Methods and materials for removing metals in block copolymers
View Patent ↗The present invention relates to a method for treating a block copolymer solution, wherein the method comprises: providing a solution comprising a block copolymer in a non aqueous solvent; and, treating the solution to remove metals using an ion exchange resin. The invention also relates to a method of forming patterns using the treated block copolymer.
1. A method of treating a block copolymer solution comprising:
a. providing a solution comprising a block copolymer in a non aqueous solvent;
b. adding a basic ion exchange resin to the solution to form a slurry; and,
c. filtering the slurry to remove the ion exchange resin, thereby reducing metal ion contamination of the block copolymer solution.
2. The method of claim 1 , wherein the basic ion exchange resin has a morphology chosen from gel-type, macroreticular or porous; and
wherein, as a result of treating the block copolymer solution, one or more metal ion contaminants chosen from aluminum, calcium, chromium, copper, iron, magnesium, manganese, nickel, potassium, sodium, zinc, tin, cadmium, cobalt, germanium, lead, lithium, silver, or titanium are reduced by at least 5% from their initial pretreatment values.
3. The method of claim 1 , wherein the solution comprises a concentration of 0.1%-20% w/w of the block copolymer.
4. The method of claim 1 , wherein, as a result of treating the block copolymer solution, the percent exposure latitude of the block copolymer is increased by at least 2 percentage points.
5. The method of claim 1 , further comprising adding a sulfonic acid cation exchange resin to form a mixed slurry.
6. The method of claim 5 , wherein the sulfonic acid cation exchange resin has a morphology chosen from gel-type, macroreticular or porous; and wherein, as a result of treatment, one or more metal ion contaminants chosen from aluminum, calcium, chromium, copper, iron, magnesium, manganese, nickel, potassium, sodium, zinc, tin, cadmium, cobalt, germanium, lead, lithium, silver, or titanium are reduced by at least 5% from their initial values.
7. The method of claim 5 , wherein, as a result of treating the block copolymer solution, the percent exposure latitude is increased by at least 2 percentage points.
8. The method of claim 1 where the basic ion exchange resin is dehydrated by contact with an organic solvent prior to contact with the solution.
9. The method of claim 5 where the sulfonic acid cation exchange resin is dehydrated by contact with an organic solvent prior to contact with the solution.
10. The method of claim 1 , wherein the block copolymer is chosen from poly(styrene-b-methyl (meth)acrylate), poly(styrene-b-vinyl pyridine), poly(styrene-b-polyethylene glycol), poly(styrene-b-dimethylsiloxane), poly(styrene-b-ethyl methylsiloxane), poly(styrene-b-lactide), poly(styrene-b-2-hydroxyethyl (meth)acrylate), poly(styrene-b-2-hydroxypropyl (meth)acrylate), poly(dimethylsiloxane-b-n-butyl (meth)acrylate), poly(dimethylsiloxane-b-t-butyl (meth)acrylate), poly(dimethylsiloxane-b-hydroxy ethyl (meth)acrylate), poly(dimethylsiloxane-b-methyl methacrylate-co-t-butyl methylacrylate), poly(dimethylsiloxane-b-1-ethoxy ethyl (meth)acrylate), poly(dimethylsiloxane-b-ε-caprolactone), poly(dimethylsiloxane-b-lactide), or poly(propylene oxide-b-styrene-co-4-vinyl pyridine).
11. A method of treating a block copolymer solution, comprising:
a. providing a solution comprising a block copolymer in a non aqueous solvent;
b. treating the solution with a basic ion-exchange resin.
12. The method of claim 11 , wherein treating the solution comprises passing the solution through a bed column comprising the basic ion-exchange resin.
13. The method of claim 11 , wherein treating the solution comprises passing the solution through a mixed bed column comprising the strong acid cation exchange resin and free-base tertiary amine ion-exchange resin.
14. The method of claim 13 , wherein treating the solution comprises forming a slurry comprising the solution and a mixture comprising the strong acid cation exchange resin and the basic ion-exchange resin; and wherein the process further comprises filtering the slurry.
15. The method of claim 11 , wherein the block copolymer is chosen from poly(styrene-b-methyl (meth)acrylate), poly(styrene-b-vinyl pyridine), poly(styrene-b-polyethylene glycol), poly(styrene-b-dimethylsiloxane), poly(styrene-b-ethyl methylsiloxane), poly(styrene-b-lactide), poly(styrene-b-2-hydroxyethyl (meth)acrylate), poly(styrene-b-2-hydroxypropyl (meth)acrylate), poly(dimethylsiloxane-b-n-butyl (meth)acrylate), poly(dimethylsiloxane-b-t-butyl (meth)acrylate), poly(dimethylsiloxane-b-hydroxy ethyl (meth)acrylate), poly(dimethylsiloxane-b-methyl methacrylate-co-t-butyl methylacrylate), poly(dimethylsiloxane-b-1-ethoxy ethyl (meth)acrylate), poly(dimethylsiloxane-b-ε-caprolactone), poly(dimethylsiloxane-b-lactide), or poly(propylene oxide-b-styrene-co-4-vinyl pyridine).
16. The method of claim 11 , wherein the basic ion exchange resin has a morphology chosen from gel-type, macroreticular or porous; and
wherein, as a result of treating the block copolymer solution, one or more metal ion contaminants chosen from aluminum, calcium, chromium, copper, iron, magnesium, manganese, nickel, potassium, sodium, zinc, tin, cadmium, cobalt, germanium, lead, lithium, silver, or titanium are reduced to less than 5% of their initial values.
17. The method of claim 13 , wherein the sulfonic acid cation exchange resin has a morphology chosen from gel-type, macroreticular or porous; and wherein, as a result of treatment, one or more metal ion contaminants chosen from aluminum, calcium, chromium, copper, iron, magnesium, manganese, nickel, potassium, sodium, zinc, tin, cadmium, cobalt, germanium, lead, lithium, silver, or titanium are reduced to less than 5% of their initial values.
18. The method of claim 11 , wherein, as a result of treating the block copolymer solution, the percent exposure latitude is increased by at least 2 percentage points.