Highly sequenced copolymer for dual-tone photoresists, resist composition and patterning process thereof

An ordered photolithographic resin, wherein the photolithographic resin is a copolymer comprising structure 1, structure 2 and structure 3,

• wherein,
• the number of structure 1 is m, m is selected from the group consisting of 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5 and 20;
• the number of structure 2 is p, p is an integer selected from 0 to 30;
• the number of structure 3 is x, x is an integer selected from 1 to 30;
• Ra1 and Rb1 are each independently selected from the group consisting of H, C1-C6 alkyl, and halogenated C1-C6 alkyl;
• each Ra2 is independently selected from the group consisting of C1-C6 alkylene;
• each Ra3 is independently selected from the group consisting of C1-C6 alkylene, —(C1-C6 alkylene)-O—, and —(C1-C6 alkylene)-O—(C═O)—;
• each Rb2 is independently selected from the group consisting of
• Rb21, Rb22, and Rb23 are each independently selected from the group consisting of, H, C1-C6 alkyl, adamantyl, OH-substituted adamantyl, and C3-C8 cycloalkyl,
• or Rb21, Rb22, and Rb23 together form a structure selected from the group consisting of
• n is 0, 1, 2, 3, 4 or 5;
• Rb24 is selected from the group consisting of —O— and —(C═O)—;
• Rb25, Rb26, and Rb27 are each independently selected from the group consisting of, hydrogen, ═O, C1-C6 alkyl, C1-C6 alkoxy, —(C═O)—O—C(C1-C6 alkyl)2-adamantyl, —O—(C3-C8 cycloalkyl), —O—(C1-C6 alkylene)-(C6-C10 aryl), C6-C10 aryl, and —O—(C1-C6 alkylene)-O—(C═O)—(C6-C10 aryl);
• each L1—L2 is independently selected from the group consisting of

An ordered photolithographic resin,

• wherein the photolithographic resin is a copolymer comprising structure 1, structure 2, structure 3 and structure 4,
• wherein,
• the number of structure 1 is m, m is selected from the group consisting of 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, and 20;
• the number of structure 2 is p, p is an integer selected from 0 to 20;
• the number of structure 3 is x, x is an integer selected from 1 to 15;
• the number of structure 4 is y, y is an integer selected from 1 to 15;
• Ra1, Rb1 and Rb3 are each independently selected from the group consisting of H, C1-C6 alkyl, and halogenated C1-C6 alkyl;
• each Ra2 is independently selected from the group consisting of C1-C6 alkylene;
• each Ra3 is independently selected from the group consisting of C1-C6 alkylene;
• each Rb2 is independently selected from the group consisting of
• Rb21, Rb22, and Rb23 are each independently selected from the group consisting of, H, C1-C6 alkyl, adamantyl, OH-substituted adamantyl, and C3-C8 cycloalkyl,
• or Rb21, Rb22 and Rb23 together form a structure selected from the group consisting of
• n is 0, 1, 2, 3, 4 or 5;
• Rb24 is selected from the group consisting of —O— and —(C═O)—;
• Rb25, Rb26, and Rb27 are each independently selected from the group consisting of, hydrogen, ═O, C1-C6 alkyl, C1-C6 alkoxy, —(C═O)—O—C(C1-C6 alkyl)2-adamantyl, —O—(C3-C8 cycloalkyl), —O—(C1-C6 alkylene)-(C6-C10 aryl), C6-C10 aryl, and —O—(C1-C6 alkylene)-O—(C═O)—(C6-C10 aryl);
• Rb4 is a combination of anions and cations, where the anion is selected from the group consisting of
• Rb41 and Rb42 are each independently selected from the group consisting of hydrogen, halogenated or unsubstituted C1-C15 straight-chain or branched-chain alkyl, substituted or unsubstituted C1-C15 straight-chain or branched-chain alkoxy;
• the substituted means being substituted by a substitutent selected from the group consisting of halogen, hydroxyl, carbonyl, amino, amide, ether bonded oxygen atom, and lactone structure;
• p is an integer from 0 to 5;
• the cation is selected from the group consisting of iodonium salts (B1) and sulfonium salts (B2) shown as follows:
• in formulas (B1) and (B2), Rc1, Rc2, Rc3, Rc1′, Rc2′, Rc3′, and Rc4′ are each independently represent substituents;
• Rc1 and Rc1′ are selected from the group consisting of hydrogen, halogen, unsubstituted or hydroxyl or halogen substituted C1-C10 straight-chain or branched-chain alkyl, unsubstituted or hydroxyl or halogen substituted C1-C10 straight-chain or branched-chain alkoxy, unsubstituted or hydroxyl or halogen substituted C1-C10 straight-chain or branched-chain alkoxy carbonyl;
• the halogen is selected from the group consisting of fluorine, chlorine, bromine and iodine;
• Rc2 and Rc2′ are selected from the group consisting of hydrogen, halogenated or unsubstituted C1-C15 straight-chain or branched-chain alkyl, substituted or unsubstituted C1-C15 straight-chain or branched-chain alkoxy;
• the substituted means being substituted by a substitutent selected from the group consisting of halogen, hydroxyl, carbonyl, amino, amide, ether bonded oxygen atom, and lactone structure;
• Rc3, Rc3′, and Rc4′ are selected from the group consisting of substituted or unsubstituted C1-C11 straight-chain or branched-chain alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted naphthyl;
• the substituted means being substituted by a substitutent selected from the group consisting of halogen, hydroxyl, carbonyl, amino, amide, and lactone structure;
• Rc3′ and Rc4′ are optionally combined to form a divalent group;
• q is 0, 1, 2 or 3;
• p′ is 0, 1, 2, 3, 4 or 5;
• each L1—L2 is independently selected from the group consisting of