Methods for manufacturing block copolymers and articles manufactured therefrom

1. A method of forming an article comprising:

disposing upon a substrate a composition comprising:

a first block copolymer that comprises a first block and a second block; where the first block has a higher surface energy than the second block;

a second block copolymer that comprises a first block and a second block; where the first block of the first block copolymer is chemically the same as or similar to the first block of the second block copolymer and the second block of the first block copolymer is chemically the same as or similar to the second block of the second block copolymer; where the weight percent based on total solids of the first block of the second block copolymer is greater than that of the first block of the first block copolymer; where the first and the second block copolymer have a chi parameter greater than 0.04 at a temperature of 200° C.;

where the first block copolymer phase separates into a first morphology of cylindrical or lamellar domains when disposed singly on a substrate; where the second block copolymer phase separates into a second morphology of cylindrical, lamellar or spherical domains when singly disposed on a substrate; and where the first morphology and the second morphology are different; and

a first polymer that is chemically the same as or similar to the first block of the first block copolymer and to the first block of the second block copolymer; where the first polymer is a homopolymer or random copolymer; and

annealing the composition to form a pattern comprising:

a first region having a thickness of T a that comprises alternating domains disposed perpendicular to the substrate surface and contacting the substrate;

a second region having a thickness of T b that comprises a single layer comprising two domains; where the single layer is oriented substantially parallel to the substrate surface, such that the first region and the second region have a total thickness of T c ; and where at least one domain of the second region contacts air while at least one of the domains of the second region directly contacts the first region; where the relationship between the thickness of the first region and the second region is expressed by Equation (1):

T a =T c −KL o   (1)

where Lo is a pitch between successive domains in the first region and were K is a constant having a value of 0.3 to 0.6.

2. The method of claim 1 , where the substrate comprises a pattern that directs the composition to form lamellar or cylindrical domains registered to the pattern on the substrate after annealing.

3. The method of claim 1 , the composition further comprises a second polymer; where the second polymer is chemically the same as or similar to the second block of the first block copolymer and to the second block of the second block copolymer; where the second polymer is different from the first polymer.

4. The method of claim 1 , where the first block of the first block copolymer comprises a polystyrene, a poly(meth)acrylate, a polyolefin, a polyacrylic, a polycarbonate, a polyester, a polyamide, a polyamideimide, a polyvinyl ether, a polyvinyl thioether, a polyvinyl alcohol, a polyurea, a poly(vinyl pyridine), a poly(vinyl imidazole), a poly(vinyl pyrazole), or a combination thereof.

5. The method of claim 1 , where the first block of the first block copolymer comprises polystyrene or polymethylmethacrylate and where the second block of the first block copolymer comprises polydimethylsiloxane.

6. The method of claim 1 , where the second block of the first block copolymer comprises a structure represented by formula (1)

wherein each R is independently a C 1 -C 10 alkyl, a C 3 -C 10 cycloalkyl, a C 6 -C 14 aryl, a C 7 -C 13 alkylaryl or a C 7 -C 13 arylalkyl and where a degree of polymerization n in the formula (1) is 10 to 5,000.

7. The method of claim 1 , where the composition comprises cylindrical and/or lamellar domains and has an interdomain spacing of less than or equal to about 25 nanometers after being cast on the substrate and being annealed at a temperature above the glass transition temperature and below the order-disorder transition temperature and the decomposition temperature.