Aug. 4, 2016  65  US 2016/0223905 Al  examples thereof include 1-butanol, 1-hexanol, 1-pentanol,  3-methyl-1-butanol, 2-ethylbutanol, and perfluorobutyl tet› rahydrofuran.  [0637]  Furthermore, as the resin for a top coat composition,  the resins containing acid groups described in JP2009- 134177 A and JP2009-91798A can also be preferably used.  [0638]  The weight-average molecular weight of the water› soluble resin is not particularly limited, and is preferably  2,000 to 1,000,000, more preferably 5,000 to 500,000, and  particularly preferably 10,000 to 100,000. Herein, the  weight-average molecular weight of the resin refers to a poly› styrene-equivalent molecular weight measured by GPC ( car› rier: THF or N-methyl-2-pyrrolidone (NMP)).  [0639]  The pH of the top coat composition is not particu› larly limited, but is preferably Oto 10, more preferably Oto 8,  and particularly preferably 1 to 7.  [0640]  The top coat composition may contain an additive  such as a photoacid generator and a nitrogen-containing basic  compound. Examples of the top coat composition including  the nitrogen-containing basic compound include those in  US2013/0244438Al.  [0641]  The concentration of the resin in the top coat com› position is preferably 0.1 % by mass 10% by mass, more  preferably 0.2% by mass 5% by mass, and particularly pref› erably 0.3% by mass 3% by mass. The top coat material may  include components other than the resin, but the proportion of  the resin occupying the solid content of the top coat compo› sition is preferably 80% by mass 100% by mass, more pref› erably 90% by mass 100% by mass, and particularly prefer› ably 95% by mass 100% by mass.  [0642]  The solid content concentration in the top coat com› position in the present invention is preferably 0.1 % by mass to  10% by mass, more preferably 0.2% by mass to 6% by mass,  and still more preferably 0.3% by mass to 5% by mass. By  setting the solid content concentration to the range, the top  coat composition can be uniformly coated on the resist film.  [0643]  In the pattern forming method of the present inven› tion, a resist pattern can be formed on a substrate using the  composition, and a top coat layer can also be formed on the  resist film using the top coat composition. The film thickness  of the resist film is preferably 10 nm to 100 nm, and the film  thickness of the top coat layer is preferably 10 nm to 200 nm,  more preferably 20 nm to 100 nm, and particularly preferably  40 nm to 80 nm.  [0644]  The method for coating the composition on a sub› strate is preferably spin coating, and the rotation speed is  preferably 1,000 rpm to 3,000 rpm.  [0645]  For example, the composition is coated on a sub› strate (e.g.: silicon/silicon dioxide coating), such as one for  use in the manufacture of precision integrated circuit ele› ments, by appropriate coating means, such as a spinner and a  coater, and dried, thereby forming a resist film. Further, a  heretofore known antireflection film can also be coated in  advance. In addition, it is preferable that the resist film is dried  before the top coat layer is formed.  [0646]  Then, the top coat composition can be coated and  dried on the obtained resist film in the same manner as in the  method for forming the resist film, thereby forming a top coat  layer.  [0647]  The resist film having the top coat layer provided on  the upper layer thereof is exposed, usually through a mask, to  active light or radiation, preferably baked (heated), and devel› oped. Thus, a good pattern can be obtained.  [0648]  In the liquid immersion exposure step, the liquid for  liquid immersion needs to move on a wafer following the  movement of an exposure head that scans on the wafer at a  high speed and forms an exposure pattern, and thus the con› tact angle of the liquid for liquid immersion for the resist film  in a dynamic state is important, and the resist requires a  performance of following the high-speed scanning of the  exposure head, while a liquid droplet no longer remains.  [0649]  A developer for use in the step of developing the  active light-sensitive or radiation-sensitive composition film  formed using the composition of the present invention is not  particularly limited, but, for example, an alkali developer or a  developer containing an organic solvent (hereinafter also  referred to as an organic developer) can also be used. Among  these, a developer containing an organic solvent is preferably  used.  [0650]  As the alkali developer, an alkaline aqueous solution  containing, for example, an inorganic alkali such as sodium  hydroxide, potassium hydroxide, sodium carbonate, sodium  silicate, sodium metasilicate, and aqueous ammonia; a pri› mary amine such as ethy !amine and n-propy !amine, a second› ary amine such as diethylamine and di-n-butylamine, a ter› tiary amine such as triethylamine andmethyldiethylamine; an  alcoholamine such as dimethylethanolamine and triethanola› mine; a tetraalkylammonium hydroxide such as as tetram› ethylammonium hydroxide, tetraethylammoniumhydroxide,  tetrapropylammonium  hydroxide,  tetrabutylammonium  hydroxide, tetrapentylammonium hydroxide, tetrahexylam› monium hydroxide, tetraoctylammonium hydroxide, ethylt› rimethylammonium hydroxide, butyltrimethylammonium  hydroxide, methyltriamylammonium hydroxide, and dibu› tyldipentylammonium hydroxide; a quaternary ammonium  salt such as trimethylphenylammonium hydroxide, trimeth› ylbenzylammonium hydroxide, and triethylbenzylammo› nium hydroxide; or a cycloamine such as pyrrole and piperi› dine can be used. Further, an appropriate amount of alcohols  or a surfactant can be added to the alkaline aqueous solution  and the mixture can be used. The alkali concentration of the  alkali developer is usually O .1 % by mass to 20% by mass. The  pH of the alkali developer is usually 10.0 to 15.0. The alkali  concentration and the pH of the alkali developer can be appro› priately adjusted and used. A surfactant or an organic solvent  is added to the alkali developer and the mixture is used.  [0651]  As for the rinsing liquid in the rinse treatment car› ried out after the alkali development, pure water is used, and  further, an appropriate amount of a surfactant can also be  added thereto and used.  [0652]  In addition, after the development treatment or the  rinse treatment, a treatment of removing the developer or  rinsing liquid adhering on the pattern by a supercritical fluid  can be carried out.  [0653]  As the organic developer, a polar solvent such as a  ketone-based solvent, an ester-based solvent, an alcohol› based solvent, an amide-based solvent, and an ether-based  solvent, and a hydrocarbon-based solvent can be used, and  specific examples thereof include the solvents described in  paragraph "0507" of JP2013-218223A, and isoamyl acetate,  butyl butanoate, and methyl 2-hydroxyisobutyrate.  [0654]  As the solvent, the solvents in plural numbers may  be mixed, and further, solvents other than the above solvents  or water may be mixed therewith and used. However, in order  to exhibit the effects of the present invention sufficiently, it is  preferable that the water content of the entire developer is less 