Techniques herein include methods of patterning a substrate using surface energy differences found in some fluorinated polymers or polymers with long chain alkyl functionality that promotes surface or top layer segregation in a bilayer polymer system to facilitate overburden removal when the polymer mixture is deposited over a relief pattern. The method allows for fast removal of the overburden to expose the anti-spacer region which, after acid diffusion and subsequent deprotection, is also soluble in a developer. Incorporating the highly developer-soluble polymer at the top of the top layer removes the need for the remaining polymer to have a specific dissolution rate in developer.

It is an object of the present invention to form a resist film that is highly sensitive and enables high-resolution patterning. The present invention relates to a resist material that comprises a polymer comprising a unit derived from a structure represented by the following formula (101). In the formula (101), R.sup.1 each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an acyl group optionally having a substituent, an allyl group optionally having a substituent, an alkoxy group optionally having a substituent, or an alkylsilyl group optionally having a substituent, and a plurality of R.sup.1 may be the same or different. R.sup.11 represents a hydrogen atom or an alkyl group optionally having a substituent. R.sup.2 represents a hydrogen atom, an alkyl group, a fluorine atom, a chlorine atom, a bromine atom, or a halogenated alkyl group; and Y.sup.1 represents a single bond or a linking group.

##STR00001##

Photoresist pattern trimming compositions comprise a polymer, an aromatic sulfonic acid, and an organic-based solvent system, wherein the polymer comprises polymerized units of general formulas (I) and (II): ##STR00001##
wherein: X independently represents a halogen atom; Q represents a single bond, —O—, or —C(O)O—; R.sub.1 independently represents hydrogen, a halogen atom, C1-C12 alkyl or C1-C12 fluoroalkyl; R.sub.2 represents C1-C3 alkyl or C1-C3 fluoroalkyl; and m is an integer from 0 to 4; and wherein the polymerized units of general formula (I) are present in the polymer in an amount of 10 to 90 mol % and the polymerized units of general formula (II) are present in the polymer in an amount from 10 to 60 mol %, based on total polymerized units of the polymer. The photoresist pattern trimming compositions and their use in pattern formation methods find particular applicability in the manufacture of semiconductor devices.

The present disclosure provides a method for lithography patterning in accordance with some embodiments. The method includes forming a photoresist layer over a substrate; performing an exposing process to the photoresist layer using an extreme ultraviolet (EUV) radiation; performing an infiltration process to the photoresist layer using a metal-containing chemical; and performing a developing process to the photoresist layer to form a patterned resist layer.

Novel photoresist developing compositions including a deprotonation agent, such as a nitrogen containing organic base capable of deprotonating a surface of portions of a photoresist layer exposed to radiation.

Patterning of organometallic radiation sensitive compositions is facilitated using a gaseous form of a contrast enhancing agent, which can include a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof, in which the mixture can be of the same class or different class of compounds. Contact with the contrast enhancing reactive compound is provided after irradiation of the organometallic composition to form a latent image. The contrast enhancing agent can be delivered before or after physical pattern development, and processing with the contrast enhancing agent can involve removal in a thermal process of some or substantially all of the non-irradiated organometallic composition. The contrast enhancing agent can be used in a dry thermal development step. If the contrast enhancing agent is used after a distinct development step, use of the contrast enhancing agent can involve improvement of the pattern quality. Apparatuses for performing processing with contrast enhancing agents are described.

Embodiments of the present disclosure generally relate to methods for enhancing photoresist (PR) to have improved profile control. A method for treating a PR includes positioning a workpiece within a process region of a processing chamber, where the workpiece contains a patterned PR disposed on an underlayer, and treating the patterned PR by exposing the workpiece to a sequential infiltration synthesis (SIS) process to produce a treated patterned PR which is denser and harder than the patterned PR. The SIS process includes one or more infiltration cycles of exposing the patterned PR to a precursor containing silicon or boron, infiltrating the patterned PR with the precursor, purging to remove remnants of the precursor, exposing the patterned PR to an oxidizing agent, infiltrating the patterned PR with the oxidizing agent to produce oxide coating disposed on inner surfaces of the patterned PR, and purging to remove remnants of the oxidizing agent.

A method for forming photoresist patterns and a semiconductor device on which a photoresist pattern manufactured according to the method is formed are disclosed. The method includes forming a preliminary photoresist pattern on a substrate; coating an organic topcoat composition including an acrylic polymer, the acrylic polymer including a structural unit containing a hydroxy group and a fluorine, and an acid compound on the preliminary photoresist pattern; drying and heating the substrate on which the organic topcoat composition is coated to coat it with a topcoat; and spraying a rinse solution including an acetate-based compound on the substrate coated with the topcoat to remove the topcoat.

A method of forming a pattern includes forming an etching object layer on a substrate. A photoresist layer including a metal, oxygen and an organic material is formed on the etching object layer. An exposure process is performed on the photoresist layer. A developing process is performed on the photoresist layer to form a photoresist pattern including a metal oxide. Ozone is provided onto the substrate to remove a residue of the photoresist layer that includes the organic material, The etching object layer is etched using the photoresist pattern as an etching mask.

The present disclosure provides a method for lithography patterning in accordance with some embodiments. The method includes forming a photoresist layer over a substrate; performing an infiltration process to introduce a metallic compound into the photoresist to enhance a sensitivity of the photoresist layer to an extreme ultraviolet (EUV) radiation; performing an exposing process to the photoresist layer using the EUV radiation; and performing a developing process to the photoresist layer to form a patterned resist layer.