Neutral layer polymer composition for directed self assembly and processes thereof
View Patent ↗The present invention relates to a novel polymeric composition comprising a novel polymer having two or more repeat units and a terminus having the structure (1): wherein R 1 represents a C 1 -C 20 substituted or unsubstituted alkyl group, w is a number from 1-8, X is oxygen (O) or nitrogen (N), and R d is a reactive group. The invention also relates to a process for forming a pattern using the novel polymeric composition. The invention further relates to a process of making the novel polymer.
1. A polymeric composition comprising a polymer comprising a) two or more repeat units and b) a terminus having the structure (1)
wherein R 1 represents a C 1 -C 20 substituted or unsubstituted alkyl group, w is a number from 1-8, X is O or N and R d is at least one group chosen from i) to viii);
i)
where Q 1 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms; y = 1-5;
ii)
where Q 2 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms, R 3 represents hydrogen, an alkyl or substituted alkyl group having 1-20 carbon atoms, and R 4 , and R 5 represent, independently, hydrogen or an alkyl or substituted alkyl group having 1-20 carbon atoms, or a hydroxy, alkoxy or substituted alkoxy group having 1-20 carbon atoms;
iii)
where Q 1 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms; y = 1-5;
iv)
—Ar—CH 2 OH
where Ar represents a substituted or unsubstituted arylene group having 6 to 20 atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms;
v)
where Q 3 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms;
vi)
where U represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; and z is 1-2;
vii)
where Ar represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms.
viii)
(RO) 2 OP—(CH 2 ) w —
where R represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms, and w is a number from 1-10.
2. The polymeric composition of claim 1 , where X is oxygen.
3. The polymeric composition of claim 1 , where X is nitrogen.
4. The polymeric composition of claim 1 , where X is oxygen and R d is at least one group selected from a group consisting of i) to vii).
5. The polymeric composition of claim 1 , where X is oxygen and R d is at least one group chosen from i) or ii),
6. The polymeric composition of claim 1 , where X is nitrogen and R d is at least one group chosen from viii) (RO) 2 OP—(CH 2 ) w —.
7. The polymeric composition of claim 1 , wherein the polymer comprising two or more repeat units is chosen from poly(methylmethacrylate-styrene)poly(butadiene-butylmethacrylate), poly(butadiene-dimethylsiloxane), poly(butadiene-methylmethacrylate), poly(butadiene-vinylpyridine), poly(isoprene-methylmethacrylate), (polyisoprene-vinylpyridine), poly(butylacrylate-methylmethacrylate), poly(butylacrylate-vinylpyridine), (polyhexylacrylate-vinylpyridine), poly(isobutylene-butylmethacrylate), poly(isobutylene-dimethoxysiloxane), poly(isobutylene-methylmethacrylate), poly(isobutylene-vinylpyridine), poly(isoprene-ethyleneoxide), poly(butylmethacrylate-butylacrylate), poly(butylmethacrylate-vinylpyridine), poly(ethylene-methylmethacrylate), poly(methylmethacrylate-butylacrylate), poly(methylmethacrylate-butylmethacrylate), poly(styrene-butadiene), poly(styrene-butylacrylate), polystyrene-butylmethacrylate), poly(styrene-butylstyrene), poly(styrene-dimethoxysiloxane), poly(styrene-isoprene), poly(styrene-methylmethacrylate), poly(styrene-vinylpyridine), poly(ethylene-vinylpyridine), poly(vinylpyridine-methylmethacrylate), poly(ethyleneoxide-isoprene), poly(ethyleneoxide-butadiene), poly(ethyleneoxide-styrene), or poly(ethyleneoxide-methylmethacrylate).
8. The polymeric composition of claim 1 , further comprising a thermal acid generator.
9. The polymeric composition of claim 1 , further comprising a photoacid generator.
10. The polymeric composition of claim 9 , wherein the photoacid generator is an aliphatic or aromatic sulfonium or iodonium salt.
11. A process of forming an image comprising;
a) forming a neutral layer of the polymeric composition of claim 1 on a substrate;
b) forming a layer with a solution containing a block copolymer;
c) annealing the block copolymer thermally so as to allow the block copolymer to undergo directed self assembly;
d) pattern transferring the self assembled block copolymer using a dry or wet etching process, thereby producing fine patterns.
12. The process of claim 11 , where the block copolymer is selected from poly(styrene-b-vinyl pyridine), poly(styrene-b-butadiene), poly(styrene-b-isoprene), poly(styrene-b-methyl methacrylate), poly(styrene-b-alkenyl aromatics), poly(isoprene-b-ethylene oxide), poly(styrene-b-(ethylene-propylene)), poly(ethylene oxide-b-caprolactone), poly(butadiene-b-ethylene oxide), poly(styrene-b-t-butyl(meth)acrylate), poly(methyl methacrylate-b-t-butyl methacrylate), poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(methyl methacrylate-b-dimethylsiloxane).
13. A polymeric composition, formed by a process, the process comprising:
a. providing, to a reaction vessel, a salt of 4,4′-azobis(4-cyanovaleric acid), wherein the salt comprises at least one quaternary cation;
b. providing one or more monomers to the reaction vessel to form a reactive mixture;
c. heating the reactive mixture at a temperature less than 100° C. for a time of 1-80 hours to form a polymer, then;
d. providing, to the resulting polymer, a halogenated compound, the halogenated compound chosen from:
where Q 1 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms and X represents a halogen; y = 1-5;
where Q 2 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms, R 3 represents hydrogen an alkyl or substituted alkyl group having 1-20 carbon atoms, and R 4 , and R 5 represent, independently, hydrogen or an alkyl or substituted alkyl group having 1-20 carbon atoms, or a hydroxy, alkoxy or substituted alkoxy group having 1-20 carbon atoms and X represents a halogen;
where Q 1 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms, and y is 1-5 and z is 1-2 and X represents a halogen;
X—Ar—CH 2 OH
where Ar represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms and X represents a halogen;
where Q 3 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms and X represents a halogen;
where Ar represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms and X represents a halogen;
where Ar represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms and X represents a halogen.
14. A functionalized free radical initiator comprising: a compound having the structure
wherein R 1 represents a substituted or unsubstituted alkyl group having 1-20 carbon atoms, w is 1-8, X is O or N and R d is at least one reactive group selected from a group consisting of i) to viii):
i)
where Q 1 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms; y = 1-5;
ii)
where Q 2 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms, R 3 represents hydrogen, an alkyl or substituted alkyl group having 1-20 carbon atoms, and R 4 , and R 5 represent, independently, hydrogen or an alkyl or substituted alkyl group having 1-20 carbon atoms, or a hydroxy, alkoxy or substituted alkoxy group having 1-20 carbon atoms;
iii)
where Q 1 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms; y = 1-5;
iv)
—Ar—CH 2 OH
where Ar represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms;
v)
where Q 3 represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms;
vi)
where U represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; and z is 1-2;
vii)
where Ar represents a substituted or unsubstituted group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms.
viii)
(RO) 2 OP—(CH 2 ) w —
where R represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group, having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms, and w is a number from 1 -10.
15. A polymeric composition formed by a process comprising:
e. providing, to a reaction vessel, the functionalized free radical initiator of claim 14 ;
f. providing one or more monomers to the reaction vessel to form a reactive mixture; and
g. heating the reactive mixture at a temperature less than 100° C. for a time of 1-80 hours.