WO2021187189A1 - マスクブランク、転写用マスク、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、及び半導体デバイスの製造方法 Download PDF

Info

Publication number
WO2021187189A1
WO2021187189A1 PCT/JP2021/008915 JP2021008915W WO2021187189A1 WO 2021187189 A1 WO2021187189 A1 WO 2021187189A1 JP 2021008915 W JP2021008915 W JP 2021008915W WO 2021187189 A1 WO2021187189 A1 WO 2021187189A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
film
thin film
mask
mask blank
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/008915
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
野澤　順
圭司 穐山
シュ・ダー・リン
タン・フュイ・ジュン
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoya Corp
Hoya Electronics Singapore Pte Ltd
Original Assignee
Hoya Corp
Hoya Electronics Singapore Pte Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoya Corp, Hoya Electronics Singapore Pte Ltd filed Critical Hoya Corp
Priority to CN202180020424.2A priority Critical patent/CN115280236B/zh
Priority to KR1020227030750A priority patent/KR102948025B1/ko
Priority to US17/801,377 priority patent/US20230097280A1/en
Publication of WO2021187189A1 publication Critical patent/WO2021187189A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
    • G03F1/24—Reflection masks; 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
    • G03F1/54—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
    • G03F1/60—Substrates
    • 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
    • G03F1/80—Etching

Definitions

  • the present invention relates to a mask blank, a transfer mask manufactured by using the mask blank, and a method of manufacturing a semiconductor device using the above transfer mask.
  • a fine pattern is formed by using a photolithography method.
  • a number of substrates called transfer masks are usually used to form this fine pattern.
  • the wavelength has been shortened from KrF excimer laser (wavelength 248 nm) to ArF excimer laser (wavelength 193 nm).
  • the mask pattern formed on the transparent substrate has a portion (light transmitting portion) that transmits light having an intensity that substantially contributes to exposure and an intensity that does not substantially contribute to exposure. It is composed of a part that transmits light (light semitransmissive part), and the phase of the light that passes through this semi-transmissive part is shifted, and the phase of the light that has passed through the semi-transmissive part is the light transmissive part.
  • the light transmitted near the boundary between the light transmitting portion and the semi-transmissive portion cancels each other out, and the contrast of the boundary portion is achieved. Is made to be able to hold well.
  • the wavelength of the laser light used for exposure becomes shorter, the energy of the laser light becomes larger, so that the damage to the semitransmissive film due to the exposure becomes larger.
  • it is effective to densify the light semi-transmissive film.
  • the sheet resistance of the light semi-transmissive film becomes large, when the resist film formed on the sheet resistance is drawn with an electron beam and patterned, the light semi-transmissive film is charged with electric charges and is accurate. There was a problem that the pattern could not be drawn.
  • Patent Document 1 an exposed portion 5 in which the phase shift film 2 does not exist is formed on the peripheral edge portion on the transparent substrate 1, and the resist film 4 is conductive to such an extent that it does not charge up when drawn with an electron beam and patterned.
  • a technique for suppressing charge-up is disclosed by forming a light-shielding film made of a material having the above-mentioned material so as to cover the exposed portion 5 and the phase shift film 2.
  • the light-shielding film is formed on a chamfered surface or a wide area extending over the side surface of the substrate.
  • the light-shielding film which is also used as a hard mask, is being further thinned to a film thickness of 40 nm or less.
  • a thin film containing a light-shielding film of a mask blank is formed on a substrate by a sputtering method.
  • the thickness of the thin film formed on the chamfered surface and the side surface is significantly thinner than the thickness of the thin film formed on the main surface.
  • the adhesive force of the thin film formed on the chamfered surface or the side surface is weaker than the adhesive force of the thin film formed on the main surface. Due to these circumstances, there is a problem that the light-shielding film on the chamfered surface or the portion formed on the side surface of the substrate is easily peeled off, and the light-shielding film on the portion is easily peeled off during handling of the mask blank to generate dust.
  • sputtering is performed with a masking plate installed on the substrate to mask the region where the thin film is not desired to be formed. That is, sputtering is performed in a state where only the region on the main surface of the substrate on which the thin film is to be formed (hereinafter, this may be referred to as a “design region”) is exposed. If sputtering is performed in a state where the masking plate is in contact with the main surface of the substrate, it is possible to prevent the thin film from wrapping around the chamfered surface or the side surface of the substrate.
  • the masking plate is arranged in a non-contact state with the main surface of the substrate, and sputtering is performed.
  • sputtering most of the sputtered particles are incident on the main surface of the substrate in a direction inclined to some extent from a direction perpendicular to the main surface of the substrate.
  • a highly conductive thin film such as a light-shielding film
  • the thin film is formed outside the position where the earth pin of an electron beam drawing device or the like contacts.
  • the position where the ground pin comes into contact is often a position close to the ridgeline with the chamfered surface on the main surface of the substrate.
  • the masking plate As a method of confirming the position accuracy of the masking plate, the masking plate is actually installed on the substrate, the light-shielding film is formed by sputtering, and the area where the light-shielding film is formed is magnified and visually recognized by an optical camera. rice field. As a result, it may be difficult to confirm the boundary between the region where the light-shielding film is formed and the region where the light-shielding film is not formed, which has been a problem. Further, such a problem is not limited to the light-shielding film, and may occur in a mask for other purposes in which a thin film is provided on the substrate.
  • the present invention has been made to solve the conventional problems, and when a thin film is formed on a substrate, a region where the thin film is formed and a region where the thin film is not formed (a region where the substrate is exposed).
  • the purpose is to make it easy to visually recognize the boundary with.
  • a mask blank capable of easily adjusting the position of the masking plate provided in the sputtering apparatus for forming the thin film so as to prevent the thin film from being formed around the side surface or the chamfered surface of the substrate is provided.
  • the purpose is to provide.
  • An object of the present invention is to provide a method for manufacturing a semiconductor device using such a transfer mask.
  • a mask blank that includes a substrate and a thin film.
  • the substrate has two main surfaces and side surfaces, and a chamfered surface is provided between the two main surfaces and the side surfaces.
  • One of the two main surfaces has an inner region including the center of the main surface and an outer peripheral region outside the inner region.
  • the thin film is provided on the inner region of the main surface.
  • the surface reflectance Rs of the outer peripheral region of the main surface with respect to light having a wavelength of 400 nm to 700 nm is 10% or less.
  • the contrast ratio (Rf / Rs) is 3.0 when the surface reflectance for light having a wavelength of 400 nm to 700 nm at one of the locations where the thickness of the thin film is in the range of 9 nm to 10 nm is Rf.
  • the mask blank of the present invention when a thin film is formed on a substrate, it becomes easy to visually recognize the boundary between the region where the thin film is formed and the region where the thin film is not formed. As a result, the position of the masking plate provided in the sputtering apparatus for forming the thin film can be easily adjusted so as to avoid being formed around the side surface or the chamfered surface of the substrate.
  • the present inventors can easily visually recognize the boundary between the region where the thin film is formed and the region where the thin film is not formed (the region where the substrate is exposed). As a result, the position of the masking plate provided in the sputtering device for forming the thin film can be easily adjusted so as to avoid being formed around the side surface or the chamfered surface of the substrate. I did a study.
  • the design region on the main surface of the substrate is formed with a desired thickness, but a thin film is formed slightly outside the boundary of the design region, although the thickness is thin.
  • the formed thin film is formed to have a substantially uniform thickness in the region not covered by the masking plate on the main surface.
  • the end portion of the thin film does not have a shape having a vertical side wall. That is, the end of the thin film is outside the design area of the main surface by a certain distance, and the thin film formed outside the design area has a thickness from the boundary position of the design area toward the end. Has a shape that becomes thinner.
  • this method uses image data captured by an imaging camera such as a CCD to identify the edge of the thin film (hereinafter, this method is referred to as "this method”.
  • image identification method it is sometimes called "image identification method".
  • image identification method it is difficult to accurately detect the boundary between the region where the thin film is formed and the region where the thin film is not formed (the region where the main surface is exposed) on the main surface.
  • the thin film is located where a certain contrast ratio or more can be obtained between the light reflected in the region where the thin film is not formed and the light reflected in the region where the thin film is formed. Identified as existing.
  • the position of the outermost end of the region where the thin film identified by this image identification method exists is slightly inside the position of the outermost end of the region where the thin film actually exists.
  • the present inventors investigated the tendency of the thickness of the thin film from the design region of the thin film formed on the main surface of the substrate by sputtering to the edge of the thin film, and then examined the thickness of the thin film and visible light ( Specifically, we focused on the relationship with the reflectance of light having a wavelength of 400 nm to 700 nm. Hereinafter, light in this wavelength band may be referred to as “light in the visible light region”), and further diligent studies were conducted.
  • the existence of the thin film can be identified at the position where the thickness of the thin film is 10 nm at the maximum by the above image acquisition method, the outermost end of the region where the thin film actually exists It was found that the difference from the position of the masking plate is small and the position of the masking plate can be adjusted with high accuracy.
  • the surface reflectance to light in the visible light region in the outer peripheral region where the thin film is not formed on the main surface of the substrate is low. It was found that the surface reflectance should be 10% or less.
  • the surface reflectance of the thin film to light in the visible light region at that part and the part where the main surface of the substrate is exposed is 3.0 or more.
  • the above contrast ratio can be maintained at 3.0 or more even if the thickness of the thin film is reduced by 10 nm to 1 nm.
  • the mask blank of the present invention is a mask blank including a substrate and a thin film, and the substrate has two main surfaces and side surfaces, and a chamfered surface is provided between the two main surfaces and the side surfaces.
  • the main surface of one of the two main surfaces is provided and has an inner region including the center of the main surface and an outer peripheral region outside the inner region, and the thin film is provided on the inner region of the main surface.
  • the surface reflectance Rs of the outer peripheral region of the main surface with respect to light having a wavelength of 400 nm to 700 nm is 10% or less, and the film thickness of the thin film is in the range of 9 nm to 10 nm at one of the locations.
  • the contrast ratio (Rf / Rs) is 3.0 or more.
  • FIG. 1 is a cross-sectional view showing the configuration of the mask blank 100 according to the embodiment of the present invention.
  • the mask blank 100 of the present invention shown in FIG. 1 has a structure in which a phase shift film 20, a light shielding film 30, and a hard mask film 31 are laminated in this order on a translucent substrate 10.
  • the translucent substrate 10 can be formed of, in addition to synthetic quartz glass, quartz glass, aluminosilicate glass, soda lime glass, low thermal expansion glass (SiO 2- TiO 2 glass, etc.) and the like.
  • synthetic quartz glass is particularly preferable as a material for forming a translucent substrate for a mask blank because it has high transmittance for ArF exposure light and has sufficient rigidity to prevent deformation.
  • the substrate 10 housed in the chamber (not shown) is chamfered formed by chamfering the two main surfaces 11 (11a, 11b), the side surface 12, and the boundary between the main surface 11 and the side surface 12. It has a surface 13.
  • the boundary between the main surface 11 and the chamfered surface 13 is preferably less than 0.5 mm from the side surface 12 of the substrate when viewed from the main surface 11 side, and more preferably 0.4 mm or less.
  • one of the two main surfaces 11 has an inner region 14 including the center 17 of the main surface 11a and an outer outer peripheral region 15 of the inner region 14. ..
  • a light-shielding film 30 which is a thin film is provided on the inner region 14.
  • the light-shielding film 30 is not substantially formed on the outer peripheral region 15, that is, the main surface 11a is substantially exposed.
  • sputter particles constituting the light-shielding film 30 are slightly adhered and deposited at less than 1 nm. The state is also included.
  • the boundary line and the center 17 of the inner region 14 and the outer peripheral region 15 shown in FIG. 2 are virtual ones attached for explanation, and are not necessarily actually attached on an actual substrate. I will add a point just in case.
  • the boundary line between the inner region 14 and the outer peripheral region 15 is preferably 0.05 mm or more and inside from the boundary between the chamfered surface 13 of the substrate 10 and the main surface 11a.
  • the surface reflectance Rs of the outer peripheral region 15 of the substrate 10 with respect to light having a wavelength of 400 nm to 700 nm is preferably 10% or less, more preferably 8% or less, and further preferably 7% or less. preferable. Both the surface reflectance Rs and the surface reflectance Rf described later can be measured based on image data taken by an imaging camera such as a CCD.
  • the surface reflectance Rf of the thin film With respect to light having a wavelength of 400 nm to 700 nm when the film thickness of the thin film is in the range of 9 nm to 10 nm. It becomes easy to adjust the contrast ratio so that it becomes 3.0 or more.
  • phase shift film 20 which is an intermediate film is provided between the two.
  • the phase shift film 20 is made of a material containing silicon.
  • the phase shift film 20 has a function of transmitting the exposure light of the ArF excimer laser with a transmittance of 1% or more (transmittance) and the same thickness as the phase shift film 20 with respect to the exposure light transmitted through the phase shift film 20.
  • the light transmissive film has a function of causing a phase difference of 150 degrees or more and 210 degrees or less with the exposed light that has passed through the air for a distance.
  • the transmittance of the phase shift film 20 is preferably 1% or more, and more preferably 2% or more.
  • the transmittance of the phase shift film 20 is preferably 30% or less, and more preferably 20% or less.
  • the thickness of the phase shift film 20 is preferably 80 nm or less, and more preferably 70 nm or less.
  • the thickness of the phase shift film 20 is preferably 50 nm or more. This is because 50 nm or more is required to make the phase difference of the phase shift film 20 150 degrees or more while forming the phase shift film 20 from an amorphous material.
  • the refractive index n of the phase shift film with respect to the exposure light is preferably 1.9 or more, and 2 It is more preferable that it is 0.0 or more.
  • the refractive index n of the phase shift film 20 is preferably 3.1 or less, and more preferably 2.7 or less.
  • the extinction coefficient k of the phase shift film 20 with respect to ArF exposure light is preferably 0.26 or more, and more preferably 0.29 or more.
  • the extinction coefficient k of the phase shift film 20 is preferably 0.62 or less, and more preferably 0.54 or less.
  • the refractive index n and the extinction coefficient k of the thin film including the phase shift film 20 are not determined only by the composition of the thin film.
  • the film density and crystal state of the thin film are also factors that influence the refractive index n and the extinction coefficient k. Therefore, various conditions for forming the thin film by reactive sputtering are adjusted so that the thin film has a desired refractive index n and extinction coefficient k.
  • a mixed gas of a noble gas and a reactive gas oxygen gas, nitrogen gas, etc.
  • Adjusting the ratio is effective, but not limited to it.
  • There are various positional relationships such as the pressure in the film forming chamber when forming by reactive sputtering, the electric power applied to the sputtering target, and the distance between the target and the translucent substrate 10. Further, these film forming conditions are unique to the film forming apparatus, and are appropriately adjusted so that the formed phase shift film 20 has a desired refractive index n and extinction coefficient k.
  • the mask blank 100 includes a light-shielding film 30 which is a thin film on the phase shift film 20.
  • a binary type transfer mask the outer peripheral region of a region where a transfer pattern is formed (transfer pattern forming region) is transmitted through the outer peripheral region when exposure-transferred to a resist film on a semiconductor wafer using an exposure apparatus. It is required to secure an optical density (OD) equal to or higher than a predetermined value so that the resist film is not affected by the exposure light. This point is the same for the phase shift mask.
  • OD optical density
  • it is desirable that the OD is 3.0 or more, and it is required that the OD is at least 2.0 or more.
  • the phase shift film 20 has a function of transmitting exposure light with a predetermined transmittance, and it is difficult to secure a predetermined value of optical density only with the phase shift film 20. Therefore, at the stage of manufacturing the mask blank 100, it is necessary to laminate the light-shielding film 30 on the phase-shift film 20 in order to secure the insufficient optical density. With such a configuration of the mask blank 100, the light-shielding film 30 in the region where the phase shift effect is used (basically the transfer pattern forming region) is removed during the production of the phase shift mask 200 (see FIG. 3). Then, the phase shift mask 200 in which the optical density of a predetermined value is secured in the outer peripheral region can be manufactured.
  • the light-shielding film 30 needs to function as an etching mask during dry etching with a fluorine-based gas for forming a transfer pattern (phase shift pattern) on the phase shift film 20. Therefore, for the light-shielding film 30, it is necessary to apply a material having sufficient etching selectivity with respect to the phase shift film 20 in dry etching with a fluorine-based gas.
  • the light-shielding film 30 is required to be able to accurately form a fine pattern to be formed on the phase shift film 20.
  • the average film thickness of the light-shielding film 30 is preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 40 nm or less.
  • the average film thickness of the light-shielding film 30 is required to be larger than 10 nm, and is preferably 15 nm or more, excluding the end region that is the boundary between the inner region 14 and the outer peripheral region 15.
  • the average film thickness is not particularly limited, but the region where the light-shielding film 30 is formed is divided into an area of about 55 ⁇ m ⁇ about 55 ⁇ m, and the average film thickness measured in each area is calculated. It can be calculated by taking.
  • the light-shielding film 30 which is a thin film has a surface reflectance of Rf at one of the places where the film thickness of the light-shielding film 30 is in the range of 9 nm to 10 nm with respect to light having a wavelength of 400 nm to 700 nm.
  • the contrast ratio (Rf / Rs) is configured to be 3.0 or more. This makes it easy to distinguish the boundary between the region where the light-shielding film 30 which is a thin film is formed and the region where the light-shielding film 30 is not formed.
  • the surface reflectance Rf at the above-mentioned one location is preferably 20% or more with respect to light having a wavelength of 400 nm to 700 nm.
  • the portion of the light-shielding film 30 (thin film) that defines the surface reflectance Rf is not strictly the outermost end of the light-shielding film 30.
  • the difference from the position of the light-shielding film 30 to the position of the outermost end is small, and it is sufficiently possible to adjust the position of the masking plate with reference to this.
  • the sheet resistance value of the light-shielding film 30 is preferably 1 k ⁇ / Square or less, and more preferably 0.5 k ⁇ / Square or less.
  • the light-shielding film 30 has a surface reflectance of RfB for light having a wavelength of 400 nm at one of the locations where the film thickness is in the range of 9 nm to 10 nm, and a surface reflectance of RfG for light having a wavelength of 550 nm at the above-mentioned one location.
  • RfB surface reflectance for light having a wavelength of 400 nm at one of the locations where the film thickness is in the range of 9 nm to 10 nm
  • RfG the standard deviation calculated among the three surface reflectances RfB, RfG, and RfR is preferably 1.0 or less. .. It can be relatively easily obtained from the RGB values of the image data taken by an imaging camera such as a CCD. The smaller the deviation of each reflectance with respect to the light of the above three wavelengths, the easier it is to visually recognize the existence of the light-shielding film 30.
  • the extinction coefficient k of the light-shielding film 30 with respect to light having a wavelength of 400 nm to 700 nm is preferably 1.5 or more, and more preferably 2.0 or more. Further, the extinction coefficient k of the light-shielding film 30 with respect to the light is preferably 4.0 or less, and more preferably 3.5 or less.
  • the light-shielding film 30 can be applied to both a single-layer structure and a laminated structure having two or more layers.
  • each layer of the light-shielding film having a single-layer structure and the light-shielding film having a laminated structure of two or more layers has substantially the same composition in the thickness direction of the film or the layer, the composition is inclined in the thickness direction of the layer. It may be a configuration.
  • the light-shielding film 30 may be made of any material as long as the above contrast ratio conditions are satisfied.
  • the light-shielding film 30 is preferably formed of a material containing chromium.
  • chromium (Cr) is selected from oxygen (O), nitrogen (N), carbon (C), boron (B) and fluorine (F). Examples include materials containing one or more elements.
  • a chromium-based material is etched with a mixed gas of a chlorine-based gas and an oxygen gas, but a chromium metal does not have a very high etching rate with respect to this etching gas.
  • the material for forming the light-shielding film 30 is one or more elements selected from oxygen, nitrogen, carbon, boron and fluorine in chromium.
  • a material containing is preferable.
  • the chromium-containing material forming the light-shielding film 30 may contain one or more elements of molybdenum, indium and tin. By containing one or more elements of molybdenum, indium and tin, the etching rate for a mixed gas of chlorine-based gas and oxygen gas can be made faster.
  • the light-shielding film 30 can be formed on the phase-shift film 20 by a reactive sputtering method using a target containing chromium.
  • the sputtering method may be a direct current (DC) power supply (DC sputtering) or a radio frequency (RF) power supply (RF sputtering).
  • DC sputtering is preferable because the mechanism is simple. Further, it is preferable to use the magnetron sputtering method because the film formation rate becomes faster and the productivity is improved.
  • the film forming apparatus may be an in-line type or a single-wafer type.
  • the sputtering gas used when forming the light-shielding film 30 includes a gas containing carbon without oxygen (CH 4 , C 2 H 4 , C 2 H 6, etc.) and a gas containing oxygen without carbon (O 2). , O 3, etc.) and a noble gas (Ar, Kr, Xe, He , gas mixture containing Ne, etc.) and a mixed gas comprising a gas containing carbon and oxygen (CO 2, CO, etc.) and a noble gas, or a noble Gas and gas containing carbon and oxygen, mixed gas containing at least one of oxygen-free carbon-containing gas (CH 4 , C 2 H 4 , C 2 H 6, etc.) and carbon-free oxygen-containing gas One of them is preferable.
  • the gas can circulate uniformly over a wide range in the chamber. It is preferable from the viewpoint that the film quality of the light-shielding film 30 to be formed becomes uniform.
  • introduction method it may be introduced into the chamber separately, or several gases may be introduced together or all the gases may be mixed and introduced.
  • the target material may be not only chromium alone but also chromium as the main component, and a target in which chromium containing either oxygen or carbon or a combination of oxygen and carbon is added to chromium may be used.
  • the mask blank of the present invention is not limited to the one shown in FIG. 1, and may be configured such that another film (etching stopper film) is interposed between the phase shift film 2 and the light shielding film 30. good.
  • the etching stopper film is formed of the chromium-containing material and the light-shielding film 30 is formed of the silicon-containing material or the tantalum-containing material.
  • the mask blank of the present invention is not limited to the mask blank for the phase shift mask described above, and can be applied to the mask blank for the binary mask. In this case, the mask blank has a configuration in which the phase shift film 20 is not provided between the main surface 11a of the translucent substrate 10 and the light-shielding film 30.
  • the above-mentioned predetermined optical density is secured only by the light-shielding film 30.
  • a binary mask transfer mask
  • the mask blank of the present invention may be a reflective mask blank for EUV lithography (Extreme Ultraviolet Lithography).
  • EUV lithography Extreme Ultraviolet Lithography
  • the absorber membrane is composed of the thin film of the present embodiment.
  • the silicon-containing material forming the light-shielding film 30 may contain a transition metal or may contain a metal element other than the transition metal.
  • the pattern formed on the light-shielding film 30 is basically a light-shielding band pattern in the outer peripheral region, and the integrated irradiation amount of ArF exposure light is smaller than that in the transfer pattern region, and a fine pattern is arranged in this outer peripheral region. This is because it is rare, and even if the ArF light resistance is low, a substantial problem is unlikely to occur.
  • the transition metal when the transition metal is contained in the light-shielding film 30, the light-shielding performance is greatly improved as compared with the case where the light-shielding film 30 is not contained, and the thickness of the light-shielding film 30 can be reduced.
  • the transition metal contained in the light-shielding film 30 include molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), chromium (Cr), hafnium (Hf), nickel (Ni), and vanadium (V). , Zirconium (Zr), ruthenium (Ru), rhodium (Rh), niobium (Nb), palladium (Pd) and the like, or an alloy of these metals.
  • a hard mask film 31 formed of a material having etching selectivity with respect to the etching gas used when etching the light-shielding film 30 may be further laminated on the light-shielding film 30.
  • the hard mask film 31 since the hard mask film 31 is formed in a region inside the light-shielding film 30, there is no problem in ensuring the conductivity between the light-shielding film 30 and the resist film. It is sufficient for the hard mask film 31 to have a film thickness sufficient to function as an etching mask until the dry etching for forming a pattern on the light-shielding film 30 immediately below the hard mask film 31 is completed. Not restricted by.
  • the thickness of the hard mask film 31 can be made significantly thinner than the thickness of the light-shielding film 30.
  • the resist film made of an organic material is significantly thicker than the conventional one because it is sufficient that the resist film is thick enough to function as an etching mask until the dry etching for forming a pattern on the hard mask film is completed. The thickness can be reduced. Thinning the resist film is effective in improving the resist resolution and preventing pattern collapse, and is extremely important in meeting the miniaturization requirements.
  • the hard mask film 31 is preferably formed of the material containing silicon. Since the hard mask film 31 in this case tends to have low adhesion to the resist film of the organic material, the surface of the hard mask film 31 is subjected to HMDS (Hexamethyldisilazane) treatment to improve the adhesion of the surface. Is preferable.
  • the hard mask film in this case is more preferably formed of SiO 2 , SiN, SiON, or the like.
  • a material containing tantalum can also be applied as the material of the hard mask film 31 when the light-shielding film 30 is made of a material containing chromium.
  • a material containing tantalum in this case include, in addition to tantalum metal, a material in which tantalum contains one or more elements selected from nitrogen, oxygen, boron, carbon and silicon.
  • the hard mask film 31 is preferably formed of the above-mentioned material containing chromium.
  • a resist film made of an organic material may be formed in contact with the surface of the light-shielding film 30 (or the surface of the hard mask film 31 when the hard mask film 31 is formed).
  • SRAF Sub-Resolution Assist Feature
  • the thickness of the resist film can be suppressed by providing the hard mask film 31 as described above, whereby the cross-sectional aspect ratio of the resist pattern composed of the resist film is set to 1: 2.5. Can be lowered.
  • the resist film has a film thickness of 80 nm or less.
  • the resist film is preferably a resist for electron beam drawing exposure, and more preferably a chemically amplified resist.
  • the mask blank 100 having the above configuration is manufactured by the following procedure.
  • the translucent substrate 10 is prepared.
  • the side surface 12 and the main surface 11 are polished to a predetermined surface roughness (for example, the root mean square roughness Rq is 0.2 nm or less in the inner region of a quadrangle having a side of 1 ⁇ m), and then the surface roughness Rq is 0.2 nm or less.
  • a predetermined surface roughness for example, the root mean square roughness Rq is 0.2 nm or less in the inner region of a quadrangle having a side of 1 ⁇ m
  • phase shift film 20 is formed on the translucent substrate 10 by a sputtering method. After forming the phase shift film 20, annealing treatment is performed at a predetermined heating temperature. Next, the light-shielding film 30 is formed on the phase shift film 20 by a sputtering method.
  • FIG. 4 shows a main part of the masking plate used when forming the light-shielding film 30.
  • both ends of the substrate 10 are positioned and held by the substrate holding portion 51.
  • a shielding plate 52 that covers the peripheral edge of the substrate 10 is provided above the substrate 10.
  • the shielding plate 52 is provided in a state where the position can be adjusted so as to approach or separate from the center 17 of the main surface 11a of the substrate 10 while maintaining a non-contact state with the substrate 10. By adjusting the positions of these shielding plates 52, it is possible to prevent the light-shielding film material supplied from the sputtering target 50 from adhering to the peripheral edge of the substrate 10.
  • the above-mentioned hard mask film 31 is formed on the light-shielding film 30 by a sputtering method.
  • a sputtering target and a sputtering gas containing the materials constituting each layer in a predetermined composition ratio are used, and if necessary, a mixed gas of the above-mentioned noble gas and a reactive gas is used as a sputtering gas.
  • the formation used as is performed.
  • the surface of the hard mask film 31 is subjected to HMDS (Hexamethyldisilazane) treatment as needed.
  • a resist film is formed on the surface of the HMDS-treated hard mask film 31 by a coating method such as a spin coating method to complete the mask blank 100.
  • phase shift mask 200 which is a transfer mask of this embodiment, a transfer pattern (phase shift pattern) 20a is formed on the phase shift film 20 of the mask blank 100, and a light shielding pattern 30b including a light shielding band is formed on the light shielding film 30. It is characterized by being.
  • the hard mask film 31 is removed during the process of producing the phase shift mask 200.
  • the method for manufacturing the phase shift mask 200 according to the present invention uses the mask blank 100, and uses a step of forming a transfer pattern on the light-shielding film 30 by dry etching and a light-shielding film 30 having the transfer pattern as a mask.
  • a step of forming a transfer pattern on the phase shift film 20 by dry etching and a step of forming a light-shielding pattern 30b on the light-shielding film 30 by dry etching using a resist film (resist pattern 40b) having a light-shielding band pattern as a mask are provided. It is characterized by.
  • the method for manufacturing the phase shift mask 200 of the present invention will be described according to the manufacturing process shown in FIG.
  • a resist film is formed on the hard mask film 31 of the mask blank 100 by a spin coating method.
  • the first pattern (phase shift pattern) to be formed on the phase shift film 20 is exposed and drawn on the resist film with an electron beam.
  • a ground pin (not shown) is in contact with the light-shielding film 30 on which the resist film is formed, and a ground is secured between the resist film and the light-shielding film 30 (earth pin grounding point 16 in FIG. 2). See).
  • a predetermined process such as PEB treatment, development treatment, and post-baking treatment is performed on the resist film to form a first resist pattern 40a corresponding to the phase shift pattern on the resist film (see FIG. 3A). ..
  • the hard mask film 31 is dry-etched using a fluorine-based gas to form the first pattern, the hard mask pattern 31a, on the hard mask film 31 (FIG. 3B). reference).
  • the resist pattern 40a is removed.
  • the light-shielding film 30 may be dry-etched while the resist pattern 40a is not removed and remains. In this case, the resist pattern 40a disappears during the dry etching of the light-shielding film 30.
  • dry etching is performed using an oxygen-containing chlorine-based gas to form the first pattern, the light-shielding pattern 30a, on the light-shielding film 30 (see FIG. 3C).
  • etching using a fluorine-based gas is performed using the light-shielding pattern 30a as a mask to form the phase shift pattern 20a, which is the first pattern, on the phase shift film 20 and remove the hard mask pattern 31a (FIG. 6). 3 (d)).
  • a resist film is formed on the light-shielding pattern 30a by a spin coating method.
  • a light-shielding pattern which is a second pattern to be formed on the light-shielding film 30, is exposed and drawn on the resist film with an electron beam.
  • a predetermined process such as a developing process is performed to form a resist film having a resist pattern 40b, which is a second pattern corresponding to the light-shielding pattern (see FIG. 3E).
  • the chlorine-based gas used in the dry etching during the above manufacturing process is not particularly limited as long as it contains Cl.
  • examples of the chlorine-based gas include Cl 2 , NaCl 2 , CHCl 3 , CH 2 Cl 2 , CCl 4 , BCl 3, and the like.
  • the fluorine-based gas used in the dry etching during the above manufacturing process is not particularly limited as long as F is contained.
  • examples of the fluorine-based gas include CHF 3 , CF 4 , C 2 F 6 , C 4 F 8 , SF 6, and the like.
  • the fluorine-based gas containing no C has a relatively low etching rate with respect to the glass substrate, damage to the glass substrate can be further reduced.
  • the phase shift mask 200 of the present invention is manufactured by using the above-mentioned mask blank 100. Therefore, it is possible to secure the grounding for the resist and suppress dust generation, so that good pattern transfer can be performed.
  • a step of exposing and transferring a transfer pattern to a resist film on a semiconductor substrate using the phase shift mask 200 or the phase shift mask 200 manufactured by using the mask blank 100 is performed. It is characterized by being prepared. Therefore, the phase shift mask 200 is set in the exposure apparatus, and ArF exposure light is irradiated from the translucent substrate 1 side of the phase shift mask 200 to perform exposure transfer to a transfer target (resist film or the like on a semiconductor wafer). The desired pattern can be transferred to the transfer target with high accuracy.
  • Example 1 Manufacturing of mask blank
  • 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 6.35 mm was prepared.
  • the main surface of the translucent substrate 10 is polished to a predetermined surface roughness (0.2 nm or less in Rq), and then subjected to a predetermined cleaning treatment and a drying treatment.
  • the translucent substrate 10 has two main surfaces 11 and four side surfaces 12, and has a chamfered surface 13 between the main surface 11 and the side surfaces 12.
  • the boundary (ridge line) between the chamfered surface 13 and the main surface 11 is located 0.4 mm from the side surface 12 of the substrate on the center 17 side when viewed from the main surface 11 side.
  • the surface reflectance Rs for light having a wavelength of 400 nm to 700 nm was measured at a plurality of locations on the main surface 11a of the translucent substrate 10, it was 7% or less (wavelength 400 nm: 6.99%, wavelength) in any region. 550 nm: 6.75%, wavelength 700 nm: 6.62%).
  • a phase shift composed of molybdenum, silicon and nitrogen on the translucent substrate 10 by reactive sputtering (DC sputtering) using a mixed gas of argon (Ar), nitrogen (N 2) and helium (He) as the sputtering gas.
  • the film 20 was formed to a thickness of 69 nm.
  • a masking plate as shown in FIG. 4 was used.
  • the masking plate used has a square opening with a side of 146 mm relative to the center of the substrate.
  • the translucent substrate 10 on which the phase shift film 20 was formed was heat-treated to reduce the film stress of the phase shift film 20 and to form an oxide layer on the surface layer.
  • a heating treatment was performed in the atmosphere using a heating furnace (electric furnace) with a heating temperature of 450 ° C. and a heating time of 1 hour.
  • the transmittance and phase difference of the heat-treated phase shift film 20 with respect to light having a wavelength of 193 nm were measured using a phase shift amount measuring device (MPM193 manufactured by Lasertec), the transmittance was 6.0% and the phase difference was It was 177.0 degrees (deg).
  • a translucent substrate 10 having a phase shift film 20 formed therein is installed in a single-wafer DC sputtering apparatus, and an argon (Ar), carbon dioxide (CO 2 ) and helium are used using a chromium (Cr) target.
  • Reactive sputtering (DC sputtering) was performed in a mixed gas atmosphere of (He).
  • a light-shielding film (CrOC film) 30 made of chromium, oxygen, and carbon was formed with a film thickness of 18 nm in contact with the phase shift film 20.
  • a masking plate was also used during sputtering for forming the light-shielding film 30.
  • the masking plate used here has a square opening with a side of 150 mm with respect to the center of the substrate (that is, the design area is a square area with a side of 150 mm).
  • the size of one side of the main surface 11 of the substrate is 151.2 mm, and the margin with respect to the design area is considerably small.
  • the translucent substrate 10 on which the light-shielding film (CrOC film) 30 was formed was heat-treated. Specifically, a hot plate was used to perform heat treatment in the atmosphere at a heating temperature of 280 ° C. and a heating time of 5 minutes.
  • a spectrophotometer Cary 4000 manufactured by Azilent Technology Co., Ltd.
  • magnified image data was acquired using a CCD camera for each of the four corners of the main surface 11a of the translucent substrate 10 on which the light-shielding film 30 was formed.
  • the boundary between the light-shielding film 30 and the main surface 11a could be visually recognized.
  • a place where the main surface 11a is completely covered with the light-shielding film 30 was found (the light-shielding film 30 may wrap around to the chamfered surface 13). .. That is, it was found that the masking plate could not be placed in an appropriate position.
  • the region where the main surface 11a is exposed (the region where the light-shielding film 30 is not formed) and the region where the light-shielding film 30 is formed are defined with the side surface 12 as a reference.
  • the distance to the boundary was measured respectively. From this result, the difference between the center 17 of the translucent substrate 10 and the center of the masking plate during sputtering was calculated, and the installation position of the masking plate was finely adjusted.
  • phase shift film 20 and the light-shielding film 30 were formed by sputtering in the same procedure as described above. Further, in the same procedure as above, image data of each of the four corners of the main surface 11a of the translucent substrate 10 on which the light-shielding film 30 was formed was acquired. Then, in the same procedure as above, the distance to the boundary between the region where the main surface 11a is exposed and the region where the light-shielding film 30 is formed is based on the side surface 12 for each of the image data at the four corners. Were measured respectively.
  • the film thickness profile near the boundary between the main surface 11a and the light-shielding film 30 was measured with a contact-type fine shape measuring machine (ET-4000 manufactured by Kosaka Laboratory). The result is shown in FIG. From this result, it was found that the light-shielding film 30 began to be formed from a position at a distance between 0.47 mm and 0.53 mm inward from the side surface 12 on the main surface 11a. Further, from the above image data, the surface reflectance Rf of a plurality of measurement points (locations) where the thickness of the light-shielding film 30 is between 9 nm and 10 nm with respect to light having a wavelength of 400 nm to 700 nm was measured and found to be 23.65% on average.
  • the surface reflectance Rf for light within the above wavelength range was 20% or more. Further, when the contrast ratio (Rf / Rs) of the surface reflectance Rf of the light-shielding film 30 at the measurement point was calculated with respect to the surface reflectance Rs of the main surface 11a, the minimum was 3.29, which was 3.0 or more. It was. Further, the surface reflectance RfB for light having a wavelength of 400 nm at the measurement point where the surface reflectance Rf is maximum (24.69%) is 24.96%, and the surface reflectance RfG for light having a wavelength of 550 nm is 25.06%. The surface reflectance RfR for light having a wavelength of 700 nm was 24.08%. The standard deviation calculated among the three surface reflectances RfB, RfG, and RfR was 0.441, which was 1.0 or less.
  • the region where the light-shielding film 30 is formed (that is, the inner region 14) is divided into areas of 55 ⁇ m ⁇ 55 ⁇ m, and the average film thickness measured in each area is taken to obtain the average film thickness of the light-shielding film 30. Calculated. The calculated average film thickness of the light-shielding film 30 was 18 nm.
  • a translucent substrate 10 on which a phase shift film 20 and a light-shielding film 30 are laminated is installed in a single-wafer DC sputtering apparatus, and an argon (Ar) and nitrogen monoxide (Argon) and nitrogen monoxide (Argon) and nitrogen monoxide (Argon (Ar)) and nitrogen monoxide (Argon) are used by using a silicon (Si) target.
  • a hard mask film 31 made of silicon, nitrogen and oxygen has a thickness of 5 nm on the light-shielding film 30 and inside the edge of the light-shielding film 30 by reactive sputtering (DC sputtering) in a mixed gas atmosphere of NO). Formed with a gas.
  • a masking plate having a square opening with a side of 146 mm with respect to the center of the substrate was used. Further, a predetermined cleaning treatment was performed to produce the mask blank 100 of Example 1.
  • a light-shielding film 30 was formed on the main surface 11a of another translucent substrate 10 under the same conditions and heat-treated.
  • the sheet resistance value of the light-shielding film 30 was measured, it was 0.246 k ⁇ / Square, which was 0.5 k ⁇ / Square or less.
  • the refractive index n and the extinction coefficient k of the light-shielding film 30 with respect to light having a wavelength of 400 nm to 700 nm were measured.
  • the extinction coefficient k for light having a wavelength of 400 nm is 2.33
  • the extinction coefficient k for light having a wavelength of 550 nm is 2.53
  • the extinction coefficient k for light having a wavelength of 700 nm is 3.01, which is 2.0 or more. It was confirmed that.
  • the refractive index n for light having a wavelength of 400 nm was 2.52
  • the refractive index n for light having a wavelength of 400 nm was 2.96
  • the refractive index n for light having a wavelength of 400 nm was 3.57.
  • the light-shielding film 30 was analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction). As a result, the region near the surface of the light-shielding film 30 opposite to the translucent substrate 10 side (the region from the surface to a depth of about 2 nm) has a higher oxygen content than the other regions (composition inclined portion). It was confirmed that the oxygen content was 40 atomic% or more). Further, it was found that the content of each constituent element in the region excluding the composition inclined portion of the light-shielding film 30 was Cr: 71 atomic%, O: 14 atomic%, and C: 15 atomic% on average. Further, it was confirmed that the difference of each constituent element in the thickness direction of the region excluding the composition gradient portion of the light-shielding film 30 was 3 atomic% or less, and there was substantially no composition gradient in the thickness direction.
  • the halftone type phase shift mask 200 of Example 1 was manufactured by the following procedure. First, the surface of the hard mask film 31 was subjected to HMDS treatment. Subsequently, a resist film made of a chemically amplified resist for electron beam writing was formed with a film thickness of 80 nm in contact with the surface of the hard mask film 31 by a spin coating method. Next, a first pattern, which is a phase shift pattern to be formed on the phase shift film 20, is electron-beam-drawn on the resist film, subjected to a predetermined development process and a cleaning process, and a resist having the first pattern is performed. A pattern 40a was formed (see FIG. 3A).
  • the light-shielding film 30 was brought into contact with the ground pin (not shown) at the ground pin grounding point 16. As a result, an electron beam was drawn on the resist film at a desired position, and a desired resist pattern 40a could be formed.
  • the resist pattern 40a was removed.
  • the light-shielding pattern 30a which is the pattern of No. 1, was formed on the light-shielding film 30 (see FIG. 3C).
  • dry etching is performed using a fluorine-based gas (SF 6 + He) to form the first pattern, the phase shift pattern 20a, on the phase shift film 20, and at the same time, the hard mask pattern. 31a was removed (see FIG. 3D).
  • a resist film made of a chemically amplified resist for electron beam drawing was formed on the light-shielding pattern 30a by a spin coating method with a film thickness of 150 nm.
  • a second pattern which is a pattern to be formed on the light-shielding film (a pattern including a light-shielding band pattern), is exposed and drawn on the resist film, and further subjected to a predetermined process such as a development process to have a light-shielding pattern.
  • a resist pattern 40b was formed (see FIG. 3E).
  • Comparative Example 1 Manufacturing of mask blank
  • the mask blank of Comparative Example 1 was manufactured in the same procedure as in Example 1 except for the light-shielding film.
  • the light-shielding film of Comparative Example 1 has different film forming conditions from the light-shielding film 3 of Example 1. Specifically, a translucent substrate having a phase shift film formed in a single-wafer DC sputtering apparatus is installed, and an argon (Ar), carbon dioxide (CO 2 ), and helium are used using a chromium (Cr) target. Reactive sputtering (DC sputtering) was performed in a mixed gas atmosphere of (He).
  • a light-shielding film composed of chromium, oxygen and carbon was formed with a film thickness of 24 nm in contact with the phase shift film.
  • a masking plate having a square opening with a side of 150 mm was used as in Example 1.
  • the translucent substrate on which the light-shielding film (CrOC film) was formed was heat-treated under the same conditions as in Example 1.
  • a spectrophotometer (Cary 4000 manufactured by Azilent Technology Co., Ltd.) was used on the translucent substrate on which the phase shift film and the light shielding film were laminated, and the light of the ArF excimer laser having a laminated structure of the phase shift film and the light shielding film was used.
  • the optical density at the wavelength about 193 nm
  • the film thickness profile near the boundary between the main surface and the light-shielding film of Comparative Example 1 was measured with a contact-type fine shape measuring machine (ET-4000 manufactured by Kosaka Laboratory). From the above image data, the surface reflectance Rf of a plurality of measurement points (locations) where the thickness of the light-shielding film is between 9 nm and 10 nm with respect to light having a wavelength of 400 nm to 700 nm was measured and found to be 14.85% on average. The surface reflectance Rf for light in the above wavelength range was significantly less than 20%.
  • the contrast ratio (Rf / Rs) of the surface reflectance Rf of the light-shielding film of Comparative Example 1 at the measurement point was 2.27 at the maximum. It was well below 0.
  • the surface reflectance RfB for light having a wavelength of 400 nm at the measurement point where the surface reflectance Rf is maximum (15.51%) is 17.85%
  • the surface reflectance RfG for light having a wavelength of 550 nm is 15.37%
  • the surface reflectance RfR for light having a wavelength of 700 nm was 13.32%.
  • the standard deviation calculated among the three surface reflectances RfB, RfG, and RfR was 1.853, well above 1.0.
  • the region where the light-shielding film 30 is formed (that is, the inner region 14) is divided into an area of 55 ⁇ m ⁇ 55 ⁇ m, and the average film thickness measured in each area is taken to obtain an average film of the light-shielding film 30. The thickness was calculated. The calculated average film thickness of the light-shielding film 30 was 24 nm.
  • a light-shielding film was formed on the main surface of another translucent substrate under the same conditions and heat-treated.
  • the sheet resistance value of the light-shielding film of Comparative Example 1 was measured, it was 168 k ⁇ / Square, which was significantly higher than 1.0 k ⁇ / Square.
  • the refractive index n and the extinction coefficient k of the light-shielding film with respect to light having a wavelength of 400 nm to 700 nm were measured.
  • the extinction coefficient k for light having a wavelength of 400 nm is 1.23
  • the extinction coefficient k for light having a wavelength of 550 nm is 1.27
  • the extinction coefficient k for light having a wavelength of 700 nm is 1.2, which is 2.0. It was below.
  • the refractive index n for light having a wavelength of 400 nm was 2.42
  • the refractive index n for light having a wavelength of 400 nm was 2.64
  • the refractive index n for light having a wavelength of 400 nm was 2.67.
  • the light-shielding film was analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction). As a result, the region near the surface of the light-shielding film opposite to the translucent substrate side (the region from the surface to a depth of about 2 nm) has a higher oxygen content than the other regions (oxygen-containing). It was confirmed that the amount was 40 atomic% or more). Further, it was found that the content of each constituent element in the region excluding the composition inclined portion of the light-shielding film was Cr: 56 atomic%, O: 29 atomic%, and C: 15 atomic% on average.
  • the difference of each constituent element in the thickness direction of the region excluding the composition gradient portion of the light-shielding film was 3 atomic% or less, and there was substantially no composition gradient in the thickness direction. Since it was difficult to visually recognize the boundary between the region where the main surface is exposed and the region where the light-shielding film is formed in the light-shielding film in Comparative Example 1, fine adjustment of the installation position of the masking plate can be performed with high accuracy. It was difficult to do. For this reason, it is difficult to reliably prevent the light-shielding film from being formed around the side surface or chamfered surface of the substrate.
  • a simulation was performed. When the exposure transfer image of this simulation was verified, transfer defects were confirmed in some phase shift masks. It is presumed that this is because accurate pattern drawing cannot be performed due to the charge-up of the resist, and dust is generated due to the light-shielding film adhering to the chamfered surface of the substrate, which causes transfer defects. From this result, when the phase shift mask of Comparative Example 1 is set on the mask stage of the exposure apparatus and the exposure transfer is performed on the resist film on the semiconductor device, the circuit pattern finally formed on the semiconductor device has a defective portion. It can be said that it will occur.
  • Translucent substrate 11 (11a, 11b) Main surface 12 Side surface 13 Chamfered surface 14 Inner region 15 Outer region 16 Earthpin grounding point 17 Center 20 Phase shift film 20a Phase shift pattern 30 Shading film 30a, 30b Shading pattern 31 Hard mask film 31a Hard mask pattern 40a, 40b Resist pattern 50 Sputter target 51 Substrate holding part 52 Shielding plate 100 Mask blank 200 Phase shift mask

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
PCT/JP2021/008915 2020-03-19 2021-03-08 マスクブランク、転写用マスク、及び半導体デバイスの製造方法 Ceased WO2021187189A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202180020424.2A CN115280236B (zh) 2020-03-19 2021-03-08 掩模坯、转印用掩模及半导体器件的制造方法
KR1020227030750A KR102948025B1 (ko) 2020-03-19 2021-03-08 마스크 블랭크, 전사용 마스크, 및 반도체 디바이스의 제조 방법
US17/801,377 US20230097280A1 (en) 2020-03-19 2021-03-08 Mask blank, transfer mask, and method for manufacturing semiconductor device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-049162 2020-03-19
JP2020049162A JP7354032B2 (ja) 2020-03-19 2020-03-19 マスクブランク、転写用マスク、及び半導体デバイスの製造方法

Publications (1)

Publication Number Publication Date
WO2021187189A1 true WO2021187189A1 (ja) 2021-09-23

Family

ID=77771232

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/008915 Ceased WO2021187189A1 (ja) 2020-03-19 2021-03-08 マスクブランク、転写用マスク、及び半導体デバイスの製造方法

Country Status (6)

Country Link
US (1) US20230097280A1 (https=)
JP (1) JP7354032B2 (https=)
KR (1) KR102948025B1 (https=)
CN (1) CN115280236B (https=)
TW (1) TWI899176B (https=)
WO (1) WO2021187189A1 (https=)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12210279B2 (en) * 2021-05-27 2025-01-28 AGC Inc. Electroconductive-film-coated substrate and reflective mask blank
JP7375065B2 (ja) * 2022-02-24 2023-11-07 Hoya株式会社 マスクブランク、転写用マスクの製造方法、及び表示装置の製造方法
KR102587396B1 (ko) * 2022-08-18 2023-10-10 에스케이엔펄스 주식회사 블랭크 마스크 및 이를 이용한 포토마스크

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002090977A (ja) * 2000-09-12 2002-03-27 Hoya Corp 位相シフトマスクブランク、フォトマスクブランク、並びにそれらの製造装置及び製造方法
JP2008083194A (ja) * 2006-09-26 2008-04-10 Hoya Corp フォトマスクブランク、フォトマスクブランクの製造方法、フォトマスク、フォトマスクの製造方法、フォトマスク中間体及びパターンの転写方法
JP2014209200A (ja) * 2013-03-22 2014-11-06 Hoya株式会社 マスクブランクの製造方法および転写用マスクの製造方法
JP2016170320A (ja) * 2015-03-13 2016-09-23 信越化学工業株式会社 マスクブランクス及びその製造方法
JP2019003178A (ja) * 2017-06-14 2019-01-10 Hoya株式会社 マスクブランク、位相シフトマスク及び半導体デバイスの製造方法

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6039047U (ja) * 1983-08-24 1985-03-18 凸版印刷株式会社 マスクブランク板
TW578034B (en) * 2001-09-28 2004-03-01 Hoya Corp Method of manufacturing a mask blank and a mask, the mask blank and the mask, and useless film removing method and apparatus
WO2004051369A1 (ja) * 2002-12-03 2004-06-17 Hoya Corporation フォトマスクブランク、及びフォトマスク
TWI259329B (en) * 2003-04-09 2006-08-01 Hoya Corp Method of manufacturing a photomask, and photomask blank
JP4339214B2 (ja) * 2004-09-13 2009-10-07 Ｈｏｙａ株式会社 マスクブランク用透明基板とその製造方法及びマスクブランクとその製造方法
JP4587806B2 (ja) 2004-12-27 2010-11-24 Ｈｏｙａ株式会社 ハーフトーン型位相シフトマスクブランク及びハーフトーン型位相シフトマスク
US7632609B2 (en) * 2005-10-24 2009-12-15 Shin-Etsu Chemical Co., Ltd. Fabrication method of photomask-blank
JP5086714B2 (ja) * 2007-07-13 2012-11-28 Ｈｏｙａ株式会社 マスクブランクの製造方法及びフォトマスクの製造方法
KR101295235B1 (ko) * 2008-08-15 2013-08-12 신에쓰 가가꾸 고교 가부시끼가이샤 그레이톤 마스크 블랭크, 그레이톤 마스크, 및 제품 가공 표지 또는 제품 정보 표지의 형성방법
KR101670351B1 (ko) * 2010-11-26 2016-10-31 주식회사 에스앤에스텍 마스크 블랭크의 제조 방법 및 마스크 블랭크
WO2013146488A1 (ja) * 2012-03-28 2013-10-03 Hoya株式会社 多層反射膜付き基板の製造方法、反射型マスクブランクの製造方法、及び反射型マスクの製造方法
US9377679B2 (en) * 2012-07-31 2016-06-28 Hoya Corporation Reflective mask blank and method for manufacturing same, method for manufacturing reflective mask, and method for manufacturing semiconductor device
JP5868905B2 (ja) * 2013-07-03 2016-02-24 信越化学工業株式会社 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
DE102014216121A1 (de) * 2014-08-13 2016-02-18 Carl Zeiss Smt Gmbh Maske für die EUV-Lithographie, EUV-Lithographieanlage und Verfahren zum Bestimmen eines durch DUV-Strahlung hervorgerufenen Kontrastanteils
US20160266482A1 (en) * 2015-03-10 2016-09-15 Asahi Glass Company, Limited Glass substrate for mask blank
JP6418035B2 (ja) * 2015-03-31 2018-11-07 信越化学工業株式会社 位相シフトマスクブランクス及び位相シフトマスク
KR102368405B1 (ko) * 2015-11-06 2022-02-28 호야 가부시키가이샤 마스크 블랭크, 위상 시프트 마스크의 제조 방법 및 반도체 디바이스의 제조 방법
KR102254035B1 (ko) * 2016-08-26 2021-05-20 호야 가부시키가이샤 마스크 블랭크, 전사용 마스크 및 반도체 디바이스의 제조 방법
JP6400763B2 (ja) * 2017-03-16 2018-10-03 Hoya株式会社 マスクブランク、転写用マスクおよび半導体デバイスの製造方法
US11281088B2 (en) * 2017-04-17 2022-03-22 AGC Inc. Reflective mask blank for EUV exposure, and reflective mask
KR102688948B1 (ko) * 2017-09-21 2024-07-29 호야 가부시키가이샤 마스크 블랭크, 전사용 마스크, 및 반도체 디바이스의 제조 방법
JP7370943B2 (ja) * 2020-07-15 2023-10-30 Hoya株式会社 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
JP7581107B2 (ja) * 2021-03-29 2024-11-12 Hoya株式会社 反射型マスクブランク、反射型マスク、反射型マスクの製造方法、及び半導体装置の製造方法
JP7346527B2 (ja) * 2021-11-25 2023-09-19 Hoya株式会社 マスクブランク、転写用マスク、マスクブランクの製造方法、転写用マスクの製造方法、及び表示装置の製造方法
KR102587396B1 (ko) * 2022-08-18 2023-10-10 에스케이엔펄스 주식회사 블랭크 마스크 및 이를 이용한 포토마스크

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002090977A (ja) * 2000-09-12 2002-03-27 Hoya Corp 位相シフトマスクブランク、フォトマスクブランク、並びにそれらの製造装置及び製造方法
JP2008083194A (ja) * 2006-09-26 2008-04-10 Hoya Corp フォトマスクブランク、フォトマスクブランクの製造方法、フォトマスク、フォトマスクの製造方法、フォトマスク中間体及びパターンの転写方法
JP2014209200A (ja) * 2013-03-22 2014-11-06 Hoya株式会社 マスクブランクの製造方法および転写用マスクの製造方法
JP2016170320A (ja) * 2015-03-13 2016-09-23 信越化学工業株式会社 マスクブランクス及びその製造方法
JP2019003178A (ja) * 2017-06-14 2019-01-10 Hoya株式会社 マスクブランク、位相シフトマスク及び半導体デバイスの製造方法

Also Published As

Publication number Publication date
CN115280236A (zh) 2022-11-01
US20230097280A1 (en) 2023-03-30
KR20220156818A (ko) 2022-11-28
TWI899176B (zh) 2025-10-01
JP2021148968A (ja) 2021-09-27
TW202201117A (zh) 2022-01-01
KR102948025B1 (ko) 2026-04-06
CN115280236B (zh) 2025-07-01
JP7354032B2 (ja) 2023-10-02

Similar Documents

Publication Publication Date Title
US11048160B2 (en) Mask blank, phase shift mask and method for manufacturing semiconductor device
JP6720139B2 (ja) マスクブランク、位相シフトマスク、位相シフトマスクの製造方法および半導体デバイスの製造方法
US11022875B2 (en) Mask blank, phase shift mask, and method of manufacturing semiconductor device
JP6430155B2 (ja) マスクブランク、位相シフトマスク、位相シフトマスクの製造方法および半導体デバイスの製造方法
JP6502143B2 (ja) マスクブランク、位相シフトマスク、位相シフトマスクの製造方法および半導体デバイスの製造方法
US11442357B2 (en) Mask blank, phase-shift mask, and method of manufacturing semiconductor device
US12326656B2 (en) Mask blank and method of manufacturing photomask
KR102948025B1 (ko) 마스크 블랭크, 전사용 마스크, 및 반도체 디바이스의 제조 방법
US20210132488A1 (en) Mask blank, phase-shift mask, and semiconductor device manufacturing method
CN115917428B (zh) 掩模坯料、转印用掩模的制造方法及半导体器件的制造方法
WO2021044917A1 (ja) マスクブランク、位相シフトマスク及び半導体デバイスの製造方法
JP2023149342A (ja) マスクブランク、位相シフトマスク及び半導体デバイスの製造方法
US20230142180A1 (en) Mask blank, transfer mask, and method of manufacturing semiconductor device
US20240361683A1 (en) Mask blank and phase shift mask

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21772302

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21772302

Country of ref document: EP

Kind code of ref document: A1

WWG Wipo information: grant in national office

Ref document number: 202180020424.2

Country of ref document: CN