16  US 9,423,690 B2  15  branched or cyclic monohydric alcohol, and specifically, it is  possible to use 1-butanol, 2-butanol, 3-methyl-1-butanol,  tert-butylalcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-hep› tanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexa› nol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pentanol,  cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-bu› tanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl- 2-pentanol,  3-methyl-3-pentanol,  4-methyl-2-pentanol,  4-methyl-3-pentanol,  cyclohexanol,  5-methyl-2-hexanol,  4-methyl-2-hexanol, 4,5-dityl-2-hexanol, 6-methyl-2-hepta- no!, 7-methyl-2-octanol, 8-methyl-2-nonanol, 9-methyl-2- decanol, and the like, preferably 1-hexanol, 2-hexanol,  1-pentanol,  3-methyl-1-butanol,  3-methyl-2-pentanol,  3-methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pen› tanol, and most preferably 1-hexanol or 4-methyl-2-penta- no!.  limited as long as it may obtain a good resist pattern, and it  usually 40°  C. to 160°  C., preferably 50°  C. to 150°  C., and  most preferably 50°  C. to 110°  C. The heating time is not  particularly limited as long as it may obtain a good resist  pattern, and it is usually 15 to 300 seconds, and preferably  15 to 180 seconds.  Alkali Development  The pattern forming method of the present invention  includes further a resist pattern forming process (alkali  development process) by using an alkali aqueous solution.  Accordingly, the finer pattern may be formed.  In the present invention, the portion having weak expo› sure strength is removed by the organic solvent development  process ( 4), but by performing more the alkali development  process, the portion having strong exposure strength may be  removed. Because, by the multiple development process  performing the development multiple times, the pattern  forming method may be carried out without dissolving only  the area having an intermediate exposure strength, the finer  pattern than as usual may be formed (the same mechanism  as in [0077] of Japanese Patent Application Laid-Open No.  2008-292975).  Examples of hydrocarbon-based solvent may include an  aromatic hydrocarbon-based solvent such as toluene and  xylene, and an aliphatic hydrocarbon-based solvent such as  octane and decane.  The rinse liquid contains more preferably at least one kind  selected from the group consisting of 1-hexanol, 4-methyl- 2-pentanol and decane.  A plurality of the components may be mixed, or they may  be used in a mixture with an organic solvent other than those  described above. The solvent may be mixed with water, but  the water content ratio of the rinse liquid is usually 60% by  mass or less, preferably 30% by mass or less, more prefer› ably 10% by mass or less, most preferably 5% by mass or  less. By setting the water content 60% by mass or less, good  rinse effect may be obtained.  The alkaline development may be performed by using the  developer containing an organic solvent before or after the  development process ( 4), but developing before the organic  solvent development process (4) is more preferred.  Examples of an alkali aqueous solution which may be  used in the alkali development include inorganic alkalis such  as sodium hydroxide, potassium hydroxide, sodium carbon› ate, sodium silicate, sodium methasilicate and ammonia  water, primary amines such as ethylamine and n-propylam› ine, secondary amines such as diethylamine and di-n-bu- tylamine, tertiary amines such as triethylamine and methyl› diethylamine, alcohol amines such as dimethylethanol  amine and triethanol amine, quaternary anmionium salts  such as tetramethyl ammonium hydroxide and tetraethyl  ammonium hydroxide, and an alkaline aqueous solution of  cyclic amine such as pyrrole and piperidine.  The rinse liquid may also be used by adding an appro› priate amount of a surfactant thereto. As a surfactant, the  same surfactant may be used as in the electron beam› sensitive or extreme ultraviolet ray-sensitive resin compo› sition. The amount of the surfactant used is usually 0.001 %  by mass to 5% by mass, preferably 0.005% by mass to 2%  by mass, and more preferably 0.01 % by mass to 0.5% by  mass, based on the total amount of the rinse liquid.  Rinsing Method  In the rinsing process, the wafer subjected to development  is washed by using the rinse liquid including an organic  solvent.  The method of washing treatment is not particularly  limited, but it is possible to apply, for example, a method of  continuously ejecting a rinse liquid on a substrate spinning  at a constant speed (spin coating method), a method of  dipping a substrate in a bath filled with a rinse liquid for a  fixed time ( dipping method), a method of spraying a rinse  liquid on a substrate surface (spraying method), and the like,  and among them, it is preferred that the rinsing treatment is  performed by the spin coating method and after the rinsing,  the substrate is spun at a rotational speed from 2,000 rpm to  4,000 rpm to remove the rinse liquid from the substrate.  The temperature of the rinse liquid is preferably 0°  C. to  50°  C., and more preferably 15°  C. to 35°  C.  Further, after the development treatment or rinsing treat› ment or the treatment by supercritical fluid, the heating  treatment may be performed to remove a residual solvent in  the pattern. The heating temperature is not particularly  Further, the process of removing the residual developer or  the rinse liquid may be carried out by heating. The heating  temperature is not particularly limited as long as it may  obtain a good resist pattern, and it usually 40°  C. to 160°  C.  The heating temperature is preferably 50°  C. to 150°  C., and  most preferably 50°  C. to 110°  C. The heating time is not  In addition, after the development process or rinsing  process, the heating treatment may be performed to remove  the moisture remaining in the pattern.  After the development treatment by an alkali aqueous  solution, the rinsing treatment may be carried out. As a rinse  liquid in the rinsing treatment, the pure water is preferred,  and an appropriate amount of surfactants may be added  thereto and used.  The temperature of the alkaline development is preferably  0°  C. to 50°  C., and more preferably 15°  C. to 35°  C.  The alkaline development time is not particularly limited,  and it is usually 10 to 300 seconds, and preferably 20 to 120  seconds.  In particular, a 2.38% by mass aqueous solution of  tetramethyl ammonium hydroxide is preferred.  The pH of the alkaline development is usually 10.0 to  15.0.  The alkaline concentration of the alkali development is  usually 0.1 to 20% by mass.  Further, in the alkaline aqueous solution, an appropriate  amount of alcohol and surfactants may be added.  The time of rinsing is not particularly limited, but it is 55  usually 10 to 300 seconds, preferably 10 to 180 seconds, and  most preferably 20 to 120 seconds.  In addition, after the development treatment or rinsing 60  treatment, the process of removing the developer or the rinse  liquid attached on the pattern may be performed by super› critical fluid. 