10  US 8,637,222 B2  9  developer on the substrate surface (spraying method), and a  method of continuously ejecting the developer on the sub› strate spinning at a constant speed while scanning the devel› oper ejecting nozzle at a constant rate (dynamic dispense  method) may be applied.  Also, after the developing step, a step of stopping the  development while replacing the developer with another sol› vent may be practiced.  The developing time is preferably a time long enough to  sufficiently dissolve the resin, crosslinking agent and the like  in the unexposed area and, usually, the developing time is  preferably from 10 to 300 seconds, more preferably from 20  to 120 seconds.  The amount of the developer can be appropriately adjusted  according to the developing method.  The temperature of the developer is preferably from 0 to  50°  C., more preferably from 15 to 35°  C.  The pattern forming method of the present invention may  contain (5) a step of rinsing the film by using a rinsing solu› tion containing an organic solvent after the developing step  The organic solvent used for the rinsing solution is an  organic solvent having a vapor pressure at 20°  C. of prefer› ably from 0.05 to 5 kPa, more preferably from 0.1 to 5 kPa,  and most preferably from 0.12 to 3 kPa. By setting the vapor  pressure of the organic solvent used for the rinsing solution to  from 0.05 to 5 kPa, the temperature uniformity in the wafer  plane is enhanced and swelling ascribable to permeation of  the rinsing solution is suppressed, as a result, the dimensional  uniformity in the wafer plane is improved.  As for the rinsing solution, various organic solvents may be  used but, for example, in the case where a resin containing a  repeating unit represented by formula (1) is used as the resin  (A), a rinsing solution containing at least one kind ofa solvent  selected from a hydrocarbon-based solvent, a ketone-based  solvent, an ester-based solvent, an alcohol-based solvent, an  amide-based solvent and an ether-based solvent, or water is  preferably used.  More preferably, a step of washing the film by using a  rinsing solution containing at least one kind of an organic  solvent selected from a ketone-based solvent, an ester-based  solvent, an alcohol-based solvent, an amide-based solvent  45  and a hydrocarbon-based solvent is preformed after develop› ment. Still more preferably, a step of washing the film by  using a rinsing solution containing at least one or more kinds  of organic solvents selected from the group consisting of an  alcohol-based solvent and a hydrocarbon-based solvent is 50  preformed after development.  Specific examples of the ketone-based solvent, ester-based  solvent, alcohol-based solvent, amide-based solvent, ether› based solvent and hydrocarbon-based solvent used as the  rinsing solution are the same as those described above for the  developer.  In particular, use of a rinsing solution containing at least  one or more kinds of organic solvents selected from the group  consisting of a monohydric alcohol-based solvent and a  hydrocarbon-based solvent is preferred.  The monohydric alcohol-based solvent used in the rinsing  step after development includes a linear, branched or cyclic  monohydric alcohol, and specific examples of the monohy› dric alcohol which can be used include 1-butanol, 2-butanol,  3-methyl-1-butanol, tert-butyl alcohol isopropyl alcohol, 65  cyclopentanol and cyclohexanol, with 1-butanol, 2-butanol,  3-methyl-1-butanol and isopropyl alcohol being preferred.  The hydrocarbon-based solvent includes an aromatic  hydrocarbon-based solvent such as toluene and xylene, and  an aliphatic hydrocarbon-based solvent such as octane,  decane and dodecane.  As for these components, a plurality of kinds may be  mixed, or the component may be mixed with an organic  solvent other than those described above.  The above-described organic solvent may be mixed with  water, but the percentage of water content in the rinsing  solution is usually 30 mass% or less, preferably 10 mass% or  less, more preferably 5 mass % or less, still more preferably 3  mass% or less. The rinsing solution most preferably contains  no water. By virtue of setting the percentage of water content  to 30 mass% or less, good development characteristics can be  obtained.  The rinsing solution may also be used after adding thereto  an appropriate amount of a surfactant.  As for the surfactant, the same as the later-described sur› factant used in the resist composition may be used, and the  amount used thereof is usually from 0.001 to 5 mass %,  preferably from 0.005 to 2 mass %, more preferably from  0.01 to 0.5 mass%, based on the entire amount of the rinsing  solution.  In the rinsing step, the developed wafer is wished using the  above-described rinsing solution containing an organic sol› vent.  The method of washing treatment is not particularly lim- ited but, for example, a method of continuously ejecting the  rinsing solution on the substrate spinning at a constant speed  (spin coating method), a method of dipping the substrate in a  bath filled with the rinsing solution for a fixed time ( dipping  method), and a method of spraying the rinsing solution on the  substrate surface (spraying method) may be applied. Above  all, a method where the washing treatment is performed by  the spin coating method and after the washing, the rinsing  solution is removed from the substrate surface by spinning the  substrate at a rotation speed of 2,000 to 4,000 rpm, is pre- ferred. The spinning time of the substrate may be set accord› ing to the rotation speed in the range achieving removal of the  rinsing solution from the substrate surface but is usually from  10 seconds to 3 minutes. Incidentally, the rinsing is preferably  performed under room-temperature conditions.  The rinsing time is preferably long enough to allow for no  remaining of the developing solvent on the wafer and is  usually from 10 to 300 seconds, more preferably from 20 to  120 seconds.  The temperature of the rinsing solution is preferably from  0 to 50°  C., more preferably from 15 to 35°  C.  The amount of the rinsing solution can be appropriately  adjusted according to the rinsing method.  Also, after the development or rinsing, a treatment of  removing the developer or rinsing solution adhering on the  pattern with a supercritical fluid may be performed.  Furthermore, after the development, rinsing or treatment  with a supercritical fluid, a heating treatment for removing the  solvent remaining in the pattern may be performed. The heat› ing temperature and heating time are not particularly limited  as long as a good resist pattern can be obtained, but they are  usually from 40 to 160°  C. and from 10 seconds to 3 minutes.  The heating treatment may be performed a plurality of times.  [Negative Chemical-Amplification Resist Composition]  The negative chemical-amplification resist composition  capable of undergoing negative conversion by a crosslinking  reaction, which is used in the pattern forming method of the  present invention, is described below.  Rinsing Solution:  (4).  (5) Rinsing  Rinsing Method: 