08-19 | 2003-08-19 | ハーフトーン型位相シフトマスクブランクの製造方法、位相シフトマスクブランク製造用スパッタリングターゲット、及び、位相シフトマスクの製造方法 |
DE10393131T DE10393131B4 (de) | 2002-08-19 | 2003-08-19 | Verfahren zum Herstellen von Maskenrohlingen |
Applications Claiming Priority (2)
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JP2002238564 | 2002-08-19 | ||
JP2002-238564 | 2002-08-19 |
Publications (1)
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WO2004017140A1 true WO2004017140A1 (ja) | 2004-02-26 |
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PCT/JP2003/010438 WO2004017140A1 (ja) | 2002-08-19 | 2003-08-19 | マスクブランクの製造方法、転写マスクの製造方法、マスクブランク製造用スパッタリングターゲット |
Country Status (6)
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US (1) | US8652306B2 (ja) |
JP (2) | JP4488892B2 (ja) |
KR (3) | KR20050052471A (ja) |
AU (1) | AU2003257547A1 (ja) |
DE (1) | DE10393131B4 (ja) |
WO (1) | WO2004017140A1 (ja) |
Cited By (2)
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JP2007212965A (ja) * | 2006-02-13 | 2007-08-23 | Shin Etsu Chem Co Ltd | フォトマスクブランクの製造方法およびフォトマスクブランク |
JP2009134095A (ja) * | 2007-11-30 | 2009-06-18 | Toppan Printing Co Ltd | 不良解析システム及びそれを用いた不良解析方法 |
Families Citing this family (5)
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KR100854459B1 (ko) * | 2007-02-14 | 2008-08-27 | 주식회사 하이닉스반도체 | 포토마스크의 결함 수정방법 |
WO2013111812A1 (ja) * | 2012-01-27 | 2013-08-01 | 旭化成株式会社 | 微細凹凸構造体、ドライエッチング用熱反応型レジスト材料、モールドの製造方法及びモールド |
JP6165577B2 (ja) * | 2013-09-30 | 2017-07-19 | Hoya株式会社 | マスクブランクの製造方法及び転写用マスクの製造方法 |
KR101712185B1 (ko) * | 2016-04-05 | 2017-03-06 | 한국기계연구원 | 광소결 방법을 이용한 전도성 패턴의 형성 방법 및 이에 의해 형성된 전도성 패턴 |
JP7494672B2 (ja) | 2020-09-14 | 2024-06-04 | 株式会社ニコン | フォトマスクブランクス、フォトマスクブランクスの製造方法、学習方法およびフォトマスクブランクスの検査方法 |
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- 2003-08-19 KR KR1020057002629A patent/KR20050052471A/ko not_active Application Discontinuation
- 2003-08-19 WO PCT/JP2003/010438 patent/WO2004017140A1/ja active Application Filing
- 2003-08-19 AU AU2003257547A patent/AU2003257547A1/en not_active Abandoned
- 2003-08-19 KR KR1020097003311A patent/KR101140115B1/ko active IP Right Grant
- 2003-08-19 DE DE10393131T patent/DE10393131B4/de not_active Expired - Lifetime
- 2003-08-19 US US10/523,470 patent/US8652306B2/en active Active
- 2003-08-19 KR KR1020087019115A patent/KR20080086925A/ko active Search and Examination
- 2003-08-19 JP JP2004528898A patent/JP4488892B2/ja not_active Expired - Lifetime
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- 2009-09-07 JP JP2009205755A patent/JP5409216B2/ja not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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KR20080086925A (ko) | 2008-09-26 |
KR20050052471A (ko) | 2005-06-02 |
US20050250017A1 (en) | 2005-11-10 |
DE10393131B4 (de) | 2010-12-23 |
JP2010020335A (ja) | 2010-01-28 |
JP5409216B2 (ja) | 2014-02-05 |
KR101140115B1 (ko) | 2012-04-30 |
AU2003257547A1 (en) | 2004-03-03 |
JPWO2004017140A1 (ja) | 2005-12-08 |
DE10393131T5 (de) | 2005-08-11 |
US8652306B2 (en) | 2014-02-18 |
KR20090033270A (ko) | 2009-04-01 |
JP4488892B2 (ja) | 2010-06-23 |
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