US 10,394,127 B2  88  87  fluoroaliphatic compound which is produced by a telomer› ization method (also referred to as a telomer method) or an  oligomerization method (also referred to as an oligomer  method). Specifically, a polymer containing a fluoroaliphatic  group derived from the fluoroaliphatic compound may also  be used as the surfactant. The fluoroaliphatic compound can  be synthesized by the method described in JP2002-90991A.  In addition, surfactants other than the fluorine-based sur› factant and/or the silicon-based surfactants described in  paragraph [0280] of US2008/0248425A may be used.  These surfactants may be used singly or in combination of  two or more kinds thereof.  In a case where the actinic ray-sensitive or radiation› sensitive resin composition used in the present invention  includes a surfactant, the content thereof is preferably 0% to  2% by mass, more preferably 0.0001 % to 2% by mass, and  still more preferably 0.0005% to 1 % by mass, with respect  to the total solid content of the composition.  Other Additives (G)  The actinic ray-sensitive or radiation-sensitive resin com› position used in the present invention may further include a  compound (for example, a phenol compound having a  molecular weight of 1,000 or less, or an alicyclic or aliphatic  compound including a carboxy group) promoting solubility  with respect to a dissolution inhibiting compound, a dye, a  plasticizer, a photosensitizer, a light absorber, and/or a  developer.  The actinic ray-sensitive or radiation-sensitive resin com› position used in the present invention may further include a  dissolution inhibiting compound. Here, the "dissolution  inhibiting compound" is a compound having a molecular  weight of 3,000 or less, which decreases the degree of  solubility in an organic developer by being decomposed due  to the action of an acid.  As the dissolution inhibiting compound, an alicyclic or  aliphatic compound which contains an acid-decomposable  group such as a cholic acid derivative which includes an  acid-decomposable group described in the Proceeding of  SPIE, 2724, 355 (1996) is preferable since the transparency  with respect to light having a wavelength of 220 nm or less  is not reduced. Examples of the acid-decomposable group  and the alicyclic structure include the same as those exem› plified above.  Hereinafter, a pattern forming method using the above› mentioned resin composition will be described in more  detail.  <<Step (l)>>  A film is formed using an actinic ray-sensitive or radia› tion-sensitive resin composition including the resin (A)  having an acid-decomposable repeating unit capable of  decomposing by the action of an acid to generate an acid  having a pKa of3.0 or less. The step (1) of forming a film  on a substrate using the composition can be carried out by  a generally known method.  In the present invention, the substrate on which a film is  formed is not particularly limited. As the substrate, a sub› strate which is generally used for a process for manufactur› ing a semiconductor such as an IC, the manufacture of a  circuit board for a liquid crystal, a thermal head, or the like,  and other lithographic processes for photofabrication can be  used. Examples of such a substrate include inorganic sub› strates such as silicon, SiN, and SiO$_{2}$ ,  and coated inorganic  substrates such as SOG. Further, an organic antireflection  film may be formed between a film and a substrate, as  desired.  After film formation, a pre-heating (PB; Prebake) step is  also preferably included before the exposing step. In addi- In a case where the above-described various developing  method includes a step of discharging a developer toward a  resist film from a developing nozzle of a developing device,  the discharge pressure (flow rate per unit area of the devel› oper to be discharged) of the developer to be discharged is  preferably 2 mL/sec/mm 2  or less, more preferably 1.5  mL/sec/mm 2  or less, and still more preferably 1 mL/sec/  mm 2  or less. The lower limit of the flow rate is not particu› larly limited, but 0.2 mL/sec/mm 2  or more is preferable in  consideration of throughput.  Examples of the developing method include a method in  which a substrate is immersed in a tank filled with a  developer for a certain period of time (a dip method), a  method in which a developer is heaped up to the surface of  a substrate by surface tension and developed by stopping for  a certain period of time (a paddle method), a method in  which a developer is sprayed on the surface of a substrate ( a  spray method), and a method in which a developer is  continuously discharged on a substrate rotated at a constant  rate while scanning a developer discharging nozzle at a  constant rate (a dynamic dispense method).  A negative tone pattern is formed by carrying out devel› opment using a developer including an organic solvent after  the exposing step (2). The developing step can be carried out  by a generally known method.  <<Step (3)>>  In a case where the topcoat is released after exposure, a  developer may be used, or a separate release agent may be  used. As the release agent, a solvent which hardly permeates  into a film is preferable. From the viewpoint of being  capable of performing a releasing step simultaneously with  a developing treatment step of a film, the topcoat can be  preferably released with a developer.  In this case, a hydrophobic resin may also be added to the  composition, or after film formation, a topcoat may also be  provided on the film. Further, the performance required for  the topcoat and the method of use thereof are explained in  Chapter 7 in "Process and Ingredient of Immersion Lithog› raphy" published by CMC Publishing Co., Ltd.  The film formed using the actinic ray-sensitive or radia› tion-sensitive resin composition used in the present inven› tion may be subjected to liquid immersion exposure. Thus,  the resolution can be increased. Although the immersion  medium used is not particularly limited as long as it is liquid  having a higher refractive index than air, pure water is  preferable.  The above light source used for exposure is preferably  X-rays, extreme ultraviolet rays, or electron beams.  The film formed above is exposed using actinic rays or  radiation. The step of exposing the film can also be carried  out by a generally known method.  <<Step (2)>>  In addition, the heating time is preferably 30 seconds to  300 seconds, more preferably 30 seconds to 180 seconds,  and still more preferably 30 seconds to 90 seconds.  Both the PB step and the PEB step are carried out at a  heating temperature of preferably 40°  C. to 130°  C., more  preferably 50°  C. to 120°  C., and still more preferably 60°  C. to 120°  C. In particular, in a case where the PEB step is  carried out at a low temperature of 60°  C. to 90°  C., exposure  latitude (EL) and resolving power can be significantly  improved.  tion, after the exposing step and before the developing step,  a post-exposure heating (Post Exposure Bake; PEB) step is  also preferably included. 