WO2018221201A1 - マスクブランク、転写用マスクの製造方法及び半導体デバイスの製造方法 - Google Patents

マスクブランク、転写用マスクの製造方法及び半導体デバイスの製造方法 Download PDF

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Publication number
WO2018221201A1
WO2018221201A1 PCT/JP2018/018707 JP2018018707W WO2018221201A1 WO 2018221201 A1 WO2018221201 A1 WO 2018221201A1 JP 2018018707 W JP2018018707 W JP 2018018707W WO 2018221201 A1 WO2018221201 A1 WO 2018221201A1
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Prior art keywords
shielding film
bonds
light
mask
light shielding
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PCT/JP2018/018707
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English (en)
French (fr)
Japanese (ja)
Inventor
雅広 橋本
真理子 内田
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Hoya Corp
Hoya Electronics Singapore Pte Ltd
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Hoya Corp
Hoya Electronics Singapore Pte Ltd
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Priority to US16/615,542 priority Critical patent/US20200166833A1/en
Priority to KR1020197030979A priority patent/KR102565111B1/ko
Priority to CN201880031374.6A priority patent/CN110651225B/zh
Publication of WO2018221201A1 publication Critical patent/WO2018221201A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Definitions

  • the present invention relates to a mask blank and a method for manufacturing a transfer mask manufactured using the mask blank.
  • the present invention also relates to a method for manufacturing a semiconductor device using the transfer mask.
  • a fine pattern is formed using a photolithography method. Also, a number of transfer masks are usually used for forming this fine pattern.
  • an ArF excimer laser (wavelength: 193 nm) is increasingly used as an exposure light source for manufacturing a semiconductor device.
  • Patent Document 2 discloses a phase shift mask including a SiNx phase shift film.
  • Patent Document 3 describes that the phase shift film of SiNx was confirmed to have high ArF light resistance.
  • Patent Document 4 the black defect portion of the light-shielding film is removed by etching the black defect portion by supplying xenon difluoride (XeF 2 ) gas and irradiating the portion with an electron beam.
  • XeF 2 xenon difluoride
  • SiN-based material a material containing silicon and nitrogen that does not contain a transition metal
  • the EB defect correction was performed on the black defect portion found in the pattern of the light-shielding film of the SiN-based material, it was found that two major problems occurred.
  • the area where the surface of the binary mask after the EB defect correction is rough is an area that becomes a translucent portion that transmits ArF exposure light.
  • the ArF exposure light transmittance is likely to be reduced or diffusely reflected.
  • Another major problem is that when the black defect portion of the light shielding film is removed by correcting the EB defect, the light shielding film pattern existing around the black defect portion is etched from the sidewall (this phenomenon). Is called spontaneous etching.) When spontaneous etching occurs, the light shielding film pattern may be significantly thinner than the width before EB defect correction. In the case of a light-shielding film pattern having a narrow width before the EB defect correction, the pattern may be lost or lost.
  • Such a binary mask having a light-shielding film pattern that is likely to undergo spontaneous etching causes a significant decrease in transfer accuracy when it is used for exposure transfer by being placed on a mask stage of an exposure apparatus.
  • An object of the present invention is to provide a mask blank capable of suppressing the occurrence of surface roughness and suppressing the occurrence of spontaneous etching in the pattern of the light shielding film. Moreover, an object of this invention is to provide the manufacturing method of the mask for transfer using this mask blank. Furthermore, an object of the present invention is to provide a method for manufacturing a semiconductor device using the transfer mask.
  • the present invention has the following configuration.
  • a mask blank provided with a light-shielding film for forming a transfer pattern on a translucent substrate,
  • the light shielding film is formed of a material composed of silicon and nitrogen, or a material composed of one or more elements selected from a metalloid element and a nonmetallic element, and silicon and nitrogen.
  • the number of Si 3 N 4 bonds in the inner region excluding the region near the interface of the light shielding film with the light transmissive substrate and the surface layer region of the light shielding film opposite to the light transmissive substrate is expressed as Si 3
  • the ratio divided by the total number of N 4 bonds, Si a N b bonds (where b / [a + b] ⁇ 4/7) and Si—Si bonds is 0.04 or less
  • the ratio obtained by dividing the number of Si a N b bonds in the inner region of the light shielding film by the total number of Si 3 N 4 bonds, Si a N b bonds, and Si—Si bonds is 0.1 or more.
  • Mask blank characterized by.
  • Configuration 2 The mask blank according to Configuration 1, wherein the region excluding the surface layer region of the light shielding film has an oxygen content of 10 atomic% or less.
  • the surface layer region is a region extending from a surface of the light shielding film on the side opposite to the light transmissive substrate to a depth of 5 nm toward the light transmissive substrate side.
  • (Configuration 4) 4. The mask blank according to any one of configurations 1 to 3, wherein the neighboring region is a region extending from the interface with the translucent substrate to a depth of 5 nm toward the surface layer region.
  • Configuration 10 A method for manufacturing a semiconductor device, comprising: a step of exposing and transferring a transfer pattern onto a resist film on a semiconductor substrate using the transfer mask manufactured by the method for manufacturing a transfer mask according to Configuration 9.
  • the mask blank of the present invention can suppress the occurrence of surface roughness of a translucent substrate when EB defect correction is performed on a black defect portion of a light shielding film pattern formed of a SiN-based material. Spontaneous etching can be prevented from occurring.
  • the transfer mask manufacturing method of the present invention suppresses the occurrence of surface roughness of the translucent substrate even when EB defect correction is performed on the black defect portion of the light shielding film pattern during the transfer mask manufacturing process. It is possible to suppress spontaneous etching from occurring in the light shielding film pattern in the vicinity of the black defect portion.
  • the transfer mask manufactured by the transfer mask manufacturing method of the present invention is a transfer mask with high transfer accuracy.
  • the inventors When the EB defect correction is performed on the black defect portion of the light shielding film formed of the SiN-based material, the inventors suppress the occurrence of surface roughness of the light-transmitting substrate, and the pattern of the light shielding film. Intensive research was conducted on the structure of the light-shielding film in which spontaneous etching was suppressed. First, when EB defect correction was performed on a phase shift film pattern formed of a SiN-based material, there was a problem that the correction rate was significantly slow, but no substantial problem related to spontaneous etching occurred. It was.
  • XeF 2 gas used for EB defect correction is known as a non-excited etching gas when isotropic etching is performed on a silicon-based material.
  • the etching is performed by a process of surface adsorption of non-excited XeF 2 gas to a silicon-based material, separation into Xe and F, generation of a high-order fluoride of silicon, and volatilization.
  • a non-excited fluorine-based gas such as XeF 2 gas is supplied to the black defect portion of the thin film pattern, and the fluorine-based gas is adsorbed on the surface of the black defect portion.
  • the electron beam is irradiated to the black defect portion.
  • the silicon in the black defect portion is excited to promote the bond with fluorine, and volatilizes as a high-order fluoride of silicon much faster than when not irradiated with an electron beam.
  • the thin film pattern around the black defect portion is also etched when the EB defect is corrected.
  • silicon that is not bonded to other elements can easily be bonded to fluorine. For this reason, silicon that is not bonded to other elements is in a state where it is not excited without being irradiated with an electron beam, or is a light-shielding film pattern around a black defect portion, and slightly affects the influence of electron beam irradiation. Even those that are received tend to volatilize by combining with fluorine. This is presumed to be the mechanism of spontaneous etching.
  • the silicon film is not suitable as a material for the phase shift film because the refractive index n with respect to ArF exposure light is significantly small and the extinction coefficient k is large.
  • the material for the phase shift film among SiN materials, SiN materials that contain a large amount of nitrogen to increase the refractive index n and reduce the extinction coefficient k are suitable.
  • a phase shift film formed of such a SiN-based material has a high ratio of silicon in the film bonded to nitrogen, and it can be said that the ratio of silicon bonded to other elements is significantly low. For this reason, it is considered that the phase shift film formed of such a SiN-based material did not substantially cause the problem of spontaneous etching when the EB defect was corrected.
  • the light shielding film of the binary mask is required to be thin while having high light shielding performance against ArF exposure light, that is, an optical density (OD: Optical Density) higher than a predetermined value. For this reason, a material having a large extinction coefficient k is required as the material of the light shielding film.
  • the SiN material used for the light shielding film has a significantly lower nitrogen content than the SiN material used for the phase shift film.
  • the light shielding film of SiN-based material has a low ratio of silicon in the film bonded to nitrogen, and it can be said that the ratio of unbonded silicon to other elements is high. For this reason, it is considered that the light-shielding film made of SiN-based material is likely to cause a problem of spontaneous etching when EB defects are corrected.
  • the present inventors examined increasing the nitrogen content of the SiN material forming the light shielding film. If the nitrogen content is greatly increased as in the case of the SiN-based material of the phase shift film, the extinction coefficient k is significantly reduced, and the light shielding film needs to be greatly thickened. Decreases. In consideration of these matters, a light shielding film made of a SiN-based material having a nitrogen content increased to some extent was formed on a translucent substrate, and an EB defect correction was attempted. As a result, the light-shielding film had a sufficiently high correction rate for the black defect portion and was able to suppress the occurrence of spontaneous etching. Was. That the correction rate of the black defect portion of the light shielding film is sufficiently large means that the etching selectivity with the translucent substrate is sufficiently high, and the surface of the translucent substrate is remarkably roughened. Should not have occurred.
  • the inventors of the present invention have found that the surface of the light-transmitting substrate becomes rough at the time of EB defect correction when the ratio of Si 3 N 4 bonds in the SiN-based material forming the light-shielding film increases. I found out that it was prominent.
  • the SiN-based material there are a Si—Si bond that is in an unbonded state with elements other than silicon, a Si 3 N 4 bond that is a stoichiometrically stable bond state, and a relatively unstable bond state. It is considered that Si a N b bonds (where b / [a + b] ⁇ 4/7, the same applies hereinafter) are mainly present.
  • the Si 3 N 4 bond has a particularly high bond energy between silicon and nitrogen, when silicon is excited by irradiation with an electron beam, the bond between silicon and nitrogen is higher than that of the Si—Si bond or Si a N b bond. It is difficult to produce higher-order fluorides bonded to fluorine by cutting off.
  • the SiN material forming the light shielding film has a lower nitrogen content than the SiN material forming the phase shift film, the abundance ratio of Si 3 N 4 bonds in the material tends to be low.
  • the present inventors made the following hypothesis. That is, when the existence ratio of Si 3 N 4 bonds in a film such as a light shielding film is low, the distribution of Si 3 N 4 bonds when the light shielding film (black defect portion) is viewed in plan is sparse (non-uniform). It is thought that.
  • EB defect correction is performed by irradiating an electron beam from above on such a black defect portion of the light shielding film, silicon of Si—Si bond and Si a Nb bond is bonded to fluorine early and volatilizes.
  • Si 3 N 4 -bonded silicon requires a lot of energy to break the bond with nitrogen, so it takes time to bond with fluorine and volatilize.
  • the EB defect correction is continued in such a state that the difference in the removal amount in the plan view occurs in various places in the film thickness direction, the EB defect correction is early on the translucent substrate in the black defect portion irradiated with the electron beam. And a region where the surface of the translucent substrate is exposed and an area where the black defect portion still remains on the surface of the translucent substrate without EB defect correction reaching the translucent substrate. End up. Since it is technically difficult to irradiate only the region where the black defect portion remains, it is difficult to irradiate the electron beam while continuing the EB defect correction to remove the region where the black defect portion remains.
  • the region where the surface of the light substrate is exposed continues to be irradiated with the electron beam. Since the translucent substrate is not etched at all for the EB defect correction, the surface of the translucent substrate is roughened until the EB defect correction is completed. On the other hand, since the phase shift film of SiN-based material has a high nitrogen content, the abundance ratio of Si 3 N 4 bonds in the film is relatively high. For this reason, although the correction rate at the time of EB defect correction is significantly slowed, the distribution of Si 3 N 4 bonds in a plan view of the phase shift film (black defect portion) is relatively uniform and hardly sparse. It is considered that the problem of surface roughness of the optical substrate hardly occurs.
  • the number of Si 3 N 4 bonds in the SiN-based material that forms the light-shielding film is calculated as the sum of Si 3 N 4 bonds, Si a N b bonds, and Si—Si bonds. If the ratio divided by the number is less than a certain value, the surface roughness of the translucent substrate in the region where the black defect portion was present when the EB defect correction was performed on the black defect portion of the light shielding film. The present inventors have found out that it can be reduced to such an extent that there is no substantial influence during exposure transfer when used as a transfer mask.
  • the number of Si 3 N 4 bonds in the inner region excluding the region near the interface of the light-shielding film with the light transmissive substrate and the surface layer region on the opposite side of the light transmissive substrate is expressed as Si 3 N 4 bond, Si If the ratio divided by the total number of a N b bonds (where b / [a + b] ⁇ 4/7) and Si—Si bonds is 0.04 or less, the surface of the translucent substrate for EB defect correction It can be said that roughening can be greatly suppressed.
  • the ratio of the number of Si a N b bonds in the inner region of the light shielding film divided by the total number of Si 3 N 4 bonds, Si a N b bonds, and Si—Si bonds is 0.1 or more
  • silicon bonded to nitrogen exists in a certain ratio or more, and when the EB defect correction is performed on the black defect portion of the light shielding film, the light shielding film around the black defect portion
  • FIG. 5 is a cross-sectional view showing the configuration of the mask blank 100 according to the embodiment of the present invention.
  • a mask blank 100 shown in FIG. 5 has a structure in which a light shielding film 2 and a hard mask film 3 are laminated in this order on a translucent substrate 1.
  • the translucent substrate 1 is made of a material containing silicon and oxygen, and is formed of a glass material such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda lime glass, low thermal expansion glass (SiO 2 —TiO 2 glass or the like). can do.
  • synthetic quartz glass has a high transmittance with respect to ArF exposure light, and is particularly preferable as a material for forming a light-transmitting substrate of a mask blank.
  • the light shielding film 2 is a single layer film formed of a silicon nitride material.
  • the silicon nitride-based material in the present invention is a material composed of silicon and nitrogen, or a material composed of silicon and nitrogen, one or more elements selected from metalloid elements and nonmetallic elements.
  • the number of manufacturing steps is reduced, the production efficiency is increased, and quality control during manufacturing including defects is facilitated.
  • the light shielding film 2 is formed of a silicon nitride material, it has high ArF light resistance.
  • the light shielding film 2 may contain any metalloid element in addition to silicon.
  • metalloid elements it is preferable to include one or more elements selected from boron, germanium, antimony, and tellurium because it can be expected to increase the conductivity of silicon used as a sputtering target.
  • the light shielding film 2 may contain any nonmetallic element in addition to nitrogen.
  • the nonmetallic element in the present invention refers to a substance containing a nonmetallic element (nitrogen, carbon, oxygen, phosphorus, sulfur, selenium, hydrogen), halogen (fluorine, chlorine, bromine, iodine, etc.) and a noble gas in a narrow sense.
  • a nonmetallic element nitrogen, carbon, oxygen, phosphorus, sulfur, selenium, hydrogen
  • halogen fluorine, chlorine, bromine, iodine, etc.
  • a noble gas in a narrow sense.
  • the oxygen content is preferably suppressed to 10 atomic% or less, more preferably 5 atomic% or less, except for the surface layer region 23 described later, and oxygen is not actively contained ( It is more preferable that the composition is analyzed by X-ray photoelectron spectroscopic analysis or the like, and is below the lower limit of detection.
  • the oxygen content of the light shielding film 2 is large, the correction rate when the EB defect is corrected is significantly slowed down.
  • the noble gas is an element that can increase the deposition rate and improve the productivity by being present in the deposition chamber when the light shielding film 2 is deposited by reactive sputtering.
  • this noble gas is turned into plasma and collides with the target, the target constituent element jumps out of the target, and the light shielding film 2 is formed on the light-transmitting substrate 1 while taking in the reactive gas in the middle.
  • the noble gas in the film forming chamber is slightly taken in until the target constituent element jumps out of the target and adheres to the translucent substrate 1.
  • Preferable noble gases required for this reactive sputtering include argon, krypton, and xenon.
  • helium and neon having a small atomic weight may be actively incorporated into the light shielding film 2.
  • the light shielding film 2 is preferably formed of a material composed of silicon and nitrogen.
  • the noble gas is slightly taken in when the light shielding film 2 is formed by reactive sputtering.
  • the noble gas can also be detected by performing composition analysis such as Rutherford Backscattering Spectroscopy (RBS) or X-ray Photoelectron Spectroscopy (XPS) on the light-shielding film 2. It is an element that is not easy to do. For this reason, it can be considered that the material composed of silicon and nitrogen includes a material containing a noble gas.
  • the inside of the light shielding film 2 is divided into three regions in the order of the substrate vicinity region (near region) 21, the internal region 22, and the surface layer region 23 from the light transmitting substrate 1 side.
  • the substrate vicinity region 21 has a depth of 5 nm (more preferably) from the interface between the light-shielding film 2 and the translucent substrate 1 toward the surface side opposite to the translucent substrate 1 (that is, the surface layer region 23 side). 4 nm depth, more preferably 3 nm depth).
  • the surface layer region 23 has a depth of 5 nm (more preferably a depth of 4 nm, more preferably a depth of 3 nm) from the surface opposite to the translucent substrate 1 toward the translucent substrate 1 side. This is an area that spans the range. Since the surface layer region 23 is a region containing oxygen taken from the surface of the light-shielding film 2, a structure in which the oxygen content is compositionally inclined in the thickness direction of the film (in the film as the distance from the translucent substrate 1 increases). The composition has a composition gradient in which the oxygen content increases. That is, the surface layer region 23 has a higher oxygen content than the inner region 22. For this reason, non-uniformity in the removal amount in plan view when the EB defect is corrected in the oxidized surface layer region 23 hardly occurs.
  • the internal region 22 is a region of the light shielding film 2 excluding the substrate vicinity region 21 and the surface layer region 23.
  • Si 3 N 4 bond, Si a N b binding (although, b / [a + b] ⁇ 4/7) and dividing the existence number the Si 3 N 4 coupled by the total number of existing Si-Si bond The ratio obtained by dividing the total number of Si 3 N 4 bonds, Si a N b bonds and Si—Si bonds by the number of existing Si a N b bonds is 0.1 or more. .
  • the total content of silicon and nitrogen is preferably 97 atomic% or more, and more preferably formed of a material having 98 atomic% or more.
  • the inner region 22 preferably has a difference in the film thickness direction of the content of each element constituting the inner region 22 less than 10%. This is to reduce variation in the correction rate when the internal region 22 is removed by EB defect correction.
  • the substrate vicinity region 21 at the interface with the translucent substrate is subjected to composition analysis such as Rutherford Backscattering Spectroscopy (RBS) or X-ray Photoelectron Spectroscopy (XPS: X-ray Photoelectron Spectroscopy).
  • composition analysis such as Rutherford Backscattering Spectroscopy (RBS) or X-ray Photoelectron Spectroscopy (XPS: X-ray Photoelectron Spectroscopy).
  • RBS Rutherford Backscattering Spectroscopy
  • XPS X-ray Photoelectron Spectroscopy
  • the light shielding film 2 is most preferably an amorphous structure for reasons such as good pattern edge roughness when a pattern is formed by etching.
  • the amorphous structure and the microcrystalline structure are mixed.
  • the thickness of the light shielding film 2 is 80 nm or less, preferably 70 nm or less, and more preferably 60 nm or less. When the thickness is 80 nm or less, it is easy to form a fine light-shielding film pattern, and the load when manufacturing a transfer mask from a mask blank having the light-shielding film is reduced. Further, the thickness of the light shielding film 2 is preferably 40 nm or more, and more preferably 45 nm or more. When the thickness is less than 40 nm, it is difficult to obtain sufficient light shielding performance for ArF exposure light. On the other hand, the thickness of the inner region 22 is preferably 0.7 or more, more preferably 0.75 or more, with respect to the total thickness of the light shielding film 2.
  • the optical density of the light shielding film 2 with respect to ArF exposure light is preferably 2.5 or more, and more preferably 3.0 or more. When the optical density is 2.5 or more, sufficient light shielding performance can be obtained. For this reason, when exposure is performed using a transfer mask manufactured using this mask blank, a sufficient contrast of the projection optical image (transfer image) is easily obtained. Further, the optical density of the light shielding film 2 with respect to ArF exposure light is preferably 4.0 or less, and more preferably 3.5 or less. When the optical density exceeds 4.0, the thickness of the light-shielding film 2 becomes thick, and it becomes difficult to form a fine light-shielding film pattern.
  • the surface layer of the light shielding film 2 is different in composition from the other regions of the light shielding film 2, and the optical characteristics are also different.
  • an antireflection film may be stacked on the light shielding film 2. Since the antireflection film contains oxygen taken in from the surface and contains more oxygen than the light shielding film 2, the removal amount in plan view at the time of EB defect correction is less likely to occur.
  • the method of obtaining the Si2p narrow spectrum by performing X-ray photoelectron spectroscopy analysis on the light shielding film 2 is generally performed according to the following procedure. That is, first, a wide spectrum is obtained by performing a wide scan to obtain photoelectron intensity (number of photoelectrons emitted per unit time from a measurement object irradiated with X-rays) with a wide band of binding energy, and the light is blocked. The peak derived from the constituent element of the film 2 is specified. After that, a narrow spectrum is acquired by performing narrow scan, which has a higher resolution than that of the wide scan but has a narrow bandwidth of binding energy that can be acquired, with a bandwidth around the peak of interest (in this case, Si2p).
  • the constituent elements of the light-shielding film 2 which is a measurement object using X-ray photoelectron spectroscopy in the present invention are known in advance.
  • the narrow spectrum required in the present invention is limited to the Si2p narrow spectrum and the N1s narrow spectrum. For this reason, in the present invention, the Si2p narrow spectrum may be acquired by omitting the step of acquiring the wide spectrum.
  • the maximum peak of photoelectron intensity in the Si2p narrow spectrum obtained by performing X-ray photoelectron spectroscopic analysis on the light-shielding film 2 is the maximum peak in the range where the binding energy is 97 [eV] or more and 103 [eV] or less. Is preferred. This is because the peak outside the range of the binding energy may not be a photoelectron emitted from the Si—N bond.
  • the light-shielding film 2 is formed by sputtering, but any sputtering such as DC sputtering, RF sputtering, and ion beam sputtering can be applied.
  • a target with low conductivity such as a silicon target or a silicon compound target that does not contain a metalloid element or has a low content
  • the method for manufacturing the mask blank 100 uses a silicon target or a target made of a material containing at least one element selected from a metalloid element and a nonmetal element in silicon, and in a sputtering gas containing a nitrogen-based gas and a noble gas. It is preferable to have at least a step of forming the light shielding film 2 on the translucent substrate 1 by the reactive sputtering.
  • the optical density of the light shielding film 2 is not determined only by the composition of the light shielding film 2.
  • the film density and crystal state of the light-shielding film 2 are factors that influence the optical density. For this reason, by adjusting various conditions when forming the light-shielding film 2 by reactive sputtering, the film is formed so that the optical density with respect to ArF exposure light falls within a specified value.
  • any gas can be used as long as it contains nitrogen.
  • the light shielding film 2 preferably has a low oxygen content except for its surface layer, it is preferable to apply a nitrogen-based gas that does not contain oxygen, and to apply nitrogen gas (N 2 gas). Is more preferable.
  • nitrogen gas nitrogen gas (N 2 gas).
  • argon, krypton, and a xenon it is preferable to use argon, krypton, and a xenon.
  • helium and neon having a small atomic weight can be actively taken into the light shielding film 2.
  • a hard mask film 3 formed of a material having etching selectivity with respect to an etching gas used when etching the light shielding film 2 is further laminated on the light shielding film 2. It is good also as a structure. Since the light-shielding film 2 needs to ensure a predetermined optical density, there is a limit in reducing the thickness thereof. It is sufficient that the hard mask film 3 has a film thickness that can function as an etching mask until dry etching for forming a pattern on the light shielding film 2 immediately below the hard mask film 3 is completed. Not subject to restrictions. For this reason, the thickness of the hard mask film 3 can be made much thinner than the thickness of the light shielding film 2.
  • the resist film made of an organic material is sufficient to have a thickness sufficient to function as an etching mask until dry etching for forming a pattern on the hard mask film 3 is completed.
  • the thickness of the resist film can be greatly reduced. For this reason, problems such as resist pattern collapse can be suppressed.
  • the hard mask film 3 is preferably formed of a material containing chromium (Cr).
  • the material containing chromium has particularly high dry etching resistance against dry etching using a fluorine-based gas such as SF 6 .
  • a thin film made of a material containing chromium is generally patterned by dry etching using a mixed gas of chlorine-based gas and oxygen gas.
  • this dry etching has not so high anisotropy, etching (side etching) in the side wall direction of the pattern is likely to proceed during dry etching when patterning a thin film made of a material containing chromium.
  • the thickness of the light-shielding film 2 is relatively large, so that a problem of side etching occurs during dry etching of the light-shielding film 2.
  • problems caused by side etching hardly occur.
  • the material containing chromium examples include a material containing one or more elements selected from oxygen, nitrogen, carbon, boron and fluorine in addition to chromium metal, such as CrN, CrC, CrON, CrCO, and CrCON. .
  • the film tends to be a film having an amorphous structure, and the surface roughness of the film and the line edge roughness when the light-shielding film 2 is dry-etched are preferably suppressed.
  • a material for forming the hard mask film 3 a material containing one or more elements selected from oxygen, nitrogen, carbon, boron and fluorine in chromium is used. Is preferred.
  • a chromium-based material is etched with a mixed gas of a chlorine-based gas and an oxygen gas, but chromium metal does not have a very high etching rate with respect to this etching gas.
  • By including one or more elements selected from oxygen, nitrogen, carbon, boron and fluorine in chromium it becomes possible to increase the etching rate of the mixed gas of chlorine-based gas and oxygen gas with respect to the etching gas.
  • the hard mask film 3 made of CrCO does not contain nitrogen that tends to be large in side etching with respect to dry etching using a mixed gas of chlorine-based gas and oxygen gas, contains carbon that suppresses side etching, and further etches. It is particularly preferable because it contains oxygen that improves the rate.
  • the chromium-containing material forming the hard mask film 3 may contain one or more elements of indium, molybdenum and tin. By including one or more elements of indium, molybdenum and tin, the etching rate with respect to the mixed gas of chlorine gas and oxygen gas can be further increased.
  • a resist film of an organic material is formed with a film thickness of 100 nm or less in contact with the surface of the hard mask film 3.
  • SRAF Sub-Resolution Assist Feature
  • the resist film is more preferably 80 nm or less in thickness.
  • HMDS hexyldisilazane
  • the mask blank of the present invention is a mask blank suitable for a binary mask application, but is not limited to a binary mask, and is not limited to a binary mask. It can also be used as a mask blank for a phase lithography mask.
  • FIG. 6 shows a schematic cross-sectional view of a process of manufacturing a transfer mask (binary mask) 200 from the mask blank 100 according to the embodiment of the present invention.
  • the manufacturing method of the transfer mask 200 shown in FIG. 6 uses the mask blank 100 described above, and includes a step of forming a transfer pattern on the hard mask film 3 by dry etching, and a hard mask film 3 ( The method includes a step of forming a transfer pattern on the light shielding film 2 by dry etching using the hard mask pattern 3a) as a mask, and a step of removing the hard mask pattern 3a.
  • a material containing silicon and nitrogen is applied to the light shielding film 2
  • a material containing chromium is applied to the hard mask film 3.
  • a mask blank 100 (see FIG. 6A) is prepared, and a resist film is formed by spin coating in contact with the hard mask film 3.
  • a transfer pattern to be formed on the light-shielding film 2 is exposed and drawn on the resist film, and a predetermined process such as a development process is performed to form a resist pattern 4a (see FIG. 6B).
  • a program defect is added to the resist pattern 4a drawn with the electron beam so that a black defect is formed in the light shielding film 2.
  • the resist pattern 4a is removed using ashing or a resist stripping solution (see FIG. 6D).
  • a chlorine-based gas such as a mixed gas of chlorine and oxygen
  • the chlorine-based gas is not particularly limited as long as it contains Cl, and examples thereof include Cl 2 , SiCl 2 , CHCl 3 , CH 2 Cl 2 , and BCl 3 .
  • the resist pattern 4a is removed using ashing or a resist stripping solution (see FIG. 6D).
  • the fluorine-based gas any gas containing F can be used, but SF 6 is preferable. In addition to SF 6 , for example, CHF 3 , CF 4 , C 2 F 6 , C 4 F 8, and the like can be given. However, the fluorine-based gas containing C has an etching rate with respect to the transparent substrate 1 made of a glass material. Relatively high. SF 6 is preferable because damage to the translucent substrate 1 is small. Incidentally, more preferable the addition of such He as SF 6.
  • the hard mask pattern 3a is removed using a chrome etching solution, and a transfer mask 200 is obtained through a predetermined process such as cleaning (see FIG. 6F).
  • the step of removing the hard mask pattern 3a may be performed by dry etching using a mixed gas of chlorine and oxygen.
  • a chromium etching liquid the mixture containing ceric ammonium nitrate and perchloric acid can be mentioned.
  • a transfer mask 200 manufactured by the manufacturing method shown in FIG. 6 is a binary mask provided with a light-shielding film 2 (light-shielding film pattern 2a) having a transfer pattern on a translucent substrate 1.
  • a light-shielding film 2 light-shielding film pattern 2a
  • the black defect part was removed by EB defect correction.
  • the transfer mask 200 By manufacturing the transfer mask 200 in this way, even when the EB defect correction is performed on the black defect portion of the light shielding film pattern 2a during the manufacturing process of the transfer mask 200, the transparent mask near the black defect portion is obtained. The occurrence of surface roughness of the optical substrate 1 can be suppressed, and the spontaneous etching can be suppressed from occurring in the light shielding film pattern 2a.
  • the transfer mask of the present invention is not limited to a binary mask, and can be applied to a Levenson type phase shift mask and a CPL mask. That is, in the case of the Levenson type phase shift mask, the light shielding film of the present invention can be used as the light shielding film. In the case of a CPL mask, the light shielding film of the present invention can be used mainly in a region including a light shielding band on the outer periphery.
  • the transfer pattern is exposed and transferred onto a resist film on a semiconductor substrate using the transfer mask 200 manufactured using the transfer mask 200 or the mask blank 100. It is characterized by that.
  • the transfer mask 200 is set on the mask stage of an exposure apparatus using ArF excimer laser as exposure light, and a resist film on the semiconductor device.
  • the transfer pattern can be transferred to the resist film on the semiconductor device with high CD accuracy.
  • the circuit pattern is formed by dry-etching the lower layer film using the resist film pattern as a mask, it is possible to form a high-accuracy circuit pattern without wiring short-circuiting or disconnection due to insufficient accuracy.
  • Example 1 Manufacture of mask blanks
  • a translucent substrate 1 made of synthetic quartz glass having a main surface dimension of about 152 mm ⁇ about 152 mm and a thickness of about 6.25 mm was prepared.
  • the translucent substrate 1 had its end face and main surface polished to a predetermined surface roughness, and then subjected to a predetermined cleaning process and a drying process.
  • RF sputtering reactive sputtering
  • the translucent substrate 1 on which the light shielding film 2 was formed was subjected to a heat treatment in the atmosphere at a heating temperature of 500 ° C. for a treatment time of 1 hour.
  • the mask blank of Example 1 has the required high light-shielding performance.
  • Another light-shielding film was formed on the main surface of another light-transmitting substrate under the same film-forming conditions as those of the light-shielding film 2 of Example 1, and heat treatment was further performed under the same conditions.
  • X-ray photoelectron spectroscopic analysis was performed on the light-shielding film of another translucent substrate after the heat treatment.
  • the surface of the light-shielding film is irradiated with X-rays (AlK ⁇ rays: 1486 eV) to measure the intensity of photoelectrons emitted from the light-shielding film, and the surface of the light-shielding film is subjected to Ar gas sputtering.
  • Each step of the light shielding film is repeated by digging to a depth of about 0.65 nm and irradiating the light shielding film in the dug area with X-rays and measuring the intensity of photoelectrons emitted from the area.
  • Each Si2p narrow spectrum at depth was acquired.
  • substrate 1 being an insulator, its energy is displaced rather low with respect to the spectrum in the case of analyzing on a conductor. In order to correct this displacement, correction is made in accordance with the peak of carbon as a conductor (the same applies to Examples 2 to 5 and Comparative Examples 1 and 2 below).
  • This acquired Si2p narrow spectrum includes peaks of Si—Si bond, Si a N b bond, and Si 3 N 4 bond, respectively. Then, the peak position of each of the Si—Si bond, Si a N b bond, and Si 3 N 4 bond and the full width at half maximum (FWHM) were fixed, and peak separation was performed. Specifically, the peak position of Si—Si bond is 99.35 eV, the peak position of Si a N b bond is 100.6 eV, the peak position of Si 3 N 4 bond is 101.81 eV, and the full width at half maximum FWHM is Peak separation was performed as 1.71 (the same applies to Examples 2 to 5 and Comparative Examples 1 and 2 below).
  • FIG. 1 is a diagram showing a Si2p narrow spectrum at a predetermined depth within the range of the inner region, among the results of X-ray photoelectron spectroscopy analysis performed on the light-shielding film of the mask blank according to Example 1.
  • FIG. 1 As shown in the figure, with respect Si2p narrow spectrum, Si-Si bonds performs peak separation to each of Si a N b binding and Si 3 N 4 binding to calculate the area obtained by subtracting the background, respectively, Si- The ratio of the number of Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated.
  • the existence ratio of the number of Si-Si bonds is 0.746, Si a N b present the ratio of the number of bonds 0.254, the ratio the Si 3 N 4 present the number of bonds was 0.000. That is, the existence number the Si 3 N 4 bond, Si 3 N 4 bond, and provided that the ratio obtained by dividing the Si a N b bond and Si-Si total number of existing bonds 0.04, Si a N b binding Satisfying all of the conditions in which the ratio obtained by dividing the number of existing by the total number of Si 3 N 4 bonds, Si a N b bonds, and Si—Si bonds is 0.1 or more (the former condition is Satisfied at 0.000, the latter condition is satisfied at 0.254).
  • each Si2p narrow spectrum at a depth other than that shown in FIG. The ratio of the number of bonds, Si a N b bonds and Si 3 N 4 bonds was calculated.
  • AlK ⁇ ray 1486.6 eV
  • the photoelectron detection region was 200 ⁇ m ⁇
  • the extraction angle was 45 deg (Comparative Examples 2 to 5 below, comparison) The same applies to Examples 1 and 2.)
  • the translucent substrate 1 on which the heat-shielding light-shielding film 2 is formed is placed in a single-wafer DC sputtering apparatus, and using a chromium (Cr) target, argon (Ar), nitrogen (N 2 ), Then, reactive sputtering (DC sputtering) was performed in a mixed gas atmosphere to form a hard mask film 3 made of a CrN film having a thickness of 5 nm.
  • the film composition ratio measured by XPS was 75 atomic% for Cr and 25 atomic% for N.
  • heat treatment was performed at a lower temperature (280 ° C.) than the heat treatment performed on the light shielding film 2 to adjust the stress of the hard mask film 3.
  • a mask blank 100 having a structure in which the light shielding film 2 and the hard mask film 3 were laminated on the light transmitting substrate 1 was manufactured.
  • a transfer mask (binary mask) 200 of Example 1 was manufactured according to the following procedure.
  • the mask blank 100 of Example 1 (see FIG. 6A) was prepared, and a resist film made of a chemically amplified resist for electron beam drawing was formed with a thickness of 80 nm in contact with the surface of the hard mask film 3.
  • a transfer pattern to be formed on the light shielding film 2 was drawn on the resist film with an electron beam, and predetermined development processing and cleaning processing were performed to form a resist pattern 4a (see FIG. 6B).
  • a program defect is added to the resist pattern 4a drawn with the electron beam so that a black defect is formed in the light shielding film 2.
  • the resist pattern 4a was removed (see FIG. 6D). Subsequently, using the hard mask pattern 3a as a mask, dry etching using a fluorine-based gas (mixed gas of SF 6 and He) is performed to form a pattern (light-shielding film pattern 2a) on the light-shielding film 2 (FIG. 6E). )reference).
  • a fluorine-based gas mixed gas of SF 6 and He
  • the hard mask pattern 3a was removed using a chromium etching solution containing ceric ammonium nitrate and perchloric acid, and a transfer mask 200 was obtained through a predetermined process such as cleaning (see FIG. 6F). ).
  • the mask pattern was inspected by the mask inspection apparatus with respect to the manufactured transfer mask 200 of Example 1, the presence of black defects was confirmed in the light shielding film pattern 2a where the program defects were arranged.
  • the correction rate ratio of the light shielding film pattern 2a with respect to the light transmitting substrate 1 is sufficiently high. The etching on the surface of the light-transmitting substrate 1 can be minimized.
  • the transfer mask 200 of Example 1 when the EB defect correction is performed on the black defect portion of the light shielding film pattern 2a with respect to the transfer mask 200 of Example 1, the occurrence of surface roughness of the translucent substrate 1 can be suppressed, and It can be said that spontaneous etching can be suppressed from occurring in the light shielding film pattern 2a. Even when the transfer mask 200 of Example 1 after the EB defect correction is set on the mask stage of the exposure apparatus and exposed and transferred to the resist film on the semiconductor device, the transfer mask 200 is finally formed on the semiconductor device. It can be said that the circuit pattern can be formed with high accuracy. Therefore, it can be said that the transfer mask 200 manufactured by the transfer mask manufacturing method of Example 1 is a transfer mask with high transfer accuracy.
  • Example 2 [Manufacture of mask blanks]
  • the mask blank of Example 2 was manufactured in the same procedure as the mask blank 100 of Example 1 except that the light shielding film was changed as follows.
  • the formation method of the light shielding film of Example 2 is as follows.
  • the power of the RF power source during sputtering was 1500 W.
  • Example 2 the light-transmitting substrate 1 on which the light-shielding film 2 was formed was subjected to a heat treatment, and the optical density (OD) of the light-shielding film 2 after the heat treatment was measured. 58. From this result, the mask blank of Example 2 has the required light shielding performance.
  • Example 1 another light-shielding film is formed on the main surface of another light-transmitting substrate under the same film-forming conditions as those of the light-shielding film 2 of Example 2, and heat treatment is further performed under the same conditions. It was.
  • X-ray photoelectron spectroscopic analysis was performed on the light-shielding film of another translucent substrate after the heat treatment according to Example 2 in the same procedure as Example 1. Further, among the obtained Si2p narrow spectra at each depth of the light shielding film, Si—Si bonds are obtained by the same procedure as in Example 1 based on the Si2p narrow spectrum at a predetermined depth corresponding to the inner region of the light shielding film.
  • the ratio of the number of Si a N b bonds and Si 3 N 4 bonds was calculated. As a result, the existence ratio of the number of Si-Si bonds is 0.898, Si a N b present the ratio of the number of bonds 0.102, the ratio the Si 3 N 4 present the number of bonds was 0.000.
  • each Si2p narrow spectrum having a depth other than the predetermined depth corresponding to the inner region of the light shielding film.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated in the same procedure.
  • the above-described Si—Si bonds, Si a N b bonds, and Si It had the same tendency as the ratio of the number of 3 N 4 bonds.
  • a mask blank 100 having a structure in which the light-shielding film 2 and the hard mask film 3 were laminated on the translucent substrate 1 was manufactured in the same procedure as in Example 1.
  • Example 2 a transfer mask (binary mask) of Example 2 was produced in the same procedure as in Example 1.
  • the mask pattern was inspected by the mask inspection apparatus with respect to the manufactured transfer mask 200 of Example 1, the presence of black defects was confirmed in the light shielding film pattern 2a where the program defects were arranged.
  • the correction rate ratio of the light-shielding film pattern 2a to the translucent substrate 1 is sufficiently high, and etching on the surface of the translucent substrate 1 is minimized. I was able to.
  • the transfer mask 200 of Example 2 when the EB defect correction is performed on the black defect portion of the light shielding film pattern 2a with respect to the transfer mask 200 of Example 2, the occurrence of surface roughness of the translucent substrate 1 can be suppressed, and It can be said that spontaneous etching can be suppressed from occurring in the light shielding film pattern 2a. Even when the transfer mask 200 of Example 2 after correcting the EB defect is set on the mask stage of the exposure apparatus and exposed and transferred to the resist film on the semiconductor device, the transfer mask 200 is finally formed on the semiconductor device. It can be said that the circuit pattern can be formed with high accuracy. Therefore, it can be said that the transfer mask 200 manufactured by the transfer mask manufacturing method of Example 2 is a transfer mask with high transfer accuracy.
  • Example 3 Manufacture of mask blanks
  • the mask blank of Example 3 was manufactured in the same procedure as the mask blank 100 of Example 1 except that the light shielding film was changed as follows.
  • the formation method of the light shielding film of Example 3 is as follows.
  • the power of the RF power source during sputtering was 1500 W.
  • Example 3 the mask blank of Example 3 has the required high light-shielding performance.
  • Example 1 another light-shielding film is formed on the main surface of another light-transmitting substrate under the same film-forming conditions as those of the light-shielding film 2 of Example 3, and heat treatment is further performed under the same conditions. It was.
  • X-ray photoelectron spectroscopic analysis was performed on the light-shielding film of another translucent substrate after the heat treatment according to Example 3 in the same procedure as Example 1. Furthermore, based on the Si2p narrow spectrum (see FIG. 2) at a predetermined depth corresponding to the inner region of the light shielding film among the acquired Si2p narrow spectrum of each depth of the light shielding film, the same procedure as in Example 1 is performed.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated. As a result, the ratio of the number of Si—Si bonds was 0.605, the ratio of the number of Si a N b bonds was 0.373, and the ratio of the number of Si 3 N 4 bonds was 0.022.
  • each Si2p narrow spectrum having a depth other than the above-mentioned predetermined depth corresponding to the inner region of the light shielding film among the Si2p narrow spectra of each depth of the light shielding film obtained in Example 3 is used.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated in the same procedure.
  • a mask blank 100 having a structure in which the light-shielding film 2 and the hard mask film 3 were laminated on the translucent substrate 1 was manufactured in the same procedure as in Example 1.
  • AIMS 193 manufactured by Carl Zeiss.
  • Example 4 Manufacture of mask blanks
  • the mask blank of Example 4 was manufactured in the same procedure as the mask blank 100 of Example 1 except that the light shielding film was changed as follows.
  • RF sputtering reactive sputtering
  • Example 4 the light-transmitting substrate 1 on which the light-shielding film 2 was formed was subjected to a heat treatment, and the optical density (OD) of the light-shielding film 2 after the heat treatment was measured. 54. From this result, the mask blank of Example 4 has the required light shielding performance.
  • Example 1 another light-shielding film is formed on the main surface of another light-transmitting substrate under the same film-forming conditions as those of the light-shielding film 2 in Example 4, and heat treatment is performed under the same conditions. It was.
  • X-ray photoelectron spectroscopic analysis was performed on the light-shielding film of another translucent substrate after the heat treatment according to Example 4. Further, among the obtained Si2p narrow spectra at each depth of the light shielding film, Si—Si bonds are obtained by the same procedure as in Example 1 based on the Si2p narrow spectrum at a predetermined depth corresponding to the inner region of the light shielding film.
  • the ratio of the number of Si a N b bonds and Si 3 N 4 bonds was calculated. As a result, the existence ratio of the number of Si-Si bonds is 0.584, the ratio of Si a N b number of existing bonds 0.376, the number of existing proportion the Si 3 N 4 binding was 0.040.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated in the same procedure.
  • a mask blank 100 having a structure in which the light-shielding film 2 and the hard mask film 3 were laminated on the translucent substrate 1 was manufactured in the same procedure as in Example 1.
  • the transfer mask (binary mask) of Example 4 was manufactured in the same procedure as Example 1 using the mask blank of Example 4.
  • the mask pattern was inspected by the mask inspection apparatus with respect to the manufactured transfer mask 200 of Example 1, the presence of black defects was confirmed in the light shielding film pattern 2a where the program defects were arranged.
  • the correction rate ratio of the light-shielding film pattern 2a to the translucent substrate 1 is sufficiently high, and etching on the surface of the translucent substrate 1 is minimized. I was able to.
  • AIMS 193 manufactured by Carl Zeiss.
  • the transfer mask 200 of Example 4 when the EB defect correction is performed on the black defect portion of the light shielding film pattern 2a with respect to the transfer mask 200 of Example 4, the occurrence of surface roughness of the translucent substrate 1 can be suppressed, and It can be said that spontaneous etching can be suppressed from occurring in the light shielding film pattern 2a. Further, even when the transfer mask 200 of Example 4 after correcting the EB defect is set on the mask stage of the exposure apparatus and exposed and transferred to the resist film on the semiconductor device, it is finally formed on the semiconductor device. It can be said that the circuit pattern can be formed with high accuracy. Therefore, it can be said that the transfer mask 200 manufactured by the transfer mask manufacturing method of Example 4 is a transfer mask with high transfer accuracy.
  • Example 5 Manufacture of mask blanks
  • the mask blank of Example 5 was manufactured in the same procedure as the mask blank 100 of Example 1 except that the light shielding film was changed as follows.
  • the formation method of the light shielding film of Example 5 is as follows.
  • the power of the RF power source during sputtering was 1500 W.
  • the single-wafer RF sputtering apparatus is a single-wafer RF sputtering apparatus that has the same design specifications as those used in the first to fourth embodiments, but is different from the first to fourth embodiments.
  • Example 5 the light-transmitting substrate 1 on which the light-shielding film 2 was formed was subjected to a heat treatment, and the optical density (OD) of the light-shielding film 2 after the heat treatment was measured. 04. From this result, the mask blank of Example 5 has the required high light-shielding performance.
  • Example 1 another light-shielding film is formed on the main surface of another light-transmitting substrate under the same film-forming conditions as those of the light-shielding film 2 in Example 5, and heat treatment is further performed under the same conditions. It was.
  • Example 1 X-ray photoelectron spectroscopic analysis was performed on the light-shielding film of another translucent substrate after the heat treatment according to Example 5. Furthermore, based on the Si2p narrow spectrum (see FIG. 3) at a predetermined depth corresponding to the inner region of the light shielding film among the obtained Si2p narrow spectrum at each depth of the light shielding film, the same procedure as in Example 1 is performed.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated. As a result, the ratio of the number of Si—Si bonds was 0.700, the ratio of the number of Si a N b bonds was 0.284, and the ratio of the number of Si 3 N 4 bonds was 0.016.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated in the same procedure.
  • a mask blank 100 having a structure in which the light-shielding film 2 and the hard mask film 3 were laminated on the translucent substrate 1 was manufactured in the same procedure as in Example 1.
  • Comparative Example 1 Manufacture of mask blanks
  • the mask blank of Comparative Example 1 was manufactured in the same procedure as the mask blank 100 of Example 1 except that the light shielding film was changed as follows.
  • RF sputtering reactive sputtering
  • the light shielding film of Comparative Example 1 was formed with the same gas flow rate and sputtering output as in Example 5.
  • the single-wafer RF sputtering apparatus in Comparative Example 1 is the same single-wafer RF sputtering apparatus used in Examples 1 to 4.
  • Example 1 the light-transmitting substrate on which the light-shielding film was formed was subjected to a heat treatment, and the optical density (OD) of the light-shielding film after the heat treatment was measured. The value was 2.98. It was. From this result, the mask blank of Comparative Example 1 has the required light shielding performance.
  • Example 2 Similar to Example 1, another light-shielding film was formed on the main surface of another light-transmitting substrate under the same film-forming conditions as the light-shielding film of Comparative Example 1 above, and heat treatment was further performed under the same conditions. . Next, X-ray photoelectron spectroscopic analysis was performed on the light-shielding film of another translucent substrate after the heat treatment according to Comparative Example 1 in the same procedure as in Example 1. Further, among the obtained Si2p narrow spectrum of each depth of the light shielding film, based on the Si2p narrow spectrum (see FIG. 4) at a predetermined depth corresponding to the inner region of the light shielding film, the same procedure as in Example 1 is performed.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated. As a result, the ratio of the number of Si—Si bonds was 0.574, the ratio of the number of Si a N b bonds was 0.382, and the ratio of the number of Si 3 N 4 bonds was 0.044.
  • each Si2p narrow at a depth other than the predetermined depth corresponding to the inner region of the light shielding film.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated for the spectrum in the same procedure.
  • Comparative Example 2 Manufacture of mask blanks
  • the mask blank of Comparative Example 2 was manufactured in the same procedure as the mask blank 100 of Example 1 except that the light shielding film was changed as follows.
  • the single wafer RF sputtering apparatus in Comparative Example 2 is the same single wafer RF sputtering apparatus used in Examples 1 to 4 and Comparative Example 1.
  • Example 2 the light-transmitting substrate on which the light-shielding film was formed was subjected to a heat treatment, and the optical density (OD) of the light-shielding film after the heat treatment was measured. The value was 3.04. It was. From this result, the mask blank of Comparative Example 2 has the required high light shielding performance.
  • Example 1 another light-shielding film was formed on the main surface of another light-transmitting substrate under the same film-forming conditions as the light-shielding film of Comparative Example 2, and heat treatment was further performed under the same conditions. .
  • X-ray photoelectron spectroscopic analysis was performed on the light-shielding film of another translucent substrate after the heat treatment according to Comparative Example 2 in the same procedure as in Example 1. Further, among the obtained Si2p narrow spectra at each depth of the light shielding film, Si—Si bonds are obtained by the same procedure as in Example 1 based on the Si2p narrow spectrum at a predetermined depth corresponding to the inner region of the light shielding film.
  • the ratio of the number of Si a N b bonds and Si 3 N 4 bonds was calculated. As a result, the existence ratio of the number of Si-Si bonds is 0.978, Si a N b present the ratio of the number of bonds 0.022, the ratio the Si 3 N 4 present the number of bonds was 0.000.
  • each Si2p narrow having a depth other than the predetermined depth corresponding to the inner region of the light shielding film.
  • the ratio of the number of Si—Si bonds, Si a N b bonds, and Si 3 N 4 bonds was calculated for the spectrum in the same procedure.
  • the above-described Si—Si bonds, Si a N b bonds, and Si It had the same tendency as the ratio of the number of 3 N 4 bonds.
  • the mask blank provided with the structure where the light shielding film and the hard mask film

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PCT/JP2018/018707 2017-05-31 2018-05-15 マスクブランク、転写用マスクの製造方法及び半導体デバイスの製造方法 Ceased WO2018221201A1 (ja)

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US16/615,542 US20200166833A1 (en) 2017-05-31 2018-05-15 Mask blank, method of manufacturing transfer mask, and method for manufacturing semiconductor device
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CN201880031374.6A CN110651225B (zh) 2017-05-31 2018-05-15 光罩基底、转印用光罩的制造方法以及半导体设备的制造方法

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