WO2015072232A1 - マスクブランクおよび転写用マスク - Google Patents
マスクブランクおよび転写用マスク Download PDFInfo
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- WO2015072232A1 WO2015072232A1 PCT/JP2014/075594 JP2014075594W WO2015072232A1 WO 2015072232 A1 WO2015072232 A1 WO 2015072232A1 JP 2014075594 W JP2014075594 W JP 2014075594W WO 2015072232 A1 WO2015072232 A1 WO 2015072232A1
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- resist
- film
- molecular weight
- mixed
- mask blank
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/66—Containers specially adapted for masks, mask blanks or pellicles; Preparation thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
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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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
Definitions
- the present invention relates to a mask blank and a transfer mask.
- a semiconductor pattern is formed using a photolithography method, and a transfer mask is used in a pattern transfer step when the photolithography method is performed.
- This transfer mask is manufactured by patterning a thin film (for example, a light-shielding film) provided on a substrate to form a desired transfer pattern.
- a thin film for example, a light-shielding film
- the transfer pattern is formed using the resist film as a mask.
- a chemically amplified resist used in a semiconductor wafer microfabrication technique is used.
- the chemically amplified resist generates an acid by exposure, and the acid reacts with a functional group or a functional substance that controls the solubility of the polymer as a catalyst, thereby becoming a positive or negative resist. Since the chemically amplified resist has high sensitivity and resolution due to the acid-catalyzed reaction, a fine pattern can be formed.
- a resist film made of a chemically amplified resist is formed immediately above a thin film (for example, a light-shielding film) for forming a transfer pattern
- a thin film for example, a light-shielding film
- the solubility changes due to an acid catalytic reaction caused by exposure, but when the resist film is provided immediately above the light-shielding film, the acid catalytic reaction is inhibited.
- the thin film surface is formed of a transition metal compound, the oxidized transition metal compound is exposed on the surface, and the oxide adsorbs the base component or generates the base component in some form. it is conceivable that.
- the acid generated during exposure of the resist film is deactivated by inhibiting the reaction as a catalyst by the base component or diffusing to the light-shielding film side.
- this tendency is strong when chromium is contained in the thin film and the chromium oxide is exposed on the surface.
- the acid cannot sufficiently react during exposure, and the resolution when etched is lowered.
- a method of providing a resist base film between the light-shielding film and the resist film has been proposed (see, for example, Patent Documents 1 and 2). . That is, a mask blank in which a light-shielding film, a resist base film, and a resist film are laminated in this order on a substrate has been proposed. This resist underlayer is interposed between the light-shielding film and the resist film, thereby allowing reaction between the base component contained in the light-shielding film and the acid generated in the resist film, or diffusion of the acid into the light-shielding film. Suppress. Thereby, the resolution of the pattern of the resist film can be improved.
- the resist base film is made of an organic material, it has excellent adhesion to the light-shielding film and the resist film, and can maintain high adhesion of the resist film.
- the resist underlayer is not soluble in the developer used for forming a pattern on the resist film, but is patterned together by dry etching when etching the light-shielding film or the like using the resist film as a mask. Is done.
- the present invention provides a mask blank that has high adhesion to a resist film, and that foreign matter derived from the resist film hardly remains in the space portion during development, and that has a low foreign matter defect, and a transfer mask with excellent pattern accuracy. For the purpose.
- the foreign substance defect generated when the mask blank is developed is caused by the foreign substance derived from the resist film remaining in the space portion.
- the foreign substance defect occurs as shown in FIG.
- the space portion 120 is removed by development of the resist film 113, and a part of the resist base film 112 is exposed.
- the resist film 113 may remain as foreign matter 130 at the end of the space portion 120. Further, the residue of the resist film 113 removed by development may reattach as foreign matter 130 on the space portion 120 during cleaning.
- These foreign matters 130 cause foreign matter defects in the transfer pattern when the transfer film is formed by etching the thin film 111 using the resist film 113 as a mask.
- the foreign material 130 present at the end of the space portion 120 forms the pattern edge of the resist film 113 in an uneven shape, which may increase the line edge roughness of the transfer pattern.
- the residue left in the resist film 113 is washed away by the cleaning liquid.
- the residual residue deposits due to volatilization of the cleaning liquid, and the foreign matter 130 in the space portion 120 or the like. May re-attach. In such a case, the foreign matter 130 is reattached along the flow of the cleaning liquid and causes a foreign matter defect.
- the present inventors have studied a method for suppressing foreign matter remaining during development and reducing foreign matter defects when a resist film is provided on the resist underlayer.
- a mixed film in which the resist underlayer component and the resist film component are mixed can be formed. That is, a mixed film in which the respective components are mixed can be formed at the interface between the resist base film and the resist film.
- This mixed film contains a resist underlayer component that is insoluble in the developer, but since it contains a resist film component, the solubility in the developer changes upon exposure as in the case of the resist film.
- the mixed film when the mixed film contains a positive resist as a component of the resist film, it becomes insoluble in the developer when not exposed to light and becomes soluble in the developer when exposed.
- the mixed film when the mixed film contains a negative resist, if it is not exposed, it becomes soluble in the developer, and the exposed region becomes insoluble.
- the region located in the space portion of the resist film in the mixed film is also removed together.
- the mixed film under the resist film dissolves, so that the resist film rises and is removed from the mixed film. Therefore, in such a mask blank, when the resist film is developed, foreign matters derived from the resist film are suppressed from remaining in the space portion.
- the mixed film contains the components of the resist underlayer film and the resist film, the mixed film is excellent in adhesion to each film. For this reason, the adhesiveness of the resist film to the substrate can be maintained. Therefore, in such a mask blank, the remaining of foreign matters is reduced and foreign matter defects are suppressed, so that a transfer mask manufactured from this mask blank is excellent in pattern accuracy.
- the present invention has been made based on the above findings and is as follows.
- (Configuration 1) The first configuration of the present invention is as follows.
- the second configuration of the present invention is as follows:
- the thickness of the mixed film is a mask blank having the first configuration, which is 0.1 nm or more and 10 nm or less.
- the third configuration of the present invention is:
- the resist underlayer composition is a mask blank having a first or second configuration containing at least one organic solvent having a boiling point of 100 ° C. or higher.
- the fourth configuration of the present invention is as follows.
- the resist underlayer composition is a mask blank having a third configuration, containing a crosslinking agent, and having a crosslinking initiation temperature lower than at least one boiling point of the organic solvent.
- the fifth configuration of the present invention is:
- the resist undercoating composition contains a base polymer and a crosslinking catalyst, and contains the crosslinking catalyst in an amount of 0.05% by mass to 10% by mass with respect to 100% by mass of the base polymer. Any one of the mask blanks.
- the sixth configuration of the present invention is as follows. A transfer mask in which a transfer pattern is formed on the thin film of any one of the first to fifth mask blanks.
- the present invention it is possible to obtain a mask blank that has high adhesion to a resist film and that hardly causes foreign matters derived from the resist film to remain in the space during development, and has a high pattern accuracy. .
- FIG. 10 is a pixel histogram of a mask blank of Comparative Example 1. It is a figure explaining the foreign material defect in a mask blank.
- FIG. 1 is a schematic cross-sectional view of a mask blank according to an embodiment of the present invention.
- the mask blank 1 includes a thin film 11, a resist base film 12, and a resist film 13 on a substrate 10, and a space between the resist base film 12 and the resist film 13.
- a mixed film 14 is formed so as to intervene.
- the substrate 10 is not particularly limited, and a transparent substrate made of quartz glass or other known substrates can be used.
- the type of the thin film 11 is not particularly limited.
- a binary mask blank is manufactured, a light shielding film is formed on the substrate 10 as the thin film 11.
- a phase shift mask blank is manufactured, a phase shift film, or a phase shift film and a light shielding film are formed on the substrate 10 as the thin film 11.
- the thin film 11 may be a single layer or a plurality of layers (for example, a laminated structure of a light shielding layer and an antireflection layer). Further, when the light shielding film has a laminated structure of a light shielding layer and an antireflection layer, the light shielding layer may be composed of a plurality of layers. Further, the phase shift film and the etching mask film may be a single layer or a plurality of layers.
- a binary mask blank including a light shielding film formed of a material containing chromium (Cr), a binary mask blank including a light shielding film formed of a material containing a transition metal and silicon (Si), and tantalum (Ta )
- Cr chromium
- Si transition metal and silicon
- Ta tantalum
- the material containing the transition metal and silicon (Si) include a material containing at least one element of nitrogen, oxygen and carbon in addition to the transition metal and silicon in addition to the material containing the transition metal and silicon. It is done.
- a transition metal silicide or a material containing a transition metal silicide nitride, oxide, carbide, oxynitride, carbonate, or carbonitride is preferable.
- the transition metal molybdenum, tantalum, tungsten, titanium, chromium, hafnium, nickel, vanadium, zirconium, ruthenium, rhodium, niobium, and the like are applicable. Of these, molybdenum is particularly preferred.
- an etching mask film may be provided on the light shielding film.
- the material of the etching mask film is selected from materials that are resistant to the etchant used when patterning the light shielding film.
- the material of the light shielding film is a material containing chromium (Cr)
- the material containing silicon (Si) is selected as the material of the etching mask film.
- the material of the light shielding film is a material containing silicon (Si) or a material containing a transition metal and silicon (Si)
- the material containing chromium (Cr) is used as the material of the etching mask film. Selected.
- the resist base film 12 is a film for reducing the influence of a transition metal compound contained in the thin film 11, particularly chromium oxide, and suppressing the deactivation of the resist film 13.
- the resist underlayer 12 is formed by applying a resist underlayer composition on the thin film 11 and heating it, and is provided on the thin film 11.
- the resist underlayer 12 does not dissolve (has resistance) to the developer used when forming a pattern on the resist film 13, but is etched when the thin film 11 is dry etched using the resist film 13 as a mask.
- resist base film 12 and the resist base composition constituting the resist base film 12 will be specifically described.
- the resist underlayer composition contains a base polymer, a crosslinking agent, a crosslinking catalyst, and an organic solvent.
- a base polymer and other cross-linking agents are dissolved in an organic solvent.
- the base polymer generally varies in molecular weight, and contains a component having a relatively large molecular weight (high molecular weight component) and a component having a relatively small molecular weight (low molecular weight component).
- the resist underlayer 12 is formed by heating the resist underlayer composition to remove the organic solvent and simultaneously crosslinking the base polymer.
- the substrate on which the resist undercoating composition has been applied has been placed in a high temperature environment at a cross-linking start temperature (for example, 120 ° C.) or higher and rapidly heated. That is, from the beginning, the resist underlayer composition was heated in a relatively high temperature environment. In this case, the organic solvent is quickly removed under a high temperature environment, and a film is formed in a state where the low molecular weight component and the high molecular weight component of the base polymer are mixed. Thereafter, crosslinking (polymerization) of the base polymer proceeds.
- a cross-linking start temperature for example, 120 ° C.
- the resist underlayer film formed by crosslinking is a film having a small variation in the crosslinked state (polymerization state) and a small variation in molecular weight. Therefore, the resist base film formed by rapid heating is a film having a relatively high molecular weight in the thickness direction.
- the resist underlayer composition is heated from a low temperature and gradually heated as described later.
- the crosslinking reaction proceeds in the presence of the organic solvent (not completely removed). That is, the base polymer starts to be crosslinked (polymerized) while being dissolved in the organic solvent.
- the high molecular weight component starts to crosslink and coagulate. This is because when the high molecular weight component is polymerized, the molecules become enormous and some of the enormous molecules come into contact with and be adsorbed on the coated surface (thin film 11).
- the high molecular weight component immediately loses the degree of freedom of dissolution in the organic solvent and aggregates downward. This occurs repeatedly, and a film in which the high molecular weight component is cross-linked is formed from the lower side (the thin film 11 side) by coagulation of the high molecular weight component.
- the low molecular weight component does not crosslink, the dissolved state in the organic solvent is easily maintained, and the dissolved low molecular weight component oozes out above the film together with the organic solvent.
- low molecular weight components also begin to coagulate due to crosslinking. By this coagulation, a film in which low molecular weight components are cross-linked is formed in a laminated manner.
- the resist underlayer 12 is formed by laminating a film in which a low molecular weight component is crosslinked on a film in which a high molecular weight component is crosslinked.
- a film having a high molecular weight component cross-linked is cross-linked in an environment rich in a cross-linking agent at the initial stage of heating, and thus has a high degree of cross-linking and is polymerized.
- a film in which a low molecular weight component is cross-linked is cross-linked in an environment where the cross-linking agent has been consumed and the cross-linking agent has been consumed (the amount of the cross-linking agent is small).
- the resist base film 12 is a film whose molecular weight decreases in the thickness direction from the thin film 11 side toward the resist film 13 side, and a low molecular weight region 12a is formed on the resist film 13 side. .
- the boiling point of the organic solvent contained in the resist base composition is preferably higher than the crosslinking start temperature. This is because by increasing the boiling point, volatilization of the organic solvent during the temperature rise is suppressed, and the low molecular weight region 12a is easily formed.
- the boiling point of the organic solvent is preferably at least 100 ° C. or higher, more preferably 115 ° C. or higher and 180 ° C. or lower.
- the organic solvent volatilizes quickly, and there is a possibility that the molecular weight distribution does not occur well in the formed resist underlayer film 12.
- the organic solvent is volatilized and heated for a long time at a high temperature, which may overheat the base polymer.
- Such organic solvents include ketones such as cyclohexanone (boiling point 155 ° C.), 3-methoxybutanol (boiling point 158 ° C.), 3-methyl-3-methoxybutanol (boiling point 173 ° C.), PGME (1-methoxy- 2-propanol) (boiling point 118 ° C.), ethylene glycol monomethyl ether (boiling point 124.5 ° C.), propylene glycol monoethyl ether (boiling point 132 ° C.), diethylene glycol dimethyl ether (boiling point 162 ° C.) and other alcohols and ethers, PGMEA ( And esters such as 2- (1-methoxy) propyl acetate) (boiling point 146 ° C.), ethyl lactate (boiling point 155 ° C.), butyl acetate (boiling point 126 ° C.),
- PGME (1-methoxy-2-propanol), PGMEA (2- (1-methoxy) propyl acetate) and the like can be preferably used.
- an organic solvent as a mixed solvent, at least one organic solvent is in the vicinity of the crosslinking start temperature of the resist base composition (for example, in the range of T-10 ° C. to T + 3 ° C. when the crosslinking start temperature is T ° C.). It is advisable to mix 10 to 60% by mass, preferably 25 to 50% by mass. Use of such a mixed solvent is preferable because the reaction rate near the crosslinking start temperature continues to be low due to the volatilization of the solvent component and the low molecular weight component of the base polymer is pushed up to the upper part of the layer.
- the crosslinking initiation temperature of the resist base composition may be lower than the boiling point of the organic solvent (at least one organic solvent in the case of a mixed solvent). You may crosslink under.
- the crosslinking initiation temperature varies depending on the type of base polymer and crosslinking agent. For example, when a mixed solvent of PGM (boiling point 118 ° C.) and PGMEA (boiling point 146 ° C.) is used, the crosslinking initiation temperature is not particularly limited, but is preferably 145 ° C. or less, preferably 100 ° C. or more and 125 ° C. or less. It is particularly preferred. There is no particular limitation as long as the system has such a crosslinking initiation temperature.
- the resist underlayer composition contains a crosslinking catalyst, and when the base polymer is a novolac resin, an acidic catalyst is selected.
- the acidic catalyst include organic acids such as sulfonic acids such as paratoluenesulfonic acid and carboxylic acids such as benzoic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. Organic acids are preferred.
- a photoacid generator such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine is mixed, and an acid generated by light irradiation is used as a catalyst. You can also.
- the cross-linking reaction rate varies depending on the type of cross-linking catalyst and the pH of the resist underlayer composition liquid. For this reason, it is considered that the thickness of the low molecular weight region 12a also varies depending on the type and content of the crosslinking catalyst. Specifically, when the crosslinking reaction rate is high (for example, the content of the crosslinking catalyst is large), the low molecular weight component is likely to coagulate together with the high molecular weight component, so that the variation in molecular weight is small and the low molecular weight region 12a. The thickness decreases.
- the resist base composition contains 0.05% by mass to 10% by mass, preferably 0.05% by mass to 3% by mass of the crosslinking catalyst with respect to 100% by mass of the base polymer. . If the amount of the crosslinking catalyst is too large relative to the base polymer, it is difficult to form a molecular weight distribution of the base polymer above and below the membrane.
- the thickness of the mixed film 14 can be formed to 0.1 nm or more and 10 nm or less, for example.
- a well-known resin component can be used.
- the base polymer include novolac resins and acrylic resins.
- the resist film 13 is used as a mask when a predetermined resist pattern is formed and the thin film 11 is patterned.
- the resist film 13 is formed by applying a chemically amplified resist on the low molecular weight region 12 a of the resist base film 12 and heating it, and is provided on the resist base film 12.
- the chemically amplified resist dissolves the low molecular weight region 12a to form a mixed component mixed with the components of the low molecular weight region 12a.
- the mixed component finally becomes the mixed film 14 by heat-crosslinking.
- the mixed film 14 contains the components of the resist underlayer film 12, but since it contains the components of the resist film 13, it shows the same solubility as the resist film 13 in the developer.
- the mixed film 14 contains a positive resist component.
- This mixed film 14 has the same solubility as the positive resist in the developer, and the unexposed area becomes insoluble in the developer, and the exposed area becomes soluble in the developer.
- the mixed film 14 contains a negative resist component, so that the unexposed region of the mixed film 14 becomes soluble in the developer and is exposed. The area becomes insoluble in the developer.
- Such a mixed film 14 is removed together with the resist film 13 when the resist film 13 is developed. Specifically, as shown in FIG. 3B described later, when the resist film 13 is developed, the space portion 20 is removed and a resist pattern is formed. At this time, the region of the space portion 20 of the mixed film 14 is also removed. Thereby, in the region of the space portion 20, the mixed film 14 under the resist film 13 is dissolved and removed, so that the resist film 13 is lifted and removed so as to be removed from the mixed film 14. become. That is, the mixed film 14 dissolves during development, so that the upper resist film 13 is lifted and removed from the space portion 20 (lift-off effect). Therefore, according to the mixed film 14, it is possible to suppress the foreign matters derived from the resist film 13 from remaining in the space portion 20. Since the region of the line portion of the resist pattern of the mixed film 14 is insoluble in the developer, the resist pattern of the resist film 13 is not lifted off by the developer.
- the mixed film 14 contains the components of the resist film 13, the mixed film 14 has good wettability with respect to the developing solution and is excellent in the permeability of the developing solution.
- the mixed film 14 is formed of an organic material, the mixed film 14 has excellent adhesion to the resist base film 12 and the resist film 13, and can maintain high adhesion of the resist film 13 to the mask blank 1. it can.
- the thickness of the mixed film 14 corresponds to the thickness of the low molecular weight region 12a.
- the thickness of the mixed film 14 increases as the thickness of the low molecular weight region 12a increases.
- the thickness of the mixed film 14 is not particularly limited, but is preferably 0.1 nm or more and 10 nm or less.
- 2A to 2E are process diagrams showing a manufacturing process of a mask blank according to one embodiment of the present invention.
- a thin film 11 for forming a transfer pattern is formed on a substrate 10 by, eg, sputtering.
- a resist base composition 12 ' is applied on the thin film 11 by, for example, spin coating.
- the resist base composition 12 ' is crosslinked by heating.
- the temperature is raised from a low temperature to a high temperature and heated gently.
- the resist base composition 12 ′ is heated from a temperature lower than the boiling point of the organic solvent contained in the resist base composition 12 ′ (first temperature) to a temperature higher than the crosslinking start temperature of the resist base composition 12 ′.
- the temperature is raised to (second temperature) and heated at the second temperature.
- the temperature rise is stopped and heating is performed at the second temperature for a predetermined time.
- the base polymer is cross-linked and the organic solvent is volatilized to form the resist base film 12.
- the temperature is gradually raised and heated from the first temperature to the second temperature over a predetermined time.
- volatilization of the organic solvent can be suppressed as compared with the case of heating at the second temperature from the beginning (rapid heating).
- the crosslinking of the resist base composition 12 'proceeds in an environment where an organic solvent is present.
- a component having a relatively high molecular weight in the base polymer starts to be crosslinked and coagulated, and then a component having a relatively low molecular weight starts to coagulate.
- the resist base film 12 has a structure in which a film in which a high molecular weight component is crosslinked and a film in which a low molecular weight component is crosslinked are sequentially laminated from the thin film 11 side.
- the resist underlayer 12 is configured by laminating a film in which a high molecular weight component is crosslinked and a film in which a low molecular weight component is crosslinked in this order from the thin film 11 side. Since the high molecular weight component is crosslinked in an environment where there are many crosslinking agents at the initial stage of heating, the degree of crosslinking is high and the polymer is polymerized. On the other hand, the low molecular weight component is not polymerized as much as the high molecular weight component because the low molecular weight component is crosslinked in an environment where the crosslinking proceeds and the crosslinking agent is consumed (the crosslinking agent is small). As a result, as shown in FIG.
- the resist underlayer 12 is configured such that the molecular weight decreases in the thickness direction from the thin film 11 side to the surface side, and the low molecular weight having a low molecular weight is formed on the surface side. It will have the area
- the first temperature is a temperature at which the resist base composition starts to be heated, and is lower than the boiling point of the organic solvent contained in the resist base composition 12 ′.
- the first temperature is, for example, room temperature (23 ° C.).
- the second temperature is a temperature after the temperature is raised, and is higher than the crosslinking start temperature of the resist base composition 12 ′. Since the crosslinking start temperature varies depending on the type of the crosslinking agent or the base polymer, the second temperature can be changed depending on the type of the crosslinking agent or the base polymer.
- the cross-linking reaction proceeds quickly, and the entire layer is in a uniform cross-linked state before the low molecular weight components gather on top.
- the rate of temperature increase need not be constant, but it is preferably a rate of temperature increase enough to disperse the low molecular weight component in the vicinity of the crosslinking start temperature.
- a chemically amplified resist 13 ′ is applied on the resist base film 12 by, for example, spin coating.
- a low molecular weight region 12a is formed on the surface of the resist underlayer 12 to which the chemically amplified resist 13 'is applied, and the chemically amplified resist 13' is applied so as to cover the low molecular weight region 12a.
- the low molecular weight region 12a is dissolved by the chemically amplified resist 13 '.
- a mixed component 14 ′ in which the components of the low molecular weight region 12 a and the components of the chemically amplified resist 13 ′ are mixed is formed at the interface between the resist base film 12 and the applied chemically amplified resist 13 ′.
- the chemically amplified resist 13 ′ is heated and cross-linked to form a resist film 13.
- the mixed component 14 ′ is also heated and cross-linked at the same time to form the mixed film 14.
- the mixed film 14 is formed at the interface between the resist base film 12 and the resist film 13.
- the mask blank 1 of the present embodiment is obtained.
- FIGS. 3A to 3D are process diagrams showing a manufacturing process of a transfer mask according to an embodiment of the present invention.
- the transfer mask of this embodiment is manufactured by forming a predetermined pattern shape on the above-described mask blank. Below, the case where the resist film 13 contains a positive resist component is demonstrated.
- the mask blank 1 is exposed so as to correspond to a predetermined pattern.
- the exposed portions of the resist film 13 and the mixed film 14 become soluble in the developer.
- the mask blank 1 is developed.
- a predetermined resist pattern is formed on the resist film 13 and the mixed film 14 by development.
- the affinity between the component derived from the resist film 13 and the resist base film 12 is high, the component derived from the resist film 13 may remain in the space portion 20 of the resist pattern.
- the residue of the resist film 13 removed by the development is dispersed in the cleaning liquid or the like.
- the cleaning liquid droplets or the like remain on the substrate surface, the residue of the cleaning liquid is deposited due to volatilization of the cleaning liquid. There is a risk of reattachment.
- the mixed film 14 is provided so as to be interposed between the resist underlayer film 12 and the resist film 13, and the mixed film 14 dissolves in the developing solution, thereby removing the resist film 13. .
- the component (foreign matter) derived from the resist film 13 is removed from the space portion 20 together with the mixed film 14, and the remaining foreign matter is suppressed in the space portion 20.
- most of the residue from the resist film 13 is removed from the substrate together with the developer. Since the number of resist films 13 remaining on the substrate 10 at the stage of the cleaning process is small, redeposition is suppressed in the cleaning process. For this reason, the resist film 13 is excellent in resolution and excellent in the line edge roughness of the space portion 20.
- the exposed area is soluble in the developer, and the unexposed area is insoluble in the developer.
- the mixed film 14 is developed, only the exposed area of the mixed film 14 is scraped off in the thickness direction. That is, the mixed film 14 is not scraped away from the space portion 20 in the surface direction. For this reason, the adhesiveness of the resist film 13 that remains without being exposed to the resist base film 12 is not impaired.
- the resist base film 12 and the thin film 11 are etched using the resist film 13 on which a predetermined resist pattern is formed as a mask.
- a predetermined transfer pattern is formed on the thin film 11 by etching.
- the transfer mask 50 of this embodiment is obtained by removing the resist film 13 and the like. Since the transfer pattern of the transfer mask 50 is formed with a resist pattern with little remaining foreign matter, foreign matter defects are reduced. Moreover, it has excellent line edge roughness. Therefore, the transfer mask 50 of this embodiment is excellent in pattern accuracy.
- the present invention is not limited to this. Even if the resist film 13 contains a negative resist component, the same effect can be obtained.
- the remaining of the developer droplets and the like in which the residue from the developed resist film 13 is dispersed is suppressed.
- the residue is discharged out of the substrate together with the developer, and reattachment to the space portion 20 is suppressed. Therefore, according to the mask blank 1, when the resist film 13 is developed, the remaining foreign matter such as missing particles is reduced, so that foreign matter defects are reduced. For example, in spin cleaning or the like, there is a possibility that a vortex-like foreign substance defect may occur due to the re-attachment of the fallen residue in a vortex shape, which can be suppressed according to the present embodiment.
- the mixed film 14 is formed of a mixed component in which the components of the resist underlayer film 12 and the resist film 13 are mixed. For this reason, the mixed film 14 is excellent in adhesiveness with the resist underlayer film 12 and the resist film 13, and can maintain high adhesiveness of the resist film 13 to the mask blank 1.
- the transfer mask 50 of the present embodiment foreign matter defects are suppressed, and the transfer pattern is excellent in line edge roughness. For this reason, the transfer mask 50 is excellent in pattern accuracy.
- a chemically amplified resist is applied to a low molecular weight region to form a mixed component, and then a mixed film is formed by heating and crosslinking the mixed component simultaneously with the thermal crosslinking of the chemically amplified resist.
- the method for forming the mixed film is not limited to this.
- a resist underlayer component resist underlayer composition
- a resist film component resist film component
- a mixed film may be formed.
- the mixing ratio of the resist underlayer composition and the chemically amplified resist is not particularly limited, but is preferably 1: 9 to 9: 1, and more preferably 1: 4 to 4: 1.
- the present invention includes a mask blank in which a mixed film containing both components is formed between a resist base film and a resist film.
- Example 1 In this example, a mask blank and a transfer mask were manufactured and evaluated for each.
- a light semi-transmissive film, a light-shielding film, and a hard mask were formed as thin films on the substrate by sputtering.
- a single-layer MoSiN film (thickness: 69 nm) was formed as a light semi-transmissive film on a transparent substrate.
- three layers of a CrOCN layer (thickness 30 nm), a CrN layer (thickness 4 nm), and a CrOCN layer (thickness 14 nm) were formed in this order as a light-shielding film.
- a hard mask (thickness 10 nm) was formed.
- the HMDS process was performed on the surface of the formed thin film on predetermined conditions.
- a transparent substrate made of quartz glass was used as the substrate.
- the resist base composition used here contains the following components.
- Base polymer Novolac polymer Organic solvent: Mixed solvent of 1-methoxy-2-propanol (PGME) (boiling point 118 ° C) and 2- (1-methoxy) propyl acetate (PGMEA) (boiling point 146 ° C)
- Crosslinking agent Alkoxymethylmelamine-based crosslinking agent / crosslinking catalyst: Sulphonic acid-based acidic catalyst / crosslinking start temperature: 115 ° C
- the resist underlayer composition (thickness 10 nm) was formed by heat-crosslinking the resist underlayer composition under predetermined conditions. It took 4 minutes to raise the temperature from room temperature (20 ° C.) to 200 ° C., followed by 6 minutes of heat treatment. Thereby, a resist underlayer having a low molecular weight region on the surface side was formed.
- a chemically amplified resist (“SLV12M negative resist” manufactured by Fuji Film Electronics Materials Co., Ltd.) was applied on the low molecular weight region of the resist underlayer by spin coating.
- a mixed component is formed by dissolving the low molecular weight region at the interface between the low molecular weight region and the resist underlayer.
- the resist film (thickness 160nm) was formed by heating at 130 degreeC for 10 minute (s).
- a mixed film interposed between the resist underlayer film and the resist film was formed. Thereby, the mask blank of Example 1 was obtained.
- a predetermined transfer pattern was formed on the obtained mask blank of Example 1 to manufacture a transfer mask. Specifically, the mask blank was exposed to an electron beam and baked at 120 ° C. after the exposure. Then, the transfer pattern was formed by developing using a developing solution (tetramethylamino hydride (TMAH) aqueous solution). The dimension of the transfer pattern (space part dimension) was 100 nm.
- TMAH tetramethylamino hydride
- the presence or absence of the formation of the mixed film was confirmed as follows.
- a chemically amplified resist was dropped on the resist underlayer formed under the above heating conditions, and this was heated and crosslinked to form a resist film.
- the resist film is developed, and, for example, as shown in the pixel histogram of FIG. 4, in the resist film, the region where the chemically amplified resist is dropped (region T indicated by the arrow in the figure) is removed in a circular shape. It was confirmed.
- the circular shape indicates that the resist base film is dissolved by the chemically amplified resist and a mixed film of these components is formed.
- the developed mask blank is developed multiple times, and the amount of decrease in thickness (thickness reduction) when components such as resist film no longer elute into the developer. It was measured. Since the mixed film is scraped off by development, the amount of decrease in thickness due to development corresponds to the thickness of the mixed film.
- the electron beam irradiation was performed with respect to the formed resist layer using the electron beam irradiation apparatus. Immediately after irradiation, it was heated on a hot plate at 120 ° C. for 10 minutes. Then, it developed using TMAH with a density
- concentration of 2.38 mass%, rinsed using the pure water, and was made to dry. In this way, an isolated line pattern (IL line: space 1:> 100) was formed. The exposure dose was 35 ⁇ C / cm 2 . The case where a line having a pattern dimension of 60 nm could be formed was evaluated as acceptable ( ⁇ ), and the case where the pattern dimension could not be formed was determined as unacceptable (x).
- Foreign matter defects were evaluated by the number of defects in the manufactured transfer mask. Measure the pixel histogram by optical measurement method. If defects (pixels) of 200 nm or less are formed in high density and geometric shape, it is rejected (x). If the defects are dispersed at low density, it passes. ( ⁇ ).
- Example 1 formation of the mixed film was confirmed. The thickness was confirmed to be 4.87 nm because the amount of film reduction was 4.87 nm. Further, as shown in the pixel histogram of FIG. 5, it was confirmed that the foreign matter defects were low density and few. This is presumably because resist residue and the like were flowed together with the developer at the development stage, and the number of resist residue remaining on the substrate was small at the washing stage. The evaluation results are shown in Table 1 below.
- Comparative Example 1 In Comparative Example 1, the same procedure as in Example 1 was performed except that the heating condition of the resist underlayer composition was changed. Specifically, the resist base composition was rapidly heated at 200 ° C. and heated at 200 ° C. for 10 minutes. As shown in Table 1, in Comparative Example 1, since the low molecular weight region is not formed in the resist underlayer film, the resist film remains in the pattern portion or the residue from the resist film is reattached. It was confirmed that there are many. In addition, as shown in the pixel histogram of FIG. 6, foreign object defects were detected radially from the center of the substrate. The reason is considered as follows. After forming the pattern, the substrate was washed with a cleaning solution, and the cleaning solution was shaken off by spin rotation and dried.
- residue of the resist film is dispersed in the cleaning liquid supplied onto the substrate. It is considered that the droplets of the cleaning liquid were dried without being shaken on the substrate, so that the residue of the resist film contained in the droplets formed a radial locus and deposited on the substrate.
- Comparative Example 2 was manufactured in the same manner as in Example 1 except that a resist film was directly formed on a thin film without forming a resist base film. As shown in Table 1, in Comparative Example 2, since no resist underlayer was formed, no increase in foreign matter defects due to the remaining resist underlayer was confirmed. However, it was confirmed that the resolution was inferior because the resist film was deactivated.
- Examples 2 and 3 were produced in the same manner as Example 1 except that the content of the crosslinking catalyst contained in the resist underlayer composition was changed. Specifically, the content of the crosslinking catalyst was twice that of Example 1 in Example 2 and half that of Example 1 in Example 3. As shown in Table 1, in Examples 2 and 3, as in Example 1, it was confirmed that the resolution was excellent and there were few foreign object defects. In Examples 2 and 3, it was confirmed that the content of the crosslinking catalyst was changed and the thickness of the mixed film was different. Specifically, it was confirmed that the thickness of the mixed film was 0.6 nm in Example 2 and 4.8 nm in Example 3.
- Example 4 a mixed film of 9.7 nm was used using a coating liquid in which a resist base composition and a chemically amplified resist were mixed at a ratio of 1: 1 (volume ratio) between the resist base film and the resist film.
- a mask blank was manufactured in the same manner as in Example 1 except that was formed. Specifically, a resist underlayer composition was applied on a thin film of a substrate, rapidly heated at 200 ° C., and heated at 200 ° C. for 10 minutes to form a resist underlayer. Next, the above-mentioned coating solution was spin-coated on the resist base film and heated at 150 ° C. to form a mixed film. Next, a resist layer was formed on the mixed film under the same conditions as in Example 1. When the mask blank of Example 4 was patterned to produce a transfer mask, a transfer mask blank having excellent resolution and few foreign matter defects was obtained as in the other examples.
- a mask blank having high adhesion to the resist film and having less foreign matter defects due to the foreign matter originating from the resist film being difficult to remain in the space during development is obtained. It is done. From this mask blank, a transfer mask having excellent pattern accuracy can be obtained.
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Abstract
Description
また、混合膜は、レジスト下地膜およびレジスト膜の成分を含有するため、それぞれの膜との密着性に優れる。このため、レジスト膜の基板への密着性を保持することができる。
したがって、このようなマスクブランクでは異物の残存が低減されて異物欠陥が抑制されるので、このマスクブランクから製造される転写用マスクはパターン精度に優れることになる。
(構成1)
本発明の第1の構成は、
基板上に、転写パターンを形成するための薄膜と、レジスト下地組成物から形成され、前記薄膜上に設けられるレジスト下地膜と、化学増幅型レジストから形成され、前記レジスト下地膜上に設けられるレジスト膜と、前記レジスト下地膜と前記レジスト膜との間に介在するように設けられる混合膜と、を備え、前記レジスト下地膜は、前記薄膜側から前記レジスト膜側に向かって厚さ方向に分子量が減少するように構成され、前記レジスト膜側の表面に分子量の低い低分子量領域を有しており、前記混合膜は、前記低分子量領域の成分と前記化学増幅型レジストの成分とが混合することにより形成されるマスクブランクである。
本発明の第2の構成は、
前記混合膜の厚さは、0.1nm以上10nm以下である、第1の構成のマスクブランクである。
本発明の第3の構成は、
前記レジスト下地組成物は、沸点が100℃以上である有機溶媒を少なくとも1種以上含有する、第1または2の構成のマスクブランクである。
本発明の第4の構成は、
前記レジスト下地組成物は、架橋剤を含有しており、架橋開始温度が前記有機溶媒の少なくとも1種の沸点より低い、第3の構成のマスクブランクである。
本発明の第5の構成は、
前記レジスト下地組成物は、ベースポリマーおよび架橋触媒を含有しており、前記ベースポリマー100質量%に対して前記架橋触媒を0.05質量%以上10質量%以下含有する、第1~4の構成のいずれかのマスクブランクである。
本発明の第6の構成は、
第1~5の構成のいずれかのマスクブランの前記薄膜に転写パターンが形成されている、転写用マスクである。
1.マスクブランク
2.マスクブランクの製造方法
3.転写用マスクおよびその製造方法
4.本実施形態の効果
5.変形例等
本実施形態のマスクブランクについて、図1を用いて説明する。図1は、本発明の一実施形態に係るマスクブランクの概略断面図である。
基板10としては、特に限定されず、石英ガラスなどからなる透明基板、またはその他公知の基板を用いることができる。
薄膜11の種類は特に限定されない。バイナリマスクブランクを製造する場合、基板10上に薄膜11として遮光膜が形成される。また、位相シフト型マスクブランクを製造する場合、基板10上に薄膜11として位相シフト膜、あるいは位相シフト膜及び遮光膜が形成される。薄膜11は、単層でも複数層(例えば遮光層と反射防止層との積層構造)としてもよい。また、遮光膜を遮光層と反射防止層との積層構造とする場合、この遮光層を複数層からなる構造としてもよい。また、上記位相シフト膜、エッチングマスク膜についても、単層でも複数層としてもよい。
エッチングマスク膜の材料は、遮光膜をパターニングする際に使用するエッチャントに対して耐性を有する材料から選択される。遮光膜の材料がクロム(Cr)を含有する材料の場合、エッチングマスク膜の材料としては、例えば上記ケイ素(Si)を含有する材料が選択される。また、遮光膜の材料がケイ素(Si)を含有する材料や、遷移金属とケイ素(Si)を含有する材料の場合、エッチングマスク膜の材料としては、例えば上記クロム(Cr)を含有する材料が選択される。
レジスト下地膜12は、薄膜11に含有される遷移金属化合物、特に、酸化クロム等の影響を低減してレジスト膜13の失活化を抑制するための膜である。レジスト下地膜12は、レジスト下地組成物を薄膜11上に塗布して加熱することにより形成され、薄膜11上に設けられる。レジスト下地膜12は、レジスト膜13にパターンを形成する際に用いる現像液に対しては溶解しない(耐性を有する)が、レジスト膜13をマスクとして薄膜11をドライエッチングする際にエッチングされる。
なお、架橋触媒の種類やレジスト下地組成液のpHなどにより、架橋の反応速度は変動する。このため、架橋触媒の種類や含有量により、低分子量領域12aの厚さも変動することが考えられる。具体的には、架橋の反応速度が大きい(たとえば、架橋触媒の含有量が多い)と、高分子量成分と共に低分子量成分が凝析しやすくなるため、分子量のバラつきが小さくなり、低分子量領域12aの厚さは減少する。一方、反応速度が遅い(たとえば、含有量が少ない)と、低分子量成分の凝析が生じにくくなるため、低分子量領域12aの厚さは増加する。
このことから、レジスト下地組成物は、ベースポリマー100質量%に対して架橋触媒を0.05質量%以上10質量%以下、好ましくは、0.05%質量以上3質量%以下含有することが好ましい。なお、架橋触媒の量がベースポリマーに対して多すぎると、膜の上下でベースポリマーの分子量分布が形成されにくい。また、架橋触媒の量が少なすぎると、架橋していない低分子量(レジスト層と溶け合ってしまう部分)の厚さが厚くなりすぎてしまい、レジストパターンを形成したときの解像精度が悪くなる恐れが生じる。
これにより、混合膜14の厚さを、例えば0.1nm以上10nm以下に形成することができる。
レジスト膜13は、所定のレジストパターンが形成されて、薄膜11をパターニングする際のマスクとなる。レジスト膜13は、レジスト下地膜12の低分子量領域12a上に化学増幅型レジストを塗布して加熱することにより形成され、レジスト下地膜12上に設けられる。後述するように、化学増幅型レジストは、低分子量領域12aを溶解することにより、低分子量領域12aの成分と混合した混合成分を形成する。混合成分は、最終的に、加熱架橋することで混合膜14となる。
混合膜14は、レジスト下地膜12とレジスト膜13との間に介在するように設けられ、レジスト下地膜12の低分子量領域12aの成分と化学増幅型レジストの成分とが混合した混合成分により形成される。混合膜14が形成されるメカニズムは、以下のように推測される。
レジスト膜13を形成する際、化学増幅型レジストをレジスト下地膜12上に塗布するが、本実施形態では、その塗布面に低分子量領域12aが位置している。化学増幅型レジストには有機溶媒が含有されており、低分子量領域12aは有機溶媒により溶解する。溶解により、低分子量領域12aの成分と化学増幅型レジストとが混合した混合成分が形成される。混合成分が、化学増幅型レジストの加熱架橋の際に、加熱架橋することで混合膜14となる。
次に、上述のマスクブランク1の製造方法について図2(a)~(e)を参照しながら説明する。図2(a)~(e)は、本発明の一実施形態に係るマスクブランクの製造工程を示す工程図である。
次に、本実施形態の転写用マスクおよびその製造方法について図3(a)~(d)を参照しながら説明する。図3(a)~(d)は、本発明の一実施形態に係る転写用マスクの製造工程を示す工程図である。
しかしながら、本実施形態では、レジスト下地膜12とレジスト膜13との間に介在するように混合膜14が設けられており、この混合膜14が現像液に溶解することによりレジスト膜13をえぐりとる。これにより、レジスト膜13に由来する成分(異物)は、混合膜14と共にスペース部分20から除去され、スペース部分20では異物の残存が抑制される。また、混合膜14が除去されたスペース部分20は、レジスト膜13のほとんどの抜けカスが現像液とともに基板上から排除される。洗浄工程の段階で基板10上に残るレジスト膜13の数が少ないので、洗浄工程で再付着が抑制されることになる。このため、レジスト膜13は解像性に優れており、スペース部分20のラインエッジラフネスに優れている。
本実施形態によれば、以下に示す1つまたは複数の効果を奏する。
上述の実施形態では、低分子量領域に化学増幅型レジストを塗布して混合成分を形成し、その後、化学増幅型レジストの加熱架橋と同時に、混合成分を加熱架橋して混合膜を形成する場合について説明した。しかしながら、本発明において、混合膜の形成方法はこれに限定されない。例えば、予め、レジスト下地膜の成分(レジスト下地膜組成物)とレジスト膜の成分(化学増幅型レジスト)とを調製し、この混合成分をコート液としてレジスト下地膜上に塗布・加熱架橋して混合膜を形成してもよい。レジスト下地膜組成物と化学増幅型レジストとの混合比率は、特に限定されないが、例えば1:9~9:1とすることが好ましく、1:4~4:1とすることがより好ましい。本発明は、レジスト下地膜とレジスト膜との間に、両者の成分を含む混合膜が形成されているマスクブランクが含まれる。
本実施例では、マスクブランクおよび転写用マスクを製造し、それぞれについて評価を行った。
まず、基板上に、薄膜として光半透過膜、遮光性膜およびハードマスクをそれぞれスパッタリング法で形成した。具体的には、透明基板上に、光半透過膜として単層のMoSiN膜(厚さ69nm)を形成した。続いて、遮光性膜として、CrOCN層(厚さ30nm)、CrN層(厚さ4nm)およびCrOCN層(厚さ14nm)の3層をこの順序で形成した。続いて、ハードマスク(厚さ10nm)を形成した。そして、形成された薄膜の表面に対し、HMDS処理を所定の条件で施した。なお、本実施例では、基板として、石英ガラスからなる透明基板を用いた。
・ベースポリマー:ノボラック系ポリマー
・有機溶媒:1-メトキシ-2-プロパノール(PGME)(沸点118℃)と2-(1-メトキシ)プロピルアセテート(PGMEA)(沸点146℃)の混合溶媒
・架橋剤:アルコキシメチルメラミン系架橋剤
・架橋触媒:スルフォン酸系酸性触媒
・架橋開始温度:115℃
続いて、得られた実施例1のマスクブランクに所定の転写パターンを形成し、転写用マスクを製造した。具体的には、マスクブランクに対して、電子線により露光し、露光後に120℃でベーク処理を行った。その後、現像液(テトラメチルアミノハイドライド(TMAH)水溶液)を用いて現像することにより、転写パターンを形成した。なお、転写パターンの寸法(スペース部分の寸法)を100nmとした。
混合膜、マスクブランクおよび転写用マスクについて、以下の方法により評価した。
まず、成膜したレジスト層に対して、電子線照射装置を用いて、電子線照射を行った。照射後直ぐに、120℃で10分間ホットプレート上にて加熱した。その後、濃度2.38質量%のTMAHを用いて現像し、純水を用いてリンスした後、乾燥させた。このようにして孤立ラインパターン(IL ライン:スペース=1:>100)を形成した。なお、露光線量は35μC/cm2とした。パターン寸法が60nmのラインを形成できた場合を合格(○)とし、形成できなかった場合を不合格(×)とした。
実施例1では、混合膜の形成が確認された。その厚さは、減膜量が4.87nmであることから、4.87nmであることが確認された。また、図5のピクセルヒストグラムに示すように、異物欠陥が低密度で少ないことが確認された。これは、現像の段階でレジストの抜けカス等が現像液とともに流され、洗浄の段階で基板上に残っているレジストのカスの数が少なかったことによると推察される。
評価結果を以下の表1に示す。
比較例1では、レジスト下地組成物の加熱条件を変更した以外は実施例1と同様に行った。具体的には、レジスト下地組成物を200℃で急熱し、200℃で10分間加熱した。
表1に示すように、比較例1では、レジスト下地膜に低分子量領域が形成されないため、パターン部分にレジスト膜が残存したり、レジスト膜の抜けカスが再付着したりすることで、異物欠陥が多いことが確認された。
また、図6のピクセルヒストグラムに示すように、異物欠陥は、基板の中心から放射状に検出された。この理由は以下のように考えられる。パターンの形成後、洗浄液で洗浄し、スピン回転によって洗浄液を振り切って乾燥させた。このとき、基板上に供給された洗浄液には、レジスト膜のカスが分散している。その洗浄液の液滴等が基板上で振り切られずに乾燥したことで、その液滴に含まれていたレジスト膜のカスが放射状の軌跡を形成して基板上に析出したものと考えられる。
比較例2では、レジスト下地膜を形成せずに、薄膜上にレジスト膜を直接形成した以外は、実施例1と同様に製造した。
表1に示すように、比較例2では、レジスト下地膜を形成しなかったため、レジスト下地膜の残存による異物欠陥の増加は確認されなかった。しかし、レジスト膜が失活化したためか、解像性に劣ることが確認された。
実施例2,3では、レジスト下地組成物に含有される架橋触媒の含有量を変更した以外は実施例1と同様に製造した。具体的には、架橋触媒の含有量を、実施例2では実施例1の2倍に、実施例3では実施例1の半分にした。
表1に示すように、実施例2,3では、実施例1と同様に、解像性に優れ、異物欠陥が少ないことが確認された。なお、実施例2,3では、架橋触媒の含有量を変更しており、混合膜の厚さが異なっていることが確認された。具体的には、混合膜の厚さが、実施例2では0.6nmであり、実施例3では4.8nmであることが確認された。
実施例4では、レジスト下地膜とレジスト膜の間に、レジスト下地組成物と化学増幅型レジストとを1:1(体積比)の割合で混合したコート液を用いて、9.7nmの混合膜を形成した以外は、実施例1と同様にマスクブランクを製造した。
具体的には、基板の薄膜上にレジスト下地組成物を塗布して、200℃で急熱し、200℃で10分間加熱してレジスト下地膜を形成した。次に、レジスト下地膜の上に前述のコート液をスピンコートして150℃で加熱し混合膜を形成した。次に、混合膜の上にレジスト層を実施例1と同様の条件で成膜した。
実施例4のマスクブランクをパターニングして転写用マスクを製造したところ、他の実施例と同様に解像性に優れ、異物欠陥の少ない転写用マスクブランクが得られた。
10 基板
11 薄膜
12 レジスト下地膜
12a 低分子量領域
13 レジスト膜
14 混合膜
20 スペース部分
50 転写用マスク
Claims (6)
- 基板上に、
転写パターンを形成するための薄膜と、
レジスト下地組成物から形成され、前記薄膜上に設けられるレジスト下地膜と、
化学増幅型レジストから形成され、前記レジスト下地膜上に設けられるレジスト膜と、
前記レジスト下地膜とレジスト膜との間に介在するように設けられる混合膜と、
を備え、
前記レジスト下地膜は、前記薄膜側から前記レジスト膜側に向かって厚さ方向に分子量が減少するように構成され、前記レジスト膜側の表面に分子量の低い低分子量領域を有しており、
前記混合膜は、前記低分子量領域の成分と前記化学増幅型レジストの成分とが混合することにより形成される、マスクブランク。 - 前記混合膜の厚さは0.1nm以上10nm以下である、請求項1に記載のマスクブランク。
- 前記レジスト下地組成物は、沸点が100℃以上である有機溶媒を少なくとも1種以上含有する、請求項1又は2に記載のマスクブランク。
- 前記レジスト下地組成物は、架橋剤を含有しており、架橋開始温度が前記有機溶媒の少なくとも1種の沸点より低い、請求項3に記載のマスクブランク。
- 前記レジスト下地組成物は、ベースポリマーおよび架橋触媒を含有しており、前記ベースポリマー100質量%に対して前記架橋触媒を0.05質量%以上10質量%以下含有する、請求項1~4のいずれかに記載のマスクブランク。
- 請求項1~5のいずれかに記載のマスクブランクの前記薄膜に転写パターンが形成されている、転写用マスク。
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JPH07153666A (ja) * | 1993-11-30 | 1995-06-16 | Nec Corp | パターン形成方法 |
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