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 forming a directed self assembly pattern comprising the steps of;
a. coating a substrate with a solution with reduced metal ion contamination content, wherein the solution comprises a block copolymer where the block copolymer is derived from monomers which are arranged in blocks which are different compositionally, structurally or both and are capable of phase separating and forming domains, and further wherein the blocks have differing etch properties which can be used to remove one block while keeping the other block intact on the surface of the substrate, thus providing a pattern on the surface of the substrate and further where the solution with reduced metal ion contamination is produced by,
i. treating the solution with a basic ion exchange to form a slurry; and,
ii. filtering the slurry to remove the ion exchange resin;
b. heating the substrate to form a directed self assembly polymer layer; and
c. removing one block of the block copolymer and thereby forming a pattern.
2. The method of claim 1 , where one block is removed by wet or dry etching step.
3. 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.
4. The method of claim 1 , wherein the solution comprises a concentration of 0.1%-20% w/w of the block copolymer.
5. 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.
6. The method of claim 1 , further comprising adding a sulfonic acid cation exchange resin to form a mixed slurry.
7. The method of claim 6 , 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.
8. The method of claim 6 , wherein, as a result of treating the block copolymer solution, the percent exposure latitude is increased by at least 2 percentage points.
9. 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.
10. The method of claim 6 where the sulfonic acid cation exchange resin is dehydrated by contact with an organic solvent prior to contact with the solution.
11. 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-methylmethacrylate-co-t-butyl methyl acrylate), 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).
12. The method of claim 1 , wherein the etch properties are plasma etching.
13. The method of claim 1 , wherein the etch properties are solvent etching.
14. The method of claim 1 , wherein the etch properties are developer etching.