Patterning process

Abstract

This invention provides a pattern forming method that uses a non-chemically amplified resist composition with excellent sensitivity and limiting resolution to form a resist pattern, and then reverses the pattern using a material containing an organotitanium compound with high etching resistance. A pattern forming method, characterized by comprising the following steps: step (i), forming a resist pattern on a support using a resist film obtained from a resist composition containing a superatomic iodine compound, a carboxyl-containing compound, and a solvent; step (ii), coating the support with the formed resist pattern onto a material containing an organotitanium compound and a solvent to form a pattern reversal film; and step (iii), removing the resist pattern by etching to form a reversed pattern.

Claims

1. A pattern forming method, characterized by comprising the following steps: step (i) forming a resist pattern on a support using a resist film obtained from a resist composition comprising a superatomic iodine compound, a carboxyl-containing compound, and a solvent; step (ii) coating a material comprising an organotitanium compound and a solvent onto the support on which the resist pattern has been formed to form a pattern inversion film; and step (iii) removing the resist pattern by etching to form an inversion pattern.

2. As in the pattern forming method of request item 1, wherein, The superatomic iodine compound is selected from at least one of the superatomic iodine compounds represented by the following general formulas (1) to (10), where m1 is an integer from 0 to 2, n1 is an integer from 1 to 3 when m1 is 0, n2 is an integer from 0 to 5, and 1 ≦ n1 + n2 ≦ 6; when m1 is 1, n1 is an integer from 1 to 3, n2 is an integer from 0 to 7, and 1 ≦ n1 + n2 ≦ 8; when m1 is 2, n1 is an integer from 1 to 3, n2 is an integer from 0 to 9, and 1 ≦ n1 + n2 ≦ 10; n3 is 1 or 2; n4 is an integer from 0 to 4, and 1 ≦ n3 + n4 ≦ 5; n5 is 1 or 2; n6 is an integer from 0 to 4, and 1 ≦ n5 + n6 ≦ 5; n7 is an integer from 0 to 4; and n8 is an integer from 1 to 4. m2 is an integer from 0 to 2. When m2 is 0, n9 is an integer from 0 to 4. When m2 is 1, n9 is an integer from 0 to 6. When m2 is 2, n9 is an integer from 0 to 8. m3 is an integer from 0 to 2. When m3 is 0, n10 is an integer from 0 to 4. When m3 is 1, n10 is an integer from 0 to 6. When m3 is 2, n10 is an integer from 0 to 8. m4 is 0 or 1. When m4 is 0, n11 is an integer from 0 to 4. When m4 is 1, n11 is an integer from 0 to 6. m5 is 0 or 1. When m5 is 0, n12 is an integer from 0 to 4. When m5 is 1, n12 is an integer from 0 to 6. n13 and n14 are integers from 0 to 6. n15 and n16 are integers from 0 to 3. m6 is an integer from 0 to 2. When m6 is 0, n17 is an integer from 0 to 4. When m6 is 1, n17 is an integer from 0 to 6. When m6 is 2, n17 is an integer from 0 to 8. m7 is an integer from 0 to 2. When m7 is 0, n18 is an integer from 0 to 3. When m7 is 1, n18 is an integer from 0 to 5. When m7 is 2, n18 is an integer from 0 to 7. m8 is an integer from 0 to 2. When m8 is 0, n19 is an integer from 0 to 3. n20 is 0 or 1. When m8 is 1, n19 is an integer from 0 to 5, and n20 is 0 or 1. When m8 is 2, n19 is an integer from 0 to 7, and n20 is 0 or 1. R1 to R22 are each independently a halogen atom, or may contain a hydrocarbon group with 1 to 10 carbon atoms containing heteroatoms. Furthermore, R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10, R11 and R12, R13 and R14, R15 and R16, R17 and R18, R19 and R20, or R21 and R22 may also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between those carbon atoms. R31–R34, R37, R39–R46, R49, and R50 are each independently halogen atoms, or may contain heteroatoms in hydrocarbon groups with 1–40 carbon atoms. When n2 is 2 or more, each R31 may be the same or different. Multiple R31s may also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n4 is 2 or more, each R32 may be the same or different.Multiple R32 atoms can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n6 is 2 or more, each R33 atom can be the same or different. Multiple R33 atoms can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n7 is 2 or more, each R34 atom can be the same or different. Multiple R34 atoms can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n9 is 2 or more, each R37 atom can be the same or different. Multiple R37 atoms can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When atoms form a ring together, and n10 is 2 or more, each R39 can be the same or different. Multiple R39s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n11 is 2 or more, each R40 can be the same or different. Multiple R40s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n12 is 2 or more, each R41 can be the same or different. Multiple R41s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n13 is 2 or more, each R4...

2. R42 atoms can be the same or different from each other. Multiple R42 atoms can also bond with each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n14 is 2 or more, R43 atoms can be the same or different from each other. Multiple R43 atoms can also bond with each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n15 is 2 or more, R44 atoms can be the same or different from each other. Multiple R44 atoms can also bond with each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n16 is 2 or more, R45 atoms can be the same or different from each other. Multiple R45 atoms can also bond with each other. When n17 is 2 or more, each R46 can be the same or different from the others, and multiple R46s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n18 is 2 or more, each R49 can be the same or different from the others, and multiple R49s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. When n19 is 2 or more, each R50 can be the same or different from the others, and multiple R50s can also bond to each other and form a ring together with the carbon atoms of the aromatic rings they are bonded to. R35 is an (n8) valence hydrocarbon group with 1 to 40 carbon atoms or an (n8) valence heterocyclic group with 2 to 40 carbon atoms. When n8 is 2, R35 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, sulfonyl group, or thionyl group. Furthermore, some or all of the hydrogen atoms in the (n8) valence hydrocarbon group or (n8) valence heterocyclic group can be replaced by a group containing a heteroatom. Part of the -CH2- of the (n8) valence hydrocarbon group can also be replaced by a group containing a heteroatom. R34 and R35 can also bond to each other and form a ring together with the carbon atoms they are bonded to and the atoms between the carbon atoms. R36 is a halogen atom or can also be a hydrocarbon group with 1 to 10 carbon atoms containing a heteroatom. R38 is a carbonyl group or can also be a hydrocarbon group with 1 to 10 carbon atoms containing a heteroatom.*1 and *2 represent the atomic bonds of the carbon atoms in the aromatic ring in the formula, except that *1 and *2 are bonds to adjacent carbon atoms of the aromatic ring. L1 can be unbonded, a single bond, -O-, -S-, -NH-, or -CH2-. R47 can be a halogen atom or a hydrocarbon group with 1 to 10 carbon atoms containing heteroatoms. X can be a nitrogen atom or a sulfur atom; if it is a nitrogen atom, it can also have R48. R48 can be a hydrogen atom, a halogen atom, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms or an ester.

3. The pattern forming method as described in claim 1 or 2, wherein, The carboxyl-containing polymer containing repeating units represented by the following general formula (11) or the carboxylic acid compound represented by the following general formula (12) is used as the carboxyl-containing compound, wherein RA is a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group; XA is a single bond, an phenyl group, a naphthyl group, or *-C(=O)-O-XA1-; XA1 is a saturated alkyl group with 1 to 10 carbon atoms, an phenyl group, or a naphthyl group, which may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; * represents an atomic bond between the main chain carbon atom; and t is an integer from 1 to 4. R29 is a t-valent hydrocarbon group with 1 to 40 carbon atoms or a t-valent heterocyclic group with 2 to 40 carbon atoms. When t is 2, R29 can also be an ether bond, carbonyl group, azo group, thioether bond, carbonate bond, carbamate bond, sulfinyl group, or sulfonyl group. Furthermore, some or all of the hydrogen atoms of the t-valent hydrocarbon group or t-valent heterocyclic group can be replaced by a group containing heteroatoms, and some of the -CH2- of the t-valent hydrocarbon group can also be replaced by a group containing heteroatoms. R30 is a single bond or an extended hydrocarbon group with 1 to 10 carbon atoms. Some or all of the hydrogen atoms of the extended hydrocarbon group can also be replaced by a group containing heteroatoms, and some of the -CH2- of the extended hydrocarbon group can also be replaced by a group containing heteroatoms. When t is 2 to 4, each R30 can be the same or different from the others.

4. The pattern forming method of claim 1 or 2 is to form a resist underlayer film between the support and the resist film.

5. The pattern forming method as described in claim 1 or 2, wherein, The organotitanium compound represented by the following general formula (13) is used as the organotitanium compound, wherein R51, R52, R53 and R54 are monovalent organic groups with carbon numbers of 1 to 30 that may be the same or different, and R51 and R52 may also be bonded to each other to form a ring structure, and n is a real number of 1 or more.

Images