WO2018159392A1 - 反射型マスクブランク、反射型マスク及び半導体装置の製造方法 - Google Patents

反射型マスクブランク、反射型マスク及び半導体装置の製造方法 Download PDF

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Publication number
WO2018159392A1
WO2018159392A1 PCT/JP2018/006054 JP2018006054W WO2018159392A1 WO 2018159392 A1 WO2018159392 A1 WO 2018159392A1 JP 2018006054 W JP2018006054 W JP 2018006054W WO 2018159392 A1 WO2018159392 A1 WO 2018159392A1
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Prior art keywords
film
phase shift
alloy
shift film
reflective mask
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PCT/JP2018/006054
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English (en)
French (fr)
Japanese (ja)
Inventor
洋平 池邊
笑喜　勉
貴弘 尾上
弘文 小坂井
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Hoya Corp
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Hoya Corp
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Priority claimed from JP2017107394A external-priority patent/JP6861095B2/ja
Application filed by Hoya Corp filed Critical Hoya Corp
Priority to SG11201907623RA priority Critical patent/SG11201907623RA/en
Priority to US16/490,018 priority patent/US11003068B2/en
Priority to KR1020197028297A priority patent/KR102639087B1/ko
Priority to KR1020247005441A priority patent/KR20240025717A/ko
Publication of WO2018159392A1 publication Critical patent/WO2018159392A1/ja
Anticipated expiration legal-status Critical
Priority to US17/227,655 priority patent/US11480867B2/en
Priority to US17/946,709 priority patent/US11880130B2/en
Priority to US18/526,463 priority patent/US12135496B2/en
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
    • G03F1/22—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials

Definitions

  • the present invention relates to a reflective mask blank and a reflective mask, which are original plates for manufacturing an exposure mask used for manufacturing a semiconductor device, and a method for manufacturing a semiconductor device using the reflective mask.
  • EUV lithography using extreme ultraviolet (EUV) near 13.5 nm as a wavelength of a light source has been proposed.
  • EUV lithography a reflective mask is used because the difference in absorption rate between materials for EUV light is small.
  • a multilayer reflective film that reflects exposure light is formed on a substrate, and a phase shift film that absorbs exposure light is formed in a pattern on a protective film for protecting the multilayer reflective film.
  • a formed configuration has been proposed.
  • Light incident on a reflective mask mounted on an exposure machine (pattern transfer device) is absorbed at a portion where there is a phase shift film pattern, and is reflected by a multilayer reflective film at a portion where there is no phase shift film pattern.
  • the light image corresponding to the mask pattern is transferred onto the semiconductor substrate through the reflection optical system.
  • Part of the exposure light incident on the phase shift film pattern is reflected (phase shift) with a phase difference of about 180 degrees from the light reflected by the multilayer reflective film.
  • contrast (resolution) can be obtained.
  • Patent Documents 1 to 3 disclose a technique related to such a reflective mask for EUV lithography and a mask blank for producing the same.
  • Patent Document 1 in order to improve the transfer resolution by applying the principle of a halftone mask to EUV exposure, a material of a halftone film (phase shift film) made of a single layer film has a refractive index and extinction.
  • FIG. 2 which is represented by plane coordinates having a coefficient as a coordinate axis, it is described that selection is made from a region surrounded by a square frame.
  • TaMo composition ratio 1: 1 is described.
  • the halftone film material is Ta in order to reduce the projection effect (shadowing effect) in order to have a high degree of freedom in reflectivity selectivity and high cleaning resistance.
  • a compound of Ru and that the composition range is defined.
  • Patent Document 3 in a halftone EUV mask, in order to have a high degree of freedom in selectivity of selectivity and a high resistance to cleaning, and to increase the etching processing accuracy, the material of the halftone film is Ta and Nb.
  • the composition ratio of Ta: Nb is about 4: 1 to about 1: 2.
  • the shadowing effect is the following phenomenon.
  • an exposure apparatus that uses a reflective mask
  • light is incident on the mask with a slight inclination from the vertical direction so that the optical axes of incident light and reflected light do not overlap.
  • the phase shift film pattern of the mask is thick, a shadow based on the thickness of the phase shift film pattern is generated due to the inclination in the light incident direction.
  • the change in the size of the transfer pattern by the amount of the shadow is called a shadowing effect.
  • the phase shift film of the reflective mask is designed so that the reflectivity of the phase shift film pattern is 3% to 20% in order to improve the resolution by the phase shift effect.
  • the reflectance in the phase shift film pattern is when EUV light reflected from a multilayer reflective film (including a multilayer reflective film with a protective film) in a portion where there is no phase shift film pattern is 100% reflectance. Of EUV light reflected from the phase shift film pattern.
  • phase difference between the EUV light reflected by the multilayer reflective film that is part of the exposure light incident on the phase shift film pattern and the EUV light that is reflected by the multilayer reflective film at the part where the phase shift film pattern is not present Designed to be about 180 degrees.
  • the phase shift film between the multiple reflective mask blanks The phase difference variation is required to fall within a range of a predetermined phase difference variation (for example, ⁇ 2 degrees) with respect to a predetermined phase difference (for example, 180 degrees).
  • a predetermined phase difference variation for example, ⁇ 2 degrees
  • a predetermined phase difference for example, 180 degrees
  • the phase shift film has a predetermined reflectance variation (for example, ⁇ 0.2%) within a predetermined reflectance range (for example, 6%).
  • the thickness of the phase shift film varies slightly with respect to the design value (for example, ⁇ 0.5% of the design film thickness). Even if the range varies, a desired phase difference characteristic (for example, a phase difference variation of a plurality of reflective mask blanks in a range of 180 ° ⁇ 2 °) and a desired reflectance characteristic (for example, a plurality of reflective mask blanks)
  • the optimum condition was found for the variation in reflectance in the range of 6% ⁇ 0.2%.
  • the present inventors have found that the refractive index and the extinction coefficient of the phase shift film constituting the reflective mask blank exist in a spot as the optimum conditions, and have reached the present invention.
  • the present invention has the following configuration.
  • the present invention is a reflective mask blank having the following configurations 1 to 10, a reflective mask having the following configuration 11, and a method for manufacturing a semiconductor device having the following configuration 12.
  • a reflective mask blank comprising a multilayer reflective film formed on a substrate and a phase shift film formed on the multilayer reflective film,
  • the reflectivity for EUV light on the surface of the phase shift film with respect to the reflected light from the multilayer reflective film before forming the phase shift film is more than 3% and less than 20%, and has a phase difference of 170 degrees to 190 degrees.
  • the phase shift film is made of a material made of an alloy having two or more metals,
  • a group of metal elements satisfying the refractive index n and the extinction coefficient k in the following formula (1) is a group A
  • a group of metal elements satisfying the refractive index n and the extinction coefficient k in the following formula (2) is a group B.
  • the alloy one or more metal elements are selected from the group A and the group B, respectively, and the phase difference when the film thickness of the phase shift film varies by ⁇ 0.5% with respect to a set film thickness.
  • the reflection type mask blank is characterized in that the composition ratio is adjusted so that the change amount is within a range of ⁇ 2 degrees and the change amount in reflectance is within a range of ⁇ 0.2%.
  • Configuration 1 of the present invention when a plurality of reflective mask blanks are continuously manufactured, even if the thickness of the phase shift film varies slightly with respect to the set film thickness, desired retardation characteristics and A reflective mask blank that can stably produce a reflective mask blank having desired reflectance characteristics can be provided.
  • the thickness of the phase shift film is A reflective mask blank that can stably produce a reflective mask blank having a desired phase difference characteristic and a desired reflectance characteristic can be provided even if the film thickness varies somewhat with respect to the set film thickness.
  • the thickness of the phase shift film is A reflective mask blank that can stably produce a reflective mask blank having a desired phase difference characteristic and a desired reflectance characteristic can be provided even if the film thickness varies somewhat with respect to the set film thickness.
  • the thickness of the phase shift film is A reflective mask blank that can stably produce a reflective mask blank having a desired phase difference characteristic and a desired reflectance characteristic can be provided even if the film thickness varies somewhat with respect to the set film thickness.
  • a reflective mask blank comprising a multilayer reflective film formed on a substrate and a phase shift film formed on the multilayer reflective film,
  • the reflectivity R 0 of the EUV light on the surface of the phase shift film with respect to the reflected light from the multilayer reflective film before forming the phase shift film is 4%, 6%, or 12%, and the phase difference ⁇ 0 is 180 degrees.
  • the phase shift film is made of a material made of an alloy having two or more metals, In the alloy, the allowable range of the phase difference ⁇ when the film thickness of the phase shift film varies ⁇ 0.5% with respect to the set film thickness is ⁇ 0 ⁇ 5 degrees ⁇ ⁇ ⁇ ⁇ 0 +5 degrees, and It has a refractive index n and an extinction coefficient k at the wavelength of EUV light, and the composition ratio is adjusted so that the allowable range of the reflectance R is 0.9R 0 ⁇ R ⁇ 1.1R 0 Reflective mask blank.
  • Configuration 5 of the present invention when a plurality of reflective mask blanks are continuously manufactured, even if the thickness of the phase shift film varies slightly with respect to the set film thickness, desired retardation characteristics and A reflective mask blank that can stably produce a reflective mask blank having desired reflectance characteristics can be provided.
  • the alloy has a refractive index included in a range of 0.877 to 0.881 and an extinction coefficient included in a range of 0.046 to 0.052. 5.
  • the alloy has a refractive index included in a range of 0.901 to 0.907 and an extinction coefficient included in a range of 0.035 to 0.041. 5.
  • the reflective mask blank according to Configuration 6 or 7 of the present invention is configured to have a refractive index and an extinction coefficient that are included in a predetermined range, so that the reflectance of the reflective mask blank can correspond to a plurality of reflectances only by changing the film thickness.
  • a phase shift film having a high degree of freedom can be easily obtained.
  • a structure 8 of the present invention is the reflective mask blank according to any one of the structures 1 to 7, wherein the alloy is a multi-component alloy containing three or more metal elements.
  • the phase shift film has a desired phase difference characteristic and a desired reflectance characteristic by using a multi-component alloy containing three or more metal elements.
  • a phase shift film having an optimal refractive index and extinction coefficient can be easily obtained.
  • a ninth aspect of the present invention is the reflective mask blank according to any one of the first to eighth aspects, wherein the phase shift film has a thickness of 25 nm to 70 nm.
  • the projection effect when the film thickness of the phase shift film is 25 nm or more and 70 nm or less, the projection effect (shadowing effect) can be reduced.
  • Configuration 10 of the present invention is the reflective mask blank according to any one of Configurations 1 to 9, wherein the uppermost layer on the phase shift film side of the multilayer reflective film includes a protective film.
  • the uppermost layer on the phase shift film side of the multilayer reflective film is provided with a protective film, so that the multilayer reflective film when the reflective mask is manufactured using the reflective mask blank Damage to the surface can be suppressed. Therefore, the reflection characteristics of the reflective mask with respect to EUV light are improved.
  • Configuration 11 of the present invention is a reflective mask characterized by having a phase shift film pattern in which the phase shift film in the reflective mask blank according to any one of Configurations 1 to 10 is patterned.
  • the reflective mask according to the eleventh aspect of the present invention is manufactured using the above-described reflective mask blank, a reflective mask having a phase shift film pattern having desired phase difference characteristics and desired reflectance characteristics is obtained. Can do.
  • (Configuration 12) A method for manufacturing a semiconductor device, comprising: a pattern forming step of forming a pattern on a semiconductor substrate using the reflective mask according to Configuration 11.
  • a reflective mask having a phase shift film pattern having desired phase difference characteristics and desired reflectance characteristics can be used.
  • a semiconductor device having the transfer pattern can be manufactured.
  • a desired phase difference characteristic and a desired reflectance characteristic can be obtained even if the thickness of the phase shift film slightly varies with respect to the design value. It is possible to stably provide a reflective mask blank having the same.
  • a reflective mask blank of the present invention a reflective mask having a phase shift film pattern having desired phase difference characteristics and desired reflectance characteristics can be obtained.
  • a reflective mask having a phase shift film pattern having a desired phase difference characteristic and a desired reflectance characteristic can be used by the semiconductor device manufacturing method of the present invention, so that a fine and highly accurate transfer pattern can be used. Can be manufactured.
  • the refractive index n and extinction of an alloy satisfying predetermined phase difference characteristics and reflectance characteristics when the reflectance in EUV light is 6%. It is a graph which shows the characteristic of the coefficient k.
  • the refractive index n and extinction of an alloy satisfying predetermined phase difference characteristics and reflectance characteristics when the reflectance in EUV light is 4%. It is a graph which shows the characteristic of the coefficient k.
  • the refractive index n and extinction of an alloy satisfying predetermined phase difference characteristics and reflectance characteristics when the reflectance in EUV light is 20%. It is a graph which shows the characteristic of the coefficient k. Refractive index satisfying predetermined phase difference characteristics and reflectance characteristics when the reflectance in EUV light (wavelength: 13.5 nm) is 4%, 6%, and 12% for explaining the second embodiment of the present invention It is a graph which shows the range of n and the extinction coefficient k. It is a graph which shows the range of the refractive index n and the extinction coefficient k which satisfy
  • FIG. 1 the cross-sectional schematic diagram of the reflective mask blank 10 which is the 1st Embodiment of this invention is shown.
  • a multilayer reflective film 13 and a phase shift film 15 for shifting the phase of EUV light are formed on a substrate 12 in this order.
  • the reflective mask blank 10 for EUV lithography having the configuration shown in FIG. 1 can be used.
  • the reflectance of the surface of the phase shift film 15 with respect to EUV light (wavelength: 13.5 nm) is more than 3% and less than 20%.
  • it is made of a material made of an alloy having two or more kinds of metals so as to have a phase difference of 170 ° to 190 ° with respect to the reflected light from the multilayer reflective film 13.
  • membrane 15 is selected so that the phase difference with respect to predetermined
  • a group of metal elements satisfying the group A, the refractive index n and the extinction coefficient k of the following formula (2) is defined as a group B, and one or more metal elements are selected from the groups A and B as the alloy.
  • the composition ratio of the metal element of group A and the metal element of group B is such that the amount of change in phase difference is ⁇ 2 degrees when the film thickness of the phase shift film 15 varies ⁇ 0.5% with respect to the set film thickness.
  • the range is adjusted so that the amount of change in reflectance is within a range of ⁇ 0.2%.
  • the range in which the amount of change in the phase difference is ⁇ 2 degrees means that the phase difference ⁇ is shown in the range of ⁇ 0 ⁇ 2 degrees ⁇ ⁇ ⁇ ⁇ 0 +2 degrees when the target phase difference is ⁇ 0. means.
  • the range change in reflectance of 0.2% ⁇ the reflectance of the aim reflectance R when the R 0 is R 0 -0.2% ⁇ R ⁇ R 0 + 0.2% of Means indicated by a range.
  • “*” is a multiplication symbol. k> ⁇ * n + ⁇ Equation (1) k ⁇ * n + ⁇ Equation (2) (However, ⁇ : proportional constant, ⁇ : constant)
  • FIG. 2 is a graph showing the relationship between the refractive index n of a metal material and the extinction coefficient k in EUV light (wavelength 13.5 nm).
  • the composition ratio of the alloy constituting the phase shift film 15 of the present invention is adjusted as follows. First, ⁇ and ⁇ are set as appropriate according to the reflectance of the surface of the phase shift film 15 with respect to EUV light. One or more metal elements are selected from each of group A and group B, which are metal element groups satisfying the relational expressions of the above formulas (1) and (2). When the film thickness of the phase shift film 15 varies by ⁇ 0.5% with respect to the set film thickness, the change amount of the phase difference is in the range of ⁇ 2 degrees and the change amount of the reflectance is in the range of ⁇ 0.2%. Thus, the composition ratio of the metal elements is adjusted.
  • the metal elements belonging to the group A satisfying the formula (1) (k> ⁇ * n + ⁇ ) are Pd, Ag, Pt, Au, Ir, W, Cr, Co, Mn, Sn, Ta, V, Ni, Hf, Fe, Cu, Te, Zn, Mg, Ge, and Al are mentioned.
  • the metal element belonging to the group B that satisfies the formula (2) (k ⁇ * n + ⁇ ) include Rh, Ru, Mo, Nb, Ti, Zr, Y, and Si.
  • the alloy A can be made into a PdMo alloy (binary alloy) by selecting Pd belonging to the group A and selecting Mo belonging to the group B.
  • This PdMo alloy has a composition ratio of the alloy A that satisfies the refractive index n A and the extinction coefficient k A.
  • phase shift film 15 is a material made of a multi-component alloy containing a plurality of metal elements
  • a plurality of elements are selected from the group A
  • a plurality of elements are selected from the group B
  • these selected elements are by adjusting the composition ratio of the alloy containing, refractive index n a and alloy a satisfying extinction coefficient k a, alloy B satisfying a refractive index n B, and the extinction coefficient k B, the refractive index n C, and the extinction coefficient k It may be an alloy D satisfying alloy C, or refractive index n D and the extinction coefficient k D satisfy C.
  • FIG. 3 shows the case of a material made of a ternary alloy as a multi-component alloy that can be used as the material of the phase shift film 15 of the present invention.
  • the amount of change in phase difference of the phase shift film 15 is in the range of ⁇ 2 degrees and the amount of change in reflectance is ⁇ 0.
  • a TaPdMo alloy ternary alloy
  • the TaPdMo alloy can be made the alloy A, alloy B, alloy C, or alloy D by adjusting the composition ratio.
  • FIG. 1 is a schematic cross-sectional view for explaining the configuration of a reflective mask blank 10 for EUV lithography according to the first embodiment of the present invention.
  • a reflective mask blank 10 of the present invention will be described with reference to FIG.
  • the reflective mask blank 10 includes a substrate 12 having a back surface conductive film 11, a multilayer reflective film 13, a protective film 14, and a phase shift film 15.
  • the substrate 12 has a back surface conductive film 11 for electrostatic chuck formed on the main surface on the back surface side of the substrate 12.
  • the multilayer reflective film 13 is formed on the main surface of the substrate 12 (the main surface opposite to the side on which the back conductive film 11 is formed) and reflects EUV light that is exposure light.
  • a protective film 14 is formed on the uppermost layer of the multilayer reflective film 13.
  • the protective film 14 is formed of a material containing ruthenium (Ru) as a main component in order to protect the multilayer reflective film 13.
  • the phase shift film 15 is formed on the protective film 14.
  • the phase shift film 15 absorbs EUV light and reflects part of the EUV light to shift the phase.
  • a multilayer reflective film 13 formed on the main surface of the substrate 12 means that the multilayer reflective film 13 is disposed in contact with the surface of the substrate 12.
  • a case where it means that another film is provided between the substrate 12 and the multilayer reflective film 13 is included.
  • the film A is disposed on the film B means that the film A and the film B are not interposed between the film A and the film B without interposing another film. It means that it is arranged so that it touches directly.
  • a substrate 12 having a low thermal expansion coefficient within a range of 0 ⁇ 5 ppb / ° C. is preferably used.
  • a material having a low thermal expansion coefficient in this range for example, SiO 2 —TiO 2 glass, multicomponent glass ceramics, or the like can be used.
  • the main surface on the side where the phase shift film 15 serving as the transfer pattern of the reflective mask is formed has a surface with high flatness from the viewpoint of at least pattern transfer accuracy and position accuracy.
  • the flatness is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, particularly preferably in a 132 mm ⁇ 132 mm region of the main surface on the side where the transfer pattern of the substrate 12 is formed. 0.03 ⁇ m or less.
  • the main surface opposite to the side on which the phase shift film 15 is formed is formed with a back surface conductive film 11 for electrostatic chucking when set in the exposure apparatus.
  • the flatness of the surface on which the back conductive film 11 is formed is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, particularly preferably 0.3 ⁇ m or less in a 142 mm ⁇ 142 mm region.
  • the flatness is a value representing the warpage (deformation amount) of the surface indicated by TIR (Total Indicated Reading). This value is determined by taking the plane defined by the least square method with respect to the surface of the substrate 12 as a focal plane, and the highest position of the surface of the substrate 12 above the focal plane and the surface of the substrate 12 below the focal plane. This is the absolute value of the difference in height from the lowest position.
  • the surface roughness of the main surface of the substrate 12 on the side where the phase shift film 15 serving as a transfer pattern is formed is the root mean square roughness. (RMS) is preferably 0.1 nm or less.
  • the surface smoothness can be measured with an atomic force microscope (AFM).
  • the substrate 12 has high rigidity in order to prevent deformation due to film stress of a film (such as the multilayer reflective film 13) formed thereon.
  • the substrate 12 preferably has a high Young's modulus of 65 GPa or more.
  • the multilayer reflective film 13 has a function of reflecting EUV light in a reflective mask for EUV lithography.
  • the multilayer reflective film 13 is a multilayer film in which elements having different refractive indexes are periodically stacked.
  • a thin film (high refractive index layer) of a light element or a compound thereof, which is a high refractive index material, and a thin film (low refractive index layer) of a heavy element or a compound thereof, which is a low refractive index material, are alternately 40
  • a multilayer film having about 60 cycles is used as the multilayer reflective film 13.
  • the multilayer film can have a structure in which a plurality of high-refractive index layers / low-refractive index layers are stacked in this order from the substrate 12 side and a plurality of periods are stacked.
  • the multilayer film can have a structure in which a low refractive index layer and a high refractive index layer laminated in this order from the substrate 12 side are laminated in a plurality of periods with a laminated structure of a low refractive index layer / high refractive index layer as one period.
  • the uppermost layer has a low refractive index. Become a rate layer. For this reason, it is preferable to form a multilayer reflective film 13 by further forming a high refractive index layer on the uppermost low refractive index layer.
  • a layer containing Si can be adopted as the high refractive index layer.
  • a material containing Si Si compound containing B, C, N and / or O in addition to Si alone may be used.
  • a layer containing Si as the high refractive index layer, a reflective mask for EUV lithography having excellent EUV light reflectivity can be obtained.
  • a glass substrate is preferably used as the substrate 12.
  • Si is also excellent in adhesion to the glass substrate.
  • a single metal selected from Mo, Ru, Rh, and Pt, and alloys thereof are used as the low refractive index layer.
  • the multilayer reflective film 13 for EUV light having a wavelength of 13 to 14 nm a Mo / Si periodic laminated film in which Mo films and Si films are alternately laminated, for example, about 40 to 60 cycles is preferably used.
  • a high refractive index layer, which is the uppermost layer of the multilayer reflective film 13, is formed of silicon (Si), and a silicon oxide layer containing silicon and oxygen is interposed between the uppermost layer (Si) and the protective film 14. You may make it form. Thereby, the mask cleaning resistance (resistance to peeling of the phase shift film pattern) can be improved.
  • the reflectance of the multilayer reflective film 13 alone is, for example, 65% or more, and the upper limit is preferably 73%.
  • the film thickness and the number of periods of each constituent layer of the multilayer reflective film 13 are appropriately selected so as to satisfy Bragg's law depending on the exposure wavelength.
  • the multilayer reflective film 13 there are a plurality of high refractive index layers and low refractive index layers. All the high refractive index layers do not have to have the same film thickness. Further, all the low refractive index layers may not have the same film thickness.
  • the film thickness of the outermost Si layer of the multilayer reflective film 13 can be adjusted within a range in which the reflectance is not lowered.
  • the film thickness of the outermost Si (high refractive index layer) can be set to 3 to 10 nm, for example.
  • each layer of the multilayer reflective film 13 can be formed by ion beam sputtering.
  • an Si film having a film thickness of about 4 nm is first formed on the substrate 12 using an Si target, for example, by an ion beam sputtering method, and then a film thickness of about 3 nm is formed using the Mo target.
  • the Mo film is formed.
  • the Si film and the Mo film are formed as one cycle, and the multilayer reflective film 13 is formed by laminating a total of 40 to 60 cycles (the uppermost layer is a Si layer).
  • the reflective mask blank 10 of the present invention preferably has a protective film 14 on the uppermost layer of the multilayer reflective film 13 on the phase shift film 15 side.
  • the protective film 14 is formed on the multilayer reflective film 13 in order to protect the multilayer reflective film 13 from dry etching or cleaning liquid in the reflective mask manufacturing process described later.
  • the protective film 14 is made of, for example, a material (main component: 50 atomic% or more) containing Ru (ruthenium) as a main component.
  • the material containing Ru as a main component is Ru metal alone, Ru alloy containing a metal such as Nb, Zr, Y, B, Ti, La, Mo, Co, and / or Re in Ru, or N in these materials. It may be a material containing (nitrogen).
  • the protective film 14 can have a laminated structure of three or more layers. In this case, the lowermost layer and the uppermost layer of the protective film 14 are layers made of a substance containing Ru, and a metal or alloy other than Ru is interposed between the lowermost layer and the uppermost layer. Can do.
  • the thickness of the protective film 14 is not particularly limited as long as it can function as the protective film 14. From the viewpoint of EUV light reflectance, the thickness of the protective film 14 is preferably 1.5 to 8.0 nm, and more preferably 1.8 to 6.0 nm.
  • a known film forming method can be employed without any particular limitation.
  • Specific examples of the method for forming the protective film 14 include a sputtering method and an ion beam sputtering method.
  • the reflective mask blank 10 of the first embodiment of the present invention includes a phase shift film 15 on a multilayer reflective film 13.
  • the phase shift film 15 can be formed on and in contact with the multilayer reflective film 13. Further, when the protective film 14 is formed on the uppermost layer of the multilayer reflective film 13, it can be formed on the protective film 14.
  • ⁇ and ⁇ are appropriately set according to the reflectance with respect to the EUV light on the surface of the phase shift film 15.
  • One or more metal elements are selected from group A and group B, respectively.
  • the reflectance of the phase shift film 15 with respect to EUV light is divided into three cases: (i) more than 5% to 10% or less, (ii) more than 3% to 5% or less, and (iii) more than 10% to 20% or less. explain.
  • Examples of the metal element belonging to the group B that satisfies the formula (2) (k ⁇ 0.303 * n + 0.309) include Rh, Ru, Mo, Nb, Ti, Zr, Y, and Si.
  • One or more metal elements are selected from group A and group B, respectively.
  • FIG. 4 illustrates group A and group B, which are metal element groups satisfying the relational expression of the expressions (1) and (2) when the reflectance of the phase shift film 15 with respect to the EUV light is 6%.
  • the amount of change in the phase difference of the phase shift film 15 is in the range of ⁇ 2 degrees, and the amount of change in the reflectance is ⁇ 0.
  • the following alloys can be cited as binary alloys in the range of 2%.
  • Examples of the alloy A 6% having a refractive index of 0.883 and an extinction coefficient of 0.042 include a PdMo alloy, a PdNb alloy, and a PdZr alloy.
  • Examples of the alloy B 6% having a refractive index of 0.905 and an extinction coefficient of 0.035 include RhTa alloy and RuNi alloy.
  • Examples of the alloy C 6% having a refractive index of 0.921 and an extinction coefficient of 0.031 include TaRu alloy and CrRu alloy.
  • Examples of the alloy D 6% having a refractive index of 0.932 and an extinction coefficient of 0.027 include a MoTa alloy and a WNb alloy.
  • Examples of the alloy E 6% having a refractive index of 0.940 and an extinction coefficient of 0.024 include TaNb alloy and NiNb alloy.
  • TaPdMo alloy or NiPdMo alloy can be used to make alloy A 6% , alloy B 6% , alloy C 6% , or alloy D 6% .
  • the film thicknesses of the alloy A 6% , the alloy B 6% , the alloy C 6% , the alloy D 6% , and the alloy E 6% are respectively 28.2 nm, 35.0 nm, 41.5 nm, 48.2 nm, And 55.1 nm, the phase difference of the phase shift film 15 can be about 180 degrees and the reflectance can be about 6%.
  • Examples of the metal element belonging to the group B satisfying the formula (2) (k ⁇ 0.331 * n + 0.339) include Pd, Rh, Ru, Mo, Nb, V, Ti, Zr, Y, and Si. Can be mentioned.
  • One or more metal elements are selected from each of group A and group B, and the amount of change in the phase difference is ⁇ 2 when the film thickness of the phase shift film varies by ⁇ 0.5% with respect to the set film thickness.
  • the composition ratio of the metal elements is adjusted so that the degree of change and the amount of change in reflectance are within a range of ⁇ 0.2%.
  • FIG. 5 illustrates the group A and the group B, which are metal element groups that satisfy the relational expressions (1) and (2) when the reflectance of the phase shift film 15 with respect to the EUV light is 4%.
  • the amount of change in the phase difference of the phase shift film 15 is in the range of ⁇ 2 degrees, and the amount of change in the reflectance is ⁇ 0.
  • the following alloys can be cited as binary alloys in the range of 2%.
  • Examples of 4% alloy A having a refractive index of 0.881 and an extinction coefficient of 0.047 include RhAg alloy, PdFe alloy, and PdZn alloy.
  • Examples of 4% alloy B having a refractive index of 0.905 and an extinction coefficient of 0.040 include RhFe alloys and RhZn alloys.
  • Examples of the alloy C 4% having a refractive index of 0.921 and an extinction coefficient of 0.035 include CrRu alloy and RhHf alloy.
  • Examples of the alloy D 4% having a refractive index of 0.932 and an extinction coefficient of 0.031 include NbW alloy and ZrPt alloy.
  • Examples of the alloy E 4% having a refractive index of 0.940 and an extinction coefficient of 0.028 include CrZr alloy, WZr alloy, and TaNb alloy.
  • the film thicknesses of the alloy A 4% , the alloy B 4% , the alloy C 4% , the alloy D 4% , and the alloy E 4% are 28.4 nm, 34.9 nm, 41.4 nm, and 48.1 nm, respectively. And 55.0 nm, the phase difference of the phase shift film 15 can be about 180 degrees and the reflectance can be about 4%.
  • Examples of the metal element belonging to the group B that satisfies the formula (2) (k ⁇ 0.192 * n + 0.194) include Ru, Mo, Nb, Zr, Y, and Si.
  • One or more metal elements are selected from each of group A and group B, and the amount of change in the phase difference is ⁇ 2 when the film thickness of the phase shift film varies by ⁇ 0.5% with respect to the set film thickness.
  • the composition ratio of the metal elements is adjusted so that the degree of change and the amount of change in reflectance are within a range of ⁇ 0.2%.
  • the amount of change in the phase difference of the phase shift film 15 is in the range of ⁇ 2 degrees, and the amount of change in the reflectance is ⁇ 0.
  • the following alloys can be cited as binary alloys in the range of 2%.
  • An example of the alloy A 20% having a refractive index of 0.885 and an extinction coefficient of 0.025 includes a PdRu alloy.
  • Examples of the alloy B 20% having a refractive index of 0.907 and an extinction coefficient of 0.021 include PdMo alloys and RuGe alloys.
  • An example of the alloy C 20% having a refractive index of 0.922 and an extinction coefficient of 0.018 includes a MoCo alloy.
  • Examples of the alloy D 20% having a refractive index of 0.932 and an extinction coefficient of 0.016 include a WNb alloy and a MoHf alloy.
  • Examples of the alloy E 20% having a refractive index of 0.940 and an extinction coefficient of 0.014 include HfNb alloy and ZnNb alloy.
  • the film thicknesses of the alloy A 20% , the alloy B 20% , the alloy C 20% , the alloy D 20% , and the alloy E 20% are 28.2 nm, 35.0 nm, 41.7 nm, and 48.6 nm, respectively. And 55.4 nm, the phase difference of the phase shift film 15 can be about 180 degrees and the reflectance can be about 20%.
  • the phase shift film 15 of the present invention can contain at least one selected from oxygen, nitrogen, carbon, and boron without departing from the effects of the invention.
  • the film thickness of the phase shift film 15 is appropriately set so that the phase difference with respect to the EUV light is 170 to 190 degrees and the reflectance is more than 3% and not more than 20%. From the viewpoint of reducing the projection effect (shadowing effect), the thickness of the phase shift film 15 is preferably 25 nm or more and 70 nm or less. The thickness of the phase shift film 15 is more preferably 25 nm or more and 50 nm or less, and further preferably 25 nm or more and 40 nm or less.
  • the surface roughness of the phase shift film 15 after film formation is preferably the root mean square roughness (RMS) of 0.5 nm or less, more preferably 0.4 nm or less, and More preferably, it is 3 nm or less.
  • RMS root mean square roughness
  • an etching mask film (not shown) can be further formed on the phase shift film 15.
  • the etching mask film is formed of a material having etching selectivity with respect to the uppermost layer of the multilayer reflective film 13 and capable of being etched with an etching gas with respect to the phase shift film 15 (having no etching selectivity).
  • the etching mask film can be formed by a known method such as a DC sputtering method or an RF sputtering method.
  • the thickness of the etching mask film is preferably 5 nm or more from the viewpoint of securing the function as a hard mask. Considering the film thickness of the phase shift film 15, the film thickness of the etching mask film is 5 nm to 20 nm, preferably 5 nm to 15 nm.
  • a back surface conductive film 11 for an electrostatic chuck is formed on the back surface side of the substrate 12 (the side opposite to the formation surface of the multilayer reflective film 13).
  • the electrical characteristics required for the back surface conductive film 11 for the electrostatic chuck are normally a sheet resistance of 100 ⁇ / sq or less.
  • the back surface conductive film 11 can be formed, for example, by magnetron sputtering or ion beam sputtering using a target of a metal such as chromium or tantalum or an alloy thereof.
  • the back surface conductive film 11 is formed of, for example, CrN, it can be formed by the above sputtering method in a gas atmosphere containing N such as nitrogen gas using a Cr target.
  • the thickness of the back conductive film 11 is not particularly limited as long as it satisfies the function for an electrostatic chuck, but is usually 10 to 200 nm.
  • the reflective mask blank 10 of the present invention is not limited to the embodiment described above.
  • the reflective mask blank 10 of the present invention can include a resist film having a function as an etching mask on the phase shift film 15.
  • the reflective mask blank 10 of the present invention can include the phase shift film 15 in contact with the multilayer reflective film 13 without including the protective film 14 on the multilayer reflective film 13.
  • the present invention is a reflective mask having a phase shift film pattern in which the phase shift film 15 in the reflective mask blank 10 of the present invention is patterned.
  • the reflective mask blank 10 of the present invention described above can be used to produce the reflective mask of the present invention.
  • an electron beam lithography method that can perform high-definition patterning is most suitable.
  • a method for manufacturing a reflective mask using a photolithography method will be described by taking a case where the reflective mask blank 10 shown in FIG. 1 is used as an example.
  • a resist film (not shown) is formed on the outermost surface (phase shift film 15) of the reflective mask blank 10 shown in FIG.
  • the film thickness of the resist film can be set to 100 nm, for example.
  • a desired pattern is drawn (exposed) on the resist film, and further developed and rinsed to form a predetermined resist pattern (not shown).
  • phase shift film 15 is etched using a resist pattern (not shown) as a mask and containing a fluorine-based gas such as SF 6 or a chlorine-based gas such as Cl 2 depending on the material of the phase shift film 15.
  • a phase shift film pattern (not shown) is formed by performing dry etching with a gas. In this step, the resist pattern (not shown) is removed.
  • the etching rate of the phase shift film 15 depends on conditions such as a material for forming the phase shift film 15 and an etching gas.
  • phase shift film pattern is formed by the above process.
  • wet cleaning using an acidic or alkaline aqueous solution is performed to obtain a reflective mask for EUV lithography that has achieved high reflectivity.
  • the etching gas is a fluorine-based gas, other SF 6, CHF 3, CF 4 , C 2 F 6, C 3 F 6, C 4 F 6, C 4 F 8, CH 2 F 2, CH 3 F , C 3 F 8 , F and other fluorine-based gases, and mixed gases containing these fluorine gas and O 2 in a predetermined ratio can be used.
  • etching gas for example, a chlorine-based gas such as Cl 2 , SiCl 4 , CHCl 3 , CCl 4 , and BCl 3 , a mixed gas thereof, a mixed gas containing chlorine-based gas and He at a predetermined ratio Selected from the group consisting of a gas, a mixed gas containing chlorine-based gas and Ar at a predetermined ratio, a halogen gas containing at least one selected from fluorine gas, chlorine gas, bromine gas and iodine gas, and hydrogen halide gas At least one kind or more.
  • a mixed gas containing these gases and oxygen gas or the like can be used as the etching gas.
  • the above-described reflective mask blank 10 is used for manufacturing the reflective mask of the present invention, a reflective mask having a phase shift film pattern having desired phase difference characteristics and reflectance characteristics can be obtained.
  • the present invention is a method for manufacturing a semiconductor device, including a pattern forming step of forming a pattern on a semiconductor substrate using the above-described reflective mask of the present invention.
  • a transfer pattern based on the phase shift film pattern of the reflective mask can be formed on a semiconductor substrate by EUV lithography. Thereafter, through various other processes, a semiconductor device in which various patterns and the like are formed on the semiconductor substrate can be manufactured.
  • a known pattern transfer apparatus can be used for forming the transfer pattern.
  • a fine and highly accurate transfer pattern is provided.
  • a semiconductor device can be manufactured.
  • phase shift film 15 of the reflective mask blank 10 according to the second embodiment of the present invention has a wider allowable range of phase difference variation and reflectance variation than the first embodiment.
  • the phase shift film 15 has a reflectance R 0 of EUV light on the surface of the phase shift film 4%, 6% or 12% with respect to the reflected light from the multilayer reflective film before the phase shift film 15 is formed, and a phase difference ⁇ It is comprised with the material which consists of an alloy which has 2 or more types of metals so that 0 may become 180 degree
  • the allowable range of the phase difference ⁇ when the film thickness of the phase shift film 15 fluctuates ⁇ 0.5% with respect to the set film thickness is ⁇ 5 degrees ( ⁇ 0 -5 degrees).
  • the refractive index n and extinction coefficient k of such an alloy at the wavelength of EUV light are in a predetermined range.
  • FIG. 7 shows ranges of the refractive index n and the extinction coefficient k that satisfy the predetermined phase difference characteristic and reflectance characteristic when the reflectance in EUV light (wavelength 13.5 nm) is 4%, 6%, and 12%. It is a graph.
  • the thickness of the phase shift film 15 is ⁇ 0.
  • the allowable range of the phase difference ⁇ when fluctuating by 5% is ⁇ 5 degrees ( ⁇ 0 ⁇ 5 degrees ⁇ ⁇ ⁇ ⁇ 0 +5 degrees), and the allowable range of the reflectance R is 0.9R 0 ⁇ R ⁇ 1. It is a set when the refractive index and the extinction coefficient for 1R 0 are plotted.
  • the allowable range of the phase difference ⁇ is 175 to 185 degrees
  • the allowable range of the reflectance R is 5.4% to 6.6%.
  • the spiral H 4% in FIG. 7 is a case where the phase difference ⁇ 0 with respect to EUV light is 180 degrees and the reflectance R 0 is 4%, and the allowable range of the phase difference ⁇ is 175 degrees to 185 degrees.
  • the allowable range of the reflectance R is 3.6% to 4.4%.
  • the spiral H 12% in FIG. 7, a phase difference theta 0 for the EUV light is 180 degrees, in a case where the reflectance R 0 was 12% tolerance of the phase difference theta is 175 degrees to 185 degrees
  • the allowable range of the reflectance R is 10.8 to 13.2%.
  • the metal can be divided into a group A ′ metal and a group B ′ metal across the helix H 4% , the helix H 6%, or the helix H 12% .
  • the alloy can be obtained by selecting one or more metal elements from the group A ′ metal and the group B ′ metal.
  • the metal elements belonging to the group A ′ include Ag, Pt, Ir, W, Cr, Co, Mn, Sn, Ta, V, Ni, Hf, Fe, Cu, Te, Zn, Mg, Ge, and Al are mentioned.
  • examples of the metal element belonging to the group B ′ include Au, Pd, Rh, Ru, Mo, Nb, Ti, Zr, and Y.
  • the reflective mask blank 10 and the reflective mask are manufactured in the same manner as in the first embodiment of the present invention except that the material of the phase shift film 15 is configured as described above. Can do.
  • phase shift film 15 of the reflective mask blank 10 in the third embodiment of the present invention will be described.
  • reflective mask blanks having different reflectivities may be manufactured. In that case, it is difficult to obtain a phase shift film having desired phase difference characteristics and reflectance characteristics, and capable of dealing with a plurality of reflectances without changing the material (and its composition ratio).
  • the phase shift film 15 in the third embodiment of the present invention is made of a material made of an alloy that can handle a plurality of reflectivities by simply changing the set film thickness.
  • the phase shift film 15 has a reflectance R 0 of EUV light on the surface of the phase shift film 4%, 6% or 12% with respect to the reflected light from the multilayer reflective film before the phase shift film 15 is formed, and a phase difference ⁇ It is comprised with the material which consists of an alloy which has 2 or more types of metals so that 0 may become 180 degree
  • the allowable range of the phase difference ⁇ when the film thickness of the phase shift film 15 fluctuates ⁇ 0.5% with respect to the set film thickness is ⁇ 5 degrees ( ⁇ 0 -5 degrees).
  • the allowable range of the reflectance R is 0.9R 0 ⁇ R ⁇ 1.1R 0 .
  • the refractive index n and extinction coefficient k of such an alloy at the wavelength of EUV light are in a predetermined range. In such an alloy, it is possible to cope with a plurality of reflectivities only by changing the set film thickness.
  • FIG. 8 shows a range of the refractive index n and the extinction coefficient k satisfying the overlapping portion of FIG. It is a graph.
  • the spot S 3A and the spot S 3B in FIG. 8 are a set obtained by plotting the refractive index and the extinction coefficient that can correspond to the three reflectances of the reflectance R 0 of 4%, 6%, and 12%. is there. That is, the spot S 3A and the spot S 3B are overlapping portions of the spiral H 4% , the spiral H 6%, and the spiral H 12% in FIG.
  • the spot S 3A is included in a range where the refractive index is 0.877 to 0.881 and the extinction coefficient is 0.046 to 0.052. Further, the spot S 3B is included in a range of a refractive index of 0.901 to 0.904 and an extinction coefficient of 0.039 to 0.041.
  • the alloy is divided into a group A ′ and a group B ′ across an approximate straight line connecting the spot S 3A and the spot S 3B , and one kind each of the group A ′ and the group B ′.
  • the metal elements belonging to the group A ′ include Ag, Pt, Au, Ir, W, Cr, Co, Mn, Sn, Ta, V, Ti, Ni, Hf, Fe, Cu, Te, Zn, Mg, Ge , Al, and Si.
  • the metal element belonging to the group B ′ include Pd, Rh, Ru, Mo, Nb, Zr, and Y.
  • Binary alloys of the above alloys include AgPd alloy, PtPd alloy, AuPd alloy, IrPd alloy, CoPd alloy, SnPd alloy, NiPd alloy, TePd alloy, CuPd alloy, FePd alloy, WPd alloy, CrPd alloy, TaPd alloy, ZnPd Examples include alloys, HfPd alloys, GePd alloys, AlPd alloys, MgPd alloys, AgRh alloys, CuRh alloys, FeRh alloys, and IrRu alloys.
  • the PtPd alloy preferably has a composition ratio of 0.10: 0.90 to 0.25: 0.75.
  • the spot S 2A , the spot S 2B , the spot S 2C , the spot S 2D and the spot S 2E in FIG. It is a set when plotting the refractive index and the extinction coefficient capable of satisfying two reflectances of R 0 of 6% and 12%. That is, the spot S 2A , the spot S 2B , the spot S 2C , the spot S 2D and the spot S 2E are overlapping portions of the spiral H 6% and the spiral H 12% in FIG.
  • the spot S 2A is included in the range of the refractive index of 0.880 to 0.888 and the extinction coefficient of 0.041 to 0.046 in addition to the range of the refractive index and extinction coefficient of the spot S 3A .
  • the spot S 2B is included in the range of the refractive index of 0.901 to 0.907 and the extinction coefficient of 0.035 to 0.041 in addition to the range of the refractive index and extinction coefficient of the spot S 3B .
  • the spot S 2C is included in a range where the refractive index is 0.917 to 0.921 and the extinction coefficient is 0.030 to 0.034.
  • the spot S 2D is included in a range where the refractive index is 0.929 to 0.931 and the extinction coefficient is 0.027 to 0.028.
  • the spot S 2E is included in a range where the refractive index is 0.938 to 0.939 and the extinction coefficient is 0.024.
  • the alloy sandwiches an approximate straight line connecting the spot S 2A (including the spot S 3A ), the spot S 2B (including the spot S 3B ), the spot S 2C , the spot S 2D, and the spot S 2E.
  • group A ′ and group B ′ and one or more metal elements can be selected from group A ′ and group B ′.
  • the metal elements belonging to the group A ′ include Ag, Pt, Au, Ir, W, Cr, Co, Mn, Sn, Ta, V, Ni, Hf, Fe, Cu, Te, Zn, Mg, Ge, Al , And Si.
  • the metal element belonging to the group B ′ include Pd, Rh, Ru, Mo, Nb, Ti, Zr, and Y.
  • the binary alloy of the above alloy in addition to the alloy described in (i) above, PtMo alloy, AuMo alloy, NiMo alloy, FeMo alloy, ZnMo alloy, MnMo alloy, AgNb alloy, NiNb alloy, WNb alloy, TaNb Alloy, MnPd alloy, VPd alloy, TiPd alloy, PtRh alloy, AuRh alloy, WRh alloy, CrRh alloy, TaRh alloy, ZnRh alloy, MnRh alloy, HfRh alloy, GeRh alloy, AlRh alloy, MgRh alloy, CoRu alloy, SnRu alloy, Examples thereof include NiRu alloy, WRu alloy, CrRu alloy, TaRu alloy, ZnRu alloy, HfRu alloy, GeRu alloy, VRu alloy, IrY alloy, PtZr alloy, and the above alloy AuZr alloy.
  • the PtMo alloy preferably has a composition ratio of 0.60: 0.40 to 0.55: 0.45.
  • the reflective mask blank 10 and the reflective mask are manufactured in the same manner as in the first embodiment of the present invention except that the material of the phase shift film 15 is configured as described above. Can do.
  • Example 1 ⁇ Production of reflective mask blank 10>
  • the reflective mask blank 10 of Example 1 having the characteristic that the reflectivity of the phase shift film 15 is 6% was manufactured by the method described below.
  • a Mo / Si multilayer reflective film 13, a Ru protective film 14, and a phase shift film 15 are laminated on a substrate 12, and a CrN conductive film is formed on the back surface of the substrate 12. Has a formed structure.
  • a SiO 2 —TiO 2 glass substrate 12 was prepared.
  • a multilayer reflective film 13 was formed on the main surface of the substrate 12 opposite to the side on which the back conductive film 11 was formed.
  • a Mo / Si periodic multilayer reflective film 13 suitable for 13.5 nm EUV light was employed as the multilayer reflective film 13 formed on the substrate 12.
  • the multilayer reflective film 13 was formed by alternately stacking Mo layers and Si layers on the substrate 12 by ion beam sputtering (Ar gas atmosphere) using a Mo target and a Si target.
  • a Si film was formed with a film thickness of 4.2 nm, and then a Mo film was formed with a film thickness of 2.8 nm. This was set as one period, and 40 periods were laminated in the same manner.
  • a Si film was formed with a film thickness of 4.0 nm to form a multilayer reflective film 13 (total film thickness: 284 nm).
  • a protective film 14 containing Ru was formed to a thickness of 2.5 nm on the uppermost Si film of the multilayer reflective film 13 by ion beam sputtering (Ar gas atmosphere) using a Ru target.
  • the composition ratio of the PdMo alloy of the phase shift film 15 has the same composition ratio as the target composition ratio.
  • phase shift film 15 is measured for each reflective mask blank 10 using EUV light (wavelength 13.5 nm). did. As a result, the phase shift film 15 formed on the reflective mask blank 10 had a refractive index of 0.883 and an extinction coefficient of 0.042.
  • the phase shift film 15 of the obtained reflective mask blank 10 has a phase difference variation of 180 ° ⁇ 1.3 ° and a reflectance variation of 6% ⁇ 0.1% by simulation.
  • Example 1 ⁇ Production of reflective mask> Next, ten reflective mask blanks 10 of Example 1 described above were produced. A resist film was formed with a film thickness of 100 nm on the phase shift film 15 of each of the 10 reflective mask blanks produced, and a resist pattern was formed by drawing and development. Thereafter, using this resist pattern as a mask, the phase shift film 15 was dry-etched using a fluorine-based SF 6 gas to form a phase shift film pattern. Thereafter, the resist pattern was removed, and 10 reflective masks were produced.
  • phase difference variation was 180 degrees. It was ⁇ 1.8 degrees, and the variation in reflectance was 6% ⁇ 0.1%, which was a small value.
  • Example 1 ⁇ Manufacture of semiconductor devices>
  • the reflective mask obtained in Example 1 is set in an EUV scanner, the wafer on which the film to be processed and the resist film are formed on the semiconductor substrate 12 is subjected to EUV exposure, and the exposed resist film is developed. As a result, the film to be processed formed a resist pattern on the semiconductor substrate 12.
  • the reflective mask of Example 1 is a phase shift film pattern having desired phase difference characteristics (phase difference variation of 180 ° ⁇ 1.3 °) and reflectance properties (reflectance variation of 6% ⁇ 0.1%). Is a reflection type mask formed. Therefore, by using this reflective mask, a semiconductor device having a fine and highly accurate transfer pattern can be manufactured.
  • this resist pattern is transferred to a film to be processed by etching, and through various processes such as formation of an insulating film, a conductive film, introduction of a dopant, or annealing, a semiconductor device having desired characteristics can be obtained at a high yield.
  • etching through various processes such as formation of an insulating film, a conductive film, introduction of a dopant, or annealing, a semiconductor device having desired characteristics can be obtained at a high yield.
  • various processes such as formation of an insulating film, a conductive film, introduction of a dopant, or annealing
  • a reflective mask blank and a reflective mask were produced.
  • the refractive index of the phase shift film 15 formed on the reflective mask blank 10 was 0.883, and the extinction coefficient was 0.042.
  • the phase difference variation obtained by the simulation was 180 ° ⁇ 1.3 °, and the reflectance variation was 6% ⁇ 0.1%.
  • the phase difference variation of the reflective mask was 180 ° ⁇ 1.3 °, and the reflectance variation was 6% ⁇ 0.1%, which was a small value.
  • Examples 3 to 8 A reflective mask blank and a reflective mask were obtained in the same manner as in Example 1 except that the phase shift film 15 was changed to the following materials (alloys, composition ratios) and set film thicknesses in Table 1 in Example 1. Was made. Further, the refractive index, extinction coefficient, phase difference variation, and reflectance variation of the phase shift film 15 obtained by measurement in the same manner as in Example 1 were the results shown in Table 2.
  • Example 9 As Example 9, the reflective mask blank 10 having the characteristic that the reflectivity of the phase shift film 15 is 4%, and as Example 10, the reflective mask blank 10 having the characteristic that the reflectivity of the phase shift film 15 is 20%.
  • the back conductive film 11, the multilayer reflective film 13, and the protective film 14 are the same as in the first embodiment.
  • Example 1 the reflective mask blank and the reflective type were the same as in Example 1 except that the phase shift film 15 was changed to the materials (alloys, composition ratios) shown in Table 3 below and the set film thickness. A mask was prepared. Further, the refractive index, the extinction coefficient, the phase difference variation, and the reflectance variation of the phase shift film 15 obtained by measurement in the same manner as in Example 1 were as shown in Table 4.
  • the reflective masks of Examples 3 to 10 have desired phase difference characteristics (phase difference variation of 180 ° ⁇ 2 °) and desired reflectance characteristics (reflectance variation of 6% ⁇ 0.1%, 4%).
  • the reflective mask is formed with a phase shift film pattern having ⁇ 0.1%, 20% ⁇ 0.1%). Therefore, it was possible to manufacture a semiconductor device having a fine and highly accurate transfer pattern by using these reflective masks.
  • this resist pattern is transferred to a film to be processed by etching, and through various processes such as formation of an insulating film, a conductive film, introduction of a dopant, and / or annealing, a semiconductor device having desired characteristics is improved. It was possible to manufacture with a yield.
  • Example 11 to 15 In the above Example 1, the reflective mask blank and the reflective type were the same as in Example 1 except that the phase shift film 15 was changed to the materials (alloys, composition ratios) shown in Table 5 below and the set film thickness. A mask was prepared. Further, the refractive index, the extinction coefficient, the phase difference variation, and the reflectance variation of the phase shift film 15 obtained by measurement in the same manner as in Example 1 are the results of Table 6-1 and Table 6-2. became.
  • the material for the protective film 14 was appropriately selected from materials having etching resistance against the dry etching gas used when patterning the phase shift film 15.
  • the phase difference variation and the reflectance variation of the reflective mask blank and the reflective mask are the same as in Example 1 regardless of whether the reflectance is 4%, 6%, or 12%. Although it was larger than ⁇ 10, it was within the allowable range. Further, by changing the film thickness without changing the material and composition ratio of the phase shift film, the desired phase difference characteristics (phase difference variation of 180% are obtained in all cases where the reflectance is 4%, 6%, and 12%. Degree ⁇ 5 degrees) and a desired shift characteristic (0.9R 0 ⁇ R ⁇ 1.1R 0 ) could be obtained.
  • the reflective masks of Examples 11 to 15 have a phase shift having desired phase difference characteristics (phase difference variation of 180 ° ⁇ 5 °) and desired reflectance characteristics (0.9R 0 ⁇ R ⁇ 1.1R 0 ). It is a reflective mask on which a film pattern is formed. Therefore, it was possible to manufacture a semiconductor device having a fine and highly accurate transfer pattern by using these reflective masks.
  • Examples 16 to 22 In the above Example 1, the reflective mask blank and the reflective type were the same as in Example 1 except that the phase shift film 15 was changed to the materials (alloys, composition ratios) shown in Table 7 below and the set film thickness. A mask was prepared. Further, the refractive index, the extinction coefficient, the phase difference variation, and the reflectance variation of the phase shift film 15 obtained by measuring in the same manner as in Example 1 are the results of Tables 8-1 and 8-2. became.
  • the material for the protective film 14 was appropriately selected from materials having etching resistance against the dry etching gas used when patterning the phase shift film 15.
  • the phase difference variation and the reflectance variation of the reflective mask blank and the reflective mask are the same as those of Examples 1 to 10 regardless of whether the reflectance is 6% or 12%. Was large but within acceptable limits. Further, by changing the film thickness without changing the material and composition ratio of the phase shift film, the desired phase difference characteristics (the phase difference variation is 180 degrees ⁇ 5 in both cases where the reflectance is 6% and 12%). Degree) and a desired reflectance characteristic (0.9R 0 ⁇ R ⁇ 1.1R 0 ) could be obtained.
  • the reflective masks of Examples 16 to 22 have phase shifts having desired phase difference characteristics (phase difference variation of 180 ° ⁇ 5 °) and desired reflectance characteristics (0.9R 0 ⁇ R ⁇ 1.1R 0 ). It is a reflective mask on which a film pattern is formed. Therefore, it was possible to manufacture a semiconductor device having a fine and highly accurate transfer pattern by using these reflective masks.
  • Comparative Examples 1 to 3 As a comparative example 1, a reflective mask blank having a characteristic of 6% reflectivity of the phase shift film is used. As a comparative example, a reflective mask blank having a characteristic of 4% reflectivity of the phase shift film is used as a comparative example. 3, a reflective mask blank having a characteristic that the reflectivity of the phase shift film is 12% was prepared.
  • Example 1 a reflective mask blank and a reflective mask were produced in the same manner as in Example 1 except that the phase shift film was changed to the materials (alloys, composition ratios) shown in Table 9 below and the set film thickness. did. Further, the refractive index, extinction coefficient, phase difference variation, and reflectance variation of the phase shift film obtained by measurement in the same manner as in Example 1 were as shown in Table 10.
  • the reflective masks of Comparative Examples 1 to 3 have desired phase difference characteristics (with a phase difference variation of 180 ° ⁇ 5 °) and desired reflectance properties (with a reflectance variation of 0.9R 0 ⁇ R ⁇ 1.1R). 0 )) is a reflective mask on which a phase shift film pattern that does not satisfy ( 0 ) is formed. Therefore, a semiconductor device having a fine and high-precision transfer pattern cannot be manufactured by using these reflective masks.
  • this resist pattern is transferred to a film to be processed by etching, and a semiconductor device is manufactured through various processes such as formation of an insulating film, a conductive film, introduction of a dopant, or annealing.
  • the semiconductor device could not be manufactured with a high yield.
  • Reference Examples 1 and 2 In the above Example 1, the reflective masks of Reference Examples 1 and 2 were used in the same manner as in Example 1 except that the phase shift film 15 was changed to the materials (alloys, composition ratios) in Table 11 below and the set film thickness. A blank and a reflective mask were prepared. Further, the refractive index, the extinction coefficient, the phase difference variation, and the reflectance variation of the phase shift film 15 obtained by measuring in the same manner as in Example 1 are the results shown in Tables 12-1 and 12-2. became.
  • the reflectance variation of the reflective mask blank and the reflective mask is within the range of 0.9R 0 ⁇ R ⁇ 1.1R 0
  • the phase difference variation is the reflectance.
  • the reflectance variation is in the range of 0.9R 0 ⁇ R ⁇ 1.1R 0
  • the phase difference variation is in the range of ⁇ 5 degrees when the reflectance is 4%. It was.
  • the reflectance was 6% and 12%
  • the phase difference variation exceeded the range of ⁇ 5 degrees.
  • the desired phase difference characteristics phase difference variation of 180% are obtained in all cases where the reflectance is 4%, 6%, and 12%. Degree ⁇ 5 degrees) and a desired reflectance characteristic (0.9R 0 ⁇ R ⁇ 1.1R 0 ) could not be obtained.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
PCT/JP2018/006054 2017-03-03 2018-02-20 反射型マスクブランク、反射型マスク及び半導体装置の製造方法 Ceased WO2018159392A1 (ja)

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SG11201907623RA SG11201907623RA (en) 2017-03-03 2018-02-20 Reflective mask blank, reflective mask and method of manufacturing semiconductor device
US16/490,018 US11003068B2 (en) 2017-03-03 2018-02-20 Reflective mask blank, reflective mask and method of manufacturing semiconductor device
KR1020197028297A KR102639087B1 (ko) 2017-03-03 2018-02-20 반사형 마스크 블랭크, 반사형 마스크 및 반도체 장치의 제조 방법
KR1020247005441A KR20240025717A (ko) 2017-03-03 2018-02-20 반사형 마스크 블랭크, 반사형 마스크 및 반도체 장치의 제조 방법
US17/227,655 US11480867B2 (en) 2017-03-03 2021-04-12 Reflective mask blank, reflective mask and method of manufacturing semiconductor device
US17/946,709 US11880130B2 (en) 2017-03-03 2022-09-16 Reflective mask blank, reflective mask and method of manufacturing semiconductor device
US18/526,463 US12135496B2 (en) 2017-03-03 2023-12-01 Reflective mask blank and reflective mask

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US20230076438A1 (en) * 2020-03-10 2023-03-09 Hoya Corporation Reflective mask blank, reflective mask, and method of manufacturing semiconductor device
JP2023535300A (ja) * 2020-07-13 2023-08-17 アプライド マテリアルズ インコーポレイテッド 極端紫外線マスク吸収体材料

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