BRUSH POLYMER TERMINATED WITH PHOSPHONATE FOR DSA

Abstract

The disclosed subject matter relates compounds of structure (I), and polymers of structure (II) having a polydispersity ranging from 1 to about 1.1, compositions comprising said polymers and a spin casting solvent, the process of forming a pinning layer el selectively on metal with said composition and the process of using said pinning layers to affect chemoepitaxy directed self-assembly of an overlying block copolymer, and the subsequent process of pattern transfer of this self-assembled layer into a substrate by etching.

##STR00001##

Claims

1. A compound of structure (I), wherein R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00038##

2. The compound of claim 1, wherein R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group.

3. The compound of claim 1, wherein said compound has structure (Ia), wherein R.sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00039##

4.-6. (canceled)

7. The compound of claim 1, wherein said compound has structure (Ib), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00040##

8.-9. (canceled)

10. The compound of claim 7, wherein L.sub.1 is a direct valence bond and has structure (1c); ##STR00041##

11. A polymer of structure (II), wherein R.sub.1 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, an aryl, or an alkylenearyl; R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; B is a direct valence bond, or a methylene spacer (CH.sub.2) A is a styrenic polymer chain, or an acrylic polymer chain; and said polymer has a polydispersity ranging from 1 to 1.1; ##STR00042##

12. The polymer of claim 11, wherein R .sub.1 is H; R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; and A is a styrenic polymer chain.

13. The polymer of claim 11, having structure (IIa), wherein R.sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00043##

14.-16. (canceled)

17. The polymer of claim 13 which has structure (IIb); ##STR00044##

18. The polymer of claim 11, wherein it has structure (IIc), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00045##

19.-20. (canceled)

21. The polymer of claim 18, which has structure (IId); ##STR00046##

22. The polymer of claim 11, wherein R.sub.1 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl or a C-3 to C-8 cyclic alkyl, an aryl, an alkylenearyl; R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; and A is an acrylic polymer chain.

23. The polymer of claim 22, wherein it has structure (IIf), wherein R.sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl; R.sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00047##

24.-26. (canceled)

27. The polymer of claim 23, which has structure (IIg); ##STR00048##

28. The polymer of claim 22, wherein it has structure (IIh), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00049##

29.-30. (canceled)

31. The polymer of claim 28, wherein L.sub.1 and L.sub.2 are both a direct valence bond and the polymer of structure (II) has structure (Ili); ##STR00050##

32. The polymer of claim 12, wherein said polymer is a styrenic polymer having structure (III), wherein R .sub.e1 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, an aryl, or an alkylenearyl; R .sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R .sub.3 and R .sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; R .sub.5 is H, a C-1 to C-4 linear alkyl; R .sub.6 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; n is the number of repeat units; and said styrenic polymer has a polydispersity ranging from 1 to 1.1; ##STR00051##

33. (canceled)

34. The polymer of claim 32, wherein it has structure (IIIa), wherein R .sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R .sub.3 and R .sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00052##

35.-37. (canceled)

38. The polymer of claim 34, which has structure (IIIb); ##STR00053##

39. The polymer of any one of claim 32, wherein it has structure (IIIc), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00054##

40.-41. (canceled)

42. The polymer of claim 39, wherein L.sub.1 is a direct valence bond and has structure (IIId); ##STR00055##

43. The polymer of claim 22 wherein said polymer is an acrylic polymer having structure (IV), wherein R.sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl or a C-3 to C-8 cyclic alkyl; R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; R.sub.7 is H or a C-1 to C-4 linear alkyl; R.sub.8 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl or a C-3 to C-8 cyclic alkyl; R.sub.e2 is and end group selected from H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, or a C-3 to C-8 cyclic alkyl; n1 is the number of repeat units in said acrylate polymer of structure (IV); and said acrylic polymer has a polydispersity ranging from 1 to 1.1; ##STR00056##

44. (canceled)

45. The polymer of claim 43, wherein it has structure (IVa), wherein R.sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl; R.sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00057##

46.-48. (canceled)

49. The polymer of claim 45, which has structure (IVb); ##STR00058##

50. The polymer of claim 43, wherein it has structure (IVc), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group; ##STR00059##

51.-52. (canceled)

53. The polymer of claim 43, wherein L.sub.1 is a direct valence bond and the polymer has structure (IVd); ##STR00060##

54. A composition comprising a polymer of claim 1 and a spin casting solvent.

55. A process of forming a pinning layer brush selectively on a substrate which comprises both metallic surface areas and a non-metallic surface area, comprising the steps; i)coating said composition according to claim 54, on a said substrate, forming a film, ii) baking said film at a temperature from about 120 C. to about 250 C. for about 1 minute to about 1 hour, to form a baked film, iii) washing said baked film with a solvent to remove ungrafted polymer, forming a pinning layer brush only on said metallic surface areas of said substrate.

56. (canceled)

57. A process comprising the steps; ia) coating said composition according to claim 54, on a substrate which comprises both metallic surface areas and non-metallic surface areas, forming a film, iia) baking said film at a temperature from about 120 C. to about 250 C. for about 1 minute to about 1 hour, to form a baked film, iiia) washing said baked film with a solvent to remove ungrafted polymer, forming a grafted substrate wherein pinning layer brushes are only present on said metallic surface areas of said substrate, iva) coating said grafted substrate with a neutral layer composition, forming a neutral layer coating, va) curing said neutral layer coating, via) washing away, with a solvent, uncured neutral layer, leaving in said non-metallic areas of said substrate a neutral directing brush forming on said substrate a chemoepitaxy directing layer, viia) coating said chemoepitaxy directing layer with a block copolymer solution, forming a coating of block copolymer, viiia) annealing said coating of block copolymer, to form a directed self-assembled film of the block copolymer on said chemoepitaxy directing layer.

58.-62. (canceled)

Description

DETAILED DESCRIPTION

[0029] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and are not restrictive of the subject matter as claimed. In this application, the use of the singular includes the plural, the word a or an means at least one, and the use of or means and/or, unless specifically stated otherwise. Furthermore, the use of the term including, as well as other forms such as includes and included, is not limiting. Also, terms such as element or component encompass both elements and components comprising one unit and elements or components that comprise more than one unit, unless specifically stated otherwise. As used herein, the conjunction and is intended to be inclusive and the conjunction or is not intended to be exclusive unless otherwise indicated. For example, the phrase or, alternatively is intended to be exclusive. As used herein, the term and/or refers to any combination of the foregoing elements including using a single element.

[0030] The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to, patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that one or more of the incorporated literature references and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.

[0031] Unless otherwise indicated, alkyl refers to hydrocarbon groups which can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl and the like) or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl and the like) multicyclic (e.g., norbornyl, adamantyl and the like). These alkyl moieties may be substituted or unsubstituted as described below. The term alkyl refers to such moieties with C-1 to C-8 carbons. It is understood that for structural reasons linear alkyls start with C-1, while branched alkyls and cyclic alkyls start with C-3 and multicyclic alkyls start with C-5. Moreover, it is further understood that moieties derived from alkyls described below, such as alkyloxy, have the same carbon number ranges unless otherwise indicated. If the length of the alkyl group is specified as other than described above, the above described definition of alkyl still stands with respect to it encompassing all types of alkyl moieties as described above and that the structural consideration with regards to minimum number of carbons for a given type of alkyl group still apply.

[0032] Alkyloxy (a.k.a. Alkoxy) refers to an alkyl group on which is attached through an oxy (O) moiety (e.g. methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy cyclohexyloxy and the like). These alkyloxy moieties may be substituted or unsubstituted as described below.

[0033] Halo or halide refers to a halogen, F, Cl, Br or I which is linked by one bond to an organic moiety.

[0034] Haloalkyl refers to a linear, cyclic or branched saturated alkyl group such as defined above in which at least one of the hydrogens has been replaced by a halide selected from the group of F, Cl, Br, I or mixture of these if more than one halo moiety is present. Fluoroalkyls are a specific subgroup of these moieties.

[0035] The term alkylene refers to hydrocarbon groups which can be a linear, branched or cyclic which has two or more attachment points (e.g., of two attachment points: methylene, ethylene, 1,2-isopropylene, a 1,4-cyclohexylene and the like; of three attachment points 1,1,1-subsituted methane,1,1,2-subsituted ethane, 1,2,4-subsituted cyclohexane and the like). Here again, when designating a possible range of carbons, such as C-1 to C-20, as a non-limiting example, this range encompasses linear alkylenes starting with C-1 but only designates branched alkylenes, or cycloalkylene starting with C-3. These alkylene moieties may be substituted or unsubstituted as described below.

[0036] The term aryl or aromatic groups refers to such groups which contain 6 to 24 carbon atoms including phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls and the like. These aryl groups may further be substituted with any of the appropriate substituents, e.g., alkyl, alkoxy, acyl or aryl groups mentioned hereinabove.

[0037] Unless otherwise indicated in the text, the term substituted when referring to an aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic ring, arene, heteroarene refers to one of these moieties which also contain with one or more substituents, selected from the group of unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O).sub.2-aryl), haloaryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, cyano, nitro, acetyl, alkylcarbonyl, formyl, ethenyl (CH.sub.2CH), phenylethenyl (Ph-CHCH), arylethenyl (Aryl-CHCH), and substituents comprising ethenylenearylene moieties (e.g., Ar(CHCHAr).sub.z where z is 1-3. Specific, non-limiting examples of substituted aryl and substituted aryl ethenyl substituent are as follows where represents the point of attachment:

##STR00004##

[0038] One aspect of this invention is compound of structure (I), wherein R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R 3)(R 4), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group.

##STR00005##

[0039] In another aspect of said compound of structure (I) R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group.

[0040] In a further aspect, said above compound has structure (Ia), where R.sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R .sub.3 and R .sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group. In another aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In a further aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In a still further embodiment of this aspect of the invention the compound is one wherein L.sub.1 and L.sub.2 are both a direct valence bond.

##STR00006##

[0041] In another aspect, the compound of structure (I) has the more specific structure (Ib), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group. In another aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another more specific aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy.

##STR00007##

[0042] In a more specific embodiment of the compound of structure (Ib) it has structure (Ic). In one aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy. In another aspect R.sub.3 and R.sub.4 are ethyl. In another aspect R.sub.3 and R.sub.4 are methyl.

##STR00008##

[0043] In a more specific embodiment of the compound of structure (lb) it has structure (Id). In one aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy. In another aspect R.sub.3 and R.sub.4 are ethyl. In another aspect R.sub.3 and R.sub.4 are methyl.

##STR00009##

[0044] In a more specific embodiment of the compound of structure (lb) it has structure (Ie). In one aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy. In another aspect R.sub.3 and R.sub.4 are ethyl. In another aspect R.sub.3 and R.sub.4 are methyl.

##STR00010##

[0045] Another aspect of this invention is a polymer of structure (II) which has polydispersity ranging from 1 to about 1.1, wherein R.sub.1 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, an aryl, or an alkylenearyl (i.e. -alkylene-aryl); [0046] R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4) wherein, R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; [0047] L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; [0048] B is a direct valence bond, or a methylene spacer (CH.sub.2); and [0049] A is a styrenic polymer chain, or an acrylic polymer chain.

##STR00011##

[0050] Another aspect of the polymer of structure (II) is one wherein R.sub.1 is H; R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group and A is a styrenic polymer chain.

[0051] Another aspect of the polymer of structure (II) is one wherein it has structure (Ha), where R.sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group. In another aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In yet another aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy.

##STR00012##

[0052] In another aspect of this polymer it is any of the above embodiment of said polymer in which it has structure (Ha), wherein R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this polymer it is any of the above embodiment of said polymer in which it has structure (Ha), wherein R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In yet another aspect of this polymer it is any of the above embodiment of said polymer in which it has structure (Ha), wherein L.sub.1 and L.sub.2 are both a direct valence bond.

[0053] In another aspect of this polymer it is any of the above embodiment of said polymer in which it has structure (Ha), which has the more specific structure (IIb).

##STR00013##

[0054] In another aspect of the polymer of structure (II), it has structure (IIc), wherein R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group. In another aspect of this embodiment, R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In a further aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy.

##STR00014##

[0055] In another aspect of the polymer of structure (IIc), it has structure (IId). In one aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy. In another aspect R.sub.3 and R.sub.4 are ethyl. In another aspect R.sub.3 and R.sub.4 are methyl.

##STR00015##

[0056] In another aspect of the polymer of structure (IIc), it has structure (He). In one aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy. In another aspect R.sub.3 and R.sub.4 are ethyl. In another aspect R.sub.3 and R.sub.4 are methyl.

##STR00016##

[0057] In another aspect of the polymer of structure (II) R.sub.1 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl or a C-3 to C-8 cyclic alkyl, an aryl, an alkylenearyl (i.e. -alkylene-aryl); R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; A is an acrylic polymer chain.

##STR00017##

[0058] In another aspect of the polymer of structure (II) it has structure (IIf), wherein R .sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl; R .sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R .sub.3 and R .sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group. In another aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In yet another embodiment of this aspect, R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In still another aspect of this embodiment L.sub.1 and L.sub.2 are both a direct valence bond. In a further embodiment of this aspect it has structure (IIg).

##STR00018##

[0059] In another embodiment of the polymer of structure (II) it has structure (IIh), where R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group. In another more specific embodiment of this aspect R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another more specific embodiment of this aspect R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment L.sub.1 is a direct valence bond and the polymer of structure (II) has structure (Ili). In another aspect of this embodiment it has structure (IIj).

##STR00019##

[0060] In one aspect of the above described embodiments of this invention wherein said polymer has structures (II), said polymer a is a styrenic polymer having structure (III), where [0061] R.sub.e1 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, an aryl, or an alkylenearyl (i.e. -alkylene-aryl); R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); [0062] R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; [0063] L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; R.sub.5 is H, a C-1 to C-4 linear alkyl; R.sub.6 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; n is the number of repeat units; and further where said styrenic polymer has a polydispersity ranging from 1 to 1.1.

##STR00020##

[0064] In one aspect of the styrenic polymer of structure (III), Rei is H; R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group.

[0065] In one aspect of the styrenic polymer of structures (III) described above, it has structure (IIIa), where R.sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group.

##STR00021##

[0066] In one aspect of the styrenic polymer of structure (Ma), R .sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy.

[0067] In another aspect of the above described embodiments of the styrenic polymer of structure (Ma), R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In one aspect of this embodiment L.sub.1 and L.sub.2 are both a direct valence bond.

[0068] In another aspect of the above described styrenic polymer it has structure (IIIb); wherein the substituents R.sub.e1, R.sub.5, R.sub.6, R.sub.4, R.sub.3 may be varied in different embodiments and n and the polydispersity may be varied as described above for structures (III) and (Ma).

##STR00022##

[0069] In another aspect of the above described styrenic polymer it has structure (Mc), wherein the substituents R.sub.e1, R.sub.5, R.sub.6, R.sub.4, R.sub.3 and n and the polydispersity may be varied as described above for structures (III) and (Ma). In one specific embodiment of this aspect, R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group. In one specific embodiment of this aspect R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In yet another aspect of this embodiment it has structure (IIId) whose substituent may be varied as described above for this embodiment. In another aspect of this embodiment it has structure (Me).

##STR00023##

[0070] In another aspect of this invention the inventive polymer described above is an acrylic polymer having structure (IV), wherein R.sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl or a C-3 to C-8 cyclic alkyl; R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group; R.sub.7 is H or a C-1 to C-4 linear alkyl; R.sub.8 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl or a C-3 to C-8 cyclic alkyl; Ret is and end group selected from H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, or a C-3 to C-8 cyclic alkyl; n1 is the number of repeat units in said acrylate polymer; and further where said acrylic polymer has a polydispersity ranging from 1 to 1.1. In one aspect of this embodiment R.sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl; R.sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer. In another aspect of this embodiment, R .sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl; R .sub.2 is H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group.

##STR00024##

[0071] In another aspect, the above described acrylic polymer has structure (IVa); wherein the substituents R .sub.e2, R.sub.7, R.sub.8 and n1 and the polydispersity may be varied as described above for said acrylic polymer having structure (IV), and further where R .sub.alk is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl; R .sub.2 is H, or P(O)(R.sub.3)(R.sub.4); R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; L.sub.1 and L.sub.2 are independently a direct valence bond, or a C-1 to C-8 alkylene spacer group. In a further aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In another aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In a further aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In still another embodiment wherein L.sub.1 and L.sub.2 are both a direct valence bond. In still another embodiment, the polymer has structure (IVb).

##STR00025##

[0072] In another aspect, the above described acrylic polymer has structure (IVc); wherein the substituents R .sub.e2, R.sub.7, R.sub.8 and n1 and the polydispersity may be varied as described above in said acrylic polymer, R.sub.3 and R.sub.4 are independently an aryl, an alkylenearyl (i.e. -alkylene-aryl), a C-2 to C-8 alkyleneoxyalkyl (i.e. -alkylene-O-alkyl), a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and L.sub.1 is a direct valence bond, or a C-1 to C-8 alkylene spacer group. In one aspect of this embodiment R.sub.3 is a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy; and R.sub.4 is a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In still another aspect of this embodiment R.sub.3 and R.sub.4 are independently selected from a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy. In yet another aspect of the described acrylic polymer, L.sub.1 is a direct valence bond and L.sub.2 is a direct valence bond or a C-1 to C-8 alkylene spacer group, R .sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4), and the polymer has structure (IVd). In a more specific aspect of the embodiment where it has structure (IVc), it has structure (IVe). In a more specific embodiment where it has structure (IVd), it has structure (IVf), where R.sub.2 is H, a halide, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, or P(O)(R.sub.3)(R.sub.4).

##STR00026##

[0073] Another aspect of this invention is a composition which comprises any one of the above described inventive polymer and an organic spin casting solvent.

[0074] In the above embodiments of the novel compositions, the organic spin casting solvent is one which can dissolve said novel polymers and any other additional optional components as noted above. This organic spin casting solvent may be a single solvent or a mixture of solvents. Suitable solvents are organic solvent which may include, for example, a glycol ether derivative such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; a glycol ether ester derivative such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates such as ethyl acetate, n-butyl acetate and amyl acetate; carboxylates of di-basic acids such as diethyloxylate and diethylmalonate; dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxy carboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl-3-hydroxy propionate; a ketone ester such as methyl pyruvate or ethyl pyruvate; an alkyloxycarboxylic acid ester such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; a ketone derivative such as methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; a ketone ether derivative such as diacetone alcohol methyl ether; a ketone alcohol derivative such as acetol or diacetone alcohol; a ketal or acetal like 1,3 dioxalane and diethoxypropane; lactones such as butyrolactone; an amide derivative such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0075] The novel compositions, in addition to the polymer and the solvent, may contain surfactants as additives to facilitate coating.

[0076] Another aspect of said invention is novel compositions wherein said novel polymers are present in an amount of from about 0.1 wt % to about 10 wt % of the total weight of said composition including the organic spin casting solvent. In another aspect it is present in an amount of from about 0.1 wt % to about 2 wt %. In yet another embodiment it is present in an amount of from about 0.5 wt % to about 1.5 wt %. In yet another embodiment it is present in an amount of from about wt % to about 1.5 wt %. In yet another embodiment it is present in an amount of about 1 wt %.

[0077] Another aspect of this invention is a process of forming a pinning layer brush selectively on a substrate which comprises both metallic surface areas and a non-metallic surface area, comprising the steps: [0078] i) coating a composition as described above, on said substrate, forming a film, [0079] ii) baking said film at a temperature from about 120 C. to about 250 C. for about 1 minute to about 1 hour, to form a baked film, [0080] iii) washing said baked film with a solvent to remove ungrafted polymer, forming a pinning layer brush only on said metallic surface areas of said substrate.

[0081] Another aspect of the process comprising the steps i) to iii) is one wherein in step ii) said baking is done from about 1 minute to about 30 minutes. In yet another aspect of this embodiment in step ii) the film is baked at about 150 C. to about 170 C. In a further aspect of this embodiment, it is baked at about 180 C. In yet another aspect it is baked for about 30 minutes.

[0082] Another aspect of said process of forming a pinning layer brush selectively is one where said metallic surface areas are selected from the group consisting of Cu, Au, Ag, W, Ta, Nb, Fe, Ni, Co, Mo, Al, Pt, Rh, Pb, Cd, Ti, Zr, Hf, and Ru and said non-metallic surface areas are selected from the group consisting of Si, SiOx (silicon oxide), SiNx (silicon nitride), SiON (silicon oxynitride) and organic dielectric substrates.

[0083] Another aspect of this invention is a process comprising the steps; [0084] ia) coating a composition as described above, on a substrate which comprises both metallic surface areas and non-metallic surface areas, forming a film, [0085] iia) baking said film at a temperature from about 120 C. to about 250 C. for about 1 minute to about 1 hour, to form a baked film, [0086] iiia) washing said baked film with a solvent to remove ungrafted polymer, forming a grafted substrate wherein pinning layer brushes are only present on said metallic surface areas of said substrate, [0087] iva) coating said grafted substrate with a neutral layer composition, forming a neutral layer coating, [0088] va) curing said neutral layer coating, [0089] via) washing away, with a solvent, uncured neutral layer, leaving in said non-metallic areas of said substrate a neutral directing brush, forming on said substrate a chemoepitaxy directing layer, [0090] viia) coating said chemoepitaxy directing layer with a block copolymer solution, forming a coating of block copolymer, [0091] viiia) annealing said coating of block copolymer, to form a directed self-assembled film of the block copolymer on said chemoepitaxy directing layer.

[0092] Another aspect of the process comprising the step ia) to viiia) is one wherein in step iia) said baking is done from about 1 minute to about 30 minutes. In yet another aspect of this embodiment in step iia) the film is baked at about 150 C. to about 170 C. In a further aspect of this embodiment in it is baked at about 180 C. In yet another aspect it is baked for about 30 minutes.

[0093] Another aspect of the process comprising the step ia) to viiia) is one wherein for said substrate, said metallic surface areas are Tungsten and said non-metallic surface areas are silicon or silicon oxide.

[0094] Another aspect of the process comprising the step ia) to viiia) is one wherein said block copolymer is a block copolymer comprised of styrenic repeat units and alkyl acrylic repeat units.

[0095] Another aspect of the process comprising the step ia) to viia) is one wherein said block copolymer is either an AB diblock copolymer of alkyl acrylic repeat unit and styrenic repeat units, or an ABA triblock copolymer of alkyl acrylic repeat unit and styrenic repeat units.

[0096] Specific non-limiting examples of block copolymers are 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), or a combination comprising at least one of the above described block copolymers. All these polymeric materials share in common the presence of at least one block which is rich in repeat units resistant to etching techniques typically employed in manufacturing IC devices and at least one block which etches rapidly under these same conditions. This allows for the self-assembled polymer pattern to transfer onto the substrate.

[0097] Another aspect of this invention is the use of a compound of formula (I) as described above for the preparation of a polymer as described above.

[0098] Another aspect of this invention is the use of a polymer or composition as described above for forming a pinning layer brush on a substrate.

Examples

[0099] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. The examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0100] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter, including the descriptions provided by the following examples, covers the modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

Synthesis of DPE-phosphonate (I to IV)

Example 1: Synthesis of Diethyl 4-(1,1-diphenylethylene) phosphonate (DPE-I) (Described in Scheme 1)

[0101] A 1 L 2-neck flask and magnetic bar were well dried in an oven under vacuum. 82 g (223 mmol) of methyltriphenylphosphonium bromide was added, dried at vacuum and then charged with nitrogen. 600 mL of THF was added and the reaction vessel was cooled with an ice bath. After 156 mL of n-butyllithium (1.6 M in hexane, 249 mmol) was slowly added to the vessel under ice bath cooling, the vessel temperature naturally increased to RT by removal of ice bath. The reaction was maintained for one hour until most solid disappeared (Produced ylide is soluble in THF). During ylide reaction, the solution of 50 g (192 mmol) of 4-bromobenzophenone in 100 mL of THF in a separate 2-neck flask was prepared. 4-bromobenzophenone solution was transferred into ylide reaction vessel by cannula under ice bath and the reaction was stirred for 1 or 2 hours. The reaction was quenched with water and diluted with ethyl acetate. Mixture was extracted with 1% aq. HCl and aq. NaCl solution and dried with MgSO.sub.4. After filtering off MgSO.sub.4, the solution was concentrated by rotavap. White solid triphenylphosphonium oxide was precipitated by adding 2/1 Hexane-to-ethyl acetate and filtered off. Then solution was concentrated again. 43 g (92.7%) of colorless liquid product, 4-(1,1-diphenylethylene)-Br (I) was obtained by silica column chromatography with hexane followed by solvent evaporation and drying under vacuum. 13 g (51.7 mmol) of 4-Bromo-DPE (I) was added to a 500 mL two-neck flask and charged with nitrogen and dissolved in 200 mL of THF. 35.5 mL (56.9 mmol) of 1.6 M nBuLi was slowly added at 78 C. bath and the reaction was left for 10 min at same temperature. In a separate 500 mL 2-neck flask, 9.7 mL (67.2 mmol) of diethyl chlorophosphate was added under nitrogen. 100 mL of THF was added and solution was cooled down to 78 C. Lithiated DPE solution was transferred to the separate diethylchlorophosphate in THF via cannula for 20 minutes. The solution was stirred for 30 min, then diluted with ethyl acetate and washed with water. The water layer was extracted with ethyl acetate and combined organic layers were dried with MgSO.sub.4. After filtering to remove MgSO.sub.4, the organic layer was concentrated by evaporating solvents. 12.5 g (76.3%) of light-yellow oil was obtained by silica column chromatography through 50% hexane in ethyl acetate. .sup.1H NMR (400 MHz, CDCl.sub.3), ppm(), 7.81 (1H, dd, J=6.0 Hz), 7.79 (1H, dd, J=6.0 Hz), 7.47-7.44 (2H, m), 7.37-7.32 (5H, m), 5.57 (1H, s), 5.55 (1H, s), 4.21-4.12 (4H, m), 1.37 (6H, t, J=5.3 Hz).

Example 2: Synthesis of Dimethyl 4-(1,1-diphenylethylene) phosphonate (DPE-II)) (Described in Scheme 2)

[0102] Synthesis was similarly followed by the procedure of example 1 except using dimethyl chlorophosphate instead of diethyl chlorophosphate. .sup.1H NMR (400 MHz, CDCl.sub.3), ppm(), 7.81 (1H, dd, J=6.1 Hz), 7.77 (1H, dd, J=6.1 Hz), 7.49-7.46 (2H, m), 7.38-7.32 (5H, m), 5.58 (1H, s), 5.55 (1H, s), 3.83 (3H, s), 3.80 (3H, s).

Example 3: Synthesis of Phenyl Ethyl 4-(1,1-diphenylethylene) phosphinate (DPE-III) (Described in Scheme 3)

[0103] 25 g of diethyl 4-(1,1-diphenyleneethylene) phosphate (DPE-I) was added to 500 mL flask and oxalyl chloride was slowly added followed by a few drops of dimethylformamide at ice bath. The reaction solution was kept stirring overnight at 50 C. by letting gas evolve in fume hood. After removing all residue, excessive oxalyl chloride and solvent by evaporation, phenylmagnesium bromide (2M in diethyl ether) was slowly added in THF solution at 78 C. and the temperature was raised to RT gradually. The solution was diluted with ethyl acetate and washed with water. Water layer was extracted with ethyl acetate and combined organic layers were dried with MgSO.sub.4. Filtered organic layer by removing MgSO.sub.4 was concentrated by evaporating solvents. 14.5 g of light-yellow oil was obtained by silica column chromatography with 30% hexane in ethyl acetate. .sup.1H NMR (400 MHz, CDCl.sub.3), ppm(), 7.89-7.77 (4H, m), 7.57-7.42 (5H, m), 7.36-7.30 (5H, m), 5.55 (1H, s), 5.53 (1H, s), 4.19-4.12 (2H, m), 1.39 (3H, t, J=9.18 Hz).

Example 4: Synthesis of Ethyl Ethyl 4-(1,1-diphenylethylene) phosphinate (DPE-IV)) (Described in Scheme 4)

[0104] Synthesis was similarly followed by the procedure of example 2 using ethylmagnesium chloride (2M in diethyl ether) instead of phenylmagnesium bromide. .sup.1H NMR (400 MHz, CDCl.sub.3), ppm(), 7.77 (1H, dd, J=6.18 Hz), 7.75 (1H, dd, J=6.18 Hz), 7.48 (1H, dd, J=6.13 Hz), 7.47 (1H, dd, J=6.13 Hz), 7.40-7.32 (5H, m), 5.57 (1H, s), 5.56 (1H, s), 4.17-4.11 (1H, m), 3.95-3.89 (1H, m), 2.0-1.87 (3H, m), 1.34 (3H, t, J=5.3 Hz), 1.18 (3H, t, J=5.8 Hz), 1.13 (3H, t, J=5.8 Hz).

##STR00027##

##STR00028##

##STR00029##

##STR00030##

##STR00031##

##STR00032##

##STR00033##

##STR00034##

##STR00035##

##STR00036##

##STR00037##

Example 5: Synthesis of PMMA Capped with Diethyl 4-(1,1-Diphenylethylene) Phosphonate (PMMA-A) (described in Scheme 5)

[0105] 25 mL of MMA (alumina column passed and degassed) was taken into a calibrated ampule provided with two Rota flow stopcocks and 19F connecting glass joint. After careful degassing under dynamic vacuum while MMA kept at low temperature, desired amount of MMA (25 mL) of monomer was collected and ampule was closed under vacuum with stopcock. In the glovebox, required amount of diethyl 4-(1,1-diphenylethylene) phosphonate (DPE-I) was weighed (1.2 molar excess with respect to Sec-BuLi) in a vial and dissolved in 5-10 mL toluene and transferred in a calibrated ampule provided with single Rota flow-stopcock and 19F joint. This solution was promptly titrated with dilute hexylDPE-Li solution (toluene solution containing 2 wt.-% of 1,1-diphenylethylene and an equimolar amount of sec-butyllithium, which form an anionic complex) until a pale orange/red color was persistence. Solution color got weaker and then maintained to yellow. After closing the stopcock ampule was removed from glovebox. Both MMA ampule and DPE ampule were attached to the flask using glass joints and yellow grease. The required amount of LiCl (10 times excess with respect to Sec-BuLi) was weighed and quickly added to the flask and closed with three-way septum adaptor, which was connected with a rubber tubing for access to vacuum/argon. Vacuum was applied to the flask and LiCl was dried using heat-gun. After 10 min flask was brought to RT and filled with argon. Under positive pressure 250 mL dry THF was transferred to the flask via cannula transfer. The flask temperature was lowered to 78 C. using dry ice/acetone bath. LiCl/THF solution was titrated with Sec-BuLi (1.4M) until a persistent lemon yellow/yellow was obtained. While the flask was at 78 C., MMA ampule was filled with argon, and pressure equilibrating stopcock was closed. After 5 min, dry ice/acetone bath was removed and flask was brought to RT. It takes 15-30 min for the decay of yellow color/sec-BuLi (complete decay of excess Sec-BuLi was observed). After a colorless solution was obtained, the flask temperature was lowered to 78 C. and required amount of sec-BuLi to generate active DPE initiator was added using airtight glass syringe. Then titrated 4-diethylphosphate-DPE solution was added by opening Rota flow stopcock, this results in color change from yellow to dark red, a color of active DPE-Li initiator. After 2-3 min, while the initiator solution was kept under rapid stirring MMA was added dropwise within 3-6 min. The reaction was continued further for 10 min and terminated with 3 mL degassed methanol. Flask was brought to RT and polymer was recovered by precipitation in water mixed with several drops of HCl. The polymer was dissolved in ethyl acetate followed by washing with water and then precipitated into hexane. The precipitated polymer was filtered and dried in vacuum at 60 C. and gave quantitative yield of 4-diethylphosphate capped PMMA-A with Mn=4.8 k, PDI=1.05.

Example 6: Synthesis of PMMA Capped with Dimethyl 4-(1,1-diphenylethylene) Phosphonate (PMMA-B) (described in Scheme 6)

[0106] Synthesis was similarly followed by the procedure of example 5 using dimethyl 4-(1,1-diphenylethylene) phosphonate instead of diethyl 4-(1,1-diphenylethylene) phosphonate. Mn=4.7 k, PDI=1.06.

Example 7: Synthesis of PMMA Capped with Phenyl Ethyl 4-(1,1-diphenylethylene) Phosphinate (PMMA-C) (described in Scheme 7)

[0107] Synthesis was similarly followed by the procedure of example 5 using phenyl ethyl 4-(1,1-diphenylethylene) phosphinate instead of dimethyl 4-(1,1-diphenylethylene) phosphonate. Mn=6.5 k, PDI=1.04.

Example 8: Synthesis of PMMA Capped with 4-(1,1-diphenylethylene) Phosphonic Acid (PMMA-D) (described in Scheme 8)

[0108] PMMA capped with dimethyl 4-(1,1-diphenylethylene) phosphonate (PMMA-B) was treated with iodotrimethylsilane at RT for overnight and then precipitated into water. The filtered polymer was dried at vacuum oven. Mn=11.3 k, PDI=1.06.

Example 9: Synthesis of PS Capped with Diethyl 4-(1,1-diphenylethylene) phosphonate (PS-A) (Described in Scheme 9)

[0109] Step 1: 25 mL of Styrene (column passed and degassed) was taken into a calibrated ampule provided with two Rota flow stopcocks and 19F connecting glass joint. After careful degassing under dynamic vacuum while Styrene kept at low temperature, the 25 mL styrene monomer was collected, and ampule was closed under vacuum with stopcock. In the glovebox, diethyl 4-(1,1-diphenylethylene) phosphonate (DPE-I) was weighed (1.2 molar excess with respect to Sec-BuLi) in a vial and dissolved in 5-10 mL toluene and transferred in a calibrated ampule provided with single Rota flow-stopcock and 19F joint. This solution was promptly titrated with dilute hexylDPE-Li solution until a pale orange color was persistent. After closing the stopcock, ampule was removed from glovebox. Both the styrene ampule and DPE ampule were attached to the flask using glass joints and yellow grease. Vacuum was applied to the flask and dried using heat-gun. After 10 min, the flask was brought to RT and filled with argon. Under positive pressure, 250 mL dry THF was transferred to the flask via cannula transfer. The flask temperature was lowered to 78 C. using dry ice/acetone bath. THF solution was titrated with Sec-BuLi (1.4M) until a persistent lemon yellow/yellow color was obtained. While the flask was at 78 C., Styrene ampule was filled with argon, and pressure equilibrating stopcock was closed. After 5 min, dry ice/acetone bath was removed and flask was brought to RT. It takes 15-30 min for the decay of yellow color/sec-BuLi (complete decay of excess Sec-BuLi was observed). After a colorless solution was obtained, flask temperature was lowered to 78 C. and 7.9 mL of sec-BuLi (1.4M) initiator was added using airtight glass syringe. After 2-3 min, while the initiator solution was kept under rapid stirring, styrene was added dropwise within 3-6 min. Reaction was continued further for 30 minutes. Then, diethyl 4-(1,1-diphenylethylene) phosphonate was added from the ampule, the deep red color formed immediately indicated the living anion of DPE moiety. After 1 minute, the reaction mixture was terminated with 3 mL degassed methanol. The flask was brought to RT and the polymer was recovered by precipitation in 2 L of isopropanol. The precipitated polymer was filtered and dissolved in ethyl acetate and washed with water. The organic layer was precipitated to isopropanol and the polymer was dried in vacuum at 70 C. and gave quantitative yield of PS capped with diethyl 4-(1,1-diphenylethylene) phosphonate (PS-A), with Mn=9 k, PDI=1.08.

Example 10: Synthesis of PS Capped with Ethyl Ethyl 4-(1,1-diphenylethylene) phosphonate (PS-B) (Described in Scheme 10)

[0110] Synthesis was similarly followed by the procedure of example 9 using ethyl ethyl 4-(1,1-diphenylethylene) phosphinate instead of diethyl 4-(1,1-diphenylethylene) phosphonate. Mn=PDI=1.09.

Example 11: 9: Synthesis of PS Capped with Dimethyl 4-(1,1-diphenylethylene) phosphonate (PS-C) (Described in Scheme 11)

[0111] Synthesis was similarly followed by the procedure of example 9 using dimethyl 4-(1,1-diphenylethylene) phosphonate instead of diethyl 4-(1,1-diphenylethylene) phosphonate. Mn=10.6 k, PDI=1.07.

Brush Performance Test

[0112] The brush polymer was dissolved in PGMEA with 1 wt % solid content. 1% solution was coated at 1500 rpm on each tungsten and silicon oxide wafers and they were baked at 110 C./5 min under nitrogen and unreacted brush was rinsed away with PGMEA. After wafers were baked at 230 C. for 5 min under nitrogen, the water contact angle was measured by dropping water on each wafer.

TABLE-US-00001 TABLE 1 WCA WCA C % by C % Contrast () () XPS by XPS on W Samples on W on SiOx on W on SiOx vs. SiOx Ex 5 PMMA-A 64 56 9.1 0.26 Good Ex 6 PMMA-B 67 58 7.6 0.4 Good Ex 7 PMMA-C 62 44 3.8 0.15 Good Ex 9 PS-A 90 65 NA NA Good

[0113] PMMA-A, -B and -C brushes in the table shows good contrast when judging from WCA and XPS on between tungsten metal and silicon oxide by indicating high carbon content on W but much small carbon content on SiOx. PS-A clearly showed strong difference of water contact angle on both wafers indicating it is more hydrophobic on tungsten wafer but hydrophilic on silicon oxide.

[0114] Although the disclosed and claimed subject matter has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the disclosed and claimed subject matter.