Phosphonate-terminated brush polymers for directed self-assembly (DSA)

Abstract

The disclosed invention relates to compounds of structure (I) and polymers of structure (II) having a polydispersity in the range of 1 to about 1.1, compositions comprising said polymers and spin-casting solvents, methods of using said compositions to selectively form pinned layers on metals, and methods of using said pinned layers to induce chemoepitaxy-induced self-assembly of an overlying block copolymer, and subsequent methods of pattern-transferring this self-assembled layer into a substrate by etching. TIFF2023548791000063.tif38170

Description

[Technical Field]

[0001] The disclosed invention relates to compositions comprising novel acrylate compounds having pendant phosphonate moieties capable of forming acrylate- or styrene-containing polymers having these phosphonates as graftable end groups, and spin-casting solvents capable of selectively forming polar or nonpolar brush layers on metal substrates. The invention also relates to methods of using these compositions to form polar or nonpolar brushes on substrates, and methods of using these brushes for directed self-assembly. [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 allow 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 using 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 attracted interest for overcoming some of the drawbacks of conventional lithography as described 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, achieving feature critical dimensions (CD) on the nanoscale, typically ranging from 10 nm to 50 nm in feature size. Achieving features smaller than 10 nm using conventional strategies for directed self-assembly of block copolymers is difficult. 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 than EUV, e-beam, deep UV, or immersion lithography and / or by improving CD control. Block copolymers for directed self-assembly contain blocks of etch-resistant polymer units and blocks of etch-easy polymer units, which, when coated on a substrate, aligned, and etched, provide regions of high-resolution patterns.

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

[0006] In graphoepitaxy-guided self-assembly methods, block copolymers self-assemble on substrates that have been prepatterned with conventional lithography (ultraviolet, deep UV, and electron beam, extreme ultraviolet (EUV) exposure sources) to form topographical features such as line / space (L / S) or contact hole (CH) patterns. In one example of an L / S-guided self-assembly 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 topographical 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 contact holes 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 prepatterned hole with appropriate dimensions, offering potential shrinkage and tuning of the holes in the prepattern. As a result, graphoepitaxy has the potential to offer both pattern tuning and pattern multiplication.

[0007] In the chemical epitaxy (DSA) method, block copolymer self-assembly occurs on a surface that has regions of different chemical affinity but little or no topography to guide the self-assembly process. For example, chemical prepatterns can be generated 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 may have little or no topographical differences, but they provide a surface chemical pattern for the guided self-assembly of block copolymer domains. This technique allows for the precise displacement of these block copolymer domains with spatial frequencies greater than those of the prepattern. The aligned block copolymer domains can then be pattern-transferred into the underlying substrate after plasma or wet etching processes. In addition, chemical epitaxy has the advantage that block copolymer self-assembly can tailor variations in surface chemistry, dimensions, and roughness of the underlying chemical pattern, thus imparting improved line-edge roughness and CD control to the final self-assembled block copolymer domain pattern. Other types of patterns, such as contact hole (CH) arrays, can also be generated or tailored using chemo-epitaxy.

[0008] The ability of BCPs to undergo phase separation depends on the Flory-Huggins interaction parameter (x). 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 relatively low interaction parameter (x) between PS and PMMA. To enable further feature miniaturization, block copolymers with a larger interaction parameter (larger chi) 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 thermal 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 the BCP-air and BCP-substrate interactions. Many alignment-control methods 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 for a topcoat-free, high-ChiBCP 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 casting. As a result, due to this stronger adhesive formation, the formation of grafted polymer films on substrate materials is useful for a variety of applications. One example is biomaterials, where the substrate is made biocompatible by grafting polymers onto the surface of materials such as medical prosthetics without compromising the bulk mechanical properties.

[0011] Grafting of polymers onto substrate surfaces has also been used to render these surfaces anti-biofouling or to increase their corrosion resistance.

[0012] Coating solutions in which the grafting of polymers onto the surface of substrates changes the surface properties of these substrates, resulting in better coating; even 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.

[0013] Grafting of polymer brushes onto the surface of silicon or silicon oxide substrates can be used to form neutral layers on these surfaces that force the block copolymers to orient their domains perpendicular to the substrate surface during self-assembly or directed self-assembly.

[0014] Directed self-assembly of block copolymers is a useful method for generating ever smaller patterned features for the fabrication of microelectronic devices, achieving nanoscale feature critical dimensions (CDs). Directed self-assembly methods are desirable for extending the resolution capabilities of microlithography techniques. Conventional lithography methods can use ultraviolet (UV) radiation 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 by a developer solution or conventional IC plasma processing. Conversely, in negative-tone photoresists, UV radiation passing through the mask renders the exposed areas less removable by a developer solution or 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 using 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 and chemoepitaxy using block copolymer imaging, are highly desirable techniques used to increase resolution while reducing CD variation. These techniques can be used to augment conventional UV lithography techniques or to enable even higher resolution and CD control in methods using EUV, electron beam, deep UV, or immersion lithography.The directed self-assembly block copolymers contain blocks of etch-resistant copolymeric units and blocks of etch-prone copolymeric units, which when coated, aligned, and etched onto a substrate, provide highly dense patterned regions.

[0015] 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 alignment 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 ideal for both pattern tuning 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 would disrupt the desired vertical alignment that can be used to achieve either pattern tailoring 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 chemoepitaxy or graphoepitaxy used for pattern multiplication. Summary of the Invention [Problem to be solved by the invention]

[0016] There is a need for new materials that can undergo chemical bonding to 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 followed by a post-coat bake without the presence of activating components to promote the grafting reaction on the substrate, such as acidic compounds, thermal acid generators, photoacid generators, thermal radical generators, photochemical radical generators, basic additives, thermal base generators, or photobase generators. 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 that 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 can be made to have selective grafting to specific types of substrates by modifying the graft bake. In this way, the surface properties of these materials, such as coatability and corrosion resistance, can be modified by a simple spin-coating process without the need to use plasma deposition or electrochemical grafting. Also, in the case of the novel selective grafting process using the novel materials of the present invention, only one material can be coated in one step onto a substrate containing a topographical or chemical pattern where different materials are present on one substrate. There is also a need for new neutral layer compositions that, when formed into a layer, remain neutral with respect to the self-assembling block copolymer and remain undamaged by the process steps of directed self-assembly techniques, and further, can further enhance the lithographic performance of directed self-assembly materials and processes, particularly by reducing the number of process 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 in the neutral layer substrate to align in a desired direction. There is also a need for polar and non-polar brush compositions that selectively form only one type of material to form pinned regions on substrates containing patterns with different materials. [Means for solving the problem]

[0017] The present invention relates to novel compounds containing pendant phosphonate moieties that can react with acrylate or styrenic monomers to form polar or nonpolar pinning layer brush layers on metal substrates, i.e., polar or nonpolar pinning layer brush layers useful for directed self-assembly in specific device architectures used in DSA, where each block of the diblock or triblock copolymer forms a polar or nonpolar pinning layer brush layer that must anchor on substrates containing both metal and dielectric regions (e.g., Si, SiOx), but does not graft on nonmetallic substrates. To solve this problem, these different regions must each be coated with two different components, similar to the two blocks in a diblock copolymer. Here, compositions containing these polar and nonpolar terminal phosphonate moieties interact with the metal regions but not with the dielectric regions. DETAILED DESCRIPTION OF THE INVENTION

[0018] One aspect of the disclosed invention relates to compounds of structure (I), wherein: R2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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; L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group.

[0019] [ka] Another aspect of the invention relates to polymers of structure (II) having a polydispersity ranging from 1 to about 1.1, wherein R1 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, aryl, or alkylenearyl (i.e., -alkylene-aryl); R2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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; L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group; B is a direct valence bond or a methylene spacer (-CH-), A is a styrene-based polymer chain or an acrylic-based polymer chain.

[0020] [ka] Another aspect of the present invention is a composition comprising a polymer of structure (II) and a spin-casting solvent.

[0021] Another aspect of the present invention includes a method for forming a pinned layer using the composition, and a chemoepitaxy method using the pinned layer for the directed self-assembly of an overlying block copolymer, and a subsequent process for etching this directed self-assembled block polymer layer into a substrate.

[0022] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not limiting of the invention as claimed. In this application, the use of the singular includes the plural, and unless otherwise stated, 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. Also, references such as "element" or "component" include both elements and components containing one unit, as well as elements or components containing more than one unit, unless specifically stated otherwise. Unless otherwise stated, 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.

[0023] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All documents 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 document references and similar materials cited herein conflicts with that herein, the definition herein shall control.

[0024] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). These alkyl moieties may be substituted or unsubstituted as described below. 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, are understood to have the same carbon number range unless otherwise specified. When a different alkyl group length is specified, the above definition of alkyl remains valid in encompassing all types of alkyl moieties, and the above structural discussion regarding the minimum carbon number of a given type of alkyl group still applies.

[0025] 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, etc.) These alkyloxy moieties may be substituted or unsubstituted as described below.

[0026] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0027] 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.

[0028] The term "alkylene" refers to a hydrocarbon group having two or more bonds and which can be linear, branched, or cyclic (e.g., two-bonded groups include methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, etc.; three-bonded groups include 1,1,1-substituted methanes, 1,1,2-substituted ethanes, 1,2,4-substituted cyclohexanes, etc.). Again, when specifying a range of possible carbon numbers, such as, as a non-limiting example, C1 to C20, 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.

[0029] The term "aryl" or "aromatic group" refers to groups containing 6 to 24 carbon atoms, including phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyls, bis-phenyls, tris-phenyls, etc. These aryl groups may be further substituted with any suitable substituent, such as alkyl, alkoxy, acyl, or aryl groups as described above.

[0030] Unless otherwise indicated in the specification, the term "substituted," when referring to aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, fused aromatic rings, arenes, and heteroarenes, 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 substituents containing ethenylenearylene moieties (e.g., Ar(-CH=CH-Ar-)). z (z is 1-3)) refers to one of these moieties that also includes one or more substituents selected from the group. Specific non-limiting examples of substituted aryl and substituted arylethenyl substituents are listed below, where:

[0031] [ka] represents a bond:

[0032] [ka] One aspect of the invention is a compound of structure (I), wherein R2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group.

[0033] [ka] In another aspect of the compound of Formula (I), R2 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group.

[0034] In yet another aspect, the compound has structure (Ia), where R2 is H or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group. In another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another embodiment of this aspect of the invention, the compound is one in which L1 and L2 are both direct valence bonds.

[0035] [ka] In another aspect, the compound of structure (I) has the more specific structure (Ib), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 is a direct valence bond or a C1-C8 alkylene spacer group. In another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another more specific aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy.

[0036] [ka] In one more specific embodiment of the compound of structure (Ib), it has structure (Ic). In one aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy. In another aspect, R3 and R4 are ethyl. In another aspect, R3 and R4 are methyl.

[0037] [ka] In one more specific embodiment of the compound of structure (Ib), it has structure (Id). In one aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy. In another aspect, R3 and R4 are ethyl. In another aspect, R3 and R4 are methyl.

[0038] [ka] In one more specific embodiment of the compound of structure (Ib), it has structure (Ie). In one aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy. In another aspect, R3 and R4 are ethyl. In another aspect, R3 and R4 are methyl.

[0039] [ka] Another aspect of the invention is a polymer of structure (II) having a polydispersity ranging from 1 to about 1.1, where R1 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, aryl, or alkylenearyl (i.e., -alkylene-aryl); R2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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; L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group; B is a direct valence bond or a methylene spacer (—CH—); and A is a styrene-based polymer chain or an acrylic-based polymer chain.

[0040] [ka] Another aspect of the polymer of structure (II) is where R1 is H; R2 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4); and R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxy. and L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group, and A is a styrenic polymer chain.

[0041] Another aspect of the polymer of structure (II) is that which has formula (IIa), wherein R2 is H or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group. In another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy.

[0042] [ka] In another aspect of this polymer, it is any of the above-described aspects of the polymer in which it has structure (IIa), where R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this polymer, it is any of the above-described aspects of the polymer in which it has structure (IIa), where R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of this polymer, it is any of the above-described aspects of the polymer in which it has structure (IIa), where L1 and L2 are both direct valence bonds.

[0043] In another aspect of this polymer, it is any of the above embodiments of the polymer in which it has structure (IIa), but has the more specific structure (IIb).

[0044] [ka] In another aspect, the polymer of structure (II) has structure (IIc), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 is a direct valence bond or a C1-C8 alkylene spacer group. In another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy.

[0045] [ka] In another aspect, the polymer of structure (IIc) has structure (IId). In one aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy. In another aspect, R3 and R4 are ethyl. In another aspect, R3 and R4 are methyl.

[0046] [ka] In another aspect, the polymer of structure (IIc) has structure (IIe). In one aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy. In another aspect, R3 and R4 are ethyl. In another aspect, R3 and R4 are methyl.

[0047] [ka] In another aspect of the polymer of structure (II), R1 is C1-C8 linear alkyl, C3-C8 branched alkyl, or C3-C8 cyclic alkyl, aryl, alkylenearyl (i.e., -alkylene-aryl); R2 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4); R3 and R4 are independently aryl. L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group; and A is an acrylic polymer chain.

[0048] [ka] In another aspect of the polymer of structure (II), it has the structure (IIf), where R alkis a C1-C8 linear alkyl, a C3-C8 branched alkyl, or a C3-C8 cyclic alkyl; R2 is H or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group. In another aspect of this embodiment, R3 is C-C8 linear alkyl, C-C8 branched alkyl, C-C8 cyclic alkyl, C-C8 linear alkyloxy, C-C8 branched alkyloxy, or C-C8 cyclic alkyloxy; and R4 is C-C8 linear alkyloxy, C-C8 branched alkyloxy, or C-C8 cyclic alkyloxy. In yet another aspect of this embodiment, R3 and R4 are independently selected from C-C8 linear alkyloxy, C-C8 branched alkyloxy, or C-C8 cyclic alkyloxy. In yet another aspect of this embodiment, L1 and L2 are both direct valence bonds. In yet another aspect of this aspect, it has structure (IIg).

[0049] [ka] In another embodiment, the polymer of structure (II) has structure (IIh), where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 is a direct valence bond or a C1-C8 alkylene spacer group. In another more specific embodiment of this aspect, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another more specific embodiment of this aspect, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, L1 is a direct valence bond, and the polymer of Structure (II) has Structure (IIi). In another aspect of this embodiment, it has Structure (IIj).

[0050] [ka] In one aspect of the above embodiment of the present invention, wherein the polymer has structure (II), the polymer a is a styrene-based polymer having structure (III), wherein: R e1 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, aryl, or alkylenearyl (i.e., -alkylene-aryl); R2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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; L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group; R5 is H, C1-C4 linear alkyl; R6 is H, halide, 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; n is the number of repeat units; and further wherein the styrenic polymer has a polydispersity in the range of 1 to 1.1.

[0051] [ka] In one aspect of the styrenic polymer of structure (III), R e1 is H; R2 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group.

[0052] In one aspect of the styrenic polymer of structure (III) above, it has structure (IIIa), where R2 is H or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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; L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group.

[0053] [ka] In one aspect of the styrenic polymer of structure (IIIa), R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy.

[0054] In another aspect of the above embodiment of the styrenic polymer of structure (IIIa), R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In one aspect of this embodiment, L1 and L2 are both direct valence bonds.

[0055] In another aspect of the styrenic polymer, it has the structure (IIIb), where the substituent R e1 , R5, R6, R4, R3 may vary in different embodiments, and n and polydispersity may vary as described above for structures (III) and (IIIa).

[0056] [ka] In another aspect of the styrenic polymer, it has structure (IIIc), where substituent R e1 , R5, R6, R4, R3, and n and polydispersity can vary as described above for structures (III) and (IIIa). In one particular aspect of this embodiment, R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 is a direct valence bond or a C1-C8 alkylene spacer group. In one specific embodiment of this aspect, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of this embodiment, it has structure (IIId), where the substituents can be varied as described above for this embodiment. In another aspect of this embodiment, it has structure (IIIe).

[0057] [ka] In another aspect of the invention, the polymer of the invention is an acrylic polymer having structure (IV), where R alkis a C1-C8 linear alkyl, a C3-C8 branched alkyl, or a C3-C8 cyclic alkyl; R2 is H, halide, a C1-C8 linear alkyl, a C3-C8 branched alkyl, a C3-C8 cyclic alkyl, a C1-C8 linear alkyloxy, a C3-C8 branched alkyloxy, a C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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; L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group; R7 is H or C1-C4 linear alkyl; R8 is C1-C8 linear alkyl, C3-C8 branched alkyl, or C3-C8 cyclic alkyl; R e2 is a terminal group selected from H, C1-C8 linear alkyl, C3-C8 branched alkyl, or C3-C8 cyclic alkyl; n1 is the number of repeat units in the acrylate polymer; and further, the acrylic polymer has a polydispersity of 1 to 1.1. In one aspect of this embodiment, R alkis C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl; R2 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene and L1 and L2 are, independently, a direct valence bond or a C1-C8 alkylene spacer. In another aspect of this embodiment, R alk is C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl; R2 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene -aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 and L2 are independently a direct valence bond, or a C1-C8 alkylene spacer group.

[0058] [ka] In another aspect, the acrylic polymer has structure (IVa), where the substituent R e2, R7, R8 and n1 and polydispersity may vary as previously described for the acrylic polymer having structure (IV), further wherein R alk is a C1-C8 linear alkyl, a C3-C8 branched alkyl, or a C3-C8 cyclic alkyl; R2 is H or -P(=O)(R3)(R4); R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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; L1 and L2 are independently a direct valence bond or a C1-C8 alkylene spacer group. In yet another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In another aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another embodiment, L1 and L2 are both direct valence bonds. In yet another embodiment, the polymer has structure (IVb).

[0059] [ka] In another aspect, the acrylic polymer has the structure (IVc);e2 , R7, R8, and n1 and polydispersity can vary as previously described in the acrylic polymer, where R3 and R4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L1 is a direct valence bond, or a C1-C8 alkylene spacer group. In one aspect of this embodiment, R3 is 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 R4 is C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of this embodiment, R3 and R4 are independently selected from C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, or C3-C8 cyclic alkyloxy. In yet another aspect of the acrylic polymer, L1 is a direct valence bond, L2 is a direct valence bond or a C1-C8 alkylene spacer group, R2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4), and the polymer has structure (IVd). In a more specific aspect of the embodiment having structure (IVc), it has structure (IVe). In one more specific embodiment having structure (IVd), it has structure (IVf) where R2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R3)(R4).

[0060] [ka] Another aspect of the present invention is a composition comprising any one of the polymers according to the present invention described above and an organic spin-casting solvent.

[0061] In the above-described embodiment of the novel composition, the organic spin-casting solvent is capable of dissolving the novel polymer and any other additional optional ingredients as described above. The organic spin-casting solvent may be a single solvent or a mixture of solvents. Suitable solvents are organic solvents, including, for example, 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 dimethyl malonate; dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylic acids. carboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters such as methyl pyruvate or ethyl pyruvate; 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.

[0062] In addition to the polymer and solvent, the novel composition may contain a surfactant as an additive to facilitate coating.

[0063] Another aspect of the invention is a novel composition in which the novel polymer is present in an amount of about 0.1 wt. % to about 10 wt. % of the total weight of the composition, including the organic spin-casting solvent. In another aspect, it is present in an amount of about 0.1 wt. % to about 2 wt. %. In yet another embodiment, it is present in an amount of about 0.5 wt. % to about 1.5 wt. %. In yet another embodiment, it is present in an amount of about 0.75 wt. % to about 1.5 wt. %. In yet another embodiment, it is present in an amount of about 1 wt. %.

[0064] Another aspect of the present invention is a method for selectively forming pinned layer brushes on a substrate including both metallic and non-metallic surface regions, the method comprising the steps of: i) coating the composition described above 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 and form pinning layer brushes only on the metallic surface regions of the substrate; The method comprises:

[0065] Another aspect of the method including steps i) to iii) is the method wherein in step ii), the baking is performed for about 1 minute to about 30 minutes. In yet another aspect of this aspect in step ii), the film is baked at about 150°C to about 170°C. In yet another aspect of this aspect, it is baked at about 180°C. In yet another aspect, it is baked for about 30 minutes.

[0066] Another aspect of the method for selectively forming a pinned layer brush is a method in which 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 (silicon oxide), SiNx (silicon nitride), SiON (silicon oxynitride), and organic dielectric substrates.

[0067] Another aspect of the present invention is the steps of: ia) coating the composition described above onto a substrate containing both metallic and non-metallic surface areas to form a film; iia) baking the film at 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 to form a grafted substrate in which pinning layer brushes are present only on the metallic surface regions of the substrate; iva) coating the grafted substrate with a neutral layer composition to form a neutral layer coating; va) curing the neutral layer coating; via) removing the uncured neutral layer by washing with a solvent to leave neutral inductive brushes in the non-metallic areas of the substrate, thereby forming a chemo-epitaxy inductive layer on the substrate; viia) coating the chemo-epitaxy-derived layer with a block copolymer solution 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; The method includes:

[0068] In another aspect of the method including steps ia) to viii), in step iia), the baking is performed for about 1 minute to about 30 minutes. In yet another aspect of this embodiment, in step iia), the film is baked at about 150°C to about 170°C. In yet another aspect of this embodiment, it is baked at about 180°C. In yet another aspect, it is baked for about 30 minutes.

[0069] Another aspect of the method including steps ia) through viii) is the method wherein, for the substrate, the metallic surface region is tungsten and the non-metallic surface region is silicon or silicon oxide.

[0070] In another aspect of the method comprising steps ia) through viii), the block copolymer comprises styrenic repeat units and alkylacrylic repeat units.

[0071] Another aspect of the method including steps ia) to viia) is the method 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.

[0072] Specific non-limiting examples of block copolymers are poly(styrene-b-vinylpyridine), poly(styrene-b-butadiene), poly(styrene-b-isoprene), poly(styrene-b-methyl methacrylate), poly(styrene-b-alkenyl aromatics), poly(isoprene-b-ethylene oxide), poly(styrene-b-(ethylene-propylene)), poly(ethylene oxide-b-caprolactone), poly(butadiene-b-ethylene oxide), poly(styrene-b-t-butyl(meth)acrylate), poly(methyl methacrylate-b-t-butyl methacrylate), poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(methyl methacrylate-b-dimethylsiloxane), or a combination comprising at least one of the foregoing block copolymers. All these polymeric materials have in common the presence of at least one block rich in repeating units that are resistant to etching techniques typically used in the fabrication of IC devices, and at least one block that is rapidly etched under these same conditions, allowing the self-assembled polymer patterns to be transferred onto a substrate.

[0073] Another aspect of the present invention is the use of a compound of formula (I) as described above for the preparation of a polymer as described above.

[0074] Another aspect of this invention is the use of the polymer or composition described above to form a pinned layer brush on a substrate. [Example]

[0075] More specific embodiments of the present invention and experimental results supporting such embodiments are described below. Examples are set forth below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0076] 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 and 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.

[0077] Synthesis of DPE-phosphonates (I-IV) Example 1: Synthesis of diethyl 4-(1,1-diphenylethylene)phosphonate (DPE-I) (described in Scheme 1) A 1 L two-neck flask and magnetic bar were thoroughly dried in an oven under vacuum. 82 g (223 mmol) of methyltriphenylphosphonium bromide was added, dried under vacuum, and then backfilled with nitrogen. 600 mL of THF was added, and the reaction vessel was cooled in an ice bath. 156 mL of n-butyllithium (1.6 M in hexane, 249 mmol) was slowly added to the vessel under ice bath cooling, and the vessel temperature was allowed to warm to room temperature. The reaction was maintained for 1 hour until most of the solids had disappeared (the resulting ylide is soluble in THF). During the ylide reaction, a solution of 50 g (192 mmol) of 4-bromobenzophenone in 100 mL of TFH was prepared in a separate two-neck flask. The 4-bromobenzophenone solution was transferred to the ylide reaction vessel via cannula under ice bath conditions, and the reaction was stirred for 1 or 2 hours. The reaction was quenched with water and diluted with ethyl acetate. The mixture was extracted with 1% aqueous HCl and NaCl and dried over MgSO4. After filtering off the MgSO4, the solution was concentrated on a rotary evaporator. The white solid triphenylphosphonium oxide was precipitated by adding 2 / 1 hexane / ethyl acetate and filtered off. The solution was then concentrated again. Silica column chromatography using hexane, followed by solvent evaporation and drying under vacuum, afforded 43 g (92.7%) of 4-(1,1-diphenylethylene)-Br(I) as a colorless liquid product. 13 g (51.7 mmol) of 4-bromo-DPE(I) was added to a 500 mL two-necked flask, flushed with nitrogen, and dissolved in 200 mL of THF. 35.5 mL (56.9 mmol) of 1.6 M nBuLi was slowly added in a -78 °C bath, and the reaction was allowed to stand at the same temperature for 10 minutes. To a separate 500 mL two-neck flask was added 9.7 mL (67.2 mmol) of diethyl chlorophosphate under nitrogen. 100 mL of THF was added, and the solution was cooled to -78°C. The lithiated DPE solution was transferred via cannula over 20 minutes to the separate diethyl chlorophosphate in THF solution. This solution was stirred for 30 minutes, then diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO4. After filtration to remove the MgSO4, the organic layer was concentrated by evaporation of the solvent.Silica column chromatography through 50% hexane in ethyl acetate gave 12.5 g (76.3%) of a pale yellow oil. 1 H NMR(400MHz,CDCl3),ppm(δ),7.81(1H,dd,J=6.0Hz),7.79(1H,dd,J=6.0Hz),7.47-7.44(2H ,m),7.37-7.32(5H,m),5.57(1H,s),5.55(1H,s),4.21-4.12(4H,m),1.37(6H,t,J=5.3Hz).

[0078] Example 2: Synthesis of dimethyl 4-(1,1-diphenylethylene)phosphonate (DPE-II) (described in Scheme 2) The synthesis was carried out following the procedure of Example 1, except that dimethyl chlorophosphate was used instead of diethyl chlorophosphate. 1 H NMR(400MHz,CDCl3),ppm(δ),7.81(1H,dd,J=6.1Hz),7.77(1H,dd,J=6.1Hz),7.49- 7.46(2H,m),7.38-7.32(5H,m),5.58(1H,s),5.55(1H,s),3.83(3H,s),3.80(3H,s).

[0079] Example 3: Synthesis of phenylethyl 4-(1,1-diphenylethylene)phosphinate (DPE-III) (described in Scheme 3) 25 g of diethyl 4-(1,1-diphenyleneethylene)phosphate (DPE-I) was added to a 500 mL flask, and oxalyl chloride was slowly added, followed by a few drops of dimethylformamide in an ice bath. The reaction solution was stirred overnight at 50 °C while releasing gases in a fume hood. After all residues, excess oxalyl chloride, and solvent were removed by evaporation, phenylmagnesium bromide (2 M in diethyl ether) was slowly added to the THF solution at -78 °C, and the temperature was gradually raised to room temperature. The solution was diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over MgSO4. The MgSO4 was removed, the filtered organic layer was concentrated by evaporation, and 14.5 g of a pale yellow oil was obtained by silica column chromatography using 30% hexane in ethyl acetate. 1 H NMR(400MHz,CDCl3),ppm(δ),7.89-7.77(4H,m),7.57-7.42(5H,m),7.36-7.3 0(5H,m),5.55(1H,s),5.53(1H,s),4.19-4.12(2H,m),1.39(3H,t,J=9.18Hz).

[0080] Example 4: Synthesis of ethyl 4-(1,1-diphenylethylene)phosphinate (DPE-IV) (described in Scheme 4) The synthesis was carried out following the procedure of Example 2, using ethylmagnesium chloride (2M in diethyl ether) instead of phenylmagnesium bromide. 1 H NMR(400MHz,CDCl3),ppm(δ),7.77(1H,dd,J=6.18Hz),7.75(1H,dd,J=6.18Hz),7.48(1H,dd,J=6.13Hz),7.47(1H,dd,J=6.13Hz),7.40-7.32(5H,m), 5.57(1H,s),5.56(1H,s),4.17-4.11(1H,m),3.95-3.89(1H,m),2.0-1.87( 3H,m),1.34(3H,t,J=5.3Hz),1.18(3H,t,J=5.8Hz),1.13(3H,t,J=5.8Hz).

[0081] [ka] Scheme 1

[0082] [ka] Scheme 2

[0083] [ka] Scheme 3

[0084] [ka] Scheme 4

[0085] [ka] Scheme 5

[0086] [ka] Scheme 6

[0087] [ka] Scheme 7

[0088] [ka] Scheme 8

[0089] [ka] Scheme 9

[0090] [ka] Scheme 10

[0091] [ka] Scheme 11 Example 5: Synthesis of diethyl 4-(1,1-diphenylethylene)phosphonate-capped PMMA (PMMA-A) (described in Scheme 5) A calibrated ampoule equipped with two rotorflow stopcocks and a 19-f joint was charged with 25 mL of MMA (passed through an alumina column and degassed). After carefully degassing the MMA under strong vacuum while maintaining it at a low temperature, the desired amount of monomeric MMA (25 mL) was collected, and the ampoule was closed under vacuum using the stopcock. In a glovebox, the required amount of diethyl 4-(1,1-diphenylethylene)phosphonate (DPE-1) was weighed into a small vial (1.2 molar excess relative to Sec-BuLi) and dissolved in approximately 5–10 mL of toluene. The solution was immediately titrated with a dilute hexyl DPE-Li solution (a toluene solution containing 2 wt % 1,1'-diphenylethylene and an equimolar amount of sec-butyllithium to form an anion complex) until a pale orange / red color persisted. The solution color faded and then remained yellow. After closing the stopcock, the ampoule was removed from the glovebox. Both the MMA sample and the DPE sample were attached to the flask using glass joints and yellow grease. The required amount of LiCl (10-fold excess over Sec-BuLi) was weighed and quickly added to the flask, which was then closed with a three-way septum adapter connected to rubber tubing for vacuum / argon access. Vacuum was applied to the flask, and the LiCl was dried using a heat gun. After 10 minutes, the flask was brought to room temperature and backfilled with argon. Under positive pressure, approximately 250 mL of anhydrous THF was transferred to the flask via cannula transfer. The flask temperature was lowered to -78 °C using a dry ice / acetone bath. The LiCl / THF solution was titrated with Sec-BuLi (1.4 M) until a persistent lemon / yellow color was obtained. While the flask was at -78 °C, the MMA ampoule was backfilled with argon, and the pressure-equalizing stopcock was closed. After 5 minutes, the dry ice / acetone bath was removed and the flask was allowed to come to room temperature. Disappearance of the yellow color / sec-BuLi took 15-30 minutes (complete disappearance of excess sec-BuLi was observed).After a colorless solution was obtained, the flask temperature was lowered to -78°C, and the amount of sec-BuLi required to produce the activated DPE initiator was added using an airtight glass syringe. The rotor flow stopcock was then opened and the titrated 4-diethylphosphate-DPE solution was added. This resulted in a color change from yellow to dark red, the color of the activated DPE-Li initiator. After 2-3 minutes, MMA was added dropwise over a 3-6 minute period while maintaining the initiator solution under rapid stirring. The reaction continued for an additional 10 minutes and was then quenched with 3 mL of degassed methanol. The flask was allowed to reach room temperature, and the polymer was recovered by precipitation into water mixed with a few drops of HCl. The polymer was dissolved in ethyl acetate, washed with water, and then precipitated into hexane. The precipitated polymer was filtered and dried in vacuo at 60°C to give 4-diethylphosphate-capped PMMA with Mn = 4.8kJ and PDI = 1.05 in quantitative yield.

[0092] Example 6: Synthesis of dimethyl 4-(1,1-diphenylethylene)phosphonate-capped PMMA (PMMA-B) (described in Scheme 6) Synthesized following the procedure of Example 5, using dimethyl 4-(1,1-diphenylethylene)phosphonate instead of diethyl 4-(1,1-diphenylethylene)phosphonate. Mn=4.7k, PDI=1.06.

[0093] Example 7: Synthesis of phenylethyl 4-(1,1-diphenylethylene)phosphinate-capped PMMA (PMMA-C) (described in Example 7) Synthesized following the procedure of Example 5, using phenylethyl 4-(1,1-diphenylethylene)phosphinate instead of dimethyl 4-(1,1-diphenylethylene)phosphonate. Mn=6.5kJ, PDI=1.04.

[0094] Example 8: Synthesis of 4-(1,1-diphenylethylene)phosphinic acid capped PMMA (PMMA-D) (described in Scheme 8) Dimethyl 4-(1,1-diphenylethylene)phosphonate-capped PMMA (PMMA-B) was treated with iodotrimethylsilane overnight at room temperature and then precipitated in water. The filtered polymer was dried in a vacuum oven. Mn = 11.3kJ, PDI = 1.06.

[0095] Example 9: Synthesis of diethyl 4-(1,1-diphenylethylene)phosphonate-capped PS (PS-A) (described in Scheme 9) Step 1: 25 mL of styrene (column-passed and degassed) was placed in a calibrated ampoule equipped with two rotorflow stopcocks and a 19F connecting glass joint. After carefully degassing the styrene under strong vacuum while maintaining a low temperature, the 25 mL of styrene monomer was collected, and the ampoule was closed under vacuum using the stopcock. In a glovebox, diethyl 4-(1,1-diphenylethylene)phosphonate (DPE-I) was weighed into a small vial (1.2 molar excess relative to Sec-BuLi) and dissolved in approximately 5–10 mL of toluene. The solution was then transferred to a calibrated ampoule equipped with one rotorflow stopcock and a 19F connecting glass joint. The solution was immediately titrated with a dilute hexyl DPE-Li solution until a pale orange color persisted. After closing the stopcocks, the ampoule was removed from the glovebox. Both the styrene and DPE ampoules were attached to flasks using glass joints and yellow grease. A vacuum was applied to the flask and dried using a heat gun. After 10 minutes, the flask was brought to room temperature and backfilled with argon. Under positive pressure, approximately 250 mL of anhydrous THF was transferred to the flask via cannula transfer. The flask temperature was lowered to -78°C using a dry ice / acetone bath. The THF solution was titrated with sec-BuLi (1.4 M) until a persistent lemon / yellow color was obtained. While the flask was at -78°C, the styrene ampoule was backfilled with argon and the pressure-equalizing stopcock was closed. After 5 minutes, the dry ice / acetone bath was removed and the flask was allowed to come to room temperature. Disappearance of the yellow color / sec-BuLi took 15-30 minutes (complete disappearance of excess sec-BuLi was observed). After a colorless solution was obtained, the flask temperature was lowered to -78°C, and 7.9 mL of sec-BuLi (1.4 M) initiator was added using an airtight glass syringe. After 2-3 minutes, styrene was added dropwise within 3-6 minutes while the initiator solution was maintained under rapid stirring. The reaction was continued for an additional 30 minutes. Diethyl 4-(1,1-diphenylethylene)phosphonate was then added from the ampoule, and the immediate deep red color that resulted indicated a living anion of the DPE moiety.After 1 minute, the reaction mixture was quenched with 3 mL of degassed methanol. The flask was allowed to reach room temperature, and the polymer was recovered by precipitation into 2 L of isopropanol. The precipitated polymer was filtered, dissolved in ethyl acetate, and washed with water. The organic layer was precipitated into isopropanol, and the polymer was dried under vacuum at 70 °C to give diethyl 4-(1,1-diphenylethylene)phosphonate-capped PS (PS-A) in quantitative yield (Mn = 9k, PDI = 1.08).

[0096] Example 10: Synthesis of ethyl 4-(1,1-diphenylethylene)phosphonate-capped PS (PS-B) (described in Scheme 10) Synthesized following the procedure of Example 9, using ethyl ethyl 4-(1,1-diphenylethylene)phosphinate instead of diethyl 4-(1,1-diphenylethylene)phosphonate. Mn=5k, PDI=1.09.

[0097] Example 11:9: Synthesis of dimethyl 4-(1,1-diphenylethylene)phosphonate-capped PS (PS-C) (described in Scheme 11) Synthesized following the procedure of Example 9, using dimethyl 4-(1,1-diphenylethylene)phosphonate instead of diethyl 4-(1,1-diphenylethylene)phosphonate. Mn=10.6kJ, PDI=1.07.

[0098] Brush performance test The brush polymer was dissolved in PGMEA at 1 wt% solids content. The 1% solution was coated onto tungsten and silicon oxide wafers at 1500 rpm, respectively, and these were baked at 110°C for 5 minutes under nitrogen. Unreacted brushes were then rinsed off with PGMEA. After the wafers were baked at 230°C for 5 minutes under nitrogen, the wafer contact angle was measured by dropping water onto each wafer.

[0099] [Table 1]

[0100] The PMMA-A, -B, and -C brushes in the table show high carbon content on the W but not on the SiO as judged by WCA and XPS between the tungsten metal and silicon oxide. X The PS-A exhibits good contrast due to its significantly lower carbon content on the tungsten surface. PS-A exhibits significantly different water contact angles on both wafers, indicating that it is more oleophilic on tungsten but hydrophilic on silicon oxide.

[0101] Although the disclosed and claimed invention has been disclosed and described with a certain degree of detail, it will be recognized that the disclosure has been set forth by way of example only, and that numerous variations in the conditions and sequence of steps can be resorted to by one skilled in the art without departing from the spirit and scope of the disclosed and claimed invention. While this application is directed to the invention set forth in the claims, the disclosure of this application also includes: 1. A compound of structure (I): R 2 is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R 3 )(R 4 ) and; R 3 and R 4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L 1 and L 2 are independently a direct valence bond or a C1-C8 alkylene spacer group; The compound. [ka] 2. R 2 is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or -P(=O)(R 3 )(R 4 ) and; R 3 and R 4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L 1 and L 2 are independently a direct valence bond or a C1-C8 alkylene spacer group; The compound described in 1 above. 3. Having the following structure (Ia): R 2 is H, or -P(=O)(R 3 )(R 4 ) and; R 3 and R 4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), C2-C8 alkyleneoxyalkyl (i.e., -alkylene-O-alkyl), 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 L 1 and L 2 are independently a direct valence bond or a C1-C8 alkylene spacer group; The compound according to 1 or 2 above.

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Claims

1. A compound of the following structure (I): R ２ is a halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or —P(═O)(R ３ ) (R ４ ) and R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; The compound. 【Chemistry 1】

2. R ２ is C1 to C8 linear alkyl, C3 to C8 branched alkyl, C3 to C8 cyclic alkyl, C1 to C8 linear alkyloxy, C3 to C8 branched alkyloxy, C3 to C8 cyclic alkyloxy, or —P(═O)(R ３ ) (R ４ ) and R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; The compound of claim 1.

3. having the following structure (Ia): R ２ -P(=O)(R ３ ) (R ４ ) and R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; 3. The compound of claim 1 or 2. 【Chemistry 2】

4. A compound having the following structure (Ib): R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ is a C1-C8 alkylene spacer group; The compound. 【Transformation 3】

5. A compound of the following structure (Id): R 3 and R 4 are independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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; The compound. 【Chemistry 4】

6. A polymer of structure (II): R １ is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, aryl, or alkylenearyl (i.e., -alkylene-aryl); R ２ is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or —P(═O)(R ３ ) (R ４ ) and R ３ and R ４ are independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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; L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; B is a direct valence bond or a methylene spacer (-CH ２ -) and A is a styrene-based polymer chain or an acrylic-based polymer chain; and having a polydispersity in the range of 1 to 1.1; The polymer. 【Transformation 5】

7. R １ is H; R ２ is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or —P(═O)(R ３ ) (R ４ ) and R ３ and R ４ are independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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; L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; and A is a styrene-based polymer chain; The polymer of claim 6.

8. having the following structure (IIa): R ２ is H, or -P(=O)(R ３ ) (R ４ ) and R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; The polymer according to claim 6 or 7. 【Transformation 6】

9. 9. The polymer of claim 8 having the following structure (IIb): 【Transformation 7】

10. having the following structure (IIc): R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ is a direct valence bond or a C1-C8 alkylene spacer group; The polymer according to claim 6 or 7. 【Transformation 8】

11. 11. The polymer of claim 10 having the following structure (IId): 【Chemistry 9】

12. R １ is C1-C8 linear alkyl, C3-C8 branched alkyl or C3-C8 cyclic alkyl, aryl, alkylenearyl (i.e., -alkylene-aryl); R ２ is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or —P(═O)(R ３ ) (R ４ ) and R ３ and R ４ are independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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; L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; and A is an acrylic polymer chain; The polymer of claim 6.

13. having the following structure (IIf): R ａｌｋ is C1 to C8 linear alkyl, C3 to C8 branched alkyl, C3 to C8 cyclic alkyl; R ２ is H, or -P(=O)(R ３ ) (R ４ ) and R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; 13. The polymer of claim 6 or 12. 【Chemistry 10】

14. 14. The polymer of claim 13 having the following structure (IIg): 【Chemistry 11】

15. having the structure (IIh), R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ is a direct valence bond or a C1-C8 alkylene spacer group; 13. The polymer of claim 6 or 12. 【Chemistry 12】

16. 16. The polymer of claim 15, wherein L1 is a direct valence bond and the polymer of structure (IIh) has the following structure (IIi): 【Chemistry 13】

17. A styrenic polymer having the following structure (III): R ｅ１ is H, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, aryl, or alkylenearyl (i.e., -alkylene-aryl); R ２ is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or —P(═O)(R ３ ) (R ４ ) and R ３ and R ４ are independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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; L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; R ５ is H, C1-C4 linear alkyl; R ６ is H, halide, 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; n is the number of repeat units; and the styrenic polymer has a polydispersity in the range of 1 to 1.1; The polymer according to any one of claims 7 to 11. 【Chemistry 14】

18. having the following structure (IIIa): R ２ is H, or -P(=O)(R ３ ) (R ４ ) and R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; 18. The polymer of claim 17. 【Chemistry 15】

19. 20. The polymer of claim 18 having the following structure (IIIb): 【Chemistry 16】

20. having the following structure (IIIc): R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ is a direct valence bond or a C1-C8 alkylene spacer group; 19. The polymer of claim 17 or 18. 【Chemistry 17】

21. L １ is a direct valence bond and has the following structure (IIId): [Chemistry 18]

22. an acrylic polymer having the following structure (IV): R ａｌｋ is C1-C8 linear alkyl, C3-C8 branched alkyl, or C3-C8 cyclic alkyl; R ２ is H, halide, C1-C8 linear alkyl, C3-C8 branched alkyl, C3-C8 cyclic alkyl, C1-C8 linear alkyloxy, C3-C8 branched alkyloxy, C3-C8 cyclic alkyloxy, or —P(═O)(R ３ ) (R ４ ) and R ３ and R ４ are independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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; L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; R ７ is H or C1-C4 linear alkyl; R ８ is C1-C8 linear alkyl, C3-C8 branched alkyl, or C3-C8 cyclic alkyl; R ｅ２ is a terminal group selected from H, C1-C8 linear alkyl, C3-C8 branched alkyl, or C3-C8 cyclic alkyl; n1 is the number of repeat units in said acrylate polymer of structure (IV); and said acrylic polymer has a polydispersity in the range of 1 to 1.1; The polymer according to any one of claims 12 to 16. 【Chemistry 19】

23. having the following structure (IVa): R ａｌｋ is C1 to C8 linear alkyl, C3 to C8 branched alkyl, C3 to C8 cyclic alkyl; R ２ is H, or -P(=O)(R ３ ) (R ４ ) and R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ and L ２ is independently a direct valence bond or a C1-C8 alkylene spacer group; 23. The polymer of claim 22. 【Chemistry 20】

24. 24. The polymer of claim 23 having the following structure (IVb): 【Chemistry 21】

25. having the following structure (IVc): R ３ and R ４ is independently aryl, alkylenearyl (i.e., -alkylene-aryl), 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 L １ is a direct valence bond or a C1-C8 alkylene spacer group; 23. The polymer of claim 22. 【Chemistry 22】

26. L １ is a direct valence bond and has the following structure (IVd): 【Chemistry 23】

27. A composition comprising the polymer of any one of claims 6 to 26 and a spin-casting solvent.

28. 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 claim 27 onto the substrate to form a film; ii) baking the film at a temperature of 120°C to 250°C for 1 minute to 1 hour to form a baked film; iii) washing the baked film with a solvent to remove ungrafted polymer and form pinning layer brushes only on the metallic surface regions of the substrate; The method comprising:

29. Next steps: ia) coating the composition of claim 27 onto a substrate comprising both metallic and non-metallic surface areas to form a film; iia) baking the film at a temperature between 120°C and 250°C for 1 minute to 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 metallic 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) washing away the uncured neutral layer with a solvent to leave a neutral inductive brush on the non-metallic areas of the substrate, forming a chemo-epitaxy inductive layer on the substrate; viia) coating the chemo-epitaxy derived layer with a block copolymer solution 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:

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