Composition for forming protective film against alkaline aqueous hydrogen peroxide, substrate for producing semiconductor apparatus, method for forming protective film, and method for forming pattern

A method for forming a pattern on a substrate to be processed, the method comprising:

• (II-1) a step of forming a protective film on the substrate to be processed using a composition for forming a protective film;
• (II-2) a step of forming a silicon-containing resist intermediate film on the protective film using a silicon-containing resist intermediate film material;
• (II-3) a step of forming an organic anti-reflection film on the silicon-containing resist intermediate film;
• (II-4) a step of forming a resist upper layer film on the organic anti-reflection film using a photoresist composition to form a four-layer film structure and forming a circuit pattern in the resist upper layer film;
• (II-5) a step of transferring the pattern to the organic anti-reflection film and the silicon-containing resist intermediate film by etching with the resist upper layer film in which the pattern is formed as a mask;
• (II-6) a step of transferring the pattern to the protective film by etching with the silicon-containing resist intermediate film in which the pattern is transferred as a mask;
• and
• (II-7) a step of forming a pattern on the substrate to be processed with the protective film in which the pattern is transferred as a mask,
• wherein the composition for forming a protective film is a composition for forming a protective film against an alkaline aqueous hydrogen peroxide, the composition comprising:
• (A) a polymer represented by the following any one of (I) and (II) and having a fluorine atom and a hydroxy group, or a mixture of a polymer having a fluorine atom and a polymer having a hydroxy group represented by the following (III);
• (I) a polymer having a repeating unit represented by the following general formula (1A) and having at least one or more fluorine atoms and at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C),
• (II) a polymer having a repeating unit represented by the following general formula (2A) and having at least one or more fluorine atoms and a repeating unit represented by the following general formula (3A) and having at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C), and
• (III) a mixture of:
• a polymer having a repeating unit represented by the following general formula (2A) and having at least one or more fluorine atoms, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C);
• and a polymer having a repeating unit represented by the following general formula (3A) and having at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C);
• and
• (B) an organic solvent,
• wherein W1 represents one or more kinds of tetravalent organic groups optionally having a fluorine atom or a hydroxy group, W2 represents one or more kinds of divalent organic groups optionally having a fluorine atom or a hydroxy group, at least one of W1 and W2 has one or more fluorine atoms, and at least one of W1 and W2 has one or more hydroxy groups,
• wherein W3 represents one or more kinds of tetravalent organic groups optionally having a fluorine atom, W4 represents one or more kinds of divalent organic groups optionally having a fluorine atom, and at least one of W3 and W4 has one or more fluorine atoms,
• wherein W5 represents one or more kinds of tetravalent organic groups optionally having a hydroxy group, W6 represents one or more kinds of divalent organic groups optionally having a hydroxy group, and at least one of W5 and W6 has one or more hydroxy groups, and
• wherein R1 represents any one group represented by the following formula (1D), and two or more kinds of R1 are optionally used in combination,
• and wherein the method further comprises, after the (II-6) step, a step of removing the silicon-containing resist intermediate film in which the pattern is transferred by wet etching using an alkaline aqueous hydrogen peroxide, or
• wherein the (II-7) step comprises a step of transferring the pattern to the substrate to be processed by wet etching using an alkaline aqueous hydrogen peroxide and with the protective film in which the pattern is transferred as a mask, or
• wherein the (II-7) step comprises a step of pattern-processing the substrate to be processed by implanting ions with the protective film in which the pattern is transferred as a mask.

A method for forming a pattern on a substrate to be processed, the method comprising:

• (III-1) a step of forming a protective film on the substrate to be processed using a composition for forming a protective film;
• (III-2) a step of forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film on the protective film;
• (III-3) a step of forming a resist upper layer film on the inorganic hard mask using a photoresist composition;
• (III-4) a step of forming a circuit pattern in the resist upper layer film;
• (III-5) a step of transferring the pattern to the inorganic hard mask by etching with the resist upper layer film in which the pattern is formed as a mask;
• (III-6) a step of transferring the pattern to the protective film by etching with the inorganic hard mask in which the pattern is transferred as a mask;
• and
• (III-7) a step of forming a pattern on the substrate to be processed with the protective film in which the pattern is transferred as a mask,
• wherein the composition for forming a protective film is a composition for forming a protective film against an alkaline aqueous hydrogen peroxide, the composition comprising:
• (A) a polymer represented by the following any one of (I) and (II) and having a fluorine atom and a hydroxy group, or a mixture of a polymer having a fluorine atom and a polymer having a hydroxy group represented by the following (III);
• (I) a polymer having a repeating unit represented by the following general formula (1A) and having at least one or more fluorine atoms and at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C),
• (II) a polymer having a repeating unit represented by the following general formula (2A) and having at least one or more fluorine atoms and a repeating unit represented by the following general formula (3A) and having at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C), and
• (III) a mixture of:
• a polymer having a repeating unit represented by the following general formula (2A) and having at least one or more fluorine atoms, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C);
• and a polymer having a repeating unit represented by the following general formula (3A) and having at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C);
• and
• (B) an organic solvent,
• wherein W1 represents one or more kinds of tetravalent organic groups optionally having a fluorine atom or a hydroxy group, W2 represents one or more kinds of divalent organic groups optionally having a fluorine atom or a hydroxy group, at least one of W1 and W2 has one or more fluorine atoms, and at least one of W1 and W2 has one or more hydroxy groups,
• wherein W3 represents one or more kinds of tetravalent organic groups optionally having a fluorine atom, W4 represents one or more kinds of divalent organic groups optionally having a fluorine atom, and at least one of W3 and W4 has one or more fluorine atoms,
• wherein W5 represents one or more kinds of tetravalent organic groups optionally having a hydroxy group, W6 represents one or more kinds of divalent organic groups optionally having a hydroxy group, and at least one of W5 and W6 has one or more hydroxy groups,
• wherein R1 represents any one group represented by the following formula (1D), and two or more kinds of R1 are optionally used in combination,
• and wherein the (III-7) step comprises a step of transferring the pattern to the substrate to be processed by wet etching using an alkaline aqueous hydrogen peroxide and with the protective film in which the pattern is transferred as a mask, or
• wherein the (III-7) step comprises a step of pattern-processing the substrate to be processed by implanting ions with the protective film in which the pattern is transferred as a mask.

A method for forming a pattern on a substrate to be processed, the method comprising:

• (IV-1) a step of forming a protective film on the substrate to be processed using a composition for forming a protective film;
• (IV-2) a step of forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a titanium oxide film, and a titanium nitride film on the protective film;
• (IV-3) a step of forming an organic anti-reflection film on the inorganic hard mask;
• (IV-4) a step of forming a resist upper layer film on the organic anti-reflection film using a photoresist composition to form a four-layer film structure and forming a circuit pattern in the resist upper layer film;
• (IV-5) a step of transferring the pattern to the organic anti-reflection film and the inorganic hard mask by etching with the resist upper layer film in which the pattern is formed as a mask;
• (IV-6) a step of transferring the pattern to the protective film by etching with the inorganic hard mask in which the pattern is transferred as a mask;
• and
• (IV-7) a step of forming a pattern on the substrate to be processed with the protective film in which the pattern is transferred as a mask,
• wherein the composition for forming a protective film is a composition for forming a protective film against an alkaline aqueous hydrogen peroxide, the composition comprising:
• (A) a polymer represented by the following any one of (I) and (II) and having a fluorine atom and a hydroxy group, or a mixture of a polymer having a fluorine atom and a polymer having a hydroxy group represented by the following (III);
• (I) a polymer having a repeating unit represented by the following general formula (1A) and having at least one or more fluorine atoms and at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C),
• (II) a polymer having a repeating unit represented by the following general formula (2A) and having at least one or more fluorine atoms and a repeating unit represented by the following general formula (3A) and having at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C), and
• (III) a mixture of:
• a polymer having a repeating unit represented by the following general formula (2A) and having at least one or more fluorine atoms, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C);
• and a polymer having a repeating unit represented by the following general formula (3A) and having at least one or more hydroxy groups, a terminal group thereof being a group represented by any one of the following general formulae (1B) and (1C);
• and
• (B) an organic solvent,
• wherein W1 represents one or more kinds of tetravalent organic groups optionally having a fluorine atom or a hydroxy group, W2 represents one or more kinds of divalent organic groups optionally having a fluorine atom or a hydroxy group, at least one of W1 and W2 has one or more fluorine atoms, and at least one of W1 and W2 has one or more hydroxy groups,
• wherein W3 represents one or more kinds of tetravalent organic groups optionally having a fluorine atom, W4 represents one or more kinds of divalent organic groups optionally having a fluorine atom, and at least one of W3 and W4 has one or more fluorine atoms,
• wherein W5 represents one or more kinds of tetravalent organic groups optionally having a hydroxy group, W6 represents one or more kinds of divalent organic groups optionally having a hydroxy group, and at least one of W5 and W6 has one or more hydroxy groups, and
• wherein R1 represents any one group represented by the following formula (1D), and two or more kinds of R1 are optionally used in combination,
• and wherein the (IV-7) step comprises a step of transferring the pattern to the substrate to be processed by wet etching using an alkaline aqueous hydrogen peroxide and with the protective film in which the pattern is transferred as a mask, or
• wherein the (IV-7) step comprises a step of pattern-processing the substrate to be processed by implanting ions with the protective film in which the pattern is transferred as a mask.