Laminate, preparation of laminate and pattern forming process

A method for preparing a laminate, comprising the steps of:

• applying an adherent film-forming composition onto a substrate and heating to form an adherent film thereon, and
• applying a resist composition onto the adherent film and heating to form a resist film thereon,
• said adherent film-forming composition comprising a polymer comprising repeat units having the formula (1) or (2) and an organic solvent,
• wherein a is 0, 1 or 2, b is an integer meeting 0≤b≤4a+2, c is an integer meeting 1≤c≤4a+2, and 1≤b+c≤4a+2, d is 0, 1, 2, 3, 4 or 5, e is 0, 1, 2, 3, 4 or 5, and 1≤d+e≤5,
• R1 is hydroxy or 2-propynyloxy,
• R2 is carboxy or carboxymethoxy,
• R3 is hydroxy or 2-propynyloxy,
• R4 is carboxy or carboxymethoxy,
• said resist composition comprising at least one hypervalent iodine compound selected from a hypervalent iodine compound having the formula (3), a hypervalent iodine compound having the formula (4), and a hypervalent iodine compound having the formula (5), a carboxy-containing compound, and a solvent,
• wherein m is 0, 1 or 2;
• when m=0, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4 or 5 and 1≤n1+n2≤6;
• when m=1, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6 or 7 and 1≤n1+n2≤8;
• when m=2, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9 and 1≤n1+n2≤10, n3 is 1 or 2, n4 is 0, 1, 2, 3 or 4, 1≤n3+n4≤5, n5 is 1 or 2, n6 is 0, 1, 2, 3 or 4, 1≤n5+n6≤5, n7 is 0, 1, 2, 3 or 4, n8 is 1, 2, 3 or 4,
• R11 to R18 are each independently halogen or a C1-C10 hydrocarbyl group which may contain a heteroatom, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may bond together to form a ring with the carbon atoms to which they are attached and the intervenient atoms, and
• R21 to R24 are each independently halogen or a C1-C40 hydrocarbyl group which may contain a heteroatom;
• when n2 is 2 or more, a plurality of R21 may be identical or different and a plurality of R21 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• when n4 is 2 or more, a plurality of R22 may be identical or different and a plurality of R22 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• when n6 is 2 or more, a plurality of R23 may be identical or different and a plurality of R23 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• when n7 is 2 or more, a plurality of R24 may be identical or different and a plurality of R24 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• R25 is a C1-C40 (n8)-valent hydrocarbon group or C2-C40 (n8)-valent heterocyclic group;
• when n8=2, R25 may also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group or thioketone bond;
• some or all of the hydrogen atoms in the (n8)-valent hydrocarbon group or (n8)-valent heterocyclic group may be substituted by a heteroatom-containing moiety, some —CH2— in the (n8)-valent hydrocarbon group may be replaced by a heteroatom-containing moiety, R24 and R25 may bond together to form a ring with the carbon atoms to which they are attached and the intervenient atoms.

A method for preparing a laminate, comprising the steps of:

• applying a resist underlying film-forming composition onto a substrate and heating to form a resist underlying film thereon,
• forming a silicon-containing intermediate film on the resist underlying film,
• applying an adherent film-forming composition onto the silicon-containing intermediate layer and heating to form an adherent film thereon, and
• applying a resist composition onto the adherent film and heating to form a resist film thereon,
• said adherent film-forming composition comprising a polymer comprising repeat units having the formula (1) or (2) and an organic solvent,
• wherein a is 0, 1 or 2, b is an integer meeting 0≤b≤4a+2, c is an integer meeting 1≤c≤4a+2, and 1≤b+c≤4a+2, d is 0, 1, 2, 3, 4 or 5, e is 0, 1, 2, 3, 4 or 5, and 1≤d+e≤5,
• R1 is hydroxy or 2-propynyloxy,
• R2 is carboxy or carboxymethoxy,
• R3 is hydroxy or 2-propynyloxy,
• R4 is carboxy or carboxymethoxy,
• said resist composition comprising at least one hypervalent iodine compound selected from a hypervalent iodine compound having the formula (3), a hypervalent iodine compound having the formula (4), and a hypervalent iodine compound having the formula (5), a carboxy-containing compound, and a solvent,
• wherein m is 0, 1 or 2;
• when m=0, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4 or 5 and 1≤n1+n2≤6;
• when m=1, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6 or 7 and 1≤n1+n2≤8;
• when m=2, n1 is 1, 2 or 3, n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9 and 1≤n1+n2≤10, n3 is 1 or 2, n4 is 0, 1, 2, 3 or 4, 1≤n3+n4≤5, n5 is 1 or 2, n6 is 0, 1, 2, 3 or 4, 1≤n5+n6≤5, n7 is 0, 1, 2, 3 or 4, n8 is 1, 2, 3 or 4,
• R11 to R18 are each independently halogen or a C1-C10 hydrocarbyl group which may contain a heteroatom, R11 and R12, R13 and R14, R15 and R16, or R17 and R18 may bond together to form a ring with the carbon atoms to which they are attached and the intervenient atoms, and
• R21 to R24 are each independently halogen or a C1-C40 hydrocarbyl group which may contain a heteroatom;
• when n2 is 2 or more, a plurality of R21 may be identical or different and a plurality of R21 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• when n4 is 2 or more, a plurality of R22 may be identical or different and a plurality of R22 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• when n6 is 2 or more, a plurality of R23 may be identical or different and a plurality of R23 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• when n7 is 2 or more, a plurality of R24 may be identical or different and a plurality of R24 may bond together to form a ring with the carbon atoms on the aromatic ring to which they are attached;
• R25 is a C1-C40 (n8)-valent hydrocarbon group or C2-C40 (n8)-valent heterocyclic group;
• when n8=2, R25 may also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group or thioketone bond;
• some or all of the hydrogen atoms in the (n8)-valent hydrocarbon group or (n8)-valent heterocyclic group may be substituted by a heteroatom-containing moiety, some —CH2— in the (n8)-valent hydrocarbon group may be replaced by a heteroatom-containing moiety, R24 and R25 may bond together to form a ring with the carbon atoms to which they are attached and the intervenient atoms.