POLYMER BRUSHES WITH CHAIN-ENDS FUNCTIONALIZED WITH METAL COORDINATING TWO HETERO ELEMENTS FOR SELECTIVE SURFACE MODIFICATION

Abstract

##STR00001##

A polymer of structure (A) with two end group R.sub.3p, and R.sub.4p, and a polymer chain (R) which has either repeat units of structures (Ip) or (IIp). R.sub.3p, is either a C-1 to C-8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIpI). R.sub.3p is a C-1 to C-8 alkyl if the repeat unit is (IIp). R.sub.3p is structure (IIIp) or structure (IIIp1) if the repeat unit has (Ip). R4p is either a terminating moiety such as H, a moiety of structure (IVp), a moiety of structure (IVp1), or a moiety of structure (IVp2). R.sub.3p and R.sub.4p cannot respectively, both simultaneously, be moieties of structure (IIIp) and (IVp), simultaneously be moieties of structure (IIIp) and (IVp1), or simultaneously be moieties of structure (IIIp) and (IVp2). The polymer of structure (A) must contain, one grafting end group moiety selected from structures (IIIp), (IVp), (IVp1) or (IVp2). Composition of this with a solvent are used in DSA processing.

Claims

1. A polymer of structure (A), comprising two end groups R.sub.3p and R.sub.4p, and a polymer chain (R) comprising either a repeat unit of structure (Ip) or a repeat unit of structure (lip), wherein end group R.sub.3p, which is derived from an anionic initiator, is either a C-1 to C-8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIp1), but where R.sub.3p can only be selected from a C-1 to C-8 alkyl if the in the polymer chain (R) the repeat unit is (IIp), and further where R.sub.3p can only be selected from a moiety of structure (IIIp) or structure (IIIp1) if in the polymer chain (R) the repeat unit is of structure (Ip), end group R.sub.4p is either a moiety selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(O)), a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si), a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi), a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si), silane (H.sub.3Si), and a benzylic moiety, a moiety of structure (IVp), a moiety of structure (IVp1) or a moiety of structure (IVp2), further end groups R.sub.3p and R.sub.3p cannot respectively, both simultaneously be moieties of structure (IIIp) and (IVp), both simultaneously be moieties of structure (IIIp) and (IVp1), or both simultaneously be moieties of structure (IIIp) and (IVp2), but where said polymer of structure (A) must contain one end group moiety selected from structures (IIIp), (IVp), (IVp1) or (IVp2), in said repeat unit of structure (Ip) R.sub.m1 is a C-1 to C-8 alkyl, R.sub.1, is a C-1 to C-8 alkyl, and n1 is the number of this repeat units in polymer chain (R); in said repeat unit of structure (lip) R.sub.2 is H or a C-1 to C-8 alkyl, R.sub.2p is H or a C-1 to C-8 alkyl, n2 is the number of this repeat unit polymer chain (R); and in structure (IIIp), R.sub.1 is a chelating group, located at the para or meta position, selected from a phosphinothioic moiety of structure (Ia) an aminosulfonyl moiety of structure (Ib), a phosphonamide moiety of structure (Ic), where *** designates the attachment point of this end group moiety to the polymer of structure (A), wherein in said phosphinothioic moiety of structure (Ia), 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 a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which R.sub.9 and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and designates the attachment point of this moiety to an end group moiety of structure of (IIIp), in said aminosulfonyl moiety of structure (Ib), R.sub.5 and R.sub.6, are independently a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and said dialkyl amino moiety, N(R.sub.9)(R.sub.10), and designates the attachment point of this moiety to an end group moiety of structure of (IIIp), in said phosphonamide moiety of structure (Ic), R.sub.7 is said dialkyl amino moiety, N(R.sub.9)(R.sub.10), and R.sub.8 is selected from the group consisting of 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 designates the attachment point of this moiety to an end group moiety of structure of (IIIp), R.sub.2 is selected from the group consisting of H, 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, a C-3 to C-8 cyclic alkyloxy; a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic), and R.sub.15 is a C-1 to C-8 alkyl, and R.sub.e1 and R.sub.e2 are individually selected from H, a C-1 to C-8 alkyl, and a C-1 to C-8 alkoxy, in structure (IIIp1), R.sub.e1 and R.sub.e2 are individually selected from H, 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, a C-3 to C-8 cyclic alkyloxy, and R.sub.15 is a C-1 to C-8 alkyl, and ** designates the attachment point of this end group moiety to the polymer of structure (A), in structure (IVp), R.sub.12 is H or a C-1 to C-4 alkyl, R.sub.11 is a phosphinothioic moiety of structure (IIa), wherein designates the attachment point of this phosphinothioic moiety to structure (IVp), wherein R.sub.13 and R.sub.14 are independently selected from the group consisting of 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, a C-3 to C-8 cyclic alkyloxy; and a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which Rs and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, L.sub.1 is a linking moiety selected from the group consisting of a direct valence bond, a C-2 to C-8 alkylene moiety(-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein * designates the attachment points of the L.sub.1 organic linking moiety to the phosphorous in structure (IIa), and * designates where L.sub.1 within the moiety R.sub.11 is attached to carbonyloxy of structure (IVp), R.sub.17 is selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(O)), a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si), a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi), a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si), silane (H.sub.3Si), and a benzylic moiety, and ** designates the attachment point of this end group moiety to the polymer of structure (A), in structure (IVp1), L is either a direct valence bond or a linking group selected from a C-1 to C-8 linear alkylene, C-3 to C-8 branched alkylene, and a C-5 to C-8 cyclic alkylene, an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), and an alkylenearyl moiety (*-alkylene-aryl-**), wherein * designates the attachment points of the L linking moiety to the phosphorous in structure (IVp1), and * designates where L is attached to said polymer of structure (A), and Rs and Rs1 are individually selected from a C-1 to C-8 alkoxy or a C-1 to C-8 alkyl, and where ** designates the attachment point of this end group moiety to the polymer of structure (A), in structure (IVp2), R.sub.1 is a chelating group, located at the para or meta position, selected from said phosphinothioic moiety of structure (Ia) said aminosulfonyl moiety of structure (Ib), and said phosphonamide moiety of structure (Ic), R.sub.2 is selected from the group consisting of H, 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, a C-3 to C-8 cyclic alkyloxy; a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic), R.sub.18 is selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(O)), a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si), a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi), a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si), silane (H.sub.3Si), and a benzylic moiety, and where *** designates the attachment point of this end group moiety to the polymer of structure (A), Further, said polymer of structure (A) has a M.sub.n ranging from about 4000 to about 7000, and has a polydispersity ranging from 1 to about 1.15; ##STR00049## ##STR00050## ##STR00051##

2. The polymer of claim 1, which has structure (A-1), ##STR00052##

3. The polymer of claim 1, which has structure (A-2), ##STR00053##

4. The polymer of claim 1, which has structure (A-2a) ##STR00054##

5.-6. (canceled)

7. The polymer of claim 1, which has structure (A-2d), ##STR00055##

8.-9. (canceled)

10. The polymer of claim 1, which has structure (A-2g), ##STR00056##

11.-12. (canceled)

13. The polymer of claim 1, which has structure (A-3) ##STR00057##

14.-17. (canceled)

18. The polymer of claim 1, which has structure (A-3a) wherein R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxy and n is an integer ranging from 1 to 7, ##STR00058##

19. (canceled)

20. The polymer of claim 1, which has structure (A-3c), wherein R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxy, and n is an integer ranging from 0 to 7, ##STR00059##

21. (canceled)

22. The polymer of claim 1, which has structure (A-4), ##STR00060##

23.-31. (canceled)

32. The polymer of claim 1, which has structure (B-1), wherein R.sub.3p is a C-1 to C-8 alkyl, ##STR00061##

33. The polymer of claim 1, which has structure (B-1a), wherein R.sub.3p is a C-1 to C-8 alkyl, ##STR00062##

34.-41. (canceled)

42. The polymer of claim 1, which has structure (B-2), ##STR00063##

43.-50. (canceled)

51. The polymer of claim 1, which has structure (B-3), ##STR00064##

52. The polymer of claim 1, which has structure (B-3a) ##STR00065##

53.-54. (canceled)

55. The polymer of claim 1, which has structure (B-3d), ##STR00066##

56.-57. (canceled)

58. The polymer of claim 1, which has structure (B-3g), ##STR00067##

59.-60. (canceled)

61. A composition comprising a polymer of claim 1 and an organic spin casting solvent.

62. A composition comprising a polymer of claim 2 and an organic spin casting solvent.

63. A composition comprising a polymer of claim 3 and an organic spin casting solvent.

64. A composition comprising a polymer of claim 13 and an organic spin casting solvent.

65. A composition comprising a polymer of claim 22 and an organic spin casting solvent.

66. A composition comprising a polymer of claim 32, and an organic spin casting solvent.

67. A composition comprising a polymer of claim 33 and an organic spin casting solvent.

68. A composition comprising a polymer of claim 42 and an organic spin casting solvent.

69. A composition comprising a polymer of claim 51 and an organic spin casting solvent.

70. A process of forming a pinning layer brush selectively on a substrate which comprises both metallic surface areas and non-metallic surface areas, comprising the steps; i) coating the composition of claim 61 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.

71. (canceled)

72. A process comprising the steps; ia) coating a composition according of claim 61 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 brush 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 a neutral directing brush, forming on said substrate a chemoepitaxy directing layer, viia) coating on 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.

73.-75. (canceled)

76. A compound of structure (1), wherein R.sub.1 is a chelating group located at the meta or para position selected from a phosphinothioic moiety of structure (Ia) an aminosulfonyl moiety of structure (Ib), a phosphonamide moiety of structure (Ic) wherein * designates the attachment point of these moieties to said compound of structure (1), wherein in said phosphinothioic moiety of structure (Ia), 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 a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which Re and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, in said aminosulfonyl moiety of structure (Ib), R.sub.5 and R.sub.6, are independently a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and said dialkyl amino moiety, N(R.sub.9)(R.sub.10), in said phosphonamide moiety of structure (Ic), R.sub.7 is said dialkyl amino moiety, N(R.sub.9)(R.sub.10), and R.sub.8 is selected from the group consisting of 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, R.sub.2 is a substituent, located at the meta or para positions which is selected from the group consisting of H, 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, a C-3 to C-8 cyclic alkyloxy; a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic) ##STR00068##

77.-95. (canceled)

96. A compound of structure (II), wherein R.sub.11 is a phosphinothioic moiety of structure (IIa), wherein * designates the attachment point of this moieties to said compound of structure (II), wherein R.sub.13 and R.sub.14 are independently selected from the group consisting of 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, a C-3 to C-8 cyclic alkyloxy; and a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which R.sub.9 and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl; L.sub.1 is a linking moiety selected from the group consisting of a direct valence bond, a C-2 to C-8 alkylene moiety(-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein * designates the attachment points of the L.sub.1 organic linking moiety to the phosphorous in structure (IIa), and * designates where L.sub.1 within the moiety R.sub.1 is attached to the carbonyloxy of compound (II), R.sub.12 is H or a C-1 to C-4 alkyl,

97.-125. (canceled) ##STR00069##

Description

DETAILED DESCRIPTION

[0036] 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.

[0037] 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.

[0038] 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, unless stated otherwise. 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 (alkoxy), have the same carbon number ranges unless otherwise indicated. The same criteria apply to the designation C-1 to C4 alkyl. 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.

[0039] 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. The criteria for establishing the nature of the alkyl in C-1 to C-8 alkoxy or C-1 to C4 alkoxy are the same as previously described for alkyl moieties.

[0040] Halo or halide refers to a halogen, F, Cl, Br or I which is linked by one bond to an organic moiety.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.2=CH), 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 point of attachment;

##STR00006##

Inventive Polymers

[0045] One aspect of this invention is a polymer of structure (A), comprising two end groups R.sub.3p and R.sub.4p, and a polymer chain (R) comprising either a repeat unit of structure (Ip) or a repeat unit of structure (Ip), wherein end group R.sub.3p, which is derived from an anionic initiator, is either a C-1 to C-8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIp1), but where R.sub.3p can only be selected from a C-1 to C-8 alkyl if the in the polymer chain (R) the repeat unit is (IIp), and further where R.sub.3p can only be selected from a moiety of structure (IIIp) or structure (IIIp1) if in the polymer chain (R) the repeat unit is of structure (Ip). End group R.sub.4p is either a moiety selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(O)), a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si), a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi), a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si), silane (H.sub.3Si), and a benzylic moiety, a moiety of structure (IVp), a moiety of structure (IVp1), or a moiety of structure (IVp2), Further, end groups R.sub.3p and R.sub.4p, cannot respectively, both simultaneously be moieties of structure (IIIp) and (IVp), both simultaneously, be moieties of structure (IIIp) and (IVp1), or both simultaneously be moieties of structure (IIIp) and (IVp2), but where said polymer of structure (A) must contain one end group moiety selected from structures (IIIp), (IVp), (IVp1) or (IVp2).

[0046] In said polymer of structure (A), in the repeat unit of structure (Ip) R.sub.m1 is a C-1 to C-8 alkyl, R.sub.1p is a C-1 to C-8 alkyl, and n1 is the number of this repeat units in polymer chain (R).

[0047] In said polymer of structure (A), in the repeat unit of structure (IIp), R.sub.m2 is H or a C-1 to C-8 alkyl, R.sub.2 is H or a C-1 to C-8 alkyl, n2 is the number of this repeat unit in polymer chain (R).

[0048] Further, in said polymer of structure (A), in structure (IIIp), R.sub.1 is a chelating group, located at the para or meta position, selected from a phosphinothioic moiety of structure (Ia) an aminosulfonyl moiety of structure (Ib), a phosphonamide moiety of structure (Ic), where *** designates the attachment point of this end group moiety to the polymer of structure (A).

[0049] Further, in said phosphinothioic moiety of structure (Ia), 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 a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which R.sub.9 and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and * designates the attachment point of this moiety to an end group moiety of structure of (IIIp).

[0050] Further, in said aminosulfonyl moiety of structure (Ib), R.sub.5 and R.sub.6, are independently a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and said dialkyl amino moiety, N(R.sub.9)(R.sub.10), and * designates the attachment point of this moiety to an end group moiety of structure of (IIIp).

[0051] Further, in said phosphonamide moiety of structure (Ic), R.sub.7 is said dialkyl amino moiety, N(R.sub.9)(R.sub.10), and R.sub.8 is selected from the group consisting of 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 * designates the attachment point of this moiety to an end group moiety of structure of (IIIp).

[0052] Further, in structure (IIIp), R.sub.2 is selected from the group consisting of H, 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, a C-3 to C-8 cyclic alkyloxy; a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic), and R.sub.15 is a C-1 to C-8 alkyl, and R.sub.e1 and R.sub.e2 are individually selected from H, a C-1 to C-8 alkyl, and a C-1 to C-8 alkoxy.

[0053] Further, in said polymer of structure (A), in structure (IIIp1) R.sub.e1 and R.sub.e2 are individually selected from H, 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, a C-3 to C-8 cyclic alkyloxy, and R.sub.15 is a C-1 to C-8 alkyl, and *** designates the attachment point of this end group moiety to the polymer of structure (A).

[0054] Further, in said polymer of structure (A), in structure (IVp), R.sub.12 is H or a C-1 to C4 alkyl, R.sub.11 is a phosphinothioic moiety of structure (IIa), ** * designates the attachment point of this end group moiety to the polymer of structure (A), L.sub.1 is a linking moiety selected from the group consisting of a direct valence bond a C-2 to C-8 alkylene moiety(-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** designates the attachment points of the L.sub.1 organic linking moiety to the phosphorous in structure (IIa), and * designates where L.sub.1 within the moiety R.sub.11 is attached to carbonyloxy of structure (IVp), and R.sub.17 is selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(O)), a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si), a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi), a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si), silane (H.sub.3Si), and a benzylic moiety. In structure (IIa), * designates the attachment point of this phosphinothioic moiety to structure (IVp).

[0055] R.sub.13 and R.sub.14 are independently selected from the group consisting of 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, a C-3 to C-8 cyclic alkyloxy; and a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which R.sub.9 and R.sub.10 are independently selected from 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.

[0056] Further, in said polymer of structure (A), in structure (IVp1), L is either a direct valence bond or a linking group selected from a C-1 to C-8 linear alkylene, C-3 to C-8 branched alkylene, and a C-5 to C-8 cyclic alkylene, an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), and an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** designates the attachment points of the L linking moiety to the phosphorous in structure (IVp1), and * designates where L is attached to said polymer of structure (A), and Rs and Rs1 are individually selected from a C-1 to C-8 alkoxy or a C-1 to C-8 alkyl and further, *** designates the attachment point of this end group moiety to the polymer of structure (A).

[0057] Further, in said polymer of structure (A), in structure (IVp2), R.sub.1 is a chelating group, located at the para or meta position, selected from said phosphinothioic moiety of structure (Ia) said aminosulfonyl moiety of structure (Ib), and said phosphonamide moiety of structure (Ic), and R.sub.2 is selected from the group consisting of H, 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, a C-3 to C-8 cyclic alkyloxy; a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Tb), and a phosphonamide of structure (Ic), R.sub.18 is selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(O)), a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si), a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi), a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si), silane (H.sub.3Si), and a benzylic moiety, and where *** designates the attachment point of this end group moiety to the polymer of structure (A).

[0058] Further, said polymer of structure (A) has a M.sub.n ranging from about 4000 to about 7000 and has a polydispersity ranging from 1 to about 1.15.

##STR00007## ##STR00008##

[0059] In one aspect of the inventive polymer, described herein, when the end group R.sub.p it not either of the chelating moieties (IVp), (IVp1) or (IVp2) it is H. In another aspect of this embodiment, R.sub.4p is a C-1 to C-8 alkyl. In another aspect of this embodiment, R.sub.p is a C-1 to C-8 alkylcarbonyl (alkyl-C(O)). In another aspect of this embodiment, R.sub.4p is a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si). In another aspect of this embodiment, R.sub.4p is a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi). In another aspect of this embodiment, R.sub.4p is a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si). In another aspect of this embodiment, R.sub.4p is a silane (H.sub.3Si). In another aspect of this embodiment, R.sub.4p is a benzylic moiety.

[0060] In one aspect of the inventive polymer, when the chelating moiety (IVp) is present R.sub.17 is H. In another aspect of this embodiment, R.sub.17 is a C-1 to C-8 alkyl. In another aspect of this embodiment, In another aspect of this embodiment, R.sub.17 is a C-1 to C-8 alkylcarbonyl (alkyl-C(O)). In another aspect of this embodiment, R.sub.17 is a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si). In another aspect of this embodiment, R.sub.17 is a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi). In another aspect of this embodiment, R.sub.17 is a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si). In another aspect of this embodiment, R.sub.17 is a silane (H.sub.3Si). In another aspect of this embodiment, R.sub.17 is a benzylic moiety.

[0061] In one aspect of the inventive polymer, when the chelating moiety (IVp2) is present, R.sub.18 is H. In another aspect of this embodiment, R.sub.18 is a C-1 to C-8 alkyl. In another aspect of this embodiment, R.sub.18 is a C-1 to C-8 alkylcarbonyl (alkyl-C(O)). In another aspect of this embodiment, R.sub.18 is a C-1 to C-8 trialkylsilyl ((alkyl).sub.3Si). In another aspect of this embodiment, R.sub.18 is a C-1 to C-8 dialkysilyl ((alkyl).sub.2HSi). In another aspect of this embodiment, R.sub.18 is a C-1 to C-8 monoalkylsilyl ((alkyl)H.sub.2Si). In another aspect of this embodiment, R.sub.18 is a silane (H.sub.3Si). In another aspect of this embodiment, R.sub.18 is a benzylic moiety.

[0062] In one aspect of the inventive polymer of structure (A), it has the more specific structure (A-1).

##STR00009##

[0063] In one aspect of the inventive polymer of structure (A-1), it has structure (A-2). In one aspect of this embodiment R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl.

[0064] In yet another aspect of these embodiments, R.sub.2 is H.

##STR00010##

[0065] In another aspect of the inventive polymer of structures (A-1) or (A-2), it has structure (A-2a). In another embodiment of this structure, it has structure (A-2b). In one aspect of these embodiments, R.sub.3 and R.sub.4 are independently selected from a C-1 to C4 alkoxy or a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.3 and R.sub.4 are independently selected from a C-1 to C4 alkoxy. In another aspect of these embodiments, R.sub.3 and R.sub.4 are independently selected from a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.3 and R.sub.4 are both ethoxy. In another aspect of these embodiments, R.sub.3 and R.sub.4 are both methoxy. In yet another embodiment of this structure it has structure (A-2c). In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In yet another aspect of these embodiments, R.sub.2 is H.

##STR00011##

[0066] In another aspect of the inventive polymer of structures (A-1) or (A-2), it has structure (A-2d). In another aspect of this embodiment, it has structure (A-2e). In yet another embodiment of this structure it has structure (A-2f). In one aspect of these embodiments, R.sub.5 and R.sub.6 are independently selected from a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.5 and R.sub.6 are independently selected from a C-1 to C-2 alkyl. In one aspect of these embodiments, R.sub.5 and R.sub.6 are methyl. In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In yet another aspect of these embodiments, R.sub.2 is H.

##STR00012##

[0067] In another aspect of the inventive polymer of structures (A-1) or (A-2) it has structure (A-2g). In another embodiment of this structure, it has structure (A-2h). In yet another aspect of this embodiment it has structure (A-2i). In one aspect of these embodiments, R.sub.9 and R.sub.10 are independently selected from a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.9 and R.sub.10 are independently selected from a C-1 to C-2 alkyl. In one aspect of these embodiments, R.sub.9 and R.sub.10 are methyl. In one aspect of the embodiments where R.sub.9 and R.sub.10 are independently selected from a C-1 to C4 alkyl, R.sub.8 is selected from a C-1 to C4 alkyl or an aryl; in one aspect of this embodiment R.sub.8 is a C-1 to C-2 alkyl; in another aspect of this embodiment said aryl is phenyl. In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In et another aspect of these embodiments R.sub.2 is H.

##STR00013##

[0068] In another aspect of the inventive polymer of structures (A-1) or (A-2) it has structure (A-3). In one aspect of this polymer L.sub.1 is a direct valence bond. In another aspect of this polymer L.sub.1 is a C-2 to C-8 alkylene moiety. In another aspect of this polymer wherein L.sub.1 is an arylene moiety (-aryl-). In yet another aspect of this polymer L.sub.1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In another aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl and a C-1 to C4 alkoxy. In another aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkoxy. In another aspect of these embodiments, R.sub.13 and R.sub.14 are ethoxy. In another aspect of these embodiments, R.sub.13 and R.sub.14 are methoxy. In another aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.13 and R.sub.14 are ethyl. In another aspect of these embodiments, R.sub.13 and R.sub.14 are ethyl. In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, Rip is methyl. In yet another aspect of these embodiments, R.sub.e1 and R.sub.e2 are both H. In another aspect of these embodiments, R.sub.17 is H. In another aspect of these embodiments, R.sub.12 is H.

##STR00014##

[0069] In another aspect of the polymer of structure (A-3), where L.sub.1 is a C-2 to C-8 alkylene moiety it has structure (A-3a) or structure (A-3b) where and n is an integer ranging from 1 to 7. In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkoxy. In another aspect of this embodiment R.sub.13 is selected from a C-1 to C4 alkoxy and R.sub.14 is selected from a C-1 to C4 alkyl. In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In yet another aspect of these embodiments, R.sub.e1 and R.sub.e2 are both H. In another aspect of these embodiments, R.sub.17 is H. In another aspect of these embodiments, R.sub.12 is H.

##STR00015##

[0070] In another aspect of the polymer of structure (A-3) it has structures (A-3c) or (A-3d), wherein L.sub.1 is alkylenearyl moiety (*-alkylene-aryl-**) where n is an integer ranging from 0 to 7. In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkyl, In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkoxy. In another aspect of these embodiments, R.sub.13 is selected from a C-1 to C4 alkoxy and R.sub.14 is selected from a C-1 to C4 alkyl. In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In yet another aspect of these embodiments, Rei and R.sub.e2 are both H. In another aspect of these embodiments, R.sub.17 is H. In another aspect of these embodiments, R.sub.12 is H.

##STR00016##

[0071] In another aspect of the inventive polymer of structures (A-1) or (A-2) it has structure (A-4). In one aspect of this embodiment, L is a direct valence bond. In another aspect of this embodiment L is a C-2 to C-8 alkylene moiety. In another aspect of this embodiment L is an arylene moiety (-aryl-). In yet another aspect of this embodiment L is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In still another aspect of this embodiment L is a an alkylenearyl moiety (*-alkylene-aryl-**). In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In yet another aspect of these embodiments, R.sub.e1 and R.sub.e2 are both H.

##STR00017##

[0072] In another aspect of the inventive polymer of structures (A-4) it has structure (A-4a) or structure (A-4b), wherein n is an integer ranging from 0 to 7. In another aspect of this embodiment, it has structure (A-4b). In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C4 alkyl. In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C-4 alkoxy. In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In yet another aspect of these embodiments, R.sub.e1 and R.sub.e2 are both H.

##STR00018##

[0073] In another aspect of the inventive polymer of structures (A-4) it has structure (A-4c) or structure (A-4d), wherein n is an integer ranging from 0 to 7. In another aspect of this embodiment, it has structure (A-4d). In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C-4 alkyl. In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C-4 alkoxy. In one aspect of these embodiments, R.sub.m1 is methyl. In another aspect of these embodiments, R.sub.1p is methyl. In yet another aspect of these embodiments, R.sub.e1 and R.sub.e2 are both H.

##STR00019##

[0074] In one aspect of the inventive polymer of structure (A), it has the more specific structure (B-1), wherein R.sub.3p is a C-1 to C-8 alkyl.

##STR00020##

[0075] In another aspect of the inventive polymer of structures (B-1) it has structure (B-1a), wherein R.sub.3p is a C-1 to C-8 alkyl. In another aspect of R.sub.3p is a C-1 to C-8 alkyl, and L.sub.1 is a direct valence bond. In another aspect of R.sub.3p is a C-1 to C-8 alkyl, and L.sub.1 is a C-2 to C-8 alkylene moiety. In another aspect of this embodiment R.sub.3p is a C-1 to C-8 alkyl, and L.sub.1 is an arylene moiety (-aryl-). In another aspect of this embodiment R.sub.3p is a C-1 to C-8 alkyl, and L.sub.1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkoxy. In another aspect of these embodiments, R.sub.13 is selected from a C-1 to C4 alkoxy and R.sub.14 is selected from a C-1 to C4 alkyl.

[0076] In another aspect of these embodiments, R.sub.m2 is H. In yet another aspect of these embodiments, R.sub.2p is H.

##STR00021##

[0077] In one aspect of the inventive polymer of structure (B-1) it has structures (B-1b) or (B1c) wherein R.sub.3p is a C-1 to C-8 alkyl and n is an integer ranging from 1 to 7. In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkyl, In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkoxy. In another aspect of these embodiments, R.sub.13 is selected from a C-1 to C4 alkoxy and R.sub.14 is selected from a C-1 to C-4 alkyl. In another aspect of these embodiments, R.sub.m2 is H. In yet another aspect of these embodiments, R.sub.2p is H. In another aspect of these embodiments, R.sub.17 is H. In another aspect of these embodiments, R.sub.12 is H.

##STR00022##

[0078] In one aspect of the inventive polymer of structure (B-1), it has the more specific structures (B-1d) or (B-1e), wherein R.sub.3p is a C-1 to C-8 alkyl and n is an integer ranging from 0 to 7. In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to CA alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to CA alkyl. In another aspect of this embodiment, R.sub.13 and R.sub.14 are selected from a C-1 to C-4 alkoxy. In another aspect of these embodiments, R.sub.13 is selected from a C-1 to C-4 alkoxy and R.sub.14 is selected from a C-1 to C-4 alkyl. In another aspect of these embodiments, R.sub.m2 is H. In yet another aspect of these embodiments, R.sub.2p is H. In another aspect of these embodiments, R.sub.17 is H. In another aspect of these embodiments, R.sub.12 is H.

##STR00023##

[0079] In another aspect of the inventive polymer of structure (B-1) it has structure (B-2). In one aspect of this embodiment L is a direct valence bond. In another aspect of this embodiment L is a C-2 to C-8 alkylene moiety. In another aspect of this embodiment wherein L is an arylene moiety (-aryl-). In another aspect of this embodiment, is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In another aspect of this embodiment is where Rs and Rs1 are individually selected from a C-1 to C-4 alkyl. In another aspect of this embodiment Rs and Rs1 are individually selected from a C-1 to C-4 alkoxy. In yet another embodiment Rs and Rs1 are methyl. In another aspect of this embodiment Rs and Rs1 are methoxy. In another aspect of these embodiments, R.sub.m2 is H. In yet another aspect of these embodiments, R.sub.2p is H.

##STR00024##

[0080] In the aspect of the inventive polymer of structure (B-2), where L is a direct valence bond and it has structure (B-2aa), another aspect of this embodiment is where Rs and Rs1 are individually selected from a C-1 to C4 alkyl. In another aspect of this embodiment Rs and Rs1 are individually selected from a C-1 to C4 alkoxy. In yet another embodiment Rs and Rs1 are methyl. In another aspect of this embodiment Rs and Rs1 are methoxy. In another aspect of these embodiments, R.sub.m2 is H. In yet another aspect of these embodiments, R.sub.2p is H.

##STR00025##

[0081] In another aspect of the said polymer of structure (B-2) it has structure (B-2a) or structure (B-2b) where R.sub.15 is a C-1 to C-8 alkyl, and n is an integer ranging from 0 to 7. In one aspect of these embodiments, Rs and Rs1 are independently selected from a C-1 to C-8 alkyl or alkoxy. In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C4 alkyl. In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C4 alkoxy. In yet another embodiment Rs and Rs1 are methyl. In another aspect Rs and Rs1 are methoxy. In another aspect of these embodiments, R.sub.m2 is H. In yet another aspect of these embodiments, R.sub.2p is H.

##STR00026##

[0082] In another aspect of the said polymer of structure (B-2) it has structure (B-2c) or structure (B-2d), where R.sub.15 is a C-1 to C-8 alkyl, and n is an integer ranging from 0 to 7. In one aspect of these embodiments, Rs and Rs1 are independently selected from a C-1 to C-8 alkyl or alkoxy. In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C-4 alkyl. In another aspect of these embodiments, Rs and Rs1 are individually selected from a C-1 to C-4 alkoxy. In yet another embodiment Rs and Rs1 are methyl. In another aspect Rs and Rs1 are methoxy. In another aspect of these embodiments, R.sub.m2 is H. In yet another aspect of these embodiments, R.sub.2p is H.

##STR00027##

[0083] In another aspect of the inventive polymer of structures (B-1) it has structure (B-3). In one aspect of these embodiments, R.sub.3 and R.sub.4 are independently selected from a C-1 to C-4 alkoxy or a C-1 to C-4 alkyl. In one aspect of this embodiment R.sub.2p is H. In another aspect of this embodiment R.sub.m2 is H. In another aspect of this embodiment R.sub.2 is H. In another aspect of these embodiments, R.sub.18 is H.

##STR00028##

[0084] In another aspect of the said polymer of structure (B-3) it has structure (B-3a), structure (B-3b), or structure (B-3c). In one aspect of these embodiments, R.sub.3 and R.sub.4 are independently selected from a C-1 to C4 alkoxy or a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.3 and R.sub.4 are independently selected from a C-1 to C4 alkoxy. In another aspect of these embodiments, R.sub.3 and R.sub.4 are independently selected from a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.3 and R.sub.4 are both ethoxy. In another aspect of these embodiments, R.sub.3 and R.sub.4 are both methoxy. In one aspect of these embodiments, R.sub.2, is H. In another aspect of these embodiments, R.sub.m2 is H. In another aspect of these embodiments, R.sub.2 is H. In another aspect of these embodiments, R.sub.18 is H.

##STR00029##

[0085] In another aspect of the said polymer of structure (B-3), it has structure (B-3d), structure (B-3e) or structure (B-3f). In one aspect of these embodiments, R.sub.5 and R.sub.6 are independently selected from a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.5 and R.sub.6 are independently selected from a C-1 to C-2 alkyl. In one aspect of these embodiments, R.sub.5 and R.sub.6 are methyl. In one aspect of these embodiments, R.sub.2p is H. In another aspect of these embodiments, R.sub.m2 is H. In another aspect of these embodiments, R.sub.2 is H. In another aspect of these embodiments, R.sub.18 is H.

##STR00030##

[0086] In another aspect of the said polymer of structure (B-3), it has structure (B-3g), structure (B-3h) or structure (B-3i). In one aspect of these embodiments, R.sub.9 and R.sub.10 are independently selected from a C-1 to C4 alkyl. In another aspect of these embodiments, R.sub.9 and R.sub.10 are independently selected from a C-1 to C-2 alkyl. In one aspect of these embodiments, R.sub.9 and R.sub.10 are methyl. In one aspect of the embodiments where R.sub.9 and R.sub.10 are independently selected from a C-1 to C4 alkyl, Rs is selected from a C-1 to C4 alkyl or an aryl; in one aspect of this embodiment Rs is a C-1 to C-2 alkyl; in another aspect of this embodiment said aryl is phenyl. In one aspect of these embodiments, R.sub.2p is H. In another aspect of these embodiments, R.sub.m2 is H. In another aspect of these embodiments, R.sub.2 is H. In another aspect of these embodiments, R.sub.18 is H.

##STR00031##

Inventive Compositions

[0087] Another aspect of this invention are compositions of any one of the inventive polymers described herein having structure (A) and an organic spin casting solvent.

[0088] Another aspect of this invention are compositions of any one of the inventive polymers described herein having structure (A-1) and an organic spin casting solvent.

[0089] Another aspect of this invention are compositions comprising of any one of the inventive polymers described herein having any one of structures (A-2), (A-2a), (A-2b), (A-2c), (A-2d), (A-2e), (A-2f), (A-2g), (A-2h), or (A-2i), and an organic spin casting solvent. In one aspect of this embodiment, said polymer has structure (A-2). In one aspect of this embodiment, said polymer has structure (A-2a). In one aspect of this embodiment, said polymer has structure (A-2b). In one aspect of this embodiment, said polymer has structure (A-2c). In one aspect of this embodiment, said polymer has structure (A-2d). In one aspect of this embodiment, said polymer has structure (A-2e). In one aspect of this embodiment, said polymer has structure (A-2f). In one aspect of this embodiment, said polymer has structure (A-2g). In one aspect of this embodiment, said polymer has structure (A-2h). In one aspect of this embodiment, said polymer has structure (A-2i). In another aspect of this embodiment said composition consists of any one of the above-described polymer structures and an organic spin casting solvent.

[0090] Another aspect of this invention are compositions comprising of any one of the inventive polymers described herein having any one of structures (A-3), (A-3a), (A-3b), (A-3c), or (A-3d) and an organic spin casting solvent. In one aspect of this embodiment, said polymer has structure (A-3). In one aspect of this embodiment, said polymer has structure (A-3a). In one aspect of this embodiment, said polymer has structure (A-3b). In one aspect of this embodiment, said polymer has structure (A-3c). In one aspect of this embodiment, said polymer has structure (A-3d). In another aspect of this embodiment said composition consists only of any one the polymer structures described in this embodiment and an organic spin casting solvent.

[0091] Another aspect of this invention are compositions comprising of any one of the inventive polymers described herein having any one of structures (A-4), (A-4a), (A-4b), (A-4c), or (A-4d) and an organic spin casting solvent. In one aspect of this embodiment, said polymer has structure (A-4). In one aspect of this embodiment, said polymer has structure (A-4a). In one aspect of this embodiment, said polymer has structure (A-4b). In one aspect of this embodiment, said polymer has structure (A-4c). In one aspect of this embodiment, said polymer has structure (A-4d). In another aspect of this embodiment said composition consists only of any one the polymer structures described in this embodiment and an organic spin casting solvent.

[0092] Another aspect of this invention are compositions comprising of any one of the inventive polymers described herein having any one of structures (B-1), (B-1a), (B-1b), (B-1c), (B-1d), or (B-1e). In one aspect of this embodiment, said polymer has structure (B-1). In one aspect of this embodiment, said polymer has structure (B-1a). In one aspect of this embodiment, said polymer has structure (B-1b). In one aspect of this embodiment, said polymer has structure (B-1c). In one aspect of this embodiment, said polymer has structure (B-1d). In one aspect of this embodiment, said polymer has structure (B-1e). In another aspect of this embodiment said composition consists only of any one the polymer structures described in this embodiment and an organic spin casting solvent.

[0093] Another aspect of this invention are compositions comprising of any one of the inventive polymers described herein having any one of structures (B-2), (B-2a), (B-2b), (B-2c), or (B-2d). In one aspect of this embodiment, said polymer has structure (B-2). In one aspect of this embodiment, said polymer has structure (B-2a). In one aspect of this embodiment, said polymer has structure (B-2b). In one aspect of this embodiment, said polymer has structure (B-2c). In one aspect of this embodiment, said polymer has structure (B-2d). In another aspect of this embodiment said composition consists only of any one the polymer structures described in this embodiment and an organic spin casting solvent.

[0094] Another aspect of this invention are compositions comprising of any one of the inventive polymers described herein having any one of structures (B-3), (B-3a), (B-3b), (B-3c), (B-3d), (B-3e), (B-3f), (B-3g), (B-3h) and (B-3i). In one aspect of this embodiment, said polymer has structure (B-2). In one aspect of this embodiment, said polymer has structure (B-2a). In one aspect of this embodiment, said polymer has structure (B-2b). In one aspect of this embodiment, said polymer has structure (B-2c). In one aspect of this embodiment, said polymer has structure (B-2d). In another aspect of this embodiment said composition consists only of any one the polymer structures described in this embodiment and an organic spin casting solvent.

[0095] 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.

[0096] The novel compositions, in addition to the polymer and the solvent, may contain surfactants as additives to facilitate coating.

[0097] Another aspect of said invention is novel compositions wherein said novel polymers comprise 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 comprises from about 0.1 wt. % to about 2 wt. %. In yet another embodiment it comprises from about 0.5 wt % to about 1.5 wt %. In yet another embodiment it comprises from about 0.75 wt. % to about 1.5 wt. %. In yet another embodiment it comprises about 1.0 wt. %.

Processes of Using Inventive Compositions

[0098] 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 non-metallic surface areas, comprising the steps; [0099] i) coating the composition comprising any one of the polymer having structure (A), or its substructures on a said substrate forming a film, [0100] 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, [0101] 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.
In one aspect of this embodiment n 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, Silicon oxide (SiOx), Silicon nitride (SiNx), Silicon oxynitride (SiON) and organic dielectric substrates.

[0102] Another aspect of this invention is a process comprising the steps; [0103] ia) coating a composition comprising any one of the polymer having structure (A), or its substructures, on a substrate which comprises both metallic surface areas and non-metallic surface areas forming a film, [0104] 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, [0105] iiia) washing said baked film with a solvent to remove ungrafted polymer forming a grafted substrate wherein pinning layer brush are only present on said metallic surface areas of said substrate, [0106] iva) coating said grafted substrate with a neutral layer composition forming a neutral layer coating, [0107] va) curing said neutral layer coating, [0108] via) washing away, with a solvent, uncured neutral layer, leaving in said non-metallic areas a neutral directing brush, forming on said substrate a chemoepitaxy directing layer, [0109] viia) coating on said chemoepitaxy directing layer with a block copolymer solution forming a coating of block copolymer, [0110] viiia) annealing said coating of block copolymer to form a directed self-assembled film of the block copolymer on said chemoepitaxy directing layer.
In one aspect of this process in said substrate, said metallic surface areas are Tungsten and said non-metallic surface areas are Silicon or Silicon oxide. In another aspect of this said block copolymer is a block copolymer comprised of styrenic repeat units and alkyl acrylic repeat units.
In another aspect of this embodiment said 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.

Inventive Compounds

[0111] Another aspect of this invention are novel compounds which are useful in the synthesis of the inventive polymers of structure (A) and its substructures as described herein.

[0112] One embodiment of these novel compounds is those having structure (I), wherein R.sub.1 is a chelating group located at the meta or para position selected from a phosphinothioic moiety of structure (Ia) an aminosulfonyl moiety of structure (Ib), a phosphonamide moiety of structure (Ic) wherein * designates the attachment point of these moieties to said compound of structure (I).

[0113] Further, in said phosphinothioic moiety of structure (Ia), 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 a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which R.sub.9 and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl.

[0114] Further, in said aminosulfonyl moiety of structure (Ib), R.sub.5 and R.sub.6, are independently a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and dialkyl amino moiety, N(R.sub.9)(R.sub.10).

[0115] Further, in said phosphonamide moiety of structure (Ic), R.sub.7 is said dialkyl amino moiety, N(R.sub.9)(R.sub.10), and R.sub.8 is selected from the group consisting of 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. In one aspect of this embodiment Rs is an aryl, and in a more specific aspect of this embodiment is phenyl. In one aspect of this embodiment Rs is an alkylenearyl. In one aspect of this embodiment R.sub.8 is a C-2 to C-8 alkyleneoxyalkyl. In one aspect of this embodiment R.sub.8 is a C-2 to C-8 haloalkyl. In one aspect of this embodiment R.sub.8 is a C-1 to C-8 linear alkyl. In one aspect of this embodiment R.sub.8 is a C-3 to C-8 branched alkyl. In one aspect of this embodiment R.sub.8 is a C-3 to C-8 cyclic alkyl. In one aspect of this embodiment R.sub.8 is a C-1 to C-8 linear alkyloxy. In one aspect of this embodiment Rs is a C-3 to C-8 branched alkyloxy. In one aspect of this embodiment R.sub.8 is or a C-3 to C-8 cyclic alkyloxy.

[0116] Further, in said compound of structure (I), R.sub.2 is a substituent, located at the meta or para positions which is selected from the group consisting of H, 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, a C-3 to C-8 cyclic alkyloxy; a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic).

[0117] Specifically, when both R.sub.1 and R.sub.2 are a phosphonamide moiety of structure (Ic), R.sub.8 may individually be selected form the group consisting of 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. In one aspect of this embodiment R.sub.8 is an aryl, and in a more specific aspect of this embodiment is phenyl. In one aspect of this embodiment R.sub.8 is an alkylenearyl. In one aspect of this embodiment R.sub.8 is a C-2 to C-8 alkyleneoxyalkyl. In one aspect of this embodiment R.sub.8 is a C-2 to C-8 haloalkyl. In one aspect of this embodiment R.sub.8 is a C-1 to C-8 linear alkyl. In one aspect of this embodiment R.sub.8 is a C-3 to C-8 branched alkyl. In one aspect of this embodiment R.sub.8 is a C-3 to C-8 cyclic alkyl. In one aspect of this embodiment R.sub.8 is a C-1 to C-8 linear alkyloxy. In one aspect of this embodiment Rs is a C-3 to C-8 branched alkyloxy. In one aspect of this embodiment R.sub.8 is or a C-3 to C-8 cyclic alkyloxy.

##STR00032##

[0118] In another embodiment of the compound of structure (I) it has the more specific structure (I-1).

##STR00033##

[0119] In another embodiment of the compound of structure (I), it has the more specific structure (I-2).

##STR00034##

[0120] In more specific embodiments of the compounds of structure (I), (I-1) or (I-2), R.sub.1 is said chelating group is a phosphinothioic moiety of structure (Ia). In more specific embodiments of the compounds of structure (I), (I-1) or (I-2), R.sub.1 is said chelating group is an aminosulfonyl moiety of structure (Ib). In more specific embodiments of the compounds of structure (I), (I-1) or (I-2), R.sub.1 is said is a phosphonamide moiety of structure (Ic). In one aspect of these embodiments, R.sub.2 is H. In another aspect of these embodiments, R.sub.2 is an aryl. In another aspect of these embodiments, R.sub.2 is an alkylenearyl. In another aspect of these embodiments. R.sub.2 is a C-2 to C-8 alkyleneoxyalkyl. In another aspect of these embodiments, R.sub.2 is a C-2 to C-8 haloalkyl. In another aspect of these embodiments, R.sub.2 is a C-1 to C-8 linear alkyl. In another aspect of these embodiments, R.sub.2 is a C-3 to C-8 branched alkyl. In another aspect of these embodiments, R.sub.2 is a C-3 to C-8 cyclic alkyl. In another aspect of these embodiments, R.sub.2 is a C-1 to C-8 linear alkyloxy. In another aspect of these embodiments, R.sub.2 is a C-3 to C-8 branched alkyloxy. In another aspect of these embodiments, R.sub.2 is a C-3 to C-8 cyclic alkyloxy. In another aspect of these embodiments, R.sub.2 is a phosphinothioic moiety of structure (Ia). In another aspect of these embodiments, R.sub.2 is an aminosulfonyl moiety of structure (Ib). In another aspect of these embodiments, R.sub.2 is a phosphonamide moiety of structure (Ic).

[0121] One embodiment of these novel compounds are those having structure (II), wherein R.sub.11 is a phosphinothioic moiety of structure (IIa), wherein * designates the attachment point of this moieties to said compound of structure (II), R.sub.13 and R.sub.14 are independently selected from the group consisting of 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, a C-3 to C-8 cyclic alkyloxy; and a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which R.sub.9 and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl.

[0122] Further, in these compounds of structure (II), L.sub.1 is a linking moiety selected from the group consisting of a direct valence bond, a C-2 to C-8 alkylene moiety(-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein ** designates the attachment points of the L.sub.1 organic linking moiety to the phosphorous in structure (IIa), and * designates where L.sub.1 within the moiety R.sub.11 is attached to the carbonyloxy of compound (II).

[0123] Further, in these compounds of structure (II), R.sub.12 is H or a C-1 to C-4 alkyl.

##STR00035##

[0124] In a more specific embodiments of the aforementioned compounds of structure (II), R.sub.13 is a C-1 to C-8 linear alkyloxy. In another aspect of these embodiments, R.sub.13 is a C-3 to C-8 branched alkyloxy. In another aspect of these embodiments, R.sub.13 is a-C-3 to C-8 cyclic alkyloxy.

[0125] In a more specific embodiments of the aforementioned compounds of structure (II), R.sub.14 is an aryl. In another aspect of these embodiments, R.sub.14 is an alkylenearyl. In another aspect of these embodiments, R.sub.14 is a C-2 to C-8 alkyleneoxyalkyl. In another aspect of these embodiments, R.sub.14 is a C-2 to C-8 haloalkyl. In another aspect of these embodiments, R.sub.14 is a C-1 to C-8 linear alkyl. In another aspect of these embodiments, R.sub.14 is a C-3 to C-8 branched alkyl. In another aspect of these embodiments, R.sub.14 is a C-3 to C-8 cyclic alkyl. In another aspect of these embodiments, R.sub.14 is a C-1 to C-8 linear alkyloxy. In another aspect of these embodiments, R.sub.14 is a C-3 to C-8 branched alkyloxy. In another aspect of these embodiments, R.sub.14 is, a C-3 to C-8 cyclic alkyloxy. In another aspect of these embodiments, R.sub.14 is a dialkyl amino moiety, N(R.sub.9)(R.sub.10).

[0126] In another more specific embodiment R.sub.13 and R.sub.14 are independently selected from the group consisting of 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, a C-3 to C-8 cyclic alkyloxy; and a dialkyl amino moiety, N(R.sub.9)(R.sub.10), in which R.sub.9 and R.sub.10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl.

[0127] In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkoxy. In another aspect of this embodiment R.sub.13 is selected from a C-1 to C4 alkoxy and R.sub.14 is selected from a C-1 to C4 alkyl.

[0128] In more specific embodiments of the aforementioned compounds of structure (II), R.sub.9 is a C-1 to C-8 linear alkyl. In another aspect of these embodiments, R.sub.9 is a C-3 to C-8 branched alkyl.

[0129] In another aspect of these embodiments, R.sub.9 is a C-3 to C-8 cyclic alkyl.

[0130] In more specific embodiments of the aforementioned compounds of structure (II), L.sub.1 is direct valence bond. In another aspect of these embodiments, L.sub.1 is a C-2 to C-8 alkylene moiety. In another aspect of these embodiments, L.sub.1 is an arylene moiety (-aryl-). In more specific embodiments of these embodiments, L.sub.1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

[0131] In more specific embodiments of the aforementioned compounds of structure (II), it has structure (IIc) or structure (IIc1), where n is 1 to 7. In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to C4 alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C4 alkoxy. In another aspect of this embodiment R.sub.13 is selected from a C-1 to C4 alkoxy and R.sub.14 is selected from a C-1 to C4 alkyl.

##STR00036##

[0132] In more specific embodiments of the aforementioned compounds of structure (II), it has structure (IIb) or structure (IIb1), wherein n is an integer ranging from 1 to 7. In one aspect of these embodiments, R.sub.13 and R.sub.14 are independently selected from a C-1 to C-8 alkyl or alkoxyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are independently selected from a C-1 to C-4 alkyl or alkoxy. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C-4 alkyl. In another aspect of this embodiment R.sub.13 and R.sub.14 are selected from a C-1 to C-4 alkoxy. In another aspect of this embodiment R.sub.13 is selected from a C-1 to C-4 alkoxy and R.sub.14 is selected from a C-1 to C-4 alkyl.

##STR00037##

[0133] In more specific embodiments of the aforementioned compounds of structure (II), it has structure (IIb2), wherein R.sub.13a and R.sub.14a and individually selected from a C-1 to C4 alkyl.

##STR00038##

EXAMPLES

[0134] 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.

[0135] 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.

[0136] 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.

Chemicals

[0137] All chemicals unless otherwise indicated were purchased from Sigma Aldrich (3050 Spruce St., St. Louis, MO 63103). Chemicals used in anionic polymerization were purified as described in the literature (e.g. Techniques in High-Vacuum Anionic Polymerization By David Uhrig and Jimmy Mays and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005))

[0138] Phenyl acrylate derivatives were synthesized by esterification of acryloyl chloride with corresponding hydroxyl compound under basic condition and DPE derivatives were synthesized by alkoxylation of DPE-(m)-CH.sub.2Br (1-(bromomethyl)-3-(1-phenylvinyl)benzene) with corresponding hydroxyl compound under basic condition.

[0139] All synthetic experiments were carried out under N.sub.2 atmosphere. Lithographic experiments were carried out as described in the text. The molecular weight of the copolymers was measured with a Gel Permeation Chromatograph. Gel permeation chromatography equipped with 100 , 500 , 10.sup.3 , 10.sup.5 and 10.sup.6 -ultrastyragel columns

[0140] Lithographic Experiments were done using a TEL Clean ACT8 track. SEM pictures were taken with an applied Materials NanoSEM_3D Scanning electron microscope picture are shown at either 1 FOV magnification or 2 FOV magnification (Field of view (FOV)=5 m).

[0141] Etching experiments were done using standard isotropic oxygen etching conditions for self-assembled films block copolymer of methyl methacrylate and styrene.

[0142] Gel permeation chromatography equipped with styrene-DVB gel, 100 , 500 , 103 , 104 and 106 porosities columns connected in series (PSS (polymer standard services), Germany) and THF as mobile phase at 1 ml/min. Polystyrene standards (18 samples) ranging M.sub.n from 1,000 g/mol to 200,000 g/mol (PSS, Germany) were used to construct a calibration curve for determining molecular weight and poly distribution index (PDI) of the synthesized polymers. Bruker 400 M Hz NMR unit was used for molecular characterization.

[0143] .sup.1H NMR spectra were recorded using Bruker Advanced III 400 MHz spectrometer in CDCl.sub.3.

[0144] Coating studies were performed using blanket dielectric as well as metal coupons. The films were baked at desired temperature and time and rinsed with excess material. The grafted brushes were studied using water contact-angle, FT, and XPS.

[0145] Coating of polymeric brushes on a blanket metal or dielectric wafers using 230 C./5 min baking condition and rinsing excess material out with organic solvents were done and the substrates were analyzed using WCA, FT and XPS.

Experimental

Preparation of Polymer Formulation

[0146] The polymers described here were separately dissolved in PGMEA to form 1 wt. % solutions. These solutions where individually filtered in using in using a Nylon filter (Entegris, Billerica, Ma). These solutions were separately coated at 1500 rpm on both metal (Cu, W) and SiO.sub.2 wafers, and the wafers were subsequently baked at 230 C. for 5 min. Following the bake, the wafers were rinsed with PGMEA for 2 min to remove any un-grafted polymer from the wafer which were then spun dried by spinning 1,500 rpm, followed by baking at 110 C. for 1 min. Then water contact angle, XPS were measured to understand the grafting efficiency and the results were shown in Table 1. Subsequently, the second brush of hydroxyl terminated PSOH or PMMA-OH containing polymer formulation was made in PGMEA at 1 wt. % solid. Then after filtering with 0.25-micron Nylon filter, the solution was spin coated on to previously brushed metal and SiO.sub.2 substrates. After baking at various temp. and time, the double brushed substrates were rinsed to remove unreacted second brushes. Then the double brushed substrates were examined by water contact angle (WCA) and X-ray photoelectron spectroscopy (XPS) to understand cross-grafting to judge the first brush's efficiency and selectivity to metal substrates.

Example 1 Synthesis of Dimethyl Thiophophine Terminated Polystyrene

[0147] Anionic polymerization was performed in nitrogen dried 250 mL round bottom flask equipped with, a magnetic stir bar, a septum adaptor that enables connection to either vacuum or nitrogen atmosphere, and a rubber septum for reagent addition via using syringe or cannula. Anhydrous cyclohexane, 100 mL was transferred into the flask using a cannula under nitrogen. Purified styrene monomer, 20 mL (18 g) was added to the cyclohexane solution. The reaction mixture was degassed and filled with nitrogen.

##STR00039##

[0148] A required amount of initiator, sec-butyl lithium (1.3M) solution in hexane was added into the monomer solution under fast stirring. Immediately, an orange color of carbanion formed indicating propagation of polystyryl lithium with warmness of the reaction increased slightly. Reaction was kept stirring at 35 C.-45 C. for 2 h. Then, a purified dimethyl thiophosphinoyl chloride (distilled over CaH.sub.2) was transferred via cannula into the living polystyryl lithium anion solution. The color of the reaction slowly disappeared over 5 mins. The reaction mixture was diluted with THF (2) and then precipitated into excess (5) isopropanol:water (80:20) mixture. The polymer was filtered and dried under vacuum at 80 C., over 18 h. Yield: 17.2 grams (96%), M.sub.n, GPC=6,600 g/mol, PDI=1.05, .sup.31P NMR showed a signal at 44 ppm confirming presence of end group with PS. A solution of this polymer in PGMEA (1 wt. %) spin-coated on to the tungsten and silicon coupons after bake (200 C./15 min/N.sub.2) and rinse (2 min, dynamic) showed 90 on W and 52 on Silicon coupons, respectively. This confirms the selectivity of this polymer to W. XPS studies showed elemental ratio of C/W and C/Si as 25.84 and 0.43, respectively.

Example 2. Synthesis of Diethylthiophosphonate Terminated Polymethyl Methacrylate

[0149] In the first step, the diethylthiophosphonate DPE derivative was prepared from the thiolation of MTAG-10. Diethylphosphonate terminated PMMA was synthesized using an initiator made from diethylthiophosphonate DPE derivative and sec-BuLi. The reaction was carried out at 78 C. in tetrahydrofuran.

##STR00040##

Step 1: Synthesis of Diethylthiophosphonate DPE

[0150] Diethylphosphonate DPE (MTAG-10) (29.0 g, 91.67 mmol) and Lawesson's reagent (18.7 g, 404.471 mmol) were weighed in two necks round bottom flask, attached with a reflux condenser and rubber septum. 250 mL anhydrous toluene was cannula transferred. Flask was kept in an oil bath and the temperature increased to 120 C. The reaction was left to run overnight (although, 2-4 hr are enough). Toluene was removed on rotovap. The brownish-red liquid was loaded on a silica column and separated using a mixture of hexane:ethyl acetate with a 70:30 ratio. Excess Lawesson reagent and its side products elute very close to the desired product. Desired DPE derivative (O,O-diethyl (4-(1-phenylvinyl)phenyl)phosphonothioate [DPE-PS(OEt).sub.2] was obtained as a pale-yellowish-colored liquid. Lawesson reagent and MTAG-26 have a very stinky odor, a typical of thiol compounds. Yield: 20g, % yield 65.6%. .sup.1H NMR, CDCl.sub.3 : 1.4, dt, 6H; 4.0, m, 4H; 5H; 7.3m, 2H; 7.4, 2H, 7.6, m, 2H., 31P CPD m, 87.4 ppm

Step 2: Synthesis of PMMA Terminated with Diethylthiophosphonate

##STR00041##

[0151] O,O-diethyl (4-(1-phenylvinyl)phenyl)phosphonothioate [DPE-PS(OEt).sub.2](1.72 g, 5 mmol) was dissolved in hexyl lithium titrated 6 ml toluene and added into an ampule. 28 mL methyl methacrylate was added into a separate ampule and degassed under a dynamic vacuum to 25 mL (23.3 g, 23.3 mmol) of methyl methacrylate. The ampules were attached to the sidearms of the reactor containing lithium chloride (2.2 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under a vacuum and charged with nitrogen. Tetrahydrofuran (300 mL) was added via cannula and the mixture was stirred and cooled to 78 C. where the mixture was titrated with sBuLi until a yellow color persists. The mixture was warmed to room temperature where the yellow color dissipates. The mixture was cooled to 78 C. and the DPE-P(S)(OEt).sub.2) solution was added. sBuLi (4.0 mL, 1.17M in cyclohexane, 4.68 mmol) was then added slowly to produce a red mixture. Methyl methacrylate was added dropwise over 6 minutes at which the red color turns colorless. The mixture was stirred for an additional 12 minutes at which time, 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in excess hexane (7 times of the polymer solution), filtered, and dried at 40 C. for 1 h. Redissolved in ethyl acetate and washed with Milli-Q water. Ethyl acetate was rotovated and the polymer was further dried under vacuum to give a white powder (22 g, 97% yield). GPC: 4,600 g/mol M.sub.n, 4,460 g/mole Mw, 1.046 PDI., .sup.1H NMR MW 6,000 g/mol. The presence of the end-functional group was confirmed using .sup.1HNMR and .sup.31P NMR analysis.

Example 3 Synthesis of Diethylthiophosphonate Terminated Polystyrene

##STR00042##

[0152] (2.0 g, 3.322 mmol) diethylthiophosphonate DPE was dissolved in 6 ml toluene, titrated with 1,1-diphenyl-3-methylpentyllithium (made from the reaction of sec-butyllithium with DPE) and added into an ampule. 28 mL styrene was added into a separate ampule and degassed under a dynamic vacuum to 25 mL (24.543 g, 23.65 mmol) of styrene. The ampules were attached to the sidearms of the reactor containing lithium chloride (2.2 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under a vacuum and charged with nitrogen. Tetrahydrofuran (300 mL) was added via cannula and the mixture was stirred and cooled to 78 C. where the mixture was titrated with sBuLi until a yellow color persists. The mixture was warmed to room temperature where the yellow color dissipates. The mixture was cooled to 78 C. and sBuLi (4.0 mL, 1.17M in cyclohexane, 4.68 mmol) was added to produce a pale-yellow mixture. Styrene was added dropwise over 10 minutes at which the orange color forms. The mixture was stirred for an additional 5 minutes at which time, the DPE-P(S)(OEt).sub.2) solution was added. Red colored solution was stirred for few minutes and reaction was terminated with 1 mL degassed methanol.

[0153] The polymer recovered by precipitation in excess isopropanol (7 times of the polymer solution), filtered, and dried at 40 C. for 1 h. Redissolved in ethyl acetate and washed with Milli-Q water and precipitate in excess isopropanol. Filtered and dried under vacuum to give a white powder (24 g, 92% yield). GPC: 3,900 g/mol M.sub.n, 4,800g/mole Mw, 1.14 PDI., .sup.1H NMR MW 4,700 g/mol. Presence of end-functional group was confirmed using .sup.1HNMR and .sup.31P NMR analysis.

Example 4 Synthesis of Ethyl Dimethylphosphonamide Terminated Polymethyl Methacrylate (

4.1 Synthesis of 1-phenyl-1-[4-ethyl(dimethylphosphonamido)]-phenylethylene

##STR00043##

[0154] 4-Bromobenzophenone (25 g, 95.7 mmol) and THF were stirred together and cooled to 0 C. nButyllithium (71.38 mL, 114.9 mmol) was added, followed by methyl triphenylphosphonium bromide (41 g, 114.9 mmol). The mixture was warmed to RT. The reaction was quenched with water and diluted with ethyl acetate. The mixture was washed with 1% aq. HCl and aq. NaCl solution and dried over MgSO.sub.4. The MgSO.sub.4 was filtered out and the filtrate was concentrated in vacuo. The white solid triphenylphosphonium oxide was precipitated by slurring in hexane: ethyl acetate (2:1) and then filtered off. Then the filtrate was concentrated and purified by silica gel column chromatography using hexane as eluant followed by concentration to give 4-bromo-1,1-diphenylethylene as a colorless oil (18g % yield 72%)

[0155] Step-1: Ethylphosphonic dichloride (1.70 mL, 15.9 mmol) and dimethylammonium chloride (1.30 g, 16.0 mmol) were dissolved in dichloromethane and cooled to 0 C. in an ice-water bath. Triethylamine (4.46 mL, 32.0 mmol) was added, and the mixture warmed to RT for 30 minutes. The slurry was filtered, and the filtrate concentrated in-vacuo. The residue was redissolved in dichloromethane and triturated with ether. The mixture was filtered and concentrated, then repeated to remove the salt. This gave the chloroethyl(dimethylphosphonamido) as a sticky solid (2.3 g, 95% yield).

[0156] Step-2: 4-Bromo-1,1-diphenylethylene generated from (a) (1 g, 3.86 mmol) was dissolved in tetrahydrofuran and cooled to 78 C. nBuLi (2.4 mL, 3.86 mmol, 1.6M in hexane) was added and stirred 30 minutes. In a separate flask, the chloroethyl(dimethylphosphoramide) generated from (b) (0.6 g, 3.86 mmol) was slurred in THF and cooled to 78 C. The 4-lithium-1,1-diphenylethylene generated previously was added in by cannula and the mixture warmed to RT and stirred for 72 hours. The mixture was diluted with ethyl acetate, washed with water, and dried over MgSO.sub.4. The MgSO.sub.4 was filtered out and the filtrate concentrated in vacuo and purified by silica gel column chromatography using 50% ethyl acetate in hexane as eluant. Concentration of the product fractions gave 1-phenyl-1-[4-ethyl(dimethylphosphonamido)]-phenylethylene as a pale-yellow oil (0.7g yield 60%).sup.1H NMR, CDCl.sub.3 : 1.10, dt, 3H; 1.98, m, 2H; 2.66, s, 3H; 2.69, s, 3H; 5.53, s, 2H; 7.33, m, 5H; 7.40, m, 2H; 7.68, m, 2H.

##STR00044##

4.2 Synthesis of PMMA-ethyl(dimethylphosphonamide) Terminated

[0157] 1-Phenyl-1-(4-ethyldimethylphosphonamido)phenylethylene [DPE-P(O)(Et)(NMe.sub.2)] (1.43 g, 5 mmol) in 6 ml of dry toluene was added into an ampule. Methyl methacrylate (20.7 g, 207 mmol) was added into a separate ampule and freeze-thawed 3 times to degas. The ampules were attached to the sidearms of the reactor containing lithium chloride (1.75 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and charged with nitrogen. Tetrahydrofuran (210 mL) was added via cannula and the mixture stirred and cooled to 78 C. where the mixture was titrated with sBuLi until a yellow color persists. The mixture was warmed to room temperature where the yellow color dissipates. The mixture was cooled to 78 C. once again and the DPE-P(O)(Et)(NMe.sub.2) solution was added in. sBuLi (1.2 mL) was added dropwise to titrate the mixture until a yellow color persists. sBuLi (2.96 mL, 1.4M in cyclohexane, 4 mmol) was then added slowly to produce a red mixture. Methyl methacrylate was added rapid dropwise to the mixture over 2 minutes at which the red color turns colorless. The mixture was stirred for an additional 30 minutes at which time, 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in excess hexane (7 times of the polymer solution), filtered, and dried at 40 C. for 12 h under vacuum to give a white powder (21 g, 97% yield). GPC: 4,195 g/mol M.sub.n, 4,460 g/mole Mw, 1.06 PDI.

Example 5. Synthesis of Phenyl Dimethyl Phosphonamide Terminated Polymethyl Methacrylate

##STR00045##

5.1 Synthesis of 1-phenyl-1-[4-phenyl(dimethylphosphonamido)]-phenylethylene

[0158] Step-1: 4-Bromobenzophenone (25 g, 95.7 mmol) and THF were stirred together and cooled to 0 C. nButyllithium (71.38 mL, 114.9 mmol) was added, followed by methyl triphenylphosphonium bromide (41 g, 114.9 mmol). The mixture was warmed to RT. The reaction was quenched with water and diluted with ethyl acetate. The mixture was washed with 1% aq. HCl and aq. NaCl solution and dried over MgSO.sub.4. The MgSO.sub.4 was filtered out and the filtrate was concentrated in vacuo. The white solid triphenylphosphonium oxide was precipitated by slurring in hexane: ethyl acetate (2:1) and then filtered off. Then the filtrate was concentrated and purified by silica gel column chromatography using hexane as eluant followed by concentration to give 4-bromo-1,1-diphenylethylene as a colorless oil 20g, 80% ield)

[0159] Step-2: Phenylphosphonic dichloride (15 mL, 105.8 mmol) and dimethylammonium chloride (8.64 g, 106.0 mmol) were dissolved in dichloromethane and cooled to 0 C. in an ice-water bath. Triethylamine (29.5 mL, 211.6 mmol) was added, and the mixture was warmed to RT for 30 minutes. The slurry was filtered, and the filtrate concentrated in-vacuo. The residue was redissolved in dichloromethane and triturated with ether. The mixture was filtered and concentrated, then repeated to remove the salt. This gave the chlorophenyl(dimethylphosphoramide) a sticky solid (12 g, 80% yield)

[0160] Step-3: 4-Bromo-1,1-diphenylethylene generated from 5.1 (3 g, 11.6 mmol) was dissolved in tetrahydrofuran and cooled to 78 C. nBuLi (8.7 mL, 13.9 mmol, 1.6M in hexane) was added and stirred 30 minutes. In a separate flask, the chlorophenyl(dimethylphosphoramide) generated from (b) (3.4 g, 16.7 mmol) was slurried in THF and cooled to 78 C. The 4-lithium-1,1-diphenylethylene generated previously was added in by cannula and the mixture warmed to RT and stirred for 72 hours. The mixture was diluted with ethyl acetate, washed with water, and dried over MgSO.sub.4. The MgSO.sub.4 was filtered out and the filtrate concentrated in vacuo and purified by silica gel column chromatography using 50% ethyl acetate in hexane as eluant. Concentration of the product fractions gave 1-phenyl-1-[4-phenyl(dimethylphosphonamido)]-phenylethylene as a pale-yellow oil (3.5 g, 70% yield).sup.1H NMR, CDCl.sub.3 : 2.68, s, 3H; 2.70, s, 3H; 5.50, s, 2H; 7.30, m, 5H; 7.47, m, 5H; 7.80, m, 4H.

##STR00046##

5.2: Synthesis of Phenyl Dimethyl Phosphonamide Terminated Polymethyl Methacrylate

[0161] 1-Phenyl-1-(4-phenyldimethylphosphonamido)phenylethylene[DPE-P(O)(Ph)(NMe.sub.2)] (1.58 g, 5 mmol) of in 6 ml of dry toluene was added into an ampule. Methyl methacrylate (20.68 g, 207 mmol) was added into a separate ampule and freeze-thawed 3 times to degas. The ampules were attached to the sidearms of the reactor containing lithium chloride (1.75 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and charged with nitrogen. Tetrahydrofuran (210 mL) was added via cannula and the mixture stirred and cooled to 78 C. where the mixture was titrated with sBuLi until a yellow color persists. The mixture was warmed to room temperature where the yellow color dissipates. The mixture was cooled to 78 C. once again and the DPE-P(O)(Ph)(NMe.sub.2) solution was added in. sBuLi (1.2 mL) was added dropwise to titrate the mixture until a yellow color persists. sBuLi (3 mL, 1.4M in cyclohexane, 4 mmol) was then added slowly to produce a red mixture. Methyl methacrylate was added rapid dropwise to the mixture over 2 minutes at which the red color turns colorless. The mixture was stirred for an additional 30 minutes at which time, 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in excess hexane (7 times of the polymer solution), filtered, and dried at 40 C. for 12 h under vacuum to give a white powder (21 g, 99% yield). GPC: 5,602 g/mol M.sub.n, 6,158 g/mole Mw, 1.10 PDI.

Example 6. Synthesis of Dimethylsulfonamide Terminated Polymethyl Methacrylate

6.1 Synthesis of 1-phenyl-1-[4-(dimethylsulfonamido)]-phenylethylene

[0162] Step-1: Acetophenone (3.31 mL, 28.4 mmol) was dissolved in tetrahydrofuran and cooled to 78 C. nBuLi (12.6 mL, 20.2 mmol, 1.6M in hexane) was added, stirred for 30 minutes, 4-bromobenzenedimethylsulfonamide (4.85 g, 18.4 mmol) was added and the mixture was stirred for 30 minutes, then warmed to RT for 1 hour. The mixture was diluted with ethyl acetate, washed with water, and dried over MgSO.sub.4. The MgSO.sub.4 was filtered out and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 33% ethyl acetate in hexane as eluant. The concentration of the product fractions gave 1-phenyl-1-[4-(dimethylsulfonamido)]-phenylethan-1-ol as a white solid (2.7 g, 48% yield).

##STR00047##

[0163] Step-2: 1-Phenyl-1-[4-(dimethylsulfonamido)]-phenylethan-1-ol generated from (a) (2.7 g, x mmol) and p-toluenesulfonic acid monohydrate (cat.) were slurred in toluene and heated to 70 C. for 3 hours. The mixture was diluted with ethyl acetate and washed with water and dried over MgSO.sub.4. The MgSO.sub.4 was filtered out and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 33% ethyl acetate in hexane as eluant. Concentration of the product fractions gave 1-phenyl-1-[4-(dimethylsulfonamido)]-phenylethylene as a pale yellow oil (2.6 g, 99% yield). .sup.1H NMR, CDCl.sub.3 : 2.74, s, 6H; 5.56, s, 1H; 5.59, s, 1H; 7.30, m, 2H; 7.36, m, 3H; 7.50, d, 2H; 7.74, d, 2H 6:2: PMMA-brush synthesis:

##STR00048##

[0164] 1-Phenyl-1-[4-(dimethylsulfonamido)]-phenylethylene [DPE-SO.sub.2(NMe.sub.2)](1.02 g, 3.6 mmol) in 3 ml of dry toluene was added into an ampule. Methyl methacrylate (15.8 g, 157 mmol) was added into a separate ampule and freeze-thawed 3 times to degas. The ampules were attached to the sidearms of the reactor containing lithium chloride (0.4 g, 10 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and charged with nitrogen. Tetrahydrofuran (200 mL) was added via cannula and the mixture stirred and cooled to 78 C. where the mixture was titrated with sBuLi until a yellow color persists. The mixture was warmed to room temperature where the yellow color dissipates. The mixture was cooled to 78 C. once again and the DPE-SO.sub.2(NMe.sub.2) solution was added in. sBuLi (1.2 mL) was added dropwise to titrate the mixture until a yellow color persists. sBuLi (2.1 mL, 1.4M in cyclohexane, 3 mmol) was then added slowly to produce a red mixture. Methyl methacrylate was added rapid dropwise to the mixture over 2 minutes at which the red color turns colorless. The mixture was stirred for an additional 30 minutes at which time, 1 mL of degassed methanol was added to terminate the reaction. The polymer brush was recovered by precipitation in excess hexane (7 times of the polymer solution), filtered, and dried at 40 C. for 12 h under vacuum to give a white powder (15 g, 95% yield). GPC: 5,773 g/mol M.sub.n, 5,946 g/mole Mw, 1.03 PDI.

Preparation of Polymer Formulation

[0165] The polymers described here were separately dissolved in PGMEA to form 1 wt. % solutions. These solutions where individually filtered in using in using a Nylon filter (Entegris, Billerica, Ma). These solutions were separately coated at 1500 rpm on both metal (Cu, W) and SiO.sub.2 wafers, and the wafers were subsequently baked at 230 C. for 5 min. Following the bake, the wafers were rinsed with PGMEA for 2 min to remove any un-grafted polymer from the wafer which were then spun dried by spinning 1,500 rpm, followed by baking at 110 C. for 1 min. Then water contact angle, XPS were measured to understand the grafting efficiency and the results were shown in Table 1. Subsequently, the second brush of hydroxyl terminated PSOH or PMMA-OH containing polymer formulation was made in PGMEA at 1 wt. % solid. Then after filtering with a 0.25-micron Nylon filter, the solution was spin coated on to previously brushed metal and SiO2 substrates. After baking at various temp. and time, the double brushed substrates were rinsed to remove unreacted second brushes. Then the double brushed substrates were examined by WCA and XPS to understand cross-grafting to judge the first brush's efficiency and selectivity to metal substrates.

Coating of Brushes:

[0166] Coating of polymeric brushes on a blanket metal or dielectric wafers using 230 C./5 min baking condition and rinsing excess material out with organic solvents were done and the substrates were analyzed using WCA, FT and XPS.

[0167] Table 1 shows data for selective grafting of metals with different materials which showed high carbon ratios with substrates and appropriate high contact angles depending on the polarity of grafted polymer on metal. Polymers were coated at 1% solution in PGMEA and baked at 230 C./5 min and then rinsed for 2 mins with PGMEA solvent. All the polymers used in these tests had an M.sub.n of around 5,000 g/mol.

TABLE-US-00001 TABLE 1 At % C 1 s C/W or C/Si WCA Materials Name/Mn W SiOx W SiOx W SiOx Example 1 5k 84.6 22.5 25.84 0.43 90 52 PSPS(Me).sub.2 Example 2 4.6K 43.9 5.9 14.5 0.10 67 39 PMMADPEPS(OEt).sub.2 Example 3 4.8K 83.0 26.3 50.6 0.56 90 70 PSDPEPS(OEt).sub.2 Example 4 4.2k 63.1 25.5 7.35 1.00 66 65 PMMADPEPOEt N(Me).sub.2 Example 5 4.5k 48.7 3.42 2.56 0.10 87 52 PMMADPEP(O)Ph N(Me).sub.2 Example 6 5.8k 31.2 2.44 1.3 0.07 62 44 PMMADPES(O).sub.2(NMe.sub.2)

Preparation of Polymer Formulation

[0168] The polymers described here were separately dissolved in PGMEA to form 1 wt. % solutions. These solutions where individually filtered in using in using a Nylon filter (Entegris, Billerica, Ma). These solutions were separately coated at 1500 rpm on both metal (Cu, W) and SiO.sub.2 wafers, and the wafers were subsequently baked at 230 C. for 5 min. Following the bake, the wafers were rinsed with PGMEA for 2 min to remove any un-grafted polymer from the wafer which were then spun dried by spinning 1,500 rpm, followed by baking at 110 C. for 1 min. Then water contact angle, XPS were measured to understand the grafting efficiency and the results were shown in Table 1. Subsequently, the second brush of hydroxyl terminated PSOH or PMMA-OH containing polymer formulation was made in PGMEA at 1 wt. % solid. Then after filtering with 0.25-micron Nylon filter, the solution was spin coated on to previously brushed metal and SiO.sub.2 substrates. After baking at various temp. and time, the double brushed substrates were rinsed to remove unreacted second brushes. Then the double brushed substrates were examined by WCA and XPS to understand cross-grafting to judge the first brush's efficiency and selectivity to metal substrates.