US 10,175,578 B2  124  123  Examples of the commercially available surfactant  include MEGAFACE F178, F-470, F-473, F-475, F-476,  and F-472 (manufactured by DIC Corp.): a copolymer of an  acrylate ( or methacrylate) having a C$_{6}$F $_{13 }$ group with a  (poly(oxyalkylene)) acrylate (or methacrylate); and a capo- lymer of an acrylate (or methacrylate) having a C$_{3}$ F$_{7 }$ group  with a (poly(oxyethylene)) acrylate (or methacrylate) and a  (poly(oxypropylene)) acrylate (or methacrylate).  Moreover, in the present invention, surfactants other than  fluorine-based and/or silicon-based surfactants can also be  used. Specific examples thereof include nonionic surfac› tants, for example, polyoxyethylene alkyl ethers such as  polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,  polyoxyethylene cetyl ether, and polyoxyethylene oleyl  ether, polyoxyethylene alkylallyl ethers such as polyoxyeth- ylene octylphenol ether and polyoxyethylene nonylphenol  ether, polyoxyethylene/polyoxypropylene block copoly› mers, sorbitan fatty acid esters such as sorbitan monolaurate,  sorbitan monopalmitate, sorbitan monostearate, sorbitan  ;~;~~~e~:;1~~:b~!!i~~l~=t~ :i~  ~~~~!~~u~~s~:~~tl~o:;~  ethylene sorbitan monolaurate, polyoxyethylene sorbitan  monopalmitate, polyoxyethylene sorbitan monostearate,  polyoxyethylene sorbitan trioleate, and polyoxyethylene  sorbitan tristearate.  These surfactants may be used singly or in combination of  some kinds thereof.  The content of the surfactant (F) to be used is preferably  0.01 % to 10% by mass, and more preferably 0.1 % to 5°  %  by mass, with respect to the total amount ( excluding the  solvent) of the actinic ray-sensitive or radiation-sensitive  resin composition.  (G) Onium Carboxylate Salt  The actinic ray-sensitive or radiation-sensitive resin com› position in the present invention may contain an onium  carboxylate salt (G). Examples of the onium carboxylate salt  include a sulfonium carboxylate salt, an iodonium carboxy› late salt, and an ammonium carboxylate salt. In particular, as  the onium carboxylate salt (G), an iodonium carboxylate salt  and a sulfonium carboxylate salt are particularly preferable.  Further, it is preferable that the carboxylate residue of the  onium carboxylate salt (H) does not contain an aromatic  group and a carbon-carbon double bond. As the anionic  moiety, a linear, branched, monocyclic, or polycyclic alky› lcarboxylate anion having 1 to 30 carbon atoms is prefer› able. Further, a carboxylate anion in which a part or all of the  alkyl groups are substituted with fluorine is more preferable.  An oxygen atom may be contained in the alkyl chain, by  which the transparency to the lights of 220 nm or less is  ensured, thus, sensitivity and resolving power are enhanced,  and density dependency and exposure margin are improved.  Examples of the fluorine-substituted carboxylate anion  include anions of fluoroacetic acid, difluoroacetic acid,  trifluoroacetic acid, pentafluoropropionic acid, heptafluo› robutyric acid, nonafluoropentanoic acid, perfluorodode› canoic acid, perfluorotridecanoic acid, perfluorocyclohexan› ecarboxylic acid, 2,2-bistrifluoromethylpropionic acid, and  the like.  These onium carboxylate salts (G) can be synthesized by  reacting sulfonium hydroxide, iodonium hydroxide, or  ammonium hydroxide and carboxylic acid with silver oxide  in an appropriate solvent.  The content of the onium carboxylate salt (G) in the  composition is generally 0.1 % to 20% by mass, preferably  0.5% to 10% by mass, and more preferably 1 % to 7% by  mass, with respect to the total solid contents of the compo› sition.  (H) Other Additives  The actinic ray-sensitive or radiation-sensitive resin com› position of the present invention can further contain a dye,  a plasticizer, a light sensitizer, a light absorbent, an alkali› soluble resin, a dissolution inhibitor, a compound that pro› motes solubility in a developer (for example, a phenol  compound with a molecular weight of 1,000 or less, an  alicyclic or aliphatic compound having a carboxyl group),  and the like, if desired.  Such a phenol compound having a molecular weight of  1,000 or less may be easily synthesized by those skilled in  the art with reference to the method described in, for  example, JP1992-122938A (JP-H04-122938A), JP1990- 28531A (JP-H02-28531A),  U.S.  Pat.  No.  4,916,210,  EP219294B, and the like.  Specific examples of the alicyclic compound or aliphatic  compound having a carboxyl group include, but not limited  to, a carboxylic acid derivative having a steroid structure  such as a cholic acid, deoxycholic acid or lithocholic acid,  an adamantane carboxylic acid derivative, adamantane  dicarboxylic acid, cyclohexane carboxylic acid, and cyclo› hexane dicarboxylic acid.  In the organic solvent developer, the alkali developer,  and/or the rinsing liquid which can be used in the present  invention, the content of various fine particles or impurities  such as metal element is preferably small. In order to obtain  such a chemical solution with few impurities, it is preferable  to reduce the impurities, for example, by producing the  chemical solution in a clean room or carrying out filtration  through various filters such as a Teflon (registered trade- mark) filer, a polyolefin-based filter, and an ion exchange  filter. As for the metal element, any of metal element  concentrations of Na, K. Ca, Fe, Cu, Mg,  Mn, Li, Al, Cr, Ni,  and Zn is preferably 10 ppm or less, and more preferably 5  ppm or less.  Furthermore, the container for storing the developer or  rinsing liquid is not particularly limited, and a container  made of a polyethylene resin, a polypropylene resin, a  polyethylene-polypropylene resin or the like, which is used  in the application of electronic materials, may be used, but  in order to reduce impurities dissolved out from the con› tainer, it is also preferred to select a container that is less  likely to cause elution of a component from the inner wall  of the container to the chemical solution. Such a container  includes a container where the inner wall of the container is  formed of a perfluororesin (for example, a FluoroPure PFA  composite drum (inner surface coming into contact with  liquid: PFA resin lining) manufactured by Entegris, and a  steel-made drum (inner surface coming into contact with  liquid: zinc phosphate coat) manufactured by JFE), and the  like.  It is preferable that various materials (for example, a  developer, a rinsing liquid, a composition for forming an  antireflection film, and a composition for forming a topcoat)  used in the actinic ray-sensitive or radiation-sensitive resin  composition of the present invention, and the pattern form- ing method of the present invention do not include impuri› ties such as a metal. The content of the metal components  included in these materials is preferably 10 ppm or less,  more preferably 5 ppm or less, still more preferably 1 ppm  or less, and particularly preferably substantially not metal  components (no higher that the detection limit of a mea› surement device).  Examples of the method for removing impurities such as  a metal from various materials include filtration using a  filter. As for the filter pore diameter, the pore size is  preferably 50 nm or less, more preferably 10 nm or less, and  still more preferably 5 nm or less. As the material of the  filter, a polytetrafluoroethylene-made filter, a polyethylene› made filter, or a nylon-made filter is preferable. In the step  of filtration using a filter, plural kinds of filters may be  connected in series or in parallel, and used. In a case of using  plural kinds of filters, a combination of filters having dif-