Mar. 26, 2015  119  US 2015/0086912 Al  sensitive resin composition of the invention is coated on a  substrate by a proper coating method such as spin coating, roll  coating, flow coating, dip coating, spray coating, or doctor  coating, and then the composition is subjected to pre-baking  at 60°  C. to 150°  C. for 1 min to 20 min, preferably at 80°  C.  to 130°  C. for 1 min to 10 min to form a film. The thickness of  the coated film is preferably 30 nm to 200 nm.  [0480]  The substrates suitable for the invention are a silicon  substrate and a substrate provided with a metal deposited film  or a film containing a metal, and more suitable substrates are  substrates provided with a deposited film of Cr, Mo Si, TaSi,  or oxides or nitrides thereof on the surface.  [0481]  The invention also relates to a resist-coated mask  blank obtained by coating the resist film formed as above. For  obtaining such a resist-coated mask blank, in the case of  forming a resist pattern on a photomask blank for the manu› facture of a photomask, a transparent substrate of quartz or  calcium fluoride is used. In general, necessary functional  films such as a light-shielding film, an antireflection film,  further, a phase shift film, additionally an etching stopper  film, and an etching mask film are laminated on a substrate.  Functional films containing such materials as silicon, or tran› sition metals, e.g., chromium, molybdenum, zirconium, tan› talum, tungsten, titanium and niobium are laminated. The  materials which are used for the outermost surface layer  include materials comprising silicon, or materials comprising  silicon and oxygen and/or nitrogen as main components,  silicon compound materials comprising the materials con› taining transition metals as the main components in addition  to the above silicon components, and transition metal com› pound materials comprising materials containing transition  metals, in particular, one or more kinds selected from chro› mium, molybdenum, zirconium, tantalum, tungsten, titanium  and niobium, or further containing one or more elements  selected from oxygen, nitrogen and carbon as the main com› ponents are exemplified.  [0482]  The light-shielding film may be a single layer but is  more preferably a multiple layered structure by recoating a  plurality of materials, one on another. In the case of a multiple  layered structure, the layer thickness per one layer is not  especially restricted, but is preferably 5 nm to 100 nm, and  more preferably 10 nm to 80 nm. The thickness of the light› shielding material at large is not especially restricted but is  preferably 5 nm to 200 nm, and more preferably 10 nm to 150  nm.  [0483]  When a pattern is formed by using the actinic ray› sensitive or radiation-sensitive resin composition on a photo› mask blank having the outermost surface layer of the material  generally containing oxygen and nitrogen in chromium, of  the above materials, trailing is formed in the vicinity of the  substrate and liable to be a tapered form, but when the com› position of the invention is used, a tapered form can be  improved as compared with conventional materials.  [0484]  In the next place, the resist film is subjected to irra› diation with an actinic ray or radiation ( electron beam and the  like), and development, preferably after baking (usually 80°  C. to 150°  C., and preferably 90°  C. to 130°  C.), thereby a  good pattern can be obtained. A semiconductor fine circuit, a  mold structure for imprinting, a photomask and the like are  manufactured by using the pattern as the mask and properly  performing etching treatment, ion injection and the like.  [0485]  Incidentally, the processes in the case of manufac› turing a mold for imprinting with the composition of the  invention are described, for example, in Japanese Patent  [0492]  When the solvent for the topcoat composition is an  organic solvent, the topcoat composition preferably contains  [0491]  The pH of the topcoat is not especially restricted, but  is preferably 1 to 10, more preferably 2 to 8, and especially  preferably 3 to 7.  [0490]  The weight average molecular weight of the water› soluble resin is not particularly limited, but is preferably  2,000 to 1,000,000, more preferably 5,000 to 500,000, and  especially preferably 10,000 to 100,000. The weight average  molecular weight of the resin is the molecular weight in terms  of polystyrene measured by GPC ( carrier: THF or N-methyl- 2-pyrrolidone (NMP)).  [0489]  When the solvent for the topcoat composition of the  invention is water, it is preferred for the composition to con› tain a water-soluble resin. By such selection, it is presumed  that the uniformity of the wettability by the developer can be  further enhanced. As preferred water-soluble resins, poly› acrylic acid, polymethacrylic acid, polyhydroxystyrene,  polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl ether,  polyvinyl acetal, polyacrylimide, polyethylene glycol, poly› ethylene oxide, polyethyleneimine, polyester polyol, poly› ether polyol, and polysaccharide are exemplified. Especially  preferred are polyacrylic acid, polymethacrylic acid, polyhy› droxystyrene, polyvinyl pyrrolidone, and polyvinyl alcohol.  Incidentally,  water-soluble resins  are not limited to  homopolymers alone, and copolymers can also be used. For  example, copolymers having monomers corresponding to the  repeating unit of homopolymers described above and other  monomer units may be used. Specifically, acrylic acid-meth› acrylic acid copolymers, and acrylic acid-hydroxystyrene  copolymers can also used in the invention. Further, as the  resins for the topcoat composition, resins having an acidic  group as described in JP-A-2009-134177 and JP-A-2009- 91798 can also be preferably used.  [0488]  When the solvent for the topcoat composition is an  organic solvent, the resist film is preferably insoluble in the  solvent. The usable solvents are alcohol-based solvents, fluo› rine-based solvents and hydrocarbon-based solvents, and  non-fluorine alcohol-based solvents are more preferably  used. As the alcohol-based solvents, primary alcohols are  preferably used from the point of coating property, and more  preferably primary alcohols having 4 to 8 carbon atoms. The  primary alcohols having 4 to 8 carbon atoms may be linear,  branched or cyclic, but linear or branched alcohols are pref› erably used. The specific examples thereof include, for  example, 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1- butanol.  [0487]  The solvent for the topcoat composition in the  invention is preferably water or an organic solvent, and more  preferably water.  [0486]  In the pattern forming method of the invention, a  topcoat layer may be formed on the above-described resist  film. The topcoat composition used for forming the topcoat  layer is described below.  4109085, JP-A-2008-162101, and compiled by Yoshihiko  Hirai, Fundamentals, Technical Development and Develop› ment of Applications of Nano-Imprinting-Techniques on  The Substrates And The Latest Technical Development of  Nano-Imprinting, published by Frontier Publishing Com› pany.  <Topcoat Composition> 