Polymer brushes with chain ends functionalized with two metal-coordinating heteroelements for selective surface modification

Abstract

Two end groups R 3p and R 4p and a polymer chain (R) comprising repeating units of structure (Ip) or structure (IIp). 3p is a C1-C8 alkyl, a portion of structure (IIIp), or a portion of structure (IIIp1). When the repeating unit is (IIp), R 3p is a C1-C8 alkyl. When the repeating unit has (Ip), R 3p is structure (IIIp) or structure (IIIp1). R 4p is a stop moiety such as H, a portion of structure (IVp), a portion of structure (IVp1), or a portion of structure (IVp2). 3p and R 4p cannot simultaneously be both portions of structures (IIIp) and (IVp), cannot simultaneously be portions of structures (IIIp) and (IVp1), or cannot simultaneously be portions of structures (IIIp) and (IVp2), respectively. The polymer of structure (A) must contain one grafted end group moiety selected from structures (IIIp), (IVp), (IVp1), or (IVp2). This composition with a solvent is used for DSA processing. TIFF2025527461000102.tif26170

Description

[Technical Field]

[0001] The disclosed invention relates to novel graftable polymers with one reactive end group containing two heteroatoms that have narrow polydispersities and are selective for metal substrates, and their compositions in organic spin-casting solvents, methods for using these compositions to form polar or nonpolar brushes on substrates, and methods for using these brushes for directed self-assembly. Novel compounds useful for making these polymers are also disclosed. The invention also relates to methods for using these compositions to form polar or nonpolar brushes on substrates, and methods for using these brushes for directed self-assembly (DSA). [Background technology]

[0002] Conventional lithography approaches can use ultraviolet (UV) radiation to expose a photoresist coated on a substrate or layer of substrate through a mask. Positive- or negative-tone photoresists are useful, and they can also contain refractory elements such as silicon to enable dry development using conventional integrated circuit (IC) plasma processing techniques. In positive-tone photoresists, UV radiation passing through a mask causes a photochemical reaction in the photoresist, rendering the exposed areas removable with a developer solution or conventional IC plasma processing. Conversely, in negative-tone photoresists, UV radiation passing through a mask renders the exposed areas less removable with a developer solution or conventional IC plasma processing. Integrated circuit features such as gates, vias, or interconnects are then etched into the substrate or layer of substrate, and the remaining photoresist is removed. Using conventional lithography exposure processes, there are limitations to the feature size of integrated circuit features. Further reduction in pattern size is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture. Directed self-assembly is one promising approach that has gained interest in overcoming some of the drawbacks of conventional lithography outlined above.

[0003] Specifically, directed self-assembly of block copolymers is a useful method for generating very small patterned features for the fabrication of microelectronic devices, and such methods can achieve feature critical dimensions (CDs) on the nanoscale, typically ranging from 10 nm to 50 nm. Using conventional strategies for directed self-assembly of block copolymers, it is difficult to achieve feature sizes below 10 nm. Directed self-assembly methods, such as those based on graphoepitaxy and chemical epitaxy of block copolymers, are desirable for extending the resolution capabilities of lithography techniques.

[0004] These techniques can be used to enhance conventional UV lithography techniques by enabling the generation of patterns with higher resolution and / or improving CD control in the case of EUV, e-beam, deep UV, or immersion lithography. Directed self-assembly block copolymers contain blocks of etch-resistant polymer units and blocks of highly etchable polymer units, which when coated, aligned, and etched onto a substrate, provide regions of high-resolution patterns.

[0005] Known examples of block copolymers suitable for directed self-assembly are those capable of microphase separation and containing a carbon-rich block (e.g., styrene or some other element, such as Si, Ge, or Ti) that is resistant to plasma etching, and a highly plasma-etchable or removable block, allowing for high-resolution pattern definition. An example of a highly etchable block is oxygen-rich, free of refractory elements, and can contain a monomer, such as methyl methacrylate, that can form a highly etchable block. The plasma etching gases used in the etching process that defines the self-assembly pattern are typically those used in methods for manufacturing integrated circuits (ICs). In this way, much finer patterns can be produced on typical IC substrates than with conventional lithography techniques, thereby achieving pattern multiplication.

[0006] In graphoepitaxy-guided self-assembly, the block copolymers self-assemble on substrates that have been prepatterned using conventional lithography (ultraviolet, deep UV, and electron beam, extreme UV (EUV) exposure sources) to form line / space (L / S) or contact hole (CH) patterns. In one example of an L / S-guided self-assembled array, the block copolymers can form self-aligned lamellar regions with sublithographic pitch in the trenches between the sidewalls of the prepattern, thereby enhancing pattern resolution by dividing the spaces in the trenches between the topographic lines into finer patterns. Similarly, features such as contact holes can be produced more densely using graphoepitaxy, where suitable block copolymers align themselves by guided self-assembly within prepatterned hole or prepatterned post arrays defined by conventional lithography, forming a denser array of etchable and etch-resistant domains that, when etched, give a denser array of contact holes. In addition, block copolymers can form a single smaller etchable domain in the center of a prepattern hole with appropriate dimensions, offering potential shrinkage and correction of the hole in the prepattern. As a result, graphoepitaxy has the potential to offer both pattern correction and pattern multiplication.

[0007] In the chemical epitaxy (chemoepitaxy) DSA method, block copolymer self-assembly occurs on a surface that contains regions of different chemical affinity but has little or no topography to guide the self-assembly process. For example, chemical prepatterns can be created using lithography (UV, deep UV, e-beam, EUV) and nanofabrication processes to create surfaces with different chemical affinities in line-and-space (L / S) patterns. These regions have little or no topographical differences, but provide a surface chemical pattern that guides the self-assembly of block copolymer domains. This technique allows for precise positioning of these block copolymer domains with a spatial frequency greater than that of the prepattern. The aligned block copolymer domains can then be pattern-transferred into the underlying substrate after plasma or wet-etching processing techniques. In addition, chemical epitaxy has the advantage that block copolymer self-assembly can modify variations in the surface chemistry, dimensions, and roughness of the underlying chemical pattern, thus providing improved line edge roughness and CD control in the final self-assembled block copolymer domain pattern. Other types of patterns, such as contact hole (CH) arrays, can also be generated or modified using chemoepitaxy.

[0008] The ability of BCPs to undergo phase separation depends on the Flory-Huggins interaction parameter (χ). PS-b-PMMA (poly(styrene-block-methyl methacrylate)) is the most promising candidate for directed self-assembly (DSA) applications. However, the minimum half pitch of PS-b-PMMA is limited to approximately 10 nm due to the low interaction parameter (χ) between PS and PMMA. To enable further feature miniaturization, block copolymers with a larger interaction parameter (larger χ) between the two blocks are highly desirable.

[0009] For lithography applications, alignment of block copolymer domains perpendicular to the substrate is desirable. For conventional block copolymers such as PS-b-PMMA, where both blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermally annealing the block copolymer onto a layer of non-preferential or neutral material that is grafted or crosslinked at the polymer-substrate interface. Due to the relatively large difference in interaction parameters between domains of high-Chi block copolymers, it is important to control both the BCP-air interaction and the BCP-substrate interaction. Many alignment control strategies for producing perpendicularly aligned BCP domains have been implemented using high-Chi BCPs. For example, solvent vapor annealing has been used to control the orientation of polystyrene-b-polyethylene oxide (PS-b-PEO), polystyrene-b-polydimethylsiloxane (PS-b-PDMS), polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP), polylactide-b-poly(trimethylsilylstyrene), PLA-b-PTMSS, and PDMS-b-PHOST. The introduction of a solvent vapor chamber and dynamics in the solvent vapor annealing method can complicate the DSA fabrication process. Instead, a combination of a neutral underlayer and a topcoat material has been applied to PS-b-P2VP, PS-b-PTMSS, and PLA-b-PTMSS to achieve perpendicular orientation of the polymer domains. However, the additional topcoat material can increase process costs and complexity. Therefore, there is a need to provide a topcoat-free, high-chi BCP system that uses simple thermal annealing on a range of preferred and non-preferential substrates.

[0010] Grafted polymers that form covalently bonded films on the surface of a substrate can be produced by plasma deposition, electrochemical deposition, or self-assembly. The strength of the covalent bond determines the adhesiveness of the film, and these films are generally much more adhesive than films that interact with the substrate surface only through secondary forces, such as films produced by spin coating. As a result, due to this stronger adhesion, the formation of grafted polymer films on substrate materials is useful for a variety of applications. These include biomaterials, where substrates are made biocompatible by grafting polymers onto the surface of materials such as medical prosthetics without compromising bulk mechanical properties. Another example is polymers on substrate surfaces, which have also been used to impart anti-biofouling properties or improve corrosion resistance to these surfaces. Another example is coating solutions, where grafting polymers onto substrate surfaces can alter the surface properties of these substrates, resulting in better coatings; and in suspensions of metal or metal oxide nanoparticles, the coatability and stability of these suspensions can be improved by grafting polymers onto the surface of these nanoparticles. Another example is self-assembly and directed self-assembly, where the grafting of polymer brushes onto the surfaces of silicon or silicon oxide substrates can be used to form neutral layers on these surfaces that allow block copolymers to orient their domains perpendicular to the surface substrate during self-assembly or directed self-assembly.

[0011] Directed self-assembly of block copolymers is a useful method for generating ever smaller patterned features for the fabrication of microelectronic devices, achieving feature critical dimensions (CDs) on the nanoscale. Directed self-assembly methods are desirable for extending the resolution capabilities of microlithography techniques. In conventional lithography, ultraviolet (UV) radiation can be used to expose a photoresist layer coated on a substrate or layered substrate through a mask. Positive- or negative-tone photoresists are useful, and they can also contain refractory elements such as silicon to enable dry development using conventional integrated circuit (IC) plasma processing techniques. In positive-tone photoresists, UV radiation passing through the mask causes a photochemical reaction in the photoresist, rendering the exposed areas removable with a developer solution or by conventional IC plasma processing. Conversely, in negative-tone photoresists, UV radiation passing through the mask renders the exposed areas less removable with a developer solution or by conventional IC plasma processing. Integrated circuit features, such as gates, vias, or interconnects, are then etched into the substrate or layered substrate, and the remaining photoresist is removed. Using conventional lithographic exposure processes, there are limitations to the feature size of integrated circuit features. Further reduction in pattern size is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture. Due to the need for large-scale integration, device circuit dimensions and features have continually been reduced. In the past, the final resolution of features has depended on the wavelength of light used to expose the photoresist, which has its own limitations. Guided assembly techniques, such as graphoepitaxy or chemoepitaxy using block copolymer imaging, are highly desirable techniques used to increase resolution while reducing CD variation. These techniques can be used to enhance conventional UV lithography techniques or to enable even higher resolution and CD control in approaches using EUV, electron beam, deep UV, or immersion lithography.The directed self-assembly block copolymers contain blocks of etch-resistant copolymer units and blocks of etch-prone copolymer units, which when coated, aligned, and etched onto a substrate, provide highly dense patterned regions.

[0012] A neutral layer is a layer on a substrate or a surface of a treated substrate that has no affinity for any of the block segments of the block copolymer used in the directed self-assembly. Neutral layers are useful in graphoepitaxy methods of directed self-assembly of block copolymers because they allow for proper placement or orientation of the block polymer segments for directed self-assembly, resulting in proper placement of the etch-resistant and etch-resistant block polymer segments relative to the substrate. For example, in a surface containing line-and-space features defined by conventional radiation lithography, the neutral layer allows for the block segments to be oriented perpendicular to the surface of the substrate, which is an ideal orientation for both pattern modification and pattern multiplication, depending on the length of the block segments in the block copolymer relative to the length between the lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, this segment will lie flat on its surface, maximizing the contact area between the segment and the substrate; such a surface will disrupt the desired vertical alignment, which can be used to achieve either pattern modification or pattern multiplication based on features generated by conventional lithography. Modifying or pinning selected small regions of the substrate so that they interact strongly with one block of the block copolymer, while leaving the rest of the substrate coated with a neutral layer, can be useful for aligning the domains of the block copolymer in a desired direction, and this is the basis for pinned chemo- or graphoepitaxy used for pattern multiplication. [Prior art documents] [Non-patent literature]

[0013] [Non-Patent Document 1] David Uhrig and Jimmy Mays, “Techniques in High-Vacuum Anionic Polymerization”, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005) Summary of the Invention [Problem to be solved by the invention]

[0014] There is a need for novel materials that can form grafted polymer layers on semiconductor (e.g., Si, GaAs, etc.), metal (Cu, W, Mo, Al, Zr, Ti, Hf, Au, etc.), and metal oxide (copper oxide, aluminum oxide, hafnium oxide, zirconium oxide, titanium oxide, etc.) substrates via simple spin coating without the presence of activating components, such as acidic compounds, thermal acid generators, photoacid generators, thermal radical generators, photochemical radical generators, basic additives, thermal base generators, or photobase generators, to promote the grafting reaction on the substrate, followed by a post-coat bake to effect chemical bonding. The presence of such thermally or photochemically reactive additive compounds is undesirable because the small size and reactivity of these compounds can cause them to diffuse from the grafted film to other layers, potentially resulting in undesirable reactions such as corrosion. Another need exists for grafted materials in which the graftable polymer does not contain overly reactive grafting sites, which could adversely affect the shelf life of solutions of the grafting solution in organic solvents, such as spin-casting solvents. There is also a need for new grafting materials that allow selective grafting to specific types of substrates by varying the grafting bake. In this way, the surface properties of these materials, such as coatability and corrosion resistance, can be altered by a simple spin-coating process without the need for plasma deposition or electrochemical grating. The novel selective grafting process using the novel materials of the present invention also allows for the one-step coating of only one material onto a substrate containing a topographical or chemical pattern where different materials are present on a single substrate. There is also a need for new neutral layer compositions that, when formed into layers, remain neutral to the self-assembling block copolymers but are still not damaged by the processing steps of directed self-assembly techniques and can further enhance the lithographic performance of directed self-assembly materials and processes, particularly by reducing the number of processing steps and providing better pattern resolution with good lithographic performance.There is also a need for coatable pinning materials for small areas of metal or metal oxide substrates that are otherwise coated with a neutral layer, for example in a chemo-epitaxy approach, to force vertically oriented domains using a neutral layer foundation to align these domains in a desired direction. There is also a need for polar and non-polar brush compositions that selectively form only one material on a substrate containing a pattern of a different material to create pinned regions. [Means for solving the problem]

[0015] One aspect of the disclosed invention relates to a polymer containing one grafted end group having at least two heteroatoms. Specifically, this polymer of structure (A) has two end groups R 3p and R 4p and a polymer chain (R) comprising repeating units of structure (Ip) or repeating units of structure (IIp), wherein the terminal group R derived from an anionic initiator 3p is a C1-C8 alkyl, a portion of the structure (IIIp), or a portion of the structure (IIIp1), provided that when the repeating unit in the polymer (R) is (IIp), R 3p can be selected only from C1-C8 alkyl, and in the polymer chain (R), when the repeating unit is structure (Ip), R 3p can be selected only from the portion of structure (IIIp) or structure (IIIp1), and the terminal group R 4p is a moiety selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si-), C1-C8 dialkylsilyl ((alkyl)2HSi-), C1-C8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-), and benzyl-based moieties, a moiety of structure (IVp), a moiety of structure (IVp1), or a moiety of structure (IVp2), and further comprising a terminal group R 3p and R 4pcannot both simultaneously be portions of Structures (IIIp) and (IVp), cannot both simultaneously be portions of Structures (IIIp) and (IVp1), or cannot both simultaneously be portions of Structures (IIIp) and (IVp2), respectively, provided that said polymer of Structure (A) must contain one end group moiety selected from Structures (IIIp), (IVp), (IVp1), or (IVp2).

[0016] In the polymer of structure (A), the repeating unit of structure (Ip) is R m1 is a C1-C8 alkyl, and R 1p is a C1-C8 alkyl, and n1 is the number of this repeat unit in the polymer chain (R).

[0017] In the polymer of structure (A), the repeating unit of structure (IIp) is R m2 is H or C1-C8 alkyl, and R 2p is H or C1-C8 alkyl, and n2 is the number of this repeat unit in the polymer chain (R).

[0018] Further, in said polymer of structure (A), in structure (IIIp), R1 is a chelating group located in the para or meta position selected from a phosphinothioic acid group of structure (Ia), an aminosulfonyl moiety of structure (Ib), and a phosphonamide moiety of structure (Ic), where *** indicates the point of attachment of this end group moiety to the polymer of structure (A).

[0019] Further, in the phosphinothioic acid moiety of structure (Ia), R3 and R4 are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy; and a dialkylamino moiety -N(R9)(R 10 ) where R9 and R 10are independently selected from C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, and * indicates the point of attachment of this moiety to the end group moiety of Structure (IIIp), provided that said polymer of Structure (A) must contain one end group moiety selected from Structure (IIIp), (IVp), (IVp1) or (IVp2).

[0020] Additionally, in the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, and the dialkylamino moiety -N(R9)(R 10 ), and * indicates the point of attachment of this moiety to the terminal moiety of structure (IIIp).

[0021] Additionally, in the phosphonamide moiety of structure (Ic), R7 is the dialkylamino moiety -N(R9)(R 10 ), and R8 is selected from the group consisting of aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy, and * indicates the point of attachment of this moiety to the terminal group moiety of structure (IIIp).

[0022] Further, in structure (IIIp), R2 is selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moiety of structure (Ia), aminosulfonyl of structure (Ib), and phosphonamide of structure (Ic), and R 15 is C1-C8 alkyl, and R e1 and R e2 is independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy.

[0023] Furthermore, in the polymer of structure (A), in structure (IIIp1), R e1 and R e2 is independently selected from H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, and C3-C8 cyclic alkyloxy; and R 15 is a C1-C8 alkyl, and *** indicates the point of attachment of this end group moiety to the polymer of structure (A).

[0024] Further, in the polymer of structure (A), in structure (IVp), R 12 is H or C1-C4 alkyl, and R 11 is the phosphinothioic acid moiety of structure (IIa), *** indicates the point of attachment of this end group moiety to the polymer of structure (A), L1 is a linking group selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), where ** indicates the point of attachment of said L1 organic linking moiety to phosphorus in structure (IIa), and * indicates the moiety R 11 L1 in the formula (IVp) indicates the point of attachment to the carbonyloxy, and R 17 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)Si-), C1-C8 dialkylsilyl ((alkyl)HSi-), C1-C8 monoalkylsilyl ((alkyl)HSi-), silane (HSi-), and benzyl-based moieties. In structure (IIa), * indicates the point of attachment of the phosphinothioic acid moiety to structure (IVp), and R 13 and R 14are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; and the dialkylamino moiety -N(R9)(R 10 ), and R and R 10 is independently selected from C1 to C8 linear alkyl, C3 to C8 branched alkyl, and C3 to C8 cyclic alkyl.

[0025] Further, in the polymer of Structure (A), in Structure (IVp1), L is a linking moiety that is a direct valence bond or a linking group selected from C1-C8 linear alkylene, C3-C8 branched alkylene, and C5-C8 cyclic alkylene, alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), and alkylenearyl moiety (*-alkylene-aryl-**), where ** indicates the point of attachment of the L linking moiety to phosphorus in Structure (IVp1), and * indicates the point where L is attached to the polymer of Structure (A), and Rs and Rs1 are independently selected from C1-C8 alkoxy or C1-C8 alkyl, and further, *** indicates the point of attachment of this end group moiety to the polymer of Structure (A).

[0026] Further, in said polymer of Structure (A), in Structure (IVp2), R1 is a chelating group located at the para or meta position selected from said phosphinothioic acid moiety of Structure (Ia), said aminosulfonyl moiety of Structure (Ib), and said phosphonamide moiety of Structure (Ic), and R2 is selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moiety of Structure (Ia), aminosulfonyl of Structure (Ib), and phosphonamide of Structure (Ic), and R 18is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si-), C1-C8 dialkylsilyl ((alkyl)2HSi-), C1-C8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-), and benzylic moieties, and *** indicates the point of attachment of this end group moiety to the polymer of structure (A).

[0027] Additionally, said polymer of structure (A) has an M in the range of from about 4000 to about 7000. n and a polydispersity ranging from 1 to about 1.15.

[0028] [ka] Another aspect of the present invention relates to compositions of the polymers of structure (A) in organic spin-casting solvents.

[0029] Other aspects of the invention include a process of forming a pinned layer using the composition, and a chemoepitaxy process using the pinned layer for directed self-assembly of an overlying block copolymer, and a subsequent process of etching this directed self-assembled block copolymer layer into a substrate.

[0030] Yet another aspect of the present invention is novel compounds of structure (I) and their use in the preparation of polymers, wherein R1 is a chelating group located in the meta or para position selected from a phosphinothioic acid moiety of structure (Ia), an aminosulfonyl moiety of structure (Ib), and a phosphonamide moiety of structure (Ic), and * indicates the point of attachment of these moieties to the compound of structure (I).

[0031] In the phosphinothioic acid moiety of structure (Ia), R3 and R4 are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy; and the dialkylamino moiety -N(R9)(R 10 ) and R9 and R 10 is independently selected from C1 to C8 linear alkyl, C3 to C8 branched alkyl, and C3 to C8 cyclic alkyl.

[0032] In the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, and the dialkylamino moiety -N(R9)(R 10 )

[0033] In the phosphonamide moiety of structure (Ic), R7 is the dialkylamino moiety -N(R9)(R 10 ) and R8 is selected from the group consisting of aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy.

[0034] Further, in the novel compounds of structure (I), R2 is a substituent located at the meta or para position selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moieties of structure (Ia), aminosulfonyls of structure (Ib), and phosphonamides of structure (Ic).

[0035] [ka] Yet another aspect of the present invention is novel compounds of structure (II) and their use in the preparation of polymers, wherein R 11 is the phosphinothioic acid moiety of structure (IIa), * indicates the point of attachment of this moiety to the compound of structure (II), R 13 and R 14 are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; and the dialkylamino moiety -N(R9)(R 10 ), and R and R 10 is independently selected from C1 to C8 linear alkyl, C3 to C8 branched alkyl, and C3 to C8 cyclic alkyl.

[0036] Further, in this compound, L1 is a linking moiety selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), where ** indicates the point of attachment of said L1 organic linking moiety to phosphorus in structure (IIa), and * indicates the attachment point of the moiety R 11 indicates the position where L1 is bonded to the carbonyloxy of compound (II), and R 12 is H or C1-C4 alkyl.

[0037] [ka] DETAILED DESCRIPTION OF THE INVENTION

[0038] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive with respect to the invention as claimed. As used herein, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of "comprises" and other verb forms, such as "comprises," is not limiting. Furthermore, references to "elements" or "components" include both elements and components containing one unit and elements or components containing more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead" is intended to be exclusive. As used herein, the conjunction "and" refers to any combination of the aforementioned elements, including the use of a single element.

[0039] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions thereof cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials cited herein conflicts with that herein, the definition herein shall control.

[0040] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that can be linear or branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, adamantyl, and the like). These alkyl moieties may be substituted or unsubstituted as described below. Unless otherwise specified, the term "alkyl" refers to such moieties having C1 to C8 carbons. For structural reasons, it is understood that linear alkyls begin at C1, while branched and cyclic alkyls begin at C3, and polycyclic alkyls begin at C5. Furthermore, moieties derived from alkyls described below, such as alkyloxy (alkoxy), are understood to have the same carbon number range unless otherwise specified. This same rule applies to the description C1 to C4 alkyl. Where a different alkyl group length than those above is specified, the above definition of alkyl remains valid in that it encompasses all types of alkyl moieties above, and the structural considerations above regarding the minimum carbon number of a given type of alkyl group still apply.

[0041] Alkyloxy (also known as alkoxy) refers to an alkyl group 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 type of alkyl in a C1-C8 alkoxy or C1-C4 alkoxy are the same as those described above for the alkyl moiety.

[0042] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0043] Haloalkyl refers to a saturated linear, cyclic, or branched alkyl group, such as those described above, in which at least one of the hydrogens has been replaced by a halide selected from the group F, Cl, Br, I, or mixtures thereof when more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0044] The term "alkylene" refers to a hydrocarbon group that can be linear, branched, or cyclic and has two or more points of attachment (two points of attachment include, for example, methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like; three points of attachment include, for example, 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, and the like). Again, when specifying a range of possible carbon numbers, such as, for example, C1 to C20 as a non-limiting example, this range includes linear alkylene starting from C1, but specifies only branched alkylene or cycloalkylene starting from C3. These alkylene moieties may be substituted or unsubstituted, as described below.

[0045] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls, and the like. These aryl groups may be further substituted with any of the suitable substituents described above, such as alkyl, alkoxy, acyl, or aryl groups described above.

[0046] Unless otherwise indicated in the specification, the term "substituted," when referring to aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic ring, arene, or heteroarene, includes unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), haloaryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, cyano, nitro, acetyl, alkylcarbonyl, formyl, ethenyl (CH2=CH-), phenylethenyl (Ph-CH=CH-), arylethenyl (aryl-CH=CH), and ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)). z (z is 1-3)) refers to one of these moieties that also contains one or more substituents selected from the group. Non-limiting examples of substituted aryl and substituted arylethenyl substituents are:

[0047] [ka] represents the point of attachment.

[0048] [ka] Polymers of the Invention One aspect of the present invention is a method for producing a compound having two terminal groups R 3p and R 4p and a polymer chain (R) comprising repeating units of structure (Ib) or repeating units of structure (IIb), wherein the polymer has an end group R derived from an anionic initiator. 3p is a C1-C8 alkyl, a portion of the structure (IIIp), or a portion of the structure (IIIp1), provided that when the repeating unit in the polymer chain (R) is (IIp), R 3p can be selected only from C1 to C8 alkyl, and further, in the polymer chain (R), when the repeating unit is structure (Ip), R 3pcan be selected only from the portion of structure (IIIp) or structure (IIIp1). 4p is a moiety selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si-), C1-C8 dialkylsilyl ((alkyl)2HSi-), C1-C8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-), and benzyl-based moieties, a moiety of structure (IVp), a moiety of structure (IVp1), or a moiety of structure (IVp2), and further comprising a terminal group R 3p and R 4p cannot both simultaneously be part of Structures (IIIp) and (IVp), cannot both simultaneously be part of Structures (IIIp) and (IVp1), or cannot both simultaneously be part of Structures (IIIp) and (IVp2), respectively, provided that said polymer of Structure (A) must contain one end group selected from Structures (IIIp), (IVp), (IVp1), or (IVp2).

[0049] In the polymer of Structure (A), in the repeating unit of Structure (Ip), R m1 is C1-C8 alkyl, and R 1p is a C1-C8 alkyl, and n1 is the number of this repeat unit in the polymer chain (R).

[0050] In the polymer of structure (A), the repeating unit of structure (IIp) is R m2 is H or C1-C8 alkyl, and R 2p is H or C1-C8 alkyl, and n2 is the number of this repeat unit in the polymer chain (R).

[0051] Further, in said polymer of Structure (A), in the structure of Structure (IIIp), R1 is a chelating group located in the para or meta position selected from a phosphinothioic acid moiety of Structure (Ia), an aminosulfonyl moiety of Structure (Ib), and a phosphonamide moiety of Structure (Ic), where *** indicates the point of attachment of this end group moiety to the polymer of Structure (A).

[0052] Further, in the phosphinothioic acid moiety of structure (Ia), R3 and R4 are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy; and a dialkylamino moiety -N(R9)(R 10 ) and R9 and R 10 is independently selected from C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, and * indicates the point of attachment of this moiety to the terminal group moiety of structure (IIIp).

[0053] Additionally, in the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, and the dialkylamino moiety -N(R9)(R 10 ), and * indicates the point of attachment of this moiety to the terminal moiety of structure (IIIp).

[0054] Additionally, in the phosphonamide moiety of structure (Ic), R7 is the dialkylamino moiety -N(R9)(R 10 ), and R8 is selected from the group consisting of aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy, and * indicates the point of attachment of this moiety to the terminal group moiety of structure (IIIp).

[0055] Further, in structure (IIIp), R2 is selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moiety of structure (Ia), aminosulfonyl of structure (Ib), and phosphonamide of structure (Ic), and R 15 is C1-C8 alkyl, and R e1 and R e2 is independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy.

[0056] Furthermore, in the polymer of structure (A), in structure (IIIp1), R e1 and R e2 is independently selected from H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, and C3-C8 cyclic alkyloxy; and R 15 is a C1-C8 alkyl, and *** indicates the point of attachment of this end group moiety to the polymer of structure (A).

[0057] Further, in the polymer of structure (A), in structure (IVp), R 12 is H or C1-C4 alkyl, and R 11 is the phosphinothioic acid moiety of structure (IIa), *** indicates the point of attachment of this end group moiety to the polymer of structure (A), L1 is a linking moiety selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), ** indicates the point of attachment of said L1 organic linking moiety to phosphorus in structure (IIa), and * indicates the moiety R11 L1 in the formula (IVp) indicates the point of attachment to the carbonyloxy, and R 17 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)Si-), C1-C8 dialkylsilyl ((alkyl)HSi-), C1-C8 monoalkylsilyl ((alkyl)HSi-), silane (HSi-), and benzylic moieties. In structure (IIa), the * indicates the point of attachment of the phosphinothioic acid moiety to structure (IVp).

[0058] R 13 and R 14 are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; and the dialkylamino moiety -N(R9)(R 10 ), and R and R 10 is independently selected from C1 to C8 linear alkyl, C3 to C8 branched alkyl, or C3 to C8 cyclic alkyl.

[0059] Further, in said polymer of Structure (A), in Structure (IVp1), L is a direct valence bond or a linking group selected from C1-C8 linear alkylene, C3-C8 branched alkylene, and C5-C8 cyclic alkylene, alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), and alkylenearyl moiety (*-alkylene-aryl-**), ** indicates the point of attachment of said L linking moiety to phosphorus in Structure (IVp1), * indicates the point where L is attached to said polymer of Structure (A), and Rs and Rs1 are independently selected from C1-C8 alkoxy or C1-C8 alkyl, and further, *** indicates the point of attachment of this end group moiety to the polymer of Structure (A).

[0060] Further, in said polymer of Structure (A), in Structure (IVp2), R1 is a chelating group located at the para or meta position selected from said phosphinothioic acid moiety of Structure (Ia), said aminosulfonyl moiety of Structure (Ib), and said phosphonamide moiety of Structure (Ic), and R2 is selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moiety of Structure (Ia), aminosulfonyl of Structure (Ib), and phosphonamide of Structure (Ic), and R 18 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si-), C1-C8 dialkylsilyl ((alkyl)2HSi-), C1-C8 monoalkylsilyl ((alkyl)H2Si-), silane (H3Si-), and benzylic moieties, and *** indicates the point of attachment of this end group moiety to the polymer of structure (A).

[0061] Additionally, said polymer of structure (A) has an M in the range of from about 4000 to about 7000. n and has a polydispersity ranging from 1 to about 1.15.

[0062] [ka] In one aspect of the polymers of the invention described herein, the terminal group R 4p is not a chelating moiety (IVp), (IVp1) or (IVp2), then it is H. In another aspect of this embodiment, R 4p is C1-C8 alkyl. In another aspect of this embodiment, R 4p is C1-C8 alkylcarbonyl (alkyl-C(=O)-). In another aspect of this embodiment, R 4pis C1-C8 trialkylsilyl ((alkyl)3Si-). In another aspect of this embodiment, R 4p is C1-C8 dialkylsilyl ((alkyl)2HSi-). In another aspect of this embodiment, R 4p is C1-C8 monoalkylsilyl ((alkyl)H2Si-). In another aspect of this embodiment, R 4p is silane (HSi-). In another aspect of this embodiment, R 4p is a benzylic moiety.

[0063] In one aspect of the polymer of the invention, the chelating moiety (IVp), when present, is R 17 is H. In another aspect of this embodiment, R 17 is C1-C8 alkyl. In another aspect of this embodiment, R 17 is C1-C8 alkylcarbonyl (alkyl-C(=O)-). In another aspect of this embodiment, R 17 is C1-C8 trialkylsilyl ((alkyl)3Si-). In another aspect of this embodiment, R 17 is C1-C8 dialkylsilyl ((alkyl)2HSi-). In another aspect of this embodiment, R 17 is C1-C8 monoalkylsilyl ((alkyl)H2Si-). In another aspect of this embodiment, R 17 is silane (HSi-). In another aspect of this embodiment, R 17 is a benzylic moiety.

[0064] In one aspect of the polymer of the invention, the chelating moiety (IVp2), when present, is R 18 is H. In another aspect of this embodiment, R 18 is C1-C8 alkyl. In another aspect of this embodiment, R 18 is C1-C8 alkylcarbonyl (alkyl-C(=O)-). In another aspect of this embodiment, R 18 is C1-C8 trialkylsilyl ((alkyl)3Si-). In another aspect of this embodiment, R18 is C1-C8 dialkylsilyl ((alkyl)2HSi-). In another aspect of this embodiment, R 18 is C1-C8 monoalkylsilyl ((alkyl)H2Si-). In another aspect of this embodiment, R 18 is silane (HSi-). In another aspect of this embodiment, R 18 is a benzylic moiety.

[0065] In one aspect of the inventive polymer of structure (A), it has the more specific structure (A-1).

[0066] [ka] In one aspect of the inventive polymer of structure (A-1), it has structure (A-2): In one aspect of this embodiment, R m1 is methyl. In another aspect of these embodiments, R 1p is methyl. In yet another aspect of these embodiments, R2 is H.

[0067] [ka] In another aspect of the polymer of the invention having structure (A-1) or (A-2), it has structure (A-2a). In another aspect of this structure, it has structure (A-2b). In one aspect of these embodiments, R3 and R4 are independently selected from C1-C4 alkoxy or C1-C4 alkyl. In another aspect of these embodiments, R3 and R4 are independently selected from C1-C4 alkoxy. In another aspect of these embodiments, R3 and R4 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, R3 and R4 are both ethoxy. In another aspect of these embodiments, R3 and R4 are both methoxy. In yet another aspect of this structure, it has structure (A-2c). In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R1p is methyl. In yet another aspect of these embodiments, R2 is H.

[0068] [ka] In another aspect of the polymer of the invention having structure (A-1) or (A-2), it has structure (A-2d). In another aspect of this embodiment, it has structure (A-2e). In yet another aspect of this embodiment, it has structure (A-2f). In one aspect of these embodiments, R5 and R6 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, R5 and R6 are independently selected from C1-C2 alkyl. In one aspect of these embodiments, R5 and R6 are methyl. In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R 1p is methyl. In yet another aspect of these embodiments, R2 is H.

[0069] [ka] In another aspect of the polymer of the invention having structure (A-1) or (A-2), it has structure (A-2g). In another aspect 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 and R 10 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, R9 and R 10 are independently selected from C1-C2 alkyl. In one aspect of these embodiments, R9 and R 10 is methyl. R9 and R 10 is independently selected from C1-C4 alkyl, R8 is selected from C1-C4 alkyl or aryl; in one aspect of this embodiment, R8 is C1-C2 alkyl; in another aspect of this embodiment, the aryl is phenyl. In one aspect of these embodiments, Rm1 is methyl. In another aspect of these embodiments, R 1p is methyl. In yet another aspect of these embodiments, R2 is H.

[0070] [ka] In another aspect of the polymer of the invention having structure (A-1) or (A-2), it has structure (A-3). In one aspect of this polymer, L1 is a direct valence bond. In another aspect of this polymer, L1 is a C2-C8 alkylene moiety. In another aspect of this polymer, L1 is an arylene moiety (-aryl-). In yet another aspect of this polymer, L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In another aspect of these embodiments, R 13 and R 14 is independently selected from C1-C4 alkyl and C1-C4 alkoxy. In another aspect of these embodiments, R 13 and R 14 is independently selected from C1-C4 alkoxy. In another aspect of these embodiments, R 13 and R 14 In another aspect of these embodiments, R 13 and R 14 In another aspect of these embodiments, R 13 and R 14 is independently selected from C1-C4 alkyl. In another aspect of these embodiments, R 13 and R 14 is ethyl. In another aspect of these embodiments, R 13 and R 14 In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 and R are both H. In another aspect of these embodiments, R17 is H. In another aspect of these embodiments, R 12 is H.

[0071] [ka] In another aspect of the polymer of Structure (A-3), where L1 is a C2-C8 alkylene moiety, it has Structure (A-3a) or Structure (A-3b), where n is an integer ranging from 1 to 7. In one aspect of these embodiments, R 13 and R 14 is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14 is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkoxy. In another aspect of this embodiment, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1-C4 alkyl. In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 and R are both H. In another aspect of these embodiments, R 17 is H. In another aspect of these embodiments, R 12 is H.

[0072] [ka] In another aspect of the polymer of structure (A-3), it has structure (A-3c) or (A-3d), where L is an alkylenearyl moiety (*-alkylene-aryl-**) and n' is an integer ranging from 0 to 7. In one aspect of these embodiments, R 13 and R 14 is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14 is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl, and in another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkoxy. In another aspect of these embodiments, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1-C4 alkyl. In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 and R are both H. In another aspect of these embodiments, R 17 is H. In another aspect of these embodiments, R 12 is H.

[0073] [ka] In another aspect of the inventive polymer of structure (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 C2-C8 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 yet another aspect of this embodiment, L is an alkylenearyl moiety (*-alkylene-aryl-**). In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 are both H.

[0074] [ka] In another aspect of the polymer of the invention of structure (A-4), it has structure (A-4a) or structure (A-4b), where 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 independently selected from C1-C4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C1-C4 alkoxy. In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 are both H.

[0075] [ka] In another aspect of the inventive polymer of structure (A-4), it has structure (A-4c) or structure (A-4d), where 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 independently selected from C1-C4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C1-C4 alkoxy. In one aspect of these embodiments, R m1 is methyl. In another aspect of these embodiments, R 1p In yet another aspect of these embodiments, R e1 and R e2 are both H.

[0076] [ka] In one aspect of the polymer of the invention of structure (A), it has the more specific structure (B-1), where R 3p is a C1-C8 alkyl.

[0077] [ka] In one aspect of the polymer of the invention of structure (B-1), it has structure (B-1a) and R 3p is C1-C8 alkyl. In another aspect, R 3p is a C1-C8 alkyl, and L1 is a direct valence bond. In another aspect, R 3p is a C1-C8 alkyl and L1 is a C2-C8 alkylene moiety. 3p is a C1-C8 alkyl and L1 is an arylene moiety (-aryl-). In another aspect of this embodiment, R 3p is a C1-C8 alkyl, and L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In one aspect of these embodiments, R 13 and R 14is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14 is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkoxy. In another aspect of these embodiments, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1-C4 alkyl. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p is H.

[0078] [ka] In one aspect of the polymer of the invention of structure (B-1), it has structure (B-1b) or (B-1c), where R 3p is C1-C8 alkyl, and n is an integer ranging from 1 to 7. In one aspect of these embodiments, R 13 and R 14 is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14 is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkoxy. In another aspect of these embodiments, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1-C4 alkyl. In another aspect of these embodiments, R m2is H. In yet another aspect of these embodiments, R 2p is H. In another aspect of these embodiments, R 17 is H. In another aspect of these embodiments, R 12 is H.

[0079] [ka] In one aspect of the inventive polymer of structure (B-1), it has the more specific structure (B-1d) or (B-1e), where R 3p is C1-C8 alkyl, and n' is an integer ranging from 0 to 7. In one aspect of these embodiments, R 13 and R 14 is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14 is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkoxy. In another aspect of these embodiments, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1-C4 alkyl. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p is H. In another aspect of these embodiments, R 17 is H. In another aspect of these embodiments, R 12 is H.

[0080] [ka] 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 C2-C8 alkylene moiety. In another aspect of this embodiment, L is an arylene moiety (-aryl-). In another aspect of this embodiment, L is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**). In another aspect of this embodiment, Rs and Rs1 are independently selected from C1-C4 alkyl. In another aspect of this embodiment, Rs and Rs1 are independently selected from C1-C4 alkoxy. In yet another aspect, Rs and Rs1 are methyl. In another aspect of this embodiment, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p is H.

[0081] [ka] In view of the polymer of the invention of Structure (B-2) where L is a direct valence bond, it has Structure (B-2aa). In another aspect of this embodiment, Rs and Rs1 are independently selected from C1-C4 alkyl. In another aspect of this embodiment, Rs and Rs1 are independently selected from C1-C4 alkoxy. In yet another aspect of this embodiment, Rs and Rs1 are methyl. In another aspect of this embodiment, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p is H.

[0082] [ka] In another aspect, the polymer of structure (B-2) has structure (B-2a) or structure (B-2b), provided that R 15is C1-C8 alkyl, and n' is an integer ranging from 0 to 7. In one aspect of these embodiments, Rs and Rs1 are independently selected from C1-C8 alkyl or alkoxy. In another aspect of these embodiments, Rs and Rs1 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C1-C4 alkoxy. In yet another aspect, Rs and Rs1 are methyl. In another aspect, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p is H.

[0083] [ka] In another aspect, the polymer of structure (B-2) has structure (B-2c) or structure (B-2d), provided that R 15 is C1-C8 alkyl, and n' is an integer ranging from 0 to 7. In one aspect of these embodiments, Rs and Rs1 are independently selected from C1-C8 alkyl or alkoxy. In another aspect of these embodiments, Rs and Rs1 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, Rs and Rs1 are independently selected from C1-C4 alkoxy. In yet another aspect, Rs and Rs1 are methyl. In another aspect, Rs and Rs1 are methoxy. In another aspect of these embodiments, R m2 is H. In yet another aspect of these embodiments, R 2p is H.

[0084] [ka] In another aspect of the inventive polymer of structure (B-1), it has structure (B-3). In one aspect of these embodiments, R3 and R4 are independently selected from C1-C4 alkoxy or C1-C4 alkyl. In one aspect of this embodiment, R 2p is H. In another aspect of this embodiment, R m2 is H. In another aspect of this embodiment, R2 is H. In another aspect of these embodiments, R 18 is H.

[0085] [ka] In one aspect of the polymer of Structure (B-3), it has Structure (B-3a), Structure (B-3b), or Structure (B-3c). In one aspect of these embodiments, R3 and R4 are independently selected from C1-C4 alkoxy or C1-C4 alkyl. In another aspect of these embodiments, R3 and R4 are independently selected from C1-C4 alkoxy. In another aspect of these embodiments, R3 and R4 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, R3 and R4 are both ethoxy. In another aspect of these embodiments, R3 and R4 are both methoxy. In another aspect of these embodiments, R 2p is H. In another aspect of these embodiments, R m2 is H. In another aspect of these embodiments, R2 is H. In another aspect of these embodiments, R 18 is H.

[0086] [ka] In another aspect of the polymer of structure (B-3), it has structure (B-3d), structure (B-3e), or structure (B-3f). In one aspect of these embodiments, R5 and R6 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, R5 and R6 are independently selected from C1-C2 alkyl. In one aspect of these embodiments, R5 and R6 are methyl. In one aspect of these embodiments, R 2p is H. In another aspect of these embodiments, R m2 is H. In another aspect of these embodiments, R2 is H. In another aspect of these embodiments, R 18 is H.

[0087] [ka] In another aspect of the polymer of structure (B-3), it has structure (B-3g), structure (B-3h), or structure (B-3i). In one aspect of these embodiments, R and R 10 are independently selected from C1-C4 alkyl. In another aspect of these embodiments, R9 and R 10 are independently selected from C1-C2 alkyl. In one aspect of these embodiments, R9 and R 10 is methyl. R9 and R 10 is independently selected from C1-C4 alkyl, R8 is selected from C1-C4 alkyl or aryl; in one aspect of this embodiment, R8 is C1-C2 alkyl; in another aspect of this embodiment, the aryl is phenyl. In one aspect of these embodiments, R 2p is H. In another aspect of these embodiments, R m2 is H. In another aspect of these embodiments, R2 is H. In another aspect of these embodiments, R 18 is H.

[0088] [ka] Compositions of the Invention Another aspect of the present invention is a composition of any one of the polymers of the present invention described herein having structure (A) and an organic spin-casting solvent.

[0089] Another aspect of the present invention is a composition of any one of the polymers of the present invention described herein having the structure (A-1) and an organic spin-casting solvent.

[0090] Another aspect of the present invention is a composition comprising any one of the polymers of the present invention 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, the polymer has structure (A-2). In one aspect of this embodiment, the polymer has structure (A-2a). In one aspect of this embodiment, the polymer has structure (A-2b). In one aspect of this embodiment, the polymer has structure (A-2c). In one aspect of this embodiment, the polymer has structure (A-2d). In one aspect of this embodiment, the polymer has structure (A-2e). In one aspect of this embodiment, the polymer has structure (A-2f). In one aspect of this embodiment, the polymer has structure (A-2g). In one aspect of this embodiment, the polymer has structure (A-2h). In one aspect of this embodiment, the polymer has structure (A-2i). In another aspect of this embodiment, the composition comprises any one of the above polymer structures and an organic spin-casting solvent.

[0091] Another aspect of the present invention is a composition comprising any one of the polymers of the present invention 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, the polymer has structure (A-3). In one aspect of this embodiment, the polymer has structure (A-3a). In one aspect of this embodiment, the polymer has structure (A-3b). In one aspect of this embodiment, the polymer has structure (A-3c). In one aspect of this embodiment, the polymer has structure (A-3d). In another aspect of this embodiment, the composition consists solely of any one of the polymer structures described herein and an organic spin-casting solvent.

[0092] Another aspect of the present invention is a composition comprising any one of the polymers of the present invention 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, the polymer has structure (A-4). In one aspect of this embodiment, the polymer has structure (A-4a). In one aspect of this embodiment, the polymer has structure (A-4b). In one aspect of this embodiment, the polymer has structure (A-4c). In one aspect of this embodiment, the polymer has structure (A-4d). In another aspect of this embodiment, the composition consists solely of any one of the polymer structures described herein and an organic spin-casting solvent.

[0093] Another aspect of the invention is a composition comprising any one of the polymers of the invention 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, the polymer has structure (B-1). In one aspect of this embodiment, the polymer has structure (B-1a). In one aspect of this embodiment, the polymer has structure (B-1b). In one aspect of this embodiment, the polymer has structure (B-1c). In one aspect of this embodiment, the polymer has structure (B-1d). In one aspect of this embodiment, the polymer has structure (B-1e). In another aspect of this embodiment, the composition consists solely of any one of the polymer structures described in this embodiment and an organic spin-casting solvent.

[0094] Another aspect of this invention is a composition comprising any one of the polymers of the invention described herein having any one of structures (B-2), (B-2a), (B-2b), (B-2c), or (B-2d). In one aspect of this embodiment, the polymer has structure (B-2). In one aspect of this embodiment, the polymer has structure (B-2a). In one aspect of this embodiment, the polymer has structure (B-2b). In one aspect of this embodiment, the polymer has structure (B-2c). In one aspect of this embodiment, the polymer has structure (B-2d). In another aspect of this embodiment, the composition consists solely of any one of the polymer structures described in this embodiment and an organic spin-casting solvent.

[0095] Another aspect of the invention is a composition comprising any one of the polymers of the invention 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, the polymer has structure (B-2). In one aspect of this embodiment, the polymer has structure (B-2a). In one aspect of this embodiment, the polymer has structure (B-2b). In one aspect of this embodiment, the polymer has structure (B-2c). In one aspect of this embodiment, the polymer has structure (B-2d). In another aspect of this embodiment, the composition consists solely of any one of the polymer structures described herein and an organic spin-casting solvent.

[0096] In the above aspects of the novel composition, the organic spin-casting solvent is capable of dissolving the novel polymer and any other additional optional ingredients described above. The organic spin-casting solvent may be a single solvent or a mixture of solvents. Suitable solvents are organic solvents, such as glycol ether derivatives, 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; glycol ether ester derivatives, 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 dibasic acids, such as diethyl oxylate and diethyl malonate; dicarboxylates of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters, such as methyl pyruvate or ethyl pyruvate; Mention may be made of alkyloxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methyl ethoxypropionate; ketone derivatives, such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives, such as diacetone alcohol methyl ether; ketone alcohol derivatives, such as acetol or diacetone alcohol; ketals or acetals, such as 1,3 dioxalane and diethoxypropane; lactones, such as butyrolactone; amide derivatives, such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0097] In addition to the polymer and the solvent, the novel composition may contain a surfactant as an additive to facilitate coating.

[0098] Another aspect of the invention is a novel composition in which the novel polymer is present in an amount of from about 0.1% to about 10% by weight of the total weight of the composition, including the organic spin-casting solvent. In another aspect, the amount is from about 0.1% to about 2% by weight. In yet another embodiment, the amount is from about 0.5% to about 1.5% by weight. In yet another embodiment, the amount is from about 0.75% to about 1.5% by weight. In yet another embodiment, the amount is about 1.0% by weight.

[0099] Methods of Using the Compositions of the Invention Another aspect of the present invention is a method for selectively forming pinned layer brushes on a substrate that includes both metallic and non-metallic surface regions, the method comprising the steps of: i) coating a composition comprising a polymer having structure (A) or any one of its substructures onto the substrate to form a film; ii) baking the film at a temperature of from about 120° C. to about 250° C. for from about 1 minute to about 1 hour to form a baked film; iii) washing the baked film with a solvent to remove ungrafted polymer, thereby forming pinning layer brushes only on the metal surface regions of the substrate; The method comprises:

[0100] In one aspect of this embodiment, the metallic surface region is 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 the non-metallic surface region is selected from the group consisting of Si, silicon oxide (SiOx), silicon nitride (SiNx), silicon oxynitride (SiON), and organic dielectric substrates.

[0101] Yet another aspect of the present invention is a method comprising the steps of: ia) coating a composition comprising any one of the polymers having structure (A) or a substructure thereof onto a substrate comprising both metallic and non-metallic surface regions to form a film; iia) baking the film at a temperature of from about 120°C to about 250°C for from about 1 minute to about 1 hour to form a baked film; iiia) washing the baked film with a solvent to remove ungrafted polymer to form a grafted substrate in which pinning layer brushes are present only on the metal surface regions of the substrate; iva) coating the grafted substrate with a neutral layer composition to form a neutral layer coating; va) curing said neutral layer coating; via) washing away the uncured neutral layer with a solvent, leaving neutral-inducing brushes on the non-metallic areas, thereby forming a chemo-epitaxy-inducing layer on the substrate; viia) coating a block copolymer solution onto the chemo-epitaxy-derived layer to form a block copolymer coating; viiia) annealing said coating of block copolymer to form a directed self-assembled film of block copolymer on said chemo-epitaxy directed layer.

[0102] In one aspect of this method, the substrate has a metal surface region of tungsten and a non-metal surface region of silicon or silicon oxide. In another aspect of this embodiment, the block copolymer is a block copolymer comprising styrene-based repeating units and alkylacrylic repeating units. In another aspect of this embodiment, the block copolymer is an AB block copolymer of alkylacrylic repeating units and styrene-based repeating units, or an ABA triblock copolymer of alkylacrylic repeating units and styrene-based repeating units.

[0103] Compounds of the Invention Another aspect of the present invention is novel compounds useful in the synthesis of the polymers of the present invention of structure (A) and substructures thereof described herein.

[0104] One embodiment of these novel compounds has structure (I), where R1 is a chelating group located in the meta or para position selected from a phosphinothioic acid moiety of structure (Ia), an aminosulfonyl moiety of structure (Ib), and a phosphonamide moiety of structure (Ic), and * indicates the point of attachment of these moieties to the compound of structure (I).

[0105] Further, in the phosphinothioic acid moiety of structure (Ia), R3 and R4 are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy; and a dialkylamino moiety -N(R9)(R 10 ) and R9 and R 10 is independently selected from C1 to C8 linear alkyl, C3 to C8 branched alkyl, and C3 to C8 cyclic alkyl.

[0106] Additionally, in the aminosulfonyl moiety of structure (Ib), R5 and R6 are independently selected from C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, and dialkylamino moieties -N(R9)(R 10 )

[0107] Additionally, in the phosphonamide moiety of structure (Ic), R7 is the dialkylamino moiety -N(R9)(R 10and R8 is selected from the group consisting of aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In one aspect of this embodiment, R8 is aryl, and in one more specific aspect of this embodiment, it is phenyl. In one aspect of this embodiment, R8 is alkylenearyl. In one aspect of this embodiment, R8 is C2-C8 alkyleneoxyalkyl. In one aspect of this embodiment, R8 is C2-C8 haloalkyl. In one aspect of this embodiment, R8 is C1-C8 linear alkyl. In one aspect of this embodiment, R8 is C3-C8 branched alkyl. In one aspect of this embodiment, R8 is C3-C8 cyclic alkyl. In one aspect of this embodiment, R8 is C1-C8 linear alkyloxy. In one aspect of this embodiment, R8 is C3-C8 branched alkyloxy. In one aspect of this embodiment, R8 is C3-C8 cyclic alkyloxy.

[0108] Further, in said compound of structure (I), R2 is a substituent located at the meta or para position selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moiety of structure (Ia), aminosulfonyl of structure (Ib), and phosphonamide of structure (Ic).

[0109] Specifically, when R1 and R2 are both phosphonamide moieties of structure (Ic), R8 can be independently selected from the group consisting of aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In one aspect of this embodiment, R8 is aryl, and in one more specific aspect of this embodiment, it is phenyl. In one aspect of this embodiment, R8 is alkylenearyl. In one aspect of this embodiment, R8 is C2-C8 alkyleneoxyalkyl. In one aspect of this embodiment, R8 is C2-C8 haloalkyl. In one aspect of this embodiment, R8 is C1-C8 linear alkyl. In one aspect of this embodiment, R8 is C3-C8 branched alkyl. In one aspect of this embodiment, R8 is C3-C8 cyclic alkyl. In one aspect of this embodiment, R8 is C1-C8 linear alkyloxy. In one aspect of this embodiment, R8 is C3-C8 branched alkyloxy. In one aspect of this embodiment, R8 is C3-C8 cyclic alkyloxy.

[0110] [ka] In another embodiment, the compound of structure (I) has the more specific structure (I-1).

[0111] [ka] In another embodiment, the compound of structure (I) has the more specific structure (I-2).

[0112] [ka] In more specific embodiments of compounds of structure (I), (I-1), or (I-2), R1 is the chelating group that is a phosphinothioic acid moiety of structure (Ia). In more specific embodiments of compounds of structure (I), (I-1), or (I-2), R1 is the chelating group that is an aminosulfonyl moiety of structure (Ib). In more specific embodiments of compounds of structure (I), (I-1), or (I-2), R1 is the chelating group that is a phosphonamide moiety of structure (Ic). In one aspect of these embodiments, R2 is H. In another aspect of these embodiments, R2 is aryl. In another aspect of these embodiments, R2 is alkylenearyl. In another aspect of these embodiments, R2 is C2-C8 alkyleneoxyalkyl. In another aspect of these embodiments, R2 is C2-C8 haloalkyl. In another aspect of these embodiments, R2 is C1-C8 linear alkyl. In another aspect of these embodiments, R2 is a C3-C8 branched alkyl. In another aspect of these embodiments, R2 is a C3-C8 cyclic alkyl. In another aspect of these embodiments, R2 is a C1-C8 linear alkyloxy. In another aspect of these embodiments, R2 is a C3-C8 branched alkyloxy. In another aspect of these embodiments, R2 is a C3-C8 cyclic alkyloxy. In another aspect of these embodiments, R2 is a phosphinothioic acid moiety of structure (Ia). In another aspect of these embodiments, R2 is an aminosulfonyl moiety of structure (Ib). In another aspect of these embodiments, R2 is a phosphonamide moiety of structure (Ic).

[0113] One embodiment of these novel compounds has the structure (II), where R 11 is a phosphinothioic acid moiety of structure (IIa), * indicates the point of attachment of this moiety to the compound of structure (II), R 13 and R 14are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; and the dialkylamino moiety -N(R9)(R 10 ), and R and R 10 are independently selected from C1 to C8 linear alkyl, C3 to C8 branched alkyl, and C3 to C8 cyclic alkyl.

[0114] Further, in these compounds of structure (II), L1 is a linking moiety selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), where ** indicates the point of attachment of said L1 organic linking moiety to phosphorus in structure (IIa), and * indicates the attachment point of the moiety R 11 This indicates the position where L1 binds to the carbonyloxy of compound (II).

[0115] Furthermore, in these compounds of structure (II), R 12 is H or C1-C4 alkyl.

[0116] [ka] In one more specific embodiment of the compound of structure (II), R 13 is C1-C8 linear alkyloxy. In another aspect of these embodiments, R 13 is a C3-C8 branched alkyloxy. In another aspect of these embodiments, R 13 is a C3-C8 cyclic alkyloxy.

[0117] In one more specific embodiment of the compound of structure (II), R 14 is aryl. In another aspect of these embodiments, R14 is alkylenearyl. In another aspect of these embodiments, R 14 is a C2-C8 alkyleneoxyalkyl. In another aspect of these embodiments, R 14 is C2-C8 haloalkyl. In another aspect of these embodiments, R 14 is a C1-C8 linear alkyl. In another aspect of these embodiments, R 14 is a C3-C8 branched alkyl. In another aspect of these embodiments, R 14 is a C3-C8 cyclic alkyl. In another aspect of these embodiments, R 14 is C1-C8 linear alkyloxy. In another aspect of these embodiments, R 14 is a C3-C8 branched alkyloxy. In another aspect of these embodiments, R 14 is a C3-C8 cyclic alkyloxy. In another aspect of these embodiments, R 14 is a dialkylamino moiety -N(R9)(R 10 )

[0118] In another more specific embodiment, R 13 and R 14 are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; and the dialkylamino moiety -N(R9)(R 10 ), and R and R 10 is independently selected from C1 to C8 linear alkyl, C3 to C8 branched alkyl, and C3 to C8 cyclic alkyl.

[0119] In one aspect of these embodiments, R 13 and R 14 is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkoxy. In another aspect of this embodiment, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1 to C4 alkyl.

[0120] In more specific embodiments of the compounds of structure (II), R9 is C1-C8 linear alkyl. In another aspect of these embodiments, R9 is C3-C8 branched alkyl. In another aspect of these embodiments, R9 is C3-C8 cyclic alkyl.

[0121] In more specific embodiments of the compounds of structure (II), L1 is a direct valence bond. In another aspect of these polymers, L1 is a C2-C8 alkylene moiety. In another aspect of these embodiments, L1 is an arylene moiety (-aryl-). In more specific embodiments of these polymers, L1 is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

[0122] In a more specific embodiment of the compound of structure (II), it has structure (IIc) or structure (IIc1), where n is 1 to 7. In one aspect of these embodiments, R 13 and R 14 is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14 is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl. In another aspect of this embodiment, R 13 and R 14is selected from C1-C4 alkoxy. In another aspect of this embodiment, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1 to C4 alkyl.

[0123] [ka] In a more specific embodiment of the compound of structure (II), it has structure (IIb) or structure (IIb1), where n is an integer ranging from 1 to 7. In one aspect of these embodiments, R 13 and R 14 is independently selected from C1-C8 alkyl or alkoxyl. In another aspect of this embodiment, R 13 and R 14 is independently selected from C1-C4 alkyl or alkoxy. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkyl. In another aspect of this embodiment, R 13 and R 14 is selected from C1-C4 alkoxy. In another aspect of this embodiment, R 13 is selected from C1-C4 alkoxy, and R 14 is selected from C1 to C4 alkyl.

[0124] [ka] In a more specific embodiment of the compound of structure (II), it has structure (IIb2), wherein R 13a and R 14a is independently selected from C1-C4 alkyl.

[0125] [ka] [Example]

[0126] More specific embodiments of the present disclosure and experimental results supporting such embodiments are described below. These examples are provided below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0127] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed invention and the specific examples provided herein without departing from the spirit or scope of the disclosed invention. Thus, the disclosed invention, including the description provided by way of example below, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0128] Although the disclosed and claimed invention has been described and illustrated with a certain degree of detail, it will be understood that this disclosure is made by way of example only and that those skilled in the art may resort to numerous variations in the conditions and order of the steps without departing from the spirit and scope of the disclosed and claimed invention.

[0129] chemicals Unless otherwise indicated, all chemicals were purchased from Sigma-Aldrich (3050 Spruce Street, St. Louis, MO 63103). Chemicals used in anionic polymerization were purified as described in the literature (e.g., David Uhrig and Jimmy Mays, "Techniques in High-Vacuum Anionic Polymerization," Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 6179-6222 (2005)).

[0130] Phenyl acrylate derivatives were synthesized by esterifying acryloyl chloride with the corresponding hydroxyl compounds under basic conditions, and DPE derivatives were synthesized by alkoxylating DPE-(m)-CHBr (1-(bromomethyl)-3-(1-phenylvinyl)benzene) with the corresponding hydroxyl compounds under basic conditions.

[0131] All synthesis experiments were carried out in a N2 atmosphere. Lithography experiments were carried out as described herein. The molecular weight of the copolymer was measured using gel permeation chromatography. 3 Å, 10 5 Å and 10 6 Åμ—Gel permeation chromatography equipped with an ultrastyragel column.

[0132] Lithography experiments were performed using a TEL Clean ACT8 track. SEM images were taken using an Applied Materials NanoSEM 3D. Scanning electron micrographs are shown at either 1 FOV magnification or 2 FOV magnification (field of view (FOV) = 5 μm).

[0133] Etching experiments were performed using standard isotropic oxygen etching conditions for self-assembled film block copolymers of methyl methacrylate and styrene.

[0134] 100 Å, 500 Å, and 10 Å of styrene-DVB gel connected in series 3 Å, 10 4 Å and 10 6 Gel permeation chromatography was performed using a Å porosity column (PSS (Polymer Standard Services, Germany)) and THF as the mobile phase at 1 ml / min. Polystyrene standards (PSS, Germany) ranging from 1,000 g / mol to 200,000 g / mol (18 samples) were used to generate calibration curves for determining the molecular weight and polydispersity index (PDI) of the synthesized polymers. A Bruker 400 MHz NMR unit was used for molecular characterization.

[0135] 1 1 H NMR spectra were recorded in CDCl 3 on a Bruker Advanced III 400 MHz spectrometer.

[0136] Coating characterization was performed using blanket dielectrics and metal coupons. Films were baked at the desired temperature and time, and excess material was washed away. The grafted brushes were characterized using water contact angle, FT, and XPS.

[0137] Polymer brushes were coated onto blanket metal or dielectric wafers using bake conditions of 230°C / 5 min, and excess material was cleaned off using organic solvents, and the substrates were analyzed using WCA, FT, and XPS.

[0138] experiment: Preparation of polymer formulations: Each polymer described herein was dissolved separately in PGMEA to prepare a 1 wt% solution. These solutions were individually filtered using nylon filters (Entegris, Billerica, MA). These solutions were separately coated onto both metal (Cu, W) and SiO2 wafers at 1500 rpm, and then the wafers were baked at 230°C for 5 minutes. After this bake, the wafers were rinsed with PGMEA for 2 minutes to remove ungrafted polymer from the wafers, then spun dry at 1500 rpm, and baked at 110°C for 1 minute. Water contact angle and XPS measurements were then performed to determine the grafting efficiency. The results are shown in Table 1. Secondary brushes of polymer formulations containing hydroxyl-terminated PS-OH or PMMA-OH were then prepared in PGMEA at 1 wt% solids content. After filtering using a 0.25 micron nylon filter, the solutions were spin-coated onto the pre-brushed metal and SiO2 substrates. After baking at various temperatures and times, these double-brushed substrates were washed to remove unreacted second brushes. These double-brushed substrates were then examined by water contact angle (WCA) and X-ray photoelectron spectroscopy (XPS) to understand cross-grafting and determine the efficiency of the first brush and its selectivity to the metal substrate.

[0139] Example 1. Synthesis of dimethylthiophophine-terminated polystyrene Anionic polymerization was carried out in a nitrogen-dried 250 mL round-bottom flask equipped with a magnetic stir bar, a septum adapter allowing connection to a vacuum or nitrogen atmosphere, and a rubber septum for the addition of reagents via syringe or cannula. 100 mL of anhydrous cyclohexane was transferred to the flask using a cannula under nitrogen. 20 mL (18 g) of purified styrene monomer was added to the cyclohexane solution. The reaction mixture was degassed and backfilled with nitrogen.

[0140] [ka] Scheme 1: Synthesis of thiophophine-terminated polystyrene The required amount of initiator sec-butyllithium (1.3 M) in hexane was added to the monomer solution under high-speed stirring. The orange color of the formed carbanion immediately increased slightly, indicating the increase in polystyryllithium due to the heat of reaction. The reaction was maintained at 35-45°C for 2 hours with stirring. Purified dimethylthiophosphinoyl chloride (distilled over CaH2) was then transferred via cannula into the living polystyryllithium anion solution. The color of the reaction slowly disappeared over 5 minutes. The reaction mixture was diluted with THF (2 volumes) and then precipitated into an excess (5 volumes) of isopropanol:water (80:20) mixture. The polymer was filtered and dried under vacuum at 80°C for 18 hours. Yield: 17.2 grams (96%), M n , GPC=6,600 g / mol, PDI=1.05. 31 P NMR showed a signal at 44 ppm, confirming the presence of end groups with -P=S. A solution of this polymer in PGMEA (1 wt %) was spin-coated onto tungsten and silicon coupons, which showed an orientation of 90° on the W coupon and 52° on the silicon coupon, respectively, after baking (200°C / 15 min / N) and washing (2 min, dynamic). This confirms the selectivity of this polymer for W. XPS studies showed the elemental ratios of C / W and C / Si as 25.84 and 0.43, respectively.

[0141] Example 2. Synthesis of diethylthiophosphonate-terminated polymethyl methacrylate In the first step, a diethylthiophosphonate DPE derivative was prepared by thiolation of MTAG-10. Diethylphosphonate-terminated PMMA was synthesized using an initiator prepared from the diethylthiophosphonate DPE derivative and sec-BuLi. The reaction was carried out in tetrahydrofuran at -78 °C.

[0142] [ka] Scheme 2.1: Synthesis of DPE derivatives (diethylthiophosphonate DPE) Step 1: Synthesis of diethylthiophosphonate DPE Diethyl phosphonate DPE (MTAG-10) (29.0 g, 91.67 mmol) and Lawesson's reagent (18.7 g, 404.471 mmol) were weighed into a two-neck round-bottom flask equipped with a reflux condenser and a rubber septum. 250 mL of anhydrous toluene was transferred via cannula. The flask was maintained in an oil bath, and the temperature was raised to 120 °C. The reaction was allowed to stand overnight (although 2–4 h was sufficient). The toluene was removed on a rotary evaporator. The brown-red liquid was loaded onto a silica column and separated using a 70:30 mixture of hexane and ethyl acetate. Excess Lawesson's reagent and its by-products eluted very close to the desired product. The desired DPE derivative (O,O-diethyl(4-(1-phenylvinyl)phenyl)phosphonothioate [DPE-PS(OEt)2]) was obtained as a pale yellow liquid. Lawesson's reagent and MTAG-26 have a very unpleasant odor typical of thiol compounds. Yield: 20 g, 65.6%. 1 H NMR, CDCl3δ:1.4,dt,6H;4.0,m,4H;5H;7.3m,2H;7.4,2H,7.6,m,2H.,31P CPD m,87.4ppm.

[0143] Step 2: Synthesis of diethylthiophosphonate-terminated PMMA

[0144] [ka] Scheme 2.2: Diethylthiophosphonate-terminated polymethyl methacrylate O,O-Diethyl (4-(1-phenylvinyl)phenyl)phosphonothioate [DPE-PS(OEt)2] (1.72 g, 5 mmol) was dissolved in 6 mL of toluene titrated with hexyllithium and added to an ampoule. 28 mL of methyl methacrylate was added to another ampoule and degassed under dynamic vacuum to yield 25 mL (23.3 g, 23.3 mmol) of methyl methacrylate. These ampoules were attached to the side arm of a reactor containing lithium chloride (2.2 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and backfilled with nitrogen. Tetrahydrofuran (300 mL) was added via cannula, and the mixture was stirred and cooled to −78°C. sBuLi was then titrated into the mixture until a persistent yellow color developed. The mixture was allowed to warm to room temperature, at which point the yellow color dissipated. The mixture was cooled to -78°C, and the DPE-P(S)(OEt)2 solution was added. sBuLi (4.0 mL, 1.17 M in cyclohexane, 4.68 mmol) was then added slowly, producing a red mixture. Methyl methacrylate was added dropwise over 6 h, whereupon the red color changed to colorless. The mixture was stirred for an additional 12 min, at which point 1 mL of degassed methanol was added to quench the reaction. The polymer brushes were recovered by precipitation into excess hexane (7 times the volume of the polymer solution), filtration, and drying at 40°C for 1 h. They were redissolved in ethyl acetate and washed with Milli-Q water. The ethyl acetate was rotary evaporated, and the polymer was further dried under vacuum to give a white powder (22 g, 97% yield). GPC: 4,600 g / mol M n , 4,460g / mol Mw, 1.046 PDI, 1 H NMR MW 6,000 g / mol. The presence of terminal functional groups 1 HNMR and 31 This was confirmed by P NMR analysis.

[0145] Example 3. Synthesis of diethylthiophosphonate-terminated polystyrene:

[0146] [ka] Scheme 3: Diethylthiophosphonate-terminated polystyrene Diethylthiophosphonate DPE (2.0 g, 3.322 mmol) was dissolved in 6 mL of toluene, and 1,1-diphenyl-3-methylpentyllithium (prepared by reacting DPE with sec-butyllithium) was titrated into the ampoule. 28 mL of styrene was added to a separate ampoule and degassed under dynamic vacuum to yield 25 mL (24.543 g, 23.65 mmol) of styrene. These ampoules were attached to the side arm of a reactor containing lithium chloride (2.2 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and backfilled with nitrogen. Tetrahydrofuran (300 mL) was added via cannula, and the mixture was stirred and cooled to -78 °C. sBuLi was then titrated into the mixture until a persistent yellow color was obtained. The mixture was allowed to warm to room temperature, at which point the yellow color dissipated. The mixture was cooled to -78°C, and sBuLi (4.0 mL, 1.17 M in cyclohexane, 4.68 mmol) was added, producing a pale yellow mixture. Styrene was added dropwise over 10 minutes, resulting in an orange color. The mixture was stirred for an additional 5 minutes, at which time the DPE-P(S)(OEt)2 solution was added. The red solution was stirred for several minutes, and the reaction was quenched with 1 mL of degassed methanol. The polymer was recovered by precipitation into excess isopropanol (7 times the volume of the polymer solution), filtration, and drying at 40°C for 1 hour. It was redissolved in ethyl acetate, washed with Milli-Q water, and precipitated into excess isopropanol. Filtration and drying under vacuum yielded a white powder (24 g, 92% yield). GPC: 3,900 g / mol M n , 4,800g / mol Mw, 1.14 PDI, 1 H NMR M W 4,700 g / mol. The presence of terminal functional groups 1 H NMR and 31 This was confirmed by P NMR analysis.

[0147] Example 4 Synthesis of ethyldimethylphosphonamide-terminated polymethyl methacrylate 4.1 Synthesis of 1-phenyl-1'-[4-ethyl(dimethylphosphonamido)]-phenylethylene

[0148] [ka] Scheme 4.1: Synthesis of 1-phenyl-1'-[4-ethyl(dimethylphosphonamido)]-phenylethylene 4-Bromobenzophenone (25 g, 95.7 mmol) and THF were stirred together and cooled to 0°C. n-Butyllithium (71.38 mL, 114.9 mmol) was added, followed by methyltriphenylphosphonium bromide (41 g, 114.9 mmol). The mixture was allowed to warm to room temperature. The reaction was quenched with water and diluted with ethyl acetate. The mixture was washed with 1% aqueous HCl and aqueous NaCl, and dried over MgSO4. The MgSO4 was filtered off, and the filtrate was concentrated in vacuo. A white solid, triphenylphosphonium oxide, was precipitated by slurrying in hexane:ethyl acetate (2:1) and then filtered off. The filtrate was then concentrated and purified by silica gel column chromatography using hexane as the eluent, followed by concentration to give 4-bromo-1,1'-diphenylethylene as a colorless oil (18 g, 72% yield).

[0149] Step-1: Ethylphosphonic acid 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 was allowed to warm to room temperature for 30 minutes. The slurry was filtered, and the filtrate was concentrated in vacuo. The residue was redissolved in dichloromethane and triturated with ether. The mixture was filtered and concentrated, then repeatedly filtered to remove salts. This gave chloroethyl (dimethylphosphonamide) as a sticky solid (2.3 g, 95% yield).

[0150] Step-2: 4-Bromo-1,1'-diphenylethylene (1 g, 3.86 mmol) prepared in (a) was dissolved in tetrahydrofuran and cooled to -78°C. n-BuLi (2.4 mL, 3.86 mmol, 1.6 M in hexane) was added and stirred for 30 minutes. In a separate flask, chloroethyl(dimethylphosphoramide) (0.6 g, 3.86 mmol) prepared in (b) was slurried in THF and cooled to -78°C. Preformed 4-lithium-1,1'-diphenylethylene was added via cannula, and the mixture was warmed to room temperature and stirred for 72 hours. The mixture was diluted with ethyl acetate, washed with water, and dried over MgSO4. The MgSO4 was filtered off, and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 50% ethyl acetate in hexane as the eluent. The product fractions were concentrated to give 1-phenyl-1'-[4-ethyl(dimethylphosphonamido)]-phenylethylene as a pale yellow oil (0.7 g, 60% yield). 1 H NMR, CDCl3δ: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.

[0151] [ka] Scheme 4.2: Ethyldimethylphosphonamide-terminated polymethyl methacrylate 4.2 Synthesis of PMMA-ethyl(dimethylphosphonamide) terminated: 1-Phenyl-1'-(4-ethyldimethylphosphonamido)phenylethylene [DPE-P(O)(Et)(NMe2)] (1.43 g, 5 mmol) in 6 mL of anhydrous toluene was added to an ampoule. Methyl methacrylate (20.7 g, 207 mmol) was added to a separate ampoule and degassed by freeze-thawing three times. These ampoules were attached to the side arm of a reactor containing lithium chloride (1.75 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and backfilled with nitrogen. Tetrahydrofuran (210 mL) was added via cannula, and the mixture was stirred and cooled to -78 °C. sBuLi was then titrated into the mixture until a persistent yellow color developed. The mixture was allowed to warm to room temperature, at which point the yellow color dissipated. The mixture was once again cooled to -78 °C, and the DPE-P(O)(Et)(NMe2) solution was added. sBuLi (1.2 mL) was titrated into the mixture until a persistent yellow color was achieved. Then, sBuLi (2.96 mL, 1.4 M in cyclohexane, 4 mmol) was slowly added, producing a red mixture. Methyl methacrylate was rapidly added dropwise to the mixture over a 2-minute period, causing the red color to change to colorless. The mixture was stirred for an additional 30 minutes, at which point 1 mL of degassed methanol was added to quench the reaction. The polymer brushes were recovered by precipitation into excess hexane (7 times the volume of the polymer solution), filtration, and drying at 40°C under vacuum for 12 hours, yielding a white powder (21 g, 97% yield). GPC: 4,195 g / mol M n , 4,460 g / mol Mw, 1.06 PDI.

[0152] Example 5. Synthesis of phenyldimethylphosphonamide-terminated polymethyl methacrylate

[0153] [ka] Scheme 5.1: Synthesis of 1-phenyl-1'-[4-phenyl(dimethylphosphonamido)-phenylethylene 5.1 Synthesis of 1-phenyl-1'-[4-phenyl(dimethylphosphonamido)-phenylethylene: Step 1: 4-Bromobenzophenone (25 g, 95.7 mmol) and THF were stirred together and cooled to 0°C. n-Butyllithium (71.38 mL, 114.9 mmol) was added, followed by methyltriphenylphosphonium bromide (41 g, 114.9 mmol). The mixture was allowed to warm to room temperature. The reaction was quenched with water and diluted with ethyl acetate. The mixture was washed with 1% aqueous HCl and aqueous NaCl, and dried over MgSO4. The MgSO4 was filtered off, and the filtrate was concentrated in vacuo. A white solid triphenylphosphonium oxide was precipitated by slurrying in hexane:ethyl acetate (2:1) and then filtered off. The filtrate was then concentrated and purified by silica gel column chromatography using hexane as the eluent, followed by concentration to give 4-bromo-1,1'-diphenylethylene as a colorless oil (20 g, 80% yield).

[0154] Step-2: Phenylphosphonic acid 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 allowed to warm to room temperature for 30 minutes. The slurry was filtered, and the filtrate was concentrated under vacuum. The residue was redissolved in dichloromethane and triturated with ether. The mixture was filtered and concentrated, then repeatedly filtered to remove salts. This gave chlorophenyl(dimethylphosphoramide) as a sticky solid (12 g, 80% yield).

[0155] Step-3: 4-Bromo-1,1'-diphenylethylene (3 g, 11.6 mmol) prepared in 5.1 was dissolved in tetrahydrofuran and cooled to -78 °C. n-BuLi (8.7 mL, 13.9 mmol, 1.6 M in hexane) was added and stirred for 30 minutes. In a separate flask, chlorophenyl(dimethylphosphoramide) (3.4 g, 16.7 mmol) prepared in (b) was slurried in THF and cooled to -78 °C. Preformed 4-lithium-1,1'-diphenylethylene was added via cannula, and the mixture was warmed to room temperature and stirred for 72 hours. The mixture was diluted with ethyl acetate, washed with water, and dried over MgSO4. The MgSO4 was filtered off, and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 50% ethyl acetate in hexane as the eluent. The product fractions were concentrated to give 1-phenyl-1'-[4-phenyl(dimethylphosphonamido)]-phenylethylene as a pale yellow oil (3.5 g, 70% yield). 1 H NMR, CDCl3δ:2.68,s,3H;2.70,s,3H;5.50,s,2H;7.30,m,5H;7.47,m,5H;7.80,m,4H.

[0156] [ka] Scheme 5.2: Phenylphosphonamide-terminated polymethyl methacrylate 5.2: Synthesis of phenyldimethylphosphonamide-terminated polymethyl methacrylate: 1-Phenyl-1'-(4-phenyldimethylphosphonamido)phenylethylene [DPE-P(O)(Ph)(NMe2)] (1.58 g, 5 mmol) in 6 mL of anhydrous toluene was added to an ampoule. Methyl methacrylate (20.68 g, 207 mmol) was added to a separate ampoule and degassed by freeze-thawing three times. These ampoules were attached to the side arm of a reactor containing lithium chloride (1.75 g, 41 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and backfilled with nitrogen. Tetrahydrofuran (210 mL) was added via cannula, and the mixture was stirred and cooled to -78 °C. sBuLi was then titrated into the mixture until a persistent yellow color developed. The mixture was allowed to warm to room temperature, at which point the yellow color dissipated. The mixture was once again cooled to -78 °C, and the DPE-P(O)(Ph)(NMe2) solution was added. sBuLi (1.2 mL) was titrated into the mixture until a persistent yellow color was achieved. Then, sBuLi (3 mL, 1.4 M in cyclohexane, 4 mmol) was slowly added, producing a red mixture. Methyl methacrylate was rapidly added dropwise to the mixture over a 2-minute period, causing the red color to change to colorless. The mixture was stirred for an additional 30 minutes, at which point 1 mL of degassed methanol was added to quench the reaction. The polymer brushes were recovered by precipitation into excess hexane (7 times the volume of the polymer solution), filtration, and drying at 40°C under vacuum for 12 hours, yielding a white polymer (21 g, 99% yield). GPC: 5,602 g / mol M n , 6,158g / mol Mw, 1.10PDI.

[0157] Example 6. Synthesis of dimethylsulfonamide-terminated polymethyl methacrylate: 6.1 Synthesis of 1-phenyl-1'-[4-(dimethylphosphonamido)]-phenylethylene: 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, 1.6 M in hexane) was added and 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 room temperature for 1 hour. The mixture was diluted with ethyl acetate, washed with water, and dried over MgSO. The MgSO was filtered off, and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 33% ethyl acetate in hexane as the eluent. The product fractions were concentrated to give 1-phenyl-1-[4-(dimethylsulfonamido)]-phenylethan-1-ol (2.7 g, 48% yield) as a white solid.

[0158] [ka] Scheme 6.1: Synthesis of 1-phenyl-1'-[4-(dimethylsulfonamido)]-phenylethylene Step-2: 1-Phenyl-1-[4-(dimethylsulfonamido)]-phenylethan-1-ol (2.7 g, x mmol) produced in (a) and p-toluenesulfonic acid monohydrate (cat.) were slurried in toluene and heated to 70°C for 3 hours. The mixture was diluted with ethyl acetate, washed with water, and dried over MgSO4. The MgSO4 was filtered off, and the filtrate was concentrated in vacuo and purified by silica gel column chromatography using 33% ethyl acetate in hexane as the eluent. The product fractions were concentrated to give 1-phenyl-1'-[4-(dimethylsulfonamido)]-phenylethylene as a pale yellow oil (2.6 g, 99% yield). 1 H NMR, CDCl3δ: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 Composite:

[0159] [ka] Scheme 6.2: Dimethylsulfonamide-terminated polymethyl methacrylate 1-Phenyl-1'-[4-(dimethylsulfonamido)]-phenylethylene [DPE-SO2(NMe2)] (1.02 g, 3.6 mmol) in 3 mL of anhydrous toluene was added to an ampoule. Methyl methacrylate (15.8 g, 157 mmol) was added to a separate ampoule and degassed by freeze-thawing three times. These ampoules were attached to the side arm of a reactor containing lithium chloride (0.4 g, 10 mmol) and a magnetic stir bar. The reactor was evacuated under vacuum and backfilled with nitrogen. Tetrahydrofuran (200 mL) was added via cannula, and the mixture was stirred and cooled to -78 °C. sBuLi was then titrated into the mixture until a persistent yellow color developed. The mixture was allowed to warm to room temperature, at which point the yellow color dissipated. The mixture was once again cooled to -78 °C, and the DPE-SO2(NMe2) solution was added. sBuLi (1.2 mL) was titrated into the mixture until a persistent yellow color developed. Then, sBuLi (2.1 mL, 1.4 M in cyclohexane, 3 mmol) was slowly added, producing a red mixture. Methyl methacrylate was rapidly added dropwise to the mixture over a 2-minute period, causing the red color to change to colorless. The mixture was stirred for an additional 30 minutes, at which point 1 mL of degassed methanol was added to quench the reaction. The polymer brushes were recovered by precipitation into excess hexane (7 times the volume of the polymer solution), filtration, and drying at 40°C under vacuum for 12 hours, yielding a white powder (15 g, 95% yield). GPC: 5,773 g / mol M n , 5,946g / mol Mw, 1.03 PDI.

[0160] Preparation of polymer formulations: Each polymer described herein was dissolved separately in PGMEA to form a 1 wt% solution. These solutions were individually filtered using nylon filters (Entegris, Billerica, MA). These solutions were separately coated onto both metal (Cu, W) and SiO2 wafers at 1500 rpm, and then the wafers were baked at 230°C for 5 minutes. After this bake, the wafers were rinsed with PGMEA for 2 minutes to remove ungrafted polymer from the wafers, then spun dry at 1500 rpm and baked at 110°C for 1 minute. Water contact angle and XPS measurements were used to determine the grafting efficiency. The results are shown in Table 1. Secondary brushes of polymer formulations containing hydroxyl-terminated PS-OH or PMMA-OH were then prepared in PGMEA at 1 wt% solids content. After filtering using a 0.25 micron nylon filter, the solutions were spin-coated onto the pre-brushed metal and SiO2 substrates. After baking at various temperatures and times, these double-brushed substrates were washed to remove unreacted second brushes. These double-brushed substrates were then examined by WCA and XPS to understand cross-grafting and determine the efficiency of the first brush and its selectivity to the metal substrate.

[0161] Brush Coating: Polymer brushes were coated onto blanket metal or dielectric wafers using bake conditions of 230°C / 5 min, and excess material was removed by rinsing with organic solvents, and the substrates were analyzed using WCA, FT, and XPS.

[0162] Table 1 shows data for the selective grafting of metals with various materials that exhibit high carbon to substrate ratios and suitably high contact angles depending on the polarity of the grafted polymer on the metal. The polymers were coated from a 1% solution in PGMEA, baked at 230°C / 5 min, and then washed with PGMEA solvent for 2 min. All polymers used in these studies had an M of approximately 5,000 g / mol. n had.

[0163] [Table 1]

[0164] Preparation of polymer formulations Each polymer described herein was dissolved separately in PGMEA to prepare a 1 wt% solution. These solutions were individually filtered using nylon filters (Entegris, Billerica, MA). These solutions were separately coated onto both metal (Cu, W) and SiO2 wafers at 1500 rpm, and then the wafers were baked at 230°C for 5 minutes. After this bake, the wafers were rinsed with PGMEA for 2 minutes to remove ungrafted polymer from the wafers, then spun dry at 1500 rpm and baked at 110°C for 1 minute. Water contact angle and XPS measurements were used to determine the grafting efficiency. The results are shown in Table 1. Secondary brushes of polymer formulations containing hydroxyl-terminated PS-OH or PMMA-OH were then prepared in PGMEA at 1 wt% solids content. After filtering using a 0.25 micron nylon filter, the solutions were spin-coated onto the pre-brushed metal and SiO2 substrates. After baking at various temperatures and times, these double-brushed substrates were washed to remove unreacted second brushes. These double-brushed substrates were then examined by WCA and XPS to understand cross-grafting and determine the efficiency of the first brush and its selectivity to the metal substrate.

Claims

1. Two terminal groups R ３ｐ and R ４ｐ and a polymer chain (R) comprising a repeating unit of structure (Ip) or a repeating unit of structure (IIp), end groups R derived from anionic initiators ３ｐ is a C1-C8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIp1), provided that when the repeating unit in the polymer chain (R) is (IIp), R ３ｐ can be selected only from C1 to C8 alkyl, and further, in the polymer chain (R), when the repeating unit is structure (Ip), R ３ｐ can be selected only from the moieties of structure (IIIp) or structure (IIIp1), Terminal group R ４ｐ is H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl) ３ Si-), C1-C8 dialkylsilyl ((alkyl) ２ HSi-), C1-C8 monoalkylsilyl ((alkyl)H ２ Si-), silane (H ３ Si—), and a benzyl-based moiety, a moiety of structure (IVp), a moiety of structure (IVp1), or a moiety of structure (IVp2), and further comprising a terminal group R ３ｐ and R ４ｐ cannot simultaneously both be portions of Structures (IIIp) and (IVp), or cannot simultaneously be portions of Structures (IIIp) and (IVp1), or cannot simultaneously be portions of Structures (IIIp) and (IVp2), respectively, provided that said polymer of Structure (A) must contain one end group moiety selected from Structures (IIIp), (IVp), (IVp1), or (IVp2); In the repeating unit of structure (Ip), R ｍ１ is C1-C8 alkyl, and R １ｐ is a C1-C8 alkyl, and n1 is the number of this repeat unit in the polymer chain (R); In the repeating unit of structure (IIp), R ｍ２ is H or C1-C8 alkyl, and R ２ｐ is H or C1-C8 alkyl, and n2 is the number of this repeat unit in the polymer chain (R); and In structure (IIIp), R １ is a chelating group located in the para or meta position selected from a phosphinothioic acid moiety of structure (Ia), an aminosulfonyl moiety of structure (Ib), and a phosphonamide moiety of structure (Ic), where *** indicates the point of attachment of this end group moiety to the polymer of structure (A); In the phosphinothioic acid moiety of structure (Ia), R ３ and R ４ are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy; and a dialkylamino moiety -N(R ９ ) (R １０ ) and R ９ and R １０ are independently selected from C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, and * indicates the point of attachment of this moiety to the terminal group moiety of structure (IIIp); In said aminosulfonyl moiety of structure (Ib), R ５ and R ６ are independently C1 to C8 linear alkyl, C3 to C8 branched alkyl, C3 to C8 cyclic alkyl, and the dialkylamino moiety -N(R ９ ) (R １０ ), and * indicates the point of attachment of this moiety to the terminal group moiety of structure (IIIp); In the phosphonamide moiety of structure (Ic), R ７ is the dialkylamino moiety -N(R ９ ) (R １０ ) and R ８ is selected from the group consisting of aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy, and * indicates the point of attachment of this moiety to the terminal group moiety of structure (IIIp); R ２ is selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moieties of structure (Ia), aminosulfonyls of structure (Ib), and phosphonamides of structure (Ic), and R １５ is C1-C8 alkyl, and R ｅ１ and R ｅ２ is independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy; In structure (IIIp1), R ｅ１ and R ｅ２ is individually selected from H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, and R １５ is a C1-C8 alkyl, and *** indicates the point of attachment of this end group moiety to the polymer of structure (A); In structure (IVp), R １２ is H or C1-C4 alkyl, R １１ is the phosphinothioic acid moiety of structure (IIa), and * indicates the point of attachment of this phosphinothioic acid moiety to structure (IVp); R １３ and R １４ are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; and a dialkylamino moiety -N(R ９ ) (R １０ ) and R ９ and R １０ are independently selected from C1-C8 linear alkyl, C3-C8 branched alkyl, and C3-C8 cyclic alkyl; L １ is a linking moiety selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), and ** is a linking moiety selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-aryl-**), and an alkylenearyl moiety (*-alkylene-aryl-**) to phosphorus in structure (IIa). １ indicates the point of attachment of the organic linking moiety, and * indicates the moiety R １１ Inside L １ indicates the position of binding to the carbonyloxy of structure (IVp), R １７ is H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl) ３ Si-), C1-C8 dialkylsilyl ((alkyl) ２ HSi-), C1-C8 monoalkylsilyl ((alkyl)H ２ Si-), silane (H ３ Si—), and benzyl-based moieties, and *** indicates the point of attachment of this end group moiety to the polymer of structure (A); In structure (IVp1), L is a direct valence bond or a linking group selected from C1-C8 linear alkylene, C3-C8 branched alkylene, and C5-C8 cyclic alkylene, alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), and alkylenearyl moiety (*-alkylene-aryl-**), where ** indicates the point of attachment of said L linking moiety to phosphorus in Structure (IVp1), and * indicates the point where L is attached to said polymer of Structure (A), and Rs and Rs1 are independently selected from C1-C8 alkoxy or C1-C8 alkyl, and *** indicates the point of attachment of this end group moiety to the polymer of Structure (A); In structure (IVp2), R １ is a chelating group located at the para or meta position selected from the phosphinothioic acid moiety of structure (Ia), the aminosulfonyl moiety of structure (Ib), and the phosphonamide moiety of structure (Ic); R ２ is selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; phosphinothioic acid moieties of structure (Ia), aminosulfonyls of structure (Ib), and phosphonamides of structure (Ic); R １８ is H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl) ３ Si-), C1-C8 dialkylsilyl ((alkyl) ２ HSi-), C1-C8 monoalkylsilyl ((alkyl)H ２ Si-), silane (H ３ Si—), and benzyl-based moieties; and *** indicates the point of attachment of this end group moiety to the polymer of structure (A); Additionally, said polymer of structure (A) has an M in the range of from about 4000 to about 7000. ｎ and having a polydispersity ranging from 1 to about 1.15; The polymer. 【Chemical 1】

2. The polymer of claim 1 having the structure (A-1): 【Chemistry 2】

3. The polymer of claim 1 or 2, having the structure (A-2): 【Chemistry 3】

4. The polymer according to any one of claims 1 to 3, having the structure (A-2a): 【Chemistry 4】

5. The polymer according to any one of claims 1 to 4, having the structure (A-2b): 【Chemistry 5】

6. The polymer of any one of claims 1 to 4, having the structure (A-2c): 【Chemistry 6】

7. The polymer of any one of claims 1 to 3, having the structure (A-2d): 【Chemistry 7】

8. The polymer of any one of claims 1 to 3, having the structure (A-2e): 【Chemistry 8】

9. The polymer of any one of claims 1 to 3 and 8 having the structure (A-2f): 【Chemistry 9】

10. The polymer of any one of claims 1 to 3, having the structure (A-2g): 【Chemistry 10】

11. 11. The polymer of any one of claims 1 to 3 and 10 having the structure (A-2h): 【Chemistry 11】

12. The polymer of any one of claims 1 to 3 and 10 having the structure (A-2i): 【Chemistry 12】

13. The polymer of claim 1 or 2, having the structure (A-3): 【Chemistry 13】

14. L １ 14. The polymer of claim 1, 2, or 13, wherein is a direct valence bond.

15. L １ 14. The polymer of any one of claims 1, 2 and 13, wherein is a C2 to C8 alkylene moiety.

16. L １ 14. The polymer of any one of claims 1, 2 and 13, wherein is an arylene moiety (-aryl-).

17. L １ 14. The polymer of any one of claims 1, 2 and 13, wherein is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

18. having the structure (A-3a), and R １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n is an integer ranging from 1 to 7. 【Chemistry 14】

19. having the structure (A-3b), and R １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n is an integer ranging from 1 to 7. 【Chemistry 15】

20. having the structure (A-3c), and R １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7. 【Chemistry 16】

21. having the structure (A-3d), and R １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7. 【Chemistry 17】

22. The polymer of claim 1 or 2, having the structure (A-4): 【Chemistry 18】

23. 23. The polymer of any one of claims 1, 2 and 22, wherein L is a direct valence bond.

24. 23. The polymer of any one of claims 1, 2 and 22, wherein L is a C2 to C8 alkylene moiety.

25. 23. The polymer of any one of claims 1, 2 and 22, wherein L is an arylene moiety (-aryl-).

26. 23. The polymer of any one of claims 1, 2 and 22, wherein L is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

27. 23. The polymer of any one of claims 1, 2 and 22, wherein L is an alkylene aryl moiety (*-alkylene-aryl-**).

28. 23. The polymer of any one of claims 1, 2 and 22 having the structure (A-4a) wherein n' is an integer ranging from 0 to 7. 【Chemistry 19】

29. 30. The polymer of any one of claims 1, 2, 22 and 28 having the structure (A-4b) wherein n' is an integer ranging from 0 to 7. 【Chemistry 20】

30. 3. The polymer of claim 1 or 2 having the structure (A-4c) wherein n' is an integer ranging from 0 to 7. 【Chemical 21】

31. having the structure (A-4d), and R ｓ and R ｓ１ is independently selected from C1-C8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7. 【Chemical 22】

32. having the structure (B-1), R ３ｐ The polymer of claim 1 , wherein is a C1-C8 alkyl. 【Chemical 23】

33. having the structure (B-1a), and R ３ｐ is a C1-C8 alkyl. 【Chemistry 24】

34. R ３ｐ is C1-C8 alkyl, and L １ 34. The polymer of any one of claims 1, 32 and 33, wherein is a direct valence bond.

35. R ３ｐ is C1-C8 alkyl, and L １ 34. The polymer of any one of claims 1, 32 and 33, wherein is a C2 to C8 alkylene moiety.

36. R ３ｐ is C1-C8 alkyl, and L １ 34. The polymer of any one of claims 1, 32 and 33, wherein is an arylene moiety (-aryl-).

37. R ３ｐ is C1-C8 alkyl, and L １ 34. The polymer of any one of claims 1, 32 and 33, wherein is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

38. having the structure (B-1b), and R ３ｐ is C1-C8 alkyl, and R １３ and R １４ is independently selected from C1-C4 alkyloxy; and n is an integer ranging from 1 to 7. 【Chemistry 25】

39. having the structure (B-1c), and R ３ｐ is C1-C8 alkyl, and R １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n is an integer ranging from 1 to 7. 【Chemical 26】

40. having the structure (B-1d), and R ３ｐ is C1-C8 alkyl, and R １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7. 【Chemical 27】

41. having the structure (B-1e), and R ３ｐ is C1-C8 alkyl, and R １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n' is an integer ranging from 0 to 7. 【Chemical formula 28】

42. The polymer of claim 1 or 32, having the structure (B-2): 【Chemical 29】

43. 43. The polymer of any one of claims 1, 32 and 42, wherein L is a direct valence bond.

44. 43. The polymer of any one of claims 1, 32, and 42, wherein L is a C2 to C8 alkylene moiety.

45. 43. The polymer of any one of claims 1, 32 and 42, wherein L is an arylene moiety (-aryl-).

46. 43. The polymer of any one of claims 1, 33 and 42, wherein L is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

47. having the structure (B-2a), wherein Rs and Rs1 are independently selected from C1-C4 alkyloxy; １５ 43. The polymer of any one of claims 1, 33 and 42, wherein n is a C1-C8 alkyl and n' is an integer ranging from 0 to 7. 【Chemistry 30】

48. having the structure (B-2b), wherein Rs and Rs1 are independently selected from C1-C8 alkyl or alkoxy; １５ 50. The polymer of any one of claims 1, 33, 42 and 47, wherein n is a C1-C8 alkyl and n' is an integer ranging from 0 to 7. 【Chemical 31】

49. having the structure (B-2c), wherein Rs and Rs1 are independently selected from C1-C8 alkyl or alkoxy; １５ 43. The polymer of any one of claims 1, 33 and 42, wherein n is a C1-C8 alkyl and n' is an integer ranging from 0 to 7. 【Chemical 32】

50. having the structure (B-2d), wherein Rs and Rs1 are independently selected from C1-C8 alkyl or alkoxy; １５ 50. The polymer of any one of claims 1, 2, 45 and 49, wherein n is a C1-C8 alkyl and n' is an integer ranging from 0 to 7. 【Chemical 33】

51. The polymer of claim 1 or 32, having the structure (B-3): 【Chemical Formula 34】

52. 52. The polymer of claim 1 or 51 having the structure (B-3a): 【Chemistry 35】

53. 53. The polymer of any one of claims 1, 51 and 52, having the structure (B-3b): 【Chemical 36】

54. 53. The polymer of any one of claims 1, 51 and 52, having the structure (B-3c): 【Chemical 37】

55. 52. The polymer of claim 1 or 51 having the structure (B-3d): 【Chemical Formula 38】

56. 56. The polymer of any one of claims 1, 51 and 55 having the structure (B-3e): 【Chemical 39】

57. 56. The polymer of any one of claims 1, 51 and 55 having the structure (B-3f): 【Chemistry 40】

58. 52. The polymer of claim 1 or 51 having the structure (B-3g): 【Chemistry 41】

59. 60. The polymer of any one of claims 1, 51 and 58 having the structure (B-3h): 【Chemistry 42】

60. 60. The polymer of any one of claims 1, 51 and 58 having the structure (B-3i): 【Chemistry 43】

61. A composition comprising a polymer according to any one of claims 1 to 60 and an organic spin-casting solvent.

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

63. A composition comprising the polymer according to any one of claims 3 to 12 and an organic spin-casting solvent.

64. A composition comprising the polymer of any one of claims 13 to 21 and an organic spin-casting solvent.

65. A composition comprising the polymer of any one of claims 22 to 31 and an organic spin-casting solvent.

66. 33. A composition comprising the polymer of claim 32 and an organic spin-casting solvent.

67. A composition comprising the polymer of any one of claims 33 to 41 and an organic spin-casting solvent.

68. A composition comprising the polymer of any one of claims 42 to 50 and an organic spin-casting solvent.

69. A composition comprising the polymer of any one of claims 51 to 60 and an organic spin-casting solvent.

70. 1. A method for selectively forming pinned layer brushes on a substrate including both metallic and non-metallic surface regions, comprising the steps of: i) coating the composition of any one of claims 61 to 69 onto the substrate to form a film; ii) baking the film at a temperature of about 120° C. to about 250° C. for about 1 minute to about 1 hour to form a baked film; iii) washing the baked film with a solvent to remove ungrafted polymer, thereby forming pinning layer brushes only on the metal surface regions of the substrate; The method comprising:

71. 71. The method of claim 70, wherein the metallic surface region is 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 the non-metallic surface region is selected from the group consisting of Si, SiOx, SiNx, SiON, and organic dielectric substrates.

72. Next steps: ia) coating the composition of any one of claims 51 to 58 onto a substrate comprising both metallic and non-metallic surface regions to form a film; iia) baking the film at a temperature of about 120° C. to about 250° C. for about 1 minute to about 1 hour to form a baked film; iiia) washing the baked film with a solvent to remove ungrafted polymer, thereby forming a grafted substrate in which pinning layer brushes are present only on the metal surface regions of the substrate; iv) coating the grafted substrate with a neutral layer composition to form a neutral layer coating; va) curing the neutral layer coating; via) forming a chemo-epitaxy inducing layer on the substrate by washing away the uncured neutral layer with a solvent, leaving neutral inducing brushes on the non-metallic areas; viia) coating a block copolymer solution onto the chemo-epitaxy-derived layer to form a block copolymer coating; viii) annealing the coating of block copolymer to form a directed self-assembled film of block copolymer on the chemo-epitaxy-directed layer. A method comprising:

73. 73. The method of claim 72, wherein in the substrate, the metallic surface region is tungsten and the non-metallic surface region is silicon or silicon oxide.

74. 74. The method of claim 72 or 73, wherein the block copolymer is a block copolymer comprising styrenic repeat units and alkylacrylic repeat units.

75. 75. The method of any one of claims 72 to 74, wherein the block copolymer is an AB diblock copolymer of alkylacrylic repeating units and styrenic repeating units, or an ABA triblock copolymer of alkylacrylic repeating units and styrenic repeating units.

76. A compound of structure (I): In the formula, R １ is a chelating group located in the para or meta position selected from a phosphinothioic acid moiety of structure (Ia), an aminosulfonyl moiety of structure (Ib), and a phosphonamide moiety of structure (Ic), and * indicates the point of attachment of these moieties to said compound of structure (I); In the phosphinothioic acid moiety of structure (Ia), R ３ and R ４ are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy; and a dialkylamino moiety -N(R ９ ) (R １０ ) and R ９ and R １０ are independently selected from C1-C8 linear alkyl, C3-C8 branched alkyl, and C3-C8 cyclic alkyl; In said aminosulfonyl moiety of structure (Ib), R ５ and R ６ are independently C1 to C8 linear alkyl, C3 to C8 branched alkyl, C3 to C8 cyclic alkyl, and the dialkylamino moiety -N(R ９ ) (R １０ ) and In the phosphonamide moiety of structure (Ic), R ７ is the dialkylamino moiety -N(R ９ ) (R １０ ) and R ８ is selected from the group consisting of aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy; R ２ is a substituent located at the meta or para position selected from the group consisting of H, aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; a phosphinothioic acid moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic), The compound. 【Chemical 44】

77. 77. The compound of claim 76 having the structure (I-1): 【Chemistry 45】

78. 77. The compound of claim 76 having the structure (I-2): 【Chemistry 46】

79. R in the chelating group １ 77. The compound of claim 76, wherein is a phosphinothioic acid moiety of structure (Ia).

80. R in the chelating group １ 77. The compound of claim 76, wherein is an aminosulfonyl moiety of structure (Ib).

81. R in the chelating group １ 77. The compound of claim 76, wherein is a phosphonamide moiety of structure (Ic).

82. R ２ The compound of any one of claims 76 to 81, wherein is H.

83. R ２ The compound of any one of claims 76 to 81, wherein is aryl.

84. R ２ The compound of any one of claims 76 to 81, wherein is alkylenearyl.

85. R ２ The compound of any one of claims 76 to 81, wherein is a C2 to C8 alkyleneoxyalkyl.

86. R ２ The compound of any one of claims 76 to 81, wherein is C2 to C8 haloalkyl.

87. R ２ 82. The compound of any one of claims 76 to 81, wherein is a C1 to C8 linear alkyl.

88. R ２ The compound of any one of claims 76 to 81, wherein is a C3 to C8 branched alkyl.

89. R ２ The compound of any one of claims 76 to 81, wherein is a C3 to C8 cyclic alkyl.

90. R ２ The compound of any one of claims 76 to 81, wherein is C1 to C8 linear alkyloxy.

91. R ２ The compound according to any one of claims 76 to 81, wherein is a C3 to C8 branched alkyloxy.

92. R ２ The compound according to any one of claims 76 to 81, wherein is a C3 to C8 cyclic alkyloxy.

93. R ２ 82. The compound of any one of claims 76-81, wherein is a phosphinothioic acid moiety of structure (Ia).

94. R ２ 82. The compound of any one of claims 76-81, wherein is an aminosulfonyl moiety of structure (Ib).

95. R ２ 82. The compound of any one of claims 76-81, wherein is a phosphonamide moiety of structure (Ic).

96. A compound of structure (II): R １１ is a phosphinothioic acid moiety of structure (IIa), and * indicates the point of attachment of this moiety to said compound of structure (II); R １３ and R １４ are independently aryl, alkylenearyl, C2-C8 alkyleneoxyalkyl, C2-C8 haloalkyl, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy; and a dialkylamino moiety -N(R ９ ) (R １０ ) and R ９ and R １０ is independently selected from C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl; L １ is a linking moiety selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), and ** is a linking moiety selected from the group consisting of a direct valence bond, a C2-C8 alkylene moiety (-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-aryl-**), and an alkylenearyl moiety (*-alkylene-aryl-**) to phosphorus in structure (IIa). １ indicates the point of attachment of the organic linking moiety, and * indicates the moiety R １１ Inside L １ indicates the position of bonding to the carbonyloxy of compound (II), R １２ is H or C1-C4 alkyl; The compound. 【Chemistry 47】

97. R １３ is a C1-C8 linear alkyloxy.

98. R １３ is a C3-C8 branched alkyloxy.

99. R １３ is a C3-C8 cyclic alkyloxy.

100. R １４ 100. The compound of any one of claims 96 to 99, wherein is aryl.

101. R １４ 100. The compound of any one of claims 96 to 99, wherein is alkylenearyl.

102. R １４ The compound of any one of claims 96 to 99, wherein is a C2 to C8 alkyleneoxyalkyl.

103. R １４ The compound of any one of claims 96 to 99, wherein is C2 to C8 haloalkyl.

104. R １４ 100. The compound of any one of claims 95 to 99, wherein is a C1 to C8 linear alkyl.

105. R １４ 100. The compound of any one of claims 96 to 99, wherein is a C3 to C8 branched alkyl.

106. R １４ The compound of any one of claims 96 to 99, wherein is a C3 to C8 cyclic alkyl.

107. R １４ is a C1-C8 linear alkyloxy.

108. R １４ The compound of any one of claims 96 to 99, wherein is a C3 to C8 branched alkyloxy.

109. R １４ The compound of any one of claims 96 to 99, wherein is a C3 to C8 cyclic alkyloxy.

110. R １４ is the dialkylamino moiety -N(R ９ ) (R １０ 99. The compound according to claim 96, wherein

111. R ９ is a C1-C8 linear alkyl.

112. R ９ is a C3-C8 branched alkyl.

113. R ９ is a C3-C8 cyclic alkyl.

114. L １ is a direct valence bond.

115. L １ is a C2 to C8 alkylene moiety.

116. L １ is an arylene moiety (-aryl-).

117. L １ is an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**).

118. 118. The compound of claim 117, having the structure (IIc), wherein n is 1 to 7. 【Chemistry 48】

119. having the structure (IIc1), １３ and R １４ is independently selected from C1-C8 alkyl or alkoxy, and n is an integer from 1 to 7. 【Chemistry 49】

120. having the structure (IIa1), １３ and R １４ is independently selected from C1-C4 alkyl or alkoxy, and n is an integer ranging from 1 to 7. 【Chemistry 50】

121. L １ is an alkylenearyl moiety (*-alkylene-aryl-**).

122. 122. The compound of claim 121, having the structure (IIb), wherein n is an integer ranging from 1 to 7. 【Chemistry 51】

123. 123. The compound of claim 121 or 122, having the structure (IIb1): 【Chemistry 52】

124. having the structure (IIb2), １３ａ and R １４ａ is independently selected from C1-C4 alkyl. 【Chemistry 53】

125. Use of a compound according to any one of claims 76 to 124 in the manufacture of a polymer.

Images