Neutral layer polymers, methods of manufacture thereof and articles comprising the same

1. A composition comprising:

a block copolymer comprising a first segment and a second segment that are covalently bonded to each other and that are chemically different from each other; where the first segment has a first surface free energy and where the second segment has a second surface free energy;

an additive copolymer; comprising segment A and segment B and a surface energy reducing moiety X, where segment A comprises repeat units of unit A and segment B comprises repeat units of unit B, where the surface free energy reducing moiety X has a lower surface free energy than that of the segment A and the segment B; where segment A or segment B has an affinity for either the first segment or the second segment; where the surface free energy reducing moiety X is chemically different from the first segment and from the second segment and comprises a fluorine atom, a silicon atom, an unsubstituted or substituted C 1 -C 12 hydrocarbyl, or a combination thereof; where the additive copolymer is not water miscible; where the additive copolymer is not covalently bonded with the block copolymer; where the additive copolymer is operative to form a neutral layer on a surface of the block copolymer and to facilitate formation of domains in the block copolymer that are perpendicular to a surface of a substrate that the composition is disposed on; where the surface free energy reducing moiety X is covalently bonded to either segment A or segment B; and where the surface free energy reducing moiety X is a single repeat unit, an oligomeric repeat unit, or a polymeric repeat unit; and

a solvent.

2. The composition of claim 1 , where the additive copolymer is a random copolymer, or a block copolymer having the structure of formula (1)

where segment A and segment B are chemically similar to the first segment and the second segment in the block copolymer, where n is 1 to 50, m is 1 to 50 and where p is 1 to 50, where n, m and p are independent or each other.

3. The composition of claim 2 , where the random copolymer or a block copolymer comprises repeat units A, C, or X and having the structure of formula (2)

where C is an alternative unit that can be combined with the units A or B to achieve neutrality for the additive copolymer, where the neutrality provides an appropriate surface energetic character to promote domain formation in the block copolymer.

4. The composition of claim 1 , where the additive copolymer can comprise a block copolymer comprising blocks of units A and B and blocks of X as shown by a structure of formula (3)

where units of A and B are arranged to alternate with each other and form a first block while the surface free energy reducing moiety X forms a second block; where o has a value of 1 to 50 and p has a value of 1 to 50; and where o and p are independent of each other.

5. The composition of claim 1 , where the additive copolymer is a gradient polymerized polymer or a blend of gradient polymerized polymers where the gradient polymerized polymer is a gradient random polymer of A, B and X with an increasing value of X as the copolymer chain is traversed from one end to the other as seen in formula (7):

where n, m and p each can have a value of 1 to 50 and can be the same or different or independent to each other.

6. The composition of claim 1 , where in the formula (7), n=m for each segment.

7. The composition of claim 1 , where the additive copolymer is a block copolymer of A and B with increasing X as the copolymer chain is traversed from one end to the other as shown in the formula (8)

where n, m and p each can have a value of 1 to 50 and can be the same or different or independent to each other.

8. The composition of claim 1 , where the additive copolymer is a block copolymer with the random incorporations of X into the blocks as seen in the formula (9)

A-r-X k b B-r-X h   (9)

where “r” indicates that A and X are randomly copolymerized in a first segment, “b” indicates that segment (A-r-X) and segment (B-r-X) are in the form of a block copolymer; and where k and h are the same or different and are 1 to 50.

9. The composition of claim 8 , where the additive copolymer is a block copolymer that comprises repeat units of A that are copolymerized with segments comprising B and X that are randomly copolymerized a shown in the formula (10)

A k b B-r-X h   (10).

10. The composition of claim 8 , where the additive copolymer comprises structures shown in the formulas (11), (12) and (13) each of which can be employed in either a comb topology or in a bottle brush topology

where in the formulas (11) through (13) repeat units of D form the additive copolymer backbone, while repeat units of A, B and X are grafted onto the backbone; where the number of repeat units e, f and g can be the same or different from each other; where the number of repeat units x, y and z can be the same or different from each other and where each of e, f and g are an amount of 1 to 50; where x, y and z are an amount of 1 to 50; where in the formula in formula (12), “a” and “b” can be the same or different from each other and can independently be an amount of 1 to 50; where in the formula (13), “a”, “b” and “c” can be the same or different from each other and can independently be an amount of 1 to 50; where “a′”, “b′” and “c′” can be the same or different from each other and are independently an amount of 1 to 50; where a, b and c or a′, b′ and c′ are the same or different from x, y and z.