A resist composition that generates an acid upon exposure and has solubility in a developing solution, which is changed by action of an acid, the resist composition containing a resin component having a constitutional unit represented by General Formula (a01-1) and a constitutional unit represented by General Formula (a02-1). In General Formula (a01-1), R represents a hydrogen atom, an alkyl group, or a halogenated alkyl group; Yax.sup.01 represents a linking group; Ax represents a sulfonyl group or a sulfoxide group; Rax.sup.01 represents an alkyl group, an alkoxy group, a halogen atom, or a halogenated alkyl group; s0 and v0 represent an integer of 0 to 6; and 1≤s0+v0≤6 and u0≤s0+v0. In General Formula (a02-1), Ra.sup.00 represents an acid-dissociable group represented by General Formula (a02-r2-1) ##STR00001##

An object of the present invention is to provide a pattern forming method using a non-chemically amplified resist composition, which has excellent washing properties in a washing step with an EBR liquid and is less likely to cause a film loss in a non-exposed portion during development using an organic solvent-based developer.

Another object of the present invention to provide a method for manufacturing an electronic device using the pattern forming method.

The pattern forming method of the present invention includes a resist film forming step of forming a resist film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition, a washing step of washing an outer peripheral portion of the substrate with a washing solution including an organic solvent while rotating the substrate on which the resist film is formed, an exposing step of exposing the resist film, a developing step of positively developing the exposed resist film using an organic solvent-based developer, in which the actinic ray-sensitive or radiation-sensitive resin composition includes a resin having a polar group, a compound including an ion pair which is decomposed by an irradiation with an actinic ray or a radiation, and a solvent, and all of expressions (1) to (4) are satisfied.

An onium salt consisting of an anion containing an iodized aromatic group and two sulfonate groups and a sulfonium or iodonium cation is a useful photoacid generator. A chemically amplified resist composition comprising the photoacid generator forms a pattern of rectangular profile with a good balance of sensitivity, CDU, LWR, MEF, and DOF when it is processed by photolithography using high-energy radiation.

A composition comprising (A) a polymer comprising recurring units (a1) having a carboxyl group protected with an acid labile group and recurring units (a2) having a cyclic ester, cyclic carbonate or cyclic sulfonate structure, (B) a thermal acid generator, and (C) an organic solvent is suited to form a protective film between a substrate and a resist film. Even when a metal-containing resist film is used, the protective film is effective for preventing the substrate from metal contamination.

A substrate processing method includes supplying a first developer at a first temperature onto a substrate in a development device, thereby performing a development process, supplying a process fluid at a second temperature lower than the first temperature onto the substrate, thereby replacing a residue of the first developer remaining after the development process with a second developer, transferring the substrate from the development device to a supercritical drying device, and supplying, by the supercritical drying device, at least one of a supercritical fluid and a subcritical fluid onto the substrate, thereby drying the second developer.

Compositions comprising R.sub.qSnO.sub.m(OH).sub.x(HCO.sub.3).sub.y(CO.sub.3).sub.z are disclosed, where R is (i) C.sub.1—C.sub.10 hydrocarbyl or (ii) heteroaliphatic, heteroaryl, or heteroaryl-aliphatic including 1-10 carbon atoms and one or more heteroatoms; q = 0.1-1; x ≤ 4; y ≤ 4; z ≤ 2; m = 2 - q/2 - x/2 - y/2 - z; and (q/2 + x/2 + y/2 + z) ≤ 2 Methods of making a photoresist film comprising [(RSn).sub.12O.sub.14(OH).sub.6](OH).sub.2 on a substrate also are disclosed. The photoresist film may be irradiated to form R.sub.qSnO.sub.m(OH).sub.x(HCO.sub.3).sub.y(CO.sub.3).sub.z.

A negative resist composition is provided comprising a base polymer, a quencher in the form of a sulfonium salt of a weaker acid than a sulfonic acid which is fluorinated at α- and/or β-position of the sulfo group, the sulfonium salt having at least two polymerizable double bonds in the molecule, and an acid generator capable of generating a sulfonic acid which is fluorinated at α- and/or β-position of the sulfo group. The resist composition adapted for organic solvent development exhibits a high resolution and improved LWR or CDU.

A negative resist composition is provided comprising a base polymer and an acid generator in the form of a sulfonium salt consisting of a sulfonate anion having a maleimide group and a cation having a polymerizable double bond. The resist composition adapted for organic solvent development exhibits a high resolution and improved LWR or CDU.

A radiation-sensitive resin composition includes: an onium salt compound represented by formula (1′); a resin including a structural unit having an acid-dissociable group; and a solvent. E.sup.A is a substituted or unsubstituted (α+β)-valent organic group having 1 to 40 carbon atoms; Z.sup.+ is a monovalent radiation-sensitive onium cation; and α and β are each independently 1 or 2.

##STR00001##

Provided are a method for forming a resist pattern that demonstrates excellent performance in sensitivity, resolution, etc. in an exposure step when a next-generation exposure technique is applied, and a radiation-sensitive resin composition. The method for forming a resist pattern includes step (1) of forming a resist film in which a content of a radiation-sensitive acid generator (C) is 0.1% by mass or less, step (2) of exposing the resist film to EUV or an electron beam (EB), and step (3) of developing the resist film exposed in the step (2).