Silicone skeleton-containing polymer compound, chemically amplified negative resist composition, photo-curable dry film and method for producing same, patterning process, layered product, substrate, and semiconductor apparatus
The present invention provides a silicone skeleton-containing polymer compound containing a repeating unit shown by the general formula (1). There can be provided a silicone skeleton-containing polymer compound suitable used as a base resin of a chemically amplified negative resist composition that can remedy the problem of delamination generated on a metal wiring such as Cu and Al, an electrode, and a substrate, especially on a substrate such as SiN, and can form a fine pattern without generating a scum and a footing profile in the pattern bottom and on the substrate.
1. A silicone skeleton-containing polymer compound comprising a repeating unit shown by the general formula (1),
wherein R 1 to R 4 may be the same or different, and represent a monovalent organic group having 1 to 15 carbon atoms and optionally containing an oxygen atom; R 5 and R 6 may be the same or different, and represent a monovalent organic group having 1 to 28 carbon atoms and optionally containing an oxygen atom; “1” represents an integer of 0 to 100; “m” represents an integer of 0 to 100; “n” represents an integer of 1 or more; and T represents a divalent organic group shown by the general formula (2),
wherein Q is any of
and the dotted line represents a bond.
2. The silicone skeleton-containing polymer compound according to claim 1 , wherein the silicone skeleton-containing polymer compound contains a repeating unit shown by the general formula (3) and has a weight average molecular weight of 3,000 to 500,000,
wherein “a”, “b”, “c”, “d”, “e”, “f”, “g”, and “h” are each 0 or a positive number, and “i” and “j” are each a positive number, provided that a+b+c+d+e+f+g+h+i+j=1; X is a divalent organic group shown by the general formula (4); Y is a divalent organic group shown by the general formula (5); W is a divalent organic group shown by the general formula (6); and U is a divalent organic group shown by the general formula (7),
wherein Z represents a divalent organic group selected from any of
the dotted line represents a bond; “o” represents 0 or 1; R 7 and R 8 each represent an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other; and “k” is 0, 1, or 2,
wherein V is a divalent organic group selected from any of
the dotted line represents a bond; “p” represents 0 or 1; R 9 and R 10 each represent an alkyl group or alkoxy group having 1 to 4 carbon atoms, and may be the same or different from each other; and “q” is 0, 1, or 2,
wherein the dotted line represents a bond; M represents an alkylene group having 1 to 12 carbon atoms or a divalent aromatic group; and R 11 represents a hydrogen atom or a methyl group,
wherein the dotted line represents a bond; and
R 12 represents a monovalent carboxyl-containing organic group.
3. The silicone skeleton-containing polymer compound according to claim 2 , wherein R 12 in the general formula (7) is a monovalent carboxyl-containing organic group shown by the general formula (8),
wherein the dotted line represents a bond; R 13 to R 16 may be the same or different, and represent a hydrogen atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, or an aromatic group; R 13 and R 15 may be bonded respectively to R 14 and R 16 to form a substituted or unsubstituted ring structure having 1 to 12 carbon atoms; and “r” is any of 1 to 7.
4. The silicone skeleton-containing polymer compound according to claim 3 , wherein in the general formula (3), 0≤a≤0.5, 0≤b≤0.3, 0≤c≤0.5, 0≤d≤0.3, 0≤e≤0.8, 0≤f≤0.5, 0≤g≤0.8, 0≤h≤0.5, 0<i≤0.8, and 0<j≤0.5.
5. The silicone skeleton-containing polymer compound according to claim 4 , wherein in the general formula (3), a=0, b=0, c=0, d=0, e=0, f=0, 0<g≤0.8, 0<h≤0.5, 0<i≤0.8, and 0<j≤0.5.
6. The silicone skeleton-containing polymer compound according to claim 3 , wherein in the general formula (1) or the general formula (3), “m” is an integer of 1 to 100; R 1 to R 4 represent an identical or different monovalent hydrocarbon group having 1 to 8 carbon atoms; R 5 represents a phenyl substituent containing a hydroxyl group or an alkoxy group as shown by the general formula (9); R 6 may be the same or different from R 1 to R 4 , and represents a monovalent organic group having 1 to 10 carbon atoms and optionally containing an oxygen atom, or R 6 may be the same or different from R 5 , and represents a phenyl substituent containing a hydroxyl group or an alkoxy group as shown by the general formula (9),
wherein “s” is an integer of 0 to 10; and R 17 represents a hydroxyl group or a linear, branched, or cyclic alkoxy group having 1 to 12 carbon atoms.
7. The silicone skeleton-containing polymer compound according to claim 6 , wherein the phenyl substituent shown by the general formula (9) is one group, or two or more groups selected from the formula (10),
wherein the line with a wavy line represents a bonding arm.
8. The silicone skeleton-containing polymer compound according to claim 2 , wherein in the general formula (3), 0≤a≤0.5, 0≤b≤0.3, 0≤c≤0.5, 0≤d≤0.3, 0≤e≤0.8, 0≤f≤0.5, 0≤g≤0.8, 0≤h≤0.5, 0<i≤0.8, and 0<j≤0.5.
9. The silicone skeleton-containing polymer compound according to claim 8 , wherein in the general formula (3), a=0, b=0, c=0, d=0, e=0, f=0, 0<g≤0.8, 0<h≤0.5, 0<i≤0.8, and 0<j≤0.5.
10. The silicone skeleton-containing polymer compound according to claim 2 , wherein in the general formula (1) or the general formula (3), “m” is an integer of 1 to 100; R 1 to R 4 represent an identical or different monovalent hydrocarbon group having 1 to 8 carbon atoms; R 5 represents a phenyl substituent containing a hydroxyl group or an alkoxy group as shown by the general formula (9); R 6 may be the same or different from R 1 to R 4 , and represents a monovalent organic group having 1 to 10 carbon atoms and optionally containing an oxygen atom, or R 6 may be the same or different from R 5 , and represents a phenyl substituent containing a hydroxyl group or an alkoxy group as shown by the general formula (9),
wherein “s” is an integer of 0 to 10; and R 17 represents a hydroxyl group or a linear, branched, or cyclic alkoxy group having 1 to 12 carbon atoms.
11. The silicone skeleton-containing polymer compound according to claim 10 , wherein the phenyl substituent shown by the general formula (9) is one group, or two or more groups selected from the formula (10),
wherein the line with a wavy line represents a bonding arm.
12. The silicone skeleton-containing polymer compound according to claim 2 , wherein the divalent organic group shown by the general formula (6) is a divalent organic group shown by the general formula (11), and the divalent organic group shown by the general formula (7) is a divalent organic group shown by the general formula (12),
wherein the dotted line represents a bond; and
“t” represents a positive number of 1 to 12.
13. The silicone skeleton-containing polymer compound according to claim 2 , wherein the divalent organic group shown by the general formula (6) is a divalent organic group shown by the general formula (13), and the divalent organic group shown by the general formula (7) is a divalent organic group shown by the general formula (14),
wherein the dotted line represents a bond.
14. The silicone skeleton-containing polymer compound according to claim 1 , wherein in the general formula (1), “m” is an integer of 1 to 100; R 1 to R 4 represent an identical or different monovalent hydrocarbon group having 1 to 8 carbon atoms; R 5 represents a phenyl substituent containing a hydroxyl group or an alkoxy group as shown by the general formula (9); R 6 may be the same or different from R 1 to R 4 , and represents a monovalent organic group having 1 to 10 carbon atoms and optionally containing an oxygen atom, or R 6 may be the same or different from R 5 , and represents a phenyl substituent containing a hydroxyl group or an alkoxy group as shown by the general formula (9),
wherein “s” is an integer of 0 to 10; and R 17 represents a hydroxyl group or a linear, branched, or cyclic alkoxy group having 1 to 12 carbon atoms.
15. The silicone skeleton-containing polymer compound according to claim 14 , wherein the phenyl substituent shown by the general formula (9) is one group, or two or more groups selected from the formula (10),
wherein the line with a wavy line represents a bonding arm.
16. A chemically amplified negative resist composition comprising:
(A) the silicone skeleton-containing polymer compound according to claim 1 ,
(B) a photosensitive acid generator capable of generating an acid by decomposition with light having a wavelength of 190 to 500 nm;
(C) one or more crosslinking agents selected from an amino condensate modified by formaldehyde or formaldehyde-alcohol, a phenol compound having on average two or more methylol groups or alkoxymethylol groups per molecule, a polyhydric phenol compound in which a hydrogen atom of a phenolic hydroxyl group is substituted by a glycidyl group, a polyhydric phenol compound in which a hydrogen atom of a phenolic hydroxyl group is substituted by a substituent shown by the formula (C-1), and a compound having two or more nitrogen atoms bonded to a glycidyl group as shown by the formula (C-2),
wherein the dotted line represents a bond; R c represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; and “z” is 1 or 2;
(D) a solvent; and
(E) a basic compound.
17. A photo-curable dry film comprising a supporting film, a top coat film, and a photo-curable resin layer having a film thickness of 10 to 100 μm, the photo-curable resin layer being sandwiched between the supporting film and the top coat film, wherein the photo-curable resin layer is formed of the chemically amplified negative resist composition according to claim 16 .
18. A patterning process comprising:
(i) separating the top coat film from the photo-curable dry film according to claim 17 and bringing an exposed photo-curable resin layer into close contact with a substrate;
(ii) exposing the photo-curable resin layer to a high energy beam having a wavelength of 190 to 500 nm or an electron beam via a photomask either through the supporting film or in a peeled-off state of the supporting film;
(iii) subjecting to a heat treatment after the exposure; and
(iv) subjecting to development by using an alkaline aqueous solution or an organic solvent as a developer.
19. The patterning process according to claim 18 , wherein the substrate includes a trench and/or a hole each having an aperture width of 10 to 100 μm and a depth of 10 to 120 μm.
20. A method for producing a photo-curable dry film, comprising:
(I) continuously applying the chemically amplified negative resist composition according to claim 16 onto a supporting film to form a photo-curable resin layer,
(II) continuously drying the photo-curable resin layer, and further
(III) laminating a top coat film onto the photo-curable resin layer.
21. A patterning process comprising:
(1) applying the chemically amplified negative resist composition according to claim 16 onto a substrate to form a photosensitive material film;
(2) exposing the photosensitive material film to a high energy beam having a wavelength of 190 to 500 nm or an electron beam via a photomask after a heat treatment; and
(3) subjecting to development by using an alkaline aqueous solution or an organic solvent as a developer after a heat treatment.
22. The patterning process according to claim 21 , further comprising post-curing a patterned film formed by the development at 100 to 250° C. after the development.
23. A substrate that is protected by a film obtained by curing a pattern formed by the patterning process according to claim 21 .
24. A semiconductor apparatus comprising a film obtained by curing a pattern formed by the patterning process according to claim 21 .
25. A layered product comprising
a substrate including a trench and/or a hole each having an aperture width of 10 to 100 μm and a depth of 10 to 120 μm, and
a photo-curable resin layer laminated on the substrate, wherein
the photo-curable resin layer has a film thickness of 10 to 100 μm and is formed of the chemically amplified negative resist composition according to claim 16 .